CN101199884B - Method of photochemical degradation of total fluorination substituted compound induced by dissoluble iron salt - Google Patents
Method of photochemical degradation of total fluorination substituted compound induced by dissoluble iron salt Download PDFInfo
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- CN101199884B CN101199884B CN2007101219285A CN200710121928A CN101199884B CN 101199884 B CN101199884 B CN 101199884B CN 2007101219285 A CN2007101219285 A CN 2007101219285A CN 200710121928 A CN200710121928 A CN 200710121928A CN 101199884 B CN101199884 B CN 101199884B
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- fluorine
- iron salt
- caprylic acid
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- dissolubility
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Abstract
The invention discloses a method of dissolved ferric salt inducing photochemical degradation of total fluorine substitution compound, belonging to the technical field of photochemical degradation of fluorine-containing organic compound in environmental protection. Under the atmosphere of air, oxygen and nitrogen, the mixed solution of total fluorine substitution compound and dissolved ferric salt in the reactor produces the decomposition reaction under the light-source irradiation for 100 to 300 minutes, so that the fluorine atom turns into the fluorine ion. The method which is easy to apply can react under the normal temperature and normal pressure, without complex equipment and strict reaction condition. The toxicity of the decomposition product is reduced, so that other subsequent methods can be easily adopted for further disposal. In addition, in the reaction, the concentration of the dissolvable ferric salt is reduced and the total fluorine is degraded into the harmless substance to avoid the pollution of the total fluorine compound to the environment.
Description
Technical field
The invention belongs to photochemical degradating organic fluorocompound technical field in the environmental protection, particularly be used for eliminating a kind of method of dissolubility iron salt induction photochemical degradation total fluorination substituted compound of the fluorine substituted compounds of water, air and soil.
Background technology
Fluorine substituted compounds (PFCs) is meant the organic matter that the hydrogen that links to each other with carbon atom in the organic constitution is all replaced by fluorine, for example perfluoro caprylic acid (PFOA)--CF
3-CF
2-CF
2-CF
2-CF
2-CF
2-CF
2-COOH and perfluorooctane sulfonate (PFOS) CF
3-CF
2-CF
2-CF
2-CF
2-CF
2-CF
2-CF
2-SO
3H.Perfluorochemical was brought into use from the 1950's, was widely used in the industry and the consumer goods, comprised surface conditioning agent, surfactant, insecticide component etc.Enter environment by two kinds of approach, i.e. directly production and the use of source-PFCs; Indirect source-as the impurity of chemical reaction and the catabolite of organic fluoride.
Generally in fish body, wild animal even human body, detect PFCs in recent years, very pay close attention to potential hazard, especially perfluorocarboxylic acid (PFCAs) and the perfluorinated sulfonic acid (PFSAs) of these materials both at home and abroad.EPAs in 1999 begin to carry out the investigation of perfluorochemical, just recognize the issuable harm of perfluoro caprylic acid (PFOA) in June, 2000, in April, 2003 issue illustrates that about the preliminary Risk Assessment Report of PFOA and its esters low-level PFOA exposes the possible risk to the people.PFOA is mainly used in the intermediate of producing fluorine-containing product, as polytetrafluoroethylene (PTFE) (PTFE, teflon), Kynoar and fluorubber.(Fluorotelomer alcohols, oxidation product FTOHs) are that the perfluor that comprises PFOA replaces organic carboxyl acid to the fluorine polyalcohols simultaneously.
PFOS can (perfluorooctanesulfonyl fluoride POSF) be transformed, and also is simultaneously the oxidation product that perfluor replaces sulfanilamide (SN) alcohol (perfluorinated sulfonamido alcohols) by full-fluorine octyl sulfuryl fluoride.PFOS mainly contains three aspect purposes: surface treatment, paper coating and performance chemicals.In several years before 2000,4500 tons of PFOS Related products of the annual production in the whole world, because its potential uncertain risk, as the main manufacturer of global PFOS, 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.In November, 2002, OECD (OECD) issue is about the hazard evaluation report of PFOS and its esters.
At present, the U.S., Canada, Japan, Europe etc. have given great attention to perfluorochemical potential risks such as PFOS and PFOA, carried out environmental survey widely, finding all has perfluorochemical in various degree to exist in the serum, breast milk, wild animal the people.The toxicity test of relevant these materials carrying out, there are some researches show constantly that also these materials have certain toxicity to grow and internal system etc., has accumulation property and persistence in environment.Therefore, under the suggestion of some countries, perfluoro octyl sulfonic acid salt, perfluoro caprylic acid and its esters are put into candidate's register of the persistent organism of " about the Convention of Stockholm of persistent organism ".
PFOA and PFOS stable in properties, anti-strong acid also has very high chemical inertness and higher heat endurance, just may decompose under up to 1200 degrees centigrade high temperature.This class material can not be decomposed by biology.The report of at present relevant their degradeds is very limited, and promptly heteropoly acid is the reduction and the Sonochemical degradation of Zero-valent Iron under the homogeneous phase photocatalytic degradation of catalyst, photochemical degradating that persulfate is oxidant, the undercritical conditions.These methods need the intensifying device or the harsh conditions of high energy consumption, for example ultrasonic device, subcritical atmosphere, and perhaps needed chemical reagent amount is a lot, as decomposing the PFOA of 1.35mM, needs to add the persulfate of 6.4～50.0mM.Therefore seek a kind of simple, temperate condition degradation pathway down, have great importance for tackling the risk that perfluorochemical, especially perfluoro caprylic acid and perfluorooctane sulfonate may bring.
Summary of the invention
The object of the present invention is to provide a kind of method of dissolubility iron salt induction photochemical degradation total fluorination substituted compound.It is characterized in that in air, oxygen or nitrogen atmosphere, the mixed reaction solution of fluorine substituted compounds and dissolubility molysite produces decomposition reaction in the reactor under the light source irradiation, reacts 100～300 minutes, makes fluorine atom wherein be converted into fluorine ion.
Described fluorine substituted compounds comprises perfluoro caprylic acid, perfluorooctane sulfonate.
In described decomposition reaction process, add the dissolubility molysite of concentration less than 100 micromoles per liter.
Described soluble ferric iron salt is a kind of among ferric sulfate, ferrous sulfate, iron chloride, ferric nitrate and the ferric perchlorate.
The molar concentration rate of ferric iron and fluorine substituted compounds is 0.5: 1～2: 1 in the described soluble ferric iron salt.
Or in above-mentioned course of reaction, also adding oxalic acid, ferric iron and oxalic acid molar concentration rate are 1: 3～1: 1000.
Described light source is the ultraviolet light of wavelength 〉=254nm.
The invention has the beneficial effects as follows that this method is simple, can carry out at normal temperatures and pressures, need not complex apparatus and harsh reaction condition.Catabolite toxicity reduces, and is easy to adopt other follow-up methods further to handle.And concentration to soluble ferric iron salt is low in the reaction, less than 100 micromoles per liter (ferric iron Fe in the atmosphere drop usually
3+Concentration range) condition under good degradation effect is just arranged.In addition, Fe (III) is one of slaine common in the natural water body, and this method is for explaining that PFOS and PFOA also have great importance in the conversion of occurring in nature.With fluorine substituted compounds (PFCs), perfluoro caprylic acid especially wherein (PFOA) and perfluoro octyl sulfonic acid salt (PFOS) are decomposed into harmless material, prevent the pollution of fluorine substituted compounds (PFCs) to environment.
Description of drawings
The photochemistry that Fig. 1 induces for the dissolubility molysite is decomposed the perfluorochemical installation drawing, wherein: 1. light source (can launch the ultraviolet light of multi-wavelength or 254nm); 2. quartz socket tube; 3. reaction vessel; 4. distribution device; 5. air inlet
Fig. 2 and Fig. 3 are under the different atmosphere, degraded, defluorination effect comparison diagram under (PFOA) 254nm ultraviolet light that soluble ferric iron salt is induced.
Fig. 4 and Fig. 5 are under the oxygen atmosphere, degraded, defluorination effect comparison diagram under (PFOA) 254nm ultraviolet light that the variable concentrations soluble ferric iron salt is induced.
