CN113893827A - Fluorine adsorption material and preparation method and application thereof - Google Patents
Fluorine adsorption material and preparation method and application thereof Download PDFInfo
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- CN113893827A CN113893827A CN202111367452.XA CN202111367452A CN113893827A CN 113893827 A CN113893827 A CN 113893827A CN 202111367452 A CN202111367452 A CN 202111367452A CN 113893827 A CN113893827 A CN 113893827A
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- aminosilane
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- 229910052731 fluorine Inorganic materials 0.000 title claims abstract description 61
- 239000011737 fluorine Substances 0.000 title claims abstract description 61
- 238000001179 sorption measurement Methods 0.000 title claims abstract description 60
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 title claims abstract description 59
- 239000000463 material Substances 0.000 title claims abstract description 45
- 238000002360 preparation method Methods 0.000 title claims abstract description 25
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 47
- 239000000741 silica gel Substances 0.000 claims abstract description 32
- 229910002027 silica gel Inorganic materials 0.000 claims abstract description 32
- 238000006243 chemical reaction Methods 0.000 claims abstract description 30
- 229910052751 metal Inorganic materials 0.000 claims abstract description 15
- 239000002184 metal Substances 0.000 claims abstract description 15
- 239000000243 solution Substances 0.000 claims abstract description 15
- FZHAPNGMFPVSLP-UHFFFAOYSA-N silanamine Chemical compound [SiH3]N FZHAPNGMFPVSLP-UHFFFAOYSA-N 0.000 claims abstract description 14
- 239000000203 mixture Substances 0.000 claims abstract description 12
- 239000002253 acid Substances 0.000 claims abstract description 10
- 238000002156 mixing Methods 0.000 claims abstract description 6
- 230000003213 activating effect Effects 0.000 claims abstract description 3
- 239000012670 alkaline solution Substances 0.000 claims abstract description 3
- 239000003929 acidic solution Substances 0.000 claims abstract 2
- 229910052782 aluminium Inorganic materials 0.000 claims description 21
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 21
- 239000004005 microsphere Substances 0.000 claims description 17
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 12
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 10
- 238000000034 method Methods 0.000 claims description 9
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 8
- 238000006115 defluorination reaction Methods 0.000 claims description 8
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 6
- 230000020477 pH reduction Effects 0.000 claims description 6
- 229910052684 Cerium Inorganic materials 0.000 claims description 5
- GWXLDORMOJMVQZ-UHFFFAOYSA-N cerium Chemical class [Ce] GWXLDORMOJMVQZ-UHFFFAOYSA-N 0.000 claims description 5
- 230000009920 chelation Effects 0.000 claims description 5
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 4
- 239000002245 particle Substances 0.000 claims description 4
- 239000011148 porous material Substances 0.000 claims description 4
- 229910052746 lanthanum Chemical class 0.000 claims description 3
- FZLIPJUXYLNCLC-UHFFFAOYSA-N lanthanum atom Chemical class [La] FZLIPJUXYLNCLC-UHFFFAOYSA-N 0.000 claims description 3
- IFZUFHWISBKFJP-UHFFFAOYSA-N n'-[4-[dimethoxy(methyl)silyl]oxybutyl]ethane-1,2-diamine Chemical compound CO[Si](C)(OC)OCCCCNCCN IFZUFHWISBKFJP-UHFFFAOYSA-N 0.000 claims description 3
- 238000003756 stirring Methods 0.000 claims description 3
- WYTZZXDRDKSJID-UHFFFAOYSA-N (3-aminopropyl)triethoxysilane Chemical compound CCO[Si](OCC)(OCC)CCCN WYTZZXDRDKSJID-UHFFFAOYSA-N 0.000 claims description 2
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims description 2
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical class [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 claims description 2
- 230000004913 activation Effects 0.000 claims description 2
- 229910052744 lithium Inorganic materials 0.000 claims description 2
- 229910044991 metal oxide Inorganic materials 0.000 claims description 2
- 150000004706 metal oxides Chemical class 0.000 claims description 2
- YLBPOJLDZXHVRR-UHFFFAOYSA-N n'-[3-[diethoxy(methyl)silyl]propyl]ethane-1,2-diamine Chemical compound CCO[Si](C)(OCC)CCCNCCN YLBPOJLDZXHVRR-UHFFFAOYSA-N 0.000 claims description 2
- 239000003960 organic solvent Substances 0.000 claims description 2
- 150000003839 salts Chemical class 0.000 claims description 2
