CN115354010A - Method for increasing content of low-toxicity reduction product in microorganism reduction chlorophenol system - Google Patents

Method for increasing content of low-toxicity reduction product in microorganism reduction chlorophenol system Download PDF

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CN115354010A
CN115354010A CN202211013507.1A CN202211013507A CN115354010A CN 115354010 A CN115354010 A CN 115354010A CN 202211013507 A CN202211013507 A CN 202211013507A CN 115354010 A CN115354010 A CN 115354010A
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chlorophenol
tourmaline
low
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CN115354010B (en
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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 microorganism-reduced chlorophenol system, which utilizes tourmaline to improve the content of the low-toxicity reduction products in the microorganism-reduced chlorophenol system, wherein the concentration of the tourmaline in the microorganism-reduced chlorophenol system is more than or equal to 0.8g/L. The method for improving the content of the low-toxicity reduction product in the microbial chlorophenol reduction system is characterized in that a proper amount of tourmaline is added into the microbial chlorophenol reduction system, so that the content of the low-toxicity reduction product in the microbial chlorophenol reduction system can be effectively improved, the overall toxicity of the reduction product can be further reduced, the rapid reduction of the chlorophenol can be realized, the overall degradation efficiency of a bioremediation chlorophenol system can be improved, the use value is high, the application prospect is good, and the method has a very important significance for effectively solving the threat of the chlorophenol to the environmental safety and the human health.

Description

Method for increasing content of low-toxicity reduction product in microorganism 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 microorganism reduction chlorophenol system.
Background
Chlorophenols are a class of persistent organic pollutants widely distributed in the nature, the toxicity of which is enhanced with the increase of the number of chlorine substituents, and the reduction of the toxicity of which is currently the mainstream and economical treatment process by reducing the number of chlorine substituents through microbial reductive dechlorination. For example, thiobacillus is a group of anaerobic microorganisms with extensive dechlorination activity, which can reduce polychlorinated phenol into low-chlorophenol with lower toxicity by using dechlorination respiration, thereby reducing the threat of chlorophenol pollutants to environmental safety and human health. Although the toxicity of chlorophenol can be reduced by microbial reduction, it was found during the actual research of the inventors of the present application that: in a system for reducing chlorophenol by using microorganisms, the microorganisms can preferentially attack ortho-position and meta-position chlorine substituents, and as a result, the chlorophenols with the chlorine substituents at meta-position and para-position in the reduction product are mainly obtained, namely, the lower chlorophenols with the chlorine substituents at meta-position and para-position have higher proportions in the reduction product compared with the ortho-position lower chlorophenols, and meanwhile, the lower chlorophenols with the chlorine substituents at meta-position and para-position have stronger toxicity compared with the ortho-position lower chlorophenols, so that the overall toxicity of the reduction product in the existing microorganism reduction chlorophenol system is still higher. In addition, the inventors of the present application have also found that: the existing microorganism reduction chlorophenol system can not effectively regulate and control the reduction path of the chlorophenol, namely, the prior attack of the microorganism on ortho-position chemical bonds is difficult to effectively avoid, so that the chlorophenol is difficult to effectively reduce into the chlorophenol with lower toxicity (such as ortho-chlorophenol), which is a root cause that the proportion/content of low-toxicity chlorophenol in the reduction product of the microorganism reduction chlorophenol system is still lower, and is also an important reason that the overall toxicity of the reduction product in the existing microorganism reduction chlorophenol system is still higher. So far, relevant reports on how to effectively regulate the reduction path of the chlorophenol and how to improve the ratio/content of the low-toxic chlorophenol in the reduction product are not seen. Therefore, how to effectively regulate and control the path of microorganism for reducing the chlorophenol and further improve the content of the low-toxicity chlorophenol in the reduction product has 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 of the prior art and provides a method for improving the content of low-toxicity reduction products in a microorganism chlorophenol reduction system.
In order to solve the technical problems, the invention adopts the following technical scheme.
A method for increasing the content of low-toxicity reduction products in a microorganism chlorophenol reduction system is characterized in that tourmaline is used for increasing the content of low-toxicity reduction products in the microorganism chlorophenol reduction system; the concentration of tourmaline in the microorganism reduced chlorophenol system is more than or equal to 0.8g/L.
The method for improving the content of the low-toxicity reduction product in the microbial reduction chlorophenol system is further improved, and the concentration of the 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 product in the microbial chlorophenol reduction system is further improved, and the concentration of tourmaline in the microbial chlorophenol reduction system is more than or equal to 1.6g/L.
The method for improving the content of the low-toxicity reduction product 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 particle size of the tourmaline is 400 nm-500 nm.
The method for improving the content of the low-toxicity reduction product in the microbial chlorophenol reduction system is further improved, wherein the inoculation amount of the microbes in the microbial chlorophenol reduction system is 1-5% of the total volume of the system; the microorganism is a disulfite strain DCB-2.
The method for improving the content of the low-toxicity reduction product in the microbial chlorophenol reduction system is further improved, and when the tourmaline is used for improving the content of the low-toxicity reduction product in the microbial chlorophenol reduction system, the method comprises the following steps:
s1, mixing tourmaline, microorganisms and chlorophenol with a culture medium to obtain a mixture;
and S2, culturing the microorganisms in the mixture obtained in the step S1, and finishing the reductive dechlorination treatment of the chlorophenol in the mixture.
In the method for increasing the content of the low-toxicity reduction product in the microorganism chlorophenol reduction system, the further improvement is that in the step S1, the initial concentration of the chlorophenol in the mixture is 100-200 μ 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 the low-toxicity reduction product in the microorganism chlorophenol reduction system, in a further improvement, in step S1, the microorganism further comprises the following treatment before use: inoculating the microorganism into culture medium to OD 600 The value remains relatively stable; the culture is carried out at the temperature of 25-40 ℃; the culture time is 3 to 7 days; the culture medium is an improved DMSZ 720 culture medium.
In the above method for increasing the content of low-toxic reduction products in the microbial chlorophenol reduction system, step S2 is further improved, wherein the culturing is performed under anaerobic conditions; introducing a mixed gas of nitrogen and carbon dioxide in the culture process to keep the system in an anaerobic state; the volume ratio of nitrogen to carbon dioxide in the mixed gas of nitrogen and carbon dioxide is 4:1; the culture is carried out at the temperature of 25-40 ℃; the culture time is 54-120 h in one time.
Compared with the prior art, the invention has the advantages that:
(1) Aiming at the defects that the existing microorganism-reduced chlorophenol system cannot regulate the reduction path of chlorophenol and the toxicity of the reduction product in the microorganism-reduced chlorophenol system is high and the like, the invention creatively provides a method for improving the content of the low-toxicity reduction product in the microorganism-reduced chlorophenol system, wherein tourmaline in the microorganism-reduced chlorophenol system is more than or equal to 0.8g/L by utilizing tourmaline. In the invention, a proper amount of tourmaline is added into a microorganism-reduced chlorophenol system, the tourmaline is taken as a functional material, and the charge distribution of the chlorophenol can be changed, specifically: under the action of tourmaline, the charges of atoms on the chlorophenol can be transferred to different degrees, at the moment, the charges distributed on the chemical bonds of the ortho-position chlorine substituent are less, the stability of the chlorophenol is higher, and the chlorophenol is more difficult to attack, so that in a system for reducing the chlorophenol by microorganisms, the chlorophenol can be reduced into ortho-position low-toxicity chlorophenol with lower toxicity due to the increase of the attack difficulty of the ortho-position chlorine substituent, the proportion of the low-toxicity chlorophenol in a reduction product is obviously improved, and the overall toxicity of the reduction product is favorably reduced; meanwhile, the tourmaline also has the characteristics of automatically adjusting the pH value of the solution to be neutral, releasing trace elements, generating from a power generation field and the like, so that a stable and suitable neutral environment can be provided for microorganisms under the action of the tourmaline, the activation process of the microorganisms is stimulated and accelerated by a generated weak electric field, the total time required by the dechlorination process is favorably reduced, the dechlorination efficiency is favorably improved, and the aim of efficiently reducing chlorophenol is favorably fulfilled. According to the method for improving the content of the low-toxicity reduction product in the microbial chlorophenol reduction system, by adding a proper amount of tourmaline into the microbial chlorophenol reduction system, the content of the low-toxicity reduction product in the microbial chlorophenol reduction system can be effectively improved, so that the overall toxicity of the low-toxicity reduction product can be further reduced, and the rapid reduction of chlorophenol can be realized, so that the overall degradation efficiency of bioremediation of the chlorophenol system can be improved, the use value is high, the application prospect is good, and the method has a very important significance in 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 generate the effect after being added due to good structural stability and long-acting property, so when being used as a functional material for bioremediation, the tourmaline is beneficial to reducing the restoration cost and does not cause secondary pollution to the environment.
Drawings
In order to make the objects, technical solutions and advantages of the embodiments of the present invention clearer, the technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the 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 microbial reduction system of 2, 3-dichlorophenol 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 microbial reduction system of 2, 3-dichlorophenol 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 microbial reduction system 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 microbial reduction 2, 3-dichlorophenol system in example 2 of the present invention.
FIG. 5 is a graph showing the effect of cyclic treatment of 2, 3-dichlorophenol when different tourmaline additive amounts are added to a microbial reduction system in example 2 of the present invention.
FIG. 6 is an SEM photograph of a system after dechlorination in example 1 of the present invention.
FIG. 7 is an FTIR chart before and after the tourmaline-promoted reduction of 2, 3-dichlorophen by thiobacillus in example 2 of the present invention.
FIG. 8 is an XRD pattern before and after the tourmaline-promoted thiobacillus thioparus reduction 2, 3-dichlorophen in example 2 of the present invention.
FIG. 9 is a schematic diagram illustrating the concept of increasing the 2-chlorophenol content in a microbial reduction system of 2, 3-dichlorophen using tourmaline according to the present invention.
Detailed Description
The invention is further described below with reference to the drawings and specific preferred embodiments of the description, without thereby limiting the scope of protection of the invention.
The materials and instruments used in the following examples are 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
Make up of Concentration of Make up of Concentration of
Sodium chloride 1.0595g/L Microelement SL9 0.1mL/L
Magnesium chloride 0.5298g/L Se-Wo solution 0.2mL/L
Potassium dihydrogen phosphate 0.2119g/L Wolin vitamins 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 extract 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 SL9 solution needs to be purged with nitrogen to ensure anaerobic conditions and filter sterilized before use.
In Table 1, the composition of the Se-Wo solution: 3mg/L of sodium selenite pentahydrate, 4mg/L of sodium tungstate monohydrate and 500mg/L of sodium hydroxide. The Se-Wo solution requires nitrogen to be sparged to ensure anaerobic conditions and is filter sterilized prior to 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 nicotinic acid, 50mg/L pantothenic acid, 50mg/L vitamin B12, 50mg/L para-aminobenzoic acid, 50mg/L zincthioic acid. The Wolin vitamin solution requires filter sterilization prior to use.
Example 1:
a method for improving the content of low-toxicity reduction products (2-chlorophenol) in a microbial chlorophenol reduction system, in particular to a method for improving the content of low-toxicity reduction products (2-chlorophenol) in a microbial chlorophenol reduction system by using tourmaline, which comprises the following steps:
s1, adding tourmaline (purchased from markets) with the purity of 99% and the average particle size of 430nm into 100mL of improved DMSZ 720 culture medium according to the addition amounts of 0g/L, 1.0g/L, 2.5g/L, 5.0g/L and 8.0g/L, respectively inoculating deintourous acid strain DCB-2 according to the inoculation amount of 2% of the volume of the culture medium, respectively adding 2, 3-dichlorophenol, and controlling the concentration of the 2, 3-dichlorophenol in each system to be 200 mu M to obtain a mixture.
And S2, placing the mixture obtained in the step S1 in a constant-temperature incubator at 35 ℃, and culturing the microorganisms in the mixture for 5 days under anaerobic conditions, wherein a mixed gas of nitrogen and carbon dioxide (the volume ratio of nitrogen to carbon dioxide is 4.
In this example, the desulfur strain DCB-2 used further includes the following treatments before inoculation: inoculation of the Desulfite Strain DCB-2 to modified DActivation was carried out in SMZ 720 medium at 35 ℃ in a constant temperature incubator for 5 days, during which the OD was periodically measured 600 Value up to OD 600 The values remained relatively stable.
The concentrations of 2, 3-dichlorophenol and its dechlorinated products (2-chlorophenol, 3-chlorophenol) were measured by high performance liquid chromatography, and the results are shown in FIGS. 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 microbial reduction system of 2, 3-dichlorophenol in example 1 of the present invention.
TABLE 2 influence of different tourmaline addition amounts on the content of 2-chlorophenol in the reduction system under different treatment time conditions
Figure BDA0003811834590000051
As can be seen from FIG. 1 and Table 2, the proportion of 2-chlorophenol increases with the addition of tourmaline within the same treatment time, wherein when the addition of tourmaline is more than or equal to 2.5g/L, the proportion of 2-chlorophenol is significantly increased and is higher than that of other groups, which shows that the proportion of 2-chlorophenol in the reduction product can be significantly increased by adding a proper amount of tourmaline; meanwhile, as can be seen from the results in fig. 1 and table 2, under the condition of relatively low microbial inoculum size, the proportion of 2-chlorophenol in the reduction product is increased by increasing the addition amount of tourmaline, 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 microbial reduction system of 2, 3-dichlorophenol in example 1 of the present invention.
TABLE 3 influence of different tourmaline addition amounts on the content of 3-chlorophenol in the reduction system under different treatment time conditions
Figure BDA0003811834590000052
Figure BDA0003811834590000061
As can be seen from FIG. 2 and Table 3, the proportion of 3-chlorophenol in the reduced product is contrary to the results of 2-chlorophenol, and the proportion of 3-chlorophenol in the reduced product decreases with the increase of tourmaline addition in the same time period, which corresponds to the fact that the total amount of the reduced product is conserved. Meanwhile, the toxicity of the monochlorophenol is as follows in sequence: the 4-chlorophenol is more than 3-chlorophenol is more than 2-chlorophenol, which further proves that the method can improve the content of the low-toxicity reduction product, and is favorable for reducing the overall toxicity of the reduction product by improving the proportion 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 microbial reduction system in example 1 of the present invention. In FIG. 3, the blank control is the case where tourmaline and the desulfurated bacterial strain DCB-2 are not added, and other conditions are the same; the tourmaline is only added in contrast, and other conditions are the same; DCB-2 control was the addition of only the disulfite strain DCB-2, with the other conditions being the same. As can be seen from FIG. 3, after tourmaline is added, the reduction of 2, 3-dichlorophen by the thiobacillus thiofide can be accelerated, particularly, when the addition amount of the tourmaline is more than or equal to 2.5g/L, the thiobacillus thiofide can complete the reduction of the 2, 3-dichlorophen more rapidly, and the time for completely reducing the 2, 3-dichlorophen is reduced from 96h to 72h, namely, the reduction dechlorination efficiency of the 2, 3-dichlorophen can be greatly improved; meanwhile, the addition of the tourmaline can shorten the time required by activating the thiobacillus thiofidus from 36h to 18h, which is favorable for greatly shortening the time required by completely reducing the 2, 3-dichlorophen and further improving the reduction dechlorination efficiency of the 2, 3-dichlorophen.
