CN108607502A - A kind of Low Cost Sorbents and preparation method carrying lithium for high Mg/Li ratio brine - Google Patents
A kind of Low Cost Sorbents and preparation method carrying lithium for high Mg/Li ratio brine Download PDFInfo
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- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
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- B01J20/04—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising compounds of alkali metals, alkaline earth metals or magnesium
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Abstract
The invention belongs to salt lake bittern extractive technique fields, specifically provide a kind of Low Cost Sorbents and preparation method carrying lithium for high Mg/Li ratio brine.A kind of Low Cost Sorbents carrying lithium for high Mg/Li ratio brine of the present invention, raw material is wanted using based on low-grade slag of the spodumene after selected, characteristic using its structure easily with lithium symbiosis, there is a large amount of lithium gap in its slag structure, further using alumine hydroxide colloid as supporter, make lithium occupy-place in colloidal grinding and sintering, and pickling obtains lithium gap, it has excellent Selective adsorption to lithium, and resists molten damage with good;In addition, using the electron deficient property that boron in boric acid is added, stable complex is generated with the class hydroxyl interface atoms of low-grade spodumene finely-powdered minerals at high temperature, maintains the activity of spodumene low-grade slag and lithium symbiosis.
Description
Technical field
The invention belongs to salt lake bittern extractive technique field, specifically provides and a kind of carrying the low of lithium for high Mg/Li ratio brine
Cost adsorbents and preparation method.
Background technology
Liquid puies forward lithium method and is broadly divided into three classes:The precipitation method, solvent extraction and absorption method.Wherein, law technology is precipitated
Maturation, has realized industrial applications, but the method carries that lithium technological process is more complex, and alkali consumption is larger, and environmental pollution is serious, and
And it is only applicable to the brine of low Mg/Li ratio.The main reason for China's liquid lithium is resourceful, but exploitation falls behind so far is brine
The content of middle magnesium is higher, and the critical problem that lithium is this technology how is carried from high Mg/Li ratio brine.Solvent extraction is applicable in
In high Mg/Li than brine, but brine need to be concentrated, equipment seriously corroded, and organic solvent is toxic and high volatility, thus
Production cost is high and unfriendly to environment.Seawater of the adsorption separation method especially suitable for high Mg/Li ratio brine and low lithium concentration, and
Technical process is simple, green high-efficient, production cost is low, is that most prospects for commercial application puies forward lithium method.
The key of absorption method is to develop the adsorbent of function admirable, it requires adsorbent to have excellent selection to adsorb lithium
Property, so that the interference of the alkali metal largely coexisted in brine, alkaline-earth metal ions can be excluded.It can be by it according to the property of adsorbent
It is divided into organic ion exchange adsorbing substance and Inorganic-ion-exchange agent.Ion exchange organic resin is difficult control to the selectivity of lithium
System, still in the stage of fumbling.And inorganic ions adsorbent has preferable selectivity to lithium, has unformed hydroxide absorption at present
Agent, ion-sieve type oxide adsorbent, layered adsorbent, compound stibate adsorbent and aluminum salt adsorbent etc..But exists and inhale
Attached amount is low, of high cost, and molten loss rate is big, and adsorption selectivity existing defects affect the scale application in industrial abstract lithium.
Chinese invention patent application number 201310694536.3 discloses a kind of lithium slag adsorbent carrying lithium for liquid
Preparation method.The present invention relates to a kind of preparation methods for the lithium slag adsorbent carrying lithium for liquid, and essence is purified by lithium mine waste residue
System, then 0%~20% coagent, 1%~20% binder and 0~20% water are added, lithium slag adsorbent is prepared in shaping and roasting.
The lithium slag adsorbent is selectively good to the lithium resource in extraction seawater and salt lake bittern.Raw material of the present invention is easy to get, preparation process letter
Single, production cost is low.
