CN113845134A - Method for synthesizing porous lithium-aluminum hydrotalcite - Google Patents
Method for synthesizing porous lithium-aluminum hydrotalcite Download PDFInfo
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- CN113845134A CN113845134A CN202111124049.4A CN202111124049A CN113845134A CN 113845134 A CN113845134 A CN 113845134A CN 202111124049 A CN202111124049 A CN 202111124049A CN 113845134 A CN113845134 A CN 113845134A
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- lithium
- aluminum hydrotalcite
- aluminum
- reaction
- porous lithium
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- GDVKFRBCXAPAQJ-UHFFFAOYSA-A dialuminum;hexamagnesium;carbonate;hexadecahydroxide Chemical compound [OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Al+3].[Al+3].[O-]C([O-])=O GDVKFRBCXAPAQJ-UHFFFAOYSA-A 0.000 title claims abstract description 82
- 229960001545 hydrotalcite Drugs 0.000 title claims abstract description 82
- 229910001701 hydrotalcite Inorganic materials 0.000 title claims abstract description 82
- JFBZPFYRPYOZCQ-UHFFFAOYSA-N [Li].[Al] Chemical compound [Li].[Al] JFBZPFYRPYOZCQ-UHFFFAOYSA-N 0.000 title claims abstract description 69
- 238000000034 method Methods 0.000 title claims abstract description 28
- 230000002194 synthesizing effect Effects 0.000 title claims description 12
- 238000006243 chemical reaction Methods 0.000 claims abstract description 24
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 21
- 239000011259 mixed solution Substances 0.000 claims abstract description 18
- 239000012716 precipitator Substances 0.000 claims abstract description 16
- 238000001035 drying Methods 0.000 claims abstract description 12
- 238000001027 hydrothermal synthesis Methods 0.000 claims abstract description 12
- 238000005406 washing Methods 0.000 claims abstract description 12
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 11
- 230000001105 regulatory effect Effects 0.000 claims abstract description 4
- 238000000605 extraction Methods 0.000 claims abstract description 3
- KWGKDLIKAYFUFQ-UHFFFAOYSA-M lithium chloride Chemical compound [Li+].[Cl-] KWGKDLIKAYFUFQ-UHFFFAOYSA-M 0.000 claims description 14
- 239000008367 deionised water Substances 0.000 claims description 13
- 229910021641 deionized water Inorganic materials 0.000 claims description 13
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims description 11
- 239000004202 carbamide Substances 0.000 claims description 11
- 229910052782 aluminium Inorganic materials 0.000 claims description 10
- -1 aluminum ions Chemical class 0.000 claims description 10
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 claims description 8
- 229910001416 lithium ion Inorganic materials 0.000 claims description 7
- 229920002873 Polyethylenimine Polymers 0.000 claims description 6
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 6
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 6
- 229920002401 polyacrylamide Polymers 0.000 claims description 6
- 239000000243 solution Substances 0.000 claims description 6
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 5
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 5
- 239000000047 product Substances 0.000 claims description 5
- REYJJPSVUYRZGE-UHFFFAOYSA-N Octadecylamine Chemical compound CCCCCCCCCCCCCCCCCCN REYJJPSVUYRZGE-UHFFFAOYSA-N 0.000 claims description 4
- 239000003463 adsorbent Substances 0.000 claims description 4
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 claims description 4
- IIPYXGDZVMZOAP-UHFFFAOYSA-N lithium nitrate Chemical compound [Li+].[O-][N+]([O-])=O IIPYXGDZVMZOAP-UHFFFAOYSA-N 0.000 claims description 4
- 238000001308 synthesis method Methods 0.000 claims description 4
- GVGUFUZHNYFZLC-UHFFFAOYSA-N dodecyl benzenesulfonate;sodium Chemical compound [Na].CCCCCCCCCCCCOS(=O)(=O)C1=CC=CC=C1 GVGUFUZHNYFZLC-UHFFFAOYSA-N 0.000 claims description 3
- 229940080264 sodium dodecylbenzenesulfonate Drugs 0.000 claims description 3
- BNGXYYYYKUGPPF-UHFFFAOYSA-M (3-methylphenyl)methyl-triphenylphosphanium;chloride Chemical compound [Cl-].CC1=CC=CC(C[P+](C=2C=CC=CC=2)(C=2C=CC=CC=2)C=2C=CC=CC=2)=C1 BNGXYYYYKUGPPF-UHFFFAOYSA-M 0.000 claims description 2
- QGLWBTPVKHMVHM-KTKRTIGZSA-N (z)-octadec-9-en-1-amine Chemical compound CCCCCCCC\C=C/CCCCCCCCN QGLWBTPVKHMVHM-KTKRTIGZSA-N 0.000 claims description 2
