CN103058319B - Degradation method of perfluorinated compounds - Google Patents
Degradation method of perfluorinated compounds Download PDFInfo
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- CN103058319B CN103058319B CN201210571774.0A CN201210571774A CN103058319B CN 103058319 B CN103058319 B CN 103058319B CN 201210571774 A CN201210571774 A CN 201210571774A CN 103058319 B CN103058319 B CN 103058319B
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- perfluorochemical
- perfluorinated compounds
- sodium persulfate
- pfoa
- hydrogen peroxide
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Abstract
The invention discloses a degradation method of perfluorinated compounds. The degradation method of the perfluorinated compounds comprises carrying out ultraviolet-irradiation on liquid-phase perfluorinated compounds, and meanwhile adding oxidant and catalyst into the liquid-phase perfluorinated compounds. The catalyst is titanium dioxide supported heteropoly acid. The oxidant is sodium persulfate or/and hydrogen peroxide. The degradation method of the perfluorinated compounds is simple, easy to carry out, capable of being carried out at normal temperatures and pressures, free from the need of complicated equipment and free from requirements of concentration of the perfluorinated compounds in sewage. After treatment with the degradation method of the perfluorinated compounds, toxicity of decomposition products is reduced, and further treatment is easy.
Description
Technical field
The present invention relates to the decomposition technique field of perfluorochemical, be specifically related to a kind of degradation method of perfluorochemical.
Background technology
Perfluorochemical is the fluorinated organic compound that a class has significant application value, and it is that fluorine atom substitutes all hydrogen atoms in hydrocarbon polymer and the fluorocarbon that forms, and its production and using can be traced back to before 50 years.The perfluorochemical existing in environment mainly contains perfluori piated carboxylic acids, perfluorinated sulfonic acid class, perfluor amides etc., wherein Perfluorooctane sulfonates (PFOS) and Perfluorocaprylic Acid (PFOA) are most typical two kinds of perfluorochemicals in environment, and these two kinds of compounds are multiple perfluorochemical (PFCs) final converted products in environment.Perfluorochemical contains the C-F covalent linkage with high chemical bond energy (bond energy is about 110kcal/mol), and therefore this compounds has very high stability in environment, and has biological accumulation and biological amplification.
PFCs pollutent is prevalent in the water globe environment including the ice sheet of the arctic.At present, the perfluorochemical of different concns in waste water and mud, surface water, underground water, seawater, marine bottom sediment and tap water (tap water), all detected.
Existing Pollutant Treatment method, as physical adsorption separates, burns the technology such as degraded, catalyzed degradation, photodissociation, all decomposed P FOA and PFOS very effectively.Therefore urgent a kind of find energy efficient degradation perfluorochemical method, to tackle the risk that may bring.
For example publication number is that the Chinese invention patent application of CN 100389857C discloses a kind of Catalyst And Method for waste gas decomposition perfluorochemical, and this catalyzer makes in alumina surface load phosphorus (P) component take the molar ratio range of aluminium/phosphorus as 10-100.
Publication number is a kind of method that the Chinese invention patent application of CN 100347137A discloses defluorinating and degrading complete fluorine substituted compounds, for eliminating the full-fluorine substituted organic matter of water, air and soil.The fluorine substituted compounds such as PFOS and PFOA under oxygen free condition is carried out to vacuum-ultraviolet light irradiation; make fluorine substituted compounds carry out defluorination reaction; reaction can be under the ultraviolet mercury lamp of 185nm irradiates; or wavelength be 172nm xenon molecular exciton light irradiate under carry out; can pass into protectiveness rare gas element or reducing gas and realize oxygen free condition; also can in reaction process, add reducing substances and the semiconductor catalyst with high conduction level, to improve defluorinate rate of decomposition.
Publication number is that method the method that the Chinese invention patent application of CN 102351272A discloses a kind of degrading perfluorooctanoic acid in water through visible light catalysis comprises two steps: the preparation of photocatalyst and utilize its Perfluorocaprylic Acid in catalyzed degradation water under visible ray.Specifically, first take strontium chloride as raw material, take five water Bismuth trinitrates as bismuth source, utilize solvent thermal process to prepare strontium doping bismuth oxide photocatalyst, then utilize this catalyzer photocatalytic degradation Perfluorocaprylic Acid.
