CN106507704B - The preparation technology of lithium adsorbent - Google Patents
The preparation technology of lithium adsorbentInfo
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- CN106507704B CN106507704B CN200510097245.1A CN200510097245A CN106507704B CN 106507704 B CN106507704 B CN 106507704B CN 200510097245 A CN200510097245 A CN 200510097245A CN 106507704 B CN106507704 B CN 106507704B
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- lithium
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- aluminum oxide
- adsorbent
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Abstract
The present invention relates to a kind of preparation technology of lithium adsorbent, powdery aluminium hydroxide or aluminum oxide are first made ball with organic bond or inorganic bond by which, again the compound and alkali compounds of lithium are dissolved in the water, add spherical aluminium hydroxide obtained above or aluminum oxide, the compound and aluminium hydroxide of lithium or aluminum oxide addition press lithium aluminium weight ratio for 1: 2.5～1: 300, the addition of alkali compounds should be able to maintain solution pH value more than 8, carry out reaction until be enough to form LiX.2Al (OH)3Crystallite, reaction finish separating, washing and obtain lithium adsorbent.Lithium adsorbent obtained in of the invention is spherical, hydraulic performance is good, and intensity is high, spherical is not easy to wear and tear, spherical volume capacity is higher than irregular shape adsorbent, without volatile organic solvent, low cost, preparation process is simple, it is beneficial to environmental protection, can be used to enriching lithium is reclaimed from the solution such as bittern, have higher adsorption capacity to lithium, service life is long.
Description
Technical field
The present invention relates to the preparation technology of the adsorbent of metal ion is extracted, specifically a kind of lithium absorption
The preparation technology of agent.
Background technology
Lithium is industrially of many uses, and electrolytic aluminium adds the lithium carbonate can be with energy-conservation, it is possible to manufacture special glass,
It is deoxidier and deaeration agent in metallurgical industry etc..Which is more mainly for the manufacture of special alloy, and thermonuclear
The indispensable critical materials of weapon, Al-Li, Al-Mg-Li Bimary and trinary alloy are important from now on
Aeronautics and Astronautics material, has very high strategic value.With the progress of technology, lithium battery, controlled thermonuclear
Fusion reactor will become the new energy, therefore lithium have " energy metal ", the title of " strategic element ".
The world will be more and more to the demand of lithium, increasingly come important.China is that lithium resource reserves are big
State, explored lithium resource commercial reserves are only second to Bolivia in the world, occupy second, and China
Qinghai-Tibet Platean has abundant lithium resource, and stock number is up to 7,830,000 tons.Qinghai-Tibet salt lake Li Zhan China lithium total amount
82%, account for the world more than 1/5.Lithium is got over as high-tech and the important materials of military project, in recent years consumption
Come bigger, salt lake should be accelerated and carry lithium technological industrialization.But because Qinghai Salt Lake Mg, Li are than too high extraction
Lithium is difficult, so far in the world without industrial successful experience.
Document report：The method for extracting lithium from bittern has：The precipitation method, solvent extraction, absorption, from
Sub- exchange process.From economical and environmentally friendly considering, absorption, ion-exchange should be paid the utmost attention to.
Ion exchange organic resin is low to the selectivity of lithium, some inorganic adsorbents：Such as：Hydrated aluminum-iron
Oxide, metaantimmonic acid tin, manganese oxide etc. have higher adsorptivity to lithium.Inorganic adsorbent be usually powder or
Crystallite, it is difficult to industrially apply.
A kind of new anion exchange resin for reclaiming lithium from bittern of 70 years American inventions of eighties of last century.
It is in the hole of the anion exchange resin of macropore, is dispersed with LiCl.2Al (OH)3Crystallite, by this
Plant LiCl.2Al (OH)3The mixture of/resin, loads in exchange column, when bittern passes through exchange column, tree
Fat with regard to energy selective absorption and is enriched with the lithium in bittern.Then with containing a small amount of Li+Solution washing resin,
Can be obtained by the lithium being enriched with LiCl forms.This resin life is longer, and experiment shows to hand over through bittern
After flowing, recycling, resin does not significantly reduce to lithium exchange capacity.Its shortcoming is：System
Make that the cycle is long, operation is more, high cost.
Chinese patent application 02145583.X is referred to and prepares lithium adsorbent, and which is first by LiCl and Al (OH)3
Reaction, then adopt high molecular polymer to be reacted for adhesive in organic solvent, then granulate and lithium suction is obtained
Attached dose.Lithium adsorbent obtained in the method is irregular shape, must adopt volatile organic solvent during preparation,
High cost, unfavorable environmental protection.
