CN100509642C - Method for degrading organic contaminant in water through gas and liquid cascaded discharge - Google Patents
Method for degrading organic contaminant in water through gas and liquid cascaded discharge Download PDFInfo
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- CN100509642C CN100509642C CNB2006100689946A CN200610068994A CN100509642C CN 100509642 C CN100509642 C CN 100509642C CN B2006100689946 A CNB2006100689946 A CN B2006100689946A CN 200610068994 A CN200610068994 A CN 200610068994A CN 100509642 C CN100509642 C CN 100509642C
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Abstract
This invention relates to method and apparatus for degrading organic pollutants in water by using high-activity chemical particles produced by high-voltage pulse discharge. The method comprises: introducing pressurized air or oxygen into the gas chamber through glass pipes, introducing the discharge zone through stainless steel network electrode to uniformly distribute air or oxygen in the discharge zone, applying high-voltage pulse onto high-voltage electrode and ground electrode by high-voltage pulse supply to produce low-temperature plasma by the liquid phase and ozone by the gas phase, and degrading organic pollutants in wastewater. The stainless steel obstruction net in the pre-treated water solution can increase the utility of ozone. During the degradation of organic pollutants in water by gas-liquid series discharge, activated carbon fibers and H2O2 are added into the solution. The adsorbed catalysis of activated carbon, photochemical oxidation of UV/H2O2/O3, and high-voltage pulse discharge together can largely increase the degradation rate of organic pollutants.
Description
Technical field
The invention belongs to the application of lower temperature plasma technology, relate to the method and the device that utilize organic pollutant in the high pressure pulse discharge degradation water in environmental pollution control field.
Background technology
Liquid phase high pressure pulse discharge by applying steep-front, spike pulse high pressure between nonequilibrium earth polar and high voltage electrode, makes the extra light electronics of quality moment obtain energy and quickens, ion since its quality be difficult to greatly obtain acceleration in moment.Electronics obtains to become the high energy unbound electron behind the energy, with other molecular impact, makes molecular dissociation in moving process, causes series of chemical, produces H
2O
2, OH, O, HO
2The isoreactivity material.These active substances contact with organic pollutant, and making organic pollutant degradation is carbonic acid gas, water and nontoxic byproduct.In discharge process, because the ionization of molecule, transition etc. also can produce some physical influences, as UV-light, ultrasonic, shockwave, localized hyperthermia etc., these physical processes also can be impelled the degraded of organic pollutant.
The gas phase high pressure pulse discharge, high voltage electrode is suspended in gas phase usually, and the earth polar is placed on the container bottom or is immersed in liquid phase, and in the dry atmosphere of oxygen enrichment, oxygen and the reaction of high energy unbound electron directly produce ozone; Continual being dissolved in the water of ozone that produces with the organic pollutant direct reaction in the water, generates carbonic acid gas, water and nontoxic byproduct.
Ozone for the gentle phase discharge generation of the chemically-active particle that utilizes discharge in water to produce, the reaction unit in early stage is used in combination the two, promptly the ozone that ozonizer is produced feeds in the discharge in water reactor, and whole device not only is not optimized, and the waste electric energy.The device in later stage moves to gas phase on the liquid level to the ground electrode in the discharge in water reactor from liquid phase, so that utilize the ozone of gas phase discharge generation, but only utilized the part ozone that is dissolved in the water, most of gaseous ozone enters atmosphere as waste gas, has polluted atmospheric environment.
Summary of the invention
The invention provides the method and apparatus of organic pollutant in a kind of high-efficiency environment friendly and the gas-liquid discharged in series degradation water.
Its technical scheme comprises:
The method of organic pollutant is in the gas-liquid discharged in series degradation water: pressurized air or oxygen enter the gas phase electrical discharge zone through the Stainless Steel Wire Mesh ground electrode, make air or oxygen be uniformly distributed in electrical discharge zone; High-voltage pulse power source applies high-voltage pulse to high voltage electrode and ground electrode, discharge simultaneously at liquid and gas, ozone that is dissolved in liquid phase that the chemically-active particle that produces in the liquid phase and gas phase produce and the gaseous ozone that enters pretreated water solution directly act on organic pollutant; Pretreated water solution makes pretreated water solution and treating water solution constitute circulation by circulation tube, pump and water container.The hydrogen peroxide that adds gac, active carbon fibre peacekeeping 30% in solution, the add-on of gac, active carbon fibre peacekeeping hydrogen peroxide is respectively 3-15g/L, 0.3-1.5g/L and 0.1-10g/L.The adsorption catalysis of activated carbon fiber, UV/H
2O
2/ O
3Photochemical oxidation and high pressure pulse discharge form synergistic effect.
