CN113292141A - Electrocatalytic membrane component for water treatment and water treatment method - Google Patents
Electrocatalytic membrane component for water treatment and water treatment method Download PDFInfo
- Publication number
- CN113292141A CN113292141A CN202110768069.9A CN202110768069A CN113292141A CN 113292141 A CN113292141 A CN 113292141A CN 202110768069 A CN202110768069 A CN 202110768069A CN 113292141 A CN113292141 A CN 113292141A
- Authority
- CN
- China
- Prior art keywords
- membrane
- cathode
- wiring port
- electrocatalytic
- shell
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/46—Treatment of water, waste water, or sewage by electrochemical methods
- C02F1/461—Treatment of water, waste water, or sewage by electrochemical methods by electrolysis
- C02F1/467—Treatment of water, waste water, or sewage by electrochemical methods by electrolysis by electrochemical disinfection; by electrooxydation or by electroreduction
- C02F1/4672—Treatment of water, waste water, or sewage by electrochemical methods by electrolysis by electrochemical disinfection; by electrooxydation or by electroreduction by electrooxydation
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/44—Treatment of water, waste water, or sewage by dialysis, osmosis or reverse osmosis
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/30—Organic compounds
Abstract
The application relates to the technical field of water treatment, in particular to an electrocatalytic membrane component for water treatment and a water treatment method. The electrocatalysis membrane component used for water treatment comprises an electrocatalysis membrane, a cathode metal net, a cathode wiring port, an anode wiring port, a water inlet, a water outlet, a shell, an upper cover, a lower cover and an upper sealing element; the electrocatalysis membrane and the cathode metal net are arranged in the shell in parallel, the cathode wiring port is connected with one end of the cathode metal net, and the anode wiring port is connected with one end of the electrocatalysis membrane; the anode wiring port and the cathode wiring port are used for being connected with an external power supply through leads; the upper sealing piece is connected with the upper cover and separates and seals the cathode wiring port and the anode wiring port. The electrocatalytic membrane component for water treatment in the application has a more compact structure, is suitable for water purification equipment, and has lower energy consumption.
Description
Technical Field
The application relates to the technical field of water treatment, in particular to an electrocatalytic membrane component for water treatment and a water treatment method.
Background
It is well known that water is a source of life. In recent years, the water environment is continuously polluted, and residents in rural areas and remote areas in China often drink polluted water to cause diseases, so that the health and the work of the residents are seriously influenced. Especially, some artificially synthesized dyes are left in the water environment and are difficult to degrade, and are enriched in water with time, so that the artificially synthesized dyes have long-term and chronic toxicity to human beings and other organisms, and even have carcinogenic and teratogenic effects.
The water purifier can well solve the problems. The water purifier which appears earliest in recent times is a diatomite ceramic water filtering tank in UK in 1835 years, and can filter out large-particle suspended matters in water and reduce the turbidity of the water body. In 1906, a diatomite ceramic water filter capable of filtering bacteria appeared, and the diatomite ceramic water filter is widely applied to public places such as schools, hospitals and the like. Modern water purifiers originate in the last 70 th year of the United states, enter China in the middle 80 th year, and in the middle 90 th year, more than 800 enterprises for producing water purifiers in China are produced and are distributed throughout 18 provincial and municipal autonomous regions. The product is also developed from the original single activated carbon water purifier to the water purifier with single process or combined process such as microfiltration, ultrafiltration, KDF (copper zinc alloy), reverse osmosis, electrodialysis and the like. After 2000 years, the produced water purifier mainly adopts the combined process modes of microfiltration, activated carbon, ultrafiltration and the like. After 2010, with the development of industry, water pollution is mainly chemical pollution, pollutants such as heavy metals in water can be removed by a reverse osmosis technology, and a reverse osmosis water purification machine begins to become a main product of each large enterprise.
Membrane separation is a high-efficiency, energy-saving and environment-friendly separation technology, and becomes a key technology for solving important problems of energy, resources, environment and the like in China. However, in the membrane wastewater treatment process, contaminants are deposited on the surface or pores of the membrane, which causes membrane fouling and increases the transmembrane pressure difference, decreases the membrane flux, and shortens the membrane service life. Ultrafiltration and microfiltration membranes are used in a great variety of applications in wastewater treatment. Microfiltration is as easy to clog as other membrane technologies, and is not easy to clean and regenerate. The pore size of the ultrafiltration membrane is 0.001-0.1 μm, the ultrafiltration membrane can filter heat source substances and bacteria in water and can also remove organic matters of certain macromolecules, the required working pressure of the ultrafiltration membrane cannot be lower than 0.1MPa, the working pressure is higher than that of microfiltration, and the flux is lower. The reverse osmosis and nanofiltration technologies are suitable for filtering inorganic substances, ions, small molecules and partial organic substances in water, the required working pressure is very high, and the blockage is easy to occur. Moreover, this is a bottleneck limiting the application of reverse osmosis and nanofiltration technologies in the field of wastewater treatment. The electrocatalytic membrane combines the membrane separation technology and the electrocatalytic oxidation technology, so that the service life of the membrane can be effectively prolonged, and the filtering effect is improved.
