CN100391858C - Ultraviolet ray device for treating liquid and method thereof - Google Patents
Ultraviolet ray device for treating liquid and method thereof Download PDFInfo
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- CN100391858C CN100391858C CNB021527431A CN02152743A CN100391858C CN 100391858 C CN100391858 C CN 100391858C CN B021527431 A CNB021527431 A CN B021527431A CN 02152743 A CN02152743 A CN 02152743A CN 100391858 C CN100391858 C CN 100391858C
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Abstract
The present invention relates to a treating device and a treating method for liquid by ultraviolet rays. The treating device can suppress peroxides from generating which is easy occur in the process of decomposition treatment of organic substances in the liquid by the ultraviolet rays in a region with less than 220 nm of short wave length. The ultraviolet rays radiated from a discharge lamp simultaneously emitting the ultraviolet rays of less than 220 nm and the ultraviolet rays of 254 nm are used for irradiating the liquid which is used as a treated object, and the organic substances in the liquid are decomposed, etc. A discharge lamp forming a metal oxide film on the inner surface of a luminous tube is used as the discharge lamp to prevent mercuric oxide generated when the discharge lamp is lighted on from being adsorbed on the inner surface of the luminous tube, and the reduction of the illumination intensity of the ultraviolet rays of 254 nm with the time can be suppressed. Because the ultraviolet rays of 254 nm can be used for decomposing the peroxides, the generating quantity of the peroxides in the treated liquid can be suppressed for a long time by maintaining the illumination intensity of the ultraviolet rays of 254 nm with the time.
Description
Technical field
The present invention relates to use the ultraviolet ray of sending the following short wavelength of 220nm zone together and the ultraviolet discharge lamp of 254nm, carry out the fluid treatment appts and the method for the processing of the organism decomposition etc. in the liquid.
Background technology
Because the ultraviolet ray in the following short wavelength of 220nm zone has strong energy, so can be used for many aspects such as nuisance and organic decomposition.Figure 10 represents an example of the UV irradiation equipment that the treatment liq of the locking type known is at all times used.Discharge lamp 30 is collected in the outer tube (protective tube) 20, but the uviolizing of using the discharge lamp 30 in the cylinder 1 that is collected in stainless steel to send imports the processed liquid in this cylinder 1.As discharge lamp 30, can use the low voltage mercury-vapour discharge lamp of the ultraviolet ray of the ultraviolet ray in radiation 185nm short wavelength zone for example and 254nm wavelength region may.The luminous envelope 10 of discharge lamp 30 is to be made by the silica glass of ultraviolet perviousness brilliance.Discharge lamp 30 is collected in the inside of the outer tube (protective tube) 20 with ultraviolet perviousness, this discharge lamp 30 hydraulic seals ground is isolated with processed liquid.This outer tube 20 also is to be made by the silica glass of ultraviolet perviousness brilliance.Use flange 1a, the two ends of 1b closed cylinder 1, the processed liquid that is taken into from water-in 10c is subjected to ultraviolet irradiation by the process in the cylinder 1, discharge from water outlet 1d.Processed liquid flows to water outlet 1d from water-in 1c in cylinder 1, but not really short for the path that processed liquid flow is crossed, and forms the structure that has disposed polylith (being 5 among the figure) plate 1e～1i that backflows on the way.In addition, for convenience's sake, in Figure 10, drawn and only carried the device of 1 discharge lamp, but the practical situation that goes up the large vol device that uses multi-lamp type is a lot.The ultraviolet ray of sending from discharge lamp 30 sees through outer tube 20, shines processed liquid.The ultraviolet ray of irradiation plays and for example makes the organism that exists in the water resolve into harmless CO, CO with being shown below
2, H
2The effect of O.
H
2O+hv (185nm) → H+OH base
C
nH
mO
k+ OH base → CO, CO
2, H
2O
(n, m, k are 1,2,3........)
This organism decomposition is to be undertaken by the action of ultraviolet ray in 185nm short wavelength zone, and still, the ultraviolet ray in short wavelength zone too much can produce and comprise hydrogen peroxide (H
2O
2) at interior all undesirable superoxide as intermediate.In order to remove this superoxide, the back segment setting of handling in uviolizing makes the operation of the processed liquid of end uviolizing processing by ion exchange resin.Thereby when processed liquid is removed these superoxide during by ion exchange resin, but too much superoxide causes the lost of life of ion exchange resin.
Summary of the invention
The present invention proposes in view of the above problems, the purpose of this invention is to provide ultraviolet liquid treatment unit and method that liquid treatment is carried out in the generation that suppresses superoxide as far as possible like that.The purpose of this invention is to provide again and can prolong the life-span of handling the ion exchange resin of back segment use in uviolizing therewith, long lifetime, photoresponse treatment unit and method that saving energy and saving are safeguarded together.
In addition, the present invention 1 provides a kind of organism to decompose and uses discharge lamp, this discharge lamp send the water molecules in liquid disassociation can be generated be used for to the contained organism of this liquid carry out disaggregating treatment the OH base, wavelength is the ultraviolet ray below the 220nm, utilize the above-mentioned OH base that is generated to come decomposing organic matter, it is characterized in that, with above-mentioned wavelength is ultraviolet ray below the 220nm, also send can with the peroxide breakdown that in the organism decomposition course, generates by the OH base of surplus, wavelength is the ultraviolet ray of 254nm; And on the internal surface of the luminotron pipe shaft that constitutes by silica glass, be formed for suppressing the film that above-mentioned wavelength is the metal oxide that descends of the ultraviolet illumination of 254nm, utilize the film of this metal oxide be used for preventing the red precipitate that when this discharge tube lighting, generated on the internal surface of above-mentioned luminotron pipe shaft absorption and suppress above-mentioned wavelength and descend for the ultraviolet illumination process in time of 254nm.
