CN1037426C - Method and apparatus for ozone decomposition by stimulated emission of electromagnetic wave - Google Patents

Method and apparatus for ozone decomposition by stimulated emission of electromagnetic wave Download PDF

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CN1037426C
CN1037426C CN94190201A CN94190201A CN1037426C CN 1037426 C CN1037426 C CN 1037426C CN 94190201 A CN94190201 A CN 94190201A CN 94190201 A CN94190201 A CN 94190201A CN 1037426 C CN1037426 C CN 1037426C
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ozone
wavelength
oxygen
air
singlet oxygen
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CN1105177A (en
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持麾正
南馆诚
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Humanecology Co Ltd
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Humanecology Co Ltd
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Priority claimed from JP11092993A external-priority patent/JP3255488B2/en
Priority claimed from JP13269493A external-priority patent/JP3428069B2/en
Priority claimed from JP13269593A external-priority patent/JP3365819B2/en
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    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61L—METHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
    • A61L9/00—Disinfection, sterilisation or deodorisation of air
    • A61L9/015—Disinfection, sterilisation or deodorisation of air using gaseous or vaporous substances, e.g. ozone
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61L—METHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
    • A61L2/00—Methods or apparatus for disinfecting or sterilising materials or objects other than foodstuffs or contact lenses; Accessories therefor
    • A61L2/16—Methods or apparatus for disinfecting or sterilising materials or objects other than foodstuffs or contact lenses; Accessories therefor using chemical substances
    • A61L2/20—Gaseous substances, e.g. vapours
    • A61L2/202—Ozone
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B13/00—Oxygen; Ozone; Oxides or hydroxides in general
    • C01B13/02—Preparation of oxygen
    • C01B13/0203—Preparation of oxygen from inorganic compounds

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  • Chemical & Material Sciences (AREA)
  • Veterinary Medicine (AREA)
  • Animal Behavior & Ethology (AREA)
  • General Health & Medical Sciences (AREA)
  • Public Health (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Epidemiology (AREA)
  • Organic Chemistry (AREA)
  • Inorganic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Treatment Of Water By Oxidation Or Reduction (AREA)
  • Physical Water Treatments (AREA)

Abstract

This invention relates to a method of ozone decomposition, which comprises the steps of irradiating ozone with ultraviolet rays having a wavelength of 240 nm to 360 nm to generate singlet oxygen, and irradiating it with visible light having a wavelength of 600 nm to 650 nm and near infrared rays having a wavelength of 1,200 nm to 1,300 nm, wherein ozone is converted to ground-state oxygen through singlet oxygen by stimulated emission of electromagnetic waves. The transition energy obtained from the processing of concentrated ozone is utilized, whereas residual ozone is decomposed so as to effect sterilization of air and water for preserving environment, or deodorization and purification of water or air.

Description

Method and device with the hertzian wave ozone decomposition of stimulated emission
Technical field
The present invention relates to make ozone with high concentration to be transformed into ground state oxygen, meanwhile utilize its switching energy to decompose remaining ozone, reach the sterilization of required air of environmental protection and water by this by creating singlet oxygen by using, or the deodorization of air and water and purification etc.
In addition, the invention relates to increase and be dissolved in tap water, sewage, well water, the rivers and creeks, lakes and marhshes, the ocean, the oxygen in the water such as draining carries out water purification, the production method of the dissolved oxygen in the germ-resistant water by this.
Background technology
When using air disinfection in the prior art, great majority use the uviolizing of wavelength 185nm and ozoniferous method, or carry out germ-resistant method with the germicidal lamp irradiation ultraviolet radiation of wavelength 254nm, or and with the method for aforesaid method.
Water purification method has high-concentrated ozone is exposed to method in the water, and uses two kinds of water treatment method such as ozone and ultraviolet combined oxidation method.
The decomposition method of remaining ozone has the activated carbon adsorption method with activated carbon adsorption ozone, with the thermolysis process of thermolysis ozone, and utilizes the decomposition method of catalyzer.
Yet utilize in the ultraviolet ozoniferous method of wavelength 185nm, in the time of must fully decomposing at the ozone end, make it become remaining ozone and discharge in atmosphere, not only greatly influence is taken place human body, it also handles very difficulty.If independent carrying out during with the germicidal lamp irradiation ultraviolet radiation, is the ultraviolet ray based on wavelength 254nm, the creating singlet oxygen by using that is excited directly spreads, and can not expect to carry out sterilization effects in moment.
Utilize high-concentrated ozone to carry out air disinfection, when the sterilization of water or the surface active of a certain material, the treatment process of the remaining ozone that produces because of irradiation ultraviolet radiation, if use the activated carbon adsorption method of prior art, thermolysis process, and utilize the decomposition method of catalyzer, be not suitable for the decomposition of large vol ozone, and up to the present still do not have suitable treatment process, thereby become the big obstacle that the ozone height utilizes.