- 229910052726 zirconium Inorganic materials 0.000 claims description 2
- 125000001931 aliphatic group Chemical group 0.000 claims 1
- 125000002029 aromatic hydrocarbon group Chemical group 0.000 claims 1
- 238000002386 leaching Methods 0.000 claims 1
- 239000003463 adsorbent Substances 0.000 abstract description 24
- 239000002351 wastewater Substances 0.000 abstract description 4
- -1 aminosilane Modified silica gel Chemical class 0.000 abstract description 3
- 230000008929 regeneration Effects 0.000 abstract description 2
- 238000011069 regeneration method Methods 0.000 abstract description 2
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 12
- 229910052761 rare earth metal Inorganic materials 0.000 description 9
- 230000000052 comparative effect Effects 0.000 description 8
- 229920006395 saturated elastomer Polymers 0.000 description 8
- 239000002131 composite material Substances 0.000 description 7
- 238000005516 engineering process Methods 0.000 description 6
- 239000007864 aqueous solution Substances 0.000 description 5
- 239000011259 mixed solution Substances 0.000 description 5
- 239000000969 carrier Substances 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- 229920001222 biopolymer Polymers 0.000 description 3
- 239000008367 deionised water Substances 0.000 description 3
- 229910021641 deionized water Inorganic materials 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 229910010272 inorganic material Inorganic materials 0.000 description 3
- 239000011147 inorganic material Substances 0.000 description 3
- 238000011068 loading method Methods 0.000 description 3
- 239000011159 matrix material Substances 0.000 description 3
- 239000012528 membrane Substances 0.000 description 3
- 238000011084 recovery Methods 0.000 description 3
- 238000004065 wastewater treatment Methods 0.000 description 3
- KRHYYFGTRYWZRS-UHFFFAOYSA-M Fluoride anion Chemical compound [F-] KRHYYFGTRYWZRS-UHFFFAOYSA-M 0.000 description 2
- 239000003513 alkali Substances 0.000 description 2
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 2
- 238000009388 chemical precipitation Methods 0.000 description 2
- FOCAUTSVDIKZOP-UHFFFAOYSA-N chloroacetic acid Chemical compound OC(=O)CCl FOCAUTSVDIKZOP-UHFFFAOYSA-N 0.000 description 2
- 229940106681 chloroacetic acid Drugs 0.000 description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 2
- 238000011065 in-situ storage Methods 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 229920001277 pectin Polymers 0.000 description 2
- 239000001814 pectin Substances 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- 229910052710 silicon Inorganic materials 0.000 description 2
- 239000010703 silicon Substances 0.000 description 2
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 description 2
- 230000003068 static effect Effects 0.000 description 2
- 229920001661 Chitosan Polymers 0.000 description 1
- 229910002651 NO3 Inorganic materials 0.000 description 1
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 1
- AZDRQVAHHNSJOQ-UHFFFAOYSA-N alumane Chemical class [AlH3] AZDRQVAHHNSJOQ-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 230000001351 cycling effect Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000003795 desorption Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 230000036541 health Effects 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 238000012423 maintenance Methods 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 150000002736 metal compounds Chemical class 0.000 description 1
- 229910000000 metal hydroxide Inorganic materials 0.000 description 1
- 150000004692 metal hydroxides Chemical class 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 229910001960 metal nitrate Inorganic materials 0.000 description 1
- 239000002808 molecular sieve Substances 0.000 description 1
- 125000000896 monocarboxylic acid group Chemical group 0.000 description 1
- MQWFLKHKWJMCEN-UHFFFAOYSA-N n'-[3-[dimethoxy(methyl)silyl]propyl]ethane-1,2-diamine Chemical compound CO[Si](C)(OC)CCCNCCN MQWFLKHKWJMCEN-UHFFFAOYSA-N 0.000 description 1
- 239000002105 nanoparticle Substances 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- 235000015097 nutrients Nutrition 0.000 description 1
- 230000008520 organization Effects 0.000 description 1
- 235000010987 pectin Nutrition 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 150000002910 rare earth metals Chemical class 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 239000012266 salt solution Substances 0.000 description 1
