CN100444934C - Method and apparatus for removing ozone - Google Patents
Method and apparatus for removing ozone Download PDFInfo
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- CN100444934C CN100444934C CNB2005101374116A CN200510137411A CN100444934C CN 100444934 C CN100444934 C CN 100444934C CN B2005101374116 A CNB2005101374116 A CN B2005101374116A CN 200510137411 A CN200510137411 A CN 200510137411A CN 100444934 C CN100444934 C CN 100444934C
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
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- Y02A—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE
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- Y02A50/20—Air quality improvement or preservation, e.g. vehicle emission control or emission reduction by using catalytic converters
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Abstract
The invention provides a method and means of removal of ozone. The invention of the means including: a reaction tank, containing a solution of ferrous ions, ozone into contact with a redox reaction, make ozone reduction into oxygen, oxidation of ferrous into iron ions; And a reduction means will make iron ions reduction into ferrous ions, in a sustained supply reaction to the trough redox reaction. The present invention also provides a method of removal of ozone, including: Introduction of ozone gas to a solution containing ferrous ions reaction trough so that ferrous ions in contact with the ozone oxidation, then redox reaction take place, which ozone into oxygen reduction, ferrous into iron ions oxidation; And through a reduction means will make iron ions reduction into ferrous ions, in a sustained supply reaction to the trough redox reaction. This invention has considerable economic value, so that ozone gas in the minimum amount of chemicals added to properly handle the situation.
Description
Technical field
The present invention relates to a kind of Environmental security device, particularly a kind of device and method of removing ozone.
Background technology
At present, high-tech industry such as photoelectricity, semiconductor all can use a large amount of ozone to make the oxide layer film or wafer, glass baseplate surface are cleaned in processing procedure.Because the ozone basis is as strong oxidizer and have highly corrosive, add that the low very easily loss of water solubility to air, causes low concentration and promptly human respiratory produced harmful effect, therefore, if ozone remaining in the processing procedure fails to deal carefully with, will cause greatest harm to processing procedure safety and health.
The technology that present stage is handled residual ozone roughly can be divided into following several, comprise with manganese dioxide-catalyst and decomposing, penetrate decomposition with UV illumination, with methods such as reduction of sodium sulfite chemical agent or the outer gas dilutions of importing, yet, said method is all because of factor such as processing cost costliness or effect be not remarkable, still can't provide perfect solution, for example ozone decomposition is penetrated in manganese dioxide-catalyst (needing heating) or UV illumination, its material all has age limit and running cost costliness on using, the cost of sodium sulfite chemical agent is expensive and can't reuse, and outer gas dilution rule can't effectively reduce the harmfulness of ozone to industry security and health.
Summary of the invention
In view of this, the invention provides a kind of device of removing ozone, comprising: a reactive tank, contain a ferrous ion (Fe
2+) solution, it contacts with the gas ozoniferous that imports redox reaction takes place, and makes ozone reduction become oxygen, and ferrous ion is oxidized to iron ion (Fe
3+); And a reduction apparatus, iron ion is reduced into ferrous ion, carry out redox reaction to continue this reactive tank of supply.In addition, the device of this removal ozone further can comprise deacidification device, an air-lift device or its combination.
In the device of removal ozone of the present invention, the concentration of this ferrous ion in this solution is 200~10,000 mg/litre, and the pH value scope of this solution is 0.5~3.0.
In the device of removal ozone of the present invention, waste gas or waste liquid that this ozone produces from semiconductor, flat-panel screens or photoelectric process.
In the device of removal ozone of the present invention, this waste gas or waste liquid also contain the acid of organic or inorganic.
The device of removal ozone of the present invention also comprises a deacidification device, contains acid in the ozone gas with removal.
The device of removal ozone of the present invention also comprises an air-lift device, so that ozone gas in waste liquid is put forward to import this reactive tank.
In the device of removal ozone of the present invention, this reduction apparatus is arranged at the inside of this reactive tank.
In the device of removal ozone of the present invention, this reduction apparatus is arranged at the outside of this reactive tank.
In the device of removal ozone of the present invention, this reduction apparatus is an electrolysis unit.
Preferably, reactive tank of the present invention can be not to be packed bed, packed column, Ban Ta, scrubbing tower, hypergravity machine (RPB) or aeration tank/bottle but do not limit.
