CN106944005A - A kind of depth removes resin-base nano compound adsorbent of Micro fluoride and its preparation method and application - Google Patents
A kind of depth removes resin-base nano compound adsorbent of Micro fluoride and its preparation method and application Download PDFInfo
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- 239000003463 adsorbent Substances 0.000 title claims abstract description 46
- 150000001875 compounds Chemical class 0.000 title claims abstract description 30
- KRHYYFGTRYWZRS-UHFFFAOYSA-M Fluoride anion Chemical compound [F-] KRHYYFGTRYWZRS-UHFFFAOYSA-M 0.000 title claims abstract description 23
- 238000002360 preparation method Methods 0.000 title claims abstract description 12
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 claims abstract description 181
- 229910052731 fluorine Inorganic materials 0.000 claims abstract description 181
- 239000011737 fluorine Substances 0.000 claims abstract description 181
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 128
- 239000011148 porous material Substances 0.000 claims abstract description 126
- 239000002131 composite material Substances 0.000 claims abstract description 116
- 125000001302 tertiary amino group Chemical group 0.000 claims abstract description 7
- 229920003053 polystyrene-divinylbenzene Polymers 0.000 claims abstract description 5
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 240
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 126
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 claims description 123
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 claims description 96
- 229910001928 zirconium oxide Inorganic materials 0.000 claims description 95
- 239000011259 mixed solution Substances 0.000 claims description 83
- 238000003795 desorption Methods 0.000 claims description 80
- 239000011780 sodium chloride Substances 0.000 claims description 79
- 238000005406 washing Methods 0.000 claims description 74
- 238000001179 sorption measurement Methods 0.000 claims description 48
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 claims description 44
- 229910052726 zirconium Inorganic materials 0.000 claims description 44
- 238000010521 absorption reaction Methods 0.000 claims description 43
- 230000007704 transition Effects 0.000 claims description 40
- 229920005990 polystyrene resin Polymers 0.000 claims description 39
- 229910006213 ZrOCl2 Inorganic materials 0.000 claims description 38
- IPCAPQRVQMIMAN-UHFFFAOYSA-L zirconyl chloride Chemical compound Cl[Zr](Cl)=O IPCAPQRVQMIMAN-UHFFFAOYSA-L 0.000 claims description 38
- 238000013019 agitation Methods 0.000 claims description 37
- 239000002585 base Substances 0.000 claims description 32
- 238000000034 method Methods 0.000 claims description 10
- 150000001447 alkali salts Chemical class 0.000 claims description 7
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 6
- 239000003513 alkali Substances 0.000 claims description 6
- 238000001035 drying Methods 0.000 claims description 6
- 150000003839 salts Chemical class 0.000 claims description 6
- 239000007864 aqueous solution Substances 0.000 claims description 5
- 230000008569 process Effects 0.000 claims description 5
- 239000003795 chemical substances by application Substances 0.000 claims description 4
- 238000012545 processing Methods 0.000 claims description 4
- 230000008929 regeneration Effects 0.000 claims description 4
- 238000011069 regeneration method Methods 0.000 claims description 4
- 239000000243 solution Substances 0.000 claims description 4
- 229910003130 ZrOCl2·8H2O Inorganic materials 0.000 claims description 3
- 239000002594 sorbent Substances 0.000 claims description 2
- 239000000463 material Substances 0.000 abstract description 120
- 239000002114 nanocomposite Substances 0.000 abstract description 115
- 239000005416 organic matter Substances 0.000 abstract description 10
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 abstract description 8
- 238000005516 engineering process Methods 0.000 abstract description 5
- 239000002105 nanoparticle Substances 0.000 abstract description 4
- 230000007717 exclusion Effects 0.000 abstract description 3
- 229920005989 resin Polymers 0.000 description 75
- 239000011347 resin Substances 0.000 description 75
- 235000013339 cereals Nutrition 0.000 description 46
- 239000002245 particle Substances 0.000 description 38
- 238000007654 immersion Methods 0.000 description 37
- QJZYHAIUNVAGQP-UHFFFAOYSA-N 3-nitrobicyclo[2.2.1]hept-5-ene-2,3-dicarboxylic acid Chemical compound C1C2C=CC1C(C(=O)O)C2(C(O)=O)[N+]([O-])=O QJZYHAIUNVAGQP-UHFFFAOYSA-N 0.000 description 36
- 229910020489 SiO3 Inorganic materials 0.000 description 36
- 230000005540 biological transmission Effects 0.000 description 36
- 238000002474 experimental method Methods 0.000 description 36
- 239000011521 glass Substances 0.000 description 36
- 239000004021 humic acid Substances 0.000 description 36
- 238000009616 inductively coupled plasma Methods 0.000 description 36
- 150000002500 ions Chemical class 0.000 description 36
- 238000002336 sorption--desorption measurement Methods 0.000 description 36
- 150000003512 tertiary amines Chemical class 0.000 description 35
- 230000000694 effects Effects 0.000 description 11
- 239000007788 liquid Substances 0.000 description 5
- 210000000988 bone and bone Anatomy 0.000 description 4
- 208000004042 dental fluorosis Diseases 0.000 description 3
- 239000004088 foaming agent Substances 0.000 description 3
- 239000008239 natural water Substances 0.000 description 3
- 206010016818 Fluorosis Diseases 0.000 description 2
- 230000002411 adverse Effects 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 238000007334 copolymerization reaction Methods 0.000 description 2
- 239000003651 drinking water Substances 0.000 description 2
- 235000020188 drinking water Nutrition 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 230000009467 reduction Effects 0.000 description 2
- 239000007790 solid phase Substances 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 1
- 240000007594 Oryza sativa Species 0.000 description 1
- 235000007164 Oryza sativa Nutrition 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- 239000004793 Polystyrene Substances 0.000 description 1
- 230000000274 adsorptive effect Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000033228 biological regulation Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000011575 calcium Substances 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000006115 defluorination reaction Methods 0.000 description 1
- 230000001627 detrimental effect Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- 208000037265 diseases, disorders, signs and symptoms Diseases 0.000 description 1
- 238000010889 donnan-equilibrium Methods 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 230000029142 excretion Effects 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 238000011065 in-situ storage Methods 0.000 description 1
- 230000002779 inactivation Effects 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 239000003446 ligand Substances 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 230000004060 metabolic process Effects 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 231100000572 poisoning Toxicity 0.000 description 1
- 230000000607 poisoning effect Effects 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 229920002223 polystyrene Polymers 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 230000002940 repellent Effects 0.000 description 1
- 239000005871 repellent Substances 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 235000009566 rice Nutrition 0.000 description 1
- 241000894007 species Species 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
Classifications
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- 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
- B01J20/22—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising organic material
- B01J20/223—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising organic material containing metals, e.g. organo-metallic compounds, coordination complexes
- B01J20/226—Coordination polymers, e.g. metal-organic frameworks [MOF], zeolitic imidazolate frameworks [ZIF]
-
- 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
- B01J20/28057—Surface area, e.g. B.E.T specific surface area
- B01J20/28064—Surface area, e.g. B.E.T specific surface area being in the range 500-1000 m2/g
-
- 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
- B01J20/28057—Surface area, e.g. B.E.T specific surface area
- B01J20/28066—Surface area, e.g. B.E.T specific surface area being more than 1000 m2/g
-
- 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
- B01J20/28069—Pore volume, e.g. total pore volume, mesopore volume, micropore volume
- B01J20/28071—Pore volume, e.g. total pore volume, mesopore volume, micropore volume being less than 0.5 ml/g
-
- 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
- B01J20/28069—Pore volume, e.g. total pore volume, mesopore volume, micropore volume
- B01J20/28073—Pore volume, e.g. total pore volume, mesopore volume, micropore volume being in the range 0.5-1.0 ml/g
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- 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
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- 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
- B01J20/28078—Pore diameter
- B01J20/2808—Pore diameter being less than 2 nm, i.e. micropores or nanopores
-
- 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
- C02F1/285—Treatment of water, waste water, or sewage by sorption using synthetic organic sorbents
-
- 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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- Hydrology & Water Resources (AREA)
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- Solid-Sorbent Or Filter-Aiding Compositions (AREA)
- Water Treatment By Sorption (AREA)
Abstract
Resin-base nano compound adsorbent of Micro fluoride and its preparation method and application is removed the invention discloses a kind of depth, belongs to water-treatment technology field.The resin-base nano compound adsorbent of the present invention is using tertiary-aminated Hypercrosslinked polystyrene divinylbenzene as skeleton, tertiary amine groups content is 0.2 1.5mmol/g, loaded zirconia nano particle in organic backbone, load capacity is calculated as 10 30wt% with zr element, and nanoparticle size is 10 80nm；Below 2nm hole accounts for ratio >=90% of total pore volume in composite.The nano composite material microcellular structure of the present invention is enriched, and the influence for reducing natural organic matter to composite fluorine removal can be acted on by size exclusion, the deep purifying to Micro fluoride can be still realized under high organic matter background.
Description
Technical field
It is to be related to the tree that a kind of depth removes Micro fluoride more specifically the invention belongs to water-treatment technology field
Aliphatic radical nano-compound adsorbent and its preparation method and application.
Background technology
Fluorine is a kind of human essential elementses, and appropriate fluorine has important effect to tooth and bone；But if intake
Fluorine it is excessive, it will many detrimental effects are produced to human body, such as：Cause den tal fluorosis, fluorosis of bone, destroy normal calcium, phosphorus
Metabolism.At present, the fluorine-containing exception of natural water body is a global significant problem, the meeting when the Oil repellent in drinking water is exceeded
Cause endemic fluorosis disease.Fluorine poisoning is one of endemic illness of China's harm most serious, both at home and abroad all to drinking
Water fluorinated volume has done strict regulation, needs the efficient floride pollution of water control technology of development badly.
In past 20 years, absorption method turns into and most preferably removed because of advantages such as fluorine removal is simple to operate, effect stability, economically feasibles
One of fluorine method.Wherein, nano hydrated zirconium oxide is because having the spies such as adsorptive selectivity is high, adsorption capacity is big, stability of material is strong
Put and turn into one of preferable fluorine adsorbent.Nano hydrated zirconium oxide has high specific surface area and reactivity, and surface is big
The hydroxyl of amount can produce specific adsorption by ligand exchange to fluorine.But nano hydrated zirconium oxide, which has, is difficult to reclaim again sharp
With, be easy to inactivation of reuniting, and pressure drop is big in use, high energy consumption, the defect such as be easy to run off, and this is also the nano hydrated oxygen of limitation
Change the main difficult technical of zirconium defluorinating process.In order to overcome disadvantages described above, it is normal that exploitation, which carries nano hydrated zirconium oxide composite material,
The processing means for the solution industrial applications problem seen.