Chinese invention patent application number 201410065121.4 discloses a kind of high-performance brine for preparing and carries lithium adsorbent
Method and its adsorbent of preparation, the invention discloses a kind of high-performance brine for preparing to put forward the method for lithium adsorbent using in situ poly-
Synthetic method is closed, active aluminium hydroxide powder is dispersed in absorption resin duct, then is reacted with lithium salt solution, is improved anti-
Answer efficiency, it is ensured that the activity of adsorbent.This method is wound using the crosslinking of resin nano hole inner macromolecule chain, effectively inhibits work
The loss of property nano particle, it is ensured that the service life of adsorbent.Lithium is carried the invention also discloses the preparation high-performance brine to inhale
Adsorbent prepared by attached dose of method.
From the point of view of the above-mentioned prior art, there are of high cost, selectivity for carrying lithium from brine for the adsorbent synthesized at present
The defects of poor, molten loss rate is big, adsorption selectivity is poor, especially to the brine of high Mg/Li ratio, which separating magnesium lithium is more stranded, sternly
The scale application in industrial abstract lithium is affected again.
Invention content
In view of the deficienciess of the prior art, the present invention proposes that a kind of selective absorption performance is good, molten loss rate is small to be used for
High Mg/Li ratio brine carries the Low Cost Sorbents and preparation method of lithium.
To solve the above problems, the present invention uses following technical scheme:
A kind of preparation method for the Low Cost Sorbents carrying lithium for high Mg/Li ratio brine is strong with dense media-by spodumene ore mining
The progress of magnetic concentration process is selected, obtains spodumene concentrate of the oxidation lithium content 6% or more;It will sort remaining low-grade
Boric acid, ultra fine is added in slag;By fine powder and Al (OH)3Gel, lithium hydroxide mixed grinding, 500~800
High-temperature roasting under the conditions of DEG C, pickling obtain inexpensive lithium adsorbent;Specifically include following steps:
A, spodumene ore mining is sorted with dense media-strong magnetic ore separation process, obtains oxidation lithium content 6% or more
Spodumene concentrate and oxidation lithium content are rough less than 6% spodumene;
B, the rough middle addition boric acid of spodumene obtained to a steps, impregnate 12~for 24 hours after, take out, washing, obtain acidification
Spodumene afterwards is rough, carries out ultra fine, obtains fine powder;
C, the fine powder for obtaining b step and Al (OH)3Gel, lithium hydroxide mixed grinding, roast at 500~800 DEG C
3~5h is burnt, pickling obtains inexpensive lithium adsorbent.
Spodumene category monoclinic system, crystal are often in the form of a column, granular or plate.Color is in greyish white, grayish green, purple or yellow
Deng, hardness 6.5~7,3.03~3.22g/cm of density3.As lithium chemicals raw material, it is widely used in lithiumation work, glass, pottery
Porcelain industry enjoys the good reputation of " industrial monosodium glutamate ".The dense media of spodumene ore mining of the present invention-strong magnetic ore separation technique is conventional work
Skill, main includes broken, washup, ore dressing, most important of which is that ore-dressing technique passes through according to different ore properties
Ferrous contaminants in spodumene mine are removed, obtain high-grade spodumene concentrate by gravity and magnetic separation(Aoxidize lithium content 6% with
On), spodumene concentrate can be used for the fields such as ceramics, accessories, and will sort remaining low-grade slag and be used to prepare lithium absorption
Agent provides a kind of new purposes for the application of low-grade spodumene slag, reduces injury of the slag to environment, avoid wave
Take.The low-grade spodumene slag of what is more important is the good homobium of lithium, the characteristic using its structure easily with lithium symbiosis,
There is a large amount of lithium gap in slag structure, preferable basis is provided for selective absorption lithium.
Further, the preparation method of above-mentioned a kind of Low Cost Sorbents carrying lithium for high Mg/Li ratio brine, wherein b steps
The mass concentration of boric acid described in rapid is 20~30%.