Preferably, air-lift device of the present invention can be not to be aeration tank/bottle, packed column, plate tower or hypergravity machine but do not limit.
Preferably, deacidification device of the present invention can be not to be wet scrubbing tower, dry washing tower or adsorbent bed but do not limit.
The present invention also provides a kind of method of removing ozone, comprises the following steps: that gas ozoniferous is directed into one contains ferrous ion (Fe
2+) reactive tank of solution, redox reaction takes place so that ferrous ion contacts with ozone, wherein ozone reduction becomes oxygen, and ferrous ion is oxidized to iron ion (Fe
3+); And become ferrous ion by a reduction apparatus reduced iron ion, carry out redox reaction to continue this reactive tank of supply.In addition, the method for this removal ozone further comprises deacidification, gas is carried or its combined treatment step.
In the method for removal ozone of the present invention, the concentration of this ferrous ion in this solution is 200~10,000 mg/litre, and the pH value scope of this solution is 0.5~3.0.
In the method for removal ozone of the present invention, waste gas or waste liquid that this gas ozoniferous produces from semiconductor, flat-panel screens or photoelectric process.
In the method for removal ozone of the present invention, this waste gas or waste liquid also contain the acid of organic or inorganic.
The method of removal ozone of the present invention also is included in before this waste gas imports this reactive tank, removes the step of the acid in this waste gas.
The method of removal ozone of the present invention also comprises the step that ozone gas in waste liquid is put forward to import this reactive tank.
In the method for removal ozone of the present invention, the flow of this ozone is substantially between 0.1~100,000 liter/minute.
In the method for removal ozone of the present invention, the temperature of this redox reaction is substantially between 4~95 degrees centigrade.
In the method for removal ozone of the present invention, the pressure of this redox reaction is substantially between 0.8~1.2 atmospheric pressure.
In the method for removal ozone of the present invention, this ozone reduction becomes the efficient of oxygen to be higher than 85%.
In the method for removal ozone of the present invention, this reactive tank comprises packed column, Ban Ta, hypergravity machine or aeration tank.
In the method for removal ozone of the present invention, this reduction apparatus provides 3~10 volts reduction potential substantially.
In the method for removal ozone of the present invention, this reduction apparatus provides the reduction current density of 20~200 amperes per square meter substantially.
In the method for removal ozone of the present invention, the reduction reaction that iron ion is reduced into ferrous ion betides the inside of this reactive tank.
In the method for removal ozone of the present invention, the reduction reaction that iron ion is reduced into ferrous ion betides the outside of this reactive tank.
In the method for removal ozone of the present invention, this reduction apparatus is an electrolysis unit.
The present invention utilizes ferrous ion that ozone is reduced processing, to reduce its oxidability and corrosivity, and the clean harmless oxygen of formation, reach the purpose of removing residual ozone, simultaneously, by the ferric ion of ozone oxidation can be again mode by electroreduction revert back original divalence ferrous ion and continue to use, quite economical and practical, make ozone gas under the condition of minimum chemicals addition, obtain to deal carefully with.
Description of drawings
Fig. 1 to Fig. 4 removes the schematic diagram of ozone equipment for the present invention.
Fig. 5 is for carrying out the result of ozone treatment test of the present invention in A factory.
Fig. 6 is for carrying out the result of ozone treatment test of the present invention in B factory.
Fig. 7 to Figure 15 is the result of ozone treatment of the present invention test, and during as contact arrangement, different ferrous ion concentration cleaning solutions and rotating speed are to the relation of ozone gas treatment effeciency with RPB in expression.
The specific embodiment
For above-mentioned purpose of the present invention, feature and advantage can be become apparent, hereinafter enumerate preferred embodiment especially, and conjunction with figs., be described in detail below:
See also Fig. 1, the device of removal ozone of the present invention is described.The device 10 of removal ozone of the present invention comprises a reactive tank 20 and a reduction apparatus 30.Reactive tank 20 contains a ferrous ion (Fe
2+) solution 40, it can contact with the gas ozoniferous 70 that imports redox reaction takes place, and makes ozone reduction become oxygen, and ferrous ion is oxidized to iron ion (Fe
3+).And reduction apparatus 30 can revert back the ferric ion of oxidation the divalence ferrous ion, carries out redox reaction to continue supply reactive tank 20.