Through retrieval, on nano hydrated zirconium oxide is loaded on matrix material, the patent of compound defluorination material is prepared
Report is existing a large amount of open.Such as, Chinese patent 201210524428.7 is disclosed with the polystyrene tree with nano-pore structure
Fat is carrier, and nano hydrated zirconia particles are supported in the duct of polymer support by in-situ precipitate technology, successfully ground
Organic-inorganic hybrid nanocomposite sorbing material is made, harmless dosage has been arrived into micro- fluoride pollution processing in water, successfully solved
The problem of fluorine of having determined is difficult to advanced treating.This nano composite adsorption material possess selective high, hydrodynamic performance it is excellent,
The features such as high mechanical strength.What is more important, because abundant charged group is contained on organic carrier surface, can pass through Donnan
Effect realizes the preenrichment to fluorine ion, so as to significantly improve the Fluoride-Absorption Capacity of nano composite adsorption material.
However, the hole of nano composite material involved in above-mentioned application case is based on macroporous structure, most nanometers
Hydrous zirconium oxide(HZO) is distributed in more than 30nm hole.Such pore structure feature to be widely present in natural in natural water body
Organic matter (NOM) is very easy to be diffused into hole, avtive spot is occupied with nano particle interaction, so as to influence fluorine removal mistake
Journey.Research shows that natural organic matter concentration is in the case of 10-500mg/L in water, using nano combined in above-mentioned application case
Material can decline more than 90% to the clearance and adsorbance highest of fluorine (Environ Sci Technol, 2013,47,9347).
It is made in addition, porous resin is general by suspension copolymerization method, it is necessary to additionally add pore-foaming agent；Pore-foaming agent is generally liquid, is being suspended
Pore-foaming agent formation nano-liquid droplet occupies solid phase space so as to pore in copolymerization liquid-solid phase transition process.Due to being caused in course of reaction
Hole agent is difficult to be dispersed into uniform small size nano-liquid droplet, thus almost all of porous resin has abundant macropore knot
Structure, using this kind of material as the loading nanometer zirconia materials theory obtained by carrier on be difficult to exclude NOM to its fluorine removal mistake
The adverse effect of journey.
The content of the invention
1. the invention technical problem to be solved
It is an object of the invention to overcome to remove in natural water body using existing resin-base nano zirconium oxide composite material
During fluorine, influenceed larger by natural organic matter in water body, affected not enough there is provided one kind so as to cause the removal effect of fluorine
Depth removes resin-base nano compound adsorbent of Micro fluoride and its preparation method and application.The present invention utilizes size exclusion
Effect effectively reduces adverse effect of the natural organic matter to Zirconium oxide nano grain fluorine removal, higher in natural organic matter content
The Trace Fluoride that still can be efficiently gone in water removal in water.
2. technical scheme
To reach above-mentioned purpose, the technical scheme that the present invention is provided is：
First, the present invention a kind of depth remove Micro fluoride resin-base nano compound adsorbent, the adsorbent with
Hypercrosslinked polystyrene-divinylbenzene is to be loaded with Zirconium oxide nano grain in organic backbone, organic backbone, and this is nano combined
The pore volume of adsorbent is 0.3-0.9cm3/ g, specific surface area is 600-1500m2/ g, and diameter accounts for total pore volume in below 2nm hole
Ratio >=90%.
Further, the load capacity of zirconium oxide is calculated as 10-30wt% with zr element in the compound adsorbent, and zirconium oxide is received
The size of rice grain is 10-80nm.
Further, the organic backbone is covalently bonded with tertiary amine groups, and the content of tertiary amine groups is 0.2-1.5mmol/g,
Pore volume is 0.5-1.2cm3/ g, specific surface area is 400-1200m2/g。
Second, a kind of preparation method of resin-base nano compound adsorbent of the present invention, its process is as follows：By drying process
Tertiary-aminated Polystyrene resin immersion ZrOCl afterwards2·8H2In O, HCl and the mixed solution of ethanol, and in stirring
Under the conditions of be evaporated；Drying to obtain resin-base nano after NaOH the and NaCl aqueous solution is washed through transition, washing, alcohol is subsequently added to aoxidize
Zirconium composite material.
Further, ZrOCl2·8H2In O, HCl and the mixed solution of ethanol, ZrOCl2·8H2O, HCl and ethanol
Mass ratio is (2.5-8): 1: 6.
Further, the NaOH solution and the mass concentration of the NaCl aqueous solution are 3-6%.
Third, a kind of depth of the present invention removes the application of the resin-base nano compound adsorbent of Micro fluoride, use
The resin-base nano compound adsorbent of the present invention carries out adsorption treatment to the fluorine in water, and the concentration of fluorine can drop to 1mg/ after processing
Below L.
Further, when being handled using the nano-compound adsorbent fluorinated water, the oxidation of sorbent-loaded
The adsorbable fluorine 40-120mg of averagely every gram in terms of zirconium of zirconium nano particle.
Further, to the nano-compound adsorbent after absorption, desorption and regeneration is carried out by alkali salt mixed solution, fluorine
Alkali in desorption rate ＞ 90%, wherein alkali salt mixed solution is NaOH or KOH, and salt is NaCl or KCl, and the quality of alkali, salt is dense
Degree is 3-6%.
3. beneficial effect
The technical scheme provided using the present invention, compared with prior art, with following remarkable result：
(1) a kind of depth of the invention removes the resin-base nano compound adsorbent of Micro fluoride, and the adsorbent is with super
High crosslinked polystyrene-divinylbenzene is to be loaded with Zirconium oxide nano grain in organic backbone, organic backbone, the nano combined suction
Attached dose of pore volume is 0.3-0.9cm3/ g, specific surface area is 600-1500m2/ g, and diameter accounts for total pore volume in below 2nm hole
Ratio >=90%.Because the pore structure of the nano composite material of the present invention is mainly distributed on range of micropores, thus size can be passed through
Excretion reduces influence of the natural organic matter to fluorine removal, when organic matter concentration is larger in water, to the removal effect of fluorine almost
It is unaffected, remain to realize advanced treating and the security control of Micro fluoride.
(2) a kind of depth of the invention is removed in the resin-base nano compound adsorbent of Micro fluoride, adsorbent and aoxidized
The load capacity of zirconium is calculated as 10-30wt% with zr element, and the size of Zirconium oxide nano grain is 10-80nm, compared with prior art
The load capacity of Zirconium oxide nano grain is high, and size is tiny, adsorption area is substantially increased, so as to effectively increase the absorption to fluorine
Amount.
(3) a kind of preparation method of resin-base nano compound adsorbent of the invention, can be had using the method for the present invention
Pore size on effect reduction adsorbing agent carrier, and the load capacity of zirconia particles is improved, so as to ensure to prepare gained adsorbent
To the depth removal effect of Micro fluoride.
(4) a kind of depth of the invention removes the application of the resin-base nano compound adsorbent of Micro fluoride, using this
The resin-base nano compound adsorbent of invention carries out adsorption treatment to the fluorine in water, the concentration of fluorine in water can effectively be dropped into 1mg/
Below L, and adsorbent after adsorption treatment is that can carry out desorption and regeneration using alkali salt mixed solution, the desorption rate of fluorine is up to
90%.
Embodiment
A kind of depth of the present invention removes the resin-base nano compound adsorbent of Micro fluoride, and the adsorbent is with tertiary-aminated
Hypercrosslinked polystyrene-divinylbenzene be organic backbone, the contents of tertiary amine groups is 0.2-1.5mmol/g, organic backbone
Pore volume is 0.5-1.2cm3/ g, specific surface area is 400-1200m2Hole on/g, and organic backbone includes macropore and the species of aperture two
Type, macropore with diameter greater than 30nm, the diameter of aperture is less than 2nm, and the ratio in two kinds of holes is 40-60%.Above-mentioned organic bone
Zirconium oxide nano grain is loaded with frame, the load capacity of zirconium oxide is calculated as 10-30wt% with zr element, Zirconium oxide nano grain
Size is 10-80nm, and Zirconium oxide nano grain basic load is in the macropore on organic backbone, the gained composite adsorption after load
The pore volume of agent is 0.3-0.9cm3/ g, specific surface area is 600-1500m2/ g, and diameter accounts for the ratio of total pore volume in below 2nm hole
Example >=90%.
The preparation method of the above-mentioned resin-base nano compound adsorbent of the present invention, its process is as follows：After drying process
Tertiary-aminated Polystyrene resin immerses ZrOCl2·8H2In O, HCl and the mixed solution of ethanol, and in stirring condition
Under be evaporated, ZrOCl in above-mentioned mixed solution2·8H2O, HCl and the mass ratio of ethanol are (2.5-8): 1: 6；Then sequentially add
Mass concentration is the 3-6% NaOH and NaCl aqueous solution, drying to obtain resin-base nano oxygen after being washed through transition, washing, alcohol
Change zirconium composite material.
When carrying out adsorption treatment to the fluorine in water using present invention preparation gained resin-base nano compound adsorbent, due to warp
The pore structure of nano composite material is mainly distributed on range of micropores after load, thus can naturally have by size exclusion effect reduction
Influence of the machine thing to fluorine removal, when organic matter concentration is larger in water, the removal effect to fluorine is barely affected, and remains to realize water
The advanced treating of middle Trace Fluoride and security control.Averagely every gram in terms of zirconium of the Zirconium oxide nano grain loaded in adsorbent is adsorbable
Fluorine 40-120mg, adsorption rate is higher, the concentration of fluorine in water can effectively be dropped into below 1mg/L.Meanwhile, pass through alkali salt mixed solution
Nano-compound adsorbent after absorption can be carried out in desorption and regeneration, the desorption rate ＞ 90% of fluorine, above-mentioned alkali salt mixed solution
Alkali be NaOH or KOH, salt is NaCl or KCl, and the mass concentration of alkali, salt is 3-6%.
To further appreciate that present disclosure, in conjunction with specific embodiment, the present invention is described in detail.
Embodiment 1
By the tertiary-aminated Polystyrene resins of dried 10g, (tertiary amine groups content is 0.8mmol/g, organic bone
It is 1.0cm that frame aperture, which is held,3/ g, specific surface area is 800m2/ g) immersion 30gZrOCl2·8H2The mixing of O, 10g HCl, 60g ethanol is molten
Liquid 200mL is simultaneously evaporated under agitation.The subsequent NaCl solution transition for sequentially adding the NaOH and 5% that mass concentration is 5%,
Washing, alcohol are dried to obtain resin-base nano zirconium oxide composite material (nano-compound adsorbent) after washing.
Zirconium in composite is measured after clearing up by acidifying using inductively coupled plasma atomic emission (ICP-AES) to contain
Measure as 12wt%, can be obtained by transmission electron microscope observation, the particle diameter of Zirconium oxide nano grain is 10- in composite
80nm.Pass through N2The pore volume that the experiment of-adsorption/desorption measures nano composite material is 0.6cm3/ g, specific surface area is 900m2/ g, directly
Footpath accounts for the 95% of total pore volume for below 2nm hole.
