CN113955901B - Biological pretreatment method for thiabendazole production wastewater - Google Patents
Biological pretreatment method for thiabendazole production wastewater Download PDFInfo
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- CN113955901B CN113955901B CN202111274601.8A CN202111274601A CN113955901B CN 113955901 B CN113955901 B CN 113955901B CN 202111274601 A CN202111274601 A CN 202111274601A CN 113955901 B CN113955901 B CN 113955901B
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Abstract
The application relates to the technical field of wastewater treatment, and discloses a biological pretreatment method of thiabendazole production wastewater, which comprises the following steps: (1) Performing biotoxicity detection on the multi-strand thiabendazole production wastewater to distinguish high-toxicity wastewater from non-high-toxicity wastewater; (2) After advanced oxidation treatment is carried out on the high-toxicity wastewater, mixing is carried out on the non-high-toxicity wastewater to obtain mixed water; (3) The mixed water is fermented by using the leucinia CQ4-1 or the complex flora containing the leucinia CQ4-1. According to the application, after the high-grade oxidation treatment is carried out on the thiabendazole production wastewater, the fermentation treatment is carried out by adopting the leucinbacterium CQ4-1 or the compound strain containing the leucinbacterium CQ4-1, so that the toxicity of the wastewater can be reduced, the load of the wastewater after biological pretreatment on a subsequent biochemical treatment system is reduced, and the biochemical treatment efficiency is improved.
Description
Technical Field
The application relates to the technical field of wastewater treatment, in particular to a biological pretreatment method of thiabendazole production wastewater.
Background
With the rapid development of agriculture, the types and the dosage of pesticides are rapidly increased, and most pesticides used in China at the present stage belong to organic pesticides, and many pesticides have the characteristics of high toxicity, difficult decomposition and the like, so that pesticide wastewater becomes a great difficulty in the field of water treatment. The thiabendazole is named as terbutryn, thiabendazole and thiabendazole, has the inward-to-top conduction performance, but cannot conduct to a base, has long lasting period, has interactive resistance with benzimidazole bactericides, has inhibiting activity on ascomycetes, basidiomycetes and half-known bacteria, is used for preventing and controlling various crop fungal diseases and preventing and preserving fruits and vegetables, and is a high-efficiency, broad-spectrum and internationally universal bactericide. In the prior art, thiabendazole can be obtained by condensing thiazole derivatives serving as intermediates with aniline and derivatives thereof, and the wastewater contains bromine, ethanol, pyruvic acid, o-phenylenediamine, thiazole substances and the like.
At present, few reports are about the treatment method of thiabendazole production wastewater. The common treatment process for the wastewater in pesticide production is a 'advanced oxidation + biochemical' treatment process, namely, firstly, advanced oxidation treatment such as wet oxidation, fenton, iron-carbon micro-electrolysis and the like is carried out on the wastewater to detoxify and improve the biochemistry, and then, biochemical treatment is carried out by adopting an activated sludge method and the like (for example, patent CN 201410336460.1). When the thiabendazole production wastewater is treated by adopting the treatment process, the following problems exist: the thiabendazole production wastewater after the advanced oxidation treatment still has higher toxicity, and the existing activated sludge and other bacterial groups have poor tolerance to the wastewater, so that the biochemical treatment efficiency is low.
Disclosure of Invention
In order to solve the technical problems, the application provides a biological pretreatment method of thiabendazole production wastewater. According to the application, after the high-grade oxidation treatment is carried out on the thiabendazole production wastewater, the fermentation treatment is carried out by adopting the leucinbacterium CQ4-1 or the compound strain containing the leucinbacterium CQ4-1, so that the toxicity of the wastewater can be further reduced, the load of the wastewater after biological pretreatment on a subsequent biochemical treatment system is reduced, and the biochemical treatment efficiency is improved.
The specific technical scheme of the application is as follows:
a biological pretreatment method of thiabendazole production wastewater comprises the following steps:
(1) Performing biotoxicity detection on the multi-strand thiabendazole production wastewater to distinguish high-toxicity wastewater from non-high-toxicity wastewater;
(2) After advanced oxidation treatment is carried out on the high-toxicity wastewater, mixing is carried out on the non-high-toxicity wastewater to obtain mixed water;
(3) Fermenting the mixed water by adopting the leucinbacterium or the compound bacteria group containing the leucinbacterium; the leucinia is named CQ4-1 and is preserved in China general microbiological culture Collection center (CGMCC) No.23302 at the month 8 and 26 of 2021, and the microorganism classification is named leucinia Leucobacter sp.
