CN107721034A - A kind of wastewater treatment equipment of low temperature plasma combined catalyst and adsorbent - Google Patents
A kind of wastewater treatment equipment of low temperature plasma combined catalyst and adsorbent Download PDFInfo
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- CN107721034A CN107721034A CN201710982314.XA CN201710982314A CN107721034A CN 107721034 A CN107721034 A CN 107721034A CN 201710982314 A CN201710982314 A CN 201710982314A CN 107721034 A CN107721034 A CN 107721034A
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- 239000003054 catalyst Substances 0.000 title claims abstract description 43
- 239000003463 adsorbent Substances 0.000 title claims abstract description 37
- 238000004065 wastewater treatment Methods 0.000 title claims abstract description 16
- 239000002351 wastewater Substances 0.000 claims abstract description 39
- 238000011069 regeneration method Methods 0.000 claims abstract description 12
- 230000008929 regeneration Effects 0.000 claims abstract description 11
- 238000011065 in-situ storage Methods 0.000 claims abstract description 5
- 238000011049 filling Methods 0.000 claims abstract description 3
- 229910052751 metal Inorganic materials 0.000 claims description 28
- 239000002184 metal Substances 0.000 claims description 28
- 238000006731 degradation reaction Methods 0.000 claims description 23
- 238000000034 method Methods 0.000 claims description 23
- 230000015556 catabolic process Effects 0.000 claims description 22
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 20
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 claims description 11
- PNEYBMLMFCGWSK-UHFFFAOYSA-N Alumina Chemical compound [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 10
- 238000007599 discharging Methods 0.000 claims description 9
- 239000000203 mixture Substances 0.000 claims description 9
- 239000007921 spray Substances 0.000 claims description 8
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- 239000010865 sewage Substances 0.000 claims description 7
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 6
- 239000000919 ceramic Substances 0.000 claims description 6
- -1 polytetrafluoroethylene Polymers 0.000 claims description 6
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- 238000000926 separation method Methods 0.000 claims description 4
- 239000002594 sorbent Substances 0.000 claims description 4
- 229910001845 yogo sapphire Inorganic materials 0.000 claims description 4
- 229910021536 Zeolite Inorganic materials 0.000 claims description 3
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 claims description 3
- 238000003825 pressing Methods 0.000 claims description 3
- 239000011347 resin Substances 0.000 claims description 3
- 229920005989 resin Polymers 0.000 claims description 3
- 239000010457 zeolite Substances 0.000 claims description 3
- 229910000278 bentonite Inorganic materials 0.000 claims description 2
- 239000000440 bentonite Substances 0.000 claims description 2
- SVPXDRXYRYOSEX-UHFFFAOYSA-N bentoquatam Chemical compound O.O=[Si]=O.O=[Al]O[Al]=O SVPXDRXYRYOSEX-UHFFFAOYSA-N 0.000 claims description 2
- 239000011810 insulating material Substances 0.000 claims description 2
- 230000035515 penetration Effects 0.000 claims description 2
- 238000007750 plasma spraying Methods 0.000 claims description 2
- 238000005507 spraying Methods 0.000 claims description 2
- 238000012545 processing Methods 0.000 abstract description 9
- 238000001179 sorption measurement Methods 0.000 abstract description 6
- 238000006555 catalytic reaction Methods 0.000 abstract description 5
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- 241000894007 species Species 0.000 abstract description 2
- 230000004888 barrier function Effects 0.000 abstract 1
- 238000005265 energy consumption Methods 0.000 abstract 1
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- 239000007789 gas Substances 0.000 description 8
- 230000003647 oxidation Effects 0.000 description 8
- 238000007254 oxidation reaction Methods 0.000 description 8
- KHLVKKOJDHCJMG-QDBORUFSSA-L indigo carmine Chemical compound [Na+].[Na+].N/1C2=CC=C(S([O-])(=O)=O)C=C2C(=O)C\1=C1/NC2=CC=C(S(=O)(=O)[O-])C=C2C1=O KHLVKKOJDHCJMG-QDBORUFSSA-L 0.000 description 6
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- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 2
- 239000011149 active material Substances 0.000 description 2
- 239000000356 contaminant Substances 0.000 description 2
- 229910052802 copper Inorganic materials 0.000 description 2
- 239000010949 copper Substances 0.000 description 2
- 238000001914 filtration Methods 0.000 description 2
- 239000010842 industrial wastewater Substances 0.000 description 2
- 239000012528 membrane Substances 0.000 description 2
- 229910044991 metal oxide Inorganic materials 0.000 description 2
- 150000004706 metal oxides Chemical class 0.000 description 2
- 150000003254 radicals Chemical class 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 229910001069 Ti alloy Inorganic materials 0.000 description 1
- 239000002250 absorbent Substances 0.000 description 1
- 230000002745 absorbent Effects 0.000 description 1
