CN112010475A - Photocatalysis and membrane catalysis combined water treatment method and device - Google Patents
Photocatalysis and membrane catalysis combined water treatment method and device Download PDFInfo
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F9/00—Multistage treatment of water, waste water or sewage
-
- 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
- C02F1/001—Processes for the treatment of water whereby the filtration technique is of importance
-
- 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
- C02F1/30—Treatment of water, waste water, or sewage by irradiation
-
- 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
- C02F1/30—Treatment of water, waste water, or sewage by irradiation
- C02F1/32—Treatment of water, waste water, or sewage by irradiation with ultraviolet light
-
- 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
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/72—Treatment of water, waste water, or sewage by oxidation
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- 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
- C02F1/72—Treatment of water, waste water, or sewage by oxidation
- C02F1/722—Oxidation by peroxides
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- 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
- C02F1/72—Treatment of water, waste water, or sewage by oxidation
- C02F1/725—Treatment of water, waste water, or sewage by oxidation by catalytic oxidation
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- 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
- C02F1/72—Treatment of water, waste water, or sewage by oxidation
- C02F1/78—Treatment of water, waste water, or sewage by oxidation with ozone
-
- 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
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2305/00—Use of specific compounds during water treatment
- C02F2305/02—Specific form of oxidant
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- Environmental & Geological Engineering (AREA)
- Water Supply & Treatment (AREA)
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Treatment Of Water By Oxidation Or Reduction (AREA)
- Physical Water Treatments (AREA)
- Catalysts (AREA)
Abstract
The invention provides a method and a device for treating water by combining photocatalysis and membrane catalysis. The method comprises the following steps: A. filtering the waste water by a preposed security filter; B. the filtered wastewater enters a mixer, and oxygen is added into the mixer; C. the wastewater leaving the mixer enters a photocatalytic reactor; D. the wastewater leaving the photocatalytic reactor enters the membrane filtration catalytic reactor, and the water penetrating through the submerged membrane module enters the clean water tank. From the perspective of improving the oxidation efficiency and solving the residual ozone, the photocatalytic oxidation technology and the membrane catalysis technology are coupled, and the effects of photodegradation, photocatalytic oxidation, ozone/photocatalysis and membrane catalytic ozone oxidation are cooperatively exerted, so that the photocatalytic efficiency is improved, the membrane flux is improved, the membrane pollution is effectively slowed down, and the problem of residual ozone is solved.
Description
Technical Field
The invention relates to an advanced treatment technology of organic wastewater, in particular to a method and a device for treating water by combining photocatalysis and membrane catalysis.
Technical Field
With the development of industries such as petrifaction, medicine, pesticide, dye and the like in China, various refractory organic waste water is increasing day by day, and the waste water generally has the characteristics of high pollutant concentration, high toxicity and poor biodegradability; if the treatment is not effective, the water body can be seriously polluted. At present, the industrial wastewater is usually diluted or pretreated and then treated by conventional physicochemical and biochemical methods, but some refractory substances still remain in the wastewater, and the wastewater needs further advanced treatment to meet increasingly strict discharge standards or recycling requirements. Therefore, the development of environment-friendly and efficient advanced treatment technology has important significance for environmental protection and water conservation.
At present, advanced oxidation technology is commonly used for advanced treatment of wastewater, and mainly strong oxidative hydroxyl radicals generated by advanced oxidation technology are used for degrading organic matters to enable the organic matters to be micromolecular or completely mineralized, so that the advanced oxidation technology is beneficial to subsequent treatment or directly reaches the standard for discharge. The advanced oxidation technology mainly comprises catalytic ozone oxidation, photocatalytic oxidation, Fenton oxidation, electrochemical oxidation, supercritical oxidation and the like. The catalytic ozonation has the problem of low ozone utilization rate, the Fenton oxidation has the problem of iron mud, the electrochemical oxidation has high energy consumption, byproducts are generated by oxidation, secondary pollution is easily caused, and the supercritical oxidation has high requirements on equipment. However, photocatalytic oxidation is an environment-friendly deep oxidation technology, and can decompose toxic harmful refractory organic matters into small molecular compounds or completely mineralize the small molecular compounds into final products such as water, carbon dioxide and the like under mild conditions; particularly, the vacuum ultraviolet light catalysis technology developed in recent years utilizes two wave bands (185nm +254nm) and can directly photolyze water to generate hydroxyl radical oxidized organic matters and decompose O under the catalysis of 185nm vacuum ultraviolet light2Generation of O3Oxidizing the organic matter; the other remaining O3Can further generate ozone/ultraviolet light catalytic reaction at the waveband of 254 nm; but residual O in the solution and in the off-gas3The concentration is still higher, the ozone concentration>1mg/L is easy to cause discomfort such as cough, and higher concentration can bring more serious harm to human body, namely, the risk of secondary pollution and the problem that the oxidation efficiency needs to be improved exist.