The above-mentioned bacterium, identified, was identified as a new species of the genus Leucobacter and designated Leucobacter sp.CQ4-1. The thiabendazole production wastewater contains solvents such as ethanol, ethyl acetate and the like, thiazole derivative intermediates and aniline substances, has high toxicity inhibition on microorganisms, can generate larger toxicity and difficult biochemistry on the existing activated sludge and other bacterial groups after advanced oxidation treatment, and limits the biochemical treatment efficiency of the wastewater. The leubacter CQ4-1 has higher tolerance to the thiabendazole production wastewater, can effectively remove COD in the wastewater, has better treatment effect on the thiabendazole production wastewater, and can reduce the toxicity of the wastewater by adopting the leubacter CQ4-1 to ferment the high-grade oxidation-treated thiabendazole production wastewater, and the wastewater after biological pretreatment is introduced into a biochemical treatment system, so that the load of a subsequent biochemical treatment system can be reduced, the biochemical treatment efficiency is improved, and the treatment effect of the thiabendazole production wastewater is ensured.
In the existing advanced oxidation and biochemical treatment process, due to lack of source wastewater biotoxicity detection means, each single-strand wastewater is basically subjected to biochemical treatment after pretreatment and attenuation by advanced oxidation equipment, and wastewater toxicity is not distinguished from the source, so that advanced oxidation treatment is also performed on non-advanced wastewater without advanced oxidation, equipment resource waste and treatment cost are high, and secondary pollution is easy to generate in the advanced oxidation process. Aiming at the technical problems, the application adopts the source toxicity management and control technology to carry out biological toxicity detection on source wastewater, distinguishes non-high-toxicity wastewater which can be directly subjected to fermentation treatment and high-toxicity wastewater which can be subjected to fermentation treatment after being attenuated by advanced oxidation treatment, and can avoid blindly and completely carrying out advanced oxidation on all the wastewater, thereby saving the cost of advanced oxidation treatment, avoiding resource waste and reducing secondary pollution.
Preferably, in step (3), the complex bacterial population further comprises pseudomonas putida (Pseudomonas alloputida) and/or sphingobacterium polycephalum (Sphingobacterium multivorum).
The leucinbacterium CQ4-1 and the pseudomonas putida and the sphingobacterium polyrhachis have a synergistic effect, and after the leucinbacterium CQ4-1 and the sphingobacterium polyrhachis are compounded, the COD removal effect in the thiabendazole production wastewater can be improved.
Further, the content of the leucinia bacteria or mutants in the complex bacterial flora is 2×10 11 ～4×10 11 CFU/g, pseudomonas putida content of 2×10 11 ～4×10 11 CFU/g, content of Sphingobacterium polycephalum is 2×10 11 ～4×10 11 CFU/g。
Preferably, in step (1), the specific process of biotoxicity detection comprises the following steps:
(1.1) adding tryptone, yeast extract, ferric citrate and esculin into water, and uniformly mixing to prepare a culture medium;
(1.2) adding thiabendazole production wastewater into a culture medium to prepare a mixed system, wherein the volume fraction of the wastewater in the mixed system is 25-35%; inoculating lactobacillus plantarum into the mixed system according to the inoculum size of 1-3.4 w/v percent to prepare a culture system;
the lactobacillus plantarum is named as CR3 and is preserved in the China general microbiological culture Collection center of China Committee for culture Collection of microorganisms for 3 months and 15 days, the address is North Chen Xili No. 1 and 3 in the Korean area of Beijing, the preservation number is CGMCC No.22011, and the microorganism classification is named as lactobacillus plantarum Lactobacillus plantarum;
and (1.3) culturing the culture system, observing the color development condition, wherein if the color development is not black, the thiabendazole production wastewater is high-toxic wastewater, and if the color development is black, the thiabendazole production wastewater is non-high-toxic wastewater.