- 239000004411 aluminium Substances 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 230000003373 anti-fouling effect Effects 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
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- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical class C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 1
- 244000005700 microbiome Species 0.000 description 1
- 239000003987 organophosphate pesticide Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 description 1
- 230000002093 peripheral effect Effects 0.000 description 1
- 238000006303 photolysis reaction Methods 0.000 description 1
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- 230000015843 photosynthesis, light reaction Effects 0.000 description 1
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- 231100000614 poison Toxicity 0.000 description 1
- 230000007096 poisonous effect Effects 0.000 description 1
- 125000005575 polycyclic aromatic hydrocarbon group Chemical group 0.000 description 1
- 229910052573 porcelain Inorganic materials 0.000 description 1
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- 238000000197 pyrolysis Methods 0.000 description 1
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- 238000007142 ring opening reaction Methods 0.000 description 1
- 150000003384 small molecules Chemical class 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
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- 229910001220 stainless steel Inorganic materials 0.000 description 1
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- 229920002994 synthetic fiber Polymers 0.000 description 1
- 239000012209 synthetic fiber Substances 0.000 description 1
- 239000013076 target substance Substances 0.000 description 1
- BFKJFAAPBSQJPD-UHFFFAOYSA-N tetrafluoroethene Chemical compound FC(F)=C(F)F BFKJFAAPBSQJPD-UHFFFAOYSA-N 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
- 238000010287 warm spraying Methods 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
- 238000003911 water pollution Methods 0.000 description 1
- 229910001928 zirconium oxide Inorganic materials 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
- C02F9/00—Multistage treatment of water, waste water or sewage
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/28—Treatment of water, waste water, or sewage by sorption
- C02F1/281—Treatment of water, waste water, or sewage by sorption using inorganic sorbents
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/30—Treatment of water, waste water, or sewage by irradiation
- C02F1/32—Treatment of water, waste water, or sewage by irradiation with ultraviolet light
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/46—Treatment of water, waste water, or sewage by electrochemical methods
- C02F1/4608—Treatment of water, waste water, or sewage by electrochemical methods using electrical discharges
-
- 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
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/72—Treatment of water, waste water, or sewage by oxidation
- C02F1/78—Treatment of water, waste water, or sewage by oxidation with ozone
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/30—Organic compounds
-
- 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
- C02F2201/007—Modular design
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2301/00—General aspects of water treatment
- C02F2301/08—Multistage treatments, e.g. repetition of the same process step under different conditions
Landscapes
- Life Sciences & Earth Sciences (AREA)
- Hydrology & Water Resources (AREA)
- Engineering & Computer Science (AREA)
- Environmental & Geological Engineering (AREA)
- Water Supply & Treatment (AREA)
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Water Treatment By Electricity Or Magnetism (AREA)
- Treatment Of Water By Oxidation Or Reduction (AREA)
Abstract
The invention discloses a kind of low temperature plasma combined catalyst and the wastewater treatment equipment of adsorbent.The device can be run under three kinds of mode of operations, acted synergistically using plasma adsoption catalysis and handle waste water, suitable mode of operation is selected for the waste water of different quality parameter, solves the problems such as dielectric barrier discharge device processing energy consumption is big, operating cost is high, catalyst filling difficulty is big.The high-field electrode of the device and ground electrode surface attachment catalyst coat, with array way cross arrangement；Adsorber module is positioned between adjacent two row electrode, form being intervally arranged for plasma discharge region adsorption zone, both active specy caused by plasma discharge can be made fully to be contacted with the organic pollution on adsorbent, saturation adsorber module is set to reach the purpose of in-situ regeneration, also catalyst coat can be utilized to improve the uniform and stable property of plasma discharge, the common efficiency for improving persistent organic pollutants of three's synergy, reach the purpose of thorough mineralising.
Description
Technical field
The invention belongs to wastewater degradation field, and in particular to a kind of low temperature plasma combined catalyst and adsorbent give up
Water treatment facilities.
