CN113509912B - Preparation method of lithium ion sieve adsorbent particles for extracting liquid lithium resources - Google Patents
Preparation method of lithium ion sieve adsorbent particles for extracting liquid lithium resources Download PDFInfo
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Abstract
The invention discloses a preparation method of lithium ion sieve type adsorbent particles for extracting liquid lithium resources such as salt lake brine, seawater, underground water and the like. The adsorbent particles are prepared by using water-absorbing polymer as carrier, and adding lithium ion sieve type adsorbent such as metatitanic acid type Li2TiO3Spinel type Li4Ti5O12Spinel type Li1.6Mn1.6O4Spinel-type LiMn2O4And the preparation is carried out in a secondary crosslinking mode, and the preparation process is simple and is suitable for industrial production. The prepared adsorbent particles have the characteristics of high elasticity, porosity, high water absorption, good permeability and the like. The resin matrix resists strong acid and strong alkali, the polyhydroxy structure on the surface of the matrix can effectively adsorb adsorbent particles, the dissolution loss rate is effectively reduced, the resin matrix can be applied to extraction of lithium elements in salt lake original brine, old brine, seawater and underground water resources, and meanwhile, the high-strength corrosion-resistant matrix is suitable for an industrial adsorption column process.
Description
Technical Field
The invention belongs to the technical field of chemical materials, and particularly relates to a preparation method of lithium ion sieve adsorbent particles for extracting liquid lithium resources.
Background
With the rapid development of industries such as lithium batteries, lithium alloys, lubricants and the like, the demand of the market for lithium is increasing day by day. Lithium resources in China are mostly stored in salt lakes, underground water and seawater, and the liquid lithium resources are low in content, coexist with a large amount of magnesium ions, calcium ions and the like, and can be utilized after enrichment and purification. At present, the technologies for extracting lithium from liquid lithium resources such as salt lakes mainly comprise a solvent extraction method, a precipitation method and an adsorption method. The precipitation method is only suitable for systems with high lithium content such as old brine, the precipitated lithium needs to be dissolved and purified for the second time, and the acid and alkali consumption is large. The solvent extraction method is simultaneously suitable for brine systems with various lithium contents, but the method has high requirements on corrosion resistance of equipment, the extraction and back-extraction process flow is complex, the used organic reagent can pollute the environment, the adsorption method is suitable for separating and extracting lithium from a low-grade system, and the method has the advantages of simple and convenient operation, short flow, good effect, high recovery rate and the like.
The inorganic ion adsorbent has high selectivity to lithium, and can adsorb lithium from low-grade original halogen or other resources. The inorganic ion adsorbent with large adsorption capacity comprises a manganese ion sieve type adsorbent, a titanium ion sieve adsorbent, a lithium-aluminum hydrotalcite adsorbent, a magnesium-aluminum hydrotalcite adsorbent, lithium iron phosphate, lithium nickelate, lithium ferrophosphorus, a ternary positive electrode material, graphite, a mesophase microsphere, a carbon nano tube, graphene, carbon fiber, a tin-based oxide material and the like for electrochemical adsorption. The manganese ion sieve type adsorbent and the titanium ion sieve adsorbent have the characteristics of good selectivity, high adsorption capacity and the like, but are often powdery and cannot meet the operation of an industrial adsorption column, and meanwhile, the two ion sieve adsorbents have the optimal adsorption effect under the alkaline condition, and the desorption needs under the acidic condition, so that the adsorbent powders are bonded together by adopting various modes to be made into particles, the adsorption and desorption operations are carried out after the column is filled, and the binder needs to be acid-resistant and alkali-resistant.
Chinese patent CN 111282449 discloses a method for preparing an HMO/cellulose composite membrane for seawater lithium extraction, which comprises dissolving alpha-cellulose with an ionic liquid and mixing and casting manganese ion sieve powder to form a membrane. The ionic liquid used in the method has high cost, and the ionic liquid is toxic and easy to cause pollution. Chinese patent CN 108543521 discloses a method for preparing fibers for extracting lithium from salt lake brine, wherein ceramic fiber-based lithium adsorption materials with loose cores are prepared by electrostatic spinning, and the fibers are used as carriers to enable the loading mode to have large specific surface area. The preparation process includes dissolving lithium source and manganese source in organic solvent, preparing precursor fiber containing lithium adsorbent via electrostatic spinning, and roasting to obtain composite lithium-manganese oxide fiber. Chinese patent CN 110975845 discloses a preparation method of a porous material loaded with a lithium ion sieve. The adsorbent powder is loaded in the resin particles through free radical polymerization, and the processing mode uses a large amount of organic solvent and has low loading.
At present, most lithium salt adsorption plants generally select polymer materials such as polyvinyl chloride, polyvinylidene fluoride and the like as carrier materials, and granulate the materials by a certain method in an extrusion or tabletting mode, and because polymer base materials such as polyvinyl chloride, polyvinylidene fluoride and the like have poor water permeability, the particles are tightly stacked by high pressure in the granulating and tabletting process, so brine slowly permeates into the adsorbent particles in the adsorption process.
Therefore, the preparation method simultaneously satisfies the conditions of large loading capacity, porous structure, high strength, corrosion resistance and low dissolution loss rate, and has wide application prospect.
