CN111569818A - Drinking water defluorinating agent and preparation method and application thereof - Google Patents
Drinking water defluorinating agent and preparation method and application thereof Download PDFInfo
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- CN111569818A CN111569818A CN202010373045.9A CN202010373045A CN111569818A CN 111569818 A CN111569818 A CN 111569818A CN 202010373045 A CN202010373045 A CN 202010373045A CN 111569818 A CN111569818 A CN 111569818A
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- solution
- fluorine
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- drinking water
- defluorinating agent
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- 239000003795 chemical substances by application Substances 0.000 title claims abstract description 74
- 239000003651 drinking water Substances 0.000 title claims abstract description 24
- 235000020188 drinking water Nutrition 0.000 title claims abstract description 24
- 238000002360 preparation method Methods 0.000 title claims abstract description 14
- 239000011737 fluorine Substances 0.000 claims abstract description 82
- 229910052731 fluorine Inorganic materials 0.000 claims abstract description 82
- 210000003278 egg shell Anatomy 0.000 claims abstract description 73
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 claims abstract description 71
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims abstract description 45
- 229910052742 iron Inorganic materials 0.000 claims abstract description 29
- 229910052782 aluminium Inorganic materials 0.000 claims abstract description 26
- 239000007787 solid Substances 0.000 claims abstract description 18
- 229910000329 aluminium sulfate Inorganic materials 0.000 claims abstract description 13
- DIZPMCHEQGEION-UHFFFAOYSA-H aluminium sulfate (anhydrous) Chemical compound [Al+3].[Al+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O DIZPMCHEQGEION-UHFFFAOYSA-H 0.000 claims abstract description 13
- 239000007788 liquid Substances 0.000 claims abstract description 12
- 229910021578 Iron(III) chloride Inorganic materials 0.000 claims abstract description 11
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical group Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 claims abstract description 11
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims abstract description 10
- 238000004140 cleaning Methods 0.000 claims abstract description 8
- 239000002994 raw material Substances 0.000 claims abstract description 5
- 239000002699 waste material Substances 0.000 claims abstract description 4
- 239000000243 solution Substances 0.000 claims description 95
- 238000000034 method Methods 0.000 claims description 37
- 102000002322 Egg Proteins Human genes 0.000 claims description 35
- 108010000912 Egg Proteins Proteins 0.000 claims description 35
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 33
- -1 fluorine ions Chemical class 0.000 claims description 30
- 238000001035 drying Methods 0.000 claims description 24
- 238000005406 washing Methods 0.000 claims description 19
- 241001122767 Theaceae Species 0.000 claims description 16
- 238000003756 stirring Methods 0.000 claims description 15
- 235000014347 soups Nutrition 0.000 claims description 12
- 230000008569 process Effects 0.000 claims description 10
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical class [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 claims description 9
- 238000001914 filtration Methods 0.000 claims description 9
- 238000001994 activation Methods 0.000 claims description 6
- 238000007873 sieving Methods 0.000 claims description 6
- 150000001875 compounds Chemical class 0.000 claims description 5
- 230000004913 activation Effects 0.000 claims description 4
- 239000011259 mixed solution Substances 0.000 claims description 4
- AZDRQVAHHNSJOQ-UHFFFAOYSA-N alumane Chemical compound [AlH3] AZDRQVAHHNSJOQ-UHFFFAOYSA-N 0.000 claims description 2
- 230000007935 neutral effect Effects 0.000 claims description 2
- 230000009972 noncorrosive effect Effects 0.000 claims description 2
- 230000035622 drinking Effects 0.000 abstract description 12
- 238000006115 defluorination reaction Methods 0.000 abstract description 6
- 238000011068 loading method Methods 0.000 abstract description 5
- 238000001179 sorption measurement Methods 0.000 description 18
- PUZPDOWCWNUUKD-UHFFFAOYSA-M sodium fluoride Chemical compound [F-].[Na+] PUZPDOWCWNUUKD-UHFFFAOYSA-M 0.000 description 16
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 16
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 13
- 239000000203 mixture Substances 0.000 description 12
- 239000011575 calcium Substances 0.000 description 10
- 230000000694 effects Effects 0.000 description 10
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 9
- 239000003463 adsorbent Substances 0.000 description 9
- 229910052791 calcium Inorganic materials 0.000 description 9
- 238000001816 cooling Methods 0.000 description 8
- 239000008367 deionised water Substances 0.000 description 8
- 229910021641 deionized water Inorganic materials 0.000 description 8
- 239000011775 sodium fluoride Substances 0.000 description 8
- 235000013024 sodium fluoride Nutrition 0.000 description 8
- 239000002245 particle Substances 0.000 description 7
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 6
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 6
- 238000006243 chemical reaction Methods 0.000 description 6
- 229910021645 metal ion Inorganic materials 0.000 description 6
