CN105776404A - Method for fast removing PFOA and PFOS in wastewater - Google Patents
Method for fast removing PFOA and PFOS in wastewater Download PDFInfo
- Publication number
- CN105776404A CN105776404A CN201610226286.4A CN201610226286A CN105776404A CN 105776404 A CN105776404 A CN 105776404A CN 201610226286 A CN201610226286 A CN 201610226286A CN 105776404 A CN105776404 A CN 105776404A
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- Prior art keywords
- nylon
- adsorbent
- pfos
- pfoa
- waste water
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- 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
- C02F2101/30—Organic compounds
- C02F2101/36—Organic compounds containing halogen
Abstract
The invention relates to a method for fast removing PFOA and PFOS in wastewater. The method includes the following steps of 1 preparing nylon adsorbent, wherein the nylon adsorbent is nylon membrane adsorbent or nylon particle adsorbent, a preparing method of the nylon particle adsorbent includes the steps that nylon 6 particles are used as a raw material and mechanically pulverized, particles in a certain particle size are screened, a NaOH solution is used for cleaning away impurities on the surface, the particles are washed to be neutral with distilled water and dried for use, and a preparing method of the nylon membrane adsorbent includes the steps that an aliphatic nylon millipore filter membrane is adopted as a raw material and cut into a suitable size and shape for use according to needs; 2 putting the nylon adsorbent prepared in the step 1 into PFOA and PFOS wastewater to conduct absorption. The method is simple, low in cost and good in removal effect, and regeneration is easy.
Description
Technical field
Patent of the present invention relates to a kind of method of PFOA and PFOS in quick removal waste water, belongs to the technical field of wastewater treatment.
Background technology
Perfluorooctane sulfonates (PerfluorooctaneSulfonate, it is called for short PFOS) and perfluoro caprylic acid (Perfluorooctanoate, it is called for short PFOA) it is the important perfluorochemical of a class, owing to perfluorochemical has water resistant, oil resistant, chemically and thermally stability characteristic (quality), it is widely used in the production processes such as textile, leather, paper products, packaging material, carpet, shampoo, optical disc surface material.Research shows that PFOS compounds is that class novel lasting a contact scar thing, particularly PFOS has the harm such as genotoxicity, neurotoxicity, interference thyroid function simultaneously, can be accumulated in animal tissue such as human liver, serum etc. by food chain transmission.PFOS and PFOA is difficult to be degraded in nature, a large amount of uses of this compounds so that it is entered into global range by all means.European Union issued " about the instruction that restriction Perfluorooctane sulfonates is sold and used " in 2006.The problem of environmental pollution of PFOS and PFOA has caused the extensive concern of researcher and government department.
For the treatment technology containing PFOA and PFOS waste water, currently mainly there are chemical oxidation degraded and the big class of physical absorption two.Owing in PFOA and PFOS molecule, C-F key is very firm, being difficult to be degraded, there is the problem that oxidation efficiency is less high, oxidizing condition is harsher in chemical oxidation method.Physical adsorption process is the treatment technology that an other class is main, and the adsorbing material being seen in report at present mainly includes activated carbon, aluminium oxide, molecular sieve etc..Wherein adsorption effect of activated carbon in water is best, is a most frequently used class adsorbent.But it is comparatively strict to there is regeneration condition in activated carbon, the more high deficiency of price.Nylon is as a kind of common industrial chemicals, cheap and easy to get, and regeneration is simple.Amide functional group in nylon molecules structure, strong hydrogen bond action can be formed with the F in PFOS and PFOA molecule, nylon surface easily produces electrostatic interaction and has strong hydrophobicity, and these features above-mentioned can greatly facilitate PFOS and PFOA absorption on nylon.The present invention mainly utilizes the These characteristics exploitation one of nylon with nylon for adsorbent, rapidly and efficiently synchronizes the technology of PFOA and PFOS in waste water of removing.