Aiming at the problems, the Chinese patent CN1304059C develops a device for purifying air and water by vacuum ultraviolet light catalysis, combines the advantages of vacuum ultraviolet photolysis and photocatalysis, improves the oxidation efficiency, but does not consider tail gas O3Secondary pollution problem of。
Chinese invention patent CN107364924A developed a deep water treatment device integrating photocatalysis, vacuum ultraviolet light and ozone oxidation, which utilizes multiple oxidation to degrade organic matters, but because the amount of ozone generated by photocatalysis is limited, a high-efficiency catalyst is needed to play the role of ozone oxidation, so the device of the invention still can retain ozone and has the risk of secondary pollution.
The Chinese invention patent CN104016511B develops an ozone/photocatalytic oxidation-membrane separation integrated method and an integrated device for advanced wastewater treatment, organic matters are degraded by utilizing the coupling action of photolysis, photocatalysis and ozone/photocatalytic oxidation, residual ozone still exists in membrane effluent, the risk of secondary pollution exists, and meanwhile, TiO is used for the purpose of using the residual ozone2And the catalyst is easy to cause the condition of membrane blockage.
Therefore, there is a need to develop new technologies to improve the photocatalytic efficiency, increase the membrane flux and effectively slow down membrane fouling and solve the problem of residual ozone.
Disclosure of Invention
The invention aims to provide a photocatalysis and membrane catalysis combined water treatment method. In order to realize the purpose, the invention fully utilizes the direct photolysis and photocatalysis of vacuum ultraviolet light to degrade organic matters in the photocatalysis stage; in the membrane filtration stage, the synergistic catalytic effect of the nanometer pore canal in the membrane medium is utilized to fully play the oxidation role of the residual ozone in the photocatalytic effluent, thereby being beneficial to the degradation of organic matters and eliminating the secondary pollution problem of the residual ozone.
The invention also provides a photocatalysis and membrane catalysis combined water treatment device.
The invention provides a photocatalysis and membrane catalysis combined water treatment method, which comprises the following steps:
A. filtering the waste water by a preposed security filter;
B. the filtered wastewater enters a mixer, and oxygen is added into the mixer;
C. the wastewater leaving the mixer enters a photocatalytic reactor;
D. the wastewater leaving the photocatalytic reactor enters the membrane filtration catalytic reactor, and the water penetrating through the submerged membrane module enters the clean water tank.
Further, after the wastewater in the step A passes through a front security filter, suspended impurities in the wastewater are removed by filtration.
Further, the mixer in the step B is used for mixing the wastewater and the oxygen to form a large amount of micro-bubbles and dissolved oxygen in the system. Hydrogen peroxide may also be added as needed to improve the oxidation efficiency. O is2The flow rate may be 0 to 1 time, preferably 0.01 to 0.1 time, of the wastewater treatment amount.
Further, the photocatalytic reactor in the step C is provided with 1-7 stages of photocatalytic reactors, the number of stages to be opened is determined according to the requirement of effluent, and a dual-band ultraviolet lamp tube is arranged in each stage, so that ultraviolet light of 185nm and 254nm can be generated, for the ultraviolet light of 185nm, organic matters can be directly photolyzed, the organic matters can be oxidized by hydroxyl radicals generated by photolysis of water, and dissolved oxygen can be converted into ozone; for 254nm ultraviolet light, dissolved ozone can be converted into hydroxyl radicals to oxidize and degrade organic matters, and generated ozone can be used for generating ozone/ultraviolet light catalytic reaction to cooperatively degrade the organic matters.
