CN106512936B - A kind of hydro-thermal method prepares de-fluoridation adsorbent and its application - Google Patents
A kind of hydro-thermal method prepares de-fluoridation adsorbent and its application Download PDFInfo
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- CN106512936B CN106512936B CN201610993793.0A CN201610993793A CN106512936B CN 106512936 B CN106512936 B CN 106512936B CN 201610993793 A CN201610993793 A CN 201610993793A CN 106512936 B CN106512936 B CN 106512936B
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- biomass carbon
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- fluoridation adsorbent
- composite oxides
- nitrogen protection
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- 239000003463 adsorbent Substances 0.000 title claims abstract description 39
- 238000004334 fluoridation Methods 0.000 title claims abstract description 38
- 238000001027 hydrothermal synthesis Methods 0.000 title claims abstract description 19
- PNEYBMLMFCGWSK-UHFFFAOYSA-N Alumina Chemical compound [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims abstract description 75
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims abstract description 66
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 59
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 59
- 239000002028 Biomass Substances 0.000 claims abstract description 58
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 39
- 229910052757 nitrogen Inorganic materials 0.000 claims abstract description 37
- 239000002131 composite material Substances 0.000 claims abstract description 32
- 238000000034 method Methods 0.000 claims abstract description 20
- 229910052761 rare earth metal Inorganic materials 0.000 claims abstract description 14
- 238000007598 dipping method Methods 0.000 claims abstract description 12
- 238000002360 preparation method Methods 0.000 claims abstract description 11
- 239000010893 paper waste Substances 0.000 claims abstract description 10
- 150000002910 rare earth metals Chemical class 0.000 claims abstract description 10
- 239000002994 raw material Substances 0.000 claims abstract description 10
- KRHYYFGTRYWZRS-UHFFFAOYSA-M Fluoride anion Chemical compound [F-] KRHYYFGTRYWZRS-UHFFFAOYSA-M 0.000 claims abstract description 8
- 229910001404 rare earth metal oxide Inorganic materials 0.000 claims abstract description 8
- 159000000013 aluminium salts Chemical class 0.000 claims abstract description 5
- 229910000329 aluminium sulfate Inorganic materials 0.000 claims abstract description 5
- 238000011065 in-situ storage Methods 0.000 claims abstract description 4
- -1 hexa-methylene four Amine Chemical compound 0.000 claims description 20
- 238000005406 washing Methods 0.000 claims description 16
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 8
- 239000012153 distilled water Substances 0.000 claims description 8
- 238000002156 mixing Methods 0.000 claims description 8
- 229920001343 polytetrafluoroethylene Polymers 0.000 claims description 8
- 239000004810 polytetrafluoroethylene Substances 0.000 claims description 8
- 229910002651 NO3 Inorganic materials 0.000 claims description 7
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 6
- 229910052751 metal Inorganic materials 0.000 claims description 6
- 239000002184 metal Substances 0.000 claims description 6
- FGIUAXJPYTZDNR-UHFFFAOYSA-N potassium nitrate Chemical compound [K+].[O-][N+]([O-])=O FGIUAXJPYTZDNR-UHFFFAOYSA-N 0.000 claims description 6
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 claims description 5
- 229910052749 magnesium Inorganic materials 0.000 claims description 5
- 239000011777 magnesium Substances 0.000 claims description 5
- 150000003839 salts Chemical class 0.000 claims description 5
- XTEGARKTQYYJKE-UHFFFAOYSA-M Chlorate Chemical compound [O-]Cl(=O)=O XTEGARKTQYYJKE-UHFFFAOYSA-M 0.000 claims description 4
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims description 4
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 claims description 4
- 239000011159 matrix material Substances 0.000 claims description 4
- 230000003647 oxidation Effects 0.000 claims description 4
- 238000007254 oxidation reaction Methods 0.000 claims description 4
- 229910052725 zinc Inorganic materials 0.000 claims description 4
- 239000011701 zinc Substances 0.000 claims description 4
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 claims description 3
- 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 description 3
- 238000004821 distillation Methods 0.000 claims description 3
- 229910052759 nickel Inorganic materials 0.000 claims description 3
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 claims description 2
- 229910052684 Cerium Inorganic materials 0.000 claims description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 2
- 229910052777 Praseodymium Inorganic materials 0.000 claims description 2
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 claims description 2
- 238000001816 cooling Methods 0.000 claims description 2
