CN1737542A - The method of chemical oxygen consumption (COC) and total organic carbon is measured in ultrasound wave and ozone cooperative effect - Google Patents
The method of chemical oxygen consumption (COC) and total organic carbon is measured in ultrasound wave and ozone cooperative effect Download PDFInfo
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Abstract
The invention provides a kind of ultrasound wave and ozone cooperative effect and measure the method for chemical oxygen consumption (COC) and total organic carbon, it is characterized in that ozone mixes at the water sample reaction chamber with water sample, ultrasonic generator transducer head produces mechanical vibration water body is produced cavitation effect simultaneously, cavitation effect further makes and can mix between ozone and the water sample fully, both synergies produce light signal; With photomultiplier light signal is gathered amplification, and convert electric signal to and send into the microcomputer data handling system, the signal of gathering is handled the back shows with standard TOC, COD relation curve contrast back, printout.Method of the present invention need not added reagent, does not produce secondary pollution, can test water body total organic carbon and chemical oxygen consumption (COC) accurately, continuously, fast.
Description
Technical field
The invention belongs to the environmental chemistry monitoring technical field, specifically utilize chemiluminescence in ultrasonic cavitation effect and the ozone oxidation collaborative processes to measure the method for water body chemical oxygen utilization (COD) and water body total organic carbon (TOC).
Background technology
Chemical oxygen consumption (COC), English name are Chemical Oxygen Demand, are abbreviated as COD; Total organic carbon, English name are Total Organic Carbon, are abbreviated as TOC.
The method of present domestic measurement water body chemical oxygen utilization (COD) is still carried out on based on the laboratory platform substantially, adopt the analytical approach of alkaline permanganate oxidimetric titration, this method longer duration, analytic process is numerous and diverse, condition harshness, reagent consumption be big, produce secondary pollution etc., for environment complicated and changeable, for example: pollute organic structure and concentration and influenced greatly by space-time, majority is in interrelated, interactional state again; Temperature, pressure changes greatly in the environment; To the Yu Haiyang high concentration ion, as chlorion, factor such as content is relatively stable, its result's accuracy and credibility will be under suspicion.
In recent years, along with electronic technology, new material, new technology, the development of new optical device, especially computer technology makes rapid progress, the corresponding appearance of method of adopting manganese method titration automatic analyzer and measuring the sewater chemistry oxygen utilization based on the photometric analyzer of flow injection mode, but because the technical difficulty of some realization aspect is too big, though these have broken away from some shortcomings of lab analysis, but the pattern from on-the-spot real-time working also has a segment distance, big as reagent consumption, on-the-spot, the real time execution cycle is short, poor stability, sensitivity and resolution are low, the defective that ion interference etc. are difficult to overcome does not truly realize the pattern of on-the-spot real-time continuous work.
The method of present domestic measurement total organic carbon (TOC) is to carry out on based on the laboratory platform substantially equally, and the principle of employing mainly contains following several (1) high temperature catalytic combustion-NDIR (Non-Dispersive Infrared) and surveys (NDIR), i.e. high-temperature oxidation; (2) use oxygenant oxidation-NDIR (Non-Dispersive Infrared) such as persulfate and survey (NDIR), i.e. wet oxidation; (3) ultraviolet (UV)-persulfate oxidation-NDIR (Non-Dispersive Infrared) is surveyed (NDIR), i.e. ultraviolet ray adds analytical approachs such as wet method oxidation.
(1) high temperature catalytic combustion oxidation-NDIR (Non-Dispersive Infrared) is surveyed (NDIR) measuring principle: with the quartz ampoule in a certain amount of water sample injection high temperature furnace, under 900-950 ℃ of temperature, with platinum and three cobalt oxides or chrome green is catalyzer, make the organic compound combustion cracking be converted into carbon dioxide, utilize NDIR (Non-Dispersive Infrared) to survey (NDIR) principle then and measure CO with infrared ray gas analyzer
2Content, thereby the content of total organic carbon (TOC) in definite water sample,
(2) wet oxidation (persulfate)-NDIR (Non-Dispersive Infrared) detection (NDIR) measuring principle is: potassium persulfate is an oxygenant, in course of reaction, will be in conjunction with high temperature and high pressure, with this understanding, potassium persulfate oxidation organic carbon material generates carbon dioxide, and the carbon dioxide that is generated imports the NDIR (Non-Dispersive Infrared) detecting device equally, by detecting device carbon dioxide is measured, can be obtained the concentration of TOC.
