A microbial composite material and method for removing pollutants from tail water

Abstract

The invention belongs to the field of sewage treatment, and specifically relates to a microbial composite material comprising a fixed carrier, algae, a composite bacterial agent and a composite enzyme; the algae, the composite bacterial agent and the composite enzyme are loaded on the fixed carrier, and the algae are loaded on the outermost layer; the fixed carrier is one or more combinations of composite activated carbon, graphite, coke, biochar, modified activated carbon, porous alumina and porous ceramics; the algae is one or more combinations of chlorella, spirulina, scenedesmus, diatoms, fibrous algae, cerulean algae and phyllostachys; the microbial composite material of the invention can oxidatively remove nutrients, some estrogens, phenols, amines, aldehydes, benzenes and the like in tail water, and remove emerging pollutants in tail water; the invention also proposes a method for removing pollutants in tail water by using a microbial composite material, wherein the microbial composite material is immersed in tail water to be treated, the treatment is carried out under light and aeration conditions, and the air-water volume ratio is maintained at (0.5-1.5):1.

Description

Technical Field

[0001] The invention belongs to the technical field of sewage treatment, and in particular relates to a microbial composite material and a method for removing pollutants in tail water thereof. Background Art

[0002] The main indicators of urban sewage purification include BOD5 (biochemical oxygen demand in 5 days), COD (chemical oxygen demand), ammonia nitrogen, phosphorus and suspended solids.

[0003] Emerging pollutants such as personal care products, drugs, pesticides and environmental hormones produced by industry, animal husbandry and residents' lives in tailwaters exist for a long time in water bodies, which may cause harm to the ecological environment (aquatic organisms and humans) such as chronic poisoning, gene induction or endocrine disruption, and the conventional treatment technology of existing sewage treatment plants is not ideal for the removal of new pollutants. Therefore, it is necessary to further develop high-efficiency and low-cost emerging pollutant removal products and process technologies suitable for urban sewage to better treat urban sewage.

[0004] Therefore, it is necessary to provide an improved technical solution to address the above-mentioned deficiencies in the prior art. Summary of the invention

[0005] The purpose of the present invention is to overcome the shortcomings of the prior art and provide a microbial composite material and a method for removing pollutants in tail water. By adopting an algae-bacteria-enzyme combination and loading it with a fixed carrier, it can efficiently degrade emerging pollutants such as endocrine disruptors and antibiotics in the water environment, and can also have a certain degree of degradation for traditional pollutants.

[0006] In order to achieve the above object, the present invention provides the following technical solutions:

[0007] A microbial composite material comprises a fixed carrier, algae, a composite bacterial agent and a composite enzyme; the algae, the composite bacterial agent and the composite enzyme are loaded on the fixed carrier, and the algae is loaded on the outermost layer;

[0008] The fixed carrier is one or more combinations of composite activated carbon, graphite, coke, biochar, modified activated carbon, porous alumina, and porous ceramics;

[0009] The algae is one or more combinations of Chlorella, Spirulina, Scenedesmus, Diatom, Fibrophyte, Lunaphalium, and Plectranthus;

[0010] The composite bacterial agent is a combination of one or more of Achromobacter, Ochrobacterium, ammonia oxidizing bacteria, Microbacterium, Gordonia, Sphingobacterium, Bacillus and Pseudomonas;

[0011] The complex enzyme is one or more combinations of biological sludge enzyme, lipase, oxidoreductase, dehydrogenase, laccase, cellulase, peroxidase and amylase.

[0012] Furthermore, the weight ratio of the fixed carrier, algae, composite bacterial agent, and composite enzyme is (8-10):(0.4-0.7):(16-21):(6-11); wherein the interference of the composite enzyme on the composite bacterial agent is reduced by controlling the addition ratio of the composite enzyme and the composite bacterial agent, so that the two can achieve a good synergistic effect.

[0013] Furthermore, the composite activated carbon is a composite of activated carbon and a nutrient matrix; the activated carbon is a spherical honeycomb activated carbon, and the pore size of the spherical honeycomb activated carbon is 50nm-200nm; by adopting spherical honeycomb activated carbon, the composite bacterial agent and composite enzyme can be better loaded, which can improve the degradation effect of emerging pollutants to a certain extent.

[0014] The nutrient matrix is ​​one of broth culture medium, starch agar culture medium, starch culture medium, beef extract peptone culture medium, peptone water culture medium and oil culture medium.

[0015] Furthermore, the nutrient matrix is ​​a peptone water culture medium; when compounding activated carbon, the following steps are included: after stirring the peptone water culture medium evenly, adding activated carbon, stirring evenly, after standing for 1-3 hours, taking it out, drying it in the shade, and obtaining compound activated carbon.

[0016] Furthermore, the algae is a mixture of Scenedesmus, Chlorella and Spirulina, and the mass ratio / mass fraction of the Scenedesmus, Chlorella and Spirulina is (2-3):(1-2):(1-2); the present invention selects Chlorella and Spirulina to cooperate with each other, which can synergistically treat the nutrient elements in the tail water, including but not limited to protein, sugar, fat, alkaloids, ammonia nitrogen, nitrate, phosphate, etc.; and then the organic matter in the tail water is decomposed by Scenedesmus, thereby reducing the organic pollutants in the tail water; and Scenedesmus can also synergize with bacteria to provide oxygen and some nutrients for the growth of bacteria, making it easier for bacteria to survive, thereby enhancing the degradation of pollutants in the tail water.

