CN116173925A - High-adsorption-rate lithium extraction adsorbent and preparation method and application thereof - Google Patents
High-adsorption-rate lithium extraction adsorbent and preparation method and application thereof Download PDFInfo
- Publication number
- CN116173925A CN116173925A CN202310336038.5A CN202310336038A CN116173925A CN 116173925 A CN116173925 A CN 116173925A CN 202310336038 A CN202310336038 A CN 202310336038A CN 116173925 A CN116173925 A CN 116173925A
- Authority
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- China
- Prior art keywords
- lithium
- salt
- high adsorption
- adsorption rate
- porous polymer
- Prior art date
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- Granted
Links
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 title claims abstract description 73
- 229910052744 lithium Inorganic materials 0.000 title claims abstract description 73
- 239000003463 adsorbent Substances 0.000 title claims abstract description 53
- 238000000605 extraction Methods 0.000 title claims abstract description 48
- 238000002360 preparation method Methods 0.000 title claims abstract description 11
- 238000001179 sorption measurement Methods 0.000 claims abstract description 58
- 229920000642 polymer Polymers 0.000 claims abstract description 27
- 238000000034 method Methods 0.000 claims abstract description 19
- AQTIRDJOWSATJB-UHFFFAOYSA-K antimonic acid Chemical compound O[Sb](O)(O)=O AQTIRDJOWSATJB-UHFFFAOYSA-K 0.000 claims abstract description 18
- 229910021626 Tin(II) chloride Inorganic materials 0.000 claims abstract description 9
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical class [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 claims abstract description 7
- 230000032683 aging Effects 0.000 claims abstract description 7
- 150000002751 molybdenum Chemical class 0.000 claims abstract description 7
- 150000003608 titanium Chemical class 0.000 claims abstract description 7
- 150000003754 zirconium Chemical class 0.000 claims abstract description 7
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 claims description 36
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 claims description 30
- 238000003756 stirring Methods 0.000 claims description 29
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- FBCQUCJYYPMKRO-UHFFFAOYSA-N prop-2-enyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OCC=C FBCQUCJYYPMKRO-UHFFFAOYSA-N 0.000 claims description 11
- NHARPDSAXCBDDR-UHFFFAOYSA-N propyl 2-methylprop-2-enoate Chemical compound CCCOC(=O)C(C)=C NHARPDSAXCBDDR-UHFFFAOYSA-N 0.000 claims description 11
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- OZAIFHULBGXAKX-UHFFFAOYSA-N 2-(2-cyanopropan-2-yldiazenyl)-2-methylpropanenitrile Chemical compound N#CC(C)(C)N=NC(C)(C)C#N OZAIFHULBGXAKX-UHFFFAOYSA-N 0.000 claims description 8
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- OMOVVBIIQSXZSZ-UHFFFAOYSA-N [6-(4-acetyloxy-5,9a-dimethyl-2,7-dioxo-4,5a,6,9-tetrahydro-3h-pyrano[3,4-b]oxepin-5-yl)-5-formyloxy-3-(furan-3-yl)-3a-methyl-7-methylidene-1a,2,3,4,5,6-hexahydroindeno[1,7a-b]oxiren-4-yl] 2-hydroxy-3-methylpentanoate Chemical compound CC12C(OC(=O)C(O)C(C)CC)C(OC=O)C(C3(C)C(CC(=O)OC4(C)COC(=O)CC43)OC(C)=O)C(=C)C32OC3CC1C=1C=COC=1 OMOVVBIIQSXZSZ-UHFFFAOYSA-N 0.000 claims description 6
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- XFCMNSHQOZQILR-UHFFFAOYSA-N 2-[2-(2-methylprop-2-enoyloxy)ethoxy]ethyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OCCOCCOC(=O)C(C)=C XFCMNSHQOZQILR-UHFFFAOYSA-N 0.000 claims description 4
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- CHQMHPLRPQMAMX-UHFFFAOYSA-L sodium persulfate Substances [Na+].[Na+].[O-]S(=O)(=O)OOS([O-])(=O)=O CHQMHPLRPQMAMX-UHFFFAOYSA-L 0.000 claims description 4
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- MEFBJEMVZONFCJ-UHFFFAOYSA-N molybdate Chemical compound [O-][Mo]([O-])(=O)=O MEFBJEMVZONFCJ-UHFFFAOYSA-N 0.000 claims description 2
- CMOAHYOGLLEOGO-UHFFFAOYSA-N oxozirconium;dihydrochloride Chemical compound Cl.Cl.[Zr]=O CMOAHYOGLLEOGO-UHFFFAOYSA-N 0.000 claims description 2
- DCKVFVYPWDKYDN-UHFFFAOYSA-L oxygen(2-);titanium(4+);sulfate Chemical compound [O-2].[Ti+4].[O-]S([O-])(=O)=O DCKVFVYPWDKYDN-UHFFFAOYSA-L 0.000 claims description 2
- 229920002451 polyvinyl alcohol Polymers 0.000 claims description 2
