CN100347137C - Method for defluorinating and degrading complete fluorine substituted compounds - Google Patents
Method for defluorinating and degrading complete fluorine substituted compounds Download PDFInfo
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- CN100347137C CN100347137C CNB200510011126XA CN200510011126A CN100347137C CN 100347137 C CN100347137 C CN 100347137C CN B200510011126X A CNB200510011126X A CN B200510011126XA CN 200510011126 A CN200510011126 A CN 200510011126A CN 100347137 C CN100347137 C CN 100347137C
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- acid salt
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- octyl sulfonic
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Abstract
The present invention provides a method for defluorinating and degrading full fluorine substituted compounds, which relates to the technical field of the decomposition of full fluorine substituted organic matters and is used for eliminating the full fluorine substituted organic matters in water, air and soil. The method is characterized in that the full fluorine substituted compounds, such as PFOS, PFOA, etc., are irradiated by vacuum ultraviolet light under oxygen free conditions, defluorination reactions are carried out to the full fluorine substituted compounds and are carried out under the irradiation of a mercury lamp which can emit ultraviolet rays of 185 nm or an exciting lamp which can emit xenon excimer whose wavelength is 172 nm, and the oxygen free conditions can be realized by the introduction of protective inert gas or reducing gas. Reducing substances and semiconductor catalysts with high conducting band energy levels can also be added to the reaction processes so as to increase the defluorination decomposition rate. The present invention is simple and easy to enforce, can be carried out under the conditions of normal temperature and normal pressure and can have no requirements to the initial concentration of the full fluorine compounds. The toxicity of decomposed products is decreased, and the decomposed products are easily and further treated by other methods.
Description
Technical field
The present invention relates to the decomposition technique field of Perfluorocaprylic Acid or perfluoro octyl sulfonic acid salt, be used for eliminating the Perfluorocaprylic Acid or the perfluoro octyl sulfonic acid salt of water, air and soil.
Background technology
Fluorine substituted compounds (PFCs) is meant that the hydrogen (H) that links to each other with carbon atom (C) in the organic constitution is all by the organism of fluorine (F) replacement, for example tetrafluoro-methane (CF
4) and perfluoro octyl sulfonic acid salt (PFOS)---CF
3-CF
2-CF
2-CF
2-CF
2-CF
2-CF
2-CF
2-SO
3 -Perfluorochemical was brought into use from the 1950's, was widely used in the industry and the consumer's goods, comprised supercoat as fabric and carpet, paper coating, insecticide component, tensio-active agent etc.
Owing to there is a lot of research reports to show, after a kind of widely used perfluorochemical-perfluoro octyl sulfonic acid salt (PFOS) existed in the wildlife in the whole world, human body and has persistence and biological accumulation, EPA began the investigation to perfluorochemical in 1999.PFOS is that (perfluorooctanesulfonyl fluoride's full-fluorine octyl sulfuryl fluoride POSF) is transformed.POSF prepares with Simons electrochemical fluorination method, and POSF must arrive PFOS through oversulfonate, and reaction process POSF and derivative thereof by complexity in environment also can be converted into PFOS.PFOS mainly contains the purposes of three aspects: surface treatment, paper protection, performance chemicals.In several years before 2000,4500 tons of PFOS related productss of the annual production in the whole world.Because the potential uncertain risk of PFOS, global PFOS principal manufacturer-Minnesota Mining and Manufacturing Company's declaration will stop to produce the perfluoro capryl compound that comprises PFOS in the end of the year 2002.Economic Co-operation Organization (OECD) has issued a hazard evaluation report about PFOS and its esters in November, 2002.
Except that PFOS, in June, 2000, EPA began to notice the possible harm of Perfluorocaprylic Acid (PFOA), and PFOA is mainly as the reaction intermediate of producing fluoropolymer, for example tetrafluoroethylene (PTFE, teflon), polyvinylidene difluoride (PVDF) and viton.These polymkeric substance are having extensive use aspect industry and the running stores, as weaving anti-pollution layer, person nursing, non-sticky metallic coating, also use in industries such as automobile, machinery, aviation, chemistry, electric power, medicine and buildings.In April, 2003, EPA has been issued the preliminary Risk Assessment Report about PFOA, illustrates that low-level PFOA exposes the possible risk to the people.
At present, the risk that the U.S., Canada, Japan, Europe etc. may be brought perfluorochemicals such as PFOS and PFOA is paid much attention to, and has carried out environmental surveys widely, finds all to have in the serum, wildlife the people perfluorochemical accumulation in various degree.Also carrying out, there are some researches show constantly that these materials have toxicity such as certain growth, internal secretion, have cumulative bad, persistence in environment about the toxicity test of these materials.For example the transformation period (from enter human body to the time that excretes) of PFOS in human body reaches several years.
At present, the means that still do not have perfluorochemicals such as effective decomposed P FOS and PFOA in the world.Unique may decomposed P the method for FOS be to burn, but the variation that takes place in burning process for PFOS is still unclear.Existing Pollutant Treatment method is to burn as method, but the variation that takes place in burning process for PFOS is still unclear.Existing Pollutant Treatment method is as biological degradation, hydrolysis, photodissociation all decomposed P FOA and PFOS effectively.Therefore be necessary very much to seek a kind of method that can effectively decompose these materials, to tackle the risk that perfluorochemical may bring.
Summary of the invention
The objective of the invention is to, in order to prevent and treat the especially environmental pollution of Perfluorocaprylic Acid (PFOA) and perfluoro octyl sulfonic acid salt (PFOS) of fluorine substituted compounds (PFC), propose a kind of decomposition method, make it become harmless material, be suitable for additive method and further handle.
The invention is characterized in, be that the Perfluorocaprylic Acid of the liquid phase under the oxygen free condition or perfluoro octyl sulfonic acid salt are carried out the vacuum-ultraviolet light irradiation, make Perfluorocaprylic Acid or perfluoro octyl sulfonic acid salt carry out defluorination reaction, described vacuum ultraviolet (VUV) only wavelength less than the ultraviolet ray of 200nm.
Described reaction is under the irradiation of the ultraviolet mercury lamp of 185nm, or is to carry out under the xenon molecular exciton light irradiation of 172nm at wavelength.
Add reducing substances in above-mentioned reaction process, the mol ratio of described Perfluorocaprylic Acid or perfluoro octyl sulfonic acid salt and described reducing substances is 1: 0.05～1: 20.The reducing substances that adds is a kind of of sodium sulphite, potassiumiodide, Sulfothiorine or hydrogen.
Add the semiconductor catalyst that the conduction band position is higher than the hydrogen electrode current potential in described reaction process, the dosage of this catalyzer is 0.02g/L-1g/L.Described catalyzer is LiNbO
3, Ta
2O
5, Nb
2O
5, SrTiO
3Or NaTaO
3A kind of.
Adding reducing substances and conduction band position are higher than the semiconductor catalyst of hydrogen electrode current potential in above-mentioned reaction process, the described reducing substances that adds and the mol ratio of Perfluorocaprylic Acid or perfluoro octyl sulfonic acid salt are 1: 0.05～1: 20, and the dosage of described catalyzer is 0.02g/L-1g/L.
The present invention makes the ultimate principle of perfluorochemical defluorinating and degrading complete be: under the vacuum ultraviolet ray irradiation, water molecules is decomposed and produces hydrogen atom (H), hydrated electron (e
Aq -) and hydroxyl radical free radical materials such as (OH), wherein H and hydrated electron have very strong reducing property, can make fluorine on the perfluorochemical obtain an electronics and come off, simultaneously hydrogen atom is added to the position of fluorine on the original perfluorochemical by nucleophilic reaction (carbon atom that links to each other with fluorine on the perfluorochemical has electropositivity), is shown below:
More than reaction should be carried out under oxygen free condition, otherwise oxygen can with reactions such as H and hydrated electron, consume H and hydrated electron, thereby reduce the speed of perfluorochemical defluorinate.The method of PFOA that the past attempts or PFOS degraded is not considered to carry out under reductive condition, but carries out under conditions such as strong oxidizing property or strongly-acid.And fluorine atom is the strongest atom of occurring in nature oxidisability, there be not an oxidisability (the taking Electronic Performance by force) group stronger than fluorine, can not replace fluorine on the perfluorochemical with the group of a strong oxidizing property such as hydroxyl radical free radical (OH) like this, so under the strong oxidizing property condition, can not realize the defluorinating and degrading complete of perfluorochemical.
In addition, ultimate principle according to above perfluorochemical defluorinating and degrading complete, the vacuum ultraviolet ray irradiation down, water molecules also decomposes product and answers and the efficient of reduction perfluorochemical defluorinating and degrading complete, so in order to accelerate the speed of defluorinating and degrading complete, can add the reducing substances (as sodium sulphite, potassiumiodide, Sulfothiorine, hydrogen etc.) of removing hydroxyl radical free radical, add the mol ratio of perfluorochemical and reducing substances can be 1: 0.05-1: between 20.
