CN101781012A - Method for decoloring and degrading soluble azo dyes through catalysis of chloroperoxidase and oxidation of H2O2 - Google Patents
Method for decoloring and degrading soluble azo dyes through catalysis of chloroperoxidase and oxidation of H2O2 Download PDFInfo
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- CN101781012A CN101781012A CN200910254619A CN200910254619A CN101781012A CN 101781012 A CN101781012 A CN 101781012A CN 200910254619 A CN200910254619 A CN 200910254619A CN 200910254619 A CN200910254619 A CN 200910254619A CN 101781012 A CN101781012 A CN 101781012A
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Abstract
The invention discloses a method for decoloring and degrading soluble azo dyes through catalysis of chloroperoxidase and oxidation of H2O2, which comprises the following steps: preparing solution; decoloring and degrading; and computing the decoloring and degrading rate of the azo dyes. In the established method for decoloring and degrading soluble azo dyes orange II, bromophenol blue, methylene blue and soluble aniline blue wastewater through the catalysis of the chloroperoxidase and the oxidation of the H2O2, the H2O2 is used as an oxidant based on a bio-enzyme catalysis degradation system, a large conjugate system and azo structures and other chormophoric groups in the dyes are quickly damaged, irreversible decoloration and degradation of the dyes are realized, and the biochemical quality is improved. The method has the advantages of high speed of decoloring and degrading, high efficiency, simple operating steps, low consumption of the chloroperoxidase and the H2O2, and the like, and can be applied to treatment of industrial wastewater with soluble azo dyes.
Description
Technical field
The invention belongs to the processing technology field of water, waste water or sewage, be specifically related to a kind of enzyme catalysis H that utilizes
2O
2Oxidation style realizes the quick decolored degradation of azo dyes waste water.
Background technology
China is first big country of textile printing and dyeing, and textile printing and dyeing industry is the rich and influential family of industrial wastewater discharge, accounts for 35% of whole discharged volume of industrial waste water.According to data, the quantity discharged of China's dyeing waste water is approximately m3 every days 4,000,000, and waste water from dyestuff has become one of environment major polluting sources.
Orange II, tetrabromophenol sulfonphthalein, methylene blue and water-soluble aniline blue are soluble azo dyes, are widely used in printing and dyeing industry, are one of main components of dyeing waste water.Containing in the structure of this class dyestuff and be difficult for biodegradable benzene ring structure and by the big conjugated system that azo bond forms, make chroma in waste water very high, is more unmanageable dyeing waste water composition.At present the Coagulation Method of generally using can't be handled this class water-soluble dye substantially, and various chemical oxidization method all exists that chroma removal rate is not high, the treatment effect fluctuation is big, complex process and produce secondary pollution problems.Current press for can rapid damage soluble azo dyes chromophoric group effective ways.
Chloroperoxidase (CPO) is a kind of protoheme peroxidase (42kDa) of separating from thalassiomycetes Caldariomyces fumago.CPO has oxidation activity very widely, have the catalytic characteristics of protoheme peroxidase (single electron and two electronics peroxidation, organic halogenation), catalase (hydrogen peroxide disproportionation, monohydroxy-alcohol oxidation) and cytochrome P-450 plurality of enzymes such as (dealkylation, ethylene linkage epoxidation, sulfoxidations etc.) concurrently, be considered to most widely used enzyme in the superoxide enzyme family at present.
Summary of the invention
Technical problem to be solved by this invention is to overcome the shortcoming of above-mentioned soluble azo dyes treatment process, and the chloroperoxidase catalysis that a kind of treatment process is simple, cost is low, processing efficiency is high, effective H is provided
2O
2The method for decoloring and degrading of oxidation soluble azo dyes.