In the application, the biotoxicity detection of source wastewater adopts the method in a patent CN202110960186.5 (patent applied by the inventor before), lactobacillus plantarum CR3 is utilized, the toxicity of the wastewater is intuitively reflected through color development, and non-high-toxicity wastewater which can be directly subjected to fermentation treatment and high-toxicity wastewater which can be subjected to fermentation treatment after attenuation through advanced oxidation treatment are distinguished.
The lactobacillus plantarum CR3 is easy to culture, can secrete esculin hydrolase, and can decompose esculin into glucose and esculin, the esculin reacts with iron ions to generate black compounds, and the more the lactobacillus plantarum CR3 is, the darker the black is, so that the inhibition effect of wastewater on the lactobacillus plantarum CR3 can be intuitively reflected by observing the color depth. In addition, the lactobacillus plantarum CR3 has proper tolerance to the toxicity of the wastewater, can show the strength of the toxicity of the wastewater, and has obvious and stable color development.
According to experience, the wastewater concentration of 25-35% (i.e., the volume of the wastewater after dilution is 25-35% of the total volume) is taken as a critical point for determining that the toxicity degree of the wastewater is high, and the wastewater concentration is preferably 30%. Lactobacillus plantarum CR3 can distinguish high-toxic wastewater from non-high-toxic wastewater when the wastewater concentration is 25-35% under the condition that the inoculation amount is 1-3.4 w/v%, namely, the high-toxic wastewater does not appear black, and the non-high-toxic wastewater does not appear black when cultured under the condition that the wastewater concentration is 25-35%. Therefore, the lactobacillus plantarum CR3 can be applied to biological toxicity detection of source wastewater, and can judge whether the wastewater can be directly subjected to fermentation treatment according to the color development condition when the wastewater is cultured at the concentration of 25-35%.
In addition, when the esculin and the ferric citrate are added into the conventional lactobacillus culture medium to culture the lactobacillus plantarum CR3, the culture system cannot develop color, which indicates that the conventional lactobacillus culture medium cannot be used for detecting the biotoxicity of the source wastewater. Therefore, a culture medium formula is innovated in biotoxicity detection, and when the culture medium is used for culturing lactobacillus plantarum CR3, the culture system can develop color, so that the culture medium can be used for biotoxicity detection of source wastewater.
Further, in the step (1.1), the concentrations of tryptone, yeast extract, ferric citrate and esculin in the medium are 3.3 to 10g/L, 1.67 to 5g/L, 0.5 to 0.6g/L and 1 to 1.2g/L, respectively, more preferably 3.3g/L, 1.67g/L, 0.5g/L and 1g/L.
Too high or too low concentrations of the components in the culture medium can affect the detection of the biotoxicity of the source wastewater, and specifically: when the concentration is too low, the culture system cannot develop color, so that the toxicity of the wastewater cannot be reflected; when the concentration is too high, the nutrient content in the culture medium is too high, so that the influence of the nutrient content in the wastewater on the growth of the strain can be covered. Thus, when the concentrations of tryptone, yeast extract, ferric citrate and esculin are controlled in the ranges of 3.3 to 10g/L, 1.67 to 5g/L, 0.5 to 0.6g/L and 1 to 1.2g/L, respectively, the culture system is capable of developing color; further preferably 3.3g/L, 1.67g/L, 0.5g/L and 1g/L, at which the nutrient content in the medium is low, without masking the effect of the nutrient content in the wastewater on the growth of the strain.
Preferably, the specific process of step (3) comprises the following steps:
(3.1) adjusting the water quality of the mixed water to obtain wastewater to be treated;
and (3.2) inoculating the leuobacterium, the mutant or the complex bacterial colony into the wastewater to be treated in an inoculum size of 5-15 w/v%, and controlling the hydraulic retention time to be 3-4 d for fermentation treatment.
Further, in the step (3.2), in the fermentation treatment, when the treatment efficiency is lowered, the leucinbacterium or the mutant or the complex bacterial group is added, and ethanol is added.
Further, in the step (3.1), the specific process of water quality regulation comprises the following steps: KH was added to the mixed water 2 PO 4 And adjusting the pH to 6.8-7.2 to obtain the productTreating the wastewater.
Further, in step (3.1), the KH 2 PO 4 The mass volume ratio of the water to the mixed water is 0.3-0.7 g/1L.
Compared with the prior art, the application has the following advantages:
(1) Firstly, performing biotoxicity detection on source wastewater by using lactobacillus plantarum CR3 to distinguish high-toxic wastewater and non-high-toxic wastewater, and avoiding blindly performing advanced oxidation treatment on all wastewater, thereby reducing cost, avoiding resource waste and reducing secondary pollution;
(2) The leubacter CQ4-1 has higher tolerance to the thiabendazole production wastewater, can effectively remove COD therein, has synergistic effect with pseudomonas putida and Sphingobacterium polycephalum, and can further improve the treatment effect on COD in the thiabendazole production wastewater after being compounded;
(3) After advanced oxidation treatment, the fermentation treatment is carried out by adopting the leucinbacterium CQ4-1 or the compound strain containing the leucinbacterium CQ4-1, so that the toxicity of the thiabendazole production wastewater can be further reduced, and the load of a subsequent biochemical treatment system is reduced.
Drawings
FIG. 1 shows the effect of the Leucobacter CQ4-1 on the COD treatment of wastewater;
FIG. 2 shows the treatment effect of the Leucobacter CQ4-1 MFES process on the COD of wastewater;
FIG. 3 shows the treatment effect of complex flora on COD of wastewater;
FIG. 4 shows the treatment effect of the complex bacterial MFES process on the COD of wastewater.
Detailed Description
The application is further described below with reference to examples.
General examples
A biological pretreatment method of thiabendazole production wastewater comprises the following steps:
(1) Biotoxicity detection:
(1.1) adding tryptone, yeast extract, ferric citrate and esculin into water, uniformly mixing, and preparing a culture medium, wherein the concentration of the tryptone, the yeast extract, the ferric citrate and the esculin in the culture medium is 3.3-10 g/L, 1.67-5 g/L, 0.5-0.6 g/L and 1-1.2 g/L respectively, and more preferably 3.3g/L, 1.67g/L, 0.5g/L and 1g/L;
(1.2) adding thiabendazole production wastewater into a culture medium to prepare a mixed system, wherein the volume fraction of the wastewater in the mixed system is 25-35%; inoculating lactobacillus plantarum into the mixed system according to the inoculum size of 1-3.4 w/v percent to prepare a culture system;
and (1.3) culturing the culture system, observing the color development condition, wherein if the color development is not black, the thiabendazole production wastewater is high-toxic wastewater, and if the color development is black, the thiabendazole production wastewater is non-high-toxic wastewater.
(2) After advanced oxidation treatment is carried out on the high-toxicity wastewater, mixing is carried out on the non-high-toxicity wastewater to obtain mixed water;
(3) Fermentation treatment:
(3.1) adding KH to the mixed water 2 PO 4 The KH 2 PO 4 The mass volume ratio of the wastewater to the mixed water is 0.3-0.7 g to 1L, and the pH value is regulated to 6.8-7.2, so as to obtain wastewater to be treated;
(3.2) inoculating the leucinia bacteria, the mutant or the complex bacterial colony into the wastewater to be treated in an inoculum size of 5-15 w/v%, and controlling the hydraulic retention time to be 3-4 d for fermentation treatment; optionally, during fermentation treatment, when the treatment efficiency is reduced, the leucinbacterium or the mutant or the complex flora is dosed, and ethanol is dosed.
