CN105413627B - The material of selective absorption perfluorochemical, preparation method and application - Google Patents

The material of selective absorption perfluorochemical, preparation method and application Download PDF

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CN105413627B
CN105413627B CN201510894494.7A CN201510894494A CN105413627B CN 105413627 B CN105413627 B CN 105413627B CN 201510894494 A CN201510894494 A CN 201510894494A CN 105413627 B CN105413627 B CN 105413627B
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montmorillonite
pfcs
fluoronated
mont
morillonite
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CN105413627A (en
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邓述波
杜子文
余刚
王斌
黄�俊
王玉珏
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Tsinghua University
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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
    • B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
    • B01J20/10—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising silica or silicate
    • B01J20/12—Naturally occurring clays or bleaching earth
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/30—Processes for preparing, regenerating, or reactivating
    • B01J20/32—Impregnating or coating ; Solid sorbent compositions obtained from processes involving impregnating or coating
    • B01J20/3202—Impregnating or coating ; Solid sorbent compositions obtained from processes involving impregnating or coating characterised by the carrier, support or substrate used for impregnation or coating
    • B01J20/3204—Inorganic carriers, supports or substrates
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/30—Processes for preparing, regenerating, or reactivating
    • B01J20/32—Impregnating or coating ; Solid sorbent compositions obtained from processes involving impregnating or coating
    • B01J20/3214—Impregnating or coating ; Solid sorbent compositions obtained from processes involving impregnating or coating characterised by the method for obtaining this coating or impregnating
    • B01J20/3217—Resulting in a chemical bond between the coating or impregnating layer and the carrier, support or substrate, e.g. a covalent bond
    • B01J20/3219—Resulting in a chemical bond between the coating or impregnating layer and the carrier, support or substrate, e.g. a covalent bond involving a particular spacer or linking group, e.g. for attaching an active group
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/30—Processes for preparing, regenerating, or reactivating
    • B01J20/32—Impregnating or coating ; Solid sorbent compositions obtained from processes involving impregnating or coating
    • B01J20/3231—Impregnating or coating ; Solid sorbent compositions obtained from processes involving impregnating or coating characterised by the coating or impregnating layer
    • B01J20/3242—Layers with a functional group, e.g. an affinity material, a ligand, a reactant or a complexing group
    • B01J20/3244—Non-macromolecular compounds
    • B01J20/3246—Non-macromolecular compounds having a well defined chemical structure
    • B01J20/3248—Non-macromolecular compounds having a well defined chemical structure the functional group or the linking, spacer or anchoring group as a whole comprising at least one type of heteroatom selected from a nitrogen, oxygen or sulfur, these atoms not being part of the carrier as such
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00—Treatment of water, waste water, or sewage
    • C02F1/28—Treatment of water, waste water, or sewage by sorption
    • C02F1/281—Treatment of water, waste water, or sewage by sorption using inorganic sorbents
    • 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
    • C02F2101/30—Organic compounds
    • C02F2101/36—Organic compounds containing halogen

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Abstract

The invention discloses a kind of preparation method of selective absorption perfluorochemical (PFCs) material, this method includes：(1) with 1:5~1:Montmorillonite is placed in 0.5% 1% salting liquid by 15 ratio, and to obtain metal cation montmorillonite, alleged salting liquid includes metal cation, and alleged metal cation is selected from Na+、Li+、K+And Mg2+At least one of；(2) with 1:5~1:Metal cation montmorillonite in (1) is placed in 0.025~0.3mol/L quaternary ammonium fluoride salting liquid by 15 ratio, to obtain fluoronated mont-morillonite；(3) fluoronated mont-morillonite in organic solvent washing (2) is utilized, to obtain alleged selective absorption PFCs materials, organic solvent is selected from least one of methanol, ethanol, acetone and acetonitrile.There is high selectivity, excellent adsorbance to PFCs using sorbing material made from this method, and easily regenerate and reuse.

Description

The material of selective absorption perfluorochemical, preparation method and application
Technical field
The present invention relates to chemical material field, specifically, the present invention relates to selective absorption PFCs materials, preparation method and It is applied, and more specifically, the present invention relates to a kind of material for being capable of selective absorption PFCs, one kind to prepare selective absorption PFCs The method of material, the purposes one of selective absorption PFCs materials and a kind of method for regenerating selective absorption PFCs materials.
Background technology
Perfluorochemical (PFCs) causes the extensive concern in the whole world as a kind of main persistent organism pollutant, Wherein PFOS (PFOS) has been put into the violated chemicals list in Stockholm.At present, use or production PFCs mistakes Cheng Douhui causes the PFCs of water environment to pollute.For the removal of PFCs in water, the technology of comparative maturity is to use activated carbon at present As PFCs in adsorbent Adsorption water.But absorption of the activated carbon to PFCs in by water coexisted organic compounds influenceed it is serious, The active-carbon bed Competition due to coexisted organic compounds can lose the removal ability to PFCs in a short time.It is in addition, organic molten Agent regenerated carbon can bring other organic matters into regenerated liquid together, and the purification for being unfavorable for PFCs recycles.Therefore, exploitation is efficient And selective excellent sorbing material is the focus that PFCs removes research field in current water.Preferable sorbing material needs Possess and prepare the advantages that cost is low, and adsorbance is high, adsorptive selectivity is good, regenerating easily.Though but sorbing material conventional at present Right adsorbance is high but selectivity is bad, and often inorganic salts and organic matter competition are influenceed in by water in actual applications, absorption effect Fruit is poor.