Gained nano composite material (4mL) is fitted into the glass adsorption column of jacketed (12 × 240mm of Φ), fluorine will be simulated
(water body pH is about 6.5 to micropollutant water, and the concentration of fluorine is 5mg/L, and the concentration of humic acid is 2.5mg/L (DOC), background ions
Cl-、SO4 2-、NO3 -、SiO3 2-Be 250mg/L) with 20mL/h flow by resin bed, treating capacity is 160BV (BV herein
Refer to resin bed volume), the concentration of water outlet fluorine can effectively drop to below 1mg/L.It is NaOH (5%)-NaCl with 200ml concentration
(5%) mixed solution is desorbed with 4mL/h flow downstream through resin bed, the desorption rate ＞ 90% of fluorine, after desorption
Nano composite material can continue on for circulation absorption next time.
Embodiment 2
By the tertiary-aminated Polystyrene resins of dried 10g, (tertiary amine content is 0.8mmol/g, organic backbone
Pore volume is 1.0cm3/ g, specific surface area is 800m2/ g) immersion 30g ZrOCl2·8H2The mixing of O, 10g HCl, 60g ethanol is molten
Liquid 200mL is simultaneously evaporated under agitation.Then sequentially add NaCl transition, the water for the NaOH and 5% that mass concentration is 5%
Wash, alcohol is dried to obtain resin-base nano zirconium oxide composite material after washing.
Zirconium in composite is measured after clearing up by acidifying using inductively coupled plasma atomic emission (ICP-AES) to contain
Measure as 12wt%, can be obtained by transmission electron microscope observation, the particle diameter of the Zirconium oxide nano grain in composite is 10-
80nm.Pass through N2The pore volume that the experiment of-adsorption/desorption measures nano composite material is 0.6cm3/ g, specific surface area is 900m2/ g, 2nm
Following hole accounts for the 95% of total pore volume.
Gained nano composite material (4mL) is fitted into the glass adsorption column of jacketed (12 × 240mm of Φ), fluorine will be simulated
(water body pH is about 6.5 to micropollutant water, and the concentration of fluorine is 10mg/L, and the concentration of humic acid is 2.5mg/L (DOC), background ions
Cl-、SO4 2-、NO3 -、SiO3 2-Be 250mg/L) with 20mL/h flow by resin bed, treating capacity is 140BV, water outlet fluorine
Concentration drop to below 1mg/L.It is suitable with 4mL/h flow with the mixed solution that 200ml concentration is NaOH (5%)-NaCl (5%)
Stream is desorbed by resin bed, the desorption rate ＞ 90% of fluorine, and the nano composite material after desorption can continue on for next time
Circulation absorption.
Embodiment 3
By the tertiary-aminated Polystyrene resins of dried 10g, (tertiary amine content is 0.2mmol/g, and pore volume is
1.2cm3/ g, specific surface area is 1200m2/ g) immersion 25g ZrOCl2·8H2The mixed solution of O, 10g HCl, 60g ethanol
200mL is simultaneously evaporated under agitation.Then sequentially add mass concentration be 3% NaOH and 3% NaCl transition, washing,
Alcohol is dried to obtain resin-base nano zirconium oxide composite material after washing.
Zirconium in composite is measured after clearing up by acidifying using inductively coupled plasma atomic emission (ICP-AES) to contain
Measure as 10wt%, can be obtained by transmission electron microscope observation, the particle diameter of the Zirconium oxide nano grain in composite is 10-
80nm.Pass through N2The pore volume that the experiment of-adsorption/desorption measures nano composite material is 0.9cm3/ g, specific surface area is 1500m2/ g,
Below 2nm hole accounts for the 96% of total pore volume.
Gained nano composite material (4mL) is fitted into the glass adsorption column of jacketed (12 × 240mm of Φ), fluorine will be simulated
(water body pH is about 6.5 to micropollutant water, and the concentration of fluorine is 20mg/L, and the concentration of humic acid is 2.5mg/L (DOC), background ions
Cl-、SO4 2-、NO3 -、SiO3 2-Be 250mg/L) with 20mL/h flow by resin bed, treating capacity is 80BV, water outlet fluorine
Concentration drop to below 1mg/L.It is suitable with 4mL/h flow with the mixed solution that 200ml concentration is NaOH (3%)-NaCl (3%)
Stream is desorbed by resin bed, the desorption rate ＞ 90% of fluorine, and the nano composite material after desorption can continue on for next time
Circulation absorption.
Embodiment 4
By the tertiary-aminated Polystyrene resins of dried 10g, (tertiary amine content is 1.5mmol/g, and pore volume is
0.5cm3/ g, specific surface area is 400m2/ g) immersion 80g ZrOCl2·8H2The mixed solution 200mL of O, 10g HCl, 60g ethanol
And be evaporated under agitation.The NaCl transition, washing, alcohol for then sequentially adding 6% NaOH and 6% are dried to obtain tree after washing
Aliphatic radical nano zirconium oxide composite material.
Zirconium in composite is measured after clearing up by acidifying using inductively coupled plasma atomic emission (ICP-AES) to contain
Measure as 30wt%, can be obtained by transmission electron microscope observation, the particle diameter of the Zirconium oxide nano grain in composite is 10-
80nm.Pass through N2The pore volume that the experiment of-adsorption/desorption measures nano composite material is 0.3cm3/ g, specific surface area is 600m2/ g, 2nm
Following hole accounts for the 95% of total pore volume.
Gained nano composite material (4mL) is fitted into the glass adsorption column of jacketed (12 × 240mm of Φ), fluorine will be simulated
(water body pH is about 6.5 to micropollutant water, and the concentration of fluorine is 5mg/L, and the concentration of humic acid is 5mg/L (DOC), background ions
Cl-、SO4 2-、NO3 -、SiO3 2-Be 250mg/L) with 20mL/h flow by resin bed, treating capacity is 160BV, water outlet fluorine
Concentration drop to below 1mg/L.Be NaOH (6%)-NaCl6% with 200ml concentration) mixed solution it is suitable with 4mL/h flow
Stream is desorbed by resin bed, the desorption rate ＞ 90% of fluorine, and the nano composite material after desorption can continue on for next time
Circulation absorption.
Embodiment 5
By the tertiary-aminated Polystyrene resins of dried 10g, (tertiary amine content is 0.6mmol/g, and pore volume is
0.8cm3/ g, specific surface area is 1000m2/ g) immersion 65g ZrOCl2·8H2The mixed solution of O, 10g HCl, 60g ethanol
200mL is simultaneously evaporated under agitation.The NaCl transition, washing, alcohol for then sequentially adding 5% NaOH and 5% are dried after washing
Obtain resin-base nano zirconium oxide composite material.
Zirconium in composite is measured after clearing up by acidifying using inductively coupled plasma atomic emission (ICP-AES) to contain
Measure as 25wt%, can be obtained by transmission electron microscope observation, the particle diameter of the Zirconium oxide nano grain in composite is 10-
80nm.Pass through N2The pore volume that the experiment of-adsorption/desorption measures nano composite material is 0.5cm3/ g, specific surface area is 800m2/ g, 2nm
Following hole accounts for the 93% of total pore volume.
Gained nano composite material (4mL) is fitted into the glass adsorption column of jacketed (12 × 240mm of Φ), fluorine will be simulated
(water body pH is about 6.5 to micropollutant water, and the concentration of fluorine is 10mg/L, and the concentration of humic acid is 5mg/L (DOC), background ions
Cl-、SO4 2-、NO3 -、SiO3 2-Be 250mg/L) with 20mL/h flow by resin bed, treating capacity is 140BV, water outlet fluorine
Concentration drop to below 1mg/L.It is suitable with 4mL/h flow with the mixed solution that 200ml concentration is NaOH (5%)-NaCl (5%)
Stream is desorbed by resin bed, the desorption rate ＞ 90% of fluorine, and the nano composite material after desorption can continue on for next time
Circulation absorption.
Embodiment 6
By the tertiary-aminated Polystyrene resins of dried 10g, (tertiary amine content is 0.gmmol/g, and pore volume is
1.0cm3/ g, specific surface area is 800m2/ g) immersion 30g ZrOCl2·8H2The mixed solution 200mL of O, 10g HCl, 60g ethanol
And be evaporated under agitation.The NaCl transition, washing, alcohol for then sequentially adding 5% NaOH and 5% are dried to obtain tree after washing
Aliphatic radical nano zirconium oxide composite material.
Zirconium in composite is measured after clearing up by acidifying using inductively coupled plasma atomic emission (ICP-AES) to contain
Measure as 12wt%, can be obtained by transmission electron microscope observation, the particle diameter of the Zirconium oxide nano grain in composite is 10-
80nm.Pass through N2The pore volume that the experiment of-adsorption/desorption measures nano composite material is 0.6cm3/ g, specific surface area is 900m2/ g, 2nm
Following hole accounts for the 95% of total pore volume.
Gained nano composite material (4mL) is fitted into the glass adsorption column of jacketed (12 × 240mm of Φ), fluorine will be simulated
(water body pH is about 6.5 to micropollutant water, and the concentration of fluorine is 20mg/L, and the concentration of humic acid is 5mg/L (DOC), background ions
Cl-、SO4 2-、NO3 -、SiO3 2-Be 250mg/L) with 20mL/h flow by resin bed, treating capacity is 80BV, water outlet fluorine
Concentration drop to below 1mg/L.It is suitable with 4mL/h flow with the mixed solution that 200ml concentration is NaOH (5%)-NaCl (5%)
Stream is desorbed by resin bed, the desorption rate ＞ 90% of fluorine, and the nano composite material after desorption can continue on for next time
Circulation absorption.
Embodiment 7
By the tertiary-aminated Polystyrene resins of dried 10g, (tertiary amine content is 0.8mmol/g, and pore volume is
1.0cm3/ g, specific surface area is 800m2/ g) immersion 30g ZrOCl2·8H2The mixed solution 200mL of O, 10g HCl, 60g ethanol
And be evaporated under agitation.The NaCl transition, washing, alcohol for then sequentially adding 5% NaOH and 5% are dried to obtain tree after washing
Aliphatic radical nano zirconium oxide composite material.
Zirconium in composite is measured after clearing up by acidifying using inductively coupled plasma atomic emission (ICP-AES) to contain
Measure as 12wt%, can be obtained by transmission electron microscope observation, the particle diameter of the Zirconium oxide nano grain in composite is 10-
80nm.Pass through N2The pore volume that the experiment of-adsorption/desorption measures nano composite material is 0.6cm3/ g, specific surface area is 900m2/ g, 2nm
Following hole accounts for the 95% of total pore volume.
