CN102219338A - Method for removing organic contaminants in water through electrochemical oxidation and biological enzyme catalyzing - Google Patents
Method for removing organic contaminants in water through electrochemical oxidation and biological enzyme catalyzing Download PDFInfo
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- CN102219338A CN102219338A CN 201110094753 CN201110094753A CN102219338A CN 102219338 A CN102219338 A CN 102219338A CN 201110094753 CN201110094753 CN 201110094753 CN 201110094753 A CN201110094753 A CN 201110094753A CN 102219338 A CN102219338 A CN 102219338A
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Abstract
The invention discloses a method for removing organic contaminants in water through electrochemical oxidation and biological enzyme catalyzing, and belongs to the technical field of water treatment. With the method, energy consumption of the electrochemical oxidation for the organic contaminants in the water is reduced, applicability of the biological enzyme for catalyzing and oxidizing the organic contaminants is developed, and service life of the biological enzyme is prolonged. A technical scheme of the method comprises that: titanium-base lead dioxide electrode containing a reactive metal (such as bismuth, nickel, lanthanum, cerium or erbium) and fluorine is combined with a biological enzyme to degrade the organic contaminants in the water. The method has advantages of simple process, convenient operation management, high removal rate of the organic contaminants, and is applicable for small scale and dispersing type wastewater treatment.
Description
Technical field
The present invention relates to a kind of electrochemical oxidation biological enzyme and remove the method for organic pollutant in the water, specifically be to utilize the ti-supported lead dioxide electric pole that contains a kind of activity metal (as bismuth, nickel, lanthanum, cerium or erbium) and fluorine that organic pollutant in the water is carried out preoxidation earlier, re-use biological enzyme the preoxidation product is further carried out catalyzed degradation, belong to water-treatment technology field.
Background technology
Along with industrial expansion and human living standard's raising, the kind and the quantity discharged of trade effluent and sanitary sewage are increasing, and composition is also complicated more.The organic pollutant that wherein contains many difficult degradations, as chlorophenol, polycyclic aromatic hydrocarbons, polychlorobiphenyl, arylamine, sterilant, dyestuff etc., these materials enter the continuous enrichment of organism by food chain, and human and organism health are had great harm.Therefore, how to eliminate organic pollution in the environment and become a focus in the present water treatment field.
Electrochemical oxidation process can directly or indirectly produce OH by the electrode reaction that catalytic activity is arranged at normal temperatures and pressures as a kind of advanced oxidization method, thus most organic pollutant in effective degradation water.Electrochemical oxidation process has the oxidation capacity stronger than general chemical reaction, with environmental compatible, substantially chemical agent consumption not, easily be automated control, can unite advantage such as use, therefore in the processing that contains organic pollutants such as phenol, oil of mirbane, chlorinated phenols, waste water from dyestuff, be applied gradually with several different methods.But use this method degradation of organic substances energy consumption height, be difficult to realize industrialization.