- 229910052802 copper Inorganic materials 0.000 claims description 2
- 239000010949 copper Substances 0.000 claims description 2
- 229910052746 lanthanum Inorganic materials 0.000 claims description 2
- FZLIPJUXYLNCLC-UHFFFAOYSA-N lanthanum atom Chemical compound [La] FZLIPJUXYLNCLC-UHFFFAOYSA-N 0.000 claims description 2
- 239000007788 liquid Substances 0.000 claims description 2
- PUDIUYLPXJFUGB-UHFFFAOYSA-N praseodymium atom Chemical compound [Pr] PUDIUYLPXJFUGB-UHFFFAOYSA-N 0.000 claims description 2
- 238000009938 salting Methods 0.000 claims description 2
- 239000004411 aluminium Substances 0.000 claims 2
- 229910052782 aluminium Inorganic materials 0.000 claims 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims 2
- 229910052779 Neodymium Inorganic materials 0.000 claims 1
- 229910017435 S2 In Inorganic materials 0.000 claims 1
- 239000004809 Teflon Substances 0.000 claims 1
- 229920006362 Teflon® Polymers 0.000 claims 1
- GWXLDORMOJMVQZ-UHFFFAOYSA-N cerium Chemical compound [Ce] GWXLDORMOJMVQZ-UHFFFAOYSA-N 0.000 claims 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 claims 1
- 229910052737 gold Inorganic materials 0.000 claims 1
- 239000010931 gold Substances 0.000 claims 1
- QEFYFXOXNSNQGX-UHFFFAOYSA-N neodymium atom Chemical compound [Nd] QEFYFXOXNSNQGX-UHFFFAOYSA-N 0.000 claims 1
- 239000000463 material Substances 0.000 abstract description 22
- 238000010521 absorption reaction Methods 0.000 abstract description 17
- 238000006115 defluorination reaction Methods 0.000 abstract description 11
- 239000003575 carbonaceous material Substances 0.000 abstract description 6
- 230000015572 biosynthetic process Effects 0.000 abstract description 2
- 238000003786 synthesis reaction Methods 0.000 abstract description 2
- 239000003403 water pollutant Substances 0.000 abstract description 2
- 229910052731 fluorine Inorganic materials 0.000 description 19
- 239000011737 fluorine Substances 0.000 description 19
- 239000000243 solution Substances 0.000 description 15
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 13
- 239000011358 absorbing material Substances 0.000 description 6
- GJKFIJKSBFYMQK-UHFFFAOYSA-N lanthanum(3+);trinitrate;hexahydrate Chemical compound O.O.O.O.O.O.[La+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O GJKFIJKSBFYMQK-UHFFFAOYSA-N 0.000 description 6
- 230000003068 static effect Effects 0.000 description 6
- BNGXYYYYKUGPPF-UHFFFAOYSA-M (3-methylphenyl)methyl-triphenylphosphanium;chloride Chemical compound [Cl-].CC1=CC=CC(C[P+](C=2C=CC=CC=2)(C=2C=CC=CC=2)C=2C=CC=CC=2)=C1 BNGXYYYYKUGPPF-UHFFFAOYSA-M 0.000 description 5
- 239000003651 drinking water Substances 0.000 description 5
- 235000020188 drinking water Nutrition 0.000 description 5
- 239000002699 waste material Substances 0.000 description 4
- 210000000988 bone and bone Anatomy 0.000 description 3
- CPLXHLVBOLITMK-UHFFFAOYSA-N Magnesium oxide Chemical compound [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 2
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000000835 fiber Substances 0.000 description 2
- MRELNEQAGSRDBK-UHFFFAOYSA-N lanthanum(3+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[La+3].[La+3] MRELNEQAGSRDBK-UHFFFAOYSA-N 0.000 description 2
- 231100000572 poisoning Toxicity 0.000 description 2
- 230000000607 poisoning effect Effects 0.000 description 2
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- QPLDLSVMHZLSFG-UHFFFAOYSA-N Copper oxide Chemical compound [Cu]=O QPLDLSVMHZLSFG-UHFFFAOYSA-N 0.000 description 1
- 239000005751 Copper oxide Substances 0.000 description 1
- 206010016818 Fluorosis Diseases 0.000 description 1
- 241000282412 Homo Species 0.000 description 1
- 241001465754 Metazoa Species 0.000 description 1
- 239000004113 Sepiolite Substances 0.000 description 1
- 229910021536 Zeolite Inorganic materials 0.000 description 1
- 239000002250 absorbent Substances 0.000 description 1
- 230000002745 absorbent Effects 0.000 description 1
- AZDRQVAHHNSJOQ-UHFFFAOYSA-N alumane Chemical class [AlH3] AZDRQVAHHNSJOQ-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- ZMIGMASIKSOYAM-UHFFFAOYSA-N cerium Chemical compound [Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce] ZMIGMASIKSOYAM-UHFFFAOYSA-N 0.000 description 1
- 229910000420 cerium oxide Inorganic materials 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 238000011109 contamination Methods 0.000 description 1
- 229910000431 copper oxide Inorganic materials 0.000 description 1
- 208000004042 dental fluorosis Diseases 0.000 description 1
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 1
- 230000035622 drinking Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000003344 environmental pollutant Substances 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 239000003673 groundwater Substances 0.000 description 1
- 229910001385 heavy metal Inorganic materials 0.000 description 1
- 230000002401 inhibitory effect Effects 0.000 description 1
- 238000005342 ion exchange Methods 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 239000000395 magnesium oxide Substances 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- PLDDOISOJJCEMH-UHFFFAOYSA-N neodymium(3+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[Nd+3].[Nd+3] PLDDOISOJJCEMH-UHFFFAOYSA-N 0.000 description 1
- CFYGEIAZMVFFDE-UHFFFAOYSA-N neodymium(3+);trinitrate Chemical compound [Nd+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O CFYGEIAZMVFFDE-UHFFFAOYSA-N 0.000 description 1
- 229910000480 nickel oxide Inorganic materials 0.000 description 1
- BMMGVYCKOGBVEV-UHFFFAOYSA-N oxo(oxoceriooxy)cerium Chemical compound [Ce]=O.O=[Ce]=O BMMGVYCKOGBVEV-UHFFFAOYSA-N 0.000 description 1
- GNRSAWUEBMWBQH-UHFFFAOYSA-N oxonickel Chemical compound [Ni]=O GNRSAWUEBMWBQH-UHFFFAOYSA-N 0.000 description 1
- MMKQUGHLEMYQSG-UHFFFAOYSA-N oxygen(2-);praseodymium(3+) Chemical compound [O-2].[O-2].[O-2].[Pr+3].[Pr+3] MMKQUGHLEMYQSG-UHFFFAOYSA-N 0.000 description 1
- 231100000719 pollutant Toxicity 0.000 description 1
- 229910003447 praseodymium oxide Inorganic materials 0.000 description 1
- 238000003672 processing method Methods 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 239000012266 salt solution Substances 0.000 description 1
- 235000019355 sepiolite Nutrition 0.000 description 1
- 229910052624 sepiolite Inorganic materials 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 239000002352 surface water Substances 0.000 description 1
- 239000000052 vinegar Substances 0.000 description 1
- 235000021419 vinegar Nutrition 0.000 description 1
- 238000003911 water pollution Methods 0.000 description 1
- 239000010457 zeolite Substances 0.000 description 1
- 239000011787 zinc oxide Substances 0.000 description 1
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
- B01J20/28—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties
- B01J20/28054—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties characterised by their surface properties or porosity
-
- 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
- B01J20/305—Addition of material, later completely removed, e.g. as result of heat treatment, leaching or washing, e.g. for forming pores
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B09—DISPOSAL OF SOLID WASTE; RECLAMATION OF CONTAMINATED SOIL
- B09B—DISPOSAL OF SOLID WASTE NOT OTHERWISE PROVIDED FOR
- B09B3/00—Destroying solid waste or transforming solid waste into something useful or harmless
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B09—DISPOSAL OF SOLID WASTE; RECLAMATION OF CONTAMINATED SOIL
- B09B—DISPOSAL OF SOLID WASTE NOT OTHERWISE PROVIDED FOR
- B09B3/00—Destroying solid waste or transforming solid waste into something useful or harmless
- B09B3/40—Destroying solid waste or transforming solid waste into something useful or harmless involving thermal treatment, e.g. evaporation
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B09—DISPOSAL OF SOLID WASTE; RECLAMATION OF CONTAMINATED SOIL
- B09B—DISPOSAL OF SOLID WASTE NOT OTHERWISE PROVIDED FOR
- B09B5/00—Operations not covered by a single other subclass or by a single other group in this subclass
-
- 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
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- Chemical & Material Sciences (AREA)
- Environmental & Geological Engineering (AREA)
- Engineering & Computer Science (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Analytical Chemistry (AREA)
- Thermal Sciences (AREA)
- Physics & Mathematics (AREA)
- Hydrology & Water Resources (AREA)
- Inorganic Chemistry (AREA)
- Water Supply & Treatment (AREA)
- Life Sciences & Earth Sciences (AREA)
- Solid-Sorbent Or Filter-Aiding Compositions (AREA)
- Water Treatment By Sorption (AREA)
Abstract
The invention belongs to composite material synthesis technical field, it is related to the preparation of de-fluoridation adsorbent more particularly to hydro-thermal method prepares de-fluoridation adsorbent and its application.First aluminium oxide/biomass carbon material is prepared through 500~800 DEG C of 3~6h of roasting under aluminium salt dipping, nitrogen protection using waste paper as raw material; then use hydro-thermal method in one layer of nanometer sheet of biomass carbon material surface growth in situ; composite oxides/biomass carbon is made; its surface is modified by rare earth nitrades again, is made after 200~400 DEG C of 3~6h of roasting under nitrogen protection.High-specific surface area prepared by the present invention and high absorption property defluorination material are made of biomass carbon, composite oxides nanometer sheet and rare earth oxide, fully combine the advantage of biomass carbon material, composite oxides and the rare earth material fluorine ion in adsorbed water body.Mainly for the purified treatment of water pollutant, the sorbing material of preparation is high, of low cost and simple for process with absorption property, meets the purport of Green Chemistry for the application of de-fluoridation adsorbent.
