CN107555528B - Integrated mechanical photocatalytic membrane separation coupling reactor and wastewater treatment method thereof - Google Patents
Integrated mechanical photocatalytic membrane separation coupling reactor and wastewater treatment method thereof Download PDFInfo
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Abstract
The invention discloses an integrated mechanical photocatalytic membrane separation coupling reactor, which comprises a water inlet area, a mixing area, a reaction area and a water outlet area; the water inlet area is provided with a water inlet; the mixing zone at least comprises a mixing zone side wall and a bottom, the mixing zone side wall can move up and down relative to the bottom, a mechanical stirrer is arranged in the mixing zone, the mixing zone is communicated with the water inlet zone through the bottom of the mixing zone, and the mixing zone is sealed and isolated from the reaction zone through the mixing zone side wall; the reaction zone at least comprises a reaction zone side wall, a filtering membrane is arranged on the reaction zone side wall, an ultraviolet lamp is arranged in the reaction zone, and the reaction zone at least surrounds the lower part of the mixing zone side wall; the side wall of the reaction zone separates the reaction zone from the water outlet zone, and the water outlet zone is provided with a water collecting pipe. The invention also discloses a method for treating wastewater by using the integrated mechanical photocatalytic membrane separation coupling reactor. The reactor disclosed by the invention is high in integration degree, convenient to carry, convenient to operate, low in production cost, high in photocatalyst use efficiency and good in application prospect.
Description
Technical Field
The invention relates to the technical field of wastewater treatment, in particular to an integrated mechanical photocatalytic membrane separation coupling reactor and a wastewater treatment method thereof.
Background
In recent years, due to the demand of industrial and economic development, many industrial waste water containing toxic substances is continuously discharged into the environment, and the toxic substances in the industrial waste water are difficult to biodegrade, so that great harm is brought to industrial and agricultural production, people's life and human health. How to effectively treat the wastewater causing environmental pollution becomes a research hotspot in the environmental field. The photocatalytic oxidation technology is a novel water pollution treatment technology, has the characteristics of high efficiency, energy conservation, wide application range and the like, is commonly used for treating organic matters which are difficult to biodegrade in wastewater, and has wide application prospect. Among them, the photocatalyst is used in two forms, one is fixed on a carrier (i.e., a supported catalyst), and the other is suspended and dispersed in a solution (i.e., a suspended catalyst). In the case of supported catalysts, the mass transfer of contaminants to the catalyst surface is limited, resulting in a decrease in photocatalytic efficiency. The suspended catalyst is uniformly distributed, the surface area is large, the catalytic efficiency is higher, but the fine photocatalyst particles are not easy to separate and recycle by the traditional separation technology, the recycling rate is low, the discharged liquid is easy to generate secondary pollution, and the application of the suspended catalyst is severely limited.
The membrane separation technology is a novel separation and purification technology which is rapidly developed in recent years. In the water treatment process, the purpose of separating pollutants in concentrated water is achieved through the micro-pore interception effect on the surface of the membrane, the membrane separation process generally has no phase change and secondary pollution, can be continuously operated at normal temperature, and has the advantages of low energy consumption, small equipment volume, convenient operation and the like. However, the membrane fouling problem causes the membrane flux to decrease and shortens the service life of the membrane, and although some research progress has been made in controlling the membrane fouling measures, it is still a major bottleneck in the development of the membrane separation technology.
The photocatalytic oxidation technology and the membrane separation technology have respective advantages, but have respective disadvantages, the photocatalytic oxidation technology and the membrane separation technology are combined and applied in the water treatment industry in few cases, and the photocatalytic-membrane separation technology is not mature enough. Accordingly, the prior art is yet to be improved and developed.
The photocatalytic oxidation technology and the membrane separation technology have respective advantages, but have respective disadvantages, the photocatalytic oxidation technology and the membrane separation technology are combined and applied in the water treatment industry in few cases, and the photocatalytic-membrane separation technology is not mature enough. Accordingly, the prior art is yet to be improved and developed.
