CN116809013A - Titanium lithium ion sieve particle and preparation method thereof - Google Patents
Titanium lithium ion sieve particle and preparation method thereof Download PDFInfo
- Publication number
- CN116809013A CN116809013A CN202310828615.2A CN202310828615A CN116809013A CN 116809013 A CN116809013 A CN 116809013A CN 202310828615 A CN202310828615 A CN 202310828615A CN 116809013 A CN116809013 A CN 116809013A
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- China
- Prior art keywords
- titanium
- lithium ion
- water
- ion sieve
- lithium
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- 229910001416 lithium ion Inorganic materials 0.000 title claims abstract description 45
- 239000002245 particle Substances 0.000 title claims abstract description 37
- SWAIALBIBWIKKQ-UHFFFAOYSA-N lithium titanium Chemical compound [Li].[Ti] SWAIALBIBWIKKQ-UHFFFAOYSA-N 0.000 title claims abstract description 26
- 238000002360 preparation method Methods 0.000 title claims abstract description 14
- 239000000843 powder Substances 0.000 claims abstract description 32
- 239000002243 precursor Substances 0.000 claims abstract description 24
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 claims abstract description 19
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 42
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 36
- 229910052719 titanium Inorganic materials 0.000 claims description 33
- 239000010936 titanium Substances 0.000 claims description 33
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 32
- 238000000034 method Methods 0.000 claims description 31
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims description 25
- 229910052744 lithium Inorganic materials 0.000 claims description 25
- 239000012071 phase Substances 0.000 claims description 25
- 239000003463 adsorbent Substances 0.000 claims description 24
- 239000000243 solution Substances 0.000 claims description 20
- 238000005406 washing Methods 0.000 claims description 20
- 239000011164 primary particle Substances 0.000 claims description 19
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 18
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 18
- 239000002253 acid Substances 0.000 claims description 14
- 238000001035 drying Methods 0.000 claims description 14
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N titanium dioxide Inorganic materials O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 14
- 230000008569 process Effects 0.000 claims description 13
- MYRTYDVEIRVNKP-UHFFFAOYSA-N 1,2-Divinylbenzene Chemical compound C=CC1=CC=CC=C1C=C MYRTYDVEIRVNKP-UHFFFAOYSA-N 0.000 claims description 12
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 12
- 238000006243 chemical reaction Methods 0.000 claims description 12
- 239000003431 cross linking reagent Substances 0.000 claims description 11
- 239000011163 secondary particle Substances 0.000 claims description 11
- -1 (ethyleneoxy) silane Chemical class 0.000 claims description 10
- 238000005245 sintering Methods 0.000 claims description 10
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims description 9
- 239000003795 chemical substances by application Substances 0.000 claims description 9
- 239000002270 dispersing agent Substances 0.000 claims description 9
- 239000000178 monomer Substances 0.000 claims description 9
- 235000002639 sodium chloride Nutrition 0.000 claims description 9
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 claims description 8
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- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 claims description 6
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 claims description 6
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- 239000007822 coupling agent Substances 0.000 claims description 6
- 229910017053 inorganic salt Inorganic materials 0.000 claims description 6
- 239000000376 reactant Substances 0.000 claims description 6
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- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 5
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 5
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- 230000007935 neutral effect Effects 0.000 claims description 5
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- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims description 4
- YNQLUTRBYVCPMQ-UHFFFAOYSA-N Ethylbenzene Chemical compound CCC1=CC=CC=C1 YNQLUTRBYVCPMQ-UHFFFAOYSA-N 0.000 claims description 4
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 4
- 238000009835 boiling Methods 0.000 claims description 4
- 238000004140 cleaning Methods 0.000 claims description 4
- NKDDWNXOKDWJAK-UHFFFAOYSA-N dimethoxymethane Chemical compound COCOC NKDDWNXOKDWJAK-UHFFFAOYSA-N 0.000 claims description 4