- NCBISIFFSNXYQJ-UHFFFAOYSA-N 1-dodecyl-4,5-dihydroimidazole Chemical compound CCCCCCCCCCCCN1CCN=C1 NCBISIFFSNXYQJ-UHFFFAOYSA-N 0.000 claims description 2
- LZZYPRNAOMGNLH-UHFFFAOYSA-M Cetrimonium bromide Chemical compound [Br-].CCCCCCCCCCCCCCCC[N+](C)(C)C LZZYPRNAOMGNLH-UHFFFAOYSA-M 0.000 claims description 2
- RCEAADKTGXTDOA-UHFFFAOYSA-N OS(O)(=O)=O.CCCCCCCCCCCC[Na] Chemical compound OS(O)(=O)=O.CCCCCCCCCCCC[Na] RCEAADKTGXTDOA-UHFFFAOYSA-N 0.000 claims description 2
- 229910019142 PO4 Inorganic materials 0.000 claims description 2
- 229920001214 Polysorbate 60 Polymers 0.000 claims description 2
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 claims description 2
- NWGKJDSIEKMTRX-AAZCQSIUSA-N Sorbitan monooleate Chemical compound CCCCCCCC\C=C/CCCCCCCC(=O)OC[C@@H](O)[C@H]1OC[C@H](O)[C@H]1O NWGKJDSIEKMTRX-AAZCQSIUSA-N 0.000 claims description 2
- HVUMOYIDDBPOLL-XWVZOOPGSA-N Sorbitan monostearate Chemical compound CCCCCCCCCCCCCCCCCC(=O)OC[C@@H](O)[C@H]1OC[C@H](O)[C@H]1O HVUMOYIDDBPOLL-XWVZOOPGSA-N 0.000 claims description 2
- 125000000217 alkyl group Chemical group 0.000 claims description 2
- DIZPMCHEQGEION-UHFFFAOYSA-H aluminium sulfate (anhydrous) Chemical compound [Al+3].[Al+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O DIZPMCHEQGEION-UHFFFAOYSA-H 0.000 claims description 2
- INHCSSUBVCNVSK-UHFFFAOYSA-L lithium sulfate Inorganic materials [Li+].[Li+].[O-]S([O-])(=O)=O INHCSSUBVCNVSK-UHFFFAOYSA-L 0.000 claims description 2
- LSHROXHEILXKHM-UHFFFAOYSA-N n'-[2-[2-[2-(2-aminoethylamino)ethylamino]ethylamino]ethyl]ethane-1,2-diamine Chemical compound NCCNCCNCCNCCNCCN LSHROXHEILXKHM-UHFFFAOYSA-N 0.000 claims description 2
- AQGNVWRYTKPRMR-UHFFFAOYSA-N n'-[2-[2-[2-[2-(2-aminoethylamino)ethylamino]ethylamino]ethylamino]ethyl]ethane-1,2-diamine Chemical compound NCCNCCNCCNCCNCCNCCN AQGNVWRYTKPRMR-UHFFFAOYSA-N 0.000 claims description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 claims description 2
- 239000010452 phosphate Substances 0.000 claims description 2
- 238000006116 polymerization reaction Methods 0.000 claims description 2
- 229910052700 potassium Inorganic materials 0.000 claims description 2
- 239000011591 potassium Substances 0.000 claims description 2
- 230000001376 precipitating effect Effects 0.000 claims description 2
- 230000035484 reaction time Effects 0.000 claims description 2
- RYYKJJJTJZKILX-UHFFFAOYSA-M sodium octadecanoate Chemical compound [Na+].CCCCCCCCCCCCCCCCCC([O-])=O RYYKJJJTJZKILX-UHFFFAOYSA-M 0.000 claims description 2
- 239000007787 solid Substances 0.000 claims description 2
- 239000012265 solid product Substances 0.000 claims description 2
- RBTVSNLYYIMMKS-UHFFFAOYSA-N tert-butyl 3-aminoazetidine-1-carboxylate;hydrochloride Chemical compound Cl.CC(C)(C)OC(=O)N1CC(N)C1 RBTVSNLYYIMMKS-UHFFFAOYSA-N 0.000 claims description 2
- FAGUFWYHJQFNRV-UHFFFAOYSA-N tetraethylenepentamine Chemical compound NCCNCCNCCNCCN FAGUFWYHJQFNRV-UHFFFAOYSA-N 0.000 claims description 2
- 239000000463 material Substances 0.000 abstract description 20
- 238000002360 preparation method Methods 0.000 abstract description 9
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 abstract description 4
- 229910052744 lithium Inorganic materials 0.000 abstract description 4
- 229910003002 lithium salt Inorganic materials 0.000 abstract description 3
- 159000000002 lithium salts Chemical class 0.000 abstract description 3
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 abstract description 2
- AZDRQVAHHNSJOQ-UHFFFAOYSA-N alumane Chemical class [AlH3] AZDRQVAHHNSJOQ-UHFFFAOYSA-N 0.000 abstract description 2
- 238000006555 catalytic reaction Methods 0.000 abstract description 2
- 229910052731 fluorine Inorganic materials 0.000 abstract description 2
- 239000011737 fluorine Substances 0.000 abstract description 2
- 239000011574 phosphorus Substances 0.000 abstract description 2
- 229910052698 phosphorus Inorganic materials 0.000 abstract description 2
- 238000001179 sorption measurement Methods 0.000 abstract description 2
- 239000012266 salt solution Substances 0.000 abstract 2
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 abstract 1
- 239000012267 brine Substances 0.000 abstract 1
- 230000000694 effects Effects 0.000 abstract 1
- 238000001914 filtration Methods 0.000 abstract 1
- HPALAKNZSZLMCH-UHFFFAOYSA-M sodium;chloride;hydrate Chemical compound O.[Na+].[Cl-] HPALAKNZSZLMCH-UHFFFAOYSA-M 0.000 abstract 1
- 239000002244 precipitate Substances 0.000 description 15
- 238000002441 X-ray diffraction Methods 0.000 description 10
- 230000001276 controlling effect Effects 0.000 description 7
- 239000013078 crystal Substances 0.000 description 6
- 238000002425 crystallisation Methods 0.000 description 6
- 230000008025 crystallization Effects 0.000 description 6
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 description 5
- 238000004220 aggregation Methods 0.000 description 5
- 230000002776 aggregation Effects 0.000 description 5
- 238000007605 air drying Methods 0.000 description 5
- JGDITNMASUZKPW-UHFFFAOYSA-K aluminium trichloride hexahydrate Chemical compound O.O.O.O.O.O.Cl[Al](Cl)Cl JGDITNMASUZKPW-UHFFFAOYSA-K 0.000 description 5
- 229940009861 aluminum chloride hexahydrate Drugs 0.000 description 5
- 238000001000 micrograph Methods 0.000 description 5
- 238000001878 scanning electron micrograph Methods 0.000 description 5
- 238000003756 stirring Methods 0.000 description 5
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 4
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical group [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 description 4
- 230000015572 biosynthetic process Effects 0.000 description 4
- 239000004094 surface-active agent Substances 0.000 description 4
- 238000003786 synthesis reaction Methods 0.000 description 4
- DBMJMQXJHONAFJ-UHFFFAOYSA-M Sodium laurylsulphate Chemical compound [Na+].CCCCCCCCCCCCOS([O-])(=O)=O DBMJMQXJHONAFJ-UHFFFAOYSA-M 0.000 description 3
- 150000001450 anions Chemical class 0.000 description 3
- 239000010410 layer Substances 0.000 description 3
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- 229910021529 ammonia Inorganic materials 0.000 description 2
- 239000003054 catalyst Substances 0.000 description 2
- 230000003197 catalytic effect Effects 0.000 description 2
- 150000001768 cations Chemical class 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 239000011229 interlayer Substances 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 229910021645 metal ion Inorganic materials 0.000 description 2
- 239000000693 micelle Substances 0.000 description 2
- 230000000877 morphologic effect Effects 0.000 description 2
- 238000006386 neutralization reaction Methods 0.000 description 2
- 239000011148 porous material Substances 0.000 description 2
- 238000001556 precipitation Methods 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 1
- 241000446313 Lamella Species 0.000 description 1
- 238000009825 accumulation Methods 0.000 description 1
- 229940063656 aluminum chloride Drugs 0.000 description 1
- 125000000129 anionic group Chemical group 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 229910052599 brucite Inorganic materials 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 238000000975 co-precipitation Methods 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 1
- 229910010272 inorganic material Inorganic materials 0.000 description 1
- 239000011147 inorganic material Substances 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 238000009830 intercalation Methods 0.000 description 1
- 230000002687 intercalation Effects 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 239000013535 sea water Substances 0.000 description 1
- 239000002351 wastewater Substances 0.000 description 1
- 238000004065 wastewater treatment Methods 0.000 description 1
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
- B01J20/06—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising oxides or hydroxides of metals not provided for in group B01J20/04
- B01J20/08—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising oxides or hydroxides of metals not provided for in group B01J20/04 comprising aluminium oxide or hydroxide; comprising bauxite
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/28—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties
- B01J20/28054—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 surface properties or porosity
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2002/00—Crystal-structural characteristics
- C01P2002/20—Two-dimensional structures
- C01P2002/22—Two-dimensional structures layered hydroxide-type, e.g. of the hydrotalcite-type
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/30—Particle morphology extending in three dimensions
- C01P2004/45—Aggregated particles or particles with an intergrown morphology
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2006/00—Physical properties of inorganic compounds
- C01P2006/12—Surface area
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2006/00—Physical properties of inorganic compounds
- C01P2006/16—Pore diameter
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- Chemical & Material Sciences (AREA)
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- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Inorganic Chemistry (AREA)
- Solid-Sorbent Or Filter-Aiding Compositions (AREA)
- Compounds Of Alkaline-Earth Elements, Aluminum Or Rare-Earth Metals (AREA)
Abstract
The invention discloses a preparation method of porous lithium-aluminum hydrotalcite, which comprises the steps of carrying out normal-pressure hydrothermal reaction on a mixed solution containing a lithium salt solution, an aluminum salt solution, a morphology regulating agent and a precipitator, and then filtering, washing and drying to obtain the porous lithium-aluminum hydrotalcite material. The method has the characteristics of simple preparation process, no use of a high-pressure reaction kettle, operation at normal pressure, mesoporous and macroporous structures of the prepared lithium-aluminum hydrotalcite, large specific surface area, stable structure of a crystalline lamellar layer, regular appearance and contribution to contact with other media such as water and gas, and can be applied to the fields of lithium extraction from brine, catalysis, adsorption of harmful phosphorus and fluorine in water and the like. The lithium-aluminum hydrotalcite material disclosed by the invention is simple in preparation process, can be produced under normal pressure, is large in specific surface area and high in reaction activity, and has a wide application prospect.
Description
Technical Field
The invention belongs to the technical field of inorganic chemistry, and particularly relates to a synthesis method of porous lithium-aluminum hydrotalcite.
Background
The hydrotalcite layered double hydroxide is a compound which is assembled by a main body laminate with positive charge consisting of divalent metal ions and trivalent metal ions, interlayer anions and water molecules through the interaction of non-covalent bonds, belongs to an anionic layered compound, has exchangeability and is an inorganic material with a layered structure. The specific molecular formula can be expressed as [ M1-x 2+M3+(OH)2]x+[Ax/n]nmH2And O. The hydrotalcite has the characteristics of variable types and proportions of main layer plate elements, adjustable interlaminar anions, controllable grain size and thickness and the like, and has various appearance changes and uniform layer plate element distribution. Due to their unique structure, special properties and wide application, they are widely used in the fields of catalysis, energy, biology, medicine and materials. Lithium aluminum hydrotalcite has a crystalline aluminum hydroxide structure similar to brucite, with one-third of the octahedral metal cation vacancies, i.e., the Al3+ ions, accounting for only two-thirds of the octahedral cation vacancies. When the vacancies in the aluminum hydroxide layer are filled with Li +, lithium aluminum hydrotalcite is formed, giving excess positive charge for interlayer anion neutralization. The synthesis, structure and properties of lithium aluminum based hydrotalcite have been widely studied. Lithium aluminum hydrotalcite in catalyst, waste water treatment adsorbent and CO2Has wide application prospect in the aspects of trapping, metal corrosion and protection, lithium ion batteries and the like. Methods for synthesizing lithium aluminum hydrotalcite are numerous, such as lithium salt or LiOH intercalation into aluminum hydroxide by coprecipitationThe synthesis is carried out by a precipitation method, a hydrothermal method, a mechanochemical method and the like. The common industrial synthesis mode is that aluminum hydroxide and lithium hydroxide are hydrothermally synthesized and then are dripped into a mixed solution of aluminum salt and lithium salt through hydrochloric acid neutralization or a precipitator for coprecipitation, the crystallization form of the method is not easy to control, and the adsorption or catalytic performance of a finished product is poor due to the accumulation of the shape.
Disclosure of Invention
The invention aims to overcome the defects of the prior art and provide a method for synthesizing porous lithium aluminum hydrotalcite, which has the advantages of simple synthesis conditions, easy production, regular appearance of the product lithium aluminum hydrotalcite, higher specific surface area and wide application prospect.
The invention is realized by the following technical scheme:
a synthesis method of porous lithium aluminum hydrotalcite comprises the following steps:
carrying out hydrothermal reaction on a mixed solution containing lithium ions, aluminum ions, a precipitating agent and a morphology regulating agent, washing the solid obtained after the reaction with water, and drying to obtain a product, namely the porous lithium-aluminum hydrotalcite;
the concentration of lithium ions in the mixed solution is 0.3-1.2 mol/L;
the concentration of aluminum ions in the mixed solution is 0.15-0.40 mol/L;
the precipitator is an alkaline precipitator, and the amount of the precipitator is 1-20: 1 of the molar ratio of hydroxide radicals to aluminum ions in the precipitator;
the morphology regulator is one or more of oleylamine, octadecylamine, tetraethylenepentamine, pentaethylenehexamine, hexaethyleneheptamine, dodecyl imidazoline, polyethyleneimine, polyacrylamide, lauryl sodium sulfate, sodium dodecyl benzene sulfonate, hexadecyl trimethyl ammonium bromide, span-60, span-80, tween-60, potassium alkyl phosphate and sodium stearate, and the molar ratio of the dosage of the morphology regulator to the aluminum ions is 1: 1-80;
the pressure of the hydrothermal reaction is normal pressure, the reaction temperature is 85-95 ℃, and the reaction time is 12-24 hours.
In the above technical scheme, the precipitant can be added at one time at the initial stage of the reaction, or can be added into the reaction system at a certain speed in the reaction process.
In the technical scheme, the aluminum ions are from one or more of aluminum nitrate, aluminum chloride and aluminum sulfate.
In the technical scheme, the lithium ions are one or more of lithium chloride, lithium sulfate and lithium nitrate.
In the technical scheme, the alkaline precipitator is one or more of urea, ammonia water, sodium hydroxide and potassium hydroxide.
In the technical scheme, when the alkaline precipitator is a precipitator containing urea or ammonia water, the alkaline precipitator is added at one time in the initial reaction stage; when the precipitant does not contain urea, the precipitant is gradually added at a certain speed in the reaction process. When the precipitator is urea or ammonia water, the precipitator is added at one time, gradually decomposes in the heating process, releases ammonia, and plays a role of gradual precipitation; the precipitant, ammonia when added dropwise, changes the reaction too quickly.
In the technical scheme, the solid product obtained by the reaction is washed by water, and the washing process adopts deionized water at the temperature of 80-90 ℃ for washing. The higher temperature deionized water is used for washing the crystal particles which can be washed to remove salt, and the cleaning capability is stronger compared with the low temperature water.
In the technical scheme, the drying temperature is 40-80 ℃ and the drying time is 12-24 hours in the drying process.
In the technical scheme, the molecular weight of the polyethyleneimine is 300-10000, and the solution concentration is 50%; the polymerization degree of the polyacrylamide is 800-1000 ten thousand.
The porous lithium aluminum hydrotalcite is applied to the extraction process of lithium elements.
The porous lithium aluminum hydrotalcite is applied as an adsorbent in the process of extracting lithium elements.
The invention has the advantages and beneficial effects that:
the invention synthesizes the lithium aluminum hydrotalcite with regular crystallization form and porous structure through the function of the morphology regulator. Can be applied to the recycling of lithium resources in salt lakes and seawater; adsorbing phosphorus and fluorine elements in the wastewater; the catalyst has the characteristics of porous structure, higher specific surface area, thinner lamella and the like, and has wide application prospect.
The preparation method provided by the invention is simple and safe, the porous lithium aluminum hydrotalcite material is obtained by a hydrothermal method under normal pressure, the product has a mesoporous and macroporous structure, the specific surface area is high, the morphological structure is regular, the morphological control agent can promote the crystallization of the lithium aluminum hydrotalcite, and the yield is improved. Suitable as an adsorbent or catalytic material.
In the prior art, hydrotalcite with the morphology is generally synthesized in a pressurized reaction kettle. In the application, a surfactant with a certain concentration is used for forming a critical micelle in a solution, the critical micelle has a function of regulating and controlling the morphology in the crystallization process of the lithium-aluminum hydrotalcite, and generally, different types of surfactants for controlling crystallization are different in type and concentration, so that how to determine the type of the surfactant for controlling the crystallization morphology of the lithium-aluminum hydrotalcite and the concentration range of the surfactant in the solution are key factors.
Drawings
FIG. 1 is a representation of porous lithium aluminum hydrotalcite prepared in example 1 of the present invention, wherein a) is a scanning electron micrograph; b) is an XRD pattern.
FIG. 2 is a representation of porous lithium aluminum hydrotalcite prepared in example 2 of the present invention, wherein a) is a scanning electron micrograph; b) is an XRD pattern.
FIG. 3 is a representation of porous lithium aluminum hydrotalcite prepared in example 3 of the present invention, wherein a) is a scanning electron micrograph; b) is an XRD pattern.
FIG. 4 is a representation of porous lithium aluminum hydrotalcite prepared in example 4 of the present invention, wherein a) is a scanning electron micrograph; b) is an XRD pattern.
FIG. 5 is a representation of porous lithium aluminum hydrotalcite prepared in example 5 of the present invention, wherein a) is a scanning electron micrograph; b) is an XRD pattern.
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 1
A preparation method of porous lithium-aluminum hydrotalcite,
the method comprises the following steps:
adding anhydrous lithium chloride (13.4g), aluminum chloride hexahydrate (36.2g), sodium dodecyl sulfate (10g) and urea (90g) into 500ml of deionized water, stirring for 60min, fully dissolving to prepare a mixed solution, transferring the mixed solution into a 1000ml four-neck flask, carrying out normal-pressure hydrothermal reaction at 88 ℃ for 24 hours to obtain a precipitate, centrifugally washing the precipitate with the deionized water at 85 ℃, and then drying the precipitate in a forced air drying oven at 70 ℃ for 12 hours to obtain the porous lithium-aluminum hydrotalcite.
Fig. 1 is (a) a scanning electron microscope image and (b) an XRD image of the lithium aluminum hydrotalcite material prepared with sodium dodecyl sulfate as a morphology controlling agent in example 1. From the figure (a), it can be seen that the lithium aluminum hydrotalcite synthesized by the method provided in the present invention has a flower-shaped structure formed by the aggregation of hydrotalcite crystals and forms hierarchical channels.
FIG. 1(b) is an X-ray diffraction pattern of the porous lithium aluminum hydrotalcite material prepared in example 1. From this figure, it can be seen that the characteristic peaks ((002), (004), etc.) of the porous lithium aluminum hydrotalcite material are identical to those of the common hydrotalcite.
Example 2
A preparation method of porous lithium-aluminum hydrotalcite,
the method comprises the following steps:
adding anhydrous lithium chloride (13.4g), aluminum chloride hexahydrate (36g), octadecylamine (6g) and urea (90g) into 500ml of deionized water, stirring for 60min, fully dissolving to prepare a mixed solution, transferring the mixed solution into a 1000ml four-neck flask, carrying out normal-pressure hydrothermal reaction at the reaction temperature of 90 ℃ for 24 hours to obtain a precipitate, carrying out centrifugal washing on the precipitate by using deionized water at the temperature of 85 ℃, and then placing the precipitate in a forced air drying oven to dry for 12 hours at the temperature of 70 ℃ to obtain the porous lithium-aluminum hydrotalcite.
Fig. 2 is (a) a scanning electron microscope image and (b) an XRD image of the lithium aluminum hydrotalcite material prepared with octadecylamine as a morphology controlling agent in example 2. From the figure (a), it can be seen that the lithium aluminum hydrotalcite synthesized by the method provided in the present invention has a flower-shaped structure formed by the aggregation of hydrotalcite crystals and forms hierarchical channels.
FIG. 2(b) is an X-ray diffraction pattern of the porous lithium aluminum hydrotalcite material prepared in example 2. From this figure, it can be seen that the characteristic peaks ((002), (004), etc.) of the porous lithium aluminum hydrotalcite material are identical to those of the common hydrotalcite.
Example 3
A preparation method of porous lithium-aluminum hydrotalcite,
the method comprises the following steps:
adding anhydrous lithium chloride (13.4g), aluminum chloride hexahydrate (36g), sodium dodecyl benzene sulfonate (15g) and urea (90g) into 500ml of deionized water, stirring for 60min, fully dissolving to prepare a mixed solution, transferring the mixed solution into a 1000ml four-neck flask, carrying out normal-pressure hydrothermal reaction at the reaction temperature of 90 ℃ for 24 hours to obtain a precipitate, centrifugally washing the precipitate by using the deionized water at the temperature of 85 ℃, and then drying the precipitate in a forced air drying oven at the temperature of 70 ℃ for 12 hours to obtain the porous lithium-aluminum hydrotalcite.
Fig. 3 is (a) a scanning electron microscope image and (b) an XRD image of the lithium aluminum hydrotalcite material prepared with sodium dodecyl sulfate as a morphology controlling agent in example 3. From the figure (a), it can be seen that the lithium aluminum hydrotalcite synthesized by the method provided in the present invention has a flower-shaped structure formed by the aggregation of hydrotalcite crystals and forms hierarchical channels.
FIG. 3(b) is an X-ray diffraction pattern of the porous lithium aluminum hydrotalcite material prepared in example 3. From this figure, it can be seen that the characteristic peaks ((002), (004), etc.) of the porous lithium aluminum hydrotalcite material are identical to those of the common hydrotalcite.
Example 4
A preparation method of porous lithium-aluminum hydrotalcite,
the method comprises the following steps:
adding anhydrous lithium chloride (13.4g), aluminum chloride hexahydrate (36g), polyacrylamide (0.5g) and urea (90g) into 500ml of deionized water, stirring for 60min, fully dissolving to prepare a mixed solution, transferring the mixed solution into a 1000ml four-neck flask, carrying out normal-pressure hydrothermal reaction at the reaction temperature of 90 ℃ for 24 hours to obtain a precipitate, centrifugally washing the precipitate by using the deionized water at the temperature of 85 ℃, and then drying the precipitate in a forced air drying oven at the temperature of 70 ℃ for 12 hours to obtain the porous lithium-aluminum hydrotalcite.
Fig. 4 is (a) a scanning electron microscope image and (b) an XRD image of the lithium-aluminum hydrotalcite material prepared with polyacrylamide as a morphology controlling agent in example 4. From the figure (a), it can be seen that the lithium aluminum hydrotalcite synthesized by the method provided in the present invention has a flower-shaped structure formed by the aggregation of hydrotalcite crystals and forms hierarchical channels.
FIG. 4(b) is an X-ray diffraction pattern of the porous lithium aluminum hydrotalcite material prepared in example 1. From this figure, it can be seen that the characteristic peaks ((002), (004), etc.) of the porous lithium aluminum hydrotalcite material are identical to those of the common hydrotalcite.
Example 5
A preparation method of porous lithium-aluminum hydrotalcite,
the method comprises the following steps:
adding anhydrous lithium chloride (13.4g), aluminum chloride hexahydrate (36.8g), polyethyleneimine (5g) and urea (90g) into 500ml of deionized water, stirring for 60min, fully dissolving to prepare a mixed solution, transferring the mixed solution into a 1000ml four-neck flask, carrying out normal-pressure hydrothermal reaction at the reaction temperature of 90 ℃ for 24 hours to obtain a precipitate, centrifugally washing the precipitate with the deionized water at the temperature of 85 ℃, and then drying the precipitate in a forced air drying oven at the temperature of 70 ℃ for 12 hours to obtain the porous lithium-aluminum hydrotalcite.