(3) ultraviolet (UV)-persulfate oxidation-NDIR (Non-Dispersive Infrared) detection (NDIR) method is basic identical with (2), just adds the irradiation of ultraviolet (UV) line, the cooxidant oxidation.
Said method exists following defective in various degree: 1, must finish in the laboratory, application can not be in real time on-the-spot, and scope is restricted.2, analyze longer duration, need 1 hour at least.3, analytic process is numerous and diverse, and condition harshness, energy consumption are big, requires high to experimenter's technical merit.4, must use chemical reagent, produce secondary pollution, be unfavorable for environmental protection.
Though in recent years, along with electronic technology, new material, new technology, the development of new optical device, especially computer technology makes rapid progress, adopt full-automatic analytical model automatically and based on the corresponding appearance of pattern of flow injection mode, but because the technical difficulty of some realization aspect is too big, though these have broken away from some shortcomings of lab analysis, but the pattern from on-the-spot real-time working also has a segment distance, big as reagent consumption, on-the-spot, the real time execution cycle is short, poor stability, sensitivity and resolution are low, Deng the defective that is difficult to overcome, truly do not realize the pattern of on-the-spot real-time continuous work.
Summary of the invention
In order to solve the problem and shortage that prior art exists, the present invention proposes a kind of on-site measurement method of novelty, promptly utilize chemiluminescence in ultrasonic cavitation effect and the ozone oxidation collaborative processes to measure the method for water body chemical oxygen utilization (COD) and water body total organic carbon (TOC).
In order to reach the purpose that solves above-mentioned technology technical matters, method step of the present invention is as follows:
(1). utilize ultrasonic generator, the band transducer produces mechanical vibration, and the transducer head inserts the concerted reaction chamber;
(2). utilize ozone generator to produce ozone, it is sent into the Ozone chamber of concerted reaction chamber, isolator enters in the water sample reaction chamber after filtration;
(3). detected water sample is through heating apparatus, after the intensification, by the water sample reaction chamber of flow pump input concerted reaction chamber;
(4). ozone mixes at the water sample reaction chamber with water sample, ultrasonic generator transducer head produces mechanical vibration water body is produced cavitation effect simultaneously, cavitation effect further makes and can mix between ozone and the water sample fully, and both synergies produce light signal;
(5). utilize the photomultiplier of concerted reaction chamber to gather amplification to reacting the light intensity signal that is sent, and convert electric signal to and send into the microcomputer data handling system, the light signal that sent of reaction is faint chemiluminescence signal, to the signal of gathering quantize, show with standard TOC, COD relation curve contrast back after the time series Integral Processing, printout.
In the present invention, also has following technical characterictic: the frequency 100KHz-1MHz that ultrasonic generator produces.
In the present invention, also have following technical characterictic: described ozone flow is 100-200ml/min, and concentration is 2-4mg/l.
In the present invention, also have following technical characterictic: water sample is through heating, and temperature range is 40 ± 5 ℃.
In the present invention, also have following technical characterictic: described filtration isolator emerges ozone gas with porosint-teflon from the micropore of porous material surface, in the detected water sample around being mixed into.
In the present invention, also have following technical characterictic: the light signal that reaction is sent is faint chemiluminescence signal, and wavelength coverage is at 185-850nm.
In the present invention, also have following technical characterictic: photomultiplier adopts Japanese shore pine PhotosensorModules H5784 Series.
In the present invention, also have following technical characterictic: to the measure of reaction chamber optics sealing: the pipeline skin of intake-outlet is wrapped with waterproof black insulating tape, need ventilative place to take multilayer, carry out, reach the optics sealing of reaction chamber thereby make to be reflected in the dark environment every photo structure.
In the present invention, also have following technical characterictic: the microcomputer data handling system, by control and the signal Processing of software programming realization to system.
The method of utilizing chemiluminescence in ultrasonic cavitation effect and the ozone oxidation collaborative processes to measure water body chemical oxygen utilization (COD) and water body total organic carbon (TOC) of the present invention, it is the important component part in the present environmental monitoring system, it is a chemiluminescence principle in using ultrasound cavitation effect and the ozone oxidation collaborative processes, the sound cavitation effect and the ozone that are the using ultrasound ripple are handled water body organism together, the chemiluminescence signal that in processing procedure, produces, by the low-light photoelectric conversion technique light signal that produces in the course of reaction is detected and to pick up, through amplifying, quantize, after the time series Integral Processing, draw water body chemical oxygen utilization (COD) and water body total organic carbon (TOC) content.