- 238000010979 pH adjustment Methods 0.000 description 6
- 230000002354 daily effect Effects 0.000 description 5
- 238000002474 experimental method Methods 0.000 description 5
- 150000002500 ions Chemical class 0.000 description 5
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- 238000012360 testing method Methods 0.000 description 5
- 241000287828 Gallus gallus Species 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
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- 229910000019 calcium carbonate Inorganic materials 0.000 description 3
- 238000004364 calculation method Methods 0.000 description 3
- 239000001569 carbon dioxide Substances 0.000 description 3
- 229910002092 carbon dioxide Inorganic materials 0.000 description 3
- 230000008859 change Effects 0.000 description 3
- 238000001095 inductively coupled plasma mass spectrometry Methods 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- BHPQYMZQTOCNFJ-UHFFFAOYSA-N Calcium cation Chemical compound [Ca+2] BHPQYMZQTOCNFJ-UHFFFAOYSA-N 0.000 description 2
- KRHYYFGTRYWZRS-UHFFFAOYSA-M Fluoride anion Chemical compound [F-] KRHYYFGTRYWZRS-UHFFFAOYSA-M 0.000 description 2
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 2
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 2
- 239000011449 brick Substances 0.000 description 2
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- 239000006228 supernatant Substances 0.000 description 2
- BFKJFAAPBSQJPD-UHFFFAOYSA-N tetrafluoroethene Chemical group FC(F)=C(F)F BFKJFAAPBSQJPD-UHFFFAOYSA-N 0.000 description 2
- 238000005303 weighing Methods 0.000 description 2
- 229910018084 Al-Fe Inorganic materials 0.000 description 1
- 239000005995 Aluminium silicate Substances 0.000 description 1
- KLZUFWVZNOTSEM-UHFFFAOYSA-K Aluminum fluoride Inorganic materials F[Al](F)F KLZUFWVZNOTSEM-UHFFFAOYSA-K 0.000 description 1
- 229910018192 Al—Fe Inorganic materials 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 229920001661 Chitosan Polymers 0.000 description 1
- 239000002841 Lewis acid Substances 0.000 description 1
- 229910021536 Zeolite Inorganic materials 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 230000004075 alteration Effects 0.000 description 1
- KCZFLPPCFOHPNI-UHFFFAOYSA-N alumane;iron Chemical compound [AlH3].[Fe] KCZFLPPCFOHPNI-UHFFFAOYSA-N 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
- 235000012211 aluminium silicate Nutrition 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000012490 blank solution Substances 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 239000004568 cement Substances 0.000 description 1
- 238000009388 chemical precipitation Methods 0.000 description 1
- 239000004927 clay Substances 0.000 description 1
- GUJOJGAPFQRJSV-UHFFFAOYSA-N dialuminum;dioxosilane;oxygen(2-);hydrate Chemical compound O.[O-2].[O-2].[O-2].[Al+3].[Al+3].O=[Si]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O GUJOJGAPFQRJSV-UHFFFAOYSA-N 0.000 description 1
- 238000007865 diluting Methods 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
- 239000002384 drinking water standard Substances 0.000 description 1
- 238000004043 dyeing Methods 0.000 description 1
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- 235000013305 food Nutrition 0.000 description 1
- 239000010794 food waste Substances 0.000 description 1
- 238000000227 grinding Methods 0.000 description 1
- 239000010440 gypsum Substances 0.000 description 1
- 229910052602 gypsum Inorganic materials 0.000 description 1
- 230000036541 health Effects 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 150000008040 ionic compounds Chemical class 0.000 description 1
- NLYAJNPCOHFWQQ-UHFFFAOYSA-N kaolin Chemical compound O.O.O=[Al]O[Si](=O)O[Si](=O)O[Al]=O NLYAJNPCOHFWQQ-UHFFFAOYSA-N 0.000 description 1
- 150000007517 lewis acids Chemical class 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 229910052901 montmorillonite Inorganic materials 0.000 description 1
- 239000004570 mortar (masonry) Substances 0.000 description 1
- 230000008520 organization Effects 0.000 description 1
- 102000004169 proteins and genes Human genes 0.000 description 1
- 108090000623 proteins and genes Proteins 0.000 description 1
- 229910052761 rare earth metal Inorganic materials 0.000 description 1
- 150000002910 rare earth metals Chemical class 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 238000002791 soaking Methods 0.000 description 1
- 235000017557 sodium bicarbonate Nutrition 0.000 description 1
- 229910000030 sodium bicarbonate Inorganic materials 0.000 description 1
- 235000017550 sodium carbonate Nutrition 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- 239000008399 tap water Substances 0.000 description 1
- 235000020679 tap water Nutrition 0.000 description 1
- 238000004065 wastewater treatment Methods 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
- B01J20/043—Carbonates or bicarbonates, e.g. limestone, dolomite, aragonite
-
- 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
- B01J20/0225—Compounds of Fe, Ru, Os, Co, Rh, Ir, Ni, Pd, Pt
- B01J20/0229—Compounds of Fe
-
- 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
- B01J20/0203—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
- B01J20/0274—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 characterised by the type of anion
- B01J20/0281—Sulfates of compounds other than those provided for in B01J20/045
-
- 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
- B01J20/0274—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 characterised by the type of anion
