CN111085158A - Method for preparing defluorination water purifying agent by using eggshells and application thereof - Google Patents
Method for preparing defluorination water purifying agent by using eggshells and application thereof Download PDFInfo
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- CN111085158A CN111085158A CN201911351904.8A CN201911351904A CN111085158A CN 111085158 A CN111085158 A CN 111085158A CN 201911351904 A CN201911351904 A CN 201911351904A CN 111085158 A CN111085158 A CN 111085158A
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- purifying agent
- water purifying
- eggshells
- defluorination
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- 210000003278 egg shell Anatomy 0.000 title claims abstract description 76
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 title claims abstract description 63
- 238000000034 method Methods 0.000 title claims abstract description 42
- 238000006115 defluorination reaction Methods 0.000 title claims abstract description 39
- 239000012629 purifying agent Substances 0.000 title claims abstract description 36
- 102000002322 Egg Proteins Human genes 0.000 claims abstract description 41
- 108010000912 Egg Proteins Proteins 0.000 claims abstract description 41
- 239000000843 powder Substances 0.000 claims abstract description 21
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims abstract description 18
- 238000001035 drying Methods 0.000 claims abstract description 17
- 229910019142 PO4 Inorganic materials 0.000 claims abstract description 16
- 239000010452 phosphate Substances 0.000 claims abstract description 12
- 238000003756 stirring Methods 0.000 claims abstract description 11
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 claims abstract description 10
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims abstract description 9
- 238000004140 cleaning Methods 0.000 claims abstract description 9
- 238000001027 hydrothermal synthesis Methods 0.000 claims abstract description 9
- 238000002791 soaking Methods 0.000 claims abstract description 9
- 239000002253 acid Substances 0.000 claims abstract description 5
- 244000144977 poultry Species 0.000 claims abstract description 4
- 239000011737 fluorine Substances 0.000 claims description 22
- 229910052731 fluorine Inorganic materials 0.000 claims description 22
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 claims description 17
- 239000000243 solution Substances 0.000 claims description 15
- 238000006243 chemical reaction Methods 0.000 claims description 12
- -1 fluorine ions Chemical class 0.000 claims description 9
- 239000007788 liquid Substances 0.000 claims description 6
- 238000005406 washing Methods 0.000 claims description 6
- 238000000227 grinding Methods 0.000 claims description 5
- 238000000926 separation method Methods 0.000 claims description 5
- MNNHAPBLZZVQHP-UHFFFAOYSA-N diammonium hydrogen phosphate Chemical compound [NH4+].[NH4+].OP([O-])([O-])=O MNNHAPBLZZVQHP-UHFFFAOYSA-N 0.000 claims description 4
- 229910000388 diammonium phosphate Inorganic materials 0.000 claims description 4
- 235000019838 diammonium phosphate Nutrition 0.000 claims description 4
- 239000007864 aqueous solution Substances 0.000 claims description 3
- 229910000402 monopotassium phosphate Inorganic materials 0.000 claims description 3
- 235000019796 monopotassium phosphate Nutrition 0.000 claims description 3
- PJNZPQUBCPKICU-UHFFFAOYSA-N phosphoric acid;potassium Chemical compound [K].OP(O)(O)=O PJNZPQUBCPKICU-UHFFFAOYSA-N 0.000 claims description 3
- 241000272525 Anas platyrhynchos Species 0.000 claims description 2
- 241000272814 Anser sp. Species 0.000 claims description 2
- 241000286209 Phasianidae Species 0.000 claims description 2
- LFVGISIMTYGQHF-UHFFFAOYSA-N ammonium dihydrogen phosphate Chemical compound [NH4+].OP(O)([O-])=O LFVGISIMTYGQHF-UHFFFAOYSA-N 0.000 claims description 2
- 229910000387 ammonium dihydrogen phosphate Inorganic materials 0.000 claims description 2
- ZPWVASYFFYYZEW-UHFFFAOYSA-L dipotassium hydrogen phosphate Chemical compound [K+].[K+].OP([O-])([O-])=O ZPWVASYFFYYZEW-UHFFFAOYSA-L 0.000 claims description 2
- BNIILDVGGAEEIG-UHFFFAOYSA-L disodium hydrogen phosphate Chemical compound [Na+].[Na+].OP([O-])([O-])=O BNIILDVGGAEEIG-UHFFFAOYSA-L 0.000 claims description 2
