CN102260003A - Microwave electrodeless ultraviolet photocatalysis-double membrane separation coupled treatment device for industrial wastewater - Google Patents
Microwave electrodeless ultraviolet photocatalysis-double membrane separation coupled treatment device for industrial wastewater Download PDFInfo
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Abstract
The invention relates to a microwave electrodeless ultraviolet photocatalysis-double membrane separation coupled treatment device for industrial wastewater. The device mainly comprises a reactor (1), a membrane separation system (2), a microwave electrodeless ultraviolet light source system (4), an aeration system, and an ozone tail gas decomposing device (7) and a water inlet and outlet system which are communicated with the reactor, wherein a reaction zone and an aeration zone are arranged on upper and lower sides in the reactor and are separated by a water distribution plate (5); the membrane separation system and the microwave electrodeless ultraviolet light source system are positioned in the reaction zone and are separated by a corrugated clapboard (3); the aeration system consists of a microporous aeration head (6) and an air blower (8); the microporous aeration head is positioned at the bottom of the aeration zone; and the air blower supplies air to the aeration zone through an air pipeline. The device has the characteristics that the device has a high reaction rate, completely degrades organic matters, can be operated for a long time, and the like; and the device has high operability and safety, is suitable for treating non-degradable organic industrial wastewater, and is also suitable for sterilization and disinfection in the field of water supply.
Description
Technical field
The invention belongs to the technology for treating industrial waste water field, the structure design of particularly a kind of microwave electrodeless ultraviolet light catalysis oxidation and membrane sepn coupled water treatment device is applicable to the advanced treatment and the reuse of difficult trade effluents such as textile printing and dyeing wastewater.
Background technology
Along with the development of industrial technology, the organic pollutant content in the trade effluent is increasing, and kind is more and more, and composition becomes increasingly complex, thereby intractability is also increasing.Huge day by day along with China's environmental stress simultaneously, central and local governments propose the discharging of industry and have formulated more and more strict emission control standards, are the effective ways that overcomes the above problems at the advanced treatment technology of trade effluent and the research and development of equipment.
Photocatalysis oxidation technique is a kind of novel water pollution control technology, have characteristics such as efficient, energy-conservation, applied widely, almost can react, be commonly used to handle the organism of difficult for biological degradation with any organism, can be inorganic molecules with its direct mineralising, be with a wide range of applications.In this technology, light source commonly used is traditional ultraviolet source that electrode is arranged, and catalyzer mainly is suspended state TiO
2Catalyzer, this is because suspended state catalyzer TiO
2Be evenly distributed, specific surface area is big tens times than coated type, and catalytic efficiency is higher; But tiny TiO
2It is traditional isolation technique (flocculation, precipitation) Separation and Recovery that particulate (diameter is generally less than 1 μ m) is difficult for, and repeating utilization factor is low, and liquid effluent easily produces secondary pollution, has seriously limited its application.
Photochemical catalysis and membrane sepn combined utilization can effectively be solved TiO
2The loss of catalyzer and recycling problem.Chinese patent " with combined suspension photocatalytic oxidation method for treating water and the device thereof of membrane separation plant " (Granted publication number: CN1125782C) a kind of suspension photocatalytic oxidation method for treating water and device are disclosed, this method be make have vesicular structure, pulverous photocatalyst granular mixes the mixed solution that forms suspended catalyst with pending water; Mixed solution is sent into reactor, and this mixed solution is carried out pump circulation.In reactor, be provided with lamp district and film district two portions, be provided with a plurality of ultraviolet light sources in the lamp district, in the film district, membrane separation unit is set, the light that ultraviolet lamp produces can effectively be utilized by catalyzer, water is after treatment separated with granules of catalyst, treating water is drawn out of this reactor after filtering through membrane separation unit, and catalyzer is trapped within the reactor internal recycle and uses, and makes water treatment procedure realize operation continuously.Chinese patent " a kind of suspension photocatalytic oxidizing water treatment unit " (Granted publication number: CN1202020C) disclose a kind of suspension photocatalytic oxidizing water treatment unit, on the basis of CN1125782C, by the full-bottom aeration of microwell plate and the intermittent aeration of auxiliary porous air manifold tube, prevent the sinking of fine catalyst, help organic efficient decomposition simultaneously, prevent that film from stopping up, effectively prolonged the processing cycle, by ventilation plant being set, solved simultaneously because the fluorescent tube that the lamp hole temperature rising is caused shows problems such as fouling in the lamp district.Chinese patent " removing the continuously-submerged photocatalytic membrane treatment equipment of natural organic matter in the water " (Granted publication number: CN1290774C) disclose a kind of continuously-submerged photocatalytic membrane treatment equipment of removing natural organic matter in the water, it adopts cellulose filter to replace microfiltration membrane to overcome the film blockage problem, and be applicable to the processing of natural organic matter in the water, not only can reduce the COD of water outlet
Mn, TOC, the pathogenic bacteria, bacterium etc. of water outlet are reduced greatly.Other Chinese patent also comprises " integrated photo-catalytic oxidation membrane-separation fluidized bed reactor " (patent No.: ZL2006101029881.2), " photochemical catalytic oxidation-membrane separation circulating fluid bed reaction device " (application publication number: CN101875001A) etc.