- B01J20/0288—Halides of compounds other than those provided for in B01J20/046
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- 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
- B01J2220/42—Materials comprising a mixture of inorganic materials
-
- 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
- B01J2220/4806—Sorbents characterised by the starting material used for their preparation the starting material being of inorganic character
-
- 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)
- Analytical Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Life Sciences & Earth Sciences (AREA)
- Hydrology & Water Resources (AREA)
- Engineering & Computer Science (AREA)
- Environmental & Geological Engineering (AREA)
- Water Supply & Treatment (AREA)
- Water Treatment By Sorption (AREA)
- Coloring Foods And Improving Nutritive Qualities (AREA)
Abstract
The invention relates to a drinking water defluorinating agent, a preparation method and an application thereof, wherein the drinking water defluorinating agent is a solid defluorinating agent which takes waste egg shells as raw materials and is loaded with iron and aluminum, and a solution used for loading the iron and the aluminum is FeCl3·6H2O solution and Al2(SO4)3·12H2And (4) O solution. FeCl3·6H2The concentration of the O solution is 0.45-0.55mol/L, and Al2(SO4)3·12H2The concentration of the O solution is 0.3-0.5 mol/L. The prepared fluorine removal agent can be reused through simple cleaning treatment. The fluorine removing agent can be directly applied to various liquids drunk by families in daily life, and does not need to be treated again after being used.Can meet the requirement of defluorination of drinking solution in daily life, does not produce secondary pollution to the drinking solution, and has low price and convenient use.
Description
Technical Field
The invention belongs to the field of food waste processing and environmental protection, and particularly relates to a drinking water defluorinating agent and a preparation method and application thereof.
Background
China is one of the countries with serious damage to endemic fluorine diseases, people mainly take fluorine by drinking water, and drinking water type fluorine diseases account for more than 90% of the total number of patients, so that the research on fluorine removal materials in drinking water is of practical significance.
The fluorine content in the tea is high, and in regions with high fluorine content in drinking water such as northChina, northwest China, northeast China and Huang-Huai-Hai plain regions, the fluorine content in tea soup exceeds the upper safety limit when the tea is brewed by using common drinking water. At present, chemical precipitation, coagulating precipitation, adsorption and the like are reported as methods for removing fluorine in drinking water at home and abroad. The method of removing fluorine from a solution, which has been widely used in recent years, is an adsorption method. The adsorption method uses simple equipment, does not need to provide power for the adsorption method, and is suitable for treating drinking water in families.
Common defluorination adsorbing materials on the market comprise aluminum salt, zeolite, montmorillonite, kaolin, alumina, bone charcoal, fishbone, gypsum material, cement clay cluster, rare earth metal, modified chitosan and the like. Because of the factors of cost, using technology, equipment, using efficiency, safety risk and the like, the method for treating the high-fluorine water is limited to be popularized in certain regions with high-fluorine underground water in China. At present, the defluorination materials on the market are mainly used for industrial production, large-scale processing, wastewater treatment after the process and the like, but are not used in daily life of families. High fluorine treatment is not always a concern in domestic everyday water. In areas where the fluorine content of the water source is high, in some cases, such as brewing tea, preparing food, etc., the fluorine intake may be excessive and may have an adverse effect on the body. Common defluorinating materials are commonly used in large-scale industrial processes, and the treated liquid is not potable and requires post-treatment.
Therefore, it is necessary to develop an adsorbent having a high selective adsorption capacity for fluorine ions, which can be used at home.
Disclosure of Invention
In view of the problems in the prior art, the invention provides a drinking water defluorinating agent and a preparation method and application thereof, and the defluorinating agent which is convenient to use, quick in effect taking, safe and effective is obtained, the content of fluoride ions exceeding the upper limit of the content of fluorine in drinking water can be directly reduced to be within a safe range, and the drinking water defluorinating agent can be repeatedly used for multiple times after being simply treated.
In order to achieve the purpose, the invention adopts the following technical scheme:
a drinking water defluorinating agent is a solid defluorinating agent loaded with iron and aluminum by using waste egg shells as raw materials, and a solution used for loading the iron and the aluminum is FeCl3·6H2O solution and Al2(SO4)3·12H2Solution of O, FeCl3·6H2The concentration of the O solution is 0.45-0.55mol/L, and Al2(SO4)3·12H2The concentration of the O solution is 0.3-0.5 mol/L.
