CN110092399A - The co-production of battery-level lithium carbonate and magnesium-based functional material - Google Patents
The co-production of battery-level lithium carbonate and magnesium-based functional material Download PDFInfo
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- CN110092399A CN110092399A CN201910292937.3A CN201910292937A CN110092399A CN 110092399 A CN110092399 A CN 110092399A CN 201910292937 A CN201910292937 A CN 201910292937A CN 110092399 A CN110092399 A CN 110092399A
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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
- C01F—COMPOUNDS OF THE METALS BERYLLIUM, MAGNESIUM, ALUMINIUM, CALCIUM, STRONTIUM, BARIUM, RADIUM, THORIUM, OR OF THE RARE-EARTH METALS
- C01F7/00—Compounds of aluminium
- C01F7/78—Compounds containing aluminium and two or more other elements, with the exception of oxygen and hydrogen
- C01F7/784—Layered double hydroxide, e.g. comprising nitrate, sulfate or carbonate ions as intercalating anions
- C01F7/785—Hydrotalcite
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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 present invention is based on salt lake bitterns, provide the co-production of a kind of battery-level lithium carbonate and magnesium-based functional material comprising following step: S1, the preliminary separating magnesium and lithium of salt lake bittern；S2, reverse osmosis primary concentration；S3, electrodialysis secondary concentration；S4, preparation magnesium-based functional material；S5, battery-level lithium carbonate is prepared.The method that the salt lake bittern of high Mg/Li ratio provided by the invention comes coproduction magnesium-based functional material and battery-level lithium carbonate through separating magnesium and lithium, lithium enrichment, depth demagging, it not only can effectively solve previous methods complex process, technical problem at high cost, separating magnesium and lithium effect is undesirable, process flow is greatly shortened in lithium carbonate preparation process, reduce forced evaporation, adjusting pH, lithium carbonate purifying and two step demaggings becomes multiple processes such as a step demagging, the cost for preparing battery-level lithium carbonate is also greatly reduced, and has preferable industrialization prospect.
Description
Technical field
The invention belongs to salt lake chemical technology fields, it relates in particular to a kind of battery-level lithium carbonate and magnesium-based function material
The co-production of material.
Background technique
Lithium is the most light metallic element of nature, silvery white, has high specific heat, high conductivity and chemical activity strong etc. unique
Physicochemical characteristics, have extensive purposes, currently, lithium metal and its compound glass ceramics, electrolytic aluminium, lubricating grease,
Sustainable growth is applied in the traditional industries such as air conditioner refrigerating and organic synthesis, metallurgy, chemical industry, medicine and reagent field, is closed in aluminium lithium
The application in the fields such as the energy, military project, aerospace, the nuclear industry such as gold, lithium battery and nuclear fusion is also swift and violent to be expanded, therefore is known as
" industrial monosodium glutamate ", is also considered as important strategic materials by many countries.Again because of its application in terms of lithium battery, it is known as " pushing away
The energy metal of dynamic world's progress ".
In nature, the main preservation of lithium resource is in solid mineral and liquid brine.Brine lithium resource is in world's lithium resource
Critical role in exploitation has established nearly 30 years, it has caused lithium resource to develop industry in terms of applying and extracting lithium compound
Attention.The trend of lithium salts production is to be mentioned with salt lake based on lithium in the world, and ore method mentions supplemented by lithium.And China is due to salt lake bittern
Mentioning lithium has many advantages, such as that stock number is big, at low cost, and as solid lithium ore resources are increasingly depleted, salt lake bittern has been increasingly becoming lithium
The main source of resource.
The prevailing technology for proposing lithium technology for high Mg/Li ratio salt lake at present, specifically includes that salt field process, separating magnesium and lithium, contains
The processing steps such as the removal of impurities of lithium solution, the precipitating conversion of lithium carbonate.Existing separating magnesium and lithium method specifically includes that the precipitation method, calcining
Method, absorption method, extraction, membrane separation process etc., but distinct methods have respective advantage and disadvantage are required to certain improve and change
Into.Such as the use of ordinary organic solvents a large amount of in solvent extraction, equipment seriously corroded can be made, and serious environment can be brought
Pollution；Ionic adsorption method is suitable for the low salt lake bittern of ion concentration and directly mentions lithium, but since processing brine amount is big, water consume,
Resin consumption, power consumption increase accordingly, and are especially somewhat limited in the poorer area of freshwater resources, together
When lead to resin poison in process of production and broken also need to solve；Calcination method is able to achieve the salt lake bittern of high Mg/Li ratio
The separation of magnesium lithium, but this method generates hydrogen chloride gas in process of production and easily corrodes equipment, and evaporated water is larger, energy
Consumption is high, higher cost.In addition, the lithium-containing solution after separating magnesium and lithium needs further demagging, adjusts acid, concentration, add sodium carbonate conversion system
Standby lithium carbonate, this in the process needs that a large amount of chemical reagent such as a large amount of soda ash, caustic soda, hydrochloric acid are added, during solution enrichment method
Forced evaporation means are mostly used, investment is big, and energy consumption is high, and process flow is long, complex process.And current battery level lithium carbonate mostly uses
Industrial level lithium carbonate purifying is made.