Fig. 6 is under the oxygen atmosphere, the degradation effect comparison diagram under (PFOS) 254nm ultraviolet light that soluble ferric iron salt is induced.
Fig. 7 is degraded, the defluorination effect comparison diagram under Fe (III)-H2C2O4 (PFOA) 254nm ultraviolet light of inducing.
The specific embodiment
The invention provides a kind of method of dissolubility iron salt induction photochemical degradation total fluorination substituted compound.This decomposition method is with fluorine substituted compounds (PFCs), and perfluoro caprylic acid especially wherein (PFOA) and perfluoro octyl sulfonic acid salt (PFOS) are decomposed into harmless material, prevents fluorine substituted compounds (PFCs) environmental pollution.
Dissolubility molysite induction photochemical makes the basic principle of fluorine substituted compounds degraded be: perfluoro caprylic acid in the fluorine substituted compounds and perfluorooctane sulfonate absorb to 254nm and greater than the light of 254nm wavelength is not tangible, but the adding of soluble ferric iron salt causes ferric iron and PFOA to form complex, thereby make reaction system can absorb 254nm and greater than the light of 254nm wavelength, and then induce the degraded of perfluoro caprylic acid and perfluorooctane sulfonate, reaction path following (is example with the perfluoro caprylic acid):
PFOA+Fe(III)→PFOA...Fe(III) (1)
PFOA...Fe(III)+hv(＞＝254nm)→PFOA
*...Fe(III) (2)
PFOA
*...Fe(III)→PFOA
++Fe(II) (3)
Fe(II)+O
2→Fe(III) (4)
PFOA.
++H
+→C7F15
++HCOOH (5)
C7F15.|
++H
2O→C7F15OH+H
+ (6)
C7F15OH→C6F13COF+H
++F
- (7)
C6F13COF+H2O→C6F13COOH+H
++F
- (8)
As shown in Figure 1, device of the present invention comprises following parts: light source 1, can launch 254nm and multi-wavelength ultraviolet light, and promptly can be the low pressure mercury lamp that can launch the 254nm ultraviolet light, also can be the medium and high pressure mercury lamp; Quartz socket tube 2 is used to isolate light source and treatment media, can see through ultraviolet rays; Reaction vessel 3 is places that perfluorochemical decomposes; Distribution device 4 is used for gases such as air, oxygen, nitrogen are fed reaction solution; Air inlet 5, gases such as air, oxygen, nitrogen enter reaction vessel 3 thus.Contain perfluoro caprylic acid or perfluorooctane sulfonate and soluble ferric iron salt or perfluoro caprylic acid and Fe (III)-H
2C
2O
4Solution at first put into reaction vessel 3, feed gases by air inlet 5 then, perfluoro caprylic acid or perfluorooctane sulfonate decompose under the irradiation of light source.
Embodiment 1: ultraviolet (254nm) photodissociation of the perfluoro caprylic acid that soluble ferric iron salt is induced under the different atmosphere (PFOA)
As shown in Figure 1, the 500mL mixed reaction solution is put in the reactor 3, this solution contains PFOA (concentration is 48 μ M) and Fe
2(SO
4)
3(wherein the concentration of Fe (III) is 50 μ M).Oxygen enters reactor 3 by air inlet 5 through bottom air distribution plate 4, is that PFOA takes place to decompose and the effect of defluorinate is seen Fig. 2, Fig. 3 under uviol lamp 1 irradiation of 254nm in 23W dominant wavelength.Degradation rate is that the change calculations according to PFOA concentration in the solution obtains, and the concentration of PFOA is led the detector analysis by the HPLC-electricity in the solution.The defluorinate rate calculates according to fluorinion concentration changing value in the water in the course of reaction, and fluorinion concentration adopts chromatography of ions (IC) to measure in the water.(be labeled as " 254nm+O among Fig. 2, Fig. 3 under the situation of oxygen atmosphere 254nm UV-irradiation
2"); the concentration of PFOA reduces gradually with the carrying out of reaction in the reaction solution; fluorinion concentration then increases gradually; react after 240 minutes; the degradation rate of PFOA reaches 79%; the defluorinate rate of PFOA reaches 35%, 15 fluorine (F) that contained in the PFOA molecule on average have 5.3 fluorine to be shed in the solution approximately.And under the situation of air atmosphere 254nm UV-irradiation, (be labeled as " 254nm+Air " among Fig. 2, Fig. 3), react after 240 minutes, the degradation rate of PFOA is 72%, and the defluorinate rate is 33%, and on average existing 5.0 fluorine of 15 fluorine (F) that contained in the PFOA molecule are shed in the solution.(Fig. 2, Fig. 3 are labeled as " 254nm+N and under the condition of feeding nitrogen
2"), reacting 240 minutes, degradation rate only is 40%, the defluorinate rate is 14%, on average only has 2.1 Organic fluoride to come off and forms inorganic fluorine and enter into solution.The defluorinating and degrading complete that helps PFOA under oxygen and the air atmosphere is described.