Summary of the invention
For the above-mentioned technical problem of prior art, the invention provides a kind of with nylon for adsorbent, rapidly and efficiently synchronize the technology of PFOA and PFOS in waste water of removing, its method is simple, with low cost, regeneration is easy and removal effect is good.
For reaching above-mentioned purpose, the present invention is achieved by the following technical solutions:
A kind of method of PFOA and PFOS in quick removal waste water, comprises the following steps:
(1) preparation of nylon adsorbent: described nylon adsorbent is nylon membrane adsorbent or nylon particles adsorbent；
The preparation method of described nylon particles adsorbent is: adopting nylon 6 granule is raw material, screens the granule of certain particle size respectively, first washes away surface impurity by NaOH solution, be then washed with distilled water to neutrality after mechanical activation comminution, dries, standby；
The preparation method of described nylon membrane adsorbent is: adopting amorphous nylon microporous filter membrane is raw material, and filter membrane is cut to suitable size and shape as required, standby；
(2) the nylon adsorbent being configured in step (1) is put in PFOA and PFOS waste water adsorb.
Described PFOA and PFOS concentration adopts LC-MS/MS method to measure.
The clearance computational methods of described PFOA and PFOS are: solution concentration before clearance (%)=100 ' (before absorption solution concentration after solution concentration-absorption)/absorption.
In described step (1), NaOH solution is the NaOH solution of 0.1M.
Drying temperature in described step (1) is 80 DEG C.
The aperture of described nylon membrane adsorbent is 0.22mm-0.8mm.
Described nylon particles adsorbent can at least recycle 10 times.
Beneficial effects of the present invention is as follows:
The present invention quickly removes the method for PFOA and PFOS in waste water, uses nylon membrane or nylon particles as adsorbent,
Nylon is as a kind of common industrial chemicals, cheap and easy to get, and regeneration is simple.Amide functional group in nylon molecules structure, strong hydrogen bond action can be formed with the F in PFOS and PFOA molecule, nylon surface easily produces electrostatic interaction and has strong hydrophobicity, These characteristics can greatly facilitate PFOS and PFOA absorption on nylon, rapidly and efficiently synchronizes to remove the technology of PFOA and PFOS in waste water.The inventive method is simple, with low cost, regeneration is easy and removal effect is good.
Accompanying drawing explanation
Fig. 1 is the adsorption curve schematic diagram of nylon particles adsorbent.
Detailed description of the invention
Below in conjunction with specific embodiment, the present invention is further illustrated, but protection scope of the present invention is not limited to this.
The method of PFOA and PFOS in a kind of quick removal waste water of the present invention, comprises the following steps:
(1) preparation of nylon adsorbent: nylon adsorbent is nylon membrane adsorbent or nylon particles adsorbent；
The preparation method of nylon particles adsorbent is: adopting nylon 6 granule is raw material, screens the granule of certain particle size respectively, first wash away surface impurity by the NaOH solution of 0.1M, be then washed with distilled water to neutrality after mechanical activation comminution, dries at 80 DEG C, standby；
The preparation method of nylon membrane adsorbent is: adopting amorphous nylon microporous filter membrane is raw material, and filter membrane is cut to suitable size and shape as required, standby；This filter membrane has good hydrophilic, the soda acid of resistance to debita spissitudo, is applicable not only to the aqueous solution containing Acidity of Aikalinity, is also applicable to containing organic solvent.
(2) the nylon adsorbent being configured in step (1) is put in PFOA and PFOS waste water adsorb.
PFOA and PFOS concentration adopts LC-MS/MS method to measure.The clearance computational methods of PFOA and PFOS are: solution concentration before clearance (%)=100 ' (before absorption solution concentration after solution concentration-absorption)/absorption.
The aperture of the nylon membrane adsorbent in the present invention is 0.22mm-0.8mm, wherein best results during 0.22mm.
Nylon particles adsorbent in the present invention can at least recycle 10 times.