Disclosure of Invention
The purpose of the invention is as follows: the invention aims to provide a photocatalysis-membrane separation reactor which can overcome the problems that the existing photocatalysis membrane device is complex in structure, the solid photocatalyst of the reactor is difficult to separate, and the service life of the membrane is short, and has the advantages of long service life, low cost and high integration degree.
The invention also aims to provide a method for treating wastewater, which can efficiently remove trace organic matters in water and has a simple back washing program.
The technical scheme is as follows: the invention provides an integrated mechanical photocatalytic membrane separation coupling reactor, which comprises a water inlet area, a mixing area, a reaction area and a water outlet area, wherein the water inlet area is connected with the mixing area; the water inlet area is provided with a water inlet; the mixing zone at least comprises a mixing zone side wall and a bottom, the mixing zone side wall can move up and down relative to the bottom, a mechanical stirrer is arranged in the mixing zone, the mixing zone is communicated with the water inlet zone through the bottom of the mixing zone, and the mixing zone is sealed and isolated from the reaction zone through the mixing zone side wall; the reaction zone at least comprises a reaction zone side wall, a filtering membrane is arranged on the reaction zone side wall, an ultraviolet lamp is arranged in the reaction zone, and the reaction zone at least surrounds the lower part of the mixing zone side wall; the side wall of the reaction zone separates the reaction zone from the water outlet zone, and the water outlet zone is provided with a water collecting pipe.
In order to improve the wastewater treatment efficiency of the reactor and reduce the volume of the reactor, the mixing zone, the reaction zone and the water outlet zone are in concentric sleeve shapes which are sequentially arranged from inside to outside, and the water inlet zone is arranged below the mixing zone, the reaction zone and the water outlet zone.
In order to fully mix the wastewater in the mixing zone with the catalyst, the bottom of the mixing zone is provided with a conical structure protruding towards the lower side of the mixing zone, and a plurality of water inlet holes are uniformly distributed; the inclination angle of the bottom of the mixing area relative to the bottom of the water inlet area is 25-35 degrees, and the lower end of the bottom of the mixing area is in contact with the bottom of the water inlet area, so that the structure is favorable for the wastewater to form circulation, and the wastewater is fully mixed with the catalyst in the mixing area.
In order to improve the photocatalytic reaction efficiency in the reaction zone, a plurality of ultraviolet lamps are arranged in the reaction zone in parallel around the mixing zone, the wavelength of light emitted by the ultraviolet lamps is 253.7nm, and quartz protective sleeves are arranged outside the ultraviolet lamps; in order to reduce the temperature of the reaction zone and improve the reaction efficiency, cooling coils are respectively coiled outside the quartz protective sleeve.
In order to separate the solid catalyst and the wastewater efficiently and improve the stability of the filtering membrane, the side wall of the reaction zone comprises a support plate and the filtering membrane tightly attached to the support plate, a plurality of water permeable holes are distributed in the support plate, and the aperture of the filtering membrane is 0.01-0.03 micrometer.
In another aspect, the present invention provides a method for treating wastewater using the integrated mechanical photocatalytic membrane separation coupled reactor, comprising: adding the photocatalyst into the mixing zone through the top of the mixing zone, injecting wastewater into the reactor from the water inlet, enabling the wastewater to enter the mixing zone through the bottom of the mixing zone, opening the mechanical stirrer to uniformly mix the wastewater and the photocatalyst, opening the ultraviolet lamp, and upwards lifting the side wall of the mixing zone to enable the mixture of the wastewater and the photocatalyst to enter the reaction zone for photocatalytic reaction.
Wherein the photocatalyst is a mixture of 75% anatase and 25% rutile.
In order to prolong the service life of the filtering membrane, the photocatalyst is recycled, and after the photocatalytic reaction is finished, the water collecting pipe is connected to a back washing system for back washing, so that the photocatalyst on the filtering membrane is washed into the reaction zone; setting the backwashing frequency to be 1/7-1/10, preferably 1/9; the backwashing frequency is the ratio of the backwashing time to the time of the reactor running for wastewater treatment.