Using nanofiltration separation technology, it is able to solve the problem of separating magnesium and lithium in salt lake brine with high magnesium-lithium ratio.The technology has
Green, efficiently, energy conservation, investment is small, low energy consumption, pollution less the advantages that, obtained rich lithium brine Mg/Li ratio value be down to 1:1 hereinafter,
And the process equipment is simple, and operating process is short, and it is easily controllable, it is suitable for the popularization of industrialization.Utilize nanofiltration membrane from salt as a kind of
The method of separating magnesium and enriching lithium in lake bittern water, although this method can be effectively reduced brine Mg/Li ratio and to a certain extent reality
Lithium ion content, which has not yet been reached, in the rich lithium brine for having showed the enrichment of lithium, but finally having obtained carries out the dense of precipitating conversion lithium carbonate
Degree also needs further to be enriched with concentration；And a kind of method of the separation and Extraction lithium from brine, the method using multistage nanofiltration and
The separation and enrichment of multi-stage reverse osmosis technique progress lithium.The patent application keeps lithium concentration rich by the method for multi-stage reverse osmosis
Collect 16000ppm, the salt content in pregnant solution is up to 10% or so, but under High Concentration Situation using reverse osmosis process into
Row enrichment concentration, will increase cost of investment and equipment energy consumption.
To sum up, in the prior art for the salt lake bittern processing method of high Mg/Li ratio, generally there are asking for following several respects
Topic: (1) existing separating magnesium and lithium method is at high cost, complex process；(2) after separating magnesium and lithium, depth demagging need to be carried out in two steps, first plus
Soda ash, then plus caustic soda, complex process it is at high cost；(3) solution needs to be added salt acid for adjusting pH after demagging, is in neutrality solution
It can be carried out evaporation and concentration, increase cost；(4) the demagging lithium-containing solution obtained just can be carried out after needing further enrichment to be concentrated and turn
Change prepares lithium carbonate, and enrichment concentration mostly uses forced evaporation means, and investment is big, and energy consumption is high, at high cost；(5) salt lake bittern is utilized
The lithium carbonate of preparation is mostly technical grade, and wherein the foreign ions such as chloride ion, sodium ion, magnesium ion are higher, cannot reach LITHIUM BATTERY
The requirement of lithium carbonate.
At the same time, magnalium hydrotalcite (MgAl-LDH) is the double-metal hydroxide with layer structure, metallic element
It is arranged alternately on laminate, anion can be inserted in interlayer, forms the important stratiform functional material of a major class, urges in high dispersive
The fields such as change, selective absorption, function additive (fire retardant, ultraviolet-resistant agent, heat stabilizer etc.), biological medicine have answers extensively
With.
Summary of the invention
To solve the above-mentioned problems of the prior art, the present invention provides a kind of co-production of battery-level lithium carbonate,
The co-production carries out the concentration of separating magnesium and lithium and lithium using a variety of membrane coupling techniques using the salt lake bittern of high Mg/Li ratio as raw material
Enrichment, lithium concentration has also obtained efficiently concentrating while making the magnesium lithium in the salt lake bittern of high Mg/Li ratio obtain efficiently separating, and adopts
Depth demagging is carried out with secondary concentration liquid of the reaction-separation coupling one-step method to low Mg/Li ratio while preparing the magnesium-based of high added value
Functional material optimizes two step technology for removal of magnesium from phosphorous, while demagging lithium-containing solution obtained can be directly used for conversion precipitating and obtain
Battery-level lithium carbonate.
A kind of co-production of battery-level lithium carbonate and magnesium-based functional material, comprising steps of
S1, the preliminary separating magnesium and lithium of salt lake bittern；
The salt lake bittern is diluted and obtains dilution brine, the dilution brine is subjected to magnesium lithium point in film separation system
From the rich lithium solution of acquisition；Wherein, in the salt lake bittern, Mg/Li ratio is 5:1~100:1；In the dilution brine, Li+
Content be 0.1g/L~0.8g/L；In the rich lithium solution, Li+Concentration be 0.1g/L~3g/L, Mg/Li ratio 0.01:
1~1:1；
S2, reverse osmosis primary concentration；
The rich lithium solution is subjected to primary concentration in counter-infiltration system, obtains primary concentration liquid；Wherein, described one
In grade concentrate, Li+Concentration be 2.5g/L~8.0g/L, Mg/Li ratio be 0.01:1~1:1；
S3, electrodialysis secondary concentration；
The primary concentration liquid is subjected to secondary concentration in electrodialysis system, obtains secondary concentration liquid；Wherein, described
In secondary concentration liquid, Li+Concentration be 13.0g/L~22.0g/L, Mg/Li ratio be 0.03:1~1.5:1；
The preparation of S4, magnesium-based functional material；
Water-soluble aluminum salt is added into the secondary concentration liquid, mixing salt solution is made；By the mixing salt solution and by
Sodium carbonate and the mixed ammonium/alkali solutions of sodium hydroxide preparation are added drop-wise in reactor jointly, to carry out coprecipitation reaction, are nucleated
System；It is separated by solid-liquid separation after the nucleating systems ageing, gained solid phase is washed, drying obtains magnalium hydrotalcite, gained liquid
It is mutually demagging richness lithium solution；Wherein, in the demagging richness lithium solution, Li+Concentration be 13.0g/L~22.0g/L, Mg2+'s
Concentration is no more than 10ppm；
The preparation of S5, battery-level lithium carbonate；
Na is added into the demagging richness lithium solution2CO3Solution is until the pH of system reaches 8~14, and controls obtained
Na in mixed solution+Content be 31g/L~77g/L, Cl-Content be 115g/L~195g/L, it is anti-at 80 DEG C~110 DEG C
40min~90min is answered, the battery-level lithium carbonate is obtained.