The adsorption curve of nylon particles adsorbent
Weigh the while that 1.0 grams of 60-80 order nylon particles adsorbents being placed in 500 milliliters containing, in 100ppmPFOA and 100ppmPFOS simulated wastewater solution, carrying out adsorption test under 100 revs/min of stirring conditions.Take 0.5 ml sample at regular intervals to be analyzed.Result is as shown in Figure 1.As shown in Figure 1, with the increase of adsorption time within the scope of about 0-30 minute, PFOA and PFOS clearance increases sharply, and basically reaches adsorption equilibrium after 30 minutes.Under adsorption equilibrium, the clearance of PFOA and PFOS respectively reaches 95.6% and 100%.
The comparison of different adsorbing materials
Weigh respectively the while that 0.5 gram of 60-80 order nylon particles, activated carbon and kieselguhr being respectively placed in 500 milliliters containing, in 50ppmPFOA and 50ppmPFOS simulated wastewater solution, carrying out adsorption test under 100 revs/min of stirring conditions.Take 0.5 ml sample at regular intervals to be analyzed, measure nylon particles, activated carbon and diatomaceous equilibrium adsorption time and to the clearance of PFOA and PFOS in simulated wastewater.Result is as shown in table 1.As shown in Table 1, the clearance of PFOA and PFOS slightly below activated carbon, but is significantly larger than kieselguhr by nylon adsorbent.The time of equilibrium adsorption of nylon adsorbent only needed 30 minutes simultaneously, far below 180 minutes of activated carbon, it is possible to reach quick adsorption balance.
The table 1. different equilibrium adsorption time of adsorbing material, clearance and adsorbance
The comparison of different pore size nylon membrane adsorbent
Respectively clipping aperture be 0.22mm, 0.45mm and 0.8mm 5cm ' 4cm nylon membrane be placed in 50 milliliters while containing in 20ppmPFOA and 20ppmPFOS simulated wastewater solution, carry out adsorption test in standing situation, measure the clearance to PFOA and PFOS when the absorption of different pore size filter membrane reaches to balance.Result is as shown in table 2.
As shown in Table 2, the nylon membrane adsorption effect of 0.22mm is best, and total adsorbance reaches mg/m2.
Table 2. different pore size nylon membrane is to the clearance of PFOA and PFOS and adsorbance
Nylon adsorbent regeneration test
Nylon adsorbent after using is put into immersion 30 minutes in alcoholic solution, dries after taking out distilled water flushing, reuse.The data that nylon membrane if table 3 is nylon particles repeatedly recycles.As known from Table 3, circulating the adsorption effect of nylon particles adsorbent after using 10 times and only about have dropped 10%, nylon membrane adsorbent have dropped about 15%.Nylon particles adsorbent can repeatedly recycle.
Table 3 nylon adsorbent repeatedly recycles situation
Above-described embodiment is only for illustrating the inventive concept of the present invention, but not the restriction to rights protection of the present invention, all changes utilizing this design that the present invention carries out unsubstantiality, protection scope of the present invention all should be fallen into.
Claims (8)
1. the method for PFOA and PFOS in a quick removal waste water, it is characterised in that comprise the following steps:
(1) preparation of nylon adsorbent: described nylon adsorbent is nylon membrane adsorbent or nylon particles adsorbent；
The preparation method of described nylon particles adsorbent is: adopting nylon 6 granule is raw material, screens the granule of certain particle size respectively, first washes away surface impurity by NaOH solution, be then washed with distilled water to neutrality after mechanical activation comminution, dries, standby；
The preparation method of described nylon membrane adsorbent is: adopting amorphous nylon microporous filter membrane is raw material, and filter membrane is cut to suitable size and shape as required, standby；
(2) the nylon adsorbent being configured in step (1) is put in PFOA and PFOS waste water adsorb.
2. quickly remove the method for PFOA and PFOS in waste water as claimed in claim 1, it is characterised in that: described PFOA and PFOS concentration adopts LC-MS/MS method to measure.
3. quickly remove the method for PFOA and PFOS in waste water as claimed in claim 1, it is characterised in that the clearance computational methods of described PFOA and PFOS are: solution concentration before clearance (%)=100 ' (before absorption solution concentration after solution concentration-absorption)/absorption.
