CN114044608A

CN114044608A - MABR-bio-trickling filter coupled wastewater treatment device and process

Info

Publication number: CN114044608A
Application number: CN202111325711.2A
Authority: CN
Inventors: 朱轶宁; 孙峰; 仲超; 徐卿
Original assignee: Taizhou Jiurun Environmental Protection Technology Co ltd
Current assignee: Taizhou Jiurun Environmental Protection Technology Co ltd
Priority date: 2021-11-10
Filing date: 2021-11-10
Publication date: 2022-02-15

Abstract

The utility model relates to an MABR membrane-biological trickling filter coupled wastewater treatment device and a process, wherein a spiral spring piece filter is used for treating silt and suspended matters in wastewater before MABR treatment, ozone is introduced for comprehensive treatment while the spiral spring piece filter is used for treating the wastewater, the treated wastewater is subjected to MABR membrane treatment, overflowed oxygen is generated and carries a small amount of organic waste gas in the MABR membrane treatment process, the overflowed organic waste gas is treated by a post-positioned biological trickling filter, so that the waste gas reaches the standard and is discharged, the biological trickling filter and an MABR membrane treatment reactor share a filter tank, thereby simplifying the flora culture, saving the control cost, a hydrophobic PVDF membrane is used as a base membrane, a compact PDMS layer is covered on the surface, the selectivity of the oxygen is enhanced, the flux of the oxygen is ensured, high-silicon zeolite is blended in the PDMS, the permeability and the selectivity of the membrane to the oxygen are enhanced, and the permeated oxygen can be adsorbed and slowly released, the dissolving amount of the wastewater to the oxygen is increased, the high-silicon zeolite is modified by using the aminosiloxane, the mixing uniformity between the high-silicon zeolite and the PDMS is increased, the dopamine layer is formed on the PDMS, the hydrophilicity and the affinity of the outer side of the hollow fiber membrane are increased, and the biological membrane is easier to form on the outer side of the membrane.

Description

MABR-bio-trickling filter coupled wastewater treatment device and process

Technical Field

The utility model relates to an MABR-bio-trickling filter coupled wastewater treatment device and a process.

Background

In recent years, with the continuous development of marine aquaculture industry, the amount of marine wastewater is gradually increased, which affects the marine ecological balance of people and threatens the survival of marine organisms, so that the treatment of marine aquaculture wastewater is urgent. The pollutants of the mariculture wastewater mainly comprise suspended particles, organic matters, ammonia nitrogen, nitrite, nitrate, phosphate and other pollutants, and the eutrophication degree of coastal water bank water areas can be aggravated if the pollutants are not treated. The mariculture wastewater has the defects of high salinity effect, complex technology and weak professional technology.

Pollutants in the mariculture wastewater mainly have two sources, firstly, excessive feed is added in the mariculture process, and the feed which is not used up is directly put into the sea bottom; on the other hand, metabolites generated in the metabolic process of marine products and antibiotics used in the cultivation process pollute the sea. Nitrate nitrogen NO in marine culture wastewater₃Too high a concentration of-N causes an imbalance in the local nutritional conditions and is converted to nitrite Nitrogen (NO) under local anaerobic conditions₂N), not only has certain toxic effect on marine organisms, but also pollutes nearby water bodies.

At present, the treatment process of the marine aquaculture wastewater mainly comprises the following steps: physical, chemical and microbiological methods, but each method has the corresponding disadvantages, such as large operation space and high cost; the chemical method can bring secondary pollution; the microbiological method has no ideal effect. Therefore, it is necessary to find a good method and process for treating the marine culture wastewater.

In recent years, as a common process for removing organic matters, nitrogen oxides and phosphorus compounds, MABR (membrane aeration membrane bioreactor) is widely applied to treatment of various types of wastewater, but the MABR urgently needs to increase oxygen permeability of a membrane, reduce operation pressure of the membrane and increase biocompatibility of the membrane, and in the MABR treatment process, a lot of waste gas is often generated due to aeration, so that additional air pollution is caused.

Disclosure of Invention

The application aims to provide a technology and a device for treating marine culture wastewater by coupling a physical-chemical-MABR-biological trickling filter.