From the above results shown in fig. 1-3, it can be seen that the ratio of low-toxicity 2-CP in the reductive dechlorination product is only about 15% when the concentration of tourmaline is less than 2.5g/L, and the ratio is increased to more than 20% when the concentration of tourmaline exceeds 2.5g/L, which means that adding a proper amount of tourmaline can provide a suitable and stable living environment for the thiosulfite removing bacteria, and can affect the charge distribution of 2, 3-dichlorophen, stabilize the ortho-chemical bonds of the pollutant molecules, further increase the ratio of 2-chlorophenol, reduce the overall toxicity of the reduction product, and at the same time, accelerate the activation process of the bacteria, reduce the total time required for dechlorination, and improve the dechlorination efficiency.
Example 2
A method for improving the content of low-toxicity reduction products (2-chlorophenol) in a microbial chlorophenol reduction system, in particular to a method for improving the content of low-toxicity reduction products (2-chlorophenol) in a microbial chlorophenol reduction system by using tourmaline, which comprises the following steps:
s1, tourmaline (purchased from markets) with the purity of 99% and the average particle size of 430nm is added into 100mL of improved DMSZ 720 culture medium according to the addition amounts of 0g/L, 0.5g/L, 1.0g/L and 1.5g/L, the domesticated sulfolobus desulfurizates DCB-2 in the embodiment 1 are respectively inoculated according to the inoculation amount of 4% of the volume of the culture medium, 2, 3-dichlorophenol is respectively added, and the concentration of the 2, 3-dichlorophenol in each system is controlled to be 100 mu M, so as to obtain a mixture.
And S2, placing the mixture obtained in the step S1 in a constant-temperature incubator at 35 ℃, and culturing the microorganisms in the mixture for 96-120 h under anaerobic conditions, wherein mixed gas of nitrogen and carbon dioxide (the volume ratio of nitrogen to carbon dioxide is 4.
S3, when all of the 2,3-dichlorophenol in the bacteria-containing system was consumed, 2,3-dichlorophenol was newly added to the system to restore the concentration to 100. Mu.M, and the method in step S2 was repeated for 3 cycles in total.
The concentrations of 2, 3-dichlorophenol and its dechlorinated product (2-chlorophenol) were measured by high performance liquid chromatography, and the results are shown in FIGS. 4 and 5.
FIG. 4 is a graph showing the effect of different tourmaline addition amounts on the content of 2-chlorophenol in a microbial reduction 2, 3-dichlorophenol system in example 2 of the present invention.
TABLE 4 influence of different tourmaline addition amounts on the 2-chlorophenol content in the reduction system under different treatment time conditions
Figure BDA0003811834590000071
As can be seen from FIG. 4 and Table 4, when the tourmaline is added in an amount of 1.0g/L and 1.5g/L in each cycle, the proportion of 2-chlorophenol in the system is always higher than that in the other two groups, and the proportion of 2-chlorophenol is gradually increased with the increase of the cycle number, and the above results show that: when the addition amount of the tourmaline is low, microorganisms can be promoted to reduce chlorophenol with low concentration, and the capability of improving the content of low-toxicity reduction products is shown.
FIG. 5 is a graph showing the effect of cyclic treatment of 2, 3-dichlorophenol when different tourmaline additive amounts are added to a microbial reduction system in example 2 of the present invention. As can be seen from FIG. 5, when the addition amount of tourmaline is 1.0 and 1.5g/L, the thiobacillus thioparus can completely reduce 2, 3-dichlorophen within 96 h; when the content of tourmaline is 0 and 0.5g/L, the time required for complete reduction of 2, 3-dichlorophenol increases because the stimulation activation of microorganisms is weak by low concentration of tourmaline when the content of microorganisms in the system is high, thus increasing the time required for complete reduction. Meanwhile, as can be seen from the results in fig. 5, tourmaline in the reduction system exhibits very excellent stability, and is capable of continuously promoting the reduction of chlorophenol by microorganisms and continuously reducing more chlorophenol into 2-chlorophenol with lower toxicity.