Contrast as follows: water body chemical oxygen utilization (COD)
| The contrast feature | Classic method | SERES-COD/ France | Method of the present invention |
| Measurement range mg/L | 3-32000 | 30-70 | 0.2-100 |
| The measurement number of times/hour | 1-2 | 4-6 | Continuously |
| Whether need reaction reagent | Need | Need | Do not need |
| Noxious material forms | Have | Have | No |
| Environment for use | Only for the laboratory | The laboratory | On-the-spot |
Water body total organic carbon (TOC)
| The contrast feature | Classic method (laboratory) | Day island proper Tianjin | U.S.'s Hash | Method of the present invention |
| Measurement range | Lower limit 0.15 | 0.2-20000 | 0.2～ | 0.1-20000 |
| Whether sample is located | Need | Need | Need | Do not need |
| Measuring Time/each | 4-6 | 1 | 1 is little | (less than 10 minutes) continuously |
| Whether need react | Need | Need | Need | Do not need |
| Have or not noxious material to form | Have | Have | Have | No |
| Environment for use | Only for the laboratory | The laboratory | The laboratory | On-the-spot |
| Working method | Burning | Combustion catalysis | Combustion catalysis | Chemiluminescence |
| Measuring accuracy % | 20-30 | 20 | 15 | 10 |
By last table as can be seen, method of the present invention compared with prior art has significant effect.
Specifically utilize chemiluminescence in ultrasonic cavitation effect and the ozone oxidation collaborative processes to measure the method for water body chemical oxygen utilization (COD) and water body total organic carbon (TOC), may further comprise the steps and measure:
1. utilize ultrasonic generator, the band transducer produces the mechanical vibration in the frequency 100KHz-1MHz scope, and the transducer head inserts the reaction chamber 2cm degree of depth;
2. utilize ozone generator to produce ozone, and guarantee that the concentration of ozone under the 100-200ml/min flow is 2-4mg/l, it is sent into reaction chamber;
3. water sample is warmed up to 40 ± 5 ℃ through filtration, heating apparatus, by flow pump input reaction chamber;
4. ozone mixes at reaction chamber with water body, ultrasonic generator transducer point mouth produces mechanical vibration water body is produced cavitation effect simultaneously, both synergies, for the light signal that guarantees to produce in this process can be detected by complete, reaction chamber is carried out the optics sealing, and be provided with the detection window detectable signal.Utilize porosint-teflon that ozone gas is emerged from the aperture of porous material surface, in the detected water sample around being mixed into, increase the gas-liquid area that contacts, the microjet of ultrasound wave generation simultaneously strengthens the mass transfer power between the gas phase liquid phase, make gas-liquid mixed abundant, reaction efficiency is strengthened.
5. the measure of optics sealing: during chamber designs, adopt light-proof material, the pipeline skin of intake-outlet is wrapped with waterproof black insulating tape, needs ventilative place to take multilayer every photo structure, carry out thereby make to be reflected in the dark environment, reach the optics sealing of reaction chamber.
6. reaction chamber is carried out corrosion-resistant design, because ozone and a large amount of testing samples have highly corrosive, so ozone transfer pipeline, waste water are got rid of pipeline and adopted poly-PTFE, reaction chamber adopts stainless steel material;
7. utilize photomultiplier that the light intensity signal that sent of reaction is gathered amplification, and convert electric signal to and send into the microcomputer data handling system, to the signal of gathering quantize, time series Integral Processing, demonstration, printout.
The light signal that sent of reaction is that the faint general wavelength coverage of chemiluminescence signal is at 185-850nm, photomultiplier can be gathered the light signal of this scope, the faint optical signal that reaction chamber produces is through the optical lens cumulative, import photomultiplier, light signal is electric signal output through the photomultiplier treatment conversion, the output electric signal is changed through the feeble signal amplifying circuit, being amplified to the certain voltage amplitude send the A/D ALT-CH alternate channel of data processing section to quantize the time series Integral Processing.
Photomultiplier of the present invention adopts Japanese shore pine Photosensor Modules H5784 Series.Utilize the microcomputer data handling system, by control and the signal Processing of software programming realization to system.
