CN105413627A - Material capable of selectively adsorbing perfluorochemicals as well as preparation method and application of material - Google Patents
Material capable of selectively adsorbing perfluorochemicals as well as preparation method and application of material Download PDFInfo
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Abstract
The invention discloses a preparation method of a material capable of selectively adsorbing perfluorochemicals (PFCs). The method comprises the following steps: (1) putting montmorillonite into 0.5 to 1% salt solution according to the ratio of (1: 5)-(1: 15), thus obtaining metal cationized montmorillonite, wherein the salt solution comprises metal cations selected from at least one of Na<+>, Li<+>, K<+> and Mg<2+>; (2) putting the metal cationized montmorillonite into 0.025 to 0.3mol/L fluorinated quaternary ammonium salt solution according to the ratio of (1: 5)-(1: 15), thus obtaining fluorinated montmorillonite; and (3) washing the fluorinated montmorillonite in the step (2) with an organic solvent, thus obtaining the material capable of selectively adsorbing PFCs, wherein the organic solvent is selected from at least one of methyl alcohol, ethyl alcohol, acetone and acetonitrile. The adsorption material prepared by the method is extremely high in selectivity for PFCs, excellent in adsorption amount and easy to regenerate, and is repeatedly used.
Description
Technical field
The present invention relates to chemical material field, concrete, the present invention relates to selective absorption PFCs material, preparation method and application thereof, more specifically, the present invention relates to a kind of can selective absorption PFCs material, a kind ofly prepare the method for selective absorption PFCs material, the purposes one of selective absorption PFCs material and a kind of method regenerating selective absorption PFCs material.
Background technology
Perfluorochemical (PFCs) causes the extensive concern in the whole world as the persistent organism pollutant that a class is main, and wherein PFOS (PFOS) has been put into the violated chemicals list in Stockholm.At present, use or production PFCs process all can cause the PFCs of water environment to pollute.For the removal of PFCs in water, the technology of current comparative maturity uses active carbon to remove PFCs in water as adsorbent.But active carbon is serious by the impact of coexisted organic compounds in water on the absorption of PFCs, and the active-carbon bed Competition due to coexisted organic compounds can lose the removal ability to PFCs at short notice.In addition, organic solvent regenerated carbon can bring other organic matters into regenerated liquid together, is unfavorable for the purification recycling of PFCs.Therefore, the sorbing material developing efficient and selective excellence is the focus that in current water, PFCs removes research field.It is low that desirable sorbing material needs to possess preparation cost, the advantages such as adsorbance is high, adsorptive selectivity good, regenerating easily.But although sorbing material adsorbance conventional is at present high but selective bad, in actual applications often by the impact that inorganic salts in water and organic matter are competed, adsorption effect is poor.
Therefore, a kind of high selectivity of removing for PFCs in water is developed and efficiently sorbing material is necessary.
Summary of the invention
The present invention one of is intended to solve the problems of the technologies described above at least to a certain extent or at least provides a kind of business to select.
Below finding and imagine, is that inventor makes basis of the present invention:
PFCs has the characteristic of hydrophobic oleophobic, and in water, carbon fluorine chain had both repelled hydrone simultaneously also not affine hydrocarbon substance, and had the tendency of mutually reuniting between carbon fluorine chain.Therefore, " similar compatibility " principle can be utilized, carry out organic fluoride modification at adsorbent surface, utilize the PFCs in the carbon fluorine chain adsorbed water of material surface.And the hydrophobic oleophobic effect of carbon fluorine chain can repel hydrocarbon organic matter, thus reach the object of selective removal PFCs.
Montmorillonite is cheap and have excellent cation exchange capacity (CEC).If select cheap montmorillonite as matrix material, react upper quaternary ammonium fluoride salt by its excellent cation exchange capacity (CEC), design experiment, may can prepare the selective absorbent with fluorinated surface and nanometer layer structure.And, compared with other sorbing materials, if the surface carbon fluorine chain of the selective absorbent prepared stretches to outside, repel hydrocarbon organic matter, optionally may can trap the PFCs in water; And probably can adsorb PFCs efficiently and not affect by coexisted organic compounds, the far super commercial activated carbons of adsorption capacity.
According to an aspect of of the present present invention, the invention provides a kind of preparation method of selective absorption PFCs material, comprise step: montmorillonite is placed in the salting liquid of 0.5%-1% by (1) with the ratio of 1:5 ~ 1:15, to obtain metal cation montmorillonite, described salting liquid comprises metal cation, and described metal cation is selected from Na
+, Li
+, K
+and Mg
2+in at least one; (2) with the ratio of 1:5 ~ 1:15, the metal cation montmorillonite in (1) is placed in the quaternary ammonium fluoride salting liquid of 0.025 ~ 0.3mol/L, to obtain fluoronated mont-morillonite; (3) utilize the fluoronated mont-morillonite in organic solvent washing (2), to obtain described selective absorption PFCs material, described organic solvent is selected from least one in methyl alcohol, ethanol, acetone and acetonitrile.Alleged salt generates the compound of metal cation (or ammonium radical ion) and acid ion when referring to ionize.