Further, the preparation method of above-mentioned a kind of Low Cost Sorbents carrying lithium for high Mg/Li ratio brine, wherein b steps
Suddenly the ultra fine is:By the spodumene after washing, rough, water and grinding aid are mixed by certain weight ratio, in high speed dispersion
Disperse certain time on machine so that concentration slurry is made;In bucket inner wall for alloy material and in the grinder with chuck cooling device
Water and ball milling pearl is added, thickened pulp is added after being preheated to 30~50 DEG C and is ground;It is ground to after a certain period of time production
Product are filtered, washed and dried to get fine powder.
Further, a kind of preparation method of above-mentioned Low Cost Sorbents carrying lithium for high Mg/Li ratio brine, wherein institute
The mass ratio for stating the rough spodumene after washing, water and grinding aid is 3~8:20~40:5~12.
Further, a kind of preparation method of above-mentioned Low Cost Sorbents carrying lithium for high Mg/Li ratio brine, wherein institute
It is at least one of Sodium Polyacrylate or isooctyl acid potassium to state grinding aid.
Further, a kind of preparation method of above-mentioned Low Cost Sorbents carrying lithium for high Mg/Li ratio brine, wherein institute
The rotating speed for stating high speed dispersor is 1500~2000r/min, and jitter time is 2~5h.
Further, a kind of preparation method of above-mentioned Low Cost Sorbents carrying lithium for high Mg/Li ratio brine, wherein institute
Grinding is stated using one kind in three-roller type grinder or four-roller type grinder, milling time is 60~90min.
Further, a kind of preparation method of above-mentioned Low Cost Sorbents carrying lithium for high Mg/Li ratio brine, wherein institute
State fine powder and Al (OH)3Gel, lithium hydroxide mass ratio are 10~30:3~10:5~20.
Further, the preparation method of above-mentioned a kind of Low Cost Sorbents carrying lithium for high Mg/Li ratio brine, wherein the acid
Wash use mass concentration for 1~10% H2SO4Solution, liquid-solid ratio be 2.5~3, under the conditions of 50~90 DEG C pickling 15~
60min。
The present invention also provides a kind of above-mentioned preparation method be prepared it is a kind of for high Mg/Li ratio brine carry lithium it is low at
This adsorbent.
A kind of Low Cost Sorbents carrying lithium for high Mg/Li ratio brine of the present invention, it is low-grade after selected using spodumene
Slag is primary raw material, the characteristic using its structure easily with lithium symbiosis, there is a large amount of lithium gap in slag structure, further with
Alumine hydroxide colloid is supporter, makes lithium occupy-place in colloidal grinding and sintering, and pickling obtains lithium gap, is had to lithium excellent
Different Selective adsorption, and resist molten damage with good;In addition, using the electron deficient property that boron in boric acid is added, in high temperature
The lower class hydroxyl interface atoms with low-grade spodumene finely-powdered minerals generate stable complex, maintain spodumene low-grade ore
The activity of slag and lithium symbiosis.The adsorbent cost is low, and selectivity is strong, and lithium is carried suitable for high Mg/Li ratio brine.
Specific implementation mode
In the following, the present invention will be further described in detail by way of specific embodiments, but this should not be interpreted as to the present invention
Range be only limitted to example below.Without departing from the idea of the above method of the present invention, according to ordinary skill
The various replacements or change that knowledge and customary means are made, should be included in the scope of the present invention.