In steps (1) to (3), the microorganisms involved are as follows:
the lactobacillus plantarum is named as CR3 and is preserved in the China general microbiological culture Collection center of China Committee for culture Collection of microorganisms for 3 months and 15 days, the address is North Chen Xili No. 1 and 3 in the Korean area of Beijing, the preservation number is CGMCC No.22011, and the microorganism classification is named as lactobacillus plantarum Lactobacillus plantarum;
the Leucobacter is named CQ4-1, is preserved in China general microbiological culture Collection center (China Committee for culture Collection of microorganisms) on the 8 th month of 2021, has an address of Hospital No. 1 and No. 3 of North Chen West Lu in the Korean area of Beijing, has a preservation number of CGMCC No.23302, and has a microorganism classification of Leucobacter sp;
the mutant is obtained by carrying out mutagenesis, domestication, gene recombination or natural mutation on the leucinia;
the complex flora comprises the leucinia bacteria or the mutant, and also comprises pseudomonas putida and sphingobacterium polyrhachis, wherein the content of the leucinia bacteria or the mutant is 2 multiplied by 10 11 ～4×10 11 CFU/g, pseudomonas putida content of 2×10 11 ～4×10 11 CFU/g, content of Sphingobacterium polycephalum is 2×10 11 ～4×10 11 CFU/g。
Example 1: biotoxicity detection
The method comprises the steps of collecting a plurality of waste water streams of a thiabendazole production workshop, wherein the numbers of the waste water streams are #1 to #7, and carrying out biotoxicity detection on each waste water stream, and the specific process is as follows:
(1.1) adding tryptone, yeast extract, ferric citrate and esculin into water, uniformly mixing, and then adjusting pH to 6.2 to prepare a culture medium, wherein the concentrations of the tryptone, the yeast extract, the ferric citrate and the esculin in the culture medium are 3.3g/L, 1.67g/L, 0.5g/L and 1g/L respectively;
(1.2) adding thiabendazole production wastewater into a culture medium to prepare a mixed system, wherein the volume fraction of the wastewater in the mixed system is 30%; inoculating lactobacillus plantarum CR3 into the mixed system according to the inoculation amount of 1w/v percent to prepare a culture system; the lactobacillus plantarum CR3 is preserved in China general microbiological culture collection center (CGMCC) in the 3 rd month 15 of 2021, and the preservation number is CGMCC NO.22011, and the microorganism classification is named as lactobacillus plantarum Lactobacillus plantarum;
and (1.3) culturing the culture system, observing the color development condition, wherein if the color development is not black, the thiabendazole production wastewater is high-toxic wastewater, and if the color development is black, the thiabendazole production wastewater is non-high-toxic wastewater.
The biotoxicity detection results of wastewater #1 to #7 are shown in Table 1.
TABLE 1
Example 2: advanced oxidation treatment
The high-toxic wastewater identified in example 1 was subjected to advanced oxidation treatment and then mixed with the non-high-toxic wastewater identified in example 1 to obtain mixed water.
The water quality of the mixed water is detected as follows: COD 20000mg/L, TDS 2%, pH 9.
Example 3: strain screening for fermentation treatment
The wastewater culture medium is prepared according to the following method: KH was supplemented to the mixed water obtained in example 2 2 PO 4 ，KH 2 PO 4 The mass volume ratio of the wastewater to the mixed water is 0.5g to 1L, and the pH value is adjusted to 7.0, so as to obtain the wastewater culture medium.
LB medium was prepared according to the following recipe: yeast extract 5g/L, tryptone 10g/L, naCl g/L, ph=7.0. Sterilizing at 121deg.C for 30min.
The waste water culture medium is sub-packed in a 96-well plate, and strains of a strain library (containing tens of thousands of bacteria and fungi microorganisms separated from high-salt environments such as oceans, salt lakes, salt ores and chemical waste water) activated by the LB culture medium are inoculated into the waste water culture medium according to an inoculum size of 1w/v%, and are cultured for 3 days at 30 ℃. After the cultivation is finished, the strain OD in the 96-well plate is measured by an enzyme-labeled instrument 600 Value, OD 600 After repeated transfer of strains with the concentration of more than 0.5, selecting strains which can still grow stably as target strains.
Inoculating the target strain into 100mL of wastewater culture medium according to the inoculum size of 10w/v%, periodically detecting COD in the wastewater, and checking the treatment effect of the strain on the wastewater.
Results: the 4 strains are screened to have high-efficiency treatment effect, wherein the strain CQ4-1 has the highest treatment effect on the wastewater, the treatment effect is shown in figure 1, the COD of the wastewater can be reduced from 20000mg/L to 10233mg/L within 5 days, and the COD removal rate is about 51.8%.
