CN117003364B - Advanced oxidation film reactor based on MOFs activated PS and wastewater treatment method - Google Patents
Advanced oxidation film reactor based on MOFs activated PS and wastewater treatment method Download PDFInfo
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- CN117003364B CN117003364B CN202311172003.9A CN202311172003A CN117003364B CN 117003364 B CN117003364 B CN 117003364B CN 202311172003 A CN202311172003 A CN 202311172003A CN 117003364 B CN117003364 B CN 117003364B
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- 239000012621 metal-organic framework Substances 0.000 title claims abstract description 80
- 102100033069 Histone acetyltransferase KAT8 Human genes 0.000 title claims abstract description 79
- 101000944170 Homo sapiens Histone acetyltransferase KAT8 Proteins 0.000 title claims abstract description 79
- 230000003647 oxidation Effects 0.000 title claims abstract description 37
- 238000007254 oxidation reaction Methods 0.000 title claims abstract description 37
- 238000004065 wastewater treatment Methods 0.000 title description 9
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 128
- 239000002002 slurry Substances 0.000 claims abstract description 55
- 238000002156 mixing Methods 0.000 claims abstract description 46
- 239000002351 wastewater Substances 0.000 claims abstract description 40
- 238000003541 multi-stage reaction Methods 0.000 claims abstract description 30
- 239000000463 material Substances 0.000 claims abstract description 27
- 238000012546 transfer Methods 0.000 claims abstract description 16
- 238000000034 method Methods 0.000 claims abstract description 10
- 230000000630 rising effect Effects 0.000 claims abstract description 5
- 238000004519 manufacturing process Methods 0.000 claims abstract description 3
- 238000006243 chemical reaction Methods 0.000 claims description 23
- 239000007788 liquid Substances 0.000 claims description 23
- 238000011001 backwashing Methods 0.000 claims description 16
- 239000003814 drug Substances 0.000 claims description 13
- 238000007667 floating Methods 0.000 claims description 13
- 239000012528 membrane Substances 0.000 claims description 11
- 239000003344 environmental pollutant Substances 0.000 claims description 9
- 231100000719 pollutant Toxicity 0.000 claims description 9
- 239000011259 mixed solution Substances 0.000 claims description 8
- 239000000725 suspension Substances 0.000 claims description 6
- 238000009792 diffusion process Methods 0.000 claims description 4
- 239000012510 hollow fiber Substances 0.000 claims description 3
- 239000000203 mixture Substances 0.000 claims description 2
- 206010016807 Fluid retention Diseases 0.000 claims 1
- 230000000717 retained effect Effects 0.000 claims 1
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 abstract description 13
- 239000003054 catalyst Substances 0.000 abstract description 11
- 238000005516 engineering process Methods 0.000 abstract description 8
- 229910052742 iron Inorganic materials 0.000 abstract description 5
- 230000004913 activation Effects 0.000 abstract description 4
- 230000014759 maintenance of location Effects 0.000 abstract description 4
- 229910052723 transition metal Inorganic materials 0.000 abstract description 4
- 238000005265 energy consumption Methods 0.000 abstract description 3
- 150000003624 transition metals Chemical class 0.000 abstract description 3
- JRKICGRDRMAZLK-UHFFFAOYSA-L persulfate group Chemical class S(=O)(=O)([O-])OOS(=O)(=O)[O-] JRKICGRDRMAZLK-UHFFFAOYSA-L 0.000 description 32
- 230000000694 effects Effects 0.000 description 11
- 238000006116 polymerization reaction Methods 0.000 description 5
- 239000000126 substance Substances 0.000 description 5
- 238000005243 fluidization Methods 0.000 description 4
- 230000003197 catalytic effect Effects 0.000 description 3
- 230000001590 oxidative effect Effects 0.000 description 3
- 239000002245 particle Substances 0.000 description 3
- 239000002957 persistent organic pollutant Substances 0.000 description 3
- 239000000243 solution Substances 0.000 description 3
- 238000009303 advanced oxidation process reaction Methods 0.000 description 2
- 238000013019 agitation Methods 0.000 description 2
- 230000008602 contraction Effects 0.000 description 2
- 239000006185 dispersion Substances 0.000 description 2
- 229940079593 drug Drugs 0.000 description 2
- 238000012423 maintenance Methods 0.000 description 2
- 238000010791 quenching Methods 0.000 description 2
- 230000000171 quenching effect Effects 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- 238000007581 slurry coating method Methods 0.000 description 2
- -1 transition metal activated Persulfate Chemical class 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- CWYNVVGOOAEACU-UHFFFAOYSA-N Fe2+ Chemical compound [Fe+2] CWYNVVGOOAEACU-UHFFFAOYSA-N 0.000 description 1
- 238000009825 accumulation Methods 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 230000002860 competitive effect Effects 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 229910001448 ferrous ion Inorganic materials 0.000 description 1
- 238000000265 homogenisation Methods 0.000 description 1
- 238000009434 installation Methods 0.000 description 1
- 238000002386 leaching Methods 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 239000010865 sewage Substances 0.000 description 1
- 230000003068 static effect Effects 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/72—Treatment of water, waste water, or sewage by oxidation
- C02F1/725—Treatment of water, waste water, or sewage by oxidation by catalytic oxidation
-
- 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