Aspect data processing, adopt standard substance can cause that to optical system gain, sample turbidity etc. the factor of systematic error carries out the data correction processing.
Through measures such as laboratory demarcation and on-the-spot test, obtain the signal correction coefficient of different water bodys, set up the correction factor database.According to the corresponding relation of signal time sequence integration data and standard C OD and TOC, chemical oxygen consumption (COC) (COD) total organic carbon (TOC) that can the measure detected water sample line output of going forward side by side shows.
Described ozone generating-device is that the dry after filtration back of air is pulled the trigger by high pressure, produces high-concentrated ozone.
The present invention utilizes chemiluminescence in ultrasonic cavitation effect and the ozone oxidation collaborative processes to measure the method for water body chemical oxygen utilization (COD) and water body total organic carbon (TOC), need not add reagent, do not produce secondary pollution, can test water body total organic carbon (TOC) and chemical oxygen consumption (COC) (COD) accurately, continuously, fast, can be at the medium-term and long-term reliably working of rugged environment.
Description of drawings
Fig. 1 is the process flow diagram that method of the present invention is measured.
Fig. 2 is reaction chamber and optical system configuration composition.
In Fig. 2,1. photomultiplier; 2. detection window; 3. water sample reaction chamber; 4. ultrasonic transducer; 4-1. O-ring seal; 5. water delivering orifice; 6. water inlet; 7. filtration isolator; 8. ozone air intake opening; 9. Ozone chamber; 10. reversal valve connector; 11. concerted reaction chamber.
Embodiment
The present invention is described in further detail below in conjunction with drawings and Examples.
As shown in Figure 1: in measuring process, system's Control Flow pump carries out water sample by predetermined flow to be carried, and water sample is transported to reaction chamber by filtration unit and temperature control module.The purpose of filtration unit is to guarantee that water sample does not have floating material and low concentration suspension.Temperature control module is to guarantee that microorganisms in water in oxidizing process, biological luminescence can not occur.
As shown in Figure 1, ozone generating-device is made up of air strainer, instrument air dryer, pneumatic pump and controlling and driving part thereof, controllable high-voltage generator, ozone generation ionization chamber etc.Ozone generation ionization chamber is sent into by pneumatic pump in the dry after filtration back of air, is excited the generation high-concentrated ozone by high voltage here, sends into reaction chamber., adopt control principle here, control the voltage output of adjustable high pressure generator, and cooperate control, guarantee that ozoniferous concentration and flow satisfy the requirement of this method pneumatic pump.
Reaction chamber is the core of total system, it by reaction chamber, air chamber, porosint-teflon is little and air chamber pressure warning system etc. is formed.
Water sample is sent into reaction chamber, ultrasonic generator produces the cavitation effect synergy ozone and reacts rapidly with water sample together, optical detecting gear-the photomultiplier of the optical signals reaction chamber sidewall that produces (Japanese shore pine Photosensor Modules H5784 Series) is gathered amplification, and converts electric signal to and send into the microcomputer data handling system; Utilize the microcomputer data handling system, realize signal is handled by software programming, behind the time series integration, the total organic carbon (TOC) and chemical oxygen consumption (COC) (COD) output of measuring water sample according to the TOC and the COD contrast relationship of data behind the integration and standard show.
Referring to Fig. 2, mark 11 chief representatives are used in the concerted reaction chamber.Concerted reaction chamber 11 mainly is made of photomultiplier 1, detection window 2, ultrasonic transducer 4, water sample reaction chamber 3, filtration isolator 7 and Ozone chamber 9.
The effect of filtering isolator 7 is not only to isolate the water sample whereabouts but also can make ozone enter water sample reaction chamber 3.
In order to guarantee fully to mix between ozone and the water sample, filter isolator 7 and adopt porosint-teflon, ozone gas is emerged from the micropore of porous material surface, in the detected water sample around being mixed into, porosint-teflon application target is to increase the gas-liquid area that contacts, strengthen mass transfer power, mix fully, reaction efficiency is strengthened.
During 3 designs of water sample reaction chamber, adopt light-proof material, the pipeline skin of intake-outlet is wrapped with waterproof black insulating tape, needs ventilative place to take multilayer every photo structure, carries out thereby make to be reflected in the dark environment, reaches the optics sealing of reaction chamber.
Water sample reaction chamber 3 is carried out corrosion-resistant design, because ozone and a large amount of testing samples have highly corrosive, so ozone transfer pipeline, waste water are got rid of pipeline and adopted poly-PTFE, water sample reaction chamber 3 adopts stainless steel materials to make.
In measuring process, water sample is sent into water sample reaction chamber 3, and ozone from Ozone chamber 9 after filtration isolator 7 enter water sample reaction chamber 3, simultaneously ultrasonic generator transducer 4 sharp mouths produce mechanical vibration water body are produced cavitation effect, both synergies.Utilize porosint-teflon that ozone gas is emerged from the aperture of porous material surface, in the detected water sample around being mixed into, increase the gas-liquid area that contacts, the microjet of ultrasound wave generation simultaneously strengthens the mass transfer power between the gas phase liquid phase, make gas-liquid mixed abundant, reaction efficiency is strengthened.
The light signal that sent of reaction is that the faint general wavelength coverage of chemiluminescence signal is at 185-850nm, photomultiplier 1 can be gathered the light signal of this scope, the faint optical signal that water sample reaction chamber 3 produces is through the optical lens cumulative, import photomultiplier 1, light signal is electric signal output through photomultiplier 1 treatment conversion, the output electric signal is changed through the feeble signal amplifying circuit, being amplified to the certain voltage amplitude send the A/D ALT-CH alternate channel of data processing section to quantize, the time series Integral Processing, demonstration, printout.
(1). ultrasonic transducer 4 produces the mechanical vibration in the frequency 100KHz-1MHz scope, and the ultrasonic transducer head inserts the about 2cm degree of depth of reaction chamber;
(2). utilize ozone generator to produce ozone, it is sent into the Ozone chamber of concerted reaction chamber, isolator 7 enters in the water sample reaction chamber 3 after filtration, and the flow of ozone is 100ml/min, and concentration is 2mg/l;
(3). detected water sample is warming up to 40 ℃ through heating apparatus, by the water sample reaction chamber 3 of flow pump input concerted reaction chamber 11;
(4). ozone mixes at water sample reaction chamber 3 with water sample, ultrasonic generator transducer 4 heads produce mechanical vibration water body are produced cavitation effect simultaneously, cavitation effect further makes and can mix between ozone and the water sample fully, and both synergies produce light signal;
(5). the light intensity signal that utilizes 1 pair on the photomultiplier reaction of concerted reaction chamber 11 to be sent is gathered amplification, and convert electric signal to and send into the microcomputer data handling system, the light signal that sent of reaction is faint chemiluminescence signal, to the signal of gathering quantize, show with standard TOC, COD relation curve contrast back after the time series Integral Processing, printout.
(1). ultrasonic transducer 4 produces the mechanical vibration in the frequency 100KHz-1MHz scope, and the ultrasonic transducer head inserts the about 2cm degree of depth of reaction chamber;
(2). utilize ozone generator to produce ozone, it is sent into the Ozone chamber of concerted reaction chamber, isolator 7 enters in the water sample reaction chamber 3 after filtration, and the flow of ozone is 200ml/min, and concentration is 4mg/l;
(3). detected water sample is warming up to 45 ℃ through heating apparatus, by the water sample reaction chamber 3 of flow pump input concerted reaction chamber 11;
(4). ozone mixes at water sample reaction chamber 3 with water sample, and simultaneously ultrasonic generator transducer 4 heads produce mechanical vibration water body is produced cavitation effect, and both synergies make between ozone and the water sample and can fully mix, and produce light signal;
(5). the light intensity signal that utilizes 1 pair on the photomultiplier reaction of concerted reaction chamber 11 to be sent is gathered amplification, and convert electric signal to and send into the microcomputer data handling system, the light signal that sent of reaction is faint chemiluminescence signal, to the signal of gathering quantize, show with standard TOC, COD relation curve contrast back after the time series Integral Processing, printout.