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- 239000003999 initiator Substances 0.000 claims description 4
- XGZVUEUWXADBQD-UHFFFAOYSA-L lithium carbonate Chemical compound [Li+].[Li+].[O-]C([O-])=O XGZVUEUWXADBQD-UHFFFAOYSA-L 0.000 claims description 4
- 229910052808 lithium carbonate Inorganic materials 0.000 claims description 4
- TVMXDCGIABBOFY-UHFFFAOYSA-N octane Chemical compound CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 claims description 4
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- YIVJZNGAASQVEM-UHFFFAOYSA-N Lauroyl peroxide Chemical compound CCCCCCCCCCCC(=O)OOC(=O)CCCCCCCCCCC YIVJZNGAASQVEM-UHFFFAOYSA-N 0.000 description 2
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 2
- AZDRQVAHHNSJOQ-UHFFFAOYSA-N alumane Chemical class [AlH3] AZDRQVAHHNSJOQ-UHFFFAOYSA-N 0.000 description 2
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- 239000011230 binding agent Substances 0.000 description 2
- 238000003795 desorption Methods 0.000 description 2
- AJNVQOSZGJRYEI-UHFFFAOYSA-N digallium;oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[Ga+3].[Ga+3] AJNVQOSZGJRYEI-UHFFFAOYSA-N 0.000 description 2
- ZLNAFSPCNATQPQ-UHFFFAOYSA-N ethenyl-dimethoxy-methylsilane Chemical compound CO[Si](C)(OC)C=C ZLNAFSPCNATQPQ-UHFFFAOYSA-N 0.000 description 2
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- LWRXNMLZNDYFAW-UHFFFAOYSA-N 1-octylperoxyoctane Chemical compound CCCCCCCCOOCCCCCCCC LWRXNMLZNDYFAW-UHFFFAOYSA-N 0.000 description 1
- YCGHFAAWVULVDV-UHFFFAOYSA-N 1-trimethylsilyloxyethyl 2-methylprop-2-enoate Chemical compound C[Si](C)(C)OC(C)OC(=O)C(C)=C YCGHFAAWVULVDV-UHFFFAOYSA-N 0.000 description 1
- SJECZPVISLOESU-UHFFFAOYSA-N 3-trimethoxysilylpropan-1-amine Chemical compound CO[Si](OC)(OC)CCCN SJECZPVISLOESU-UHFFFAOYSA-N 0.000 description 1
- BESKSSIEODQWBP-UHFFFAOYSA-N 3-tris(trimethylsilyloxy)silylpropyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OCCC[Si](O[Si](C)(C)C)(O[Si](C)(C)C)O[Si](C)(C)C BESKSSIEODQWBP-UHFFFAOYSA-N 0.000 description 1
- GKQSBQCNFMRMCC-UHFFFAOYSA-N 4-trimethylsilyloxypentyl 2-methylprop-2-enoate Chemical compound C(C(=C)C)(=O)OCCCC(C)O[Si](C)(C)C GKQSBQCNFMRMCC-UHFFFAOYSA-N 0.000 description 1
- 239000004801 Chlorinated PVC Substances 0.000 description 1
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 description 1
- 239000006087 Silane Coupling Agent Substances 0.000 description 1
- 229910001069 Ti alloy Inorganic materials 0.000 description 1
- LCKIEQZJEYYRIY-UHFFFAOYSA-N Titanium ion Chemical compound [Ti+4] LCKIEQZJEYYRIY-UHFFFAOYSA-N 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000004075 alteration Effects 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- KGURQEYMEHYOKV-UHFFFAOYSA-N but-3-en-2-yloxy(trimethyl)silane Chemical compound C=CC(C)O[Si](C)(C)C KGURQEYMEHYOKV-UHFFFAOYSA-N 0.000 description 1
- 238000001354 calcination Methods 0.000 description 1
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- 238000005342 ion exchange Methods 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 238000004898 kneading Methods 0.000 description 1
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- 229910052751 metal Inorganic materials 0.000 description 1
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 1
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- 239000004800 polyvinyl chloride Substances 0.000 description 1
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- 238000011084 recovery Methods 0.000 description 1
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Landscapes
- Solid-Sorbent Or Filter-Aiding Compositions (AREA)
Abstract
The invention provides titanium lithium ion sieve particles and a preparation method thereof. The titanium-series lithium ion sieve particles are spherical in appearance and have an internal cross-linked structure, and are formed by bonding doped titanium-series lithium ion sieve precursor powder and polymers through covalent bonds.
Description
Technical Field
The invention relates to the field of lithium extraction in salt lakes, in particular to a spherical lithium adsorbent suitable for extracting neutral to alkaline liquid lithium resources and a preparation method thereof.
Technical Field
With the rapid development of new energy industry, the global lithium salt productivity is rapidly increased. The Chinese lithium resource is mainly located in the salt lake brine and accounts for 80% of the total reserve, and the current process method suitable for extracting lithium from the salt lake brine mainly comprises a calcination leaching method, a solar pond method, a precipitation method, an extraction method, a full membrane method and an adsorption and membrane method, wherein the adsorption and membrane method is the most competitive lithium extraction process suitable for extracting lithium from low-medium-grade brine.