The power consumption of the vacuum ultraviolet lamp is 0.1-10 kW, preferably 1-3 kW, per ton of water treated.
Further, the immersed membrane module in the step D is a flat ceramic membrane loaded with a metal oxide catalyst, and the metal oxide catalyst can be selected from MnO2、NiO、Co3O4、Fe2O3、Ag2O、CeO2Etc., preferably MnO2The loading capacity of the catalyst is 0.1-5%, preferably 1-2% based on the mass of the alumina ceramic membrane. The aperture range of the flat ceramic membrane is 50-200 nm, the average aperture is 0.08-0.12 mu m, preferably 0.1 mu m, and the membrane flux is 40-200L/m2H, preferably 60 to 150L/m2H, the residual O of photocatalysis can be treated by utilizing ceramic membrane catalysis and nano-channel effect3Further plays a role in oxidative degradation.
And further, backwashing the membrane component by using clean water pool water at regular intervals, refluxing from the bottom of the membrane catalytic reactor to the front end of the cartridge filter, and returning to the step A.
The raw water applicable to the method has the water quality of 30-120 mg/L COD and 0-60 mg/L SS.
The invention also provides a photocatalysis and membrane filtration catalysis combined water treatment device, which sequentially comprises the following components in the flow direction of wastewater: the device comprises a pre-cartridge filter 1, a waste water delivery pump 2, a mixer 3, an oxygen input pipeline 4, a photocatalytic reactor 5, a membrane filtration catalytic reactor 6, at least one immersed membrane component 7 in the membrane filtration catalytic reactor 6, a membrane filtration suction pump 8, a clean water tank 9, a pipeline 11 connecting an upper outlet of the mixer and a lower inlet of the photocatalytic reactor, a pipeline 12 connecting an upper outlet of the photocatalytic reactor and an upper inlet of the membrane filtration catalytic reactor, and necessary connecting pipelines between other adjacent devices.
According to a preferred embodiment of the present invention, the water treatment apparatus further comprises a backwash pump 10 connected to the clean water tank 9 and the membrane filtration catalytic reactor 6 for periodically backwashing the submerged membrane module 7, the backwash liquid being discharged from the bottom of the membrane filtration catalytic reactor 6 to the cartridge filter 1 through a line 13.
The front-mounted security filter adopts PP cotton, nylon, melt-blown and other different materials as filter elements and is used for removing impurities in wastewater.
Wherein, be equipped with 1 ~ 7 grades of photocatalytic reactors in photocatalytic reactor 5, and be equipped with the ultraviolet fluorescent tube of dual band in each grade.
The membrane filtration catalytic reactor 6 is a container made of a conventional material, and a container made of 304 stainless steel, 316L stainless steel or titanium can be considered. The immersed flat membrane component is mainly made of Al2O3The material is that the catalyst is loaded on the supporting layer and the film layer.
From the perspective of improving the oxidation efficiency and solving the residual ozone, the photocatalytic oxidation technology and the membrane catalysis technology are coupled, and the effects of photodegradation, photocatalytic oxidation, ozone/photocatalysis and membrane catalytic ozone oxidation are cooperatively exerted, so that the photocatalytic efficiency is improved, the membrane flux is improved, the membrane pollution is effectively slowed down, and the problem of residual ozone is solved. The invention has the advantages that:
(1) the photocatalytic unit is provided with 1-7 levels of photocatalytic reactors which are dual-waveband ultraviolet lamp tubes, and the number of opened levels can be determined according to the water outlet requirement; meanwhile, the wave number of the ultraviolet light is 185nm and 254nm, so that various oxidation effects such as direct photolysis of organic matters, generation of hydroxyl radical oxidation by photocatalytic water, generation of ozone oxidation by photocatalysis, ozone/photocatalysis and the like are fully exerted, and the residual ozone is subjected to subsequent film catalysis and is reused;
(2) according to the membrane filtration catalytic reactor, the catalyst loaded on the ceramic membrane and the ceramic membrane nano-pore channel effect are utilized, the ozone which is not fully reacted is further oxidized to degrade organic matters in water and organic pollutants on the surface of the membrane, the ozone utilization rate is improved, the membrane pollution is effectively relieved, and the membrane replacement period is prolonged.
