Treatment method of wastewater containing endocrine disrupter

Abstract

The invention relates to a method for treating wastewater containing endocrine disrupters, the endocrine disrupters comprise at least one of nonylphenol, bisphenol A, estriol and oestrone, and the method for treating the wastewater containing the endocrine disrupters comprises the following steps: sequentially carrying out anaerobic-aerobic treatment and membrane-activated sludge treatment on to-be-treated wastewater, equipment adopted in the membrane-activated sludge process treatment process is filled with filler, and activated sludge is inoculated with microorganisms including antibiotic degrading bacteria and progestational hormone degrading bacteria. In the application, through anaerobic-aerobic treatment, endocrine disruptors such as nonyl phenol and bisphenol in the wastewater can be removed by utilizing the metabolism of microorganisms in anaerobic and aerobic environments, the endocrine disruptors are adsorbed through the filler, and antibiotics such as estriol in the wastewater are degraded into small molecular compounds by utilizing antibiotic degrading bacteria; and progestational hormone such as oestrone is degraded into small molecular compounds by using progestational hormone degrading bacteria, and impurities are intercepted through an ultrafiltration membrane, so that the water quality is effectively purified.

Description

Technical Field

[0001] The present application relates to the field of water treatment technology, and in particular to a method for treating wastewater containing endocrine disruptors. Background Art

[0002] Endocrine disruptors (DCs), also known as environmental hormones, environmental hormones, environmental estrogens, etc., refer to exogenous chemical substances that are released into the environment due to human production and life and affect the normal hormone levels in the body. Endocrine disruptors interfere with the synthesis, release, transport, metabolism, and binding of normal secretory substances in the body, activate or inhibit the function of the endocrine system, destroy the endocrine homeostasis of the body, and have adverse effects on reproduction, growth and development. Endocrine disruptors are highly stable, difficult to decompose, and easy to enrich. Long-term low-dose exposure may pose great risks to human health and the ecological environment. Starting from the early stages of life, exposure to endocrine disruptors in life may affect the transmission of hormone signals and interfere with the homeostasis of the human immune system, just like breaking the "golden bell" of allergy defense, leading to the occurrence of allergic diseases. Endocrine disruptors are widely present in people's lives and are exposed to the human body through the respiratory tract, digestive tract, and skin contact. They can also be transmitted from the mother through the placenta, umbilical cord blood, and breast milk.

[0003] In recent years, different concentrations of endocrine disruptors have been detected in natural water bodies such as rivers, lakes, and oceans, and have caused abnormal phenomena such as feminization and hermaphroditism in organisms in water bodies in some areas. Urban sewage is one of the important sources of endocrine disruptors in natural water bodies. The endocrine disruptors in urban sewage, especially the estrogen effect, are relatively clear. Endocrine disruptors can affect the human endocrine system and immune system, affect the reproductive development of the human body, have carcinogenic effects, and produce neurotoxic effects. Summary of the invention

[0004] In view of the above-mentioned shortcomings of the prior art, the present application provides a method for treating wastewater containing endocrine disruptors, so as to effectively reduce the content of endocrine disruptors in the wastewater.

[0005] To achieve the above objectives, the scheme of this application is as follows:

[0006] The present application provides a method for treating wastewater containing endocrine disruptors, wherein the endocrine disruptors include at least one of nonylphenol, bisphenol A, estriol and estrone, and the method for treating wastewater containing endocrine disruptors includes the following steps:

[0007] The wastewater to be treated is sequentially subjected to anaerobic-aerobic treatment and membrane-activated sludge process (i.e., MBR process). The equipment used in the membrane-activated sludge process is filled with fillers and the activated sludge is inoculated with microorganisms including antibiotic-degrading bacteria and progesterone-degrading bacteria.

