CN115920834B - Composite defluorinating agent for water purification and preparation method thereof - Google Patents
Composite defluorinating agent for water purification and preparation method thereof Download PDFInfo
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- 239000002131 composite material Substances 0.000 title claims abstract description 75
- 239000003795 chemical substances by application Substances 0.000 title claims abstract description 48
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 title claims abstract description 42
- 238000000746 purification Methods 0.000 title claims abstract description 20
- 238000002360 preparation method Methods 0.000 title abstract description 12
- 239000000843 powder Substances 0.000 claims abstract description 44
- 239000011159 matrix material Substances 0.000 claims abstract description 40
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 claims abstract description 32
- 239000000395 magnesium oxide Substances 0.000 claims abstract description 29
- 238000006243 chemical reaction Methods 0.000 claims abstract description 26
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 claims abstract description 26
- -1 fluorine ions Chemical class 0.000 claims abstract description 15
- 238000000034 method Methods 0.000 claims abstract description 14
- 238000005956 quaternization reaction Methods 0.000 claims abstract description 8
- 239000007788 liquid Substances 0.000 claims description 54
- 238000001035 drying Methods 0.000 claims description 52
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 38
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 30
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 30
- 238000003756 stirring Methods 0.000 claims description 27
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 24
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 24
- 229910052757 nitrogen Inorganic materials 0.000 claims description 21
- 239000002244 precipitate Substances 0.000 claims description 21
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 claims description 18
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims description 17
- 238000001132 ultrasonic dispersion Methods 0.000 claims description 17
- 239000004202 carbamide Substances 0.000 claims description 16
- 230000008878 coupling Effects 0.000 claims description 16
- 238000010168 coupling process Methods 0.000 claims description 16
- 238000005859 coupling reaction Methods 0.000 claims description 16
- 239000008367 deionised water Substances 0.000 claims description 16
- 229910021641 deionized water Inorganic materials 0.000 claims description 16
- 238000005406 washing Methods 0.000 claims description 15
- 238000002156 mixing Methods 0.000 claims description 13
- 239000006087 Silane Coupling Agent Substances 0.000 claims description 12
- 150000001875 compounds Chemical class 0.000 claims description 12
- 230000001276 controlling effect Effects 0.000 claims description 12
- 238000010438 heat treatment Methods 0.000 claims description 10
- 230000001105 regulatory effect Effects 0.000 claims description 10
- 238000004321 preservation Methods 0.000 claims description 8
- 230000003301 hydrolyzing effect Effects 0.000 claims description 7
- CMOAHYOGLLEOGO-UHFFFAOYSA-N oxozirconium;dihydrochloride Chemical compound Cl.Cl.[Zr]=O CMOAHYOGLLEOGO-UHFFFAOYSA-N 0.000 claims description 7
- 238000001704 evaporation Methods 0.000 claims description 6
- 229910052742 iron Inorganic materials 0.000 claims description 6
- FPFSGDXIBUDDKZ-UHFFFAOYSA-N 3-decyl-2-hydroxycyclopent-2-en-1-one Chemical compound CCCCCCCCCCC1=C(O)C(=O)CC1 FPFSGDXIBUDDKZ-UHFFFAOYSA-N 0.000 claims description 5
- 230000032683 aging Effects 0.000 claims description 5
- IMBKASBLAKCLEM-UHFFFAOYSA-L ferrous ammonium sulfate (anhydrous) Chemical compound [NH4+].[NH4+].[Fe+2].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O IMBKASBLAKCLEM-UHFFFAOYSA-L 0.000 claims description 5
- 230000004048 modification Effects 0.000 claims description 5
- 238000012986 modification Methods 0.000 claims description 5
- 238000010992 reflux Methods 0.000 claims description 5
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 claims description 4
- 230000008569 process Effects 0.000 claims description 4
- PUVAFTRIIUSGLK-UHFFFAOYSA-M trimethyl(oxiran-2-ylmethyl)azanium;chloride Chemical compound [Cl-].C[N+](C)(C)CC1CO1 PUVAFTRIIUSGLK-UHFFFAOYSA-M 0.000 claims description 3
- 238000009775 high-speed stirring Methods 0.000 claims description 2
- 230000035484 reaction time Effects 0.000 claims description 2
- 238000005507 spraying Methods 0.000 claims description 2
- 238000001291 vacuum drying Methods 0.000 claims description 2
- 239000011737 fluorine Substances 0.000 abstract description 47
- 229910052731 fluorine Inorganic materials 0.000 abstract description 47
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 abstract description 39
- 238000001179 sorption measurement Methods 0.000 abstract description 15
- 239000010865 sewage Substances 0.000 abstract description 7
- 239000011148 porous material Substances 0.000 abstract description 6
- IVORCBKUUYGUOL-UHFFFAOYSA-N 1-ethynyl-2,4-dimethoxybenzene Chemical compound COC1=CC=C(C#C)C(OC)=C1 IVORCBKUUYGUOL-UHFFFAOYSA-N 0.000 abstract description 5
- 125000002887 hydroxy group Chemical group [H]O* 0.000 abstract description 4
- 230000002378 acidificating effect Effects 0.000 abstract description 3
- 238000011065 in-situ storage Methods 0.000 abstract description 3
- 230000003197 catalytic effect Effects 0.000 abstract description 2
- 230000008021 deposition Effects 0.000 abstract description 2
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- 239000000835 fiber Substances 0.000 abstract description 2
- 238000001027 hydrothermal synthesis Methods 0.000 abstract description 2
- 239000003446 ligand Substances 0.000 abstract description 2
- 230000006911 nucleation Effects 0.000 abstract description 2
- 238000010899 nucleation Methods 0.000 abstract description 2
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 abstract 2
- 239000000243 solution Substances 0.000 description 24
