CN112082902B - Device for improving density of OH free radicals discharged in water and measuring method thereof - Google Patents
Device for improving density of OH free radicals discharged in water and measuring method thereof Download PDFInfo
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- CN112082902B CN112082902B CN202010726137.0A CN202010726137A CN112082902B CN 112082902 B CN112082902 B CN 112082902B CN 202010726137 A CN202010726137 A CN 202010726137A CN 112082902 B CN112082902 B CN 112082902B
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- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 title claims abstract description 37
- 238000000034 method Methods 0.000 title claims abstract description 16
- 150000003254 radicals Chemical class 0.000 claims abstract description 62
- 230000001965 increasing effect Effects 0.000 claims abstract description 8
- 238000006243 chemical reaction Methods 0.000 claims abstract description 7
- 239000000243 solution Substances 0.000 claims description 25
- 238000004448 titration Methods 0.000 claims description 12
- 239000000523 sample Substances 0.000 claims description 11
- 230000005611 electricity Effects 0.000 claims description 9
- 239000007864 aqueous solution Substances 0.000 claims description 6
- 238000000691 measurement method Methods 0.000 claims 1
- 230000001960 triggered effect Effects 0.000 claims 1
- 150000002500 ions Chemical class 0.000 abstract description 7
- 230000009471 action Effects 0.000 abstract description 2
- 230000000694 effects Effects 0.000 description 7
- 238000005516 engineering process Methods 0.000 description 6
- 230000003647 oxidation Effects 0.000 description 6
- 238000007254 oxidation reaction Methods 0.000 description 6
- 238000007599 discharging Methods 0.000 description 4
- 230000035939 shock Effects 0.000 description 4
- 230000005684 electric field Effects 0.000 description 3
- 238000005259 measurement Methods 0.000 description 3
- 230000002708 enhancing effect Effects 0.000 description 2
- 239000013307 optical fiber Substances 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 230000010349 pulsation Effects 0.000 description 2
- 230000005855 radiation Effects 0.000 description 2
- 230000009257 reactivity Effects 0.000 description 2
- 241001076939 Artines Species 0.000 description 1
- 230000006978 adaptation Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000010525 oxidative degradation reaction Methods 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 238000004611 spectroscopical analysis Methods 0.000 description 1
- 230000001954 sterilising effect Effects 0.000 description 1
- 238000004659 sterilization and disinfection Methods 0.000 description 1
Classifications
-
- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N9/00—Investigating density or specific gravity of materials; Analysing materials by determining density or specific gravity
- G01N9/24—Investigating density or specific gravity of materials; Analysing materials by determining density or specific gravity by observing the transmission of wave or particle radiation through the material
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/46—Treatment of water, waste water, or sewage by electrochemical methods
- C02F1/4608—Treatment of water, waste water, or sewage by electrochemical methods using electrical discharges
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/46—Treatment of water, waste water, or sewage by electrochemical methods
- C02F1/461—Treatment of water, waste water, or sewage by electrochemical methods by electrolysis
- C02F1/467—Treatment of water, waste water, or sewage by electrochemical methods by electrolysis by electrochemical disinfection; by electrooxydation or by electroreduction
- C02F1/4672—Treatment of water, waste water, or sewage by electrochemical methods by electrolysis by electrochemical disinfection; by electrooxydation or by electroreduction by electrooxydation
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/72—Treatment of water, waste water, or sewage by oxidation
- C02F1/722—Oxidation by peroxides
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/72—Treatment of water, waste water, or sewage by oxidation
- C02F1/725—Treatment of water, waste water, or sewage by oxidation by catalytic oxidation
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2209/00—Controlling or monitoring parameters in water treatment
- C02F2209/01—Density
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2305/00—Use of specific compounds during water treatment
- C02F2305/02—Specific form of oxidant
- C02F2305/026—Fenton's reagent
Abstract
The invention relates to a device for improving density of OH free radical discharged in water and a measuring method thereof, which think of a device for improving density of OH free radical discharged in water, a delay trigger triggers a high-voltage pulse power supply to output positive pulse, the pulse voltage reaches between a needle electrode and a flat plate electrode of a reactor, a discharge plasma channel is formed near the needle electrode, OH free radical is generated, and Fe in solution 2+ Under the action of ions, the OH free radical generates Fenton reaction to promote the density of the OH free radical to be increased; simultaneously, the measuring method is provided, a delay trigger is adopted to trigger a pulse power supply, an ultraviolet lamp and an oscilloscope at the same time, so that plasma is generated in water, meanwhile, monochromatic light can detect and record OH free radicals, and finally, the light intensity of the OH free radicals is displayed on the oscilloscopeFrom the free radical light intensity, the OH radical density was calculated.
Description
Technical Field
The invention relates to the field of water discharge, in particular to a device for improving density of OH free radicals discharged in water and a measuring method thereof.
Background
The high-voltage pulse in-water discharge technology has been rapidly developed in the past 20 years, and the application effect in the environment-friendly field is remarkable. As an advanced oxidation technology, the in-water discharging technology has the advantages of high efficiency, mild running condition, strong oxidation and sterilization effects, strong oxidizing capability and thorough treatment. Active particles such as OH free radicals and the like can be generated in the water discharging process, and meanwhile, the effects such as ultraviolet light, shock waves, strong electric fields, bubble pulsation and the like are also generated. OH free radical is used as the most main active species in the discharge process, the number of the OH free radical is a powerful index for representing the oxidation capability of the advanced oxidation technology, and the measurement of the generation amount of the OH free radical in a reaction system is important for researching the mechanism of the OH free radical for oxidative degradation of organic matters. However, due to the short lifetime of OH (10 -6 s), high reactivity, low concentration, and still much unclear effect of OH on water solution transfer, thereby limiting the application of OH in the field of water treatment. At present, how to increase the OH density and how to accurately measure the OH density is an urgent problem to be solved.
On the one hand, due to the short life, high reactivity and low existing concentration of OH, the advanced oxidation technology based on the discharge in water needs to improve the density of OH to enhance the oxidation capability; on the other hand, when OH is formed, effects such as shock wave, ultraviolet light and bubble pulsation are generated by discharging in water, so that the traditional measurement technology is difficult to accurately measure, for example, in an optical fiber spectrometry, propagation of the shock wave is hindered by the existence of an optical fiber probe, and OH is transmitted in an aqueous solution along with the shock wave, so that OH density distribution is influenced, and measurement errors are caused. Based on the background, the invention provides a device for improving the density of discharged OH free radicals in water and a measuring method. The same patent literature and practical applications as the measuring device and method of the present invention have not been found so far.
Disclosure of Invention
The present invention is directed to the prior artIn the technical problem, creatively conceived is a device for improving density of OH free radicals discharged in water, which utilizes a delay trigger to trigger a high-voltage pulse power supply to output positive pulse, the pulse voltage reaches between a needle electrode and a flat plate electrode of a reactor, a discharge plasma channel is formed near the needle electrode, OH free radicals are generated, and Fe in solution 2+ Under the action of ions, the OH free radical generates Fenton reaction to promote the density of the OH free radical to be increased; meanwhile, the measuring method is provided, the ultraviolet lamp emits a beam of ultraviolet light, the ultraviolet light passes through the lens and the monochromator and is converted into monochromatic light in the monochromator, the characteristic wavelength of the monochromatic light is 309nm, the monochromatic light can be absorbed by OH free radicals, meanwhile, the monochromatic light has stable performance, and the interference of the monochromatic light to discharge radiation entering a needle electrode discharge area is small, so that the effect of the monochromatic light on discharge plasma can be ignored, and short-service-life OH free radicals can be effectively detected; the monochromatic light passes through a lens, a pinhole, a discharge reactor, a needle electrode discharge area, a pinhole and a photomultiplier, and finally displays the intensity of OH free radicals on an oscilloscope, and the density of the OH free radicals is calculated according to the intensity of the free radicals.
