CN100543455C - Ozone oxidation and ultraviolet scanning spectrum integral way is measured the method for total organic carbon - Google Patents
Ozone oxidation and ultraviolet scanning spectrum integral way is measured the method for total organic carbon Download PDFInfo
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Abstract
The invention provides a kind of ozone oxidation and ultraviolet scanning spectrum integral way and measure the method for water body total organic carbon, it can solve the analysis longer duration that prior art exists, and analytic process is numerous and diverse, and condition harshness, energy consumption are big, produce secondary pollution problems.The present invention is based on organism has very strong absorption at ultraviolet spectrum district (220nm-400nm) principle, by the ozone oxidation pre-service, make in the water body and not absorb or the part larger molecular organics of faint absorption becomes micromolecule and produces absorption under the ozone oxidation effect at ultraviolet spectrum district (220nm-400nm), organism directly calculates the method for water body TOC in the absorbance integrated value of ultraviolet spectrum district (220nm-400nm) and the relation between the TOC in the water body of back according to handling again.
Description
Technical field
The present invention relates to the environmental chemistry monitoring technical field, specifically ozone oxidation and ultraviolet scanning spectrum integral way is measured the method for total organic carbon.
Background technology
Total organic carbon is called for short TOC.The method of present domestic measurement TOC is to carry out on the platform of laboratory basically equally, and the principle of employing mainly contains following several: (1) high temperature catalytic combustion-NDIR (Non-Dispersive Infrared) is surveyed (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 and is: 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 TOC in definite water sample.
(2). wet oxidation (persulfate)-NDIR (Non-Dispersive Infrared) is surveyed (NDIR) measuring principle and 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). it is basic identical with (2) that ultraviolet (UV)-persulfate oxidation-NDIR (Non-Dispersive Infrared) is surveyed (NDIR) method, just adds the irradiation of ultraviolet (UV) line, the cooxidant oxidation.
From said method these methods analyst longer durations as can be seen, analytic process is numerous and diverse, condition harshness, energy consumption are big, especially 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; For the ocean water body high concentration ion, as factor such as chloride ion content is relatively stable, its result's accuracy and reliability are under suspicion.
Though in recent years, development along with electronic technology, new material, new technology, new optical device, especially computer technology makes rapid progress, adopt the full-automatic corresponding appearance of method of analytical model automatically, but because the technical difficulty of some realization aspect is too big, though broken away from some shortcomings of lab analysis, the defective that reagent consumption is big, poor stability, sensitivity and resolution are low etc. is difficult to overcome does not obtain popularization truly equally.
Summary of the invention
The invention provides a kind of ozone oxidation and ultraviolet scanning spectrum integral way and measure the method for water body total organic carbon, it can solve the analysis longer duration that prior art exists, and analytic process is numerous and diverse, and condition harshness, energy consumption are big, produce secondary pollution problems.
In order to reach the purpose that solves the problems of the technologies described above, technical scheme of the present invention is, a kind of ozone oxidation and ultraviolet scanning spectrum absorbance integrated value is calculated the method for total organic charcoal, this method adopts pick-up unit, pick-up unit comprises electrolysis type ozone generator, ozone solution balance cylinder, sensing chamber, uv scan sniffer, control device, computer data processing unit, the pump of delivery of ozone solution and water sample, connect by pipeline between ozone solution balance cylinder and sensing chamber and other liquid, described method is undertaken by following step by pick-up unit:
(1) utilize electrolysis type ozone generator to produce the ozone solution of steady concentration, make ozone solution circulation ozone solution balance cylinder by pump, the ozone solution mobile equilibrium pipe of optical glass system is housed in the ozone solution balance cylinder, when ozone solution circulation mobile equilibrium pipe, so that the concentration mobile equilibrium of ozone solution;
(2) ozone solution is after flowing through ozone solution mobile equilibrium pipe, mixes with water sample in the detected water sample pipeline, and mixed reaction solution is ozone solution oxidation larger molecular organics under flox condition, after enter sensing chamber;
(3) mixed solution enters sensing chamber after flowing through pipeline, and the uv scan sniffer carries out ultraviolet all band 220nm-400nm scanning to water sample;
(4) be contrast with blank water sample, computer data processing unit calculates the full wave absorbance data of ultraviolet according to the scanning result of blank water sample and detected water sample;
(5) computer data processing unit carries out integral and calculating according to the ultraviolet all band absorption spectra data that obtains and quantizes, and the relation according to integrated value and standard TOC calculates the TOC of water sample again, and show, printout.
