CN116272862A - Efficient fluoride ion adsorbent, preparation method and application - Google Patents
Efficient fluoride ion adsorbent, preparation method and application Download PDFInfo
- Publication number
- CN116272862A CN116272862A CN202310138883.1A CN202310138883A CN116272862A CN 116272862 A CN116272862 A CN 116272862A CN 202310138883 A CN202310138883 A CN 202310138883A CN 116272862 A CN116272862 A CN 116272862A
- Authority
- CN
- China
- Prior art keywords
- phosphogypsum
- powder
- calcium
- biochar
- fluoride ion
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 239000003463 adsorbent Substances 0.000 title claims abstract description 53
- KRHYYFGTRYWZRS-UHFFFAOYSA-M Fluoride anion Chemical compound [F-] KRHYYFGTRYWZRS-UHFFFAOYSA-M 0.000 title claims abstract description 46
- 238000002360 preparation method Methods 0.000 title claims abstract description 28
- PASHVRUKOFIRIK-UHFFFAOYSA-L calcium sulfate dihydrate Chemical compound O.O.[Ca+2].[O-]S([O-])(=O)=O PASHVRUKOFIRIK-UHFFFAOYSA-L 0.000 claims abstract description 160
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 claims abstract description 95
- 239000011575 calcium Substances 0.000 claims abstract description 95
- 229910052791 calcium Inorganic materials 0.000 claims abstract description 95
- 239000000843 powder Substances 0.000 claims abstract description 79
- 239000011737 fluorine Substances 0.000 claims abstract description 49
- 229910052731 fluorine Inorganic materials 0.000 claims abstract description 49
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 claims abstract description 43
- 239000002994 raw material Substances 0.000 claims abstract description 37
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 35
- 238000000034 method Methods 0.000 claims abstract description 32
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 claims abstract description 30
- 238000001035 drying Methods 0.000 claims abstract description 26
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 claims abstract description 24
- 239000000203 mixture Substances 0.000 claims abstract description 23
- 238000007873 sieving Methods 0.000 claims abstract description 21
- 239000002699 waste material Substances 0.000 claims abstract description 21
- OSGAYBCDTDRGGQ-UHFFFAOYSA-L calcium sulfate Chemical compound [Ca+2].[O-]S([O-])(=O)=O OSGAYBCDTDRGGQ-UHFFFAOYSA-L 0.000 claims abstract description 18
- 239000008367 deionised water Substances 0.000 claims abstract description 17
- 229910021641 deionized water Inorganic materials 0.000 claims abstract description 17
- 238000002156 mixing Methods 0.000 claims abstract description 16
- 229910000019 calcium carbonate Inorganic materials 0.000 claims abstract description 15
- 238000000227 grinding Methods 0.000 claims abstract description 14
- 238000003756 stirring Methods 0.000 claims abstract description 14
- 238000005406 washing Methods 0.000 claims abstract description 14
- 235000017557 sodium bicarbonate Nutrition 0.000 claims abstract description 12
- 229910000030 sodium bicarbonate Inorganic materials 0.000 claims abstract description 12
- 230000007935 neutral effect Effects 0.000 claims abstract description 7
- 238000001132 ultrasonic dispersion Methods 0.000 claims abstract description 6
- 238000000197 pyrolysis Methods 0.000 claims description 20
- 239000002351 wastewater Substances 0.000 claims description 13
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 12
- 238000010926 purge Methods 0.000 claims description 12
- 238000010438 heat treatment Methods 0.000 claims description 9
- 244000025352 Artocarpus heterophyllus Species 0.000 claims description 8
- 235000008725 Artocarpus heterophyllus Nutrition 0.000 claims description 8
- 229910052757 nitrogen Inorganic materials 0.000 claims description 6
- 244000099147 Ananas comosus Species 0.000 claims description 5
- 235000007119 Ananas comosus Nutrition 0.000 claims description 5
- 239000006228 supernatant Substances 0.000 claims description 5
- 238000005303 weighing Methods 0.000 claims description 5
- 235000004936 Bromus mango Nutrition 0.000 claims description 4
- 240000007228 Mangifera indica Species 0.000 claims description 4
- 235000014826 Mangifera indica Nutrition 0.000 claims description 4
- 235000009184 Spondias indica Nutrition 0.000 claims description 4
- 240000008790 Musa x paradisiaca Species 0.000 claims description 3
- 235000018290 Musa x paradisiaca Nutrition 0.000 claims description 3
- 235000009754 Vitis X bourquina Nutrition 0.000 claims description 3
- 235000012333 Vitis X labruscana Nutrition 0.000 claims description 3
- 240000006365 Vitis vinifera Species 0.000 claims description 3
- 235000014787 Vitis vinifera Nutrition 0.000 claims description 3
- 238000004519 manufacturing process Methods 0.000 claims 1
- 239000002910 solid waste Substances 0.000 abstract description 3
- 238000001179 sorption measurement Methods 0.000 description 37
- -1 fluoride ions Chemical class 0.000 description 9
- 239000000463 material Substances 0.000 description 6
- 238000002441 X-ray diffraction Methods 0.000 description 3
- 238000010586 diagram Methods 0.000 description 3
- 238000004062 sedimentation Methods 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 238000004065 wastewater treatment Methods 0.000 description 3
- UXVMQQNJUSDDNG-UHFFFAOYSA-L Calcium chloride Chemical group [Cl-].[Cl-].[Ca+2] UXVMQQNJUSDDNG-UHFFFAOYSA-L 0.000 description 2
- 239000004343 Calcium peroxide Substances 0.000 description 2
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 2
- 239000001110 calcium chloride Substances 0.000 description 2
- 229910001628 calcium chloride Inorganic materials 0.000 description 2
- LHJQIRIGXXHNLA-UHFFFAOYSA-N calcium peroxide Chemical compound [Ca+2].[O-][O-] LHJQIRIGXXHNLA-UHFFFAOYSA-N 0.000 description 2
- 235000019402 calcium peroxide Nutrition 0.000 description 2
- 230000001112 coagulating effect Effects 0.000 description 2
- 239000003651 drinking water Substances 0.000 description 2
- 235000020188 drinking water Nutrition 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000003344 environmental pollutant Substances 0.000 description 2
- 238000005342 ion exchange Methods 0.000 description 2