Description
Technical field
The invention belongs to composite material synthesis technical fields, are related to preparation more particularly to the hydro-thermal legal system of de-fluoridation adsorbent
Standby de-fluoridation adsorbent and its application.
Background technology
Fluorine element is micro- necessary to humans and animals, is distributed mainly in tooth and bone in human body.Drinking-water
In containing appropriate fluorine (0.5~1.5mg/L) be beneficial to health, but when the high-concentration fluorine-contained drinking-water of long-term drinking, easily
Suffer from fluorine spot odontopathy；When serious fluorine poisoning, fluorine element can make textured bone, lead to fluorosis of bone.Natural geological conditions and use contain
The industry of fluorine raw material may all lead to the fluoride pollution of surface water and groundwater, so as to cause fluorine poisoning.Human body takes the photograph fluorine approach master
It to be realized by drinking water, about 80% or so fluorine can be absorbed by the body in drinking water, therefore, control the content of fluorine in drinking water
It is of great significance.
Currently, common method for removing fluor has absorption method, ion-exchange, electroosmose process and membrane processing method, wherein most widely used
General is absorption method.Common de-fluoridation adsorbent have rare earth oxide, aluminium oxide, layered double-hydroxide (LDHs), zeolite and
Sepiolite etc..Rare earth sorbing material has excellent Fluoride-Absorption Capacity, but not only price is high for rare earth material, and in preparation and reality
In water process, it is also possible to cause heavy metal pollution.Aluminium oxide is the most widely used adsorbent of fluorine removal, there is higher surface
Product, but absorption property will be less than rare earth material.Layered double-hydroxide (LDHs) is made of positively charged nanometer sheet, is had latent
The performance of fluorine ion in adsorbed water body, but LDHs surface areas are smaller, fluorine ion hardly diffuses to absorbent interior.Therefore,
It prepares high-specific surface area and high absorption property de-fluoridation adsorbent has great importance.
China is that paper consumes big country in the world, but waste paper recovery utilization rate is relatively low.The recycling of paper and exploitation profit
With for the utilization of resources and environmental protection important in inhibiting.
The present invention prepares the environment-friendly materials of high-specific surface area and high absorption property, provides not only one using waste paper as raw material
The preparation method of kind water pollution control material, additionally provides a kind of method that waste paper resources utilize.
Invention content
The disadvantage that defluorination material specific surface area is low present in for the above-mentioned prior art, defluorination effect is undesirable, this hair
The bright hydro-thermal method that discloses prepares de-fluoridation adsorbent and its application.
A purpose of the invention is to disclose a kind of hydro-thermal method and prepares de-fluoridation adsorbent, to overcome existing sorbing material to inhale
Attached efficiency is low, and preparation process is complicated, it is of high cost the shortcomings of.
Technical solution：The present invention is that raw material roast 3 through 500~800 DEG C under aluminium salt dipping, nitrogen protection first with waste paper
~6h prepares aluminium oxide/biomass carbon material, then uses hydro-thermal method in one layer of nanometer of biomass carbon material surface growth in situ
Piece is made composite oxides/biomass carbon, then is modified to its surface by rare earth nitrades, 200~400 DEG C under nitrogen protection
3~6h is roasted, compound de-fluoridation adsorbent is finally made.
A kind of method that hydro-thermal method prepares de-fluoridation adsorbent, specifically comprises the following steps：
S1. aluminium oxide/biomass carbon is prepared：
Dry 6~12h, obtains pre- at waste paper is cleaned 3~5 times, 50~80 DEG C in distilled water and in absolute ethyl alcohol successively
Handling of paper；
It is added based on 1~5g pretreatment paper by every 100mL solution, pretreatment paper is immersed in 0.05~0.5mol/L's
In aluminum salt solution, 1~2h of dipping takes out, dry 6~12h at distillation water washing 1~3 time, 50~80 DEG C, 500 under nitrogen protection
After~800 DEG C of 3~6h of roasting, roasting repetition 3~5 times, obtain aluminium oxide/biomass carbon under dipping-nitrogen protection；
S2. composite oxides/biomass carbon is prepared：
It is 1 by aluminium oxide/biomass carbon and hexa mass ratio：1~2：1 meter, preferably 1：1, divalent metal M salt
With hexa than molar ratio be 1：1~2：1 meter, preferably 2：1, aluminium oxide/biomass carbon and hexa are added
Enter into 0.05~0.5mol/L divalent metal M salting liquids, after mixing, is transferred to the reaction under high pressure of inner liner polytetrafluoroethylene
In kettle, 75~160 DEG C preferably 120 DEG C, hydro-thermal reaction 12~preferred 15h, cooling, filtering for 24 hours distills water washing 3~5 times, and 50
Dry 12 at~80 DEG C~for 24 hours, 400~600 DEG C of roasting preferred 4h of 2~6h, obtain composite oxides/biomass under nitrogen protection
Carbon；
S3. the preparation of de-fluoridation adsorbent：
By 1~5g is added in every 100mL rare earth nitrate solutions, preferably 3g composite oxides/biomass carbon meter will be compound
Oxide/biomass carbon is immersed in the rare earth nitrate solution of a concentration of 0.5~0.15mol/L, preferably 0.1mol/L, dipping
1~2h takes out, dry 6~12h at 50~80 DEG C, and 200~400 DEG C of roastings 3~6h, preferably 4h under nitrogen protection obtain fluorine removal suction
Attached dose.
