CN1177216C - Method for measuring chemistry oxygen consumption of sea water based on luminous intensity principle of ozone oxidation - Google Patents
Method for measuring chemistry oxygen consumption of sea water based on luminous intensity principle of ozone oxidationInfo
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- CN1177216C CN1177216C CNB031118526A CN03111852A CN1177216C CN 1177216 C CN1177216 C CN 1177216C CN B031118526 A CNB031118526 A CN B031118526A CN 03111852 A CN03111852 A CN 03111852A CN 1177216 C CN1177216 C CN 1177216C
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- ozone
- reaction chamber
- signal
- chemistry oxygen
- oxygen utilization
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Abstract
The present invention discloses a method for measuring chemical oxygen consumption of sea water by a luminous intensity principle of ozone oxidation. Ozone and sea water carry out hybrid reaction in a reaction chamber, and a light intensity signal generated by the reaction is collected and amplified by a photomultiplier tube. Then the light intensity signal is converted into an electric signal to be transmitted to a microcomputer data processing system, and quantification, calculation, correction, display and printout are carried out to the collected signal under the control of a program.
Description
Technical field
The present invention utilizes ozone oxidation luminescence intensity principle to measure the method for sewater chemistry oxygen utilization, belongs to thalassochemistry environmental monitoring technology field.
Background technology
The method of present domestic measurement sewater chemistry 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 marine 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 marine environment; Factors such as high concentration ion (chlorion) content is relatively stable, its result's accuracy and representativeness 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 this instrument has been 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.
Summary of the invention
In order to solve the deficiency of prior art, the present invention proposes a kind of method of utilizing ozone oxidation luminescence intensity principle to measure the sewater chemistry oxygen utilization, the contrast of this method and existing several method is as follows:
| The contrast feature | Classic method | SERES-COD/ France | Ozone method COD |
| 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 | The scene, ocean |
Sewater chemistry oxygen utilization on-the site analysis technology of the present invention, it is the important component part in the marine environmental monitoring system, it is based on ozone oxidation luminescence intensity principle and carries out, be that using ozone reacts as strong oxidizer and pollution organism, by the low-light photoelectric conversion technique light signal that produces in the course of reaction is detected and to pick up, through amplify, quantize, and machine data correcting process as calculated, draw the chemical oxygen consumption (COC) of marine environment.
Specifically utilize ozone oxidation luminescence intensity principle to measure the method for sewater chemistry oxygen utilization, comprise following step:
1. utilize ozone generator to produce ozone, and guarantee that the concentration of ozone is that 18～25mg/l and flow are 0.5～2l/min, it is sent into reaction chamber;
2. utilize automatic sample handling system that tested seawater is sent into reaction chamber;
3. ozone and seawater carry out hybrid reaction at reaction chamber, guarantee can fully to mix between ozone and the water sample, reaction chamber is carried out the optics sealing, and be provided with the detection window detectable signal.
We utilize porosint-Bubbled stone that ozone gas is emerged from the aperture of porous material surface, in the detected water sample around being mixed into, increase contact area, mix fully, and reaction efficiency is strengthened.
The measure of optics sealing: during chamber designs, adopt light-proof material, intake-outlet takes curved design to prevent that the light catadioptric from entering reaction chamber, 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.
Light-proof material is the stainless steel metal plate among the present invention, and described multilayer adopts the stainless steel metal plate that staggers every photo structure.
4. 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, calculating, correction, demonstration, printout.
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 carries out differential conversion through the feeble signal amplifying circuit, is amplified to the certain voltage amplitude and send the A/D ALT-CH alternate channel of data processing section to carry out quantification treatment.
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.
In this system, control system is born two main tasks, the one, coordinate the sequence of movement of each operating part of control total system, make system under programmed control, finish test job automatically, the 2nd, to the signal of gathering quantize, calculating, correction, demonstration, printout.
The run action rhythm of considering this system is slower, and is not high to the rate request of computing machine, but we adopt strong anti-electromagnetic interference (EMI) system from resetting, have the control module of the technical grade PLC of System self-test function as system.The drive part of each executive component, we adopt the program-controlled power model of having finalized the design and having produced.