The above prior art has the following disadvantages;
1. the preparation process of the adsorbent is complex in process, high in cost and harmful to the environment;
2. the loading capacity of the adsorbent is low;
3. the adsorbent particle matrix material has poor water permeability, the adsorption capacity is reduced after granulation, and the adsorption process is relatively slow.
Disclosure of Invention
The invention aims to overcome the defects of the prior art and provides a preparation method of a lithium ion sieve type adsorbent particle suitable for extracting lithium from both salt lake raw bittern and old bittern. The invention prepares the adsorbent particles with large loading capacity, porous structure, high strength, corrosion resistance and low dissolution loss rate by granulating the lithium ion sieve adsorbent (particularly manganese ion sieve adsorbent and titanium ion sieve adsorbent). Meanwhile, the water-absorbing polymer has a strong adsorption effect on inorganic adsorbent particles, and the adsorbent loss caused by water flow scouring is effectively reduced.
The invention is realized by the following technical scheme:
a method for preparing lithium ion sieve adsorbent particles for liquid lithium resource extraction, the method comprising:
adding the adsorption powder into the first polymer solution, and uniformly mixing to obtain a first mixture; immersing the first mixture into a first cross-linking agent aqueous solution for primary cross-linking to obtain a second mixture; in the primary crosslinking process, hydroxyl in the first polymer is crosslinked with boric acid in a first crosslinking agent; the carboxyl in the first polymer is crosslinked with the polyvalent metal ions in the first crosslinking agent;
granulating and drying the second mixture to obtain dried granules, wherein the distance between polymer molecules is shortened in the drying process, and the free volume is reduced to carry out secondary crosslinking;
immersing the dried particles into a second cross-linking agent for secondary cross-linking to obtain the lithium ion sieve adsorbent particles; in the secondary crosslinking process, the boric acid in a crosslinking state is hydrolyzed in the second crosslinking agent, the boric acid is dissolved again, and the hydroxyl in the crosslinking state is released; the polyvalent metal ions exist stably in the second cross-linking agent, and the second cross-linking agent and the hydroxyl and/or carboxyl in the first polymer are subjected to secondary cross-linking to form a stable cross-linked structure;
or the like, or, alternatively,
adding the adsorption powder into a mixed polymer solution consisting of a first polymer solution and a second polymer solution, and uniformly mixing to obtain a first mixture; immersing the first mixture into a first cross-linking agent aqueous solution for primary cross-linking to obtain a second mixture; in the primary crosslinking process, hydroxyl in the first polymer is crosslinked with boric acid in a first crosslinking agent; the carboxyl in the first polymer is crosslinked with the polyvalent metal ions in the first crosslinking agent; the carboxyl in the second polymer is crosslinked with the polyvalent metal ion in the first crosslinking agent; granulating and drying the second mixture to obtain dried granules, wherein the distance between polymer molecules is shortened in the drying process, and the free volume is reduced to carry out secondary crosslinking; immersing the dried particles into a second cross-linking agent for secondary cross-linking to obtain the lithium ion sieve adsorbent particles; in the secondary crosslinking process, the boric acid in a crosslinking state is hydrolyzed in the second crosslinking agent, the boric acid is dissolved again, and the hydroxyl in the crosslinking state is released; the polyvalent metal ions exist stably in the second cross-linking agent, and the second cross-linking agent and the hydroxyl and/or carboxyl in the mixed polymer are subjected to secondary cross-linking to form a stable cross-linked structure;
or the like, or, alternatively,
adding the adsorption powder into a mixed polymer solution consisting of a first polymer solution, a second polymer solution and a third polymer solution, and uniformly mixing to obtain a first mixture; immersing the first mixture into a first cross-linking agent aqueous solution for primary cross-linking to obtain a second mixture; in the primary crosslinking process, hydroxyl in the first polymer is crosslinked with boric acid in a first crosslinking agent; the carboxyl in the first polymer is crosslinked with the polyvalent metal ions in the first crosslinking agent; the carboxyl in the second polymer is crosslinked with the polyvalent metal ion in the first crosslinking agent; the carboxyl in the third polymer is crosslinked with the multivalent metal ion in the first crosslinking agent; granulating and drying the second mixture to obtain dried particles, and immersing the dried particles into a second cross-linking agent for secondary cross-linking to obtain the lithium ion sieve adsorbent particles; in the secondary crosslinking process, the boric acid in a crosslinking state is hydrolyzed in the second crosslinking agent, the boric acid is dissolved again, and the hydroxyl in the crosslinking state is released; the polyvalent metal ions exist stably in the second cross-linking agent, and the second cross-linking agent and the hydroxyl and/or carboxyl in the mixed polymer are subjected to secondary cross-linking to form a stable cross-linked structure;
the adsorbent powder is a lithium ion sieve type adsorbent, and the particle size is 200-1500 meshes.