- 235000019837 monoammonium phosphate Nutrition 0.000 claims description 2
- 229910000403 monosodium phosphate Inorganic materials 0.000 claims description 2
- 235000019799 monosodium phosphate Nutrition 0.000 claims description 2
- AJPJDKMHJJGVTQ-UHFFFAOYSA-M sodium dihydrogen phosphate Chemical compound [Na+].OP(O)([O-])=O AJPJDKMHJJGVTQ-UHFFFAOYSA-M 0.000 claims description 2
- 241000287828 Gallus gallus Species 0.000 claims 1
- 238000001179 sorption measurement Methods 0.000 abstract description 8
- 239000002994 raw material Substances 0.000 abstract description 5
- 239000002699 waste material Substances 0.000 abstract description 5
- 239000000463 material Substances 0.000 abstract description 4
- 229910001220 stainless steel Inorganic materials 0.000 description 9
- 239000010935 stainless steel Substances 0.000 description 9
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 8
- 229910052588 hydroxylapatite Inorganic materials 0.000 description 7
- XYJRXVWERLGGKC-UHFFFAOYSA-D pentacalcium;hydroxide;triphosphate Chemical compound [OH-].[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 XYJRXVWERLGGKC-UHFFFAOYSA-D 0.000 description 6
- 239000011575 calcium Substances 0.000 description 5
- 239000003651 drinking water Substances 0.000 description 5
- 235000020188 drinking water Nutrition 0.000 description 5
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 5
- 239000004810 polytetrafluoroethylene Substances 0.000 description 5
- 238000010438 heat treatment Methods 0.000 description 4
- PUZPDOWCWNUUKD-UHFFFAOYSA-M sodium fluoride Chemical compound [F-].[Na+] PUZPDOWCWNUUKD-UHFFFAOYSA-M 0.000 description 4
- 238000001354 calcination Methods 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
- 238000001914 filtration Methods 0.000 description 3
- 239000012535 impurity Substances 0.000 description 3
- 239000012528 membrane Substances 0.000 description 3
- 238000002360 preparation method Methods 0.000 description 3
- 230000008569 process Effects 0.000 description 3
- 238000012216 screening Methods 0.000 description 3
- 239000011257 shell material Substances 0.000 description 3
- 239000007787 solid Substances 0.000 description 3
- 239000000725 suspension Substances 0.000 description 3
- QORWJWZARLRLPR-UHFFFAOYSA-H tricalcium bis(phosphate) Chemical compound [Ca+2].[Ca+2].[Ca+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O QORWJWZARLRLPR-UHFFFAOYSA-H 0.000 description 3
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- 238000002441 X-ray diffraction Methods 0.000 description 2
- 239000003463 adsorbent Substances 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 239000001506 calcium phosphate Substances 0.000 description 2
- 229910000389 calcium phosphate Inorganic materials 0.000 description 2
- 235000011010 calcium phosphates Nutrition 0.000 description 2
- 238000012512 characterization method Methods 0.000 description 2
- 239000013043 chemical agent Substances 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 230000001112 coagulating effect Effects 0.000 description 2
- 238000009297 electrocoagulation Methods 0.000 description 2
- 238000000909 electrodialysis Methods 0.000 description 2
- 238000005265 energy consumption Methods 0.000 description 2
- 230000036541 health Effects 0.000 description 2
- 238000002329 infrared spectrum Methods 0.000 description 2
- 238000005342 ion exchange Methods 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 239000000376 reactant Substances 0.000 description 2
- 230000035484 reaction time Effects 0.000 description 2
- 230000008929 regeneration Effects 0.000 description 2
- 238000011069 regeneration method Methods 0.000 description 2
- 238000001223 reverse osmosis Methods 0.000 description 2
- 238000004062 sedimentation Methods 0.000 description 2
- 239000011775 sodium fluoride Substances 0.000 description 2
- 235000013024 sodium fluoride Nutrition 0.000 description 2
- 238000006467 substitution reaction Methods 0.000 description 2
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 1
- KRHYYFGTRYWZRS-UHFFFAOYSA-M Fluoride anion Chemical compound [F-] KRHYYFGTRYWZRS-UHFFFAOYSA-M 0.000 description 1
- 206010016818 Fluorosis Diseases 0.000 description 1