- 239000013049 sediment Substances 0.000 description 13
- MPNXSZJPSVBLHP-UHFFFAOYSA-N 2-chloro-n-phenylpyridine-3-carboxamide Chemical compound ClC1=NC=CC=C1C(=O)NC1=CC=CC=C1 MPNXSZJPSVBLHP-UHFFFAOYSA-N 0.000 description 9
- CTKINSOISVBQLD-UHFFFAOYSA-N Glycidol Chemical compound OCC1CO1 CTKINSOISVBQLD-UHFFFAOYSA-N 0.000 description 9
- 239000000047 product Substances 0.000 description 6
- KRHYYFGTRYWZRS-UHFFFAOYSA-M Fluoride anion Chemical compound [F-] KRHYYFGTRYWZRS-UHFFFAOYSA-M 0.000 description 5
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 5
- 230000000052 comparative effect Effects 0.000 description 5
- 239000010410 layer Substances 0.000 description 5
- 239000006228 supernatant Substances 0.000 description 5
- 238000009388 chemical precipitation Methods 0.000 description 4
- 238000001556 precipitation Methods 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- 239000002351 wastewater Substances 0.000 description 4
- 238000006115 defluorination reaction Methods 0.000 description 3
- 230000008020 evaporation Effects 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 241000282414 Homo sapiens Species 0.000 description 2
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 description 2
- 229910052782 aluminium Inorganic materials 0.000 description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 239000003673 groundwater Substances 0.000 description 2
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 2
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 2
- 239000010802 sludge Substances 0.000 description 2
- PUZPDOWCWNUUKD-UHFFFAOYSA-M sodium fluoride Chemical compound [F-].[Na+] PUZPDOWCWNUUKD-UHFFFAOYSA-M 0.000 description 2
- 229910052726 zirconium Inorganic materials 0.000 description 2
- VPGLGRNSAYHXPY-UHFFFAOYSA-L zirconium(2+);dichloride Chemical compound Cl[Zr]Cl VPGLGRNSAYHXPY-UHFFFAOYSA-L 0.000 description 2
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical group [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 description 1
- VTLYFUHAOXGGBS-UHFFFAOYSA-N Fe3+ Chemical compound [Fe+3] VTLYFUHAOXGGBS-UHFFFAOYSA-N 0.000 description 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- 238000007792 addition Methods 0.000 description 1
- 239000012670 alkaline solution Substances 0.000 description 1
- AZDRQVAHHNSJOQ-UHFFFAOYSA-N alumane Chemical class [AlH3] AZDRQVAHHNSJOQ-UHFFFAOYSA-N 0.000 description 1
- XKMRRTOUMJRJIA-UHFFFAOYSA-N ammonia nh3 Chemical compound N.N XKMRRTOUMJRJIA-UHFFFAOYSA-N 0.000 description 1
- 229910052586 apatite Inorganic materials 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- WUKWITHWXAAZEY-UHFFFAOYSA-L calcium difluoride Chemical compound [F-].[F-].[Ca+2] WUKWITHWXAAZEY-UHFFFAOYSA-L 0.000 description 1
- 159000000007 calcium salts Chemical class 0.000 description 1
- 230000009920 chelation Effects 0.000 description 1
- 239000003245 coal Substances 0.000 description 1
- 238000013329 compounding Methods 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- 239000003651 drinking water Substances 0.000 description 1
- 235000020188 drinking water Nutrition 0.000 description 1
- 239000003344 environmental pollutant Substances 0.000 description 1
- 125000003700 epoxy group Chemical group 0.000 description 1
- 229910001447 ferric ion Inorganic materials 0.000 description 1
- 239000010436 fluorite Substances 0.000 description 1
- 230000008570 general process Effects 0.000 description 1
- 150000004679 hydroxides Chemical class 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- 238000005342 ion exchange Methods 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 159000000003 magnesium salts Chemical class 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 208000030159 metabolic disease Diseases 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 230000000813 microbial effect Effects 0.000 description 1
- 235000010755 mineral Nutrition 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- VSIIXMUUUJUKCM-UHFFFAOYSA-D pentacalcium;fluoride;triphosphate Chemical compound [F-].[Ca+2].[Ca+2].[Ca+2].[Ca+2].[Ca+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O VSIIXMUUUJUKCM-UHFFFAOYSA-D 0.000 description 1
- 231100000719 pollutant Toxicity 0.000 description 1
- 239000002516 radical scavenger Substances 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 238000007142 ring opening reaction Methods 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 239000011775 sodium fluoride Substances 0.000 description 1
- 235000013024 sodium fluoride Nutrition 0.000 description 1
- 239000002344 surface layer Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
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- Solid-Sorbent Or Filter-Aiding Compositions (AREA)
Abstract
The invention relates to a composite defluorinating agent for water purification and a preparation method thereof, belonging to the technical field of sewage treatment. The composite defluorinating agent is a composite defluorinating agent with a nuclear fiber layer structure, magnetic composite micro powder is taken as a core, nano magnesium oxide is taken as a nucleation and catalytic center, and a hydrothermal method is utilized to combine Fe in situ 3+ And Fe (Fe) 2+ The method is characterized in that a magnetic composite matrix is formed to solve the problem that a fluorine removing agent is difficult to recover, a composite of gamma-type alumina and zirconium hydroxide is loaded in the magnetic composite matrix through deposition conversion and baking, wherein the gamma-type alumina has a large number of active sites and pore channels, the zirconium hydroxide is protonated under an acidic condition and contains a large number of free hydroxyl groups and bridging hydroxyl groups, and can exchange ligands with fluorine ions to cooperatively adsorb the fluorine ions, so that the fluorine removing agent has a good fluorine removing effect, and the surface hydrophilicity of a porous structure is improved through quaternization treatment, so that the contact area with fluorine-containing sewage is increased, and the fluorine adsorption rate is increased.