In technical scheme of the present invention, also have following technical characterictic: described ozone solution flow is 8-15ml/min, and concentration is 10-15mg/L.
In technical scheme of the present invention, also have following technical characterictic: the ratio of described ozone solution flow and detected water sample flow is 1: 0.5-0.8.
In technical scheme of the present invention, also have following technical characterictic: described ozone generator is an electrolysis type ozone generator.Electrolysis type ozone generator adopts electrolysis distilled water, belongs to the on-consumable type, have easy to operate, install simple and easy, the safety coefficient height, long service life, environmental suitability reaches characteristics such as ozone concentration height, purity height by force.
In technical scheme of the present invention, also have following technical characterictic: described water sample pump is a peristaltic pump, and described pipeline adopts polytetrafluoroethylmaterial material to make.
In technical scheme of the present invention, also have following technical characterictic: the sensing chamber both sides in the described pick-up unit are provided with silica glass window.
In technical scheme of the present invention, also have following technical characterictic: the uv scan sniffer is made of deuterium lamp, convergent lens, plane grating beam splitting system, photomultiplier, and the plane grating beam splitting system comprises collimator objective, collecting objective, stepper motor, plane grating.
In technical scheme of the present invention, also have following technical characterictic: the light that the deuterium lamp in the uv scan sniffer sends becomes directional light after by convergent lens, directional light sees through silica glass window and enters sensing chamber, after the water sample absorption, enter the plane grating beam splitting system by convergent lens again, light becomes directional light and puts into plane grating after the collimator objective reflection of plane grating beam splitting system, plane grating resolves into spectrum as dispersion element with the complex light diffraction that receives, and outgoing out-of-plane grating splitting system is to photomultiplier after collecting objective is assembled;
Motion by stepper motor in the plane grating beam splitting system, can scan and obtain the whole wave band intrinsic resolution of 220nm-400nm the absorption light intensity of each wavelength that is 1nm, photomultiplier converts the light intensity signal that is received to corresponding electric signal, therefore can obtain the light intensity signal of all band ultraviolet light after detected water sample absorbs, the spectroscopic data that obtains according to blank water sample calculates the full wave light absorption value of 220nm-400nm again;
Computer data processing unit is by the control of software programming realization to whole device, signal Processing and carry out integral and calculating and quantize according to the ultraviolet all band absorption spectra data that obtains, relation according to integrated value and standard TOC calculates the TOC of water sample again, and show, printout.
In technical scheme of the present invention, also have following technical characterictic: described photomultiplier adopts Japanese shore pine Photosensor Modules H5784 Series.
The present invention is based on organism has very strong absorption at ultraviolet spectrum district 220nm-400nm principle, but the part larger molecular organics that also exists in the water body, there is not tangible absorption spectrum as carbohydrate etc. at ultraviolet region, can make the long-chain organism be degraded to the short chain organism by the ozone oxidation pre-service, larger molecular organics is degraded to small organic molecule, its design feature is obvious, has in various degree absorption intensity at ultraviolet region, therefore utilize after the ozone oxidation pre-service that organic contaminant (TOC) has very high representativeness in the absorbance log integrated value quantitatively characterizing water body that ultraviolet region (220nm-400nm) obtains, simultaneously, for specific body of water, contained material composition is general to be changed not quite.Therefore can utilize of the reflection of ultraviolet absorptivity integrated value as the overall target (TOC) of organic contaminant, method has been simplified the traditional operation step, the consumption and the waste water pollution problem of chemical reagent have been avoided, utilize that organism directly calculates the method for water body TOC in the absorbance integrated value of ultraviolet spectrum district 220nm-400nm and the relation between the TOC in the water body.Belong to the environmental protection method.
This method adopts the ozone solution balance cylinder by the ozone solution of electrolysis type ozone generator generation concentration known, makes the concentration stabilize of ozone solution, and then can quantize.Ozone solution with carry out after water sample mixes oxidation send out should after, circulation sensing chamber, carry out all band scanning by the uv scan sniffer, the optical signals photomultiplier that produces detects, again by data handling system according to the absorbance integrated value that obtains and the relation of standard TOC, calculate water body TOC value.
Method solution conventional oxygen of the present invention or air high-voltage power generation ozone safe differential, the shortcoming that ozone concentration is low, energy consumption is big have solved tradition with wet chemical method pipeline complexity, and sensitivity is not high, the shortcoming of poor reproducibility.Realized easy to operate, install simple and easy, environmental suitability is strong, the automaticity height is measured fast the characteristics that the range of linearity is wide, lower with classic method than the technology maturity that technology itself has, complicated operation, the character that the marketing difficulty is big is compared, and the advantage that this method had can make this method developed and popularization in fields such as environmental analyses.