One of the technical schemes adopted for realizing the invention is as follows: a device for increasing the density of discharged OH radicals in water, comprising: the time delay trigger 1, the ultraviolet lamp 2, first convex lens 3, monochromator 4, second convex lens 5, first pinhole 6, discharge reactor 7, needle electrode 8, high-voltage probe 9, high-voltage pulse power supply 10, water 11, plate electrode 12, positioning sensor 13, second pinhole 14, photomultiplier 15, oscilloscope 16, direct-current bias power supply 17, burette 18 and titration solution 19, positioning sensor 13 on set up discharge reactor 7, discharge reactor 7 inner chamber bottom set up plate electrode 12, plate electrode 12 and direct-current bias power supply 17 electricity connection, discharge reactor 7 in set up water 11 discharge reactor 7 top fixed set up burette 18, the burette in set up titration solution 19, time delay trigger 1 and high-voltage pulse power supply 10 electricity connection, the high-voltage pulse power supply 10 is electrically connected with the high-voltage probe 9, the high-voltage probe 9 is electrically connected with one end of the needle electrode 8, the other end of the needle electrode 8 is arranged in the discharge reactor 7 and stretches into water 11, the delay trigger 1 is electrically connected with the oscilloscope 16, the oscilloscope 16 is electrically connected with the photomultiplier 15, the delay trigger 1 is electrically connected with the ultraviolet lamp 2, a first convex lens 3 is arranged between the light inlet of the monochromator 4 and the ultraviolet lamp 2, a first pinhole 6 and a second convex lens 5 are sequentially arranged between the discharge reactor 7 and the light outlet of the monochromator 4, a second pinhole 14 is arranged between the photomultiplier 15 and the discharge reactor 7, ultraviolet light emitted by the ultraviolet lamp 2 sequentially passes through the center of the first convex lens 3, the light inlet of the monochromator 4, the light outlet of the monochromator 4, the center of the second convex lens 5, the first pinhole 6, the ultraviolet light emitted by the ultraviolet lamp 2, the discharge reactor 7, the second pinhole 14, enters the photomultiplier tube 15.
The titration solution 19 is FeCl 2 A solution.
The diameters of the first needle hole 6 and the second needle hole 14 are 1.0mm.
The second technical scheme adopted for realizing the invention is as follows: the measuring method related to the device for improving the density of the discharged OH free radicals in the water is characterized by comprising the following steps of:
1) The burette 18 was pushed down to drop FeCl into the discharge reactor 7 2 A solution;
2) Starting a direct current bias power supply 17;
3) The delay trigger 1 is started, a high-voltage pulse power supply 10 outputs positive polarity pulse, the pulse voltage reaches between a needle electrode 8 and a flat plate electrode 12 in a discharge reactor 7, discharge plasma is formed near the needle electrode 8, the plasma interacts with an aqueous solution and OH free radicals are generated in a very short time, and the OH free radicals and Fe in the solution 2+ Ion Fenton reaction occurs; at the same time of triggering the high-voltage pulse power supply 10, starting the delay trigger 1 to trigger the ultraviolet lamp to emit ultraviolet light, and sequentially passing through the first convex lens 3, the monochromator 4, the second convex lens 5, the first pinhole 6, a needle electrode discharge area in the discharge reactor 7, the second pinhole 14 and the photomultiplier 15, and finally displaying the light intensity of OH free radicals on the oscilloscope 16;
4) From the free radical light intensity, the OH free radical density was calculated.
To said putFeCl is dripped into the electric reactor (7) 2 Solution to make Fe in discharge reactor (7) 2+ The ion concentration was 7.0mg/L.
The DC bias voltage of the plate electrode (12) is-10 kV.
The device for improving the density of the discharged OH free radicals in the water and the measuring method thereof have the beneficial effects that:
1. in a device for improving density of OH free radical discharged in water, a burette drops FeCl into a reactor before discharging 2 Solution, discharge to generate OH free radical and Fe 2+ Ion generating Fenton reaction to strengthen OH free radical density; the plate electrode is connected with a negative polarity direct current bias voltage, and the direct current bias voltage has the function of enhancing an electric field, so that a plasma obtains a higher electric field when an aqueous solution propagates, the contact area of the plasma and the aqueous solution is increased, and the high-energy electron density is enhanced, thereby enhancing the OH free radical density;
2. the device for improving the density of the OH free radicals in the water is characterized in that ultraviolet light is converted into monochromatic light in a monochromator and is output from a light emitting device, the characteristic wavelength of the monochromatic light is 309nm, the characteristic wavelength of the monochromatic light of 309nm can be absorbed by OH free radicals, meanwhile, the performance of the monochromatic light is stable, and the interference of the monochromatic light to discharge radiation in a needle electrode discharge area is small, so that the effect of the monochromatic light on discharge plasma can be ignored, and short-service-life OH free radicals can be effectively detected;
3. a device measuring method for improving the density of OH free radical discharged in water adopts a delay trigger to trigger a pulse power supply, an ultraviolet lamp and an oscilloscope at the same time, so that plasma is generated in water, meanwhile, monochromatic light can detect and record the OH free radical, finally, the intensity of the OH free radical is displayed on the oscilloscope, and the density of the OH free radical is calculated according to the intensity of the free radical.