Description
Technical Field
The invention belongs to the technical field of sewage treatment, and particularly relates to a composite defluorinating agent for water purification and a preparation method thereof.
Background
Under normal conditions, the main way of fluoride intake of human beings is through drinking water, the fluorine intake depends on the daily average intake of water and the fluoride pollution level of water, trace fluoride is necessary for normal development of human body, excessive fluorine intake can cause fluorine plaque, fluorima and metabolic disorder, and if the concentration of fluorine ions in water exceeds 8ppm, the microbial efficiency of decomposing pollutants in water can be reduced, and further the indexes of ammonia nitrogen and COD in wastewater are increased, so that fluorine-containing sewage must be defluorinated, and the first-level standard of fluorine element emission concentration is required to be not higher than 10mg/L according to GB/T8978-1996 standard.
In the nature, fluorine mainly exists in various ores, such as fluorite, apatite and the like, when groundwater flows through the ores, fluoride is slowly dissolved and gradually released into a water body in the form of fluoride ions, the release process is extremely slow, fluorine pollution is generally difficult to cause, modern fluorine pollution mainly comes from industrial sewage of mineral exploitation, pharmacy, chemical synthesis and the like, the wastewater has high fluorine pollution concentration and high acid-base value, the current defluorination means comprises a chemical precipitation method, an ion exchange method, a membrane separation method and an adsorption method, wherein the chemical precipitation method is widely adopted by the advantages of simple process, low cost and large treatment capacity, but the chemical precipitation method needs to add a large amount of inorganic salts or hydroxides such as calcium salt, magnesium salt and aluminum salt to react with fluoride ions to generate sediment, the product is a large amount of sludge, and the purification degree is not high, and the general process can only reach national standard first-level emission standard; compared with a chemical precipitation method, the adsorption method does not generate a large amount of sludge and has higher purification degree, so the prior art greatly develops the high-efficiency adsorption type fluorine removing agent, but mainly has two problems that the adsorption capacity of the existing fluorine removing agent is not high, the fluorine adsorption capacity of the high-performance fluorine removing agent which is generally excellent is about 20mg/g, and the adsorption type fluorine removing agent is generally in order to improve the adsorption capacity, and the fluorine removing agent is prepared into an ultrastructure, so that the recovery difficulty of the fluorine removing agent is high.
Disclosure of Invention
In order to solve the technical problems in the background art, the invention aims to provide a compound defluorinating agent for water purification and a preparation method thereof.
The aim of the invention can be achieved by the following technical scheme:
a compound defluorinating agent for water purification is prepared from magnetic compound micro powder through quaternization, wherein the preparation method of the magnetic compound micro powder comprises the following steps:
step A1: preparing urea solution, adding nano magnesium oxide, performing ultrasonic dispersion, standing and ageing for 24 hours at room temperature, taking a bottom layer for precipitation and washing, centrifuging, and vacuum drying, wherein the surface of the nano magnesium oxide presents a large number of crystal defect pores, urea and metal have chelation, are adsorbed in the pores of the nano magnesium oxide for crystallization, and the nano magnesium oxide loads a urea structure to prepare a magnesium oxide load matrix;
further, the solid-to-liquid ratio of the nano magnesium oxide to the urea solution is 1: 12-15%, and the concentration of urea solution is 20-25%.