The working principle is as follows: the working principle of the invention is as follows: and opening an upper cover of the mixing area, putting the photocatalyst into the mixing area of the reactor, then opening a water inlet of the water inlet area, and injecting the wastewater containing the organic pollutants into the water inlet area to enable the wastewater to flow into the mixing area through a water inlet hole at the bottom of the mixing area. Because the bottom of the mixing zone is in a conical shape protruding towards the lower side of the mixing zone, a circular flow of wastewater flowing up and down can be formed in the mixing zone, the uniform mixing of the wastewater and the photocatalyst is facilitated, the hydraulic loss is reduced, and the stirring process is more sufficient. Injecting water to about 5cm below the upper end of the side wall of the mixing area, opening the mechanical stirring device, and violently stirring for about 3 hours to uniformly disperse the catalyst in the wastewater to form a catalyst suspension. The side wall of the mixing zone is lifted upwards, so that the mixture of the wastewater and the photocatalyst enters the reaction zone, the ultraviolet lamp is turned on, the reaction of the organic pollutants in the photocatalyst catalysis wastewater begins to be carried out, and meanwhile, the cooling coil switch is turned on, so that the temperature of the reaction zone is reduced, and the reaction efficiency is improved. Then, the wastewater flows from the reaction zone to the water outlet zone through the side wall of the reaction zone, and the photocatalyst in the wastewater is separated from the wastewater by the filter membrane. After reacting for a period of time, sampling from a water collecting pipe of a water outlet area to detect the concentration of organic matters in the treated wastewater, and continuously detecting that the three treatment effects are qualified, which indicates that the reaction in the reactor is stable. And then, connecting the water collecting pipe to a back washing system for back washing, and washing the photocatalyst into the organic wastewater in the reaction zone to continuously play a role.
Has the advantages that: the technical scheme of the invention has the following beneficial effects:
1. the invention relates to an integrated mechanical photocatalytic membrane separation coupling reactor, wherein the side wall of a reaction zone comprises a support plate and a filtering membrane coated on the outer side of the support plate, and a water outlet zone is surrounded on the outer side of the side wall of the reaction zone; during back washing, the water collecting pipe of the water outlet area is directly connected to a back washing system, so that the photocatalyst on the filtering membrane enters the wastewater of the reaction area to continuously exert catalytic action, the separation effect is high, and the use efficiency of the photocatalyst is high; stirring, solid-liquid separation's operation all reacts in a reactor, needn't additionally add the device, conveniently carries, the simple operation, low in production cost for back flush operation is convenient going on more.
2. The integrated mechanical photocatalytic membrane separation coupling reactor can be designed to be fully automatic, and can run unattended for a long time or be remotely monitored through a novel wireless communication system; the continuous operation of the reactor of the present invention for treating wastewater is carried out without the waste stream requiring further treatment (i.e., no new waste stream entering the reactor), thereby allowing nearly complete recovery of clean water; the reactor does not need chemical additives or other oxidants (such as Cl) in the wastewater treatment process2，O3，H2O2) The degree of integration is very high, especially suitable for being used as laboratory pilot plant, and compared with conventional water treatment process, the energy consumption of the reactor is relatively low, and a cost-effective and environment-friendly water purification technology can be realized.
Drawings
FIG. 1 is a front view of a reactor according to the present invention;
FIG. 2 is a top view of a reactor according to the present invention.
Detailed Description
Example 1
Fig. 1 is a view showing an integrated mechanical photocatalytic membrane separation coupling reactor according to the present invention, and fig. 2 is a plan view showing the integrated mechanical photocatalytic membrane separation coupling reactor according to the present invention. As shown in fig. 1 and fig. 2, the integrated mechanical photocatalytic membrane separation coupling reactor is provided with a water inlet zone 1, a mixing zone 2, a reaction zone 3 and a water outlet zone 4. The mixing zone 2 and the reaction zone 3 are respectively columnar containers, the lower ends of the side walls of the mixing zone 2 and the reaction zone 3 are parallel and level, and the relative positions of the mixing zone 2, the reaction zone 3 and the water outlet zone 4 are in concentric sleeve shapes which are sequentially arranged from inside to outside. The water inlet zone 1 is a tubular structure lying below the mixing zone 2, the reaction zone 3 and the water outlet zone 4.