Further, in the step S1, in the salt lake bittern, Mg/Li ratio is 8:1~50:1；In the dilution
In brine, Li+Content be 0.1g/L~0.8g/L；In the rich lithium solution, Li+Concentration be 0.6g/L~2g/L, magnesium lithium
Than for 0.05:1~0.4:1.
Further, in the step S2, in the primary concentration liquid, Li+Concentration be 2.0g/L~7.5g/L,
Mg/Li ratio is 0.05:1~0.4:1.
Further, in the step S3, in the secondary concentration liquid, Li+Concentration be 15.0g/L~20.0g/
L, Mg/Li ratio are 0.05:1~1:1.
Further, in the step S4, in the demagging richness lithium solution, Li+Concentration be 15.0g/L~
20.0g/L Mg2+Concentration be no more than 10ppm.
Further, in the step S4, in the mixing salt solution, Mg2+And Al3+The ratio between the amount of substance be
2:1~4:1；OH in the mixed ammonium/alkali solutions-With the Mg in the mixing salt solution2+The ratio between the amount of substance be 2:1~4:
1；Mg in the mixing salt solution2+With the CO in the mixed ammonium/alkali solutions3 2-The ratio between the amount of substance be 3.5:1~6.5:1.
Further, in the step S4, the water-soluble aluminum salt is aluminum nitrate, aluminum sulfate or aluminium chloride.
Further, in the step S5, Na is added in Xiang Suoshu demagging richness lithium solution2CO3PH of the solution up to system
Reach 9~13, controls Na in the mixed solution+Content be 36g/L~48g/L, Cl-Content be 133g/L~177g/L,
40min~90min is reacted at 90 DEG C~100 DEG C, obtains the battery-level lithium carbonate.
Further, in the step S5, the reaction time of 40min~90min includes the charging of 20min~50min
The digestion time of time and 20min~40min.
Further, in the step S2, reverse osmosis freshwater corresponding with the primary concentration liquid phase is also obtained；It is described
Reverse osmosis freshwater is back in the step S1 for diluting the salt lake bittern；In the step S3, also obtain with it is described
The corresponding electrodialysis fresh water of secondary concentration liquid phase；The electrodialysis fresh water is back in the step S2 and the rich lithium solution one
It is same to enter in the counter-infiltration system.
The present invention carries out separating magnesium and lithium and lithium using the salt lake bittern of high Mg/Li ratio as raw material, using a variety of membrane coupling techniques
Enrichment method, lithium concentration has also obtained efficient richness while making the magnesium lithium in the salt lake bittern of high Mg/Li ratio obtain efficiently separating
Collection carries out depth demagging using secondary concentration liquid of the reaction-separation coupling one-step method to low Mg/Li ratio and prepares high added value simultaneously
Magnesium-based functional material, optimize two steps technology for removal of magnesium from phosphorous in the prior art, thus simultaneously obtain demagging richness lithium solution be not necessarily to
Add acid for adjusting pH, directly prepares battery-level lithium carbonate by controlling crystallization of lithium carbonate process under alkaline condition.The present invention provides
High Mg/Li ratio salt lake bittern through separating magnesium and lithium, lithium enrichment, depth demagging come coproduction magnesium-based functional material and LITHIUM BATTERY carbonic acid
The method of lithium not only can effectively solve previous methods complex process, technical problem at high cost, separating magnesium and lithium effect is undesirable,
Process flow is greatly shortened in lithium carbonate preparation process, reduces forced evaporation, pH, lithium carbonate purifying and two step demaggings is adjusted and becomes
For multiple processes such as a step demaggings, the cost for preparing battery-level lithium carbonate is also greatly reduced, and has preferable industrialization prospect.
Specific embodiment
Hereinafter, detailed description of the present invention embodiment in future.However, it is possible to implement this hair in many different forms
It is bright, and the present invention should not be construed as limited to the specific embodiment illustrated here.On the contrary, provide these embodiments be for
Explanation the principle of the present invention and its practical application, to make others skilled in the art it will be appreciated that of the invention is various
Embodiment and the various modifications for being suitable for specific intended application.
The present invention is based on the salt lake bitterns of high Mg/Li ratio, propose the connection of a kind of battery-level lithium carbonate and magnesium-based functional material
Production method；The co-production includes the following steps:
In step sl, the preliminary separating magnesium and lithium of salt lake bittern.
The basic composition of the salt lake bittern is as follows: Li+Content be 1g/L~10g/L, Mg/Li ratio be 5:1~100:1,
Preferably 8:1~50:1；It can be seen that the salt lake bittern is a kind of salt lake bittern of high Mg/Li ratio.
It is worth noting that in the present invention, " Mg/Li ratio " refers to the mass ratio of magnesium ion and lithium ion.
Specifically, salt lake bittern is diluted and obtains dilution brine, then by dilution brine obtained in film separation system
Middle carry out separating magnesium and lithium obtains rich lithium solution.