Content of the invention
It is an object of the invention to provide a kind of lithium is had higher adsorption capacity, low cost of manufacture, environmental protection,
Process is simple, the preparation technology of the lithium adsorbent of long service life.
The preparation technology of the lithium adsorbent of the present invention, first uses organic bond or inorganic bond by powdery hydrogen
Ball made by aluminum oxide or aluminum oxide, then the compound and alkali compounds of lithium are dissolved in the water, in addition
Obtained spherical aluminium hydroxide or aluminum oxide is stated, the compound and aluminium hydroxide of lithium or aluminum oxide addition are pressed
Lithium aluminium weight ratio is 1: 2.5～1: 300, the addition of alkali compounds should be able to maintain solution pH value 8 with
On, reaction is carried out until be enough to form LiX.2Al (OH)3Crystallite, reaction finish separating, washing and obtain lithium
Adsorbent.
The preparation technology of lithium adsorbent as above, organic bond used be acetylbutyrylcellulose,
Polyethylene, epoxy resin, phenolic resin, Pioloform, polyvinyl acetal, polystyrene or Polypropionate；Nothing
Machine is bonded as aluminum contained compound, phosphatic type, silicic acid type or borate type adhesive.
The preparation technology of lithium adsorbent as above, the preferred polystyrene of organic bond used are inorganic
The preferred aluminum contained compound of adhesive.
The preparation technology of lithium adsorbent as above, the compound of lithium used be lithium chloride, lithium hydroxide,
Or lithium sulfate.
The preparation technology of lithium adsorbent as above, the preferred lithium chloride of the compound of lithium used.
The preparation technology of lithium adsorbent as above, alkali compounds used are NaOH, hydroxide
Potassium, lithium hydroxide or ammonium hydroxide.
The preparation technology of lithium adsorbent as above, the preferred NaOH of alkali compounds used.
The preparation technology of lithium adsorbent as above, the ball that is made with organic bond or inorganic bond
, in 0.3-2.5mm, bulk density is in 0.7-0.8g/ml, resistance to compression for the granularity of shape aluminium hydroxide or aluminum oxide
Intensity is in 1100-1200 gram/every particle.
The preparation technology of lithium adsorbent as above, the LiX.2Al for being formed (OH)3In crystallite, X
Represent halogen, SO4 2-Or OH-Anion.
The preparation technology of lithium adsorbent as above, heating react fully and carry out, and reaction temperature is 90
- 100 DEG C, the reaction time is 20-30 hours.
The present invention has obvious superiority than lithium adsorbent prepared by Chinese patent application 02145583.X.
Lithium adsorbent obtained in patent 02145583.X is irregular shape, must adopt volatile organic molten during preparation
Agent, high cost, unfavorable environmental protection.Obtained in of the invention, lithium adsorbent is spherical, then hydraulic performance is substantially good
In the former, intensity is high, spherical be not easy to wear and tear, while spherical volume capacity is higher than irregular shape adsorbent,
Without volatile organic solvent, low cost, preparation process is simple, beneficial to environmental protection.Obtained in of the invention, lithium is inhaled
Attached dose, can be used to enriching lithium is reclaimed from the solution such as bittern, have higher adsorption capacity to lithium, using the longevity
Life is long.From experiment, circulate through 50 times, the adsorbent capacity change is less.
Specific embodiment
Embodiment 1
Powdery aluminium hydroxide burning bonding is made ball with 15% aluminum nitrate aqueous solution (as inorganic bond)
Shape.308 grams of NaOH and 327 grams of anhydrous reagent level lithium chlorides are dissolved in 7500 milliliters of distilled water
In.Then compare 1: 9.7 by lithium aluminium weight, add 1500 grams of spherical oxygen aluminum oxide obtained above, solution
For alkalescence, heating stirring is reacted 20 hours in the range of 95～100 DEG C, until be enough to be formed
LiCl.2Al(OH)3Crystallite.Reaction is cooled down after terminating, and is filtered, and using has the solution washing containing lithium chloride
Reactant is neutral to cleaning solution.Metering, obtains 2580ml lithium adsorbents.
Embodiment 2
Powdery aluminum burning bonding is made with aluminum chloride aqueous solution (as inorganic bond) spherical.Will
3.2 grams lithium chlorides are dissolved in 500 milliliters of distilled water, then compare 1: 300 by lithium aluminium weight, add above-mentioned being obtained
297 grams of ball-aluminium oxides, with 10% sodium hydroxide solution adjust solution PH=10, heating fill reaction
Dividing is carried out, the difference of temperature, and the reaction time should be from several minutes to a couple of days, until be enough to be formed
LiCl.2Al(OH)3Crystallite.Place cooling, filter, washing obtains 371ml adsorbents.