The concentration of above-mentioned ferrous ion in solution 40 can be 200~10,000 mg/litre, and the pH value scope of this solution is 0.5~3.0, the ozone concentration that visual desire is handled and adjusting.The gas ozoniferous 70 that imports in the reactive tank 20 can be from the Ozone Water in waste gas ozoniferous, waste liquid or the processing procedure of semiconductor, flat-panel screens or photoelectric process generation.Other sees also Fig. 2, if gas 70 ozoniferous from the processing procedure contain ozone waste liquid or Ozone Water 71 time, the device 10 that the present invention removes ozone further can comprise a gas and carry (stripping) device 60, so that the gas in liquid phase of the ozone in the waste liquid or in the Ozone Water is put forward to import reactive tank 20.Aforementioned this air-lift device can be, but do not limit is not, aeration bottle/groove, packed column, plate tower or hypergravity machine are familiar with the visual actual demand of personnel of this technology and are selected for use.
Please refer to Fig. 3, the device 10 of removal ozone of the present invention further can comprise a deacidification device 50, with the acid removal with the organic or inorganic in the gas 70 ozoniferous, for example hydrofluoric acid, hydrochloric acid, nitric acid, sulfuric acid or acetic acid.Aforesaid deacidification device 50 can be, but do not limit is not, wet scrubbing tower, dry washing tower, adsorbent bed are familiar with the visual actual demand of personnel of this technology and are selected for use.Same as above, if gas ozoniferous 70 from the processing procedure contain ozone waste liquid or Ozone Water 71 time, the device 10 that the present invention removes ozone further can comprise a gas and carry (stripping) device 60, as shown in Figure 4.
Be applicable to that reactive tank of the present invention is of a great variety, for example but be not limited to packed column, Ban Ta, hypergravity machine or aeration tank, be familiar with the visual actual demand of personnel of this technology and select for use.According to factory building space size, reduction apparatus 30 can be arranged at the inside or the outside of reactive tank 20 in addition.Aforementioned reduction apparatus 30 can be, but do not limit be not, electrolysis unit, Fenton (Fenton) device for example is familiar with the visual actual demand of personnel of this technology and is selected for use.
Then, illustrate that the present invention removes the method for ozone.See also Fig. 3, at first, gas 70 ozoniferous is taken place processing procedure, import a deacidification device 50, to remove sour gas or the drop in the gas 70 ozoniferous, for example hydrofluoric acid, hydrochloric acid, nitric acid, sulfuric acid or acetic acid.Then, the gas importing one through removing acid treatment is contained ferrous ion (Fe
2+) reactive tank 20 of solution 40.The ozone that imports in the gas promptly contact the generation redox reaction with ferrous ion in the groove, makes ozone reduction become oxygen, and ferrous ion is oxidized to iron ion (Fe
3+).At last, ferric ion is reverted back the divalence ferrous ion, carry out redox reaction to continue supply reactive tank 20 by a reduction apparatus 30.
Ozone imports the flow of reactive tank 20 substantially between 0.1~100,000 liter/minute.And the temperature of redox reactions and pressure are controlled between 4~95 degrees centigrade and 0.8~1.2 atmospheric pressure substantially in the reactive tank 20.Ozone reduction of the present invention becomes the efficient of oxygen high, can reach more than 85%.
Revert back in ferrous process at ferric iron, reduction apparatus 30 can provide the reduction potential of 3~10 volts of cardinal principles and the reduction current density of cardinal principle 20~200 amperes per square meter (negative electrode).As mentioned above, the iron ion reduction reaction that is reduced into ferrous ion can occur in the inside or the outside of reactive tank 20.
The mode that the present invention utilizes ferrous ion to contact with the ozone gas-liquid is carried out redox reaction, making originally, the ozone of highly corrosive is transformed into clean harmless oxygen and discharges, and oxidized ferric ion can restore back original divalence ferrous ion via simple electroreduction to be continued to use for reactive tank, in view of this, the suitable economically valuable of the present invention makes ozone gas obtain to deal carefully with under the situation of minimum chemicals addition.
Embodiment
Embodiment 1
The present invention carries out the ozone treatment test in A, B two factories, and test condition is as follows:
The ozone air inflow is 1.5 liters/minute, and ferrous ion cleaning solution volume is 600 milliliters, and contact arrangement is an aeration tank, and ferrous ion concentration is 2,500 mg/litre.Its ozone treatment efficient can reach more than 95%.Test result is referring to Fig. 5 (A factory) and Fig. 6 (B factory).