The application provides an MABR-biological trickling filter coupled wastewater treatment device, which comprises a pre-filter, wherein the pre-filter comprises a shell, an inner cover is fixedly arranged in the shell, a marine culture wastewater inlet is arranged on the inner cover, the marine culture wastewater inlet outwards penetrates through the shell of the pre-filter and is connected with a marine culture wastewater storage tank, the top of the inner cover protrudes out of the shell and is connected with an ozone generating device, the ozone generating device is connected with an air compression device, a spiral spring piece filter is fixedly connected with the lower part of the inner cover and is formed by spirally winding stainless steel bars, the spiral spring piece filter is concentrically arranged with the inner cover, a hollow base concentrically arranged with the spiral spring piece filter is fixedly connected with the lower part of the spiral spring piece filter, the base is hinged at one end of a supporting rod, and a cam is eccentrically hinged at the other end of the supporting rod, the cam is rotationally connected with a motor in a motor protection cover hermetically connected with the bottom of the pre-filter through a connecting shaft, the bottom of the side wall of the pre-filter is provided with a sludge discharge port, the top of the side wall of the pre-filter is provided with a filtered wastewater outlet, the filtered wastewater is discharged from the filtered wastewater outlet and enters an MABR-bio-trickling filter coupling device, the MABR-bio-trickling filter coupling device is L-shaped, the filtered and ozonized wastewater firstly enters an MABR membrane reactor, the MABR membrane reactor is a hollow membrane reactor, one end inside the hollow fiber membrane is communicated with an air compression device, the other end inside the hollow fiber membrane is connected with a compressed air outlet, the air outlet is arranged outside the MABR-bio-trickling filter coupling device, the wastewater enters the lower part of the bio-trickling filter after undergoing an MABR reaction, and organic waste gas generated in the MABR treatment process is harmlessly discharged after being treated by the bio-trickling filter, the biological liquid pool is shared by the biological trickling filter bed and the MABR bioreactor, the biological trickling filter bed comprises a circulating pump, a spray head and filler, the spray head is arranged on the upper part of the filler, a demister is arranged on the upper part of the spray head, an exhaust port is arranged at the top of the biological trickling filter bed, and a purified water discharge port is arranged on the side wall of the MABR-biological trickling filter bed coupling device.

The application still provides the processing technology of a waste water, mariculture waste water is at first from mariculture waste water entry entering in the inner cover of leading filter, simultaneously in the top entering inner cover of ozone that produces passes through the inner cover among the ozone generating device, waste water and ozone bump and react, ozone produces a large amount of hydroxyl free radicals, decompose partial organic matter, and kill harmful fungus crowd, prevent in the waste water from the harmful fungus crowd who takes to produce harmful effects to hou miaBR and biological trickling filter bed, can produce partial oxygen in the waste water among the ozone treatment process, be favorable to the reaction of the MABR and biological trickling filter bed in later stage. Under the action of pressure, ozone and wastewater collide downwards and move into the spiral spring piece filter, the wastewater and the ozone radially flow out of the spiral spring piece filter along the gaps due to the fact that the gaps are formed in the periphery of the spiral spring piece filter, suspended matters and silt are blocked off and are accumulated to a large extent, the wastewater and the ozone fall into the bottom of the pre-filter along the hollow base, then the wastewater and the silt are discharged from a mud discharge port according to needs, filtered water is further settled in the pre-filter and is discharged through a filtered wastewater outlet at the top of the side wall of the pre-filter to enter an MABR-biological trickling filter coupling device, compressed air is introduced into the MABR through an air compression device, oxygen enters the wastewater outside the hollow fiber membrane through the membrane under the action of the MABR membrane component, the hollow fiber membrane is subjected to membrane hanging treatment by applying aerobic bacteria in advance, and the oxygen continuously provides oxygen for the aerobic bacteria through the hollow fiber membrane, pollutants in the waste water are continuously purified after being degraded by a biological film, in the MABR treatment process, overflowed oxygen and partial volatile gas carried by the oxygen are generated, the mixed gas of the oxygen and the volatile gas is treated by a biological trickling filter bed part in the MABR-biological trickling filter bed coupling device and then is discharged up to the standard, the MABR and the biological trickling filter bed can be subjected to biofilm formation treatment by the same bacteria, the MABR and the biological trickling filter bed share a treatment pool, the convenient flora management is realized, the operation and the control are simpler, the waste water is discharged through a purified water outlet after being treated and purified, and the gas is discharged through an exhaust port after being biochemically treated by biological filler.