The inventive method can be divided into four parts by integrated portable injection chemiluminescence Photodetection system light, mechanical, electrical, that form by operational module:
First is the sample flow path part, mainly be to produce ozone solution (concentration known) by electrolysis type ozone generator, ozone solution passing ratio valve and detected water sample (blank water sample) are passed through separately peristaltic pump with the very high mode mixed flow sensing chamber of reappearance.
Second portion is the uv scan sniffer, is made of deuterium lamp, convergent lens, plane grating beam splitting system, photomultiplier.The absorption light intensity of each wavelength that this part mainly can scan and obtain the whole wave band intrinsic resolution of 220nm-400nm is 1nm, photomultiplier converts the light intensity signal that is received to corresponding electric signal, therefore can obtain the light intensity electric signal of all band ultraviolet light after detected water sample absorbs, the spectroscopic data that obtains according to blank water sample calculates the full wave light absorption value of 220nm-400nm again.
Third part is data acquisition, recording section, and this part is finished collection, A/D conversion, transmission and the storage of electric signal.
The 4th part is a computer data processing system, the main light intensity electric signal of all band ultraviolet light after detected water sample absorbs of being responsible for obtaining, again according to the ultraviolet absorptivity of the whole wave band of data computation of blank water sample, and carry out all band absorbance Integral Processing, then according to the corresponding relation of absorbance integrated value and TOC, calculate the TOC of water sample, and show, printout.
Is present very effective express-analysis means by integrated ozone oxidation device, uv scan sniffer, data acquisition, software processes to the measurement of water body TOC, is the effective environmental analyzing detecting method.
Contrast as follows:
Water body TOC
The contrast feature | Classic method | Day island proper Tianjin | U.S.'s Hash | The ozone oxidation and ultraviolet scanning spectrum integral method |
Measurement range (mg/l) | Lower limit 0.15 | 0.2-? 20000 | 0.2-? 20000 | 0.1-20000 |
Whether sample is handled | Need | Need | Need | Do not need |
Measuring Time/each | 4-6 hour | 1 hour | 1 hour | Less than 1 minute |
Reagent consumption | In a large number | In a large number | In a large number | Trace |
Have or not noxious material to form | Have | Have | Have | No |
Environment for use | Only for the laboratory | The laboratory | The laboratory | Laboratory/scene |
Working method | Burning | Combustion catalysis | Combustion catalysis | Uv absorption |
Measuring accuracy % | 20-30 | 20 | 15 | 10 |
The present invention-ozone oxidation and ultraviolet scanning spectrum integral way is measured the method for water body TOC, have that response speed is fast, reagent consumption is little, good stability, sensitivity and the high characteristics of resolution, can measure water body TOC accurately, continuously, fast, can be at the medium-term and long-term reliably working of water body environment.
Description of drawings
Below in conjunction with drawings and Examples method of the present invention is described in detail.
Fig. 1 is the inventive method principle of work process flow diagram;
Fig. 2 is the pick-up unit structural representation that the inventive method adopts.
1. distilled water gatherer; 2. electrolysis type ozone generator; 3. distilled water feeder; 4. cool cycles hydrophone; 5. ozone solution balance cylinder; 6. ozone mobile equilibrium pipe; 7. ozone solution peristaltic pump; 8. water sample peristaltic pump; 9. water sample; 10. sensing chamber; 11. convergent lens; 12. deuterium lamp light source; 13. water sample outlet; 14. photomultiplier; 15. control section; 16. data processing section; 17. stepper motor; 18. plane grating beam splitting system; 19. collimator objective; 20. collecting objective; 21. plane grating.
Embodiment
The inventive method is undertaken by following step by pick-up unit:
(1) utilize electrolysis type ozone generator 2 to produce the ozone solution of steady concentrations, the concentration of ozone is 10mg/l, by the peristaltic pump 7 ozone solution balance cylinder 5 of circulating under the 10ml/min flow.
(2) ozone solution mixes with water sample 9 grades that peristaltic pump 8 is carried after flowing through ozone solution mobile equilibrium pipe 6, in the mixed flow process oxidation reaction takes place, and the water sample flow is 8ml/min.
(3) mixed reaction solution is behind the one section pipeline that flows, and together stream is by sensing chamber 10, and the uv scan sniffer carries out ultraviolet all band 220-400nm scanning to water sample.