- 235000019422 polyvinyl alcohol Nutrition 0.000 claims description 2
- PNXMTCDJUBJHQJ-UHFFFAOYSA-N propyl prop-2-enoate Chemical compound CCCOC(=O)C=C PNXMTCDJUBJHQJ-UHFFFAOYSA-N 0.000 claims description 2
- 235000011150 stannous chloride Nutrition 0.000 claims description 2
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- AXZWODMDQAVCJE-UHFFFAOYSA-L tin(II) chloride (anhydrous) Chemical compound [Cl-].[Cl-].[Sn+2] AXZWODMDQAVCJE-UHFFFAOYSA-L 0.000 claims description 2
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- DUNKXUFBGCUVQW-UHFFFAOYSA-J zirconium tetrachloride Chemical compound Cl[Zr](Cl)(Cl)Cl DUNKXUFBGCUVQW-UHFFFAOYSA-J 0.000 claims description 2
- LNAZSHAWQACDHT-XIYTZBAFSA-N (2r,3r,4s,5r,6s)-4,5-dimethoxy-2-(methoxymethyl)-3-[(2s,3r,4s,5r,6r)-3,4,5-trimethoxy-6-(methoxymethyl)oxan-2-yl]oxy-6-[(2r,3r,4s,5r,6r)-4,5,6-trimethoxy-2-(methoxymethyl)oxan-3-yl]oxyoxane Chemical compound CO[C@@H]1[C@@H](OC)[C@H](OC)[C@@H](COC)O[C@H]1O[C@H]1[C@H](OC)[C@@H](OC)[C@H](O[C@H]2[C@@H]([C@@H](OC)[C@H](OC)O[C@@H]2COC)OC)O[C@@H]1COC LNAZSHAWQACDHT-XIYTZBAFSA-N 0.000 claims 1
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- 229910001416 lithium ion Inorganic materials 0.000 abstract description 31
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 abstract description 29
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Images
Classifications
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- B01J20/28002—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties characterised by their physical properties
- B01J20/28011—Other properties, e.g. density, crush strength
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- C—CHEMISTRY; METALLURGY
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Abstract
The invention discloses a high adsorption rate lithium extraction adsorbent, a preparation method and application thereof, which comprises the steps of preparing antimonic acid solution containing at least one of titanium salt, tin salt, molybdenum salt and zirconium salt, adding a porous polymer into the antimonic acid solution, impregnating active component precursors into pore channels of the porous polymer by an impregnation method, and depositing the active component precursors into the porous polymer by a precipitatorIs arranged in the pore canal of the glass fiber reinforced plastic; finally, aging and other operations are carried out to obtain the high-uniformity lithium-extracting adsorbent, wherein the active component is SbO 3 With TiO 2 、SnO 2 、MoO 3 Or ZrO(s) 2 A nano composite oxide. The invention adopts the multi-metal ion doped antimonic acid as the lithium ion exchanger, and hybridizes the antimonic acid into the pore canal of the porous polymer, and the lithium ion exchanger is anchored by utilizing the 'winding effect' of the pore canal of the porous polymer, so that the stability of the lithium ion exchanger is effectively improved, the dissolution loss rate of the lithium ion exchanger is reduced, and the adsorbent has high adsorption capacity, high adsorption rate, high adsorption selectivity, stable adsorption performance and long service life for lithium ions.
Description
Technical Field
The invention belongs to the technical field of adsorption lithium extraction, and particularly relates to a high-adsorption-rate lithium extraction adsorbent, and a preparation method and application thereof.
Background
Lithium and lithium compounds are used as an important strategic resource and widely applied to industries such as energy, aerospace, alloy materials, ceramics, construction, chemical industry and the like. In nature, lithium resources mainly exist in liquid resources such as lithium ores, salt lake brine, seawater and the like, wherein the total lithium resource reserve of the lithium ores is only 1.7 multiplied by 10t, and the increasing demands of human beings on the lithium resources can not be met far; and the total reserve of liquid lithium resources is about 15000 times that of lithium resources of lithium ores. Therefore, the development of new materials and new technologies for extracting lithium from liquid lithium resources has extremely important strategic significance and application value for national economy and national defense construction.