In addition, the present invention 2 decomposes with in the discharge lamp at the present invention's 1 described organism, above-mentioned luminotron pipe shaft constitutes by present good radioparent silica glass for the wavelength domain below the 220nm, and encloses an amount of mercury metal and rare gas in this luminotron pipe shaft; The above-mentioned metal oxide film that on the internal surface of above-mentioned luminotron pipe shaft, forms with by from aluminium, silicon, calcium, magnesium, yttrium, zirconium and hafnium, select at least a more than the oxide compound of metal be main component.
In addition, the present invention 3 is that the present invention's 2 described organism disaggregating treatment are with in the discharge lamp, the above-mentioned silica glass that constitutes above-mentioned luminotron pipe shaft use by with mineral crystal or silica sand as the raw material that sets out, by sodium, potassium, titanium and 4 kinds of total amounts of elementary composition element of iron below the 2.5ppm (mass ratio) and comprise the silica glass formation of the OH base more than the 10ppm (mass ratio).
In addition, the present invention 4 is that the present invention's 2 described organism disaggregating treatment are with in the discharge lamp, the above-mentioned silica glass that constitutes above-mentioned luminotron pipe shaft uses the synthetic quartz glass that has by internal diameter 8mm to 23mm to constitute, on the two ends of this luminotron, has a pair of filament at a distance of L centimetre of interval, lamp current with 0.4 ampere-1.4 amperes makes this discharge lamp work, apart from L centimetre, the inside diameter D millimeter of discharge path, have the following relationship formula between the modulating voltage V volt when lighting, lamp current I ampere, filament:
2.6≤X≤4.2，
Wherein, Vf is the constant factor relevant with lighting power supply, Vf=10 when being lighted by the high frequency electric source more than the 1kHz, Vf=50 when being lighted by the power supply of not enough 1kHz.
In addition, the present invention 5 provides a kind of fluid treatment appts, use one of the present invention 1～4 described organism disaggregating treatment discharge lamp, shining the wavelength that is sent by above-mentioned discharge lamp simultaneously to the liquid as process object is that ultraviolet ray and wavelength below the 220nm is the ultraviolet ray of 254nm, so that organism contained in this liquid is carried out disaggregating treatment.
In addition, the present invention 6 provides a kind of liquid treating method, use the present invention's 5 described fluid treatment apptss, it is characterized in that comprising following operation: use above-mentioned ultraviolet liquid treatment unit to come organism contained in the water as process object is carried out first operation of disaggregating treatment; With second operation of the above-mentioned water after handling through above-mentioned first operation being handled with the ion exchange resin that is located at above-mentioned back segment with the ultraviolet liquid treatment unit, make the few ultrapure water of impurity.
In addition, the feature of the ultraviolet liquid treatment unit relevant with the present invention is at the liquid of using the uviolizing that radiates from the discharge lamp that sends ultraviolet ray below the 220nm and 254nm together as process object, carry out in the fluid treatment appts of organism disaggregating treatment etc. of this liquid, as above-mentioned discharge lamp, use the discharge lamp that on its luminotron internal surface, forms metal oxide film.If according to the present invention, then by form metal oxide film on the luminotron internal surface of discharge lamp, the red precipitate that produces in the time of can preventing discharge tube lighting is adsorbed on the luminotron internal surface, can suppress the ultraviolet illumination of 254nm and descend.
Using from the ultraviolet discharge lamp that sends ultraviolet ray below the 220nm and 254nm together, the ultraviolet ray of the following wavelength region may of 220nm is relevant with the photochemical treatment that organism decomposes.On the other hand, the vital role of decomposing as the superoxide of intermediate is being undertaken in the ultraviolet ray of 254nm wavelength region may, alleviates the burden of handling the ion exchange resin of back segment use in uviolizing., the ultraviolet illumination of discharge lamp descends along with the process of duration of service, and for the ultraviolet ray in the following short wavelength of 220nm zone and the ultraviolet ray of 254nm wavelength region may, the reason that ultraviolet illumination descends is different.The reason that the ultraviolet illumination in the following short wavelength of 220nm zone descends is that the silica glass that becomes the discharge lamp body issues the matter that changes at ultraviolet irradiation ultraviolet ray transmissivity is reduced.On the other hand, the oxygen that produces in the pipe during reason discharge tube lighting that the ultraviolet illumination of 254nm wavelength region may descends and the mercury red precipitate that generates that reacts is adsorbed on the silica glass internal surface, makes the ultraviolet ray transmissivity reduction of silica glass.Therefore, we consider for the ultraviolet ray in the following short wavelength of 220nm zone and the ultraviolet ray of 254nm wavelength region may, as shown in Figure 9, it is different that ultraviolet illumination is separately kept characteristic, because 254nm ultraviolet ray one quadrature degree descends soon, so the sustainment rate of 254nm drops to after the C point of the ultraviolet illumination sustainment rate of (for example 185nm) below the 220nm among Fig. 9, cause superoxide to increase.In contrast, if according to the present invention, then by form metal oxide film on the luminotron internal surface of discharge lamp, the red precipitate that produces in the time of can preventing discharge tube lighting is adsorbed on the luminotron internal surface, can suppress the ultraviolet illumination of 254nm and descend.
Again, the feature of the ultraviolet liquid treatment unit relevant with the present invention is at the liquid of using the uviolizing that radiates from the ultraviolet discharge lamp that sends ultraviolet ray below the 220nm and 254nm together as process object, carry out in the fluid treatment appts of organism disaggregating treatment etc. of this liquid, as above-mentioned discharge lamp, the luminotron that uses this discharge lamp be by with mineral crystal or silica sand as the raw material that sets out, by sodium, potassium, 4 kinds of total amounts of elementary composition element of titanium and iron are below 2.5ppm, comprise that the silica glass of the above OH base of 10ppm constitutes, on this luminotron internal surface, form the discharge lamp of metal oxide film.
In the silica glass as the raw material that sets out, comprising various materials as impurity with mineral crystal or silica sand.In these impurity, also exist a lot of sodium (Na), potassium (K), titanium (Ti) and 4 kinds of elements of iron (Fe) become the reason that causes the silica glass transmitance to descend.On the other hand, the existence of OH base can relax the rotten of silica glass.That is, as the silicon-dioxide (SiO of the main component of silica glass
2) " Si-O " produce the free Si become the reason that transmitance descends in conjunction with decomposing owing to ultraviolet energy, can suppress this decline but the OH base combines formation " Si-OH " with free Si.The present inventor tests and studies, and the result distinguishes total amount when these 4 kinds of elements below 2.5ppm, and when comprising the above OH base of 10ppm, can improve greatly because the UV-induced silica glass deterioration in time in short wavelength zone.Therefore, by material so selected or the setting silica glass, can improve the ultraviolet illumination sustainment rate in 220nm following short wavelength zone, by on the luminotron internal surface of high performance discharge, forming metal oxide film, can further bring into play and suppress the effect that the ultraviolet illumination of 254nm descends like this.
Again, the feature of the ultraviolet liquid treatment unit relevant with the present invention is at the liquid of using the uviolizing that radiates from the ultraviolet discharge lamp that sends ultraviolet ray below the 220nm and 254nm together as process object, carry out in the fluid treatment appts of organism disaggregating treatment etc. of this liquid, as above-mentioned discharge lamp, use have the luminotron that constitutes by the synthetic quartz glass more than the internal diameter 8mm and on the two ends of this luminotron at a distance of L (cm) a pair of filament at interval, enclose rare gas in inside and contain the metal of mercury at least, modulating voltage when lighting is that V (V) is I (A) with lamp current, between filament apart from L (cm), the inside diameter D of discharge path (mm) has the following relationship formula, and forms the discharge lamp of metal oxide film on above-mentioned luminotron internal surface.
2.6≤X≤4.2
But Vf is the constant factor relevant with lighting power supply, and Vf=10 when being lighted by the high frequency electric source more than the 1kHz is as Vf=50 when lighting less than the power supply of 1kHz.Situation will be stated in the back in detail, but by as above-mentioned relational expression, imposing a condition, the ultraviolet ray in the following short wavelength of radiation 220nm zone expeditiously, by on the luminotron internal surface of this high performance discharge, forming metal oxide film, can further bring into play and suppress the effect that the ultraviolet illumination of 254nm descends.
Preferential enforcement sample attitude of the present invention is the metal oxide film that forms on the luminotron internal surface of above-mentioned discharge lamp with by aluminium, silicon, and calcium, magnesium, yttrium, the oxide compound of at least a above metal of selecting in zirconium and the hafnium is a main component.These metal oxides are because have remarkable thermotolerance, say from science also very stable, so play a part to prevent effectively that red precipitate is adsorbed on the luminotron internal surface.
The feature of further relevant with the present invention ultraviolet liquid treatment process is to use the discharge lamp that forms metal oxide film on luminotron internal surface as described above, with the liquid of uviolizing, carry out the organism disaggregating treatment of this liquid etc. as process object.
Description of drawings
Fig. 1 is the side cross-section sketch chart that is illustrated in an embodiment of the discharge lamp that uses in the ultraviolet liquid treatment unit relevant with the present invention.
Fig. 2 be expression from light for a long time by sodium (Na), the graphic representation of the ultraviolet illumination sustainment rate curve that potassium (K), titanium (Ti) and iron (Fe) obtain as the experiment of the various discharge lamps of the composition of silica glass making.
Fig. 3 is the graphic representation of " potential gradient " with the relation of " 185nm ultraviolet radiation efficient " of the experimental result of representing that for example an embodiment of discharge lamp used according to the invention obtains.
Fig. 4 is " lamp current " of the experimental result of representing that for example an embodiment of discharge lamp used according to the invention obtains and the graphic representation of the relation of best " potential gradient ".
Fig. 5 is the Glass tubing internal diameter of the experimental result of representing that for example an embodiment of discharge lamp used according to the invention obtains and the relation of best " potential gradient ", the graphic representation corresponding with each value of " lamp current ".
Fig. 6 is the graphic representation of an example of the ultraviolet illumination sustainment rate of the 185nm of the discharge lamp that uses of expression the present invention and 254nm.
Fig. 7 is that the expression fluid treatment appts relevant with the present invention is the experimental result and the existing device graphic representation relatively through changing in time of TOC disaggregating treatment ability in the UV irradiation equipment for example.
Fig. 8 be for example the expression fluid treatment appts relevant with the present invention be in the UV irradiation equipment the resistivity value of ion exchange resin outlet over time with the graphic representation of existing device comparison.
Fig. 9 is the graphic representation of an example of the ultraviolet illumination sustainment rate of the 185nm of discharge lamp of expression prior art and 254nm.
Figure 10 is the side cross-section sketch chart that an example of the UV irradiation equipment that has discharge lamp is used in expression.
Embodiment
Below we with reference to description of drawings example of the present invention.
Fig. 1 is illustrated in an embodiment of the discharge lamp that uses in liquid reactions treatment unit relevant with the present invention and the method.At first we illustrate the essential structure of this discharge lamp 31, discharge lamp 31 has the ultraviolet such formation that can send below the 220nm for example ultraviolet ray in the short wavelength zone of 185nm and 254nm together, comprise luminous envelope 11, in this luminous envelope 11, be configured in a pair of filament 21a at its two ends, 21b, be arranged on the hermetic unit 2a at these luminous envelope 11 two ends, 2b and base part 3a, 3b.By internal diameter 13mm, the synthetic quartz glass of wall thickness 1mm constitutes luminous envelope 11 as an example, forms metal oxide film 44 on interior surfaces of glass.Film 44 for example is to be made of the such chemically stable material of thermotolerance brilliance of oxidation Al.With filament 21a, 21b is configured between two filaments on the interval of 153cm.