Step A2: dissolving ferric ammonium sulfate and ferrous ammonium sulfate in deionized water under the protection of nitrogen to prepare functional modified liquid, adding a magnesium oxide loaded matrix, preheating to 70 ℃, applying ultrasonic dispersion, continuously heating to 80-85 ℃, carrying out heat preservation treatment for 1.2-1.5h, heating urea loaded on the surface of the magnesium oxide loaded matrix in aqueous solution to slowly decompose, hydrolyzing part of ferric ions on the surface of the magnesium oxide loaded matrix into flocculent gel in situ, centrifuging after reaction, taking precipitate, drying and scattering at high temperature, dehydrating the flocculent gel to form a porous structure, and preparing the magnetic composite matrix;
further, fe in the functional modification liquid 3+ And Fe (Fe) 2+ The molar ratio is 3.2-3.5:1, the molar concentration of iron ions is 0.08-0.1mol/L, and the solid-liquid ratio of the magnesium oxide loaded matrix and the functional modification liquid is 1:20-25.
Further, the high-temperature drying temperature is 120-140 ℃, the high-temperature drying time is 2-3h, and the furnace atmosphere is nitrogen.
Step A3: dissolving zirconium dichloride and aluminum chloride in deoxidized water to prepare functional load liquid, repeatedly spraying the functional load liquid on a magnetic composite matrix, evaporating the functional load liquid for a plurality of times, immersing the functional load liquid in an ethanol solution with the pH value of 8.0, heating the solution to 75-90 ℃ for reflux reaction for 10-15h, centrifuging the reaction, taking out the precipitate after the reaction is finished, drying the precipitate at high temperature, scattering, loading the zirconium dichloride and the aluminum chloride on the magnetic composite matrix, and hydrolyzing the precipitate on the surface layer of the composite matrix in an alkaline solution to prepare magnetic composite micro powder;
further, al in the functional load liquid 3+ The concentration of Zr is 1.2-1.6mol/L 4+ The concentration of the magnetic composite matrix is 0.1-0.2mol/L, and the dosage ratio of the total amount of the magnetic composite matrix and the functional load liquid is 10g:60-90mL, the concentration of ethanol solution is 30%.
Further, the high temperature baking process parameters are as follows: the first-stage baking temperature is 140-150 ℃ and the time is 1.5-2h, the second-stage baking temperature is 200-240 ℃ and the time is 0.8-1.2h, and the atmosphere in the high-temperature baking furnace is nitrogen.
Further, the quaternization treatment method of the magnetic composite micro powder comprises the following steps:
step B1: mixing a silane coupling agent KH550 and deionized water, regulating the pH value to 5.5-6.0 by using hydrochloric acid, stirring and hydrolyzing for 2-3 hours, adding magnetic composite micro powder, performing ultrasonic dispersion, regulating the pH value to 8.0-8.5 by using sodium hydroxide, stirring and reacting for 1-1.5 hours, and performing centrifugal washing and drying after the reaction is finished to prepare coupling micro powder;
further, the dosage ratio of the magnetic composite micro powder to the silane coupling agent KH550 is 10g:1.5-2.2mL.
Step B2: dispersing coupling micro powder in 80% ethanol solution by ultrasonic, adding potassium hydroxide, mixing, heating to 50-60 ℃, slowly adding glycidol trimethyl ammonium chloride under high-speed stirring, controlling the whole adding reaction time to be 3-5h, controlling the ring-opening reaction of epoxy groups in the glycidol trimethyl ammonium chloride and amino grafted on the surface of the coupling micro powder, introducing ammonium chloride groups to modify the surface of a coupling matrix, adsorbing fluorine ions to a certain extent, mainly improving the hydrophilicity of the porous magnetic composite micro powder, increasing the contact area with fluorine-containing sewage, thereby increasing the fluorine adsorption rate, ending the reaction, centrifuging, washing and drying to prepare the composite defluorinating agent;
further, the dosage ratio of the coupling micro powder, the glycidyl trimethyl ammonium chloride and the potassium hydroxide is 10g:1.8-2.3g:0.7-0.9g.
The invention has the beneficial effects that:
the defluorinating agent is a composite defluorinating agent with a nuclear fiber layer structure, the magnetic composite micro powder is taken as a core and has a porous structure, and is formed by compounding four functional elements of magnesium, iron, aluminum and zirconium, nano magnesium oxide is taken as a nucleation and catalytic center, a large number of crystal defect pores are presented on the surface of the nano magnesium oxide, urea is loaded on the surface of the nano magnesium oxide, then the urea is decomposed by a hydrothermal method, and Fe is combined in situ 3+ And Fe (Fe) 2+ Forming a magnetic composite matrix to solve the problem that the fluorine removing agent is difficult to recycle, doping aluminum and zirconium elements into surface pores of the magnetic composite matrix through deposition conversion, and fully baking to form a gamma-type aluminum oxide and zirconium hydroxide composite, wherein the gamma-type aluminum oxide has a large number of active sites and pore channels, has strong adsorption capacity on fluorine ions under an acidic condition, the zirconium hydroxide is protonated under the acidic condition to adsorb the fluorine ions, and meanwhile, the zirconium hydroxide contains a large number of free hydroxyl groups and bridging hydroxyl groups and can exchange ligands with the fluorine ions to cooperatively adsorb the fluorine ions, so that the fluorine removing agent has a good fluorine removing effect; in addition, the magnetic composite micro powder is grafted with amino through KH550 treatment and then is quaternized by glycidol trimethyl ammonium chloride, so that the surface hydrophilicity of a porous structure is improved, the contact area with fluorine-containing sewage is increased, and the fluorine adsorption rate is improved.
Detailed Description
The technical solutions of the embodiments of the present invention will be clearly and completely described below in conjunction with the embodiments of the present invention, and it is apparent that the described embodiments are only some embodiments of the present invention, not all embodiments. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention.
Example 1
The preparation method of the composite defluorinating agent for water purification comprises the following specific preparation processes:
1. preparing magnetic composite micro powder
a1, preparing urea solution with the concentration of 20% from urea and deionized water according to a solid-to-liquid ratio of 1:12 adding nano magnesium oxide, performing ultrasonic dispersion for 40min at 20kHz, standing and aging for 24h at room temperature, skimming supernatant to take out bottom sediment, adding deionized water with twice the sediment mass, stirring and washing, centrifuging to take out bottom sediment, and placing the bottom sediment in a vacuum dryer for drying treatment for 5h to obtain the magnesium oxide loaded matrix.
a2, taking ferric ammonium sulfate and ferrous ammonium sulfate according to Fe 3+ And Fe (Fe) 2+ Mixing the components according to the molar ratio of 3.2:1, adding deionized water under the protection of nitrogen, stirring and dissolving, controlling the concentration of iron ions to be 0.08mol/L, obtaining functional modified liquid, and adding the functional modified liquid according to the solid-liquid ratio of 1:20 adding a magnesia loaded matrix, preheating to raise the temperature to 70 ℃, applying 28kHz ultrasonic dispersion, simultaneously continuously raising the temperature to 80 ℃, carrying out heat preservation treatment for 1.5 hours, centrifuging to obtain a bottom layer precipitate, draining after reaction, placing the precipitate in a nitrogen drying furnace, raising the temperature to 120 ℃ under the protection of nitrogen, carrying out high-temperature drying for 3 hours, and carrying out high-speed scattering treatment on a dried product for 30 minutes by adopting a blade type high-speed pulverizer at 20000rpm to obtain the magnetic composite matrix.
a3, taking zirconium oxychloride and aluminum chloride, stirring and dissolving the zirconium oxychloride and aluminum chloride by using deoxidized water to prepare a functional load liquid, and controlling Al in the functional load liquid 3+ The concentration of Zr is 1.6mol/L 4+ The concentration of the functional load liquid is 0.1mol/L, the functional load liquid is sprayed on the magnetic composite matrix for evaporating, and the dosage ratio of the total amount of the magnetic composite matrix and the functional load liquid is controlled to be 10g:60mL; and then the ethanol solution with the concentration of 30% is taken, the pH value is regulated to 8.0 by sodium hydroxide, the product after evaporation is added into the ethanol solution with the regulated pH value according to the solid-to-liquid ratio of 1:6, the temperature is raised to 75 ℃ for reflux reaction for 15 hours, the precipitate is centrifugally taken after the reaction is finished, the precipitate is placed into a nitrogen drying oven for drying at 80 ℃ for 1 hour, then the precipitate is placed into the nitrogen drying oven, first, the first-stage drying is carried out for 2 hours at 140 ℃, then the second-stage drying is carried out for 1.2 hours at the temperature of 200 ℃, and the magnetic composite micro powder is obtained after the drying.
2. Quaternization treatment of magnetic composite micropowder
b1, taking magnetic composite micro powder and silane coupling agent KH550 according to the dosage ratio of 1.5mL/10g, firstly mixing the silane coupling agent KH550 with 15 times of deionized water, dropwise adding 2% of dilute hydrochloric acid to adjust the pH value to 6.0, stirring and hydrolyzing for 3 hours at 120rpm, then adding the magnetic composite micro powder, performing ultrasonic dispersion for 10 minutes at 33kHz, then dropwise adding 5% of sodium hydroxide solution to adjust the pH value to 8.0, stirring and reacting for 1.5 hours at 480rpm, ending centrifugal washing, and drying at 60 ℃ in a drying oven to constant weight to obtain the coupling micro powder.
b2, adding coupling micro powder into an 80% ethanol solution according to a solid-to-liquid ratio of 1:15, performing ultrasonic dispersion for 20min at 33kHz, adding potassium hydroxide, mixing, heating to 50 ℃, stirring at a high speed of 600rpm, slowly adding glycidol trimethyl ammonium chloride in 1h, continuing to perform heat preservation stirring, controlling the overall adding time to be 5h, repeatedly performing centrifugal washing twice after the reaction is finished, and drying at a constant weight in a drying box at 60 ℃ to obtain the composite defluorinating agent, wherein the dosage ratio of the coupling micro powder, the glycidol trimethyl ammonium chloride and the potassium hydroxide is 10g:1.8g:0.7g.