[0008] In the present application, through anaerobic-aerobic treatment, the metabolism of microorganisms in anaerobic and aerobic environments can be utilized to remove endocrine disruptors such as nonylphenol and bisphenol in wastewater, and then a membrane-activated sludge method is performed. During the membrane-activated sludge method, fillers are loaded in the equipment used, and the activated sludge is inoculated with microorganisms including antibiotic-degrading bacteria and progesterone-degrading bacteria. Endocrine disruptors can be adsorbed through the fillers, and antibiotic-degrading bacteria can be used to degrade antibiotics such as estriol in the wastewater into small molecular compounds, and progesterone-degrading bacteria can be used to degrade progestins such as estrone into small molecular compounds, and impurities can be retained by ultrafiltration membranes, thereby effectively purifying the water quality.

[0009] Optionally, the filler includes ceramsite, sulfur and iron-containing particles, and the iron-containing particles contain ferrous ions.

[0010] In the present application, expanded clay, sulfur and iron-containing particles are used in combination, and the pores of the expanded clay can be used to effectively intercept impurities such as suspended matter, and the micropores on the surface of the expanded clay can be used to adsorb impurities, the oxidizing properties of sulfur are used to undergo a redox reaction with the hydroxyl groups in the estriol molecule, and the pore structure on the surface of the iron-containing particles is used to adsorb impurities such as estriol and estrone. At the same time, in the presence of ferrous ions dissociated after the iron-containing particles are dissolved in the wastewater to be treated, iron-reducing bacteria grow in the system, and the iron-reducing bacteria can degrade organic matter such as nonylphenol, bisphenol A, estriol, and estrone, thereby further reducing the content of endocrine disruptors in the wastewater.

[0011] Optionally, the iron-containing particles are selected from at least one of siderite particles, hematite particles and pyrite particles.

[0012] In the present application, ceramsite includes but is not limited to clay ceramsite, expanded perlite ceramsite, shale ceramsite, fly ash ceramsite, coal gangue ceramsite, siliceous sand ceramsite, expanded vermiculite ceramsite and the like.

[0013] Optionally, the mass ratio of the ceramsite, the sulfur and the iron-containing particles is 30-45:10-15:45-58, preferably 32-45:12-15:48-58.

[0014] Optionally, the mass ratio of the antibiotic-degrading bacteria to the progesterone-degrading bacteria is 20-80:80-20, preferably 20-75:80-25.

[0015] Optionally, the antibiotic-degrading bacteria are selected from at least one of Bacillus, photosynthetic bacteria, lactic acid bacteria, actinomycetes, yeasts and fermentative filamentous bacteria.

[0016] Optionally, the progesterone-degrading bacteria are selected from the progesterone-degrading bacteria MPA-3 strain.

[0017] Optionally, the mass ratio of the microorganism to the activated sludge is 0.3-0.8:100, preferably 0.5-0.8:100.

[0018] Optionally, in the membrane-activated sludge process, the residence time of the wastewater to be treated is 3-5 hours, preferably 3.5-5 hours.

[0019] Optionally, during the membrane-activated sludge process, the wastewater to be treated is electrolyzed.

[0020] In the present application, during the membrane-activated sludge process, the wastewater to be treated is electrolyzed. The presence of voltage during the electrolysis process can drive the redox reaction in the wastewater, thereby promoting the degradation of impurities such as estriol and estrone by the above-mentioned antibiotic-degrading bacteria and progesterone-degrading bacteria, further improving the water quality; and the electrolysis process can prompt the iron-containing particles to precipitate more ferrous ions to grow more iron-type reducing bacteria, thereby degrading more organic substances such as nonylphenol, bisphenol A, estriol and estrone, thereby further reducing the content of endocrine disruptors in the wastewater.

[0021] The formed iron-carbon primary cell will generate iron ions during the electrolysis process. The iron ions can act as a catalyst to accelerate the degradation process of impurities such as estriol and estrone, and further improve the removal efficiency of endocrine disruptors such as estriol and estrone.

[0022] Optionally, during the electrolysis process, the power source used is direct current.

[0023] Optionally, the current density of the electrolysis is 10-20 mA / cm 2 , preferably 10-15 mA / cm 2 ; The voltage of the electrolysis is 5-10V, preferably 6-10V.

[0024] Optionally, after the membrane-activated sludge treatment, the method for treating wastewater containing endocrine disruptors further comprises the following steps: subjecting the wastewater to be treated to ozone catalytic oxidation treatment.