Preferably, the eggshells are selected from raw eggshells that are clean, non-corrosive, and do not require removal of biofilm.
A method for preparing a drinking water defluorinating agent comprises the following steps:
1) cleaning raw egg shell, drying, crushing, and sieving;
2) selecting 10-40 mesh raw egg shells into a beaker, adding HCl solution for activation treatment, and stirring with a magnetic stirrer to obtain activated egg shells;
3) taking out the activated egg shell, washing to be neutral, adding FeCl3·6H2O solution and Al2(SO4)3·12H2Stirring the mixed solution of the O solution by using a magnetic stirrer, adding a NaOH solution to adjust the pH value, continuously stirring by using the magnetic stirrer, standing, filtering, and keeping a solid part containing the eggshell;
4) and drying, washing and drying to obtain the fluorine removal agent.
Preferably, in the step 2), the concentration of the HCl solution is 0.005-0.015mol/L, the solid-to-liquid ratio of the eggshell to the HCl solution in the activation process is (1:4) - (1:10), and the activation treatment time is 10-20 minutes.
Preferably, in the step 3), 0.45-0.55mol/LFeCl is added3·6H2O solution and 0.3-0.5mol/LAl2(SO4)3·12H21 of O solution: 1, mixing the solution.
Preferably, in the step 3), after the mixed solution is added, the mixture is stirred by a magnetic stirrer for half an hour, after the pH is adjusted, the mixture is stirred for half an hour, and then the mixture is kept standing.
Preferably, in said step 3), the pH is adjusted to 5.5-6.5.
Preferably, in the step 4), the drying process is lower than 50 ℃, and the product is taken out and naturally cooled. In the drying process, the temperature is controlled within 100 ℃ and is slowly increased.
The fluorine removal agent or the fluorine removal agent prepared by the method is used for removing fluorine ions in the high-fluorine tea soup.
Preferably, the mass ratio of the fluorine removing agent to the solution to be subjected to fluorine removal in the using process of the fluorine removing agent prepared by the method is (1:100) - (1: 150).
The method is a treatment method for reusing the fluorine removal agent or the fluorine removal agent prepared by the method, and the method comprises the steps of putting the used fluorine removal agent into a hot saturated baking soda solution, washing for 2-3 times, taking out and drying.
Preferably, the solid-to-liquid ratio of the fluorine removal agent to the saturated baking soda solution is 1 (20-25).
Preferably, the temperature of the saturated sodium bicarbonate solution is 70-90 ℃ and the washing time is 0.4-2 hours.
The invention has the following beneficial effects:
the application provides a fluorine removal agent which can be directly used in household daily drinking water or drinking liquid and a preparation process thereof, and can be repeatedly used through a simple washing process. The defluorinating agent has the advantages of easily obtained raw materials, simple and convenient preparation process, simple use method, safety, effectiveness and low cost.
The eggshell contains more than 95% of calcium carbonate, has a natural porous structure and a large specific surface area, is a natural and good calcium source and a load matrix, and a layer of biological membrane covered inside the eggshell is protein, can be effectively modified after a simple firing process, and cannot cause secondary pollutionThe dyeing does not affect the attachment of metal ions on the eggshell basically, and the eggshell does not need to be removed intentionally before being processed. Iron, aluminum, calcium are often used in defluorination processes. AlF in aluminum trihalides3Is the only ionic compound in crystalline AlF3Because Al is hexacoordinated, it is not easily dimerized, is a Lewis acid, is easily soluble in water, and is subject to hydrolysis. However, if Al is used alone3+When the fluorine ions are ionized to form compounds, the compounds are difficult to remove from the aqueous solution, and may cause harm to human bodies after drinking. The coordination compounds of iron with fluoride ions are octahedral and highly spin. Fe3+Ions with F-The ions have stronger affinity to form FeF3Has a three-stage equilibrium constant of K1≈105；K2≈105；K3≈103It is much more extensive than its hydrolysis reaction. When the purpose of reusing the defluorinating agent is achieved by adopting alkali washing, Fe needs to be considered3+The ions are easily hydrolyzed and precipitated. Ca3+Ions with F-The ions can form ionic salts with a solubility product of 1.7 × 10-10Far less than OH-Solubility product of 1.3 × 10-6. According to the invention, by means of the natural porous calcium carbonate of the eggshell, iron ions and aluminum ions are simultaneously loaded, so that aluminum and iron are fixed, and iron, aluminum and calcium can exert coordination capacity, so that the problems of iron ions and aluminum ions are solved, and the natural porous calcium carbonate not only achieves a good fluorine removal effect, but also is convenient to use and has no safety problem.
Drawings
FIG. 1 is a state diagram of a finished defluorinating agent of the present invention;
FIG. 2 is a diagram showing a state in which a fluorine-removing agent is placed in tea soup in example 2.