The core material of the adsorption and membrane method is a lithium adsorbent, which is a method for adsorbing Li in brine + The composite functional material with specific selective adsorption is generally prepared from inorganic adsorbent powder and a binder through a proper granulating process.At present, a lot of researches are conducted on an aluminum salt adsorbent, a manganese series lithium ion sieve and a titanium series lithium ion sieve, wherein aluminum series lithium adsorbent suitable for weak acid to neutral brine is used for adsorbing Li + And then the desorption can be carried out by pure water, and the use process is simple. CN 106622103B discloses a preparation method of aluminum-based lithium adsorbent particles, which comprises mixing aluminum-based adsorbent powder with a hydrophobic polymer solution, drying, crushing, and the obtained adsorbent particles have the problems of embedded active sites and low adsorption capacity. Manganese and titanium are lithium ion sieves complementary to aluminum and suitable for neutral to alkaline brines, and selectively adsorb Li in the brines by an ion exchange mechanism + Release H + Thus alkaline brine promotes Li + Is adsorbed by the adsorbent. The manganese series and titanium series lithium ion sieves need to be desorbed by acid after being adsorbed, but the manganese series has higher dissolution loss, generally more than 1 percent, and a large amount of manganese ions which are difficult to remove are introduced into desorption liquid; the titanium system has lower melting loss than the manganese system, and has practical application value in carbonate salt lakes. CN 105238927B discloses a method for preparing titanium-series lithium ion sieve, in which titanium source and lithium source are firstly hydrothermally reacted, then Li is prepared by high-temperature solid phase method 2 TiO 3 And (5) pickling to obtain the titanium ion sieve. CN 112871127A discloses a preparation method of ion sieve particles, which comprises mixing titanium series plasma sieve powder and additives uniformly, kneading with aqueous resin emulsion to form dough, granulating by granulating equipment, drying and pickling to obtain lithium ion sieve particles, wherein the prepared adsorbent particles have irregular morphology and large long-time running loss, and the dissolution loss of inorganic adsorbent is not fundamentally solved.
Disclosure of Invention
The invention aims to provide titanium lithium ion sieve particles and a preparation method thereof, and aims to solve the problems of irregular particle morphology, high powder running rate and large dissolution loss in the existing preparation process of titanium lithium ion sieve adsorbent. The titanium-based lithium ion sieve prepared by the invention has regular morphology, stable structure, low dissolution loss and large lithium ion adsorption capacity, can be widely applied to extraction and recovery of liquid lithium resources, and has wide application prospect.
In order to achieve the above purpose, the present invention adopts the following technical scheme:
the invention provides titanium lithium ion sieve particles which are spherical in appearance, have the particle size of 0.1-5.0mm, have an internal cross-linked structure and are formed by bonding doped titanium lithium ion sieve precursor powder and a polymer through covalent bonds.
The preparation method comprises the following steps:
(1) Uniformly mixing the pretreated titanium source, lithium source and doping element, and obtaining titanium lithium ion sieve precursor powder by a high-temperature solid phase method;
(2) Uniformly dispersing titanium lithium ion sieve precursor powder in a solvent in which a coupling agent is dissolved, and obtaining modified primary particles after reaction, separation, washing and drying;
(3) Dispersing the modified primary particles into an oil phase composed of a pore-forming agent, a monomer, a crosslinking agent and an initiator, dispersing the oil phase containing the modified primary particles into a water phase, and obtaining spherical secondary particles through suspension polymerization and aftertreatment;
(4) And eluting the spherical secondary particles by dilute acid to obtain titanium lithium ion sieve particles.
In the step (1) of the invention, the particle size of the titanium lithium ion sieve precursor powder is 10-10000nm, preferably 30-500nm.
In the step (1), the titanium source is one or more selected from rutile type titanium dioxide, anatase type titanium dioxide and metatitanic acid; the particle size of the titanium source is 10-3000nm, preferably 30-300nm;
in the step (1), the lithium source is one or more selected from lithium hydroxide and lithium carbonate;
in the step (1), the doping element substances are selected from one or more of oxides or hydroxides of magnesium, aluminum, zirconium, gallium, molybdenum and tantalum;
in the step (1) of the invention, the molar ratio of the titanium source to the lithium source to the doping element is (0.9-1.0): (2.0-2.10): (0-0.1), preferably (0.9-0.97): (2.0-2.05): (0.03-0.1);
in the step (1), the titanium source pretreatment method comprises the steps of dispersing a titanium source into a soluble sugar solution, soaking, and then carrying out suction filtration and drying, wherein the soluble sugar solution is one or more of glucose, sucrose, maltose and fructose, and the concentration of the sugar solution is 5-30%; the mass ratio of the titanium source to the sugar solution is 1: (2-10).