Embodiment 2
As contact arrangement, utilize different rotating speeds that the cleaning solution of different ferrous ion concentrations is carried out the ozone treatment efficiency test with RPB, test result sees also Fig. 7 to Figure 15.
Fig. 7 represent the ozone air inflow be 2.9 liters/minute, when ferrous ion cleaning solution concentration is 1,000 mg/litre, different rotary packed bed rotating speed and gas liquid ratio are to the relation of ozone treatment efficient.Fig. 8 represent the ozone air inflow be 2.9 liters/minute, when ferrous ion cleaning solution concentration is 2,500 mg/litre, different rotary packed bed rotating speed and gas liquid ratio are to the relation of ozone treatment efficient.Fig. 9 represent the ozone air inflow be 2.9 liters/minute, when ferrous ion cleaning solution concentration is 4,000 mg/litre, different rotary packed bed rotating speed and gas liquid ratio are to the relation of ozone treatment efficient.Figure 10 represent the ozone air inflow be 4.8 liters/minute, when ferrous ion cleaning solution concentration is 1,000 mg/litre, different rotary packed bed rotating speed and gas liquid ratio are to the relation of ozone treatment efficient.Figure 11 represent the ozone air inflow be 4.8 liters/minute, when ferrous ion cleaning solution concentration is 2,500 mg/litre, different rotary packed bed rotating speed and gas liquid ratio are to the relation of ozone treatment efficient.Figure 12 represent the ozone air inflow be 4.8 liters/minute, when ferrous ion cleaning solution concentration is 4,000 mg/litre, different rotary packed bed rotating speed and gas liquid ratio are to the relation of ozone treatment efficient.Figure 13 represent the ozone air inflow be 7.6 liters/minute, when ferrous ion cleaning solution concentration is 1,000 mg/litre, different rotary packed bed rotating speed and gas liquid ratio are to the relation of ozone treatment efficient.Figure 14 represent the ozone air inflow be 7.6 liters/minute, when ferrous ion cleaning solution concentration is 2,500 mg/litre, different rotary packed bed rotating speed and gas liquid ratio are to the relation of ozone treatment efficient.Figure 15 represent the ozone air inflow be 7.6 liters/minute, when ferrous ion cleaning solution concentration is 4,000 mg/litre, different rotary packed bed rotating speed and gas liquid ratio are to the relation of ozone treatment efficient.
By test result as can be known, ozone gas can carry out reactivity with the ferrous ion cleaning solution really and absorb processing, by regulating gas-liquid contact effect,, all can improve ozone gas and handle effect as improving the cleaning solution ferrous ion concentration, increase the RPB rotating speed, dwindling gas-liquid contact ratio.As shown in Figure 9, in cleaning solution ferrous ion concentration 4,000 mg/litre, RPB rotating speed 1, under 200rpm, gas liquid ratio 100, the 6.4 seconds gas packed bed void tower time of staying condition, the gas of ozone concentration 100ppmv, its ozone treatment efficient can reach 95.3%.
The above only is preferred embodiment of the present invention; so it is not in order to limit scope of the present invention; any personnel that are familiar with this technology; without departing from the spirit and scope of the present invention; can do further improvement and variation on this basis, so the scope that claims were defined that protection scope of the present invention is worked as with the application is as the criterion.
Being simply described as follows of symbol in the accompanying drawing:
10: remove ozone equipment
20: reactive tank
30: reduction apparatus
40: ferrous ions soln
50: the deacidification device
60: air-lift device
70: gas ozoniferous
71: waste liquid ozoniferous or Ozone Water
Claims (24)
1. device of removing ozone comprises:
One reactive tank contains a ferrous ions soln, and it contacts with the ozone that imports redox reaction takes place, and makes ozone reduction become oxygen, and ferrous ion is oxidized to iron ion; And
One electrolysis unit is reduced into ferrous ion with iron ion, carries out redox reaction to continue this reactive tank of supply.
2. the device of removal ozone according to claim 1 is characterized in that, the concentration of this ferrous ion in this solution is 200~10,000 mg/litre, and the pH value scope of this solution is 0.5~3.0.