In addition, above-mentioned high-concentrated ozone is exposed to method in the water, and with uviolizing in the combined oxidation method of ozone bubbles, the decomposition of ozone is neither fully, make it become remaining ozone and remain in the water, or ozone is discharged in atmosphere, biology is produced detrimentally affect.
Therefore, reduce remaining ozone in the water, discharge the aftertreatment of the amount of the ozone in atmosphere, reaching Security Countermeasures becomes important topic, and the installation cost of the aftertreatment of head it off is very huge, becomes a big obstacle that highly utilizes ozone.
Purpose of the present invention is reduced into ground state oxygen for providing a kind of ozone that makes gas phase or liquid phase to decompose, and can carry out the asepticize of air and water by sterilization, and supplies with the decomposition method of the ozone of the high sterilized water of the concentration of dissolved oxygen.
Summary of the invention
For reaching above-mentioned purpose, the decomposition method of ozone of the present invention is that the ultraviolet ray of wavelength 240nm-360nm or ultraviolet laser are shone after ozone makes it produce creating singlet oxygen by using, near infrared ray or the infrared laser of the visible rays of illumination wavelength 600nm-650nm or visible light laser and wavelength 1200nm-1300nm, make ozone pass through creating singlet oxygen by using and the excitation-emission hertzian wave is transformed into ground state oxygen.
The sterilization of air, deodorization, and purifying method is the following ultraviolet ray of illumination wavelength 200nm, ultraviolet laser, or the ultraviolet ray of wavelength 240nm-360nm or ultraviolet laser shone in the bag ozone-containing air that utilizes discharge type ozonize device to produce make it produce creating singlet oxygen by using, visible rays or visible rays laser with wavelength 600nm-650nm, the near infrared ray of wavelength 1200nm-1300nm or near infrared ray laser are independent respectively, simultaneously, or irradiation successively makes its electromagnetic stimulated emission because of creating singlet oxygen by using be transformed into ground state oxygen in this creating singlet oxygen by using.
Also can use the air control of dust that in groove and shell, to blow or to attract and to produce and give the air ionizing device of Ionized electrostatic electric precipitation machine etc., the ultraviolet ray that illumination wavelength 200nm is following, ultraviolet laser, or utilize ozoniferous ozone generating apparatus ozone decomposition in the Ionized air of discharge type ozonize device.
The present invention also can produce dissolved oxygen in water, its means are for forming bubble with a kind of being blown in ozone or ozone and the Air mixing gas in the water, the uviolizing of wavelength 240nm-360nm is become ozone into creating singlet oxygen by using in this bubble, distinguish the visible rays of wavelength 600nm-650nm and near infrared ray or the laser of wavelength 1200nm-1300nm independent then, simultaneously or irradiation successively, utilize the hertzian wave emission that is excited to make creating singlet oxygen by using be transformed into ground state oxygen and produce dissolved oxygen in the water.Also can with the uviolizing of wavelength 240nm-360nm in ozone, or a kind of ozone that makes in ozone and the Air mixing gas phase becomes after the creating singlet oxygen by using, be sprayed on the near infrared ray of the visible rays of wavelength 600nm-650nm or wavelength 1200nm-1300nm water independent respectively, or simultaneously, or shine successively and produce be transformed into gas phase in 2 processes of ground state oxygen because of electromagnetic stimulated emission makes creating singlet oxygen by using, gas phase is passed through, or utilize water spray to increase the contact area of gas phase and water, this gas phase is dissolved in the water.
Sterilization, deodorization, refining plant with air are that example illustrates effect of the present invention.The air that sucks in the idle call groove via multiblade fan gives electrostatic precipitation by ionization apparatus with trickle dust, and because of ionization becomes easily by behind the state of ozonize, be located at ultraviolet ray below the wavelength 200nm in the groove by irradiation, or ultraviolet laser, or make it pass through discharge type ozonize device, make inhaled air produce ozone.
With the ultraviolet ray of wavelength 240-360nm, or ultraviolet laser shines in resulting from by the ozone in the suck, makes above-mentioned ozone become the O that is shown below 3+ h ν (240nm-360nm) → 2 1Δ g+ 1D also promptly produces singlet state molecular oxygen 2 1Δ g and creating singlet oxygen by using atom 1D.
Because of attracting singlet state molecular oxygen that ultraviolet ray is excited when being shone, become 2 by the visible rays of wavelength 600nm-650nm 1Δ g+h ν (600nm-650nm) → 2 3∑ g also is the stimulated emission photon, is transformed into ground state oxygen molecule 2 simultaneously 3∑ g.
Replace the irradiation of above-mentioned visible rays with the near infrared ray of wavelength 1200nm-1300nm, shine when singlet state molecular oxygen, then become 1D+h ν (1200nm-1300nm) → 3∑ g also promptly is transformed into the ground state Sauerstoffatom 3∑ g and decomposing.