(1). ultrasonic transducer 4 produces the mechanical vibration in the frequency 100KHz-1MHz scope, and the ultrasonic transducer head inserts the about 2cm degree of depth of reaction chamber;
(2). utilize ozone generator to produce ozone, it is sent into the Ozone chamber of concerted reaction chamber, isolator 7 enters in the water sample reaction chamber 3 after filtration, and the flow of ozone is 150ml/min, and concentration is 3mg/l;
(3). detected water sample is warming up to 35 ℃ through heating apparatus, by the water sample reaction chamber 3 of flow pump input concerted reaction chamber 11;
(4). ozone mixes at water sample reaction chamber 3 with water sample, and simultaneously ultrasonic generator transducer 4 heads produce mechanical vibration water body is produced cavitation effect, and both synergies make between ozone and the water sample and can fully mix, and produce light signal;
(5). the light intensity signal that utilizes 1 pair on the photomultiplier reaction of concerted reaction chamber 11 to be sent is gathered amplification, and convert electric signal to and send into the microcomputer data handling system, the light signal that sent of reaction is faint chemiluminescence signal, to the signal of gathering quantize, show with standard TOC, COD relation curve contrast back after the time series Integral Processing, printout.
(1). ultrasonic transducer 4 produces the mechanical vibration in the frequency 100KHz-1MHz scope, and the ultrasonic transducer head inserts the about 2cm degree of depth of reaction chamber;
(2). utilize ozone generator to produce ozone, it is sent into the Ozone chamber of concerted reaction chamber, isolator 7 enters in the water sample reaction chamber 3 after filtration, and the flow of ozone is 130ml/min, and concentration is 3.5mg/l;
(3). detected water sample is warming up to 39 ℃ through heating apparatus, by the water sample reaction chamber 3 of flow pump input concerted reaction chamber 11;
(4). ozone mixes at water sample reaction chamber 3 with water sample, and simultaneously ultrasonic generator transducer 4 heads produce mechanical vibration water body is produced cavitation effect, and both synergies make between ozone and the water sample and can fully mix, and produce light signal;
(5). the light intensity signal that utilizes 1 pair on the photomultiplier reaction of concerted reaction chamber 11 to be sent is gathered amplification, and convert electric signal to and send into the microcomputer data handling system, the light signal that sent of reaction is faint chemiluminescence signal, to the signal of gathering quantize, show with standard TOC, COD relation curve contrast back after the time series Integral Processing, printout.
(1). ultrasonic transducer 4 produces the mechanical vibration in the frequency 100KHz-1MHz scope, and the ultrasonic transducer head inserts the about 2cm degree of depth of reaction chamber;
(2). utilize ozone generator to produce ozone, it is sent into the Ozone chamber of concerted reaction chamber, isolator 7 enters in the water sample reaction chamber 3 after filtration, and the flow of ozone is 170ml/min, and concentration is 2.5mg/l;
(3). detected water sample is warming up to 42 ℃ through heating apparatus, by the water sample reaction chamber 3 of flow pump input concerted reaction chamber 11;
(4). ozone mixes at water sample reaction chamber 3 with water sample, and simultaneously ultrasonic generator transducer 4 heads produce mechanical vibration water body is produced cavitation effect, and both synergies make between ozone and the water sample and can fully mix, and produce light signal;
(5). the light intensity signal that utilizes 1 pair on the photomultiplier reaction of concerted reaction chamber 11 to be sent is gathered amplification, and convert electric signal to and send into the microcomputer data handling system, the light signal that sent of reaction is faint chemiluminescence signal, to the signal of gathering quantize, show with standard TOC, COD relation curve contrast back after the time series Integral Processing, printout.
(1). ultrasonic transducer 4 produces the mechanical vibration in the frequency 100KHz-1MHz scope, and the ultrasonic transducer head inserts the about 2cm degree of depth of reaction chamber;
(2). utilize ozone generator to produce ozone, it is sent into the Ozone chamber of concerted reaction chamber, isolator 7 enters in the water sample reaction chamber 3 after filtration, and the flow of ozone is 190ml/min, and concentration is 2.8mg/l;
(3). detected water sample is warming up to 38 ℃ through heating apparatus, by the water sample reaction chamber 3 of flow pump input concerted reaction chamber 11;
(4). ozone mixes at water sample reaction chamber 3 with water sample, and simultaneously ultrasonic generator transducer 4 heads produce mechanical vibration water body is produced cavitation effect, and both synergies make between ozone and the water sample and can fully mix, and produce light signal;
(5). the light intensity signal that utilizes 1 pair on the photomultiplier reaction of concerted reaction chamber 11 to be sent is gathered amplification, and convert electric signal to and send into the microcomputer data handling system, the light signal that sent of reaction is faint chemiluminescence signal, to the signal of gathering quantize, show with standard TOC, COD relation curve contrast back after the time series Integral Processing, printout.