Laccase is a kind of copper bearing polyphenoloxidase, and the oxygen to directly oxidize in can catalytic air decomposes various phenols dyestuffs, substituted phenol, chlorophenol, dredges phenol, dihydroxyphenyl propane, aromatic amine etc., existing more application in environmental pollution improvement.The katalysis of organic pollutant is to realize by collaborative transmission electronics of 4 cupric ions on the enzyme molecule and variation of valence in the laccase catalyzed degradation water, when substrate absorbs electronics the oxygen molecule the water is being reduced into water.Compare with other method, laccase catalytic oxidation energy consumption is low, degradation efficiency is high, easy to operate, use range is wide, do not produce excess sludge, simultaneously the multiple organic pollutant of catalysis is a biologic treating technique that has a extensive future.It is a lot of to influence laccase catalyzed oxidation organic pollutant factor active and stability.Some property of protein of laccase itself are not as reusing, surrounding environment (as factors such as the concentration of salt, pH, temperature) high susceptibility etc. having been limited effective use of laccase.In order to improve the stability of laccase, strengthen immunity from interference, it is a research focus in the present enzyme engineering field that laccase is carried out immobilization.Immobilization laccase has prolonged the work-ing life of laccase, but after the laccase immobilization, laccase molecule space degree of freedom is restricted, and directly has influence on the positioning action of active centre to substrate; Inside diffusional resistance descends the enzymic activity that causes near being obstructed in substrate molecule and active centre.The access times of immobilized enzyme are also relevant with the resultant of enzymic catalytic reaction with efficient.Discover that laccase can be realized dechlorination fast and effectively to orthomonochlorphenol in the water and P-Chlorophenol, be difficult to biodegradable a small amount of toxicity intermediate product but may generate in reaction process, it easily is adsorbed on the laccase surface, thereby makes enzyme deactivation; Laccase is not high for the metabolic activity of part organic pollutant (as m-Chlorophenol, high chloro aldehydes matter) simultaneously, is difficult to degraded effectively fast.These effects limit the range of application of laccase, also reduced simultaneously the effect of laccase catalyzed oxidation organic pollutant.
Therefore, we have proposed the method for organic pollutant in a kind of electrochemical oxidation and the biological enzyme coupling removal water, can bring into play the not high advantage of electrochemical oxidation selectivity on the one hand, laccase is difficult to the efficient part organic pollutant (as m-Chlorophenol, high chloro aldehydes matter) of degraded fast carries out preoxidation to reduce the concentration and the toxicity of organic pollutant, the preoxidation product can further be degraded by the laccase efficient catalytic; On the other hand, because laccase has the efficient catalytic effect to pre-product,, remedied the high defective of electrochemical oxidation energy consumption so can reduce the time of electrochemical oxidation.
Summary of the invention
The objective of the invention is in order to solve electrochemical oxidation energy consumption height and biological enzyme part organic pollutant in the water (as m-Chlorophenol, the high chloro aldehydes matter) problem that clearance is low, in particular for solving biological enzyme to the low problem of Persistent organic pollutants clearance in the water, and provide a kind of electrochemical oxidation and biological enzyme coupling, remove the method for organic pollutant in the water efficiently.
Purpose of the present invention is achieved through the following technical solutions:
The method that a kind of electrochemical oxidation biological enzyme is removed organic pollutant in the water is to utilize the organic pollutant in the electrode pair water to carry out preoxidation to reduce the concentration and the toxicity of organic pollutant earlier, re-uses biological enzyme the preoxidation product is further carried out catalyzed degradation.
Anode in the described electrochemical oxidation process is for containing the ti-supported lead dioxide electric pole of a kind of activity metal (as bismuth, nickel, lanthanum, cerium or erbium) and fluorine, negative electrode is titanium plate, stainless steel electro-conductive material, ionogen is the anhydrous slufuric acid sodium solution of 0.02mol/L, and the current density that applies between anode and cathode is 5mA/cm
2, the initial pH value of institute's treating water is 3-5, the time of electrochemical oxidation is 10-15min; Biological enzyme is with the immobilization laccase of carriers such as gac, silica gel, chitosan by the preparation of methods such as absorption, crosslinked or embedding, temperature in the biological enzyme degradable organic pollutant process is 23-25 ℃, rotating speed is 95-105rad/min, the catalyzed degradation time is 1-5 hour, and the dosage of immobilization laccase is 4-12g/L; Organic pollutant solution is phenolic compound and derivative, arylamine class and derivative, polycyclic aromatic hydrocarbons etc.
Characteristics of the present invention are:
Utilize the mode of electrochemical oxidation and biological enzyme coupling to remove organic pollutant in the water, can bring into play the not high advantage of electrochemical oxidation organic pollutant selectivity on the one hand, the part organic pollutant that laccase is difficult to the efficient catalytic degraded carries out oxidation, and oxidation products can further be degraded by the laccase efficient catalytic; On the other hand,, make the rapid oxidation of organic pollutant in the water, can remedy the high defective of electrochemical oxidation energy consumption in conjunction with the efficient catalytic effect of laccase to organic pollutant.