Near eighty liquid lithium resources in China are distributed in salt lakes of Qinghai and Tibet. However, since the salt lake in China has the natural disadvantage of high magnesium-lithium ratio, the lithium extraction technology of the lithium ore commercially applied in China is applied to extracting lithium from the salt lake, and the problems of low lithium content, low purity and the like still exist. At present, the main method for extracting lithium from salt lakes comprises the following steps: precipitation, solvent extraction, evaporative crystallization, calcination leaching, salting-out, carbonization, electrodialysis, fused salt electrolysis, adsorption, etc. The adsorption method has the advantages of simple process, high recovery rate, good selectivity, environmental friendliness and the like, and is widely studied as a lithium extraction method with commercial prospect.
At present, aiming at the lithium extraction adsorption technology of the salt lake: including aluminum-based lithium ion sieves, manganese-based lithium ion sieves, titanium-based lithium ion sieves, and the like. At present, lithium ion sieve powder is prepared through high-temperature solid-phase reaction, and then the lithium ion sieve powder is molded, so that the problem that the practical application of a lithium ion sieve is difficult is solved. The forming process mainly comprises two methods, namely, polymerization forming, namely, mixing a powder ion sieve adsorbent with a polymerizer to perform polymerization reaction under certain conditions, and crosslinking to obtain the adsorbent with certain granularity; the other is to use a bonding method, that is, an effective binder is used to bond the adsorbent powder, and a certain pressure is applied at a certain temperature to squeeze the powder into a certain shape. Chinese patent application No. 201010280648.0 discloses a granular lithium ion sieve for extracting lithium from (metal) lithium-containing solution such as salt lake brine, seawater, well brine or geothermal water, wherein the granular lithium ion sieve is obtained by coating lithium ion sieve powder in a polymer in the process of forming a crosslinked polymer by inverse suspension polymerization of acrylic monomers. The granular ion sieve prepared by the invention has the advantages of good mechanical strength, high selectivity, high adsorption capacity, fast adsorption rate and good stability, but has obvious defects in the separation efficiency of the adsorbent from brine. Chinese patent application No. 201010278813.9 discloses a lithium ion sieve membrane and a preparation method thereof, polyvinylidene fluoride is dissolved in N, N-dimethylacetamide to prepare a casting solution, then a lithium manganese oxide precursor is added, and the mixture is heated and stirred; fully dispersing lithium manganese oxide in the casting film liquid by ultrasonic, standing, curing and completely defoaming, scraping the film on a clean glass plate to prepare a film, and immersing the film into a coagulation bath for gelation; and finally, carrying out acid washing on the prepared membrane, and extracting lithium ions in the precursor to obtain the lithium ion sieve membrane. The inorganic lithium ion sieve nano particles are made into the membrane material, so that the continuity of separation operation can be improved, but the inorganic lithium ion sieve nano particles fall off due to the fact that the common membrane material is denatured when being used in an acid solution for a long time, and the service life is short.
The traditional lithium extraction adsorption materials (mainly comprising an aluminum lithium ion sieve, a manganese lithium ion sieve and a titanium lithium ion sieve) are all in powder form, and have the problems of low adsorption capacity, low adsorption selectivity, high dissolution loss rate, low adsorption rate and the like, and the traditional lithium extraction adsorption materials are all required to be granulated and formed into granular (the uniformity coefficient of 3.0-6.0mm is more than or equal to 85 percent is less than or equal to 5.0) lithium extraction adsorbents, so that the traditional lithium extraction adsorption materials can be applied to extracting lithium from salt lake brine, and the adsorption performance of the traditional lithium extraction adsorption materials is greatly reduced. This also severely restricts its engineering applications in salt lake brine or oilfield brine, etc.
The present invention has been made to solve the above-mentioned problems occurring in the prior art.
Disclosure of Invention
Aiming at the defects in the prior art, the invention provides a high adsorption rate lithium extraction adsorbent and a preparation method and application thereof; then, dipping the active component precursor into the pore canal of the porous polymer by adopting a dipping method, and depositing the active component precursor into the pore canal of the porous polymer by using a precipitator; finally, aging, filtering, washing and drying are carried out to obtain the high-uniformity lithium extraction adsorbent, and the high-uniformity lithium extraction adsorbent has high adsorption capacity, high adsorption rate, high adsorption selectivity, stable adsorption performance and long service life on lithium ions.