- 239000010865 sewage Substances 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 238000002336 sorption--desorption measurement Methods 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
Classifications
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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
- B01J20/0203—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising compounds of metals not provided for in B01J20/04
- B01J20/0207—Compounds of Sc, Y or Lanthanides
-
- 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
- B01J20/0203—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising compounds of metals not provided for in B01J20/04
- B01J20/0248—Compounds of B, Al, Ga, In, Tl
-
- 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
-
- 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
- B01J20/10—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising silica or silicate
- B01J20/103—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising silica or silicate comprising silica
-
- 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
- B01J20/22—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising organic material
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/28—Treatment of water, waste water, or sewage by sorption
- C02F1/288—Treatment of water, waste water, or sewage by sorption using composite sorbents, e.g. coated, impregnated, multi-layered
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/10—Inorganic compounds
- C02F2101/12—Halogens or halogen-containing compounds
- C02F2101/14—Fluorine or fluorine-containing compounds
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Analytical Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Inorganic Chemistry (AREA)
- Life Sciences & Earth Sciences (AREA)
- Hydrology & Water Resources (AREA)
- Engineering & Computer Science (AREA)
- Environmental & Geological Engineering (AREA)
- Water Supply & Treatment (AREA)
- Solid-Sorbent Or Filter-Aiding Compositions (AREA)
Abstract
本发明提供了一种氟吸附材料及其制备方法和应用，所述制备方法包括以下步骤：(1)对硅胶进行活化处理，将活化的硅胶与氨基硅烷的有机溶液混合，反应后得到氨基硅烷修饰的硅胶；(2)将氨基硅烷修饰的硅胶与多元羧酸在酸性溶液中酸化反应后，加入金属混合物进行螯合反应，经碱液处理后得到所述氟吸附材料，本发明所述氟吸附材料具有高吸附容量、高选择性、易再生能力及高循环性的吸附剂，可以有效用于含氟废水的处理。The invention provides a fluorine adsorption material and a preparation method and application thereof. The preparation method includes the following steps: (1) activating silica gel, mixing the activated silica gel with an organic solution of aminosilane, and reacting to obtain aminosilane Modified silica gel; (2) after acidifying reaction of aminosilane-modified silica gel and polycarboxylic acid in an acidic solution, adding a metal mixture to carry out a chelating reaction, and treating with alkaline solution to obtain the fluorine adsorption material, the fluorine adsorption material of the present invention The adsorbent material has high adsorption capacity, high selectivity, easy regeneration and high recyclability, and can be effectively used in the treatment of fluorine-containing wastewater.
Description
Technical Field
The invention belongs to the technical field of wastewater treatment, and relates to a fluorine adsorption material, and a preparation method and application thereof.
Background
The fluorine-containing wastewater still can not reach the standard that the sewage discharge is lower than 1.5mg/L after being pretreated by common chemical precipitation. The membrane technology has higher equipment cost, easy pollution of the membrane and difficult later maintenance. The adsorption technology has the advantages of high adsorption speed, strong dynamic property, convenient operation, simple equipment and the like, and is widely applied to the research and industrial fields. The core of the adsorption technology is the preparation and selection of the adsorbent, but the existing defluorination adsorbent generally exists: small adsorption capacity, difficult reuse, high cost and the like. The rare earth element has the advantages of large adsorption capacity, high affinity to fluorine ions, small pollution and the like, but the pure rare earth element is used for removing the fluorine ions, the cost is high, most of the adsorbent is powder, the defects of difficult solid-liquid separation, easy generation of secondary pollution and the like exist after the fluorine-containing wastewater is treated, the adsorption column is easy to block due to large column pressure generated in the continuous dynamic wastewater treatment, the flow rate is slow, and the method is not suitable for the dispersed dynamic wastewater treatment in the industry.