Background technology
In recent years, developing rapidly with industries such as petrochemical industry, papermaking, synthetic fibers, coking, printing and dyeing, it is various containing
The waste water of the organic pollution of a large amount of difficult for biological degradation accordingly increases, and a large amount of industrial wastewaters not standard discharge, causes China to occur
The dual environmental problem of shortage of water resources and water pollution seriously.
The processing of organic wastewater with difficult degradation thereby is the difficult point and emphasis of water treatment field.Hardly degraded organic substance refers to by microorganism
Speed is very slow during decomposition, decomposes halfway organic matter (metabolite for also including some organic matters), this pollutant easily exists
It is enriched with organism, also easily becomes the potential pollution source of water body.The common feature of organic wastewater with difficult degradation thereby is that toxicity is big, composition
Complicated, concentration height, biodegradability are poor, including surfactant, heterocycle compound, polycyclic aromatic hydrocarbon, halogenated hydrocarbons, organic cyaniding
The poisonous and harmful substances such as thing, organophosphorus pesticide and organic dyestuff.
Organic wastewater with difficult degradation thereby is using traditional materialization, biochemical processing process technology, it is extremely difficult to which it is thoroughly degraded.Mesh
The processing method of such preceding waste water mainly has following three kinds, i.e.,：First, absorption method；2nd, filtration method；3rd, catalytic ozonation method.
Wherein, for absorption method, because adsorbent has limited adsorption capacity, short life, selective absorption, cost height and regenerates
The shortcomings of difficult, it greatly limit the use of this method；For filtration method, because filter membrane antifouling property is poor, machinery is strong
Spend low and easily block, regenerated after blocking difficult, it has to filter membrane is frequently changed, so that operating cost is high, in commercial Application
In and be extremely limited；And for catalytic ozonation method, the factor of 3 aspects have impact on efficiency and effect below
Fruit：1) at ambient pressure, the solubility in waste water is limited for ozone, i.e., the ozone concentration dissolved in unit volume waste water is relatively low, from
And limit the speed and effect of the useless Organic substance in water of ozone oxidation；2）The aeration aperture of ozonation aerated head can not accomplish enough
It is small, cause aeration bubbles diameter excessive, it is impossible to fully to be contacted with the organic matter in sewage, and then influence its reaction with organic matter
(at present, the aperture most I of the titanium alloy aeration head of resistance to ozone oxidation is accomplished：450nm)；3）Produce the power consumption of ozone still at present
So higher, per kilogram ozone about consumes 20-35 degree, it is necessary to continue to improve production, reduces power consumption.These factors cause ozone catalytic oxygen
Change method is difficult to reach requirement to the degradation efficiency and effect of organic industrial sewage, and only can not with the catalysis oxidation ability of ozone
Difficult degradation composition in degradation of organic waste water.
Due to three of the above method existing various shortcoming in itself, their popularization and application are restricted and limit significantly, because
How inexpensive this is, efficiently processing refractory organic industrial sewage had turned into sewage treatment industry problem urgently to be resolved hurrily already.
Lower temperature plasma technology is a kind of new wastewater treatment technology of advanced oxidation, and it has free-radical oxidation, high energy concurrently
A variety of effects such as electron radiation, ozone oxidation, ultraviolet photolysis and pyrolysis can effectively remove the various pollutions in waste water in one
Thing, especially persistent organic pollutants, have the advantages that process range is wide, treatment effeciency is high and non-secondary pollution.Catalyst
（Such as TiO2、ZrO2、WO3、CeO2And Al2O3Deng）Substantial amounts of electron hole and hydroxyl radical free radical can be produced under light illumination, and there is pole
Strong oxidation, and a large amount of ultraviolets and active material are produced in plasma discharge processes, there is stronger redox
Ability, substantial amounts of living radical can also be produced under aerobic environment, therefore greatly enhance the treatment effeciency of plasma.This
Outside, adsorber module（Such as porous ceramics microballoon, zeolite, NACF, diatomite）With extraordinary adsorption capacity, energy
Enough Adsorption Concentration target contaminants.Then in OH, O isoreactivity free radical, O3, the synergy such as UV and enrichment method
Under, the degraded to target substance is reached by demethylation, deamination and ring opening, so not only macromolecular has
Machine thing becomes H2O and CO2Deng small-molecule substance, and adsorber module also reaches regeneration treatment, improves the absorption of adsorber module
Life-span and regenerability, so as to reach the purpose of thorough degradable organic pollutant.Therefore, lower temperature plasma technology degraded industry
Organic wastewater has important practical value and wide application prospect.