At these filaments 21a, be coated with for example radiator of barium oxide system of apposition on the 21b, these filaments 21a, 21b are respectively by from hermetic unit 2a, and internal lead 22a～22d that 2b draws maintains.Base part 3a, 3b are that pottery is made, and have a pair of electric terminal 31a, 31b at a base part 3a.Hermetic unit 2a, 2b play by molybdenum foil 24a～24d and keep resistance to air loss, and by internal lead 22a～22d, molybdenum foil 24a～24d, outer lead 25a, 25b and 26 makes filament 21a, 21b and electric terminal 31a, the effect that 31b is electrically connected.Mercury in luminous envelope 11 about inclosure 20mg and the rare gas of about 400Pa.In addition, in the example shown in the figure, as an example, discharge lamp 31 constitutes the discharge lamp of 2 terminal types.That is, the end of a side filament 21a is by internal lead 22b, molybdenum foil 24b, and outer lead 25a is connected with a side electric terminal 31a, and the end of the opposing party's filament 21b passes through internal lead 22c, molybdenum foil 24c, outer lead 25b, 26 are connected with the opposing party's electric terminal 31b.
As mentioned above, the ultraviolet illumination of discharge lamp descends along with the process of duration of service, the oxygen that produces in the pipe when reason that the ultraviolet illumination of 254nm wavelength region may descends is discharge tube lighting and the mercury red precipitate that generates that reacts is adsorbed on the interior surfaces of glass, makes the ultraviolet ray transmissivity reduction of silica glass.This be because as the ultraviolet ray of the 254nm of the resonance luminescence of mercury because the existence generation self-absorption of mercury, red precipitate is adsorbed on the above-mentioned interior surfaces of glass, and the ultraviolet ray transmissivity of 254nm is selectively descended.In view of this point, the feature of the discharge lamp that uses among the present invention is to form metal oxide (being oxidation Al in the present embodiment) film 44 on the interior surfaces of glass of luminous envelope 11, prevent that by this film 44 red precipitate is adsorbed on the interior surfaces of glass, can suppress the ultraviolet illumination of 254nm and descend.In addition, be coated on the Glass tubing internal surface and after super-dry, carry out heat treated, can easily form film 44 in oxidizing atmosphere by the solution that before enclosing filament, in advance the fines of oxidation Al is suspended in agglutinant in the butyl acetate.
In an embodiment of the present invention, will have above-mentioned such discharge tube that constitutes 31 as the luminescence-utraviolet source in the fluid treatment appts.The formation of fluid treatment appts self both can be a locking type fluid treatment appts for example shown in Figure 10, also can be the fluid treatment appts of water route style of opening.Again, the number of the discharge lamp 31 that uses in 1 fluid treatment appts can be not limited to 1 but many.
The material of the luminous envelope 11 of the discharge lamp 31 relevant with present embodiment both can be with mineral crystal or the silica sand fused silica glass as the raw material that sets out, and also can be synthetic quartz glass.
At first, our explanation constitutes an example of the material of luminous envelope 11 with fused silica glass.For example, the silica glass of luminous envelope 11 be with mineral crystal or silica sand as the raw material that sets out, by sodium (Na), potassium (K), 4 kinds of total amounts of elementary composition element of titanium (Ti) and iron (Fe) comprise that the gas fused silica glass of the above OH base of 10ppm constitutes below 2.5ppm.Like this, by in the silica glass of the material of the luminous envelope 11 that constitutes discharge lamp 31 except sodium (Na), potassium (K), titanium (Ti) and 4 kinds of elements of iron (Fe) also comprise the OH base outward, can improve greatly because the silica glass deterioration of process in time of the luminous envelope 11 that the short wavelength ultraviolet that discharge lamp 31 sends causes.
Fig. 2 is with as the composition of silica glass, sodium (Na), potassium (K), titanium (Ti), the total amount of iron (Fe) and the amount of OH base be as parameter, to the various discharge lamps made through lighting the uitraviolet intensity sustainment rate curve that experiment obtains for a long time.In the shape of discharge lamp, in all identical situation of size, transverse axis is the time of lighting, and the longitudinal axis is will be according to the intensity initial value of discharge lamp of the present invention uitraviolet intensity as 100% o'clock 185nm wavelength.With each curve A, B, C, the composition condition of silica glass is as shown in the table in each discharge lamp of D correspondence.
Table 1
Curve A is to satisfy the sodium (Na) of present embodiment definition, and potassium (K), 4 kinds of total amounts of elementary composition element of titanium (Ti) and iron (Fe) comprise the condition of the above OH base of 10ppm below 2.5ppm, curve B, and C, D do not satisfy this condition.As in that we see that curve A is represented the optimum among Fig. 2, by setting as the impurity natrium in the silica glass (Na) according to the present invention, potassium (K), titanium (Ti), the total amount of 4 kinds of elements of iron (Fe) and the amount of OH base can improve the ultraviolet illumination sustainment rate of the short-and-medium wavelength region may of time course greatly.In addition, when carrying out the experiment of Fig. 2, in atmosphere, take place owing to ozone,, measure so ultraviolet ray intensity meter directly is attached to the discharge lamp outside because the ozone that produces causes measured value scattered between discharge lamp and ultraviolet ray intensity meter like this to ultraviolet reaction generation.
In being suitable for the technical field of the ultraviolet organism disaggregating treatment of usefulness of the present invention etc., because no matter the size of the input density of discharge lamp, generally will use ultraviolet sustainment rate after 1 year to remain on 70% design apparatus like that, so from this viewpoint, we see that it is effective that the result's who causes Fig. 2 curve A silica glass is formed, and cause Fig. 2 curve B, and C, it obviously is invalid that the result's of D silica glass is formed.Like this, if as the impurity natrium in the silica glass (Na), potassium (K), titanium (Ti), total amount of 4 kinds of elements of iron (Fe) be at " below the 2.5ppm ", then can guarantee to use ultraviolet sustainment rate after 1 year more than 70%.In addition, if do not have note, be not enough in conjunction with effect again for Si-OH then less than 10ppm about the amount of OH base.