Embodiment 1
A kind of preparation for the Low Cost Sorbents carrying lithium for high Mg/Li ratio brine of the present invention, includes the following steps:
A, spodumene ore mining is sorted with dense media-strong magnetic ore separation process, obtains oxidation lithium content 6% or more
Spodumene concentrate and oxidation lithium content are rough less than 6% spodumene;
B, the rough middle boric acid that mass concentration is added and is 25% of spodumene obtained to a steps, after impregnating for 24 hours, takes out, washing obtains
Spodumene after to acidification is rough, carries out ultra fine, obtains fine powder;The ultra fine is:By water
Spodumene after washing is rough, water and grinding aid are by weight 5:30:8 mixing, the grinding aid are Sodium Polyacrylate or isooctyl acid
Potassium disperses certain time so that concentration slurry is made on high speed dispersor;The rotating speed of high speed dispersor is 1800r/min, dispersion
Time is 3h, and water and ball milling pearl is added for alloy material and in the grinder with chuck cooling device in bucket inner wall, is preheating
Thickened pulp is added after to 40 DEG C to be ground;It is ground to and product is filtered, washed and dried to get ultra-fine after a certain period of time
Change powder;The grinding uses three-roller type grinder, milling time 70min;
C, the fine powder for obtaining b step and Al (OH)3Gel, lithium hydroxide are 20 according to mass ratio:6:15 mixing are ground
Mill, roasts 4h, pickling at 600 DEG C, pickling use mass concentration for 8% H2SO4Solution, liquid-solid ratio 2.8, in 70 DEG C of items
Pickling 45min under part obtains inexpensive lithium adsorbent.
By the lithium adsorbent 800g that embodiment 1 is prepared be added to 8000mL content of magnesium be 120g/L, lithium content 4g/
Be stirred in the high Mg/Li ratio aqueous salt brine of L under state and adsorb lithium, when adsorbing small up to 2 after stop stirring and carry out solid-liquid point
From it is 120g/L, lithium content 0.15g/L to measure content of magnesium in the aqueous salt brine after absorption, and the adsorbent isolated is filtered
Cake sulfuric acid deviates from lithium, the lithium solution 1200mL deviate from, and the lithium concentration for measuring the lithium solution is 25.67g/L.
It is above-mentioned deviate from lithium after adsorbent 780g put into that 8000mL content of magnesium is 120g/L, lithium content is again
Be stirred in the high Mg/Li ratio aqueous salt brine of 4g/L under state and adsorb lithium, when adsorb it is small up to 2 when after stop stirring carry out solid-liquid
Separation, measure content of magnesium in the aqueous salt brine after absorption be 120g/L, lithium content 0.18g/L, and the adsorbent isolated
Filter cake sulfuric acid deviates from lithium, the lithium solution 1200mL deviate from, and the lithium concentration for measuring the lithium solution is 25.47g/L.
Embodiment 2
A kind of preparation for the Low Cost Sorbents carrying lithium for high Mg/Li ratio brine of the present invention, includes the following steps:
A, spodumene ore mining is sorted with dense media-strong magnetic ore separation process, obtains oxidation lithium content 6% or more
Spodumene concentrate and oxidation lithium content are rough less than 6% spodumene;
B, the rough middle boric acid that mass concentration is added and is 22% of spodumene obtained to a steps, after impregnating 13h, takes out, washing obtains
Spodumene after to acidification is rough, carries out ultra fine, obtains fine powder;The ultra fine is:By water
Spodumene after washing is rough, water and grinding aid are by weight 8:25:10 mixing, the grinding aid are Sodium Polyacrylate or isooctyl acid
Potassium disperses certain time so that concentration slurry is made on high speed dispersor;The rotating speed of high speed dispersor is 1600r/min, dispersion
Time is 4h, and water and ball milling pearl is added for alloy material and in the grinder with chuck cooling device in bucket inner wall, is preheating
Thickened pulp is added after to 35 DEG C to be ground;It is ground to and product is filtered, washed and dried to get ultra-fine after a certain period of time
Change powder;The grinding uses four-roller type grinder, milling time 65min;
C, the fine powder for obtaining b step and Al (OH)3Gel, lithium hydroxide are 18 according to mass ratio:5:12 mixing are ground
Mill, roasts 5h, pickling at 560 DEG C, pickling use mass concentration for 6% H2SO4Solution, liquid-solid ratio 3, in 80 DEG C of conditions
Lower pickling 50min, obtains inexpensive lithium adsorbent.