A preparation method of lithium ion sieve adsorbent particles for extracting liquid lithium resources comprises the following steps:
step 1, adding adsorbent powder into a polymer mixed solution, and uniformly mixing to obtain a first mixture; the mass ratio of the adsorbent powder to the polymer mixed solution is 1 (2-20);
the adsorbent powder is a lithium ion sieve type adsorbent, and the particle size is 200-1500 meshes;
the polymer mixed solution comprises the following components in parts by mass: 50-90 parts of a first polymer solution, 0-40 parts of a second polymer solution and 0-10 parts of a third polymer solution;
the first polymer solution is 1-50 wt% aqueous solution of polyhydroxy and polycarboxyl-containing polymer, preferably 1-20 wt%;
the second polymer solution is 1-50 wt% of aqueous solution of long carbon chain-containing polymer, preferably 1-10 wt%, and the aqueous solution of the second polymer has high viscosity and more carboxyl, amino and other groups;
the third polymer solution is 1-50 wt% of water solution containing natural polysaccharide polymer, preferably 1-10 wt%; natural polysaccharide compounds for extracting autobotanic plants;
step 2, immersing the first mixture obtained in the step 1 into a first cross-linking agent aqueous solution for primary cross-linking, and obtaining a second mixture after cross-linking solidification;
the first cross-linking agent is a mixture of at least one of boric acid or borax and soluble multivalent metal salt; the soluble multivalent metal salt is at least one of soluble ferric salt, soluble aluminum salt, soluble calcium salt, soluble magnesium salt, soluble zinc salt, soluble strontium salt or soluble barium salt;
step 3, granulating and drying the second mixture to obtain dried particles;
the temperature in the drying process is 30-100 ℃, and the time in the drying process is 12-24 hours;
step 4, immersing the dried particles into a second cross-linking agent for secondary cross-linking, wherein the time of the secondary cross-linking is 12-72 hours, and the temperature of the secondary cross-linking is 25-80 ℃; washing the solid particles obtained after secondary crosslinking to obtain the adsorbent particles for extracting the liquid lithium resource;
the second cross-linking agent is an alkaline mixed solution or an acidic mixed solution;
the alkaline mixed solution is a mixture of an epoxy compound and an alkaline solution, and the pH value is 8-14; the adsorbent powder is alkali-resistant powder or acid-resistant and alkali-resistant powder;
the acid mixed solution is a mixture of ethanol, water, acid and aldehyde compounds, and the acid concentration is 0.1-5 mol/L; when the adsorbent powder is an acid resistant powder or a powder that is both acid and base resistant.
In the above technical scheme, the first polymer is one or more of polyvinyl alcohol, polyvinyl alcohol graft copolymer, polyacrylic acid, hyperbranched polyol, polyester polyol, and isocyanate.
In the above technical scheme, the second polymer is one or more of isobutylene-maleic anhydride copolymer, sodium polyacrylate, polyacrylamide-maleic anhydride copolymer, polyvinyl alcohol-maleic anhydride copolymer, polyvinylpyrrolidone, polyethylene glycol, and polyethylene oxide.
In the above technical scheme, the third polymer is one or more of chitosan, gelatin, pectin, carrageenan, sodium alginate, sodium carboxymethylcellulose, water-soluble cellulose, guar gum and soluble starch.
In the above technical solution, in the step 2, the first mixture and the first cross-linking agent powder or the first cross-linking agent solution are uniformly mixed;
the first cross-linking agent powder is powder formed by uniformly mixing at least one of boric acid and borax with soluble multivalent metal salt, wherein the soluble multivalent metal salt is at least one of soluble ferric salt, soluble aluminum salt, soluble calcium salt, soluble magnesium salt, soluble zinc salt, soluble strontium salt or soluble barium salt;
the first cross-linking agent solution is a solution obtained by dissolving a mixture of at least one of boric acid or borax and soluble multivalent metal salt in water, and the soluble multivalent metal salt is at least one of soluble ferric salt, soluble aluminum salt, soluble calcium salt, soluble magnesium salt, soluble zinc salt, soluble strontium salt or soluble barium salt.
In the above technical scheme, in the step 3, an extrusion granulation mode is adopted in the granulation process, and the particle size is 2-5 mm.
In the above technical scheme, when the second crosslinking agent is an alkaline mixed solution; the epoxy compound is one or more of propylene oxide, epichlorohydrin, epibromohydrin, 1, 2-epoxybutane, epoxybutene, epoxypropanol, glycidyl methacrylate and ethylene oxide-PEG-ethylene oxide; the dosage of the epoxy compound is 1-15 ml per 30 g of the dried particles;
the alkali solution is one or two of calcium hydroxide solution, sodium hydroxide solution and lithium hydroxide solution; the dosage of the alkali solution is 20-100 times of the weight of the dried particles.
In the above technical scheme, when the second crosslinking agent is an acidic mixed solution; the volume ratio of the ethanol, the water, the acid and the aldehyde compound is (10-40): 2-10): 1-3): 1-2, wherein the aldehyde compound is one or more of formaldehyde, acetaldehyde, malonaldehyde, glutaraldehyde, benzaldehyde, phenylacetaldehyde, cinnamaldehyde and methylglyoxal; the acid is one or more of hydrochloric acid, sulfuric acid and nitric acid, wherein the H of the second cross-linking agent+The ion concentration is 0.1-5 mol/L, the dosage of the acid is 20-100 times of the weight of the dried particles, and the dosage of the aldehyde compound is 1-15 ml per 30 g of the dried particles.