- 229910021536 Zeolite Inorganic materials 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 229910052586 apatite Inorganic materials 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- 229910000019 calcium carbonate Inorganic materials 0.000 description 1
- BRPQOXSCLDDYGP-UHFFFAOYSA-N calcium oxide Chemical compound [O-2].[Ca+2] BRPQOXSCLDDYGP-UHFFFAOYSA-N 0.000 description 1
- 239000000292 calcium oxide Substances 0.000 description 1
- ODINCKMPIJJUCX-UHFFFAOYSA-N calcium oxide Inorganic materials [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 208000002925 dental caries Diseases 0.000 description 1
- 208000004042 dental fluorosis Diseases 0.000 description 1
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 1
- 229940012466 egg shell membrane Drugs 0.000 description 1
- 239000007772 electrode material Substances 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- ZLNQQNXFFQJAID-UHFFFAOYSA-L magnesium carbonate Chemical compound [Mg+2].[O-]C([O-])=O ZLNQQNXFFQJAID-UHFFFAOYSA-L 0.000 description 1
- 239000001095 magnesium carbonate Substances 0.000 description 1
- 229910000021 magnesium carbonate Inorganic materials 0.000 description 1
- 239000002086 nanomaterial 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
- 150000003016 phosphoric acids Chemical class 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000009707 resistance sintering Methods 0.000 description 1
- 239000006228 supernatant Substances 0.000 description 1
- 208000024891 symptom Diseases 0.000 description 1
- 239000011573 trace mineral Substances 0.000 description 1
- 235000013619 trace mineral Nutrition 0.000 description 1
- 239000002351 wastewater Substances 0.000 description 1
- 239000010457 zeolite Substances 0.000 description 1
Images
Classifications
-
- 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
- B01J20/04—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising compounds of alkali metals, alkaline earth metals or magnesium
- B01J20/048—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising compounds of alkali metals, alkaline earth metals or magnesium containing phosphorus, e.g. phosphates, apatites, hydroxyapatites
-
- 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
- C02F1/281—Treatment of water, waste water, or sewage by sorption using inorganic sorbents
-
- 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
- B01J2220/00—Aspects relating to sorbent materials
- B01J2220/40—Aspects relating to the composition of sorbent or filter aid materials
- B01J2220/48—Sorbents characterised by the starting material used for their preparation
- B01J2220/4875—Sorbents characterised by the starting material used for their preparation the starting material being a waste, residue or of undefined composition
- B01J2220/4881—Residues from shells, e.g. eggshells, mollusk shells
-
- 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
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- Chemical & Material Sciences (AREA)
- Inorganic Chemistry (AREA)
- Organic Chemistry (AREA)
- Life Sciences & Earth Sciences (AREA)
- Hydrology & Water Resources (AREA)
- Engineering & Computer Science (AREA)
- Environmental & Geological Engineering (AREA)
- Water Supply & Treatment (AREA)
- Analytical Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Solid-Sorbent Or Filter-Aiding Compositions (AREA)
Abstract
The invention belongs to the technical field of water treatment materials, and discloses a method for preparing a defluorination water purifying agent by using eggshells and application thereof. The method comprises the following steps: 1) soaking eggshells in an acid solution, cleaning, drying and crushing to obtain eggshell powder; 2) stirring and reacting the eggshell powder in phosphoric acid or phosphate solution, carrying out hydrothermal reaction, and carrying out subsequent treatment to obtain the defluorination water purifying agent. The method utilizes the poultry eggshells as the raw material, adopts the hydrothermal method to prepare the defluorination water purifying agent with high efficiency, and carries out resource utilization on the wastes; the prepared defluorination water purifying agent has large adsorption capacity and high defluorination speed. The defluorination water purifying agent is applied to the removal of fluorinion in water body.