Solving the problems of the technologies described above the technical scheme that is adopted is that it comprises the steps:
1, obtain solution
Preparation amount of substance concentration is the KH of 0.1mol/L
2PO
4-K
2HPO
4Buffered soln, regulating its pH with 3mol/L hydrochloric acid is 5.5, is the chloroperoxidase solution of 0.1mmol/L with this damping fluid preparation amount of substance concentration, is 30% H with massfraction
2O
2Solution and distilled water are prepared the H that amount of substance concentration is 0.2mol/L according to a conventional method
2O
2The aqueous solution.
2, decolored degradation
Adding amount of substance concentration in azoic dyestuff solution is the chloroperoxidase solution of 0.1mmol/L, mix, azoic dyestuff solution and amount of substance concentration are that the volume ratio of the chloroperoxidase solution of 0.1mmol/L is 1: 0.01～0.06, are the H of 3mol/L with amount of substance concentration
2SO
4Solution or amount of substance concentration are that the NaOH solution of 3mol/L is regulated pH to 2～5, and adding amount of substance concentration is the H of 0.2mol/L
2O
2The aqueous solution, azoic dyestuff solution and amount of substance concentration are the H of 0.2mol/L
2O
2The volume ratio of the aqueous solution is 1: 0.04～0.08, stirring at room 1～5 minute.
Above-mentioned azoic dyestuff solution is the water-soluble aniline blue solution that the orange II solution of 10mmol/L or tetrabromophenol sulfonphthalein solution that amount of substance concentration is 10mmol/L or the amount of substance concentration methylene blue solution that is 10mmol/L or amount of substance concentration are 10mmol/L for amount of substance concentration.
3, calculate azoic dyestuff decolored degradation rate
Azoic dyestuff decolored degradation rate is calculated by (1) formula:
η＝[(A
0-A
t)/A
0]×100％ (1)
η is an azoic dyestuff decolored degradation rate in the formula, A
0Be the initial absorbance of this azoic dyestuff characteristic wave strong point, A
tAbsorbancy when being time t.
In decolored degradation step 2 of the present invention, adding amount of substance concentration in azoic dyestuff solution is the chloroperoxidase solution of 0.1mmol/L, mix, azoic dyestuff solution and amount of substance concentration are that the preferred volume ratio of the chloroperoxidase solution of 0.1mmol/L is 1: 0.03～0.06, are the H of 3mol/L with amount of substance concentration
2SO
4Solution or amount of substance concentration are that the NaOH solution of 3mol/L is regulated pH preferably to 2～4, and adding amount of substance concentration is the H of 0.2mol/L
2O
2The aqueous solution, azoic dyestuff solution and amount of substance concentration are the H of 0.2mol/L
2O
2The preferred volume ratio of the aqueous solution is 1: 0.05～0.08.
In decolored degradation step 2 of the present invention, adding amount of substance concentration in azoic dyestuff solution is the chloroperoxidase solution of 0.1mmol/L, mix, azoic dyestuff solution and amount of substance concentration are that the optimum volume ratio of the chloroperoxidase solution of 0.1mmol/L is 1: 0.04, are the H of 3mol/L with amount of substance concentration
2SO
4Solution or amount of substance concentration are that the NaOH solution of 3mol/L is regulated pH the best to 3, and adding amount of substance concentration is the H of 0.2mol/L
2O
2The aqueous solution, azoic dyestuff solution and amount of substance concentration are the H of 0.2mol/L
2O
2The optimum volume ratio of the aqueous solution is 1: 0.07.
The chloroperoxidase catalysis H that the present invention sets up
2O
2The method for decoloring and degrading of the orange II of oxidation soluble azo dyes, tetrabromophenol sulfonphthalein, methylene blue, water-soluble aniline blue waste water is based on biological enzyme degraded system, with H
2O
2Be oxygenant, chromophoric groups such as big conjugated system and azo structure in the above-mentioned dyestuff of rapid damage are realized the irreversible decolored degradation of dyestuff, and are improved its biodegradability.The present invention has that decolored degradation speed is fast, efficient is high, operation steps is simple, chloroperoxidase and H
2O
2Advantages such as consumption is little can be used in the processing of soluble azo dyes trade effluent.