In the preferred embodiment of the present invention, aluminium salt described in S1 is a kind of or more in aluminum nitrate, aluminium chloride and aluminum sulfate
Kind combination.
In the preferred embodiment of the present invention, the divalent metal M described in S2 is one or more of magnesium, nickel, zinc or copper
Combination, M salt are the combination of one or more of nitrate, chlorate, sulfate or acetate.
In the preferred embodiment of the present invention, the rare earth nitrades described in S3 are one or more of lanthanum, cerium, praseodymium or neodymium
Nitrate combines.
According to de-fluoridation adsorbent made from the above method, by biomass carbon, composite oxides nanometer sheet and rare earth oxide
It constitutes, there is graded porous structure, it is matrix, combined oxidation which, which is biomass carbon prepared by raw material by waste paper,
For object nanometer sheet growth in situ in matrix surface, rare earth oxide is attached to biomass carbon and composite oxides nanometer sheet surface.
The de-fluoridation adsorbent, the biomass carbon have fibre structure, by waste paper for raw material and presoma prepare and
At；The composite oxides nanometer sheet is answered by one or more in magnesia, nickel oxide, zinc oxide or copper oxide with aluminium oxide
It closes, size is 500nm~1 μm；The rare earth oxide is by lanthana, cerium oxide, praseodymium oxide or neodymia are a kind of or
Person's multiple combinations.
Another object of the present invention is the application for disclosing de-fluoridation adsorbent fluorine ion in going water removal.
Advantageous effect
The present invention is raw material using cheap paper, prepares high-specific surface area and high absorption property defluorination material.The material
Material is made of biomass carbon, composite oxides nanometer sheet and rare earth oxide, fully combines biomass carbon material, combined oxidation
The advantage of object and the rare earth material fluorine ion in adsorbed water body.The present invention application mainly for the purification of water pollutant at
The sorbing material of reason, preparation has absorption property high, of low cost and simple for process, meets the purport of Green Chemistry.
The features of the present invention is：
(1), raw material of the invention are paper, and raw material sources have popularity and recyclability, provide not only one
The cheap contamination control material of kind, also provides a kind of method that waste paper resources utilize.
(2), the defluorination material prepared by the present invention has efficient absorption property, combines biomass carbon, combined oxidation
Object and rare earth material the advantages of fluorine ion, can effectively control the content of fluorine ions in water body, and this hair in adsorbed water body
The sorbing material of bright preparation can apply other pollutant controls in water body.
(3), hydro-thermal method disclosed in this invention prepares de-fluoridation adsorbent, and the preparation process of sorbing material is controllable, adsorption material
The component of material is adjustable, not can cause environmental pollution.
Description of the drawings
Fig. 1 is the scanning electron microscope (SEM) photograph of de-fluoridation adsorbent fibre structure；
Fig. 2 is the scanning electron microscope (SEM) photograph of de-fluoridation adsorbent nano surface piece.
Specific implementation mode
The following describes the present invention in detail with reference to examples, so that those skilled in the art more fully understand this hair
It is bright, but the invention is not limited in following embodiments.
Embodiment 1
Using waste newspaper as carbon source and presoma, waste newspaper is cleaned 3 times in distilled water and in absolute ethyl alcohol respectively,
Dry 12h, obtains pretreatment paper at 80 DEG C.5g pretreatment paper is taken to be immersed in 100mL aluminum nitrate solutions, dip time 2h,
It takes out, dry 12h at water washing 3 times, 50~80 DEG C is distilled, after lower 600 DEG C of nitrogen protection roasts 4h, under dipping-nitrogen protection
Roasting is repeated 3 times, and obtains aluminium oxide/biomass carbon；
Aluminium oxide/biomass carbon 0.28g and hexa 0.28g is taken to be added to the nitre of a concentration of 0.1mol/L of 20mL
In sour magnesium solution, after mixing, transfer in the autoclave to inner liner polytetrafluoroethylene, will react 12h at 120 DEG C, cold
But it, filters, distills dry 12h at water washing 3 times, 80 DEG C, the lower 500 DEG C of roastings 4h of nitrogen protection obtains composite oxides/biomass
Carbon；
3g composite oxides/biomass carbon is taken to be added in the lanthanum nitrate hexahydrate of a concentration of 0.1mol/L of 100mL, when dipping
Between 2h, take out, dry 12h at 80 DEG C, the lower 300 DEG C of roastings 4h of nitrogen protection obtains de-fluoridation adsorbent.