Therefore, it is necessary to develop a kind of high selectivity removed for PFCs in water and efficient sorbing material.
The content of the invention
It is contemplated that at least solve one of above-mentioned technical problem to a certain extent or provide at a kind of business selection.
Find and contemplate below, be the basis that inventor makes the present invention：
PFCs has the characteristic of hydrophobic oleophobic, in water carbon fluorine chain both repelled hydrone while or not affine hydrocarbon substance, And have the tendency of mutually to reunite between carbon fluorine chain.Therefore, using " similar compatibility " principle, Organic fluoride is carried out in adsorbent surface Change modification, utilize the PFCs in the carbon fluorine chain absorption water of material surface.And the hydrophobic oleophobic effect of carbon fluorine chain can repel carbon Hydrogen organic matter, so as to reach selective removal PFCs purpose.
Montmorillonite is cheap and has excellent cation exchange capacity (CEC).If the cheap montmorillonite of selection is as matrix material Material, upper quaternary ammonium fluoride salt, design experiment, it may be possible to prepare with fluorine are reacted by its excellent cation exchange capacity (CEC) Change the selective absorbent of surface and nano-layer structure.Moreover, compared with other sorbing materials, if the selectivity prepared is inhaled The surface carbon fluorine chain of enclosure material stretches to outside, repels hydrocarbon organic matter, it may be possible to optionally traps the PFCs in water；And very It can may efficiently adsorb PFCs and not influenceed by coexisted organic compounds, the far super commercial activated carbons of adsorption capacity.
According to an aspect of of the present present invention, the present invention provides a kind of preparation method of selective absorption PFCs materials, including step Suddenly：(1) with 1:5~1:Montmorillonite is placed in 0.5%-1% salting liquid by 15 ratio, is taken off with obtaining metal cationization and covering Stone, the salting liquid include metal cation, and the metal cation is selected from Na+、Li+、K+And Mg2+At least one of；(2) With 1:5~1:The quaternary ammonium fluoride salt that metal cation montmorillonite in (1) is placed in 0.025~0.3mol/L by 15 ratio is molten In liquid, to obtain fluoronated mont-morillonite；(3) fluoronated mont-morillonite in organic solvent washing (2) is utilized, is inhaled with obtaining the selectivity Attached PFCs materials, the organic solvent are selected from least one of methanol, ethanol, acetone and acetonitrile.When alleged salt refers to ionization Generate the compound of metal cation (or ammonium ion) and acid ion.
The preparation method of the selective absorption PFCs materials of the invention described above this aspect, made with cheap montmorillonite For matrix material, by cationization and fluorination reaction, the selection with fluorinated surface and nano-layer structure can be prepared Property sorbing material.Moreover, compared with other sorbing materials, the surface carbon fluorine chain for the selective absorbent prepared is stretched to outside Side, repel hydrocarbon organic matter, can optionally trap the PFCs in water body, can efficiently adsorb PFCs and not coexisted organic Thing influences, the far super commercial activated carbons of adsorption capacity.High adsorption capacity is plus it for selectivity excellent PFCs and the spy easily regenerated Point, the fluoronated mont-morillonite material for making to be prepared into using this method of the invention PFCs and PFCs recyclings etc. in water removal is gone Field has good application prospect.
According to an embodiment of the invention, the method for the preparation selective absorption PFCs materials of the invention described above one side, also There can be the additional technical feature of at least one of：
According to one embodiment of present invention, the step of this method (1) includes：With 1:5~1:15 ratio is by montmorillonite It is placed in 0.5%-1% salting liquid, 70~90 degrees Celsius of constant temperature centrifuge after stirring at least 2 hours, and profit is washed with deionized The centrifugation product of acquisition, the centrifugation product after drying washing, sieving is ground to the centrifugation product after drying.According to the present invention Preferred embodiment, inventor's test of many times adjusting and optimizing determines the actual conditions or combination condition of step (1), can facilitate The efficient montmorillonite for obtaining metal cation, for example, with 1:The sodium salt that montmorillonite is placed in 0.5%-1% by 10 ratio is molten In liquid；And/or the sodium bicarbonate solution that the sodium salt solution of the 0.5%-1% is 0.73%；80 C water bath's constant temperature stir Centrifuged after 3 hours；And/or the centrifugation product of acquisition is washed with deionized to pH weakly acidic pHs in profit；And/or in 105 degrees Celsius Centrifugation product after lower drying washing；And/or ground 200 mesh sieve.
According to one embodiment of present invention, alleged quaternary ammonium fluoride salt is C14H16F17IN2O2S。
According to the preferred embodiment of the present invention, step (2) is：With 1:5~1:15 ratio is by the gold in step (1) Category cationization montmorillonite is sequentially placed into the quaternary ammonium fluoride salting liquid of multiple concentration and increasing concen-trations.Allow to obtain fluorine Change the fabulous montmorillonite of effect.
According to presently preferred embodiments of the present invention, step (2) includes：With 1:5~1:15 ratio is by the metal in step (1) Cationization montmorillonite, which is sequentially placed into the quaternary ammonium fluoride salting liquid of following concentration, to be stirred at least 10 hours：025mol/L、 0.05mol/L, 0.1mol/L, 0.15mol/L, 0.2mol/L and 0.3mol/L.It so, it is possible to obtain the fabulous fluorine of fluorination effect Change montmorillonite.More preferably, it is 1 to make the ratio of the metal cation montmorillonite and the quaternary ammonium fluoride salting liquid:10；With/ Or stir 12 hours.
According to one embodiment of present invention, step (3) is that the fluorination rinsed repeatedly in (2) using 90% methanol is covered De- stone, until being detected in the solution flushed out without organic nitrogen.
According to an embodiment of the invention, after using the fluoronated mont-morillonite in organic solvent washing step (2), in 50-70 Fluoronated mont-morillonite under degree Celsius after drying washing, grinding sieving.Preferably, the fluorination under 60 degrees Celsius after drying washing is covered De- stone；And/or ground 200 mesh sieve.
According to an embodiment of the invention, before step (1) is carried out, montmorillonite organism material is carried out to purify homogeneous place Reason, it is following including carrying out successively：With 1:8~1:The montmorillonite is placed in deionized water by 15 ratio, stirring at least 2 Hour, settle at least 8 hours, isolate the montmorillonite that granularity is less than 4 μm, the montmorillonite isolated is dried, to the illiteracy after drying De- stone is ground sieving.According to presently preferred embodiments of the present invention, inventor's test of many times adjusting and optimizing determines that the purification is equal The actual conditions or combination condition of one processing, are effectively carried out beneficial to subsequent step, for example, with 1:10 ratio is by the montmorillonite Insert in the deionized water；And/or stir 3 hours；And/or settle 12 hours；And/or after carrying out the sedimentation, utilize Siphonage purifies；And/or isolate the montmorillonite that granularity is less than 2 μm；And/or the illiteracy isolated is dried under 105 degrees Celsius and is taken off Stone；And/or ground 200 mesh sieve.
According to another aspect of the present invention, present invention offer one kind utilizes the invention described above on the one hand or any embodiment In the selective absorption PFCs materials that are prepared into of method.
According to one embodiment of present invention, the interlamellar spacing for the selective absorption PFCs materials being prepared into is in 1.48- Between 3.24nm.So so that the material can stop the macromolecule contaminant coexisted in water environment, organic macromolecular be present During thing, moreover it is possible to maintain to PFCs efficient absorptions.
The selective absorption PFCs materials of this aspect of the present invention, using cheap montmorillonite as matrix material, lead to Cross cation exchange reaction to be fluorinated, so as to prepare the selective absorption material with fluorinated surface and nano-layer structure Material.Compared with other sorbing materials, the material is that the surface carbon fluorine chain of fluoronated mont-morillonite stretches to outside, repels hydrocarbon organic matter, Optionally trap the PFCs in water.Therefore, the fluoronated mont-morillonite can efficiently adsorb PFCs and not influenceed by coexisted organic compounds, The far super commercial activated carbons of adsorption capacity.High adsorption capacity, for selectivity excellent PFCs and easy the characteristics of regenerating, makes this plus it The fluoronated mont-morillonite material of invention this aspect field such as PFCs and PFCs recyclings in water removal is gone, which has, well should Use prospect.
According to another aspect of the invention, the selective absorption PFCs materials that the present invention provides the invention described above one side exist The purposes in PFCs in adsorbed water body.The technical characteristic of the above-mentioned selective absorption PFCs materials to one aspect of the present invention and excellent The description of point, the purposes of the selective absorption PFCs materials of equally applicable this aspect of the present invention, will not be repeated here.
According to another aspect of the present invention, the present invention provides a kind of selective absorption for regenerating the invention described above one side The method of PFCs materials, this method include the selective absorption PFCs materials being placed in organic solvent at least 10 hours, with Regenerate the material, the ability for making the material recover selective absorption PFCs, the organic solvent be selected from methanol, ethanol, acetone and At least one of acetonitrile.The renovation process is simple, the material is recovered complete selective absorption PFCs's Ability.
According to one embodiment of present invention, the selective absorption PFCs materials after are placed in 90% methanol solution In 12 hours, the selective absorption PFCs of material ability can be recovered, make the material to PFCs adsorbance frees of losses.
To sum up, according to embodiments of the present invention, the preparation method of selective absorption PFCs materials of the invention, selective absorption PFCs materials, selective absorption PFCs materials purposes and regenerate the methods of selective absorption PFCs materials, at least have One of following advantages：
1st, the selective absorption PFCs materials of the embodiment of the present invention, i.e. fluoronated mont-morillonite, there is nano-scale layers structure, it is right PFCs absorption is not influenceed by macromolecule contaminant coexists.
2nd, the fluoronated mont-morillonite of the embodiment of the present invention is about that common commercial is lived to typical perfluorochemical PFOS adsorbance 3 times of property charcoal.
3rd, the fluoronated mont-morillonite of the embodiment of the present invention has excellent absorption selection in the presence of other organic matters to PFCs Property.
4th, the fluoronated mont-morillonite of the embodiment of the present invention has higher absorption in the presence of inorganic ions to PFCs.
5th, the fluoronated mont-morillonite of the embodiment of the present invention can be realized regeneration completely by methanol solution, after can reusing 5 times Adsorbance free of losses.
Brief description of the drawings
The above-mentioned and/or additional aspect and advantage of the present invention is from combining in description of the accompanying drawings below to embodiment by change Obtain substantially and be readily appreciated that, wherein：
Fig. 1 is the X-ray diffraction result schematic diagram of the fluoronated mont-morillonite in one embodiment of the present of invention.
Fig. 2 is adsorption isotherm figure of the fluoronated mont-morillonite in one embodiment of the present of invention to PFOS.
Fig. 3 be fluoronated mont-morillonite in one embodiment of the present of invention when PFOS and different organic matters coexist to PFOS and To the contrast schematic diagram of organic matter adsorbance；
Fig. 4 be fluoronated mont-morillonite in one embodiment of the present of invention in the presence of different inorganic salts to PFOS and PFOA The adsorbance contrast schematic diagram of (PFO carboxyl compound)；
Fig. 5 is that PFOS and PFOA is inhaled after the fluoronated mont-morillonite in one embodiment of the present of invention continuous 5 takes turns absorption regeneration The schematic diagram of attached amount change.
Embodiment
Embodiments of the invention are described below in detail, the example of the embodiment is shown in the drawings, wherein, from beginning to end Same or similar label represents same or similar element or the element with same or like function.
The embodiments described below with reference to the accompanying drawings are exemplary, be only used for explain the present invention, and it is not intended that Limitation of the present invention.Need what is illustrated, term " first " used herein, " second " etc. are only for convenience of describing, it is impossible to It is interpreted as indicating or implying relative importance, there is sequencing relation between can not being interpreted as.In the description of the invention, remove Non- to be otherwise noted, " multiple " are meant that two or more.
Following embodiment facilitates a better understanding of the present invention, but does not limit the present invention.Experiment in following embodiments Method, it is conventional method unless otherwise specified.Material used, reagent etc. in following embodiments, unless otherwise specified, Commercially obtain.
Embodiment 1
1st, the preparation of adsorbent
(1) stirred 3 hours after 100g montmorillonite being added into appropriate deionized water by soil ratio 10: 1, sedimentation 12 is small When.Purified with siphonage, choose granularity<3 μm of part is centrifuged, and is dried at 105 DEG C, ground 200 mesh sieve.
(2) took 200 mesh sieves 5g montmorillonites be added to 0.73% Na2CO3Solution, the suspension of solid-to-liquid ratio 1: 10 is made into, 80 DEG C of constant temperature water baths stir 3h, product centrifugation, are washed to pH weakly acidic pHs with deionized water, are dried at 105 DEG C, and ground 200 Mesh sieve.
(3) montmorillonite of sodium being placed in 80 DEG C of quaternary ammonium fluoride salting liquids, quaternary ammonium fluoride salinity is 0.3mol/L, Gu Liquor ratio 1: 10, stir 12h.
(4) montmorillonite after fluorination is rinsed repeatedly in 90% methanol, until being measured in rinse water without organic nitrogen, after washing Fluoronated mont-morillonite dried at 60 DEG C, ground 200 mesh sieve.
Fig. 1 shows the X-ray diffractogram for the sorbing material being prepared into, and shows the interlamellar spacing of the material in 1.48-3.24nm Between.
2nd, adsorption effect experiment and result
2.1 put into 5mg fluoronated mont-morillonites (i.e. sorbing material) in 0.05-1mmol/L PFOS solution, in shaking table 48h is shaken under 170rpm.With the concentration of PFOS in solution after efficient liquid phase and the analysis absorption of mass spectrometry instrument.
As a result as shown in Fig. 2 the highest adsorbance of fluoronated mont-morillonite is up to 2.46mmol/g.
2.2 are respectively added to 1.5mg fluoronated mont-morillonites in solution of the initial concentration for the 5 μm of ol/L only solute containing PFOS And contain a variety of solutes (including PFOS, phenol, neopelex, phenanthrene, pyridine, respective concentration are 5 μm of ol/L) Solution in, 48h is shaken under 170rpm in shaking table, with PFOS in solution after efficient liquid phase and the analysis absorption of mass spectrometry instrument Concentration, with the concentration of remaining organic matter of spectrophotometric analysis.
Clearances of the PFOS in unitary system and compound system is 86%, as shown in figure 3, fluoronated mont-morillonite is to other Organic removal rate is no more than 5%, and adsorptive selectivity parameter S (PFOS clearances/coexisted organic compounds clearance) is reached as high as 353。
2.3 respectively by 1.5mg fluoronated mont-morillonites be added to initial concentration for 5 μm of ol/L containing different salt (NaCl, Na2SO4、CaCl2) PFOS and PFOA (PFO carboxyl compound) solution in, shake 48h under 170rpm in shaking table, use Efficient liquid phase and the concentration of PFOS and PFOA in solution after the analysis absorption of mass spectrometry instrument.
