CN115354010B - Method for improving content of low-toxicity reduction products in microbial reduction chlorophenol system - Google Patents

Method for improving content of low-toxicity reduction products in microbial reduction chlorophenol system Download PDF

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CN115354010B
CN115354010B CN202211013507.1A CN202211013507A CN115354010B CN 115354010 B CN115354010 B CN 115354010B CN 202211013507 A CN202211013507 A CN 202211013507A CN 115354010 B CN115354010 B CN 115354010B
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鲁玥
梁方艺
钟林芮
秦钒治
张绶娟
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Hunan University
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Abstract

The invention discloses a method for improving the content of low-toxicity reduction products in a microbial reduction chlorophenol system, which utilizes tourmaline to improve the content of the low-toxicity reduction products in the microbial reduction chlorophenol system, wherein the concentration of the tourmaline in the microbial reduction chlorophenol system is more than or equal to 0.8g/L. The method for improving the content of the low-toxicity reduction products in the microbial reduction chlorophenol system, disclosed by the invention, has the advantages that by adding a proper amount of tourmaline into the microbial reduction chlorophenol system, the content of the low-toxicity reduction products in the microbial reduction chlorophenol system can be effectively improved, so that the overall toxicity of the reduction products can be further reduced, the rapid reduction of chlorophenol can be realized, the overall degradation efficiency of the bioremediation chlorophenol system can be improved, the use value is high, the application prospect is good, and the method has very important significance for effectively solving the threat of the chlorophenol to environmental safety and human health.

Description

Method for improving content of low-toxicity reduction products in microbial reduction chlorophenol system
Technical Field
The invention belongs to the field of bioremediation, and relates to a method for improving the content of low-toxicity reduction products in a microbial reduction chlorophenol system.
Background
Chlorophenols are a class of persistent organic pollutants widely distributed in nature, the toxicity of which increases with the increase of the number of chlorine substituents, while reducing the number of chlorine substituents by microbial reductive dechlorination, so that the reduction of the toxicity is a currently mainstream and economical treatment process. For example, desulphurisation bacteria are a class of anaerobic microorganisms with broad dechlorination activity that can utilize dechlorination respiration to reduce polychlorinated phenols to less toxic low chlorophenols, thereby reducing the environmental safety and human health risks of chlorophenol pollutants. Although the toxicity of chlorophenols can be reduced by microbial reduction, it was found during the actual research by the inventors of the present application that: in a system for reducing chlorophenols by using microorganisms, the microorganisms can preferentially attack chlorine substituents at the ortho position and the meta position, and as a result, low chlorophenols mainly with chlorine substituents at the meta position and the para position in the reduction product are obtained, namely, compared with the ortho-position low chlorophenols, the ratio of the chlorine substituents at the meta position and the para position of the low chlorophenols in the reduction product is higher, and meanwhile, compared with the ortho-position low chlorophenols, the chlorine substituents at the meta position and the para position of the low chlorophenols have stronger toxicity, so that the overall toxicity of the reduction product in the traditional microorganism reduction chlorophenol system is still higher. In addition, the inventors also found that: none of the existing microbial reduction chlorophenol systems can effectively regulate and control the reduction path of chlorophenol, namely, the preferential attack of microorganisms on ortho-position chemical bonds is difficult to effectively avoid, so that chlorophenol is difficult to effectively reduce to chlorophenol with lower toxicity (such as ortho-position chlorophenol), which is the root cause that the ratio/content of low-toxicity chlorophenol in reduction products of the microbial reduction chlorophenol system is still lower, and is also an important cause that the overall toxicity of reduction products in the existing microbial reduction chlorophenol system is still higher. So far, no report is known on how to effectively regulate the reduction path of chlorophenol and how to improve the ratio/content of low-toxicity chlorophenol in the reduction product. Therefore, how to effectively regulate the path of microorganism to reduce chlorophenol and further improve the content of low-toxicity chlorophenol in the reduction product is of great significance for effectively reducing the overall toxicity of the reduction product and effectively solving the threat of chlorophenol pollutants to environmental safety and human health.