Description
Technical Field
The invention belongs to the technical field of water treatment material preparation, and particularly relates to a method for preparing a defluorination water purifying agent by using eggshells and application thereof.
Background
Fluorine is one of trace elements necessary for human bodies, the concentration of fluorine in drinking water has important influence on the health of the human bodies, the taking of a proper amount of fluorine in the human bodies is beneficial to preventing dental caries, but if the taking amount of the fluorine is excessive, fluorosis can be caused, symptoms such as fluoroossium, fluoromottle and the like can be caused, and the health of the human bodies is seriously influenced. Fluorine in drinking water is a main source of fluorine taken by human bodies, and the maximum limit of fluoride in the sanitary Standard for Drinking Water (GB5749-2006) in China is 1.0 mg/L.
At present, the drinking water defluorination method mainly comprises the following steps: the method comprises the following steps of (1) an adsorption filtration method, a coagulating sedimentation method, an ion exchange method, an electrodialysis method, an electrocoagulation method, an electro-adsorption method, a reverse osmosis method and the like, wherein the methods have advantages and disadvantages, and the coagulating sedimentation method is suitable for treating high-concentration fluorine-containing wastewater but can generate a large amount of waste residues; the ion exchange method has simple operation and stable defluorination effect, but has the regeneration problem of the ion exchanger; the electrodialysis method has high fluorine reduction efficiency but large equipment investment; the electrocoagulation method has simple equipment and convenient operation, does not need to add any chemical agent in the treatment process, but has unstable defluorination effect; the electro-adsorption method has the advantages of low energy consumption, convenient operation and no need of adding any chemical agent in the treatment process, but the adsorption capacity of the electrode material actually applied needs to be further improved; the reverse osmosis method has high defluorination efficiency and good effluent quality, but has higher equipment investment cost. The adsorption filtration method realizes the removal of the fluorine ions in the water by utilizing the adsorption effect of the adsorbent on the fluorine ions in the water, has the advantages of simple process flow, stable effluent quality, low operation cost and the like, and is particularly suitable for treating low-fluorine water. The zeolite, bone charcoal, activated carbon, activated alumina and hydroxyapatite are commonly used adsorbents at present, wherein the hydroxyapatite has the advantages of high defluorination capacity, no pollution to the environment, high regeneration efficiency and the like, and has good application prospect in the field of drinking water defluorination.