Aspect data processing, we adopt standard sources, standard water sample can cause that to optical system gain, sample turbidity etc. the factor of systematic error carries out data correction and handle.
Through measures such as on-the-spot test, laboratory demarcation, obtain the signal correction coefficient of different waters, Various Seasonal, set up the correction factor database, the database that passes through to be built according to the signal power is the corresponding relation of signal intensity and COD, and the chemical oxygen consumption (COC) 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.
Described automatic sample handling system is that seawater and titer from monitoring pipe road, sampling pipe are sent into reaction chamber by reversal valve, flow pump.
The present invention utilizes ozone oxidation luminescence intensity principle to measure the method for the chemical oxygen consumption (COC) of seawater, need not add reagent, do not produce secondary pollution, avoided of the influence of water body high concentration ion chlorion to accuracy, can be accurate, continuously, test the chemical oxygen consumption (COC) of seawater fast, can be at the medium-term and long-term reliably working of abominable marine environment, be suitable for boat-carrying and ocean observation station, occasions such as offshore platform and oceanographic buoy station are used, can be to coastal, the scene is carried out in river mouth and coastal ocean economy-zone, in real time, continuous measurement, total system unmanned for a long time under programmed control, operation continuously.This method has changed Our Ocean Environment Pollution to chemical oxygen consumption (COC) index monitoring means, and chemico-analytic conventional test methodologies is carried out in promptly long-term on-the-spot extraction water sample, the laboratory of adopting.Improved China's marine eco-environment field monitoring ability.
Description of drawings
Fig. 1 is the process flow diagram that utilizes method measure CO D of the present invention.
Fig. 2 is an automatic sample handling system control block diagram.
Fig. 3 is an ozone generating-device control block diagram.
Fig. 4 is reaction chamber and optical system control block diagram.
Fig. 5 is reaction chamber structure figure.
Embodiment
The present invention is described in further detail below in conjunction with drawings and Examples.
As shown in Figure 2: automatic sample handling system comprises seawater filtering device, " sample/titer " reversal valve, flow pump and flow (or pressure) monitoring feedback assembly.
In measuring process, system's control reversal valve switches to the seawater sample passage, and the Control Flow pump carries out sample delivery by predetermined flow simultaneously, and water sample is transported to reaction chamber by reversal valve, filtration unit by pump.The purpose of filtration unit is to guarantee that water sample does not have floating material and low concentration suspension.When needs carry out timing signal to system, system's control reversal valve makes it switch to the titer passage, demarcates correction automatically.
For the stability of flow that makes water sample, continuously and keep constant compression force, by the monitoring feedback to the flow (or pressure) of sample introduction pipeline, we adopt the running status that can be subjected to the program control miniature digital speed-control module of system to drive flow pump to realize this purpose.
As shown in Figure 3, ozone generating-device is made up of air strainer, instrument air dryer, pneumatic pump and controlling and driving part thereof, air themperature pressure monitoring feedback fraction, 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.Here, we adopt fuzzy control principle, and pressure, the temperature of air are monitored feedback, control the voltage output of adjustable high pressure generator, and cooperate the control to pneumatic pump, guarantee that ozoniferous concentration and flow satisfy the requirement of this method.
Reaction chamber is the core of total system, and it partly is made up of reaction chamber, reaction chamber well heater, water sample preheating apparatus and reaction chamber temperature Monitoring and Controlling.
Automatic sample handling system is sent seawater sample into reaction chamber, ozone and seawater sample react rapidly, optics pickup apparatus-the photomultiplier of the optical signals reaction chamber sidewall that produces (Japanese shore pine PhotosensorModules 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, the chemical oxygen consumption (COC) of judging detected water sample according to the signal power line output of going forward side by side shows.Demarcate with the standard water sample, find out the systematic error line data correcting process of going forward side by side.
For the temperature of reaction condition that guarantees reaction chamber satisfies 200 ℃, by reaction chamber temperature is monitored feedback, control heater keeps reaction chamber temperature constant, simultaneously, be even, the no thermograde of temperature that guarantees reaction chamber, we adopt the way of multiple spot monitoring, multiple spot heating to realize.