When above-mentioned visible rays and near infrared irradiation are carried out successively or simultaneously, become 2 1Δ g+h ν (600nm-650nm) → 2 3∑ g 1D+h ν (1200nm-1300nm) → 3∑ g all converts 2 to when arbitrary state 3The molecule of the ground state oxygen of ∑ g, or 3The atom of the ground state oxygen of ∑ g.
When being transformed into the ground state oxygen that is decomposed, because creating singlet oxygen by using becomes the excited state of the high de-agglomeration energy of 22.5Kcal/mol,, carry out sterilization to sucking air so present the strong disinfecting effect, deodorization, and purify.
Water purification of the present invention and germ-resistant application examples are as follows.At first, with ozone, or ozone and Air mixing gas is blown in the water, forms ozone in needing the former water of sterilization and purification, or the bubble of ozone and Air mixing gas, and the ultraviolet ray of illumination wavelength 240-360nm on this bubble then becomes O 3+ h ν (240nm-360nm) → 2 1Δ g+ 1D ... (1)
O 3: ozone
H ν: ultraviolet 240-360nm
2 1Δ g: creating singlet oxygen by using atom
1D: singlet state molecular oxygen becomes the ozone in the bubble into creating singlet oxygen by using.
When shining in the bubble of the singlet state molecular oxygen that produces excited state because of ultraviolet irradiation, then become 2 as if visible rays with wavelength 600-650nm 1Δ g+h ν (600-650nm) → 2 3∑ g ... (2)
H ν: visible rays 600-650nm
2 3Δ g: ground state oxygen molecule
When the near infrared ray of wavelength 1200-1300nm is shone bubble in the singlet state molecular oxygen that produces excited state because of ultraviolet irradiation, become 1D+h ν (1200-1300nm) → 3∑ g ... (3) h ν: near infrared ray 1200-1300nm 3∑ g: ground state oxygen molecule
Begin to shine successively or simultaneously visible rays or the near infrared ray any from the wavelength shorter one, creating singlet oxygen by using is excited and launching electromagnetic wave decomposes simultaneously, be transformed into stable ground state oxygen.
Above-mentioned creating singlet oxygen by using becomes the high-octane excitatory state that this more stable ground state oxygen is higher than 22.5Kcal/mol, therefore the dehydration that presents the hydrogen atom in the bacterium, that is oxygenizement, the sterilization of the pollution substance brute force in the water will be contained in, and decompose and purified, and the ground state oxygen of bubble is dissolved in the water, and becomes the dissolved oxygen in the water.
Creating singlet oxygen by using becomes hydroxyl radical free radical with the water reaction in water, …(4)
OH: hydroxyl radical free radical seizes the organism hydrogen in the water and becomes …(5)
RH: organism or bacterium carry out the sterilization of water powerfully.
In the production process of creating singlet oxygen by using, and be transformed in the gas phase in the transition process of ground state oxygen, to spray or the device of the contact area of increase gas phase such as water spray and water is dissolved in the water this gas phase, utilize the high-octane excited state of 22.5Kcal/mol that creating singlet oxygen by using has, with the dehydration of the hydrogen atom in aseptic, promptly oxygenizement is carried out more powerful sterilization.
Shown in (4) formula, creating singlet oxygen by using and water reaction and become hydroxyl radical free radical, capturing the organic hydrogen in the water and present its germicidal action shown in (5) formula, and also gas phase is dissolved in the water ground state oxygen is dissolved in the water.
Summary of drawings
Fig. 1 is the sectional drawing of the device of the embodiment of the invention 1;
Fig. 2 is the sectional drawing of the device of the embodiment of the invention 2;
Fig. 3 is the chamfer map of the embodiment of the invention 3;
Fig. 4 is the sectional drawing of the embodiment of the invention 3;
Fig. 5 is the skiagraph of the embodiment of the invention 4;
Fig. 6 is the cross-sectional view of the embodiment of the invention 4;
Fig. 7 is the skiagraph of the embodiment of the invention 5;
Fig. 8 is the cross-sectional view of the embodiment of the invention 5.
Preferred forms of the present invention
The ozone decomposition of the embodiment of the invention 1 and the ozone decomposition method and the device thereof of Air mixing gas below are described.
(see figure 1) in this method and device manually to produce ozone and Air mixing gas in advance, makes it by having the ultraviolet ray of irradiation 254nm, and the visible rays of 633nm reaches near infrared light belt indoor of 1270nm.
In this device, the air of sending into from air-blaster 1 is admitted in the top of ozone generation tube 2, in this ozone generation chamber 2 with the irradiate light of ozone generation lamp 3 in the air that is admitted to, when the air that is admitted to arrives the bottom of ozone generation chamber 2, a part of ozonize 4 wherein.