More specifically, the basic composition of the dilution brine is as follows: Li+Content be 0.1g/L~0.8g/L, preferably
For 0.2g/L~0.7g/L；Also, in the rich lithium solution of acquisition, Li+Concentration be 0.1g/L~3g/L, preferably 0.6g/L
~2g/L, Mg/Li ratio are 0.01:1~1:1, preferably 0.05:1~0.4:1.
Preferably, above-mentioned film separation system refers specifically to nanofiltration separation system.
Further, after dilution brine being carried out separating magnesium and lithium in film separation system, in addition to film in the film separation system
The other side of the rich lithium solution that side obtains, corresponding film has also obtained low lithium solution；The low lithium solution in this part can be discharged into salt Tanaka
It is tedded, with used for other purposes.
In step s 2, reverse osmosis primary concentration.
Specifically, rich lithium solution is subjected in counter-infiltration system primary concentration, obtains primary concentration liquid.
The basic composition of primary concentration liquid obtained is as follows: Li+Concentration be 1.5g/L~8.0g/L, preferably
2.0g/L~7.5g/L, Mg/Li ratio are 0.01:1~1:1, preferably 0.05:1~0.4:1.
Further, after rich lithium solution being carried out primary concentration in counter-infiltration system, in addition to film one in counter-infiltration system
The other side of the primary concentration liquid that side obtains, corresponding film has also obtained reverse osmosis freshwater (hereinafter referred to as RO fresh water)；This part RO
Fresh water may return in step S1 for diluting salt lake bittern, on the one hand further recycle the part Li in the RO fresh water+, improve
Li+The rate of recovery, on the other hand reduce the consumption of dilution fresh water, be greatly reduced cost input and fresh water consumption, for
The poor Salt Lake Area of freshwater resources has more practical significance.
In step s3, electrodialysis secondary concentration.
Specifically, primary concentration liquid is subjected in electrodialysis system secondary concentration, obtains secondary concentration liquid.
The basic composition of secondary concentration liquid obtained is as follows: Li+Concentration be 13.0g/L~22.0g/L, preferably
15.0g/L~20.0g/L, Mg/Li ratio are 0.03:1~1.5:1, preferably 0.05:1~1:1.
Further, after primary concentration liquid being carried out secondary concentration in electrodialysis system, in addition to film in electrodialysis system
The other side of the secondary concentration liquid that side obtains, corresponding film has also obtained electrodialysis fresh water (hereinafter referred to as ED fresh water)；This part
ED fresh water may return to for carrying out primary concentration by counter-infiltration system together with rich lithium solution in step S2, on the one hand into one
Step recycles the part Li in the ED fresh water+, improve Li+The rate of recovery, on the other hand recycled freshwater resources.
In step s 4, the preparation of magnesium-based functional material.
Specifically, firstly, water-soluble aluminum salt is added into secondary concentration liquid, mixing salt solution is made；Then, this is mixed
It closes salting liquid and is added drop-wise in reactor jointly by mixed ammonium/alkali solutions prepared by sodium carbonate and sodium hydroxide, it is anti-be co-precipitated
It answers, obtains nucleating systems；Finally, being separated by solid-liquid separation after nucleating systems ageing, gained solid phase is washed, drying obtains magnalium
Hydrotalcite, gained liquid phase are demagging richness lithium solution.
Further, mixing salt solution and mixed ammonium/alkali solutions can control to mix in equal volume；Also, in mixing salt solution,
Mg2+And Al3+The ratio between the amount of substance be 2:1~4:1；OH in mixed ammonium/alkali solutions-With the Mg in mixing salt solution2+Substance
The ratio between amount be 2:1~4:1；Mg in mixing salt solution2+With the CO in mixed ammonium/alkali solutions3 2-The ratio between the amount of substance be 3.5:1
~6.5:1.
More specifically, water-soluble aluminum salt can be any one in aluminum nitrate, aluminum sulfate or aluminium chloride.
It is preferred that mixing salt solution and mixed ammonium/alkali solutions are added dropwise in reactor using the speed of 1mL/min~5mL/min,
To carry out coprecipitation reaction；The coprecipitation reaction is pH static method, and keeping its pH is 8~13, preferably 9~11, reaction temperature
It is 25 DEG C~70 DEG C, preferably 30 DEG C~50 DEG C.
In this way, the nucleation process of pre-prepared magnalium hydrotalcite is completed, wherein the magnalium hydrotalcite nucleus formed is i.e.
It can be used as the basis of subsequent magnalium hydrotalcite growth.
Preferably use hydro-thermal method or circumfluence method to be aged nucleating systems, control Aging Temperature be 50 DEG C~150 DEG C, it is old
Change 6h~48h, be then separated by solid-liquid separation, obtains magnalium hydrotalcite filter cake.
The magnalium hydrotalcite filter cake of above-mentioned acquisition is washed, is dried, is i.e. acquisition magnalium hydrotalcite.
Preferably, the magnalium hydrotalcite filter cake after washing is dried to 12h~48h at 60 DEG C~120 DEG C, can be obtained magnesium
Aluminum hydrotalcite.
At the same time, the basic composition of demagging richness lithium solution obtained is as follows: Li+Concentration be 13.0g/L~
22.0g/L, preferably 15.0g/L~20.0g/L, Mg2+Concentration be no more than 100ppm.