(3) The invention provides a combined advanced treatment process of photocatalysis and membrane filtration catalysis, which improves the oxidation efficiency in multiple steps through the steps (1) and (2) and utilizes residual O3The resources are saved and the effect is improved; the membrane effluent solution does not need to enter an ozone buffer pool to eliminate ozone, and can directly enter a biochemical unit subsequently, so that the space and the cost are saved.
Drawings
FIG. 1 is a schematic structural diagram of a combined water treatment process of photocatalysis and membrane filtration catalysis provided by an embodiment of the invention.
In the figure, 1, a front security filter; 2. a wastewater delivery pump; 3. a mixer; 4. an oxygen input line; 5. a photocatalytic reactor; 6. a membrane filtration catalytic reactor; 7. an immersed membrane module; 8. a membrane filtration suction pump; 9. a clean water tank; 10. a backwashing pump, a pipeline 11 connecting the upper outlet of the mixer and the lower inlet of the photocatalytic reactor, a pipeline 12 connecting the upper outlet of the photocatalytic reactor and the upper inlet of the membrane filtration catalytic reactor, and a pipeline 13 connecting the bottom outlet of the membrane filtration catalytic reactor and the inlet of the cartridge filter.
Detailed Description
The technical scheme of the invention is further explained by the specific implementation mode in combination with the attached drawings.
The preferred embodiment of the present invention comprises:
when wastewater is introduced for the first time, the wastewater is filtered by a front security filter 1 and then enters a mixer 3 through a wastewater conveying pump 2, oxygen gas enters the mixer 3 through an oxygen input pipeline 4, the wastewater coming out of the mixer 3 enters a photocatalytic reactor 5 to generate a series of photocatalytic reactions and generate ozone, the wastewater after the photocatalytic reactions enters a membrane filtration catalytic reactor 6, the wastewater penetrates through an immersed membrane component 7 under the action of a membrane filtration suction pump 8 to generate catalytic ozone oxidation on the surface and in a membrane pore channel, the wastewater is sucked into a clean water tank 9 through the pump 8, a membrane runs for a period of time, a backwashing pump 10 is started to backwash, and backwash liquid flows back to the security filter 1 to be treated as the wastewater.
Example 1
The combined process of photocatalysis and membrane filtration catalysis is adopted to treat certain petrochemical wastewater, and the conditions are as follows: raw water COD is 100mg/L, chroma is 20 degrees, and SS is 20 mg/L; starting the 1-level photocatalysis to treat one ton of wastewater, wherein the dual-waveband vacuum ultraviolet lamp consumes 2kW of electric energy and O2The flow rate is 0.02 times of the wastewater treatment capacity; 1% MnO loaded in membrane filtration catalytic reactor2The average pore diameter of the flat ceramic membrane is 0.1 mu m, and the membrane flux is 80L/m2H, the effluent indexes after treatment are as follows: COD 60mg/L, chroma<10 degrees, SS is 4 mg/L.
Example 2
The combined process of photocatalysis and membrane filtration catalysis is adopted to treat certain petrochemical wastewater, and the conditions are as follows: raw water COD is 100mg/L, chroma is 20 degrees, and SS is 20 mg/L; starting the 1-level photocatalysis to treat one ton of wastewater, wherein the dual-waveband vacuum ultraviolet lamp consumes 2kW of electric energy and O2The flow rate is 0.02 times of the wastewater treatment capacity; 0.1% MnO loaded in membrane filtration catalytic reactor2The average pore diameter of the flat ceramic membrane is 0.1 mu m, and the membrane flux is 80L/m2H, the effluent indexes after treatment are as follows: COD 70mg/L, color number<10 degrees, SS is 4 mg/L.