Moreover the principle that can also utilize the UV-irradiation semiconductor catalyst to produce electronics is accelerated the speed of defluorinating and degrading complete.Semiconductor catalyst is under the irradiation of light, the valence band transition of electron is to conduction band, obtain light induced electron at conduction band, this electronics has very strong reducing power, the reducing power of this electronics is relevant with the residing level of energy of conduction band simultaneously, conduction level is high more, and the reducing power of conduction band electron is strong more, just more might be with the perfluorochemical defluorinating and degrading complete.So, can in reaction system, add semiconductor catalyst, as LiNbO with high conduction level in order to accelerate the defluorinating and degrading complete of perfluorochemical
3, Ta
2O
5, Nb
2O
5, SrTiO
3, NaTaO
3Deng.The dosage of semiconductor catalyst can be between 0.02g/L-1g/L.
Experiment showed, that the present invention is simple, carry out at normal temperatures and pressures, do not need complex apparatus; And the starting point concentration to perfluorochemical does not require, and the perfluorochemical of concentration all can adopt present method to handle arbitrarily; Degradation production toxicity reduces, and is easy to adopt additive method further to handle.
Description of drawings
Fig. 1 is a vacuum-ultraviolet light reduction decomposition perfluorochemical setting drawing, wherein: 1. 2. quartz socket tube 3. reaction vessels 4. distribution devices 5. gases 6. reductibility things 7. semiconductor catalysts of light source (can emission wavelength less than 200nm vacuum ultraviolet ray).
Fig. 2 is Perfluorocaprylic Acid (PFOA) vacuum ultraviolet (VUV) defluorination effect comparison diagram.
Fig. 3 is perfluoro octyl sulfonic acid salt (PFOS) vacuum ultraviolet (VUV) photoreduction defluorination effect figure.
Fig. 4 is the promoter action design sketch of semiconductor catalyst to the defluorinate of PFOA vacuum ultraviolet (VUV).
Fig. 5 is the promoter action design sketch of sodium sulphite to the PFOA defluorinating and degrading complete.
Embodiment
As shown in Figure 1, device of the present invention comprises following parts: light source 1, and energy emissioning line (wavelength is less than 200nm) can be to launch the ultraviolet mercury lamp of 185nm, also can be that wavelength is the xenon molecular exciton light of 172nm; Quartz socket tube 2 is used to isolate light source and treatment media, can see through vacuum ultraviolet rays; Reaction vessel 3 is places that perfluorochemical decomposes; Distribution device 4 is used for oxygen-free reductibility or rare gas element feeding reaction solns such as nitrogen, argon gas; Gas 5 can be the protectiveness rare gas element, also can be reducing gas, for decomposing, perfluorochemical provides suitable reaction environment, avoid reaction soln to contact with oxygen, can also with the oxidisability species reaction that produces in the reaction process, improve perfluorochemical defluorinate efficient; Reducing substances 6 joins in the reaction soln, can quicken the perfluorochemical defluorinate; Semiconductor catalyst 7 can be powder or loading type, for example Lithium niobium trioxide (LiNbO
3) or other conduction band positions be higher than the semiconductor material of hydrogen electrode current potential.The solution or the gas that contain perfluorochemical are at first put into reaction vessel 3, feed gas 5 then, and the perfluorochemical defluorinate is decomposed under the irradiation of light source.In order to accelerate the decomposition of perfluorochemical, reducing substances 6 and semiconductor catalyst 7 can add separately or together.
Embodiment 1: the vacuum ultraviolet (VUV) reduction decomposition of Perfluorocaprylic Acid (PFOA)
As shown in Figure 1, the PFOA aqueous solution that 800mL is contained 15mg/L is put into reactor 3, and nitrogen feeds reactor 3 from bottom air distribution plate 4, and under the irradiation of 15W emission 185nm vacuum ultraviolet rays lamp 1, the effect that the PFOA defluorinate is decomposed is seen Fig. 2.The defluorinate rate calculates according to fluorinion concentration value in the water in the reaction process, and fluorinion concentration adopts the fluorine reagent spectrophotometry in the water.The irradiation of 185nm vacuum ultraviolet ray feeds under the situation (being labeled as " 185nm leads to nitrogen " among Fig. 2) of nitrogen down, fluorinion concentration rose with the reaction times in the reaction soln, react that the defluorinate rate of PFOA reaches 28.7% after 380 minutes, existing 4.3 fluorine of 15 fluorine (F) that contained in the PFOA molecule are shed in the solution fifty-fifty.And under the irradiation of 185nm vacuum ultraviolet ray, under the situation of aerating oxygen (being labeled as " 185nm leads to oxygen " among Fig. 2), react after 390 minutes, the defluorinate rate of PFOA only is 19.5%, the defluorinate that this explanation oxygen has suppressed PFOA is decomposed.And under the condition of general ultraviolet line 254nm irradiation feeding nitrogen (Fig. 2 is labeled as " 254nm leads to nitrogen "), reacted 360 minutes, the defluorinate rate only is 5.4%; Under the situation of aerating oxygen under the 254nm ultraviolet radiation (Fig. 2 be labeled as " 254nm leads to oxygen), react PFOA not defluorinate substantially in 500 minutes.The 185nm ultraviolet radiation more than being described and avoiding solution to contact with oxygen is the condition of impelling PFOA effectively to decompose.