This ozone 4 produces in the tube 6 by being admitted to creating singlet oxygen by using bottom communicating pipe 5, with the ultraviolet ray of uviolizing pipe 7 illumination wavelength 253.7nm, makes ozone 4 produce creating singlet oxygen by using 8.
This creating singlet oxygen by using 8 decomposes in the tube 10 by being admitted to excitation-emission top communicating pipe 9 again, the inner face that this excitation-emission is decomposed tube 10 is equiped with mirror 11, and, make it pass through prism 13 irradiations and produce light film 14 with the visible light He-Ne laser 12 of optic fibre guide wavelength 633nm.
Be formed with the near infrared ray that the near infrared laser 15 with optic fibre guide illumination wavelength 1270nm is produced in the bottom that this excitation-emission is decomposed tube 10, make it pass through prism 16 and shine in mirror 11 and produce light film 16.
Therefore, be admitted to excitation-emission and decompose the creating singlet oxygen by using 8 of tube 10 and by light film 14 time, be excited and launching electromagnetic wave, be decomposed into ground state oxygen after, when being located at the light film 16 of its downside, excite oxygen all to become stable ground state oxygen 17, discharge from bottom relief outlet 18.
In order to monitor that ozone is transformed into ground state oxygen 17, in each communicating pipe 5,9,18, insert ozone concn meter 21,22,23, measure the concentration of ozone with monitor 20.
The room temperature of this moment is 18 ℃, and the throughput in each communicating pipe 5,9,18 is 2 liters/minute, and the ozone concn meter is to use gas phase OZM-21-2～200 types of cut sieve Knicks corporate system difficult to understand.
At this moment, the concentration determination of each ozone concn meter 21,22,23 value is as follows.Densitometer 21 22 23 measured value 160ppM 18ppM 0.02＞
The ozone that among the embodiment 2 explanation is dissolved in the water, or in water, become the decomposition method and the device (Fig. 2) thereof of the ozone of trickle bubble.
Dissolved ozone water 31 in the concentration of known dissolved ozone in advance is admitted to the round shape tube 32 from the bottom inlet, will be amplified via prism 36 and is shone on the mirror 34 that is located at tube 32 inboards and form light film 37 by the ultraviolet ray of the wavelength 254nm of optical fiber 35 guidings.
In tube 32, in light film 37 upsides, the visible light linear light film 38 of formation wavelength 633nm same as described above is at these light film 38 upsides, with the near infrared ray of irradiate near infrared rays Wavelength of Laser 1270 formation light same as described above film 39.
Therefore, the dissolved ozone water of sending in the tube 32 from the inlet 33 of tube 32 bottoms 31 passes through light film 37,38,39 successively from tube 32 top overflows.But passing through the light film at 37,38,39 o'clock, be subjected to effect same as the previously described embodiments, the oxygen of process singlet state state becomes stable ground state oxygen.
In order to measure the remaining ozone amount of this moment when the tube 32 top overflows, on tube 32 tops 40 dissolved ozone sensor 41 is set, measure the dissolved ozone amount that these dissolved ozone sensors 41 sense with monitor 42.
At this moment, the water yield of passing through is 1 liter/minute, and water temperature is 16 ℃.The dissolved ozone meter is to use the barrier film polarography mode/OC-100 type of visiing Europe Knicks corporate system.Below represent its measurement result.The dissolved ozone concentration 0.01 of the ozone concn 7ppM top overflow water by preceding dissolved ozone water＞
In the invention of embodiment 2, the ultraviolet uviolizing pipe 7 of the illumination wavelength 253.6nm of the various embodiments described above ultraviolet laser with 240nm-360nm is replaced, the visible light He-Ne laser 12 of wavelength 633nm is replaced with visible rays laser, the laser 15 of wavelength 1270nm is replaced with near infrared ray laser.So can get action effect same as the previously described embodiments.
Above-mentioned two embodiment carry out the example of visible rays irradiation and near infrared ray irradiation successively for explanation.Only carry out wherein any irradiation and all can decompose dissolved ozone.Certainly carry out two kinds of irradiations such as visible rays irradiation and near infrared ray irradiation, its decomposition efficiency is higher.
Following with reference to description of drawings embodiments of the invention 3.
Fig. 3 and Fig. 4 represent the method and apparatus that this is routine.Wherein, in groove 101, send mouthful 103 sides with the air of air suction inlet 102 opposition sides multi blade fan 104 is set, so that suck air from air suction inlet 102.
In the groove 101 of these air suction inlet 102 sides, be provided with and be used for the bigger prefilter 105 of mesh of the big dust in the absorbed air.Via this prefilter 105, the ionization apparatus 106 of the next position of the suction air of removing the bigger dust of particle by being located at prefilter 105 makes the finer dust of its particle have positive charge.
Next position at ionization apparatus 106 is provided with electronegative collecting plate 107.The above-mentioned fine dust particle that has positive charge is attached on the collecting plate 107 because of static, and the suction air by collecting plate 107 has negative charge, becomes easily by the state of ozonize.