In the above technical scheme, when the adsorbent powder is acid-resistant and alkali-resistant powder, the adsorbent powder may specifically be manganese ion sieve type adsorbent, titanium ion sieve adsorbent, graphite, mesophase microspheres, carbon nanotubes, graphene, or carbon fiber powder.
In the above technical solution, the preparation method of the polymer mixed solution comprises the following steps:
step 1.1, dissolving the first polymer in water to obtain a first polymer solution, wherein the concentration of the first polymer solution is 1-50 wt%;
step 1.2, dissolving the second polymer in water to obtain a second polymer solution, wherein the concentration of the second polymer solution is 1-50 wt%;
step 1.3, dissolving the third polymer in water to obtain a third polymer solution, wherein the concentration of the third polymer solution is 1-50 wt%;
step 1.4, mixing the first polymer solution, the second polymer solution and the third polymer solution to obtain a polymer mixed solution;
the first polymer is one or more of polyvinyl alcohol, polyvinyl alcohol graft copolymer, polyacrylic acid, hyperbranched polyol, polyester polyol and isocyanate;
the second polymer is one or more of isobutylene-maleic anhydride copolymer, sodium polyacrylate, polyacrylamide-maleic anhydride copolymer, polyvinyl alcohol-maleic anhydride copolymer, polyvinylpyrrolidone, polyethylene glycol and polyethylene oxide;
the third polymer is one or more of chitosan, gelatin, pectin, carrageenan, sodium alginate, sodium carboxymethylcellulose, water-soluble cellulose, guar gum and soluble starch.
In the above technical scheme, the step 1.4 adopts a high-speed stirrer or a grinder to mix.
In the technical scheme, the lithium ion sieve type adsorbent is lithium titanate, lithium manganate, lithium iron phosphate, lithium nickelate, lithium ferrophosphate, a ternary cathode material, graphite, an intermediate phase microsphere, a carbon nanotube, graphene, carbon fiber and a tin-based oxide material.
The lithium titanate may be metatitanic acid type Li2TiO3Spinel type Li4Ti5O12(ii) a The lithium manganate may be spinel type Li1.6Mn1.6O4Spinel-type LiMn2O4。
The invention has the advantages and beneficial effects that:
the invention discloses a preparation method of lithium ion sieve adsorbent (especially manganese series titanium adsorbent) particles for extracting liquid lithium resources such as salt lake brine, seawater, underground water and the like. The adsorbent particles use water-absorbing polymer as carrier, and manganese is added in high loadTitanium-based adsorbent powder such as metatitanic acid type Li2TiO3Spinel type Li4Ti5O12Spinel type Li1.6Mn1.6O4Spinel-type LiMn2O4The graphite, the mesophase microspheres, the carbon nanotubes, the graphene, the carbon fibers and the like are prepared in a secondary crosslinking mode, and the preparation process is simple and is suitable for industrial production. The prepared novel lithium ion sieve adsorbent particles have the characteristics of large loading capacity, high elasticity, low dissolution loss rate, porosity, high water absorption, good permeability and the like
The first polymer is one or a mixture of more than two of polyvinyl alcohol, polyvinyl alcohol graft copolymer, polyacrylic acid, hyperbranched polyol, polyester polyol and isocyanate; the first polymer is a polymer containing polyhydroxy and polycarboxyl, the functions of the carboxyl and the hydroxyl are realized (1) boric acid in the first cross-linking agent can be cross-linked with the hydroxyl, the carboxyl can be cross-linked with polyvalent metal ions, and viscous polymer liquid forms a solidified form after being cross-linked by the first cross-linking agent and can be granulated. (2) Hydroxyl and carboxyl can improve the adsorbent powder content (3) in the granule through hydrogen bond adsorbent powder and cross-link the shaping the second time, these carboxyl and hydroxyl structure can last to have an adsorption effect to the adsorbent powder, still have an adsorption effect to the adsorbent powder after adsorbing the desorption many times, therefore finished product polymer granule has longer life (4) first polymer has the long chain structure, the polymer long chain has better acid and alkali resistance, the stable performance, it is stable at secondary crosslinking or later stage acid desorption in-process adsorbent granule base member.
The second polymer is one or a mixture of more than two of isobutene-maleic anhydride copolymer, sodium polyacrylate, polyacrylamide-maleic anhydride copolymer, polyvinyl alcohol-maleic anhydride copolymer, polyvinylpyrrolidone, polyethylene glycol and polyethylene oxide; the second polymer is also a long carbon chain polymer, and different from the first polymer, the aqueous solution of the second polymer has larger viscosity and more carboxyl, amino and other groups, and the polymer functions (1) to assist the absorption of the first polymer to the absorbent powderBy effect, if only the first type of polymer, e.g. LiMn, is used2O4And the powder can fall off in the process of multiple adsorption and desorption of the powder particles. (2) The filling amount of the adsorbent powder can be increased (3), the first polymer and the second polymer can form an interpenetrating network copolymer structure through first crosslinking and second crosslinking after being uniformly mixed, the finished product particles have two crosslinking structures of polyvalent metal ion crosslinking and chemical crosslinking, the structure can increase the strength and toughness of a polymer material, the strength of the finished product adsorbent particles is high, and the dissolution loss and the falling off of the adsorbent powder are reduced in the using process.