From the results shown in fig. 4-5, it can be seen that the addition of a proper amount of tourmaline can improve the proportion of low-toxic 2-chlorophenol, and the improvement effect is more obvious in continuous pollution, and the proportion is finally improved to more than 30%, which further verifies that a proper amount of tourmaline can change the charge distribution of 2, 3-dichlorophenol, and can improve the stability of ortho-position chemical bonds and the attack difficulty, thereby being beneficial to improving the proportion of low-toxic chlorophenol (2-chlorophenol) in the reductive dechlorination product and reducing the overall biotoxicity.
FIG. 6 is an SEM photograph of a system after dechlorination in example 1 of the present invention. As can be seen from fig. 6, tourmaline and the desulfurated bacteria strain DCB-2 can still keep the original state after the reduction dechlorination is completed together, which shows that the tourmaline and the desulfurated bacteria have good compatibility.
FIG. 7 is an FTIR chart before and after the tourmaline-promoted reduction of 2, 3-dichlorophen by thiobacillus in example 2 of the present invention.
FIG. 8 is an XRD pattern before and after reduction of 2, 3-dichlorophenol by tourmaline-promoted thiosulfite bacteria in example 2 of the present invention.
As can be seen from figures 7 and 8, after three times of circular treatment, the characteristic peak and the absorption peak of the tourmaline are not obviously changed, which shows that the tourmaline has good stability and long-term effect in the process of reductive dechlorination, can be repeatedly used and is beneficial to realizing the treatment of continuous pollution.
FIG. 9 is a schematic diagram illustrating the concept of increasing the 2-chlorophenol content in a microbial reduction system of 2, 3-dichlorophen using tourmaline according to the present invention. As can be seen from fig. 9, the charge distribution of 2, 3-dichlorophenol can be changed by adding a proper amount of tourmaline to the microbial reduction system of 2, 3-dichlorophenol and using the tourmaline as a functional material, specifically: under the action of tourmaline, the charges of all atoms on the 2, 3-dichlorophen can be transferred to different degrees, and at the moment, the charges distributed on the chemical bonds of the ortho-position chlorine substituent are less, so that the stability of the system is higher, and the system is more difficult to attack, therefore, in a system for reducing the 2, 3-dichlorophen by microorganisms, because the attack difficulty of the ortho-position chlorine substituent is increased, the system reduces the 2, 3-dichlorophen into ortho-position low-toxicity chlorophenol (2-chlorophenol) with lower toxicity, the proportion of the low-toxicity chlorophenol in the reduced product is obviously improved, and the overall toxicity of the reduced product is favorably reduced.
According to the results, the invention adds a proper amount of tourmaline into a microorganism-reduced chlorophenol system, takes the tourmaline as a functional material, and can change the charge distribution of the chlorophenol, and specifically: under the action of tourmaline, the charges of atoms on the chlorophenols can be transferred to different degrees, and at the moment, the charges distributed on the chemical bonds of the ortho-position chlorine substituent are less, the stability of the compounds is higher, and the compounds are more difficult to attack, so that in a system for reducing the chlorophenols by microorganisms, the chlorophenols are reduced into ortho-position low-toxicity chlorophenols with lower toxicity by the system due to the increase of the attack difficulty of the ortho-position chlorine substituent, the proportion of the low-toxicity chlorophenols in the reduction products is obviously improved, and the overall toxicity of the reduction products is favorably reduced; meanwhile, tourmaline also has the characteristics of automatically adjusting the pH value of the solution to be neutral, releasing trace elements, generating from a power generation field and the like, so that a stable and suitable neutral environment can be provided for microorganisms under the action of the tourmaline, the activation process of the microorganisms is stimulated and accelerated by a generated weak electric field, the total time required by dechlorination is favorably reduced, the dechlorination efficiency is improved, and the aim of efficiently reducing chlorophenol is favorably fulfilled. According to the method for improving the content of the low-toxicity reduction product in the microbial chlorophenol reduction system, the proper amount of tourmaline is added into the microbial chlorophenol reduction system, so that the content of the low-toxicity reduction product in the microbial chlorophenol reduction system can be effectively improved, the overall toxicity of the low-toxicity reduction product can be further reduced, the rapid reduction of the chlorophenol can be realized, the overall degradation efficiency of a bioremediation chlorophenol system can be improved, the use value is high, the application prospect is good, and the method has a very important significance for effectively solving the threat of chlorophenol pollutants to environmental safety and human health.
