CN113562899A - Method for treating organic pollutants in water body - Google Patents
Method for treating organic pollutants in water body Download PDFInfo
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- CN113562899A CN113562899A CN202110788737.4A CN202110788737A CN113562899A CN 113562899 A CN113562899 A CN 113562899A CN 202110788737 A CN202110788737 A CN 202110788737A CN 113562899 A CN113562899 A CN 113562899A
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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
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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
- C02F1/30—Treatment of water, waste water, or sewage by irradiation
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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
- C02F1/44—Treatment of water, waste water, or sewage by dialysis, osmosis or reverse osmosis
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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
- C02F1/66—Treatment of water, waste water, or sewage by neutralisation; pH adjustment
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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
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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
- C02F2101/00—Nature of the contaminant
- C02F2101/30—Organic compounds
Abstract
The invention discloses a method for treating organic pollutants in water, which adopts the following devices: the quartz reactor is internally provided with an embedded quartz baffle; the quartz cold hydrazine is covered on the upper opening of the quartz reactor in a sealing way and is used for placing a lamp source, and the front end of a cooling water inlet is connected with the circulating cooler; the ozone generator is connected with an air inlet at the bottom of the quartz reactor; the processing steps are as follows: (1) introducing the sewage into the quartz reactor, adding a catalyst into the sewage, and aerating to fully and uniformly mix the catalyst and a water body; and adjusting the pH value; (2) introducing cooling water into the quartz cold hydrazine, and adjusting the reaction temperature to be 20-30 ℃; (3) and turning on a lamp source to synchronously turn on the ozone generator, and leading ozone to enter the sewage through the gas distribution plate by the air pump to carry out photocatalytic reaction on the mixed solution. The device of the invention has good synergistic effect of photocatalysis and ozone oxidation, and the catalytic efficiency is obviously improved, thereby accelerating the catalytic degradation of organic pollutants.
Description
Technical Field
The invention relates to the technical field of environmental protection, in particular to a method for treating organic pollutants in water by utilizing a universal high-efficiency photocatalysis/ozone oxidation device.
Background
The textile printing and dyeing wastewater has the characteristics of large water quantity, high organic pollutant content, high alkalinity, large water quality change and the like, 100-200 tons of water are consumed for every 1 ton of textiles processed by printing and dyeing, wherein 80-90% of the water becomes wastewater, and the treatment method mainly comprises a physical and chemical method, a biochemical method, a chemical method and a treatment method combining a plurality of processes. The advanced oxidation technology has the advantages of no secondary pollution, unique technical property, stability and the like, and has good degradation effect on industrial wastewater with high concentration, high toxicity and poor biodegradability.
However, the existing photocatalytic or ozone oxidation single catalytic device has the following defects when degrading organic pollutants: 1. the catalyst is static and does not come into sufficient contact with contaminants in the water; 2. the catalyst is easy to agglomerate; 3. sunlight cannot be fully utilized; 4. the recombination rate of photon-generated carriers is high; 5. the utilization rate of ozone is low; 6. the time of ozone retention in the water body is short; 7. the degradation efficiency is low, and the energy consumption is high. Therefore, the effect of degrading organic pollutants by a single photocatalysis or ozone oxidation device is not ideal, and the existing photocatalysis/ozone oxidation device has the defects of high energy consumption, low degradation efficiency, low ozone utilization rate, incapability of utilizing sunlight and the like, and is difficult to put into practical application.
Disclosure of Invention
Aiming at the technical problems in the prior art, the invention provides a universal photocatalysis/ozone oxidation device capable of efficiently treating organic pollutants in water and a method for treating the organic pollutants in the water by using the universal photocatalysis/ozone oxidation device, so as to solve the problem that the existing photocatalysis/ozone oxidation device has an unsatisfactory effect of degrading the organic pollutants.