The technical scheme of the invention is as follows:
the invention provides a preparation method of a high adsorption rate lithium extraction adsorbent, which comprises the following steps:
s1, preparing an antimonic acid solution containing at least one of titanium salt, tin salt, molybdenum salt and zirconium salt, wherein the mass content of the titanium salt is 0-10%, the mass content of the tin salt is 0-5%, the mass content of the molybdenum salt is 0-8%, the mass content of the zirconium salt is 0-15%, and the antimonate concentration is 0.5-3.0mol/L;
s2, adding the porous polymer serving as a carrier into the antimonic acid solution in the step S1, stirring for 5-12h, and filtering out redundant solution;
s3, adding the product obtained in the step S2 into a precipitator, aging for 8-16h, and filtering, washing and drying to obtain the lithium extraction adsorbent with high adsorption rate.
Preferably, the method of preparing the porous polymer comprises the steps of:
s21, adding a dispersing agent and NaCl into the water phase, and stirring at room temperature until the dispersing agent and the NaCl are dissolved, wherein the mass percentages of the dispersing agent and the NaCl are respectively 0.5-2.0% and 5-22%;
s22, the oil phase consists of reactants and a pore-foaming agent, wherein the mass ratio of the reactants to the pore-foaming agent is 2:1-1:2, the reactants comprise monomers and a cross-linking agent, and the mass ratio of the monomers to the cross-linking agent is 1:3-3:1;
s23, adding 0.1-2% of initiator by mass percent into the oil phase formed in the step S22, and stirring at room temperature until the initiator is completely dissolved;
s24, adding the water phase formed in the step S21 into a reactor with a stirring and temperature controlling device, adding the oil phase formed in the step S23, and stirring to disperse the oil phase into oil beads with the particle size of 0.8-1.0mm in the water phase; then, the temperature-rising reaction is carried out, the temperature-rising reaction is divided into two stages, the reaction temperature of the first stage is 70-75 ℃, the reaction time is 4-6h, the reaction temperature of the second stage is 85-90 ℃, the reaction time is 8-24h, and after the reaction is finished, the porous polymer is obtained through cooling, filtering, washing and drying.
Preferably, the dispersing agent in the step S21 is at least one of gelatin, polyvinyl alcohol, methyl cellulose, hydroxyethyl cellulose and methyl hydroxypropyl cellulose.
Preferably, the monomer in the step S22 is at least one of methyl acrylate, propyl acrylate, butyl acrylate, methyl methacrylate, propyl methacrylate, and butyl methacrylate;
the cross-linking agent in the step S22 is at least one of divinylbenzene, allyl itaconate, diethylene glycol dimethacrylate, allyl methacrylate and allyl isocyanurate.
The pore-forming agent in the step S22 is at least one of toluene, isoamyl alcohol, heptanol, octanol, xylene, gasoline and ethyl acetate.
Preferably, the initiator in step S23 is one or both of benzoyl peroxide and azobisisobutyronitrile.
Preferably, the titanium salt in the step S1 is at least one of titanium tetrachloride, titanium sulfate and titanyl sulfate; the tin salt is at least one of tin tetrachloride, tin dichloride and stannous sulfate; the molybdenum salt is at least one of potassium molybdate, sodium molybdate and ammonium molybdate; the zirconium salt is one or two of zirconium oxychloride and zirconium tetrachloride.
Preferably, the precipitant in the step S3 is a mixed aqueous solution of the substance A and the substance B, and the volume of the precipitant is 10-20 times of the volume of the added product obtained in the step S2; wherein the substance A is ammonium persulfate and/or sodium persulfate, the substance B is sodium hydroxide and/or potassium hydroxide, and the mass ratio of the substance A to the substance B is (0.5-3.0) (1-3).
Preferably, the precipitant is a mixed aqueous solution of ammonium persulfate and sodium hydroxide, a mixed aqueous solution of ammonium persulfate and potassium hydroxide, or a mixed aqueous solution of sodium persulfate and sodium hydroxide.
Preferably, the porogens are recovered simultaneously in step S2.
The invention also provides a high adsorption rate lithium extraction adsorbent which is prepared by adopting the preparation method and comprises a carrier and an active component loaded on the carrier, wherein the adsorption capacity of the adsorbent is 20-30mg/g, the carrier is a porous polymer, and the active component is SbO 3 With TiO 2 、SnO 2 、MoO 3 Or ZrO(s) 2 A composed nanocomposite oxide, expressed as xSbO a ·yMO b ·nH 2 O, wherein M represents at least one of Ti, sn, mo and Zr, a=2-3, b=2-3, x=0.1-1, y=0.1-0.5, n=0.5-1.
The invention also provides application of the high-adsorption-rate lithium extraction adsorbent in extracting lithium from salt lake brine or oilfield brine, such as a lithium extraction process applied to salt lake brine with low lithium ion concentration (about 100-200 ppm).