- 239000012528 membrane Substances 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 239000002686 phosphate fertilizer Substances 0.000 description 2
- 229910052698 phosphorus Inorganic materials 0.000 description 2
- 239000011574 phosphorus Substances 0.000 description 2
- 231100000719 pollutant Toxicity 0.000 description 2
- 230000000630 rising effect Effects 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- 238000006467 substitution reaction Methods 0.000 description 2
- NWUYHJFMYQTDRP-UHFFFAOYSA-N 1,2-bis(ethenyl)benzene;1-ethenyl-2-ethylbenzene;styrene Chemical compound C=CC1=CC=CC=C1.CCC1=CC=CC=C1C=C.C=CC1=CC=CC=C1C=C NWUYHJFMYQTDRP-UHFFFAOYSA-N 0.000 description 1
- BHPQYMZQTOCNFJ-UHFFFAOYSA-N Calcium cation Chemical compound [Ca+2] BHPQYMZQTOCNFJ-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 206010028980 Neoplasm Diseases 0.000 description 1
- 208000012902 Nervous system disease Diseases 0.000 description 1
- 206010033799 Paralysis Diseases 0.000 description 1
- 206010061481 Renal injury Diseases 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
- 238000004458 analytical method Methods 0.000 description 1
- 150000001450 anions Chemical class 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000008468 bone growth Effects 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical compound [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 description 1
- 201000011510 cancer Diseases 0.000 description 1
- 238000011109 contamination Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000006115 defluorination reaction Methods 0.000 description 1
- 208000002925 dental caries Diseases 0.000 description 1
- 201000010099 disease Diseases 0.000 description 1
- 208000037265 diseases, disorders, signs and symptoms Diseases 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000003337 fertilizer Substances 0.000 description 1
- 229910021389 graphene Inorganic materials 0.000 description 1
- 229910001385 heavy metal Inorganic materials 0.000 description 1
- 229910052588 hydroxylapatite Inorganic materials 0.000 description 1
- 208000000509 infertility Diseases 0.000 description 1
- 230000036512 infertility Effects 0.000 description 1
- 231100000535 infertility Toxicity 0.000 description 1
- 239000003014 ion exchange membrane Substances 0.000 description 1
- 239000003456 ion exchange resin Substances 0.000 description 1
- 229920003303 ion-exchange polymer Polymers 0.000 description 1
- 208000037806 kidney injury Diseases 0.000 description 1
- 238000012423 maintenance Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 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 1
- 239000011148 porous material Substances 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 239000011573 trace mineral Substances 0.000 description 1
- 235000013619 trace mineral Nutrition 0.000 description 1
- 238000003911 water pollution Methods 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
- B01J20/20—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising free carbon; comprising carbon obtained by carbonising processes
-
- 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
- B01J20/04—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
- B01J20/045—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 sulfur, e.g. sulfates, thiosulfates, gypsum
-
- 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
- B01J20/30—Processes for preparing, regenerating, or reactivating
- B01J20/3021—Milling, crushing or grinding
-
- 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
- B01J20/30—Processes for preparing, regenerating, or reactivating
- B01J20/3071—Washing or leaching
-
- 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
- B01J20/30—Processes for preparing, regenerating, or reactivating
- B01J20/3078—Thermal treatment, e.g. calcining or pyrolizing
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/28—Treatment of water, waste water, or sewage by sorption
- C02F1/288—Treatment of water, waste water, or sewage by sorption using composite sorbents, e.g. coated, impregnated, multi-layered
-
- 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
- B01J2220/4887—Residues, wastes, e.g. garbage, municipal or industrial sludges, compost, animal manure; fly-ashes
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/10—Inorganic compounds
- C02F2101/12—Halogens or halogen-containing compounds
- C02F2101/14—Fluorine or fluorine-containing compounds
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Analytical Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Inorganic Chemistry (AREA)
- Thermal Sciences (AREA)
- Physics & Mathematics (AREA)
- Life Sciences & Earth Sciences (AREA)
- Hydrology & Water Resources (AREA)
- Engineering & Computer Science (AREA)
- Environmental & Geological Engineering (AREA)
- Water Supply & Treatment (AREA)
- Solid-Sorbent Or Filter-Aiding Compositions (AREA)
Abstract
The invention provides a high-efficiency fluoride ion adsorbent, a preparation method and application thereof, wherein the method comprises the following steps: washing the collected pericarp waste with water, drying to constant weight, grinding into powder, and sieving with 100 mesh sieve to obtain biochar raw material; drying phosphogypsum to constant weight, grinding the phosphogypsum into powder, sieving the powder with a 100-mesh sieve to obtain phosphogypsum powder, mixing sodium bicarbonate solution and the phosphogypsum powder, stirring the mixture until calcium sulfate in the phosphogypsum powder is converted into calcium carbonate, washing the calcium carbonate with deionized water to be neutral, drying the calcium carbonate to constant weight, and finally crushing the calcium carbonate powder and sieving the crushed calcium carbonate powder with the 100-mesh sieve to obtain phosphogypsum calcium powder; mixing the biochar raw material with phosphogypsum calcium powder according to a preset proportion to obtain a raw material mixture, adding deionized water into the raw material mixture, stirring, then performing ultrasonic dispersion for 30min, and drying and pyrolyzing to obtain the phosphogypsum calcium-based biochar. The invention can realize harmless utilization of solid waste and has great significance in the field of fluorine pollution treatment.