The electrocatalytic membrane is mainly divided into a metal membrane and a carbon membrane. The carbon membrane is a porous carbon-based membrane material and is prepared by pyrolyzing and carbonizing an organic polymer at high temperature, and the carbon membrane integrates the excellent structural characteristics of the carbon material and the high-efficiency energy-saving advantages of a membrane separation technology. The metal film is high temperature resistant and strong in conductivity, and is one of the first electrocatalytic films used by researchers, and titanium is the most common film material in the metal film. The deep research is carried out on the electrocatalysis membrane and the components thereof, the electrocatalysis membrane component with high water purification efficiency, long service life and small volume and quality is researched and developed, the electrocatalysis membrane component has important significance for wastewater treatment, and the trouble that drinking water is lacked in remote areas can be relieved or even solved.
Patent CN101597096A discloses an electrocatalytic membrane reactor device. The reactor consists of a feed liquid tank, an electrocatalytic composite membrane, an auxiliary electrode, a stabilized voltage power supply, a vacuum meter, a peristaltic pump and the like. The device is simple to operate, has low energy consumption, and can effectively solve the problem of membrane pollution. However, the device has larger volume and loose structure, and is only suitable for treating oily wastewater and dye wastewater in a laboratory. Patent CN211688639U discloses an electrocatalytic membrane reactor for water treatment. The reactor comprises a purifier, a motor, a fan, a reactor and a filter. The device reduces the load of the electro-catalytic membrane reactor through the primary purification of the purifier; the purification efficiency of the wastewater is improved by accelerating the fan; the purified water can be finally filtered through a filter and an active carbon filter screen. However, the device is bulky and heavy.
In view of this, the present application is specifically made.
Disclosure of Invention
The primary object of the present application is to provide an electrocatalytic membrane module for water treatment.
A second object of the present invention is to provide a water treatment method.
In order to achieve the purpose of the invention of the application, the technical scheme is as follows:
the application relates to an electrocatalytic membrane component for water treatment, which comprises an electrocatalytic membrane, a cathode metal mesh, a cathode wiring port, an anode wiring port, a water inlet, a water outlet, a shell, an upper cover, a lower cover and an upper sealing element;
the electrocatalytic membrane and the cathode metal mesh are arranged in the shell in parallel;
the upper cover is positioned at the top of the shell, and the lower cover is positioned at the bottom of the shell;
the cathode wiring port is connected with one end of the cathode metal net, and the anode wiring port is connected with one end of the electro-catalytic membrane;
the anode wiring port and the cathode wiring port are used for being connected with an external power supply through leads;
the upper sealing piece is connected with the upper cover, separates the cathode wiring port from the anode wiring port and seals the cathode wiring port and the anode wiring port.
Optionally, the assembly is of a vertical tubular structure, and the electrocatalytic membrane is a tubular electrocatalytic membrane and is arranged in parallel inside the shell;
the cathode metal net is also tubular and is concentrically arranged outside the electrocatalytic membrane and inside the shell.
Optionally, the water inlet is located on the lower cover, and the water outlet is located at the upper part of the shell.
Preferably, the top end of the tubular electrocatalytic membrane is connected with the anode wiring port;
the tail end of the tubular electro-catalysis membrane is connected with the water outlet.
Optionally, the upper sealing element comprises a cathode sealing sleeve, an anode sealing sleeve, a fixing seat, a first sealing ring and a second sealing ring;
the top end of the cathode metal net is fixed in the fixed seat;
the first sealing ring is arranged between the shell and the cathode metal net, and the second sealing ring is arranged between the cathode metal net and the tubular electro-catalytic membrane;
the upper edges of the first sealing ring and the second sealing ring are connected with the lower edge of the fixed seat.
Optionally, the anode sealing sleeve is wrapped outside the anode wiring port and used for sealing the anode wiring port; the cathode sealing sleeve is coated outside the cathode wiring port and used for sealing the cathode wiring port; the anode sealing sleeve and the cathode sealing sleeve are arranged in the fixing seat.
Optionally, a third sealing ring and a fourth sealing ring are further arranged at the bottom end of the assembly;
the third sealing ring is arranged between the bottom of the shell and the tail end of the cathode metal net, and the fourth sealing ring is arranged between the tail end of the cathode metal net and the tail end of the tubular electro-catalytic membrane;
and the lower edges of the third sealing ring and the fourth sealing ring are connected with the upper edge of the lower cover.
Optionally, the electrocatalytic membrane module further comprises a gland, and the gland is arranged between the upper cover and the upper sealing element;
preferably, the outer side of the upper edge of the shell is provided with threads, and the shell and the upper cover are matched through the threads.
More preferably, the upper edge of the lower cover is provided with a buckle, and the shell and the lower cover are matched through the buckle.
Optionally, the assembly is of a plate structure, the electrocatalytic membrane is a plate electrocatalytic membrane, and the cathode metal mesh is a plate cathode metal mesh;
the plate-shaped electrocatalytic membrane and the plate-shaped cathode metal mesh are arranged in the shell in parallel.
Optionally, the water outlet and the water inlet are both arranged in the middle of the shell and located on two opposite side surfaces of the shell.
Preferably, the upper sealing member includes a sealing gasket and a gland; the cathode wiring port and the anode wiring port are arranged in the gland;
the gland covers the upper ends of the plate-shaped electrocatalytic membrane and the plate-shaped cathode metal mesh;
the sealing gasket is arranged between the gland and the upper cover.
Optionally, the opening of the cathode wiring port and the opening of the anode wiring port are arranged on the upper cover, and the sealing gasket and the upper cover are provided with through holes for installing the cathode wiring port and the anode wiring port.
Preferably, the bottom end of the shell is further provided with a base, and the ends of the plate-shaped electrocatalytic membrane and the plate-shaped cathode metal mesh are both arranged in the base.
More preferably, the housing and the upper cover are matched through screws for fixing the sealing gasket and the pressing cover.
Optionally, the electrocatalytic membrane is a carbon membrane coated with an electrocatalyst; the electrocatalyst is preferably Bi-SnO2(ii) a The cathode metal net is a titanium net or a stainless steel net.
The invention also relates to a water treatment method using the electrocatalytic membrane module, which comprises the following steps:
s1, allowing the organic wastewater to enter the electro-catalytic membrane through the water inlet, pass through the cathode metal mesh, and flow out along the water outlet; adsorbing organic matters and bacteria in the organic wastewater;
preferably, the temperature is 18-25 ℃, and more preferably 20 ℃;
further preferably, the flow rate is 1-2.5 mL/min, more preferably 1.5 mL/min;
s2, starting an external power supply, taking the electrocatalytic membrane as an anode and the cathode metal net as a cathode to form an electrocatalytic device, and electrochemically degrading and inactivating organic matters and bacteria in the organic wastewater;
preferably, the voltage of the external power source is 3V.
The application has at least the following beneficial effects:
the electro-catalytic membrane component for water treatment has a more compact structure, is suitable for water purifying equipment, and has lower energy consumption.
Drawings
FIG. 1 is a cross-sectional view of a tubular electrocatalytic membrane module according to one embodiment of the present application;
FIG. 2 is an enlarged view of a portion of FIG. 1;
FIG. 3 is a schematic structural view of a tubular electrocatalytic membrane module according to one embodiment of the present disclosure;
FIG. 4 is a cross-sectional view of a plate-type electrocatalytic membrane module according to an embodiment of the present application;
FIG. 5 is a schematic diagram of a plate-type electrocatalytic membrane module according to an embodiment of the present disclosure;
reference numerals:
1-covering the upper cover;
2-a shell;
3-pressing the cover;
4-a cathode wiring port;
5-an anode wiring port;
6-tubular cathode metal mesh;
6' -plate-like cathode metal mesh;
7-a tubular electrocatalytic membrane;
7' -plate-like electrocatalytic membrane;
8-lower cover;
9-a water inlet;
10-a water outlet;
11-cathode seal cartridge;
12-anode gland;
13-a fixed seat;
14-a first sealing ring;
15-a second sealing ring;
16-a third sealing ring;
17-a fourth seal ring;
18-buckling;
19-threading;
19-a base;
20-a seal gasket;
21-screw.
FIG. 6 is a diagram showing the effect of an electro-catalytic membrane module in degrading tetracycline in water;
FIG. 7 is a diagram of the pathway of tetracycline degradation by an electrocatalytic membrane module;
FIG. 8 is a diagram showing the effect of an electro-catalytic membrane module in degrading bisphenol A in water;
FIG. 9 is a diagram of the pathway for degrading bisphenol A by an electrocatalytic membrane module;
FIG. 10 is a diagram showing the effect of an electrocatalytic membrane module on inactivation of Escherichia coli;
FIG. 11 is an SEM image of E.coli before and after inactivation of the electrocatalytic membrane module;
FIG. 12 is a diagram showing the effect of an electro-catalytic membrane module on inactivation of colonies in natural water.
Detailed Description
It should be noted that the following detailed description is exemplary and is intended to provide further explanation of the disclosure. Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this application belongs.
It is noted that the terminology used herein is for the purpose of describing particular embodiments only and is not intended to be limiting of example embodiments according to the present application. As used herein, the singular forms also include the plural forms unless the context clearly dictates otherwise, and further, it is understood that when the terms "comprises" and/or "comprising" are used in this specification, they specify the presence of the stated features, steps, operations, devices, components, and/or combinations thereof.
The technical solutions of the present application will be described clearly and completely with reference to the following embodiments, and it should be understood that the described embodiments are some, but not all embodiments of the present application. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present application.
The embodiment of the application provides an electro-catalytic membrane component for water treatment, and the component can be widely applied to small and medium-sized water purifying equipment or devices. The electrocatalytic membrane technology is a new technology combining an electrocatalytic oxidation technology and a membrane separation technology, compared with the traditional membrane technology, the electrocatalytic membrane has certain advantages, and in the membrane separation process, due to the screening and interception effects of membrane pores, the problems of membrane pore blockage, membrane pollution and the like can often occur, and strong oxidizing radicals generated in the electrocatalytic oxidation process can degrade organic matters, so that the problems are effectively alleviated.