Disclosure of Invention
The invention aims to solve the technical problem of overcoming the defects in the prior art and providing a method for improving the content of low-toxicity reduction products in a microbial reduction chlorophenol system.
In order to solve the technical problems, the invention adopts the following technical scheme.
A method for improving the content of low-toxicity reduction products in a microbial reduction chlorophenol system comprises the steps of utilizing tourmaline to improve the content of low-toxicity reduction products in the microbial reduction chlorophenol system; the concentration of tourmaline in the microorganism reduction chlorophenol system is more than or equal to 0.8g/L.
The method for improving the content of the low-toxicity reduction products in the microbial reduction chlorophenol system is further improved, and the concentration of tourmaline in the microbial reduction chlorophenol system is more than or equal to 1.2g/L.
The method for improving the content of the low-toxicity reduction products in the microbial reduction chlorophenol system is further improved, and the concentration of tourmaline in the microbial reduction chlorophenol system is more than or equal to 1.6g/L.
The method for improving the content of the low-toxicity reduction products in the microbial reduction chlorophenol system is further improved, and the concentration of tourmaline in the microbial reduction chlorophenol system is less than or equal to 8.0g/L; the purity of the tourmaline is more than 99 percent; the average granularity of the tourmaline is 400 nm-500 nm.
The method for improving the content of the low-toxicity reduction products in the microbial reduction chlorophenol system is further improved, and the inoculation amount of the microorganisms in the microbial reduction chlorophenol system is 1-5% of the total volume of the system; the microorganism is a desulphurisation bacterial strain DCB-2.
The method for improving the content of the low-toxicity reduction products in the microbial reduction chlorophenol system is further improved, and when tourmaline is used for improving the content of the low-toxicity reduction products in the microbial reduction chlorophenol system, the method comprises the following steps of:
s1, mixing tourmaline, microorganisms and chlorophenol with a culture medium to obtain a mixture;
and S2, culturing microorganisms in the mixture obtained in the step S1, and completing the reduction dechlorination treatment of chlorophenol in the mixture.
In the method for improving the content of the low-toxicity reduction products in the microbial reduction chlorophenol system, which is further improved, in the step S1, the initial concentration of the chlorophenol in the mixture is 100 mu M-200 mu M; the chlorophenol is 2, 3-dichlorophenol; the culture medium is an improved DMSZ 720 culture medium.
In the above method for increasing the content of low-toxicity reduction products in a microbial reduction chlorophenol system, further improved, in step S1, the microorganism further comprises the following treatments before use: inoculating the microorganism into culture medium for culturing until OD 600 The values remain relatively stable; the culture is carried out at a temperature of 25-40 ℃; the culture time is 3-7 days; the culture medium is an improved DMSZ 720 culture medium.
The method for improving the content of low-toxicity reduction products in the microbial reduction chlorophenol system, which is further improved, wherein in the step S2, the culture is performed under anaerobic conditions; introducing mixed gas of nitrogen and carbon dioxide in the culture process to keep the system in an anaerobic state; the volume ratio of the nitrogen to the carbon dioxide in the mixed gas of the nitrogen and the carbon dioxide is 4:1, a step of; the culture is carried out at a temperature of 25-40 ℃; the culture time is 54-120 hours at a time.