[0025] In the present application, by adding an ozone catalytic oxidation treatment step after the membrane treatment, ozone can be used to oxidize the remaining impurities such as nonylphenol, bisphenol A, estriol, estrone, etc. in the water body, thereby further improving the water quality.

[0026] Optionally, during the ozone catalytic oxidation treatment process, the catalyst used is selected from at least one of an iron-based homogeneous catalyst, an aluminum-based homogeneous catalyst, a copper-based homogeneous catalyst, a manganese-based homogeneous catalyst, a cobalt-based homogeneous catalyst, a zinc-based homogeneous catalyst, a nickel-based homogeneous catalyst, a cadmium-based homogeneous catalyst and a chromium-based homogeneous catalyst.

[0027] In the present application, the iron-based homogeneous catalyst includes but is not limited to: iron oxide, iron chloride, iron nitrate, iron sulfate and the like.

[0028] In the present application, aluminum-based homogeneous catalysts include but are not limited to aluminum chloride, aluminum nitrate, aluminum sulfate and the like.

[0029] In the present application, copper-based homogeneous catalysts include but are not limited to: copper chloride, copper nitrate, copper sulfate and the like.

[0030] In the present application, the manganese-based homogeneous catalyst includes but is not limited to: manganese chloride, manganese nitrate, manganese sulfate and the like.

[0031] In the present application, the cobalt-based homogeneous catalyst includes but is not limited to: cobalt chloride, cobalt nitrate, cobalt sulfate and the like.

[0032] In the present application, zinc-based homogeneous catalysts include but are not limited to: zinc chloride, zinc nitrate, zinc sulfate and the like.

[0033] In the present application, the nickel-based homogeneous catalyst includes but is not limited to: nickel chloride, nickel nitrate, nickel sulfate and the like.

[0034] In the present application, the cadmium-based homogeneous catalyst includes but is not limited to: cadmium chloride, cadmium nitrate, cadmium sulfate and other substances.

[0035] In the present application, the chromium-based homogeneous catalyst includes but is not limited to: chromium chloride, chromium nitrate, chromium sulfate and the like.

[0036] Optionally, the amount of the catalyst is 3-5 g / L, preferably 3.5-5 g / L.

[0037] Optionally, during the ozone catalytic oxidation treatment process, the residence time of the wastewater to be treated is 0.5-1.5h. DETAILED DESCRIPTION

[0038] The technical solutions in the embodiments of the present application are described clearly and completely below. Obviously, the described embodiments are only part of the embodiments of the present application, not all of the embodiments. Based on the embodiments in the present application, all other embodiments obtained by ordinary technicians in this field without creative work are within the scope of protection of the present application.

[0039] An embodiment of the present application provides a method for treating wastewater containing endocrine disruptors, comprising the following steps:

[0040] The wastewater to be treated is sequentially treated by anaerobic-aerobic treatment and membrane-activated sludge process;

[0041] The equipment used in the membrane-activated sludge process is filled with fillers, and the activated sludge is inoculated with microorganisms including antibiotic degrading bacteria and progesterone degrading bacteria. The fillers include ceramsite, sulfur and iron-containing particles. The mass ratio of ceramsite, sulfur and iron-containing particles is 30-45:10-15:45-58. The iron-containing particles are selected from at least one of siderite particles, hematite particles and pyrite particles. The mass ratio of microorganisms to activated sludge is 0.3-0.8:100. The microorganisms include antibiotic degrading bacteria and progesterone degrading bacteria. The mass ratio of antibiotic degrading bacteria to progesterone degrading bacteria is 20-80:80-20. The antibiotic degrading bacteria are selected from at least one of bacillus, photosynthetic bacteria, lactic acid bacteria, actinomycetes, yeast and fermentation filamentous bacteria. The progesterone degrading bacteria are selected from the progesterone degrading bacteria MPA-3 strain.

[0042] In another embodiment of the present application, during the membrane-activated sludge process, a current density of 10-20 mA / cm 2 The wastewater to be treated is electrolyzed by direct current with a voltage of 5-10V.