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2201/00—Apparatus for treatment of water, waste water or sewage
- C02F2201/002—Construction details of the apparatus
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2303/00—Specific treatment goals
- C02F2303/14—Maintenance of water treatment installations
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- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Life Sciences & Earth Sciences (AREA)
- Hydrology & Water Resources (AREA)
- Engineering & Computer Science (AREA)
- Environmental & Geological Engineering (AREA)
- Water Supply & Treatment (AREA)
- Organic Chemistry (AREA)
- Treatment Of Water By Oxidation Or Reduction (AREA)
Abstract
The invention discloses an advanced oxidation film reactor based on MOFs activated PS and a method for treating wastewater, which comprises the following steps: the reactor comprises a reactor main body, wherein a slurry breaking mixing zone, a flow guiding zone, a multi-stage reaction zone and a water interception and discharge zone are respectively arranged in the reactor main body from bottom to top, a slurry breaking mixing device is arranged in the center of the slurry breaking mixing zone, the flow guiding zone is provided with a flow guiding device, MOFs materials are filled in the multi-stage reaction zone, a multi-stage dosing ring is arranged in the multi-stage reaction zone, and a water production device is arranged in the water interception and discharge zone; in the invention, MOFs is utilized to activate PS, so that Fe is effectively avoided 2+ The transition metal activation has the problems of high iron mud yield, secondary pollution, low catalyst utilization rate, high subsequent treatment cost and the like, and compared with the existing advanced oxidation technology, the mass transfer efficiency is higher, the rising flow rate is improved, the hydraulic retention time is shortened, and the occupied area, the capital cost and the energy consumption are effectively reduced.
Description
Technical Field
The invention relates to the technical field of sewage purification treatment, in particular to an advanced oxidation membrane reactor based on MOFs activated PS and a wastewater treatment method.
Background
The new pollutant has the characteristic of difficult degradation, and because advanced oxidation technology (AOPs) can generate a large number of strong oxidative active free radicals, the molecular structure of the organic pollutant difficult to degrade can be effectively destroyed, and the organic pollutant is oxidized into harmless mineralized products, the novel pollutant is widely studied in a novel pollutant treatment technology system.
SO based 4 - The persulfate advanced oxidation technology has become a research hot spot for AOPs in recent years due to the characteristics of cleaning, high efficiency and the like, and compared with the Fenton technology based on OH, SO 4 - Longer half-life, and wider pH range of use, which is more advantageous in practical applications. However, fe is currently utilized 2+ Equal transition metal activated Persulfate (PS) has the same problems as the Fenton technique: (1) generating a large amount of iron mud to form secondary pollution, and increasing the load of the subsequent treatment wastewater; (2) the iron ions introduced in a large amount cannot fully react, and part of the ferrous ions cannot activate PS to generate SO 4 - Instead, it will form a competitive relationship with organic pollutants to consume SO 4 - The waste of resources is caused; (3) fe (Fe) 3+ The accumulation of a large amount of the wastewater can increase the chromaticity of the wastewater, the wastewater can not be discharged normally, the subsequent treatment difficulty is increased, the pipeline is easy to erode, and the operation and maintenance cost of wastewater treatment is increased.
The Metal Organic Framework (MOFs) has the characteristics of large surface area, controllable size, high catalytic activity, stable material structure and the like, and compared with the traditional catalyst, the catalyst not only can efficiently activate PS to generate SO 4 - Meanwhile, the metal leaching can be reduced, and secondary pollution can be reduced or even avoided, so that MOFs show excellent activation performance and application prospect in the persulfate advanced oxidation technology.
However, there is a need to address a few problems to achieve widespread use of MOFs in persulfate advanced oxidation techniques, including: (1) MOFs are in a slurry polymerization state in the wastewater, are unevenly distributed, are difficult to fully contact with the wastewater in the slurry, and greatly reduce the catalytic effect; conventional mechanical agitation is difficult to break the slurry, and mechanical agitation can limit the shape of the reactor and increase the operation and maintenance costs; (2) MOFs have smaller particle size, usually in the micron order of 0.1-10 mu m, are extremely easy to run off along with water, reduce the treatment effect and increase the raw material cost; (3) MOFs in treated effluent are difficult to separate, and the quality of the effluent is affected or the separation cost is too high.
In summary, there is an urgent need for a reactor with good fluidization and homogenization effects, easy water separation of MOFs, and low loss rate, and a method for treating wastewater.
Disclosure of Invention
The invention mainly aims to provide an advanced oxidation membrane reactor based on MOFs activated PS and a wastewater treatment method, aiming at solving the prior technical problems.