The water inlet area 1 is provided with a water inlet 5; mixing area 2 includes mixing area lateral wall 6 and mixing area bottom 7, mixing area lateral wall 6 can reciprocate relatively mixing area bottom 7, be equipped with mechanical agitator 8 in the mixing area 2, mixing area bottom 7 is hugged closely into 1 upper end in district, be to the convex conical structure of mixing area downside, this conical structure is intake the inclination of district bottom 13 relatively and is 30 (mixing area bottom 7 is about 30 degrees with the horizontal angle promptly), 7 evenly distributed in mixing area bottom have a plurality of inlet openings, mixing area 2 communicates each other with intake area 1 through the inlet opening of mixing area bottom 7, mixing area bottom 7 most advanced and intake area bottom 13 contact. The arrangement of the inclined angle at the bottom of the mixing zone 2 can form a circular flow of wastewater flowing up and down in the mixing zone, so that the wastewater and the catalyst are uniformly mixed, the hydraulic loss is reduced, and the stirring process is more sufficient. The lower part of the mixing zone 2 is surrounded by the reaction zone 3, the upper part extends out of the upper end of the reaction zone 3, and the mixing zone 2 is sealed and isolated from the reaction zone 3 by a mixing zone side wall 6.
The reaction zone 3 comprises a reaction zone side wall 9 and a reaction zone upper end 17, the reaction zone is sealed by the reaction zone upper end 17, 4 ultraviolet lamps 11 of 39W are arranged in the reaction zone 3 in parallel around the mixing zone 2, the wavelength of light emitted by the ultraviolet lamps 11 is 253.7nm, each ultraviolet lamp 11 is respectively provided with a quartz protective sleeve, the ultraviolet lamps 11 are immersed in the reaction chamber of the reaction zone 3, cooling coils 14 are respectively wound outside the quartz protective sleeves, and the cooling coils 14 enter from the bottom of the reactor and then are wound from bottom to top along the outer walls of the quartz protective sleeves outside the ultraviolet lamps 11. The mixing zone side wall 6 can move up and down relative to the mixing zone bottom 7. Because mixing area 2 is less for 3 volumes in the reaction area, mix after completely, when opening mixing area 2's lateral wall 6, the liquid after the mixture gets into reaction area 3, and the surface of water must descend, if reaction area 3's height is as high as mixing area 2, must lead to having the unable utilization of a large part upper space and extravagant, consequently makes mixing area lateral wall 6 be higher than reaction area lateral wall 9, guaranteed to mix after district lateral wall 6 pulls up, the space utilization is comparatively abundant.
The water outlet zone 4 is arranged around the reaction zone 3, and the lower end of the side wall of the water outlet zone 4 is provided with a water collecting pipe 12 which is parallel to the water inlet zone 1. The side wall 9 of the reaction zone is composed of a support plate 15 and a filtering membrane 10 tightly attached to the support plate 15, the filtering membrane 10 is in a plate type filtering membrane form, the aperture is 0.03 micrometer, a plurality of water permeable holes 16 are distributed on the support plate 15, the aperture of the filtering membrane 10 is 0.03 micrometer, and the reaction zone 3 is communicated with the water outlet zone 4 through the filtering membrane 10 of the side wall 9 of the reaction zone.