Gained nano composite material (4mL) is fitted into the glass adsorption column of jacketed (12 × 240mm of Φ), fluorine will be simulated
(water body pH is about 6.5 to micropollutant water, and the concentration of fluorine is 5mg/L, and the concentration of humic acid is 10mg/L (DOC), background ions
Cl-、SO4 2-、NO3 -、SiO3 2-Be 250mg/L) with 20mL/h flow by resin bed, treating capacity is 160BV, water outlet fluorine
Concentration drop to below 1mg/L.It is suitable with 4mL/h flow with the mixed solution that 200ml concentration is NaOH (5%)-NaCl (5%)
Stream is desorbed by resin bed, the desorption rate ＞ 90% of fluorine, and the nano composite material after desorption can continue on for next time
Circulation absorption.
Embodiment 8
By the tertiary-aminated Polystyrene resins of dried 10g, (tertiary amine content is 0.8mmol/g, and pore volume is
1.0cm3/ g, specific surface area is 800m2/ g) immersion 30g ZrOCl2·8H2The mixed solution 200mL of O, 10g HCl, 60g ethanol
And be evaporated under agitation.The NaCl transition, washing, alcohol for then sequentially adding 5% NaOH and 5% are dried to obtain tree after washing
Aliphatic radical nano zirconium oxide composite material.
Zirconium in composite is measured after clearing up by acidifying using inductively coupled plasma atomic emission (ICP-AES) to contain
Measure as 12wt%, can be obtained by transmission electron microscope observation, the particle diameter of the Zirconium oxide nano grain in composite is 10-
80nm.Pass through N2The pore volume that the experiment of-adsorption/desorption measures nano composite material is 0.6cm3/ g, specific surface area is 900m2/ g, 2nm
Following hole accounts for the 95% of total pore volume.
Gained nano composite material (4mL) is fitted into the glass adsorption column of jacketed (12 × 240mm of Φ), fluorine will be simulated
(water body pH is about 6.5 to micropollutant water, and the concentration of fluorine is 10mg/L, and the concentration of humic acid is 10mg/L (DOC), background ions
Cl-、SO4 2-、NO3 -、SiO3 2-Be 250mg/L) with 20mL/h flow by resin bed, treating capacity is 140BV, water outlet fluorine
Concentration drop to below 1mg/L.It is suitable with 4mL/h flow with the mixed solution that 200ml concentration is NaOH (5%)-NaCl (5%)
Stream is desorbed by resin bed, the desorption rate ＞ 90% of fluorine, and the nano composite material after desorption can continue on for next time
Circulation absorption.
Embodiment 9
By the tertiary-aminated Polystyrene resins of dried 10g, (tertiary amine content is 0.8mmol/g, and pore volume is
1.0cm3/ g, specific surface area is 800m2/ g) immersion 30g ZrOCl2·8H2The mixed solution 200mL of O, 10g HCl, 60g ethanol
And be evaporated under agitation.The NaCl transition, washing, alcohol for then sequentially adding 5% NaOH and 5% are dried to obtain tree after washing
Aliphatic radical nano zirconium oxide composite material.
Zirconium in composite is measured after clearing up by acidifying using inductively coupled plasma atomic emission (ICP-AES) to contain
Measure as 12wt%, can be obtained by transmission electron microscope observation, the particle diameter of the Zirconium oxide nano grain in composite is 10-
80nm.Pass through N2The pore volume that the experiment of-adsorption/desorption measures nano composite material is 0.6cm3/ g, specific surface area is 900m2/ g, 2nm
Following hole accounts for the 95% of total pore volume.
Gained nano composite material (4mL) is fitted into the glass adsorption column of jacketed (12 × 240mm of Φ), fluorine will be simulated
(water body pH is about 6.5 to micropollutant water, and the concentration of fluorine is 20mg/L, and the concentration of humic acid is 10mg/L (DOC), background ions
Cl-、SO4 2-、NO3 -、SiO3 2-Be 250mg/L) with 20mL/h flow by resin bed, treating capacity is 80BV, water outlet fluorine
Concentration drop to below 1mg/L.It is suitable with 4mL/h flow with the mixed solution that 200ml concentration is NaOH (5%)-NaCl (5%)
Stream is desorbed by resin bed, the desorption rate ＞ 90% of fluorine, and the nano composite material after desorption can continue on for next time
Circulation absorption.
Embodiment 10
By the tertiary-aminated Polystyrene resins of dried 10g, (tertiary amine content is 0.8mmol/g, and pore volume is
1.0cm3/ g, specific surface area is 800m2/ g) immersion 30g ZrOCl2·8H2The mixed solution 200mL of O, 10g HCl, 60g ethanol
And be evaporated under agitation.The NaCl transition, washing, alcohol for then sequentially adding 5% NaOH and 5% are dried to obtain tree after washing
Aliphatic radical nano zirconium oxide composite material.
Zirconium in composite is measured after clearing up by acidifying using inductively coupled plasma atomic emission (ICP-AES) to contain
Measure as 12wt%, can be obtained by transmission electron microscope observation, the particle diameter of the Zirconium oxide nano grain in composite is 10-
80nm.Pass through N2The pore volume that the experiment of-adsorption/desorption measures nano composite material is 0.6cm3/ g, specific surface area is 900m2/ g, 2nm
Following hole accounts for the 95% of total pore volume.
Gained nano composite material (4mL) is fitted into the glass adsorption column of jacketed (12 × 240mm of Φ), fluorine will be simulated
(water body pH is about 6.5 to micropollutant water, and the concentration of fluorine is 5mg/L, and the concentration of humic acid is 2.5mg/L (DOC), background ions
Cl-、SO4 2-、NO3 -、SiO3 2-Be 500mg/L) with 20mL/h flow by resin bed, treating capacity is 160BV, water outlet fluorine
Concentration drop to below 1mg/L.It is suitable with 4mL/h flow with the mixed solution that 200ml concentration is NaOH (5%)-NaCl (5%)
Stream is desorbed by resin bed, the desorption rate ＞ 90% of fluorine, and the nano composite material after desorption can continue on for next time
Circulation absorption.
Embodiment 11
By the tertiary-aminated Polystyrene resins of dried 10g, (tertiary amine content is 0.8mmol/g, and pore volume is
1.0cm3/ g, specific surface area is 800m2/ g) immersion 30g ZrOCl2·8H2The mixed solution 200mL of O, 10g HCl, 60g ethanol
And be evaporated under agitation.The NaCl transition, washing, alcohol for then sequentially adding 5% NaOH and 5% are dried to obtain tree after washing
Aliphatic radical nano zirconium oxide composite material.
Zirconium in composite is measured after clearing up by acidifying using inductively coupled plasma atomic emission (ICP-AES) to contain
Measure as 12wt%, can be obtained by transmission electron microscope observation, the particle diameter of the Zirconium oxide nano grain in composite is 10-
80nm.Pass through N2The pore volume that the experiment of-adsorption/desorption measures nano composite material is 0.6cm3/ g, specific surface area is 900m2/ g, 2nm
Following hole accounts for the 95% of total pore volume.
Gained nano composite material (4mL) is fitted into the glass adsorption column of jacketed (12 × 240mm of Φ), fluorine will be simulated
(water body pH is about 6.5 to micropollutant water, and the concentration of fluorine is 10mg/L, and the concentration of humic acid is 2.5mg/L (DOC), background ions
Cl-、SO4 2-、NO3 -、SiO3 2-Be 500mg/L) with 20mL/h flow by resin bed, treating capacity is 140BV, water outlet fluorine
Concentration drop to below 1mg/L.It is suitable with 4mL/h flow with the mixed solution that 200ml concentration is NaOH (5%)-NaCl (5%)
Stream is desorbed by resin bed, the desorption rate ＞ 90% of fluorine, and the nano composite material after desorption can continue on for next time
Circulation absorption.
Embodiment 12
By the tertiary-aminated Polystyrene resins of dried 10g, (tertiary amine content is 0.8mmol/g, and pore volume is
1.0cm3/ g, specific surface area is 800m2/ g) immersion 30g ZrOCl2·8H2The mixed solution 200mL of O, 10g HCl, 60g ethanol
And be evaporated under agitation.The NaCl transition, washing, alcohol for then sequentially adding 5% NaOH and 5% are dried to obtain tree after washing
Aliphatic radical nano zirconium oxide composite material.
Zirconium in composite is measured after clearing up by acidifying using inductively coupled plasma atomic emission (ICP-AES) to contain
Measure as 12wt%, can be obtained by transmission electron microscope observation, the particle diameter of the Zirconium oxide nano grain in composite is 10-
80nm.Pass through N2The pore volume that the experiment of-adsorption/desorption measures nano composite material is 0.6cm3/ g, specific surface area is 900m2/ g, 2nm
Following hole accounts for the 95% of total pore volume.
Gained nano composite material (4mL) is fitted into the glass adsorption column of jacketed (12 × 240mm of Φ), fluorine will be simulated
(water body pH is about 6.5 to micropollutant water, and the concentration of fluorine is 20mg/L, and the concentration of humic acid is 2.5mg/L (DOC), background ions
Cl-、SO4 2-、NO3 -、SiO3 2-Be 500mg/L) with 20mL/h flow by resin bed, treating capacity is 80BV, water outlet fluorine
Concentration drop to below 1mg/L.
With the mixed solution that 200ml concentration is NaOH (5%)-NaCl (5%) with 4mL/h flow downstream through resin bed
Layer is desorbed, the desorption rate ＞ 90% of fluorine, and the nano composite material after desorption can continue on for circulation absorption next time.
Embodiment 13
By the tertiary-aminated Polystyrene resins of dried 10g, (tertiary amine content is 0.8mmol/g, and pore volume is
1.0cm3/ g, specific surface area is 800m2/ g) immersion 30g ZrOCl2·8H2The mixed solution 200mL of O, 10g HCl, 60g ethanol
And be evaporated under agitation.The NaCl transition, washing, alcohol for then sequentially adding 5% NaOH and 5% are dried to obtain tree after washing
Aliphatic radical nano zirconium oxide composite material.
Zirconium in composite is measured after clearing up by acidifying using inductively coupled plasma atomic emission (ICP-AES) to contain
Measure as 12wt%, can be obtained by transmission electron microscope observation, the particle diameter of the Zirconium oxide nano grain in composite is 10-
80nm.Pass through N2The pore volume that the experiment of-adsorption/desorption measures nano composite material is 0.6cm3/ g, specific surface area is 900m2/ g, 2nm
Following hole accounts for the 95% of total pore volume.
Gained nano composite material (4mL) is fitted into the glass adsorption column of jacketed (12 × 240mm of Φ), fluorine will be simulated
(water body pH is about 6.5 to micropollutant water, and the concentration of fluorine is 5mg/L, and the concentration of humic acid is 5mg/L (DOC), background ions
Cl-、SO4 2-、NO3 -、SiO3 2-Be 500mg/L) with 20mL/h flow by resin bed, treating capacity is 160BV, water outlet fluorine
Concentration drop to below 1mg/L.
With the mixed solution that 200ml concentration is NaOH (5%)-NaCl (5%) with 4mL/h flow downstream through resin bed
Layer is desorbed, the desorption rate ＞ 90% of fluorine, and the nano composite material after desorption can continue on for circulation absorption next time.