The utility model also provides an MABR membrane and a corresponding preparation method, and the preparation method of the MABR membrane comprises the following steps: (1) adding the nano high-silicon zeolite into a DMF solvent, uniformly stirring, adding a small amount of aminosiloxane for reacting for a period of time, centrifugally separating after the reaction is finished, and drying the separated solid for 8 hours at room temperature for later use. (2) Mixing the high-silicon zeolite modified by the aminosiloxane with raw materials of amino-terminated polydimethylsiloxane, a cross-linking agent and a catalyst according to a certain mass ratio to form a casting solution. (3) And spraying a membrane casting solution on the surface of the hydrophobic hollow fiber PVDF membrane, then putting the membrane into a vacuum oven, and drying for 10 hours at 100 ℃ to obtain the hydrophobic oxygen permeable membrane with the PDMS layer on the surface. (4) Preparing a hydrophilic and hydrophilic biological modified solution, dissolving dopamine in an alkaline buffer solvent to prepare a dopamine-containing buffer solution with the concentration of 5.0g/L, specifically, adding dopamine into a sodium carbonate and sodium bicarbonate buffer solution with the pH value of 10, coating the solution on a hydrophobic oxygen permeable membrane with a PDMS layer on the surface, and reacting at 30 ℃ for 20 hours to obtain the hydrophilic and hydrophilic biological modified hollow fiber membrane. (5) The membranes were assembled to form MABR membrane modules.

Advantageous effects

(1) This application is handled silt and suspended solid in to waste water through applying the spiral spring piece filter before MABR handles, can prevent that silt and suspended solid from polluting the MABR membrane at the back, lets in ozone in waste water in the application, can get rid of harmful bacterium before MABR membrane treatment, for follow-up MABR technology provides partial oxygen, and produces a large amount of hydroxyl free radicals in the ozone treatment process, can realize preliminary processing to organic pollutant.

(2) The special spiral spring piece filter's of this application setting for ozone and waste water mix and get rid of silt, suspended solid simultaneously, can realize the set of multiple effect, and area is little, and the treatment effect is good.

(2) According to the preparation method, the hydrophobic PVDF membrane is used as the base membrane, the surface of the PVDF membrane is covered with the compact PDMS layer, the selectivity to oxygen is increased, the flux of oxygen is ensured, and the PDMS with the amino end capping is selected to be comb-shaped, so that the prepared membrane is more uniform. The PDMS is blended with the high-silicon zeolite, which has two functions, one is to increase the permeability and selectivity of the membrane to oxygen, and the other is to be used as a substance with adsorption performance, so that the permeated oxygen can be adsorbed and slowly released, the dissolution amount of the wastewater to the oxygen is increased, the high-silicon zeolite is modified by using the amino siloxane, and the mixing uniformity between the high-silicon zeolite and the PDMS is increased. The dopamine layer is formed on the PDMS, so that the hydrophilicity and the affinity of the outer side of the hollow fiber membrane are increased, the biological membrane is easier to form on the outer side of the membrane, a cross-linked bond is formed by an addition reaction of a quinone group on a polydopamine molecular layer and amino-terminated polydimethylsiloxane, the binding force of the hydrophilic affinity layer and the PDMS layer is increased, and the service life of the membrane is prolonged.

(3) This application utilizes the bio-trickling filter to handle its volatile waste gas after MABR, has prevented to appear new exhaust pollution in the MABR processing procedure, and the pond is handled in the two sharing, has simplified the cultivation and the growth detection control of flora, has practiced thrift the cost.

Drawings

FIG. 1 is a process flow diagram in the present application.

In the figure: 1. a pre-filter; 1-1, a marine aquaculture wastewater inlet; 1-2, inner cover; 1-3, an ozone generating device; 1-4, an air compression device; 1-8, spiral spring leaf filter; 1-9, a hollow base; 1-7, a cam; 1-6, a motor protective cover; 1-5, a motor; 1-11, a sludge discharge port; 1-10, and a filtered wastewater outlet; 2. MABR-bio-trickling filter bed; 2-2, circulating pump; 2-3, a spray head; 2-4, filling; 2-5, a demister; 2-6, an exhaust port; 2-7, an MABR membrane reactor; 2-8, a purified water discharge port; 2-9 and a compressed air outlet.

Detailed Description

It should be understood that the above-mentioned embodiments are merely illustrative of the technical concepts and features of the present invention, which are intended to enable those skilled in the art to understand the contents of the present invention and implement the present invention, and therefore, the protection scope of the present invention is not limited thereby. All equivalent changes and modifications made according to the spirit of the present invention should be covered within the protection scope of the present invention.