To achieve the above object, the present invention provides an advanced oxidation membrane reactor based on MOFs activated PS, comprising:
the reactor comprises a reactor main body, wherein a slurry breaking mixing region, a flow guiding region, a multi-stage reaction region and a water intercepting and yielding region are respectively arranged in the reactor main body from bottom to top, a slurry breaking mixing device is arranged in the center of the slurry breaking mixing region, the flow guiding region is provided with a flow guiding device, MOFs materials are filled in the multi-stage reaction region, multi-stage dosing rings are arranged in the multi-stage reaction region and are used for layering and dosing PS liquid medicine at different heights, the mass transfer distance between sulfate radical generated after the PS liquid medicine is catalyzed by the MOFs and pollutant is shortened, and the water intercepting and yielding region is provided with a water producing device and is used for producing treated standard water flow.
Further, the slurry breaking mixing device is composed of one or more umbrella-shaped structures, the upper part of each umbrella-shaped structure is conical, a jet pipe is fixedly arranged under each umbrella-shaped structure, the bottom end of each jet pipe is respectively connected with one end of a circulating water outlet and one end of a water inlet, the circulating water outlet is positioned in the slurry breaking mixing area and used for conveying MOFs materials, the one end of the water inlet is used for conveying wastewater, the other end of the water inlet is connected with a water inlet pump and a dosing pump, and the other end of the circulating water outlet is connected with the circulating pump.
Further, the cone angle in the umbrella-shaped structure is 120-180 degrees, the flow velocity of the lower edge of the conical bottom surface is 0.6-1.0m/s, the flow velocity of the two sides of the lower edge of the conical bottom surface is 0.1-0.3m/s, and the flow velocity in the jet pipe is 10-15m/s.
Further, the bottom of jet pipe is connected with the floating tube, the floating tube activity is inserted and is located in the sleeve pipe, just the floating tube bottom is equipped with the end plate, set up the water guide hole of installation solenoid valve on the end plate, top and jet pipe intercommunication, be equipped with the elastic component of being connected with the end plate in the sleeve pipe, the sleeve pipe passes through the back flow and communicates with the water pipe that carries waste water to get into, just be equipped with the check valve on the back flow.
Further, the jet pipe comprises an inlet section, a contraction section, a throat and a diffusion section which are sequentially connected, wherein the diffusion section is positioned on the upper portion, the inlet section is positioned on the lower portion, and a side opening is formed in the inlet section of the jet pipe.
Further, the advanced oxidation film reactor has an aspect ratio of 4-8, a residence time of 0.5-2h and a circulation ratio of 100% -200%.
Further, the first-stage dosing ring of the multi-stage dosing ring is positioned at the bottommost part of the multi-stage reaction zone, the distance between the first-stage dosing ring and the second-stage dosing ring is 0.3-0.5m from the top end of the flow guiding device, the distance between the second-stage dosing ring and the upper dosing ring is gradually increased from bottom to top, the distance between the second-stage dosing ring and the upper dosing ring is 0.5-2.0m, and the multi-stage dosing ring is in one-to-one connection with the plurality of dosing ports.
Further, the water producing device consists of a fixing frame, a retaining film, a water collecting pipe and a vibration motor, wherein the retaining film is one of a hollow fiber film and a flat plate film, and the aperture of the film is 0.02-O.1 mu m.
Further, the water collecting pipe is connected with the water outlet, the water outlet is connected with the water outlet pump and the backwashing pump, the water outlet electric valve and the backwashing electric valve are respectively installed on the connecting pipeline, a circulating water intake is arranged below the water outlet, is positioned in the multistage reaction zone, is not lower than the highest dosing port, and is connected with the circulating pump.
A method for treating wastewater by using an oxidation film reactor based on MOFs to activate PS specifically comprises the following steps,
(1) the PS added by the wastewater through the water inlet pump and the dosing pump is premixed at the front end of the water inlet, and enters a jet pipe at a slurry breaking mixing device in the advanced oxidation film reactor through the water inlet, and the wastewater is uniformly mixed through jet collision; the MOFs material reaches the slurry breaking mixing device through a circulating pump, and a slurry wrapping state formed by the dispersed MOFs material when meeting water is broken through jet collision, so that the MOFs material becomes a dispersed state;
(2) carrying out a first mixing reaction on the mixed solution of the wastewater and PS and the dispersed MOFs material in the slurry breaking mixing region under the guide flow of an umbrella-shaped structure, and controlling the flow velocity of the lower edge of the conical bottom surface to be 0.6-1.0m/s;
(3) and uniformly mixing the wastewater with the PS mixed solution and the dispersed MOFs material, uniformly rising the mixed solution through the flow guiding device, and entering a multistage reaction zone. The flow velocity of the two sides of the lower edge of the conical bottom surface is 0.1-0.3m/s, and the distance between the bottom of the flow guiding device and the top of the conical top is 0.3-0.8m, so that the flow state of the mixed liquid is stabilized after the mixed liquid is billowed from the conical bottom surface, and a homogeneous suspension bed is formed;
(4) the multistage chemical adding rings are arranged in the multistage reaction zone, PS liquid medicine is added in layers at different heights in the advanced oxidation film reaction, the mass transfer distance between sulfate radical generated after the PS is catalyzed by MOFs and the pollutant reaction is effectively shortened, and the sulfate radical is maximally controlled to generate effective reaction within the half-life period of 4 seconds;
(5) after multistage reaction, the water enters a water interception and retention area, water is pumped by a water outlet pump and discharged after reaching standards by the interception membrane, and MOFs are intercepted in the multistage reaction area;
(6) when the advanced oxidation film reactor runs for a period of time, the interception film needs backwashing, the control unit is used for closing the water inlet pump, the dosing pump, the water outlet pump and the water outlet electric valve, and the backwashing pump and the backwashing electric valve are opened to backwash the interception film.
The beneficial effects of the invention are as follows:
(1) In the invention, MOFs is utilized to activate PS, so that Fe is effectively avoided 2+ The transition metal activation has the problems of high iron mud yield, secondary pollution, low catalyst utilization rate, high subsequent treatment cost and the like, and compared with the existing advanced oxidation technology, the mass transfer efficiency is higher, the rising flow rate is improved, the hydraulic retention time is shortened, and the occupied area, the capital cost and the energy consumption are effectively reduced.
(2) Aiming at the difficult problems that MOFs are in a slurry polymerization state in wastewater and unevenly distributed and are difficult to effectively transfer mass, the invention designs the slurry breaking mixing device, the slurry polymerization state is broken through large water flow impact force, MOFs in the slurry are dispersed, and the MOFs are fully mixed with the wastewater through water flow state to form a homogeneous suspension bed, so that the slurry breaking mixing device has the advantages of high catalyst utilization rate, high mass transfer efficiency, large space utilization, small occupied area and the like.
(3) Aiming at the problems that MOFs has small particle size and is difficult to effectively separate from wastewater, the invention utilizes the interception membrane to effectively discharge water and simultaneously reduce MOFs loss, improves the quality of discharged water, and reduces the catalyst cost.
(4)SO 4 - The half life is about 4s, and the strong oxidizing property disappears after quenching, and the invention can lead the advanced oxidation film reactor to always and effectively generate new-born free radicals in the radial direction through layered dosing of the multistage dosing rings, thereby keeping the high activity of the reaction system, leading the utilization rate of the liquid medicine to be higher and the treatment efficiency to be higher.
Drawings
FIG. 1 is a schematic diagram of the structure of the present invention;
FIG. 2 is an enlarged schematic view of the structure of the slurry breaking mixing zone in FIG. 1 according to the present invention.
Reference numerals illustrate:
1. a reactor body; 2. breaking slurry mixing area; 3. a diversion area; 4. a multistage reaction zone; 5. intercepting a water outlet area; 6. a water inlet; 7. a water inlet pump; 8. a circulating water outlet; 9. a circulation pump; 10. a water outlet pump; 11. a backwash pump; 12. a dosing pump; 13. a water outlet; 14. a circulating water intake; 15. a flow guiding device; 16. an umbrella-shaped structure; 17. jet pipe; 18. a floating pipe; 19. an end plate; 20. a sleeve; 21. an elastic member; 22. and (5) a return pipe.
Detailed Description
The following description of the embodiments of the present invention will be made clearly and fully with reference to the accompanying drawings, in which it is evident that the embodiments described are only some, but not all embodiments of the invention. Embodiments and features of embodiments in this application may be combined with each other without conflict. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention.
Embodiment one: referring to fig. 1, an advanced oxidation membrane reactor based on MOFs-activated PS according to the present invention comprises:
the reactor comprises a reactor main body 1, wherein a slurry breaking mixing zone 2, a flow guiding zone 3, a multistage reaction zone 4 and a water interception and discharge zone 5 are respectively arranged in the reactor main body from bottom to top, a slurry breaking mixing device is arranged in the center of the slurry breaking mixing zone 2 and used for breaking a slurry coating state formed by dispersed MOFs materials meeting wastewater to enable the slurry coating state to be in a dispersed state, the flow guiding zone 3 is used for conveying mixed liquid of wastewater and PS and the dispersed MOFs materials to the multistage reaction zone 4 through the flow guiding device 15, the multistage reaction zone 4 is filled with MOFs materials and is provided with multistage dosing rings, PS liquid medicines are layered and fed at different heights, the mass transfer distance between sulfate radical generated by the PS liquid medicines after the MOFs catalysis and pollutants is shortened, and the water interception and discharge zone 5 is provided with a water production device for producing treated standard water flow.
In the embodiment, MOFs are utilized to activate PS, so that Fe is effectively avoided 2+ The problems of high iron mud yield, secondary pollution, color reversion, low catalyst utilization rate, high subsequent treatment cost and the like in transition metal activation are solved, and compared with the existing advanced oxidation technology, the mass transfer efficiency is higher, the rising flow rate is improved, the hydraulic retention time is shortened, and the occupied area, the capital cost and the energy consumption are effectively reduced; aiming at the difficult problems that MOFs are in a slurry polymerization state in wastewater and unevenly distributed and are difficult to effectively transfer mass, a slurry breaking mixing device is designed, the slurry polymerization state is destroyed by large water flow impact force, MOFs in the slurry are dispersed, and the MOFs are fully mixed with the wastewater to form a homogeneous suspension bed through water flow state, so that the catalyst has the advantages of high catalyst utilization rate, high mass transfer efficiency, large space utilization, small occupied area and the like.
The slurry breaking mixing device is composed of one or more umbrella-shaped structures 16, the upper part of each umbrella-shaped structure 16 is conical, a jet pipe 17 is fixedly arranged under each umbrella-shaped structure 16, the bottom end of each jet pipe 17 is respectively connected with one end of a circulating water outlet 8 positioned in the slurry breaking mixing zone 2 and used for conveying MOFs materials and one end of a water inlet 6 used for conveying wastewater, the other end of each water inlet 6 is connected with a water inlet pump 7 and a dosing pump 12, and the other end of each circulating water outlet 8 is connected with a circulating pump 9.
Specifically, PS added by the wastewater through the water inlet pump 7 and the dosing pump 12 is premixed at the front end of the water inlet 6, and enters a slurry breaking mixing device in the advanced oxidation film reactor through the water inlet 6, and is uniformly mixed through jet collision; MOFs material reaches the slurry breaking and mixing device through the circulating pump 9, the slurry package is broken through jet collision, so that the MOFs material becomes a dispersion state, and the contact mass transfer of each substance in the reaction system is greatly increased through the flow state of water flow, so that the MOFs material and wastewater are fully mixed to form a homogeneous suspension bed, and the MOFs material has the advantages of high catalyst utilization rate, high mass transfer efficiency, large space utilization, small occupied area and the like.
Preferably, the baffle is evenly arranged on the surface of the umbrella-shaped structure, so that the hydraulic slurry breaking force can be enhanced, MOFs slurry is dispersed more fully, and then the MOFs slurry can be fully contacted with the wastewater, and the wastewater treatment effect is further improved.
The cone angle in the umbrella-shaped structure 16 is 120-180 degrees, the flow velocity of the lower edge of the conical bottom surface is 0.6-1.0m/s, the flow velocity of the two sides of the lower edge of the conical bottom surface is 0.1-0.3m/s, and the flow velocity in the jet pipe 17 is 10-15m/s.
Specifically, according to the formula that the flow rate is equal to the flow rate divided by the area, the flow rate of the mixed liquid in the jet pipe 17 can be adjusted, so that the flow rate at the lower edge of the bottom surface and the flow rates at the two sides of the umbrella-shaped structure 16 can be adjusted, and the effect of ensuring a certain flow rate is that the MOFs slurry can be fully broken, that the turbulent state of the water flow and the mixing of the phases are kept in a proper state, and that the shape of the umbrella-shaped structure 16 is adapted.
Meanwhile, by the arrangement, the mixing reaction intensity can be ensured, and the bottom of the advanced oxidation film reaction zone is prevented from being deposited.
Referring to fig. 2, a floating tube 18 is connected to the bottom end of a jet tube 17, the floating tube 18 is movably inserted into a sleeve 20, an end plate 19 is provided at the bottom end of the floating tube 18, a water guide hole for installing an electromagnetic valve is provided on the end plate 19, the top end is communicated with the jet tube 17, an elastic member 21 connected with the end plate 19 is provided in the sleeve 20, the sleeve 20 is communicated with a water pipe for delivering wastewater through a return pipe 22, and a check valve is provided on the return pipe 22.
Specifically, in the wastewater treatment process, the problem of fluidization dead zone possibly exists in the slurry breaking mixing zone 2, whether the problem of fluidization dead zone exists is judged according to the observation of the subsequent treatment effect, if so, a part of mixed liquid enters the sleeve 20 by controlling the electromagnetic valve on the end plate 19 to open and close the one-way valve, so that the floating pipe 18 slides in the sleeve 20, and the jet pipe 17 moves synchronously, the distance between the umbrella-shaped structure 16 and the bottom of the slurry breaking mixing zone 2 is adjusted, the position for fully flowing and reacting the wastewater with PS and MOFs materials is provided, the occurrence of fluidization dead zone is reduced, and the wastewater treatment effect is improved; when the wastewater treatment standard is observed to return to a normal value, the electromagnetic valve is closed, the one-way valve is opened, and the floating pipe 18 redirects the wastewater introduced before back to the water pipe into which the wastewater enters through the return pipe 22 under the action of the elastic member 21.
Jet pipe 17 includes inlet section, constriction section, throat and diffuser section that connect gradually, wherein, the diffuser section is located in the upper portion, and the inlet section is located in the lower part.
Specifically, the waste water, the mixed solution of PS liquid medicine and the reflowed MOFs enter the jet pipe 17, the flow velocity starts to rise in the contraction section until the flow velocity in the throat is maximized, so that the negative pressure is formed behind the flow direction of the liquid, and the liquid outside the jet pipe is sucked into the jet pipe due to the static pressure, namely, the MOFs are sucked into the jet pipe, so that the MOFs in the slurry breaking mixing area form a small cycle, and the slurry breaking effect is enhanced.
Preferably, the jet pipe 17 is provided with a side opening for sucking surrounding MOFs into the jet pipe 17 to realize circulating flow.
The high-grade oxidation film reactor has an aspect ratio of 4-8, a residence time of 0.5-2h and a circulation ratio of 100% -200%.
The first stage dosing ring of the multistage dosing ring is positioned at the bottommost part of the multistage reaction zone 4, the distance from the top end of the flow guiding device 15 to the top end is 0.3-0.5m, the distance between the second stage dosing ring and the above dosing ring is gradually increased from bottom to top, the distance is 0.5-2.0m, and the multistage dosing ring is connected with a plurality of dosing ports in a one-to-one manner.
Specifically, SO 4 - The half life is about 4s, and the strong oxidizing property disappears after quenching, and the invention can lead the advanced oxidation film reactor to always and effectively generate new free radicals in the radial direction through the layered dosing of the multistage dosing rings, thereby improving the reaction efficiency of the advanced oxidation film reactor, keeping the high activity of the reaction system, leading the utilization rate of the liquid medicine to be higher and the treatment efficiency to be higher.
The water producing device consists of a fixing frame, a retaining film, a water collecting pipe and a vibration motor, wherein the retaining film is one of a hollow fiber film and a flat plate film, and the aperture of the film is 0.02-O.1 mu m.
Specifically, aiming at the problems that MOFs has small particle size and is difficult to effectively separate from wastewater, the interception membrane is utilized to effectively discharge water and reduce MOFs loss, so that the quality of discharged water is improved, the reuse rate of MOFs is increased, and the cost of a catalyst is reduced.
To the jam risk that the trapping film itself exists, set up vibrating motor, through the vibration, effectively reduce dirty stifled risk, backwash frequency to reduce cost, green low carbon.
The water collecting pipe is connected with a water outlet 13, the water outlet 13 is connected with a water outlet pump 10 and a backwash pump 11, a water outlet electric valve and a backwash electric valve are respectively arranged on the connecting pipelines, a circulating water intake 14 is arranged below the water outlet 13, and the circulating water intake 14 is positioned in the multistage reaction zone 4, is not lower than the highest dosing port, and is connected with the circulating pump 9.
Specifically, when the advanced oxidation film reactor runs for a period of time, the interception film needs backwashing, the control unit is used for closing the water inlet pump 7, the dosing pump 12, the water outlet pump 10 and the water outlet electric valve, and the backwashing pump 11 and the backwashing electric valve are opened to backwash the interception film, so that the use state of the interception film is ensured.
Embodiment two: a method for treating wastewater by using an oxidation membrane reactor based on MOFs-activated PS, characterized by: in particular comprising the following steps of the method,
(1) the PS added by the water inlet pump 7 and the chemical adding pump 12 is premixed at the front end of the water inlet 6, and enters a slurry breaking mixing device in the advanced oxidation film reactor through the water inlet 6, and is uniformly mixed through jet collision; MOFs material reaches the slurry breaking mixing device through the circulating pump 9, and the slurry package is broken through jet collision, so that the MOFs material becomes a dispersion state, and the contact mass transfer of each substance of a reaction system is greatly increased;
(2) the mixed solution of the wastewater and PS and the dispersed MOFs material are subjected to primary mixing reaction in a slurry breaking mixing zone 2 under the flow guide of an umbrella-shaped structure 16, and the mixing reaction intensity is ensured and the bottom of a high-grade oxide film reaction zone is prevented from being deposited by controlling the flow velocity of the lower edge of a conical bottom surface to be 0.6-1.0m/s;
(3) after the first mixing reaction, the mixture evenly rises through a flow guiding device 15 and enters a multi-stage reaction zone 4. The flow velocity of the two sides of the lower edge of the conical bottom surface is 0.1-0.3m/s, and the distance between the bottom of the flow guiding device 15 and the conical top point is 0.3-0.8m, so that the flow state of the mixed liquid is stable after the mixed liquid is billowed from the conical bottom surface, the uniform water distribution effect of the flow guiding device is ensured, and a homogeneous suspension bed is formed;
(4) the multistage chemical adding rings are arranged in the multistage reaction zone 4, PS liquid medicine is added in layers at different heights in the advanced oxidation film reaction, the mass transfer distance between sulfate radicals generated after the PS is catalyzed by MOFs and the pollutant reaction is effectively shortened, the sulfate radicals are maximally controlled to generate effective reaction within the half-life period of 4 seconds, and the reaction efficiency of the advanced oxidation film reactor is improved;
(5) after multistage reaction, the water enters a interception water outlet area 5, water is sucked by a water outlet pump 10 and discharged after reaching the standard through an interception membrane, so that the water quality of the water outlet is ensured, MOFs are intercepted in the multistage reaction area 4, the loss is avoided, the catalytic effect is ensured, and the medicine consumption is reduced;
(6) when the advanced oxidation film reactor runs for a period of time, the interception film needs backwashing, the control unit is used for closing the water inlet pump 7, the dosing pump 12, the water outlet pump 10 and the water outlet electric valve, and the backwashing pump 11 and the backwashing electric valve are opened to backwash the interception film.
It should be noted that, in the embodiment of the present invention, directional indications such as up, down, left, right, front, and rear … … are referred to, and the directional indication is merely used to explain the relative positional relationship, movement conditions, and the like between the components in a specific posture such as that shown in the drawings, and if the specific posture is changed, the directional indication is changed accordingly.
In addition, if there is a description of "first", "second", etc. in the embodiments of the present invention, the description of "first", "second", etc. is for descriptive purposes only and is not to be construed as indicating or implying a relative importance or implicitly indicating the number of technical features indicated. Thus, a feature defining "a first" or "a second" may explicitly or implicitly include at least one such feature. In addition, the meaning of "and/or" as it appears throughout includes three parallel schemes, for example "A and/or B", including the A scheme, or the B scheme, or the scheme where A and B are satisfied simultaneously. In addition, "a plurality of" means two or more. In addition, the technical solutions of the embodiments may be combined with each other, but it is necessary that the combination of the technical solutions should be regarded as not existing when the combination of the technical solutions contradicts or cannot be realized on the basis of the realization of those skilled in the art.
The foregoing description of the preferred embodiments of the invention is not intended to be limiting, but rather is intended to cover all modifications, equivalents, alternatives, and improvements that fall within the spirit and scope of the invention.
Claims (7)
1. An advanced oxidation membrane reactor based on MOFs activated PS, comprising:
the reactor comprises a reactor main body (1), wherein a slurry breaking mixing region (2), a flow guiding region (3), a multistage reaction region (4) and a water interception and discharge region (5) are respectively arranged in the reactor main body from bottom to top, a slurry breaking mixing device is arranged in the center of the slurry breaking mixing region (2), a flow guiding device (15) is arranged in the flow guiding region (3), MOFs materials are filled in the multistage reaction region (4) and multistage dosing rings are arranged for layered dosing of PS liquid medicine at different heights, the mass transfer distance between sulfate radicals generated after the PS liquid medicine is catalyzed by the MOFs and pollutants is shortened, and a water production device is arranged in the water interception and discharge region (5) and used for producing treated water reaching standards;
the slurry breaking mixing device is composed of one or more umbrella-shaped structures (16), the upper part of each umbrella-shaped structure (16) is conical, a jet pipe (17) is fixedly arranged under each umbrella-shaped structure, the bottom end of each jet pipe (17) is respectively connected with one end of a circulating water outlet (8) which is positioned in a slurry breaking mixing area (2) and is used for conveying MOFs materials and one end of a water inlet (6) which is used for conveying wastewater, the other end of each water inlet (6) is connected with a water inlet pump (7) and a dosing pump (12), and the other end of each circulating water outlet (8) is connected with a circulating pump (9);
the bottom end of the jet pipe (17) is connected with a floating pipe (18), the floating pipe (18) is movably inserted into a sleeve (20), an end plate (19) is arranged at the bottom end of the floating pipe (18), a water guide hole for installing an electromagnetic valve is formed in the end plate (19), the top end of the floating pipe is communicated with the jet pipe (17), an elastic piece (21) connected with the end plate (19) is arranged in the sleeve (20), the sleeve (20) is communicated with a water pipe for conveying wastewater to enter through a return pipe (22), and a one-way valve is arranged on the return pipe (22);
the cone angle in the umbrella-shaped structure (16) is 120-180 degrees, the flow velocity of the lower edge of the conical bottom surface is 0.6-1.0m/s, the flow velocity of the two sides of the lower edge of the conical bottom surface is 0.1-0.3m/s, and the flow velocity in the jet pipe (17) is 10-15m/s.
2. An oxide film reactor based on MOFs-activated PS as claimed in claim 1, characterized in that: jet pipe (17) are including entrance section, shrink section, throat and the diffusion section that connects gradually, wherein, the diffusion section is located upper portion, and the entrance section is located the lower part, wherein, the side mouth has been seted up to the entrance section of jet pipe (17).
3. An oxide film reactor based on MOFs-activated PS as claimed in claim 1, characterized in that: the advanced oxidation film reactor has an aspect ratio of 4-8, a residence time of 0.5-2h and a circulation ratio of 100% -200%.
4. An oxide film reactor based on MOFs-activated PS as claimed in claim 1, characterized in that: the first-stage dosing ring of the multi-stage dosing ring is positioned at the bottommost part of the multi-stage reaction zone (4), the distance from the top end of the flow guiding device (15) to the top end is 0.3-0.5m, the distance between the second-stage dosing ring and the above dosing ring is gradually increased from bottom to top, the distance is 0.5-2.0m, and the multi-stage dosing ring is connected with a plurality of dosing ports in a one-to-one mode.
5. An oxide film reactor based on MOFs-activated PS as claimed in claim 1, characterized in that: the water producing device consists of a fixing frame, a retaining film, a water collecting pipe and a vibration motor, wherein the retaining film is one of a hollow fiber film and a flat plate film, and the aperture of the film is 0.02-0.1 mu m.
6. An oxide film reactor based on MOFs-activated PS as claimed in claim 5, characterized in that: the water collecting pipe is connected with the water outlet (13), the water outlet (13) is connected with the water outlet pump (10) and the backwashing pump (11), the water outlet electric valve and the backwashing electric valve are respectively installed on the connecting pipeline, a circulating water intake (14) is arranged below the water outlet (13), the circulating water intake (14) is positioned in the multistage reaction zone (4), the position of the circulating water intake is not lower than the highest dosing port, and the circulating water intake is connected with the circulating pump (9).
7. A method for treating wastewater using a MOFs-activated PS-based oxidation membrane reactor according to any one of claims 1-6, wherein: in particular comprising the following steps of the method,
(1) PS added by the wastewater through the water inlet pump (7) and the dosing pump (12) is premixed at the front end of the water inlet (6), and enters a jet pipe at a slurry breaking mixing device in the advanced oxidation film reactor through the water inlet (6) to be uniformly mixed through jet collision; the MOFs material reaches the slurry breaking mixing device through a circulating pump (9), and a slurry wrapping state formed by the dispersed MOFs material when meeting water is broken through jet collision so as to be in a dispersed state;
(2) the mixed solution of the wastewater and PS and the dispersed MOFs material are subjected to primary mixing reaction in the slurry breaking mixing region (2) under the diversion of an umbrella-shaped structure (16), and the flow velocity of the lower edge of the conical bottom surface is controlled to be 0.6-1.0m/s;
(3) uniformly mixing the wastewater with the PS mixed solution and the dispersed MOFs material, uniformly rising the mixed solution through the flow guiding device (15), and entering a multistage reaction zone (4); the flow velocity of the two sides of the lower edge of the conical bottom surface is 0.1-0.3m/s, and the distance between the bottom of the flow guiding device (15) and the conical top point is 0.3-0.8m, so that the flow state of the mixed liquid is stabilized after the mixed liquid is billowed from the conical bottom surface, and a homogeneous suspension bed is formed;
(4) a multistage dosing ring is arranged in the multistage reaction zone (4), PS liquid medicine is layered and added at different heights in the advanced oxidation film reaction, the mass transfer distance between sulfate radical generated after the PS is catalyzed by MOFs and the pollutant reaction is effectively shortened, and the sulfate radical is maximally controlled to generate effective reaction within the half-life period of 4 seconds;
(5) after multistage reaction, the mixture enters a retention water outlet area (5), water is pumped by a water outlet pump (10) and discharged after reaching standards, and MOFs are retained in a multistage reaction area (4);
(6) when the advanced oxidation film reactor runs for a period of time, the interception film needs backwashing, the control unit is used for closing the water inlet pump (7), the dosing pump (12), the water outlet pump (10) and the water outlet electric valve, and the backwashing pump (11) and the backwashing electric valve are opened to backwash the interception film.
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Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103214079A (en) * | 2013-04-27 | 2013-07-24 | 华南理工大学 | Bidirectional flow internal circulation type PS advanced oxidation reactor and sewage treatment method |
| CN107792932A (en) * | 2017-11-30 | 2018-03-13 | 华南理工大学 | A kind of advanced oxidation reactor based on MOFs activation PS and its method for handling waste water |
| US20190060834A1 (en) * | 2017-08-24 | 2019-02-28 | Gary P. Katz | Apparatus system and method to separate brine from water |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103214079A (en) * | 2013-04-27 | 2013-07-24 | 华南理工大学 | Bidirectional flow internal circulation type PS advanced oxidation reactor and sewage treatment method |
| US20190060834A1 (en) * | 2017-08-24 | 2019-02-28 | Gary P. Katz | Apparatus system and method to separate brine from water |
| CN107792932A (en) * | 2017-11-30 | 2018-03-13 | 华南理工大学 | A kind of advanced oxidation reactor based on MOFs activation PS and its method for handling waste water |
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