Embodiment 14
By the tertiary-aminated Polystyrene resins of dried 10g, (tertiary amine content is 0.8mmol/g, and pore volume is
1.0cm3/ g, specific surface area is 800m2/ g) immersion 30g ZrOCl2·8H2The mixed solution 200mL of O, 10g HCl, 60g ethanol
And be evaporated under agitation.The NaCl transition, washing, alcohol for then sequentially adding 5% NaOH and 5% are dried to obtain tree after washing
Aliphatic radical nano zirconium oxide composite material.
Zirconium in composite is measured after clearing up by acidifying using inductively coupled plasma atomic emission (ICP-AES) to contain
Measure as 12wt%, can be obtained by transmission electron microscope observation, the particle diameter of the Zirconium oxide nano grain in composite is 10-
80nm.Pass through N2The pore volume that the experiment of-adsorption/desorption measures nano composite material is 0.6cm3/ g, specific surface area is 900m2/ g, 2nm
Following hole accounts for the 95% of total pore volume.
Gained nano composite material (4mL) is fitted into the glass adsorption column of jacketed (12 × 240mm of Φ), fluorine will be simulated
(water body pH is about 6.5 to micropollutant water, and the concentration of fluorine is 10mg/L, and the concentration of humic acid is 5mg/L (DOC), background ions
Cl-、SO4 2-、NO3 -、SiO3 2-Be 500mg/L) with 20mL/h flow by resin bed, treating capacity is 140BV, water outlet fluorine
Concentration drop to below 1mg/L.
With the mixed solution that 200ml concentration is NaOH (5%)-NaCl (5%) with 4mL/h flow downstream through resin bed
Layer is desorbed, the desorption rate ＞ 90% of fluorine, and the nano composite material after desorption can continue on for circulation absorption next time.
Embodiment 15
By the tertiary-aminated Polystyrene resins of dried 10g, (tertiary amine content is 0.8mmol/g, and pore volume is
1.0cm3/ g, specific surface area is 800m2/ g) immersion 30g ZrOCl2·8H2The mixed solution 200mL of O, 10g HCl, 60g ethanol
And be evaporated under agitation.The NaCl transition, washing, alcohol for then sequentially adding 5% NaOH and 5% are dried to obtain tree after washing
Aliphatic radical nano zirconium oxide composite material.
Zirconium in composite is measured after clearing up by acidifying using inductively coupled plasma atomic emission (ICP-AES) to contain
Measure as 12wt%, can be obtained by transmission electron microscope observation, the particle diameter of the Zirconium oxide nano grain in composite is 10-
80nm.Pass through N2The pore volume that the experiment of-adsorption/desorption measures nano composite material is 0.6cm3/ g, specific surface area is 900m2/ g, 2nm
Following hole accounts for the 95% of total pore volume.
Gained nano composite material (4mL) is fitted into the glass adsorption column of jacketed (12 × 240mm of Φ), fluorine will be simulated
(water body pH is about 6.5 to micropollutant water, and the concentration of fluorine is 20mg/L, and the concentration of humic acid is 5mg/L (DOC), background ions
Cl-、SO4 2-、NO3 -、SiO3 2-Be 500mg/L) with 20mL/h flow by resin bed, treating capacity is 80BV, water outlet fluorine
Concentration drop to below 1mg/L.
With the mixed solution that 200ml concentration is NaOH (5%)-NaCl (5%) with 4mL/h flow downstream through resin bed
Layer is desorbed, the desorption rate ＞ 90% of fluorine, and the nano composite material after desorption can continue on for circulation absorption next time.
Embodiment 16
By the tertiary-aminated Polystyrene resins of dried 10g, (tertiary amine content is 0.8mmol/g, and pore volume is
1.0cm3/ g, specific surface area is 800m2/ g) immersion 30g ZrOCl2·8H2The mixed solution 200mL of O, 10g HCl, 60g ethanol
And be evaporated under agitation.The NaCl transition, washing, alcohol for then sequentially adding 5% NaOH and 5% are dried to obtain tree after washing
Aliphatic radical nano zirconium oxide composite material.
Zirconium in composite is measured after clearing up by acidifying using inductively coupled plasma atomic emission (ICP-AES) to contain
Measure as 12wt%, can be obtained by transmission electron microscope observation, the particle diameter of the Zirconium oxide nano grain in composite is 10-
80nm.Pass through N2The pore volume that the experiment of-adsorption/desorption measures nano composite material is 0.6cm3/ g, specific surface area is 900m2/ g, 2nm
Following hole accounts for the 95% of total pore volume.
Gained nano composite material (4mL) is fitted into the glass adsorption column of jacketed (12 × 240mm of Φ), fluorine will be simulated
(water body pH is about 6.5 to micropollutant water, and the concentration of fluorine is 5mg/L, and the concentration of humic acid is 10mg/L (DOC), background ions
Cl-、SO4 2-、NO3 -、SiO3 2-Be 500mg/L) with 20mL/h flow by resin bed, treating capacity is 160BV, water outlet fluorine
Concentration drop to below 1mg/L.
With the mixed solution that 200ml concentration is NaOH (5%)-NaCl (5%) with 4mL/h flow downstream through resin bed
Layer is desorbed, the desorption rate ＞ 90% of fluorine, and the nano composite material after desorption can continue on for circulation absorption next time.
Embodiment 17
By the tertiary-aminated Polystyrene resins of dried 10g, (tertiary amine content is 0.8mmol/g, and pore volume is
1.0cm3/ g, specific surface area is 800m2/ g) immersion 30g ZrOCl2·8H2The mixed solution 200mL of O, 10g HCl, 60g ethanol
And be evaporated under agitation.The NaCl transition, washing, alcohol for then sequentially adding 5% NaOH and 5% are dried to obtain tree after washing
Aliphatic radical nano zirconium oxide composite material.
Zirconium in composite is measured after clearing up by acidifying using inductively coupled plasma atomic emission (ICP-AES) to contain
Measure as 12wt%, can be obtained by transmission electron microscope observation, the particle diameter of the Zirconium oxide nano grain in composite is 10-
80nm.Pass through N2The pore volume that the experiment of-adsorption/desorption measures nano composite material is 0.6cm3/ g, specific surface area is 900m2/ g, 2nm
Following hole accounts for the 95% of total pore volume.
Gained nano composite material (4mL) is fitted into the glass adsorption column of jacketed (12 × 240mm of Φ), fluorine will be simulated
(water body pH is about 6.5 to micropollutant water, and the concentration of fluorine is 10mg/L, and the concentration of humic acid is 10mg/L (DOC), background ions
Cl-、SO4 2-、NO3 -、SiO3 2-Be 500mg/L) with 20mL/h flow by resin bed, treating capacity is 140BV, water outlet fluorine
Concentration drop to below 1mg/L.
With the mixed solution that 200ml concentration is NaOH (5%)-NaCl (5%) with 4mL/h flow downstream through resin bed
Layer is desorbed, the desorption rate ＞ 90% of fluorine, and the nano composite material after desorption can continue on for circulation absorption next time.
Embodiment 18
By the tertiary-aminated Polystyrene resins of dried 10g, (tertiary amine content is 0.8mmol/g, and pore volume is
1.0cm3/ g, specific surface area is 800m2/ g) immersion 30g ZrOCl2·8H2The mixed solution 200mL of O, 10g HCl, 60g ethanol
And be evaporated under agitation.The NaCl transition, washing, alcohol for then sequentially adding 5% NaOH and 5% are dried to obtain tree after washing
Aliphatic radical nano zirconium oxide composite material.
Zirconium in composite is measured after clearing up by acidifying using inductively coupled plasma atomic emission (ICP-AES) to contain
Measure as 12wt%, can be obtained by transmission electron microscope observation, the particle diameter of the Zirconium oxide nano grain in composite is 10-
80nm.Pass through N2The pore volume that the experiment of-adsorption/desorption measures nano composite material is 0.6cm3/ g, specific surface area is 900m2/ g, 2nm
Following hole accounts for the 95% of total pore volume.
Gained nano composite material (4mL) is fitted into the glass adsorption column of jacketed (12 × 240mm of Φ), fluorine will be simulated
(water body pH is about 6.5 to micropollutant water, and the concentration of fluorine is 20mg/L, and the concentration of humic acid is 10mg/L (DOC), background ions
Cl-、SO4 2-、NO3 -、SiO3 2-Be 500mg/L) with 20mL/h flow by resin bed, treating capacity is 80BV, water outlet fluorine
Concentration drop to below 1mg/L.
With the mixed solution that 200ml concentration is NaOH (5%)-NaCl (5%) with 4mL/h flow downstream through resin bed
Layer is desorbed, the desorption rate ＞ 90% of fluorine, and the nano composite material after desorption can continue on for circulation absorption next time.
Embodiment 19
By the tertiary-aminated Polystyrene resins of dried 10g, (tertiary amine content is 0.8mmol/g, and pore volume is
1.0cm3/ g, specific surface area is 800m2/ g) immersion 60g ZrOCl2·8H2The mixed solution 200mL of O, 10g HCl, 60g ethanol
And be evaporated under agitation.The NaCl transition, washing, alcohol for then sequentially adding 5% NaOH and 5% are dried to obtain tree after washing
Aliphatic radical nano zirconium oxide composite material.
Zirconium in composite is measured after clearing up by acidifying using inductively coupled plasma atomic emission (ICP-AES) to contain
Measure as 22wt%, can be obtained by transmission electron microscope observation, the particle diameter of the Zirconium oxide nano grain in composite is 10-
80nm.Pass through N2The pore volume that the experiment of-adsorption/desorption measures nano composite material is 0.9cm3/ g, specific surface area is 1200m2/ g,
Below 2nm hole accounts for the 95% of total pore volume.
Gained nano composite material (4mL) is fitted into the glass adsorption column of jacketed (12 × 240mm of Φ), fluorine will be simulated
(water body pH is about 6.5 to micropollutant water, and the concentration of fluorine is 5mg/L, and the concentration of humic acid is 2.5mg/L (DOC), background ions
Cl-、SO4 2-、NO3 -、SiO3 2-Be 250mg/L) with 20mL/h flow by resin bed, treating capacity is 300BV, water outlet fluorine
Concentration drop to below 1mg/L.
With the mixed solution that 200ml concentration is NaOH (5%)-NaCl (5%) with 4mL/h flow downstream through resin bed
Layer is desorbed, the desorption rate ＞ 90% of fluorine, and the nano composite material after desorption can continue on for circulation absorption next time.
Embodiment 20
By the tertiary-aminated Polystyrene resins of dried 10g, (tertiary amine content is 0.8mmol/g, and pore volume is
1.0cm3/ g, specific surface area is 800m2/ g) immersion 60g ZrOCl2·8H2The mixed solution 200mL of O, 10g HCl, 60g ethanol
And be evaporated under agitation.The NaCl transition, washing, alcohol for then sequentially adding 5% NaOH and 5% are dried to obtain tree after washing
Aliphatic radical nano zirconium oxide composite material.
