CN101289244B - 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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- CN101289244B CN101289244B CN2007100110459A CN200710011045A CN101289244B CN 101289244 B CN101289244 B CN 101289244B CN 2007100110459 A CN2007100110459 A CN 2007100110459A CN 200710011045 A CN200710011045 A CN 200710011045A CN 101289244 B CN101289244 B CN 101289244B
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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
本发明涉及一种用于自然光催化降解氯酚类污染物的方法。首先于质量浓度为10-2-300mg/L的氯酚类污染物水溶液中加入催化剂，所述催化剂由组分A和B组成，A为二价或三价可溶性铁盐，B为碱金属的可溶性盐；A、B的物质的量之比为0.01～1；催化剂与氯酚类物质的量之比为0.01～1。本发明反应条件为室外太阳光照射，价格低廉，降解率高，没有二次污染，适用于分布广、浓度较低的氯酚类污染物及有氯酚类污染物产生的废水的降解，工业化应用前景大。The invention relates to a method for natural photocatalytic degradation of chlorophenol pollutants. First, a catalyst is added to the aqueous solution of chlorophenol pollutants with a mass concentration of 10 -2 -300 mg/L. The catalyst is composed of components A and B, A is a divalent or trivalent soluble iron salt, and B is an alkali metal Soluble salt; the ratio of the amount of substances A and B is 0.01-1; the ratio of the amount of catalyst to chlorophenols is 0.01-1. The reaction condition of the present invention is outdoor sunlight irradiation, low price, high degradation rate, no secondary pollution, suitable for the degradation of chlorophenol pollutants with wide distribution and low concentration and waste water produced by chlorophenol pollutants, industrialization The application prospect is great.
Description
Technical field
The present invention relates to the light degradation removal method of chlorophenol pollutants, specifically a kind of method that shines upon down the catalytic degradation chlorophenol pollutant.
Background technology
Since the thirties in 20th century, chlorophenols compound (CPs) is widely used as timber preservative, antirust agent, bactericide and herbicide 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 snail fever, and is therefore very huge in the production 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 blacklist of priority pollutants by U.S. EPA.A large amount of uses of chlorophenols compound make a large amount of CPs pollutants enter environment, cause very big harm to natural 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, liquid membrane separating method.But the time that bioanalysis needs is long especially, and inapplicable for the processing of high concentration chlorophenol waste water.In addition, biodegradation 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 pollution of the processing difficult degradation that grows up the eighties in 20th century, and its main feature is to produce hydroxyl radical free radical by chemical reaction, makes organic pollution be degraded into water effectively, carbon dioxide and inorganic ions; 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 oxidant with hydrogen peroxide, iron-phthalocyanine is a catalyst, handle the chlorophenols organic pollution, the mineralization rate of carbon is 14% in the trichlorophenol, 2,4,6,-T, and the mineralization rate of chlorine is 70%.Metal phthalocyanine catalyst has been invented in world patent application (S.Muriel, WO0059836,2000), is oxidant with hydrogen peroxide, is used for handling trichlorophenol, 2,4,6,-T waste water.In addition, in the catalyst system and catalyzing of Collins, in (Science 2002), be catalyst with tetramino iron macrocyclic compound, hydrogen peroxide is an oxidant, and the mineralization rate of trichlorophenol, 2,4,6,-T is 35%, and the mineralization rate of chlorine is 83%.The problem that exists mainly is used oxidant 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 catalyst 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 condition 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 catalyst in the chlorophenol pollutant aqueous solution of-300mg/L;
Described catalyst 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; Catalyst is 0.01～1 with the ratio of chlorophenols amount of substance.
Described trivalent soluble ferric iron salt is ferric trichloride, ferric 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; Catalyst is preferably 0.4～1 with the ratio of the amount of substance of chlorophenol.
Described natural environment is meant environment temperature at-25 ℃ to 45 ℃, and irradiation of sunlight time every day is 8-16 hour natural environment.This method reaction condition gentleness is exposed in the natural 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 condition gentleness.The present invention is in having the small test tube of ground, adds the catalyst of the salting liquid composition of trivalent soluble ferric iron salt and nontransition metal, is oxidant with the air, chlorophenol can be degraded to carbon dioxide, water and the little carboxylic acids 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.Oxidant and the catalyst amount used owing to the present invention are little, and cheaply be easy to get, processing procedure 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 pollutant.Catalyst 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 condition 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.
The specific 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 teat glass of 20ml band grinding port plug, and in test tube, add catalyst, cover lid, and with sealing the film sealing, put into the laboratory roof, timing sampling detects, and has done control reaction simultaneously and has amplified reaction, and the clearance of reaction back trichlorophenol sees Table 1.Environment 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 conditions
Mol% is the ratio of catalyst and trichlorophenol
Embodiment 2
According to the operating procedure of the foregoing description 1, use FeCl
3/ NaNO
2Be catalyst, under same condition, handle 20mg/L orthomonochlorphenol pollutant, the results are shown in Table 2.Environment 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 conditions
Embodiment 3
According to the operating procedure of the foregoing description 1, use FeCl
3/ NaNO
2Be catalyst, under same condition, handle 20mg/L parachlorphenol pollutant, the results are shown in Table 3.Environment temperature is at-25 ℃ to 10 ℃, and irradiation of sunlight time every day is 8-10 hour.
The result of photocatalytic degradation parachlorphenol under table 3 natural conditions
Embodiment 4
According to the operating procedure of the foregoing description 1, use FeCl
3/ NaNO
2Be catalyst, handle 20mg/L 2 under same condition, 4-two chlorophenol pollutants the results are shown in Table 4.Environment temperature is at-25 ℃ to 10 ℃, and irradiation of sunlight time every day is 8-10 hour.
Photocatalytic degradation 2 under table 4 natural conditions, the result of 4-two chlorophenols
Embodiment 5
According to the operating procedure of the foregoing description 1, use FeCl
3/ NaNO
2Be catalyst, under same condition, handle 20mg/L pentachlorophenol pollutant, the results are shown in Table 5.Environment 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 conditions
Embodiment 6
According to the operating procedure of the foregoing description 1, use FeCl
3/ NaNO
2Be catalyst, at 20 ℃ to 35 ℃, irradiation of sunlight time every day is under 12-14 hour the condition in environment temperature, handles 20mg/L trichlorophenol pollutant, the results are shown in Table 6.
The result of photocatalytic degradation trichlorophenol under table 6 natural conditions
Claims (4)
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| CN101289244B true CN101289244B (en) | 2011-04-20 |
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| CN110683637A (en) * | 2019-10-14 | 2020-01-14 | 临沂大学 | A method for domesticating aerobic microorganisms capable of degrading 2-chlorophenol using phenol as an 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 |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20020153329A1 (en) * | 2001-03-23 | 2002-10-24 | Degussa Ag | Process for the conditioning 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 |
| CN1935687A (en) * | 2005-09-20 | 2007-03-28 | 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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Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20020153329A1 (en) * | 2001-03-23 | 2002-10-24 | Degussa Ag | Process for the conditioning 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 |
| CN1935687A (en) * | 2005-09-20 | 2007-03-28 | 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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