In traditional degradation method and the disclosed technology of above-mentioned patent documentation, all limited for the degradation efficiency of perfluorochemical, be restricted in actual applications.
Summary of the invention
The invention provides a kind of degradation method of perfluorochemical, at normal temperatures and pressures Perfluorocaprylic Acid (PFOA) and perfluoro octyl sulfonic acid salt (PFOS) are decomposed into harmless material, degradation efficiency is high.
A degradation method for perfluorochemical, comprising:
The perfluorochemical of liquid phase is carried out to UV-irradiation, in the perfluorochemical of liquid phase, add oxygenant and catalyzer simultaneously; Described catalyzer is titanium dichloride load heteropolyacid; Described oxygenant is that Sodium Persulfate is or/and hydrogen peroxide.
The perfluorochemical of liquid phase refers to the aqueous solution of perfluorochemical, when degraded, the concentration of perfluorochemical in this aqueous solution is not had to particular requirement.
As preferably, described perfluorochemical is Perfluorocaprylic Acid or perfluoro octyl sulfonic acid salt.
As preferably, described oxygenant is Sodium Persulfate and hydrogen peroxide, and the mol ratio of Sodium Persulfate and hydrogen peroxide is 3: 1～1, is preferably 2: 1.Hydrogen peroxide adopts commercially available 30% hydrogen peroxide, and in sodium persulfide and hydrogen peroxide, the mol ratio of hydrogen peroxide is 3: 1～1.
As preferably, the dosage of described oxygenant and the mol ratio of perfluorochemical are 2～25: 1, are preferably 4～10: 1.
When perfluorochemical is Perfluorocaprylic Acid or perfluoro octyl sulfonic acid salt, oxygenant is Sodium Persulfate or/and when hydrogen peroxide, the dosage of oxygenant and the mol ratio of perfluorochemical all get 2～25: 1, are preferably 4～25: 1.
As preferably, described catalyzer is titanium dichloride load heteropolyacid.Described titanium dichloride load heteropolyacid is prepared by pickling process.
More preferably, described catalyzer is titanium dichloride load phospho-wolframic acid.
More preferably, the dosage of described catalyzer is 0.01g/L-2g/L.Be to add 0.01～2g catalyzer in the perfluorochemical of every liter of liquid phase.
As preferably, the time of described UV-irradiation is 30min-360min, more preferably 250min-360min.
As preferably, described ultraviolet light wavelength is less than 200nm, for example, can be the arbitrary wavelength between 150-200nm.
Most preferably, described perfluorochemical is Perfluorocaprylic Acid or perfluoro octyl sulfonic acid salt; Described oxygenant is Sodium Persulfate and hydrogen peroxide, and the mol ratio of Sodium Persulfate and hydrogen peroxide is 2: 1; The dosage of described oxygenant and the mol ratio of perfluorochemical are 4: 1; Described catalyzer is titanium dichloride load phospho-wolframic acid; The dosage of described catalyzer is 0.01g/L-2g/L; The time of described UV-irradiation is 250-360min.
The degradation principles of the inventive method is:
Activate to promote PFCs that effectively degraded occurs catalyzer and oxygenant by UV-light.Under UV-irradiation condition, catalyzer titanium dichloride load heteropoly acid catalysis destroys F-C key, and the strong oxidizing property free radical that has of collaborative composite oxidant system (Sodium Persulfate and hydrogen peroxide) generation makes PFOA and PFOS degraded.Heteropolyacid-TiO
2compound system can complete the transmission of electronics, UV/H expeditiously
2o
2/ S
2o
8 2-system makes oxygenant produce more free radical SO
4-and OH, thus the degradation efficiency of PFOA and PFOS improved.
Compared with prior art beneficial effect of the present invention:
The present invention is simple, carries out at normal temperatures and pressures, does not need complicated equipment, and to the not requirement of the concentration of perfluorochemical in sewage, after present method is processed, degradation production toxicity reduces, and is easy to further processing; The present invention adopts titanium dichloride load heteropolyacid catalyst, and very effective for the perfluorochemical in water of decomposition under UV-irradiation under the coordinative role of composite oxidant, degradation efficiency is up to more than 97%.