Embodiment 2: the vacuum ultraviolet (VUV) reduction decomposition of perfluoro octyl sulfonic acid salt (PFOS)
As shown in Figure 1,800mL contains the PFOS aqueous solution of 20mg/L and puts into reactor 3, nitrogen feeds reactor 3 from bottom air distribution plate 4, under the irradiation of 15W emission 185nm vacuum ultraviolet rays lamp 1, the effect that the PFOS defluorinate is decomposed is seen Fig. 3, with fluorinion concentration in the fluorine reagent spectrophotometry solution, fluorinion concentration rose with the reaction times in the reaction soln, react that the defluorinate rate of PFOS reaches 15% after 675 minutes, fifty-fifty, existing 2.55 fluorine of 17 fluorine (F) that contained in the PFOS molecule are shed in the solution.And under the situation of 185nm vacuum UV irradiation and aerating oxygen, not defluorinate of PFOS is decomposed; Under the 254nm radiation, no matter aerating oxygen and nitrogen also not defluorinate decompose.
Embodiment 3: Perfluorocaprylic Acid is decomposed in vacuum ultraviolet (VUV) photochemical catalysis defluorinate
As shown in Figure 1,800mL contains the PFOA aqueous solution of 19mg/L and puts into reactor 3, and nitrogen feeds reactor 3 from the bottom air distribution plate, adds semiconductor light-catalyst LiNbO simultaneously
3, the concentration in its reaction soln is 0.1g/L, under the irradiation of 15W emission 185nm vacuum ultraviolet rays lamp 1, the effect that the PFOA defluorinate is decomposed is seen Fig. 4.Concentration with fluorion in the fluorine reagent spectrophotometry reaction soln, fluorinion concentration rose with the reaction times in the reaction soln, react that the defluorinate rate of PFOA reaches 23.5% after 210 minutes, fifty-fifty, existing 3.5 fluorine of 15 fluorine (F) that contained in the PFOA molecule are shed in the solution.And correspondingly, if in solution, do not add LiNbO
3Catalyzer, the defluorinate rate of then reacting after 270 minutes also has only 18.2%.LiNbO
3The existence of catalyzer has promoted the vacuum ultraviolet (VUV) reduction defluorinate speed of PFOA.When catalyst amounts was 0.02g/L, the defluorinate rate of reacting 250 minutes was 19%, demonstrates certain enhancement; Because the scattering of light effect of catalyzer when the catalyst concn that adds in the solution is 1g/L, was reacted 250 minutes, the defluorinate rate is 22%.
The vacuum ultraviolet (VUV) defluorinate of embodiment 4 Perfluorocaprylic Acids under reductive condition
As shown in Figure 1,800mL contains Perfluorocaprylic Acid (PFOA) aqueous solution of 25mg/L and puts into reactor 3, nitrogen feeds reactor 3 from bottom air distribution plate 4, add sodium sulphite (14mg/L simultaneously, Perfluorocaprylic Acid/sodium sulphite mol ratio 1: 3.1), under the irradiation of 15W emission 185nm vacuum ultraviolet rays lamp 1, the effect that the PFOA defluorinate is decomposed is seen Fig. 5.Adopt fluorinion concentration in the fluorine reagent spectrophotometry water, can calculate defluorinate according to the variation of fluorinion concentration in the water.React after 30 minutes, the defluorinate rate of Perfluorocaprylic Acid just reaches 16.5%, promptly on average has 2.5 fluorine to come off from the Perfluorocaprylic Acid molecule nearly.And correspondingly, if do not add sodium sulphite, reacted so 30 minutes, have only 2.2% defluorinate rate.The dosage of sodium sulphite has considerable influence to the defluorinate speed of PFOA, when the dosage of sodium sulphite is 0.22mg/L (Perfluorocaprylic Acid/sodium sulphite mol ratio 1: 0.05), and reaction 30min, the defluorinate rate of PFOA is 2.5%; When the dosage of sodium sulphite is 90mg/L (Perfluorocaprylic Acid/sodium sulphite mol ratio 1: 20), reaction 30min, the defluorinate rate of PFOA is 3%.