Description
Technical Field
The invention relates to the technical field of chemical adsorbent preparation, in particular to a high-efficiency fluoride ion adsorbent, a preparation method and application.
Background
Fluorine is an essential trace element for human body, and trace fluorine can promote bone growth and prevent dental caries, but excessive fluorine can threaten physical health, for example, cause diseases such as floxuan, fluorimatosis, nervous system diseases and paralysis, cancer, kidney injury and infertility. For this country, strict requirements are imposed on the concentration of fluoride ions in water, and the latest revision of sanitary Standard for Drinking Water (GB 5749-2022) prescribes that the concentration of fluoride in drinking water should not exceed 1.0mg/L, and the national Integrated wastewater discharge Standard (GB 8978-1996) prescribes that the maximum allowable discharge concentration be 10mg/L. Therefore, the removal of fluorine contamination has been receiving close attention in the field of environmental protection.
The method for removing the fluoride ions in the water body comprises a coagulating sedimentation method, an ion exchange method, a membrane separation method and an adsorption method. Specifically, the coagulating sedimentation method is greatly limited by factors such as equipment conditions, sedimentation time operation and the like, has poor specificity for removing fluorine ions, and is easily influenced by other anions to cause unstable water quality of effluent; the ion exchange method and the membrane separation method have complex equipment operation, high operation and maintenance cost, high cost of common ion exchange resin and membrane, secondary pollution and the like; the adsorption method for removing fluorine has been paid close attention to widely because of its advantages of simple process and high treatment efficiency.
The common adsorbent has small adsorption quantity to fluorine, and the common adsorbent has the defects of difficult preparation, high cost, poor applicability and the like. Therefore, the adsorbent with low cost, strong applicability and high adsorption efficiency is far-reaching in the removal of fluorine ions in water. Common calcium source for calcium-based biochar is calcium chloride (CaCl) 2 ) Calcium hydroxide (Ca (OH) 2 ) Calcium peroxide (CaO) 2 ) And the like, which are all calcium-based by using chemicals as biochar, have relatively high cost, and the main component in phosphogypsum is CaSO 4 ·2H 2 O, phosphogypsum itself belongs to solid waste, and the cost of the phosphogypsum as a calcium source is negligible, but the existence of pollutants such as fluoride, phosphorus, heavy metal and the like contained in the phosphogypsum itself needs to be considered. For example, the Chinese patent publication No. CN108927109B, a phosphogypsum modified biochar method and application thereof only consider the adsorption effect of the prepared material on phosphorus, do not pretreat phosphogypsum, and do not study the release condition of the material on water pollution in the adsorption process, and ignore other secondary pollution possibly brought to water in the adsorption process. With the development of agriculture, the demand of chemical fertilizers is rising year by year, phosphogypsum is used as a byproduct of the phosphate fertilizer industry, the yield is rising year by year, and phosphogypsum in the phosphate fertilizer industry is mainly accumulated in an open-air field, has almost no utilization value, and also can pollute the environment, so that the harmless utilization of phosphogypsum is significant.
Based on the above, in order to improve the adsorption performance of the adsorbent and reduce the secondary pollution of the adsorbent, it is necessary to provide a high-efficiency fluoride ion adsorbent, a preparation method and application thereof, so as to solve the potential problem of using phosphogypsum in the preparation of the adsorbent, and fully utilize the calcium element in the phosphogypsum.
Disclosure of Invention
Based on the above, the invention aims to provide a high-efficiency fluoride ion adsorbent, a preparation method and application thereof, so as to improve the adsorption performance of the adsorbent and reduce the secondary pollution of the adsorbent.
Specifically, the invention provides a preparation method of a high-efficiency fluoride ion adsorbent, wherein the high-efficiency fluoride ion adsorbent is phosphogypsum calcium-based biochar, and the method comprises the following steps:
step one, peel waste treatment:
washing the collected pericarp waste with water, then controlling the temperature to be dried to constant weight at the first temperature, grinding the pericarp waste into powder, and sieving the powder with a 100-mesh sieve to obtain a biochar raw material;
step two, extracting a calcium source:
drying phosphogypsum at a second temperature to constant weight, grinding the phosphogypsum into powder, sieving the powder with a 100-mesh sieve to obtain phosphogypsum powder, mixing sodium bicarbonate solution and the phosphogypsum powder, stirring the mixture until calcium sulfate in the phosphogypsum powder is converted into calcium carbonate, washing the calcium carbonate with deionized water to be neutral, continuously drying the phosphogypsum at the second temperature to constant weight, and finally crushing the phosphogypsum powder and sieving the crushed phosphogypsum powder with the 100-mesh sieve to obtain phosphogypsum calcium powder;
preparing phosphogypsum calcium-based biochar:
mixing the biochar raw material prepared in the first step with phosphogypsum calcium powder prepared in the second step according to a preset proportion to obtain a raw material mixture, adding deionized water into the raw material mixture, stirring, performing ultrasonic dispersion for 30min, and controlling the temperature to be at a third temperature for drying and pyrolysis to obtain the phosphogypsum calcium-based biochar.
The preparation method of the efficient fluoride ion adsorbent comprises the steps of enabling the first temperature, the second temperature and the third temperature to be 105 ℃.
The preparation method of the efficient fluoride ion adsorbent comprises the steps of pineapple peel, jackfruit peel, grape peel, orange peel, banana peel and mango peel.
The preparation method of the efficient fluoride ion adsorbent comprises the step two, wherein the mass concentration of the sodium bicarbonate solution is 10%.
In the third step, the mass ratio of the biochar raw material to phosphogypsum calcium powder in the raw material mixture is 1:4-2:1.