Accompanying drawing explanation
Fig. 1 is that ultraviolet catalytic oxidation decomposes perfluorochemical setting drawing.
Fig. 2 is Perfluorocaprylic Acid (PFOA) ultraviolet degradation effect comparison diagram.
Fig. 3 is perfluoro octyl sulfonic acid salt (PFOS) ultraviolet degradation effect comparison diagram.
Embodiment
As shown in Figure 1, device of the present invention comprises: light source 1, quartz socket tube 2, reaction vessel 3 and distribution device 4.
Reaction vessel 3 is reacting environment that perfluorochemical decomposes; On the sidewall of the bottom of reaction vessel 3, with injection port, for add the material such as catalyzer 6, oxygenant 7 to reaction vessel 3, oxygenant 6 can accelerate perfluorochemical and decompose; Catalyzer 7 can be heteropolyacid, the titanium dioxide composite catalyst of powder or loading type; The bottom of reaction vessel 3 is provided with distribution device 4, for passing into air to reaction vessel 3, improves perfluorochemical decomposition efficiency; Reaction vessel 3 outsides are provided with light source 1, and this light source 1 emission wavelength is less than the ultraviolet ray of 200nm; The outer sheathed quartz socket tube 2 of reaction vessel 3, for isolating light source 1 and the interior treatment media of reaction vessel 3, this quartz socket tube 2 can see through ultraviolet ray.
First the reaction soln 8 (concentration to perfluorochemical in reaction soln does not have particular requirement) that contains perfluorochemical is put in reaction vessel 3, then pass into air 5, under the irradiation of light source 1, perfluorochemical decomposes, in order to accelerate the decomposition of perfluorochemical, oxygenant 6 and catalyzer 7 can be separately or together with add.
Embodiment 1
With the TiO of the phospho-wolframic acid acid dipping 5g of the 0.05mol/L of 20mL
2powder 24h; By after the solid-carrying heteropolyacid drying and grinding of having flooded, then under microwave oven 650W power sintering 30min, after washing and drying, make catalyzer titanium dichloride load phospho-wolframic acid, use for following examples.
The ultraviolet catalytic of embodiment 2 Perfluorocaprylic Acids (PFOA) decomposes
As shown in Figure 1,500mL is put in reaction vessel 3 containing the aqueous solution of 41.4mg/L PFOA, air passes into reaction vessel 3 from bottom distribution device 4, under the irradiation of light source 1 of launching 185nm vacuum ultraviolet rays, add catalyzer titanium dichloride load phospho-wolframic acid, dosage is 0.05g/L (the PFOA aqueous solution).
The effect that PFOA decomposes is shown in Fig. 2 curve A, and as seen from the figure, in reaction soln, PFOA degradation rate rose with the reaction times, reacted the degradation rate of PFOA after 360 minutes and reached 85.3%.
Degradation rate refers in reaction process the ratio of PFOA concentration minimizing value and initial value in solution.
The ultraviolet catalytic oxygenolysis of embodiment 3 Perfluorocaprylic Acids (PFOA)
As shown in Figure 1, 500mL is put into reaction vessel 3 containing the aqueous solution of 41.4mg/L PFOA, air passes into reaction vessel 3 from bottom distribution device 4, under the irradiation of light source 1 of launching 185nm vacuum ultraviolet rays, add catalyzer titanium dichloride load phospho-wolframic acid, dosage is 0.01g/L (the PFOA aqueous solution), add Sodium Persulfate (Sodium Persulfate/Perfluorocaprylic Acid mol ratio is 4: 1) simultaneously, the effect that PFOA decomposes is shown in Fig. 2 curve B, as seen from the figure, in reaction soln, PFOA degradation rate rose with the reaction times, react the degradation rate of PFOA after 360 minutes and reach 95.2%.