[0043] In another embodiment of the present application, after the membrane-activated sludge treatment, the method for treating wastewater containing endocrine disruptors also includes the following steps: treating the wastewater to be treated by ozone catalytic oxidation, and during the ozone catalytic oxidation treatment, the catalyst used is selected from at least one of an iron-based homogeneous catalyst, an aluminum-based homogeneous catalyst, a copper-based homogeneous catalyst, a manganese-based homogeneous catalyst, a cobalt-based homogeneous catalyst, a zinc-based homogeneous catalyst, a nickel-based homogeneous catalyst, a cadmium-based homogeneous catalyst and a chromium-based homogeneous catalyst, and the amount of the catalyst used is 3-5g / L.

[0044] The present application is described in detail below by specific examples. It should also be understood that the following examples are only used to specifically illustrate the present application and cannot be understood as limiting the scope of protection of the present application. Some non-essential improvements and adjustments made by those skilled in the art based on the above content of the present application belong to the scope of protection of the present application. The specific process parameters and the like in the following examples are also only examples within a suitable range, that is, those skilled in the art can make a selection within a suitable range through the description herein, and are not limited to the specific values ​​​​exemplified below.

[0045] It should be understood that in the following embodiments, only Bacillus is listed as an antibiotic degrading bacteria, clay ceramsite is used as ceramsite, siderite particles are used as iron-containing particles, and ferric chloride is used as a catalyst. Those skilled in the art may also select other antibiotic degrading bacteria other than Bacillus, such as photosynthetic bacteria, lactic acid bacteria, actinomycetes, yeasts, fermentation filamentous bacteria, etc., other iron-containing particles other than siderite particles, such as hematite particles, pyrite particles, etc., other catalysts other than ferric chloride, such as ferric nitrate, ferric sulfate, aluminum chloride, aluminum nitrate, aluminum sulfate, copper chloride, copper nitrate, copper sulfate, manganese chloride, manganese nitrate, manganese sulfate, cobalt chloride, cobalt nitrate, cobalt sulfate, zinc chloride, zinc nitrate, zinc sulfate, nickel chloride, nickel nitrate, nickel sulfate, cadmium chloride, cadmium nitrate, cadmium sulfate, chromium chloride, chromium nitrate, chromium sulfate, etc., other ceramsites other than clay ceramsite, such as expanded perlite ceramsite, shale ceramsite, fly ash ceramsite, coal gangue ceramsite, siliceous sand ceramsite, expanded vermiculite ceramsite, etc.

[0046] Example 1

[0047] A method for treating wastewater containing endocrine disruptors, the specific steps are as follows:

[0048] S1. Anaerobic-aerobic treatment of the wastewater (i.e., influent, containing nonylphenol, bisphenol A, estriol and estrone) discharged from a sewage treatment plant;

[0049] S2. Filling a membrane bioreactor (i.e., an MBR reactor, in which activated sludge is filled) with a filler (the filler is composed of clay ceramsite, sulfur and siderite particles in a mass ratio of 30:10:58), and inoculating the activated sludge with microorganisms (the microorganisms are composed of Bacillus and progesterone-degrading bacteria MPA-3 strains in a mass ratio of 80:20), the mass ratio of microorganisms to activated sludge is 0.3:100, the microorganisms are evenly divided into three portions and added three times, and the interval between adjacent batches is 3h;

[0050] The wastewater treated in step S1 is introduced into the membrane bioreactor from the bottom. After 3 hours, the wastewater is discharged from the membrane bioreactor from the top (ie, effluent).

[0051] Example 2

[0052] A method for treating wastewater containing endocrine disruptors, the specific steps are as follows:

[0053] S1. The wastewater (ie, the influent, the source of which is the same as in Example 1) is subjected to anaerobic-aerobic treatment;

[0054] S2. Filling a membrane bioreactor (i.e., an MBR reactor, in which activated sludge is filled) with a filler (the filler is composed of clay ceramsite, sulfur and siderite particles in a mass ratio of 45:15:45), and inoculating the activated sludge with microorganisms (the microorganisms are composed of Bacillus and progesterone-degrading bacteria MPA-3 strains in a mass ratio of 20:80), the mass ratio of microorganisms to activated sludge is 0.8:100, the microorganisms are evenly divided into three portions and added three times, and the interval between adjacent batches is 1 hour;

[0055] The wastewater treated in step S1 is introduced into the membrane bioreactor from the bottom. After 5 hours, the wastewater is discharged from the membrane bioreactor from the top (ie, effluent).

[0056] Example 3

[0057] A method for treating wastewater containing endocrine disruptors, the specific steps are as follows:

[0058] S1. The wastewater (ie, the influent, the source of which is the same as in Example 1) is subjected to anaerobic-aerobic treatment;

[0059] S2. Filling a membrane bioreactor (i.e., an MBR reactor, in which activated sludge is filled) with a filler (the filler is composed of clay ceramsite, sulfur and siderite particles in a mass ratio of 35:12:53), and inoculating the activated sludge with microorganisms (the microorganisms are composed of Bacillus and progesterone-degrading bacteria MPA-3 strain in a mass ratio of 50:50), the mass ratio of microorganisms to activated sludge is 0.5:100, the microorganisms are evenly divided into three portions and added three times, and the interval between adjacent batches is 2h;

[0060] The wastewater treated in step S1 is introduced into the membrane bioreactor from the bottom. After 4 hours, the wastewater is discharged from the membrane bioreactor from the top (ie, effluent).

[0061] Example 4

[0062] The wastewater was treated in the same manner as in Example 3 except for the following conditions:

[0063] S2. Filling a membrane bioreactor (i.e., an MBR reactor, in which activated sludge is filled) with a filler (the filler is composed of clay ceramsite, sulfur and siderite particles in a mass ratio of 35:12:53), and inoculating the activated sludge with microorganisms (the microorganisms are composed of Bacillus and progesterone-degrading bacteria MPA-3 strains in a mass ratio of 50:50), the mass ratio of microorganisms to activated sludge is 0.5:100, the microorganisms are evenly divided into three portions and added three times, and the interval between adjacent batches is 2h;

[0064] The wastewater treated in step S1 is introduced into the membrane bioreactor from the bottom. After 4 hours, the wastewater is discharged from the membrane bioreactor from the top (i.e., effluent). During the treatment process in the membrane bioreactor, a current density of 10-20 mA / cm 2 The wastewater is electrolyzed by direct current with a voltage of 5-10V.

[0065] That is, the difference between this embodiment and embodiment 3 is that during the membrane bioreactor treatment, the current density is 15 mA / cm 2 The wastewater is electrolyzed by direct current with a voltage of 8V.

[0066] Example 5

[0067] The wastewater was treated in the same manner as in Example 4 except for the following conditions:

[0068] S2. Filling a membrane bioreactor (i.e., an MBR reactor, in which activated sludge is filled) with a filler (the filler is composed of clay ceramsite, sulfur and siderite particles in a mass ratio of 35:12:53), and inoculating the activated sludge with microorganisms (the microorganisms are composed of Bacillus and progesterone-degrading bacteria MPA-3 strains in a mass ratio of 50:50), the mass ratio of microorganisms to activated sludge is 0.5:100, the microorganisms are evenly divided into three portions and added three times, and the interval between adjacent batches is 2h;

[0069] The wastewater treated in step S1 is introduced into the membrane bioreactor from the bottom. After 4 hours, the wastewater is discharged from the membrane bioreactor from the top. During the treatment process of the membrane bioreactor, a current density of 15 mA / cm 2 The wastewater is electrolyzed by direct current with a voltage of 8V;

[0070] S3. Send the wastewater treated in step S2 into an ozone catalytic oxidation reactor, and add ferric chloride in an amount of 4 g / L. After 1 hour, discharge the wastewater (ie, effluent).

[0071] That is, the difference between this embodiment and embodiment 4 is that after the membrane-activated sludge process treatment, the wastewater is subjected to ozone catalytic oxidation treatment.

[0072] Comparative Example 1

[0073] The wastewater was treated in the same manner as in Example 3 except for the following conditions:

[0074] S2. The wastewater treated in step S1 is introduced into the membrane bioreactor (i.e., MBR reactor, which is filled with activated sludge) from the bottom. After 4 hours, the wastewater is discharged from the membrane bioreactor from the top (i.e., effluent).

[0075] That is, the difference between this comparative example and Example 3 is that no filler is filled in the MBR reactor and no microorganisms are inoculated into the activated sludge.

[0076] Comparative Example 2

[0077] The wastewater was treated in the same manner as in Example 5 except for the following conditions:

[0078] S2. Filling a membrane bioreactor (i.e., an MBR reactor, in which activated sludge is filled) with clay ceramsite (the filling amount of clay ceramsite is the same as the filling amount of the filler in Example 5), and inoculating microorganisms into the activated sludge (the microorganisms are composed of Bacillus and progesterone-degrading bacteria MPA-3 strains in a mass ratio of 50:50), the mass ratio of microorganisms to activated sludge is 0.5:100, and the co-microorganisms are evenly divided into three portions and added three times, and the interval between adjacent batches is 2h;

[0079] The wastewater treated in step S1 is introduced into the membrane bioreactor from the bottom, and after 4 hours, the wastewater is discharged from the membrane bioreactor from the top.

[0080] That is, the difference between this comparative example and Example 5 is that the filler only includes clay ceramsite but does not include sulfur and siderite, and the wastewater is not electrolyzed during the membrane bioreactor treatment process.

[0081] Comparative Example 3

[0082] The wastewater was treated in the same manner as in Example 5 except for the following conditions:

[0083] S2. Filling a membrane bioreactor (i.e., an MBR reactor, in which activated sludge is filled) with a filler (the filler is composed of clay ceramsite and sulfur in a mass ratio of 35:12, and the filling amount of the filler is the same as the filling amount of the filler in Example 5), and inoculating microorganisms into the activated sludge (the microorganisms are composed of Bacillus and progesterone-degrading bacteria MPA-3 strains in a mass ratio of 20-80:80-20), the mass ratio of microorganisms to activated sludge is 0.5:100, and the co-microorganisms are evenly divided into three portions and added three times, and the interval between adjacent batches is 2h;

[0084] The wastewater treated in step S1 is introduced into the membrane bioreactor from the bottom, and after 4 hours, the wastewater is discharged from the membrane bioreactor from the top.

[0085] That is, the difference between this comparative example and Example 5 is that the filler only includes clay ceramsite and sulfur but not siderite, and the wastewater is not electrolyzed during the membrane bioreactor treatment process.

[0086] Comparative Example 4

[0087] The wastewater was treated in the same manner as in Comparative Example 3 except for the following conditions:

[0088] S2. Filling a membrane bioreactor (i.e., an MBR reactor, in which activated sludge is filled) with a filler (the filler is composed of clay ceramsite and sulfur in a mass ratio of 35:12, and the filling amount of the filler is the same as the filling amount of the filler in Example 5) and inoculating microorganisms into the activated sludge (the microorganisms are composed of Bacillus and progesterone-degrading bacteria MPA-3 strains in a mass ratio of 50:50), the mass ratio of microorganisms to activated sludge is 0.5:100, and the co-microorganisms are evenly divided into three portions and added three times, and the interval between adjacent batches is 2h;

[0089] The wastewater treated in step S1 is introduced into the membrane bioreactor from the bottom. After 4 hours, the wastewater is discharged from the membrane bioreactor from the top. During the treatment process in the membrane bioreactor, a density of 15 mA / cm 2 And the voltage is 8V DC.

[0090] That is, the difference between this comparative example and comparative example 3 is that in the membrane bioreactor treatment process, the current density is 15 mA / cm 2 The wastewater is electrolyzed by direct current with a voltage of 8V.

[0091] test

[0092] The endocrine disrupting substances removal rates of Examples 3-5 and Comparative Examples 1-4 were tested. Specifically, the contents of nonylphenol, bisphenol A, estriol and estrone in the inlet and outlet water were respectively tested by solid phase extraction-gas chromatography. The total content of nonylphenol, bisphenol A, estriol and estrone was taken as the content of endocrine disrupting substances. Then, according to the formula The removal rate of endocrine disruptors was calculated and the results are shown in Table 1.

[0093] Table 1 Test results

[0094] Group Endocrine disruptors removal rate Example 3 59.9％ Example 4 86.3％ Example 5 91.6％ Comparative Example 1 36.2％ Comparative Example 2 60.0％ Comparative Example 3 71.7％ Comparative Example 4 80.8％

[0095] As can be seen from Table 1, compared with Comparative Example 1 (no filler is loaded in the MBR reactor, and no microorganisms are inoculated into the activated sludge), the endocrine disruptor removal rate of Example 3 is significantly improved. The results show that in the present application, by anaerobic-aerobic treatment, the metabolism of microorganisms in anaerobic and aerobic environments can be utilized to remove endocrine disruptors such as nonylphenol and bisphenol in wastewater, followed by membrane-activated sludge treatment, during which fillers are loaded in the equipment used, and activated sludge is inoculated with microorganisms including antibiotic degrading bacteria and progesterone degrading bacteria, endocrine disruptors can be adsorbed by fillers, antibiotics such as estriol in wastewater are degraded into small molecule compounds by antibiotic degrading bacteria, and progesterone degrading bacteria are used to degrade progestins such as estrone into small molecule compounds, and impurities are intercepted by ultrafiltration membranes, thereby effectively purifying water quality.

[0096] As shown in Table 1, compared with Example 3, Example 4 (in the membrane bioreactor process, the current density is 15 mA / cm 2 The removal rate of endocrine disruptors is significantly improved when the wastewater is electrolyzed by direct current with a voltage of 8V. The results show that in the present application, during the membrane-activated sludge process, the wastewater to be treated is electrolyzed, and the presence of voltage during the electrolysis process can drive the redox reaction in the wastewater, thereby promoting the degradation of impurities such as estriol and estrone by the above-mentioned antibiotic degrading bacteria and progesterone degrading bacteria, further improving the water quality. At the same time, the electrolysis process can cause the iron-containing particles to dissociate more ferrous ions, so as to grow more iron-type reducing bacteria, thereby degrading more organic substances such as nonylphenol, bisphenol A, estriol, and estrone, thereby further reducing the content of endocrine disruptors in the wastewater.

[0097] As shown in Table 1, compared with Example 4, the endocrine disruptor removal rate of Example 5 (after membrane-activated sludge treatment, wastewater is subjected to ozone catalytic oxidation treatment) is significantly improved. This result shows that in this application, by adding an ozone catalytic oxidation treatment step after the membrane treatment, it is possible to use ozone to oxidize the remaining impurities such as nonylphenol, bisphenol A, estriol, and estrone in the water body, thereby further improving the water quality.

[0098] It can be seen from Table 1 that compared with Comparative Example 2 (the filler only includes clay ceramsite but not sulfur and siderite, and the wastewater is not electrolyzed during the membrane bioreactor treatment process) and Comparative Example 3 (the filler only includes clay ceramsite and sulfur but not siderite, and the wastewater is not electrolyzed during the membrane bioreactor treatment process), the endocrine disruptor removal rate of Example 5 is significantly improved. The results show that in the present application, the compound use of expanded clay, sulfur and iron-containing particles can utilize the pores of expanded clay to effectively intercept impurities such as suspended matter, utilize the micropores on the surface of expanded clay to adsorb impurities, utilize the oxidizing properties of sulfur to undergo redox reaction with the hydroxyl groups in the estriol molecule, and utilize the pore structure on the surface of the iron-containing particles to adsorb impurities such as estriol and estrone. At the same time, in the presence of ferrous ions dissociated after the iron-containing particles are dissolved in the wastewater to be treated, iron-reducing bacteria grow in the system, and the iron-reducing bacteria can degrade organic matter such as nonylphenol, bisphenol A, estriol, and estrone, thereby further reducing the content of endocrine disruptors in the wastewater. The presence of voltage during the electrolysis process can drive the redox reaction in the wastewater, thereby promoting the degradation of impurities such as estriol and estrone by the above-mentioned antibiotic-degrading bacteria and progesterone-degrading bacteria, thereby further improving the water quality.

[0099] As shown in Table 1, compared with Comparative Example 3, Comparative Example 4 (in the membrane bioreactor process, the current density is 15 mA / cm 2 The removal rate of endocrine disruptors in the wastewater was significantly improved by using 8V direct current to electrolyze the wastewater. The results show that in the present application, the presence of voltage during the electrolysis process can drive the redox reaction in the wastewater, thereby promoting the degradation of impurities such as estriol and estrone by the above-mentioned antibiotic-degrading bacteria and progesterone-degrading bacteria, thereby further improving the water quality.

[0100] The above embodiments are merely illustrative of the principles and effects of the present application, and are not intended to limit the present application. Anyone familiar with the technology may modify or change the above embodiments without violating the spirit and scope of the present application. Therefore, all equivalent modifications or changes made by a person of ordinary skill in the art without departing from the spirit and technical ideas disclosed in the present application shall still be covered by the claims of the present application.

Claims

1. A method for treating wastewater containing endocrine disruptors, wherein the endocrine disruptors include at least one of nonylphenol, bisphenol A, estriol and estrone, characterized in that: The method for treating wastewater containing endocrine disruptors comprises the following steps: The wastewater to be treated is subjected to anaerobic-aerobic treatment and membrane-activated sludge treatment in sequence. The equipment used in the membrane-activated sludge treatment process is filled with fillers and the activated sludge is inoculated with microorganisms including antibiotic-degrading bacteria and progesterone-degrading bacteria.

2. The method for treating wastewater containing endocrine disruptors according to claim 1, characterized in that: The filler comprises ceramsite, sulfur and iron-containing particles, and the iron-containing particles contain ferrous ions.

3. The method for treating wastewater containing endocrine disruptors according to claim 2, characterized in that: The iron-containing particles are selected from at least one of siderite particles, hematite particles and pyrite particles.

4. The method for treating wastewater containing endocrine disruptors according to claim 2, characterized in that: The mass ratio of the ceramsite, the sulfur and the iron-containing particles is 30-45:10-15:45-58.

5. The method for treating wastewater containing endocrine disruptors according to claim 1, characterized in that: The mass ratio of the antibiotic degrading bacteria to the progesterone degrading bacteria is 20-80:80-20.

6. The method for treating wastewater containing endocrine disruptors according to claim 1, characterized in that: The antibiotic degrading bacteria are selected from at least one of bacillus, photosynthetic bacteria, lactic acid bacteria, actinomycetes, yeast and fermentative filamentous bacteria; And / or, the progesterone-degrading bacteria is selected from the progesterone-degrading bacteria MPA-3 strain; And / or, the mass ratio of the microorganism to the activated sludge is 0.3-0.8:

100.

7. The method for treating wastewater containing endocrine disruptors according to claim 2, characterized in that: During the membrane-activated sludge process, the wastewater to be treated is electrolyzed; And / or, after the membrane-activated sludge process treatment, the method for treating wastewater containing endocrine disruptors further comprises the following steps: subjecting the wastewater to be treated to ozone catalytic oxidation treatment.

8. The method for treating wastewater containing endocrine disruptors according to claim 7, characterized in that: During the electrolysis process, the power source used is direct current; And / or, the current density of the electrolysis is 10-20 mA / cm 2 , the voltage of the electrolysis is 5-10V.

9. The method for treating wastewater containing endocrine disruptors according to claim 7, characterized in that: During the ozone catalytic oxidation treatment process, the catalyst used is selected from at least one of an iron-based homogeneous catalyst, an aluminum-based homogeneous catalyst, a copper-based homogeneous catalyst, a manganese-based homogeneous catalyst, a cobalt-based homogeneous catalyst, a zinc-based homogeneous catalyst, a nickel-based homogeneous catalyst, a cadmium-based homogeneous catalyst and a chromium-based homogeneous catalyst.

10. The method for treating wastewater containing endocrine disruptors according to claim 9, characterized in that: The dosage of the catalyst is 3-5 g / L.