In the wastewater treatment, the upper cover of the mixing zone 2 is opened, and the photocatalyst which is a mixture of 75% anatase and 25% rutile is put into the mixing zone 2 of the reactor. Then, the water inlet 5 of the water inlet area 1 is opened, and the wastewater containing trace organic pollutants is injected into the water inlet area 1, so that the wastewater flows into the mixing area 2 through the water inlet hole at the bottom 7 of the mixing area. Because the bottom 7 of the mixing zone is of a conical structure protruding towards the lower side of the mixing zone, a circular flow of the wastewater flowing up and down can be formed in the mixing zone 2, so that the stirring process is more complete. Injecting water to about 5cm below the upper end of the side wall 6 of the mixing area, opening the mechanical stirring device 8, and violently stirring for about 3 hours to uniformly disperse the photocatalyst in the wastewater to form a catalyst suspension. The ultraviolet lamp 11 is turned on, the side wall 6 of the mixing zone is lifted upwards, the mixture suspension of the wastewater and the photocatalyst enters the reaction zone, the reaction of the organic pollutants in the photocatalyst catalysis wastewater begins, the switch of the cooling coil 14 is turned on, and the cooling coil 14 is used for reducing the temperature of the reaction zone and improving the reaction efficiency. Then, the waste water flows from the reaction zone 3 to the effluent zone 4 through the reaction zone side wall 9, and the photocatalyst in the waste water is separated from the waste water by the filtration membrane 10. After reacting for a period of time, sampling from the outlet of the water collecting pipe 12 of the water outlet area 4 to detect the concentration of organic matters in the treated wastewater, and continuously detecting the three treatment effects to be qualified, which indicates that the reaction in the reactor is stable. And then, the water collecting pipe 12 is connected into a back flushing system for back flushing, and the photocatalyst on the filtering membrane 10 is flushed into the organic wastewater in the reaction zone 3 to continuously play a role, so that the reuse of the photocatalyst is realized. The backwash frequency was 1/9 (i.e., the reactor was operated with a wastewater treatment time to backwash time ratio of 9: 1).
Example 2
The integrated mechanical photocatalytic membrane separation coupling reactor of example 1 is used for treating coking wastewater, the initial COD value of the coking wastewater is 163.5mg/L, the TOC value is 12mg/L, and the treatment conditions are as follows:
treatment time: 60 min;
the dosage of the photocatalyst is as follows: 2.5 g/L;
the COD value and the TOC value of the treated wastewater are respectively 70.3mg/L and 2.8 mg/L;
in addition, the coking wastewater is treated by adopting a common photocatalytic process device, the initial COD value of the coking wastewater is 163.5mg/L, the TOC value is 12mg/L, the experimental conditions (the treatment time and the dosage of the photocatalyst) are completely consistent, the treated COD value is 98.8mg/L, and the treated TOC value is 3.9 mg/L.
Example 3
The water to be treated is prepared by using the integrated mechanical photocatalytic membrane separation coupling reactor of the example 1 to treat commercial humic acid, the COD value is 89.8mg/L, the TOC value is 8.7mg/L, and the treatment is carried out under the following conditions:
treatment time: 40 min;
the dosage of the photocatalyst is as follows: 1.5 mg/L;
after treatment, the COD value is 38.6mg/L, and the TOC value is 1.6 mg/L;
in addition, a common photocatalysis process device is adopted to treat commodity humic acid to prepare water to be treated, the COD value is 89.8mg/L, the TOC value is 8.7mg/L, the experimental conditions (treatment time and photocatalyst dosage) are completely consistent, the treated COD value is 49.1mg/L, and the treated TOC value is 2.9 mg/L.
Example 4
A micro-polluted surface water with turbidity of 12-15, TOC value of 5.8mg/L and permanganate index of 3.6mg/L is taken and treated by using the integrated mechanical photocatalytic membrane separation coupling reactor of the example 1 under the following conditions:
treatment time: 30 min;
the dosage of the photocatalyst is as follows: 1mg/L
After treatment, the turbidity is 0, the TOC value is 0.9mg/L, and the permanganate index is 1.1 mg/L;
in addition, the micro-polluted surface water is treated by adopting a common photocatalytic process device, the experimental conditions (the treatment time and the dosage of the photocatalyst) are completely consistent, the turbidity is 0 after treatment, the TOC value is 1.8mg/L, and the permanganate index is 2.3 mg/L.