Be provided with the ultraviolet ultra violet bulb 108 of emission wavelength 185nm behind at collecting plate 107, and be provided with ultraviolet the 2nd ultra violet bulb 109 of emission wavelength 254nm at the rear of ultra violet bulb 108.Become easily by the suction part of air of ozonize, because of being subjected to the ultraviolet irradiation ozonize of ultra violet bulb 108 by collecting plate 107.
Be contained in and suck airborne ozone and be subjected to the ultraviolet ray of the wavelength 254nm that next ultra violet bulb 109 shines and become creating singlet oxygen by using.
In the groove 101 at ultra violet bulb 109 rears, be provided with the visible rays bulb 110 of the visible rays of emission wavelength 633nm, and the near infrared near infrared ray bulb 111 of emission wavelength 1278nm, and visible rays bulb 110 is being set, be provided with the mirror 112 of the above-mentioned light of reflection in the groove 101 of the part of near infrared ray bulb 111,113, with the above-mentioned light of mirror 112,113 reflections, form the light film and the near infrared smooth film of visible rays by this.
Make ozone become the suction air of creating singlet oxygen by using successively by visible light linear light film and near infrared light film.By visible light linear light film the time, be subjected to the irradiation of the visible rays of wavelength 633nm, in the electromagnetic while of stimulated emission, its singlet state molecular oxygen is transformed into the ground state oxygen molecule.
Pass through the near infrared light film of wavelength 1278nm by the suction air of visible light linear light film.Simultaneously, the ozone that is not transformed into the ground state oxygen molecule makes its singlet state molecular oxygen be transformed into the ground state Sauerstoffatom by the near infrared irradiation that is subjected to this wavelength.
When being transformed into ground state oxygen, the energy that creating singlet oxygen by using produced reaches 22.5Kcal/mol.Be contained in the sterilization that sucks airborne bacterium class by this energy, and because the synergism of this sterilization and the removal of dust, carry out sterilization, deodorization, and purification sucking air.
Swim in the bactericidal assay of indoor general bacterium according to the foregoing description, its condition is as follows:
Room temp: 22 ℃
The floor area of testing laboratory: 60m 2
Handle air quantity: 4.2m 3/ min
Ultraviolet ray: 184nm, 40W
Ultraviolet ray: 254nm, 75W
Based on halogen bulb: visible rays 600nm, near infrared
Line 1300nm, 500W
Test method: RSC sampling (40 liters of sampling quantities)
Culture condition: 35 ℃, cultivated in 48 hours
The bacterium quantity of swimming in 40 liters of elapsed time
0 45
1 21
2 15
3 8
4 2
5 1＞
In the foregoing description, the irradiation of visible rays and near infrared irradiation are carrying out in succession.Also can only carry out wherein a kind of, and, then multi blade fan needn't be set if groove is provided with air-supply arrangement in addition.
Following with reference to Fig. 5, Fig. 6 illustrates embodiments of the invention 4.In this example, in floatingization tube 201 bottoms the influx 202 of sending into the former water that needs purification is set, sends into 19 ℃ of temperature from this influx 202, the former water of the amount of 30 liters/min is in purifying tube 201.The former water of sending in purifying tube 201 towards above flow.
Be provided with the ozone induction pipe 203 of sending into the air that contains ozone in these purifying tube 201 bottoms, the front end of this induction pipe 203 becomes the diffuser 204 that is provided with many apertures in purifying tube 201, and the air of sending into from induction pipe 203 that contains ozone is spread in the former water from the aperture ozonize bubble 205 of diffuser 204, floats with former water in purifying tube 201.For example send/go into the air that contains ozone of 40 liters/min from induction pipe 203.
The ultraviolet ray that is provided with emission wavelength 254nm in purifying tube 201 inside 3 above this diffuser 204 are output as 15W, amount to the ultra violet bulb 206 of 45W.206 ultraviolet light emitted of this ultra violet bulb are in ozone bubbles 205 and as shown in (1) formula, produce singlet state molecular oxygen in the ozone in ozone bubbles 205, with the creating singlet oxygen by using atom, and this bubble 205 becomes the bubble 207 that contains singlet state molecular oxygen and creating singlet oxygen by using atom.
This creating singlet oxygen by using atom reacts with water in water, becomes hydroxyl radical free radical shown in (4) formula, and the hydrogen of capturing the bacterium in the former water shown in (5) formula carries out powerful germicidal action to former water.
The visible rays that is provided with emission wavelength 600-650nm above ultra violet bulb 206 is output as the high-pressure sodium bulb 208 of 500W, and the bubble 207 that 208 visible light emitted line irradiations of this high-pressure sodium bulb are floated with former water with containing singlet state molecular oxygen and creating singlet oxygen by using atom.So, shown in (2) formula,, make singlet state molecular oxygen be transformed into the ground state oxygen molecule in the electromagnetic while of stimulated emission.