In addition, by the silica glass that above-mentioned starting material constitute, be not limited to the luminous envelope of discharge lamp self, also can be used in any part of using in the ultraviolet ray that is exposed to the following wavelength region may of 220nm, portion's product are in the device.The material of for example, can the be enough relevant silica glass conduct ultraviolet perviousness glass wall on outer tube (protective tube) 20 as shown in Figure 4 with the present invention.The outer tube of this collection discharge tube (protective tube) is that the shape of container is not limited to round shape, also can be Any shape.
Certainly, the type of fused silica glass that constitutes the luminous envelope 11 of the discharge lamp 31 relevant with present embodiment is not limited to the above-mentioned gas fusion, for example also can be the electrofuse type.
Further, the feature of other example of the discharge lamp 31 relevant with present embodiment is to constitute luminous envelope 11 with synthetic quartz glass, at this moment, in the make decision size (between envelope internal diameter and filament distance etc. all sizes) of this discharge lamp 31 of the ultraviolet institute fixed condition that can send wavelength 185nm expeditiously.
We will carry out detailed stating in the back, still, therefore, can reach the ultraviolet illumination sustainment rate in the short wavelength zone of improving discharge lamp, and, the purpose of the ultraviolet illumination efficient in raising short wavelength zone.In this high performance discharge lamp, the use for discharge lamp that descends when the ultraviolet illumination that will suppress 254nm is in the UV irradiation equipment that treatment liq is used the time, improve processing power and make the purpose that increases by leaps and bounds device lifetime because can reach, so have great meaning.
Our explanation is now constituting in the situation of luminous envelope 11 example that imposes a condition of the size of discharge lamp 31 (between envelope internal diameter and filament distance etc. all sizes) with synthetic quartz glass.The feature of the discharge lamp 31 relevant with present embodiment be for the ultraviolet ray that can send wavelength 185nm expeditiously like that, the inside diameter D (mm of unit) of the luminous envelope 11 that is made of synthetic quartz glass is of a size of more than the 8mm, make filament 21a, 21b is spaced apart L (cm of unit), modulating voltage when lighting is V (V of unit (volt)), when lamp current is I (A of unit (peace)), has the relation that the following relationship formula is set each value like that.
Here, Vf is an anode drop voltage, is by the factor of lighting the unique decision of power supply (constant factor), and Vf=10 when being lighted by the high frequency electric source more than the 1kHz is as Vf=50 when lighting less than the power supply of 1kHz.
Secondly, we illustrate the basis that derives relational expression as described above as the ultraviolet condition of sending wavelength 185nm expeditiously.
Present inventors are ready to the identical discharge lamp of a plurality of essential structures with various size and discharge lamp shown in Figure 1 31, and they are carried out all experiments as object, and the electrical characteristic of discharge lamp and the relation of 185nm uitraviolet intensity are reviewed.Specifically, the size of each used discharge lamp is to use internal diameter 8mm in these experiments, 13mm, and 18mm, each caliber of 23mm, wall thickness 1mm, the synthetic quartz glass pipe of pipe range 100～160cm will be set at 95～153cm apart from L (cm) between filament.When experiment, with the arm that is used to measure the 185nm uitraviolet intensity, constitute the interior discharge lamp that inserts as experimental subjects of Glass tubing of T font at middle body, in this Glass tubing, be full of nitrogen and water coolant in flows outside.Again, be ready to the electric ballast (stabilizer) of about 40kHz and the such two kinds of barretters in electromagnetic ballast (stabilizer) of commercial frequency in lighting power supply, the lamp current when order is lighted is divided into 0.4A, 0.6A, 0.8A, 1.0A, 5 stages of 1.4A (peace).In addition, carry out the mensuration of 185nm uitraviolet intensity with ultraviolet luxmeter UV-185 (trade(brand)name).
Under these conditions, it is constant that electric current roughly keeps, and it is modulating voltage V that the temperature that one side changes water coolant is simultaneously measured various electrical characteristic, lamp current I, lamp power and 185nm uitraviolet intensity.The reason that changes temperature of cooling water is in order to change mercury vapour pressure.That is, this is because consider that 185nm ultraviolet radiation efficient is relevant with mercury vapour pressure with electrical characteristic, so want clear and definite this relation.The temperature of the coldest part by changing that temperature of cooling water changes that residue mercury is detained changes mercury vapour pressure.By the way say, because the mercury vapour pressure in modulating voltage V and the lamp is that steam output is relevant, so, can set modulating voltage V changeably by changing the temperature of cold part.In the discharge lamp that constitutes by this physical size, because lamp current I also is the constant factor by barretter decision, so factor that can left and right sides 185nm uitraviolet intensity mainly is modulating voltage V.Therefore, by changing temperature of cooling water, the result can change modulating voltage V makes it have various values, by the each simultaneously 185nm of mensuration uitraviolet intensity of the value of measuring this modulating voltage V, can distinguish by this physical size and decide under the condition that lamp current I constitutes the dependency of 185nm uitraviolet intensity and modulating voltage V.For this reason, carry out such mensuration.
According to this measurement result, about the 185nm uitraviolet intensity, viewpoint from " uitraviolet intensity of per unit consumption of electric power ", with the value of the 185nm uitraviolet intensity measured divided by the lamp electric power of measuring, with its merchant as the index (i.e. " 185nm ultraviolet radiation efficient ") of " radiation efficiency ".Again, about modulating voltage, viewpoint from " voltage of per unit length ", deduct the fixed value Vf (V) that is called anode drop voltage (Vf) from the lamp voltage value V (V) that measures, with it result " V-Vf " divided by between filament apart from L, this is discussed as " potential gradient " (that is the modulating voltage of distance between the filament of per unit length).Promptly, be converted into " 185nm ultraviolet radiation efficient " and " potential gradient " (modulating voltage of distance between the filament of per unit length) respectively by " the 185nm uitraviolet intensity " and " modulating voltage V " that will measure, can contrast the value of " 185nm ultraviolet radiation efficient " corresponding with each value of " potential gradient ", should be which type of thereby can grasp the high condition of radiation efficiency.In addition, about anode drop voltage Vf, as mentioned above, Vf=10 when being lighted by the high frequency electric source more than the 1kHz is as Vf=50 when lighting less than the power supply of 1kHz.