Detailed Description
The present invention is further illustrated by the following specific examples.
Example 1
This example provides a method for preparing a fluorine removal agent and a washing method for measuring the fluorine removal capacity and the secondary utilization effect of a prepared sodium fluoride solution.
The preparation method of the fluorine removing agent comprises the following steps:
cleaning ovum gallus Domesticus crusta, drying, crushing, and sieving. Egg shells with the size of 20-40 meshes are selected, 4.0g of the egg shells are weighed and put into a 50mL beaker. 24mL of a 0.01mol/L HCl solution was added, and the mixture was stirred with a magnetic stirrer for 15 minutes, filtered off, and dried. In the reaction process, calcium in the egg shell reacts with hydrochloric acid to generate carbon dioxide, a large amount of bubbles are generated on the surface of the egg shell at the beginning, the egg shell floats in the liquid, the revolution of the magnetic stirrer needs to be increased, and the generation process of the bubbles tends to be gentle along with the reaction. 0.5mol/L FeCl3·6H2O solution and 0.4mol/L Al2(SO4)3·12H2The O solution was mixed, 10.0mL was transferred to a 50mL conical flask with a stopper, and the activated egg shell was added and stirred with a magnetic stirrer for about half an hour. The pH was adjusted to 6.37 by addition of dilute NaOH solution and stirring was continued for about half an hour with a magnetic stirrer, with the pH adjustment being ignored. And standing for twenty minutes. Filtering to retain the solid portion comprising the eggshells. The mixture was placed in a muffle furnace and dried at 95 ℃ for about two hours. Taking out and naturally cooling. Washing the cooled solid with deionized water, removing the powdery particles, retaining the loaded eggshells, and naturally drying.
0.20 g of the finished defluorinating agent accurately weighed is placed into 20.00mL of prepared sodium fluoride solution accurately transferred, after the solution is kept still for twenty minutes, 10.00mL of the solution is transferred into a tetrafluoroethylene cup by a pipette, 10.00mL of buffer solution (TISAB) is added, and the potential of the solution is measured. The experiment was carried out at 25.0 ℃ and the Nernst equation for fluoride ions was: e-243.99813 +57.91553 XlgC
The control value for the original sodium fluoride solution without adsorbent was-220 mV (5.1927 mg/L).
From this, the adsorption capacity of the fluorine removing agent can be calculated. The experimental raw data and the calculation results are shown in table 1.
TABLE 1 measurement of adsorption Capacity of defluorinating agent in sodium fluoride solution
The adsorption amount of the fluorine removing agent was 0.457 mg/g. The fluorine ions in the solution after the fluorine removing agent is used reach the drinking safety standard specified by the national standard.
Washing and drying the used defluorinating agent by the following method:
taking out the used defluorinating agent, soaking in 20mL of 80 ℃ saturated sodium bicarbonate solution for half an hour, taking out, repeating for three times, and naturally drying. Wherein the sodium bicarbonate solution is prepared from soda ash purchased from supermarkets, and the experimental water is Yibao pure water.
The above defluorination process was then repeated and the tests were repeated with the results shown in table 2 below.
TABLE 2 measurement of adsorption capacity of fluorine-removing agent used twice in sodium fluoride solution
The results show that the adsorption capacity of the fluorine removal agent in secondary use is reduced by 9% after the fluorine removal agent is simply washed and dried, but the fluorine removal agent also has a good fluorine removal effect.
In conclusion, the fluorine removal agent is suitable for daily drinking, and can directly reduce the fluorine content in the solution to the drinking safety range regulated by the state after being used. And can be repeatedly used after being cleaned by a simple cleaning mode.
Example 2
The embodiment provides a preparation method of a fluorine removal agent and application of the fluorine removal agent in high-fluorine tea soup. In order to test the fluorine removal effect of the fluorine removal agent in a complex environment, the green brick tea soup with high fluorine content is selected for the experiment.
The preparation method of the fluorine removing agent comprises the following steps:
cleaning ovum gallus Domesticus crusta, drying, crushing, and sieving. Egg shells with the size larger than 40 meshes are selected, 4.0g of the egg shells are weighed and put into a 50mL beaker. 32mL of a 0.01mol/L HCl solution was added, and the mixture was stirred with a magnetic stirrer for 15 minutes, filtered off, and dried. During the reaction process, calcium in the egg shell reacts with hydrochloric acid to generate carbon dioxide, and the surface of the egg shell is just startedThe egg shell is floated in the liquid due to the generation of a large amount of bubbles, the revolution of the magnetic stirrer needs to be increased, and the generation process of the bubbles tends to be gentle along with the reaction. 0.5mol/L FeCl3·6H2O solution and 0.4mol/L Al2(SO4)3·12H2The O solution was mixed, 12.0mL was removed in a 50mL conical flask with a stopper, and the activated egg shell was added and stirred with a magnetic stirrer for about half an hour. The pH was adjusted to 5.81 by addition of dilute NaOH solution and stirring was continued for about half an hour with a magnetic stirrer, with the pH adjustment being ignored. Standing for two hours. Filtering to retain the solid portion comprising the eggshells. The mixture was placed in a muffle furnace and dried at 95 ℃ for about two hours. Taking out and naturally cooling. Washing the cooled solid with deionized water, removing the powdery particles, retaining the loaded eggshells, and naturally drying.