Zirconium in composite is measured after clearing up by acidifying using inductively coupled plasma atomic emission (ICP-AES) to contain
Measure as 22wt%, can be obtained by transmission electron microscope observation, the particle diameter of the Zirconium oxide nano grain in composite is 10-
80nm.Pass through N2The pore volume that the experiment of-adsorption/desorption measures nano composite material is 0.9cm3/ g, specific surface area is 1200m2/ g,
Below 2nm hole accounts for the 95% of total pore volume.
Gained nano composite material (4mL) is fitted into the glass adsorption column of jacketed (12 × 240mm of Φ), fluorine will be simulated
(water body pH is about 6.5 to micropollutant water, and the concentration of fluorine is 10mg/L, and the concentration of humic acid is 2.5mg/L (DOC), background ions
Cl-、SO4 2-、NO3 -、SiO3 2-Be 250mg/L) with 20mL/h flow by resin bed, treating capacity is 270BV, water outlet fluorine
Concentration drop to below 1mg/L.
With the mixed solution that 200ml concentration is NaOH (5%)-NaCl (5%) with 4mL/h flow downstream through resin bed
Layer is desorbed, the desorption rate ＞ 90% of fluorine, and the nano composite material after desorption can continue on for circulation absorption next time.
Embodiment 21
By the tertiary-aminated Polystyrene resins of dried 10g, (tertiary amine content is 0.8mmol/g, and pore volume is
1.0cm3/ g, specific surface area is 800m2/ g) immersion 60g ZrOCl2·8H2The mixed solution 200mL of O, 10g HCl, 60g ethanol
And be evaporated under agitation.The NaCl transition, washing, alcohol for then sequentially adding 5% NaOH and 5% are dried to obtain tree after washing
Aliphatic radical nano zirconium oxide composite material.
Zirconium in composite is measured after clearing up by acidifying using inductively coupled plasma atomic emission (ICP-AES) to contain
Measure as 22wt%, can be obtained by transmission electron microscope observation, the particle diameter of the Zirconium oxide nano grain in composite is 10-
80nm.Pass through N2The pore volume that the experiment of-adsorption/desorption measures nano composite material is 0.9cm3/ g, specific surface area is 1200m2/ g,
Below 2nm hole accounts for the 95% of total pore volume.
Gained nano composite material (4mL) is fitted into the glass adsorption column of jacketed (12 × 240mm of Φ), fluorine will be simulated
(water body pH is about 6.5 to micropollutant water, and the concentration of fluorine is 20mg/L, and the concentration of humic acid is 2.5mg/L (DOC), background ions
Cl-、SO4 2-、NO3 -、SiO3 2-Be 250mg/L) with 20mL/h flow by resin bed, treating capacity is 230BV, water outlet fluorine
Concentration drop to below 1mg/L.
With the mixed solution that 200ml concentration is NaOH (5%)-NaCl (5%) with 4mL/h flow downstream through resin bed
Layer is desorbed, the desorption rate ＞ 90% of fluorine, and the nano composite material after desorption can continue on for circulation absorption next time.
Embodiment 22
By the tertiary-aminated Polystyrene resins of dried 10g, (tertiary amine content is 0.8mmol/g, and pore volume is
1.0cm3/ g, specific surface area is 800m2/ g) immersion 60g ZrOCl2·8H2The mixed solution 200mL of O, 10g HCl, 60g ethanol
And be evaporated under agitation.The NaCl transition, washing, alcohol for then sequentially adding 5% NaOH and 5% are dried to obtain tree after washing
Aliphatic radical nano zirconium oxide composite material.
Zirconium in composite is measured after clearing up by acidifying using inductively coupled plasma atomic emission (ICP-AES) to contain
Measure as 22wt%, can be obtained by transmission electron microscope observation, the particle diameter of the Zirconium oxide nano grain in composite is 10-
80nm.Pass through N2The pore volume that the experiment of-adsorption/desorption measures nano composite material is 0.9cm3/ g, specific surface area is 1200m2/ g,
Below 2nm hole accounts for the 95% of total pore volume.
Gained nano composite material (4mL) is fitted into the glass adsorption column of jacketed (12 × 240mm of Φ), fluorine will be simulated
(water body pH is about 6.5 to micropollutant water, and the concentration of fluorine is 5mg/L, and the concentration of humic acid is 5mg/L (DOC), background ions
Cl-、SO4 2-、NO3 -、SiO3 2-Be 250mg/L) with 20mL/h flow by resin bed, treating capacity is 300BV, water outlet fluorine
Concentration drop to below 1mg/L.
With the mixed solution that 200ml concentration is NaOH (5%)-NaCl (5%) with 4mL/h flow downstream through resin bed
Layer is desorbed, the desorption rate ＞ 90% of fluorine, and the nano composite material after desorption can continue on for circulation absorption next time.
Embodiment 23
By the tertiary-aminated Polystyrene resins of dried 10g, (tertiary amine content is 0.8mmol/g, and pore volume is
1.0cm3/ g, specific surface area is 800m2/ g) immersion 60g ZrOCl2·8H2The mixed solution 200mL of O, 10g HCl, 60g ethanol
And be evaporated under agitation.The NaCl transition, washing, alcohol for then sequentially adding 5% NaOH and 5% are dried to obtain tree after washing
Aliphatic radical nano zirconium oxide composite material.
Zirconium in composite is measured after clearing up by acidifying using inductively coupled plasma atomic emission (ICP-AES) to contain
Measure as 22wt%, can be obtained by transmission electron microscope observation, the particle diameter of the Zirconium oxide nano grain in composite is 10-
80nm.Pass through N2The pore volume that the experiment of-adsorption/desorption measures nano composite material is 0.9cm3/ g, specific surface area is 1200m2/ g,
Below 2nm hole accounts for the 95% of total pore volume.
Gained nano composite material (4mL) is fitted into the glass adsorption column of jacketed (12 × 240mm of Φ), fluorine will be simulated
(water body pH is about 6.5 to micropollutant water, and the concentration of fluorine is 10mg/L, and the concentration of humic acid is 5mg/L (DOC), background ions
Cl-、SO4 2-、NO3 -、SiO3 2-Be 250mg/L) with 20mL/h flow by resin bed, treating capacity is 270BV, water outlet fluorine
Concentration drop to below 1mg/L.
With the mixed solution that 200ml concentration is NaOH (5%)-NaCl (5%) with 4mL/h flow downstream through resin bed
Layer is desorbed, the desorption rate ＞ 90% of fluorine, and the nano composite material after desorption can continue on for circulation absorption next time.
Embodiment 24
By the tertiary-aminated Polystyrene resins of dried 10g, (tertiary amine content is 0.8mmol/g, and pore volume is
1.0cm3/ g, specific surface area is 800m2/ g) immersion 60g ZrOCl2·8H2The mixed solution 200mL of O, 10g HCl, 60g ethanol
And be evaporated under agitation.The NaCl transition, washing, alcohol for then sequentially adding 5% NaOH and 5% are dried to obtain tree after washing
Aliphatic radical nano zirconium oxide composite material.
Zirconium in composite is measured after clearing up by acidifying using inductively coupled plasma atomic emission (ICP-AES) to contain
Measure as 22wt%, can be obtained by transmission electron microscope observation, the particle diameter of the Zirconium oxide nano grain in composite is 10-
80nm.Pass through N2The pore volume that the experiment of-adsorption/desorption measures nano composite material is 0.9cm3/ g, specific surface area is 1200m2/ g,
Below 2nm hole accounts for the 95% of total pore volume.
Gained nano composite material (4mL) is fitted into the glass adsorption column of jacketed (12 × 240mm of Φ), fluorine will be simulated
(water body pH is about 6.5 to micropollutant water, and the concentration of fluorine is 20mg/L, and the concentration of humic acid is 5mg/L (DOC), background ions
Cl-、SO4 2-、NO3 -、SiO3 2-Be 250mg/L) with 20mL/h flow by resin bed, treating capacity is 230BV, water outlet fluorine
Concentration drop to below 1mg/L.
With the mixed solution that 200ml concentration is NaOH (5%)-NaCl (5%) with 4mL/h flow downstream through resin bed
Layer is desorbed, the desorption rate ＞ 90% of fluorine, and the nano composite material after desorption can continue on for circulation absorption next time.
Embodiment 25
By the tertiary-aminated Polystyrene resins of dried 10g, (tertiary amine content is 0.8mmol/g, and pore volume is
1.0cm3/ g, specific surface area is 800m2/ g) immersion 60g ZrOCl2·8H2The mixed solution 200mL of O, 10g HCl, 60g ethanol
And be evaporated under agitation.The NaCl transition, washing, alcohol for then sequentially adding 5% NaOH and 5% are dried to obtain tree after washing
Aliphatic radical nano zirconium oxide composite material.
Zirconium in composite is measured after clearing up by acidifying using inductively coupled plasma atomic emission (ICP-AES) to contain
Measure as 22wt%, can be obtained by transmission electron microscope observation, the particle diameter of the Zirconium oxide nano grain in composite is 10-
80nm.Pass through N2The pore volume that the experiment of-adsorption/desorption measures nano composite material is 0.9cm3/ g, specific surface area is 1200m2/ g,
Below 2nm hole accounts for the 95% of total pore volume.
Gained nano composite material (4mL) is fitted into the glass adsorption column of jacketed (12 × 240mm of Φ), fluorine will be simulated
(water body pH is about 6.5 to micropollutant water, and the concentration of fluorine is 5mg/L, and the concentration of humic acid is 10mg/L (DOC), background ions
Cl-、SO4 2-、NO3 -、SiO3 2-Be 250mg/L) with 20mL/h flow by resin bed, treating capacity is 300BV, water outlet fluorine
Concentration drop to below 1mg/L.
With the mixed solution that 200ml concentration is NaOH (5%)-NaCl (5%) with 4mL/h flow downstream through resin bed
Layer is desorbed, the desorption rate ＞ 90% of fluorine, and the nano composite material after desorption can continue on for circulation absorption next time.
Embodiment 26
By the tertiary-aminated Polystyrene resins of dried 10g, (tertiary amine content is 0.8mmol/g, and pore volume is
1.0cm3/ g, specific surface area is 800m2/ g) immersion 60g ZrOCl2·8H2The mixed solution 200mL of O, 10g HCl, 60g ethanol
And be evaporated under agitation.The NaCl transition, washing, alcohol for then sequentially adding 5% NaOH and 5% are dried to obtain tree after washing
Aliphatic radical nano zirconium oxide composite material.
Zirconium in composite is measured after clearing up by acidifying using inductively coupled plasma atomic emission (ICP-AES) to contain
Measure as 22wt%, can be obtained by transmission electron microscope observation, the particle diameter of the Zirconium oxide nano grain in composite is 10-
80nm.Pass through N2The pore volume that the experiment of-adsorption/desorption measures nano composite material is 0.9cm3/ g, specific surface area is 1200m2/ g,
Below 2nm hole accounts for the 95% of total pore volume.