The third polymer is one or a mixture of more than two of chitosan, gelatin, pectin, carrageenan, sodium alginate, sodium carboxymethylcellulose, water-soluble cellulose, guar gum and soluble starch. The third type of polymer is (1) natural polysaccharide polymer extracted from animal and plant species, the polymer can be cross-linked with the first type of polymer and the second type of polymer, and can also form an interpenetrating network structure with the first type of polymer and the second type of polymer, (2) the third type of polymer is generally soft, and the hardness and the water content of the adsorbent particles can be adjusted by adding the third type of polymer in a small amount in the system.
The primary crosslinking has the following characteristics: (1) boric acid is crosslinked with hydroxyl in the first polymer, carboxyl in the second polymer is crosslinked with polyvalent metal ions in the first crosslinking agent, so that viscous polymer solution is changed into a solidification form capable of being processed and granulated flexibly (2) in the first crosslinking process, the polymer matrix can almost completely adsorb the adsorbent powder into a solidification phase without loss, therefore, expensive adsorbent powder cannot be wasted (3) the crosslinking of boric acid in the first crosslinking is reversible, and the other main function is to play a temporary binding role on the polymer matrix, and the granulation can be processed after the first crosslinking.
The drying process after the primary crosslinking is a key step, free water and most of bound water in the system can be removed in the process, the distance between polymer molecules is shortened, the free volume is reduced, secondary crosslinking is facilitated, and the particle strength is increased. If not dried, the second crosslinked particles are not strong enough to break or fail to crosslink.
The secondary crosslinking process has the following characteristics: (1) the boric acid crosslinking in the first crosslinking is reversible, and boric acid crosslinking points in the first crosslinking are slowly released again in the second crosslinking agent under the action of aqueous solution, and the second crosslinking agent is crosslinked with hydroxyl or carboxyl to form a stable crosslinking structure. (2) After the second crosslinking, the crosslinking structure of the boric acid crosslinking points in the adsorbent particles disappears, and the polyvalent metal ion crosslinking points still exist, so that the adsorbent particles form a double crosslinking structure of polyvalent metal ions and chemical crosslinking after the second crosslinking. In fact, there are a very large number of hydroxyl or carboxyl groups in the polymer, and boric acid does not react with all of the hydroxyl groups for the first crosslinking, and there are many hydroxyl groups. The polyvalent metal ion does not react with all of the carboxyl groups, and there are carboxyl groups remaining. Therefore, in the second crosslinking, the crosslinking agent is crosslinked with the hydroxyl group resolved by boric acid and also with other hydroxyl groups.
Meanwhile, the water-absorbing polymer (the first polymer, the second polymer and the third polymer are water-absorbing polymers) has a strong adsorption effect on the lithium ion sieve-type adsorbent powder, and the adsorbent loss and the dissolution loss caused by water flow scouring are effectively reduced. The resin matrix resists strong acid and strong alkali, the polyhydroxy structure on the surface of the matrix can effectively adsorb adsorbent powder, the dissolution loss rate is effectively reduced, the resin matrix can be applied to extraction of lithium elements in salt lake original brine, old brine, seawater and underground water resources, and meanwhile, the high-strength corrosion-resistant matrix is suitable for an industrial adsorption column process.
The method for preparing the lithium ion sieve adsorbent particles specifically comprises the following steps: dissolving a plurality of water-absorbing polymers to obtain a mixed polymer solution, adding lithium ion sieve adsorbent powder into the mixed polymer solution, uniformly mixing at 20-80 ℃, adding a certain amount of first cross-linking agent into the slurry to prepare a granulation precursor, solidifying the mixed polymer solution by viscous liquid after contacting the first cross-linking agent solution, and performing granulation processing, wherein the other function of the first cross-linking is to control the structure and time of the second cross-linking. After granulation by an extruder or a screw granulator, the granules are dried. And finally crosslinking and molding the dried particles in a second crosslinking agent to obtain finished particles. And (3) carrying out secondary crosslinking after drying the particles, and forming a stable curing structure after secondary crosslinking. Two-time crosslinking is a key step in being able to process shape and form high strength particles. Has the advantages of simple preparation process, easy operation, low cost, easy industrialization and the like.
Drawings
FIG. 1 is an adsorbent particle made in example 1.
Figure 2 is an adsorbent particle made in example 3.
For a person skilled in the art, other relevant figures can be obtained from the above figures without inventive effort.
Detailed Description
In order to make the technical solution of the present invention better understood, the technical solution of the present invention is further described below with reference to specific examples.
Example one
An adsorbent particle for liquid lithium resource extraction is carried out as follows:
step 1, spinel type Li4Ti5O12Drying at 80 ℃, and crushing to obtain adsorbent powder with the particle size of 800-1000 meshes by using a high-speed crusher.
And step 2, dissolving polyvinyl alcohol with alcoholysis degree of 85% in water to prepare a 10 wt% polyvinyl alcohol aqueous solution.