Grinding green brick tea leaves in a mortar, weighing 0.200 g, putting into a conical flask with a plug, weighing 0.400 g of defluorinating agent, putting into the conical flask, adding 40.00mL of deionized water, and heating in water bath. Taking out the solution after boiling for five minutes, naturally cooling the solution to room temperature at the normal temperature, and then measuring the content of the fluorine ions according to the same operation steps.
The measured potential value of the original tea soup without adding adsorbent was-233 mV (3.0969 mg/L).
The experimental raw data and the calculation results are shown in table 3.
TABLE 3 determination of the adsorption Capacity of the adsorbent in the high fluorine tea soup
In the high fluorine tea soup, the adsorption capacity of the adsorbent is generally increased. Although the concentration of the fluoride ion after adsorption is still higher, the fluoride ion also meets the limit value (1.0mg/L) of the content of the fluorine in the tap water specified by the national standard. The fluorine removing agent can effectively remove fluorine in tea soup, has good performance in complex environment, is not influenced by other factors, and can be conveniently used in various liquids drunk at home.
In conclusion, the fluorine removal agent can be used in the environment of tea soup, can still reduce the fluorine content in the tea soup to the drinking safety range specified by the state, and can achieve the purpose of daily use at any time.
Example 3
This example provides a method for preparing a fluorine removal agent. The experiment measures the content change of iron ions, aluminum ions and calcium ions in the solution after the defluorinating agent is used, judges the influence of the defluorinating agent on the solution and judges whether the defluorinating agent causes safety problems for drinking.
The change in the metal ion content in the solution after the use of the adsorbent was measured by inductively coupled plasma mass spectrometry (ICP-Ms).
The preparation method of the fluorine removing agent comprises the following steps:
cleaning ovum gallus Domesticus crusta, drying, crushing, and sieving. Egg shells with the size larger than 40 meshes are selected, 4.0g of the egg shells are weighed and put into a 50mL beaker. 40mL of 0.01mol/L HCl solution was added, stirred with a magnetic stirrer for 15 minutes, filtered off and dried. In the reaction process, calcium in the egg shell reacts with hydrochloric acid to generate carbon dioxide, a large amount of bubbles are generated on the surface of the egg shell at the beginning, the egg shell floats in the liquid, the revolution of the magnetic stirrer needs to be increased, and the generation process of the bubbles tends to be gentle along with the reaction. 0.5mol/L FeCl3·6H2O solution and 0.4mol/L Al2(SO4)3·12H2The O solution was mixed, 12.0mL was removed in a 50mL conical flask with a stopper, and the activated egg shell was added and stirred with a magnetic stirrer for about half an hour. The pH was adjusted to 5.56 by addition of dilute NaOH solution and stirring was continued for about half an hour with a magnetic stirrer, with the pH adjustment being ignored. Standing for two hours. Filtering to retain the solid portion comprising the eggshells. The mixture was placed in a muffle furnace and dried at 95 ℃ for about two hours. Taking out and naturally cooling. Washing the cooled solid with deionized water, removing the powdery particles, retaining the loaded eggshells, and naturally drying.
The parameters in the preparation method are all the limit values of each parameter.
According to the maximum usage amount provided in the application, the ratio of the mass of the fluorine removal agent to the volume of the sodium fluoride solution is 1:100 fluorine removal experiments were performed. Three sets of tests were conducted using the fluorine removing agents prepared by the preparation methods in example 1 and example 2 as sample 1 and sample 2, and the fluorine removing agent prepared by the above-described method as sample 3.
After standing the sodium fluoride solution using the defluorinating agent, accurately transferring 1.00mL of supernatant into a volumetric flask, diluting the supernatant to 10.00mL with 2.0% dilute nitric acid, shaking up, and testing. Each sample was tested in triplicate. Meanwhile, a blank control test is carried out by taking a 2.0% nitric acid solution as a blank solution. And preparing a standard sample and drawing a standard curve according to the national standard.
The measured data of the residual concentrations of calcium, iron and aluminum ions are shown in Table.4. The calcium and aluminum ion content of the solution was not detected.
The residual concentration of iron ions in the original solution is shown in table 5.