The content of the invention
It is an object of the invention to propose a kind of wastewater treatment equipment of low temperature plasma combined catalyst and adsorbent,
The device can be run under three kinds of mode of operations, for the organic wastewater with difficult degradation thereby of various concentrations, by selecting suitable work
Pattern, to solve the problems, such as that the operating cost for handling refractory organic industrial sewage is high, treatment effeciency is low.
The wastewater treatment equipment of a kind of low temperature plasma combined catalyst and adsorbent proposed by the present invention, by high-tension electricity
Source, high-field electrode, ground electrode, catalyst coat, shower nozzle, cistern, delivery port, air inlet, gas outlet and housing composition；
Described high-field electrode and ground electrode is made up of insulated dielectric tube and the metal electrode being inserted in insulated dielectric tube；Described
Insulated dielectric tube one end open one end is closed, and described metal electrode extends out from the openend of insulated dielectric tube；Described
Metal electrode and the inwall of insulated dielectric tube are brought into close contact；
Array of orifices is provided with two relative side walls of described housing, the diameter of aperture is corresponding with dielectric pipe diameter,
The horizontal spacing of aperture is 1-5mm；
Described high-field electrode and ground electrode respectively have some, and removably both ends are fixed on the aperture of described side wall, laterally
Compartment of terrain is arranged in parallel, forms some high-field electrode row and some ground electrodes row；The metal electrode extension of described high-field electrode
All extend housing from a side wall of housing and connect high voltage power supply in end；The metal electrode elongated end of described ground electrode is complete
Extend housing from another relative side wall of housing and be grounded in portion；Described high-field electrode row and the lateral separation of ground electrode row
It is all consistent, and horizontal spacing is adjustable, is 1-10 times of described aperture horizontal spacing；
Described cistern is in the lower section of high-field electrode and ground electrode；Described shower nozzle is fixed on the roof of described housing,
It is corresponding that spray angle and high-field electrode and ground electrode surround cross-sectional area, makes waste water uniformly by high-field electrode and ground electrode
Between discharging gap；Described delivery port is arranged on the bottom of housing；Described air inlet and gas outlet, one is arranged on shell
On the roof of body, another is arranged on below high-field electrode and ground electrode, and in the side wall above cistern, gas circuit direction is by leading to
The specific nature of gas determines；
Described catalyst coat is attached to the outer surface of insulated dielectric tube；
In the present invention, described device also includes adsorber module, and described adsorber module has water penetration, removably solid
It is scheduled in the discharging gap between high-field electrode row and ground electrode row；Or it is placed in described cistern.
In the present invention, described adsorber module is direct pressing adsorbent in blocks, or is filled with powdered, particle
Netted box made of the insulating materials of shape, strip or block adsorbent；The adsorbent of filling is resin, zeolite, active carbon fibre
It is several in dimension, diatomite or bentonite.
In the present invention, the insulated dielectric tube is in quartz glass, polytetrafluoroethylene (PTFE), aluminium oxide ceramics or zirconia ceramics
It is any to be made.
In the present invention, described catalyst coat is TiO2、ZrO2、WO3、CeO2Or Al2O3It can reach+3 Deng metal state
It is several in high-valence state metal oxide more than valency；Described catalyst coat is with refrigerator spraying process, electrostatic spray, warm
Spraying process or plasma spraying process are attached to the outer surface of described insulated dielectric tube.
In the present invention, the dielectric thickness of the blind end of described insulated dielectric tube is more than the thickness of described side wall.
In the present invention, described high voltage power supply is unipolar pulse power supply, Bipolar pulse power or AC power, voltage
Peak value is 4-100kV.
In the present invention, described wastewater treatment equipment has three kinds of mode of operations, is respectively：
（1）Low temperature plasma combined catalyst pattern；
（2）The adsorbent pattern of low temperature plasma combined catalyst and in-situ regeneration；
（3）Low temperature plasma combined catalyst and the adsorbent pattern of dystopy regeneration；
For the organic wastewater with difficult degradation thereby and sorbent characteristics of various concentrations, by selecting suitable mode of operation, to solve to locate
Manage refractory organic industrial sewage.