Drawings
FIG. 1 is a schematic diagram of an apparatus for increasing the density of discharged OH radicals in water;
FIG. 2 is a schematic view of a discharge reactor and an electrode structure;
in the figure: 1. the device comprises a time delay trigger, a UV lamp, a first convex lens, a monochromator, a second convex lens, a first pinhole, a discharge reactor, a needle electrode, a high-voltage probe, a high-voltage pulse power supply, a flat electrode, a positioning sensor, a second pinhole, a photomultiplier tube, an oscilloscope, a direct-current bias power supply, a burette and a titration solution.
Detailed Description
The present invention is described in further detail below with reference to the drawings and the specific embodiments, which are described herein for the purpose of illustrating the invention and are not to be construed as limiting the invention.
Referring to fig. 1 and 2, there is shown an apparatus for increasing the density of discharged OH radicals in water, comprising: the time delay trigger 1, the ultraviolet lamp 2, first convex lens 3, monochromator 4, second convex lens 5, first pinhole 6, discharge reactor 7, needle electrode 8, high-voltage probe 9, high-voltage pulse power supply 10, water 11, plate electrode 12, positioning sensor 13, second pinhole 14, photomultiplier 15, oscilloscope 16, direct-current bias power supply 17, burette 18 and titration solution 19, positioning sensor 13 on set up discharge reactor 7, discharge reactor 7 inner chamber bottom set up plate electrode 12, plate electrode 12 and direct-current bias power supply 17 electricity connection, discharge reactor 7 in set up water 11 discharge reactor 7 top fixed set up burette 18, the burette in set up titration solution 19, time delay trigger 1 and high-voltage pulse power supply 10 electricity connection, the high-voltage pulse power supply 10 is electrically connected with the high-voltage probe 9, the high-voltage probe 9 is electrically connected with one end of the needle electrode 8, the other end of the needle electrode 8 is arranged in the discharge reactor 7 and stretches into water 11, the delay trigger 1 is electrically connected with the oscilloscope 16, the oscilloscope 16 is electrically connected with the photomultiplier 15, the delay trigger 1 is electrically connected with the ultraviolet lamp 2, a first convex lens 3 is arranged between the light inlet of the monochromator 4 and the ultraviolet lamp 2, a first pinhole 6 and a second convex lens 5 are sequentially arranged between the discharge reactor 7 and the light outlet of the monochromator 4, a second pinhole 14 is arranged between the photomultiplier 15 and the discharge reactor 7, ultraviolet light emitted by the ultraviolet lamp 2 sequentially passes through the center of the first convex lens 3, the light inlet of the monochromator 4, the light outlet of the monochromator 4, the center of the second convex lens 5, the first pinhole 6, the ultraviolet light emitted by the ultraviolet lamp 2, the discharge reactor 7, the second pinhole 14, enters the photomultiplier tube 15.
Example 1:
the titration solution 19 is FeCl 2 A solution.
The diameters of the first needle hole 6 and the second needle hole 14 are 1.0mm.
The measuring method related to the device for improving the density of the discharged OH free radicals in water is characterized by comprising the following steps of:
1) The burette 18 was pushed down to drop FeCl into the discharge reactor 7 2 Solution to make Fe in discharge reactor (7) 2+ Ion concentration is 7.0mg/L;
2) Starting a direct current bias power supply 17, wherein the direct current bias voltage of the flat plate electrode (12) is-10 kV;
3) The delay trigger 1 is started, a high-voltage pulse power supply 10 outputs positive polarity pulse, the pulse voltage reaches between a needle electrode 8 and a flat plate electrode 12 in a discharge reactor 7, discharge plasma is formed near the needle electrode 8, the plasma interacts with an aqueous solution and OH free radicals are generated in a very short time, and the OH free radicals and Fe in the solution 2+ Ion Fenton reaction occurs; at the same time of triggering the high-voltage pulse power supply 10, starting the delay trigger 1 to trigger the ultraviolet lamp to emit ultraviolet light, and sequentially passing through the first convex lens 3, the monochromator 4, the second convex lens 5, the first pinhole 6, a needle electrode discharge area in the discharge reactor 7, the second pinhole 14 and the photomultiplier 15, so that the pinhole is vertical to the flat plate electrode from the end part of the needle electrode as an upper boundary, measuring 5.0mm in the vertical direction, measuring 5mm in the horizontal direction and obtaining OH free radical density in the area of the measuring position of the pinhole on the two side wall surfaces of the reactor, and finally displaying the OH free radical light intensity on the oscilloscope 16;
4) From the free radical light intensity, the OH free radical density was calculated.
The foregoing is merely a preferred embodiment of the invention, and it should be noted that modifications and adaptations to those skilled in the art may be made without departing from the principles of the invention, which are intended to be comprehended within the scope of the invention.
Claims (5)
1. A device for increasing the density of discharged OH radicals in water, comprising: the utility model provides a time delay trigger (1), ultraviolet lamp (2), first convex lens (3), monochromator (4), second convex lens (5), first pinhole (6), discharge reactor (7), needle electrode (8), high-voltage probe (9), high-voltage pulse power supply (10), water (11), flat electrode (12), location sensor (13), second pinhole (14), photomultiplier (15), oscilloscope (16), direct current bias power supply (17), buret (18) and titration solution (19) location sensor (13) on set up discharge reactor (7), discharge reactor (7) inner chamber bottom set up flat electrode (12), flat electrode (12) be connected with direct current bias power supply (17) electricity, discharge reactor (7) in set up water (11) discharge reactor (7) top fixed set up buret (18), the buret in set up titration solution (19), time delay trigger (1) be connected with high-voltage pulse power supply (10) electricity, high-voltage pulse probe (10) electricity and high-voltage pulse power supply (9) one end be connected with high-voltage probe (9), the utility model provides a photoelectric titration device, including discharge reactor (7), time delay trigger (1), oscilloscope (16), time delay trigger (1), ultraviolet lamp (2) and ultraviolet lamp (2), time delay trigger (8) other end set up in discharge reactor (7), stretch into in water (11), time delay trigger (1) be connected with oscilloscope (16) electricity, oscilloscope (16) be connected with photomultiplier (15) electricity time delay trigger (1) ultraviolet lamp (2) go into between light mouth and ultraviolet lamp (2) monochromator (4) set up first convex lens (3) discharge reactor (7) and monochromator (4) go out light mouth between set gradually first pinhole (6) and second convex lens (5) photomultiplier (15) and discharge reactor (7) between set up second pinhole (14), ultraviolet lamp (2) transmit ultraviolet light and pass through first convex lens (3) center, monochromator (4) light mouth, second convex lens (5) center, first pinhole (6), discharge reactor (7), second pinhole (14) in proper order, get into photoelectric titration solution (19), it is the photoelectric titration solution (19) to get into 2 A solution.
2. A device for increasing the density of discharged OH radicals in water according to claim 1, wherein the diameter of the first pinhole (6) and the second pinhole (14) are each 1.0mm.
3. A method according to claim 1 or claim 2, characterized in that it comprises the following steps:
1) The burette (18) is pressed, feCl is dripped into the discharge reactor (7) 2 A solution;
2) Starting a DC bias power supply (17);
3) Starting a delay trigger (1), outputting positive pulse by a high-voltage pulse power supply (10), enabling the pulse voltage to reach between a needle electrode (8) and a flat plate electrode (12) in a discharge reactor (7), forming discharge plasma near the needle electrode (8), enabling the plasma to interact with an aqueous solution, and generating OH free radicals in a very short time, wherein the OH free radicals and Fe in the solution 2+ Ion Fenton reaction occurs; when the high-voltage pulse power supply (10) is triggered, the delay trigger (1) is started to trigger the ultraviolet lamp to emit ultraviolet light, and the ultraviolet light sequentially passes through the first convex lens (3), the monochromator (4), the second convex lens (5), the first pinhole (6), a needle electrode discharge area in the discharge reactor (7), the second pinhole (14) and the photomultiplier (15), and finally the light intensity of OH free radicals is displayed on the oscilloscope (16);
4) From the free radical light intensity, the OH free radical density was calculated.
4. The measuring method according to claim 3, wherein FeCl is added dropwise into the discharge reactor (7) 2 Solution to make Fe in discharge reactor (7) 2+ The ion concentration was 7.0mg/L.
5. A measurement method according to claim 3, wherein the dc bias of the plate electrode (12) is-10 kV.
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