The beneficial effects of the invention are as follows:
(1) According to the invention, the multi-metal ion doped antimonic acid is adopted as the lithium ion exchanger, and is hybridized into the pore canal of the porous polymer, and the lithium ion exchanger is anchored by utilizing the 'winding effect' of the pore canal of the porous polymer, so that the stability of the lithium ion exchanger is effectively improved, and the dissolution loss rate of the lithium ion exchanger is reduced;
(2) The particle size distribution of the lithium extraction adsorbent synthesized by the invention has high uniformity (the sphere rate is 0.60-1.0mm more than or equal to 95 percent and the uniformity coefficient is less than or equal to 1.2), so that the external diffusion and internal diffusion rate of lithium ions in the lithium extraction adsorbent are high; in addition, the lithium extraction adsorbent has the advantages of high adsorption rate, high adsorption selectivity, high adsorption capacity and stable adsorption performance for adsorbing lithium ions from brine, and can realize the desorption of lithium ions only by changing acidity;
(3) The high-uniformity lithium extraction adsorbent has the advantages of simple preparation process and no pollution to the environment.
Drawings
The invention is further described below with reference to the accompanying drawings and examples:
FIG. 1 is a process route diagram of the preparation of a high adsorption rate lithium extraction adsorbent of the present invention;
FIG. 2 is a graph showing the particle size distribution of a high adsorption rate lithium-extracted adsorbent prepared in example 3 of the present invention;
fig. 3 shows a lithium extraction process route diagram of the high adsorption rate lithium extraction adsorbent applied to salt lake brine.
Detailed Description
The objects, technical solutions and advantages of the present invention will become more apparent by the following detailed description of the present invention with reference to the accompanying drawings. It should be understood that the description is only illustrative and is not intended to limit the scope of the invention. In addition, in the following description, descriptions of well-known structures and techniques are omitted so as not to unnecessarily obscure the present invention.
Example 1
The process for preparing the lithium extraction adsorbent in this embodiment is shown in fig. 1, and specifically comprises the following steps:
(1) Preparing an antimonic acid solution containing 5% of stannic chloride and 3% of sodium molybdate, wherein the concentration of antimonate is 2.0mol/L for later use;
(2) Adding gelatin and NaCl into the water phase, and stirring at room temperature until the gelatin and the NaCl are dissolved, wherein the mass percentages of the gelatin and the NaCl are respectively 1.0% and 10%;
(3) The oil phase consists of (methyl acrylate and allyl itaconate) and toluene, wherein the mass ratio of the methyl acrylate to the allyl itaconate is 2:1, and the mass ratio of the methyl acrylate to the allyl itaconate to the toluene is 1:2;
(4) Adding benzoyl peroxide accounting for 1.0% of the mass percent into the oil phase formed in the step (3), and stirring at room temperature until the benzoyl peroxide is completely dissolved;
(5) Adding 500mL of the water phase formed in the step (2) into a 2000mL reactor with a stirring and temperature controlling device, adding 500mL of the oil phase formed in the step (4), and stirring to disperse the oil phase into oil beads with the particle size of 0.8-1.0mm in the water phase; then, carrying out a heating reaction, wherein the heating reaction is divided into two stages, the reaction temperature in the first stage is 70 ℃, the reaction time is 4 hours, the reaction temperature in the second stage is 85 ℃, the reaction time is 8 hours, and after the reaction is finished, cooling, filtering, washing and drying are carried out to obtain the porous polymer;
(6) Adding 100mL of the high-uniformity porous polymer obtained in the step (5) into 100mL of the antimonic acid solution obtained in the step (1), stirring for 10h, and filtering out redundant antimonic acid solution;
(7) Adding the porous polymer obtained in the step (6) into se:Sup>A precipitant solution (ammonium persulfate+potassium hydroxide, wherein the mass concentration of the ammonium persulfate is 8.0 percent, and the mass ratio of the ammonium persulfate to the potassium hydroxide is 2:1) with 15 times of the volume, aging for 10 hours, and filtering, washing and drying to obtain the lithium-extracted adsorbent HPS-A.