The eggshells mainly comprise 94 percent of calcium carbonate, the balance of calcium phosphate (1 percent) and magnesium carbonate (1 percent) and the like, can be used as a natural green calcium source, and the data shows that the annual egg yield of China is about 2500 ten thousand tons, the annual egg yield of discarded eggshells is about 40 thousand tons, and a large amount of discarded eggshells bring serious environmental pollution and resource waste. It is reported that the preparation and characterization of hydroxyapatite powder material [ Dong Yanlin, Wang Qing Liang, preparation and characterization of hydroxyapatite synthesized by eggshell calcination, environmental engineering report, 2011, 5(9) can be prepared by calcining eggshell as raw material and calcium phosphate as reactant for 2h at 450 ℃ in a rapid heating box type electric furnace and then heating to 900 ℃ for 4 h: 2156 to 2159 ]. The method comprises the following steps of taking eggshells as raw materials, taking pure diammonium hydrogen phosphate as a reactant, stirring and reacting at a constant temperature of 90 ℃ for 3 hours, washing, standing, settling, filtering out supernatant, and calcining in a resistance sintering furnace at 800 ℃ for 3 hours to obtain the nano-hydroxyapatite (Putongmei, Sunpeng, Wangsheng, Wangshizhu, synthesized by an eggshell hydrothermal method, Chunpei university report, 2013, 37 (1): 60 to 64. The patent application (CN109621913A) discloses a method for preparing biological supported hydroxyapatite by adopting a biological shell material, which comprises the steps of soaking the biological shell material in a phosphate aqueous solution, and reacting at room temperature to boiling to obtain the biological shell nano material loaded with a hydroxyapatite ordered nano array. Although the above methods all use eggshells as raw materials, in the technical scheme, some eggshells need to be calcined into calcium oxide at 900 ℃, the energy consumption is high, and the reaction time is too long (reaction is carried out for 7 days at 40 ℃) although the eggshells are carried out at low temperature, and the reaction efficiency is low.
Disclosure of Invention
Aiming at the market demand of the defluorination water purifying agent and the defects of the method for preparing hydroxyapatite by using eggshells, the invention aims to provide a method for preparing the defluorination water purifying agent by using eggshells.
The invention also aims to provide application of the defluorination water purifying agent obtained by the method.
The purpose of the invention is realized by the following technical scheme:
a method for preparing a defluorination water purifying agent by using eggshells comprises the following steps:
1) soaking eggshells in an acid solution, cleaning, drying and crushing to obtain eggshell powder;
2) stirring and reacting the eggshell powder in phosphoric acid or phosphate solution, carrying out hydrothermal reaction, and carrying out subsequent treatment to obtain the defluorination water purifying agent.
The acid solution is an aqueous solution with the pH value less than 2.5, and the grain size of the eggshell powder is 50-100 meshes;
the soaking time is 10-15 min.
The eggshell is poultry eggshell, and is one or more of egg shell, duck eggshell, goose eggshell and quail eggshell. The eggshell is free of eggshell membrane.
The phosphate in the step 2) is more than one of diammonium hydrogen phosphate, dipotassium hydrogen phosphate, disodium hydrogen phosphate, ammonium dihydrogen phosphate, potassium dihydrogen phosphate and sodium dihydrogen phosphate.
The concentration of the phosphoric acid or the phosphate is 0.5-1.5 mol/L (calculated by phosphate radical).
The temperature of the stirring reaction in the step 2) is 70-90 ℃, and the stirring reaction time is 1-1.5 h; the hydrothermal reaction is carried out for 0.5 to 6 hours at the temperature of between 150 and 200 ℃;
the molar ratio of the eggshell powder to the phosphoric acid or phosphate (Ca/PO)4 3-) 1: 1.2-0.8.
The subsequent treatment in the step 2) refers to solid-liquid separation, washing, drying and grinding after the reaction is finished.
The defluorination water purifying agent is obtained by the method.
The application of the fluorine-removing water purifying agent in removing fluorine ions in water bodies.
The invention has the beneficial effects that:
1. the method is characterized in that waste poultry eggshells are used as raw materials, a hydrothermal method is adopted to prepare the defluorination water purifying agent with high efficiency, and the waste is recycled;
2. the prepared defluorination water purifying agent has large adsorption capacity and high defluorination speed, for example, for sodium fluoride solution with the concentration of 15mg/L, the defluorination speed is 1.41 mg/g.h, which is obviously higher than that of the defluorination material-hydroxyphosphite sold on the market at present (0.67 mg/g.h).