In the step (1), the high-temperature solid-phase sintering atmosphere is air or oxygen; the heating rate is 1-10 ℃/min, preferably 3-6 ℃/min; the sintering temperature is 600-850 ℃, preferably 650-750 ℃; the sintering time is 2-24 hours, preferably 3-15 hours.
In the step (2) of the invention, the surface of the modified primary particles is grafted with polymerizable double bonds, and the particle size is 10-10000nm, preferably 30-500nm.
In the step (2) of the invention, the coupling agent is selected from one or more of vinyltrimethylethoxysilane, vinyltris (2-methoxyethoxy) silane, vinyltriacetoxysilane, vinyltriisopropoxysilane, vinyltriisopropenyloxysilane, methylvinyldimethylsilane, vinyltributylketoximosilane, methacryloxytrimethylethoxysilane, tetramethyldivinyl disiloxane, tetramethyltetravinylcyclotetrasiloxane, methacryloxypropylmethyldimethylethoxysilane, methacryloxypropyltris (trimethylsiloxy) silane; the concentration of the coupling agent is 0.5-10wt%;
in the step (2), the solvent is a mixed solution of an organic solvent and water, wherein the mass fraction of the water is 0-15%; the organic solvent is selected from one or more of methanol, ethanol, isopropanol, toluene, N-dimethylamide, N-dimethylacetamide, dimethyl sulfoxide and N-methylpyrrolidone; the mass ratio of the titanium lithium ion sieve precursor powder to the solvent is 1: (1-100), preferably 1: (3-20);
in step (2) of the present invention, the reaction temperature is 30 to 120 ℃, preferably 40 to 85 ℃; the reaction time is 0.5 to 48 hours, preferably 2 to 24 hours; the separation is suction filtration or centrifugation; the washing is washing with ethanol or methanol, and the number of times of washing is not particularly limited as long as the washing effect can be achieved, preferably 1 to 10 times; the drying temperature is 25-120 ℃, preferably 40-80 ℃; the drying time is 0.5-24h.
In the step (3) of the invention, the particle size of the spherical secondary particles is 0.1-5.0mm, preferably 0.3-1.5mm; the inside is in an alternating network structure, and is formed by bonding the doped titanium lithium ion sieve precursor powder and a polymer through a covalent bond, wherein the inorganic component accounts for 30-85%, preferably 50-80%.
In the step (3), the pore-forming agent is selected from one or more of toluene, ethylbenzene, xylene, n-heptane, n-octane, isooctane, cyclohexane, liquid paraffin, solvent oil, white oil, ethyl acetate, butyl acetate and isobutyl acetate;
in the step (3), the monomer is selected from one or more of styrene, methyl styrene, ethyl styrene, chlorostyrene, bromostyrene, methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, butyl (meth) acrylate and glycidyl methacrylate;
in the step (3) of the present invention, the crosslinking agent is one or more selected from divinylbenzene, trivinylbenzene, divinylbenzene, allyl methacrylate, vinyl methacrylate, ethylene glycol dimethacrylate, diethylene glycol dimethacrylate, triethylene glycol dimethacrylate, butanediol dimethacrylate, trimethylolpropane trimethacrylate, triallyl isocyanurate or allyl itaconate. The mass percent of the cross-linking agent is 20-100%, preferably 40-80% based on 100% of the total mass of the monomer and the cross-linking agent;
in the step (3), the ratio of the total mass of the monomer and the cross-linking agent to the mass of the pore-forming agent is 1 (0.3-2).
In the step (3), the initiator is one or more selected from azodiisobutyronitrile, azodiisoheptonitrile, lauroyl peroxide, benzoyl peroxide, dioctyl peroxide and the like; the initiator accounts for 0.5-2% of the total mass of the monomer and the cross-linking agent.
In the step (3), the water phase comprises deionized water, inorganic salt and a dispersing agent; the inorganic salt is one or more of water-soluble inorganic salts such as sodium chloride, potassium chloride, sodium sulfate, potassium sulfate and the like, and the inorganic salt accounts for 0-10wt%, preferably 3-10wt% of the water phase;
in the method of the invention, the dispersing agent is one or more of gelatin, polyvinyl alcohol, carboxymethyl cellulose, hydroxyethyl cellulose, methyl hydroxyethyl cellulose and hydroxypropyl cellulose; the dispersant is 0.05-0.5wt% of the water phase;
the mass ratio of the oil phase containing the primary particles to the water phase is 1:1.5-1:5;
the suspension polymerization temperature is 60-95 ℃, preferably 80-95 ℃; the polymerization time is from 5 to 24 hours, preferably from 8 to 15 hours. Filtering out reactants after the reaction is finished, cleaning the reactants by using a water-soluble solvent with a low boiling point, and then cleaning the reactants by using water until the residual TOC is lower than 20ppm; the low boiling point water-soluble solvent is selected from one or more of methanol, ethanol, acetone and methylal.