Example 4: strain identification for fermentation treatment
The strain CQ4-1 is gram positive bacteria, the cells are rod-shaped and largeSmall length 0.8-1.8 μm and wide width 0.3-0.6 μm. Culturing for 3d at 30 ℃ on LB culture medium, wherein the bacterial colony is milky, round, convex on the surface, smooth and opaque in edge, and the size of the bacterial colony is 0.8-1.5 mm. The strain can grow in the range of 4-50 ℃ and the optimal temperature is 30-37 ℃; can grow in the pH range of 5.0-10.0, and the optimal pH is 7.0-8.0; can grow in the range of 0-6.5% NaCl, and the optimal salinity is 1-2%. Positive for oxidase, catalase and nitric acid reduction; indole can be produced. Acid phosphatase, alkaline phosphatase, arginine bihydrolase, cysteine aromatic amidase, esterase (C4), esterase (C8), gelatinase, alpha-glucosidase (starch hydrolysis), beta-glucosidase, leucine aromatic amidase positive, beta-galactosidase, lipase (C14), alpha-mannosidase, trypsin, urease, and valine aromatic amidase negative. Acetic acid, ethanol, adipic acid, L-arabinose, capric acid, citric acid, D-glucose, L-histidine, L-malic acid, D-sucrose, D-maltose, L-mannose, 3-hydroxybenzoic acid, 4-hydroxybenzoic acid, D-maltose, salicylic acid are used as carbon sources, and L-trehalose, glycogen, L-arabinose, D, L-lactic acid, L-rhamnose are not used as carbon sources. The main respiratory quinone is MK11, and contains a small amount of MK10; the main fatty acid is antais-C 15:0 、iso-C 16:0 、anteiso-C 17:0 The method comprises the steps of carrying out a first treatment on the surface of the The main polar lipid is PG and DPG; the cell wall amino acid component is 2,4-DBA, GABA, alanine, glutamic acid, glycine; the genome (G+C) content was 68.2mol%.
The strain CQ4-1 was most similar to Leucobacter margaritiformis JCM 17538 by comparison of the 16S rRNA gene in the EzBioCloud database, with a similarity of 96.92%. By constructing 16S rRNA phylogenetic tree (NJ), it was found that the strain CQ4-1 was clustered on one branch with Leucobacter genus and was relatively stable, and therefore, the strain CQ4-1 was likely classified in Leucobacter genus. The strain CQ4-1 is identified as a new species of Leucobacter, and is preserved in China general microbiological culture Collection center (CGMCC) with the preservation number of CGMCC NO.23302 in the year 8 and 26 of 2021.
Example 5: MFES process fermentation treatment of leucinbacterium CQ4-1Effect KH was supplemented to the mixed water obtained in example 2 2 PO 4 ，KH 2 PO 4 The mass volume ratio of the wastewater to the mixed water is 0.5 g/1L, the pH is regulated to 7.0, DO is controlled to 3.0mg/L, and the wastewater to be treated is obtained.
The MFES process is adopted to carry out continuous water inlet and outlet dynamic experiments, and the wastewater to be treated is fermented, and the specific process is as follows:
(3.1) inoculating the leucinia CQ4-1 into the wastewater to be treated in an inoculum size of 10w/v%, and controlling the hydraulic retention time to be 4d for fermentation treatment;
(3.2) in the operation process, when the treatment efficiency is reduced, re-adding the composite flora and a small amount of ethanol; the marks of the reduction of the treatment efficiency are as follows: the removal rate of COD is lower than 40 percent, or the system operation temperature is 5-10 ℃ lower than the normal treatment efficiency.
Results: as shown in FIG. 2, the average value of COD of inflow water is 20520mg/L, the hydraulic retention time is controlled to be 4 days, the average value of COD of outflow water after the treatment of the MFES process is 8144mg/L, and the COD removal rate is 60.3%.
The wastewater after fermentation treatment in the embodiment and the mixed water in the embodiment 2 are respectively introduced into an activated sludge treatment system for biochemical treatment, and COD removal rates after the biochemical treatment for 3 days are 61.8% and 46.6%, which shows that after advanced oxidation treatment, the fermentation treatment is carried out by adopting the leucinbacterium CQ4-1, so that the toxicity of the production wastewater of the thiabendazole can be further reduced, and the efficiency of the subsequent biochemical treatment is improved.
Example 6: flora construction for fermentation treatment
Compared with single strain, the compound flora forms a stable microecological system by co-metabolism or more sound degradation metabolism genes and utilizing functional complementation among strains, and can also effectively avoid intermediate product accumulation in degradation paths and have stronger adaptation to environment, thereby obviously improving the water treatment efficiency.
Activated CQ4-1 strains are mixed with pseudomonas putida (Pseudomonas alloputida), sphingosine bacillus (Sphingobacterium multivorum) and water bacillus cave (Aquabacter cavernae) in a volume ratio of 1:1, inoculated into 150mL wastewater, the initial total concentration of thalli is kept at OD600 = 0.5, and the COD degradation capability of the mixed strains on the wastewater is measured. In the same time, the ratio of the COD degradation rate of the mixed group and the COD degradation rate of the CQ4-1 single strain is recorded as R, and the synergy or antagonism among the strains executes the following judgment standard: r is less than or equal to 1, and the two strains are considered to have antagonism; r > 1, is considered synergistic. The antagonistic strains are removed from the bacterial colony structural design, and the strains with synergistic effect are selected. And (3) preparing strains according to the standard, and designing and developing the strains into specific flora. And the prepared special-effect flora is repeatedly transferred until the treatment effect reaches the maximum and is stable.
Results: the R value of the combination of the strain CQ4-1 and the pseudomonas putida is 1.3, and the two strains have a synergistic effect; the R value of the combination of the strain CQ4-1 and the sphingobacterium is 1.2, and the two strains have a synergistic effect; the R value of the combination of the strain CQ4-1 and the bacillus cave is 0.8, and the two strains have antagonism. Thus, it was constructed as a complex flora consisting of strain CQ4-1, pseudomonas putida and Sphingobacterium sp.
Example 7: effect of fermentation treatment of Complex microbial group KH was supplemented to the mixed water obtained in example 2 2 PO 4 ，KH 2 PO 4 The mass volume ratio of the wastewater to the mixed water is 0.5 g/1L, the pH is regulated to 7.0, DO is controlled to 3.0mg/L, and the wastewater to be treated is obtained.
The complex flora obtained in example 5 (wherein the content of Leucobacter CQ4-1, pseudomonas putida, sphingobacterium polycephalum was 4X 10, respectively) 11 CFU/g、2×10 11 CFU/g、2×10 11 CFU/g) was inoculated into the wastewater to be treated in an inoculum size of 10w/v%, fermentation was conducted for 4d, and the change in COD concentration in the wastewater medium was recorded.
Results: as shown in FIG. 3, the COD removal rate can reach 74.9% in 4d fermentation treatment by adopting the complex bacterial colony of the application.
Example 8: effect of MFES process fermentation treatment of complex flora KH was supplemented to the mixed water obtained in example 2 2 PO 4 ，KH 2 PO 4 The mass volume ratio of the water to the mixed water is 0.5g to 1L, the pH value is regulated to 7.0, and DO is controlled to be 3.0mg/L, thus obtainingTo obtain wastewater to be treated.
The MFES process is adopted to carry out continuous water inlet and outlet dynamic experiments, and the wastewater to be treated is fermented, and the specific process is as follows:
(3.1) mixing the complex bacterial groups (wherein the content of Leptobacter CQ4-1, pseudomonas putida, sphingobacterium polycephalum is 4×10, respectively) 11 CFU/g、2×10 11 CFU/g、2×10 11 CFU/g) is inoculated into the wastewater to be treated in an inoculum size of 10w/v%, and the hydraulic retention time is controlled to be 3d for fermentation treatment;
(3.2) in the operation process, when the treatment efficiency is reduced, re-adding the composite flora and a small amount of ethanol; the marks of the reduction of the treatment efficiency are as follows: the removal rate of COD is lower than 40 percent, or the system operation temperature is 5-10 ℃ lower than the normal treatment efficiency.
Results: as shown in FIG. 4, the average value of COD of the inlet water is 20675mg/L, the hydraulic retention time is controlled to be 3 days, the average value of COD of the outlet water after the treatment of the MFES process is 4159mg/L, and the COD removal rate is 78.7%.
The wastewater after fermentation treatment in the embodiment and the mixed water in the embodiment 2 are respectively introduced into an activated sludge treatment system for biochemical treatment, and COD removal rates after the biochemical treatment for 3 days are 74.0% and 46.6% respectively, which shows that after advanced oxidation treatment, the toxicity of the thiabendazole production wastewater can be further reduced and the efficiency of subsequent biochemical treatment can be improved by adopting the composite flora for fermentation treatment.
The raw materials and equipment used in the application are common raw materials and equipment in the field unless specified otherwise; the methods used in the present application are conventional in the art unless otherwise specified.
The foregoing description is only a preferred embodiment of the present application, and is not intended to limit the present application, and any simple modification, variation and equivalent transformation of the above embodiment according to the technical substance of the present application still fall within the scope of the technical solution of the present application.
Claims (10)
1. The biological pretreatment method of the thiabendazole production wastewater is characterized by comprising the following steps of:
(1) Performing biotoxicity detection on the multi-strand thiabendazole production wastewater to distinguish high-toxicity wastewater from non-high-toxicity wastewater;
(2) After advanced oxidation treatment is carried out on the high-toxicity wastewater, mixing is carried out on the non-high-toxicity wastewater to obtain mixed water;
(3) Fermenting the mixed water by adopting the leucinbacterium or the compound bacteria group containing the leucinbacterium; the Lithobacterium is named CQ4-1 and has been preserved in China general microbiological culture Collection center (CGMCC) No.23302, and the microorganism classification is named LithobacteriumLeucobacter sp.。
2. The method for biological pretreatment of thiabendazole production wastewater of claim 1, wherein in the step (3), the complex bacterial group further comprises pseudomonas putida and/or sphingobacterium polyvidans.
3. The method for biological pretreatment of thiabendazole production wastewater of claim 2, wherein the content of the leucinbacterium in the complex bacterial group is 2 x 10 11 ~4×10 11 CFU/g, pseudomonas putida content of 2×10 11 ~4×10 11 CFU/g, content of Sphingobacterium polycephalum is 2×10 11 ~4×10 11 CFU/g。
4. The biological pretreatment method of thiabendazole production wastewater of claim 1, wherein in the step (1), the specific process of biotoxicity detection comprises the following steps:
(1.1) adding tryptone, yeast extract, ferric citrate and esculin into water, and uniformly mixing to prepare a culture medium;
(1.2) adding thiabendazole production wastewater into a culture medium to prepare a mixed system, wherein the volume fraction of the wastewater in the mixed system is 25-35%; inoculating lactobacillus plantarum into the mixed system according to the inoculum size of 1-3.4 w/v%, and preparing a culture system;
the Lactobacillus plantarum is named CR3 and is alreadyThe microbial strain is preserved in China general microbiological culture Collection center (China Committee for culture Collection of microorganisms) for 3 months and 15 days in 2021, and has an address of 1 st national institute No. 3, 3 rd, and a preservation number of 22011 CGMCC, and is named as Lactobacillus plantarum by microorganism classificationLactobacillus plantarum；
And (1.3) culturing the culture system, observing the color development condition, wherein if the color development is not black, the thiabendazole production wastewater is high-toxic wastewater, and if the color development is black, the thiabendazole production wastewater is non-high-toxic wastewater.
5. The biological pretreatment method of thiabendazole production wastewater of claim 4, wherein in the step (1.1), concentrations of tryptone, yeast extract, ferric citrate and esculin in the culture medium are 3.3 to 10g/L, 1.67 to 5g/L, 0.5 to 0.6g/L and 1 to 1.2g/L, respectively.
6. The method for biological pretreatment of thiabendazole production wastewater of claim 5, wherein in the step (1.1), concentrations of tryptone, yeast extract, ferric citrate and esculin in the medium are 3.3g/L, 1.67g/L, 0.5g/L and 1g/L, respectively.
7. The biological pretreatment method of thiabendazole production wastewater of claim 1, wherein the specific process of the step (3) comprises the following steps:
(3.1) adjusting the water quality of the mixed water to obtain wastewater to be treated;
and (3.2) inoculating the leucinia or the compound flora into the wastewater to be treated according to the inoculum size of 5-15 w/v%, and controlling the hydraulic retention time to be 3-4 d for fermentation treatment.
8. The biological pretreatment method of thiabendazole production wastewater of claim 7, wherein in the step (3.2), the leucinbacterium or the complex bacterial group is added and ethanol is added when the treatment efficiency is lowered during the fermentation treatment.
9. The biological pretreatment method of thiabendazole production wastewater of claim 7, wherein in the step (3.1), the specific process of water quality regulation comprises the following steps: KH was added to the mixed water 2 PO 4 And adjusting the pH to 6.8-7.2 to obtain wastewater to be treated.
10. The biological pretreatment method of thiabendazole production wastewater of claim 9, wherein in the step (3.1), the KH 2 PO 4 The mass volume ratio of the water to the mixed water is 0.3-0.7 g/1L.
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