All adopted traditional electrode ultraviolet source that has in Shen Qing the patent, membrane separation assemblies also has inorganic membrane assembly based on organic curtain type film assembly, also comprises the secondary filter assembly in the past; Based on integrated reactor, also comprise the separated type reactor of photochemical catalysis and membrane sepn in form.Generally speaking, mainly have following drawback: because the light source that adopts is traditional electrode ultraviolet source that has, it is more complicated on structure design, light source is shorter on the life-span, spectral radiance is inhomogeneous, needs custom-designed light source cooling system that it is cooled off simultaneously, and is bigger on energy consumption; It two is that in the past patent all is a kind of simply integrated of photochemical catalysis and membrane sepn, does not embody the coupled meaning, therefore must influence its economic economy.
Summary of the invention
Technical problem to be solved by this invention is: a kind of trade effluent microwave electrodeless ultraviolet light catalysis-two membrane sepn coupling treatment unit are provided, the microwave electrodeless ultraviolet light source of adopting in this device can overcome the deficiency of conventional light source, and light-source system, film separating system are realized organically coupling by air system, the final advanced treatment that realizes trade effluent, especially dyeing waste water.
The present invention solves its technical problem and adopts following technical scheme:
Trade effluent microwave electrodeless ultraviolet light catalysis provided by the invention-two membrane sepn coupling treatment unit, it is mainly by reactor, film separating system, the microwave electrodeless ultraviolet light origin system, aerating system, and the ozone tail gas decomposer that is communicated with reactor, inlet and outlet system form, and wherein: the upper and lower of inside reactor is respectively reaction zone and aeration zone, and they separate with water distribution board; Film separating system and microwave electrodeless ultraviolet light origin system are arranged in reaction zone, and are separated by corrugated separator plate; Aerating system is made up of micro porous aeration head and gas blower, and micro porous aeration head is positioned at the bottom of aeration zone, and gas blower is blown to the aeration zone by air line.
Described reactor, its inside can be according to the difference filling different mass concentration of water quality, the TiO of different-grain diameter
2, its mass concentration is 1g/L-4g/L, its particle diameter is 20nm-100 μ m.
Described film separating system can adopt commercial curtain formula hollow fiber film assembly or the plate film assembly used, and the material of this membrane module is PVDF, and the aperture is 0.1-0.2 μ m.
Described film separating system can have two covers, and they are arranged symmetrically in the periphery of microwave electrodeless ultraviolet light origin system; Two cover film separating system alternations, in the time of a cover film separating system work water outlet therein, an other cover film separating system then carries out aeration and cleans.
Described corrugated separator plate, the angle of itself and horizontal direction is 60 °.
Described microwave electrodeless ultraviolet light origin system can be made up of microwave device and electrodeless ultraviolet light source, they are realized connecting and sealing by connecting screw, cylinder lever connecting rod and sealing-ring, wherein: microwave device is positioned at the top in electrodeless ultraviolet light source, this microwave device mainly is made up of waveguide head, magnetron, by water-cool control, be installed into the mouth of a river and water outlet respectively at the upper and lower of magnetron.