As a result as shown in figure 4, in the solution of saliferous, absorption of the fluoronated mont-morillonite to PFOS and PFOA is not suppressed, It is improved on the contrary, 77% can be improved to PFOS adsorbances highest, 88% can be improved to PFOA adsorbance highest.
3rd, regeneration effect is tested
5mg fluoronated mont-morillonites are added in PFOS and PFOA solution of the initial concentration for 5 μm of ol/L respectively, in shaking table 48h is shaken under 170rpm, with the concentration of PFOS and PFOA in solution after efficient liquid phase and the analysis absorption of mass spectrometry instrument.
After the fluoronated mont-morillonite filtering of adsorption saturation, methanol solution regeneration 12h is placed in.
Adsorbent after regeneration is put into PFOS and PFOA solution again, carries out the second wheel absorption.
5 absorption regeneration experiments are so repeated, as a result as shown in figure 5, repeatedly using rear fluoronated mont-morillonite pair PFOS and PFOA adsorbance keeps constant.
Embodiment 2
1st, the preparation of adsorbent
(1) stir 4 hours, settle 12 hours after 100g montmorillonite being added into appropriate deionized water by soil ratio 5: 1. Purified with siphonage, choose granularity<2 μm of part is centrifuged, and is dried at 105 DEG C, ground 200 mesh sieve.
(2) 200 5g montmorillonites now are added to 1% MgCl2Solution, is made into the suspension of solid-to-liquid ratio 1: 15,80 DEG C Constant temperature water bath stirs 3h, product centrifugation, is washed to pH weakly acidic pHs with deionized water, is dried at 105 DEG C, ground 200 mesh sieve.
(3) montmorillonite of magnesium being placed in 80 DEG C of quaternary ammonium fluoride salting liquids, quaternary ammonium fluoride salinity is 0.025mol/L, Solid-to-liquid ratio 1: 10, stir 12h.
(4) montmorillonite after fluorination is rinsed repeatedly under acetonitrile, until being measured in rinse water without organic nitrogen, after washing Fluoronated mont-morillonite is dried at 60 DEG C, ground 200 mesh sieve.
2nd, adsorption effect experiment and result
2.1 are respectively added to 1.5mg fluoronated mont-morillonites in solution of the initial concentration for the 5 μm of ol/L only solute containing PFOS And contain a variety of solutes (including PFOS, phenol, neopelex, phenanthrene, pyridine, respective concentration are 5 μm of ol/L) Solution in, 48h is shaken under 170rpm in shaking table, with PFOS in solution after efficient liquid phase and the analysis absorption of mass spectrometry instrument Concentration, with the concentration of remaining organic matter of spectrophotometric analysis.
As a result show, clearances of the PFOS in unitary system and compound system is 46%, and fluoronated mont-morillonite is to other Organic removal rate is no more than 3%, and adsorptive selectivity parameter S (PFOS clearances/coexisted organic compounds clearance) reaches as high as 99.
3rd, regeneration effect experiment and result
5mg fluoronated mont-morillonites are added in PFOS and PFOA solution of the initial concentration for 5 μm of ol/L respectively, in shaking table 48h is shaken under 170rpm, with the concentration of PFOS and PFOA in solution after efficient liquid phase and the analysis absorption of mass spectrometry instrument.
After the fluoronated mont-morillonite filtering of adsorption saturation, acetonitrile solution regeneration 10h is placed in.
Adsorbent after regeneration is put into PFOS and PFOA solution again, carries out the second wheel absorption.So it is repeated 5 Secondary absorption regeneration experiment, test result indicates that, repeatedly use rear fluoronated mont-morillonite and PFOS and PFOA adsorbance is kept It is constant.
Embodiment 3
1st, the preparation of adsorbent
1.1 100g montmorillonite is added into appropriate deionized water by soil ratio 15: 1 after stir 3 hours, it is small to settle 12 When.Purified with siphonage, choose granularity<2 μm of part is centrifuged, and is dried at 105 DEG C, ground 200 mesh sieve.
1.2 are added to 200 5g montmorillonites now 0.6% K2CO3Solution, is made into the suspension of solid-to-liquid ratio 1: 7,80 DEG C Constant temperature water bath stirs 3h, product centrifugation, is washed to pH weakly acidic pHs with deionized water, is dried at 105 DEG C, ground 200 mesh sieve.
1.3 are placed in the montmorillonite of potassium in 80 DEG C of quaternary ammonium fluoride salting liquids, and quaternary ammonium fluoride salinity is 0.05mol/L, Solid-to-liquid ratio 1: 10, stir 12h.
1.4 rinse the montmorillonite after fluorination in 90% methanol repeatedly, until being measured in rinse water without organic nitrogen, after washing Fluoronated mont-morillonite dried at 60 DEG C, ground 200 mesh sieve.
2nd, adsorption effect experiment and result
2.1 are respectively added to 1.5mg fluoronated mont-morillonites in solution of the initial concentration for the 5 μm of ol/L only solute containing PFOS And contain the molten of a variety of solutes (including PFOS, phenol, neopelex, phenanthrene, pyridine, concentration are 5 μm of ol/L) In liquid, shake 48h under 170rpm in shaking table, with solution after the analysis absorption of efficient liquid phase and mass spectrometry instrument PFOS it is dense Degree, with the concentration of remaining organic matter of spectrophotometric analysis.