Compared with the prior art, the invention has the advantages that:
(1) Aiming at the defects that the reduction path of chlorophenol can not be regulated and controlled by the existing microorganism reduction chlorophenol system, the toxicity of reduction products in the microorganism reduction chlorophenol system is high, and the like, the invention creatively provides a method for improving the content of low-toxicity reduction products in the microorganism reduction chlorophenol system, and the method utilizes tourmaline to improve the content of low-toxicity reduction products in the microorganism reduction chlorophenol system, wherein the concentration of tourmaline in the microorganism reduction chlorophenol system is more than or equal to 0.8g/L. In the invention, a proper amount of tourmaline is added into a microorganism reduction chlorophenol system, and the tourmaline is used as a functional material to change the charge distribution of chlorophenol, in particular: under the action of tourmaline, the charges of atoms on chlorophenol can be transferred to different degrees, at the moment, the charges distributed on the chemical bonds of the ortho-chlorine substituents are less, the stability is higher and the chlorophenol is more difficult to attack, so that in a system for reducing chlorophenol by microorganisms, the chlorophenol can be reduced into ortho-low-toxicity chlorophenol with lower toxicity due to the increase of the attack difficulty of the chlorine substituents on the ortho-position, the occupation ratio of the low-toxicity chlorophenol in a reduction product is obviously improved, and the overall toxicity of the reduction product is reduced; meanwhile, tourmaline also has the characteristics of automatically regulating the pH value of the solution to be neutral, releasing trace elements, generating a spontaneous electric field and the like, so that a stable and proper neutral environment can be provided for microorganisms under the action of the tourmaline, and the activation process of the microorganisms is stimulated and accelerated through the generated weak electric field, thereby being beneficial to reducing the total time required by the dechlorination process and improving the dechlorination efficiency, and further being beneficial to realizing the purpose of efficiently reducing chlorophenol. The method for improving the content of the low-toxicity reduction products in the microbial reduction chlorophenol system, disclosed by the invention, has the advantages that by adding a proper amount of tourmaline into the microbial reduction chlorophenol system, the content of the low-toxicity reduction products in the microbial reduction chlorophenol system can be effectively improved, so that the overall toxicity of the low-toxicity reduction products can be further reduced, and the rapid reduction of chlorophenol can be realized, so that the overall degradation efficiency of the bioremediation chlorophenol system can be improved, the use value is high, the application prospect is good, and the method has very important significance for effectively solving the threat of chlorophenol pollutants to environmental safety and human health.
(2) The tourmaline adopted in the invention is used as a natural ore, has the advantages of wide source, low cost, no secondary pollution, no environmental threat and the like, and can continuously act after being added due to good structural stability and long-acting property, so that the tourmaline is beneficial to reducing the repairing cost and no secondary pollution to the environment when being used as a bioremediation functional material.
Drawings
In order to make the objects, technical solutions and advantages of the embodiments of the present invention more clear, the technical solutions of the embodiments of the present invention will be clearly and completely described below with reference to the accompanying drawings in the embodiments of the present invention.
FIG. 1 is a graph showing the effect of different tourmaline addition amounts on the content of 2-chlorophenol in a system for reducing 2, 3-dichlorophenol by microorganisms in example 1 of the present invention.
FIG. 2 is a graph showing the effect of different tourmaline addition amounts on the content of 3-chlorophenol in a system for reducing 2, 3-dichlorophenol by microorganisms in example 1 of the present invention.
FIG. 3 is a graph showing the effect of different tourmaline addition amounts on the removal rate of 2, 3-dichlorophenol in a system for reducing 2, 3-dichlorophenol by microorganisms in example 1 of the present invention.
FIG. 4 is a graph showing the effect of different tourmaline addition amounts on the content of 2-chlorophenol in a system for reducing 2, 3-dichlorophenol by microorganisms in example 2 of the present invention.
FIG. 5 is a graph showing the effect of cyclic treatment of 2, 3-dichlorophenol corresponding to the addition of different tourmaline amounts to the microbial reduction 2, 3-dichlorophenol system in example 2 of the present invention.
FIG. 6 is an SEM image of the system after completion of dechlorination in example 1 of the present invention.
FIG. 7 is a FTIR chart showing the process before and after tourmaline promotes the reduction of 2, 3-dichlorophenol by the desulphating bacteria in example 2 of the present invention.
FIG. 8 is an XRD pattern of tourmaline before and after reduction of 2, 3-dichlorophenol by using a desulphating bacterium in example 2 of the present invention.
FIG. 9 is a schematic diagram of the principle of the invention for increasing the content of 2-chlorophenol in a system for reducing 2, 3-dichlorophenol by microorganisms using tourmaline.
Detailed Description
The invention is further described below in connection with the drawings and the specific preferred embodiments, but the scope of protection of the invention is not limited thereby.
The materials and instruments used in the examples below are all commercially available.
The composition of the modified DMSZ 720 medium used in the present invention is shown in table 1.
Table 1 formulation of modified DMSZ 720 Medium
Base solution 86.8mL Auxiliary solution 7.2mL
Composition of the composition Concentration of Composition of the composition Concentration of
Sodium chloride 1.0595g/L Microelement SL9 0.1mL/L
Magnesium chloride 0.5298g/L Se-Wo solution 0.2mL/L
Monopotassium phosphate 0.2119g/L Wolin vitamin 0.1mL/L
Ammonium chloride 0.3179g/L Lactate salt 500mmol/L
Potassium chloride 0.3179g/L Sodium bicarbonate 750mmol/L
Calcium chloride 0.0159g/L L-cysteine 30mmol/L
- - Dithiothreitol 50mmol/L
- - Sodium sulfide 200mmol/L
Yeast paste solution 40g/L
In table 1, the composition of trace element SL 9: 12.8g/L of nitrilotriacetic acid, 2.0g/L of ferrous chloride tetrahydrate, 190mg/L of cobalt chloride hexahydrate, 100mg/L of manganese chloride dihydrate, 70mg/L of zinc chloride, 6mg/L of boric acid, 24mg/L of nickel chloride hexahydrate, 2mg/L of copper chloride dihydrate, 36mg/L of sodium molybdate dihydrate and 26.4g/L of sodium carbonate. The microelement SL9 solution needs to be filled with nitrogen to ensure anaerobic state, and is filtered and sterilized before use.
In Table 1, the composition of Se-Wo solution: 3mg/L sodium selenite pentahydrate, 4mg/L sodium tungstate monohydrate and 500mg/L sodium hydroxide. The Se-Wo solution needs to be introduced with nitrogen to ensure an anaerobic state, and is filtered and sterilized before use.
In table 1, the composition of Wolin vitamins: 20mg/L biotin, 20mg/L folic acid, 100mg/L pyridoxine hydrochloride, 50mg/L riboflavin, 50mg/L thiamine, 50mg/L niacin, 50mg/L pantothenic acid, 50mg/L vitamin B12, 50mg/L para-aminobenzoic acid, 50mg/L thiozinc acid. The Wolin vitamin solution needs to be filter sterilized prior to use.
Example 1:
a method for improving the content of low-toxicity reduction products in a microbial reduction chlorophenol system, in particular to a method for improving the content of low-toxicity reduction products (2-chlorophenol) in a microbial reduction 2, 3-dichlorophenol system by using tourmaline, comprising the following steps:
s1, adding tourmaline (commercially available) with the purity of 99% and the average granularity of 430nm into 100mL of modified DMSZ 720 culture medium according to the addition amount of 0g/L, 1.0g/L, 2.5g/L, 5.0g/L and 8.0g/L, respectively, inoculating the strain DCB-2 of the desulphation bacteria according to the inoculation amount of 2% of the volume of the culture medium, simultaneously adding 2, 3-dichlorophenol respectively, and controlling the concentration of the 2, 3-dichlorophenol in each system to be 200 mu M, so as to obtain a mixture.
S2, placing the mixture obtained in the step S1 in a constant temperature incubator at 35 ℃, and culturing microorganisms in the mixture for 5 days under anaerobic conditions, wherein mixed gas of nitrogen and carbon dioxide (the volume ratio of the nitrogen to the carbon dioxide is 4:1) is introduced in the culture process, so that the system is kept in an anaerobic state, and the reduction dechlorination treatment of chlorophenol in the mixture is completed.