By the lithium adsorbent 800g that embodiment 2 is prepared be added to 8500mL content of magnesium be 120g/L, lithium content 4g/
Be stirred in the high Mg/Li ratio aqueous salt brine of L under state and adsorb lithium, when adsorbing small up to 2 after stop stirring and carry out solid-liquid point
From it is 120g/L, lithium content 0.2g/L to measure content of magnesium in the aqueous salt brine after absorption, and the adsorbent filter cake isolated
Deviate from lithium, the lithium solution 1200mL deviate from sulfuric acid, the lithium concentration for measuring the lithium solution is 26.92g/L.
It is above-mentioned deviate from lithium after adsorbent 790g put into that 8500mL content of magnesium is 120g/L, lithium content is again
Be stirred in the high Mg/Li ratio aqueous salt brine of 4g/L under state and adsorb lithium, when adsorb it is small up to 2 when after stop stirring carry out solid-liquid
Separation, measure content of magnesium in the aqueous salt brine after absorption be 120g/L, lithium content 0.25g/L, and the adsorbent isolated
Filter cake sulfuric acid deviates from lithium, the lithium solution 1300mL deviate from, and the lithium concentration for measuring the lithium solution is 26.56g/L.
Embodiment 3
A kind of preparation for the Low Cost Sorbents carrying lithium for high Mg/Li ratio brine of the present invention, includes the following steps:
A, spodumene ore mining is sorted with dense media-strong magnetic ore separation process, obtains oxidation lithium content 6% or more
Spodumene concentrate and oxidation lithium content are rough less than 6% spodumene;
B, the rough middle boric acid that mass concentration is added and is 20% of spodumene obtained to a steps, after impregnating 20h, takes out, washing obtains
Spodumene after to acidification is rough, carries out ultra fine, obtains fine powder;The ultra fine is:By water
Spodumene after washing is rough, water and grinding aid are by weight 3:35:12 mixing, the grinding aid are Sodium Polyacrylate or isooctyl acid
Potassium disperses certain time so that concentration slurry is made on high speed dispersor;The rotating speed of high speed dispersor is 2000r/min, dispersion
Time is 2h, and water and ball milling pearl is added for alloy material and in the grinder with chuck cooling device in bucket inner wall, is preheating
Thickened pulp is added after to 50 DEG C to be ground;It is ground to and product is filtered, washed and dried to get ultra-fine after a certain period of time
Change powder;The grinding is using one kind in three-roller type grinder or four-roller type grinder, milling time 80min;
C, the fine powder for obtaining b step and Al (OH)3Gel, lithium hydroxide are 25 according to mass ratio:10:12 mixing are ground
Mill, roasts 5h, pickling at 700 DEG C, pickling use mass concentration for 8% H2SO4Solution, liquid-solid ratio 2.9, in 75 DEG C of items
Pickling 55min under part obtains inexpensive lithium adsorbent.
By the lithium adsorbent 800g that embodiment 3 is prepared be added to 8500mL content of magnesium be 120g/L, lithium content 4g/
Be stirred in the high Mg/Li ratio aqueous salt brine of L under state and adsorb lithium, when adsorbing small up to 2 after stop stirring and carry out solid-liquid point
From it is 120g/L, lithium content 0.16g/L to measure content of magnesium in the aqueous salt brine after absorption, and the adsorbent isolated is filtered
Cake sulfuric acid deviates from lithium, the lithium solution 1200mL deviate from, and the lithium concentration for measuring the lithium solution is 27.2g/L.