In the step (4), the dilute acid is one or more selected from hydrochloric acid, nitric acid and sulfuric acid solution, preferably a dilute acid solution with the hydrogen ion concentration of 0.1-1 mol/L; the dosage of the eluent in the elution process is 20-100mL/g of the adsorbent precursor; the elution process temperature is 15-80 ℃, preferably 15-50 ℃; the time is 0.5-48h, preferably 2-24h; the elution process needs water washing to be neutral after acid washing.
The titanium lithium ion sieve prepared by the technical scheme of the invention has the following beneficial effects:
(1) The titanium source is pretreated in the preparation process of the titanium lithium ion sieve precursor, so that caking in the sintering process is avoided; (2) The crystal structure is optimized by doping other metal elements, so that the titanium alloy is more resistant to acid washing and lower in titanium dissolution loss; (3) The titanium lithium ion sieve precursor is modified with carbon-carbon double bonds in situ, can be linked with an organic part through chemical bonds, has stable structure and low powder running rate; (4) The adsorbent particles obtained by suspension polymerization are spherical, the running friction loss is lower, the inside is of a cross-linked network structure, and the adsorption quantity is high.
Detailed Description
The following embodiments are described in detail with reference to the foregoing summary of the invention, and appropriate substitutions and alterations are possible without departing from the scope of the invention.
Table 1: main raw materials and sources
| Raw material name | Provenance of origin |
| Titanium dioxide | XUANCHENG JINGRUI NEW MATERIAL Co.,Ltd. |
| Metatitanic acid | SHANGHAI MACKLIN BIOCHEMICAL Co.,Ltd. |
| Lithium hydroxide monohydrate | Tianyi lithium industry |
| Lithium carbonate | Shandong Ruifeng lithium industry |
| Zirconia (zirconia) | XUANCHENG JINGRUI NEW MATERIAL Co.,Ltd. |
| Alumina oxide | XUANCHENG JINGRUI NEW MATERIAL Co.,Ltd. |
| Gallium oxide | Peak grinding technology |
| Vinyl trimethoxy silane | ALADDIN REAGENT (SHANGHAI) Co.,Ltd. |
| Vinyl triisopropoxysilane | ALADDIN REAGENT (SHANGHAI) Co.,Ltd. |
| Methyl vinyl dimethoxy silane | ALADDIN REAGENT (SHANGHAI) Co.,Ltd. |
Other conventional raw materials used in the invention are available from reagent companies such as Allatin, inoka and the like.
Test method
Adsorption amount: adding 1g of the delithiated adsorbent into 50g of brine with the lithium concentration of C0 (ppm), vibrating and adsorbing at the speed of 140rpm at the temperature of 25 ℃ for 16 hours, and sampling to measure the lithium concentration of C1 (ppm) in the supernatant, so that the adsorption quantity (mg/g) = (C0-C1)/20.
The adsorption brine is zabuyen raw brine, and the main components are shown in the following table 2:
table 2: the main composition of zabuyen raw halogen
Titanium dissolution loss: the volume V (L) of the pickling solution in the elution process was collected, and the concentration C (ppm) of titanium ions therein was tested, and the dissolution loss (mg titanium/g adsorbent) =cv/m, m being the adsorbent mass (g).
Powder running rate: 20g of the eluted lithium adsorbent is weighed into a 250mL round bottom flask, 100mL of water is added, the stirring rotation speed is regulated to 200rpm, after stirring for 24 hours, the mixture is filtered by a 0.1mm filter screen, the filtered particles are respectively collected, the mass after drying is m1 (g) and m2 (g), and the powder leakage rate (%) = m 2/(m1+m2) is 100%.
The mass of the granular adsorbent is the mass of the adsorbent after free water is removed.
Example 1
(1) 100g of rutile titanium dioxide powder having a particle size of 500nm was dispersed in 200g of an aqueous solution having a glucose content of 5% and immersed, followed by suction filtration and drying. Uniformly mixing the pretreated titanium source, 108.28g of lithium hydroxide monohydrate and 1.97g of aluminum oxide, heating to 750 ℃ at 3 ℃/min in an air atmosphere, and sintering for 3 hours to obtain titanium lithium ion sieve precursor powder.
(2) 150g of an ethanol/water mixed solution of vinyltrimethoxysilane having a concentration of 10% was prepared, wherein the mass fraction of water was 15%. 50g of the prepared titanium lithium ion sieve precursor powder is dispersed into the solution, reacted for 2 hours at 40 ℃, washed for 3 times with fresh ethanol, and dried for 24 hours at 40 ℃ to obtain modified primary particles with the particle size of 500nm.