Embodiment
The present invention is described in more detail below in conjunction with embodiment, but the invention is not restricted to these embodiment.
Embodiment 1
With 1000mL amount of substance concentration is that the decolored degradation of the water-soluble aniline blue solution of 10mmol/L is an example, raw materials used and method for decoloring and degrading is as follows:
1, obtain solution
Preparation amount of substance concentration is the KH of 0.1mol/L
2PO
4-K
2HPO
4Buffered soln, regulating its pH with 3mol/L hydrochloric acid is 5.5, is the chloroperoxidase solution of 0.1mmol/L with this damping fluid preparation amount of substance concentration, is 30% H with massfraction
2O
2Solution and distilled water are prepared the H that amount of substance concentration is 0.2mol/L according to a conventional method
2O
2The aqueous solution.
2, decolored degradation
To 1000mL amount of substance concentration is that to add 40mL amount of substance concentration in the water-soluble aniline blue solution of 10mmol/L be the chloroperoxidase solution of 0.1mmol/L, mix, amount of substance concentration is that the water-soluble aniline blue solution of 10mmol/L and the volume ratio of the chloroperoxidase solution that amount of substance concentration is 0.1mmol/L are 1: 0.04, is the H of 3mol/L with amount of substance concentration
2SO
4Solution or amount of substance concentration are that the NaOH solution of 3mol/L is regulated pH to 3, and adding 70mL amount of substance concentration is the H of 0.2mol/L
2O
2The aqueous solution, amount of substance concentration are that water-soluble aniline blue solution and the amount of substance concentration of 10mmol/L is the H of 0.2mol/L
2O
2The volume ratio of the aqueous solution is 1: 0.07, stirring at room 1～5 minute.
3, calculate azoic dyestuff decolored degradation rate
Azoic dyestuff decolored degradation rate is calculated by (1) formula:
η＝[(A
0-A
t)/A
0]×100％ (1)
η is an azoic dyestuff decolored degradation rate in the formula, A
0Be that amount of substance concentration is the initial absorbance of the water-soluble aniline blue solution of 10mmol/L at the 600nm place, A
tAbsorbancy when being time t.Experimental result sees Table 1～3.
Calculate by (1) formula, amount of substance concentration is that the decolored degradation rate of the water-soluble aniline blue solution of 10mmol/L is 93.9%.
Embodiment 2
With 1000mL amount of substance concentration is that the decolored degradation of the water-soluble aniline blue solution of 10mmol/L is an example, raw materials used and method for decoloring and degrading is as follows:
In the decolored degradation step 2 of present embodiment, to 1000mL amount of substance concentration is that to add 10mL amount of substance concentration in the water-soluble aniline blue solution of 10mmol/L be the chloroperoxidase solution of 0.1mmol/L, mix, amount of substance concentration is that the water-soluble aniline blue solution of 10mmol/L and the volume ratio of the chloroperoxidase solution that amount of substance concentration is 0.1mmol/L are 1: 0.01, is the H of 3mol/L with amount of substance concentration
2SO
4Solution or amount of substance concentration are that the NaOH solution of 3mol/L is regulated pH to 3, and adding 40mL amount of substance concentration is the H of 0.2mol/L
2O
2The aqueous solution, amount of substance concentration are that water-soluble aniline blue solution and the amount of substance concentration of 10mmol/L is the H of 0.2mol/L
2O
2The volume ratio of the aqueous solution is 1: 0.04, stirring at room 1～5 minute.Other steps are identical with embodiment 1.