The device of organic pollutant in the gas-liquid discharged in series degradation water comprises the cooling sandwith layer of reactor, reactor ectosome and the high-voltage pulse power source of the high voltage electrode in the reactor, ground electrode and outside.High voltage electrode is positioned at the bottom of liquid phase, and by being connected with high-voltage pulse power source by lead after several apicule needle parallel connections, the prong diameter is not more than 0.25mm, and pin spacing is 4-11mm, and needle point exceeds bottom surface 2-10mm.Metal net shaped ground electrode is on the interface of gas phase and pretreated water solution, and ground electrode is not more than 200mm to the distance of liquid phase level, and its diameter is more smaller than reactor inner diameter of steel flue.Treating water solution constitutes circulation in circulation tube, pump, water container and the reactor.Inlet pipe is inserted into gas phase zone downwards from reactor head portion, and fixed interval has several layers of parallel metal barrier net on inlet pipe, stops that the spacing of net and the number of plies can regulate.The polarity of high voltage electrode can be that negative high voltage pulse or positive high voltage pulse become, and the polarity of high voltage electrode and ground electrode can be put upside down.
Characteristic feature of an invention:
1. the Stainless Steel Wire Mesh in the gas phase is not only done electrode but also play even gas distribution, reduces discharge inception voltage and makes discharge evenly, increases the ozone concn of discharge generation.
2. the gas-liquid spacing is little, and the aqueous solution is in flow state, is convenient to ozone mass transfer in solution, and diffusion is fast.
Maximum using the chemically-active particle of discharge generation, particularly gasiform ozone, through after the stopping of multiple layer metal net, utilization ratio is higher.
4. the adsorption catalysis of activated carbon fiber, UV/H
2O
2/ O
3Photochemical oxidation and high pressure pulse discharge form synergistic effect, improve the degradation efficiency of organic pollutant.
Description of drawings
Accompanying drawing 1 is the structural representation of apparatus of the present invention; 1 is high voltage electrode among the figure, the 2nd, and ground electrode, the 3rd, time, the 4th, liquid phase, the 5th, gas phase, the 6th, circulation tube, the 7th, stainless steel metal stops net, the 8th, and treating water outlet, the 9th, peristaltic pump, the 10th, the outlet of flooding, the 11st, pretreated waste water, the 12nd, gas-bearing formation, the 13rd, cooling water sandwich, the 14th, inlet pipe (Glass tubing), the 15th, air outlet, the 16th, inlet mouth, the 17th, grounding wire, the 18th, loam cake, the 19th, cooling water outlet, the 20th, entrance of cooling water, the 21st, water container, the 22nd, liquid flowing tube, the 23rd, lower cover, the 24th, connect the high-voltage pulse power source lead-in wire.
Accompanying drawing 2 is the efficient comparison diagrams with existing reference reaction device.
Accompanying drawing 3 is to add the influence comparison diagram of activated carbon fiber to degradation rate.
Accompanying drawing 4 is to add H
2O
2The comparison diagram that influences to degradation rate.
Embodiment
The invention will be further elaborated below by example, but the present invention is not constituted any qualification.
Method of the present invention is with reference to as shown in Figure 1, and pressurized air or oxygen enter air chamber by Glass tubing 14, enter gas phase electrical discharge zone 5 through Stainless Steel Wire Mesh ground electrode 2, make even air be distributed in electrical discharge zone; High-voltage pulse power source applies high-voltage pulse to high voltage electrode 1 and Stainless Steel Wire Mesh ground electrode 2, discharge simultaneously in gas phase 5 and liquid phase 4, ozone that is dissolved in liquid phase that the chemically-active particle that produces in the liquid phase and gas phase produce and the ozone that enters pretreated water solution directly act on organic pollutant.Stainless steel metal in the pretreated water solution stops that net 7 can further improve the utilization ratio of ozone, circulation tube 6, peristaltic pump 9 and water container 21 make pretreated water solution and treating water solution constitute circulation, realize the combination of multiple oxidation technology, accelerate treatment progress.The hydrogen peroxide that adds gac, active carbon fibre peacekeeping 30% in solution, the add-on of gac, active carbon fibre peacekeeping hydrogen peroxide is respectively 3-15g/L, 0.3-1.5g/L and 0.1-10g/L.Activated carbon fiber plays adsorption on the one hand, and katalysis is also played on porous activated carbon fiber surface on the other hand, makes the organic pollutant accelerated degradation that is adsorbed on the activated carbon fiber surface.H
2O
2With the O that produces in the discharge process
3Contact with UV, produce OH, fast reaction speed is with the adsorption catalysis formation synergistic effect of high pressure pulse discharge and activated carbon fiber.Also can be on activated carbon fiber loaded optic catalyst, utilize the UV-light in the discharge process to produce photocatalysis, further improve degradation rate.In the present invention, activated carbon fiber, H
2O
2Dosage be respectively 0.045g, 3ml/L.