Example 3
The combined process of photocatalysis and membrane filtration catalysis is adopted to treat certain petrochemical wastewater, and the conditions are as follows: raw water COD is 100mg/L, chroma is 20 degrees, and SS is 20 mg/L; opening level 1Photocatalysis, one ton of waste water is treated, the double-waveband vacuum ultraviolet lamp consumes 2kW of electric energy, and O2The flow rate is 0.02 times of the wastewater treatment capacity; 2% MnO loaded in membrane filtration catalytic reactor2The average pore diameter of the flat ceramic membrane is 0.1 mu m, and the membrane flux is 80L/m2H, the effluent indexes after treatment are as follows: COD 55mg/L, color number<10 degrees, SS is 4 mg/L.
Example 4
The combined process of photocatalysis and membrane filtration catalysis is adopted to treat certain petrochemical wastewater, and the conditions are as follows: raw water COD is 100mg/L, chroma is 20 degrees, and SS is 20 mg/L; starting the 1-level photocatalysis to treat one ton of wastewater, wherein the dual-waveband vacuum ultraviolet lamp consumes 2kW of electric energy and O2The flow rate is 0; 1% MnO loaded in membrane filtration catalytic reactor2The average pore diameter of the flat ceramic membrane is 0.1 mu m, and the membrane flux is 80L/m2H, the effluent indexes after treatment are as follows: COD 80mg/L, chroma 12 degree, SS 4 mg/L.
Example 5
The combined process of photocatalysis and membrane filtration catalysis is adopted to treat certain petrochemical wastewater, and the conditions are as follows: raw water COD is 100mg/L, chroma is 20 degrees, and SS is 20 mg/L; starting the 1-level photocatalysis to treat one ton of wastewater, wherein the dual-waveband vacuum ultraviolet lamp consumes 2kW of electric energy and O2The flow rate is 0.04 times of the wastewater treatment capacity; 1% MnO loaded in membrane filtration catalytic reactor2The average pore diameter of the flat ceramic membrane is 0.1 mu m, and the membrane flux is 80L/m2H, the effluent indexes after treatment are as follows: COD 55mg/L, color number<10 degrees, SS is 4 mg/L.
Example 6
The combined process of photocatalysis and membrane filtration catalysis is adopted to treat certain petrochemical wastewater, and the conditions are as follows: raw water COD is 100mg/L, chroma is 20 degrees, and SS is 20 mg/L; starting 3-level photocatalysis to treat one ton of wastewater, wherein the dual-waveband vacuum ultraviolet lamp consumes 3kW of electric energy and O2The flow rate is 0.02 times of the wastewater treatment capacity; 1% MnO loaded in membrane filtration catalytic reactor2The average pore diameter of the flat ceramic membrane is 0.1 mu m, and the membrane flux is 80L/m2H, the effluent indexes after treatment are as follows: COD 50mg/L, color number<10 times, SS is 4 mg/L.
Example 7
The combined process of photocatalysis and membrane filtration catalysis is adopted to treat certain petrochemical wastewater, and the conditions are as follows: raw water COD is 100mg/L, chroma is 20 degrees, and SS is 20 mg/L; starting 7-level photocatalysis to treat one ton of wastewater, wherein the dual-waveband vacuum ultraviolet lamp consumes 5kW of electric energy and O2The flow rate is 0.02 times of the wastewater treatment capacity; 1% MnO loaded in membrane filtration catalytic reactor2The average pore diameter of the flat ceramic membrane is 0.1 mu m, and the membrane flux is 80L/m2H, the effluent indexes after treatment are as follows: COD 40mg/L, color number<10 times, SS is 4 mg/L.
Example 8
The combined process of photocatalysis and membrane filtration catalysis is adopted to treat certain petrochemical wastewater, and the conditions are as follows: raw water COD is 100mg/L, chroma is 20 degrees, and SS is 20 mg/L; starting the 1-level photocatalysis to treat one ton of wastewater, wherein the dual-waveband vacuum ultraviolet lamp consumes 2kW of electric energy and O2The flow rate is 0.02 times of the wastewater treatment capacity, H2O2The adding amount is 10 mg/L; 1% MnO loaded in membrane filtration catalytic reactor2The average pore diameter of the flat ceramic membrane is 0.1 mu m, and the membrane flux is 80L/m2H, the effluent indexes after treatment are as follows: COD 52mg/L, chroma<10 degrees, SS is 4 mg/L.