Described electrodeless ultraviolet light source is provided with a twinkler that is arranged in quartz socket tube, and this twinkler can link to each other with base by the twinkler support, establishes air inlet port and production well respectively at the upper and lower of quartz socket tube.
Described water inlet system can be made up of the inlet chest and the intake pump that link to each other with pipeline, and intake pump is communicated with inside reactor by inlet channel.Described outlet system can by link to each other with pipeline go out water pump and water tank is formed, go out water pump and be communicated with film separating system by outlet conduit.
Above-mentioned trade effluent microwave electrodeless ultraviolet light catalysis provided by the invention-two membrane sepn coupling treatment unit, it is used for Industrial Wastewater Treatment.
Described trade effluent is a textile printing and dyeing wastewater.
The present invention compares with conventional art, has the following advantages and the high-lighting progress:
The present invention is by installing one deck quartz socket tube additional outside electrodeless lamp, make the twinkler of electrodeless lamp to be immersed in fully in the water body, and use this system and replaced traditional electrode ultraviolet source that has, for the operation of this device provides more uniform spectra radiation and short wavelength's ultraviolet source more, can improve the work-ing life of device and help improving the degradation efficiency of reactor; The 2nd, a kind of source of the gas satisfies three functional requirements, realizes the cooling of twinkler simultaneously, reaches the source of the gas that is used as aeration as ozoniferous source of the gas, realizes the coupling of photochemical catalysis and membrane sepn by effective utilization of source of the gas; The 3rd, in same reactor, under the prerequisite of not adding extra oxygenant, realize the UV/O of hardly degraded organic substance
3/ TiO
2The concerted catalysis oxidation.
Simultaneously, the present invention has also made improvement to patent of invention in the past in the following areas: when realizing the waste water water conservancy diversion by the ripple dividing plate, produce local turbulent flow at the film near surface, effectively reduce the process that film pollutes, the 2nd, in same reactor, make up the two film system of two cover alternate runs, further overcome film and pollute the continuous operation of realization response device.
The present invention compares with prior art: light source life can reach 20,000 hours (with the work-ing life of microwave head in the family expenses microwave oven), short wave ultraviolet light (254nm) intensity is compared with traditional light source and can be improved 10 times simultaneously, reactor does not need to be provided with the special-purpose aerating apparatus in special film district, the ozone amount that reactor produces can reach 0.045mg/min, percent of decolourization can improve 20%, and the TOC clearance can improve 40%.
Description of drawings
Fig. 1 is a structural representation of the present invention.
Fig. 2 is the structural representation of microwave electrodeless ultraviolet light origin system.
Among the figure: 1. reactor; 2. film separating system; 3. corrugated separator plate; 4. microwave electrodeless ultraviolet light origin system; 5. water distribution board; 6. micro porous aeration head; 7. ozone tail gas decomposer; 8. gas blower; 9. inlet chest; 10. intake pump; 11. go out water pump; 12. water tank; 13. production well; 14. quartz socket tube; 15. air inlet port; 16. waveguide head; 17. water-in; 18. magnetron; 19. water outlet; 20. twinkler support; 21. twinkler; 22. base.
Embodiment
The invention will be further described below in conjunction with embodiment and accompanying drawing.
Trade effluent microwave electrodeless ultraviolet light catalysis provided by the invention-two membrane sepn coupling treatment unit, its structure is as shown in Figure 1: mainly by reactor 1, film separating system 2, microwave electrodeless ultraviolet light origin system 4, aerating system, and the ozone tail gas decomposer 7 that is communicated with reactor 1, inlet and outlet system are formed.Wherein: the upper and lower of reactor 1 inside is respectively reaction zone and aeration zone, and they separate with water distribution board 5.Film separating system 2 and microwave electrodeless ultraviolet light origin system 4 are arranged in reaction zone, and are separated by corrugated separator plate 3.Aerating system is made up of gas blower 8 and micro porous aeration head 6, and micro porous aeration head 6 is positioned at the bottom of aeration zone, and gas blower 8 is blown to the aeration zone by air line.
Described reactor 1, the difference filling different mass concentration of its internal condition water quality, the TiO of different-grain diameter
2, its particle diameter is between 20nm-100 μ m, and its mass concentration is between 1g/L-4g/L.
Described film separating system 2 has two covers, and they are arranged symmetrically in the periphery of microwave electrodeless ultraviolet light origin system 4, and is separated by corrugated separator plate 3.Every cover film separating system is commercial curtain formula hollow fiber film assembly or the plate film assembly used, and the material of membrane module is PVDF, and the aperture is 0.1-0.2 μ m.Two cover film separating system alternations, in the time of a cover film separating system work water outlet therein, an other cover film separating system then carries out aeration and cleans.
Described corrugated separator plate 3, the angle of itself and horizontal direction is 60 °, finishes three functions simultaneously: the one, film separating system and microwave electrodeless ultraviolet light origin system are separated, guarantee that membrane module is not subjected to the irradiation of UV-light; The 2nd, in reactor, current are played a kind of guide functions; The 3rd, near membrane module, cause local turbulent flow, to alleviate the pollution process of membrane module.
Described microwave electrodeless ultraviolet light origin system 4, it is made up of microwave device and electrodeless ultraviolet light source, and they are realized connecting and sealing by connecting screw, cylinder lever connecting rod and sealing-ring.As shown in Figure 2: microwave device is positioned at the top in electrodeless ultraviolet light source, and this device mainly is made up of waveguide 16 and magnetron 18, by water-cool control.The lower end of waveguide 16 is contained in the top of microwave device, and the sidepiece of waveguide 16 is installed magnetron 18.Upper and lower at magnetron 18 is installed into the mouth of a river 17 and water outlet 19 respectively.The electrodeless ultraviolet light source is provided with a twinkler 21 that is arranged in quartz socket tube 14, and this twinkler links to each other with base 22 by twinkler support 20, establishes air inlet port 15 and production well 13 respectively at the upper and lower of quartz socket tube 14.
Described water inlet system is made up of the inlet chest 9 and the intake pump 10 that link to each other with pipeline, and intake pump is by inlet channel and reactor 1 internal communication.
Described outlet system by link to each other with pipeline go out water pump 11 and water tank 12 is formed, go out water pump and be communicated with film separating system 2 by outlet conduit.
Described ozone tail gas decomposer 7 according to treatment scale, is made up of with the ozone tail gas decomposer the commerce of different treatment ability.
Described gas blower 8, its air that provides is finished three functions simultaneously, and realize the coupling operation of microwave electrodeless ultraviolet light catalysis oxidation system and film separating system in the whole device, the one, air at first passes through the microwave electrodeless ultraviolet light origin system with the cooling twinkler, the 2nd, as ozoniferous air source, under the short wave ultraviolet light that twinkler produces, produce certain density ozone, the 3rd, after through the microwave electrodeless ultraviolet light system, reactor is carried out aeration by micro porous aeration head.This gas is the mixed gas of air and ozone, can guarantee the abundant suspension of catalyzer, membrane module is cleaned, but while ozone gas cooperative with ultraviolet radiation (UV) is wherein degraded to organic pollutant.
Trade effluent microwave electrodeless ultraviolet light catalysis provided by the invention-two membrane sepn coupling treatment unit, its working process is as follows:
Water flow process: waste water is stored in the inlet chest 9, pumps into reactor 1 by inlet channel and intake pump 10, and at reactor bottom, waste water is by fluorinated ethylene propylene (PVC) water distribution board 5 water distributions, and behind corrugated separator plate 3 water conservancy diversion, the organic pollutant in the waste water is at UV/O
3/ TiO
2Synergy under obtain the degraded, pump into water tank 12 by the water pump 11 that goes out that is connected with membrane module separation system 2 then, in the course of the work, two mantle components apart systems replace water outlet according to certain time interval.
The air-flow process: the air that gas blower 8 produces at first enters microwave electrodeless ultraviolet light origin system 4 by air inlet port 15, provide twinkler 21 coolings needed air, in the process of twinkler, the short-wave ultraviolet radiation that twinkler produces excites airborne O at airflow
2Produce O
3, air and O
3Mixed gas link to each other with the micro porous aeration head 6 of reactor bottom through production well 13, and by being evenly arranged in the micro-pore aeration dish aeration of reactor bottom, aeration guarantees the catalyzer TiO in the reactor on the one hand
2Be in suspended state, on the other hand the film surface formed to wash away to reduce film and pollute, simultaneously O
3Collaborative UV/TiO
2Organism in the waste water is explained, last, air and remaining O
3Enter atmosphere behind the ozone tail gas decomposer 7 by the top.
The working process of microwave electrodeless ultraviolet light origin system 4: the microwave generation system of the adjustable power of forming by major partss such as magnetron 18 and waveguides 16 produces microwave, microwave power is between 300w-1000w, twinkler 21 is luminous by microwave-excitation, organism effect degradation of organic substances in light transmission quartz socket tube 42 and the water, by with airborne O
2Effect produces O
3Being shaped as of twinkler 21 is bar-shaped, and it fills rare gas element is Ar gas, and filler metal is Hg, and its diameter is 15mm, and length is 600-800mm, and the number of twinkler is that 6-12 props up in the cover microwave ultraviolet system.The twinkler support 20 of twinkler by quartzy material supports and is fixing, in same reactor, many cover microwave electrodeless ultraviolet light origin systems can be set according to the needs of actual water quality and quantity.In the process of microwave electrodeless ultraviolet light origin system work, magnetron 18 need be provided with cooling system, and the present invention adopts water-cooling system, and water coolant flows into through water-in 17, flows out through water outlet 19.
Above-mentioned trade effluent microwave electrodeless ultraviolet light catalysis provided by the invention-two membrane sepn coupling treatment unit, its working process is: the air that air supply system produces at first passes through the electrodeless lamp ultraviolet system of microwave-excitation, when stablizing lamp hole temperature, short-wave radiation by electrodeless ultraviolet lamp produces certain density ozone, ozone and Air mixing gas carry out continuous aeration by microporous aeration device to reactor, and ozone cooperative with ultraviolet radiation carries out O to the organic pollutant in the waste water
3/ UV, O
3/ UV/TiO
2Synergistic oxidation and concerted catalysis oxidation.At same reactor two film systems are set, in a cover membrane module work water outlet, the empty aeration of an other cover membrane module cleans, and cycle operation guarantees that complete assembly can the long-time continuous operation.
Above-mentioned trade effluent microwave electrodeless ultraviolet light catalysis provided by the invention-two membrane sepn coupling treatment unit, it is used for Industrial Wastewater Treatment, is specially adapted to the advanced treatment and the reuse of difficult trade effluents such as textile printing and dyeing wastewater.
Be example with the treatment of dyeing and printing below, the effect of this device and the structure of relevant parts are described.
Process object is a 100mg/L reactive brilliant red x-3b dye wastewater, photocatalyst particle diameter 0.1 μ m, concentration 1g/L, tolerance 1.2m
3/ h.
Microwave light oxidation-membrane sepn coupling device is of a size of L * W * H=400mm * 250mm * 400mm, and reactor volume 40L installs two cover curtain type film assemblies near reactor wall, and material is PVDF, membrane pore size 0.1-0.2 μ m, membrane area 1m
2, flux 10L/m
2H, 2 hours alternate run cycles.Microwave electrodeless ultraviolet light source one is placed on reactor middle part, 6 of lamp numbers, microwave power 1000w.Water distribution board is polyvinyl chloride (PVC) material, borehole diameter 2mm, and pitch of holes 5mm, circular micro-pore aeration dish aeration is adopted in the bottom.Tail gas is discharged by stink cupboard.
Under 60 days situations of continuous operation, membrane module can keep stable flux to move no latch up phenomenon.This device is handled reactive brilliant red x-3b, and percent of decolourization reaches 100%, and the TOC clearance reaches 80%.Delivery turbidity 0.5NTU.
Claims (10)
1. a trade effluent microwave electrodeless ultraviolet light catalysis-two membrane sepn coupling treatment unit, it is characterized in that this device is mainly by reactor (1), film separating system (2), microwave electrodeless ultraviolet light origin system (4), aerating system, and the ozone tail gas decomposer (7) that is communicated with reactor (1), inlet and outlet system form, and wherein: the inner upper and lower of reactor (1) is respectively reaction zone and aeration zone, and they separate with water distribution board (5); Film separating system (2) and microwave electrodeless ultraviolet light origin system (4) are arranged in reaction zone, and are separated by corrugated separator plate (3); Aerating system is made up of micro porous aeration head (6) and gas blower (8), and micro porous aeration head (6) is positioned at the bottom of aeration zone, and gas blower (8) is blown to the aeration zone by air line.
2. according to the described trade effluent microwave electrodeless ultraviolet light catalysis of claim 1-two membrane sepn coupling treatment unit, it is characterized in that: described reactor (1), the difference filling different mass concentration of its internal condition water quality, the TiO of different-grain diameter
2, its mass concentration is 1g/L-4g/L, its particle diameter is 20nm-100 μ m.
3. according to the described trade effluent microwave electrodeless ultraviolet light catalysis of claim 1-two membrane sepn coupling treatment unit, it is characterized in that: described film separating system (2) is commercial curtain formula hollow fiber film assembly or the plate film assembly used, the material of this membrane module is PVDF, and the aperture is 0.1-0.2 μ m.
4. according to the described trade effluent microwave electrodeless ultraviolet light catalysis of claim 3-two membrane sepn coupling treatment unit, it is characterized in that: described film separating system (2) has two covers, and they are arranged symmetrically in the periphery of microwave electrodeless ultraviolet light origin system (4); Two cover film separating system alternations, in the time of a cover film separating system work water outlet therein, an other cover film separating system then carries out aeration and cleans.
5. according to the described trade effluent microwave electrodeless ultraviolet light catalysis of claim 1-two membrane sepn coupling treatment unit, it is characterized in that: described corrugated separator plate (3), the angle of itself and horizontal direction is 60 °.
6. according to the described trade effluent microwave electrodeless ultraviolet light catalysis of claim 1-two membrane sepn coupling treatment unit, it is characterized in that described microwave electrodeless ultraviolet light origin system (4) is made up of microwave device and electrodeless ultraviolet light source, they are realized connecting and sealing by connecting screw, cylinder lever connecting rod and sealing-ring, wherein: microwave device is positioned at the top in electrodeless ultraviolet light source, this microwave device mainly is made up of waveguide head (16), magnetron (18), by water-cool control, be installed into the mouth of a river (17) and water outlet (19) respectively at the upper and lower of magnetron (18).
7. according to the described trade effluent microwave electrodeless ultraviolet light catalysis of claim 6-two membrane sepn coupling treatment unit, it is characterized in that: described electrodeless ultraviolet light source (4) is provided with a twinkler (21) that is arranged in quartz socket tube (14), this twinkler links to each other with base (22) by twinkler support (20), establishes air inlet port (15) and production well (13) respectively at the upper and lower of quartz socket tube (14).
8. according to the described trade effluent microwave electrodeless ultraviolet light catalysis of claim 1-two membrane sepn coupling treatment unit, it is characterized in that: described water inlet system is made up of the inlet chest (9) and the intake pump (10) that link to each other with pipeline, and intake pump is by inlet channel and reactor (1) internal communication; Described outlet system by link to each other with pipeline go out water pump (11) and water tank (12) is formed, go out water pump and be communicated with film separating system (2) by outlet conduit.
9. the purposes of the described trade effluent microwave electrodeless ultraviolet light catalysis of arbitrary claim in the claim 1 to 8-two membrane sepn coupling treatment unit, it is characterized in that: this device is used for Industrial Wastewater Treatment.
10. purposes according to claim 9 is characterized in that: described trade effluent is a textile printing and dyeing wastewater.
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