The invention is realized by adopting the following technical scheme:
a method for treating organic pollutants in a water body adopts the following device for treatment, and the device comprises:
the quartz reactor is internally provided with an embedded quartz baffle for increasing the reaction time of ozone in water and can also be used as a carrier of a film-shaped catalyst; the bottom of the quartz reactor is provided with an air inlet, and the air inlet is provided with an air distribution plate; the lower end of the quartz reactor is provided with a purified water discharge port, and the upper end of the quartz reactor is provided with a sewage inlet and a sewage outlet;
the tail gas collecting device is arranged at the gas outlet and is used for collecting tail gas;
the quartz cold hydrazine is covered on the upper opening of the quartz reactor in a sealing way and is used for placing a lamp source, and the front end of a cooling water inlet is connected with a circulating cooler;
the ozone generator is connected with an air inlet at the bottom of the quartz reactor;
the processing steps are as follows:
(1) introducing the sewage into the quartz reactor, adding a catalyst into the sewage, and opening an air pump to explode air into the water body so as to fully and uniformly mix the catalyst and the water body; adding NaOH solution or H into the mixed solution2SO4The solution is used for adjusting the pH value of the mixed solution to 4-6;
(2) turning on a power supply of a circulating cooler, introducing circulating cooling water into the quartz cold hydrazine, and adjusting the reaction temperature to be 20-30 ℃;
(3) turning on a lamp source and synchronously turning on an ozone generator, allowing ozone to enter sewage through an air distribution plate through an air pump, carrying out photocatalytic reaction on the mixed solution, controlling the illumination intensity of the reaction to be 50-200W/m 2, controlling the ozone yield to be 1-5 g/min, controlling the gas flow rate to be 100-400L/min through the air pump, and controlling the concentration of a catalyst in the mixed solution to be 0.1-0.5 g/L; the catalyst is g-C3N4Or a nano-heterojunction material.
The catalyst can also be selected from ZnO, BiFeO3, BiVO4 and other oxides.
Preferably, the embedded quartz baffles are fixed on two opposite side walls of the quartz reactor in an alternating manner so as to form a circuitous flow passage.
Preferably, a quartz cold trap through hole is reserved on the embedded quartz baffle, the quartz cold trap is inserted into the through hole to fix the embedded quartz baffle, and sealing elements are arranged between the embedded quartz baffle and the quartz reactor, and between the embedded quartz baffle and the quartz cold trap.
Preferably, the device is further provided with a light-operated switch for controlling the power of the lamp source. The light-operated switch is arranged at the front end of the xenon lamp and controls the power of the xenon lamp according to the illumination intensity of sunlight.
Preferably, the device also comprises an exhaust gas collecting device arranged at the air outlet, wherein a spherical container is arranged in the exhaust gas collecting device, and the exhaust gas collecting device contains a sodium thiosulfate solution.
Preferably, the concentration of the catalyst in the mixed solution is 0.2g/L, and the light intensity controlled by the light-operated switch is 100W/m2The pH value of the mixed solution is 5, and the reaction temperature is 25 ℃.
Preferably, the ozone yield of the ozone generator is 2g/min, the gas flow rate is controlled by an air pump to be 300L/min, and the time of the photocatalytic reaction is 10 min.
Preferably, an organic filter membrane is arranged at the purified water discharge port.
Preferably, the device is used in 2-6 stages in series, and a purified water discharge port at the lower end of the upper stage device is connected with a sewage water inlet at the upper end of the lower stage device to perform flowing catalytic degradation on sewage.
Preferably, the flow rate of the water body is controlled to be 1000L/min when the 6 stages are used in series.
Compared with the prior art, the invention has the following beneficial effects:
the photocatalysis/ozone oxidation device capable of efficiently treating the organic pollutants in the water body and the treatment method thereof enable the catalyst and the sewage to be fully and uniformly mixed through the air blasting of the air pump, prevent the catalyst from agglomerating, enable the catalyst to be fully contacted with the organic pollutants and the ozone in the water body, and utilize the light-operated switch to control the comprehensive illumination intensity to carry out catalytic degradation on the organic pollutants, so as to realize the purpose of degrading the organic pollutants. According to the invention, the ozone generator is arranged to generate ozone, the photocatalysis and ozone oxidation have good synergistic effect, more oxidation active factors are generated, the utilization efficiency of photon-generated carriers, free radicals, ozone and the like is effectively improved, the catalytic efficiency is remarkably improved, and the catalytic degradation of organic pollutants is accelerated. In addition, the device of the invention is embedded with a quartz barrier, thereby increasing the detention time of ozone in water, improving the utilization efficiency of ozone and simultaneously providing a carrier for the film-shaped catalyst. The whole set of device can realize 6-level serial use, the flow rate of the water body is controlled to be 1000L/min, and the organic pollutants are subjected to flow catalytic degradation.
Meanwhile, the device is made of quartz, has good transmittance to visible light and ultraviolet light, can fully utilize sunlight, can improve the utilization rate of the sunlight by using a light-operated switch of the device, achieves the aim of energy conservation, is reasonable and ingenious in design, and has good application prospect.
Drawings
FIG. 1 is a schematic structural diagram of a photocatalytic/ozonation apparatus for efficiently treating organic pollutants in a water body according to the present invention. 1. An ozone generator; 2. a tail gas collecting device; 3. a sewage inlet; 4. a purified water discharge port; 5. a cooling water inlet; 6. a cooling water discharge port; 7. quartz cold hydrazine; 8. a xenon lamp; 9. a gate valve; 10. an organic filter membrane; 11. a gas distribution plate; 12. a cuboid quartz reactor; 13. an embedded quartz barrier; 14. and a light-operated switch.
FIG. 2 is a schematic diagram of an alternative organic filter membrane in a photocatalytic/ozonation apparatus.
FIG. 3 is a schematic view of the structure of the tail gas collecting device in the photocatalytic/ozonation apparatus.
FIG. 4 is a schematic diagram of the structure of an embedded quartz barrier in a photocatalytic/ozonation apparatus.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more apparent, the present invention is described in further detail below with reference to the accompanying drawings and embodiments. It should be understood that the specific embodiments described herein are merely illustrative of the invention and are not intended to limit the invention.
Example 1
As shown in fig. 1, the photocatalytic/ozonation device of the present invention includes an ozone generator 1, a tail gas collection device 2, a quartz cold trap 7, a xenon lamp 8, a gas distribution plate 11, a quartz reactor 12, an embedded quartz barrier 13, and a light control switch 14.
The quartz reactor 12 is used to contain a body of water and is a vessel for catalytically reacting the body of water. The sewage inlet 3 and the purified water outlet 4 of the quartz reactor 12 are respectively positioned at the upper left end and the lower right end, and are provided with gate valves 9 for controlling the water to flow in and out, and the air inlet and the air outlet are respectively positioned at the lower left end and the upper right end. The purified water discharge port 4 is provided at the lower end of the quartz reactor 12, and a replaceable organic filter membrane 10 having a pore size of 0.45 μm is installed to prevent the loss of the catalyst, as shown in FIG. 2. The quartz reactor 12 is made of quartz, has good transmittance to sunlight, does not absorb ultraviolet light and visible light, is designed into a cuboid, is convenient for being embedded into a quartz baffle 13, has length, width and height of 1600, 800, 1940mm respectively, and has a volume of 2m3. The ozone generator 1 is arranged at the air inlet and is used for generating ozone with certain concentrationOxygen. The bottom of the quartz reactor 12 is provided with a gas distribution plate 11, so that ozone is uniformly dispersed in the water body from the bottom in a small bubble form, and the contact area of the ozone with the water body and the catalyst is increased.
A quartz cold trap 7 was placed in the quartz reactor and used to house a xenon lamp 8. The front end of the cooling water inlet 5 is connected with a circulating cooler, cooling water of the circulating cooler enters the quartz cold trap 7, heat generated by the xenon lamp 8 is reduced, the xenon lamp 8 is prevented from being damaged due to overheating, and the temperature of a water body can be adjusted. The quartz cold trap 7 is made of double-layer quartz, cooling water can freely circulate, the transmittance of ultraviolet light and visible light is good, and the size of the quartz cold trap 7 can cover the upper opening of the quartz reactor 12 to prevent ozone from overflowing to pollute the environment. The quartz cold trap 7 is formed by two cylindrical lamp sleeves for placing the xenon lamp 8, a quartz tube is arranged at the water inlet of the lamp sleeve and communicated with the bottom of the lamp sleeve, cooling water flows in from the bottom of the lamp sleeve, the cooling water flows out from the upper part of the lamp sleeve, the cooling effect is ensured, and the xenon lamp 8 is positioned at the axis position of the lamp sleeve, so that the uniform illumination of a water body is ensured.
The embedded quartz barrier 13 is disposed in the quartz reactor 12 and is used to increase the reaction time of ozone in water, and also can be used as a carrier of a film-shaped catalyst, as shown in fig. 4. The embedded quartz baffle 13 is provided with a quartz cold trap 7 through hole, a sewage inlet 3 through hole and a tail gas through hole, and the embedded quartz baffle 13 and the quartz reactor 12, and the embedded quartz baffle 13 and the quartz cold trap 7 have good sealing performance. The embedded quartz baffle 13 is divided into a left part and a right part which are meshed with each other, the quartz cold trap 7 is inserted into a reserved through hole of the embedded quartz baffle 13 to complete fixation, and ozone flows along the baffle from bottom to top and from left to right alternately, so that the detention time of the ozone in the water body is prolonged. The embedded quartz barrier 13 can be freely taken out, which is convenient for cleaning the quartz reactor.
The light-operated switch 14 is arranged at the front end of the xenon lamp 8 and controls the power of the xenon lamp 8 according to the illumination intensity of sunlight. The light-operated switch 14 can fully utilize sunlight, maintain stable water illumination intensity and achieve the aim of energy conservation.
Before the reaction starts, the ozone generator 1 is closed, the air pump is opened to explode air to the water body, the catalyst and the water body are fully mixed, the catalyst is prevented from agglomerating, after the adsorption-desorption balance between the catalyst and organic pollutants is achieved, the ozone generator 1 and the xenon lamp 8 are simultaneously opened to start catalytic degradation, the catalytic ozone oxidation generates oxidation active factors such as hydroxyl radicals and superoxide radicals, the photocatalysis generates photon-generated carriers, the good degradation effect on the organic pollutants is achieved, the photocatalysis and ozone oxidation have excellent synergistic effect, and more oxidation active factors can be generated to improve the degradation efficiency. The ozone generator 1 can adjust the ozone yield and the gas flow rate, the working principle is to decompose and polymerize oxygen into ozone by utilizing high-voltage ionization, and the core technology and equipment are discharge tubes in the generator.
The tail gas collecting device 2 is arranged at the gas outlet and is used for collecting the tail gas, as shown in fig. 3. The tail gas collection device 2 is internally provided with a spherical container, 10L of sodium thiosulfate solution with the concentration of 100g/L is contained in the spherical container, redundant ozone can pollute air, the spherical container can prolong the retention time of tail gas, and the strong reducing performance of the sodium thiosulfate can quickly reduce the ozone. The tail gas collecting device 2 is provided with an ozone detector which can detect the concentration of ozone entering and exiting to check the effectiveness of the tail gas collecting device 2, so that the consumed part can be replaced in time.
Example 2
Referring to fig. 1, the embodiment provides a photocatalytic/ozonation apparatus capable of efficiently treating organic pollutants in a water body, which is similar to the apparatus of embodiment 1, except that a 6-stage series apparatus is adopted in the embodiment, the flow rate of the water body is controlled to be 1000L/min, and the catalytic degradation of sewage flow is realized.
The first-stage to the sixth-stage devices are positioned at the same horizontal height, and the purified water outlet of the upper-stage device is connected to the sewage inlet of the secondary device, so that natural flow of a water body is ensured. The exhaust port of the superior device is connected with the branch pipe of the air inlet of the secondary device, the ozone utilization efficiency is improved, and the exhaust port of the last device is only provided with the tail gas collecting device 2. And an air pressure sensor is arranged in the quartz reactor 12 of each stage of device, and the air pressure in the quartz reactor 12 of each stage of device is kept consistent by adjusting the rotor flow meter arranged at the air outlet of each stage of device, so that the natural flow of the water body is ensured.
Example 3
Referring to fig. 1, the present embodiment provides a photocatalytic/ozonation apparatus capable of efficiently treating organic pollutants in a water body, which is similar to the apparatus of embodiment 2, and is different in that exhaust ports of each stage of apparatus in the present embodiment are respectively connected to a tail gas collecting apparatus 2, an air pressure sensor in a quartz reactor 12 of each stage of apparatus is subtracted from the exhaust ports, and a rotameter is disposed at the exhaust ports of each stage of apparatus, so as to maintain the air pressure in the quartz reactor 12 of each stage of apparatus to be consistent with the atmospheric pressure.
Example 4
The embodiment provides a method for efficiently treating organic pollutants in a water body, which applies the catalytic device of the embodiment 1 and is used for treating printing and dyeing wastewater. The method for efficiently treating the organic pollutants in the water body by placing the printing and dyeing wastewater in the quartz reactor 12 comprises the following steps:
the method comprises the following steps: adding a catalyst into the printing and dyeing wastewater, opening an air pump to explode air into a water body, controlling the flow rate of the air to be 300L/min by the air pump, and fully mixing the air and the water uniformly by the explosion of the air for 15min to achieve adsorption-desorption balance; wherein the catalyst is g-C3N4 with the concentration of 0.2 g/L;
step two: adding NaOH solution or H into the mixed solution2SO4A solution to adjust the pH of the mixed liquor to 5;
step three: turning on a power supply of a circulating cooler, introducing circulating cooling water into the quartz cold hydrazine 7, and adjusting the reaction temperature to 25 ℃;
step four: the mixed solution is subjected to illumination reaction through a xenon lamp 8, and the light-operated switch 14 controls the comprehensive illumination intensity to be 100W/m2(ii) a Synchronously turning on a power supply of the ozone generator 1, wherein the ozone yield is 2 g/min;
step five: samples were taken every 5min and the rate of degradation of the dye was determined using a spectrophotometer. When the treatment time reaches 10min, the degradation rate of the solution dye is 99.12 percent.
Example 5
This embodiment is different from embodiment 4 in that:
by using the ozone generator 1 alone, the ozone yield was 2g/min, and the gas flow rate was controlled by the gas pump to be 300L/min. Samples were taken every 5min and the rate of degradation of the dye was determined using a spectrophotometer. When the treatment time reaches 10min, the degradation rate of the solution dye is 12.13 percent.
Example 5
This embodiment is different from embodiment 4 in that:
the light control switch 14 controls the comprehensive illumination intensity to be 100W/m2 by using the xenon lamp (8) singly. Samples were taken every 5min and the rate of degradation of the dye was determined using a spectrophotometer. When the treatment time reaches 10min, the degradation rate of the solution dye is 18.21 percent.
It can be found from the above examples 4 to 6 that when both the ozone generator 1 and the xenon lamp 8 are used, the degradation rate of the solution dye is much greater than that when a single solution dye is used. Therefore, in practical applications, the following settings may be made: the g-C3N4 concentration of the mixed solution is 0.2g/L, and the light-operated switch 14 controls the comprehensive illumination intensity to be 100W/m2The ozone yield of the ozone generator (1) is 2g/min, the gas flow rate controlled by the gas pump is 300L/min, the pH value of the mixed solution is 5, the reaction temperature is 25 ℃, and the water flow rate controlled by the 6-stage series device is 1000L/min; and the treatment time for treating the organic pollutants in the printing and dyeing wastewater is 10 min. The method for efficiently treating organic pollutants in water in the embodiment shows that photocatalysis and ozone oxidation have good synergistic effect, so that the yield of oxidation activity factors such as photo-generated carriers, hydroxyl radicals and superoxide radicals is remarkably improved, and the effect of organic pollution caused by photocatalysis/ozone oxidation is further improved.
The above description is only for the purpose of illustrating the preferred embodiments of the present invention and is not to be construed as limiting the invention, and any modifications, equivalents and improvements made within the spirit and principle of the present invention are intended to be included within the scope of the present invention.
Claims (10)
1. A method of treating organic pollutants in a body of water, the method comprising:
the quartz reactor is internally provided with an embedded quartz baffle; the bottom of the quartz reactor is provided with an air inlet, and the air inlet is provided with an air distribution plate; the lower end of the quartz reactor is provided with a purified water discharge port, and the upper end of the quartz reactor is provided with a sewage inlet and a sewage outlet;
the quartz cold hydrazine is covered on the upper opening of the quartz reactor in a sealing way and is used for placing a lamp source, and the front end of a cooling water inlet is connected with the circulating cooler;
the ozone generator is connected with an air inlet at the bottom of the quartz reactor;
the processing steps are as follows:
(1) introducing the sewage into the quartz reactor, adding a catalyst into the sewage, and opening an air pump to explode air into the water body so as to fully and uniformly mix the catalyst and the water body; adjusting the pH value of the mixed solution to 4-6;
(2) introducing circulating cooling water into the quartz cold hydrazine, and adjusting the reaction temperature to be 20-30 ℃;
(3) turning on a lamp source and synchronously turning on an ozone generator, leading ozone to enter sewage through an air distribution plate through an air pump, and carrying out photocatalytic reaction on the mixed solution, wherein the illumination intensity of the reaction is controlled to be 50-200W/m2The ozone yield is 1-5 g/min, and the concentration of the catalyst in the mixed solution is 0.1-0.5 g/L; the catalyst is g-C3N4Or a nano-heterojunction material.
2. The method as claimed in claim 1, wherein the embedded quartz baffles are alternately fixed to two opposite sidewalls of the quartz reactor to form a circuitous flow path.
3. The method as claimed in claim 2, wherein the embedded quartz barrier is provided with a quartz cold trap through hole, the quartz cold trap is inserted into the through hole to fix the embedded quartz barrier, and sealing members are arranged between the embedded quartz barrier and the quartz reactor, and between the embedded quartz barrier and the quartz cold trap.
4. A method according to claim 3, characterized in that the device is further provided with a light control switch for controlling the power of the lamp source.
5. The method of claim 4, wherein the device further comprises a tail gas collecting device arranged at the gas outlet, wherein a spherical container is arranged in the tail gas collecting device, and the spherical container contains the sodium thiosulfate solution.
6. The method of claim 5, wherein the concentration of the catalyst in the mixed solution is 0.2g/L, and the light-operated switch controls the illumination intensity to be 100W/m2The pH value of the mixed solution is 5, and the reaction temperature is 25 ℃.
7. The method of claim 6, wherein the ozone yield of the ozone generator is 2g/min, the gas flow rate is controlled by a gas pump to be 300L/min, and the time of the photocatalytic reaction is 10 min.
8. The method as claimed in claim 7, wherein an organic filter membrane is provided at the purified water discharge port.
9. The method according to any one of claims 1 to 8, wherein the devices are used in 2-6 stages in series, and a purified water discharge port at the lower end of an upper stage device is connected with a sewage water inlet port at the upper end of a lower stage device to perform flow catalytic degradation on sewage.
10. The method of claim 9, wherein the flow rate of the water body is controlled to be 1000L/min when the 6 stages are used in series.
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Application publication date: 20211029 |
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