The preparation method of the efficient fluoride ion adsorbent comprises the step three, wherein the mass ratio of the added deionized water to the raw material mixture is 2:1.
The preparation method of the efficient fluoride ion adsorbent comprises the following steps of:
and (3) carrying out pyrolysis by adopting a tube furnace, keeping nitrogen purging during pyrolysis, controlling the purging rate to be 0.5L/min, heating the pyrolysis furnace to be 5 ℃/min, and keeping the pyrolysis furnace at 800 ℃ for 120min to finish pyrolysis operation.
The invention also provides a high-efficiency fluoride ion adsorbent, wherein the high-efficiency fluoride ion adsorbent is phosphogypsum calcium-based biochar, and the phosphogypsum calcium-based biochar is prepared by adopting the preparation method.
The invention also provides application of the high-efficiency fluoride ion adsorbent, wherein the high-efficiency fluoride ion adsorbent is phosphogypsum calcium-based biochar, and the phosphogypsum calcium-based biochar is prepared by adopting the preparation method;
the application comprises: and (3) treating the fluorine-containing wastewater by using the high-efficiency fluoride ion adsorbent.
The application of the high-efficiency fluoride ion adsorbent, wherein the method for treating the fluoride-containing wastewater by using the high-efficiency fluoride ion adsorbent specifically comprises the following steps:
weighing 0.025g phosphogypsum calcium-based biochar, putting the phosphogypsum calcium-based biochar into 50ml of wastewater containing 100mg/L of fluorine, and then putting the wastewater into a vibrator at 25 ℃ to vibrate for 24 hours, wherein the vibration speed is 200r/min;
and standing after the vibration is finished, and taking supernatant to determine the fluorine concentration in the solution.
The invention provides a preparation method of a high-efficiency fluoride ion adsorbent, which has the following beneficial effects:
1. the sodium bicarbonate is used for modifying phosphogypsum, calcium sulfate in the phosphogypsum is converted into indissolvable calcium carbonate, so that pollutants contained in the phosphogypsum can be effectively eluted, calcium in the phosphogypsum is fully utilized, the purpose of treating waste with waste is achieved, and the pollution of the phosphogypsum to the environment is fully relieved;
2. the phosphogypsum calcium-based biochar prepared by the method can efficiently remove fluoride ions in water, has the adsorption capacity of 133mg/g to fluorine, has large specific surface area and has adsorption performance exceeding that of most of the existing adsorbents;
3. the phosphogypsum calcium-based biochar prepared by the method has higher adsorption capacity (all larger than 117 mg/g) in different pH ranges (3-11), is high in adsorption efficiency, low in preparation cost and simple in process, and has the advantages of high efficiency in defluorination and strong applicability.
Additional features and advantages of the disclosure will be set forth in the description which follows, or in part will be obvious from the description, or may be learned by practice of the techniques of the disclosure.
In order to make the above objects, features and advantages of the present invention more comprehensible, preferred embodiments accompanied with figures are described in detail below.
Drawings
FIG. 1 is an X-ray diffraction pattern (XRD) of phosphogypsum and phosphogypsum calcium powder in the present invention;
FIG. 2 is a graph showing the comparison of the adsorption performance of materials with different components, wherein the adsorption amount of fluorine in the first embodiment changes with the equilibrium concentration of fluorine in wastewater;
FIG. 3 is a schematic diagram of the amount of fluorine adsorbed by phosphogypsum calcium-based biochar in fluorine-containing wastewater under different pH (3-11) conditions;
FIG. 4 is an SEM scanning image of jackfruit peel biochar and phosphogypsum calcium-based biochar according to the first embodiment of the present invention;
FIG. 5 is an SEM-EDS diagram of phosphogypsum calcium-based biochar after saturation of fluorine adsorption.
Detailed Description
In order that the invention may be readily understood, a more complete description of the invention will be rendered by reference to the appended drawings. Preferred embodiments of the present invention are shown in the drawings. This invention may, however, be embodied in many different forms and should not be construed as limited to the embodiments set forth herein. Rather, these embodiments are provided so that this disclosure will be thorough and complete.
Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. The terminology used herein in the description of the invention is for the purpose of describing particular embodiments only and is not intended to be limiting of the invention. The term "and/or" as used herein includes any and all combinations of one or more of the associated listed items.
The invention provides a preparation method of a high-efficiency fluoride ion adsorbent, wherein the high-efficiency fluoride ion adsorbent is phosphogypsum calcium-based biochar, and the method comprises the following steps:
step one, peel waste treatment:
and (3) washing the collected pericarp waste with water, drying at a first temperature to constant weight, grinding into powder, and sieving with a 100-mesh sieve to obtain the biochar raw material.
In this step, the peel waste includes pineapple peel, jackfruit peel, grape peel, orange peel, banana peel and mango peel. It should be noted that the peel waste is not limited to the above listed ones, and the peel waste meeting the requirements may be selected according to the actual situation.
Step two, extracting a calcium source:
and (3) drying phosphogypsum at a second temperature to constant weight, grinding the phosphogypsum into powder, sieving the powder with a 100-mesh sieve to obtain phosphogypsum powder, mixing and stirring the phosphogypsum powder with sodium bicarbonate solution until calcium sulfate in the phosphogypsum powder is converted into calcium carbonate, washing the phosphogypsum powder to be neutral by deionized water, continuously drying the phosphogypsum powder at the second temperature to constant weight, and finally crushing the phosphogypsum powder and sieving the crushed phosphogypsum powder with the 100-mesh sieve to obtain phosphogypsum calcium powder.
In this step, the mass concentration of sodium bicarbonate solution was 10%.