[0017] Furthermore, the composite bacterial agent is a mixture of Achromobacter, Sphingobacterium, Bacillus and Pseudomonas, and the ratio of Achromobacter, Sphingobacterium, Bacillus and Pseudomonas is (6-9):(4-6):(8-16):(6-12);

[0018] The present invention can synergistically improve the degradation efficiency of antibiotics in tail water through the mutual cooperation of colorless bacteria, sphingobacterium, bacillus and pseudomonas, and can all participate in the decomposition of antibiotics such as sulfonamides, tetracyclines, fluoroquinolones, macrolides, β-lactams and polypeptides in the tail water, and can also decompose endocrine disruptors in the tail water, such as estrogen, ethinyl estradiol, etc., so as to degrade most of the antibiotics and endocrine disruptors in the tail water, thereby improving the quality of the tail water; at the same time, because the invented microbial composite material is combined with algae, the algae can enrich the pollutants in the tail water and supply oxygen, which can make these bacteria survive more easily, thereby enhancing the degradation of emerging pollutants in the tail water.

[0019] Furthermore, the colorless bacteria are described in Colorless Bacillus JL9 and Denitrifying Colorless Bacillus PR1; the sphingobacterium is a mixture of Sphingobacterium and Sphingomonas; the Bacillus is Bacillus cereus J2 and Bacillus licheniformis DC-01; and the Pseudomonas is Pseudomonas CE22 and Pseudomonas CE21.

[0020] Furthermore, the complex enzyme is a mixture of biological sludge enzyme, lipase and peroxidase, and the mass ratio of the biological sludge enzyme, lipase and peroxidase is 1:(1-3):(2-3);

[0021] The present invention adopts a mixture of biological sludge enzyme, lipase and peroxidase, which can not only remove pollutants such as COD, BOD, ammonia nitrogen in the tail water, but also oxidatively remove nutrients, some estrogens, phenols, amines, aldehydes, benzenes, etc. in the tail water, thereby further removing emerging pollutants in the tail water.

[0022] The method for preparing the microbial composite material comprises the following steps:

[0023] S1. Immerse the fixed carrier in peptone water culture medium, then add the complex enzyme, stir evenly, let stand for 1h-2h, filter, and dry in the shade to obtain the fixed carrier preliminarily loaded with the complex enzyme;

[0024] S2, adding the composite enzyme and the composite bacterial agent into the peptone water culture medium, stirring evenly, adding the fixed carrier preliminarily loaded with the composite enzyme and the chitosan solution, ultrasonicating for 5min-20min, and then standing for 1h-2h, filtering, and drying in the shade to obtain the fixed carrier loaded with the composite bacterial agent and the composite enzyme;

[0025] S3. Add the algae into the peptone water culture medium, culture for 1d-2d, and then inoculate onto the fixed carrier treated in step S2 after screening, culture for 12-24h, remove the culture medium, dry in the shade, and store at low temperature to obtain a microbial composite material.

[0026] Furthermore, in step S3, the index for screening after culturing the algae is to culture the algae to the budding stage to facilitate the subsequent growth of the algae on the fixed carrier.

[0027] The present invention loads the composite enzyme on a fixed carrier first, then loads the composite enzyme and the composite bacterial agent on the fixed carrier to form a composite layer, and finally inoculates algae on the composite layer to form a composite fixed carrier. On the one hand, the environmental stress resistance of the microbial material can be improved; on the other hand, during water treatment, the pollutants can be first enriched and degraded by the algae to form a primary treatment, and at the same time, the enriched pollutants are treated by the composite enzyme and the composite bacterial agent to form a secondary treatment. In this process, under the action of the composite bacterial agent, antibiotics such as sulfonamides, tetracyclines, fluoroquinolones, macrolides, beta-lactams and polypeptides, as well as endocrine disruptors such as estrogen and ethinyl estradiol can be decomposed, and due to the decomposition of traditional pollutants by the composite enzyme and algae, the interference with the composite bacterial agent is reduced to a certain extent, and it is also beneficial to the activity of the composite bacterial agent; finally, after a long time, the traditional organic pollutants in the water environment are treated again by the composite enzyme and the fixed carrier inside the composite layer to improve the treatment effect.

[0028] The present invention also provides a method for removing pollutants from tail water using a microbial composite material, using the aforementioned microbial composite material, comprising the following steps:

[0029] The microbial composite material is immersed in the tail water to be treated, and 4-20g is added per liter of tail water; the microbial composite material is treated under light and aeration conditions, and the air-water volume ratio is maintained at (0.5-1.5):1; the water-air ratio during aeration is controlled, on the one hand, to provide a certain amount of oxygen to enable the microbial material to survive better; on the other hand, the disturbance to the microbial composite material is reduced.

[0030] Furthermore, during aeration, the air-water volume ratio is 0.6:1.

[0031] The beneficial effects of the present invention are:

[0032] The present invention adopts an algae-bacteria-enzyme combination and uses a fixed carrier load to, when treating tail water, on the one hand, enrich pollutants and microorganisms in water and degrade them, and then cooperate with composite enzymes and composite bacterial agents to efficiently degrade emerging pollutants such as endocrine disruptors and antibiotics in the water environment; on the other hand, through the fixed carrier load, the stress resistance of algae, composite bacterial agents and composite enzymes is improved, and the degradation efficiency of emerging pollutants can be synergistically improved. BRIEF DESCRIPTION OF THE DRAWINGS

[0033] Figure 1 The following are test results of the embodiments of the present invention.