Embodiment 3
With 1000mL amount of substance concentration is that the decolored degradation of the water-soluble aniline blue solution of 10mmol/L is an example, raw materials used and method for decoloring and degrading is as follows:
In the decolored degradation step 2 of present embodiment, to 1000mL amount of substance concentration is that to add 60mL amount of substance concentration in the water-soluble aniline blue solution of 10mmol/L be the chloroperoxidase solution of 0.1mmol/L, mix, amount of substance concentration is that the water-soluble aniline blue solution of 10mmol/L and the volume ratio of the chloroperoxidase solution that amount of substance concentration is 0.1mmol/L are 1: 0.06, is the H of 3mol/L with amount of substance concentration
2SO
4Solution or amount of substance concentration are that the NaOH solution of 3mol/L is regulated pH to 3, and adding 80mL amount of substance concentration is the H of 0.2mol/L
2O
2The aqueous solution, amount of substance concentration are that water-soluble aniline blue solution and the amount of substance concentration of 10mmol/L is the H of 0.2mol/L
2O
2The volume ratio of the aqueous solution is 1: 0.08, stirring at room 1～5 minute.Other steps are identical with embodiment 1.
Embodiment 4
With 1000mL amount of substance concentration is that the decolored degradation of the orange II solution of 10mmol/L is an example, raw materials used and method for decoloring and degrading is as follows:
In the decolored degradation step 2 of embodiment 1, be that the water-soluble aniline blue solution of 10mmol/L is that the orange II solution of 10mmol/L is replaced with equal-volume amount of substance concentration with 1000mL amount of substance concentration, other steps of this step are identical with embodiment 1.
In calculating azoic dyestuff decolored degradation rate step 3, the amount concentration of pressing (1) formula substance for calculation is the decolored degradation rate of the orange II solution of 10mmol/L, A in the formula
0Be that amount of substance concentration is the initial absorbance of the orange II solution of 10mmol/L at the 485nm place.Other steps are identical with embodiment 1.Experimental result sees Table 1～3.
Calculate by (1) formula, amount of substance concentration is that the decolored degradation rate of the orange II solution of 10mmol/L is 49.2%.
Embodiment 5
With 1000mL amount of substance concentration is that the decolored degradation of the orange II solution of 10mmol/L is an example, raw materials used and method for decoloring and degrading is as follows:
In the decolored degradation step 2 of embodiment 2,3, be that the water-soluble aniline blue solution of 10mmol/L is that the orange II solution of 10mmol/L is replaced with equal-volume amount of substance concentration with 1000mL amount of substance concentration, other steps of this step are identical with embodiment 1.Other steps are identical with embodiment 4.
Embodiment 6
With 1000mL amount of substance concentration is that the decolored degradation of the tetrabromophenol sulfonphthalein solution of 10mmol/L is an example, raw materials used and method for decoloring and degrading is as follows:
In the decolored degradation step 2 of embodiment 1, be that the water-soluble aniline blue solution of 10mmol/L is that the tetrabromophenol sulfonphthalein solution of 10mmol/L is replaced with equal-volume amount of substance concentration with 1000mL amount of substance concentration, other steps of this step are identical with embodiment 1.
In calculating azoic dyestuff decolored degradation rate step 3, the amount concentration of pressing (1) formula substance for calculation is the decolored degradation rate of the tetrabromophenol sulfonphthalein solution of 10mmol/L, A in the formula
0Be that amount of substance concentration is the initial absorbance of the tetrabromophenol sulfonphthalein solution of 10mmol/L at the 438nm place.Other steps are identical with embodiment 1.Experimental result sees Table 1～3.
Calculate by (1) formula, amount of substance concentration is that the decolored degradation rate of the tetrabromophenol sulfonphthalein solution of 10mmol/L is 45.8%.
Embodiment 7
With 1000mL amount of substance concentration is that the decolored degradation of the tetrabromophenol sulfonphthalein solution of 10mmol/L is an example, raw materials used and method for decoloring and degrading is as follows:
In the decolored degradation step 2 of embodiment 2,3, be that the water-soluble aniline blue solution of 10mmol/L is that the tetrabromophenol sulfonphthalein solution of 10mmol/L is replaced with equal-volume amount of substance concentration with 1000mL amount of substance concentration, other steps of this step are identical with embodiment 1.Other steps are identical with embodiment 6.