The electrocatalysis membrane component of the embodiment of the application comprises an electrocatalysis membrane, a cathode metal net, a cathode wiring port, an anode wiring port, a water inlet, a water outlet, a shell, an upper cover, a lower cover and an upper sealing element; wherein the electrocatalytic membrane is an anode, the cathode metal mesh is a cathode, the cathode wiring port is connected with one end of the cathode metal mesh, and the anode wiring port is connected with one end of the electrocatalytic membrane; the anode wiring port and the cathode wiring port are used for being connected with an external power supply through leads; thereby forming an electrocatalytic device. It is characterized by that the described membrane separation mechanism mainly is sieving effect and adsorption action, and the driving force of separation process is static pressure difference of two sides of membrane. The electrocatalytic oxidation mechanism is that OH with strong oxidation capacity is generated by the electrode under the action of an electric field, so that a plurality of organic pollutants which are difficult to degrade are decomposed into CO2、H2O or other simple compounds. The membrane component combines a membrane separation technology and an electrocatalysis technology, utilizes the conductivity of the membrane, and coats an electrocatalyst on the surface of the membrane which is used as a substrate of a composite electrode so as to enhance the electrocatalysis performance of an original membrane and further improve the degradation efficiency of the electrode on organic matters in wastewater. The electrocatalysis membrane and the cathode metal net are arranged in the shell in parallel, so that the electrocatalysis membrane and the cathode metal net are prevented from contacting with each other; the whole electro-catalytic device is arranged in a shell, the shell comprises a shell body, an upper cover and a lower cover, the upper cover is positioned at the top of the shell body, and the lower cover is positioned at the bottom of the shell body; since the assembly of the present application is used for water treatment, it is necessary to seal the anode and cathode wiring ports to ensure that they do not come into contact with water, and therefore, the design is such thatThe upper sealing piece is connected with the upper cover, separates the cathode wiring port from the anode wiring port and seals the cathode wiring port and the anode wiring port.
As an improvement of the embodiment of the present application, the electrocatalytic membrane module is a vertical tubular electrocatalytic membrane module, and a cross-sectional view thereof is as shown in fig. 1, a schematic structural view thereof is as shown in fig. 3, and fig. 2 is an enlarged structural view of fig. 1. As can be seen from fig. 1 to 3, the electrocatalytic membrane module in the present embodiment includes a tubular electrocatalytic membrane 7, a tubular cathode metal mesh 6, a cathode wiring port 4, an anode wiring port 5, a water inlet 9, a water outlet 10, a housing 2, an upper cover 1, a lower cover 8, and an upper sealing member; wherein the tubular electrocatalytic membrane 7 is an anode, the tubular cathode metal mesh 6 is a cathode, the cathode wiring port 4 is connected with one end of the tubular cathode metal mesh 6, and the anode wiring port 5 is connected with one end of the tubular electrocatalytic membrane 7; the anode wiring port 5 and the cathode wiring port 4 are used for being connected with an external power supply through leads; thereby forming an electrocatalytic device; wherein the tubular electrocatalytic membrane 7 and the tubular cathode metal mesh 6 are arranged in parallel in the shell 2 to ensure that the two are not contacted with each other; the whole electro-catalytic device is arranged in a shell, the shell comprises a shell body 2, an upper cover 1 and a lower cover 8, the upper cover 1 is positioned at the top of the shell body 2, and the lower cover 8 is positioned at the bottom of the shell body 2. The water inlet 9 is positioned on the lower cover 8, and the water outlet 10 is positioned on the upper part of the shell 2. The top end of the tubular electrocatalytic membrane 7 is connected with the anode wiring port 5; the end of the tubular electrocatalytic membrane 7 is connected with the water outlet 10. Because the assembly of this application is used for water treatment, consequently need with positive pole wiring mouth 5 and negative pole wiring mouth 4 sealed, guarantee that it does not take place the contact with water, consequently, design has the upper seal to be connected with upper cover 1, and separates negative pole wiring mouth 4, positive pole wiring mouth 5, and seals in it. The upper sealing element comprises a cathode sealing sleeve 11, an anode sealing sleeve 12, a fixed seat 13, a first sealing ring 14 and a second sealing ring 15; the top end of the tubular cathode metal mesh 6 is fixed in the fixed seat 13; the first sealing ring 14 is arranged between the shell 2 and the tubular cathode metal mesh 6, and the second sealing ring 15 is arranged between the tubular cathode metal mesh 6 and the tubular electro-catalytic membrane 7; the upper edges of the first sealing ring 14 and the second sealing ring 15 are connected with the lower edge of the fixed seat 13. The anode sealing sleeve 12 is coated outside the anode wiring port 5 and used for sealing the anode wiring port 5; the cathode sealing sleeve 11 is coated outside the cathode wiring port 4 and used for sealing the cathode wiring port 4; the anode sealing sleeve 12 and the cathode sealing sleeve 11 are arranged in the fixing seat 13.
As an improvement of the vertical tubular electro-catalytic membrane module, the bottom end of the electro-catalytic membrane module is also provided with a third sealing ring 16 and a fourth sealing ring 17; the third sealing ring 16 is arranged between the bottom of the shell 2 and the tail end of the tubular cathode metal mesh 6, and is used for avoiding the contact between the shell 2 and the tubular cathode metal mesh 6 and playing a role in sealing; the fourth sealing ring 17 is disposed between the end of the tubular cathode metal mesh 6 and the end of the tubular electro-catalytic membrane 7, and is used for preventing the tubular cathode metal mesh 6 from contacting the tubular electro-catalytic membrane 7 and simultaneously playing a role in sealing. The lower edges of the third sealing ring 16 and the fourth sealing ring 17 are connected with the upper edge of the lower cover 8, preferably fixedly connected or integrally designed.
As an improvement of the vertical tubular electro-catalytic membrane component, the electro-catalytic membrane component further comprises a gland 3, and the gland 3 is arranged between the upper cover 1 and the upper sealing element and used for fixing and sealing a cathode sealing sleeve 11 and an anode sealing sleeve 12.
As an improvement of the vertical tubular electro-catalytic membrane module, the outer side of the upper edge of the shell 2 is provided with threads 19, the shell 2 and the upper cover 1 are matched through the threads 19, and the threads are designed to increase the convenience of assembly.