[0034] Figure 2 These are the test results of comparative examples 1-6 of the present invention.

[0035] Figure 3 These are the test results of Comparative Examples 7-13 of the present invention. DETAILED DESCRIPTION

[0036] The technical solutions in the embodiments of the present invention are described clearly and completely below. Obviously, the described embodiments are only part of the embodiments of the present invention, rather than all the embodiments. Based on the embodiments of the present invention, all other embodiments obtained by ordinary technicians in this field belong to the scope of protection of the present invention.

[0037] A microbial composite material comprises a fixed carrier, algae, a composite bacterial agent and a composite enzyme; the algae, the composite bacterial agent and the composite enzyme are loaded on the fixed carrier, and the algae is loaded on the outermost layer;

[0038] The fixed carrier is one or more combinations of composite activated carbon, graphite, coke, biochar, modified activated carbon, porous alumina, and porous ceramics;

[0039] The algae is one or more combinations of Chlorella, Spirulina, Scenedesmus, Diatom, Fibrophyte, Lunaphalium, and Plectranthus;

[0040] The composite bacterial agent is a combination of one or more of Achromobacter, Ochrobacterium, ammonia oxidizing bacteria, Microbacterium, Gordonia, Sphingobacterium, Bacillus and Pseudomonas;

[0041] The complex enzyme is one or more combinations of biological sludge enzyme, lipase, oxidoreductase, dehydrogenase, laccase, cellulase, peroxidase and amylase.

[0042] Furthermore, the weight ratio of the fixed carrier, algae, composite bacterial agent, and composite enzyme is (8-10):(0.4-0.7):(16-21):(6-11); wherein the interference of the composite enzyme on the composite bacterial agent is reduced by controlling the addition ratio of the composite enzyme and the composite bacterial agent, so that the two can achieve a good synergistic effect.

[0043] Preferably, the composite activated carbon is a composite of activated carbon and a nutrient matrix; the activated carbon is a spherical honeycomb activated carbon, and the pore size of the spherical honeycomb activated carbon is 50nm-200nm; by adopting spherical honeycomb activated carbon, the composite bacterial agent and the composite enzyme can be better loaded, which can improve the degradation effect of emerging pollutants to a certain extent.

[0044] The nutrient matrix is ​​one of broth culture medium, starch agar culture medium, starch culture medium, beef extract peptone culture medium, peptone water culture medium and oil culture medium.

[0045] Furthermore, the nutrient matrix is ​​a peptone water culture medium; when compounding activated carbon, the following steps are included: after stirring the peptone water culture medium evenly, adding activated carbon, stirring evenly, after standing for 1-3 hours, taking it out, drying it in the shade, and obtaining compound activated carbon.

[0046] Preferably, the algae is a mixture of Scenedesmus, Chlorella and Spirulina, and the mass ratio / mass fraction of the Scenedesmus, Chlorella and Spirulina is (2-3):(1-2):(1-2); the present invention selects Chlorella and Spirulina to cooperate with each other, which can synergistically treat the nutrient elements in the tail water, including but not limited to protein, sugar, fat, alkaloids, ammonia nitrogen, nitrate, phosphate, etc.; and then the organic matter in the tail water is decomposed by Scenedesmus, thereby reducing the organic pollutants in the tail water; and Scenedesmus can also synergize with bacteria to provide oxygen and some nutrients for the growth of bacteria, making it easier for bacteria to survive, thereby enhancing the degradation of pollutants in the tail water.

[0047] Preferably, the composite bacterial agent is a mixture of Achromobacter, Sphingobacterium, Bacillus and Pseudomonas, and the ratio of Achromobacter, Sphingobacterium, Bacillus and Pseudomonas is (6-9):(4-6):(8-16):(6-12);

[0048] The present invention can synergistically improve the degradation efficiency of antibiotics in tail water through the mutual cooperation of colorless bacteria, sphingobacterium, bacillus and pseudomonas, and can all participate in the decomposition of antibiotics such as sulfonamides, tetracyclines, fluoroquinolones, macrolides, β-lactams and polypeptides in the tail water, and can also decompose endocrine disruptors in the tail water, such as estrogen, ethinyl estradiol, etc., so as to degrade most of the antibiotics and endocrine disruptors in the tail water, thereby improving the quality of the tail water; at the same time, because the invented microbial composite material is combined with algae, the algae can enrich the pollutants in the tail water and supply oxygen, which can make these bacteria survive more easily, thereby enhancing the degradation of emerging pollutants in the tail water.

[0049] Preferably, the colorless bacteria are Colorless Bacillus JL9 and Colorless Bacillus denitrifyingus PR1; the sphingobacterium is a mixture of Sphingobacterium and Sphingomonas; the Bacillus is Bacillus cereus J2 and Bacillus licheniformis DC-01; and the Pseudomonas is Pseudomonas CE22 and Pseudomonas CE21.