(3) Into a flask, 150.8g of deionized water, 0.32g of polyvinyl alcohol, and 8.0g of sodium chloride were added and mixed uniformly to obtain an aqueous phase. Adding a premixed oil phase, wherein the oil phase comprises the following components: 80g of modified primary particles, 12g of styrene, 8g of divinylbenzene, 6g of toluene and 0.4g of azobisisobutyronitrile. Stirring is started, the rotating speed is regulated, and the temperature is increased to 80 ℃ for reaction for 12 hours. Filtering after the reaction, washing with hot water to remove the dispersing agent, extracting with acetone to remove the pore-forming agent, and washing with water to remove the acetone to obtain spherical secondary particles with the particle size of 1.0 mm.
Example 2
(1) 122.5g of a metatitanic acid powder having a particle size of 120nm was dispersed in 1225g of an aqueous solution having a sucrose content of 30% and immersed, followed by suction filtration and drying. Uniformly mixing the pretreated titanium source with 116.7g of lithium hydroxide monohydrate and 17.1g of zirconium dioxide, heating to 700 ℃ at 5 ℃/min under an oxygen atmosphere, and sintering for 5 hours to obtain titanium lithium ion sieve precursor powder.
(2) 1000g of an isopropanol solution of vinyltriisopropoxysilane was prepared at a concentration of 0.5%. 50g of the prepared titanium lithium ion sieve precursor powder is dispersed into the solution, reacted for 24 hours at 60 ℃, washed for 2 times with fresh ethanol, and dried for 5 hours at 50 ℃ to obtain modified primary particles with the particle size of 150 nm.
(3) Into a flask were added 387.8g deionized water, 0.2g gelatin, 12g potassium chloride and mixed well to form a water phase. Adding a premixed oil phase, wherein the oil phase comprises the following components: 50g of modified primary particles, 10g of methyl methacrylate, 10g of divinylbenzene, 30g of ethylene glycol dimethacrylate, 50g of toluene, 50g of ethyl acetate and 0.5g of benzoyl peroxide. Stirring is started, the rotating speed is regulated, and the temperature is increased to 90 ℃ for reaction for 8 hours. Filtering after the reaction, washing with hot water to remove the dispersing agent, extracting with ethanol to remove the pore-forming agent, and washing with water to remove the ethanol to obtain the spherical secondary particles with the particle size of 1.5 mm.
Example 3
(1) 100g of anatase titanium dioxide powder having a particle size of 30nm was dispersed in 500g of an aqueous solution having a fructose content of 6% and immersed, followed by suction filtration and drying. Uniformly mixing the pretreated titanium source with 99.8g of lithium carbonate and 6.2g of gallium oxide, heating to 650 ℃ at a speed of 6 ℃/min in an air atmosphere, and sintering for 15 hours to obtain titanium lithium ion sieve precursor powder.
(2) 500g of a mixed N, N-dimethylamide/water solution of methylvinyldimethoxysilane having a concentration of 3% was prepared, wherein the mass fraction of water was 3%. 50g of the prepared titanium lithium ion sieve precursor powder is dispersed into the solution, reacted for 6 hours at 85 ℃, washed for 3 times with fresh ethanol, and dried for 0.5 hour at 80 ℃ to obtain modified primary particles with the particle size of 30 nm.
(3) Into a flask were charged 373.2g deionized water, 2.1g carboxymethyl cellulose, 41.7g sodium sulfate, and mixed well into a water phase. Adding a premixed oil phase, wherein the oil phase comprises the following components: 50g of modified primary particles, 3.7g of styrene, 3g of glycidyl methacrylate, 10g of trimethylolpropane trimethacrylate, 10g of butyl acetate, 6.7g of white oil and 0.084g of lauroyl peroxide. Stirring is started, the rotating speed is regulated, and the temperature is raised to 95 ℃ for reaction for 15 hours. Filtering after the reaction, washing with hot water to remove the dispersing agent, extracting with methylal to remove the pore-forming agent, and washing with water to remove methylal to obtain spherical secondary particles with the particle size of 0.3 mm.
Comparative example 1
A lithium ion sieve was prepared in the same manner as in example 1, except that the sintered titanium-based lithium ion sieve precursor was directly subjected to suspension polymerization granulation without modification in step (2).
Comparative example 2
A lithium ion sieve was prepared in the same manner as in example 1, except that the silane coupling agent for modification in step (2) was 3-aminopropyl trimethoxysilane.
Comparative example 3
Modified primary particles were prepared in the same manner as in example 1, and granulation was carried out according to the scheme of CN115845825, specifically as follows:
50g of modified primary particles, 10g of PVC, 1.25g of TPU, 1.25g of CPVC, 30.5 g of PVPk, 1.5g of PEG, 125g of N, N-dimethylacetamide and the like are weighed, stirred for 5 hours at 65 ℃ until the materials are fully and uniformly mixed, then a spinning device is used for spinning into 65 ℃ water to obtain filaments, after spinning is finished, the filaments are continuously soaked in the water for 30 minutes, then the filaments are washed for 5 times by normal-temperature water, and cylindrical secondary particles with the diameter of 1mm are obtained after the filaments are cut.
For parallel comparison, the examples and comparative samples were pickled under the same conditions, as follows: 50g of the secondary particles are weighed and added into 2500mL of dilute hydrochloric acid with the concentration of 0.25mol/L, and the mixture is heated to 50 ℃ for eluting for 4 hours, and then the lithium adsorbent is obtained by water washing.
Table 3: evaluation results
As shown in Table 2, the sample prepared by the method has higher adsorption capacity in real brine, and low dissolution loss and powder leakage rate, and can meet the requirement of long-term operation in engineering. In comparative example 1, the titanium-based lithium ion sieve precursor powder is not modified, so that the titanium-based lithium ion sieve precursor powder is difficult to stably disperse in the oil phase in the step (3), can be dispersed in the water phase in the polymerization process, and is difficult to form uniform spheres, so that the adsorption quantity is low, and the dissolution loss and the powder leakage rate are high; the modified primary particles of comparative example 2 are not linked with the organic part through chemical bonds, and are not firmly fixed in the adsorbent particles, so that the dissolution loss and the powder running rate are high; comparative example 3 was directly granulated by mixing the binder with the modified primary particles, the effective adsorption sites were severely embedded, and the morphology was irregular, so that the overall performance was inferior to that of the examples.
Claims (10)
1. A method for preparing titanium-based lithium ion sieve particles, which is characterized by comprising the following steps:
(1) Uniformly mixing the pretreated titanium source, lithium source and doping element, and obtaining titanium lithium ion sieve precursor powder by a high-temperature solid phase method;
(2) Uniformly dispersing titanium lithium ion sieve precursor powder in a solvent in which a coupling agent is dissolved, and obtaining modified primary particles after reaction, separation, washing and drying;
(3) Dispersing the modified primary particles into an oil phase composed of a pore-forming agent, a monomer, a crosslinking agent and an initiator, dispersing the oil phase containing the modified primary particles into a water phase, and obtaining spherical secondary particles through suspension polymerization and aftertreatment;
(4) And eluting the spherical secondary particles by dilute acid to obtain titanium lithium ion sieve particles.
2. The method according to claim 1, wherein in step (1), the particle size of the titanium-based lithium ion sieve precursor powder is 10 to 10000nm, preferably 30 to 500nm; and/or the titanium source is selected from one or more of rutile type, anatase type titanium dioxide and meta-titanic acid; the particle size of the titanium source is 10-3000nm, preferably 30-300nm; and/or the lithium source is selected from one or more of lithium hydroxide and lithium carbonate; and/or the doping element substance is selected from one or more of oxides or hydroxides of magnesium, aluminum, zirconium, gallium, molybdenum and tantalum; and/or, the molar ratio of the titanium source, the lithium source and the doping element is (0.9-1.0): (2.0-2.10): (0-0.1), preferably (0.9-0.97): (2.0-2.05): (0.03-0.1).
3. The method according to claim 1 or 2, wherein in the step (1), the pretreatment of the titanium source is carried out by dispersing the titanium source into a soluble sugar solution, and then leaching and drying, wherein the soluble sugar solution is one or more of glucose, sucrose, maltose and fructose solution, and the concentration of the sugar solution is 5-30%; the mass ratio of the titanium source to the sugar solution is 1: (2-10); and/or the high-temperature solid-phase sintering atmosphere is air or oxygen; the heating rate is 1-10 ℃/min, preferably 3-6 ℃/min; the sintering temperature is 600-850 ℃, preferably 650-750 ℃; the sintering time is 2-24 hours, preferably 3-15 hours.