Preparing phosphogypsum calcium-based biochar:
mixing the biochar raw material prepared in the first step with phosphogypsum calcium powder prepared in the second step according to a preset proportion to obtain a raw material mixture, adding deionized water into the raw material mixture, stirring, performing ultrasonic dispersion for 30min, and controlling the temperature to be at a third temperature for drying and pyrolysis to obtain the phosphogypsum calcium-based biochar.
In the present invention, the first temperature, the second temperature, and the third temperature are all 105 ℃. In addition, in the raw material mixture, the mass ratio of the biochar raw material to phosphogypsum calcium powder is 1:4-2:1, and the mass ratio of the added deionized water to the raw material mixture is 2:1.
Meanwhile, the method for performing pyrolysis includes the steps of:
and (3) carrying out pyrolysis by adopting a tube furnace, keeping nitrogen purging during pyrolysis, controlling the purging rate to be 0.5L/min, heating the pyrolysis furnace to be 5 ℃/min, and keeping the pyrolysis furnace at 800 ℃ for 120min to finish pyrolysis operation.
The invention also provides a high-efficiency fluoride ion adsorbent, wherein the high-efficiency fluoride ion adsorbent is phosphogypsum calcium-based biochar, and the phosphogypsum calcium-based biochar is prepared by adopting the preparation method.
The technical scheme of the invention is described in detail below by using a few specific embodiments.
Example 1:
the invention provides a preparation method of a high-efficiency fluoride ion adsorbent, which comprises the following steps:
(1) And (3) peel waste treatment:
washing the collected jackfruit peel with water, then controlling the temperature to be 105 ℃ and drying to constant weight, grinding the jackfruit peel into powder, and sieving the powder with a 100-mesh sieve to obtain a biochar raw material;
(2) Extracting a calcium source:
drying phosphogypsum at 105 ℃ to constant weight, grinding the phosphogypsum into powder, sieving the powder with a 100-mesh sieve to obtain phosphogypsum powder, mixing and stirring the phosphogypsum powder with excessive sodium bicarbonate solution with the mass fraction of 10% until calcium sulfate in the phosphogypsum is converted into calcium carbonate, washing the phosphogypsum to be neutral by deionized water, continuously drying the phosphogypsum at 105 ℃ to constant weight, and finally crushing the phosphogypsum powder and sieving the crushed phosphogypsum powder with the 100-mesh sieve to obtain phosphogypsum calcium powder;
(3) Preparing phosphogypsum calcium-based biochar:
mixing biochar raw materials and phosphogypsum calcium powder according to a mass ratio of 1:1 to obtain a raw material mixture, adding deionized water into the raw material mixture, stirring, then performing ultrasonic dispersion for 30min, drying at 105 ℃, pyrolyzing by a tube furnace, keeping nitrogen purging during pyrolysis, wherein the purging rate is 0.5L/min, the heating rate is 5 ℃/min, and keeping for 120min after heating to 800 ℃ to obtain the phosphogypsum calcium-based biochar.
Fluorine-containing wastewater treatment:
in this embodiment, after the phosphogypsum calcium-based biochar is prepared, the prepared phosphogypsum calcium-based biochar is used for treating the fluorine-containing wastewater, and the specific method comprises the following steps:
weighing 0.025g phosphogypsum calcium-based biochar, putting the phosphogypsum calcium-based biochar into 50ml of 100mg/L fluorine-containing water (calculated by fluorine), and putting the phosphogypsum calcium-based biochar into a vibrator at 25 ℃ to vibrate for 24 hours, wherein the vibration speed is 200r/min;
and standing after the vibration is finished, and taking supernatant to determine the fluorine concentration in the solution.
The phosphogypsum calcium-based biochar prepared by the first embodiment of the invention has a plurality of active adsorption sites and high adsorption efficiency, and the specific surface area measured by a specific surface area analyzer is 124.3126m 2 The adsorption quantity of the fluorine ions per gram is 133mg/g, and the adsorption quantity of the fluorine ions per gram is larger (more than 117 mg/g) under different initial pH conditions, so that the fluorine-removing adsorbent has strong applicability and high efficiency.
Example 2:
the invention provides a preparation method of a high-efficiency fluoride ion adsorbent, which comprises the following steps:
(1) And (3) peel waste treatment:
washing the collected mango peel with water, drying at 105 ℃ to constant weight, grinding into powder, and sieving with a 100-mesh sieve to obtain a biochar raw material;
(2) Extracting a calcium source:
drying phosphogypsum at 105 ℃ to constant weight, grinding the phosphogypsum into powder, sieving the powder with a 100-mesh sieve to obtain phosphogypsum powder, mixing and stirring the phosphogypsum powder with excessive sodium bicarbonate solution with the mass fraction of 10% until calcium sulfate in the phosphogypsum is converted into calcium carbonate, washing the phosphogypsum to be neutral by deionized water, continuously drying the phosphogypsum at 105 ℃ to constant weight, and finally crushing the phosphogypsum powder and sieving the crushed phosphogypsum powder with the 100-mesh sieve to obtain phosphogypsum calcium powder;
(3) Preparing phosphogypsum calcium-based biochar:
mixing biochar raw materials and phosphogypsum calcium powder according to a mass ratio of 2:1 to obtain a raw material mixture, adding deionized water into the raw material mixture, stirring, then performing ultrasonic dispersion for 30min, drying at 105 ℃, pyrolyzing by a tube furnace, keeping nitrogen purging during pyrolysis, wherein the purging rate is 0.5L/min, the heating rate is 5 ℃/min, and keeping 120min after heating to 800 ℃ to obtain the phosphogypsum calcium-based biochar.