[0050] Preferably, the complex enzyme is a mixture of biological sludge enzyme, lipase and peroxidase, and the mass ratio of the biological sludge enzyme, lipase and peroxidase is 1:(1-3):(2-3);

[0051] The present invention adopts a mixture of biological sludge enzyme, lipase and peroxidase, which can not only remove pollutants such as COD, BOD, ammonia nitrogen in the tail water, but also oxidatively remove nutrients, some estrogens, phenols, amines, aldehydes, benzenes, etc. in the tail water, thereby further removing emerging pollutants in the tail water.

[0052] The method for preparing the microbial composite material comprises the following steps:

[0053] S1. Immerse the fixed carrier in peptone water culture medium, then add the complex enzyme, stir evenly, let stand for 1h-2h, filter, and dry in the shade to obtain the fixed carrier preliminarily loaded with the complex enzyme;

[0054] S2, adding the composite enzyme and the composite bacterial agent into the peptone water culture medium, stirring evenly, adding the fixed carrier preliminarily loaded with the composite enzyme and the chitosan solution, ultrasonicating for 5min-20min, and then standing for 1h-2h, filtering, and drying in the shade to obtain the fixed carrier loaded with the composite bacterial agent and the composite enzyme;

[0055] S3, adding algae to a peptone water culture medium, culturing for 1d-2d until the budding stage, inoculating on the fixed carrier treated in step S2 after screening, culturing for 12-24h, removing the culture medium, drying in the shade, and storing at low temperature to obtain a microbial composite material; culturing the algae to the budding stage to facilitate the subsequent growth of the algae on the fixed carrier;

[0056] The fixed carrier was treated with the compound enzyme twice in peptone water culture, which increased the loading capacity of the fixed carrier on the peptone hydroponic nutrient medium and improved the retention rate.

[0057] The present invention loads the composite enzyme on a fixed carrier first, then loads the composite enzyme and the composite bacterial agent on the fixed carrier to form a composite layer, and finally inoculates algae on the composite layer to form a composite fixed carrier. On the one hand, the environmental stress resistance of the microbial material can be improved; on the other hand, during water treatment, the pollutants can be first enriched and degraded by the algae to form a primary treatment, and at the same time, the enriched pollutants are treated by the composite enzyme and the composite bacterial agent to form a secondary treatment. In this process, under the action of the composite bacterial agent, antibiotics such as sulfonamides, tetracyclines, fluoroquinolones, macrolides, beta-lactams and polypeptides, as well as endocrine disruptors such as estrogen and ethinyl estradiol can be decomposed, and due to the decomposition of traditional pollutants by the composite enzyme and algae, the interference with the composite bacterial agent is reduced to a certain extent, and it is also beneficial to the activity of the composite bacterial agent; finally, after a long time, the traditional organic pollutants in the water environment are treated again by the composite enzyme and the fixed carrier inside the composite layer to improve the treatment effect.

[0058] The present invention also provides a method for removing pollutants from tail water using a microbial composite material. The aforementioned microbial composite material comprises the following steps:

[0059] The microbial composite material is immersed in the tail water to be treated, and 4-20g is added per liter of tail water; the microbial composite material is treated under light and aeration conditions, and the air-water volume ratio is maintained at (0.5-1.5):1; the water-air ratio during aeration is controlled, on the one hand, to provide a certain amount of oxygen to enable the microbial material to survive better; on the other hand, the disturbance to the microbial composite material is reduced.

[0060] Preferably, during aeration, the air-water volume ratio is 0.6:1.

[0061] Next, the following raw materials are used to illustrate different component embodiments:

[0062] The fixed carrier is a composite activated carbon, wherein the activated carbon is a spherical honeycomb activated carbon, and the pore size of the spherical honeycomb activated carbon is 50nm-200nm; the nutrient matrix is ​​a peptone water culture medium;

[0063] The algae are Scenedesmus, Chlorella, and Spirulina;

[0064] The composite bacterial agent is Achromobacter, Sphingobacter, Bacillus and Pseudomonas; wherein Achromobacter is the powder of Achromobacter JL9 and Achromobacter denitrificans PR1, and the addition ratio of Achromobacter JL9 and Achromobacter denitrificans PR1 is 1:2; Sphingobacter is the powder of Sphingobacter and Sphingomonas; the addition ratio of Sphingobacter and Sphingomonas is 1:1; Bacillus is the powder of Bacillus cereus J2 and Bacillus licheniformis DC-01; the addition ratio of Bacillus cereus J2 and Bacillus licheniformis DC-01 is 1:3; Pseudomonas is the powder of Pseudomonas CE21 and Pseudomonas CE22; the addition ratio of Pseudomonas CE21 and Pseudomonas CE22 is 1:2;

[0065] The complex enzyme is biological sludge enzyme, lipase and peroxidase, and the adding ratio of biological sludge enzyme, lipase and peroxidase is 1:(1-3):(2-3).

[0066] Example 1

[0067] Preparation of compound activated carbon: After 15 parts by weight of peptone water culture medium is stirred evenly, 8 parts by weight of spherical honeycomb activated carbon is added and stirred evenly. After standing for 2 hours, the mixture is fished out and dried in the shade to obtain compound activated carbon.

[0068] Preparation of microbial composites:

[0069] S1, immersing 8 parts by weight of the composite activated carbon in 10 parts by weight of peptone water culture medium, adding 0.5 parts by weight of biological sludge enzyme, 0.5 parts by weight of lipase and 1 part by weight of peroxidase, stirring evenly, standing for 2 hours, filtering, and drying in the shade to obtain a fixed carrier with preliminary loading;

[0070] S2, 1 weight part of biological sludge enzyme, 1 weight part of lipase and 2 weight parts of peroxidase, 1 weight part of Achromobacter JL9 and 2 weight parts of Achromobacter denitrifying PR1 are added to 20 weight parts of peptone water culture medium, and then 1 weight part of Pseudomonas CE21, 2 weight parts of Pseudomonas CE22, 1 weight part of Sphingobacillus and 1 weight part of Sphingobacillus are added, and then 1 weight part of Bacillus cereus J2 and 3 weight parts of Bacillus licheniformis DC-01 are added, and stirred evenly; then 8 weight parts of the fixed carrier of the preliminary load and 1.5 weight parts of chitosan solution are added, the concentration of the chitosan solution is 0.35 mg / ml, and the solution is ultrasonicated at a power of 50w for 8min, and then allowed to stand for 1h, filtered, and dried in the shade to obtain a fixed carrier loaded with a composite bacterial agent and a composite enzyme;

[0071] S3. Add 0.2 parts by weight of Scenedesmus, 0.1 parts by weight of Chlorella and 0.1 parts by weight of Spirulina into a peptone water culture medium, culture for 1 day, screen and then inoculate onto the fixed carrier treated in step S2, culture for 12-24 hours, remove the culture medium, dry in the shade, and store at low temperature to obtain a microbial composite material.

[0072] Method for removing pollutants from tail water by microbial composite materials: immerse the microbial composite materials in the tail water to be treated, and treat for 5 days under light and aeration conditions, while maintaining an air-to-water volume ratio of 0.6:1.

[0073] Example 2

[0074] Preparation of compound activated carbon: After 30 parts by weight of peptone water culture medium is stirred evenly, 20 parts by weight of spherical honeycomb activated carbon is added and stirred evenly. After standing for 2 hours, the mixture is fished out and dried in the shade to obtain compound activated carbon.

[0075] Preparation of microbial composites:

[0076] S1, immersing 10 parts by weight of the composite activated carbon in 15 parts by weight of peptone water culture medium, then adding 1 part by weight of biological sludge enzyme, 2 parts by weight of lipase and 2 parts by weight of peroxidase, stirring evenly, standing for 2 hours, filtering, and drying in the shade to obtain a fixed carrier with preliminary loading;

[0077] S2, 1 weight part of biological sludge enzyme, 2 weight parts of lipase and 2 weight parts of peroxidase, 1 weight part of Achromobacter JL9 and 2 weight parts of Achromobacter denitrifying PR1 are added to 20 weight parts of peptone water culture medium, and then 1.5 weight parts of Pseudomonas CE21, 3 weight parts of Pseudomonas CE22, 1.5 weight parts of Sphingobacillus and 1.5 weight parts of Sphingobacillus are added, and then 1.5 weight parts of Bacillus cereus J2 and 4.5 weight parts of Bacillus licheniformis DC-01 are added, and stirred evenly; then 10 weight parts of the fixed carrier of the preliminary load and 2.3 weight parts of chitosan solution are added, the concentration of the chitosan solution is 0.35 mg / ml, and the solution is ultrasonicated at a power of 50w for 8min, and then allowed to stand for 1h, filtered, and dried in the shade to obtain a fixed carrier loaded with a composite bacterial agent and a composite enzyme;

[0078] S3. Add 0.3 parts by weight of Scenedesmus, 0.2 parts by weight of Chlorella and 0.2 parts by weight of Spirulina into a peptone water culture medium, culture for 1 day, screen and then inoculate onto the fixed carrier treated in step S2, culture for 12-24 hours, remove the culture medium, dry in the shade, and store at low temperature to obtain a microbial composite material.

[0079] The method for removing pollutants in tail water by the microbial composite material is consistent with that in Example 1.

[0080] Example 3

[0081] Compared with Example 2, the dosage of peroxidase, Chromobacterium JL9, Achromobacter denitrificans PR1, Pseudomonas CE21, Pseudomonas CE22, Sphingobacillus, Sphingomonas, Bacillus cereus J2 and Bacillus licheniformis DC-01 in Example 3 is adjusted.

[0082] The preparation method of the composite activated carbon is consistent with that in Example 2.

[0083] Preparation of microbial composites:

[0084] S1, immersing 10 parts by weight of the composite activated carbon in 15 parts by weight of peptone water culture medium, then adding 1 part by weight of biological sludge enzyme, 2 parts by weight of lipase and 2 parts by weight of peroxidase, stirring evenly, standing for 2 hours, filtering, and drying in the shade to obtain a fixed carrier with preliminary loading;

[0085] S2, 1 weight part of biological sludge enzyme, 2 weight parts of lipase and 3 weight parts of peroxidase, 1.5 weight parts of Achromobacter JL9 and 3 weight parts of Achromobacter denitrifying PR1 are added to 20 weight parts of peptone water culture medium, and then 2 weight parts of Pseudomonas CE21, 4 weight parts of Pseudomonas CE22, 1 weight part of Sphingobacillus and 1 weight part of Sphingobacillus are added, and then 2 weight parts of Bacillus cereus J2 and 6 weight parts of Bacillus licheniformis DC-01 are added, and stirred evenly; then 10 weight parts of the fixed carrier of the preliminary load and 2.3 weight parts of chitosan solution are added, the concentration of the chitosan solution is 0.35 mg / ml, and the solution is ultrasonicated at a power of 50w for 8min, and then allowed to stand for 1h, filtered, and dried in the shade to obtain a fixed carrier loaded with a composite bacterial agent and a composite enzyme;

[0086] S3. Add 0.3 parts by weight of Scenedesmus, 0.2 parts by weight of Chlorella and 0.2 parts by weight of Spirulina into a peptone water culture medium, culture for 1 day, screen and then inoculate onto the fixed carrier treated in step S2, culture for 12-24 hours, remove the culture medium, dry in the shade, and store at low temperature to obtain a microbial composite material.

[0087] The method for removing pollutants in tail water by the microbial composite material is consistent with that in Example 1 and Example 2.

[0088] The results of removing pollutants from tail water by the microbial composite materials in Examples 1-3 were tested. During the test, 20 g of the microbial composite materials were added per liter of tail water. The test results are as follows: Figure 1 (Table 1) Figure 1 (Table 1) It can be seen that the microbial composite materials in Examples 1-3 of the present application have good removal efficiency for traditional pollutants, and also have good removal efficiency for antibiotics such as sulfonamides, tetracyclines, fluoroquinolones, macrolides, β-lactams and peptides. It also has high removal efficiency for endocrine disruptors such as estrogen and ethinyl estradiol, so that emerging pollutants and traditional pollutants in tail water can be efficiently removed to improve the quality of tail water. Compared with Example 1, Example 2 and Example 3 have a better removal effect. Compared with Example 2, Example 3 increases the input of composite enzyme by 1 weight part, and the input of composite bacterial agent by 4 weight parts, but the removal rate does not change much. Therefore, in general, Example 2 is the best embodiment.

[0089] Based on Example 2, the present invention also provides 13 comparative examples in which individual components are missing.

[0090] Comparative Example 1

[0091] In this comparative example 1, no fixed carrier is used, and the algae, compound enzyme and compound bacterial agent are directly put into the tail water to be treated, and the treatment is carried out for 5 days under the conditions of light and aeration, and the air-water volume ratio is maintained at 0.6:1.

[0092] Comparative Example 2

[0093] In Comparative Example 2, algae was not used, and the composite activated carbon in Example 2 was used as the fixed carrier.

[0094] Preparation of microbial composites

[0095] S1, immersing 10 parts by weight of the composite activated carbon in 15 parts by weight of peptone water culture medium, then adding 1 part by weight of biological sludge enzyme, 2 parts by weight of lipase and 2 parts by weight of peroxidase, stirring evenly, standing for 2 hours, filtering, and drying in the shade to obtain a fixed carrier with preliminary loading;

[0096] S3, 1 weight part of biological sludge enzyme, 2 weight parts of lipase and 2 weight parts of peroxidase, 1 weight part of Achromobacter JL9 and 2 weight parts of Achromobacter denitrifying PR1 are added to 20 weight parts of peptone water culture medium, and after stirring, 1.5 weight parts of Pseudomonas CE21, 3 weight parts of Pseudomonas CE22, 1.5 weight parts of Sphingobacillus and 1.5 weight parts of Sphingobacillus are added, and after stirring, 1.5 weight parts of Bacillus cereus J2 and 4.5 weight parts of Bacillus licheniformis DC-01 are added, and stirred evenly; 10 weight parts of the fixed carrier of the preliminary load and 2.3 weight parts of chitosan solution are added, the concentration of the chitosan solution is 0.35 mg / ml, ultrasonicated at a power of 50w for 8min, then allowed to stand for 1h, filtered, and dried in the shade to obtain a fixed carrier loaded with a composite bacterial agent and a composite enzyme.

[0097] Method for removing pollutants from tail water by microbial composite materials:

[0098] The fixed carrier loaded with the composite bacterial agent and the composite enzyme was immersed in the tail water to be treated, and the treatment was carried out for 5 days under the conditions of light and aeration, and the air-water volume ratio was maintained at 0.6:1.

[0099] Comparative Example 3

[0100] In this comparative example 3, no composite enzyme is used, and the composite activated carbon in Example 2 is used as the fixed carrier.

[0101] Preparation of microbial composites:

[0102] S1, add 1 weight part of biological sludge enzyme, 2 weight parts of lipase and 2 weight parts of peroxidase, 1 weight part of Achromobacter JL9 and 2 weight parts of Achromobacter denitrifying PR1 to 20 weight parts of peptone water culture medium, stir evenly, then add 1.5 weight parts of Pseudomonas CE21, 3 weight parts of Pseudomonas CE22, 1.5 weight parts of Sphingobacillus and 1.5 weight parts of Sphingobacillus, stir evenly, then add 1.5 weight parts of Bacillus cereus J2 and 4.5 weight parts of Bacillus licheniformis DC-01, stir evenly; then add 10 weight parts of the fixed carrier of the preliminary load and 2.3 weight parts of chitosan solution, the concentration of the chitosan solution is 0.35 mg / ml, ultrasonically treat for 8 min at a power of 50 w, then stand for 1 h, filter with suction, and dry in the shade to obtain a fixed carrier loaded with composite bacterial agent and composite enzyme;

[0103] S2. Add 0.3 parts by weight of Scenedesmus, 0.2 parts by weight of Chlorella and 0.2 parts by weight of Spirulina into a peptone water culture medium, culture for 1 day, screen and then inoculate onto the fixed carrier treated in step S2, culture for 12-24 hours, remove the culture medium, dry in the shade, and store at low temperature to obtain a microbial composite material.

[0104] Method for removing pollutants from tail water by microbial composite materials: immerse the microbial composite materials in the tail water to be treated, and treat for 5 days under light and aeration conditions, while maintaining an air-to-water volume ratio of 0.6:1.

[0105] Comparative Example 4

[0106] In this comparative example 4, the composite bacterial agent only uses Achromobacter, and the preparation of the composite activated carbon and microbial composite material and the treatment method of the tail water are the same as those in Example 2.

[0107] Comparative Example 5

[0108] In this comparative example 5, the composite bacterial agent only uses sphingosine bacteria, and the preparation of the composite activated carbon and microbial composite material and the treatment method of the tail water are the same as those in Example 2.

[0109] Comparative Example 6

[0110] In this comparative example 6, the composite bacterial agent only uses Bacillus, and the preparation of the composite activated carbon and microbial composite material and the treatment method of the tail water are the same as those in Example 2.

[0111] Comparative Example 7

[0112] In this comparative example 7, the composite bacterial agent only uses Pseudomonas, and the preparation of the composite activated carbon and microbial composite material and the treatment method of the tail water are the same as those in Example 2.

[0113] Comparative Example 8

[0114] In this comparative example 8, the composite bacterial agent only uses achromobacter and sphingobacterium, and the preparation of the composite activated carbon and microbial composite material and the treatment method of the tail water are the same as those in Example 2.

[0115] Comparative Example 9

[0116] In this comparative example 9, the composite bacterial agent only uses achromobacter and bacillus, and the preparation of the composite activated carbon and microbial composite material and the treatment method of the tail water are the same as those in Example 2.

[0117] Comparative Example 10

[0118] In this comparative example 10, the composite bacterial agent only uses Achromobacter and Pseudomonas, and the preparation of the composite activated carbon and microbial composite material and the treatment method of the tail water are the same as those in Example 2.

[0119] Comparative Example 11

[0120] In this comparative example 11, the composite bacterial agent only uses sphingobacteria and Bacillus, and the preparation of the composite activated carbon and microbial composite material and the treatment method of the tail water are the same as those in Example 2.

[0121] Comparative Example 12

[0122] In this comparative example 12, the composite bacterial agent only uses sphingobacterium and Pseudomonas, and the preparation of the composite activated carbon and microbial composite material and the treatment method of the tail water are the same as those in Example 2.

[0123] Comparative Example 13

[0124] In this comparative example 13, the composite bacterial agent only uses Bacillus and Pseudomonas, and the preparation of the composite activated carbon and microbial composite material and the treatment method of the tail water are the same as those in Example 2.

[0125] In Comparative Examples 1-13, the results of removing pollutants from tail water by microbial materials were tested. During the test, 20 g of microbial composite material was added per liter of tail water. The test results are as follows: Figure 2 (Table 2), Figure 3 (Table 3) shows.

[0126] according to Figure 2 (Table 2), Figure 3 (Table 3) Data. By comparing the data in Comparative Example 1 with that in Example 2, it can be seen that when no fixed carrier is used, the removal efficiency of the microbial material for traditional pollutants and emerging pollutants is reduced, indicating that the fixed carrier can synergistically improve the removal efficiency of the microbial material for traditional pollutants and emerging pollutants to a certain extent.

[0127] according to Figure 2 (Table 2), Figure 3 (Table 3) Data, by comparing the data in Comparative Example 2 with that in Example 2, it can be seen that when algae are not used, the removal efficiency of microbial materials for traditional pollutants and emerging pollutants is reduced, and the removal efficiency of endocrine disruptors is particularly reduced, indicating that algae not only has a significant effect on the removal of traditional pollutants, but also has a significant impact on the removal of endocrine disruptors.

[0128] according to Figure 2 (Table 2), Figure 3 (Table 3) Data, by comparing the data in comparative example 3 with that in embodiment 2, it can be seen that when the composite enzyme is not used, the degradation efficiency of the microbial material on traditional pollutants is significantly reduced, and the removal efficiency on emerging pollutants is not significantly affected, indicating that the composite enzyme is mainly used to remove traditional pollutants, and the removal effect on emerging pollutants is not obvious.

[0129] according to Figure 2 (Table 2), Figure 3 (Table 3) Data, by comparing the data of Comparative Examples 4-7 with those of Example 2, it can be seen that when the composite bacterial agent uses only one of the genera Achromobacter, Sphingobacterium, Bacillus and Pseudomonas, it has little effect on the removal efficiency of traditional pollutants, but has a more obvious effect on emerging pollutants. Different bacterial species have different removal efficiencies for different emerging pollutants.

[0130] according to Figure 2 (Table 2), Figure 3 (Table 3) Data, by comparing the data of Comparative Examples 8-13 with those of Example 2, it can be seen that when the composite bacterial agent only uses two of the genera Chromobacterium, Sphingobacterium, Bacillus and Pseudomonas, it has little effect on the removal efficiency of traditional pollutants, but has a more obvious effect on emerging pollutants, that is, different bacterial species can cooperate to improve the removal efficiency of different types of antibiotics and endocrine disruptors, indicating that different bacterial species can play a synergistic role and improve the removal efficiency of some types of antibiotics and endocrine disruptors to a certain extent.

[0131] Therefore, by adopting the combination of algae-bacteria-enzyme and loading it with a fixed carrier, when treating tail water, on the one hand, it can enrich pollutants and microorganisms in the water and degrade them. Combined with composite enzymes and composite bacterial agents, it can efficiently degrade emerging pollutants such as endocrine disruptors and antibiotics in the water environment. On the other hand, through fixed carrier loading, algae, composite bacterial agents and composite enzymes can improve the overall stress resistance and synergistically improve the degradation efficiency of emerging pollutants.

[0132] It should be noted that if no specific experimental steps or conditions are specified in the examples, the conventional experimental steps or conditions described in the literature in the art can be used. If no manufacturer is specified for the reagents or instruments used, they are all conventional reagent products that can be purchased commercially.

[0133] The above is a detailed introduction to a microbial composite material provided by the present invention and a method for removing pollutants from tail water. The description of the specific embodiment is only used to help understand the method of the present invention and its core idea. It should be pointed out that for ordinary technicians in this technical field, without departing from the principle of the present invention, the present invention can also be improved and modified, and these improvements and modifications also fall within the scope of protection of the claims of the present invention.

Claims

1. A microbial composite material, characterized in that: It comprises a fixed carrier, algae, a composite bacterial agent and a composite enzyme; the algae, the composite bacterial agent and the composite enzyme are loaded on the fixed carrier, and the algae is loaded on the outermost layer; the weight proportion of the fixed carrier, the algae, the composite bacterial agent and the composite enzyme is (8-10):(0.4-0.7):(16-21):(6-11); The fixed carrier is one or more combinations of composite activated carbon, graphite, coke, biochar, modified activated carbon, porous alumina, and porous ceramics; The algae is one or more combinations of Chlorella, Spirulina, Scenedesmus, Diatom, Fibrophyte, Lunaphalium, and Plectranthus; The composite bacterial agent is a combination of one or more of Achromobacter, Ochrobacterium, ammonia oxidizing bacteria, Microbacterium, Gordonia, Sphingobacterium, Bacillus and Pseudomonas; The complex enzyme is one or more combinations of biological sludge enzyme, lipase, oxidoreductase, dehydrogenase, laccase, cellulase, peroxidase, and amylase; The method for preparing the microbial composite material comprises the following steps: S1. Immerse the fixed carrier in peptone water culture medium, then add the complex enzyme, stir evenly, let stand for 1h-2h, filter, and dry in the shade to obtain the fixed carrier preliminarily loaded with the complex enzyme; S2, adding the composite enzyme and the composite bacterial agent into the peptone water culture medium, stirring evenly, adding the fixed carrier preliminarily loaded with the composite enzyme and the chitosan solution, ultrasonicating for 5min-20min, and then standing for 1h-2h, filtering, and drying in the shade to obtain the fixed carrier loaded with the composite bacterial agent and the composite enzyme; S3. Add the algae into the peptone water culture medium, culture for 1d-2d, and then inoculate onto the fixed carrier treated in step S2 after screening, culture for 12h-24h, remove the culture medium, dry in the shade, and store at low temperature to obtain a microbial composite material.

2. The microbial composite material according to claim 1, characterized in that: The compound activated carbon is a compound of activated carbon and a nutrient matrix; the activated carbon is a spherical honeycomb activated carbon, and the pore size of the spherical honeycomb activated carbon is 50nm-200nm; the nutrient matrix is ​​one of broth culture medium, starch agar culture medium, starch culture medium, beef extract peptone culture medium, peptone water culture medium, and oil culture medium.

3. The microbial composite material according to claim 1, characterized in that: The algae is a mixture of Scenedesmus, Chlorella and Spirulina, and the mass ratio of Scenedesmus, Chlorella and Spirulina is (2-3):(1-2):(1-2).

4. The microbial composite material according to claim 1, characterized in that: The composite bacterial agent is a mixture of colorless bacteria, sphingobacterium, bacillus and pseudomonas, and the ratio of the colorless bacteria, sphingobacterium, bacillus and pseudomonas is (6-9): (4-6): (8-16): (6-12).

5. The microbial composite material according to claim 4, characterized in that: The colorless bacteria are colorless bacteria JL9 and denitrifying colorless bacteria PR1; the sphingobacterium is a mixture of sphingobacterium and sphingomonas; the bacillus is Bacillus cereus J2 and Bacillus licheniformis DC-01; the pseudomonas are Pseudomonas CE22 and Pseudomonas CE21.

6. The microbial composite material according to claim 1, characterized in that: The complex enzyme is a mixture of biological sludge enzyme, lipase and peroxidase, and the mass ratio of the biological sludge enzyme, lipase and peroxidase is 1:(1-3):(2-3).

7. The microbial composite material according to claim 1, characterized in that: In step S3, the algae are cultured to the budding stage and then inoculated onto a fixed carrier to facilitate subsequent growth.

8. A method for removing pollutants from tail water using a microbial composite material, characterized in that: Using the microbial composite material according to any one of claims 1 to 7 comprises the following steps: The microbial composite material is immersed in the tail water to be treated, and 4g-20g of the microbial composite material is added per liter of tail water. The process is carried out under light and aeration conditions, and the air-water volume ratio is maintained at (0.5-1.5):1.

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