Example 2
The process for preparing the lithium extraction adsorbent in this embodiment is shown in fig. 1, and specifically comprises the following steps:
(1) Preparing an antimonic acid solution containing 1% of stannic chloride, 3% of sodium molybdate and 10% of zirconium oxychloride octahydrate, wherein the concentration of antimonate is 3.0mol/L for later use;
(2) Adding gelatin and NaCl into the water phase, and stirring at room temperature until the gelatin and the NaCl are dissolved, wherein the mass percentages of the gelatin and the NaCl are respectively 1.0% and 10%;
(3) The oil phase consists of (propyl methacrylate and allyl methacrylate) and toluene, the mass ratio of the propyl methacrylate to the allyl methacrylate is 1:1, and the mass ratio of the propyl methacrylate and the allyl methacrylate to the xylene is 1:1;
(4) Adding benzoyl peroxide accounting for 1.0% of the mass percent into the oil phase formed in the step (3), and stirring at room temperature until the benzoyl peroxide is completely dissolved;
(5) Adding 500mL of the water phase formed in the step (2) into a 2000mL reactor with a stirring and temperature controlling device, adding 500mL of the oil phase formed in the step (4), and stirring to disperse the oil phase into oil beads with the particle size of 0.8-1.0mm in the water phase; then, carrying out a heating reaction, wherein the heating reaction is divided into two stages, the reaction temperature in the first stage is 70 ℃, the reaction time is 4 hours, the reaction temperature in the second stage is 85 ℃, the reaction time is 8 hours, and after the reaction is finished, cooling, filtering, washing and drying are carried out to obtain the porous polymer;
(6) Adding 100mL of the high-uniformity porous polymer obtained in the step (5) into 100mL of the antimonic acid solution obtained in the step (1), stirring for 10h, and filtering out redundant antimonic acid solution;
(7) Adding the porous polymer obtained in the step (6) into a precipitant solution (ammonium persulfate+potassium hydroxide, wherein the mass concentration of the ammonium persulfate is 5.0 percent, and the mass ratio of the ammonium persulfate to the potassium hydroxide is 3:1) with 15 times of the volume, aging for 10 hours, and filtering, washing and drying to obtain the lithium-extracted adsorbent HPLS-B.
Example 3
The process for preparing the lithium extraction adsorbent in this embodiment is shown in fig. 1, and specifically comprises the following steps:
(1) Preparing an antimonic acid solution containing 3% of stannic chloride, 3% of sodium molybdate, 5% of zirconium oxychloride octahydrate and 5% of titanium tetrachloride, wherein the concentration of antimonate is 3.0mol/L for later use;
(2) Adding gelatin and NaCl into the water phase, and stirring at room temperature until the gelatin and the NaCl are dissolved, wherein the mass percentages of the gelatin and the NaCl are respectively 1.0% and 10%;
(3) The oil phase consists of (propyl methacrylate and allyl methacrylate) and toluene, the mass ratio of the propyl methacrylate to the allyl methacrylate is 2:1, and the mass ratio of the propyl methacrylate and the allyl methacrylate to the xylene is 1:1;
(4) Adding 1.0 mass percent of azodiisobutyronitrile into the oil phase formed in the step (3), and stirring at room temperature until the azodiisobutyronitrile is completely dissolved;
(5) Adding 500mL of the water phase formed in the step (2) into a 2000mL reactor with a stirring and temperature controlling device, adding 500mL of the oil phase formed in the step (4), and stirring to disperse the oil phase into oil beads with the particle size of 0.8-1.0mm in the water phase; then, carrying out a heating reaction, wherein the heating reaction is divided into two stages, the reaction temperature in the first stage is 70 ℃, the reaction time is 4 hours, the reaction temperature in the second stage is 85 ℃, the reaction time is 8 hours, and after the reaction is finished, cooling, filtering, washing and drying are carried out to obtain the porous polymer;
(6) Adding 100mL of the high-uniformity porous polymer obtained in the step (5) into 100mL of the antimonic acid solution obtained in the step (1), stirring for 10h, and filtering out redundant antimonic acid solution;
(7) Adding the porous polymer obtained in the step (6) into a precipitant solution (ammonium persulfate+sodium hydroxide, wherein the mass concentration of the ammonium persulfate is 8.0 percent, and the mass ratio of the ammonium persulfate to the sodium hydroxide is 2.5:1) with 15 times of the volume, aging for 10 hours, and filtering, washing and drying to obtain the lithium-extracted adsorbent HPLS-C.
FIG. 2 is a graph showing the particle size distribution of the lithium-extracted adsorbent obtained in example 3, wherein the synthesized lithium-extracted adsorbent was measured by a particle size analyzer, and the synthesized adsorbent was shown to have high uniformity and a particle size of 0.6 to 0.7mm.