Example 9
The combined process of photocatalysis and membrane filtration catalysis is adopted to treat certain petrochemical wastewater, and the conditions are as follows: raw water COD is 80mg/L, chroma is 20 degrees, and SS is 20 mg/L; starting the 1-level photocatalysis to treat one ton of wastewater, wherein the dual-waveband vacuum ultraviolet lamp consumes 2kW of electric energy and O2The flow rate is 0.02 times of the wastewater treatment capacity; 1% MnO loaded in membrane filtration catalytic reactor2The average pore diameter of the flat ceramic membrane is 0.1 mu m, and the membrane flux is 80L/m2H, the effluent indexes after treatment are as follows: COD 45mg/L, color number<10 times, SS is 4 mg/L.
Example 10
The combined process of photocatalysis and membrane filtration catalysis is adopted to treat certain petrochemical wastewater, and the conditions are as follows: raw water COD is 60mg/L, chroma is 20 degrees, and SS is 20 mg/L; starting the 1-level photocatalysis to treat one ton of wastewater, and eliminating the dual-waveband vacuum ultraviolet lampConsuming 2kW of electric energy, O2The flow rate is 0.02 times of the wastewater treatment capacity; 1% MnO loaded in membrane filtration catalytic reactor2The average pore diameter of the flat ceramic membrane is 0.1 mu m, and the membrane flux is 80L/m2H, the effluent indexes after treatment are as follows: COD 32mg/L, color number<10 times, SS is 4 mg/L.
Example 11
The combined process of photocatalysis and membrane filtration catalysis is adopted to treat certain petrochemical wastewater, and the conditions are as follows: raw water COD is 40mg/L, chroma is 20 degrees, SS is 20 mg/L; starting the 1-level photocatalysis to treat one ton of wastewater, wherein the dual-waveband vacuum ultraviolet lamp consumes 2kW of electric energy and O2The flow rate is 0.02 times of the wastewater treatment capacity; 1% MnO loaded in membrane filtration catalytic reactor2The average pore diameter of the flat ceramic membrane is 0.1 mu m, and the membrane flux is 80L/m2H, the effluent indexes after treatment are as follows: COD 28mg/L, color number<10 times, SS is 4 mg/L.
Comparative example 1
Only the photocatalysis process is adopted to treat certain petrochemical wastewater, and the conditions are as follows: raw water COD is 100mg/L, chroma is 20 degrees, and SS is 20 mg/L; starting the 1-level photocatalysis to treat one ton of wastewater, wherein the dual-waveband vacuum ultraviolet lamp consumes 2kW of electric energy and O2The flow rate is 0.02 time of the wastewater treatment capacity, and the effluent indexes after treatment are as follows: COD 75mg/L, color number<10 times, SS 7 mg/L.
Comparative example 2
By adopting the photocatalysis process and no MnO loading2The membrane filtration process of (2) treats certain petrochemical wastewater, and the conditions are as follows: raw water COD is 100mg/L, chroma is 20 degrees, and SS is 20 mg/L; starting the 1-level photocatalysis to treat one ton of wastewater, wherein the dual-waveband vacuum ultraviolet lamp consumes 2kW of electric energy and O2The flow rate is 0.02 times of the wastewater treatment capacity, and the membrane flux is 80L/m2H, the effluent indexes after treatment are as follows: COD 70mg/L, color number<10 times, SS is 4 mg/L.
Comparative example 3
Only adopts a combined process of membrane filtration to treat certain petrochemical wastewater, and the conditions are as follows: raw water COD is 100mg/L, chroma is 20 degrees, and SS is 20 mg/L; 1% MnO loaded in membrane filtration catalytic reactor2Flat ceramic membrane of (2), average pore diameter0.1 μm, and a membrane flux of 80L/m2H, the effluent indexes after treatment are as follows: COD 97mg/L, chroma 16 times, SS 4 mg/L.
The invention combines photocatalysis and membrane filtration catalysis for application, and realizes the synergistic effect of deep oxidation technology and membrane separation catalysis technology. It can be seen from the combination of examples and comparative examples that the synergistic effect of the combined use of the photocatalysis and the membrane filtration catalysis is significantly higher than the effect of the photocatalysis or the membrane filtration catalysis alone.