It is above-mentioned deviate from lithium after adsorbent 795g put into that 8500mL content of magnesium is 120g/L, lithium content is again
Be stirred in the high Mg/Li ratio aqueous salt brine of 4g/L under state and adsorb lithium, when adsorb it is small up to 2 when after stop stirring carry out solid-liquid
Separation, measure content of magnesium in the aqueous salt brine after absorption be 120g/L, lithium content 0.2g/L, and the adsorbent isolated is filtered
Cake sulfuric acid deviates from lithium, the lithium solution 1200mL deviate from, and the lithium concentration for measuring the lithium solution is 26.92g/L.
Embodiment 4
A kind of preparation for the Low Cost Sorbents carrying lithium for high Mg/Li ratio brine of the present invention, includes the following steps:
A, spodumene ore mining is sorted with dense media-strong magnetic ore separation process, obtains oxidation lithium content 6% or more
Spodumene concentrate and oxidation lithium content are rough less than 6% spodumene;
B, the rough middle boric acid that mass concentration is added and is 28% of spodumene obtained to a steps, after impregnating 16h, takes out, washing obtains
Spodumene after to acidification is rough, carries out ultra fine, obtains fine powder;The ultra fine is:By water
Spodumene after washing is rough, water and grinding aid are by weight 4:32:7 mixing, the grinding aid are Sodium Polyacrylate or isooctyl acid
Potassium disperses certain time so that concentration slurry is made on high speed dispersor;The rotating speed of high speed dispersor is 1500r/min, dispersion
Time is 5h, and water and ball milling pearl is added for alloy material and in the grinder with chuck cooling device in bucket inner wall, is preheating
Thickened pulp is added after to 32 DEG C to be ground;It is ground to and product is filtered, washed and dried to get ultra-fine after a certain period of time
Change powder;The grinding uses three-roller type grinder, milling time 85min;
C, the fine powder for obtaining b step and Al (OH)3Gel, lithium hydroxide are 26 according to mass ratio:6:16 mixing are ground
Mill, roasts 4h, pickling at 750 DEG C, pickling use mass concentration for 4% H2SO4Solution, liquid-solid ratio 2.5, in 64 DEG C of items
Pickling 55min under part obtains inexpensive lithium adsorbent.
By the lithium adsorbent 800g that embodiment 4 is prepared be added to 8000mL content of magnesium be 120g/L, lithium content 4g/
Be stirred in the high Mg/Li ratio aqueous salt brine of L under state and adsorb lithium, when adsorbing small up to 2 after stop stirring and carry out solid-liquid point
From it is 120g/L, lithium content 0.12g/L to measure content of magnesium in the aqueous salt brine after absorption, and the adsorbent isolated is filtered
Cake sulfuric acid deviates from lithium, the lithium solution 1200mL deviate from, and the lithium concentration for measuring the lithium solution is 25.87g/L.
It is above-mentioned deviate from lithium after adsorbent 790g put into that 8000mL content of magnesium is 120g/L, lithium content is again
Be stirred in the high Mg/Li ratio aqueous salt brine of 4g/L under state and adsorb lithium, when adsorb it is small up to 2 when after stop stirring carry out solid-liquid
Separation, measure content of magnesium in the aqueous salt brine after absorption be 120g/L, lithium content 0.15g/L, and the adsorbent isolated
Filter cake sulfuric acid deviates from lithium, the lithium solution 1200mL deviate from, and the lithium concentration for measuring the lithium solution is 25g/L.