TABLE 4 content of Al and Fe in the solution measured by ICP-Ms
TABLE 5 measured concentration of iron ions and residual concentration of iron ions in the original solution
The aluminum ions and the calcium ions of the samples 1, 2 and 3 are not remained, and the residual concentration of the iron ions is lower than the drinking water standard of the world health organization (Fe is less than 0.3mg/L), which shows that the fluorine removal agent can not cause safety problem to the drinking of the solution while reducing the fluorine content in the solution, and can be used safely.
Namely, the defluorinating agent can not generate new pollution in the using process, can not bring aluminum and calcium contained in the defluorinating agent into the solution, the residue of iron is also in the safety standard range of drinking water, and the iron ions per se have no harm to human bodies. Therefore, the defluorinating agent can be used in various daily drinking solutions without worry, and the used liquid can be continuously drunk without being treated.
Comparative example 1
Cleaning ovum gallus Domesticus crusta, drying, crushing, and sieving. Egg shells with the size larger than 40 meshes are selected, 4.0g of the egg shells are weighed and put into a 50mL beaker. Adding 32mL of 0.01mol/L HCl solution, stirring with a magnetic stirrer for 15 minutes, adding a dilute NaOH solution to adjust the pH to 6.06, filtering, and drying. The mixture was placed in a muffle furnace and dried at 95 ℃ for about two hours. Taking out and naturally cooling. Washing the cooled solid with deionized water, removing powdery particles, keeping the eggshells, and naturally drying to obtain the unloaded eggshells.
Comparative example 2
Transferring 6.0mL0.5mol/L FeCl3·6H2The O solution was placed in a 50mL conical flask with a stopper, the activated egg shell was added, stirred with a magnetic stirrer for about fifteen minutes, and then diluted NaOH solution was added to adjust the pH to 5.56. Then transferring 6.0mL0.4mol/LAl2(SO4)3·12H2The O solution was added and stirred with a magnetic stirrer for about fifteen minutes. The pH was adjusted to 6.06 by addition of dilute NaOH solution and stirring was continued for about half an hour with a magnetic stirrer, the pH adjustment was ignored. Standing for two hours. Filtering to retain the solid portion comprising the eggshells. The mixture was placed in a muffle furnace and dried at 95 ℃ for about two hours. Taking out and naturally cooling. And washing the cooled solid by using deionized water, removing powdery particles, retaining the loaded eggshell, and naturally drying to obtain the Fe-Al loaded eggshell.
Comparative example 3
Transferring 6.0mL0.4mol/L Al2(SO4)3·12H2The O solution was placed in a 50mL conical flask with a stopper, the activated egg shell was added, stirred with a magnetic stirrer for about fifteen minutes, and then diluted NaOH solution was added to adjust the pH to 5.58. Then 6.0mL0.5mol/L FeCl is transferred3·6H2The O solution was added and stirred with a magnetic stirrer for about fifteen minutes. The pH was adjusted to 6.12 by addition of dilute NaOH solution and stirring was continued for about half an hour with a magnetic stirrer, the pH adjustment was ignored. Standing for two hours. Filtering to retain the solid portion comprising the eggshells. The mixture was placed in a muffle furnace and dried at 95 ℃ for about two hours. Taking out and naturally cooling. Washing the cooled solid with deionized water to remove powdery particles,and (4) keeping the loaded egg shells, and naturally drying to obtain the Al-Fe-loaded egg shells.
Comparative example 4
0.5mol/L FeCl3·6H2O solution and 0.4mol/L Al2(SO4)3·12H2The O solution was mixed, 16.0mL was removed in a 50mL conical flask with a stopper, and the activated egg shell was added and stirred with a magnetic stirrer for about half an hour. The pH was adjusted to 6.02 by adding dilute NaOH solution and stirring was continued for about half an hour with a magnetic stirrer, the pH adjustment was ignored. Standing for two hours. Filtering to retain the solid portion comprising the eggshells. The mixture was placed in a muffle furnace and dried at 95 ℃ for about two hours. Taking out and naturally cooling. And washing the cooled solid by using deionized water, removing powdery particles, retaining the loaded egg shells, and naturally drying to obtain the egg shells loaded with Al and Fe at the same time.
0.40 g of the eggshells prepared in the four different ways are accurately weighed and placed into 20.00mL of prepared 10.0mg/L sodium fluoride solution which is accurately moved, after the eggshells are kept still for twenty minutes, 10.00mL of the solution is moved into a tetrafluoroethylene cup by a pipette, 10.00mL of buffer solution (TISAB) is added, and the potential of the solution is measured. The adsorption capacity of each adsorbent was calculated by comparing the change in potential before and after the use of the adsorbent. The results are summarized in Table 6.