Comparative example 1
(1) Adding gelatin and NaCl into the water phase, and stirring at room temperature until the gelatin and the NaCl are dissolved, wherein the mass percentages of the gelatin and the NaCl are respectively 1.2% and 15%;
(2) The oil phase consists of (propyl methacrylate and allyl methacrylate), divinylbenzene and toluene, reactants comprise propyl methacrylate, allyl methacrylate and divinylbenzene, the mass ratio of the reactants to toluene is 2:1, and the mass ratio of the propyl methacrylate, the allyl methacrylate to the divinylbenzene is 1:1:1;
(3) Adding 1.0% of azodiisobutyronitrile in mass ratio into the oil phase formed in the step (2), and stirring at room temperature until the azodiisobutyronitrile is completely dissolved;
(4) Adding aluminum hydroxide powder with the particle size of 0.01-1 mu m into the oil phase formed in the step (3), wherein the mass ratio of the aluminum hydroxide powder to the reactant is 1:3;
(5) Adding 500mL of the water phase formed in the step (1) into a 2000mL reactor with a stirring and temperature controlling device, adding 500mL of the oil phase formed in the step (4), stirring at a set rotating speed to disperse the oil phase into oil beads with the particle size of 0.3-1.2mm in the water phase, and then carrying out a heating reaction, wherein the heating reaction is divided into two stages, the temperature is controlled at 70 ℃ in the first stage and is controlled at 90 ℃ for 3 hours, the temperature is controlled at 90 ℃ in the second stage and is controlled at 8 hours, and then cooling and washing are carried out to obtain the adsorption resin loaded with aluminum hydroxide;
(6) And (3) adding 100mL of lithium nitrate solution with mass concentration of 30% into 100mL of the adsorption resin obtained in the step (5), controlling the temperature at 80 ℃, reacting for 10 hours, cooling, and filtering to obtain the lithium extraction adsorbent HPLA-D.
Examples 1-3 and comparative example 1 salt lake brine extraction of lithium:
1. 100mL of lithium-extracted adsorbent (HPLS- (A, B, C or D) is filled into 10 industrial chromatographic columns (the height-to-diameter ratio is 2:1), and the industrial chromatographic columns are connected in series (as shown in figure 3) and sequentially marked as columns 1-10;
2. at a flow rate of 7L/h, 18L of salt lake brine (Li + :206ppm，Mg 2+ :1326541ppm，Na + :1032331ppm，K + 9654102 ppm) is passed through columns 1-10 in sequence;
3. after lithium is extracted through series adsorption, the concentration of lithium, sodium, magnesium and potassium is measured;
4. the desorption solution was desorbed with 100mL of 8.0% hydrochloric acid and the concentration of lithium, sodium, magnesium and potassium was measured.
TABLE 1 Table of the compositions of lithium, sodium, magnesium and Potassium in salt lake brine
| Salt lake brine component | Li + | Na + | Mg 2+ | K + |
| Ion concentration (ppm) | 206 | 1032331 | 1326541 | 9654102 |
TABLE 2 lithium, sodium, magnesium and potassium concentrations in the effluent after 10 column series adsorption
| Name of the name | Lithium concentration (ppm) | Sodium concentration (ppm) | Magnesium concentration (ppm) | Potassium concentration (ppm) |
| HPLS-A | 12.6 | 986548 | 1300254 | 9421035 |
| HPLS-B | 5.6 | 975462 | 1315487 | 9534056 |
| HPLS-C | 8.2 | 965243 | 1294568 | 9559245 |
| HPLA-D | 82.5 | 568425 | 865425 | 7254556 |
TABLE 3 lithium, sodium, magnesium and potassium concentrations in the desorbed solution after hydrochloric acid desorption
The lithium extraction adsorbent with high adsorption rate synthesized by the invention has the advantages of high adsorption rate, high adsorption selectivity, high adsorption capacity, stable adsorption performance and the like on lithium ions. The high adsorption rate lithium extraction adsorbent prepared by the invention is coupled with the serial adsorption technology of the industrial chromatographic column, so that the defects of high production cost, poor mechanical strength, high dissolution loss rate, low adsorption rate, granulation molding requirement, difficult engineering and the like of the traditional aluminum lithium extraction adsorbent, manganese lithium extraction adsorbent and titanium lithium extraction adsorbent can be fundamentally solved. In addition, the method has the advantages of simple operation, low energy consumption, stable water output, high concentration ratio, capability of preparing high-purity lithium carbonate and the like.
It is to be understood that the above-described embodiments of the present invention are merely illustrative of or explanation of the principles of the present invention and are in no way limiting of the invention. Accordingly, any modification, equivalent replacement, improvement, etc. made without departing from the spirit and scope of the present invention should be included in the scope of the present invention. Furthermore, the appended claims are intended to cover all such changes and modifications that fall within the scope and boundary of the appended claims, or equivalents of such scope and boundary.