Drawings
FIG. 1 is a scanning electron microscope photograph of eggshell powder at 5 ten thousand times magnification in the example;
FIG. 2 is a SEM photograph of the water purifying agent with fluorine removal prepared in example 1 at 5 ten thousand times magnification;
FIG. 3 is an X-ray diffraction pattern of the water purifying agent for removing fluorine and egg shell prepared in example 1;
FIG. 4 is an infrared spectrum of the water purifying agent for removing fluorine and egg shell prepared in example 1.
Detailed Description
The present invention will be described in further detail below with reference to comparative examples and examples, but the embodiments of the present invention are not limited thereto.
Materials, reagents and the like used in the following examples are commercially available unless otherwise specified.
The hydrochloric acid, phosphoric acid or phosphoric acid salts used in the following examples were of analytical purity.
Example 1
Ultrasonically cleaning the collected eggshells with water for 30 minutes, stripping eggshell membranes from the insides of the eggshells, then soaking the eggshells in 0.1mol/L hydrochloric acid solution (pH is 1.1) for 10 minutes, then cleaning with water for 3 times, removing surface impurities, drying, crushing, and then screening 50-100-mesh eggshell powder; adding egg shell powder into 1.0mol/L potassium dihydrogen phosphate solution, Ca/PO4 3-The mol ratio is 1: 1, then stirring and reacting for 1h in a thermostatic water bath at 90 ℃, then pouring into a stainless steel water thermal reaction kettle with a capacity of 50 ml and a polytetrafluoroethylene lining, covering a cover of a polytetrafluoroethylene inner container tightly, screwing a stainless steel outer cover, putting into a drying box, reacting for 2h at 180 ℃, pouring out suspension after the stainless steel water thermal reaction kettle is cooled, carrying out solid-liquid separation, washing solid powder with deionized water for three times, then putting into the drying box, drying for 2h at 60 ℃, and grinding to obtain the defluorination water purifying agent F1.
FIG. 1 is a scanning electron microscope photograph of eggshell powder at 5 ten thousand times magnification in the example; FIG. 2 is a SEM photograph of the water purifying agent with fluorine removal prepared in example 1 at 5 ten thousand times magnification; FIG. 3 is an X-ray diffraction pattern of the water purifying agent for removing fluorine and egg shell prepared in example 1; FIG. 4 is an infrared spectrum of the water purifying agent for removing fluorine and egg shell prepared in example 1.
Example 2
Ultrasonically cleaning the collected eggshells with water for 30 minutes, stripping eggshell membranes from the insides of the eggshells, then soaking the eggshells in 0.1mol/L hydrochloric acid solution (pH is 1.1) for 10 minutes, then cleaning with water for 3 times, removing surface impurities, drying, crushing, and then screening 50-100-mesh eggshell powder; adding egg shell powder into 1.0mol/L phosphoric acid solution, Ca/PO4 3-The mol ratio is 1: 1, then stirring and reacting for 1h in a constant temperature water bath at 80 ℃, then pouring into a stainless steel hydrothermal reaction kettle with a capacity of 50 ml and a polytetrafluoroethylene lining, and tightly covering the polytetrafluoroethyleneAnd (3) screwing the stainless steel outer cover on the inner container cover, putting the inner container cover into a drying box, reacting for 0.5h at 200 ℃, pouring out suspension for solid-liquid separation after the stainless steel hot reaction kettle is cooled, washing solid powder with deionized water for three times, then putting the inner container cover into the drying box, drying for 2h at 60 ℃, and grinding to obtain the defluorination water purifying agent F2.