Embodiment: 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.
Experiment shows that both methods have good corresponding relation, its as a result the COD deviation smaller or equal to 10%.
Being compared as follows of this method and national marine monitoring standard (HY003.4-91) measured COD 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 |
Claims (6)
1. utilize ozone oxidation luminescence intensity principle to measure the method for sewater chemistry oxygen utilization, may further comprise the steps:
(1). utilize ozone generator to produce ozone, and guarantee that the concentration of ozone is that 18～25mg/l and flow are 0.5～21/min, it is sent into reaction chamber;
(2). utilize automatic sample handling system that tested seawater is sent into reaction chamber;
(3). ozone and seawater carry out hybrid reaction at reaction chamber, guarantee can fully to mix between ozone and the water sample, reaction chamber is carried out the optics sealing, and be provided with the detection window detectable signal;
(4). 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, calculating, correction, demonstration, printout.
2. according to the method for the measurement sewater chemistry oxygen utilization of claim 1, it is characterized in that, guarantee in the step (3) between ozone and the water sample can well-mixed method be: adopt porosint-Bubbled stone that ozone gas is emerged from the aperture of porous material surface, in the detected water sample around being mixed into.
3. according to the method for the measurement sewater chemistry oxygen utilization of claim 1, it is characterized in that, the measure that in the step (3) reaction chamber optics is sealed: during chamber designs, adopt light-proof material, intake-outlet takes curved design to prevent that the light catadioptric from entering reaction chamber, needs ventilative place to take multilayer every photo structure.
4. according to the method for the measurement sewater chemistry oxygen utilization of claim 3, it is characterized in that described light-proof material is the stainless steel metal plate, described multilayer adopts the stainless steel metal plate that staggers every photo structure.
5. according to the method for the measurement sewater chemistry oxygen utilization of claim 1, it is characterized in that the photomultiplier in the step (4) adopts Japanese shore pine Photosensor Modules H5784 Series.
6. according to the method for the measurement sewater chemistry oxygen utilization of claim 1, it is characterized in that the microcomputer data handling system in the step (4) realizes control and signal Processing to system by software programming.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB031118526A CN1177216C (en) | 2003-01-30 | 2003-01-30 | Method for measuring chemistry oxygen consumption of sea water based on luminous intensity principle of ozone oxidation |
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| Application Number | Priority Date | Filing Date | Title |
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| CNB031118526A CN1177216C (en) | 2003-01-30 | 2003-01-30 | Method for measuring chemistry oxygen consumption of sea water based on luminous intensity principle of ozone oxidation |
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| CN1431485A CN1431485A (en) | 2003-07-23 |
| CN1177216C true CN1177216C (en) | 2004-11-24 |
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Families Citing this family (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100504358C (en) * | 2005-08-29 | 2009-06-24 | 山东省科学院海洋仪器仪表研究所 | Method for measuring chemical oxygen consumption and total organic carbon by cooperation of ultrasonic wave and ozone |
| CN100476409C (en) * | 2005-08-29 | 2009-04-08 | 山东省科学院海洋仪器仪表研究所 | Method for measuring total organic carbon in water body by chemiluminescence in ozone oxidizing process |
| 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 |
| CN100454005C (en) * | 2006-11-03 | 2009-01-21 | 山东省科学院海洋仪器仪表研究所 | Method for examining deposit or organic matter content in soil by ozone oxidation |
| CN102103088A (en) * | 2010-12-27 | 2011-06-22 | 山东省科学院海洋仪器仪表研究所 | Device and method for measuring water quality chemical oxygen demand by ozone method for acquiring total light intensity |
| CN103196961B (en) * | 2013-04-18 | 2014-11-05 | 中国科学院大气物理研究所 | Ozone air sounding detector |
| CN105067596B (en) * | 2015-07-23 | 2018-04-13 | 山东省科学院海洋仪器仪表研究所 | Ozone-detecting element and detection method |
| CN108982479A (en) * | 2018-06-21 | 2018-12-11 | 天津大学 | The luminous device and method for detecting extra large Organic substance in water of ozone chemistry is miniaturized |
| 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 |
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