Claims (10)
1. The preparation method of the lithium extraction adsorbent with high adsorption rate is characterized by comprising the following steps of:
s1, preparing an antimonic acid solution containing at least one of titanium salt, tin salt, molybdenum salt and zirconium salt, wherein the mass content of the titanium salt is 0-10%, the mass content of the tin salt is 0-5%, the mass content of the molybdenum salt is 0-8%, the mass content of the zirconium salt is 0-15%, and the antimonate concentration is 0.5-3.0mol/L;
s2, adding the porous polymer serving as a carrier into the antimonic acid solution in the step S1, stirring for 5-12h, and filtering out redundant solution;
s3, adding the product obtained in the step S2 into a precipitator, aging for 8-16h, and filtering, washing and drying to obtain the lithium extraction adsorbent with high adsorption rate.
2. The method for preparing the high adsorption rate lithium extraction adsorbent according to claim 1, wherein the method for preparing the porous polymer comprises the following steps:
s21, adding a dispersing agent and NaCl into the water phase, and stirring at room temperature until the dispersing agent and the NaCl are dissolved, wherein the mass percentages of the dispersing agent and the NaCl are respectively 0.5-2.0% and 5-22%;
s22, the oil phase consists of reactants and a pore-foaming agent, wherein the mass ratio of the reactants to the pore-foaming agent is 2:1-1:2, the reactants comprise monomers and a cross-linking agent, and the mass ratio of the monomers to the cross-linking agent is 1:3-3:1;
s23, adding 0.1-2% of initiator by mass percent into the oil phase formed in the step S22, and stirring at room temperature until the initiator is completely dissolved;
s24, adding the water phase formed in the step S21 into a reactor with a stirring and temperature controlling device, adding the oil phase formed in the step S23, and stirring to disperse the oil phase into oil beads with the particle size of 0.8-1.0mm in the water phase; then, the temperature-rising reaction is carried out, the temperature-rising reaction is divided into two stages, the reaction temperature of the first stage is 70-75 ℃, the reaction time is 4-6h, the reaction temperature of the second stage is 85-90 ℃, the reaction time is 8-24h, and after the reaction is finished, the porous polymer is obtained through cooling, filtering, washing and drying.
3. The method for preparing a high adsorption rate lithium extraction adsorbent according to claim 2, wherein the dispersant in step S21 is at least one of gelatin, polyvinyl alcohol, methylcellulose, hydroxyethyl cellulose, and methyl hydroxypropyl cellulose.
4. The method for producing a high adsorption rate lithium-extracted adsorbent according to claim 2, wherein the monomer in step S22 is at least one of methyl acrylate, propyl acrylate, butyl acrylate, methyl methacrylate, propyl methacrylate, and butyl methacrylate;
the cross-linking agent in the step S22 is at least one of divinylbenzene, allyl itaconate, diethylene glycol dimethacrylate, allyl methacrylate and allyl isocyanurate;
the pore-forming agent in the step S22 is at least one of toluene, isoamyl alcohol, heptanol, octanol, xylene, gasoline and ethyl acetate.
5. The method for preparing a high adsorption rate lithium extraction adsorbent according to claim 2, wherein the initiator in step S23 is one or both of benzoyl peroxide and azobisisobutyronitrile.
6. The method for preparing a high adsorption rate lithium extraction adsorbent according to claim 1, wherein the titanium salt in step S1 is at least one of titanium tetrachloride, titanium sulfate and titanyl sulfate; the tin salt is at least one of tin tetrachloride, tin dichloride and stannous sulfate; the molybdenum salt is at least one of potassium molybdate, sodium molybdate and ammonium molybdate; the zirconium salt is one or two of zirconium oxychloride and zirconium tetrachloride.
7. The method for preparing a high adsorption rate lithium extraction adsorbent according to claim 1, wherein the precipitant in the step S3 is a mixed aqueous solution of a substance a and a substance B, and the volume of the precipitant is 10-20 times the volume of the product obtained in the step S2; wherein the substance A is ammonium persulfate and/or sodium persulfate, the substance B is sodium hydroxide and/or potassium hydroxide, and the mass ratio of the substance A to the substance B is (0.5-3.0) (1-3).
8. The method for preparing a high adsorption rate lithium extraction adsorbent according to claim 7, wherein the precipitant is a mixed aqueous solution of ammonium persulfate and sodium hydroxide, a mixed aqueous solution of ammonium persulfate and potassium hydroxide, or a mixed aqueous solution of sodium persulfate and sodium hydroxide.
9. The lithium extraction adsorbent with high adsorption rate is characterized by comprising a carrier and an active component supported on the carrier, wherein the carrier is a porous polymer, and the active component is xSbO a ·yMO b ·nH 2 O, wherein M represents at least one of Ti, sn, mo and Zr, a=2-3, b=2-3, x=0.1-1, y=0.1-0.5, n=0.5-1.
10. The use of a high adsorption rate lithium extraction adsorbent as claimed in claim 9 in extracting lithium from salt lake brine or oilfield brine.
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