The beneficial effects of the present invention are：
（1）Device is simple, and adsorber module is detachable；
（2）Operation is flexible, both adsorber module can be positioned over into discharge space, strengthens plasma discharge field effect；
Tail end can be placed in and carry out advanced treating absorption；
（3）In degradation process, chemical agent is not added, does not produce secondary pollution, be suitable for further industrial applications.
Brief description of the drawings
Fig. 1 is the electrode structural chart of the present invention.
Fig. 2 is the front view of device A in the present invention.
Fig. 3 is the top view of device B in the present invention.
Fig. 4 is the front view of device C in the present invention.
Label in figure：1 is shower nozzle, and 2 be housing, and 3 be insulated dielectric tube, and 4 be metal electrode, and 5 be cistern, and 6 be water outlet
Mouthful, 7 be adsorber module, and 8 be grounding plate, and 9 be high-pressure metal plate, and 10 be high voltage power supply, and 11 be catalyst coat, and 12 are
Air inlet, 13 be gas outlet.
Embodiment
The present invention is further illustrated below by embodiment combination accompanying drawing.These embodiments be merely to illustrate the present invention without
For limiting the scope of the present invention.
Embodiment 1：Fig. 1 is the electrode structural chart of the present invention, insulated dielectric tube 3 internal diameter 3mm, external diameter 5mm, one end open one
End seal is closed, and the thickness 15mm of blind end, more than the thickness of side wall；The tight of insulated dielectric tube 3 is peripheral in metal electrode 4,
The diameter 3mm of metal electrode 4, makes air-gap-free between the two；Extend from the openend of insulated dielectric tube 3 one end of metal electrode 4
Come；Described catalyst coat 11 is attached to the outer surface of insulated dielectric tube 3.
Fig. 2 is device A front view, is provided with array of orifices in two relative side walls of the housing 2 of device, aperture it is straight
Footpath is corresponding with the diameter of insulated dielectric tube 3；Removably both ends are fixed on the aperture of described side wall for high-field electrode and ground electrode,
Lateral separation it is arranged in parallel, form some high-field electrodes row and some ground electrodes row；One end of high-field electrode is all from housing 2
Left side wall extend housing and high voltage power supply 10 connected by high-pressure metal plate 9, the other end is fixed on the small of the right side wall of housing 2
Kong Zhong, because the blind end of insulated dielectric tube 3 has certain thickness, the end of metal electrode 4 does not stretch into housing sidewall, avoids electrode
The electric field distortion of end causes to climb electric sparking；All extend housing and by connecing from the right side wall of housing 2 in one end of ground electrode
Ground metallic plate 8 is grounded, and the other end is fixed in the aperture of the left side wall of housing 2, because the blind end of insulated dielectric tube 3 has certain thickness
Degree, the end of metal electrode 4 does not stretch into the side wall of housing 2；Described high-field electrode row and the lateral separation whole one of ground electrode row
Cause, and horizontal spacing is adjustable, is 1-10 times of described aperture horizontal spacing；Described cistern 5 is in high-field electrode and ground electricity
The lower section of pole；Described shower nozzle 1 is fixed on the roof of described housing 2, and spray angle surrounds with high-field electrode and ground electrode
Cross-sectional area is corresponding, makes waste water uniformly by the discharging gap between high-field electrode and ground electrode；Described delivery port 6 is set
Put in the bottom of housing 2；Described air inlet 12 is arranged on below high-field electrode and ground electrode, in the side wall above cistern；
Gas outlet 13 is arranged on the roof of housing, the space that gas circuit direction is surrounded by high-field electrode and ground electrode from the bottom to top.
The mode of operation of the present invention has three kinds：
（1）Low temperature plasma combined catalyst pattern
For low concentration organic wastewater with difficult degradation thereby（BOD/COD<0.2, though and CODcr concentration be less than 150mg/L, but still reach
Less than a kind of waste water about industrial wastewater discharge standard）, on the one hand organic concentration is too low in such waste water does not have back substantially
Receive value；On the other hand such waste water, which had not both reached the wastewater discharge standard of corresponding industry, can not meet the corresponding of waste water recycling
Standard, so must not be without advanced treating.For such waste water, applied under normal circumstances only with plasma combined catalyst
Layer can reach emission request, it is not necessary to introduce adsorber module.Specific embodiment device A as shown in Figure 2, in plasma
The media inside surface of body sparking electrode plates catalyst coat, and low concentration of being degraded under the synergy of plasma-catalysis is difficult
Degradation of organic waste water, it is cheap to run simple, easy to maintenance and cost.
For high concentration hard-degraded organic waste water（CODcr concentration is more than 150mg/L, and BOD values are also smaller）, only with wait from
The synergy of daughter-catalysis can not thoroughly in degrading waste water difficult degradation composition, be unable to reach discharge standard, now need
Adsorber module, the device C shown in device B and Fig. 4 as shown in Figure 3 are added in a device.
（2）The adsorbent pattern of low temperature plasma combined catalyst and in-situ regeneration
Because the composition of different organic wastewaters is different, suitable adsorbent species are also different, and different adsorbents has difference
Physical property and electrical characteristics.Shown according to research, some sorbent structures are stable, in the plasma will not be by serious
Destroy, and dielectric constant is higher, and new electric discharge can be produced in surface and micropore, can generate more active materials, therefore can
Adsorbent is placed in region of discharge, that is, device B mode of operation.In this operating mode, can select adsorbing
During regenerate simultaneously, the structure of such plasma-absorption-catalysis-regeneration one, there is high organic wastewater degraded
Efficiency and energy efficiency；
Or first with adsorber module effectively adsorb and be enriched with, after to be adsorbed dose reaches adsorption saturation, it is placed on
The adsorber module that pollutant is enriched with plasma discharge space carries out in-situ regeneration processing.Compared to direct using plasma
Degraded, this mode degraded afterwards that first concentrates can effectively reduce caused energy dissipation.
（3）Low temperature plasma combined catalyst and the adsorbent pattern of dystopy regeneration
Some adsorbent compressive resistances are low, structural instability, in the plasma easily destroyed inactivation.Therefore it can be only put at electric discharge
The waste water residue after plasma degradation is adsorbed after region, that is, device C mode of operation.Organic wastewater
After synergy by plasma-catalysis, for most of pollutant by plasma degradation, being harmful on a small quantity for not being degraded is residual
Excess composition is adsorbed with the adsorbent being placed in cistern again, reaches discharge standard.Adsorbent after adsorption saturation
Because self-characteristic can not carry out desorption and regeneration with gas discharge plasma, dystopy is carried out by way of the thermal desorptions such as burning
Regeneration.
Embodiment 2：
The present embodiment uses device A as shown in Figure 2, and metal electrode 4 uses thin copper bar, and insulated dielectric tube 3 uses quartz glass；
Wherein high-field electrode and ground electrode share 4 row × 4 row totally 16, aperture horizontal spacing 1mm, and high-field electrode is arranged with ground electrode interval
Row, interelectrode horizontal spacing is 1mm, and all high-field electrodes are connected with high-pressure metal plate 9 by binding post, high-pressure metal plate 9
It is connected with the high-pressure side of high voltage power supply 10；High voltage power supply 10 uses unipolar high voltage clock, and the frequency of output voltage is 1kHz,
Peak value is 4kV；All ground electrodes are connected and are grounded by binding post with grounding plate 8；Method is electrostatically sprayed in dielectric
3 surface attachment of pipe, one layer of TiO2Catalyst coat 11.
Specific experiment process is as follows：
（1）50mg/L indigo carmine solution is configured, as pending low concentration wastewater sample；
（2）Water pump is opened, and opens high voltage power supply 10；Pending low concentration wastewater sample equably leads to after the atomization of shower nozzle 1
The discharging gap crossed between high-field electrode and ground electrode；
（3）Water sample after discharge of plasma in low temperature is handled is fallen into cistern 5, determines to be arranged depending on specific disposition
Put or be passed through processing unit circular treatment again.
Embodiment 3：
The present embodiment uses device B as shown in Figure 3, and metal electrode 4 uses the thin rod of stainless steel, and insulated dielectric tube 3 is using oxidation
Aluminium ceramics；Wherein high-field electrode and ground electrode share 8 row × 8 row totally 64, aperture horizontal spacing 5mm, high-field electrode and ground electricity
Pole is spaced, and high-field electrode and ground electrode horizontal spacing are 50mm；Granular resin sorbent particle is processed into mounted in poly-
In netted box made of tetrafluoroethene, it is placed in the discharging gap between high-field electrode row and ground electrode row；All high-tension electricities
Pole is connected with high-pressure metal plate 9 by binding post, and high-pressure metal plate 9 is connected with the high-pressure side of high voltage power supply 10；High voltage power supply 10
Using bipolarity high-voltage pulsed source, the frequency of output voltage is 5kHz, peak value 100kV；All ground electrodes and grounding plate 8
It is connected by binding post and is grounded；With ionomer spray method in 3 surface attachment of insulated dielectric tube, one layer of CeO2And Al2O3Mixture
Catalyst coat 11.
Specific experiment process is as follows：
（1）500mg/L indigo carmine solution is configured, as pending high-concentration waste water sample；
（2）Water pump is opened, and opens high voltage power supply 10；Pending high-concentration waste water sample equably leads to after the atomization of shower nozzle 1
The adsorber module 7 crossed in the discharging gap between high-field electrode and ground electrode；Indigo carmine in water sample is adsorbed agent mould
While block 7 adsorbs, it is dropped between absorbent particles of the low temperature plasma in module and in internal microcellular structure
Solution desorption；
（3）Water sample after discharge of plasma in low temperature is handled is fallen into cistern 5, determines to be arranged depending on specific disposition
Put or be passed through processing unit circular treatment again.
Embodiment 4：
The present embodiment uses device C as shown in Figure 4, and metal electrode 4 uses thin copper bar, and insulated dielectric tube 3 is made pottery using zirconium oxide
Porcelain；Wherein high-field electrode and ground electrode share 4 row × 4 row totally 16, aperture horizontal spacing 4mm, between high-field electrode and ground electrode
Every arrangement, interelectrode horizontal spacing is 4mm；Direct pressing activated carbon fiber adsorbing substance module 7 in blocks, is placed in cistern
In；All high-field electrodes are connected with high-pressure metal plate 9 by binding post, high-pressure metal plate 9 and the high-pressure side phase of high voltage power supply 10
Even；High voltage power supply 10 uses unipolar high voltage clock, and the frequency of output voltage is 500Hz, peak value 35kV；All ground electrodes
It is connected and is grounded by binding post with grounding plate 8；With hot spray process in 3 surface attachment of insulated dielectric tube, one layer of ZrO2And WO3
Mixture catalyzer coating 11.
Specific experiment process is as follows：
（1）250mg/L indigo carmine solution is configured, as pending high-concentration waste water sample；
（2）Water pump is opened, and opens high voltage power supply 10；Pending high-concentration waste water sample equably leads to after the atomization of shower nozzle 1
The discharging gap crossed between high-field electrode and ground electrode；
（3）Water sample after discharge of plasma in low temperature is handled is fallen into cistern 5, by the adsorbent mould being placed in cistern
Block 7 is adsorbed again to the residue in water sample after processing, is then discharged through delivery port 6.
In the above embodiments 2, embodiment 3 and embodiment 4, the indigo carmine that have chosen three kinds of various concentrations is molten
Liquid, concentration are respectively 50 mg/L, 250 mg/L and 500 mg/L, and with the A devices of unattached catalyst figure coating as a comparison
Case, other water quality parameters are consistent, as target waste water water sample.Under 25 DEG C of room temperature environments, processing time is
10min, final degradation efficiency and energy efficiency are shown in Table 1.
Degradation rate and energy efficiency contrast table of the indigo carmine solution of table 1 after the degraded of differential responses device
As a result show：In the outer surface of sparking electrode, attachment high-valence state metal oxide catalyst coating can effectively improve low temperature
Degradation rate of the plasma to waste water.Wherein, the device B acted on using low temperature plasma-catalysis-absorbing synergic degradation rate
With energy efficiency highest；And do not use the device A of adsorbent degradation rate and energy efficiency minimum；Waste strength is higher, wait from
Sub- degradation rate reduces, but energy efficiency improves explanation, is recycled after using adsorbent, the target contaminant in waste water is concentrated low
The mode of isothermal plasma degraded, can effectively improve its energy utilization efficiency.