In this example, the adopted strain DCB-2 of Desulfurous acid bacteria before inoculation, further comprises the following treatments: the strain DCB-2 of Desulfurous acid bacteria was inoculated into a modified DSMZ 720 medium, activated in a constant temperature incubator at 35℃for 5 days, and its OD was measured periodically during the cultivation 600 Value up to OD 600 The values remained relatively stable.
The concentration of 2, 3-dichlorophenol and its dechlorinated products (2-chlorophenol, 3-chlorophenol) was measured by high performance liquid chromatograph, and the results are shown in fig. 1, 2 and 3.
FIG. 1 is a graph showing the effect of different tourmaline addition amounts on the content of 2-chlorophenol in a system for reducing 2, 3-dichlorophenol by microorganisms in example 1 of the present invention.
TABLE 2 influence of different tourmaline addition amounts on the content of 2-chlorophenol in reduction system under different treatment time conditions
As can be seen from fig. 1 and table 2, the ratio of 2-chlorophenol increases with the addition amount of tourmaline in the same treatment time, wherein the ratio of 2-chlorophenol is significantly increased when the addition amount of tourmaline is more than or equal to 2.5g/L and is higher than other groups, which means that adding a proper amount of tourmaline can significantly increase the ratio of 2-chlorophenol in the reduction products; meanwhile, as can be seen from the results in fig. 1 and table 2, by increasing the addition amount of tourmaline under the condition that the microbial inoculum size is relatively low, the ratio of 2-chlorophenol in the reduction product is more advantageously increased, and particularly, the optimal addition amount of tourmaline is 2.5g/L.
FIG. 2 is a graph showing the effect of different tourmaline addition amounts on the content of 3-chlorophenol in a system for reducing 2, 3-dichlorophenol by microorganisms in example 1 of the present invention.
TABLE 3 influence of different tourmaline addition amounts on 3-chlorophenol content in reduction system under different treatment time conditions
As can be seen from fig. 2 and table 3, the ratio of 3-chlorophenol in the reduction product is contrary to the result of 2-chlorophenol, and the ratio of 3-chlorophenol in the reduction product is reduced with the increase of the tourmaline addition amount in the same time, which accords with the fact that the total amount of the reduction product is conserved. Meanwhile, the toxicity of the monochlorophenol is as follows in sequence: the fact that 4-chlorophenol > 3-chlorophenol > 2-chlorophenol further proves that the method can improve the content of the low-toxicity reduction product, and is beneficial to reducing the overall toxicity of the reduction product by improving the ratio of the low-toxicity reduction product.
FIG. 3 is a graph showing the effect of different tourmaline addition amounts on the removal rate of 2, 3-dichlorophenol in a system for reducing 2, 3-dichlorophenol by microorganisms in example 1 of the present invention. In FIG. 3, the blank is the strain DCB-2 without tourmaline and sulfite removed, and the other conditions are the same; the tourmaline is only added as the comparison, and other conditions are the same; the DCB-2 control was supplemented with only the Desulfurous acid strain DCB-2, except for the same conditions. As shown in FIG. 3, after tourmaline is added, the reduction of 2, 3-dichlorophenol by the sulfite removing bacteria can be accelerated, particularly, when the adding amount of tourmaline is more than or equal to 2.5g/L, the sulfite removing bacteria can more rapidly complete the reduction of 2, 3-dichlorophenol, and the time for completely reducing the 2, 3-dichlorophenol is reduced from 96 hours to 72 hours, namely, the reduction and dechlorination efficiency of the 2, 3-dichlorophenol can be greatly improved; meanwhile, the tourmaline can shorten the time required for activating the desulphurisation bacteria from 36 hours to 18 hours, which is also beneficial to greatly shortening the time required for completely reducing the 2, 3-dichlorophenol and further improving the reduction dechlorination efficiency of the 2, 3-dichlorophenol.