Fig. 3 is expression, as an example, be of a size of internal diameter 13mm at discharge lamp with the synthetic quartz glass pipe of wall thickness 1mm, pipe range 154cm, under the physical condition apart from 147cm between filament, when as electric condition, lamp current I is 1A (peace), the figure of the measurement result of " potential gradient " and " 185nm ultraviolet radiation efficient " when using the electric ballast (being Vf=10) of about 40kHz, be that to make the value of " potential gradient " be transverse axis, with the value of its corresponding " 185nm ultraviolet radiation efficient " be the longitudinal axis, with the figure of curve representation measurement result.As mentioned above, by changing the temperature change modulating voltage V of water coolant.If according to Fig. 2, then we distinguish when " potential gradient " is about 0.88 (V/cm), and " 185nm ultraviolet radiation efficient " reaches maximum (" 6 " approximately).If thereby judge make " 185nm ultraviolet radiation efficient " be in the maximum that comprises it be in the peak value suitable allowed band of (being about " 6 " in the example of Fig. 2) like that, set all conditions of physics and electricity, ultraviolet discharge lamp of radiation 185nm and UV irradiation equipment expeditiously then can be provided.As this allowed band,, distinguish that it is suitable that about 60～70% of " 185nm ultraviolet radiation efficient " peak value is included in the allowed band by observing actual uviolizing state.For example, in the example of Fig. 3, if " 185nm ultraviolet radiation efficient " even if value minimum also more than 3.6, then can think to access high efficiency radiation.At this moment, can distinguish preferably that from figure " potential gradient " is in about 0.72～1.16 the scope sets all conditions like that.
Further we illustrate other measured result.At the size caliber 13mm identical with Fig. 3, pipe range 154cm, in the discharge lamp apart from 147cm between filament, change lamp current I and make it have various value, make " 185nm ultraviolet radiation efficient " become the best " potential gradient " of peak value in each lamp current value exploration.The best " potential gradient " (transverse axis) of each lamp current value (longitudinal axis) that will obtain from this result is drawn as graphic representation, as shown in Figure 4.From Fig. 4 we judge the best " potential gradient " roughly with the square root of lamp current value (I) (
) be inversely proportional to.
Below similarly, discharge lamp for the above-mentioned overall dimension of using in this experiment, exploration makes " 185nm ultraviolet radiation efficient " become the best " potential gradient " of peak value, the result, we find at the caliber of sample whatsoever, best " potential gradient " roughly with the square root of lamp current value (I) (
) be inversely proportional to.Again, as the parameter the best " potential gradient " of drawing, we distinguish as shown in Figure 5 at the electric current of sample whatsoever as a result with caliber (D), best " potential gradient " also roughly with the square root of caliber (D) (
) be inversely proportional to.That is, we find at internal diameter (D) is in the discharge lamp of 8～23mm, when in the scope of lamp current 0.4～1.4A, working, for the best " potential gradient " of the radiation efficiency that obtains maximum 185nm and the square root of caliber (D) and current value (I) (
With
) be inversely proportional to.Result if this becomes the factor of only considering the some light current in any one situation of the electromagnetic ballast of high-frequency electric ballast and commercial frequency in also it being included in.
As mentioned above, in best " potential gradient ", " potential gradient " promptly " (V-Vf)/L " have and the square root of caliber (D) (
) and the square root of lamp current I (
) relation that is inversely proportional to, when making this rate constant be X, represent by following such relational expression.
In the example of above-mentioned Fig. 3, because inside diameter D=13mm, lamp current I=1A, so (
) be about 3.605, so for " potential gradient " is in above-mentioned about 0.72～1.16 the allowed band, rate constant X preferably gets the roughly value in the scope of " 2.6≤X≤4.2 ".
Consider above experimental result, in discharge lamp 31 with the luminotron that constitutes by synthetic quartz glass 11 shown in Figure 1, the inside diameter D (mm of unit) of the luminotron 11 that is made of synthetic quartz glass is of a size of more than the 8mm, make filament 21a, 21b is spaced apart L (cm of unit), modulating voltage when lighting is V (V of unit (volt)), when lamp current is I (A of unit (peace)), have the following relationship formula and set the relation of each value like that, obtain for the conclusion preferably and so on of the ultraviolet condition of radiation 185nm expeditiously.
Here, as mentioned above, as anode drop voltage Vf Vf=10 when lighting, as Vf=50 when lighting less than the power supply of 1kHz by the high frequency electric source more than the 1kHz by the factor of lighting the unique decision of power supply.
Like this, discharge lamp 31 related to the above-described embodiments, as a example according to above-mentioned condition, internal diameter 13mm except luminous envelope, between filament apart from 153cm, outside the material of luminous envelope 11 is made of synthetic quartz glass, as shown in Figure 1, on above-mentioned luminous envelope 11 internal surfaces, form the film 44 of metal oxide (being oxidation Al as an example in the present embodiment).
Secondly, we illustrate with reference to Fig. 6 and light the experimentize measurement result of the ultraviolet illumination sustainment rate that obtains of this discharge lamp 31 between long-term.In Fig. 6, transverse axis is the time of lighting, and the longitudinal axis is will be according to the illumination initial value of discharge lamp of the present invention ultraviolet illumination as 100% o'clock 185nm and 254nm wavelength.Form film 44 on luminous envelope 11 internal surfaces, we distinguish the decline of ultraviolet illumination that almost can't see the 254nm wavelength region may as a result, compare with above-mentioned existing discharge lamp shown in Figure 9, have improved the illumination sustainment rate by leaps and bounds.Again, we distinguish the ultraviolet illumination sustainment rate that has also greatly improved the 185nm wavelength region may.