4. A method of preparation according to any one of claims 1 to 3 wherein in step (2) the coupling agent is selected from one or more of vinyltrimethyloxy silane, vinyltris (2-methoxyethoxy) silane, vinyltriacetoxy silane, vinyltriisopropoxysilane, vinyltriisopropenyloxy silane, methylvinyldimethicone (ethyleneoxy) silane, vinyltributylketoximosilane, methacryloxytrimethyloxy silane, tetramethyl divinyl disiloxane, tetramethyl tetravinyl cyclotetrasiloxane, methacryloxypropylmethyldimethicone (ethyleneoxy) silane, methacryloxypropyltris (trimethylsiloxane) silane; the concentration of the coupling agent is 0.5-10wt%; and/or the solvent is a mixed solution of an organic solvent and water, wherein the mass fraction of the water is 0-15%; and/or the organic solvent is selected from one or more of methanol, ethanol, isopropanol, toluene, N-dimethylamide, N-dimethylacetamide, dimethyl sulfoxide and N-methylpyrrolidone; and/or the mass ratio of the titanium lithium ion sieve precursor powder to the solvent is 1: (1-100), preferably 1: (3-20).
5. The process according to any one of claims 1 to 4, wherein in step (2), the reaction temperature is 30 to 120 ℃, preferably 40 to 85 ℃; the reaction time is 0.5 to 48 hours, preferably 2 to 24 hours; the separation is suction filtration or centrifugation; the washing is washing with ethanol or methanol; the drying temperature is 25-120 ℃, preferably 40-80 ℃; the drying time is 0.5-24h.
6. The process according to any one of claims 1 to 5, wherein in step (3), the spherical secondary particles have a particle size of 0.1 to 5.0mm, preferably 0.3 to 1.5mm; the pore-forming agent is selected from one or more of toluene, ethylbenzene, xylene, n-heptane, n-octane, isooctane, cyclohexane, liquid paraffin, solvent oil, white oil, ethyl acetate, butyl acetate and isobutyl acetate; and/or the monomer is selected from one or more of styrene, methyl styrene, ethyl styrene, chlorostyrene, bromostyrene, methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, butyl (meth) acrylate and glycidyl methacrylate; and/or the cross-linking agent is selected from one or more of divinylbenzene, trivinylbenzene, divinylbenzene, allyl methacrylate, vinyl methacrylate, ethylene glycol dimethacrylate, diethylene glycol dimethacrylate, triethylene glycol dimethacrylate, butanediol dimethacrylate, trimethylolpropane trimethacrylate, triallyl isocyanurate or allyl itaconate; and/or, the mass percent of the cross-linking agent is 20-100%, preferably 40-80%, based on 100% of the total mass of the monomer and the cross-linking agent; the ratio of the total mass of the monomer and the cross-linking agent to the mass of the pore-forming agent is 1 (0.3-2).
7. The method of any one of claims 1-6, wherein in step (3), the aqueous phase comprises deionized water, an inorganic salt, a dispersant; the inorganic salt is one or more of water-soluble inorganic salts such as sodium chloride, potassium chloride, sodium sulfate, potassium sulfate and the like, and the inorganic salt accounts for 0-10wt%, preferably 3-10wt% of the water phase; and/or the dispersing agent is one or more of gelatin, polyvinyl alcohol, carboxymethyl cellulose, hydroxyethyl cellulose, methyl hydroxyethyl cellulose and hydroxypropyl cellulose; the dispersant is 0.05-0.5wt% of the water phase; and/or the mass ratio of the oil phase containing the primary particles to the water phase is 1:1.5-1:5.
8. The preparation process according to any one of claims 1 to 7, wherein the suspension polymerization temperature is 60 to 95 ℃, preferably 80 to 95 ℃; the polymerization time is from 5 to 24 hours, preferably from 8 to 15 hours. Filtering out reactants after the reaction is finished, cleaning the reactants by using a water-soluble solvent with a low boiling point, and then cleaning the reactants by using water until the residual TOC is lower than 20ppm; the low boiling point water-soluble solvent is selected from one or more of methanol, ethanol, acetone and methylal.
9. The method of any one of claims 1 to 8, wherein the dilute acid is selected from one or more of hydrochloric acid, nitric acid, sulfuric acid solution, preferably a dilute acid solution having a hydrogen ion concentration of 0.1 to 1 mol/L; the dosage of the eluent in the elution process is 20-100mL/g of the adsorbent precursor; the elution process temperature is 15-80 ℃, preferably 15-50 ℃; the time is 0.5-48h, preferably 2-24h; the elution process needs water washing to be neutral after acid washing.
10. Titanium-based lithium ion sieve particles prepared by the preparation method according to any one of claims 1 to 9; and/or the use of the titanium-based lithium ion sieve particles prepared by the preparation method according to any one of claims 1 to 9 as an adsorbent in the field of salt lake lithium extraction.
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| CN117299098B (en) * | 2023-11-28 | 2024-02-27 | 万华化学集团股份有限公司 | High-performance titanium-based lithium adsorbent and preparation method and application thereof |
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