From the results shown in fig. 1 to 3, it is known that when the tourmaline concentration is less than 2.5g/L, the low-toxicity 2-CP ratio in the reduction dechlorination product is only about 15%, and when the tourmaline concentration exceeds 2.5g/L, the ratio is increased to more than 20%, which indicates that adding a proper amount of tourmaline can provide a proper and stable living environment for the dechlorination bacteria, and can influence the charge distribution of 2, 3-dichlorophenol, stabilize the ortho-chemical bond of the pollutant molecule, further increase the ratio of 2-chlorophenol, reduce the overall toxicity of the reduction product, accelerate the activation process of the bacteria, reduce the total duration required by dechlorination, and improve the dechlorination efficiency.
Example 2
A method for improving the content of low-toxicity reduction products in a microbial reduction chlorophenol system, in particular to a method for improving the content of low-toxicity reduction products (2-chlorophenol) in a microbial reduction 2, 3-dichlorophenol system by using tourmaline, comprising the following steps:
s1, adding tourmaline (commercially available) with the purity of 99% and the average granularity of 430nm into 100mL of modified DMSZ 720 culture medium according to the addition amount of 0g/L, 0.5g/L, 1.0g/L and 1.5g/L, respectively, inoculating the domesticated Desulfurous bacteria DCB-2 in the example 1 according to the inoculation amount of 4% of the volume of the culture medium, simultaneously adding 2, 3-dichlorophenol respectively, and controlling the concentration of the 2, 3-dichlorophenol in each system to 100 mu M to obtain a mixture.
S2, placing the mixture obtained in the step S1 in a constant temperature incubator at 35 ℃, and culturing microorganisms in the mixture for 96-120 h under anaerobic conditions, wherein mixed gas of nitrogen and carbon dioxide (the volume ratio of the nitrogen to the carbon dioxide is 4:1) is introduced in the culture process, so that the system is kept in an anaerobic state, and the reduction dechlorination treatment of chlorophenols in the mixture is completed.
S3, when all 2, 3-dichlorophenol in the bacteria-containing system is consumed, replenishing the 2, 3-dichlorophenol to the system again to restore the concentration to 100 mu M, and repeating for 3 cycles according to the method in the step S2.
The concentration of 2, 3-dichlorophenol and its dechlorinated product (2-chlorophenol) was measured by high performance liquid chromatograph, and the results are shown in fig. 4 and 5.
FIG. 4 is a graph showing the effect of different tourmaline addition amounts on the content of 2-chlorophenol in a system for reducing 2, 3-dichlorophenol by microorganisms in example 2 of the present invention.
TABLE 4 influence of different tourmaline addition amounts on the content of 2-chlorophenol in reduction system under different treatment time conditions
As can be seen from fig. 4 and table 4, the ratio of 2-chlorophenol in the system was always higher than the other two groups at the addition amounts of tourmaline of 1.0g/L and 1.5g/L in each cycle, and the ratio of 2-chlorophenol was gradually increased as the number of cycles was increased, and the above results showed that: when the addition amount of tourmaline is low, the microbial reduction of low-concentration chlorophenol can be promoted, and the capability of improving the content of low-toxicity reduction products is good.
FIG. 5 is a graph showing the effect of cyclic treatment of 2, 3-dichlorophenol corresponding to the addition of different tourmaline amounts to the microbial reduction 2, 3-dichlorophenol system in example 2 of the present invention. As can be seen from FIG. 5, when the added amount of tourmaline is 1.0 and 1.5g/L, the desulphation bacteria can complete the complete reduction of 2, 3-dichlorophenol in 96 hours; when the tourmaline content is 0 and 0.5g/L, the time required for complete reduction of 2, 3-dichlorophenol increases, because the stimulus activation effect of low concentration tourmaline on microorganisms is weaker when the microorganism content in the system is higher, and thus the time required for complete reduction increases. Meanwhile, as can be seen from the results in fig. 5, tourmaline in the reduction system has very excellent stability, and can continuously promote microorganisms to reduce chlorophenols and continuously reduce more chlorophenols to less toxic 2-chlorophenols.