Fluorine is one of indispensable nutrient elements for human bodies, but the safety range of the human bodies to fluorine is low, the human bodies can be damaged by slight excess, the emission standard of the fluoride set by the world health organization is 0.5-1.0mg/L, and in order to reach the set emission standard, various fluorine removal technologies, such as a chemical precipitation method, a membrane separation method and an adsorption method, are developed.
CN113070046A discloses a preparation method of a defluorination adsorbent modified by a biopolymer composite material, which comprises the following steps: respectively dissolving chitosan and pectin in deionized water or acid, mixing the two solutions, and heating to perform biopolymer crosslinking reaction; adding a molecular sieve soaked by deionized water into the mixed solution, distilling under reduced pressure, adding chloroacetic acid and sodium hydroxide aqueous solution, and grafting chloroacetic acid to modify the chitosan-pectin biopolymer composite material; adding metal nitrate dissolved in a mixed solution of ethanol and water into the modified molecular sieve, distilling under reduced pressure, adding a sodium hydroxide solution, stirring at room temperature, and doping metal ions into crystal lattices of the modified polymer; and (3) filtering redundant mixed solution, washing the mixed solution to be neutral by deionized water, drying the mixed solution in an oven to obtain the modified defluorination adsorbent, wherein the modified defluorination adsorbent uses organic matters as carriers, and is difficult to recycle after the organic matters are invalid, so that waste is caused.
CN101507911A discloses a defluorination adsorbing material based on aluminum-based composite oxide, a preparation method and application thereof, and a special device for the preparation method. The defluorination adsorbing material based on the aluminum-based composite oxide, which is prepared by an ectopic preparation method or an in-situ preparation method, comprises two parts, namely an active component and a porous load matrix; the active component is an aluminum-based composite oxide prepared by chemical reaction of an aluminum salt solution and an inorganic alkali solution, the aluminum-based composite oxide is loaded on the surface of a porous loading matrix by an in-situ loading method, the mass ratio of the aluminum-based composite oxide to the porous loading matrix is 0.25-25: 100, and the adsorption effect of the fluorine adsorption material is poor.
The above-mentioned scheme has a problem that organic substances are used as carriers or the adsorption effect is poor, and therefore, it is necessary to develop a fluorine adsorption material which uses inorganic substances as carriers and has a good adsorption effect.
Disclosure of Invention
The invention aims to provide a fluorine adsorption material, a preparation method and application thereof, and the fluorine adsorption material has an adsorbent with high adsorption capacity, high selectivity, easy regeneration capability and high cyclicity, and can be effectively used for treating fluorine-containing wastewater.
In order to achieve the purpose, the invention adopts the following technical scheme:
in a first aspect, the present invention provides a method for preparing a fluorine adsorbing material, comprising the steps of:
(1) activating silica gel, mixing the activated silica gel with an organic solution of aminosilane, and reacting to obtain the silica gel modified by the aminosilane;
(2) and (2) acidifying the silica gel modified by aminosilane and polycarboxylic acid in an acid solution, adding a metal mixture for chelation reaction, and treating with alkali liquor to obtain the fluorine adsorbing material.
The invention adopts the grafting modification technology to prepare the fluorine adsorbent, which not only has high selectivity and high adsorption capacity to fluorine, but also has stable chemical property, difficult loss and longer service life. The silica gel used in the invention is an inorganic material, so that the subsequent recovery treatment is more convenient.
The silica gel modified by the aminosilane contains a silicon ether bond, and the silicon ether bond is formed by the reaction of hydroxyl formed by the hydrolyzed aminosilane and hydroxyl on the surface of the porous silica gel microsphere.
Preferably, the silica gel in step (1) is porous silica gel microspheres.