Above high-pressure sodium bulb 208, be provided with the high-pressure sodium bulb 209 of the near infrared 500W of being output as of emission wavelength 1200nm, and shine the bubble 207 that floats with former water behind the illuminated visible rays with near infrared ray.Therefore, shown in (3) formula, be excited to excite the electromagnetic while, making the creating singlet oxygen by using atomic transformation that is contained in the bubble become the ground state Sauerstoffatom.
Because the visible rays of illumination wavelength 600nm and the near infrared ray of wavelength 1200nm make the creating singlet oxygen by using that has produced be transformed into stable ground state oxygen, it is remaining that the former ozone that is contained in the bubble can not become remaining ozone, become dissolved oxygen and be dissolved in the former water, improve the amount of the dissolved oxygen in the former water.
Because creating singlet oxygen by using becomes the high-energy excited state that exceeds 22.5Kcal/mol than ground state oxygen, thus the dehydration of the hydrogen atom in the bacterium produced, that is oxygenizement, so can carry out the bactericidal purifying effect.
The former water that so carries out sterilization and purification and improve the amount of dissolved oxygen is discharged from from relief outlet 210 overflows that are located at purifying tube 201 tops, but the bubble that is dissolved in the ozone in the former water becomes the air condition that contains a small amount of remaining ozone in former portion waterborne, discharges in atmosphere from vapor pipe 211.
In the purification and sterilizing unit of present embodiment, contain several 190/mg that are if send into colibacillus, when general livings bacterium contains number and is the former water of 120/mg, through the colibacillus after purification and the sterilization, the quantity of general living bacterium all becomes 0, the air of sending into from induction pipe 203 that contains gas phase ozone concn 200ppM can drop to 0.002ppm when the vapor pipe 211 on purifying tube 201 tops is discharged in atmosphere.
The amount that is contained in the dissolved oxygen from the former water that influx 202 flows into is 7.2ppm, and from relief outlet 210 discharges the time, the amount of its dissolved oxygen is increased to 8.7ppm.
Following with reference to Fig. 7, the used device of embodiments of the invention 5 is implemented in 8 explanations.In this example, what be provided with the air that contains ozone on purifying tube 221 tops of internal diameter 250mm is blown into mouthfuls 222, and the 40 liters/min of air that will for example contain gas phase ozone concn 200ppm is blown into towards the below.
Be provided with the sprinkler head 223 that former water is injected into spray form in purifying tube 221 on purifying tube 221 tops, with for example colibacillus amount 920/mg, the former water of general bacterium amount 120/mg sprays towards the below from sprinkler head 223 and nebulizes, and it is fallen in purifying tube 221 with containing the air mixed of ozone.
Below sprinkler head 223, be provided with 3 uviolizing pipes 224 of the ultraviolet 15W of being output as of emission wavelength 254nm, amount to 45W, this uviolizing is in former water that falls in purifying tube 221 and the air that contains ozone, shown in (1) formula, the ozone that contains in the air that mixes with former water and fall is provoked into creating singlet oxygen by using, becomes active state.
This is excited and the activatory creating singlet oxygen by using becomes the high-energy excited state that more stable ground state oxygen exceeds 22.5Kcal/mol, and this creating singlet oxygen by using atom reacts with water in water, during becoming hydroxyl radical free radical and contain water and fall shown in (4) formula, shown in (5) formula, capture hydrogen in the former water, produce the dehydration of the hydrogen atom in the bacterium, that is oxygenizement, to being contained in the colibacillus in the former water, reaching general bacterium and carry out powerful germicidal action.
Below uviolizing pipe 224, the high-pressure sodium bulb 225 that is provided with emission wavelength 600nm same as the previously described embodiments, and thereunder be provided with the near infrared infrared ray bulb 226 of emission wavelength 1300nm, and to as above-mentioned carry out sterilization and become former water that spray form falls with visible rays, near infrared order irradiation light.
Because this irradiation, the creating singlet oxygen by using of a part is transformed into stable ground state oxygen, launches above-mentioned high-energy, carries out the colibacillus in the former water, the generally sterilization of living bacterium, and be dissolved in the water and become dissolved oxygen in the water, become the more water of amount of dissolved oxygen.
So dissolved oxygen is more, and the water that is cleaned through sterilization is stored in the bottom 227 of purifying tube 221, by the communicating pipe 228 that is located at this bottom 227 being stored in reservoir 229, flow out from relief outlet 230 overflows, utilize it as processed sterilized water, and the air that contains active oxygen that can not be dissolved in the water is discharged in atmosphere from the vapor pipe 231 that is located at purifying tube 221 lower side.
In the present embodiment, be contained in the colibacillus from the water of finishing processing that relief outlet 230 is discharged, the quantity of general living bacterium is all reduced to 0 by sterilization, the gas phase ozone concn that is contained in from the exhaust that vapor pipe 231 is discharged is decreased to 0.08ppm, and concentration of liquid phase ozone also is 0, be increased to 8.4ppm for the dissolved oxygen of 6.2ppm before can handling.
Industrial applicability
The thermolysis process of decomposition method of the present invention and prior art, utilize decomposition method and the active carbon adsorption method of catalyst different, in decomposable process, resolve into ground state oxygen via creating singlet oxygen by using, so oxygen is recovered, air is by asepticize, simultaneously by decomposing the energy sterilization. Therefore as the groove of air-conditioning, or during the air cleaner assembling, can reach the inside-hospital infection that becomes at present problem and the sterile air in the mansion.
The decomposition too of the water of dissolved ozone eliminates to result from the evils of dissolved ozone, the water of cultivation fishing gear, hospital toilet, food processing water drinks water, well water etc. can be become safe water supply, and its effect is very big.
Therefore, sterilization of the present invention, deodorization, purifier pass through not produce resistance to air in processing air-polluting process, can with jumbo air moment give sterilization and deodorization, again because with the creating singlet oxygen by using that produces in the ozone decomposed process, that is active oxygen is transformed into ground state oxygen, so can make purifying simultaneously of oxygen post-equalization.
So, ozone is transformed in the ground state oxygen pit sends, so the method such as prior art can not occur, use makes the air ozonisation because of ultraviolet irradiation, and utilize ultraviolet ray to carry out sterilization, or both are merged when using, before being decomposed, ozone do not discharge in atmosphere as remaining ozone, human body is produced harmful effect, reach the problems such as difficult treatment.
When separately using ultraviolet germicidal lamp, take the ultraviolet ray of wavelength 254nm as main body, and the creating singlet oxygen by using that is excited directly spreads, so can not expect that the instantaneous sterilization effect is arranged. But be that the transformation energy when utilizing creating singlet oxygen by using to be transformed into ground state oxygen carries out sterilization, so can expect the bactericidal effect of moment in the present invention.
Therefore, if with the sterilization of this air, deodorization, when purifier uses as air-supply arrangement, not only can prevent to become at present the nosocomial infection (MRSA) of problem, and can reach in the mansion, the aseptic and deodorization of the air in the living space of transport body. If when being applied to the place of sterilized space of other food processings, kitchen, medical institutions etc., also can bring into play its effect.
The present invention can carry out again coliform, generally sterilization and the purification of living bacterium in the contaminated former water, can increase again the amount of the dissolved oxygen that is dissolved in the water, and can be suitable for the breeding water purifier of fish and shellfish.
Utilize embodiment 5 described methods, also can decompose the polluter that the generation because of hydroxyl radical free radical forms, can decompose the organic chlorides such as three fontanel methane, trichloro-ethylene especially again, the generation of nosocomial infection (MRSA) can be prevented, and the moss in pond from the beginning, mould etc. generation can be prevented to result from.
In addition, also can be with the sewage asepticize, with sewage purification Cheng Zhongshui, Jiang Zhongshui is cleaned into running water, for the water saving of guaranteeing water resource great impact is arranged.

Claims (9)

1, a kind of method of the hertzian wave ozone decomposition with stimulated emission, it is characterized by: with the uviolizing of wavelength 240nm-360nm and after producing creating singlet oxygen by using in ozone, the near infrared light of the visible rays of illumination wavelength 600nm-650nm and wavelength 1200nm-1300nm, make ozone be excited to be transformed into ground state oxygen simultaneously through the creating singlet oxygen by using launching electromagnetic wave.
2, a kind of method of the hertzian wave ozone decomposition with stimulated emission, it is characterized by: the ultraviolet laser of wavelength 240nm-360nm is shone in ozone and after producing creating singlet oxygen by using, the visible light laser of illumination wavelength 600-650nm, and the infrared laser of wavelength 1200nm-1300nm, make ozone be excited to be transformed into ground state oxygen simultaneously through the creating singlet oxygen by using launching electromagnetic wave.
3, the method for ozone decomposition as claimed in claim 1 or 2, wherein ozone is included in because of the ultraviolet ray below the illumination wavelength 200nm, ultraviolet laser or the airborne ozone that produced by discharge type ozonize device.
4, the method for ozone decomposition as claimed in claim 1 or 2, wherein ozone is included in for air-supply in the groove or in the shell or attracts and the air that produces gives control of dust and carry out in the ionised air that air ionizing device produced such as Ionized electrostatic air precipitron, or because of the ultraviolet ray below the illumination wavelength 200nm, ultraviolet laser or give ozone in the ionised air that contains ozone after the ionization by discharge type ozonize device.
5, the method for ozone decomposition as claimed in claim 1 or 2, wherein ozone is will to be blown into one of in ozone or ozone and the Air mixing gas in the water and the ozone that contains in the bubble that produces.