(4), calculate the full wave extinction spectrum data of ultraviolet according to the scanning result of blank solution and water sample.
(5) data processing equipment 16 is according to the ultraviolet all band absorption spectra data that obtains, and carries out integral and calculating and quantizes, and calculates water sample TOC according to the relation of integrated value and TOC, and show, printout.
Ozone solution mixes with water sample, the flow of ozone solution is greater than the flow of water sample, on the one hand water sample is carried out oxidation, on the other hand water sample had diluting effect, because the organic basis of ultra-violet absorption spectrum quantitatively characterizing is lambert-Bill's law of light absorption, this law only is applicable to lean solution, intermolecular force is big in the highly concentrated solution, can cause absorbance and concentration linearity to depart from, because concentration can be very high sometimes for organism in the water body, so device can solve the problem that the correlativity of absorption spectrum parameter and TOC departs from sometimes by the equal proportion dilution.
The uv scan sniffer is made of deuterium lamp 12, convergent lens 11, plane grating beam splitting system 18, photomultiplier 14.The absorption light intensity of each wavelength that this part mainly can scan and obtain the whole wave band intrinsic resolution of 220-400nm is 1nm, photomultiplier 14 converts the light intensity signal that is received to corresponding electric signal, therefore can obtain the light intensity electric signal of all band ultraviolet light after detected water sample absorbs, the spectroscopic data that obtains according to blank water sample further can calculate the full wave light absorption value of 220nm-400nm again.
The uv scan sniffer constitutes 14 by deuterium lamp 12, convergent lens 11, plane grating beam splitting system 18, photomultiplier.The plane grating beam splitting system is by collimator objective 19, collecting objective 20, stepper motor 17, plane grating 21 compositions such as grade, the light that deuterium lamp 12 sends becomes directional light after by convergent lens 11, directional light sees through silica glass window and enters sensing chamber 10, after the water sample absorption, enter plane grating beam splitting system 18 by convergent lens 11 again, light becomes directional light and puts into plane grating 21 after collimator objective 19 reflections of plane grating beam splitting system, plane grating 21 resolves into spectrum as dispersion element with the complex light diffraction that receives, and outgoing out-of-plane grating splitting system is to photomultiplier 14 after collecting objective 20 is assembled.Motion by stepper motor 17 in the plane grating beam splitting system, can scan and obtain the whole wave band intrinsic resolution of 220nm-400nm the absorption light intensity of each wavelength that is 1nm, photomultiplier converts the light intensity signal that is received to corresponding electric signal, therefore can obtain the light intensity electric signal of all band ultraviolet light after detected water sample absorbs, the spectroscopic data that obtains according to blank water sample further can calculate the full wave light absorption value of 220nm-400nm again.
Electrolysis type ozone generator 2 adopts the electrode film treatment technology, and ozone solution balance cylinder 5 has the effect that keeps ozone solution concentration.
Utilize computer data processing unit 16, realize that by software programming to the control of system and the processing of absorbance signal, integration by the corresponding relation of integrated value and standard method TOC, calculates water sample TOC again, and show, printout.
Experiment is for example: from the bathing beach, several sea areas samplings such as harbours, off-lying sea, be divided into two parts.Portion detects in Shandong Province's ocean monitoring technologytechnologies key lab, and portion is measured with method of the present invention.
Experiment shows that both methods have good corresponding relation, and its result error is smaller or equal to 10%.
This method is compared as follows with " marine monitoring standard-sea water analysis (GB17378.4-1998) " measured TOC value:
The above only is preferred embodiment of the present invention, is not to be the restriction of the present invention being made other form, and any those skilled in the art may utilize the technology contents of above-mentioned announcement to be changed or be modified as the equivalent embodiment of equivalent variations.But every technical solution of the present invention content that do not break away to any simple modification, equivalent variations and remodeling that above embodiment did, still belongs to the protection domain of technical solution of the present invention according to technical spirit of the present invention.