As an improvement of the vertical tubular electro-catalytic membrane module, the upper edge of the lower cover 8 is provided with a buckle 18, and the shell 2 and the lower cover 8 are matched through the buckle 18, and the buckle can play a sealing role.
As an improvement of the embodiment of the application, the electrocatalytic membrane module is of a plate type structure. The cross-sectional view is shown in fig. 4, and the structural schematic diagram is shown in fig. 5. As can be seen from fig. 4 and 5, the electrocatalytic membrane module in the present embodiment includes a plate-shaped electrocatalytic membrane 7 ', a plate-shaped cathode metal mesh 6', a cathode wiring port 4, an anode wiring port 5, a water inlet 9, a water outlet 10, a housing 2, an upper cover 1, a lower cover 8, and an upper sealing member; wherein the plate-shaped electrocatalysis membrane 7 'is an anode, the plate-shaped cathode metal net 6' is a cathode, the cathode wiring port 4 is connected with one end of the plate-shaped cathode metal net 6 ', and the anode wiring port 5 is connected with one end of the plate-shaped electrocatalysis membrane 7'; the anode wiring port 5 and the cathode wiring port 4 are used for being connected with an external power supply through leads; thereby forming an electrocatalytic device; wherein, the plate-shaped electrocatalysis membrane 7 'and the plate-shaped cathode metal net 6' are arranged in the shell 2 in parallel to ensure that the electrocatalysis membrane and the cathode metal net are not contacted with each other; the whole electro-catalytic device is arranged in a shell, the shell comprises a shell body 2, an upper cover 1 and a lower cover 8, the upper cover 1 is positioned at the top of the shell body 2, and the lower cover 8 is positioned at the bottom of the shell body 2. The lower cover 8 and the housing 2 may be designed in one piece. The housing 2 and the upper cover 1 are engaged with each other by four screws 21, and the packing 20 and the pressing cover 3 are fixed.
As an improvement of the plate-type electrocatalysis membrane component, the water outlet 10 and the water inlet 9 are both arranged in the middle of the shell 2 and positioned on two opposite side surfaces of the shell 2.
As an improvement of the plate-type electrocatalytic membrane module, the upper sealing member comprises a sealing gasket 20 and a gland 2; the cathode wiring port 4 and the anode wiring port 5 are arranged in the gland 3; the gland 3 coats the upper ends of the plate-shaped electrocatalytic membrane 7 'and the plate-shaped cathode metal mesh 6'; the packing 20 is disposed between the cover 3 and the upper cover 1.
As an improvement of the plate type electrocatalysis membrane component, the openings of the cathode wiring port 4 and the anode wiring port 5 are arranged on the upper cover 1, and the sealing gasket 20 and the upper cover 1 are both provided with through holes for installing the cathode wiring port 4 and the anode wiring port 5.
As an improvement of the plate-type electrocatalytic membrane module, the bottom end of the shell 2 is also provided with a base 19, and the tail ends of the plate-type electrocatalytic membrane 7 'and the plate-type cathode metal mesh 6' are both arranged in the base 19.
As a modification of the plate type electrocatalytic membrane module, the housing 2 and the upper cover 1 are matched by screws 21 for fixing the sealing gasket and the pressing cover.
In the structure, the shapes of the upper cover, the gland, the cathode sealing sleeve, the anode sealing sleeve, the fixed seat and the like are designed by the application according to the performance requirement of the electro-catalytic membrane component.
Compared with the existing membrane component and the existing electro-catalytic device, the membrane component and the electro-catalytic device have the following advantages: the structure and the process are simple, and the operation is convenient; secondary pollution can not be caused; the structure is compact, and the device can be conveniently integrated on certain equipment or devices; the electrolysis process is carried out under the condition of low voltage, and the energy consumption is lower.
As an improvement of the embodiment of the application, the electrocatalytic membrane is a carbon membrane coated with an electrocatalytic agent; the electrocatalyst is preferably Bi-SnO2. The preparation process of the electrocatalytic membrane can refer to the preparation and performance research of carbon nanotube electrocatalytic membrane of the master thesis, authors: zhang Xinqi (2009). The electrocatalysis membrane is not only used for membrane separation, but also takes the membrane element as an anode and selects titanium, stainless steel or other metal materials as a cathode by utilizing the conductivity and corrosion resistance of the carbon-based membrane material, and is connected with a power supply through a wiring port to realize the electrocatalysis effect. The organic pollutants which are only attached to the surface and in the holes of the membrane in the membrane separation process are degraded by the electro-catalytic membrane component, so that the energy consumption is very low. The voltage of the power supply used is usually around 3V and the current is around 0.1A, at which the energy consumption is about 32.2 kWh/kgTOC.
The embodiment of the application also relates to a water treatment method, which uses the electrocatalytic membrane module and comprises the following steps:
s1, allowing the organic wastewater to enter the electro-catalytic membrane through the water inlet, pass through the cathode metal mesh, and flow out along the water outlet; adsorbing organic matters and bacteria in the organic wastewater;
wherein the temperature is 18-25 ℃, and preferably 20 ℃; the flow rate is 1-2.5 mL/min, preferably 1.5 mL/min;
s2, starting an external power supply, taking the electrocatalytic membrane as an anode and the cathode metal net as a cathode to form an electrocatalytic device, and electrochemically degrading and inactivating organic matters and bacteria in the organic wastewater;
the voltage of the external power supply is equal to or less than 3V, preferably 3V.