And 3, taking the polyvinyl alcohol aqueous solution and the adsorbent powder according to the mass ratio of 3: 1 proportion, and uniformly mixing by using a three-roll grinder.
And 4, adding a certain amount of first cross-linking agent aqueous solution into the mixture obtained in the step 3, wherein the mass ratio of the mixture to the first cross-linking agent aqueous solution is 1: and 2, the first cross-linking agent aqueous solution is composed of 3 wt% of boric acid, 1 wt% of borax, 1 wt% of aluminum chloride and 1 wt% of calcium chloride, and is mechanically and fully stirred and kneaded to form a solidified cross-linking product.
And 5, extruding and granulating the solidified and crosslinked product obtained in the step 4 to obtain particles with the particle size of 2mm, and drying at the drying temperature of 60 ℃ for 8 hours to obtain dried particles.
And (3) immersing the dried particles obtained in the steps 6 and 5 in a second cross-linking agent aqueous solution, and cross-linking for 24 hours at the cross-linking temperature of 45 ℃, wherein the second cross-linking agent aqueous solution comprises 0.26 wt% of NaOH and 1 wt% of epichlorohydrin.
And 7, washing the particles subjected to crosslinking in the step 6 with clear water to obtain finished adsorbent particles for extracting the liquid lithium resource.
The finished product has a particle size shown in figure 1, an adsorbent content of 75% (calculated after water is subtracted), a water content of 45% and a Shore A hardness of 45.
The lithium ion adsorption material can be used for lithium adsorption under the alkaline condition of pH 8-12, can be recycled under the desorption condition of pH 1-4, and has no swelling and contraction of particles
Example two
An adsorbent particle for liquid lithium resource extraction is carried out as follows:
step 1, spinel type Li1.6Mn1.6O4Drying at 80 ℃, and crushing to obtain adsorbent powder with the particle size of 800-1000 meshes by using a high-speed crusher;
step 2, dissolving polyvinyl alcohol with alcoholysis degree of 85% in water to prepare 10 wt% solution
Step 3, sodium polyacrylate with average molecular weight of 125 ten thousand is dissolved in water to prepare solution with concentration of 3 wt%.
Step 4, mixing the polymer aqueous solutions prepared in the steps 2 and 3 according to the mass ratio of 10: 1 proportion, and uniformly mixing by using a high-viscosity stirring paddle to obtain a high-viscosity polymer mixed solution.
And 5, adding the adsorbent powder obtained in the step 1 into the high-viscosity polymer mixed solution obtained in the step 4 according to the mass ratio of 1: 3, stirring or grinding until the mixture is uniformly mixed.
And 6, adding a certain amount of first cross-linking agent aqueous solution into the mixture obtained in the 5 step, wherein the mass ratio of the mixture to the first cross-linking agent aqueous solution is 1: and 2, the first cross-linking agent aqueous solution comprises 3 wt% of boric acid, 1 wt% of borax, 1 wt% of ferric chloride and 1 wt% of calcium chloride, and is mechanically and fully stirred and kneaded to form a solidified cross-linking product.
And 7, extruding and granulating the solidified and crosslinked product obtained in the step 6, wherein the particle size is 2mm, and drying at the drying temperature of 45 ℃ for 24 hours to obtain dried particles.
And (3) crosslinking the dried particles obtained in the 8 th step and the 7 th step in a second crosslinking agent aqueous solution for 24 hours at the crosslinking temperature of 42 ℃, wherein the second crosslinking agent aqueous solution comprises 3 vol% of hydrochloric acid, 3 vol% of glutaraldehyde, 80 vol% of alcohol and 14 vol% of water.
And 9, washing the particles subjected to crosslinking in the step 8 with clear water to obtain finished adsorbent particles for extracting the liquid lithium resource. The finished product granule adsorbent content is 75% (calculated after deducting moisture), the moisture content is 40%, and the Shore A hardness is 42.
EXAMPLE III
An adsorbent particle for liquid lithium resource extraction is carried out as follows:
step 1, spinel type Li4Ti5O12Drying the adsorbent powder at 80 ℃, and crushing the adsorbent powder to be 800-1000 meshes by a high-speed crusher to obtain adsorbent powder;
step 2, dissolving polyvinyl alcohol with alcoholysis degree of 85% in water to prepare 10 wt% solution
Step 3, polyacrylic acid with an average molecular weight of 125 ten thousand is dissolved in water to prepare a solution with a concentration of 4 wt%.
Step 4, dissolving sodium alginate in water to prepare 3 wt% solution
Step 5, mixing the polymer aqueous solutions prepared in the steps 2, 3 and 4 according to the mass ratio of 10: 1: 1 proportion, and uniformly mixing by using a high-viscosity stirring paddle to obtain a high-viscosity polymer mixed solution.
And 6, adding the adsorbent powder obtained in the step 1 into the high-viscosity polymer mixed solution obtained in the step 5 according to the mass ratio of 1: 3, stirring or grinding until the mixture is uniformly mixed.
And 7, adding a certain amount of first cross-linking agent aqueous solution into the mixture obtained in the step 6, wherein the mass ratio of the mixture to the first cross-linking agent aqueous solution is 1: 2, the components of which are 3 weight percent of boric acid, 0.5 weight percent of borax, 1 weight percent of aluminum chloride and 1 weight percent of zinc chloride, and the solidification cross-linking product is formed after the materials are fully stirred and kneaded mechanically.