In the above-described embodiments, photomultiplier 1 adopts Japanese shore pine Photosensor Modules H5784Series.
From the bathing beach, several sea areas sampling such as harbour, off-lying sea, be divided into two parts.Portion detects in Shandong Province's ocean monitoring technologytechnologies key lab, and portion is monitored with method of the present invention.
This method is compared as follows with " marine monitoring standard-sea water analysis (GB17378.4-1998) " measured COD, TOC value:
| The sample sequence number | COD | |||||
| Method mg/L of the present invention | National marine monitoring standard (HY003.4-91) mg/L | Relative deviation (%) | ||||
| 1 | 1.10 | 1.08 | 4.3 | |||
| 2 | 0.98 | 1.01 | 5.2 | |||
| 3 | 0.89 | 0.92 | 6.6 | |||
| 4 | 1.06 | 1.10 | 7.5 | |||
| 5 | 1.11 | 1.02 | 7.8 | |||
| 6 | 1.2 | 1.15 | 3.4 | |||
| 7 | 1.05 | 0.97 | 8.8 | |||
| The sample sequence number | TOC | |||||
| Method mg/L of the present invention | National marine monitoring standard (HY003.4-91) mg/L | Relative deviation (%) | ||||
| 1 | 1.49 | 1.42 | 4.9 | |||
| 2 | 2.82 | 2.79 | 1.0 | |||
| 3 | 2.95 | 2.89 | 2.0 | |||
| 4 | 2.12 | 2.07 | 2.4 | |||
| 5 | 3.45 | 3.31 | 4.2 | |||
| 6 | 4.98 | 4.82 | 3.3 | |||
| 7 | 4.56 | 4.42 | 3.2 | |||
Experiment shows that both methods have good corresponding relation, and its result error is smaller or equal to 10%.
Claims (9)
1. method of utilizing ultrasound wave and ozone cooperative effect to measure chemical oxygen consumption (COC) and total organic carbon is characterized in that may further comprise the steps:
(1). utilize ultrasonic generator, the band transducer produces mechanical vibration, and the transducer head inserts the concerted reaction chamber;
(2). utilize ozone generator to produce ozone, it is sent into the Ozone chamber of concerted reaction chamber, isolator enters in the water sample reaction chamber after filtration;
(3). detected water sample is through heating apparatus, after the intensification, by the water sample reaction chamber of flow pump input concerted reaction chamber;
(4). ozone mixes at the water sample reaction chamber with water sample, ultrasonic generator transducer head produces mechanical vibration water body is produced cavitation effect simultaneously, cavitation effect further makes and can mix between ozone and the water sample fully, and both synergies produce light signal;
(5). utilize the photomultiplier of concerted reaction chamber to gather amplification to reacting the light intensity signal that is sent, and convert electric signal to and send into the microcomputer data handling system, the light signal that sent of reaction is faint chemiluminescence signal, to the signal of gathering quantize, show with standard TOC, COD relation curve contrast back after the time series Integral Processing, printout.
2. according to the measurement chemical oxygen consumption (COC) of claim 1 and the method for total organic carbon, it is characterized in that the frequency 100KHz-1MHz that ultrasonic generator produces.
3. according to the measurement chemical oxygen consumption (COC) of claim 1 or 2 and the method for total organic carbon, it is characterized in that described ozone flow is 100-200ml/min, concentration is 2-4mg/l.
4. according to the measurement chemical oxygen consumption (COC) of claim 3 and the method for total organic carbon, it is characterized in that water sample is through heating, temperature range is 40 ± 5 ℃.
5. according to the measurement chemical oxygen consumption (COC) of claim 4 and the method for total organic carbon, it is characterized in that described filtration isolator emerges ozone gas with porosint-teflon from the micropore of porous material surface, in the detected water sample around being mixed into.
6. according to the measurement chemical oxygen consumption (COC) of claim 1 and the method for total organic carbon, it is characterized in that the light signal that reaction is sent is faint chemiluminescence signal, wavelength coverage is at 185-850nm.
7. according to the measurement chemical oxygen consumption (COC) of claim 6 and the method for total organic carbon, it is characterized in that photomultiplier adopts Japanese shore pine Photosensor Modules H5784 Series.