Embodiment 2: ultraviolet (254nm) photodissociation of the perfluoro caprylic acid that the variable concentrations soluble ferric iron salt is induced under the oxygen atmosphere (PFOA)
As shown in Figure 1, respectively the 500mL mixed reaction solution is put into reactor 3, this solution contains PFOA (concentration is 48 μ M) and Fe
2(SO
4)
3(wherein Fe (III) concentration is 0-80 μ M).Oxygen enters reactor 3 by air inlet 5 through bottom air distribution plate 4, is that PFOA takes place to decompose and the effect of defluorinate is seen Fig. 4, Fig. 5 under uviol lamp 1 irradiation of 254nm in 23W dominant wavelength.Degradation rate is that the change calculations according to PFOA concentration in the solution obtains, and the concentration of PFOA is led the detector analysis by the HPLC-electricity in the solution.The defluorinate rate calculates according to fluorinion concentration changing value in the water in the course of reaction, and fluorinion concentration adopts chromatography of ions (IC) to measure in the water.(be labeled as " Fe among Fig. 4, Fig. 5 by variable concentrations soluble ferric iron salt under the oxygen atmosphere
3+(concentration)) induce the degraded situation of PFOA under the 254nm UV-irradiation as can be known, increase along with iron salt concentration, the degradation rate of PFOA increases, but when the molar concentration rate of PFOA in Fe in the soluble ferric iron salt (III) and the solution during greater than 1: 1, its amplification of degrading is little.Along with the increase of iron salt concentration, also there is similar variation tendency in the defluorinate rate of PFOA equally.Therefore, in Fe in the soluble ferric iron salt (III) and solution the molar concentration rate of PFOA be about 1: 1 (i.e. 50 μ M Fe (III): in the time of 48 μ MPFOA), the degraded of PFOA and defluorination effect the best.
Embodiment 3: the perfluorooctane sulfonate that soluble ferric iron salt is induced (PFOS) ultraviolet (254nm) photodissociation
As shown in Figure 1, the 500mL mixed reaction solution is put into reactor 3, this solution contains PFOS (concentration is 40 μ M) and Fe (NO
3)
3(wherein Fe (III) concentration is 30 μ M).Oxygen enters reactor 3 by air inlet 5 through bottom air distribution plate 4, is under the irradiation of 254nm uviol lamp 1 in 23W dominant wavelength, and the effect that PFOS decomposes is seen Fig. 4.Degradation rate is that the change calculations according to PFOS concentration in the solution obtains, and the concentration of PFOS is led the detector analysis by the HPLC-electricity in the solution.React after 240 minutes, have 23% PFOS to degrade.
Embodiment 4:Fe (III)-H
2C
2O
4Degraded defluorination effect comparison diagram under (PFOA) 254nm ultraviolet light of inducing.
As shown in Figure 1, the 500mL mixed reaction solution is put into reactor 3, this solution contains PFOA (concentration is 48 μ M), FeCl
3(wherein the concentration of Fe (III) is 7 μ M) and H
2C
2O
4(concentration is 3000 μ M).Oxygen enters reactor 3 by air inlet 5 through bottom air distribution plate 4, is under the irradiation of 254nm uviol lamp 1 in 23W dominant wavelength, and the effect that PFOA decomposes is seen Fig. 5.Degradation rate is that the change calculations according to PFOA concentration in the solution obtains, and the concentration of PFOA is led the detector analysis by the HPLC-electricity in the solution.The defluorinate rate calculates according to fluorinion concentration value in the water in the course of reaction, and fluorinion concentration adopts chromatography of ions (IC) to measure in the water.In the reaction solution concentration of PFOA reduce with the reaction time and fluorinion concentration then rise with the reaction time, react after 240 minutes, the degradation rate of PFOA reaches 75%, and the defluorinate rate of PFOA reaches 21%, and existing 3.2 fluorine of 15 fluorine (F) that contained in the PFOA molecule are shed in the solution fifty-fifty.The existence that oxalic acid is described has promoted the degraded of PFOA, but has suppressed its defluorinate.
Claims (6)
1. the method for a dissolubility iron salt induction photochemical degradation total fluorination substituted compound, it is characterized in that, in air, oxygen or nitrogen atmosphere, the mixed reaction solution of perfluoro caprylic acid or perfluorooctane sulfonate and dissolubility molysite is to produce decomposition reaction under the ultra violet lamp of 254nm in 23W dominant wavelength in the reactor, reacted 100～300 minutes, and made fluorine atom wherein be converted into fluorine ion.
2. according to the method for the described dissolubility iron salt induction photochemical degradation total fluorination substituted compound of claim 1, it is characterized in that the concentration of dissolubility molysite is less than 100 micromoles per liter in the mixed reaction solution of the interior perfluoro caprylic acid of described reactor or perfluorooctane sulfonate and dissolubility molysite.
3. according to the method for the described dissolubility iron salt induction photochemical degradation total fluorination substituted compound of claim 1, it is characterized in that described dissolubility molysite is a kind of among ferric sulfate, ferrous sulfate, iron chloride, ferric nitrate and the ferric perchlorate.
4. according to the method for the described dissolubility iron salt induction photochemical degradation total fluorination substituted compound of claim 1, it is characterized in that the mol ratio of described dissolubility molysite and perfluoro caprylic acid or perfluorooctane sulfonate is 0.5: 1～2: 1.
5. according to the method for the described dissolubility iron salt induction photochemical degradation total fluorination substituted compound of claim 1, it is characterized in that also add oxalic acid in above-mentioned course of reaction, ferric iron and oxalic acid molar concentration rate are 1: 3-1: 1000.
6. the method for the described dissolubility iron salt induction photochemical degradation total fluorination substituted compound of claim 1 is characterized in that, concrete technology is for being that perfluoro caprylic acid and Fe (III) concentration of 48 μ M is the Fe of 50 μ M with 500mL concentration
2(SO
4) mixed reaction solution puts into reactor (3), oxygen enters reactor (3) by air inlet (5) through bottom air distribution plate (4), in 23W dominant wavelength is under uviol lamp (1) irradiation of 254nm, perfluoro caprylic acid takes place to decompose and defluorinate, react after 240 minutes, the degradation rate of perfluoro caprylic acid reaches 79%, and the defluorinate rate of perfluoro caprylic acid reaches 35%, and 15 fluorine (F) that contained in the perfluoro caprylic acid molecule on average have 5.3 fluorine to be shed in the solution.
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Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6875902B2 (en) * | 2002-11-06 | 2005-04-05 | National Institute Of Advanced Industrial Science And Technology | Method decomposing fluorine-containing organic material |
| CN1680219A (en) * | 2005-01-07 | 2005-10-12 | 清华大学 | Method for defluorinating and degrading complete fluorine substituted compounds |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6875902B2 (en) * | 2002-11-06 | 2005-04-05 | National Institute Of Advanced Industrial Science And Technology | Method decomposing fluorine-containing organic material |
| CN1680219A (en) * | 2005-01-07 | 2005-10-12 | 清华大学 | Method for defluorinating and degrading complete fluorine substituted compounds |
Non-Patent Citations (1)
| Title |
|---|
| 陈静，张彭义，刘剑.全氟羧酸在185nm真空紫外光下的降解研究.环境科学.2007,28(4),772－776. * |
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