The preparation method of the selective absorption PFCs material of this one side of the invention described above, using cheap montmorillonite as matrix material, by cationization and fluorination reaction, can prepare the selective absorbent with fluorinated surface and nanometer layer structure.And compared with other sorbing materials, the surface carbon fluorine chain of the selective absorbent prepared stretches to outside, repel hydrocarbon organic matter, optionally can trap the PFCs in water body, can PFCs be adsorbed efficiently and not affect by coexisted organic compounds, the far super commercial activated carbons of adsorption capacity.High adsorption capacity adds its feature for the selective of PFCs excellence and easy regeneration, and the fluoronated mont-morillonite material making to utilize this method of the present invention to be prepared into field such as PFCs and PFCs recycling in removal water has good application prospect.
According to embodiments of the invention, the invention described above method preparing selective absorption PFCs material on the one hand, can also have following additional technical feature one of at least:
According to one embodiment of present invention, the step (1) of the method comprises: the salting liquid with the ratio of 1:5 ~ 1:15, montmorillonite being placed in 0.5%-1%, 70 ~ 90 degrees Celsius of constant temperature stir after at least 2 hours centrifugal, deionized water is utilized to wash the centrifugal product obtained, dry the centrifugal product after washing, grinding is carried out to the centrifugal product after oven dry and sieves.According to preferred embodiment of the present invention, inventor's test of many times adjusting and optimizing determines actual conditions or the combination condition of step (1), can the montmorillonite of acquisition metal cation of convenience and high-efficiency, such as, with the ratio of 1:10, montmorillonite is placed in the sodium salt solution of 0.5%-1%; And/or the sodium salt solution of described 0.5%-1% is the sodium bicarbonate solution of 0.73%; 80 C water bath's constant temperature stir after 3 hours centrifugal; And/or, utilize deionized water to wash the centrifugal product of acquisition to pH weakly acidic pH; And/or, under 105 degrees Celsius, dry the centrifugal product after washing; And/or, ground 200 mesh sieves.
According to one embodiment of present invention, alleged quaternary ammonium fluoride salt is C
14h
16f
17iN
2o
2s.
According to a preferred embodiment of the present invention, step (2) is: with the ratio of 1:5 ~ 1:15, the metal cation montmorillonite in step (1) is placed in multiple concentration and the described quaternary ammonium fluoride salting liquid of increasing concen-trations successively.Allow to obtain the fabulous montmorillonite of fluorination effect.
According to preferred embodiment of the present invention, step (2) comprising: the quaternary ammonium fluoride salting liquid metal cation montmorillonite in step (1) being placed in successively following concentration with the ratio of 1:5 ~ 1:15 stirs at least 10 hours: 025mol/L, 0.05mol/L, 0.1mol/L, 0.15mol/L, 0.2mol/L and 0.3mol/L.So, the fabulous fluoronated mont-morillonite of fluorination effect can be obtained.Better, make the ratio of described metal cation montmorillonite and described quaternary ammonium fluoride salting liquid be 1:10; And/or stir 12 hours.
According to one embodiment of present invention, step (3) is, utilizes the methyl alcohol of 90% repeatedly to rinse fluoronated mont-morillonite in (2), until detect without organic nitrogen in the solution flushed out.
According to embodiments of the invention, after utilizing the fluoronated mont-morillonite in organic solvent washing step (2), under 50-70 degree Celsius, dry the fluoronated mont-morillonite after washing, grinding is sieved.Preferably, under 60 degrees Celsius, dry the fluoronated mont-morillonite after washing; And/or, ground 200 mesh sieves.
According to embodiments of the invention, before carrying out step (1), homogeneous process is purified to montmorillonite organism material, following comprising carrying out successively: with the ratio of 1:8 ~ 1:15, described montmorillonite to be placed in deionized water, stir at least 2 hours, sedimentation at least 8 hours, isolate the montmorillonite that granularity is less than 4 μm, dry isolated montmorillonite, grinding is carried out to the montmorillonite after oven dry and sieves.According to preferred embodiment of the present invention, inventor's test of many times adjusting and optimizing determines actual conditions or the combination condition of the homogeneous process of this purification, is beneficial to subsequent step and effectively carries out, and such as, inserts in described deionized water with the ratio of 1:10 by described montmorillonite; And/or, stir 3 hours; And/or, sedimentation 12 hours; And/or, after carrying out described sedimentation, utilize siphonage to purify; And/or, isolate the montmorillonite that granularity is less than 2 μm; And/or, dry isolated montmorillonite under 105 degrees Celsius; And/or, ground 200 mesh sieves.