Embodiment 8
With 1000mL amount of substance concentration is that the decolored degradation of the methylene blue solution of 10mmol/L is an example, raw materials used and method for decoloring and degrading is as follows:
In the decolored degradation step 2 of embodiment 1, be that the water-soluble aniline blue solution of 10mmol/L is that the methylene blue solution of 10mmol/L is replaced with equal-volume amount of substance concentration with 1000mL amount of substance concentration, other steps of this step are identical with embodiment 1.
In calculating azoic dyestuff decolored degradation rate step 3, the amount concentration of pressing (1) formula substance for calculation is the decolored degradation rate of the methylene blue solution of 10mmol/L, A in the formula
0Be that amount of substance concentration is the initial absorbance of the methylene blue solution of 10mmol/L at the 666nm place.Other steps are identical with embodiment 1.
Calculate by (1) formula, amount of substance concentration is that the decolored degradation rate of the methylene blue solution of 10mmol/L is 57.4%.
Embodiment 9
With 1000mL amount of substance concentration is that the decolored degradation of the methylene blue solution of 10mmol/L is an example, raw materials used and method for decoloring and degrading is as follows:
In the decolored degradation step 2 of embodiment 2,3, be that the water-soluble aniline blue solution of 10mmol/L is that the methylene blue solution of 10mmol/L is replaced with equal-volume amount of substance concentration with 1000mL amount of substance concentration, other steps of this step are identical with embodiment 1.Other steps are identical with embodiment 8.
Embodiment 10
In the decolored degradation step 2 of above embodiment 1～9, be the H of 3mol/L with amount of substance concentration
2SO
4Solution or amount of substance concentration are that the NaOH solution of 3mol/L is regulated pH to 2, and other steps of this step are identical with respective embodiments.Other steps are identical with respective embodiments.
Embodiment 11
In the decolored degradation step 2 of above embodiment 1～9, be the H of 3mol/L with amount of substance concentration
2SO
4Solution or amount of substance concentration are that the NaOH solution of 3mol/L is regulated pH to 5, and other steps of this step are identical with respective embodiments.Other steps are identical with respective embodiments.
In order to determine optimum process condition of the present invention, the contriver has carried out a large amount of laboratory study tests, and various test situation are as follows:
Experimental drug: chloroperoxidase (CPO) is produced by Sigma company; Orange II is produced by the Beijing Chemical Plant; Tetrabromophenol sulfonphthalein is produced by Tianjin good fortune chemical reagent in morning factory; Methylene blue is produced by the huge chemical reagent of Tianjin Dongli District factory; Water-soluble aniline blue is produced by Chemical Reagent Co., Ltd., Sinopharm Group.
Laboratory apparatus: UV-1700 type ultraviolet-visible pectrophotometer, produce by international trade Shanghai, Tianjin, island company limited; PHS-25 type digital display pH acidometer is produced by Shanghai Precision Scientific Apparatus Co., Ltd.
Obtain solution: preparation amount of substance concentration is the KH of 0.1mol/L
2PO
4-K
2HPO
4Buffered soln, regulating its pH with 3mol/L hydrochloric acid is 5.5, is the chloroperoxidase solution of 0.1mmol/L with this damping fluid preparation amount of substance concentration; With massfraction 30% H
2O
2Solution and distilled water are prepared the H that amount of substance concentration is 0.2mol/L according to a conventional method
2O
2The aqueous solution; Be mixed with the orange II aqueous solution, the tetrabromophenol sulfonphthalein aqueous solution, the methylene blue aqueous solution, the water-soluble aniline blue aqueous solution that amount of substance concentration is 10mmol/L according to a conventional method with distilled water respectively with orange II, tetrabromophenol sulfonphthalein, methylene blue, water-soluble aniline blue.
1, H
2O
2Consumption is to the influence of soluble azo dyes decolored degradation rate
Get the orange II aqueous solution that 1000mL amount of substance concentration is 10mmol/L, the tetrabromophenol sulfonphthalein aqueous solution, the methylene blue aqueous solution, each 7 parts of the water-soluble aniline blue aqueous solution, place the flask of 2000mL respectively, add the chloroperoxidase solution that 40mL amount of substance concentration is 0.1mmol/L respectively, mix, amount of substance concentration is the orange II aqueous solution of 10mmol/L, the tetrabromophenol sulfonphthalein aqueous solution, the methylene blue aqueous solution, the water-soluble aniline blue aqueous solution and amount of substance concentration are that the volume ratio of the chloroperoxidase solution of 0.1mmol/L is 1: 0.04, are the H of 3mol/L with amount of substance concentration
2SO
4Solution or amount of substance concentration are that the NaOH solution of 3mol/L is regulated pH to 3, add 30mL, 40mL, 50mL, 60mL, 70mL, 80mL more respectively in 7 parts of solution, 90mL amount of substance concentration is the H of 0.2mol/L
2O
2The orange II aqueous solution, the tetrabromophenol sulfonphthalein aqueous solution, the methylene blue aqueous solution, the water-soluble aniline blue aqueous solution and amount of substance concentration that the aqueous solution, amount of substance concentration are 10mmol/L are the H of 0.2mol/L
2O
2The volume ratio of the aqueous solution is 1: 0.03,1: 0.04,1: 0.05,1: 0.06,1: 0.07,1: 0.08,1: 0.09, stirring at room 1～5 minute.
With the absorbancy of the orange II aqueous solution, the tetrabromophenol sulfonphthalein aqueous solution, the methylene blue aqueous solution, the water-soluble aniline blue aqueous solution before and after the measurement of ultraviolet-visible spectrophotometer degraded, calculate azoic dyestuff decolored degradation rate according to (1) formula:
η＝[(A
0-A
t)/A
0]×100％ (1)
η is an azoic dyestuff decolored degradation rate in the formula, A
0Be the initial absorbance of this azoic dyestuff characteristic wave strong point, A
tAbsorbancy when being time t.
Test and calculation result see Table 1.
Table 1 H
2O
2Consumption is to the influence of soluble azo dyes decolored degradation rate
By table 1 as seen, to be the orange II aqueous solution, the tetrabromophenol sulfonphthalein aqueous solution, the methylene blue aqueous solution, the water-soluble aniline blue aqueous solution and the amount of substance concentration of 10mmol/L be the H of 0.2mol/L to amount of substance concentration
2O
2The volume ratio of the aqueous solution is 1: 0.04～0.08 o'clock, and decolored degradation rate effect is all better, continues to increase H
2O
2Consumption, H
2O
2Restraining effect to enzymic activity begins to manifest, and the decolored degradation rate descends rapidly.It is that 10mmol/L azoic dyestuff solution and amount of substance concentration are the H of 0.2mol/L that the present invention selects amount of substance concentration
2O
2The volume ratio of the aqueous solution is 1: 0.04～0.08, and the best is 1: 0.07.