3. the device of removal ozone according to claim 1 is characterized in that, waste gas or waste liquid that this ozone produces from semiconductor, flat-panel screens or photoelectric process.
4. the device of removal ozone according to claim 3 is characterized in that, this waste gas or waste liquid also contain the acid of organic or inorganic.
5. the device of removal ozone according to claim 4 is characterized in that, it also comprises a deacidification device, contains acid in the ozone gas with removal.
6. the device of removal ozone according to claim 3 is characterized in that, it also comprises an air-lift device, so that ozone gas in waste liquid is put forward to import this reactive tank.
7. the device of removal ozone according to claim 1 is characterized in that, this reactive tank comprises packed column, Ban Ta, hypergravity machine or aeration tank.
8. the device of removal ozone according to claim 1 is characterized in that, this electrolysis unit is arranged at the inside of this reactive tank.
9. the device of removal ozone according to claim 1 is characterized in that, this electrolysis unit is arranged at the outside of this reactive tank.
10. method of removing ozone comprises:
Import gas to one ozoniferous and contain the reactive tank of ferrous ions soln, so that ferrous ion contacts with ozone redox reaction takes place, wherein ozone reduction becomes oxygen, and ferrous ion is oxidized to iron ion; And
Become ferrous ion by an electrolysis unit reduced iron ion, carry out redox reaction to continue this reactive tank of supply.
11. the method for removal ozone according to claim 10 is characterized in that, the concentration of this ferrous ion in this solution is 200~10,000 mg/litre, and the pH value scope of this solution is 0.5~3.0.
12. the method for removal ozone according to claim 10 is characterized in that, waste gas or waste liquid that this gas ozoniferous produces from semiconductor, flat-panel screens or photoelectric process.
13. the method for removal ozone according to claim 12 is characterized in that, this waste gas or waste liquid also contain the acid of organic or inorganic.
14. the method for removal ozone according to claim 13 is characterized in that, it also is included in before this waste gas imports this reactive tank, removes the step of the acid in this waste gas.
15. the method for removal ozone according to claim 12 is characterized in that, it also comprises the step that ozone gas in waste liquid is put forward to import this reactive tank.
16. the method for removal ozone according to claim 10 is characterized in that, the flow of this ozone is between 0.1~100,000 liter/minute.
17. the method for removal ozone according to claim 10 is characterized in that, the temperature of this redox reaction is between 4~95 degrees centigrade.
18. the method for removal ozone according to claim 10 is characterized in that, the pressure of this redox reaction is between 0.8~1.2 atmospheric pressure.
19. the method for removal ozone according to claim 10 is characterized in that, this ozone reduction becomes the efficient of oxygen to be higher than 85%.
20. the method for removal ozone according to claim 10 is characterized in that, this reactive tank comprises packed column, Ban Ta, hypergravity machine or aeration tank.
21. the method for removal ozone according to claim 10 is characterized in that, this electrolysis unit provides 3~10 volts reduction potential.
22. the method for removal ozone according to claim 10 is characterized in that, this electrolysis unit provides the reduction current density of 20~200 amperes per square meter.
23. the method for removal ozone according to claim 10 is characterized in that, the reduction reaction that iron ion is reduced into ferrous ion betides the inside of this reactive tank.
24. the method for removal ozone according to claim 10 is characterized in that, the reduction reaction that iron ion is reduced into ferrous ion betides the outside of this reactive tank.
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CNB2005101374116A CN100444934C (en) | 2005-12-30 | 2005-12-30 | Method and apparatus for removing ozone |
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CNB2005101374116A CN100444934C (en) | 2005-12-30 | 2005-12-30 | Method and apparatus for removing ozone |
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CN1990090A CN1990090A (en) | 2007-07-04 |
CN100444934C true CN100444934C (en) | 2008-12-24 |
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Citations (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPS54141375A (en) * | 1978-04-26 | 1979-11-02 | Akira Kuwata | Ozone absorber |
CN1509201A (en) * | 2001-05-15 | 2004-06-30 | Լ��ѷ | Methof of treating atmospheric pollutants |
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Patent Citations (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPS54141375A (en) * | 1978-04-26 | 1979-11-02 | Akira Kuwata | Ozone absorber |
CN1509201A (en) * | 2001-05-15 | 2004-06-30 | Լ��ѷ | Methof of treating atmospheric pollutants |
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