Because being UV irradiation equipment, the ultraviolet liquid treatment unit relevant with the present invention be used for the refining of ultrapure water that semi-conductor manufacturing process for example uses, so at this moment must be able to stand the long-term continuous operation in 1 year～3 years.If use, then can reach and improve TOC (Total Organic Carbon: full organic body carbon) disaggregating treatment ability and the effect that multiplies each other that alleviates the ion exchange resin burden according to discharge lamp of the present invention.Thereby the present invention is optimum for the refinement treatment of the middle ultrapure waters that use such as semi-conductor manufacturing process.Certainly, the ultraviolet liquid treatment unit relevant with the present invention is not limited to semi-conductor manufacturing process, also can be used for drink manufacturing, food mfg, and the wide spectrum of liquid treatment is implemented in medical treatment, water treatment etc. for organic disaggregating treatment sterilization and disinfection etc.Fig. 7 is expression about carrying according to the UV irradiation equipment B of the discharge lamp of prior art and carry the UV irradiation equipment A of the described discharge lamp of embodiments of the invention, reaches the figure of the measured data of the processing power below the 1ppb than their the former water that makes TOC concentration 10ppb with the throughput ratio of per unit consumption of electric power amount.The initial value that the figure shows with device B is 100%.We can judge in existing device B and apparatus of the present invention A, have big poor performance at first in the early stage, along with the increase difference of duration of service becomes bigger.The raising of this TOC processing power is because the raising of 185nm ultraviolet radiation efficient and sustainment rate causes, but the ultraviolet ray in short wavelength zone too much, as mentioned above, generate too much superoxide, the lost of life that causes ion exchange resin, yet, if use the discharge lamp relevant with the present invention, then can descend, alleviate the burden of ion exchange resin by suppressing the ultraviolet illumination of 254nm.
Fig. 8 measures according to the UV irradiation equipment B of prior art and uses the result of the processing resistivity of water among the UV irradiation equipment A of the described discharge lamp of the embodiment of the invention in the outlet of the ion exchange resin operation of back segment.In Fig. 8, the longitudinal axis is represented resistivity value, and transverse axis is represented the time of lighting.Resistivity value is relevant with the concentration of superoxide, and the concentration of superoxide is high more, and resistivity value is low more.That is, leak increase because ion exchange resin worsens the superoxide that causes, resistivity value descends, so the resistivity value of ion exchange resin outlet becomes the index of ion exchange resin deterioration level over time.Use the resistivity value at initial stage all strong in any one device of existing device B and apparatus of the present invention A as 18M Ω at device, but the moment behind 1 year of when device is brought into use, counting, the resistivity value of existing device B is reduced to about 16M Ω that will upgrade ion exchange resin, in contrast, distinguished in apparatus of the present invention A, decline through back resistivity value between the usage period also is few, can alleviate the burden of ion exchange resin.This is because the ultraviolet illumination sustainment rate of 254nm wavelength region may improves by leaps and bounds, has kept the peroxide treatment ability.
As mentioned above, the present invention sends in the ultraviolet discharge lamp of 220nm following short wavelength zone and 254nm together, on the luminotron internal surface, form metal oxide film, improved the ultraviolet illumination sustainment rate of 254nm, use from the ultraviolet ray of this discharge lamp the liquid as process object is carried out processing such as organism decomposition, promote the invention that undesirable intermediate product is decomposed.In the above-described embodiments, we have illustrated with synthetic quartz glass and have constituted luminotron, in the make decision size of this discharge lamp of the ultraviolet institute fixed condition that can send wavelength 185nm expeditiously, though at this moment can access king-sized action effect, but enforcement sample attitude of the present invention is not limited thereto, for example, as the starting material of above-mentioned luminotron, also can access same action effect during with common (natural) silica glass.Again, we have illustrated the metal oxide as the film that forms on the interior surfaces of glass of discharge lamp, use the situation of oxidation Al as example, but be not limited thereto, if with from Al, silicon, calcium, magnesium, yttrium, the oxide compound of at least a above metal of selecting in zirconium and the hafnium is a main component, then also is effective.In addition, the form of discharge lamp, if send following wavelength region may of 220nm and the ultraviolet discharge lamp of 254nm together, then at the alloy type discharge lamp of enclosing mercury and other metal, continuous hot type that filament is always heating or filament and anode merge in any form that type or the like is set can both use the present invention, can access same action effect.
As mentioned above, if according to the present invention, then significantly improved the ultraviolet illumination sustainment rate of the 254nm in the ultraviolet discharge lamp that sends following wavelength region may of 220nm and 254nm together, improved the following ultraviolet radiation efficient of 220nm simultaneously, by having improved the illumination sustainment rate, in fluid treatment appts that uses this discharge lamp and method, can reach the long lifetime of each equipment machine and save energy, save the effect of safeguarding.
Claims (6)
1. an organism decomposes and uses discharge lamp, this discharge lamp send the water molecules in liquid disassociation can be generated be used for to the contained organism of this liquid carry out disaggregating treatment the OH base, wavelength is the ultraviolet ray below the 220nm, utilize the above-mentioned OH base that is generated to come decomposing organic matter, it is characterized in that
With above-mentioned wavelength is ultraviolet ray below the 220nm, also send can with the peroxide breakdown that in the organism decomposition course, generates by the OH base of surplus, wavelength is the ultraviolet ray of 254nm;
And on the internal surface of the luminotron pipe shaft that constitutes by silica glass, be formed for suppressing the film that above-mentioned wavelength is the metal oxide that descends of the ultraviolet illumination of 254nm,
Utilize the film of this metal oxide be used for preventing the red precipitate that when this discharge tube lighting, generated on the internal surface of above-mentioned luminotron pipe shaft absorption and suppress above-mentioned wavelength and descend for the ultraviolet illumination process in time of 254nm.