Example 3
Ultrasonically cleaning the collected eggshells with water for 30 minutes, stripping eggshell membranes from the insides of the eggshells, then soaking the eggshells in 0.1mol/L hydrochloric acid solution (pH is 1.1) for 10 minutes, then cleaning with water for 3 times, removing surface impurities, drying, crushing, and then screening 50-100-mesh eggshell powder; adding egg shell powder into 1.0mol/L diammonium hydrogen phosphate solution, Ca/PO4 3-The mol ratio is 1: 1, then stirring and reacting for 1h in a constant temperature water bath at 70 ℃, then pouring into a stainless steel water heating reaction kettle with a capacity of 50 ml and a polytetrafluoroethylene lining, tightly covering a cover of a polytetrafluoroethylene inner container, screwing a stainless steel outer cover, putting into a drying box, reacting for 6h at 150 ℃, pouring out suspension liquid after the stainless steel water heating reaction kettle is cooled, carrying out solid-liquid separation, washing solid powder with deionized water for three times, then putting into the drying box, drying for 2h at 60 ℃, and grinding to obtain the defluorination water purifying agent F3.
Example 4 (application)
1g of the prepared defluorination water purification agents F1, F2, F3 and the commercially available active apatite defluorination agent YLF are respectively added into 100ml of sodium fluoride solution and an actual water sample of fluorine-containing underground water, and are shaken for 1 hour under the condition of room temperature, and the experimental results are as follows:
the above embodiments are preferred embodiments of the present invention, but the present invention is not limited to the above embodiments, and any other changes, modifications, substitutions, combinations, and simplifications which do not depart from the spirit and principle of the present invention should be construed as equivalents thereof, and all such changes, modifications, substitutions, combinations, and simplifications are intended to be included in the scope of the present invention.
Claims (9)
1. A method for preparing a defluorination water purifying agent by using eggshells is characterized by comprising the following steps: the method comprises the following steps:
1) soaking eggshells in an acid solution, cleaning, drying and crushing to obtain eggshell powder;
2) stirring and reacting the eggshell powder in phosphoric acid or phosphate solution, carrying out hydrothermal reaction, and carrying out subsequent treatment to obtain the defluorination water purifying agent.
2. The method for preparing the defluorination water purifying agent by using eggshells as claimed in claim 1, which is characterized in that: the hydrothermal reaction in the step 2) is carried out for 0.5-6 h at the temperature of 150-200 ℃;
the molar ratio of the eggshell powder to the phosphoric acid or phosphate in step 2), namely Ca/PO4 3-1: 1.2-0.8.
3. The method for preparing the defluorination water purifying agent by using eggshells as claimed in claim 1, which is characterized in that:
the acid solution in the step 1) is an aqueous solution with the pH value less than 2.5; the grain diameter of the eggshell powder is 50 meshes to 100 meshes.
4. The method for preparing the defluorination water purifying agent by using eggshells as claimed in claim 1, which is characterized in that: the soaking time in the step 1) is 10-15 min;
the phosphate in the step 2) is more than one of diammonium hydrogen phosphate, dipotassium hydrogen phosphate, disodium hydrogen phosphate, ammonium dihydrogen phosphate, potassium dihydrogen phosphate and sodium dihydrogen phosphate;
the concentration of the phosphoric acid or the phosphate solution is 0.5-1.5 mol/L in terms of phosphate radical.
5. The method for preparing the defluorination water purifying agent by using eggshells as claimed in claim 1, which is characterized in that: the temperature of the stirring reaction in the step 2) is 70-90 ℃, and the time of the stirring reaction is 1-1.5 h.
6. The method for preparing the defluorination water purifying agent by using eggshells as claimed in claim 1, which is characterized in that: the eggshell in the step 1) is a poultry eggshell, and is one or a combination of more than two of a chicken eggshell, a duck eggshell, a goose eggshell and a quail eggshell.
7. The method for preparing the defluorination water purifying agent by using eggshells as claimed in claim 1, which is characterized in that:
the subsequent treatment in the step 2) refers to solid-liquid separation, washing, drying and grinding after the reaction is finished.
8. A water purifying agent for removing fluorine obtained by the method of any one of claims 1 to 7.
9. The use of the water purifying agent for removing fluorine according to claim 8 for removing fluorine ions in a water body.
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