In step s 5, the preparation of battery-level lithium carbonate.
Specifically, Na is added into demagging richness lithium solution2CO3Solution until the pH of system reach 8~14, preferably 9~
13, and control Na in mixed solution obtained+Content be 31g/L~77g/L, preferably 36g/L~48g/L, Cl-Contain
Amount be 115g/L~195g/L, preferably 133g/L~177g/L, control mixing speed 100rpm~150rpm, in 80 DEG C~
40min~90min is reacted at 110 DEG C, preferably 90 DEG C~100 DEG C, is filtered, washed after reaction, dries i.e. acquisition LITHIUM BATTERY
Lithium carbonate.
Further, the reaction time of above-mentioned 40min~90min specifically include 20min~50min feed time and
The digestion time of 20min~40min.
Preferably, used Na2CO3The concentration general control of solution is excessive 10%~30% (wt%), preferably
It is excessive 15%~25%；It is worth noting that the meaning of " excess " herein are as follows: will be according to Na2CO3With Li+Reaction generates
Li2CO3Required Na2CO3Na in solution2CO3Amount as 100%, and on this basis, excessive above range, with as far as possible
Ground is by Li in demagging richness lithium solution+Precipitating generates Li2CO3, sodium carbonate mass concentration be 10%~30%, preferably 18%~
25%, mixing speed is 50rpm~200rpm, preferably 100rpm~150rpm.
The test parameter for the battery-level lithium carbonate that this step obtains is as follows: Li2CO3Main content is not less than 99.5%, Cl-Contain
Amount is no more than 40ppm, Na+Content is no more than 150ppm, Mg2+Content is no more than 90ppm, Ca2+Content is no more than 50ppm.
The co-production of above-mentioned battery-level lithium carbonate, still, following implementations will be stated by specific embodiment below
The selection of parameter is only specific example in example, is not used in limitation all.
Embodiment 1
The old halogen that is generated after mentioning potassium from Qinghai salt lake of salt lake bittern that the present embodiment uses, Li in the salt lake bittern+Content is 1g/L, Mg/Li ratio 100.
The first step, into separating magnesium and lithium is carried out in film separation system, obtains rich lithium after salt lake bittern fresh water dilution
Solution.
Wherein, Li in the dilution brine obtained after dilution+Content is 0.2g/L；And the Li in the rich lithium solution obtained+Content
For 0.6g/L, Mg/Li ratio 0.01.
Rich lithium solution is entered counter-infiltration system and carries out primary concentration, obtains primary concentration liquid by second step.
Wherein, Li in primary concentration liquid+Content is 1.5g/L, Mg/Li ratio 0.01.
Primary concentration liquid is entered electrodialysis system and carries out secondary concentration, obtains secondary concentration liquid by third step.
Wherein, Li in secondary concentration liquid+Content is 22g/L, Mg/Li ratio 0.03.
The ED fresh water obtained through secondary concentration is blended with the rich lithium solution that the first step obtains, by anti-in second step
Osmosis system carries out primary concentration, to realize the remaining recycling of lithium and the reuse of fresh water.
4th step, secondary concentration liquid carry out depth demagging, prepare magnesium-based functional material.
Specifically, firstly, six water alchlors configuration Mg is added into secondary concentration liquid2+With Al3+Substance amount it
Than the mixing salt solution for 2:1, and the mixed ammonium/alkali solutions of sodium hydroxide and sodium carbonate are prepared, OH in mixed ammonium/alkali solutions-Substance
Amount concentration be mixing salt solution in Mg2+2 times of substance withdrawl syndrome, Mg in mixing salt solution2+Substance withdrawl syndrome
It is CO in mixed ammonium/alkali solutions3 2-3.5 times of substance withdrawl syndrome；Then, by mixing salt solution and mixed ammonium/alkali solutions with 1mL/
The speed of min is added drop-wise in reaction vessel simultaneously, and to carry out coprecipitation reaction, control reaction system pH is 13, and reaction temperature is
30℃；Again, slurry is filtered after hydro-thermal method ageing 6h at 50 DEG C after fully reacting, is obtained magnalium hydrotalcite filter cake and is removed
The filtrate of magnesium richness lithium solution；Finally, by dry 12h, acquisition are white at 120 DEG C after the magnalium hydrotalcite Washing of Filter Cake to neutrality
Solid magnalium hydrotalcite.
Li in demagging richness lithium solution after depth demagging+Content is 22g/L, Mg2+Content is no more than 10ppm.
Demagging richness lithium solution after depth demagging is heated to 90 DEG C by the 5th step, wherein lithium is 22g/ in rich lithium solution
L, and be added excessive 25% thereto (on the basis of quality of the reaction equation ratio after equivalent) mass fraction be 25% carbonic acid
Sodium solution, and control Na+Content be 31g/L, Cl-Content be 177g/L, pH value in reaction 13, mixing speed is
150rpm carries out precipitation reaction 90min, and wherein feed time 50min, digestion time 40min are filtered, washed after reaction, are done
It is dry, obtain battery-level lithium carbonate.
Li in prepared battery-level lithium carbonate2CO3Main content is not less than 99.5%, Cl-Content is no more than 40ppm, Na+
Content is no more than 150ppm, Mg2+Content is no more than 90ppm, Ca2+Content is no more than 50ppm.