Embodiment 3
Powdery aluminium hydroxide is made with 7% aluminum chloride aqueous solution (as inorganic bond) spherical.Will
4.7 grams lithium chlorides are dissolved in 100 milliliters of distilled water, then compare 1: 4.5 by lithium aluminium weight, and 10 grams of addition is spherical
Aluminium hydroxide, adjusts solution PH=9 value with 10% sodium hydroxide solution, in 90-100 DEG C of scope reaction 30
Hour, until be enough to form LiCl.2Al (OH)3Crystallite.Reaction is cooled down after terminating, is filtered, washing,
18ml adsorbents are obtained, its capacity 3mg Li/ml adsorbents.
Embodiment 4
Powdery aluminium hydroxide is made ball with suspension method with polystyrene (as organic bond).By 78
Grams lithium chloride is dissolved in 1250 milliliters of distilled water, then compares 1: 6.8 by lithium aluminium weight, adds obtained above
250 grams of spherical aluminium hydroxides, adjust solution PH=10 with 10% sodium hydroxide solution, and heating fills reaction
Dividing is carried out, the difference of temperature, and the reaction time should be from several minutes to a couple of days, until be enough to be formed
LiCl.2Al(OH)3Crystallite.Place cooling, filter, washing obtains 175ml adsorbents.
Embodiment 5
Powdery aluminum is made ball with polystyrene (as organic bond).Will be molten for 50 grams lithium chlorides
In 1000 milliliters of distilled water, then compare 1: 100 by lithium aluminium weight, add 2367 grams of balls obtained above
Shape aluminium hydroxide, adjusts solution PH=10 with 10% sodium hydroxide solution, reacts in the range of 90-100 DEG C
30 hours, until be enough to form LiCl.2Al (OH)3Crystallite.Place cooling, filter, washing obtains 2960ml
Adsorbent.
Embodiment 6
It is monomer with styrene, in the presence of benzoyl peroxide makees initiator and divinylbenzene makees crosslinking agent
Add powdery aluminum and ball is made with suspension method.64 grams lithium chlorides are dissolved in 1280 milliliters of distilled water,
Then compare 1: 2.5 by lithium aluminium weight, add 50 grams of ball-aluminium oxides obtained above, use 10% hydroxide
Sodium solution adjusts solution PH=10, reacts 30 hours, until be enough to be formed in the range of 90-100 DEG C
LiCl.2Al(OH)3Crystallite.Place cooling, filter, washing obtains 71ml adsorbents.
In above example, organic bond used can be replaced with other kin organic bonds, example
Such as with acetylbutyrylcellulose, polyethylene, epoxy resin, phenolic resin, Pioloform, polyvinyl acetal or poly-
Propionic ester replaces.
In above example, inorganic bond used can be replaced with other kin inorganic bonds, example
Such as replaced with phosphatic type, silicic acid type or borate type adhesive.
In above example, the compound of lithium used is lithium chloride, and which can use the change of other lithiums kin
Compound replaces, for example, replaced with lithium hydroxide or lithium sulfate, and consumption refers to lithium chloride.
In above example, alkali compounds used is NaOH, its available other alkalescence kin
Compound replaces, for example, replaced with potassium hydroxide, lithium hydroxide or ammonium hydroxide, and consumption refers to hydrogen
Sodium oxide molybdena.
The spherical aluminium hydroxide that is made with organic bond or inorganic bond in above example or oxidation
Aluminium is preferably granularity in 0.3-2.5mm, and, in 0.7-0.8g/ml, compression strength is in 1100-1200 for bulk density
Gram/per particle.
In the preparation process of lithium adsorbent, different according to the selection of reactant, obtained
LiX.2Al(OH)3In crystallite, X can represent halogen, SO4 2-Or OH-Anion.
The application of lithium adsorbent：
The above-mentioned lithium adsorbent for preparing is washed away LiCl.2Al (OH) with the aqueous solution containing lithium chloride3Micro-
Part lithium in crystalline substance, 20ml adsorbents are loaded in exchange column, water wash is used after bittern saturation,
Leacheate Li concentration is determined, the lithium capacity of adsorbent is calculated.
Adsorbent capacity Li mg/ml
Can see from result, circulate through 50, adsorbent capacity change is little, long service life.