Fluorine-containing wastewater treatment:
in this embodiment, after the phosphogypsum calcium-based biochar is prepared, the prepared phosphogypsum calcium-based biochar is used for treating the fluorine-containing wastewater, and the specific method comprises the following steps:
weighing 0.025g phosphogypsum calcium-based biochar, putting the phosphogypsum calcium-based biochar into 50ml of 100mg/L fluorine-containing water (calculated by fluorine), and putting the phosphogypsum calcium-based biochar into a vibrator at 25 ℃ to vibrate for 24 hours, wherein the vibration speed is 200r/min;
and standing after the vibration is finished, and taking supernatant to determine the fluorine concentration in the solution.
The phosphogypsum calcium-based biochar prepared by the second embodiment of the invention has a plurality of active adsorption sites and high adsorption efficiency, and the specific surface area measured by a specific surface area analyzer is 56.9432m 2 The adsorption quantity of the fluorine ions per gram is 124mg/g, and the fluorine-removing adsorbent is high-efficiency.
Example 3:
the invention provides a preparation method of a high-efficiency fluoride ion adsorbent, which comprises the following steps:
(1) And (3) peel waste treatment:
washing the collected pineapple peel with water, then controlling the temperature to be 105 ℃ and drying to constant weight, grinding the pineapple peel into powder, and sieving the powder with a 100-mesh sieve to obtain a biochar raw material;
(2) Extracting a calcium source:
drying phosphogypsum at 105 ℃ to constant weight, grinding the phosphogypsum into powder, sieving the powder with a 100-mesh sieve to obtain phosphogypsum powder, mixing and stirring the phosphogypsum powder with excessive sodium bicarbonate solution with the mass fraction of 10% until calcium sulfate in the phosphogypsum is converted into calcium carbonate, washing the phosphogypsum to be neutral by deionized water, continuously drying the phosphogypsum at 105 ℃ to constant weight, and finally crushing the phosphogypsum powder and sieving the crushed phosphogypsum powder with the 100-mesh sieve to obtain phosphogypsum calcium powder;
(3) Preparing phosphogypsum calcium-based biochar:
the method comprises the following steps of (1) mixing biochar raw materials with phosphogypsum calcium powder according to a mass ratio of 1:2, mixing to obtain a raw material mixture, adding deionized water into the raw material mixture to stir and ultrasonically disperse for 30min, drying at 105 ℃, pyrolyzing by adopting a tube furnace, keeping nitrogen purging during pyrolysis, wherein the purging rate is 0.5L/min, the heating rate is 5 ℃/min, and keeping for 120min after heating to 800 ℃ to obtain phosphogypsum calcium-based biochar.
Fluorine-containing wastewater treatment:
weighing 0.025g phosphogypsum calcium-based biochar, putting the phosphogypsum calcium-based biochar into 50ml of 100mg/L fluorine-containing water (calculated by fluorine), and putting the phosphogypsum calcium-based biochar into a vibrator at 25 ℃ to vibrate for 24 hours, wherein the vibration speed is 200r/min;
and standing after the vibration is finished, and taking supernatant to determine the fluorine concentration in the solution.
The phosphogypsum calcium-based biochar prepared by the third embodiment of the invention has a plurality of active adsorption sites and high adsorption efficiency, and the specific surface area measured by a specific surface area analyzer is 28.4329m 2 The adsorption quantity per gram of fluorine ions is 117mg/g, and the fluorine-removing adsorbent is high-efficiency.
Analysis of experimental results:
referring to fig. 1, the X-ray diffraction patterns of phosphogypsum and phosphogypsum calcium powder in the first embodiment find that: the phosphogypsum is washed by sodium bicarbonate solution, so that calcium components in the phosphogypsum can be effectively extracted, and calcium sulfate is converted into calcium carbonate, thereby realizing harmless utilization of the phosphogypsum.
Referring to fig. 2, the removal result of fluorine in water by phosphogypsum calcium-based biochar in the first embodiment is as follows: compared with the common biochar, the phosphogypsum calcium-based biochar has the adsorption capacity improved by 13 times, and the adsorption capacity is improved from 10mg/g to 133mg/g. Meanwhile, compared with the prior other common adsorption materials (such as hydroxyapatite, activated alumina, metal organic frame material, metal-loaded graphene oxide and the like), the adsorption of fluorine has the following advantages that: the adsorption capacity of most of the existing adsorption materials for fluorine is 1.08-34mg/g, which is far smaller than that of phosphogypsum calcium-based biochar in the invention.
Referring to FIG. 3, a higher adsorption capacity (> 117 mg/g) is maintained at different pH values, thereby demonstrating: the phosphogypsum calcium-based biochar provided by the invention has good adsorption effect and stability on fluorine in water bodies under different conditions.
Referring to fig. 4, according to the SEM scanning of the jackfruit peel biochar and phosphogypsum calcium-based biochar in the first embodiment, it is found that: compared with jackfruit peel biochar, the surface of phosphogypsum calcium-based biochar is rougher, which indicates that phosphogypsum is loaded into the biochar.
Referring to fig. 5, according to SEM-EDS diagram after saturation of phosphogypsum calcium-based biochar fluorine adsorption, it is found that: after the phosphogypsum calcium-based biochar is saturated by adsorbing fluorine, a large amount of fluorine is precipitated on the surface of the phosphogypsum calcium-based biochar, which further shows that calcium in the phosphogypsum calcium-based biochar is an effective fluoride ion adsorption active site.
The phosphogypsum calcium-based biochar prepared by the method provided by the invention has the advantages that calcium is loaded on the surface and pores of the biochar in a cluster form, a large number of fluoride ion adsorption active sites are provided, and the phosphogypsum calcium-based biochar can be used for treating fluoride pollution. The invention provides a preparation method of a high-efficiency fluoride ion adsorbent, which takes phosphogypsum calcium powder and pericarp waste as raw materials, has low cost, simple process, high efficiency in removing fluorine, no secondary pollution, high efficiency and environment friendliness in adsorbing fluorine wastewater with different concentrations, can realize harmless utilization of solid waste and is a low-cost high-efficiency adsorbent for treating waste with waste, and has great significance in the field of fluorine pollution treatment.