Fig. 5 is (a) a scanning electron microscope image and (b) an XRD image of the lithium-aluminum hydrotalcite material prepared by using polyethyleneimine as a morphology control agent in example 5. From the figure (a), it can be seen that the lithium aluminum hydrotalcite synthesized by the method provided in the present invention has a flower-shaped structure formed by the aggregation of hydrotalcite crystals and forms hierarchical channels.
FIG. 5(b) is an X-ray diffraction pattern of the porous lithium aluminum hydrotalcite material prepared in example 1. From this figure, it can be seen that the characteristic peaks ((002), (004), etc.) of the porous lithium aluminum hydrotalcite material are identical to those of the common hydrotalcite.
TABLE 1 specific surface area and mean pore diameter
| Examples of the invention | Specific surface area (m)2/g) | Average pore diameter (nm) |
| Example one | 11.9 | 3.8 |
| Example two | 33.1 | 3.8 |
| Example three | 78.5 | 3.4 |
| Example four | 4.4 | 3.8 |
| Example five | 93.0 | 31.3 |
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 (10)
1. A synthesis method of porous lithium aluminum hydrotalcite is characterized by comprising the following steps:
carrying out hydrothermal reaction on a mixed solution containing lithium ions, aluminum ions, a precipitating agent and a morphology regulating agent, washing the solid obtained after the reaction with water, and drying to obtain a product, namely the porous lithium-aluminum hydrotalcite;
the concentration of lithium ions in the mixed solution is 0.3-1.2 mol/L;
the concentration of aluminum ions in the mixed solution is 0.15-0.40 mol/L;
the precipitator is an alkaline precipitator, and the amount of the precipitator is 1-20: 1 of the molar ratio of hydroxide radicals to aluminum ions in the precipitator;
the morphology regulator is one or more of oleylamine, octadecylamine, tetraethylenepentamine, pentaethylenehexamine, hexaethyleneheptamine, dodecyl imidazoline, polyethyleneimine, polyacrylamide, lauryl sodium sulfate, sodium dodecyl benzene sulfonate, hexadecyl trimethyl ammonium bromide, span-60, span-80, tween-60, potassium alkyl phosphate and sodium stearate, and the molar ratio of the dosage of the morphology regulator to the aluminum ions is 1: 1-80;
the pressure of the hydrothermal reaction is normal pressure, the reaction temperature is 85-95 ℃, and the reaction time is 12-24 hours.
2. The method for synthesizing porous lithium aluminum hydrotalcite according to claim 1, wherein the precipitant is added to the reaction system at a single time during the initial period of the reaction or at a constant rate during the reaction.
3. The method for synthesizing porous lithium aluminum hydrotalcite according to claim 1, wherein the aluminum ions are derived from one or more of aluminum nitrate, aluminum chloride and aluminum sulfate.
4. The method for synthesizing porous lithium aluminum hydrotalcite according to claim 1, wherein the lithium ions are derived from one or more of lithium chloride, lithium sulfate and lithium nitrate.
5. The method for synthesizing porous lithium aluminum hydrotalcite according to claim 1, wherein the alkaline precipitant is one or more of urea, ammonia water, sodium hydroxide and potassium hydroxide.
6. The method for synthesizing porous lithium aluminum hydrotalcite according to claim 1, wherein when the alkaline precipitant is a precipitant containing urea, the alkaline precipitant is added at one time during the initial stage of the reaction; when the alkaline precipitant is ammonia water, the alkaline precipitant is gradually added at a certain speed in the reaction process.
7. The method for synthesizing porous lithium aluminum hydrotalcite according to claim 1, wherein the solid product obtained by the reaction is washed with water, and the washing process is carried out with deionized water at 80-90 ℃.
8. The method for synthesizing porous lithium aluminum hydrotalcite according to claim 1, wherein the drying temperature is 40-80 ℃ and the drying time is 12-24 hours.
9. The method for synthesizing the porous lithium aluminum hydrotalcite according to claim 1, wherein the molecular weight of polyethyleneimine is 300 to 10000, and the solution concentration is 50%; the polymerization degree of the polyacrylamide is 800-1000 ten thousand.
10. The application of the porous lithium aluminum hydrotalcite prepared by the synthesis method according to claim 1 in the lithium element extraction process, in particular as an adsorbent.
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