6, a kind of device of the hertzian wave ozone decomposition with stimulated emission, it is characterized by: for because of the ultraviolet ray below the illumination wavelength 200nm, ultraviolet laser and contain the air of ozone, or contain the air of the ozone that produces by discharge type ozonize device, the ultraviolet ray of illumination wavelength 240nm-360nm or ultraviolet laser irradiation produce creating singlet oxygen by using to make it, for visible rays or the visible rays laser of this creating singlet oxygen by using with wavelength 600-650nm, or it is independent respectively with near infrared ray or the near infrared ray laser of wavelength 1200nm-1300nm, simultaneously, or irradiation successively, make the hertzian wave of this creating singlet oxygen by using, and the transformation energy that is produced when utilizing this creating singlet oxygen by using to be transformed into ground state oxygen comes ozone decomposition because of being excited to launch.
7, a kind of device of the hertzian wave ozone decomposition with stimulated emission is characterized by and comprises: for air-supply in blast tube or in the shell or attract and the air that produces gives control of dust and carry out air ionizing device such as Ionized electrostatic air precipitron; With the ultraviolet ray that utilizes below the illumination wavelength 200nm, ultraviolet laser or by discharge type ozonize device for ozoniferous ozone generating apparatus in the air after the ionization; With for the air that contains the ozone that produces by this ozone generating apparatus, a kind of in the ultraviolet ray of illumination wavelength 240nm-360nm or the ultraviolet laser is so that it produces the creating singlet oxygen by using generation device of creating singlet oxygen by using; Reach visible rays or visible rays laser with wavelength 600nm-650nm, or it is near infrared ray or the near infrared ray laser of wavelength 1200nm-1300nm is independent respectively, simultaneously, or shine the creating singlet oxygen by using that is produced in the creating singlet oxygen by using generation device successively, make creating singlet oxygen by using because of being excited launching electromagnetic wave, and be transformed into the ground state oxygen transition device of ground state oxygen.
8, a kind ofly utilize hertzian wave ozone decomposition with stimulated emission to produce the method for oxygen in water, it is characterized by: in ozone or ozone and the Air mixing body any is blown in the water to form bubble, ultraviolet ray for this bubble illumination wavelength 240nm-360nm, make ozone be transformed into creating singlet oxygen by using, then with the visible rays of wavelength 600nm-650nm, or it is near infrared ray or the near infrared ray laser of wavelength 1200nm-1300nm is independent respectively, simultaneously, or shine successively in creating singlet oxygen by using, make creating singlet oxygen by using because of being excited launching electromagnetic wave, and the transformation energy that produces when utilizing this creating singlet oxygen by using to be transformed into ground state oxygen come ozone decomposition to produce the dissolved oxygen in the water.
9, a kind ofly utilize hertzian wave ozone decomposition with stimulated emission to produce the method for oxygen in water, it is characterized by: with in ozone or ozone and Air mixing gas phase any of the uviolizing of wavelength 240nm-360nm, after making the ozone generation creating singlet oxygen by using, visible rays with wavelength 600nm-650nm, or it is the near infrared ray of wavelength 1200nm-1300nm is independent respectively, simultaneously or shine successively in the creating singlet oxygen by using that is producing, and for producing creating singlet oxygen by using and this creating singlet oxygen by using because of being excited launching electromagnetic wave and being transformed in the gas phase in two processes of ground state oxygen, water is sprayed into water curtain so that gas phase is passed through this water curtain, or increase the contact area of gas phase and water with water spray, make gas phase be dissolved in the water and produce dissolved oxygen.
CN94190201A 1993-04-14 1994-04-07 Method and apparatus for ozone decomposition by stimulated emission of electromagnetic wave Expired - Fee Related CN1037426C (en)

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JP110929/93 1993-04-14
JP11092993A JP3255488B2 (en) 1993-04-14 1993-04-14 Ozone decomposition method
JP132695/93 1993-05-10
JP132694/93 1993-05-10
JP13269493A JP3428069B2 (en) 1993-05-10 1993-05-10 Air sterilization / deodorization / purification method and device
JP13269593A JP3365819B2 (en) 1993-05-10 1993-05-10 Method for producing dissolved oxygen in water

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CN1037426C true CN1037426C (en) 1998-02-18

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CN100346838C (en) * 2005-10-12 2007-11-07 张亚中 Two-band ultraviolet multifunctional sterilizing purifier
US9452379B2 (en) 2014-01-14 2016-09-27 International Business Machines Corporation Ozone abatement system for semiconductor manufacturing system
CN112225181A (en) * 2020-12-04 2021-01-15 陕西省石油化工研究设计院 Ultraviolet laser optical fiber ozone generator
CN115682270A (en) * 2022-10-27 2023-02-03 珠海格力电器股份有限公司 Method and device for controlling ozone concentration and air purifier

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WO1993000291A1 (en) * 1991-06-25 1993-01-07 Saitra, S.A. Ozonized water generator for sterilization and ozonotherapy

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