Claims (7)
1. an ozone oxidation and ultraviolet scanning spectrum absorbance integrated value is calculated the method for total organic carbon, it is characterized in that this method adopts pick-up unit, pick-up unit comprises electrolysis type ozone generator, ozone solution balance cylinder, sensing chamber, uv scan sniffer, control device, computer data processing unit, the pump of delivery of ozone solution and water sample, connect by pipeline between ozone solution balance cylinder and sensing chamber and other liquid, described method is undertaken by following step by pick-up unit:
(1) utilize electrolysis type ozone generator to produce the ozone solution of steady concentration, make ozone solution circulation ozone solution balance cylinder by pump, the ozone solution mobile equilibrium pipe of optical glass system is housed in the ozone solution balance cylinder, when ozone solution circulation mobile equilibrium pipe, so that the concentration mobile equilibrium of ozone solution;
(2) ozone solution is after flowing through ozone solution mobile equilibrium pipe, mixes with water sample in the detected water sample pipeline, and mixed reaction solution is ozone solution oxidation larger molecular organics under flox condition, after enter sensing chamber;
(3) mixed solution enters sensing chamber after flowing through pipeline, and the uv scan sniffer carries out ultraviolet all band 220nm-400nm scanning to water sample;
(4) be contrast with blank water sample, computer data processing unit calculates the full wave absorbance data of ultraviolet according to the scanning result of blank water sample and detected water sample;
(5) computer data processing unit carries out integral and calculating according to the ultraviolet all band absorption spectra data that obtains and quantizes, and the relation according to integrated value and standard total organic carbon calculates the total organic carbon of water sample again, and show, printout;
Described ozone solution flow is 8-15ml/min, and concentration is 10-15mg/L;
The ratio of described ozone solution flow and detected water sample flow is 1: 0.5-0.8.
2. method according to claim 1 is characterized in that described ozone generator is an electrolysis type ozone generator.
3. method according to claim 1 is characterized in that described pump is a peristaltic pump, and described pipeline adopts polytetrafluoroethylmaterial material to make.
4. method according to claim 1 is characterized in that the sensing chamber both sides in the described pick-up unit are provided with silica glass window.
5. method according to claim 1, it is characterized in that the uv scan sniffer is made of deuterium lamp, convergent lens, plane grating beam splitting system, photomultiplier, the plane grating beam splitting system comprises collimator objective, collecting objective, stepper motor, plane grating.
6. method according to claim 5, it is characterized in that becoming directional light after light that the deuterium lamp in the uv scan sniffer sends is by convergent lens, directional light sees through silica glass window and enters sensing chamber, after the water sample absorption, enter the plane grating beam splitting system by convergent lens again, light becomes directional light and puts into plane grating after the collimator objective reflection of plane grating beam splitting system, plane grating resolves into spectrum as dispersion element with the complex light diffraction that receives, and outgoing out-of-plane grating splitting system is to photomultiplier after collecting objective is assembled;
Motion by stepper motor in the plane grating beam splitting system, the absorption light intensity of each wavelength that it is 1nm that scanning obtains the whole wave band intrinsic resolution of 220nm-400nm, photomultiplier converts the light intensity signal that is received to corresponding electric signal, therefore obtain the light intensity signal of all band ultraviolet light after detected water sample absorbs, the spectroscopic data that obtains according to blank water sample calculates the full wave light absorption value of 220nm-400nm again;
Computer data processing unit is by the control of software programming realization to whole device, signal Processing and carry out integral and calculating and quantize according to the ultraviolet all band absorption spectra data that obtains, relation according to integrated value and standard total organic carbon calculates the total organic carbon of water sample again, and show, printout.
7. method according to claim 6 is characterized in that described photomultiplier adopts Japanese shore pine Photosensor Modules H5784 Series.
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GB2466664B (en) * | 2009-01-06 | 2015-04-01 | Perlemax Ltd | Plasma microreactor apparatus, sterilisation unit and analyser |
CN101793820B (en) * | 2009-03-27 | 2013-01-02 | 广州市怡文环境科技股份有限公司 | On-line monitoring method for double module linkage water quality |
CN102621046A (en) * | 2010-07-21 | 2012-08-01 | 山东省科学院海洋仪器仪表研究所 | Method for measuring total organic carbon in water body |
CN104359843A (en) * | 2014-11-13 | 2015-02-18 | 杭州纳宏光电科技有限公司 | Water quality analysis device based on Airy light beam |
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CN106770212B (en) * | 2016-11-22 | 2023-08-25 | 山东省科学院海洋仪器仪表研究所 | Device for on-line monitoring content of soluble organic carbon in seawater |
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CN1865939A (en) * | 2006-06-09 | 2006-11-22 | 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 |
CN1967215A (en) * | 2006-11-08 | 2007-05-23 | 浙江大学 | UV scanning type multispectral water-quality COD rapid detection method and device therefor |
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CN1865939A (en) * | 2006-06-09 | 2006-11-22 | 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 |
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