Embodiment 2
The old halogen that is generated after mentioning potassium from Qinghai salt lake of salt lake bittern that the present embodiment uses, Li in the salt lake bittern+Content is 10g/L, Mg/Li ratio 5.
The first step, into separating magnesium and lithium is carried out in film separation system, obtains rich lithium after salt lake bittern fresh water dilution
Solution.
Wherein, Li in the dilution brine obtained after dilution+Content is 0.8g/L；And the Li in the rich lithium solution obtained+Content
For 2g/L, Mg/Li ratio 0.4.
Rich lithium solution is entered counter-infiltration system and carries out primary concentration, obtains primary concentration liquid by second step.
Wherein, Li in primary concentration liquid+Content is 7.5g/L, Mg/Li ratio 0.4.
Primary concentration liquid is entered electrodialysis system and carries out secondary concentration, obtains secondary concentration liquid by third step.
Wherein, Li in secondary concentration liquid+Content is 15g/L, Mg/Li ratio 1.
The ED fresh water obtained through secondary concentration is blended with the rich lithium solution that the first step obtains, by anti-in second step
Osmosis system carries out primary concentration, to realize the remaining recycling of lithium and the reuse of fresh water.
4th step, secondary concentration liquid carry out depth demagging, prepare magnesium-based functional material.
Specifically, firstly, six water alchlors configuration Mg is added into secondary concentration liquid2+With Al3+Substance amount it
Than the mixing salt solution for 3:1, and the mixed ammonium/alkali solutions of sodium hydroxide and sodium carbonate are prepared, OH in mixed ammonium/alkali solutions-Substance
Amount concentration be mixing salt solution in Mg2+3 times of substance withdrawl syndrome, Mg in mixing salt solution2+Substance withdrawl syndrome
It is CO in mixed ammonium/alkali solutions3 2-4.5 times of substance withdrawl syndrome；Then, by mixing salt solution and mixed ammonium/alkali solutions with 5mL/
The speed of min is added drop-wise in reaction vessel simultaneously, and to carry out coprecipitation reaction, control reaction system pH is 8, reaction temperature 25
℃；Again, slurry is filtered after circumfluence method ageing 18h at 80 DEG C after fully reacting, is obtained magnalium hydrotalcite filter cake and is removed
The filtrate of magnesium richness lithium solution；Finally, by drying for 24 hours, obtains white at 60 DEG C after the magnalium hydrotalcite Washing of Filter Cake to neutrality
Solid magnalium hydrotalcite.
Li in demagging richness lithium solution after depth demagging+Content is 15g/L, Mg2+Content is no more than 10ppm.
Demagging richness lithium solution after depth demagging is heated to 110 DEG C by the 5th step, wherein lithium is 15g/ in rich lithium solution
L, and be added excessive 10% thereto (on the basis of quality of the reaction equation ratio after equivalent) mass fraction be 30% carbonic acid
Sodium solution, and control Na+Content be 48g/L, Cl-Content be 115g/L, pH value in reaction 8, mixing speed 50rpm
Precipitation reaction 40min is carried out, wherein feed time 20min, digestion time 20min are filtered, washed after reaction, are dried, and are obtained
Battery-level lithium carbonate.
Li in prepared battery-level lithium carbonate2CO3Main content is not less than 99.5%, Cl-Content is no more than 40ppm, Na+
Content is no more than 150ppm, Mg2+Content is no more than 90ppm, Ca2+Content is no more than 50ppm.
Embodiment 3
The old halogen that is generated after mentioning potassium from Qinghai salt lake of salt lake bittern that the present embodiment uses, Li in the salt lake bittern+Content is 7g/L, Mg/Li ratio 8.
The first step, into separating magnesium and lithium is carried out in film separation system, obtains rich lithium after salt lake bittern fresh water dilution
Solution.
Wherein, Li in the dilution brine obtained after dilution+Content is 0.7g/L；And the Li in the rich lithium solution obtained+Content
For 3g/L, Mg/Li ratio 1.
Rich lithium solution is entered counter-infiltration system and carries out primary concentration, obtains primary concentration liquid by second step.
Wherein, Li in primary concentration liquid+Content is 8g/L, Mg/Li ratio 1.
Primary concentration liquid is entered electrodialysis system and carries out secondary concentration, obtains secondary concentration liquid by third step.
Wherein, Li in secondary concentration liquid+Content is 20g/L, Mg/Li ratio 1.5.
The ED fresh water obtained through secondary concentration is blended with the rich lithium solution that the first step obtains, by anti-in second step
Osmosis system carries out primary concentration, to realize the remaining recycling of lithium and the reuse of fresh water.
4th step, secondary concentration liquid carry out depth demagging, prepare magnesium-based functional material.