8. according to the measurement chemical oxygen consumption (COC) of claim 5 and the method for total organic carbon, it is characterized in that, measure to the sealing of reaction chamber optics: the pipeline skin of intake-outlet is wrapped with waterproof black insulating tape, need ventilative place to take multilayer every photo structure, carry out thereby make to be reflected in the dark environment, reach the optics sealing of reaction chamber.
9. according to the measurement chemical oxygen consumption (COC) of claim 7 and the method for total organic carbon, it is characterized in that the microcomputer data handling system is by control and the signal Processing of software programming realization to system.
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Cited By (7)
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| CN100412530C (en) * | 2006-06-09 | 2008-08-20 | 山东省科学院海洋仪器仪表研究所 | Method for analyzing water body organism kinds by using ozone chemiluminescence spectrum |
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| CN100541181C (en) * | 2007-01-15 | 2009-09-16 | 山东省科学院海洋仪器仪表研究所 | Mode of oxidizing floating injected ozone is measured the method for chemical oxygen demand (COD) and total organic carbon |
| CN100578196C (en) * | 2007-08-01 | 2010-01-06 | 山东省科学院海洋仪器仪表研究所 | Method for measuring water body total nitrogen and total phosphorous by digestion spectrophotometry of supersonic wave cooperating with ozone |
| CN102305816A (en) * | 2011-05-23 | 2012-01-04 | 中国科学院广州能源研究所 | Method for determining total concentration of organic gas in environmental gas by photocatalytic fuel cell (PFC) photoelectrocatalysis method |
| CN113607718A (en) * | 2021-08-05 | 2021-11-05 | 山东省科学院海洋仪器仪表研究所 | Device and method for collecting seawater flash signal |
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| JP2000356631A (en) * | 1999-06-15 | 2000-12-26 | Japan Organo Co Ltd | Method and apparatus for measuring total organic carbon |
| CN1177216C (en) * | 2003-01-30 | 2004-11-24 | 山东省科学院海洋仪器仪表研究所 | Method for measuring chemistry oxygen consumption of sea water based on luminous intensity principle of ozone oxidation |
| JP2005106698A (en) * | 2003-09-30 | 2005-04-21 | Dkk Toa Corp | Method and instrument for measuring total organic carbon content |
| JP4184255B2 (en) * | 2003-12-24 | 2008-11-19 | 本田技研工業株式会社 | Goods management system |
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Cited By (10)
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| CN100412530C (en) * | 2006-06-09 | 2008-08-20 | 山东省科学院海洋仪器仪表研究所 | Method for analyzing water body organism kinds by using ozone chemiluminescence spectrum |
| CN100454004C (en) * | 2006-06-09 | 2009-01-21 | 山东省科学院海洋仪器仪表研究所 | Method for cooperative detection of chemical oxygen consumption and total organic carbon by using ozone and hydrogen peroxide |
| CN100541181C (en) * | 2007-01-15 | 2009-09-16 | 山东省科学院海洋仪器仪表研究所 | Mode of oxidizing floating injected ozone is measured the method for chemical oxygen demand (COD) and total organic carbon |
| CN100578196C (en) * | 2007-08-01 | 2010-01-06 | 山东省科学院海洋仪器仪表研究所 | Method for measuring water body total nitrogen and total phosphorous by digestion spectrophotometry of supersonic wave cooperating with ozone |
| CN102305816A (en) * | 2011-05-23 | 2012-01-04 | 中国科学院广州能源研究所 | Method for determining total concentration of organic gas in environmental gas by photocatalytic fuel cell (PFC) photoelectrocatalysis method |
| CN102305816B (en) * | 2011-05-23 | 2013-07-31 | 中国科学院广州能源研究所 | Method for determining total concentration of organic gas in environmental gas by photocatalytic fuel cell (PFC) photoelectrocatalysis method |
| CN113607718A (en) * | 2021-08-05 | 2021-11-05 | 山东省科学院海洋仪器仪表研究所 | Device and method for collecting seawater flash signal |
| CN113607718B (en) * | 2021-08-05 | 2023-12-08 | 山东省科学院海洋仪器仪表研究所 | Device and method for collecting sea water flash signals |
| CN114047228A (en) * | 2021-11-09 | 2022-02-15 | 同济大学 | Device and method for analyzing sediment oxygen-consuming pollutants |
| CN114047228B (en) * | 2021-11-09 | 2023-08-04 | 同济大学 | Device and method for analyzing oxygen-consuming pollutants of sediment |
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