And 8, extruding and granulating the crosslinked product obtained in the step 7, wherein the particle size is 2mm, and drying at the drying temperature of 70 ℃ for 24 hours to obtain dried particles.
And (3) immersing the dried particles obtained in the 9 th step and the 8 th step into a second cross-linking agent aqueous solution, and cross-linking for 24 hours, wherein the cross-linking temperature is 42 ℃, and the second cross-linking agent aqueous solution is composed of 3 vol% sulfuric acid, 4 vol% glutaraldehyde, 80 vol% alcohol and 13 vol% water.
Step 10, washing the particles after the crosslinking in the step 9 with clear water to obtain finished absorbent high-strength particles used for the absorbent particles for extracting the liquid lithium resource,
spinel type Li4Ti5O12The finished product of the titanium adsorbent particle can be shown in figure 2, the adsorbent content of the finished product particle is 75% (calculated after water is subtracted), the water content is 44%, and the Shore A hardness is 38. The lithium ion adsorption material can be used for lithium adsorption under the alkaline condition of pH 8-12, can be used for desorption under the condition of pH 1-4, can be recycled under the condition for a long time, and does not swell and shrink particles.
The high water content indicates that the particles are porous and absorb water, the water permeability is high, and if the material is obtained by a method of granulating polyvinyl chloride materials, the water absorption is low.
Relational terms such as "first" and "second," and the like, may be used solely to distinguish one element from another element having the same name, without necessarily requiring or implying any actual such relationship or order between such elements.
The invention has been described in an illustrative manner, and it is to be understood that any simple variations, modifications or other equivalent changes which can be made by one skilled in the art without departing from the spirit of the invention fall within the scope of the invention.
Claims (12)
1. A preparation method of lithium ion sieve adsorbent particles for extracting liquid lithium resources is characterized by comprising the following steps:
step 1, adding adsorbent powder into a polymer mixed solution, and uniformly mixing to obtain a first mixture; the mass ratio of the adsorbent powder to the polymer mixed solution is 1 (2-20);
the adsorbent powder is a lithium ion sieve type adsorbent, and the particle size is 200-1500 meshes;
the polymer mixed solution comprises the following components in parts by mass: 50-90 parts of a first polymer solution, 0-40 parts of a second polymer solution and 0-10 parts of a third polymer solution;
the first polymer solution is a 1-50 wt% aqueous solution of a polymer containing polyhydroxy and polycarboxyl;
the second polymer solution is 1-50 wt% of a long carbon chain-containing polymer aqueous solution, and the aqueous solution of the second polymer has high viscosity and more carboxyl and amino groups;
the third polymer solution is an aqueous solution containing 1-50 wt% of natural polysaccharide polymer; natural polysaccharide compounds for extracting autobotanic plants;
step 2, immersing the first mixture obtained in the step 1 into a first cross-linking agent aqueous solution for primary cross-linking, and obtaining a second mixture after cross-linking solidification;
the first cross-linking agent is a mixture of at least one of boric acid or borax and soluble multivalent metal salt; the soluble multivalent metal salt is at least one of soluble ferric salt, soluble aluminum salt, soluble calcium salt, soluble magnesium salt, soluble zinc salt, soluble strontium salt or soluble barium salt;
step 3, granulating the second mixture, and drying to obtain dried particles;
the temperature in the drying process is 30-100 ℃, and the time in the drying process is 12-24 hours;
step 4, immersing the dried particles into a second cross-linking agent for secondary cross-linking, wherein the time of the secondary cross-linking is 12-72 hours, and the temperature of the secondary cross-linking is 25-80 ℃; washing the solid particles obtained after secondary crosslinking to obtain the adsorbent particles for extracting the liquid lithium resource;
the second cross-linking agent is an alkaline mixed solution or an acidic mixed solution;
when the adsorbent powder is an alkali-resistant powder or a powder that is both acid-resistant and alkali-resistant, using the alkali mixed solution; the alkaline mixed solution is a mixture of an epoxy compound and an alkaline solution, and the pH value is 8-14;
using the acidic mixed solution when the adsorbent powder is an acid-resistant powder or a powder that is both acid-resistant and base-resistant; the acid mixed solution is a mixture of ethanol, water, acid and aldehyde compounds, and the concentration of the acid is 0.1-5 mol/L.
2. The method of preparing lithium ion sieve adsorbent particles according to claim 1, wherein the first polymer solution is a 1-20 wt% aqueous solution of a polyhydroxy, polycarboxy containing polymer;
the second polymer solution is a water solution containing 1-10 wt% of long carbon chain polymer;
the third polymer solution is an aqueous solution containing 1-10 wt% of a natural polysaccharide polymer.
3. The method of preparing lithium ion sieve adsorbent particles of claim 1, wherein the first polymer is one or more of polyvinyl alcohol, polyvinyl alcohol graft copolymer, polyacrylic acid, hyperbranched polyol, polyester polyol, and isocyanate.