Embodiment 5
A kind of preparation for the Low Cost Sorbents carrying lithium for high Mg/Li ratio brine of the present invention, includes the following steps:
A, spodumene ore mining is sorted with dense media-strong magnetic ore separation process, obtains oxidation lithium content 6% or more
Spodumene concentrate and oxidation lithium content are rough less than 6% spodumene;
B, the rough middle boric acid that mass concentration is added and is 23% of spodumene obtained to a steps, after impregnating 17h, takes out, washing obtains
Spodumene after to acidification is rough, carries out ultra fine, obtains fine powder;The ultra fine is:By water
Spodumene after washing is rough, water and grinding aid are by weight 6:36:7 mixing, the grinding aid are Sodium Polyacrylate or isooctyl acid
Potassium disperses certain time so that concentration slurry is made on high speed dispersor;The rotating speed of high speed dispersor is 1600r/min, dispersion
Time is 5h, and water and ball milling pearl is added for alloy material and in the grinder with chuck cooling device in bucket inner wall, is preheating
Thickened pulp is added after to 40 DEG C to be ground;It is ground to and product is filtered, washed and dried to get ultra-fine after a certain period of time
Change powder;The grinding uses four-roller type grinder, milling time 65min;
C, the fine powder for obtaining b step and Al (OH)3Gel, lithium hydroxide are 28 according to mass ratio:7:18 mixing are ground
Mill, roasts 3.5h, pickling at 720 DEG C, pickling use mass concentration for 4% H2SO4Solution, liquid-solid ratio 2.8, at 72 DEG C
Under the conditions of pickling 50min, obtain inexpensive lithium adsorbent.
By the lithium adsorbent 800g that embodiment 5 is prepared be added to 8500mL content of magnesium be 120g/L, lithium content 4g/
Be stirred in the high Mg/Li ratio aqueous salt brine of L under state and adsorb lithium, when adsorbing small up to 2 after stop stirring and carry out solid-liquid point
From it is 120g/L, lithium content 0.18g/L to measure content of magnesium in the aqueous salt brine after absorption, and the adsorbent isolated is filtered
Cake sulfuric acid deviates from lithium, the lithium solution 1200mL deviate from, and the lithium concentration for measuring the lithium solution is 27.06g/L.
It is above-mentioned deviate from lithium after adsorbent 785g put into that 8500mL content of magnesium is 120g/L, lithium content is again
Be stirred in the high Mg/Li ratio aqueous salt brine of 4g/L under state and adsorb lithium, when adsorb it is small up to 2 when after stop stirring carry out solid-liquid
Separation, measure content of magnesium in the aqueous salt brine after absorption be 120g/L, lithium content 0.22g/L, and the adsorbent isolated
Filter cake sulfuric acid deviates from lithium, the lithium solution 1200mL deviate from, and the lithium concentration for measuring the lithium solution is 26.78g/L.
Comparative example 1
A kind of preparation for the Low Cost Sorbents carrying lithium for high Mg/Li ratio brine, includes the following steps:
A, spodumene ore mining is sorted with dense media-strong magnetic ore separation process, obtains oxidation lithium content 6% or more
Spodumene concentrate and oxidation lithium content are rough less than 6% spodumene;
B, the rough middle addition Al (OH) of spodumene obtained to a steps3Gel, lithium hydroxide are 28 according to mass ratio:7:18 is mixed
Close grinding, roast 3.5h, pickling at 720 DEG C, pickling use mass concentration for 4% H2SO4Solution, liquid-solid ratio 2.8,
Pickling 50min under the conditions of 72 DEG C, obtains inexpensive lithium adsorbent.
Comparative example 1 does not use boric acid micronization processes lithium brightness mine crude product, and the lithium adsorbent 800g being prepared is added to
It is stirred in the high Mg/Li ratio aqueous salt brine that 8500mL content of magnesium is 120g/L, lithium content is 4g/L under state and adsorbs lithium, when
Absorption is separated by solid-liquid separation up to stopping stirring after 2 hours, and it is 120g/L, lithium content to measure content of magnesium in the aqueous salt brine after absorption
For 2.1g/L.Due to boric acid not being used to handle, absorption property is declined.
Comparative example 2
A kind of preparation for the Low Cost Sorbents carrying lithium for high Mg/Li ratio brine, includes the following steps:
By Al (OH)3Gel, lithium hydroxide are 7 according to mass ratio:18 mixed grindings roast 3.5h, pickling, acid at 720 DEG C
Wash use mass concentration for 4% H2SO4Solution, liquid-solid ratio 2.8, pickling 50min under the conditions of 72 DEG C obtain lithium absorption
Agent.