Claims (8)
- A kind of 1. wastewater treatment equipment of low temperature plasma combined catalyst and adsorbent, it is characterised in that by high voltage power supply, High-field electrode, ground electrode, catalyst coat, shower nozzle, cistern, delivery port, air inlet, gas outlet and housing composition；Described high-field electrode and ground electrode is made up of insulated dielectric tube and the metal electrode being inserted in insulated dielectric tube；Described Insulated dielectric tube one end open one end is closed, and described metal electrode extends out from the openend of insulated dielectric tube；Described Metal electrode and the inwall of insulated dielectric tube are brought into close contact；Array of orifices is provided with two relative side walls of described housing, the diameter of aperture is corresponding with dielectric pipe diameter, The horizontal spacing of aperture is 1-5mm；Described high-field electrode and ground electrode respectively have some, and removably both ends are fixed on the aperture of described side wall, laterally Compartment of terrain is arranged in parallel, forms some high-field electrode row and some ground electrodes row；The metal electrode extension of described high-field electrode All extend housing from a side wall of housing and connect high voltage power supply in end；The metal electrode elongated end of described ground electrode is complete Extend housing from another relative side wall of housing and be grounded in portion；Described high-field electrode row and the lateral separation of ground electrode row It is all consistent, and horizontal spacing is adjustable, is 1-10 times of described aperture horizontal spacing；Described cistern is located at the lower section of high-field electrode and ground electrode；Described shower nozzle is fixed on the roof of described housing On, it is corresponding that spray angle and high-field electrode and ground electrode surround cross-sectional area, makes waste water uniformly by high-field electrode and ground Discharging gap between electrode；Described delivery port is arranged on the bottom of housing；Described air inlet and gas outlet, a setting On the roof of housing, another is then arranged on below high-field electrode and ground electrode, in the side wall above cistern, gas circuit direction Determined by the specific nature of ventilated body；Described catalyst coat is attached to the outer surface of insulated dielectric tube.
- 2. the wastewater treatment equipment of a kind of low temperature plasma combined catalyst according to claim 1 and adsorbent, its It is characterised by that described device also includes adsorber module, described adsorber module has water penetration, is removably attached to High-field electrode is arranged in the discharging gap between ground electrode row；Or it is placed in described cistern.
- 3. the wastewater treatment equipment of a kind of low temperature plasma combined catalyst according to claim 2 and adsorbent, its Be characterised by that described adsorber module is direct pressing adsorbent in blocks, or be filled with powdered, graininess, strip or Netted box made of the insulating materials of block adsorbent；The adsorbent of filling is resin, zeolite, NACF, diatomite It is or several in bentonite.
- 4. the wastewater treatment equipment of a kind of low temperature plasma combined catalyst according to claim 1 and adsorbent, its It is any system in quartz glass, polytetrafluoroethylene (PTFE), aluminium oxide ceramics or zirconia ceramics to be characterised by the insulated dielectric tube Into.
- 5. the wastewater treatment equipment of a kind of low temperature plasma combined catalyst according to claim 1 and adsorbent, its It is characterised by that described catalyst coat is TiO2、ZrO2、WO3、CeO2Or Al2O3In it is several；Described catalyst coat The appearance of described insulated dielectric tube is attached to refrigerator spraying process, electrostatic spray, hot spray process or plasma spraying process Face.
- 6. the wastewater treatment equipment of a kind of low temperature plasma combined catalyst according to claim 1 and adsorbent, its It is characterised by that the dielectric thickness of the blind end of described insulated dielectric tube is more than the thickness of described side wall.
- 7. the wastewater treatment equipment of a kind of low temperature plasma combined catalyst according to claim 1 and adsorbent, its It is any, voltage in unipolar pulse power supply, Bipolar pulse power or AC power to be characterised by described high voltage power supply Peak value is 4-100kV.
- 8. the wastewater treatment equipment of a kind of low temperature plasma combined catalyst according to claim 2 and adsorbent, its It is characterised by that the wastewater treatment equipment has three kinds of mode of operations, is respectively：（1）Low temperature plasma combined catalyst pattern；（2）The adsorbent pattern of low temperature plasma combined catalyst and in-situ regeneration；（3）Low temperature plasma combined catalyst and the adsorbent pattern of dystopy regeneration；For the organic wastewater with difficult degradation thereby and sorbent characteristics of various concentrations, by selecting suitable mode of operation, to solve to locate Manage refractory organic industrial sewage.
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| CN110302647A (en) * | 2018-03-27 | 2019-10-08 | 深圳市创海森科技有限公司 | A kind of regenerative gas absorption decomposer |
| CN110410917A (en) * | 2019-05-23 | 2019-11-05 | 西安航科等离子体科技有限公司 | A kind of plasma fresh air system |
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