From the results shown in fig. 4-5, it is known that adding an appropriate amount of tourmaline can increase the ratio of low-toxic 2-chlorophenol, and the improvement effect is better and more obvious in continuous pollution, and the ratio is finally increased to more than 30%, which further verifies that the appropriate amount of tourmaline can change the charge distribution of 2, 3-dichlorophenol, can increase the stability of ortho-chemical bond and the difficulty of being attacked, and is further beneficial to increasing the ratio of low-toxic chlorophenol (2-chlorophenol) in the reduction dechlorination product and reducing the overall biotoxicity.
FIG. 6 is an SEM image of the system after completion of dechlorination in example 1 of the present invention. As shown in FIG. 6, after the reduction dechlorination is completed together, the tourmaline and the Desulfurous acid bacteria strain DCB-2 can still keep the original state, which indicates that the tourmaline and the Desulfurous acid bacteria have good compatibility.
FIG. 7 is a FTIR chart showing the process before and after tourmaline promotes the reduction of 2, 3-dichlorophenol by the desulphating bacteria in example 2 of the present invention.
FIG. 8 is an XRD pattern of tourmaline before and after reduction of 2, 3-dichlorophenol by using a desulphating bacterium in example 2 of the present invention.
As can be seen from fig. 7 and fig. 8, after the tertiary circulation treatment, the characteristic peak and the absorption peak of tourmaline are not changed obviously, which indicates that the tourmaline has good stability and long-acting property in the reduction dechlorination process, can be recycled for multiple times, and is beneficial to realizing the treatment of continuous pollution.
FIG. 9 is a schematic diagram of the principle of the invention for increasing the content of 2-chlorophenol in a system for reducing 2, 3-dichlorophenol by microorganisms using tourmaline. As can be seen from fig. 9, adding a proper amount of tourmaline into the microorganism reduced 2, 3-dichlorophenol system, and using tourmaline as a functional material can change the charge distribution of 2, 3-dichlorophenol, specifically: under the action of tourmaline, the charges of each atom on the 2, 3-dichlorophenol can be transferred to different degrees, at the moment, the charges distributed on the chemical bonds of the ortho-chlorine substituents are less, the stability is higher and the charges are more difficult to attack, so that in a system for reducing the 2, 3-dichlorophenol by microorganisms, the system reduces the 2, 3-dichlorophenol into the ortho-low-toxicity chlorophenol (2-chlorophenol) with lower toxicity due to the increase of the attack difficulty of the chlorine substituents on the ortho-position, the occupation ratio of the low-toxicity chlorophenol in a reduction product is obviously improved, and the reduction product overall toxicity is reduced.
From the above results, it can be seen that, in the present invention, a proper amount of tourmaline is added into the microbial chlorophenol reduction system, and the tourmaline is used as a functional material to change the charge distribution of chlorophenol, specifically: under the action of tourmaline, the charges of atoms on chlorophenol can be transferred to different degrees, at the moment, the charges distributed on the chemical bonds of the ortho-chlorine substituents are less, the stability is higher and the chlorophenol is more difficult to attack, so in a system for reducing chlorophenol by microorganisms, the system reduces chlorophenol into ortho-low-toxicity chlorophenol with lower toxicity due to the increase of the attack difficulty of the chlorine substituents on the ortho-position, the occupation ratio of the low-toxicity chlorophenol in a reduction product is obviously improved, and the overall toxicity of the reduction product is reduced; meanwhile, tourmaline also has the characteristics of automatically regulating the pH value of the solution to be neutral, releasing trace elements, generating a spontaneous electric field and the like, so that a stable and proper neutral environment can be provided for microorganisms under the action of the tourmaline, and the activation process of the microorganisms is stimulated and accelerated through the generated weak electric field, thereby being beneficial to reducing the total time required by dechlorination, improving the dechlorination efficiency and further being beneficial to realizing the purpose of efficiently reducing chlorophenol. The method for improving the content of the low-toxicity reduction products in the microbial reduction chlorophenol system, disclosed by the invention, has the advantages that by adding a proper amount of tourmaline into the microbial reduction chlorophenol system, the content of the low-toxicity reduction products in the microbial reduction chlorophenol system can be effectively improved, so that the overall toxicity of the low-toxicity reduction products can be further reduced, and the rapid reduction of chlorophenol can be realized, so that the overall degradation efficiency of the bioremediation chlorophenol system can be improved, the use value is high, the application prospect is good, and the method has very important significance for effectively solving the threat of chlorophenol pollutants to environmental safety and human health.
The above examples are only preferred embodiments of the present invention, and the scope of the present invention is not limited to the above examples. All technical schemes belonging to the concept of the invention belong to the protection scope of the invention. It should be noted that modifications and adaptations to the present invention may occur to one skilled in the art without departing from the principles of the present invention and are intended to be within the scope of the present invention.

Claims (7)

1. A method for improving the content of low-toxicity reduction products in a microbial reduction chlorophenol system is characterized in that tourmaline is utilized to improve the content of low-toxicity reduction products in the microbial reduction chlorophenol system; the concentration of tourmaline in the microbial reduction chlorophenol system is more than or equal to 2.5 g/L; the chlorophenol is 2, 3-dichlorophenol; the low-toxicity reduction product is 2-chlorophenol; the microorganism is a desulphurisation bacterial strain DCB-2.
2. The method for increasing the content of low-toxicity reduction products in a microbial reduction chlorophenol system according to claim 1, wherein the concentration of tourmaline in the microbial reduction chlorophenol system is less than or equal to 8.0g/L; the purity of the tourmaline is more than 99 percent; the average granularity of the tourmaline is 400 nm-500 nm.
3. The method for increasing the content of low-toxicity reduction products in a microbial reduction chlorophenol system according to claim 2, wherein the inoculation amount of the microorganisms in the microbial reduction chlorophenol system is 1% -5% of the total volume of the system.
4. A method for increasing the content of low-toxicity reduction products in a microbial reduction chlorophenol system according to any one of claims 1 to 3, wherein the method for increasing the content of low-toxicity reduction products in a microbial reduction chlorophenol system by tourmaline comprises the following steps:
s1, mixing tourmaline, microorganisms and chlorophenol with a culture medium to obtain a mixture;
and S2, culturing microorganisms in the mixture obtained in the step S1, and completing the reduction dechlorination treatment of chlorophenol in the mixture.
5. The method for increasing the content of low-toxic reduction products in a microbial reduction chlorophenol system according to claim 4, wherein in step S1, the initial concentration of chlorophenol in the mixture is 100 μm to 200 μm; the culture medium is an improved DMSZ 720 culture medium.
6. The method for increasing the content of low-toxic reduction products in a microbial reduction chlorophenol system according to claim 5, wherein in step S1, said microorganism further comprises the following treatments before use: inoculating the microorganism into culture medium for culturing until OD 600 The values remain relatively stable; the culture is carried out at a temperature of 25-40 ℃; the culture time is 3-7 days; the culture medium is an improved DMSZ 720 culture medium.
7. The method for increasing the content of low-toxic reduction products in a microbial reduction chlorophenol system according to claim 6, characterized in that in step S2, said cultivation is carried out under anaerobic conditions; introducing mixed gas of nitrogen and carbon dioxide in the culture process to keep the system in an anaerobic state; the volume ratio of the nitrogen to the carbon dioxide in the mixed gas of the nitrogen and the carbon dioxide is 4:1, a step of; the culture is carried out at a temperature of 25-40 ℃; the culture time is 54 h-120h for a single time.
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