As shown in Figure 1,800mL contains perfluoro octyl sulfonic acid salt (PFOS) aqueous solution of 50mg/L and puts into reactor 3, and hydrogen feeds reactor 3 from bottom air distribution plate 4, under the irradiation of 100W emission 172nm vacuum ultraviolet rays lamp 1, reacted 150 minutes, PFOS defluorinate rate just reaches 15%.
The vacuum ultraviolet (VUV) photo catalytic reduction defluorinate of embodiment 6 Perfluorocaprylic Acids
As shown in Figure 1,800mL contains Perfluorocaprylic Acid (PFOA) aqueous solution of 19mg/L and puts into reactor 3, nitrogen feeds reactor 3 from the bottom air distribution plate, the potassiumiodide (KI) that adds semiconductor light-catalyst LiNbO3 (0.2g/L) and 10mg/L simultaneously, under the irradiation of 15W emission 185nm vacuum ultraviolet rays lamp 1, the defluorinate rate of reacting 30 minutes PFOA reaches 20%.
Claims (8)
1, the method for a kind of Perfluorocaprylic Acid or perfluoro octyl sulfonic acid salt defluorinating and degrading complete, it is characterized in that, be that the Perfluorocaprylic Acid of the liquid phase under the oxygen free condition or perfluoro octyl sulfonic acid salt are carried out the vacuum-ultraviolet light irradiation, make Perfluorocaprylic Acid or perfluoro octyl sulfonic acid salt carry out defluorination reaction, described vacuum ultraviolet (VUV) only wavelength less than the ultraviolet ray of 200nm.
2, the method for Perfluorocaprylic Acid as claimed in claim 1 or perfluoro octyl sulfonic acid salt defluorinating and degrading complete is characterized in that, described reaction is under the irradiation of the ultraviolet mercury lamp of 185nm, or is to carry out under the xenon molecular exciton light irradiation of 172nm at wavelength.
3, the method for Perfluorocaprylic Acid as claimed in claim 1 or perfluoro octyl sulfonic acid salt defluorinating and degrading complete is characterized in that, described oxygen free condition is by feeding protectiveness rare gas element or reducing gas realization in reaction unit.
4, the method for Perfluorocaprylic Acid as claimed in claim 1 or perfluoro octyl sulfonic acid salt defluorinating and degrading complete, it is characterized in that, add reducing substances in above-mentioned reaction process, the mol ratio of described Perfluorocaprylic Acid or perfluoro octyl sulfonic acid salt and described reducing substances is 1: 0.05～1: 20.
5, the Perfluorocaprylic Acid of stating as claim 4 or the method for perfluoro octyl sulfonic acid salt defluorinating and degrading complete is characterized in that the reducing substances of adding is a kind of of sodium sulphite, potassiumiodide, Sulfothiorine or hydrogen.
6, the method for Perfluorocaprylic Acid as claimed in claim 1 or perfluoro octyl sulfonic acid salt defluorinating and degrading complete, it is characterized in that, add the semiconductor catalyst that the conduction band position is higher than the hydrogen electrode current potential in described reaction process, the dosage of this catalyzer is 0.02g/L-1g/L.
7, the method for Perfluorocaprylic Acid as claimed in claim 6 or perfluoro octyl sulfonic acid salt defluorinating and degrading complete is characterized in that, described catalyzer is LiNbO
3, Ta
2O
5, Nb
2O
5, SrTiO
3Or NaTaO
3A kind of.
8, the method for Perfluorocaprylic Acid as claimed in claim 1 or perfluoro octyl sulfonic acid salt defluorinating and degrading complete, it is characterized in that, adding reducing substances and conduction band position are higher than the semiconductor catalyst of hydrogen electrode current potential in above-mentioned reaction process, the described reducing substances that adds and the mol ratio of Perfluorocaprylic Acid or perfluoro octyl sulfonic acid salt are 1: 0.05～1: 20, and the dosage of described catalyzer is 0.02g/L-1g/L.
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| US20210206670A1 (en) * | 2019-09-27 | 2021-07-08 | Auburn University | Compositions and methods for removal of per- and polyfluoroalkyl substances (pfas) |
| 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 |
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| CN104193056B (en) * | 2014-09-22 | 2016-09-07 | 中国科学技术大学 | A kind of efficient degradation method of multi-fluorinated compounds PFOA in waste water |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20210206670A1 (en) * | 2019-09-27 | 2021-07-08 | Auburn University | Compositions and methods for removal of per- and polyfluoroalkyl substances (pfas) |
| 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 |
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