Embodiment
For more clearly the present invention will be described, below embodiment is described by specific embodiment.
Embodiment 1:
As anode, the titanium plate is as 2 in the cathode oxidation water with the ti-supported lead dioxide electric pole of bait modification, 4-two chlorophenols, and positive plate area and negative plate area are 15cm
2, interpole gap is 15mm, received current intensity is 5mA/cm
2, voltage is 5.2-5.4V, ionogen is the anhydrous sodium sulphate of 0.02mol/L.2,4-dichloro phenol solution starting point concentration is 24.85mg/L, and volume is 150mL, and initial pH is 5.0, after 10min is carried out in reaction, and 2, the concentration of 4-two chlorophenols is 14.04mg/L, clearance reaches 56.5%; Negate answers solution 50mL in the 100mL Erlenmeyer flask, and add the 0.4g immobilization laccase and in 25 ℃ of shaking tables, slowly stir, rotating speed 105rad/min, after 180min is carried out in reaction, 2, the concentration of 4-two chlorophenols is 0.55mg/L, clearance reaches 97.79%.
Embodiment 2
As anode, the titanium plate is as the Pentachlorophenol in the cathode oxidation water with the ti-supported lead dioxide electric pole of erbium modification, and positive plate area and negative plate area are 15cm
2, interpole gap is 15mm, received current intensity is 5mA/cm
2, voltage is 5.9-6.1V, ionogen is the anhydrous sodium sulphate of 0.02mol/L.The pentachlorophenol solution starting point concentration is 28.56mg/L, and volume is 150mL, and initial pH is 5.0, and after 15min was carried out in reaction, the concentration of Pentachlorophenol was 14.67mg/L, and clearance reaches 48.63%; Negate answers solution 50mL in the 100mL Erlenmeyer flask, and add the 0.4g immobilization laccase and in 25 ℃ of shaking tables, slowly stir, rotating speed 105rad/min, after 180min was carried out in reaction, the concentration of Pentachlorophenol was 2.19mg/L, clearance reaches 84.96%.
Claims (7)
1. an electrochemical oxidation biological enzyme is removed the method for organic pollutant in the water, it is characterized in that it is to utilize earlier that organic pollutant carries out preoxidation to reduce the concentration and the toxicity of organic pollutant in the electrode pair water that the electrochemical oxidation biological enzyme is removed the method for organic pollutant in the water, re-uses biological enzyme the preoxidation product is carried out further catalyzed degradation.
2. a kind of electrochemical oxidation biological enzyme according to claim 1 is removed the method for organic pollutant in the water, it is characterized in that the anode in the electrochemical oxidation process is the ti-supported lead dioxide electric pole that contains a kind of activity metal (as bismuth, nickel, lanthanum, cerium or erbium) and fluorine, negative electrode is titanium plate, stainless steel electro-conductive material.
3. a kind of electrochemical oxidation biological enzyme according to claim 1 is removed the method for organic pollutant in the water, it is characterized in that the ionogen in the electrochemical oxidation process is the anhydrous slufuric acid sodium solution of 0.02mol/L, the current density that applies between anode and cathode is 5mA/cm
2, the initial pH value of institute's treating water is 3-5, the time of electrochemical oxidation is 10-15min.
4. a kind of electrochemical oxidation biological enzyme according to claim 1 is removed the method for organic pollutant in the water, it is characterized in that described biological enzyme is with the immobilization laccase of carriers such as gac, silica gel or chitosan by method preparations such as absorption, crosslinked or embeddings.