Comparative example 2 does not use lithium brightness mine crude product as base material, and obtained lithium adsorbent 800g is added to 8500mL magnesium and is contained
Amount is 120g/L, is stirred under state in the high Mg/Li ratio aqueous salt brine that lithium content is 4g/L and adsorbs lithium, when adsorbing small up to 2
Stop stirring afterwards to be separated by solid-liquid separation, it is 120g/L, lithium content 3.22g/L to measure content of magnesium in the aqueous salt brine after absorption.
The adsorbent filter cake sulfuric acid isolated is deviate from lithium, deviates from the adsorbent after lithium and only has 520g, molten damage serious.
Claims (10)
1. a kind of preparation method for the Low Cost Sorbents carrying lithium for high Mg/Li ratio brine, which is characterized in that including following step
Suddenly:
A, spodumene ore mining is sorted with dense media-strong magnetic ore separation process, obtains oxidation lithium content 6% or more
Spodumene concentrate and oxidation lithium content are rough less than 6% spodumene;
B, the rough middle addition boric acid of spodumene obtained to a steps, impregnate 12~for 24 hours after, take out, washing, obtain acidification
Spodumene afterwards is rough, carries out ultra fine, obtains fine powder;
C, the fine powder for obtaining b step and Al (OH)3Gel, lithium hydroxide mixed grinding, roast at 500~800 DEG C
3~5h, pickling obtain inexpensive lithium adsorbent.
2. a kind of preparation method for the Low Cost Sorbents carrying lithium for high Mg/Li ratio brine according to claim 1, special
Sign is that the mass concentration of boric acid described in b step is 20~30%.
3. a kind of preparation method for the Low Cost Sorbents carrying lithium for high Mg/Li ratio brine according to claim 1, special
Sign is that ultra fine described in b step is:By the spodumene after washing, rough, water and grinding aid are mixed by certain weight ratio,
Disperse certain time on high speed dispersor so that concentration slurry is made;It is alloy material in bucket inner wall and carries chuck cooling device
Grinder in water and ball milling pearl is added, thickened pulp is added after being preheated to 30~50 DEG C and is ground;It is ground to certain
Product is filtered, washed and dried to get fine powder after time.
4. a kind of preparation method for the Low Cost Sorbents carrying lithium for high Mg/Li ratio brine according to claim 3, special
Sign is, the spodumene after the washing is rough, the mass ratio of water and grinding aid is 3~8:20~40:5~12.
5. a kind of preparation method for the Low Cost Sorbents carrying lithium for high Mg/Li ratio brine according to claim 3, special
Sign is that the grinding aid is at least one of Sodium Polyacrylate or isooctyl acid potassium.
6. a kind of preparation method for the Low Cost Sorbents carrying lithium for high Mg/Li ratio brine according to claim 3, special
Sign is that the rotating speed of the high speed dispersor is 1500~2000r/min, and jitter time is 2~5h.
7. a kind of preparation method for the Low Cost Sorbents carrying lithium for high Mg/Li ratio brine according to claim 3, special
Sign is that using one kind in three-roller type grinder or four-roller type grinder, milling time is 60~90min for the grinding.
8. a kind of preparation method for the Low Cost Sorbents carrying lithium for high Mg/Li ratio brine according to claim 1, special
Sign is, the fine powder and Al (OH)3Gel, lithium hydroxide mass ratio are 10~30:3~10:5~20.
9. a kind of preparation method for the Low Cost Sorbents carrying lithium for high Mg/Li ratio brine according to claim 1, special
Sign is, the pickling use mass concentration for 1~10% H2SO4Solution, liquid-solid ratio is 2.5~3, in 50~90 DEG C of conditions
15~60min of lower pickling.
10. carrying lithium for high Mg/Li ratio brine according to one kind that preparation method is prepared described in claim 1~9 any one
Low Cost Sorbents.
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