Preferably, the particle size of the porous silica gel microspheres is 50-2000 μm, for example: 50 μm, 100 μm, 500 μm, 1000 μm, 1500 μm, 2000 μm, or the like.
Preferably, the pore diameter of the porous silica gel microspheres is 1-50 nm, such as 1nm, 5nm, 10nm, 20nm, 30nm or 50 nm.
Preferably, the specific surface area of the porous silica gel microspheres is 100-2000m2G, for example: 100m2/g、200m2/g、500m2/g、1000m2/g、1500m2(ii)/g or 2000m2And/g, etc.
According to the invention, the porous silica gel microspheres are used as carriers, and the specific surface area of the porous silica gel microspheres is large, so that more adsorption sites can be formed, and the adsorption capacity of the adsorbent is increased; and the mechanical strength is high, the wear resistance and the acid resistance are good, and the service life is longer.
Preferably, the activation treatment is to mix silica gel with hydrochloric acid and stir to obtain activated silica gel.
Preferably, the concentration of the hydrochloric acid is 5-7 mol/L, such as: 5mol/L, 5.5mol/L, 6mol/L, 6.5mol/L, 7mol/L, or the like.
Preferably, the aminosilane in step (1) comprises any one of or a combination of at least two of monoaminosilanes, bisaminosilanes or polyaminosilanes.
Preferably, the aminosilane comprises any one of aminopropyl-3-methoxysilane, aminopropyl-triethoxysilane, N- (aminoethyl) -gamma-aminopropylmethyltrimethoxysilane, N- (aminoethyl) -gamma-aminopropylmethyldimethoxysilane or N- (aminoethyl) -gamma-aminopropylmethyldiethoxysilane or a combination of at least two thereof.
Preferably, the organic solvent comprises any one of ethanol, methanol, acetone or isopropanol or a combination of at least two thereof.
Preferably, the temperature of the reaction in the step (1) is 20-110 ℃, for example: 20 ℃, 30 ℃, 50 ℃, 80 ℃ or 110 ℃, preferably 75-100 ℃.
The molecular formula of the polycarboxylic acid in the step (2) is R (COOH) n, wherein n is more than or equal to 2, such as: 2. 3, 4, 5 or 6, and the like, R is aliphatic radical and/or aromatic radical.
Preferably, the temperature of the acidification reaction in the step (2) is 20-50 ℃, for example: 20 ℃, 25 ℃, 30 ℃, 35 ℃, 40 ℃ or 50 ℃, preferably 30-40 ℃.
Preferably, the metal mixture of step (2) comprises aluminum and a source of a doping metal.
Preferably, the source of doping metal comprises any one or a combination of at least two of a metal oxide or metal salt of zirconium, cerium, lanthanum.
The invention adopts the mixture of aluminum and the doped metal source to prepare the adsorbing material, thereby not only ensuring the high selectivity and the adsorption capacity of the adsorbing material, but also reducing the cost of the adsorbing material.
Preferably, the mass ratio of the aluminum to the doping metal source is 1 (0.5-3), such as: 1:0.5, 1:0.8, 1:1, 1:2 or 1:3, etc.
The invention adopts the mixture of aluminum and rare earth elements to prepare the adsorbent, controls the mass ratio of the aluminum to the rare earth elements within the range, and prepares the fluorine adsorbing material with better performance, and if the aluminum doping amount is too high, the performance of the adsorbing material is slightly poor. If the doping amount of the rare earth element is too high, the cost is higher.
Preferably, the mass ratio of the metal compound to the aminosilane-modified silica gel is 1 (0.2-2), for example: 1:0.2, 1:0.5, 1:0.8, 1:1, 1:1.5 or 1:2, etc.
Preferably, in the step (2), the temperature of the chelation reaction is 50-100 ℃, for example: 50 ℃, 55 ℃, 60 ℃, 70 ℃, 80 ℃ or 100 ℃ and the like.
The alkaline solution treatment can generate metal hydroxide on the surface of the mesoporous silica nano particle.
In a second aspect, the present invention provides a fluorine adsorbent material produced by the method of the first aspect.