2. organism as claimed in claim 1 decomposes uses discharge lamp, it is characterized in that,
Above-mentioned luminotron pipe shaft constitutes by present good radioparent silica glass for the wavelength domain below the 220nm, and encloses an amount of mercury metal and rare gas in this luminotron pipe shaft; The above-mentioned metal oxide film that on the internal surface of above-mentioned luminotron pipe shaft, forms with by from aluminium, silicon, calcium, magnesium, yttrium, zirconium and hafnium, select at least a more than the oxide compound of metal be main component.
3. organism disaggregating treatment discharge lamp according to claim 2 is characterized in that,
The above-mentioned silica glass that constitutes above-mentioned luminotron pipe shaft use by with mineral crystal or silica sand as the raw material that sets out, by sodium, potassium, titanium and 4 kinds of total amounts of elementary composition element of iron below mass ratio 2.5ppm and to comprise mass ratio be that the silica glass of the OH base more than the 10ppm constitutes.
4. organism disaggregating treatment discharge lamp according to claim 2 is characterized in that,
The above-mentioned silica glass that constitutes above-mentioned luminotron pipe shaft uses the synthetic quartz glass that has by internal diameter 8mm to 23mm to constitute, on the two ends of this luminotron, has a pair of filament at a distance of L centimetre of interval, lamp current with 0.4 ampere-1.4 amperes makes this discharge lamp work, apart from L centimetre, the inside diameter D millimeter of discharge path, have the following relationship formula between the modulating voltage V volt when lighting, lamp current I ampere, filament:
2.6≤X≤4.2，
Wherein, Vf is the constant factor relevant with lighting power supply, Vf=10 when being lighted by the high frequency electric source more than the 1kHz, Vf=50 when being lighted by the power supply of not enough 1kHz.
5. any described organism that is equipped with as claim 1～4 decomposes the ultraviolet liquid treatment unit of using discharge lamp, it is characterized in that,
Shining the wavelength that is sent by above-mentioned discharge lamp simultaneously to the liquid as process object is that ultraviolet ray and wavelength below the 220nm is the ultraviolet ray of 254nm, so that organism contained in this liquid is carried out disaggregating treatment.
6. ultraviolet liquid treatment process, this method uses ultraviolet liquid treatment unit as claimed in claim 5 to carry out, and it is characterized in that comprising following operation:
Use above-mentioned ultraviolet liquid treatment unit to come organism contained in the water as process object is carried out first operation of disaggregating treatment; With
With second operation that the ion exchange resin that is located at above-mentioned back segment with the ultraviolet liquid treatment unit is handled the above-mentioned water after handling through above-mentioned first operation, make the few ultrapure water of impurity.
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| Application Number | Priority Date | Filing Date | Title |
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| CNB021527431A CN100391858C (en) | 2002-11-27 | 2002-11-27 | Ultraviolet ray device for treating liquid and method thereof |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB021527431A CN100391858C (en) | 2002-11-27 | 2002-11-27 | Ultraviolet ray device for treating liquid and method thereof |
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| CN100391858C true CN100391858C (en) | 2008-06-04 |
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| CN100417601C (en) * | 2005-09-01 | 2008-09-10 | 上海化工研究院 | Purifying method of removing bacteria and organic compound in heavy oxygen water |
| CN101402484B (en) * | 2008-07-21 | 2011-07-13 | 北京桑德环保集团有限公司 | Free radical deep oxidization reactor |
| JP2012250166A (en) * | 2011-06-02 | 2012-12-20 | Stanley Electric Co Ltd | Liquid purification treatment apparatus of double tube structure |
| WO2019225303A1 (en) * | 2018-05-22 | 2019-11-28 | ウシオ電機株式会社 | Light transmissive material and lamp, and gas treating device and gas treating method |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN2256876Y (en) * | 1996-06-14 | 1997-06-25 | 杨昕 | Ultra-violet water sterilizer |
| JPH11300344A (en) * | 1998-04-21 | 1999-11-02 | Nippon Photo Science:Kk | Bactericidal lamp and bactericidal lamp device |
| JP2000357491A (en) * | 1999-06-11 | 2000-12-26 | Nippon Photo Science:Kk | Low-pressure mercury vapor discharge lamp and ultraviolet ray irradiating device using thereof |
| US20020024278A1 (en) * | 2000-03-14 | 2002-02-28 | Ryoutarou Matsuda | Ultraviolet ray lamp and sterilizers and cleaners using the lamp |
| JP2002097036A (en) * | 2000-09-21 | 2002-04-02 | Photoscience Japan Corp | Vitreous silica for short wavelength ultraviolet ray, discharge lamp using it, the container, and ultraviolet ray radiation device |
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2002
- 2002-11-27 CN CNB021527431A patent/CN100391858C/en not_active Expired - Lifetime
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN2256876Y (en) * | 1996-06-14 | 1997-06-25 | 杨昕 | Ultra-violet water sterilizer |
| JPH11300344A (en) * | 1998-04-21 | 1999-11-02 | Nippon Photo Science:Kk | Bactericidal lamp and bactericidal lamp device |
| JP2000357491A (en) * | 1999-06-11 | 2000-12-26 | Nippon Photo Science:Kk | Low-pressure mercury vapor discharge lamp and ultraviolet ray irradiating device using thereof |
| US20020024278A1 (en) * | 2000-03-14 | 2002-02-28 | Ryoutarou Matsuda | Ultraviolet ray lamp and sterilizers and cleaners using the lamp |
| JP2002097036A (en) * | 2000-09-21 | 2002-04-02 | Photoscience Japan Corp | Vitreous silica for short wavelength ultraviolet ray, discharge lamp using it, the container, and ultraviolet ray radiation device |
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