Claims (4)
1. An integrated mechanical photocatalytic membrane separation coupling reactor is characterized by comprising a water inlet area (1), a mixing area (2), a reaction area (3) and a water outlet area (4); the water inlet area (1) is provided with a water inlet (5); the mixing zone (2) at least comprises a mixing zone side wall (6) and a mixing zone bottom (7), the mixing zone side wall (6) can move up and down relative to the mixing zone bottom (7), a mechanical stirrer (8) is arranged in the mixing zone (2), the mixing zone (2) is communicated with the water inlet zone (1) through the mixing zone bottom (7), and the mixing zone (2) is sealed and isolated from the reaction zone (3) through the mixing zone side wall (6); the reaction zone (3) at least surrounds the lower part of the side wall (6) of the mixing zone, the reaction zone (3) at least comprises a reaction zone side wall (9), a filtering membrane (10) is arranged on the reaction zone side wall (9), and an ultraviolet lamp (11) is arranged in the reaction zone (3); the reaction zone side wall (9) separates the reaction zone (3) from the water outlet zone (4), the water outlet zone (4) is provided with a water collecting pipe (12), the mixing zone bottom (7) is a conical structure protruding towards the lower side of the mixing zone (2), a plurality of water inlet holes are uniformly distributed, the inclination angle of the mixing zone bottom (7) relative to the water inlet zone bottom (13) is 25-35 degrees, the lower end of the mixing zone bottom (7) is in contact with the water inlet zone bottom (13), a plurality of ultraviolet lamps (11) arranged in parallel around the mixing zone (2) are arranged in the reaction zone (3), cooling coils (14) are respectively coiled outside the ultraviolet lamps (11), the reaction zone side wall (9) comprises a support plate (15) and a filter membrane (10) tightly attached to the support plate (15), and a plurality of water permeable holes (16) are distributed in the support plate (15), the aperture of the filter membrane (10) is 0.01-0.03 micrometer.
2. A method for treating wastewater by using an integrated mechanical photocatalytic membrane separation coupled reactor of claim 1, comprising: adding a photocatalyst into the mixing zone (2) through the top of the mixing zone (2), injecting wastewater into the reactor from the water inlet (5), enabling the wastewater to enter the mixing zone (2) through the bottom (7) of the mixing zone (2), opening the mechanical stirrer (8) to uniformly mix the wastewater and the photocatalyst, opening the ultraviolet lamp (11), upwards lifting the side wall (6) of the mixing zone, and enabling the mixture of the wastewater and the photocatalyst to enter the reaction zone (3) for photocatalytic reaction.
3. The method according to claim 2, characterized in that after the photocatalytic reaction is finished, the water collecting pipe (12) is connected to a back washing system for back washing, and the photocatalyst on the filtering membrane (10) is washed into the reaction zone (3) for recycling.
4. The method of claim 2, wherein the backwashing frequency is 1/7-1/10, and the backwashing frequency is a ratio of the backwashing time to a time for which the reactor is operated to perform wastewater treatment.
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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN201634530U (en) * | 2010-02-10 | 2010-11-17 | 厦门市威士邦膜科技有限公司 | Photocatalytic oxidation, ultrasonic technology and membrane separation technology coupling device |
| CN202643372U (en) * | 2012-06-12 | 2013-01-02 | 常州大学 | Separation and reaction device for slight pollution raw water purified photocatalysis coupled film |
| CN105130045A (en) * | 2015-08-03 | 2015-12-09 | 河南科技大学 | Airlift photocatalytic membrane separation coupling reactor for processing organic wastewater |
| CN205011445U (en) * | 2015-08-10 | 2016-02-03 | 浙江品洁环保科技有限公司 | Vortex street mixed reaction equipment |
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Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN201634530U (en) * | 2010-02-10 | 2010-11-17 | 厦门市威士邦膜科技有限公司 | Photocatalytic oxidation, ultrasonic technology and membrane separation technology coupling device |
| CN202643372U (en) * | 2012-06-12 | 2013-01-02 | 常州大学 | Separation and reaction device for slight pollution raw water purified photocatalysis coupled film |
| CN105130045A (en) * | 2015-08-03 | 2015-12-09 | 河南科技大学 | Airlift photocatalytic membrane separation coupling reactor for processing organic wastewater |
| CN205011445U (en) * | 2015-08-10 | 2016-02-03 | 浙江品洁环保科技有限公司 | Vortex street mixed reaction equipment |
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