The above examples are merely 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 idea of the invention belong to the protection scope of the invention. It should be noted that modifications and embellishments within the scope of the invention may be made by those skilled in the art without departing from the principle of the invention, and such modifications and embellishments should also be considered as within the scope of the invention.

Claims (10)

1. A method for improving the content of low-toxicity reduction products in a microorganism-reduced chlorophenol system is characterized in that tourmaline is utilized to improve the content of the low-toxicity reduction products in the microorganism-reduced chlorophenol system; the concentration of tourmaline in the microorganism reduced chlorophenol system is more than or equal to 0.8g/L.
2. The method for increasing the content of low-toxicity reduction products in a microbial reduced chlorophenol system according to claim 1, wherein the concentration of tourmaline in the microbial reduced chlorophenol system is not less than 1.2g/L.
3. The method for increasing the content of low-toxic reduction products in a microbial reduced chlorophenol system according to claim 2, wherein the concentration of tourmaline in the microbial reduced chlorophenol system is not less than 1.6g/L.
4. The method for increasing the content of low-toxicity reduction products in a microbial reduced chlorophenol system according to claim 3, wherein the concentration of tourmaline in the microbial reduced chlorophenol system is not less than 2.2g/L.
5. The method for increasing the content of low-toxicity reduction products in the microbial reduced chlorophenol system according to claim 4, wherein the concentration of tourmaline in the microbial reduced chlorophenol system is less than or equal to 8.0g/L; the purity of the tourmaline is more than 99 percent; the average particle size of the tourmaline is 400 nm-500 nm.
6. The method for increasing the content of low-toxicity reduction products in the microbial chlorophenol reduction system according to claim 5, wherein the inoculation amount of the microorganisms in the microbial chlorophenol reduction system is 1% -5% of the total volume of the system; the microorganism is a disulfite strain DCB-2.
7. The method for increasing the content of the low-toxicity reduction products in the microbial chlorophenol reducing system according to any one of claims 1 to 6, wherein when tourmaline is used for increasing the content of the low-toxicity reduction products in the microbial chlorophenol reducing system, the method comprises the following steps:
s1, mixing tourmaline, microorganisms, chlorophenols and a culture medium to obtain a mixture;
and S2, culturing the microorganisms in the mixture obtained in the step S1, and finishing the reductive dechlorination treatment of the chlorophenol in the mixture.
8. The method for increasing the content of low-toxicity reduction products in a microbial chlorophenol reduction system according to claim 7, wherein in step S1, the initial concentration of chlorophenol in the mixture is 100 μ M to 200 μ M; the chlorophenol is 2, 3-dichlorophenol; the culture medium is an improved DMSZ 720 culture medium.
9. The improvement of claim 8The method for reducing the content of low-toxicity reduction products in chlorophenol system by microorganisms is characterized in that in step S1, the microorganisms further comprise the following treatment before use: inoculating the microorganism into culture medium to OD 600 The value remains relatively stable; the culture is carried out at a temperature of 25-40 ℃; the culture time is 3 to 7 days; the culture medium is an improved DMSZ 720 culture medium.
10. The method for increasing the content of low-toxicity reduction products in a microbial chlorophenol reduction system according to claim 9, wherein in step S2, the culturing 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 nitrogen to carbon dioxide in the mixed gas of nitrogen and carbon dioxide is 4:1; the culture is carried out at a temperature of 25-40 ℃; the culture time is 54-120 h for one time.
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