4. The method of preparing lithium ion sieve adsorbent particles according to claim 1, wherein the second polymer is one or more of isobutylene-maleic anhydride copolymer, sodium polyacrylate, polyacrylamide-maleic anhydride copolymer, polyvinyl alcohol-maleic anhydride copolymer, polyvinylpyrrolidone, polyethylene glycol, polyethylene oxide.
5. The method for preparing the lithium ion sieve adsorbent particles according to claim 1, wherein the third polymer is one or more of chitosan, gelatin, pectin, carrageenan, sodium alginate, sodium carboxymethylcellulose, water-soluble cellulose, guar gum, and soluble starch.
6. The method of preparing lithium ion sieve adsorbent particles according to claim 1, wherein in step 2, the first mixture is uniformly mixed with the first cross-linking agent powder or the first cross-linking agent solution;
the first cross-linking agent powder is powder formed by uniformly mixing at least one of boric acid and borax with soluble multivalent metal salt, wherein the soluble multivalent metal salt is at least one of soluble ferric salt, soluble aluminum salt, soluble calcium salt, soluble magnesium salt, soluble zinc salt, soluble strontium salt or soluble barium salt;
the first cross-linking agent solution is a solution obtained by dissolving a mixture of at least one of boric acid or borax and soluble multivalent metal salt in water, and the soluble multivalent metal salt is at least one of soluble ferric salt, soluble aluminum salt, soluble calcium salt, soluble magnesium salt, soluble zinc salt, soluble strontium salt or soluble barium salt.
7. The method of preparing a lithium ion sieve adsorbent particle according to claim 1, wherein when the second crosslinking agent is a basic mixed solution; the epoxy compound is one or more of propylene oxide, epichlorohydrin, epibromohydrin, 1, 2-epoxybutane, epoxybutene, epoxypropanol, glycidyl methacrylate and ethylene oxide-PEG-ethylene oxide; the dosage of the epoxy compound is 1-15 ml per 30 g of the dried particles;
the alkali solution is one or two of calcium hydroxide solution, sodium hydroxide solution and lithium hydroxide solution; the dosage of the alkali solution is 20-100 times of the weight of the dried particles.
8. The method of making lithium ion sieve adsorbent particles of claim 1, wherein the second crosslinker isWhen the solution is mixed in an acidic way; the volume ratio of the ethanol, the water, the acid and the aldehyde compound is (10-40): 2-10): 1-3): 1-2, wherein the aldehyde compound is one or more of formaldehyde, acetaldehyde, malonaldehyde, glutaraldehyde, benzaldehyde, phenylacetaldehyde, cinnamaldehyde and methylglyoxal; the acid is one or more of hydrochloric acid, sulfuric acid and nitric acid, wherein the H of the second cross-linking agent+The ion concentration is 0.1-5 mol/L, the dosage of the acid is 20-100 times of the weight of the dried particles, and the dosage of the aldehyde compound is 1-15 ml per 30 g of the dried particles.
9. The method of claim 2, wherein when the adsorbent powder is an acid-and alkali-resistant powder, the acid-and alkali-resistant powder is manganese-based ion sieve adsorbent, titanium-based ion sieve adsorbent, graphite, mesophase microspheres, carbon nanotubes, graphene, or carbon fiber powder.
10. The method of preparing the lithium ion sieve adsorbent particle of claim 2, wherein the method of preparing the polymer mixed solution comprises the steps of:
step 1.1, dissolving the first polymer in water to obtain a first polymer solution, wherein the concentration of the first polymer solution is 1-50 wt%;
step 1.2, dissolving the second polymer in water to obtain a second polymer solution, wherein the concentration of the second polymer solution is 1-50 wt%;
step 1.3, dissolving the third polymer in water to obtain a third polymer solution, wherein the concentration of the third polymer solution is 1-50 wt%;
step 1.4, mixing the first polymer solution, the second polymer solution and the third polymer solution to obtain a polymer mixed solution;
the first polymer is one or more of polyvinyl alcohol, polyvinyl alcohol graft copolymer, polyacrylic acid, hyperbranched polyol, polyester polyol and isocyanate;
the second polymer is one or more of isobutylene-maleic anhydride copolymer, sodium polyacrylate, polyacrylamide-maleic anhydride copolymer, polyvinyl alcohol-maleic anhydride copolymer, polyvinylpyrrolidone, polyethylene glycol and polyethylene oxide;
the third polymer is one or more of chitosan, gelatin, pectin, carrageenan, sodium alginate, sodium carboxymethylcellulose, water-soluble cellulose, guar gum and soluble starch.
11. The method of preparing the lithium ion sieve adsorbent particles of claim 1, wherein the lithium ion sieve type adsorbent is lithium titanate, lithium manganate, lithium iron phosphate, lithium nickelate, lithium iron phosphate, ternary cathode material, graphite, mesophase microspheres, carbon nanotubes, graphene, carbon fibers, tin-based oxide material.
12. The method of preparing the lithium ion sieve adsorbent particle of claim 11, wherein the lithium titanate is a metatitanic acid type Li2TiO3Spinel type Li4Ti5O12(ii) a The lithium manganate is spinel type Li1.6Mn1.6O4Spinel-type LiMn2O4。
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