The particular embodiment of organic pollutant device is a gas-liquid discharged in series reactor in the gas-liquid discharged in series degradation water of the present invention.As shown in Figure 1.Comprise that mainly liquid phase high voltage electrode 1, gas phase ground electrode 2, stainless steel metal stop net 7, ventilation Glass tubing 14, circulation tube 6, peristaltic pump 9, water container 21, cooling water sandwich 15, high-voltage pulse power source (not drawing), stopple coupon 22.
High voltage electrode 1 is positioned at reactor bottom, by five acupuncture needles (also can be less than or more than five) parallel connection, is connected with high-voltage pulse power source (not drawing) by lead 24, and the acupuncture needle diameter is 0.25mm, and pin spacing is 4-11mm, and needle point exceeds bottom surface 2-10mm.Needle tip insulate as much as possible with the lower section, makes the loss of energy be reduced to minimum; Pin is point as much as possible, so that produce concentration of local and very strong electric field around needle point, makes electronics obtain higher energy.
High voltage electrode can be acupuncture needle or entry needle, also can be other wires, and as filaments such as stainless steel, silver, platinum, tungsten, nichromes, diameter can be greater than or less than 0.25mm.
The polarity of high voltage electrode 1 can be changed, and as changing the setting of high-voltage pulse power source, when applying the negative high voltage pulse, the polarity of high voltage electrode 1 becomes the negative high voltage pulse by original positive high voltage pulse; When applying the positive or negative high voltage pulse, the polarity of high voltage electrode 1 changes from the positive high voltage pulse to the negative high voltage pulse cycle.In addition, the polarity of high voltage electrode 1 and ground electrode 2 can be put upside down, and pin electrode is done the earth polar, and the Stainless Steel Wire Mesh electrode is made high voltage electrode.
Stainless Steel Wire Mesh ground electrode 2 is on the interface of gas phase 5 and pretreated water solution 11, and pressurized air or oxygen enter air chamber by Glass tubing 14, enters the gas phase electrical discharge zone through the Stainless Steel Wire Mesh ground electrode.Do the earth polar with 80 order Stainless Steel Wire Meshes, because its aperture is little, can slow down air velocity, make even air be distributed in electrical discharge zone, discharge is even, and the ozone concn of generation is big, is convenient to ozone mass transfer in liquid phase 4.Its diameter is than the little 1mm of synthetic glass inner diameter of steel flue, and the slit of mixed gas between earth polar and synthetic glass inner core that helps air and ozone enters the pretreated water solution, and pretreated water solution is carried out oxidation.
The polarity of high voltage electrode 1 and ground electrode 2 can be put upside down, and high voltage electrode 1 is done the earth polar, and Stainless Steel Wire Mesh ground electrode 2 is made high voltage electrode, and ground electrode also can be other porous electro-conductive material.
Stainless steel metal stops that net 7 is fixed on the Glass tubing 14, is evenly distributed in the pretreated water solution 11, and gaseous ozone is obstructed in uphill process, stops that at stainless steel metal the lower surface of net forms gas-bearing formation, is increased in the residence time in the pretreated water solution.Solution forms liquid film on the stainless steel metal mesh simultaneously, has increased the contact area of ozone and organic pollutant, and the organic pollutant in ozone and the pretreated water solution is fully reacted, and improves the utilization ratio of ozone.In addition, stainless steel metal stops that net also may play katalysis in ozone and organic pollutant reaction process.