TABLE 6 determination of the adsorption capacities of different adsorbents in a high-fluorine solution
As can be seen from table 6, the adsorption capacity of the eggshells loaded with Al and Fe was significantly improved compared to the eggshells not loaded. Comparing the simultaneous loading of Al and Fe with the sequential loading of Al and Fe in different orders, the discovery shows that the eggshell loaded with Al and Fe has the largest adsorption capacity, the fluorine content in the solution can be reduced to below 1.0mg/L, the fluorine content standard of drinking water specified by the national standard is reached, the using effect is the best, and the eggshells loaded sequentially can not reach the standard. According to earlier experiments and theoretical calculation, when the defluorinating agent is formed, the pH value of the environment influences the precipitation of the adsorbentThe key factor of adsorption fluorine removal. When iron ions or aluminum ions are loaded on the eggshells firstly, in order to ensure the quality of the iron ions or aluminum ions deposited on the surfaces of the eggshells, the pH value is required to be adjusted to achieve the purpose of forming and using at present. But Fe3+Complete precipitation at pH 3.7, Al3+The metal ions are completely precipitated when the pH value is 4.0, so that the metal ions loaded later can be precipitated when entering the solution, only a small part of the metal ions can be attached to the outer surface of the defluorinating agent, the effect of coagulating precipitation of the aluminum-iron salt cannot be achieved, and the metal ions can easily fall off. Not only increases the production steps and wastes raw materials, but also can not achieve the best use effect. In the selection of the two metals, although the defluorination capacity of aluminum ions is higher than that of iron ions, in view of drinking safety, a moderate proportional relationship is selected in order to ensure that the loaded aluminum ions do not dissolve or fall into the solution during use. In conclusion, the eggshell loaded with the Al and the Fe can reach the standard of safe use, and the effect is better than that of other modes of loading the Al and the Fe.
The above-described embodiments are merely preferred embodiments of the present invention, and should not be construed as limiting the present invention, and features in the embodiments and examples in the present application may be arbitrarily combined with each other without conflict. The protection scope of the present invention is defined by the claims, and includes equivalents of technical features of the claims. I.e., equivalent alterations and modifications within the scope hereof, are also intended to be within the scope of the invention.
Claims (10)
1. The drinking water defluorinating agent is characterized in that waste egg shells are used as raw materials, a solid defluorinating agent loaded with iron and aluminum is used as the drinking water defluorinating agent, and FeCl is used as a solution loaded with iron and aluminum3·6H2O solution and Al2(SO4)3·12H2Solution of O, FeCl3·6H2The concentration of the O solution is 0.45-0.55mol/L, and Al2(SO4)3·12H2The concentration of the O solution is 0.3-0.5 mol/L.
2. The drinking water defluorinating agent as set forth in claim 1, wherein said egg shells are selected from raw egg shells that are clean, non-corrosive, and free of biofilm removal.
3. A method for preparing a drinking water fluorine removal agent is characterized by comprising the following steps:
1) cleaning raw egg shell, drying, crushing, and sieving;
2) selecting 10-40 mesh raw egg shells into a beaker, adding HCl solution for activation treatment, and stirring to obtain activated egg shells;
3) taking out the activated egg shell, washing to be neutral, adding 0.45-0.55mol/LFeCl3·6H2O solution and 0.3-0.5mol/LAl2(SO4)3·12H21 of O solution: 1, stirring the mixed solution, adding NaOH solution to adjust the pH, continuing stirring, standing and filtering, and reserving a solid part containing egg shells;
and drying, washing and drying to obtain the fluorine removal agent.
4. The preparation method of claim 3, wherein in the step 2), the concentration of the HCl solution is 0.005-0.015mol/L, the solid-to-liquid ratio of the eggshell to the HCl solution is (1:4) - (1:10) during the activation process, and the activation treatment time is 10-20 minutes.
5. The method according to claim 3, wherein FeCl is added in the step 3)3·6H2O solution and Al2(SO4)3·12H2And stirring the mixed solution of the O solution for half an hour by using a magnetic stirrer, adjusting the pH, continuing stirring for half an hour, and standing.
6. The method of claim 3, wherein in step 3), the pH is adjusted to 5.5-6.5.
7. The fluorine removing agent of any one of claims 1 to 2 or the fluorine removing agent prepared by the method of any one of claims 3 to 6 is used for removing fluorine ions in high fluorine tea soup.
8. A method of treating a fluorine-containing compound according to any one of claims 1 to 2 or a fluorine-containing compound produced by the method according to any one of claims 3 to 6 for reuse, wherein: the method comprises the steps of putting the used defluorinating agent into a hot saturated baking soda solution, washing for 2-3 times, taking out and drying.
9. The treatment method according to claim 8, wherein the solid-to-liquid ratio of the fluorine removal agent to the saturated baking soda solution is 1 (20-25).
10. The process according to claim 8, characterized in that the saturated baking soda solution has a temperature of 70-90 ℃ and a washing time of 0.4-2 hours.
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