According to another aspect of the present invention, the invention provides a kind of selective absorption PFCs material utilizing the method for the invention described above on the one hand or in any embodiment to be prepared into.
According to one embodiment of present invention, the interlamellar spacing of the selective absorption PFCs material be prepared into is between 1.48-3.24nm.So, the macromolecule contaminant that this material can be coexisted in block water environment, when there is larger molecular organics, can also maintain PFCs efficient adsorption.
The selective absorption PFCs material of this one side of the present invention, using cheap montmorillonite as matrix material, is fluoridized by cation exchange reaction, thus has been prepared the selective absorbent with fluorinated surface and nanometer layer structure.Compared with other sorbing materials, the surface carbon fluorine chain of this material and fluoronated mont-morillonite stretches to outside, repels hydrocarbon organic matter, optionally traps the PFCs in water.Therefore, this fluoronated mont-morillonite can adsorb PFCs efficiently and not affect by coexisted organic compounds, the far super commercial activated carbons of adsorption capacity.High adsorption capacity adds its feature for the selective of PFCs excellence and easy regeneration, makes this fluoronated mont-morillonite material on the one hand of the present invention field such as PFCs and PFCs recycling in removal water have good application prospect.
According to another aspect of the invention, the invention provides the purposes in the PFCs of the invention described above selective absorption PFCs material on the one hand in adsorbed water body.The above-mentioned technical characteristic of selective absorption PFCs material to one aspect of the present invention and the description of advantage, be suitable for the purposes of the selective absorption PFCs material of this one side of the present invention equally, do not repeat them here.
According to another aspect of the present invention, the invention provides a kind of method regenerating the invention described above selective absorption PFCs material on the one hand, the method comprises described selective absorption PFCs material is placed in organic solvent at least 10 hours, to regenerate this material, make this material recover the ability of selective absorption PFCs, described organic solvent is selected from least one in methyl alcohol, ethanol, acetone and acetonitrile.This renovation process is simple, and this material can be made efficiently to recover the ability of selective absorption PFCs completely.
According to one embodiment of present invention, the selective absorption PFCs material after using is placed in the methanol solution 12 hours of 90%, the ability of the selective absorption PFCs of this material can be recovered, make this material to the free of losses of PFCs adsorbance.
To sum up, according to the embodiment of the present invention, the purposes of the preparation method of selective absorption PFCs material of the present invention, selective absorption PFCs material, selective absorption PFCs material and regenerate the method for this selective absorption PFCs material, at least has one of following advantages:
1, the selective absorption PFCs material of the embodiment of the present invention, i.e. fluoronated mont-morillonite, has nano-scale layers structure, affects the absorption of the PFCs macromolecule contaminant that do not coexisted.
2, the adsorbance of fluoronated mont-morillonite to typical perfluorochemical PFOS of the embodiment of the present invention is about 3 times of common commercial active carbon.
3, the fluoronated mont-morillonite of the embodiment of the present invention has excellent adsorptive selectivity when other organic matters exist to PFCs.
4, the fluoronated mont-morillonite of the embodiment of the present invention is when inorganic ions exists, and has higher absorption to PFCs.
5, the fluoronated mont-morillonite of the embodiment of the present invention can be realized holomorphosis by methanol solution, adsorbance free of losses after can reusing 5 times.
Accompanying drawing explanation
Above-mentioned and/or additional aspect of the present invention and advantage will become obvious and easy understand from accompanying drawing below combining to the description of embodiment, 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 the 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 matter coexist to PFOS and the contrast schematic diagram to Adsorption of Organic amount;
Fig. 4 is that the fluoronated mont-morillonite in one embodiment of the present of invention contrasts schematic diagram when different inorganic salts exist to the adsorbance of PFOS and PFOA (PFO carboxyl compound);
Fig. 5 is the schematic diagram changed PFOS and PFOA adsorbance after the fluoronated mont-morillonite in one embodiment of the present of invention continuous 5 takes turns absorption regeneration.
Detailed description of the invention
Be described below in detail embodiments of the invention, the example of described embodiment is shown in the drawings, and wherein, same or similar label represents same or similar element or has element that is identical or similar functions from start to finish.