The two-layer spacing size of net that stops can be regulated, and according to handling liquid measure, can suitably increase the number of plies that stops net.In the present invention, be provided with 5 layers and stop net, two-layerly stop that the spacing of net is 10mm.Stop that net can replace with other porous material, as porous ceramics, molecular sieve etc., pore size can be selected as required.
Glass tubing 14 is the passage of gas, again stainless steel metal is stopped fixing and the adjustable range effect of having netted.
In the cooling water sandwich 13 water coolant being housed, also can be other cooling fluid, peristaltic pump make water coolant in the cooling water inlet 20 and cooling water outlet 19 constitute circulation, keep isothermal reaction, prevent that reactor is overheated.
Gas enters inlet mouth 16 after by gas meter (not drawing), so that control and measurement gas flow can connect the gaseous ozone analyser behind air outlet 15, so that the ozone content of analysis combustion gas.The inside and outside tube of reactor can be with silica glass or other transparent material, or other insulating material leaves transparent fenestra, so that connect spectral analysis apparatus.
Reactor of the present invention is powered with high-voltage pulse power source as far as possible.In steep-front, spike pulse discharge process, liquid phase produces H
2O
2, OH, O
3, O, H
2, H, O
2 -And other molecule, ion and active particle; Gas phase produces O
3, O, OH and other molecule, ion and active particle.Owing to increased O
3, O, OH and other excited state particle, thereby improve the degradation rate of organic pollutant.
Application example 1, the high efficiency of this device.
By the contrast of gas-liquid discharged in series reactor and reference reaction device degraded tropeolin-D, the high efficiency of gas-liquid discharged in series reactor is described, the synthetic glass inner diameter of steel flue of these two kinds of reactors all is 40mm, high 400mm.The high voltage electrode of gas-liquid discharged in series reactor and reference is made up of the acupuncture needle of five diameter 1mm, and pin spacing 1.1mm, pin exceed reactor bottom 6mm.Ground electrode is 24mm with 80 order Stainless Steel Wire Meshes, two distance between electrodes, treating water solution 20ml, pretreated water solution 30ml and 80ml.The high voltage electrode of reference reaction device also is made up of the acupuncture needle of five diameter 0.25mm, and pin spacing 1.1mm, pin exceed reactor bottom 6mm.Ground electrode places 5mm on the liquid level with 80 order Stainless Steel Wire Meshes, and two distance between electrodes are 45mm, treating water solution 50ml.These two kinds of reactors are all powered with high-voltage pulse power source, crest voltage is 44KV, frequency is 50Hz, the concentration of methyl orange aqueous solution is 40ppm, handles liquid measure 50ml, air flow quantity 118ml/min, treatment time is 15 minutes, sampling interval is 3 minutes, surveys solution absorbency with the UV762 ultraviolet-visible spectrophotometer, repeats 3 times and averages.
Fig. 2 has shown the degradation rate of gas-liquid discharged in series reactor and reference reaction device.Handle the 50ml liquid measure, gas-liquid discharged in series reactor degradation rate is 90.63%, and the degradation rate of reference reaction device is 73.58%, and the degradation rate of gas-liquid discharged in series reactor is higher 17.05 percentage points than reference reaction device.Handle the 100ml liquid measure, gas-liquid discharged in series reactor degradation rate is 72.61%, handling the 50ml liquid measure with the reference reaction device differs less than 1%, reach identical processing efficiency, gas-liquid discharged in series reactor for treatment liquid measure is the twice of reference reaction device, illustrates that the performance of gas-liquid discharged in series reactor is better than the reference reaction device.
Application example 2, the experiment condition of gas-liquid discharged in series reactor add 0.5g gac and 0.045g activated carbon fiber respectively with routine example 1 in the 100ml methyl orange solution, investigate the influence of gas-liquid discharged in series reactor to degradable organic pollutant.
Fig. 3 shows that the degradation rate of tropeolin-D is 72.61% when not adding gac and activated carbon fiber; The degradation rate of tropeolin-D is 93.12% behind the adding 0.5g gac, improves 20.51 percentage points; The degradation rate of tropeolin-D is 94.52% after the adding 0.045g activated carbon fiber, improves 21.91 percentage points, illustrates that adding activated carbon fiber specific activity charcoal is more effective.