In a third aspect, the present invention provides the use of a fluorine adsorbent material as described in the second aspect for the defluorination of lithium battery leachate.
Compared with the prior art, the invention has the following beneficial effects:
(1) the invention adopts the grafting modification technology to prepare the fluorine adsorbent, which not only has high selectivity and high adsorption capacity to fluorine, but also has stable chemical property, difficult loss and longer service life.
(2) The invention adopts silica gel as a carrier, the silica gel is an inorganic material, and is more convenient for subsequent recovery treatment, and the mixture of aluminum and rare earth elements is adopted to prepare the adsorbent, thereby not only ensuring the high selectivity and adsorption capacity of the adsorbent, but also reducing the cost of the adsorbent.
(3) The saturated adsorption capacity of the fluorine adsorption material can reach more than 7g/L, the cycle stability is more than 100 times, and the saturated adsorption capacity of the prepared fluorine adsorption material can reach 20g/L by adjusting the preparation conditions and the raw material proportion.
Detailed Description
The technical solution of the present invention is further explained by the following embodiments. It should be understood by those skilled in the art that the examples are only for the understanding of the present invention and should not be construed as the specific limitations of the present invention.
Example 1
The embodiment provides a fluorine adsorbing material, and a preparation method of the fluorine adsorbing material comprises the following steps:
(1) the particle diameter is 100 μm, the pore diameter is 20nm, and the specific surface area is 500m2Activating the porous silica gel microspheres by 6mol/L hydrochloric acid for 2 hours, mixing the activated porous silica gel microspheres with an ethanol solution of aminopropyl-3-methoxysilane, and reacting at 50 ℃ to obtain aminosilane-modified silica gel;
(2) 10g of aminosilane-modified silica gel with HOOC- (CH)2)2And (3) after acidification reaction of-COOH in an acid solution at 30 ℃, adding 5g of a sulfate mixture of aluminum and cerium with the mass ratio of 1:1, carrying out chelation reaction at 80 ℃, and treating with a sodium hydroxide solution to obtain the fluorine adsorbing material.
Example 2
The embodiment provides a fluorine adsorbing material, and a preparation method of the fluorine adsorbing material comprises the following steps:
(1) the particle diameter is 500 μm, the pore diameter is 30nm, and the specific surface area is 1500m2Activating the porous silica gel microspheres by 6mol/L hydrochloric acid for 2 hours, and reacting the activated porous silica gel microspheres with an acetone solution of N- (aminoethyl) -gamma-aminopropyl methyl trimethoxy silane at 55 ℃ to obtain aminosilane-modified silica gel;
(2) 20g of aminosilane-modified silica gel with HOOC- (CH)2)2And (3) acidifying the-COOH in an acid solution at 36 ℃, adding 15g of a nitrate mixture of aluminum and lanthanum in a mass ratio of 1:2, carrying out a chelation reaction at 80 ℃, and treating with a sodium hydroxide solution to obtain the fluorine adsorbing material.
Example 3
This example differs from example 1 only in that the temperature of the reaction described in step (1) is 30 ℃ and the other conditions and parameters are exactly the same as in example 1.
Example 4
This example differs from example 1 only in that the temperature of the reaction described in step (1) is 90 ℃ and the other conditions and parameters are exactly the same as in example 1.
Example 5
This example differs from example 1 only in that the temperature of the acidification reaction in step (2) is 20 ℃ and the other conditions and parameters are exactly the same as those in example 1.
Example 6
This example differs from example 1 only in that the temperature of the acidification reaction in step (2) is 50 ℃ and the other conditions and parameters are exactly the same as those in example 1.
Example 7
This example differs from example 1 only in that the mass ratio of aluminum and cerium in step (2) is 3:1, and the other conditions and parameters are exactly the same as those in example 1.
Example 8
This example is different from example 1 only in that the mass ratio of aluminum and cerium in step (2) is 1:5, and other conditions and parameters are exactly the same as those in example 1.
Comparative example 1
This comparative example differs from example 1 only in that step (1) uses an organic resin as a support, and the other conditions and parameters are exactly the same as those of example 1.