2, pH is to the influence of soluble azo dyes decolored degradation rate
Get the orange II aqueous solution that 1000mL amount of substance concentration is 10mmol/L, the tetrabromophenol sulfonphthalein aqueous solution, the methylene blue aqueous solution, each 5 parts of the water-soluble aniline blue aqueous solution, place the flask of 2000mL respectively, add the chloroperoxidase solution that 40mL amount of substance concentration is 0.1mmol/L respectively, mix, amount of substance concentration is the orange II aqueous solution of 10mmol/L, the tetrabromophenol sulfonphthalein aqueous solution, the methylene blue aqueous solution, water-soluble aniline blue and amount of substance concentration are that the volume ratio of the chloroperoxidase solution of 0.1mmol/L is 1: 0.04, are the H of 3mol/L with amount of substance concentration
2SO
4Solution or amount of substance concentration are that the NaOH solution of 3mol/L is regulated 5 parts of pH to 2,3,4,5,6 respectively, and adding 70mL amount of substance concentration more respectively is the H of 0.2mol/L
2O
2The orange II aqueous solution, the tetrabromophenol sulfonphthalein aqueous solution, the methylene blue aqueous solution, the water-soluble aniline blue aqueous solution and amount of substance concentration that the aqueous solution, amount of substance concentration are 10mmol/L are the H of 0.2mol/L
2O
2The volume ratio of the aqueous solution is 1: 0.07, stirring at room 1～5 minute.Calculate azoic dyestuff decolored degradation rate according to the method for test 1.
Test and calculation result see Table 2.
Table 2 pH is to the influence of soluble azo dyes decolored degradation rate
By table 2 as seen, with amount of substance concentration be the H of 3mol/L
2SO
4Solution or amount of substance concentration are that the NaOH solution adjusting pH of 3mol/L is 2～5 o'clock, chloroperoxidase catalysis H
2O
2The decolored degradation rate effect of the orange II of oxidation, tetrabromophenol sulfonphthalein, methylene blue, water-soluble aniline blue is all better.It is the H of 3mol/L that the present invention selects with amount of substance concentration
2SO
4Solution or amount of substance concentration are that the NaOH solution of 3mol/L is regulated pH to 2～5, best setting pH to 3.
3, the chloroperoxidase consumption is to the influence of soluble azo dyes decolored degradation rate
Get the orange II aqueous solution that 1000mL amount of substance concentration is 10mmol/L, the tetrabromophenol sulfonphthalein aqueous solution, the methylene blue aqueous solution, each 6 parts of the water-soluble aniline blue aqueous solution, place the flask of 2000mL respectively, be the orange II aqueous solution of 10mmol/L to 6 parts of amount of substance concentration, the tetrabromophenol sulfonphthalein aqueous solution, the methylene blue aqueous solution, add 10mL in the water-soluble aniline blue aqueous solution respectively, 20mL, 30mL, 40mL, 50mL, 60mL amount of substance concentration is the chloroperoxidase solution of 0.1mmol/L, mix, amount of substance concentration is the orange II aqueous solution of 10mmol/L, the tetrabromophenol sulfonphthalein aqueous solution, the methylene blue aqueous solution, the water-soluble aniline blue aqueous solution and amount of substance concentration are that the volume ratio of the chloroperoxidase solution of 0.1mmol/L is 1: 0.01,1: 0.02,1: 0.03,1: 0.04,1: 0.05, respectively with amount of substance concentration be the H of 3mol/L at 1: 0.06
2SO
4Solution or amount of substance concentration are that the NaOH solution of 3mol/L is regulated pH to 3, and adding 70mL amount of substance concentration more respectively is the H of 0.2mol/L
2O
2The orange II aqueous solution, the tetrabromophenol sulfonphthalein aqueous solution, the methylene blue aqueous solution, the water-soluble aniline blue aqueous solution and amount of substance concentration that the aqueous solution, amount of substance concentration are 10mmol/L are the H of 0.2mol/L
2O
2The volume ratio of the aqueous solution is 1: 0.07, stirring at room 1～5 minute.Calculate azoic dyestuff decolored degradation rate according to the method for test 1.
Test and calculation result see Table 3.
Table 3 chloroperoxidase consumption is to the influence of soluble azo dyes decolored degradation rate
By table 3 as seen, amount of substance concentration is the orange II aqueous solution of 10mmol/L, the tetrabromophenol sulfonphthalein aqueous solution, the methylene blue aqueous solution, the water-soluble aniline blue aqueous solution and amount of substance concentration are that the volume ratio of the chloroperoxidase solution of 0.1mmol/L is 1: 0.01～0.06 o'clock, decolored degradation rate effect is all better, after volume ratio is 1: 0.04, it is not remarkable to the effect that improves percent of decolourization to increase the chloroperoxidase consumption, take all factors into consideration economic factors, it is that the azoic dyestuff of 10mmol/L and the volume ratio of the chloroperoxidase solution that amount of substance concentration is 0.1mmol/L are 1: 0.01～0.06 that the present invention selects amount of substance concentration, and the best is 1: 0.04.