5. a kind of electrochemical oxidation biological enzyme according to claim 1 is removed the method for organic pollutant in the water, it is characterized in that the temperature in the biological enzyme degradation process is 23-25 ℃, and rotating speed is 95-105rad/min, and the catalyzed degradation time is 1-5 hour.
6. a kind of electrochemical oxidation biological enzyme according to claim 4 is removed the method for organic pollutant in the water, and the dosage that it is characterized in that immobilization laccase is 4-12g/L.
7. a kind of electrochemical oxidation biological enzyme according to claim 1 is removed the method for organic pollutant in the water, it is characterized in that described organic pollutant solution is phenolic compound and derivative, arylamine class and derivative, polycyclic aromatic hydrocarbons etc.
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103736241A (en) * | 2013-12-23 | 2014-04-23 | 丽水学院 | Method for biodegrading chlorophenols |
| CN104478069A (en) * | 2014-11-19 | 2015-04-01 | 武汉科技大学 | Treatment system for PAHs in underground water and application method thereof |
| CN104628192A (en) * | 2013-11-12 | 2015-05-20 | 中国石油化工股份有限公司 | Treatment method for oily wastewater |
| CN104973676A (en) * | 2014-04-10 | 2015-10-14 | 中国石油化工股份有限公司 | Composite anode electrode, preparation method and application thereof |
| CN108914122A (en) * | 2018-07-30 | 2018-11-30 | 山东龙安泰环保科技有限公司 | A kind of preparation method of ti-lead dioxide anode |
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| DE3713103A1 (en) * | 1987-04-16 | 1988-11-03 | Aloys Prof Dr Huettermann | Removing phenol cpds. or chloro-aromatics from waste water - by polymerising with phenol-oxidising enzyme and pptn. with polyimine |
| RU2058265C1 (en) * | 1991-03-26 | 1996-04-20 | Иркутский государственный университет | Method of waste waters purification from phenol |
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| CN101445281A (en) * | 2009-01-13 | 2009-06-03 | 北京师范大学 | Laccase-modified electrode and method for removing chlorophenol pollutants from water by utilizing same |
| CN101817622A (en) * | 2010-04-29 | 2010-09-01 | 南京神克隆科技有限公司 | Ozone pre-oxidation and laccase advanced water treatment method |
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| DE3713103A1 (en) * | 1987-04-16 | 1988-11-03 | Aloys Prof Dr Huettermann | Removing phenol cpds. or chloro-aromatics from waste water - by polymerising with phenol-oxidising enzyme and pptn. with polyimine |
| RU2058265C1 (en) * | 1991-03-26 | 1996-04-20 | Иркутский государственный университет | Method of waste waters purification from phenol |
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| CN101445281A (en) * | 2009-01-13 | 2009-06-03 | 北京师范大学 | Laccase-modified electrode and method for removing chlorophenol pollutants from water by utilizing same |
| CN101817622A (en) * | 2010-04-29 | 2010-09-01 | 南京神克隆科技有限公司 | Ozone pre-oxidation and laccase advanced water treatment method |
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104628192A (en) * | 2013-11-12 | 2015-05-20 | 中国石油化工股份有限公司 | Treatment method for oily wastewater |
| CN103736241A (en) * | 2013-12-23 | 2014-04-23 | 丽水学院 | Method for biodegrading chlorophenols |
| CN104973676A (en) * | 2014-04-10 | 2015-10-14 | 中国石油化工股份有限公司 | Composite anode electrode, preparation method and application thereof |
| CN104478069A (en) * | 2014-11-19 | 2015-04-01 | 武汉科技大学 | Treatment system for PAHs in underground water and application method thereof |
| CN108914122A (en) * | 2018-07-30 | 2018-11-30 | 山东龙安泰环保科技有限公司 | A kind of preparation method of ti-lead dioxide anode |
| CN108914122B (en) * | 2018-07-30 | 2020-11-27 | 山东龙安泰环保科技有限公司 | Preparation method of titanium-based lead dioxide anode |
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Application publication date: 20111019 |