Specifically, firstly, six water alchlors configuration Mg is added into secondary concentration liquid2+With Al3+Substance amount it
Than the mixing salt solution for 4:1, and the mixed ammonium/alkali solutions of sodium hydroxide and sodium carbonate are prepared, OH in mixed ammonium/alkali solutions-Substance
Amount concentration be mixing salt solution in Mg2+4 times of substance withdrawl syndrome, Mg in mixing salt solution2+Substance withdrawl syndrome
It is CO in mixed ammonium/alkali solutions3 2-5.5 times of substance withdrawl syndrome；Then, by mixing salt solution and mixed ammonium/alkali solutions with 2mL/
The speed of min is added drop-wise in reaction vessel simultaneously, and to carry out coprecipitation reaction, control reaction system pH is 11, and reaction temperature is
50℃；Again, after fully reacting slurry at 100 DEG C hydro-thermal method ageing 36h after be filtered, obtain magnalium hydrotalcite filter cake and
The filtrate of demagging richness lithium solution；Finally, by dry 36h, acquisition are white at 100 DEG C after the magnalium hydrotalcite Washing of Filter Cake to neutrality
Color solid magnalium hydrotalcite.
Li in demagging richness lithium solution after depth demagging+Content is 20g/L, Mg2+Content is no more than 10ppm.
Demagging richness lithium solution after depth demagging is heated to 100 DEG C by the 5th step, wherein lithium is 20g/ in rich lithium solution
L, and be added excessive 15% thereto (on the basis of quality of the reaction equation ratio after equivalent) mass fraction be 18% carbonic acid
Sodium solution, and control Na+Content be 77g/L, Cl-Content be 133g/L, pH value in reaction 9, mixing speed 100rpm
Precipitation reaction 70min is carried out, wherein feed time 30min, digestion time 40min are filtered, washed after reaction, are dried, and are obtained
Battery-level lithium carbonate.
Li in prepared battery-level lithium carbonate2CO3Main content is not less than 99.5%, Cl-Content is no more than 40ppm, Na+
Content is no more than 150ppm, Mg2+Content is no more than 90ppm, Ca2+Content is no more than 50ppm.
Embodiment 4
The old halogen that is generated after mentioning potassium from Qinghai salt lake of salt lake bittern that the present embodiment uses, Li in the salt lake bittern+Content is 2.5g/L, Mg/Li ratio 50.
The first step, into separating magnesium and lithium is carried out in film separation system, obtains rich lithium after salt lake bittern fresh water dilution
Solution.
Wherein, Li in the dilution brine obtained after dilution+Content is 0.1g/L；And the Li in the rich lithium solution obtained+Content
For 0.2g/L, Mg/Li ratio 0.05.
Rich lithium solution is entered counter-infiltration system and carries out primary concentration, obtains primary concentration liquid by second step.
Wherein, Li in primary concentration liquid+Content is 2g/L, Mg/Li ratio 0.05.
Primary concentration liquid is entered electrodialysis system and carries out secondary concentration, obtains secondary concentration liquid by third step.
Wherein, Li in secondary concentration liquid+Content is 13g/L, Mg/Li ratio 0.05.
The ED fresh water obtained through secondary concentration is blended with the rich lithium solution that the first step obtains, by anti-in second step
Osmosis system carries out primary concentration, to realize the remaining recycling of lithium and the reuse of fresh water.
4th step, secondary concentration liquid carry out depth demagging, prepare magnesium-based functional material.
Specifically, firstly, six water alchlors configuration Mg is added into secondary concentration liquid2+With Al3+Substance amount it
Than the mixing salt solution for 2:1, and the mixed ammonium/alkali solutions of sodium hydroxide and sodium carbonate are prepared, OH in mixed ammonium/alkali solutions-Substance
Amount concentration be mixing salt solution in Mg2+2 times of substance withdrawl syndrome, Mg in mixing salt solution2+Substance withdrawl syndrome
It is CO in mixed ammonium/alkali solutions3 2-6.5 times of substance withdrawl syndrome；Then, by mixing salt solution and mixed ammonium/alkali solutions with 4mL/
The speed of min is added drop-wise in reaction vessel simultaneously, and to carry out coprecipitation reaction, control reaction system pH is 9, reaction temperature 70
℃；Again, slurry is filtered after hydro-thermal method ageing 48h at 150 DEG C after fully reacting, is obtained magnalium hydrotalcite filter cake and is removed
The filtrate of magnesium richness lithium solution；Finally, by dry 48h, acquisition are white at 80 DEG C after the magnalium hydrotalcite Washing of Filter Cake to neutrality
Solid magnalium hydrotalcite.
Li in demagging richness lithium solution after depth demagging+Content is 13g/L, Mg2+Content is no more than 10ppm.
Demagging richness lithium solution after depth demagging is heated to 80 DEG C by the 5th step, wherein lithium is 13g/ in rich lithium solution
L, and be added excessive 30% thereto (on the basis of quality of the reaction equation ratio after equivalent) mass fraction be 10% carbonic acid
Sodium solution, and control Na+Content be 36g/L, Cl-Content be 195g/L, pH value in reaction 14, mixing speed is
200rpm carries out precipitation reaction 60min, and wherein feed time 30min, digestion time 30min are filtered, washed after reaction, are done
It is dry, obtain battery-level lithium carbonate.
Li in prepared battery-level lithium carbonate2CO3Main content is not less than 99.5%, Cl-Content is no more than 40ppm, Na+
Content is no more than 150ppm, Mg2+Content is no more than 90ppm, Ca2+Content is no more than 50ppm.
Although the present invention has shown and described referring 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 being defined by the claims and their equivalents, can carry out herein form and
Various change in details.