Example 1, the following technical scheme is adopted in this specific example: the application provides an MABR-bio-trickling filter coupled wastewater treatment device, which comprises a pre-filter 1, wherein the pre-filter 1 comprises a shell, an inner cover 1-2 is fixedly arranged in the shell, an ocean culture wastewater inlet 1-1 is arranged on the inner cover 1-2, the ocean culture wastewater inlet 1-1 outwards penetrates through the shell of the pre-filter 1 to be connected with an ocean culture wastewater storage tank, the top of the inner cover 1-2 protrudes out of the shell and is connected with an ozone generating device 1-3, the ozone generating device 1-3 is connected with an air compression device 1-4, the lower part of the inner cover is fixedly connected with a spiral spring piece filter 1-8, the spiral spring piece filter 1-8 is formed by spirally winding stainless steel sheets, the lower part of the spiral spring piece filter 1-8 is fixedly connected with a hollow base 1-9, the hollow base 1-9 is hinged at one end of a supporting rod, the other end of the supporting rod is eccentrically hinged with a cam 1-7, and the cam is rotatably connected with a motor 1-5 in a motor protective cover 1-6 which is hermetically connected with the bottom of the pre-filter 1 through a connecting shaft. The bottom of the side wall of the pre-filter 1 is provided with a sludge discharge port 1-11, and the top of the side wall of the pre-filter 1 is provided with a filtered waste water outlet 1-10. The filtered wastewater is discharged from a filtered wastewater outlet 1-10 and enters an MABR-bio-trickling filter 2 coupling device, and the MABR-bio-trickling filter 2 coupling device is L-shaped. The wastewater after filtration and ozone treatment firstly enters an MABR membrane reactor 2-7, the MABR membrane reactor is a hollow membrane reactor, one end of the inner part of the hollow fiber membrane is communicated with an air compression device 1-4, and the other end of the hollow fiber membrane is connected with a compressed air outlet 2-9. The wastewater enters the lower part of the bio-trickling filter bed rightwards after undergoing a biological reaction in the MABR, organic waste gas generated in the process is treated by the bio-trickling filter bed and then is discharged harmlessly, the bio-trickling filter bed and the MABR biological reactor share a filter tank, the bio-trickling filter bed comprises a circulating pump 2-2, a spray head 2-3 and a filler 2-4, the spray head 2-3 is arranged on the upper part of the filler 2-4, a demister 2-5 is arranged on the upper part of the spray head, and an exhaust port 2-6 is arranged at the top of the bio-trickling filter bed. The sidewall of the MABR-bio-trickling filter coupling device 2 is provided with purified water discharge ports 2-8.

The mariculture waste water firstly enters the inner cover 1-2 of the pre-filter 1 from the mariculture waste water inlet 1-1, meanwhile, ozone generated in the ozone generating device 1-3 enters the inner cover 1-2 through the top of the inner cover 1-2, the waste water and the ozone collide and react, the ozone generates a large amount of hydroxyl free radicals, partial organic matters are decomposed, harmful flora is killed, harmful flora in the waste water is prevented from generating adverse effects on a rear MABR reactor and a rear biological trickling filter bed, partial oxygen can be generated in the waste water in the ozone treatment process, and the reaction of the MABR and the biological trickling filter bed in the later period is facilitated. Under the action of pressure, ozone and wastewater collide downwards and move, then enter the spiral leaf filter 1-8, due to the fact that a plurality of gaps are formed in the periphery of the spiral leaf filter 1-8, the wastewater and the ozone radially flow out of the spiral leaf filter 1-8 along the gaps, suspended matters and silt are blocked, accumulated to a large extent and fall into the bottom of the pre-filter 1 along the hollow base 1-9, then are discharged from the mud discharge port 1-11 according to needs, filtered water is further settled in the pre-filter 1 and is discharged into the MABR-biological trickling filter bed coupling device 2 through the filtered wastewater discharge port 1-10 in the top of the side wall of the pre-filter 1, at the moment, compressed air is introduced into the MABR through the air compression device 1-4, under the action of the MABR membrane reactor 2-7, oxygen enters the wastewater outside the hollow fiber membrane through the membrane, the hollow fiber membrane is subjected to membrane hanging treatment by using aerobic bacteria in advance, the oxygen continuously provides oxygen for the aerobic bacteria through the hollow fiber membrane, pollutants in the wastewater are continuously subjected to degradation treatment through the biological membrane and then purified, in the MABR treatment process, the oxygen that spills over and the partial volatile gas that carries have been produced, the mist of oxygen and volatile gas utilizes the biological trickling filter bed part among MABR-biological trickling filter coupling device 2 to handle back discharge to reach standard, MABR and biological trickling filter bed all can utilize the same fungus to carry out the biofilm formation and handle, MABR and biological trickling filter bed sharing treatment tank, make things convenient for the flora management, the operation is simpler with control, waste water is discharged through purifying water discharge port after handling the purification, gaseous through the gas vent after bio-chemical treatment through the biofilm carrier.