The organic substance includes antibiotics and organic compounds difficult to decompose, such as polychlorinated biphenyl, polycyclic aromatic hydrocarbon, synthetic dye, synthetic pesticide, heterocyclic compounds, etc.
Example 1
The vertical tubular electro-catalytic membrane component in the embodiment of the application is used for removing tetracycline in water. To be coated with Bi-SnO2The carbon film is an anode, the stainless steel mesh is a cathode, andthe tetracycline removal effect was measured at a concentration of 50g/L, a temperature of 20 ℃ and a flow rate of 1.5mL/min with and without voltage application between the cathode and anode, respectively, as shown in FIG. 6. As can be seen from FIG. 6, when no voltage is applied, the tetracycline removal rate is high at the beginning due to the adsorption of the original carbon film, and the tetracycline removal rate in the filtrate rapidly decreases as the adsorption of tetracycline by the original carbon film becomes gradually saturated. And when 3V voltage is applied to the original carbon film, the tetracycline molecules adsorbed on the original carbon film are anodized under the action of electrochemical oxidation. When the applied voltage is 3V, the degradation rate of the tetracycline is obviously increased compared with that of 0V, after the tetracycline continuously runs for 6 hours, the degradation rate of the tetracycline is still as high as 80%, and compared with the degradation rate under 1 hour, the tetracycline basically keeps stable.
To further analyze the intermediate products of tetracycline decomposition, high performance liquid chromatography-mass spectrometry was performed on the products of tetracycline degradation. From mass spectrometry, the main products of tetracycline degradation have mass-to-charge ratios m/z of 418, 362, 306, 262, 246, 226, 218, 164, and so on, respectively. Since the tetracycline degradation intermediate is mainly formed by removing the functional group on the ring and ring-opening reaction during the electrochemical reaction, the route of the carbon-based electrocatalytic membrane for degrading the tetracycline product can be deduced, as shown in fig. 7. The tetracycline is gradually degraded into small molecular intermediate products under the action of electrochemical oxidation, and finally degraded into CO2And H2O。
Example 2
The vertical tubular electro-catalytic membrane component in the embodiment of the application is used for removing the bisphenol A in the water. To be coated with Bi-SnO2The carbon film of (1) was used as an anode, a stainless steel net was used as a cathode, the bisphenol A concentration was 30mg/L, the temperature was 20 ℃, and the flow rate was 1.5mL/min, and the removal effect of bisphenol A was measured when a voltage of 3V was applied between the cathode and the anode and when no voltage was applied, respectively, as shown in FIG. 8. As can be seen from fig. 8, when no voltage is applied, the adsorption of bisphenol a by the electrocatalytic membrane module is gradually saturated with time, which results in a rapid decrease in the removal rate of bisphenol a, indicating that the adsorption effect of the membrane module is not ideal for removing bisphenol a. When the applied voltage is 3V, the degradation rate of bisphenol A and the applied voltageThe pressure is 0V and is obviously increased, after the continuous operation is carried out for 6 hours, the degradation rate of the bisphenol A is still as high as 70.4 percent, and compared with the degradation rate under 1 hour, the degradation rate is basically kept stable.
To further analyze the intermediate product of bisphenol A decomposition, the product of bisphenol A decomposition was subjected to high performance liquid chromatography-mass spectrometry. From the mass spectrometry analysis, it can be seen that the charge-to-mass ratios m/z of the main products of bisphenol A degradation are 228, 244, 260, 94, 110, 134, 90, 92, 136 and 150, respectively. Based on the results of mass spectrometry, it is presumed that a possible degradation pathway of bisphenol A is shown in FIG. 9. Bisphenol A is gradually degraded into micromolecular intermediate products under the action of electrochemical oxidation, and finally degraded into CO2And H2O。
Example 3
The vertical tubular electro-catalytic membrane component in the embodiment of the application is used for removing escherichia coli in water. To be coated with Bi-SnO2The carbon film is used as an anode, the stainless steel net is used as a cathode, and the concentration of the Escherichia coli is 1 multiplied by 109CFU/mL, temperature of 20 ℃ and flow rate of 1.5mL/min, the removal effect of E.coli was tested with and without voltage applied between the cathode and anode, respectively, as shown in FIG. 10. As can be seen from FIG. 10, when no voltage is applied, the carbon-based electrocatalytic membrane with a pore size of 1.0 μm can remove a part of E.coli in water by adsorption and sieving, but the removal effect is poor. When the applied voltage is 3.0V, the removal rate of the escherichia coli is remarkably improved, and along with the increase of the operation time, the removal rate of the escherichia coli can be kept to be more than 99.90 percent, and the main reason is that the escherichia coli adsorbed on the surface of the membrane is inactivated by the electrocatalytic oxidation of the electrocatalytic membrane component.
FIG. 11 is a scanning electron micrograph of E.coli treated with the electrocatalytic membrane, wherein the left image is an electron micrograph in the absence of applied voltage, from which it can be seen that the E.coli surface was smooth in the absence of applied voltage and was retained on the membrane surface based on the sieving action of the electrocatalytic membrane. The right image is an electron micrograph when a voltage of 3V is applied, and it can be seen from the right image that the surface of E.coli shows remarkable dishing and shrinkage. The comparison of the shapes of the escherichia coli under the two conditions proves that the escherichia coli can be inactivated under the low-voltage condition by the strong oxidation of the electrocatalytic membrane.