Example 2
The preparation method of the composite defluorinating agent for water purification comprises the following specific preparation processes:
1. preparing magnetic composite micro powder
a1, preparing urea solution with the concentration of 25% from urea and deionized water according to a solid-to-liquid ratio of 1:15 adding nano magnesium oxide, performing ultrasonic dispersion for 30min at 20kHz, standing and aging for 24h at room temperature, skimming supernatant to take out bottom sediment, adding deionized water with twice the sediment mass, stirring and washing, centrifuging to take out bottom sediment, and placing the bottom sediment in a vacuum dryer for drying treatment for 5h to obtain the magnesium oxide loaded matrix.
a2, taking ferric ammonium sulfate and ferrous ammonium sulfate according to Fe 3+ And Fe (Fe) 2+ Mixing the components in a molar ratio of 3.5:1, adding deionized water under the protection of nitrogen, stirring and dissolving, controlling the concentration of iron ions to be 0.1mol/L, obtaining a functional modified liquid, and adding the functional modified liquid into the functional modified liquid according to a solid-liquid ratio of 1:25 adding a magnesia-loaded matrix, preheating to raise the temperature to 70 ℃, applying 28kHz ultrasonic dispersion while continuously raising the temperature to 85 ℃, carrying out heat preservation treatment for 1.2 hours, centrifuging to obtain a bottom layer precipitate after reaction, draining, placing the precipitate in a nitrogen drying furnace, raising the temperature to 140 ℃ under the protection of nitrogen, drying at a high temperature for 2 hours, and drying to obtain the productThe material is scattered for 30min at high speed by a blade type high-speed pulverizer at 20000rpm, and the magnetic composite matrix is obtained.
a3, taking zirconium oxychloride and aluminum chloride, stirring and dissolving the zirconium oxychloride and aluminum chloride by using deoxidized water to prepare a functional load liquid, and controlling Al in the functional load liquid 3+ The concentration of Zr is 1.2mol/L 4+ The concentration of the functional load liquid is 0.2mol/L, the functional load liquid is sprayed on the magnetic composite matrix for three times and evaporated to dryness, and the dosage ratio of the total amount of the magnetic composite matrix and the functional load liquid is controlled to be 10g:90mL; and then the ethanol solution with the concentration of 30% is taken, the pH value is regulated to 8.0 by sodium hydroxide, the product after evaporation is added into the ethanol solution with the regulated pH value according to the solid-to-liquid ratio of 1:8, the temperature is raised to 90 ℃ for reflux reaction for 10 hours, the precipitate is centrifugally taken after the reaction is finished, the precipitate is placed into a nitrogen drying oven for drying at 80 ℃ for 1 hour, then the precipitate is placed into the nitrogen drying oven, first, the first-stage drying is carried out at 150 ℃ for 1.5 hours, then the second-stage drying is carried out at 240 ℃ for 0.8 hours, and the magnetic composite micro powder is obtained after the drying.
2. Quaternization treatment of magnetic composite micropowder
b1, taking magnetic composite micro powder and silane coupling agent KH550 according to the dosage ratio of 2.2mL/10g, firstly mixing the silane coupling agent KH550 with deionized water which is 20 times of the silane coupling agent KH550, dropwise adding 2% of dilute hydrochloric acid to adjust the pH value to 5.5, stirring and hydrolyzing for 2 hours at 120rpm, then adding the magnetic composite micro powder, performing ultrasonic dispersion for 10 minutes at 33kHz, then dropwise adding 5% of sodium hydroxide solution to adjust the pH value to 8.5, stirring and reacting for 1 hour at 600rpm, ending centrifugal washing, and drying at 60 ℃ in a drying oven to obtain the coupling micro powder.
b2, adding coupling micro powder into an 80% ethanol solution according to a solid-to-liquid ratio of 1:15, performing ultrasonic dispersion for 20min at 33kHz, adding potassium hydroxide, mixing, heating to 60 ℃, stirring at a high speed of 600rpm, slowly adding glycidol trimethyl ammonium chloride in 1h, continuing to perform heat preservation stirring, controlling the overall adding time to be 3h, repeatedly performing centrifugal washing twice after the reaction is finished, and drying at the temperature of 60 ℃ in a drying box to obtain the composite defluorinating agent, wherein the dosage ratio of the coupling micro powder, the glycidol trimethyl ammonium chloride and the potassium hydroxide is 10g:2.3g:0.9g.
Example 3
The preparation method of the composite defluorinating agent for water purification comprises the following specific preparation processes:
1. preparing magnetic composite micro powder
a1, preparing urea solution with concentration of 22% from urea and deionized water according to a solid-to-liquid ratio of 1:12 adding nano magnesium oxide, performing ultrasonic dispersion for 40min at 20kHz, standing and aging for 24h at room temperature, skimming supernatant to take out bottom sediment, adding deionized water with twice the sediment mass, stirring and washing, centrifuging to take out bottom sediment, and placing the bottom sediment in a vacuum dryer for drying treatment for 5h to obtain the magnesium oxide loaded matrix.
a2, taking ferric ammonium sulfate and ferrous ammonium sulfate according to Fe 3+ And Fe (Fe) 2+ Mixing the components according to the molar ratio of 3.4:1, adding deionized water under the protection of nitrogen, stirring and dissolving, controlling the concentration of iron ions to be 0.09mol/L, obtaining a functional modified liquid, and adding the functional modified liquid according to the solid-liquid ratio of 1:25 adding a magnesia-loaded matrix, preheating to raise the temperature to 70 ℃, applying 28kHz ultrasonic dispersion, simultaneously continuously raising the temperature to 82 ℃, carrying out heat preservation treatment for 1.3 hours, centrifuging to obtain a bottom layer precipitate, draining after reaction, placing the precipitate in a nitrogen drying furnace, raising the temperature to 130 ℃ under the protection of nitrogen, carrying out high-temperature drying for 2.5 hours, and carrying out high-speed scattering treatment on the dried product for 30 minutes by adopting a blade type high-speed pulverizer at 20000rpm to obtain the magnetic composite matrix.
a3, taking zirconium oxychloride and aluminum chloride, stirring and dissolving the zirconium oxychloride and aluminum chloride by using deoxidized water to prepare a functional load liquid, and controlling Al in the functional load liquid 3+ The concentration of Zr is 1.4mol/L 4+ The concentration of the functional load liquid is 0.16mol/L, the functional load liquid is sprayed on the magnetic composite matrix for three times and evaporated to dryness, and the dosage ratio of the total amount of the magnetic composite matrix and the functional load liquid is controlled to be 10g:90mL; and then the ethanol solution with the concentration of 30% is taken, the pH value is regulated to 8.0 by sodium hydroxide, the product after evaporation is added into the ethanol solution with the regulated pH value according to the solid-to-liquid ratio of 1:8, the temperature is raised to 85 ℃ for reflux reaction for 13 hours, the centrifugal precipitation is taken after the reaction, the precipitation is dried in a nitrogen drying oven at 80 ℃ for 1 hour, then the precipitation is placed in the nitrogen drying oven, the primary drying is carried out at 150 ℃ for 1.8 hours, the secondary drying is carried out at 220 ℃ for 1 hour, and the magnetic composite micro powder is obtained after the drying.
2. Quaternization treatment of magnetic composite micropowder
b1, taking magnetic composite micro powder and silane coupling agent KH550 according to the dosage ratio of 2.0mL/10g, firstly mixing the silane coupling agent KH550 with deionized water which is 20 times of the silane coupling agent KH550, dropwise adding 2% of dilute hydrochloric acid to adjust the pH value to 5.5, stirring and hydrolyzing for 2.5 hours at 120rpm, then adding the magnetic composite micro powder, performing ultrasonic dispersion for 10 minutes at 33kHz, then dropwise adding 5% of sodium hydroxide solution to adjust the pH value to 8.0, stirring and reacting for 1.2 hours at 600rpm, ending centrifugal washing after the reaction, and drying at 60 ℃ in a drying oven to constant weight to obtain the coupling micro powder.
b2, adding coupling micro powder into an 80% ethanol solution according to a solid-to-liquid ratio of 1:15, performing ultrasonic dispersion for 20min at 33kHz, adding potassium hydroxide, mixing, heating to 55 ℃, stirring at a high speed of 600rpm, slowly adding glycidol trimethyl ammonium chloride in 1h, continuing to perform heat preservation stirring, controlling the overall adding time to be 4h, repeatedly performing centrifugal washing twice after the reaction is finished, and drying at a constant weight in a drying box at 60 ℃ to obtain the composite defluorinating agent, wherein the dosage ratio of the coupling micro powder, the glycidol trimethyl ammonium chloride and the potassium hydroxide is 10g:2.1g:0.8g.
Comparative example
The comparative example is a commercial fluorine scavenger, model GMS-F6.
The adsorption capacity test was performed by taking the composite defluorinating agent prepared in example 1-example 3 and the defluorinating agent provided in comparative example, and the specific test method is as follows:
preparing 100mg/L sodium fluoride solution, respectively adding more than 0.05g of fluorine removing agent into 100mL, placing in a constant temperature shaking table, stirring at 120rpm for 12h at 25 ℃, adding 0.2g of PAM, stirring for 1h, centrifuging, taking supernatant, detecting fluoride ion concentration, calculating adsorption capacity, and specifically testing data as shown in table 1:
TABLE 1
As shown in the data of Table 1, the fluorine adsorption capacity of the composite fluorine removing agent prepared by the invention reaches 58.61-64.19mg/g, and compared with the existing fluorine removing agent, the composite fluorine removing agent has high adsorption capacity.
The complex defluorinating agent prepared in example 1-example 3 and the defluorinating agent provided in comparative example were subjected to a deep defluorination test of coal mine wastewater, a batch of first-stage defluorination wastewater with a fluorine content of 18.4mg/L was taken, 10L was taken as a sample, 12.5g of the complex defluorinating agent prepared in example 1-example 3 was added, 50g of the defluorinating agent provided in comparative example was stirred at 120rpm for 12h and 24h respectively, 30g of PAM was added continuously for 1h, supernatant was centrifuged, and the fluorine content was detected, and specific test data are shown in table 2:
TABLE 2
As shown in the data of Table 2, after the composite defluorinating agent is treated for 12 hours, the fluorine content is less than 1mg/L, the highest fluorine allowable concentration of ground water is achieved, and after 24 hours treatment, the fluorine content is not higher than 0.2mg/L, and compared with the existing defluorinating agent, the composite defluorinating agent has the characteristics of high-efficiency purification and deep purification.