Comparative example 2
This comparative example differs from example 1 only in that no metal mixture is added, the other conditions and parameters being exactly the same as in example 1.
And (3) performance testing:
and testing the saturated adsorption capacity of the fluorine adsorption material by adopting a static adsorption method. 2ml of the fluorine-adsorbing material was poured into a flask, and then 500ml of a fluorine-containing aqueous solution having a fluorine ion concentration of 200mg/L (pH 3.5) was added thereto, and after mixing and shaking for 1 hour with a shaker for adsorption equilibrium, the fluorine-adsorbing material and the fluorine-containing aqueous solution were separated with a centrifuge. The fluorine concentration in the separated fluorine-containing aqueous solution was measured by an electrode method. The fluorine saturation adsorption capacity is then: q ═ C0-Ce)*V/M
Q is the fluorine saturation adsorption capacity, C0The initial fluorine concentration, Ce the fluorine concentration after adsorption equilibrium, V the fluorine-containing aqueous solution volume, M the fluorine adsorption material volume. The saturated adsorption capacity of fluorine can reach 20 g/L.
And (3) testing the cycling stability: after the adsorption is saturated, fluorine in the adsorption material is removed by desorption liquid, and then static adsorption is carried out again. And sequentially carrying out adsorption-desorption circulation until 100 times of circulation or the adsorption capacity is lower than the initial adsorption capacity by 90 percent. The test results are shown in table 1:
TABLE 1
| Saturated adsorption capacity | Stability of circulation | |
| Example 1 | 20g/L | >100 times (twice) |
| Example 2 | 18.5g/L | >100 times (twice) |
| Example 3 | 12g/L | >100 times (twice) |
| Example 4 | 15g/L | >100 times (twice) |
| Example 5 | 13g/L | >100 times (twice) |
| Example 6 | 15g/L | >100 times (twice) |
| Example 7 | 8g/L | >100 times (twice) |
| Example 8 | 15g/L | >100 times (twice) |
| Comparative example 1 | 15g/L | <50 times |
| Comparative example 2 | 5g/L | >100 times (twice) |
As can be seen from Table 1, the saturated adsorption capacity of the fluorine adsorption material of the present invention can be up to 7g/L or more, the cycle stability can be up to 100 times or more, and the saturated adsorption capacity of the fluorine adsorption material can be up to 20g/L by adjusting the preparation conditions and the raw material ratio in examples 1 to 6.
Compared with the examples 3-4, the reaction temperature of the silica gel and the aminosilane in the step (1) can affect the performance of the prepared fluorine adsorbing material, and if the reaction temperature is too high, the reaction is too violent and is not easy to control; if the reaction temperature is too low, the reaction is not complete.
Compared with the examples 5 to 6, the temperature of the acidification reaction in the step (2) can affect the performance of the prepared fluorine adsorbing material, and if the reaction temperature is too high, energy is wasted; if the reaction temperature is too low, the reaction is not complete
As can be seen from the comparison between example 1 and examples 7 to 8, the mass ratio of aluminum to rare earth metal during the production of the fluorine adsorbent affects the performance of the fluorine adsorbent, and if the amount of aluminum is too high, the performance of the adsorbent is slightly inferior. If the doping amount of the rare earth element is too high, the cost is higher.
Compared with the comparative example 1, the invention uses the silica gel carrier, the specific surface area of the porous silica gel microspheres is large, thus more adsorption sites can be formed, and the adsorption capacity of the adsorbent is increased; the silica gel microspheres are inorganic materials, so that the subsequent recovery treatment is more convenient.
Compared with the comparative example 2, the method for preparing the adsorbent by using the mixture of the aluminum and the rare earth element can ensure high selectivity and adsorption capacity of the adsorbent and reduce the cost of the adsorbent.
The applicant declares that the above description is only a specific embodiment of the present invention, but the scope of the present invention is not limited thereto, and it should be understood by those skilled in the art that any changes or substitutions that can be easily conceived by those skilled in the art within the technical scope of the present invention are within the scope and disclosure of the present invention.
Claims (10)
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