As a result show, clearances of the PFOS in unitary system and compound system is 54%, and fluoronated mont-morillonite is to other Organic removal rate is no more than 3%, and adsorptive selectivity parameter S (PFOS clearances/coexisted organic compounds clearance) is reached as high as 145。
3rd, regeneration effect experiment and result
5mg fluoronated mont-morillonites are added in PFOS and PFOA solution of the initial concentration for 5 μm of ol/L respectively, in shaking table 48h is shaken under 170rpm, with the concentration of PFOS and PFOA in solution after efficient liquid phase and the analysis absorption of mass spectrometry instrument.
After the fluoronated mont-morillonite filtering of adsorption saturation, methanol solution regeneration 12h is placed in.
Adsorbent after regeneration is put into PFOS and PFOA solution again, carries out the second wheel absorption.
5 absorption regeneration experiments are so repeated, test result indicates that, repeatedly use rear fluoronated mont-morillonite pair PFOS and PFOA adsorbance keeps constant.
Embodiment 4
1st, attached dose of preparation
Stir 2 hours, settle 12 hours after 100g montmorillonite is added into appropriate deionized water by soil ratio 10: 1.With Siphonage purifies, and chooses granularity<2 μm of part is centrifuged, and is dried at 105 DEG C, ground 200 mesh sieve.
200 5g montmorillonites now are added to 0.8% Li2CO3Solution, it is made into the suspension of solid-to-liquid ratio 1: 8,80 DEG C of water Constant temperature stirring 3h is bathed, product centrifugation, is washed to pH weakly acidic pHs with deionized water, is dried at 105 DEG C, ground 200 mesh sieve.
The montmorillonite of lithiumation is placed in 80 DEG C of quaternary ammonium fluoride salting liquids, quaternary ammonium fluoride salinity is 0.1mol/L, solid-liquid Than 1: 10,12h is stirred.Montmorillonite after fluorination is rinsed repeatedly in 90% methanol, until measured in rinse water without organic nitrogen, will Fluoronated mont-morillonite after washing is dried at 60 DEG C, ground 200 mesh sieve.
2nd, adsorption effect experiment and result
Respectively by 1.5mg fluoronated mont-morillonites be added to initial concentration in the solution of the 5 μm of ol/L only solute containing PFOS with And the solution containing a variety of solutes (including PFOS, phenol, neopelex, phenanthrene, pyridine, concentration are 5 μm of ol/L) In, shake 48h under 170rpm in shaking table, with solution after the analysis absorption of efficient liquid phase and mass spectrometry instrument PFOS it is dense Degree, with the concentration of remaining organic matter of spectrophotometric analysis.
As a result show, clearances of the PFOS in unitary system and compound system is 62%, and fluoronated mont-morillonite is to other Organic removal rate is no more than 4%, and adsorptive selectivity parameter S (PFOS clearances/coexisted organic compounds clearance) is reached as high as 168。
3rd, regeneration effect experiment and result
5mg fluoronated mont-morillonites are added in PFOS and PFOA solution of the initial concentration for 5 μm of ol/L respectively, in shaking table 48h is shaken under 170rpm, with the concentration of PFOS and PFOA in solution after efficient liquid phase and the analysis absorption of mass spectrometry instrument.
After the fluoronated mont-morillonite filtering of adsorption saturation, methanol solution regeneration 12h is placed in.
Adsorbent after regeneration is put into PFOS and PFOA solution again, carries out the second wheel absorption.
5 absorption regeneration experiments are so repeated, test result indicates that, repeatedly use rear fluoronated mont-morillonite pair PFOS and PFOA adsorbance keeps constant.
Embodiment 5
1st, the preparation process of present embodiment adsorbent is：
Stir 3 hours, settle 12 hours after 100g montmorillonite is added into appropriate deionized water by soil ratio 10: 1.With Siphonage purifies, and chooses granularity<2 μm of part is centrifuged, and is dried at 105 DEG C, ground 200 mesh sieve.
200 5g montmorillonites now are added to 0.7% Na2CO3Solution, it is made into the suspension of solid-to-liquid ratio 1: 10,80 DEG C of water Constant temperature stirring 3h is bathed, product centrifugation, is washed to pH weakly acidic pHs with deionized water, is dried at 105 DEG C, ground 200 mesh sieve.
The montmorillonite of sodium is sequentially placed into the quaternary ammonium fluoride salting liquid of 80 DEG C of increasing concen-trations, increasing concen-trations fluorination season The concentration of ammonium salt is respectively 0.15mol/L and 0.3mol/L, and solid-to-liquid ratio is 1: 10, stirs 10h.
Montmorillonite after fluorination is rinsed repeatedly in 90% methanol, until being measured in rinse water without organic nitrogen, after washing Fluoronated mont-morillonite is dried at 60 DEG C, ground 200 mesh sieve.
2nd, present embodiment adsorption effect experimental procedure is：
Respectively by 1.5mg fluoronated mont-morillonites be added to initial concentration in the solution of the 5 μm of ol/L only solute containing PFOS with And the solution containing a variety of solutes (including PFOS, phenol, neopelex, phenanthrene, pyridine, concentration are 5 μm of ol/L) In, shake 48h under 170rpm in shaking table, with solution after the analysis absorption of efficient liquid phase and mass spectrometry instrument PFOS it is dense Degree, with the concentration of remaining organic matter of spectrophotometric analysis.
As a result show, clearances of the PFOS in unitary system and compound system is 68%, and fluoronated mont-morillonite is to other Organic removal rate is no more than 4%, and adsorptive selectivity parameter S (PFOS clearances/coexisted organic compounds clearance) is reached as high as 207。
3rd, present embodiment regeneration effect experimental procedure is：
5mg fluoronated mont-morillonites are added in PFOS and PFOA solution of the initial concentration for 5 μm of ol/L respectively, in shaking table 48h is shaken under 170rpm, with the concentration of PFOS and PFOA in solution after efficient liquid phase and the analysis absorption of mass spectrometry instrument.
After the fluoronated mont-morillonite filtering of adsorption saturation, methanol solution regeneration 12h is placed in.
Adsorbent after regeneration is put into PFOS and PFOA solution again, carries out the second wheel absorption.
5 absorption regeneration experiments are so repeated, test result indicates that, repeatedly use rear fluoronated mont-morillonite pair PFOS and PFOA adsorbance keeps constant.
Embodiment 6
1st, the preparation process of present embodiment adsorbent is：
Stir 3 hours, settle 12 hours after 100g montmorillonite is added into appropriate deionized water by soil ratio 10: 1.With Siphonage purifies, and chooses granularity<2 μm of part is centrifuged, and is dried at 105 DEG C, ground 200 mesh sieve.
200 5g montmorillonites now are added to 1% Na2CO3Solution, it is made into the suspension of solid-to-liquid ratio 1: 12,80 DEG C of water-baths Constant temperature stirs 3h, product centrifugation, is washed to pH weakly acidic pHs with deionized water, is dried at 105 DEG C, ground 200 mesh sieve.
The montmorillonite of sodium is sequentially placed into the quaternary ammonium fluoride salting liquid of 60 DEG C of increasing concen-trations, quaternary ammonium fluoride salinity For 0.1mol/L and 0.2mol/L, solid-to-liquid ratio is 1: 8, each stirs 12h.
Montmorillonite after fluorination is rinsed repeatedly in 90% methanol, until being measured in rinse water without organic nitrogen, after washing Fluoronated mont-morillonite is dried at 60 DEG C, ground 200 mesh sieve.
2nd, present embodiment adsorption effect experimental procedure is：
Respectively by 1.5mg fluoronated mont-morillonites be added to initial concentration in the solution of the 5 μm of ol/L only solute containing PFOS with And the solution containing a variety of solutes (including PFOS, phenol, neopelex, phenanthrene, pyridine, concentration are 5 μm of ol/L) In, shake 48h under 170rpm in shaking table, with solution after the analysis absorption of efficient liquid phase and mass spectrometry instrument PFOS it is dense Degree, with the concentration of remaining organic matter of spectrophotometric analysis.
As a result show, clearances of the PFOS in unitary system and compound system is 74%, and fluoronated mont-morillonite is to other Organic removal rate is no more than 5%, and adsorptive selectivity parameter S (PFOS clearances/coexisted organic compounds clearance) is reached as high as 287。
3rd, present embodiment regeneration effect experimental procedure is：
5mg fluoronated mont-morillonites are added in PFOS and PFOA solution of the initial concentration for 5 μm of ol/L respectively, in shaking table 48h is shaken under 170rpm, with the concentration of PFOS and PFOA in solution after efficient liquid phase and the analysis absorption of mass spectrometry instrument.
After the fluoronated mont-morillonite filtering of adsorption saturation, methanol solution regeneration 12h is placed in.
Adsorbent after regeneration is put into PFOS and PFOA solution again, carries out the second wheel absorption.
5 absorption regeneration experiments are so repeated, test result indicates that, repeatedly use rear fluoronated mont-morillonite pair PFOS and PFOA adsorbance keeps constant.
In the description of this specification, the description meaning of reference term " one embodiment ", " some embodiments ", " example " etc. Refer at least one reality that the present invention is contained in reference to specific features, structure, material or the feature that the embodiment or example describe Apply in example or example.In this manual, identical embodiment is not necessarily referring to the schematic representation of above-mentioned term or shown Example.Moreover, specific features, structure, material or the feature of description can be in any one or more embodiments or example Combine in an appropriate manner.
Although an embodiment of the present invention has been shown and described, it will be understood by those skilled in the art that：Not In the case of departing from the principle and objective of the present invention a variety of change, modification, replacement and modification can be carried out to these embodiments, this The scope of invention is limited by claim and its equivalent.

Claims (29)

  1. A kind of 1. preparation method of selective absorption PFCs materials, it is characterised in that including：
    (1) with 1:5~1:Montmorillonite is placed in 0.5%-1% salting liquid by 15 ratio, to obtain metal cationization illiteracy De- stone, the salting liquid include metal cation, and the metal cation is selected from Na+、Li+、K+And Mg2+At least one of；
    (2) with 1:5~1:Metal cation montmorillonite in (1) is placed in 0.025~0.3mol/L fluorination by 15 ratio In quaternary ammonium salt solution, to obtain fluoronated mont-morillonite；
    (3) fluoronated mont-morillonite in organic solvent washing (2) is utilized, it is described to have to obtain the selective absorption PFCs materials Solvent is selected from least one of methanol, ethanol, acetone and acetonitrile.
  2. 2. the method for claim 1, it is characterised in that step (1) includes：
    With 1:5~1:Montmorillonite is placed in 0.5%-1% salting liquid by 15 ratio, and 70~90 degrees Celsius of constant temperature stirrings are at least Centrifuged after 2 hours, profit is washed with deionized the centrifugation product of acquisition, the centrifugation product after drying washing, to after drying from Heart product is ground sieving.
  3. 3. the method for claim 1, it is characterised in that in step (3), the fluorination rinsed repeatedly in (2) using 90% methanol Montmorillonite, until the solution after rinsing is measured without organic nitrogen.
  4. 4. the method for claim 2, it is characterised in that with 1:Montmorillonite is placed in 0.5%-1% sodium salt solution by 10 ratio In.
  5. 5. the method for claim 2, it is characterised in that the sodium acid carbonate that the sodium salt solution of the 0.5%-1% is 0.73% is molten Liquid.
  6. 6. the method for claim 2, it is characterised in that 80 C water bath's constant temperature centrifuge after stirring 3 hours.
  7. 7. the method for claim 2, it is characterised in that the sharp centrifugation product that acquisition is washed with deionized to pH weakly acidic pHs.
  8. 8. the method for claim 2, it is characterised in that the centrifugation product under 105 degrees Celsius after drying washing.
  9. 9. the method for claim 2, it is characterised in that ground 200 mesh sieve.
  10. 10. the method for claim 2, it is characterised in that step (2) is：
    With 1:5~1:Metal cation montmorillonite in (1) is sequentially placed into multiple concentration and increasing concen-trations by 15 ratio In the quaternary ammonium fluoride salting liquid, to obtain fluoronated mont-morillonite.
  11. 11. the method for claim 10, it is characterised in that step (2) includes：
    With 1:5~1:Metal cation montmorillonite in (1) is sequentially placed into the quaternary ammonium fluoride salt of following concentration by 15 ratio Stirred in solution at least 10 hours：0.025mol/L, 0.05mol/L, 0.1mol/L, 0.15mol/L, 0.2mol/L and 0.3mol/L。
  12. 12. the method for claim 11, it is characterised in that the metal cation montmorillonite and the quaternary ammonium fluoride salting liquid Ratio be 1:10.
  13. 13. the method for claim 11, it is characterised in that stirring 12 hours.
  14. 14. the method for claim 3, it is characterised in that after the fluoronated mont-morillonite in (2) is washed using organic solvent solution, Fluoronated mont-morillonite under 50-70 degrees Celsius after drying washing, grinding sieving.
  15. 15. the method for claim 14, it is characterised in that the fluoronated mont-morillonite under 60 degrees Celsius after drying washing.
  16. 16. the method for claim 14, it is characterised in that ground 200 mesh sieve.
  17. 17. claim 1-16 either method, it is characterised in that before step (1) is carried out,
    The montmorillonite is carried out to purify homogeneous processing, it is following including carrying out successively：
    With 1:8~1:The montmorillonite is placed in deionized water by 15 ratio, is stirred at least 2 hours, is settled at least 8 hours, The montmorillonite that granularity is less than 4 μm is isolated, the montmorillonite isolated is dried, sieving is ground to the montmorillonite after drying.
  18. 18. the method for claim 17, it is characterised in that with 1:The montmorillonite is inserted the deionized water by 10 ratio In.
  19. 19. the method for claim 17, it is characterised in that stirring 3 hours.
  20. 20. the method for claim 17, it is characterised in that sedimentation 12 hours.
  21. 21. the method for claim 17, it is characterised in that after carrying out the sedimentation, purified using siphonage.
  22. 22. the method for claim 17, it is characterised in that isolate the montmorillonite that granularity is less than 2 μm.
  23. 23. the method for claim 17, it is characterised in that the montmorillonite isolated is dried under 105 degrees Celsius.
  24. 24. the method for claim 17, it is characterised in that ground 200 mesh sieve.
  25. 25. a kind of selective absorption PFCs materials, it is prepared using claim 1-24 either method.
  26. 26. the selective absorption PFCs materials of claim 25, the interlamellar spacings of the selective absorption PFCs materials for 1.48~ 3.24nm。
  27. 27. the purposes in PFCs of the selective absorption PFCs materials of claim 25 or 26 in adsorbed water body.
  28. A kind of 28. method for the selective absorption PFCs materials for regenerating claim 25 or 26, it is characterised in that including by described in Selective absorption PFCs materials are placed in organic solvent at least 10 hours, and the organic solvent is selected from methanol, ethanol, acetone and second At least one of nitrile.
  29. 29. the method for claim 28, it is characterised in that be placed in 90% methanol solution 12 hours.
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