Claims (3)
1. chloroperoxidase catalysis H
2O
2The method for decoloring and degrading of oxidation soluble azo dyes is characterized in that it comprises the steps:
(1) obtain solution
Preparation amount of substance concentration is the KH of 0.1mol/L
2PO
4-K
2HPO
4Buffered soln, regulating its pH with 3mol/L hydrochloric acid is 5.5, is the chloroperoxidase solution of 0.1mmol/L with this damping fluid preparation amount of substance concentration, is 30% H with massfraction
2O
2Solution and distilled water are prepared the H that amount of substance concentration is 0.2mol/L according to a conventional method
2O
2The aqueous solution;
(2) decolored degradation
Adding amount of substance concentration in azoic dyestuff solution is the chloroperoxidase solution of 0.1mmol/L, mix, azoic dyestuff solution and amount of substance concentration are that the volume ratio of the chloroperoxidase solution of 0.1mmol/L is 1: 0.01～0.06, are the H of 3mol/L with amount of substance concentration
2SO
4Solution or amount of substance concentration are that the NaOH solution of 3mol/L is regulated pH to 2～5, and adding amount of substance concentration is the H of 0.2mol/L
2O
2The aqueous solution, azoic dyestuff solution and amount of substance concentration are the H of 0.2mol/L
2O
2The volume ratio of the aqueous solution is 1: 0.04～0.08, stirring at room 1～5 minute;
Above-mentioned azoic dyestuff solution is the water-soluble aniline blue solution that the orange II solution of 10mmol/L or tetrabromophenol sulfonphthalein solution that amount of substance concentration is 10mmol/L or the amount of substance concentration methylene blue solution that is 10mmol/L or amount of substance concentration are 10mmol/L for amount of substance concentration.
2. according to the described chloroperoxidase catalysis of claim 1 H
2O
2The method for decoloring and degrading of oxidation soluble azo dyes, it is characterized in that: in decolored degradation step (2), adding amount of substance concentration in azoic dyestuff solution is the chloroperoxidase solution of 0.1mmol/L, mix, azoic dyestuff solution and amount of substance concentration are that the volume ratio of the chloroperoxidase solution of 0.1mmol/L is 1: 0.03～0.06, are the H of 3mol/L with amount of substance concentration
2SO
4Solution or amount of substance concentration are that the NaOH solution of 3mol/L is regulated pH to 2～4, and adding amount of substance concentration is the H of 0.2mol/L
2O
2The aqueous solution, azoic dyestuff solution and amount of substance concentration are the H of 0.2mol/L
2O
2The volume ratio of the aqueous solution is 1: 0.05～0.08.
3. according to the described chloroperoxidase catalysis of claim 1 H
2O
2The method for decoloring and degrading of oxidation soluble azo dyes, it is characterized in that: in decolored degradation step (2), adding amount of substance concentration in azoic dyestuff solution is the chloroperoxidase solution of 0.1mmol/L, mix, azoic dyestuff solution and amount of substance concentration are that the volume ratio of the chloroperoxidase solution of 0.1mmol/L is 1: 0.04, are the H of 3mol/L with amount of substance concentration
2SO
4Solution or amount of substance concentration are that the NaOH solution of 3mol/L is regulated pH to 3, and adding amount of substance concentration is the H of 0.2mol/L
2O
2The aqueous solution, azoic dyestuff solution and amount of substance concentration are the H of 0.2mol/L
2O
2The volume ratio of the aqueous solution is 1: 0.07.
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