Example 4
Adopt the board-like electric catalytic membrane subassembly in this application embodiment to inactivate the colony in the natural water to scribble Bi-SnO2The carbon membrane of (1) was used as an anode, the stainless steel mesh was used as a cathode, the temperature was 20 ℃, the water sample was the water of the Tianjin crescent river, the flow rate was 1.5mL/min, and the removal effect of E.coli was measured when 3V voltage was applied between the cathode and the anode and when no voltage was applied, as shown in FIG. 12. It can be seen from figure 12 that when no voltage is applied, the electrocatalytic membrane can remove part of bacteria through adsorption and screening interception, and as time increases, the colony removal rate gradually increases, mainly because particulate matter impurities in natural river water are more, the aperture of the membrane is blocked, the average aperture of the membrane is reduced, the screening interception of bacteria is enhanced, but the colony removal effect is poor. When the applied voltage is 3.0V, the removal effect of bacterial colonies is obviously improved, and the removal rate of escherichia coli can be kept above 99.0% along with the increase of the operation time, and the main reason is that the electrocatalytic oxidation of the electrocatalytic membrane inactivates bacteria adsorbed and trapped on the surface of the membrane.
Although the present application has been described with reference to preferred embodiments, it is not intended to limit the scope of the claims, and many possible variations and modifications may be made by one skilled in the art without departing from the spirit of the application.
Claims (12)
1. An electro-catalytic membrane component for water treatment,
comprises an electro-catalytic film, a cathode metal mesh, a cathode wiring port, an anode wiring port, a water inlet, a water outlet, a shell, an upper cover, a lower cover and an upper sealing element;
the electrocatalytic membrane and the cathode metal mesh are arranged in the shell in parallel;
the upper cover is positioned at the top of the shell, and the lower cover is positioned at the bottom of the shell;
the cathode wiring port is connected with one end of the cathode metal net, and the anode wiring port is connected with one end of the electro-catalytic membrane;
the anode wiring port and the cathode wiring port are used for being connected with an external power supply through leads;
the upper sealing piece is connected with the upper cover, separates the cathode wiring port from the anode wiring port and seals the cathode wiring port and the anode wiring port.
2. The electrocatalytic membrane module as set forth in claim 1, wherein said module is a vertical tubular structure, and said electrocatalytic membrane is a tubular electrocatalytic membrane disposed in parallel inside said housing;
the cathode metal net is also tubular and is concentrically arranged outside the electrocatalytic membrane and inside the shell.
3. The assembly of claim 2, wherein the water inlet is located on the lower cover and the water outlet is located at an upper portion of the housing;
preferably, the top end of the tubular electrocatalytic membrane is connected with the anode wiring port;
the tail end of the tubular electro-catalysis membrane is connected with the water outlet.
4. The electrocatalytic membrane assembly of claim 2, wherein the upper seal comprises a cathode seal cartridge, an anode seal cartridge, a retaining seat, a first seal ring, a second seal ring;
the top end of the cathode metal net is fixed in the fixed seat;
the first sealing ring is arranged between the shell and the cathode metal net, and the second sealing ring is arranged between the cathode metal net and the tubular electro-catalytic membrane;
the upper edges of the first sealing ring and the second sealing ring are connected with the lower edge of the fixed seat.
5. The electrocatalytic membrane assembly of claim 4,
the anode sealing sleeve is coated outside the anode wiring port and used for sealing the anode wiring port; the cathode sealing sleeve is coated outside the cathode wiring port and used for sealing the cathode wiring port; the anode sealing sleeve and the cathode sealing sleeve are arranged in the fixing seat.
6. The electrocatalytic membrane assembly of claim 2, wherein the bottom end of said assembly is further provided with a third sealing ring and a fourth sealing ring;
the third sealing ring is arranged between the bottom of the shell and the tail end of the cathode metal net, and the fourth sealing ring is arranged between the tail end of the cathode metal net and the tail end of the tubular electro-catalytic membrane;
and the lower edges of the third sealing ring and the fourth sealing ring are connected with the upper edge of the lower cover.
7. The assembly of claim 2, further comprising a gland disposed between the upper cover and the upper seal member;
preferably, the outer side of the upper edge of the shell is provided with a thread, and the shell is matched with the upper cover through the thread;
more preferably, the upper edge of the lower cover is provided with a buckle, and the shell and the lower cover are matched through the buckle.
8. The electrocatalytic membrane assembly of claim 1, wherein said assembly is a plate-type structure, said electrocatalytic membrane is a plate-like electrocatalytic membrane, and said cathode metal mesh is a plate-like cathode metal mesh;
the plate-shaped electrocatalytic membrane and the plate-shaped cathode metal mesh are arranged in the shell in parallel.
9. The electrocatalytic membrane assembly of claim 8, wherein said water outlet and said water inlet are both disposed in the middle of said housing on opposite sides of said housing;
preferably, the upper sealing member includes a sealing gasket and a gland; the cathode wiring port and the anode wiring port are arranged in the gland;
the gland covers the upper ends of the plate-shaped electrocatalytic membrane and the plate-shaped cathode metal mesh;
the sealing gasket is arranged between the gland and the upper cover.