Gained nano composite material (4mL) is fitted into the glass adsorption column of jacketed (12 × 240mm of Φ), fluorine will be simulated
(water body pH is about 6.5 to micropollutant water, and the concentration of fluorine is 10mg/L, and the concentration of humic acid is 10mg/L (DOC), background ions
Cl-、SO4 2-、NO3 -、SiO3 2-Be 250mg/L) with 20mL/h flow by resin bed, treating capacity is 270BV, water outlet fluorine
Concentration drop to below 1mg/L.
With the mixed solution that 200ml concentration is NaOH (5%)-NaCl (5%) with 4mL/h flow downstream through resin bed
Layer is desorbed, the desorption rate ＞ 90% of fluorine, and the nano composite material after desorption can continue on for circulation absorption next time.
Embodiment 27
By the tertiary-aminated Polystyrene resins of dried 10g, (tertiary amine content is 0.8mmol/g, and pore volume is
1.0cm3/ g, specific surface area is 800m2/ g) immersion 60g ZrOCl2·8H2The mixed solution 200mL of O, 10g HCl, 60g ethanol
And be evaporated under agitation.The NaCl transition, washing, alcohol for then sequentially adding 5% NaOH and 5% are dried to obtain tree after washing
Aliphatic radical nano zirconium oxide composite material.
Zirconium in composite is measured after clearing up by acidifying using inductively coupled plasma atomic emission (ICP-AES) to contain
Measure as 22wt%, can be obtained by transmission electron microscope observation, the particle diameter of the Zirconium oxide nano grain in composite is 10-
80nm.Pass through N2The pore volume that the experiment of-adsorption/desorption measures nano composite material is 0.9cm3/ g, specific surface area is 1200m2/ g,
Below 2nm hole accounts for the 95% of total pore volume.
Gained nano composite material (4mL) is fitted into the glass adsorption column of jacketed (12 × 240mm of Φ), fluorine will be simulated
(water body pH is about 6.5 to micropollutant water, and the concentration of fluorine is 20mg/L, and the concentration of humic acid is 10mg/L (DOC), background ions
Cl-、SO4 2-、NO3 -、SiO3 2-Be 250mg/L) with 20mL/h flow by resin bed, treating capacity is 230BV, water outlet fluorine
Concentration drop to below 1mg/L.
With the mixed solution that 200ml concentration is NaOH (5%)-NaCl (5%) with 4mL/h flow downstream through resin bed
Layer is desorbed, the desorption rate ＞ 90% of fluorine, and the nano composite material after desorption can continue on for circulation absorption next time.
Embodiment 28
By the tertiary-aminated Polystyrene resins of dried 10g, (tertiary amine content is 0.8mmol/g, and pore volume is
1.0cm3/ g, specific surface area is 800m2/ g) immersion 60g ZrOCl2·8H2The mixed solution 200mL of O, 10g HCl, 60g ethanol
And be evaporated under agitation.The NaCl transition, washing, alcohol for then sequentially adding 5% NaOH and 5% are dried to obtain tree after washing
Aliphatic radical nano zirconium oxide composite material.
Zirconium in composite is measured after clearing up by acidifying using inductively coupled plasma atomic emission (ICP-AES) to contain
Measure as 22wt%, can be obtained by transmission electron microscope observation, the particle diameter of the Zirconium oxide nano grain in composite is 10-
80nm.Pass through N2The pore volume that the experiment of-adsorption/desorption measures nano composite material is 0.9cm3/ g, specific surface area is 1200m2/ g,
Below 2nm hole accounts for the 95% of total pore volume.
Gained nano composite material (4mL) is fitted into the glass adsorption column of jacketed (12 × 240mm of Φ), fluorine will be simulated
(water body pH is about 6.5 to micropollutant water, and the concentration of fluorine is 5mg/L, and the concentration of humic acid is 2.5mg/L (DOC), background ions
Cl-、SO4 2-、NO3 -、SiO3 2-Be 500mg/L) with 20mL/h flow by resin bed, treating capacity is 300BV, water outlet fluorine
Concentration drop to below 1mg/L.
With the mixed solution that 200ml concentration is NaOH (5%)-NaCl (5%) with 4mL/h flow downstream through resin bed
Layer is desorbed, the desorption rate ＞ 90% of fluorine, and the nano composite material after desorption can continue on for circulation absorption next time.
Embodiment 29
By the tertiary-aminated Polystyrene resins of dried 10g, (tertiary amine content is 0.5mmol/g, and pore volume is
0.7cm3/ g, specific surface area is 700m2/ g) immersion 60g ZrOCl2·8H2The mixed solution 200mL of O, 10g HCl, 60g ethanol
And be evaporated under agitation.The NaCl transition, washing, alcohol for then sequentially adding 4% NaOH and 4% are dried to obtain tree after washing
Aliphatic radical nano zirconium oxide composite material.
Zirconium in composite is measured after clearing up by acidifying using inductively coupled plasma atomic emission (ICP-AES) to contain
Measure as 22wt%, can be obtained by transmission electron microscope observation, the particle diameter of the Zirconium oxide nano grain in composite is 10-
80nm.Pass through N2The pore volume that the experiment of-adsorption/desorption measures nano composite material is 0.9cm3/ g, specific surface area is 1200m2/ g,
Below 2nm hole accounts for the 94% of total pore volume.
Gained nano composite material (4mL) is fitted into the glass adsorption column of jacketed (12 × 240mm of Φ), fluorine will be simulated
(water body pH is about 6.5 to micropollutant water, and the concentration of fluorine is 10mg/L, and the concentration of humic acid is 2.5mg/L (DOC), background ions
Cl-、SO4 2-、NO3 -、SiO3 2-Be 500mg/L) with 20mL/h flow by resin bed, treating capacity is 270BV, water outlet fluorine
Concentration drop to below 1mg/L.
With the mixed solution that 200ml concentration is NaOH (5%)-NaCl (5%) with 4mL/h flow downstream through resin bed
Layer is desorbed, the desorption rate ＞ 90% of fluorine, and the nano composite material after desorption can continue on for circulation absorption next time.
Embodiment 30
By the tertiary-aminated Polystyrene resins of dried 10g, (tertiary amine content is 0.8mmol/g, and pore volume is
1.0cm3/ g, specific surface area is 800m2/ g) immersion 60g ZrOCl2·8H2The mixed solution 200mL of O, 10g HCl, 60g ethanol
And be evaporated under agitation.The NaCl transition, washing, alcohol for then sequentially adding 5% NaOH and 5% are dried to obtain tree after washing
Aliphatic radical nano zirconium oxide composite material.
Zirconium in composite is measured after clearing up by acidifying using inductively coupled plasma atomic emission (ICP-AES) to contain
Measure as 22wt%, can be obtained by transmission electron microscope observation, the particle diameter of the Zirconium oxide nano grain in composite is 10-
80nm.Pass through N2The pore volume that the experiment of-adsorption/desorption measures nano composite material is 0.9cm3/ g, specific surface area is 1200m2/ g,
Below 2nm hole accounts for the 95% of total pore volume.
Gained nano composite material (4mL) is fitted into the glass adsorption column of jacketed (12 × 240mm of Φ), fluorine will be simulated
(water body pH is about 6.5 to micropollutant water, and the concentration of fluorine is 20mg/L, and the concentration of humic acid is 2.5mg/L (DOC), background ions
Cl-、SO4 2-、NO3 -、SiO3 2-Be 500mg/L) with 20mL/h flow by resin bed, treating capacity is 230BV, water outlet fluorine
Concentration drop to below 1mg/L.
With the mixed solution that 200ml concentration is NaOH (5%)-NaCl (5%) with 4mL/h flow downstream through resin bed
Layer is desorbed, the desorption rate ＞ 90% of fluorine, and the nano composite material after desorption can continue on for circulation absorption next time.
Embodiment 31
By the tertiary-aminated Polystyrene resins of dried 10g, (tertiary amine content is 0.8mmol/g, and pore volume is
1.0cm3/ g, specific surface area is 800m2/ g) immersion 60g ZrOCl2·8H2The mixed solution 200mL of O, 10g HCl, 60g ethanol
And be evaporated under agitation.The NaCl transition, washing, alcohol for then sequentially adding 5% NaOH and 5% are dried to obtain tree after washing
Aliphatic radical nano zirconium oxide composite material.
Zirconium in composite is measured after clearing up by acidifying using inductively coupled plasma atomic emission (ICP-AES) to contain
Measure as 22wt%, can be obtained by transmission electron microscope observation, the particle diameter of the Zirconium oxide nano grain in composite is 10-
80nm.Pass through N2The pore volume that the experiment of-adsorption/desorption measures nano composite material is 0.9cm3/ g, specific surface area is 1200m2/ g,
Below 2nm hole accounts for the 95% of total pore volume.
Gained nano composite material (4mL) is fitted into the glass adsorption column of jacketed (12 × 240mm of Φ), fluorine will be simulated
(water body pH is about 6.5 to micropollutant water, and the concentration of fluorine is 5mg/L, and the concentration of humic acid is 5mg/L (DOC), background ions
Cl-、SO4 2-、NO3 -、SiO3 2-Be 500mg/L) with 20mL/h flow by resin bed, treating capacity is 300BV, water outlet fluorine
Concentration drop to below 1mg/L.
With the mixed solution that 200ml concentration is NaOH (5%)-NaCl (5%) with 4mL/h flow downstream through resin bed
Layer is desorbed, the desorption rate ＞ 90% of fluorine, and the nano composite material after desorption can continue on for circulation absorption next time.
Embodiment 32
By the tertiary-aminated Polystyrene resins of dried 10g, (tertiary amine content is 0.8mmol/g, and pore volume is
1.0cm3/ g, specific surface area is 800m2/ g) immersion 60g ZrOCl2·8H2The mixed solution 200mL of O, 10g HCl, 60g ethanol
And be evaporated under agitation.The NaCl transition, washing, alcohol for then sequentially adding 5% NaOH and 5% are dried to obtain tree after washing
Aliphatic radical nano zirconium oxide composite material.
Zirconium in composite is measured after clearing up by acidifying using inductively coupled plasma atomic emission (ICP-AES) to contain
Measure as 22wt%, can be obtained by transmission electron microscope observation, the particle diameter of the Zirconium oxide nano grain in composite is 10-
80nm.Pass through N2The pore volume that the experiment of-adsorption/desorption measures nano composite material is 0.9cm3/ g, specific surface area is 1200m2/ g,
Below 2nm hole accounts for the 95% of total pore volume.