It should be understood that the above-described embodiments of the present invention are merely examples for clearly illustrating the present invention, and are not intended to limit the embodiments of the present invention. Other variations and modifications will be apparent to persons skilled in the art in light of the above description. And are neither required nor exhaustive of all embodiments. Any modification, equivalent replacement, and improvement made within the spirit and principle of the present invention should be included in the protection scope of the claims of the present invention.
Claims (13)
1. A photocatalysis and membrane catalysis combined water treatment method comprises the following steps:
A. filtering the waste water by a preposed security filter;
B. the filtered wastewater enters a mixer, and oxygen is added into the mixer;
C. the wastewater leaving the mixer enters a photocatalytic reactor;
D. the wastewater leaving the photocatalytic reactor enters a membrane filtration catalytic reactor, and the water penetrating through the immersed membrane component is treated wastewater and enters a clean water tank.
2. The method of claim 1, wherein O2The flow rate is 0 to 1 time, preferably 0.01 to 0.1 time of the wastewater treatment amount.
3. The method as claimed in claim 1, wherein the photocatalytic reactor of step C is provided with 1-7 stages of photocatalytic reactors, each stage being provided with a dual band ultraviolet lamp tube for generating ultraviolet light of 185nm and 254 nm.
4. The process of claim 1 wherein the submerged membrane module of step D is a flat ceramic membrane loaded with a metal oxide catalyst.
5. The method according to claim 4, wherein the flat ceramic membrane has a pore diameter in the range of 50 to 200nm, an average pore diameter of 0.08 to 0.12 μm, and a membrane flux of 40 to 200L/m2H, preferably 60 to 150L/m2·h。
6. The process of claim 4, wherein the metal oxide catalyst is selected from MnO2、NiO、Co3O4、Fe2O3、Ag2O、CeO2Preferably MnO2The loading capacity of the catalyst is 0.1-5%, preferably 1-2% based on the mass of the alumina ceramic membrane.
7. The method according to claim 1, wherein the membrane module is periodically backwashed with clean water pool water, and the membrane module is refluxed to the front end of the cartridge filter from the bottom of the membrane catalytic reactor and then returns to the step A.
8. The utility model provides a photocatalysis and membrane catalysis combination water treatment facilities includes in proper order according to the flow direction of waste water: the device comprises a pre-cartridge filter 1, a waste water delivery pump 2, a mixer 3, an oxygen input pipeline 4, a photocatalytic reactor 5, a membrane filtration catalytic reactor 6, at least one immersed membrane component 7 in the membrane filtration catalytic reactor 6, a membrane filtration suction pump 8, a clean water tank 9, a pipeline 11 connecting an upper outlet of the mixer and a lower inlet of the photocatalytic reactor, a pipeline 12 connecting an upper outlet of the photocatalytic reactor and an upper inlet of the membrane filtration catalytic reactor, and necessary connecting pipelines between other adjacent devices.
9. The apparatus of claim 8, wherein the water treatment apparatus further comprises a backwash pump 10 connected to the clean water tank 9 and the membrane filtration catalytic reactor 6 for periodically backwashing the submerged membrane module 7, the backwash liquid being discharged from the bottom of the membrane filtration catalytic reactor 6 to the cartridge filter 1 through a line 13.
10. The apparatus of claim 8, wherein the photocatalytic reactor 5 is provided with 1-7 stages of photocatalytic reactors, and each stage is provided with a dual-band ultraviolet lamp tube.
11. The apparatus of claim 8, wherein the submerged membrane module is a flat ceramic membrane, predominantly Al2O3The material is that metal oxide catalyst is loaded on both the supporting layer and the film layer.
12. The device according to claim 11, wherein the flat ceramic membrane has a pore size in the range of 50 to 200nm, an average pore size of 0.08 to 0.12 μm, and a membrane flux of 40 to 200L/m2H, preferably from 60 to 150L/m2·h。
13. The apparatus of claim 11, wherein the metal oxide catalyst is selected from MnO2、NiO、Co3O4、Fe2O3、Ag2O、CeO2Preferably MnO2The loading capacity of the catalyst is 0.1-5%, preferably 1-2% based on the mass of the alumina ceramic membrane.
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