4. quickly remove the method for PFOA and PFOS in waste water as claimed in claim 1, it is characterised in that: in described step (1), NaOH solution is the NaOH solution of 0.1M.
5. quickly remove the method for PFOA and PFOS in waste water as claimed in claim 1, it is characterised in that: the drying temperature in described step (1) is 80 DEG C.
6. quickly remove the method for PFOA and PFOS in waste water as claimed in claim 1, it is characterised in that: the aperture of described nylon membrane adsorbent is 0.22mm-0.8mm.
7. quickly remove the method for PFOA and PFOS in waste water as claimed in claim 6, it is characterised in that: the aperture of described nylon membrane adsorbent is 0.22mm.
8. quickly remove the method for PFOA and PFOS in waste water as claimed in claim 1, it is characterised in that: described nylon particles adsorbent can at least recycle 10 times.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610226286.4A CN105776404A (en) | 2016-04-13 | 2016-04-13 | Method for fast removing PFOA and PFOS in wastewater |
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| Application Number | Priority Date | Filing Date | Title |
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| CN201610226286.4A CN105776404A (en) | 2016-04-13 | 2016-04-13 | Method for fast removing PFOA and PFOS in wastewater |
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| CN105776404A true CN105776404A (en) | 2016-07-20 |
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| CN201610226286.4A Pending CN105776404A (en) | 2016-04-13 | 2016-04-13 | Method for fast removing PFOA and PFOS in wastewater |
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109799308A (en) * | 2019-01-22 | 2019-05-24 | 董文洪 | Measure drinking water resource and PFOA and the remaining method of PFOS in drinking water |
| CN109813829A (en) * | 2019-01-22 | 2019-05-28 | 董文洪 | Enrichment purification-liquid chromatography tandem mass spectrometry measurement surface water and PFOA and the remaining method of PFOS in waste water |
| CN111603946A (en) * | 2020-05-21 | 2020-09-01 | 杭州科百特科技有限公司 | Nylon membrane and preparation method and application thereof |
| CN111603948A (en) * | 2020-05-21 | 2020-09-01 | 杭州科百特科技有限公司 | Nylon membrane and preparation method and application thereof |
| WO2021143433A1 (en) | 2020-01-15 | 2021-07-22 | 西安蓝晓科技新材料股份有限公司 | Adsorbent resin for removing perfluorinated pollutants from body of water, preparation therefor, and use thereof |
-
2016
- 2016-04-13 CN CN201610226286.4A patent/CN105776404A/en active Pending
Non-Patent Citations (2)
| Title |
|---|
| YOUNG-NAM KWON ETAL: "Adsorption of Perfluorinated Compounds on Thin-Film Composite Polyamide Membranes", 《JOURNAL OF APPLIED POLYMER SCIENCE》 * |
| 林钦: "聚酰胺固相萃取法检测动物源食品中全氟辛酸和全氟辛烷磺酸", 《食品科学》 * |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109799308A (en) * | 2019-01-22 | 2019-05-24 | 董文洪 | Measure drinking water resource and PFOA and the remaining method of PFOS in drinking water |
| CN109813829A (en) * | 2019-01-22 | 2019-05-28 | 董文洪 | Enrichment purification-liquid chromatography tandem mass spectrometry measurement surface water and PFOA and the remaining method of PFOS in waste water |
| WO2021143433A1 (en) | 2020-01-15 | 2021-07-22 | 西安蓝晓科技新材料股份有限公司 | Adsorbent resin for removing perfluorinated pollutants from body of water, preparation therefor, and use thereof |
| CN111603946A (en) * | 2020-05-21 | 2020-09-01 | 杭州科百特科技有限公司 | Nylon membrane and preparation method and application thereof |
| CN111603948A (en) * | 2020-05-21 | 2020-09-01 | 杭州科百特科技有限公司 | Nylon membrane and preparation method and application thereof |
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