In the description of the present specification, the descriptions of the terms "one embodiment," "example," "specific example," and the like, mean that a particular feature, structure, material, or characteristic described in connection with the embodiment or example is included in at least one embodiment or example of the present invention. In this specification, schematic representations of the above terms do not necessarily refer to the same embodiments or examples. Furthermore, the particular features, structures, materials, or characteristics described may be combined in any suitable manner in any one or more embodiments or examples.
The foregoing is merely illustrative and explanatory of the invention, as various modifications and additions may be made to the particular embodiments described, or in a similar manner, by those skilled in the art, without departing from the scope of the invention or exceeding the scope of the invention as defined in the claims.
Claims (7)
1. The composite defluorinating agent for water purification is characterized by being prepared from magnetic composite micro powder through quaternization treatment, wherein the magnetic composite micro powder is prepared by the following steps of:
step A1: ultrasonically dispersing nano magnesium oxide and urea solution, standing and aging for 24 hours at room temperature, taking a bottom layer precipitate for washing, centrifuging, and vacuum drying to prepare a magnesium oxide load matrix;
step A2: dissolving ferric ammonium sulfate and ferrous ammonium sulfate in deionized water under the protection of nitrogen to prepare functional modified liquid, adding a magnesium oxide loaded matrix, preheating to 70 ℃, carrying out ultrasonic dispersion, heating to 80-85 ℃, carrying out heat preservation treatment for 1.2-1.5h, centrifuging after reaction, taking out precipitate, drying at high temperature, and scattering to prepare a magnetic composite matrix;
step A3: dissolving zirconium oxychloride and aluminum chloride in deoxidized water to prepare functional load liquid, repeatedly spraying the functional load liquid on a magnetic composite matrix, evaporating the functional load liquid for a plurality of times, immersing the magnetic composite matrix in ethanol solution with the pH value of 8.0, heating the magnetic composite matrix to 75-90 ℃ for reflux reaction for 10-15h, centrifuging the reaction, taking out the precipitate, drying the precipitate, and then drying and scattering the precipitate at high temperature to prepare the magnetic composite micro powder;
the high-temperature baking process parameters are as follows: the primary baking temperature is 140-150 ℃ for 1.5-2h, the secondary baking temperature is 200-240 ℃ for 0.8-1.2h, and the atmosphere in the high-temperature baking furnace is nitrogen;
the quaternization treatment method of the magnetic composite micro powder comprises the following steps:
step B1: mixing a silane coupling agent KH550 and deionized water, regulating the pH value to 5.5-6.0, stirring and hydrolyzing for 2-3h, adding magnetic composite micro powder, performing ultrasonic dispersion, regulating the pH value to 8.0-8.5 by using sodium hydroxide, stirring and reacting for 1-1.5h, and performing centrifugal washing and drying after the reaction is finished to prepare coupled micro powder;
step B2: dispersing the coupling micro powder in 80% ethanol solution by ultrasonic, adding potassium hydroxide, mixing, heating to 50-60 ℃, slowly adding glycidyl trimethyl ammonium chloride under high-speed stirring, controlling the overall adding reaction time to be 3-5h, centrifuging, washing and drying after the reaction is finished, and preparing the compound defluorinating agent.
2. The compound defluorinating agent for water purification according to claim 1, wherein the solid-to-liquid ratio of nano magnesium oxide to urea solution is 1: 12-15%, and the concentration of urea solution is 20-25%.
3. The compound defluorinating agent for water purification according to claim 2, wherein Fe in the functional modifying liquid is 3 + And Fe (Fe) 2+ The molar ratio of the magnesium oxide to the functional modification solution is 3.2-3.5:1, the molar concentration of iron ions is 0.08-0.1mol/L, and the solid-liquid ratio of the magnesium oxide loaded matrix to the functional modification solution is 1:20-25.
4. A compound defluorinating agent for water purification according to claim 3, wherein the high temperature drying temperature is 120-140 ℃, the high temperature drying time is 2-3h, and the furnace atmosphere is nitrogen.
5. The compound defluorinating agent for water purification according to claim 4, wherein Al in the functional load liquid 3 + The concentration of Zr is 1.2-1.6mol/L 4+ The concentration of the magnetic composite matrix is 0.1-0.2mol/L, and the dosage ratio of the total amount of the magnetic composite matrix and the functional load liquid is 10g:60-90mL, the concentration of ethanol solution is 30%.
6. The compound defluorinating agent for water purification according to claim 1, wherein the dosage ratio of the magnetic compound micro powder to the silane coupling agent KH550 is 10g:1.5-2.2mL.
7. The compound defluorinating agent for water purification according to claim 6, wherein the dosage ratio of the coupling micro powder, the glycidyl trimethyl ammonium chloride and the potassium hydroxide is 10g:1.8-2.3g:0.7-0.9g.
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