Claims (8)
1. a kind of preparation technology of lithium adsorbent, the technique first will with organic bond or inorganic bond
Ball made by powdery aluminium hydroxide or aluminum oxide, then the compound and alkali compounds of lithium are dissolved in the water,
Spherical aluminium hydroxide obtained above or aluminum oxide, the compound and aluminium hydroxide of lithium or aluminum oxide is added to add
It is 1: 2.5～1: 300 to enter amount by lithium aluminium weight ratio, and the addition of alkali compounds should be able to maintain solution pH value
More than 8, reaction is carried out until be enough to form LiX.2Al (OH)3Crystallite, reaction finish separating, washing
Obtain lithium adsorbent；Organic bond used is acetylbutyrylcellulose, polyethylene, epoxy resin, phenol
Urea formaldehyde, Pioloform, polyvinyl acetal, polystyrene or Polypropionate；Inorganic bond used is containing calorize
Compound；The LiX.2Al (OH) for being formed3In crystallite, X represents halogen, SO4 2-Or OH-Anion.
2. the preparation technology of lithium adsorbent according to claim 1, it is characterised in that：Used have
Machine adhesive is polystyrene.
3. the preparation technology of lithium adsorbent according to claim 1, it is characterised in that：Lithium used
Compound be lithium chloride, lithium hydroxide or lithium sulfate.
4. the preparation technology of the lithium adsorbent according to claim 1 or 3, it is characterised in that：Institute
It is lithium chloride with the compound of lithium.
5. the preparation technology of lithium adsorbent according to claim 1, it is characterised in that：Alkali used
Property compound be NaOH, potassium hydroxide, lithium hydroxide or ammonium hydroxide.
6. the preparation technology of lithium adsorbent according to claim 1 or 5, it is characterised in that：Institute
It is NaOH with alkali compounds.
7. the preparation technology of lithium adsorbent according to claim 1, it is characterised in that：With organic
Spherical aluminium hydroxide that adhesive or inorganic bond are made or the granularity of aluminum oxide in 0.3-2.5mm,
, in 0.7-0.8g/ml, compression strength is in 1100-1200 gram/every particle for bulk density.
8. the preparation technology of lithium adsorbent according to claim 1, it is characterised in that：Heating makes
Reaction is fully carried out, and reaction temperature is 90-100 DEG C, and the reaction time is 20-30 hours.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN200510097245.1A CN106507704B (en) | 2005-12-30 | 2005-12-30 | The preparation technology of lithium adsorbent |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN200510097245.1A CN106507704B (en) | 2005-12-30 | 2005-12-30 | The preparation technology of lithium adsorbent |
Publications (1)
| Publication Number | Publication Date |
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| CN106507704B true CN106507704B (en) | 2010-04-14 |
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ID=58264248
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109225124A (en) * | 2018-11-09 | 2019-01-18 | 华东理工大学 | A kind of preparation method of particle lithium adsorbent |
| CN110237829A (en) * | 2019-06-05 | 2019-09-17 | 南京亘闪生物科技有限公司 | A kind of modified lithium absorption hypercrosslinked polymeric resin microballoon and its preparation method and application |
| CN110961070A (en) * | 2018-09-30 | 2020-04-07 | 比亚迪股份有限公司 | Lithium adsorbent and preparation method thereof |
| CN112871126A (en) * | 2021-01-18 | 2021-06-01 | 江苏特丰新材料科技有限公司 | Preparation method of lithium ion sieve particles with high adsorption capacity |
| CN113677428A (en) * | 2019-04-25 | 2021-11-19 | 圣戈本陶瓷及塑料股份有限公司 | Adsorbent particles and methods of forming the same |
-
2005
- 2005-12-30 CN CN200510097245.1A patent/CN106507704B/en active Active
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110961070A (en) * | 2018-09-30 | 2020-04-07 | 比亚迪股份有限公司 | Lithium adsorbent and preparation method thereof |
| CN109225124A (en) * | 2018-11-09 | 2019-01-18 | 华东理工大学 | A kind of preparation method of particle lithium adsorbent |
| CN113677428A (en) * | 2019-04-25 | 2021-11-19 | 圣戈本陶瓷及塑料股份有限公司 | Adsorbent particles and methods of forming the same |
| US11666885B2 (en) | 2019-04-25 | 2023-06-06 | Saint-Gobain Ceramics & Plastics, Inc. | Adsorbent particles and methods of forming thereof |
| CN110237829A (en) * | 2019-06-05 | 2019-09-17 | 南京亘闪生物科技有限公司 | A kind of modified lithium absorption hypercrosslinked polymeric resin microballoon and its preparation method and application |
| CN112871126A (en) * | 2021-01-18 | 2021-06-01 | 江苏特丰新材料科技有限公司 | Preparation method of lithium ion sieve particles with high adsorption capacity |
| CN112871126B (en) * | 2021-01-18 | 2023-08-11 | 江苏特丰新材料科技有限公司 | Preparation method of lithium ion sieve particles with high adsorption capacity |
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