Gained nano composite material (4mL) is fitted into the glass adsorption column of jacketed (12 × 240mm of Φ), fluorine will be simulated
(water body pH is about 6.5 to micropollutant water, and the concentration of fluorine is 10mg/L, and the concentration of humic acid is 5mg/L (DOC), background ions
Cl-、SO4 2-、NO3 -、SiO3 2-Be 500mg/L) with 20mL/h flow by resin bed, treating capacity is 270BV, water outlet fluorine
Concentration drop to below 1mg/L.
With the mixed solution that 200ml concentration is NaOH (5%)-NaCl (5%) with 4mL/h flow downstream through resin bed
Layer is desorbed, the desorption rate ＞ 90% of fluorine, and the nano composite material after desorption can continue on for circulation absorption next time.
Embodiment 33
By the tertiary-aminated Polystyrene resins of dried 10g, (tertiary amine content is 0.gmmol/g, and pore volume is
1.0cm3/ g, specific surface area is 800m2/ g) immersion 60g ZrOCl2·8H2The mixed solution 200mL of O, 10g HCl, 60g ethanol
And be evaporated under agitation.The NaCl transition, washing, alcohol for then sequentially adding 5% NaOH and 5% are dried to obtain tree after washing
Aliphatic radical nano zirconium oxide composite material.
Zirconium in composite is measured after clearing up by acidifying using inductively coupled plasma atomic emission (ICP-AES) to contain
Measure as 22wt%, can be obtained by transmission electron microscope observation, the particle diameter of the Zirconium oxide nano grain in composite is 10-
80nm.Pass through N2The pore volume that the experiment of-adsorption/desorption measures nano composite material is 0.9cm3/ g, specific surface area is 1200m2/ g,
Below 2nm hole accounts for the 95% of total pore volume.
Gained nano composite material (4mL) is fitted into the glass adsorption column of jacketed (12 × 240mm of Φ), fluorine will be simulated
(water body pH is about 6.5 to micropollutant water, and the concentration of fluorine is 20mg/L, and the concentration of humic acid is 5mg/L (DOC), background ions
Cl-、SO4 2-、NO3 -、SiO3 2-Be 500mg/L) with 20mL/h flow by resin bed, treating capacity is 230BV, water outlet fluorine
Concentration drop to below 1mg/L.
With the mixed solution that 200ml concentration is NaOH (5%)-NaCl (5%) with 4mL/h flow downstream through resin bed
Layer is desorbed, the desorption rate ＞ 90% of fluorine, and the nano composite material after desorption can continue on for circulation absorption next time.
Embodiment 34
By the tertiary-aminated Polystyrene resins of dried 10g, (tertiary amine content is 0.8mmol/g, and pore volume is
1.0cm3/ g, specific surface area is 800m2/ g) immersion 60g ZrOCl2·8H2The mixed solution 200mL of O, 10g HCl, 60g ethanol
And be evaporated under agitation.The NaCl transition, washing, alcohol for then sequentially adding 5% NaOH and 5% are dried to obtain tree after washing
Aliphatic radical nano zirconium oxide composite material.
Zirconium in composite is measured after clearing up by acidifying using inductively coupled plasma atomic emission (ICP-AES) to contain
Measure as 22wt%, can be obtained by transmission electron microscope observation, the particle diameter of the Zirconium oxide nano grain in composite is 10-
80nm.Pass through N2The pore volume that the experiment of-adsorption/desorption measures nano composite material is 0.9cm3/ g, specific surface area is 1200m2/ g,
Below 2nm hole accounts for the 95% of total pore volume.
Gained nano composite material (4mL) is fitted into the glass adsorption column of jacketed (12 × 240mm of Φ), fluorine will be simulated
(water body pH is about 6.5 to micropollutant water, and the concentration of fluorine is 5mg/L, and the concentration of humic acid is 10mg/L (DOC), background ions
Cl-、SO4 2-、NO3 -、SiO3 2-Be 500mg/L) with 20mL/h flow by resin bed, treating capacity is 300BV, water outlet fluorine
Concentration drop to below 1mg/L.
With the mixed solution that 200ml concentration is NaOH (5%)-NaCl (5%) with 4mL/h flow downstream through resin bed
Layer is desorbed, the desorption rate ＞ 90% of fluorine, and the nano composite material after desorption can continue on for circulation absorption next time.
Embodiment 35
By the tertiary-aminated Polystyrene resins of dried 10g, (tertiary amine content is 0.8mmol/g, and pore volume is
1.0cm3/ g, specific surface area is 800m2/ g) immersion 60g ZrOCl2·8H2The mixed solution 200mL of O, 10g HCl, 60g ethanol
And be evaporated under agitation.The NaCl transition, washing, alcohol for then sequentially adding 5% NaOH and 5% are dried to obtain tree after washing
Aliphatic radical nano zirconium oxide composite material.
Zirconium in composite is measured after clearing up by acidifying using inductively coupled plasma atomic emission (ICP-AES) to contain
Measure as 22wt%, can be obtained by transmission electron microscope observation, the particle diameter of the Zirconium oxide nano grain in composite is 10-
80nm.Pass through N2The pore volume that the experiment of-adsorption/desorption measures nano composite material is 0.9cm3/ g, specific surface area is 1200m2/ g,
Below 2nm hole accounts for the 95% of total pore volume.
Gained nano composite material (4mL) is fitted into the glass adsorption column of jacketed (12 × 240mm of Φ), fluorine will be simulated
(water body pH is about 6.5 to micropollutant water, and the concentration of fluorine is 10mg/L, and the concentration of humic acid is 10mg/L (DOC), background ions
Cl-、SO4 2-、NO3 -、SiO3 2-Be 500mg/L) with 20mL/h flow by resin bed, treating capacity is 270BV, water outlet fluorine
Concentration drop to below 1mg/L.
With the mixed solution that 200ml concentration is NaOH (5%)-NaCl (5%) with 4mL/h flow downstream through resin bed
Layer is desorbed, the desorption rate ＞ 90% of fluorine, and the nano composite material after desorption can continue on for circulation absorption next time.
Embodiment 36
By the tertiary-aminated Polystyrene resins of dried 10g, (tertiary amine content is 0.8mmol/g, and pore volume is
1.0cm3/ g, specific surface area is 800m2/ g) immersion 60g ZrOCl2·8H2The mixed solution 200mL of O, 10g HCl, 60g ethanol
And be evaporated under agitation.The NaCl transition, washing, alcohol for then sequentially adding 5% NaOH and 5% are dried to obtain tree after washing
Aliphatic radical nano zirconium oxide composite material.
Zirconium in composite is measured after clearing up by acidifying using inductively coupled plasma atomic emission (ICP-AES) to contain
Measure as 22wt%, can be obtained by transmission electron microscope observation, the particle diameter of the Zirconium oxide nano grain in composite is 10-
80nm.Pass through N2The pore volume that the experiment of-adsorption/desorption measures nano composite material is 0.9cm3/ g, specific surface area is 1200m2/ g,
Below 2nm hole accounts for the 95% of total pore volume.
Gained nano composite material (4mL) is fitted into the glass adsorption column of jacketed (12 × 240mm of Φ), fluorine will be simulated
(water body pH is about 6.5 to micropollutant water, and the concentration of fluorine is 20mg/L, and the concentration of humic acid is 10mg/L (DOC), background ions
Cl-、SO4 2-、NO3 -、SiO3 2-Be 500mg/L) with 20mL/h flow by resin bed, treating capacity is 230BV, water outlet fluorine
Concentration drop to below 1mg/L.
With the mixed solution that 200ml concentration is NaOH (5%)-NaCl (5%) with 4mL/h flow downstream through resin bed
Layer is desorbed, the desorption rate ＞ 90% of fluorine, and the nano composite material after desorption can continue on for circulation absorption next time.
Claims (9)
1. a kind of depth removes the resin-base nano compound adsorbent of Micro fluoride, it is characterised in that：The adsorbent is with superelevation
Crosslinked polystyrene-divinylbenzene is to be loaded with Zirconium oxide nano grain in organic backbone, organic backbone, the nano combined absorption
The pore volume of agent is 0.3-0.9cm3/ g, specific surface area is 600-1500m2/ g, and diameter accounts for the ratio of total pore volume in below 2nm hole
Example >=90%.
2. a kind of depth according to claim 1 removes the resin-base nano compound adsorbent of Micro fluoride, its feature
It is：The load capacity of zirconium oxide is calculated as 10-30wt% with zr element in the compound adsorbent, and the size of Zirconium oxide nano grain is
10-80nm。
3. a kind of depth according to claim 1 or 2 removes the resin-base nano compound adsorbent of Micro fluoride, it is special
Levy and be：The organic backbone is covalently bonded with tertiary amine groups, and the content of tertiary amine groups is 0.2-1.5mmol/g, and load is preceding organic
The pore volume of skeleton is 0.5-1.2cm3/ g, specific surface area is 400-1200m2Hole on/g, organic backbone is included with diameter greater than 30nm
Macropore and diameter be less than 2nm aperture, the ratio that two kinds of holes account for total pore volume is 40-60%.
4. a kind of preparation method of resin-base nano compound adsorbent as any one of claim 1-3, its feature exists
In its process is as follows：Tertiary-aminated Polystyrene resin after drying process is immersed into ZrOCl2·8H2O, HCl and second
In the mixed solution of alcohol, and it is evaporated under agitation；NaOH the and NaCl aqueous solution is subsequently added through transition, washing, after alcohol washes
Drying to obtain resin-base nano zirconium oxide composite material.
5. a kind of preparation method of resin-base nano compound adsorbent according to claim 4, it is characterised in that：
ZrOCl2·8H2In O, HCl and the mixed solution of ethanol, ZrOCl2·8H2O, HCl and the mass ratio of ethanol are 2.5-8: 1: 6.
6. a kind of preparation method of resin-base nano compound adsorbent according to claim 4 or 5, it is characterised in that：Institute
The mass concentration for stating NaOH solution and the NaCl aqueous solution is 3-6%.
7. a kind of depth removes the application of the resin-base nano compound adsorbent of Micro fluoride, it is characterised in that：Using right
It is required that the resin-base nano compound adsorbent any one of 1-3 carries out adsorption treatment, the fluorine after processing to the fluorine in water
Concentration can drop to below 1mg/L.
8. a kind of depth according to claim 7 removes the application of the resin-base nano compound adsorbent of Micro fluoride,
It is characterized in that：When being handled using the nano-compound adsorbent fluorinated water, the zirconia nanopowder of sorbent-loaded
Averagely every gram in terms of zirconium adsorbable fluorine 40-120mg of grain.
9. a kind of depth according to claim 7 or 8 removes answering for the resin-base nano compound adsorbent of Micro fluoride
With, it is characterised in that：To the nano-compound adsorbent after absorption, desorption and regeneration, the desorption of fluorine are carried out by alkali salt mixed solution
Alkali in rate ＞ 90%, wherein alkali salt mixed solution is NaOH or KOH, and salt is NaCl or KCl, and the mass concentration of alkali, salt is equal
For 3-6%.
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