Finally, it should be noted that: the above examples are only specific embodiments of the present invention, and are not intended to limit the scope of the present invention, but it should be understood by those skilled in the art that the present invention is not limited thereto, and that the present invention is described in detail with reference to the foregoing examples: any person skilled in the art may modify or easily conceive of the technical solution described in the foregoing embodiments, or perform equivalent substitution of some of the technical features, while remaining within the technical scope of the present disclosure; such modifications, changes or substitutions do not depart from the spirit and scope of the technical solutions of the embodiments of the present invention, and are intended to be included in the scope of the present invention. Therefore, the protection scope of the present invention shall be subject to the protection scope of the claims.
Claims (10)
1. The preparation method of the efficient fluoride ion adsorbent is characterized by comprising the following steps of:
step one, peel waste treatment:
washing the collected pericarp waste with water, then controlling the temperature to be dried to constant weight at the first temperature, grinding the pericarp waste into powder, and sieving the powder with a 100-mesh sieve to obtain a biochar raw material;
step two, extracting a calcium source:
drying phosphogypsum at a second temperature to constant weight, grinding the phosphogypsum into powder, sieving the powder with a 100-mesh sieve to obtain phosphogypsum powder, mixing sodium bicarbonate solution and the phosphogypsum powder, stirring the mixture until calcium sulfate in the phosphogypsum powder is converted into calcium carbonate, washing the calcium carbonate with deionized water to be neutral, continuously drying the phosphogypsum at the second temperature to constant weight, and finally crushing the phosphogypsum powder and sieving the crushed phosphogypsum powder with the 100-mesh sieve to obtain phosphogypsum calcium powder;
preparing phosphogypsum calcium-based biochar:
mixing the biochar raw material prepared in the first step with phosphogypsum calcium powder prepared in the second step according to a preset proportion to obtain a raw material mixture, and then mixing the raw materialsAdding deionized water into the mixture, stirring, and then performing ultrasonic dispersion 30 m i n And (3) drying and pyrolyzing at a third temperature to obtain phosphogypsum calcium-based biochar.
2. The method of claim 1, wherein the first temperature, the second temperature, and the third temperature are all 105 ℃.
3. The method of claim 2, wherein the peel waste comprises pineapple peel, jackfruit peel, grape peel, orange peel, banana peel and mango peel.
4. A method for producing a highly efficient fluoride ion adsorbent as claimed in claim 3, wherein in the second step, the mass concentration of the sodium bicarbonate solution is 10%.
5. The method according to claim 4, wherein in the third step, the mass ratio of biochar raw material to phosphogypsum calcium powder in the raw material mixture is 1:4-2:1.
6. The method of claim 5, wherein in the third step, the mass ratio of the deionized water to the raw material mixture is 2 ∶ 1。
7. The method for preparing a high efficiency fluorine ion adsorbent according to claim 6, wherein in the third step, the method for performing pyrolysis comprises the steps of:
pyrolysis is carried out by adopting a tube furnace, nitrogen purging is kept during pyrolysis, and the purging rate is controlled to be 0 - 5L/min, the heating rate is 5 ℃/min, and the pyrolysis operation is completed after the temperature is increased to 800 ℃ and maintained for 120 min.
8. A high-efficiency fluoride ion adsorbent, characterized in that the high-efficiency fluoride ion adsorbent is phosphogypsum calcium-based biochar, and the phosphogypsum calcium-based biochar is prepared by the preparation method according to any one of the claims 1 to 7.
9. The application of the efficient fluoride ion adsorbent is characterized in that the efficient fluoride ion adsorbent is phosphogypsum calcium-based biochar, and the phosphogypsum calcium-based biochar is prepared by the preparation method according to any one of the claims 1 to 7;
the application comprises: and (3) treating the fluorine-containing wastewater by using the high-efficiency fluoride ion adsorbent.
10. The use of a high-efficiency fluoride ion adsorbent according to claim 9, wherein the method for treating fluoride-containing wastewater using the high-efficiency fluoride ion adsorbent specifically comprises the following steps:
weighing 0.025g phosphogypsum calcium-based biochar, putting into 50ml of wastewater containing 100mg/L fluorine, and putting into a vibrator at 25 ℃ to vibrate for 24 hours at a vibration speed of 200 r / m in；
And standing after the vibration is finished, and taking supernatant to determine the fluorine concentration in the solution.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202310138883.1A CN116272862B (en) | 2023-02-20 | 2023-02-20 | Efficient fluoride ion adsorbent, preparation method and application |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202310138883.1A CN116272862B (en) | 2023-02-20 | 2023-02-20 | Efficient fluoride ion adsorbent, preparation method and application |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN116272862A true CN116272862A (en) | 2023-06-23 |
| CN116272862B CN116272862B (en) | 2024-09-20 |
Family
ID=86784373
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202310138883.1A Active CN116272862B (en) | 2023-02-20 | 2023-02-20 | Efficient fluoride ion adsorbent, preparation method and application |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN116272862B (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN117258763A (en) * | 2023-11-16 | 2023-12-22 | 山东吉昌龙环境工程有限公司 | Preparation method of efficient composite deep defluorinating agent |
Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS55129189A (en) * | 1979-03-30 | 1980-10-06 | Seiji Hashimoto | Treating method for waste water containing fluorine ion and phosphoric acid ion using carbonate-added carbide |
| CN102921384A (en) * | 2012-11-22 | 2013-02-13 | 天津理工大学 | Method for preparing high-efficiency fluorine removal agent from solid wastes |
| CN105251445A (en) * | 2015-11-04 | 2016-01-20 | 中国科学院化学研究所 | Porous carbon adsorbent as well as preparation method and application thereof |
| CN106732352A (en) * | 2016-11-16 | 2017-05-31 | 广州大学 | A kind of multiporous biological charcoal and its synthetic method and application |
| CN107213872A (en) * | 2017-07-20 | 2017-09-29 | 浙江农林大学 | A kind of preparation method of the hydro-thermal biomass carbon material of efficient absorption copper ion load calcium carbonate |
| CN108927109A (en) * | 2018-07-30 | 2018-12-04 | 中国科学院地球化学研究所 | A kind of phosphogypsum modification charcoal method and its application |
| CN110156061A (en) * | 2019-05-29 | 2019-08-23 | 湖北大学 | A method of micro-nano structure calcium carbonate and ammonium sulfate are prepared using waste phosphogypsum |
| US20200316560A1 (en) * | 2019-04-03 | 2020-10-08 | Calgon Carbon Corporation | Perfluoroalkyl and polyfluoroalkyl sorbent materials and methods of use |
-
2023
- 2023-02-20 CN CN202310138883.1A patent/CN116272862B/en active Active
Patent Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS55129189A (en) * | 1979-03-30 | 1980-10-06 | Seiji Hashimoto | Treating method for waste water containing fluorine ion and phosphoric acid ion using carbonate-added carbide |
| CN102921384A (en) * | 2012-11-22 | 2013-02-13 | 天津理工大学 | Method for preparing high-efficiency fluorine removal agent from solid wastes |
| CN105251445A (en) * | 2015-11-04 | 2016-01-20 | 中国科学院化学研究所 | Porous carbon adsorbent as well as preparation method and application thereof |
| CN106732352A (en) * | 2016-11-16 | 2017-05-31 | 广州大学 | A kind of multiporous biological charcoal and its synthetic method and application |
| CN107213872A (en) * | 2017-07-20 | 2017-09-29 | 浙江农林大学 | A kind of preparation method of the hydro-thermal biomass carbon material of efficient absorption copper ion load calcium carbonate |
| CN108927109A (en) * | 2018-07-30 | 2018-12-04 | 中国科学院地球化学研究所 | A kind of phosphogypsum modification charcoal method and its application |
| US20200316560A1 (en) * | 2019-04-03 | 2020-10-08 | Calgon Carbon Corporation | Perfluoroalkyl and polyfluoroalkyl sorbent materials and methods of use |
| CN110156061A (en) * | 2019-05-29 | 2019-08-23 | 湖北大学 | A method of micro-nano structure calcium carbonate and ammonium sulfate are prepared using waste phosphogypsum |
Non-Patent Citations (1)
| Title |
|---|
| L.A. RAMÍREZ-MONTOYA: "Preparation, characterization and analyses of carbons with natural and induced calcium compounds for the adsorption of fluoride", L.A. RAMÍREZ-MONTOYAA, no. 105, 24 October 2013 (2013-10-24), pages 75 - 82 * |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN117258763A (en) * | 2023-11-16 | 2023-12-22 | 山东吉昌龙环境工程有限公司 | Preparation method of efficient composite deep defluorinating agent |
| CN117258763B (en) * | 2023-11-16 | 2024-02-02 | 山东吉昌龙环境工程有限公司 | Preparation method of efficient composite deep defluorinating agent |
Also Published As
| Publication number | Publication date |
|---|---|
| CN116272862B (en) | 2024-09-20 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Yu et al. | Phosphate removal from domestic wastewater using thermally modified steel slag | |
| CN102626607A (en) | Preparation method and application of residual activated sludge adsorbent | |
| CN106976995A (en) | A kind of river sewage inorganic agent and preparation method | |
| CN110372075A (en) | A kind of new and effective fluorine removal medicament and its application | |
| CN106111055B (en) | A kind of synchronous denitrification dephosphorizing adsorbent and its preparation method and application | |
| CN106977123A (en) | A kind of citric acid for being used to remove impurity fluorine in ardealite adds water the process washed | |
| CN116272862B (en) | Efficient fluoride ion adsorbent, preparation method and application | |
| CN100500279C (en) | Denitrifying phosphorus-removing carrier and use | |
| JP5930535B2 (en) | Phosphorus recovery and fertilizer method | |
| CN103601313B (en) | Processing method of landfill leachate | |
| CN113145073A (en) | Preparation method and application of secondary lanthanum carbide modified sludge biochar | |
| CN109574166A (en) | A kind of sewage-treating agent and its preparation process | |
| CN106396308B (en) | Recycling method of residual activated sludge | |
| JP2009274040A (en) | Inorganic porous body, regeneration method of inorganic porous body, and manufacturing method of inorganic porous body | |
| CN113000025B (en) | Phosphorus removal adsorbent and preparation method and application thereof | |
| CN109928509A (en) | Black smelly bed mud cleanser of one kind and preparation method thereof | |
| CN109354209A (en) | A kind of modified mineral-microorganism coupling water-purifying material and preparation method thereof | |
| CN108636353A (en) | A kind of domestic sewage sludge/rectorite compound and its preparation method and application | |
| CN113856627A (en) | Preparation method and application of vinasse-based biochar for deep dechromization of wet-process phosphoric acid | |
| KR20120074942A (en) | Heavy metal absorbent and method for removing heavy metal using the same | |
| CN111115846A (en) | Sewage treatment agent for aquaculture wastewater and preparation method and application thereof | |
| CN117088479A (en) | Rapid defluorination medicament and preparation method thereof | |
| CN105330056B (en) | A kind of aluminum products polish the integrated conduct method of waste water | |
| CN115400744A (en) | Method for preparing phosphorus adsorbent from sludge ash | |
| CN114733486A (en) | Preparation method of phosphorus-removing modified biochar |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |