CN101289244A - Process for degrading chlorophenol-like pollutants by natural light catalysis - Google Patents
Process for degrading chlorophenol-like pollutants by natural light catalysis Download PDFInfo
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- CN101289244A CN101289244A CNA2007100110459A CN200710011045A CN101289244A CN 101289244 A CN101289244 A CN 101289244A CN A2007100110459 A CNA2007100110459 A CN A2007100110459A CN 200710011045 A CN200710011045 A CN 200710011045A CN 101289244 A CN101289244 A CN 101289244A
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- chlorophenols
- chlorophenol
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- natural light
- catalyzer
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
- Y02W10/00—Technologies for wastewater treatment
- Y02W10/30—Wastewater or sewage treatment systems using renewable energies
- Y02W10/37—Wastewater or sewage treatment systems using renewable energies using solar energy
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Abstract
The invention relates to a method for catalyzing and decomposing chlorophenols pollutants by natural daylight. First a catalyst with a mass concentration of 0.01 mg/L to 300 mg/L is added into a chlorophenols pollutant solution; the catalyst consists of a component A which is a bivalent soluble molysite or a trivalent soluble molysite and a component B which is a soluble salt of alkali metal, and the ratio of the amounts of the substances of the component A and the component B is 0.01 to 1; the ratio of the amounts of the substances of the catalyst and the chlorophenols is 0.01 to 1. The reaction of the invention requires the condition of sunlight radiation outdoor; the method has the advantages of low cost, high decomposition rate and no secondary pollution, which is applicable to the decomposition of the chlorophenols pollutant with wide distribution and low concentration and the waste water generated by the chlorophenols pollutant, thus having good industrial application prospect.
Description
Technical field
The present invention relates to the photodegradation removal method of chlorophenol pollutants, specifically a kind of method that shines upon down the catalyzed degradation chlorophenol pollutant.
Background technology
Since the thirties in 20th century, chlorophenols compound (CPs) is widely used as wood preservative, rust-preventive agent, sterilant and weedicide etc., and in paper pulp bleaching process, also can produce the waste water of a large amount of chlorophenols, in the Asia, Africa and South America also is used for the control of schistosomicide, and is therefore very huge in the industrial scale of many industrialized country CPs.Simultaneously, 2-chlorophenol, 2,4-two chlorophenols, 2,4,6-trichlorophenol and Pentachlorophenol all are the very high materials of toxicity, are listed in the Black List of priority pollutants by U.S. EPA.A large amount of uses of chlorophenols compound make a large amount of CPs pollutents enter environment, cause very big harm to physical environment.Therefore, this compounds of removing in the environment is a major challenge that the mankind face.
The method of handling chloride phenols wastewater at present is a lot, and method commonly used is biological degradation method, absorption method, extraction process, liquid membrane separation method.But the time that biological process needs is long especially, and inapplicable for the processing of high density chlorophenol waste water.In addition, biological degradation chlorophenols waste water also can the bigger dioxin pollution thing (L.G.Oeberg, Chemosphere, 1992) of toxigenicity.High-level oxidation technology is the technology of the organic pollutant of the processing difficult degradation that grows up the eighties in 20th century, and its principal feature is to produce hydroxyl radical free radical by chemical reaction, makes organic pollutant be degraded into water effectively, carbonic acid gas and mineral ion; Mainly comprise ozone oxidation, photochemical catalytic oxidation, wet oxidation, H2O2/UV, Fenton, methods such as O3/UV.Handle in the method for chlorophenol at advanced oxidation processes, photocatalytic oxidation is because cost is lower, and mild condition has caused people's extensive concern.In the degraded of chlorophenols, most representative is the catalytic oxidation system (Science 1996) of Meunier, is oxygenant with hydrogen peroxide, iron-phthalocyanine is a catalyzer, handle the chlorophenols organic pollutant, the mineralization rate of carbon is 14% in the Trichlorophenol, and the mineralization rate of chlorine is 70%.Metal phthalocyanine catalyst has been invented in world patent application (S.Muriel, WO0059836,2000), is oxygenant with hydrogen peroxide, is used for handling Trichlorophenol waste water.In addition, in the catalyst system of Collins, in (Science 2002), be catalyzer with tetramino iron macrocylc compound, hydrogen peroxide is an oxygenant, and the mineralization rate of Trichlorophenol is 35%, and the mineralization rate of chlorine is 83%.The problem that exists mainly is used oxygenant such as H at present
2O
2And O
3Cost an arm and a leg, make processing cost higher relatively, and in catalytic oxidation process, the synthetic cost of iron-phthalocyanine catalyzer etc. is also higher relatively, in addition, and some transition-metal catalyst instabilities, easy inactivation, but the existence of these problems is feasible very little for the processing industrial prospect of chlorophenols waste water.
Summary of the invention
In order to overcome the some shortcomings that exist in the above-mentioned degrading chlorophenol class methods, the object of the present invention is to provide a kind of catalytic activity height, treatment effect is good, the reaction conditions gentleness, processing cost is low, and the industrial applications prospect is big, can realize the method for the photocatalytic degradation chlorophenol pollutant of in-situ treatment.
For achieving the above object, the technical solution used in the present invention is:
A kind of method of degrading chlorophenol-like pollutants by natural light catalysis,
Be 10 at first in mass concentration
-2Add catalyzer in the chlorophenol pollutant aqueous solution of-300mg/L;
Described catalyzer is made up of component A and B, and A is divalence or trivalent soluble ferric iron salt, and B is alkali-metal soluble salt; The ratio of the amount of substance of A, B is 0.01～1; Catalyzer is 0.01～1 with the ratio of chlorophenols amount of substance.
Described trivalent soluble ferric iron salt is iron trichloride, iron nitrate and/or ferric sulfate; Alkali-metal soluble salt is a nitrate, and these soluble salts are with NO
3 -And/or NO
2 -Be the active anion component; Catalyzer is preferably 0.4～1 with the ratio of the amount of substance of chlorophenol.
Described physical environment is meant envrionment temperature at-25 ℃ to 45 ℃, and irradiation of sunlight time every day is 8-16 hour physical environment.Present method reaction conditions gentleness is exposed in the physical environment fully, the experiment finish at the laboratory roof, adopt pure natural weather, day and night alternate cycles.
The present invention has following advantage:
1. catalyst activity height, the reaction conditions gentleness.The present invention is in having the ground-in small test tube, adds the catalyzer of the salts solution composition of trivalent soluble ferric iron salt and nontransition metal, is oxygenant with the air, chlorophenol can be degraded to carbonic acid gas, water and the small molecules carboxylic acid that some are nontoxic.This method is handled chlorophenol solution can reach 100% degradation rate, does not have secondary pollution in degradation process.
2. processing cost is low, and industrial prospect is big.Oxygenant and the catalyst levels used owing to the present invention are little, and cheaply be easy to get, treating processes is easy, but therefore catalytic oxidation of the present invention has the application prospect of industrial treatment chlorophenol pollutant, is applicable to the degraded of the chlorophenol pollutant wide, that concentration is lower that distributes; This method is handled chlorophenol waste water reaction mild condition, and is cheap, the degradation rate height.3. environmental friendliness.Reaction system of the present invention is simple, and is convenient and practical, and catalyst reaction is active high, and is thorough to the removal of pollutent.Catalyzer can not cause secondary pollution to environment in used concentration range.
4. applied widely.The present invention is applicable to chlorophenol waste water and some processing about the waste water of chlorophenol growth factory, and the structural formula of the chlorophenol that common need are processed is exemplified below:
n＝1～5。
In a word, reaction conditions of the present invention is outdoor solar light irradiation, and is cheap, and the degradation rate height does not have secondary pollution, is applicable to distribute the chlorophenol pollutant wide, that concentration is lower and the degraded of the waste water that chlorophenol pollutant produces is arranged, and the industrial applications prospect is big.
Embodiment
Give further instruction below by example to the present invention, certainly, the present invention is not limited only to following embodiment.
Embodiment 1
At first prepare the trichlorophenol solution of 200mg/L, again with 10 times of pure water dilutions, 15ml solution is packed in the glass test tube of 20ml band grinding port plug, and in test tube, add catalyzer, cover lid, and with sealing film phonograph seal, put into the laboratory roof, time sampling detects, and has done control reaction simultaneously and has amplified reaction, and the clearance of reaction back trichlorophenol sees Table 1.Envrionment temperature is at-25 ℃ to 10 ℃, and irradiation of sunlight time every day is 8-10 hour.
The result of photocatalytic degradation trichlorophenol under table 1 natural condition
Mol% is the ratio of catalyzer and trichlorophenol
Embodiment 2
According to the operation steps of the foregoing description 1, use FeCl
3/ NaNO
2Be catalyzer, under same condition, handle 20mg/L orthomonochlorphenol pollutent, the results are shown in Table 2.Envrionment temperature is at-25 ℃ to 10 ℃, and irradiation of sunlight time every day is 8-10 hour.
The result of photocatalytic degradation orthomonochlorphenol under table 2 natural condition
Embodiment 3
According to the operation steps of the foregoing description 1, use FeCl
3/ NaNO
2Be catalyzer, under same condition, handle 20mg/L P-Chlorophenol pollutent, the results are shown in Table 3.Envrionment temperature is at-25 ℃ to 10 ℃, and irradiation of sunlight time every day is 8-10 hour.
The result of photocatalytic degradation P-Chlorophenol under table 3 natural condition
Embodiment 4
According to the operation steps of the foregoing description 1, use FeCl
3/ NaNO
2Be catalyzer, handle 20mg/L 2 under same condition, 4-two chlorophenol pollutents the results are shown in Table 4.Envrionment temperature is at-25 ℃ to 10 ℃, and irradiation of sunlight time every day is 8-10 hour.
Photocatalytic degradation 2 under table 4 natural condition, the result of 4-two chlorophenols
Embodiment 5
According to the operation steps of the foregoing description 1, use FeCl
3/ NaNO
2Be catalyzer, under same condition, handle 20mg/L Pentachlorophenol pollutent, the results are shown in Table 5.Envrionment temperature is at-25 ℃ to 10 ℃, and irradiation of sunlight time every day is 8-10 hour.
The result of photocatalytic degradation Pentachlorophenol under table 5 natural condition
Embodiment 6
According to the operation steps of the foregoing description 1, use FeCl
3/ NaNO
2Be catalyzer, at 20 ℃ to 35 ℃, irradiation of sunlight time every day is under 12-14 hour the condition in envrionment temperature, handles 20mg/L trichlorophenol pollutent, the results are shown in Table 6.
The result of photocatalytic degradation trichlorophenol under table 6 natural condition
Claims (5)
1. the method for a degrading chlorophenol-like pollutants by natural light catalysis is characterized in that:
In mass concentration is 10
-2Add catalyzer in the chlorophenol pollutant aqueous solution of-300mg/L, described catalyzer is made up of component A and B, and A is divalence or trivalent soluble ferric iron salt, and B is alkali-metal soluble salt; The ratio of the amount of substance of A, B is 0.01～1; Catalyzer is 0.01～1 with the ratio of chlorophenols amount of substance, and reaction vessel is a transparent material, and its cover lid is placed on outdoor physical environment.
2, according to the method for the described degrading chlorophenol-like pollutants by natural light catalysis of claim 1, it is characterized in that: described trivalent soluble ferric iron salt is iron trichloride, iron nitrate and/or ferric sulfate.
3, according to the method for the described degrading chlorophenol-like pollutants by natural light catalysis of claim 1, it is characterized in that: described alkali-metal soluble salt is a nitrate, and these soluble salts are with NO
3 -And/or NO
2 -Be the active anion component.
4, according to the method for the described degrading chlorophenol-like pollutants by natural light catalysis of claim 1, it is characterized in that: described catalyzer is 0.4～1 with the ratio of the amount of substance of chlorophenols.
5. according to the method for the described degrading chlorophenol-like pollutants by natural light catalysis of claim 1, it is characterized in that: described physical environment is meant envrionment temperature at-25 ℃ to 45 ℃, and irradiation of sunlight time every day is 8-16 hour physical environment.
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| CN2007100110459A CN101289244B (en) | 2007-04-20 | 2007-04-20 | Process for degrading chlorophenol-like pollutants by natural light catalysis |
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| CN2007100110459A CN101289244B (en) | 2007-04-20 | 2007-04-20 | Process for degrading chlorophenol-like pollutants by natural light catalysis |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110683637A (en) * | 2019-10-14 | 2020-01-14 | 临沂大学 | Method for domesticating aerobic microorganisms capable of degrading 2-chlorophenol by taking phenol as inducer |
| CN112408660A (en) * | 2020-12-11 | 2021-02-26 | 辽宁大学 | Method for degrading 1-chloronaphthalene-containing wastewater by using nitrite based on light conversion |
Family Cites Families (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE10114177A1 (en) * | 2001-03-23 | 2002-09-26 | Degussa | Process for the treatment of polluted water |
| CN1569676A (en) * | 2003-07-25 | 2005-01-26 | 中国科学院大连化学物理研究所 | Method for eliminating aqueous solution pollution from halo-phenol compounds |
| CN100387334C (en) * | 2005-09-20 | 2008-05-14 | 中国科学院大连化学物理研究所 | Method for treating chlorophenol pollutant by catalytic oxidation |
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- 2007-04-20 CN CN2007100110459A patent/CN101289244B/en not_active Expired - Fee Related
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110683637A (en) * | 2019-10-14 | 2020-01-14 | 临沂大学 | Method for domesticating aerobic microorganisms capable of degrading 2-chlorophenol by taking phenol as inducer |
| CN112408660A (en) * | 2020-12-11 | 2021-02-26 | 辽宁大学 | Method for degrading 1-chloronaphthalene-containing wastewater by using nitrite based on light conversion |
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