Being exemplary below by the embodiment be described with reference to the drawings, only for explaining the present invention, and can not limitation of the present invention being interpreted as.Needs illustrate, term used herein " first ", " second " etc., only for convenience of describing, can not be interpreted as instruction or implying relative importance, having sequencing relation between can not being interpreted as.In describing the invention, except as otherwise noted, the implication of " multiple " is two or more.
Following embodiment is convenient to understand the present invention better, but does not limit the present invention.Experimental technique in following embodiment, if no special instructions, is conventional method.Material used in following embodiment, reagent etc., if no special instructions, all can obtain from commercial channels.
Embodiment 1
1, the preparation of adsorbent
(1) stir 3 hours after the montmorillonite of 100g being added appropriate deionized water by soil ratio 10: 1, sedimentation 12 hours.Purify with siphonage, the part choosing granularity <3 μm carries out centrifugation, dries, ground 200 mesh sieves at 105 DEG C.
(2) the 5g montmorillonite getting 200 mesh sieves joins the Na of 0.73%
2cO
3solution, is made into the suspension of solid-to-liquid ratio 1: 10, and 80 DEG C of constant temperature water baths stir 3h, and product is centrifugal, with deionized water washing to pH weakly acidic pH, dries, ground 200 mesh sieves at 105 DEG C.
(3) montmorillonite of sodium is placed in 80 DEG C of quaternary ammonium fluoride salting liquids, quaternary ammonium fluoride salinity is 0.3mol/L, solid-to-liquid ratio 1: 10, stirs 12h.
(4) montmorillonite after fluoridizing is rinsed repeatedly in 90% methyl alcohol, until measure without organic nitrogen in rinse water, the fluoronated mont-morillonite after washing is dried at 60 DEG C, ground 200 mesh sieves.
Fig. 1 shows the X-ray diffractogram of the sorbing material be prepared into, and shows the interlamellar spacing of this material between 1.48-3.24nm.
2, adsorption effect experiment and result
5mg fluoronated mont-morillonite (i.e. sorbing material) is put in the PFOS solution of 0.05-1mmol/L by 2.1, in shaking table, shake 48h under 170rpm.The concentration of PFOS in rear solution is adsorbed with efficient liquid phase and the analysis of mass spectrometry instrument.
As shown in Figure 2, the most high adsorption capacity of fluoronated mont-morillonite can reach 2.46mmol/g to result.
2.2 respectively 1.5mg fluoronated mont-morillonite is added to initial concentration be 5 μm of ol/L only (comprise PFOS, phenol, neopelex, phenanthrene, pyridine containing in the solution of PFOS solute and containing multiple solute, respective concentration is 5 μm of ol/L) solution in, 48h is shaken under 170rpm in shaking table, the concentration of PFOS in rear solution is adsorbed, by all the other organic concentration of spectrophotometric analysis with efficient liquid phase and the analysis of mass spectrometry instrument.
The clearance of PFOS in unitary system and compound system is 86%, and as shown in Figure 3, fluoronated mont-morillonite is no more than 5% to other organic removal rates, and adsorptive selectivity parameter S (PFOS clearance/coexisted organic compounds clearance) reaches as high as 353.
2.3 respectively 1.5mg fluoronated mont-morillonite is added to initial concentration be 5 μm of ol/L containing different salt (NaCl, Na
2sO
4, CaCl
2) PFOS and PFOA (PFO carboxyl compound) solution in, in shaking table, shake 48h under 170rpm, the concentration of PFOS and PFOA in solution after adsorbing with efficient liquid phase and the analysis of mass spectrometry instrument.
As shown in Figure 4, in the solution of saliferous, the absorption of fluoronated mont-morillonite to PFOS and PFOA does not have suppressed result, is improved on the contrary, improves 77% to PFOS adsorbance is the highest, improves 88% to the adsorbance of PFOA is the highest.
3, regeneration effect experiment
Respectively 5mg fluoronated mont-morillonite being joined initial concentration is in PFOS and the PFOA solution of 5 μm of ol/L, in shaking table, shake 48h under 170rpm, adsorbs the concentration of PFOS and PFOA in rear solution with efficient liquid phase and the analysis of mass spectrometry instrument.
After being filtered by fluoronated mont-morillonite saturated for absorption, be placed in methanol solution regeneration 12h.
Adsorbent after regeneration is put in PFOS and PFOA solution again, carries out second and takes turns absorption.
So repeatedly carry out 5 absorption regeneration experiments, result as shown in Figure 5, repeatedly uses the adsorbance of rear fluoronated mont-morillonite to PFOS and PFOA and remains unchanged.
Embodiment 2
1, the preparation of adsorbent
(1) stir 4 hours after the montmorillonite of 100g being added appropriate deionized water by soil ratio 5: 1, sedimentation 12 hours.Purify with siphonage, the part choosing granularity <2 μm carries out centrifugation, dries, ground 200 mesh sieves at 105 DEG C.
(2) 200 5g montmorillonites are now joined the MgCl of 1%
2solution, is made into the suspension of solid-to-liquid ratio 1: 15, and 80 DEG C of constant temperature water baths stir 3h, and product is centrifugal, with deionized water washing to pH weakly acidic pH, dries, ground 200 mesh sieves at 105 DEG C.
(3) montmorillonite of magnesium is 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, stirs 12h.
(4) montmorillonite after fluoridizing repeatedly is rinsed under acetonitrile, until measure without organic nitrogen in rinse water, the fluoronated mont-morillonite after washing is dried at 60 DEG C, ground 200 mesh sieves.
2, adsorption effect experiment and result
2.1 respectively 1.5mg fluoronated mont-morillonite is added to initial concentration be 5 μm of ol/L only (comprise PFOS, phenol, neopelex, phenanthrene, pyridine containing in the solution of PFOS solute and containing multiple solute, respective concentration is 5 μm of ol/L) solution in, 48h is shaken under 170rpm in shaking table, the concentration of PFOS in rear solution is adsorbed, by all the other organic concentration of spectrophotometric analysis with efficient liquid phase and the analysis of mass spectrometry instrument.
Result shows, and the clearance of PFOS in unitary system and compound system is 46%, and fluoronated mont-morillonite is no more than 3% to other organic removal rates, and adsorptive selectivity parameter S (PFOS clearance/coexisted organic compounds clearance) reaches as high as 99.
3, regeneration effect experiment and result
Respectively 5mg fluoronated mont-morillonite being joined initial concentration is in PFOS and the PFOA solution of 5 μm of ol/L, in shaking table, shake 48h under 170rpm, adsorbs the concentration of PFOS and PFOA in rear solution with efficient liquid phase and the analysis of mass spectrometry instrument.
After being filtered by fluoronated mont-morillonite saturated for absorption, be placed in acetonitrile solution regeneration 10h.
Adsorbent after regeneration is put in PFOS and PFOA solution again, carries out second and takes turns absorption.So repeatedly carry out 5 absorption regeneration experiments, experimental result shows, repeatedly uses the adsorbance of rear fluoronated mont-morillonite to PFOS and PFOA and remains unchanged.
Embodiment 3
1, the preparation of adsorbent
The montmorillonite of 100g to add after appropriate deionized water by soil ratio 15: 1 and stirs 3 hours by 1.1, sedimentation 12 hours.Purify with siphonage, the part choosing granularity <2 μm carries out centrifugation, dries, ground 200 mesh sieves at 105 DEG C.
200 5g montmorillonites are now joined the K of 0.6% by 1.2
2cO
3solution, is made into the suspension of solid-to-liquid ratio 1: 7, and 80 DEG C of constant temperature water baths stir 3h, and product is centrifugal, with deionized water washing to pH weakly acidic pH, dries, ground 200 mesh sieves at 105 DEG C.
The montmorillonite of potassium is placed in 80 DEG C of quaternary ammonium fluoride salting liquids by 1.3, and quaternary ammonium fluoride salinity is 0.05mol/L, solid-to-liquid ratio 1: 10, stirs 12h.
Montmorillonite after fluoridizing rinses in 90% methyl alcohol by 1.4 repeatedly, until measure without organic nitrogen in rinse water, is dried by the fluoronated mont-morillonite after washing, ground 200 mesh sieves at 60 DEG C.
2, adsorption effect experiment and result
2.1 respectively 1.5mg fluoronated mont-morillonite is added to initial concentration be 5 μm of ol/L only (comprise PFOS, phenol, neopelex, phenanthrene, pyridine containing in the solution of PFOS solute and containing multiple solute, concentration is 5 μm of ol/L) solution in, 48h is shaken under 170rpm in shaking table, the concentration of PFOS in rear solution is adsorbed, by all the other organic concentration of spectrophotometric analysis with efficient liquid phase and the analysis of mass spectrometry instrument.
Result shows, and the clearance of PFOS in unitary system and compound system is 54%, and fluoronated mont-morillonite is no more than 3% to other organic removal rates, and adsorptive selectivity parameter S (PFOS clearance/coexisted organic compounds clearance) reaches as high as 145.
3, regeneration effect experiment and result
Respectively 5mg fluoronated mont-morillonite being joined initial concentration is in PFOS and the PFOA solution of 5 μm of ol/L, in shaking table, shake 48h under 170rpm, adsorbs the concentration of PFOS and PFOA in rear solution with efficient liquid phase and the analysis of mass spectrometry instrument.
After being filtered by fluoronated mont-morillonite saturated for absorption, be placed in methanol solution regeneration 12h.
Adsorbent after regeneration is put in PFOS and PFOA solution again, carries out second and takes turns absorption.
So repeatedly carry out 5 absorption regeneration experiments, experimental result shows, repeatedly uses the adsorbance of rear fluoronated mont-morillonite to PFOS and PFOA and remains unchanged.
Embodiment 4
1, the preparation of attached dose
Stir 2 hours after the montmorillonite of 100g is added appropriate deionized water by soil ratio 10: 1, sedimentation 12 hours.Purify with siphonage, the part choosing granularity <2 μm carries out centrifugation, dries, ground 200 mesh sieves at 105 DEG C.
200 5g montmorillonites are now joined the Li of 0.8%
2cO
3solution, is made into the suspension of solid-to-liquid ratio 1: 8, and 80 DEG C of constant temperature water baths stir 3h, and product is centrifugal, with deionized water washing to pH weakly acidic pH, dries, ground 200 mesh sieves at 105 DEG C.
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-to-liquid ratio 1: 10, stirs 12h.Montmorillonite after fluoridizing is rinsed repeatedly in 90% methyl alcohol, until measure without organic nitrogen in rinse water, the fluoronated mont-morillonite after washing is dried at 60 DEG C, ground 200 mesh sieves.
2, adsorption effect experiment and result
Respectively 1.5mg fluoronated mont-morillonite is added to initial concentration is (comprise PFOS, phenol, neopelex, phenanthrene, pyridine only containing in the solution of PFOS solute and containing multiple solute of 5 μm of ol/L, concentration is 5 μm of ol/L) solution in, 48h is shaken under 170rpm in shaking table, the concentration of PFOS in rear solution is adsorbed, by all the other organic concentration of spectrophotometric analysis with efficient liquid phase and the analysis of mass spectrometry instrument.
Result shows, and the clearance of PFOS in unitary system and compound system is 62%, and fluoronated mont-morillonite is no more than 4% to other organic removal rates, and adsorptive selectivity parameter S (PFOS clearance/coexisted organic compounds clearance) reaches as high as 168.
3, regeneration effect experiment and result
Respectively 5mg fluoronated mont-morillonite being joined initial concentration is in PFOS and the PFOA solution of 5 μm of ol/L, in shaking table, shake 48h under 170rpm, adsorbs the concentration of PFOS and PFOA in rear solution with efficient liquid phase and the analysis of mass spectrometry instrument.
After being filtered by fluoronated mont-morillonite saturated for absorption, be placed in methanol solution regeneration 12h.
Adsorbent after regeneration is put in PFOS and PFOA solution again, carries out second and takes turns absorption.
So repeatedly carry out 5 absorption regeneration experiments, experimental result shows, repeatedly uses the adsorbance of rear fluoronated mont-morillonite to PFOS and PFOA and remains unchanged.
Embodiment 5
1, the preparation process of present embodiment adsorbent is:
Stir 3 hours after the montmorillonite of 100g is added appropriate deionized water by soil ratio 10: 1, sedimentation 12 hours.Purify with siphonage, the part choosing granularity <2 μm carries out centrifugation, dries, ground 200 mesh sieves at 105 DEG C.
200 5g montmorillonites are now joined the Na of 0.7%
2cO
3solution, is made into the suspension of solid-to-liquid ratio 1: 10, and 80 DEG C of constant temperature water baths stir 3h, and product is centrifugal, with deionized water washing to pH weakly acidic pH, dries, ground 200 mesh sieves at 105 DEG C.
The montmorillonite of sodium is placed in successively the quaternary ammonium fluoride salting liquid of the increasing concen-trations of 80 DEG C, the concentration of increasing concen-trations quaternary ammonium fluoride salt is respectively 0.15mol/L and 0.3mol/L, and solid-to-liquid ratio is 1: 10, all stirs 10h.
Montmorillonite after fluoridizing is rinsed repeatedly in 90% methyl alcohol, until measure without organic nitrogen in rinse water, the fluoronated mont-morillonite after washing is dried at 60 DEG C, ground 200 mesh sieves.
2, present embodiment adsorption effect experimental procedure is:
Respectively 1.5mg fluoronated mont-morillonite is added to initial concentration is (comprise PFOS, phenol, neopelex, phenanthrene, pyridine only containing in the solution of PFOS solute and containing multiple solute of 5 μm of ol/L, concentration is 5 μm of ol/L) solution in, 48h is shaken under 170rpm in shaking table, the concentration of PFOS in rear solution is adsorbed, by all the other organic concentration of spectrophotometric analysis with efficient liquid phase and the analysis of mass spectrometry instrument.
Result shows, and the clearance of PFOS in unitary system and compound system is 68%, and fluoronated mont-morillonite is no more than 4% to other organic removal rates, and adsorptive selectivity parameter S (PFOS clearance/coexisted organic compounds clearance) reaches as high as 207.
3, present embodiment regeneration effect experimental procedure is:
Respectively 5mg fluoronated mont-morillonite being joined initial concentration is in PFOS and the PFOA solution of 5 μm of ol/L, in shaking table, shake 48h under 170rpm, adsorbs the concentration of PFOS and PFOA in rear solution with efficient liquid phase and the analysis of mass spectrometry instrument.
After being filtered by fluoronated mont-morillonite saturated for absorption, be placed in methanol solution regeneration 12h.
Adsorbent after regeneration is put in PFOS and PFOA solution again, carries out second and takes turns absorption.
So repeatedly carry out 5 absorption regeneration experiments, experimental result shows, repeatedly uses the adsorbance of rear fluoronated mont-morillonite to PFOS and PFOA and remains unchanged.
Embodiment 6
1, the preparation process of present embodiment adsorbent is:
Stir 3 hours after the montmorillonite of 100g is added appropriate deionized water by soil ratio 10: 1, sedimentation 12 hours.Purify with siphonage, the part choosing granularity <2 μm carries out centrifugation, dries, ground 200 mesh sieves at 105 DEG C.
200 5g montmorillonites are now joined the Na of 1%
2cO
3solution, is made into the suspension of solid-to-liquid ratio 1: 12, and 80 DEG C of constant temperature water baths stir 3h, and product is centrifugal, with deionized water washing to pH weakly acidic pH, dries, ground 200 mesh sieves at 105 DEG C.
The montmorillonite of sodium is placed in successively the quaternary ammonium fluoride salting liquid of the increasing concen-trations of 60 DEG C, quaternary ammonium fluoride salinity is 0.1mol/L and 0.2mol/L, and solid-to-liquid ratio is 1: 8, all stirs 12h separately.
Montmorillonite after fluoridizing is rinsed repeatedly in 90% methyl alcohol, until measure without organic nitrogen in rinse water, the fluoronated mont-morillonite after washing is dried at 60 DEG C, ground 200 mesh sieves.
2, present embodiment adsorption effect experimental procedure is:
Respectively 1.5mg fluoronated mont-morillonite is added to initial concentration is (comprise PFOS, phenol, neopelex, phenanthrene, pyridine only containing in the solution of PFOS solute and containing multiple solute of 5 μm of ol/L, concentration is 5 μm of ol/L) solution in, 48h is shaken under 170rpm in shaking table, the concentration of PFOS in rear solution is adsorbed, by all the other organic concentration of spectrophotometric analysis with efficient liquid phase and the analysis of mass spectrometry instrument.
Result shows, and the clearance of PFOS in unitary system and compound system is 74%, and fluoronated mont-morillonite is no more than 5% to other organic removal rates, and adsorptive selectivity parameter S (PFOS clearance/coexisted organic compounds clearance) reaches as high as 287.
3, present embodiment regeneration effect experimental procedure is:
Respectively 5mg fluoronated mont-morillonite being joined initial concentration is in PFOS and the PFOA solution of 5 μm of ol/L, in shaking table, shake 48h under 170rpm, adsorbs the concentration of PFOS and PFOA in rear solution with efficient liquid phase and the analysis of mass spectrometry instrument.
After being filtered by fluoronated mont-morillonite saturated for absorption, be placed in methanol solution regeneration 12h.
Adsorbent after regeneration is put in PFOS and PFOA solution again, carries out second and takes turns absorption.
So repeatedly carry out 5 absorption regeneration experiments, experimental result shows, repeatedly uses the adsorbance of rear fluoronated mont-morillonite to PFOS and PFOA and remains unchanged.
In the description of this description, specific features, structure, material or feature that the description of reference term " embodiment ", " some embodiments ", " example " etc. means to describe in conjunction with this embodiment or example are contained at least one embodiment of the present invention or example.In this manual, identical embodiment or example are not necessarily referred to the schematic representation of above-mentioned term.And the specific features of description, structure, material or feature can combine in an appropriate manner in any one or more embodiment or example.
Although illustrate and describe embodiments of the invention, those having ordinary skill in the art will appreciate that: can carry out multiple change, amendment, replacement and modification to these embodiments when not departing from principle of the present invention and aim, scope of the present invention is by claim and equivalents thereof.
Claims (10)
1. a preparation method for selective absorption PFCs material, is characterized in that, comprising:
(1) with the ratio of 1:5 ~ 1:15, montmorillonite is placed in the salting liquid of 0.5%-1%, to obtain metal cation montmorillonite, described salting liquid comprises metal cation, and described metal cation is selected from Na
+, Li
+, K
+and Mg
2+in at least one;
(2) with the ratio of 1:5 ~ 1:15, the metal cation montmorillonite in (1) is placed in the quaternary ammonium fluoride salting liquid of 0.025 ~ 0.3mol/L, to obtain fluoronated mont-morillonite;
(3) utilize the fluoronated mont-morillonite in organic solvent washing (2), to obtain described selective absorption PFCs material, described organic solvent is selected from least one in methyl alcohol, ethanol, acetone and acetonitrile.
2. the method for claim 1, is characterized in that, step (1) comprising:
With the ratio of 1:5 ~ 1:15, montmorillonite is placed in the salting liquid of 0.5%-1%, 70 ~ 90 degrees Celsius of constant temperature stir after at least 2 hours centrifugal, utilize deionized water to wash the centrifugal product obtained, dry the centrifugal product after washing, grinding is carried out to the centrifugal product after oven dry and sieves;
Optional, with the ratio of 1:10, montmorillonite is placed in the sodium salt solution of 0.5%-1%;
Optional, the sodium salt solution of described 0.5%-1% is the sodium bicarbonate solution of 0.73%;
Optional, 80 C water bath's constant temperature stir after 3 hours centrifugal;
Optional, utilize deionized water to wash the centrifugal product of acquisition to pH weakly acidic pH;
Optional, under 105 degrees Celsius, dry the centrifugal product after washing;
Optional, ground 200 mesh sieves.
3. the method for claim 2, is characterized in that, step (2) is:
Metal cation montmorillonite in (1) is placed in multiple concentration and the described quaternary ammonium fluoride salting liquid of increasing concen-trations successively, to obtain fluoronated mont-morillonite with the ratio of 1:5 ~ 1:15.
4. the method for claim 3, is characterized in that, step (2) comprising:
Quaternary ammonium fluoride salting liquid metal cation montmorillonite in (1) being placed in successively following concentration with the ratio of 1:5 ~ 1:15 stirs at least 10 hours: 025mol/L, 0.05mol/L, 0.1mol/L, 0.15mol/L, 0.2mol/L and 0.3mol/L;
Optional, the ratio of described metal cation montmorillonite and described quaternary ammonium fluoride salting liquid is 1:10;
Optional, stir 12 hours.
5. the method for claim 1, is characterized in that, in step (3),
The methyl alcohol of 90% is utilized repeatedly to rinse fluoronated mont-morillonite in (2), until the solution after rinsing is measured without organic nitrogen.
6. the method for claim 5, is characterized in that, after the fluoronated mont-morillonite utilizing organic solvent solution to wash in (2), under 50-70 degree Celsius, dry the fluoronated mont-morillonite after washing, grinding is sieved;
Optional, under 60 degrees Celsius, dry the fluoronated mont-morillonite after washing;
Optional, ground 200 mesh sieves.
7. claim 1-6 either method, is characterized in that, before carrying out step (1),
Homogeneous process is purified to described montmorillonite, following comprising carrying out successively:
With the ratio of 1:8 ~ 1:15, described montmorillonite is placed in deionized water, stirs at least 2 hours, sedimentation at least 8 hours, isolate the montmorillonite that granularity is less than 4 μm, dry isolated montmorillonite, grinding is carried out to the montmorillonite after oven dry and sieves;
Optional, with the ratio of 1:10, described montmorillonite is inserted in described deionized water;
Optional, stir 3 hours;
Optional, sedimentation 12 hours;
Optional, after carrying out described sedimentation, utilize siphonage to purify;
Optional, isolate the montmorillonite that granularity is less than 2 μm;
Optional, dry isolated montmorillonite under 105 degrees Celsius;
Optional, ground 200 mesh sieves.
8. a selective absorption PFCs material, it utilizes claim 1-7 either method to prepare;
Optional, the interlamellar spacing of described selective absorption PFCs material is 1.48 ~ 3.24nm.
9. the purposes in the PFCs of the selective absorption PFCs material of claim 8 in adsorbed water body.
10. one kind regenerates the method for the selective absorption PFCs material of claim 8, it is characterized in that, comprise and described selective absorption PFCs material is placed in organic solvent at least 10 hours, described organic solvent is selected from least one in methyl alcohol, ethanol, acetone and acetonitrile;
Optional, be placed in the methanol solution 12 hours of 90%.
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN106390933A (en) * | 2016-08-31 | 2017-02-15 | 清华大学 | Magnetic fluorinated adsorbent for selective adsorption of PFOS, preparation method and application thereof |
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