The membrane module in the present application is prepared as follows: (1) weighing 0.2g of aminopropyltriethoxysilane, weighing 0.2g of nano high-silicon zeolite, dissolving the nano high-silicon zeolite and the aminopropyltriethoxysilane in 100g of DMF solvent, reacting for 10 hours, then centrifugally separating the high-silicon zeolite treated by the aminopropyltriethoxysilane, and drying for 8 hours at room temperature for later use. (2) 0.3g of hydroxy-terminated polydimethylsiloxane (viscosity 21000cSt), 0.1g of ethyl orthosilicate, 0.06g of dibutyltin dilaurate were weighed out, mixed with aminopropyltriethoxysilane-treated high-silicon zeolite and dissolved in 100g of solvent oil SOPA. And stirring and reacting for 4 hours at room temperature to form casting solution. (3) And spraying a membrane casting solution on the surface of the hydrophobic hollow fiber PVDF membrane, then putting the membrane into a vacuum oven, and drying for 10 hours at 100 ℃ to obtain the hydrophobic oxygen permeable membrane with the PDMS layer on the surface. (4) Preparing a hydrophilic and biological modification solution, dissolving dopamine in an alkaline buffer solvent to prepare a dopamine-containing buffer solution with the concentration of 5.0g/L, specifically, adding dopamine into a sodium carbonate and sodium bicarbonate buffer solution with the pH value of 10, coating the solution on a hydrophobic oxygen permeable membrane with a PDMS layer on the surface, and reacting at 30 ℃ for 20 hours to obtain the hydrophilic and biological modified hollow fiber membrane. (5) The membranes were assembled to form MABR membrane modules.

Wherein the water quality index of the wastewater is COD76mg/L, ammonia nitrogen 4.2mg/L, total phosphorus 2.3mg/L, and transparency is 18 cm.

Comparative example 2: the other processes were the same as example 1, and the difference from example 1 was mainly that the PDMS layer was not formed.

Comparative example 3: the other treatments were the same as in example 1, and the difference from example 1 was mainly that the PDMS layer was not added with the aminopropyltriethoxysilane-treated high-silica zeolite.

Comparative example 4: the other treatments were the same as in example 1, and were different from example 1 mainly in that a hydrophilic biotropic layer was not formed.

The results after treatment of the examples and comparative examples are shown in Table 1:

it can be seen from table 1 that the treatment effects of the embodiments 2-4 are all inferior to that of the embodiment 1, and it can be seen from the results that the PDMS composite layer, the modified high-silica zeolite added in the PDMS composite layer, and the hydrophilic and hydrophilic modification layer are all beneficial to the treatment of wastewater, and the membrane module of the present application has a synergistic treatment effect between layers.

Claims

1. A MABR-biological trickling filter coupled wastewater treatment device comprises a pre-filter, the pre-filter comprises a shell, an inner cover is fixedly arranged in the shell, a marine culture wastewater inlet is arranged on the inner cover, the marine culture wastewater inlet outwards penetrates through the shell of the pre-filter to be connected with a marine culture wastewater storage tank, the top of the inner cover protrudes out of the shell and is connected with an ozone generation device, the ozone generation device is connected with an air compression device, a spiral spring piece filter is fixedly connected to the lower part of the inner cover and is formed by spirally winding stainless steel strips, the spiral spring piece filter is concentrically arranged with the inner cover, a hollow base concentrically arranged with the spiral spring piece filter is fixedly connected to the lower part of the spiral spring piece filter, the base is hinged to one end of a supporting rod, and a cam is eccentrically hinged to the other end of the supporting rod, the cam is rotationally connected with a motor in a motor protection cover hermetically connected with the bottom of the pre-filter through a connecting shaft, the bottom of the side wall of the pre-filter is provided with a sludge discharge port, the top of the side wall of the pre-filter is provided with a filtered wastewater outlet, the filtered wastewater is discharged from the filtered wastewater outlet and enters an MABR-bio-trickling filter coupling device, the MABR-bio-trickling filter coupling device is L-shaped, the filtered and ozonized wastewater firstly enters an MABR membrane reactor, the MABR membrane reactor is a hollow membrane reactor, one end inside the hollow fiber membrane is communicated with an air compression device, the other end of the hollow fiber membrane is connected with an air outlet, the air outlet is arranged outside the ABR-bio-trickling filter coupling device, the wastewater enters the lower part of the bio-trickling filter after the MABR reaction, and organic waste gas generated in the MABR treatment process is harmlessly discharged after the treatment of the bio-trickling filter, the biological liquid pool is shared by the biological trickling filter bed and the MABR bioreactor, the biological trickling filter bed comprises a circulating pump, a spray head and filler, the spray head is arranged on the filler, a demister is arranged on the spray head, an exhaust port is arranged at the top of the biological trickling filter bed, and a purified water discharge port is arranged on the side wall of the MABR-biological trickling filter bed coupling device.