In the present embodiment, the impact of the degradation rate of the dosage of also having studied Sodium Persulfate on PFOA, result of study shows that the dosage of Sodium Persulfate has considerable influence to the degradation rate of PFOA, in the time that Sodium Persulfate/Perfluorocaprylic Acid mol ratio is 2: 1, reaction 30min, the degradation rate 15.8% of PFOA; In the time that Sodium Persulfate/Perfluorocaprylic Acid mol ratio is 4: 1, reaction 30min, the degradation rate 22.2% of PFOA; In the time that Sodium Persulfate/Perfluorocaprylic Acid mol ratio is 25: 1, reaction 30min, the degradation rate 25.8% of PFOA.
Embodiment 3: the ultraviolet catalytic combined oxidation of Perfluorocaprylic Acid (PFOA) decomposes
As shown in Figure 1, 500mL is put into reaction vessel 3 containing the aqueous solution of 41.4mg/L PFOA, air passes into reaction vessel 3 from bottom distribution device 4, under the irradiation of light source 1 of launching 185nm vacuum ultraviolet rays, add catalyzer titanium dichloride load phospho-wolframic acid, dosage is 0.01g/L (the PFOA aqueous solution), add Sodium Persulfate and hydrogen peroxide (Sodium Persulfate/Perfluorocaprylic Acid mol ratio is 4: 1 simultaneously, Sodium Persulfate/hydrogen peroxide mol ratio is 2: 1), the effect that PFOA decomposes is shown in Fig. 2 curve C, there is figure known, in reaction soln, PFOA degradation rate rose with the reaction times, react the degradation rate of PFOA after 360 minutes and reach 96.2%.
When Sodium Persulfate/Perfluorocaprylic Acid mol ratio is 4: 1, Sodium Persulfate/hydrogen peroxide mol ratio is 2: 1 o'clock, reaction 30min, and the degradation rate 28.3% of PFOA, the reaction system degradation rate of more single interpolation same amount Sodium Persulfate approximately improves 6 percentage points.
Embodiment 4: perfluoro octyl sulfonic acid salt (PFOS) ultraviolet catalytic decomposes
As shown in Figure 1,500mL is put into reaction vessel 3 containing the aqueous solution of 50mg/L PFOS (perfluoro octyl sulfonic acid potassium), air passes into reaction vessel 3 from bottom distribution device 4, under the irradiation of light source 1 of launching 185nm vacuum ultraviolet rays, add catalyzer titanium dichloride load phospho-wolframic acid, dosage is 2g/L (the PFOS aqueous solution), and the effect that PFOS decomposes is shown in Fig. 3 curve D.
As seen from the figure, in reaction soln, PFOS degradation rate rose with the reaction times, reaction 30min, the degradation rate 9.6% of PFOS; React the degradation rate of PFOS after 360 minutes and reach 80.9%.
Embodiment 5: perfluoro octyl sulfonic acid salt (PFOS) ultraviolet catalytic oxygenolysis
As shown in Figure 1,500mL is put into reaction vessel 3 containing the aqueous solution of 50mg/L PFOS (perfluoro octyl sulfonic acid potassium), air passes into reaction vessel 3 from bottom distribution device 4, under the irradiation of light source 1 of launching 185nm vacuum ultraviolet rays, add catalyzer titanium dichloride load phospho-wolframic acid, dosage is 2g/L, adds Sodium Persulfate (Sodium Persulfate/perfluoro octyl sulfonic acid salt mol ratio is 4: 1) simultaneously, and the effect that PFOS decomposes is shown in Fig. 3 curve E.React the degradation rate of PFOA after 360 minutes and reach 97.4%.
In the present embodiment, the impact of the degradation rate of the dosage of also having studied Sodium Persulfate on PFOA, result of study shows, in the time that Sodium Persulfate/perfluoro octyl sulfonic acid salt mol ratio is 2: 1, reaction 30min, the degradation rate 18.8% of PFOS; In the time that Sodium Persulfate/perfluoro octyl sulfonic acid salt mol ratio is 4: 1, reaction 30min, the degradation rate 23.5% of PFOS; When Sodium Persulfate/perfluoro octyl sulfonic acid salt) mol ratio is while being 25: 1, reaction 30min, the degradation rate 28.9% of PFOS.