The defluorination absorbing material in 50mg embodiments 1 is taken, is added in a concentration of 20mg/L Fluorinses of 20mL, static state is inhaled
It is attached to measure the front and back fluorinion concentration of absorption for 24 hours, to the removal rate of fluorine ions in water body up to 98.5%.
Embodiment 2
Using discarded roll paper as carbon source and presoma, roll paper is cleaned 3 times, 80 DEG C in distilled water and in absolute ethyl alcohol respectively
Lower dry 12h, obtains pretreatment paper.5g pretreatment paper is taken to be immersed in 100mL aluminum nitrate solutions, dip time 2h takes out,
It distills dry 12h at water washing 3 times, 50~80 DEG C and roasts weight under dipping-nitrogen protection after lower 600 DEG C of nitrogen protection roasts 4h
It is 3 times multiple, obtain aluminium oxide/biomass carbon；
Aluminium oxide/biomass carbon 0.28g and hexa 0.28g is taken to be added to the nitre of a concentration of 0.1mol/L of 20mL
In sour magnesium solution, after mixing, transfer in the autoclave to inner liner polytetrafluoroethylene, will react 12h at 120 DEG C, cold
But it, filters, distills dry 12h at water washing 3 times, 80 DEG C, the lower 500 DEG C of roastings 4h of nitrogen protection obtains composite oxides/biomass
Carbon；
3g composite oxides/biomass carbon is taken to be added in the lanthanum nitrate hexahydrate of a concentration of 0.1mol/L of 100mL, when dipping
Between 2h, take out, dry 12h at 80 DEG C, the lower 300 DEG C of roastings 4h of nitrogen protection obtains de-fluoridation adsorbent.
The defluorination absorbing material in 50mg embodiments 2 is taken, is added in a concentration of 20mg/L Fluorinses of 20mL, static state is inhaled
It is attached to measure the front and back fluorinion concentration of absorption for 24 hours, to the removal rate of fluorine ions in water body up to 99.2%.
Embodiment 3
Using discarded roll paper as carbon source and presoma, roll paper is cleaned 3 times, 80 DEG C in distilled water and in absolute ethyl alcohol respectively
Lower dry 12h, obtains pretreatment paper.4g pretreatment paper is taken to be immersed in 100mL aluminum sulfate solutions, dip time 2h takes out,
It distills dry 12h at water washing 3 times, 50~80 DEG C and roasts weight under dipping-nitrogen protection after lower 600 DEG C of nitrogen protection roasts 4h
It is 3 times multiple, obtain aluminium oxide/biomass carbon；
Aluminium oxide/biomass carbon 0.28g and hexa 0.28g is taken to be added to the nitre of a concentration of 0.1mol/L of 20mL
In sour zinc solution, after mixing, transfer in the autoclave to inner liner polytetrafluoroethylene, will react 12h at 120 DEG C, cold
But it, filters, distills dry 12h at water washing 3 times, 80 DEG C, the lower 500 DEG C of roastings 4h of nitrogen protection obtains composite oxides/biomass
Carbon；
3g composite oxides/biomass carbon is taken to be added in the lanthanum nitrate hexahydrate of a concentration of 0.1mol/L of 100mL, when dipping
Between 2h, take out, dry 12h at 80 DEG C, the lower 300 DEG C of roastings 4h of nitrogen protection obtains de-fluoridation adsorbent.
The defluorination absorbing material in 50mg embodiments 3 is taken, is added in a concentration of 20mg/L Fluorinses of 20mL, static state is inhaled
It is attached to measure the front and back fluorinion concentration of absorption for 24 hours, to the removal rate of fluorine ions in water body up to 96.9%.
Embodiment 4
Using waste newspaper as carbon source and presoma, newspaper is cleaned 3 times, 80 DEG C in distilled water and in absolute ethyl alcohol respectively
Lower dry 12h, obtains pretreatment paper.5g pretreatment paper is taken to be immersed in 100mL liquor alumini chloridis, dip time 2h takes out,
It distills dry 12h at water washing 3 times, 50~80 DEG C and roasts weight under dipping-nitrogen protection after lower 600 DEG C of nitrogen protection roasts 4h
It is 3 times multiple, obtain aluminium oxide/biomass carbon；
Aluminium oxide/biomass carbon 0.28g and hexa 0.28g is taken to be added to the nitre of a concentration of 0.1mol/L of 20mL
In sour nickel solution, after mixing, transfer in the autoclave to inner liner polytetrafluoroethylene, will react 12h at 120 DEG C, cold
But it, filters, distills dry 12h at water washing 3 times, 80 DEG C, the lower 500 DEG C of roastings 4h of nitrogen protection obtains composite oxides/biomass
Carbon；
3g composite oxides/biomass carbon is taken to be added in the lanthanum nitrate hexahydrate of a concentration of 0.1mol/L of 100mL, when dipping
Between 2h, take out, dry 12h at 80 DEG C, the lower 300 DEG C of roastings 4h of nitrogen protection obtains de-fluoridation adsorbent.
The defluorination absorbing material in 50mg embodiments 4 is taken, is added in a concentration of 20mg/L Fluorinses of 20mL, static state is inhaled
It is attached to measure the front and back fluorinion concentration of absorption for 24 hours, to the removal rate of fluorine ions in water body up to 95.8%.
Embodiment 5
Using discarded roll paper as carbon source and presoma, roll paper is cleaned 3 times, 80 DEG C in distilled water and in absolute ethyl alcohol respectively
Lower dry 12h, obtains pretreatment paper.5g pretreatment paper is taken to be immersed in 100mL aluminum nitrate solutions, dip time 2h takes out,
It distills dry 12h at water washing 3 times, 50~80 DEG C and roasts weight under dipping-nitrogen protection after lower 600 DEG C of nitrogen protection roasts 4h
It is 3 times multiple, obtain aluminium oxide/biomass carbon；
Aluminium oxide/biomass carbon 0.28g and hexa 0.28g is taken to be added to the vinegar of a concentration of 0.1mol/L of 20mL
In sour zinc solution, after mixing, transfer in the autoclave to inner liner polytetrafluoroethylene, will react 12h at 75 DEG C, cold
But it, filters, distills dry 12h at water washing 3 times, 80 DEG C, the lower 500 DEG C of roastings 4h of nitrogen protection obtains composite oxides/biomass
Carbon；
3g composite oxides/biomass carbon is taken to be added in the lanthanum nitrate hexahydrate of a concentration of 0.1mol/L of 100mL, when dipping
Between 2h, take out, dry 12h at 80 DEG C, the lower 300 DEG C of roastings 4h of nitrogen protection obtains de-fluoridation adsorbent.
The defluorination absorbing material in 50mg embodiments 5 is taken, is added in a concentration of 20mg/L Fluorinses of 20mL, static state is inhaled
It is attached to measure the front and back fluorinion concentration of absorption for 24 hours, to the removal rate of fluorine ions in water body up to 97.8%.
Embodiment 6
Using waste newspaper as carbon source and presoma, newspaper is cleaned 3 times, 80 DEG C in distilled water and in absolute ethyl alcohol respectively
Lower dry 12h, obtains pretreatment paper.5g pretreatment paper is taken to be immersed in 100mL aluminum nitrate solutions, dip time 2h takes out,
It distills dry 12h at water washing 3 times, 50~80 DEG C and roasts weight under dipping-nitrogen protection after lower 600 DEG C of nitrogen protection roasts 4h
It is 3 times multiple, obtain aluminium oxide/biomass carbon；
Aluminium oxide/biomass carbon 0.28g and hexa 0.28g is taken to be added to the chlorine of a concentration of 0.1mol/L of 20mL
Change in magnesium solution, after mixing, transfer in the autoclave to inner liner polytetrafluoroethylene, will react 12h at 120 DEG C, cold
But it, filters, distills dry 12h at water washing 3 times, 80 DEG C, the lower 500 DEG C of roastings 4h of nitrogen protection obtains composite oxides/biomass
Carbon；
3g composite oxides/biomass carbon is taken to be added in the lanthanum nitrate hexahydrate of a concentration of 0.1mol/L of 100mL, when dipping
Between 2h, take out, dry 12h at 80 DEG C, the lower 300 DEG C of roastings 4h of nitrogen protection obtains de-fluoridation adsorbent.
The defluorination absorbing material in 50mg embodiments 6 is taken, is added in a concentration of 20mg/L Fluorinses of 20mL, static state is inhaled
It is attached to measure the front and back fluorinion concentration of absorption for 24 hours, to the removal rate of fluorine ions in water body up to 99.3%.
Example the above is only the implementation of the present invention is not intended to limit the scope of the invention, every to utilize this hair
Equivalent structure or equivalent flow shift made by bright specification is applied directly or indirectly in other relevant technical fields,
Similarly it is included within the scope of the present invention.
Claims (9)
1. a kind of method that hydro-thermal method prepares de-fluoridation adsorbent, which is characterized in that include the following steps：
S1. aluminium oxide/biomass carbon is prepared：
Dry 6~12h, must pre-process at waste paper is cleaned 3~5 times, 50~80 DEG C in distilled water and in absolute ethyl alcohol successively
Paper；
It is added based on 1~5g pretreatment paper by every 100mL solution, pretreatment paper is immersed in the aluminium salt of 0.05~0.5mol/L
In solution, 1~2h of dipping takes out, dry 6~12h at distillation water washing 1~3 time, 50~80 DEG C, 500 under nitrogen protection~
After 800 DEG C of 3~6h of roasting, roasting repetition 3~5 times, obtain aluminium oxide/biomass carbon under dipping-nitrogen protection；
S2. composite oxides/biomass carbon is prepared：
It is 1 by aluminium oxide/biomass carbon and hexa mass ratio：1~2：1 meter, divalent metal M salt and hexa-methylene four
Amine is 1 than molar ratio：1~2：1 meter, 0.05~0.5mol/L bis- is added to by aluminium oxide/biomass carbon and hexa
In valence metal M salting liquids, after mixing, it is transferred in the autoclave of inner liner polytetrafluoroethylene, 75~160 DEG C, hydro-thermal
Reaction 12~for 24 hours, cooling is filtered, dry 12 at distillation water washing 3~5 times, 50~80 DEG C~for 24 hours, 400 under nitrogen protection~
600 DEG C of 2~6h of roasting, obtain composite oxides/biomass carbon；
S3. the preparation of de-fluoridation adsorbent：
It is added based on 1~5g composite oxides/biomass carbon by every 100mL rare earth nitrate solutions, by composite oxides/biology
Matter carbon is immersed in the rare earth nitrate solution of a concentration of 0.5~0.15mol/L, and 1~2h of dipping takes out, dry at 50~80 DEG C
6~12h, 200~400 DEG C of 3~6h of roasting, obtain de-fluoridation adsorbent under nitrogen protection.
2. the method that hydro-thermal method according to claim 1 prepares de-fluoridation adsorbent, it is characterised in that：Aluminium salt described in S1 is nitre
One or more of sour aluminium, aluminium chloride and aluminum sulfate combine.
3. the method that hydro-thermal method according to claim 1 prepares de-fluoridation adsorbent, it is characterised in that：Divalent gold described in S2
Category M is the combination of one or more of magnesium, nickel, zinc or copper, and M salt is one in nitrate, chlorate, sulfate or acetate
Kind or multiple combinations.
4. the method that hydro-thermal method according to claim 1 prepares de-fluoridation adsorbent, it is characterised in that：Rare earth nitre described in S3
Hydrochlorate is the nitrate combination of one or more of lanthanum, cerium, praseodymium or neodymium.
5. the method that hydro-thermal method according to claim 1 prepares de-fluoridation adsorbent, it is characterised in that：By oxidation described in S2
Aluminium/biomass carbon is 1 with hexa mass ratio：1, divalent metal M salt is 2 than molar ratio with hexa：1.
6. the method that hydro-thermal method according to claim 1 prepares de-fluoridation adsorbent, it is characterised in that：In being transferred to described in S2
In the autoclave of lining teflon, 120 DEG C of hydro-thermal reaction 15h.
7. the method that hydro-thermal method according to claim 1 prepares de-fluoridation adsorbent, it is characterised in that：Nitrogen protection described in S2
Lower 400~600 DEG C of roastings 4h.
8. the de-fluoridation adsorbent prepared according to any the methods of claim 1-7, it is characterised in that：The de-fluoridation adsorbent by
Biomass carbon, composite oxides nanometer sheet and rare earth oxide are constituted, and have graded porous structure, the graded porous structure is by giving up
Paper is that biomass carbon prepared by raw material is matrix, and for composite oxides nanometer sheet growth in situ in matrix surface, rare earth oxide is attached
It in biomass carbon and composite oxides nanometer sheet surface.
9. the application of de-fluoridation adsorbent described in a kind of claim 8, it is characterised in that：It is applied to fluorine ion in water removal.
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Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104707562A (en) * | 2015-04-09 | 2015-06-17 | 云南大学 | Method for preparing magnesium-aluminum ion doped mesoporous TiO2 fluorine removal agent |
| CN104923150A (en) * | 2014-03-19 | 2015-09-23 | 中国科学院生态环境研究中心 | Lanthanum-loaded activated aluminium oxide defluorinating adsorbent and preparation method thereof |
| CN105126738A (en) * | 2015-08-08 | 2015-12-09 | 常州大学 | Preparation method of porous composite material for removal of fluorine ions from water |
-
2016
- 2016-11-11 CN CN201610993793.0A patent/CN106512936B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104923150A (en) * | 2014-03-19 | 2015-09-23 | 中国科学院生态环境研究中心 | Lanthanum-loaded activated aluminium oxide defluorinating adsorbent and preparation method thereof |
| CN104707562A (en) * | 2015-04-09 | 2015-06-17 | 云南大学 | Method for preparing magnesium-aluminum ion doped mesoporous TiO2 fluorine removal agent |
| CN105126738A (en) * | 2015-08-08 | 2015-12-09 | 常州大学 | Preparation method of porous composite material for removal of fluorine ions from water |
Non-Patent Citations (1)
| Title |
|---|
| Removal of fluoride from water by adsorption onto lanthanum oxide;C.R.Nagendra Rao, et al.;《Water, Air, & Soil Pollution》;20111012;第223卷(第3期);第1101-1114页 * |
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