2. A process for wastewater treatment in an MABR-bio-trickling filter coupled wastewater treatment plant according to claim 1, characterized in that it comprises the following steps: the mariculture waste water firstly enters the inner cover of the pre-filter from the mariculture waste water inlet, meanwhile, ozone generated in the ozone generating device enters the inner cover through the top of the inner cover, the waste water collides and reacts with the ozone, the ozone generates a large amount of hydroxyl free radicals, part of organic matters are decomposed, harmful flora is killed, harmful flora is prevented from being generated by the harmful flora carried by the waste water to the MABR and the biological trickling filter bed at the back, partial oxygen can be generated in the waste water in the ozone treatment process, the reaction of the MABR and the biological trickling filter bed at the later stage is facilitated, the ozone and the waste water can move downwards in a collision way under the action of pressure and then enter the spiral spring piece filter, and as a plurality of gaps are formed in the periphery of the spiral spring piece filter, the waste water and the ozone can radially flow out of the spiral spring piece filter along the gaps, suspended matters and silt can be blocked, the accumulated amount is much, the water falls into the bottom of the pre-filter along the hollow base, silt and suspended matters are discharged from a mud discharge port, the filtered water is further settled in the pre-filter and then is discharged into an MABR-biological trickling filter coupling device through a filtered wastewater outlet at the top of the side wall of the pre-filter, at the moment, compressed air is introduced into the MABR through an air compression device, oxygen enters the wastewater outside the hollow fiber membrane through the membrane under the action of an MABR membrane component, the membrane is hung on the hollow fiber membrane by using pollutant-degradable bacteria, the oxygen provides oxygen for the pollutant-degradable bacteria through the hollow fiber membrane, pollutants in the wastewater are continuously purified after being degraded through the biological membrane, overflowed oxygen and part of volatile gas carried by the oxygen are generated in the MABR treatment process, and the gas is discharged after reaching the standard by using a biological trickling filter in the MABR-biological trickling filter coupling device, MABR and bio-trickling filter application same fungus carry out the biofilm formation and handle, and MABR and bio-trickling filter share the treatment tank, make things convenient for the flora management, and operation and control are simpler, and waste water is discharged through the purified water discharge port after handling the purification.

3. A wastewater treatment process as claimed in claim 2 wherein the MABR membrane is prepared by a process comprising the steps of: (1) adding the nano high-silicon zeolite into a DMF solvent, uniformly stirring, adding a little aminosiloxane for reacting for a period of time, and then drying for 8 hours at room temperature for later use after centrifugal separation. (2) Mixing the high-silicon zeolite modified by the aminosiloxane with raw materials of amino-terminated polydimethylsiloxane, a cross-linking agent and a catalyst according to a certain mass ratio to form a casting solution. (3) And spraying a membrane casting solution on the surface of the hydrophobic hollow fiber PVDF membrane, then putting the membrane into a vacuum oven, and drying for 8-12h at 80-120 ℃ to obtain the hydrophobic oxygen permeable membrane with the PDMS layer on the surface. (4) Preparing a hydrophilic and biological modification solution, dissolving dopamine in an alkaline buffer solvent to prepare a dopamine-containing buffer solution with the concentration of 4.0-7.0g/L, specifically, adding dopamine into a sodium carbonate and sodium bicarbonate buffer solution with the pH of 8-11, coating the solution on a hydrophobic oxygen permeable membrane with a PDMS layer on the surface, and reacting at 20-40 ℃ for 10-24h to obtain the hollow fiber membrane with the hydrophilic and biological modification layer. (5) The membranes were assembled to form MABR membrane modules.

4. A process for the treatment of waste water as claimed in claim 3, wherein said aminosilicone is aminopropyltriethoxysilane.