Application example 3, the experiment condition of gas-liquid mixed discharge reactor add 0.5g gac and 0.3ml H respectively with example 1 in the 100ml methyl orange solution
2O
2, 0.045g active carbon fibre peacekeeping 0.3ml H
2O
2, investigate of the influence of gas-liquid discharged in series reactor to degradable organic pollutant.
Fig. 4 shows adding 0.5g gac and 0.3ml H
2O
2The degradation rate of back tropeolin-D is 96.87%, improves 3.75 percentage points than independent adding 0.5g gac; Add 0.045g active carbon fibre peacekeeping 0.3ml H
2O
2The degradation rate of back tropeolin-D is 98.07%, improves 3.55 percentage points than independent adding activated carbon fiber, as seen, adds active carbon fibre peacekeeping H
2O
2After can improve the degradation rate of tropeolin-D.
Claims (1)
1, the method for organic pollutant in the gas-liquid discharged in series degradation water, pressurized air or oxygen enter the gas phase electrical discharge zone through the Stainless Steel Wire Mesh ground electrode, make air or oxygen be uniformly distributed in electrical discharge zone; High-voltage pulse power source applies high-voltage pulse to high voltage electrode and ground electrode, discharge simultaneously at liquid and gas, ozone that is dissolved in liquid phase that the chemically-active particle that produces in the liquid phase and gas phase produce and the gaseous ozone that enters pretreated water solution directly act on organic pollutant; Pretreated water solution makes pretreated water solution and treating water solution constitute circulation by circulation tube, pump and water container, and it is characterized in that: high voltage electrode is positioned at reactor bottom, and ground electrode is arranged in gas phase; The hydrogen peroxide that adds gac, active carbon fibre peacekeeping 30% in solution, the add-on of gac, active carbon fibre peacekeeping hydrogen peroxide is respectively 3-15g/L, 0.3-1.5g/L and 0.1-10g/L.
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|---|---|---|---|
| CNB2006100689946A CN100509642C (en) | 2006-09-26 | 2006-09-26 | Method for degrading organic contaminant in water through gas and liquid cascaded discharge |
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| CNB2006100689946A CN100509642C (en) | 2006-09-26 | 2006-09-26 | Method for degrading organic contaminant in water through gas and liquid cascaded discharge |
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| CN100509642C true CN100509642C (en) | 2009-07-08 |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN102190352B (en) * | 2011-04-15 | 2013-09-18 | 中国石油大学(华东) | Gas-phase high pressure pulse discharge device and method for catalytically degrading organic dyes in water by same |
| CN102329033B (en) * | 2011-09-09 | 2013-03-13 | 四川农业大学 | Independent-aeration high-voltage pulse discharging water treatment reactor and sewage treatment method thereof |
| CN103864185B (en) * | 2014-02-20 | 2015-09-30 | 中国石油大学(华东) | The efficient Quick Oxidation of glow discharge is utilized to fix method and the device thereof of arsenic in waste water |
| CN105293623B (en) * | 2015-08-13 | 2017-10-20 | 河海大学常州校区 | A kind of solid-liquid-gas three phase water processing reactor |
| RU2605084C1 (en) * | 2015-09-30 | 2016-12-20 | Акционерное общество "Ордена Трудового Красного Знамени Научно-исследовательский физико-химический институт им. Л.Я. Карпова" (АО "НИФХИ им. Л.Я. Карпова") | Electrolytic cell with fixed electrodes for electrochemical purification of waste water and obtaining several inorganic peroxide compounds |
| CN107010603A (en) * | 2017-04-11 | 2017-08-04 | 赣南师范大学 | A kind of ozone generating-device and method for water process |
| CN107583634A (en) * | 2017-09-18 | 2018-01-16 | 陈银 | A kind of high pressure pulse discharge regeneration reactor |
| CN112320886A (en) * | 2020-10-29 | 2021-02-05 | 东北大学 | Ultraviolet light and ozone combined catalytic oxidation printing and dyeing wastewater treatment device |
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Non-Patent Citations (2)
| Title |
|---|
| Hydrogen peroxide and ozone formationinhybridgas-liquidelectrical discharge reactors. Petr Lukes 等.IEEE TRANSACTIONS ON INDUSTRY APPLICATIONS,Vol.40 No.1. 2004 |
| Hydrogen peroxide and ozone formationinhybridgas-liquidelectrical discharge reactors. Petr Lukes 等.IEEE TRANSACTIONS ON INDUSTRY APPLICATIONS,Vol.40 No.1. 2004 * |
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