Embodiment 6: perfluoro octyl sulfonic acid salt (PFOS) ultraviolet catalytic combined oxidation decomposes
As shown in Figure 1,500mL is put into reaction vessel 3 containing PFOS (perfluoro octyl sulfonic acid potassium) aqueous solution of 50mg/L, air passes into reaction vessel 3 from bottom distribution device 4, under the irradiation of light source 1 of launching 185nm vacuum ultraviolet rays, add catalyzer titanium dichloride load phospho-wolframic acid, dosage is 2g/L, add Sodium Persulfate and hydrogen peroxide (Sodium Persulfate/perfluoro octyl sulfonic acid salt mol ratio is 4: 1 simultaneously, Sodium Persulfate/hydrogen peroxide mol ratio is 2: 1), the effect that PFOS decomposes is shown in Fig. 3 curve F.
The interpolation of hydrogen peroxide has considerable influence to the degradation rate of PFOS, reaction 30min, and the degradation rate 28.4% of PFOS, improves 5% degradation rate than the reaction system of adding without hydrogen peroxide.
Claims (1)
1. a degradation method for perfluorochemical, is characterized in that, comprising:
The perfluorochemical of liquid phase is carried out to UV-irradiation, in the perfluorochemical of liquid phase, add oxygenant and catalyzer simultaneously; Described catalyzer is titanium dichloride load phospho-wolframic acid; Described oxygenant is Sodium Persulfate and hydrogen peroxide, and in Sodium Persulfate and hydrogen peroxide, the mol ratio of hydrogen peroxide is 3:1～1:1; The dosage of described oxygenant and the mol ratio of perfluorochemical are 4～25:1; The dosage of described catalyzer is 0.01g/L-2g/L, and the time of described UV-irradiation is 30min～360min; Described perfluorochemical is Perfluorocaprylic Acid or perfluoro octyl sulfonic acid salt.
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| US20120277516A1 (en) | 2008-05-12 | 2012-11-01 | Enchem Engineering, Inc. | Chemical oxidation method and compounds |
| CN104974969B (en) * | 2015-07-28 | 2017-10-17 | 吉首大学 | One kind degraded PFOA bacterial strains YAB 1 and its application |
| CN105329976B (en) * | 2015-11-27 | 2018-11-09 | 清华大学 | The method for adsorbing perfluorochemical in simultaneously degradation water |
| CN105502789B (en) * | 2016-01-13 | 2017-11-14 | 衢州学院 | Utilize the method for short wave ultraviolet catalytic degradation waste water from organic fluorine industry |
| WO2017131972A1 (en) | 2016-01-25 | 2017-08-03 | Oxytec Llc | Soil and water remediation method and apparatus for treatment of recalcitrant halogenated substances |
| CN105967309A (en) * | 2016-05-25 | 2016-09-28 | 安徽普氏生态环境工程有限公司 | Fenton oxidation/UV oxidation-combined sewage treatment method |
| US10865128B2 (en) | 2018-02-06 | 2020-12-15 | Oxytec Llc | Soil and water remediation method and apparatus for treatment of recalcitrant halogenated substances |
| CN109437389A (en) * | 2018-11-28 | 2019-03-08 | 山东大学 | A method of TH-3100 is decomposed using ultraviolet oxidation |
| CN111170440B (en) * | 2020-01-14 | 2020-11-27 | 南京大学盐城环保技术与工程研究院 | High-salinity wastewater advanced oxidation method, industrial waste salt recycling method and equipment |
| US11661360B2 (en) | 2020-06-18 | 2023-05-30 | Wp&E Technologies And Solutions, Llc | System for removing per- and polyfluorinated alkyl substances from contaminated aqueous streams, via chemical aided filtration, and methods of use thereof |
| CN113072223A (en) * | 2021-03-31 | 2021-07-06 | 广东省科学院资源综合利用研究所 | Treatment method and treatment system for sewage containing persistent surface active pollutants |
| CN115140878A (en) * | 2022-07-20 | 2022-10-04 | 江苏里特曼生态环境科技有限公司 | System and method for producing hydrogen peroxide with low energy consumption and removing perfluorinated compounds in water in situ |
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| CN102351272A (en) * | 2011-07-27 | 2012-02-15 | 北京师范大学 | Method for degrading perfluorooctanoic acid in water through visible light catalysis |
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