Claims (10)
1. the co-production of a kind of battery-level lithium carbonate and magnesium-based functional material, which is characterized in that comprising steps of
S1, the preliminary separating magnesium and lithium of salt lake bittern；
The salt lake bittern is diluted and obtains dilution brine, the dilution brine is subjected to separating magnesium and lithium in film separation system,
Obtain rich lithium solution；Wherein, in the salt lake bittern, Mg/Li ratio is 5:1~100:1, Li+Content be 1g/L~10g/L；
In the dilution brine, Li+Content be 0.1g/L~0.8g/L；In the rich lithium solution, Li+Concentration be 0.3g/L
~3g/L, Mg/Li ratio are 0.01:1~1:1；
S2, reverse osmosis primary concentration；
The rich lithium solution is subjected to primary concentration in counter-infiltration system, obtains primary concentration liquid；Wherein, dense in the level-one
In contracting liquid, Li+Concentration be 1.5g/L~8.0g/L, Mg/Li ratio be 0.01:1~1:1；
S3, electrodialysis secondary concentration；
The primary concentration liquid is subjected to secondary concentration in electrodialysis system, obtains secondary concentration liquid；Wherein, in the second level
In concentrate, Li+Concentration be 13.0g/L~22.0g/L, Mg/Li ratio be 0.03:1~1.5:1；
The preparation of S4, magnesium-based functional material；
Water-soluble aluminum salt is added into the secondary concentration liquid, mixing salt solution is made；By the mixing salt solution and by carbonic acid
Sodium and the mixed ammonium/alkali solutions of sodium hydroxide preparation are added drop-wise in reactor jointly, to carry out coprecipitation reaction, obtain nucleating systems；
Be separated by solid-liquid separation after nucleating systems ageing, gained solid phase is washed, it is dry obtain magnalium hydrotalcite, gained liquid phase be except
Magnesium richness lithium solution；Wherein, in the demagging richness lithium solution, Li+Concentration be 13.0g/L~22.0g/L, Mg2+Concentration not
More than 100ppm；
The preparation of S5, battery-level lithium carbonate；
Na is added into the demagging richness lithium solution2CO3Solution is until the pH of system reaches 8~14, and controls mixing obtained
Na in solution+Content be 31g/L~77g/L, Cl-Content be 115g/L~195g/L, reacted at 80 DEG C~110 DEG C
40min~90min obtains the battery-level lithium carbonate.
2. co-production according to claim 1, which is characterized in that in the step S1, in the salt lake bittern,
Mg/Li ratio is 8:1~50:1；In the dilution brine, Li+Content be 0.1g/L~0.8g/L；In the rich lithium solution
In, Li+Concentration be 0.6g/L~2g/L, Mg/Li ratio be 0.05:1~0.4:1.
3. co-production according to claim 1, which is characterized in that in the step S2, in the primary concentration liquid
In, Li+Concentration be 2.0g/L~7.5g/L, Mg/Li ratio be 0.05:1~0.4:1.
4. co-production according to claim 1, which is characterized in that in the step S3, in the secondary concentration liquid
In, Li+Concentration be 15.0g/L~20.0g/L, Mg/Li ratio be 0.05:1~1:1.
5. co-production according to claim 1, which is characterized in that molten in the demagging richness lithium in the step S4
In liquid, Li+Concentration be 15.0g/L~20.0g/L, Mg2+Concentration be no more than 10ppm.
6. co-production according to claim 1, which is characterized in that in the step S4, in the mixing salt solution
In, Mg2+And Al3+The ratio between the amount of substance be 2:1~4:1；OH in the mixed ammonium/alkali solutions-In the mixing salt solution
Mg2+The ratio between the amount of substance be 2:1~4:1；Mg in the mixing salt solution2+With the CO in the mixed ammonium/alkali solutions3 2-'s
The ratio between amount of substance is 3.5:1~6.5:1.
7. co-production according to claim 1 or 6, which is characterized in that in the step S4, the water-soluble aluminum salt
For aluminum nitrate, aluminum sulfate or aluminium chloride.
8. co-production according to claim 1, which is characterized in that in the step S5, Xiang Suoshu demagging richness lithium is molten
Na is added in liquid2CO3Solution reaches 9~13 up to the pH of system, controls Na in the mixed solution+Content be 36g/L~
48g/L, Cl-Content be 133g/L~177g/L, at 90 DEG C~100 DEG C react 40min~90min, obtain the battery
Level lithium carbonate.
9. co-production according to claim 1 or 8, which is characterized in that in the step S5,40min~90min's
Reaction time includes the feed time of 20min~50min and the digestion time of 20min~40min.
10. co-production according to claim 1, which is characterized in that in the step S2, also obtain and the level-one
The corresponding reverse osmosis freshwater of concentrate；The reverse osmosis freshwater is back in the step S1 old for diluting the salt lake
Halogen；In the step S3, electrodialysis fresh water corresponding with the secondary concentration liquid phase is also obtained；The electrodialysis fresh water returns
Enter in the counter-infiltration system together with the rich lithium solution in the extremely step S2.
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| CN114735727A (en) * | 2022-06-13 | 2022-07-12 | 北京化工大学 | Preparation method of lithium carbonate |
| CN116477858A (en) * | 2023-02-28 | 2023-07-25 | 四川顺应锂材料科技有限公司 | Method for preparing battery-grade lithium carbonate by pressure leaching of clay lithium ore |
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