10. The electrocatalytic membrane assembly as set forth in claim 9, wherein openings of said cathode wiring port and said anode wiring port are provided on said upper cover, and said sealing gasket and said upper cover are each provided with a through hole for mounting said cathode wiring port and said anode wiring port;
preferably, the bottom end of the shell is further provided with a base, and the tail ends of the plate-shaped electrocatalytic membrane and the plate-shaped cathode metal mesh are both arranged in the base;
more preferably, the housing and the upper cover are matched through screws for fixing the sealing gasket and the pressing cover.
11. The electrocatalytic membrane assembly of any one of claims 1-10, wherein the electrocatalytic membrane is a carbon membrane coated with an electrocatalyst; the electrocatalyst is preferably Bi-SnO2；
The cathode metal net is a titanium net or a stainless steel net.
12. A water treatment method using the electrocatalytic membrane module as set forth in any one of claims 1 to 11, comprising the steps of:
s1, allowing the organic wastewater to enter the electro-catalytic membrane through the water inlet, pass through the cathode metal mesh, and flow out along the water outlet; adsorbing organic matters and bacteria in the organic wastewater;
preferably, the temperature is 18-25 ℃, and more preferably 20 ℃;
further preferably, the flow rate is 1-2.5 mL/min, more preferably 1.5 mL/min;
s2, starting an external power supply, taking the electrocatalytic membrane as an anode and the cathode metal net as a cathode to form an electrocatalytic device, and electrochemically degrading and inactivating organic matters and bacteria in the organic wastewater;
preferably, the voltage of the external power source is 3V.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202110768069.9A CN113292141A (en) | 2021-07-07 | 2021-07-07 | Electrocatalytic membrane component for water treatment and water treatment method |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202110768069.9A CN113292141A (en) | 2021-07-07 | 2021-07-07 | Electrocatalytic membrane component for water treatment and water treatment method |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN113292141A true CN113292141A (en) | 2021-08-24 |
Family
ID=77330663
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202110768069.9A Pending CN113292141A (en) | 2021-07-07 | 2021-07-07 | Electrocatalytic membrane component for water treatment and water treatment method |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN113292141A (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114749177A (en) * | 2022-05-20 | 2022-07-15 | 烟台哈尔滨工程大学研究院 | Preparation method of sewage ozone oxidation catalyst |
| CN115501767A (en) * | 2022-09-06 | 2022-12-23 | 山东省科学院海洋仪器仪表研究所 | Electrocatalysis membrane, electrocatalysis membrane component and preparation method |
-
2021
- 2021-07-07 CN CN202110768069.9A patent/CN113292141A/en active Pending
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114749177A (en) * | 2022-05-20 | 2022-07-15 | 烟台哈尔滨工程大学研究院 | Preparation method of sewage ozone oxidation catalyst |
| CN115501767A (en) * | 2022-09-06 | 2022-12-23 | 山东省科学院海洋仪器仪表研究所 | Electrocatalysis membrane, electrocatalysis membrane component and preparation method |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| US10266429B2 (en) | Efficient treatment of wastewater using electrochemical cell | |
| CN107098442B (en) | Spiral winding type electrochemical water treatment reactor | |
| CA2835727C (en) | Efficient treatment of wastewater using electrochemical cell | |
| CN113292141A (en) | Electrocatalytic membrane component for water treatment and water treatment method | |
| US20080073288A1 (en) | Multifunctional filtration and water purification systems | |
| WO2019169785A1 (en) | Use of membrane-free microbial fuel cell coupled with cathode catalytic membrane in coking wastewater treatment system | |
| KR20150092216A (en) | Method for imparting filtering capability in electrolytic cell for wastewater treatment | |
| CN106044967B (en) | Synchronous desalination removes the sewage water treatment method and device of organic matter | |
| KR101928905B1 (en) | Method for purifying contaminated water and facility using the same | |
| CN110526348B (en) | Membrane filtration-electrocatalysis sewage treatment method | |
| CN110002530B (en) | Membrane adsorption assembly, renewable membrane adsorption reactor, liquid treatment device and method | |
| CN104587841A (en) | Conductive filter membrane and preparation method and application thereof | |
| CN106698679A (en) | Filtering type cathode microorganism desalting battery and sewage treatment method | |
| CN106006929A (en) | Method for all-weather sewage treatment through coupling of photoelectrocatalysis membrane and microbial fuel cell | |
| JP7010529B2 (en) | Sterilization and cleaning method using water electrolyzer and water electrolyzer and method for decomposing and removing harmful substances | |
| US6798639B2 (en) | Fluid deionization flow through capacitor systems | |
| CN110092450B (en) | Electrochemical water treatment device | |
| CN110536868B (en) | Electrochemical cell for wastewater treatment with improved electrical protection | |
| CN216837263U (en) | Electrocatalytic membrane component for water treatment | |
| CN109534461A (en) | A kind of continuous filtering type device for electrochemical water preparation based on whole multichannel porous electrode | |
| CN105948177B (en) | A kind of high-flux electric chemical filtering sewage-treatment plant | |
| CN202808446U (en) | Circulating type electro-adsorption liquid purifying device | |
| CN109095545B (en) | Device and method for treating high-concentration organic wastewater through cooperation of electrochemistry and photocatalysis | |
| CN109133271B (en) | Portable electric filtering emergency water purifier | |
| CN114314737B (en) | Sewage treatment method and device for synchronous desalination and degradation of organic matters through photoelectric synergistic enhancement |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination |