CN100541181C - Mode of oxidizing floating injected ozone is measured the method for chemical oxygen demand (COD) and total organic carbon - Google Patents
Mode of oxidizing floating injected ozone is measured the method for chemical oxygen demand (COD) and total organic carbon Download PDFInfo
- Publication number
- CN100541181C CN100541181C CNB2007100131652A CN200710013165A CN100541181C CN 100541181 C CN100541181 C CN 100541181C CN B2007100131652 A CNB2007100131652 A CN B2007100131652A CN 200710013165 A CN200710013165 A CN 200710013165A CN 100541181 C CN100541181 C CN 100541181C
- Authority
- CN
- China
- Prior art keywords
- solution
- ozone
- cod
- water sample
- signal
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Fee Related
Links
Images
Abstract
The invention provides a kind of mode of oxidizing floating injected ozone and measure the method for chemical oxygen demand (COD) and total organic carbon, produce the ozone solution of concentration known by electrolysis type ozone generator, adopt the ozone solution balance cylinder, the oxidability of ozone solution is strengthened greatly, ozone solution mix with water sample carry out oxidation send out should after, successively mix again with sodium bicarbonate solution, luminol solution, cobalt ions solution, the chemiluminescence signal that produces is detected by photomultiplier, and calculates the chemical oxygen demand (COD) and the total organic carbon of water sample.The present invention has highly sensitive, the range of linearity is wide, and fast, favorable reproducibility, automaticity height, can be applied in fields such as environmental analyses, and solve conventional oxygen or air high-voltage power and produce ozone poor stability, ozone concentration is low, energy consumption is big shortcoming.
Description
Technical field
The present invention relates to the environmental chemistry monitoring technical field, specifically being based on luminol can be decomposed the hydroxyl radical free radical institute's oxidation that produces and produce chemiluminescent phenomenon by ozone and ozone, utilize the flow injection technology, the difference measurement chemical oxygen demand of water body (COD) of the chemiluminescence intensity that is produced by blank solution (redistilled water) and detected water sample and the method for total organic carbon (TOC).
Background technology
The method of present domestic measurement water body chemical oxygen utilization (COD) is to adopt the analytical approach of potassium dichromate or permanganate oxidation titration substantially, the 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; For the ocean water body high concentration ion, as chlorion, factor such as content is relatively stable, its result's accuracy and reliability are under suspicion.
In recent years, development along with electronic technology, new material, new technology, new optical device, especially computer technology makes rapid progress, come the corresponding appearance of method of analyzing water body chemical oxygen demand (COD) by automatic analyzer, though these technology have been broken away from some shortcomings of lab analysis, as longer duration, analytic process is numerous and diverse, condition harshness etc., but the defective that it also exists, and poor stability, sensitivity and resolution are low, ion interference etc. is difficult to overcome, make it range of application and be restricted, fail to be widely used.
The method of present domestic measurement total organic carbon (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) 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 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 total organic carbon (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, and condition harshness, energy consumption are big, especially produce secondary pollution etc.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.
In addition, also have some similar prior aries, produce ozone poor stability, ozone concentration is low, energy consumption is big shortcoming but exist oxygen or air high-voltage power, complex structure, sensitivity is not high, and error is big, shortcomings such as poor reproducibility.
Summary of the invention
In order to solve the deficiency of prior art, the invention provides a kind of mode of oxidizing floating injected ozone and measure the method for chemical oxygen demand (COD) and total organic carbon, it can solve the analysis longer duration that prior art exists, analytic process is numerous and diverse, condition harshness, energy consumption are big, especially 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 mode of oxidizing floating injected ozone is measured the method for chemical oxygen demand (COD) and total organic carbon, it is characterized in that this method adopts pick-up unit, pick-up unit comprises electrolysis type ozone generator, the distilled water feeder, the ozone solution balance cylinder, sensing chamber, Electro-Optical Sensor Set, control device, data processing equipment, the pump of delivery of ozone solution and other liquid, electrolysis type ozone generator, 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 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, be provided with uviol lamp in its side, when ozone solution circulation mobile equilibrium pipe, ozone solution is through the irradiation of uviol lamp, and part is decomposed the generation hydroxyl radical free radical, and hydroxyl radical free radical and ozone can be together as oxygenant oxidation organism.
(2). ozone solution mixes with water sample in the detected water sample pipeline earlier after flowing through ozone solution mobile equilibrium pipe, mix afterwards ozone solution immediately with water sample in organism oxidation reaction takes place under mobile non-mobile equilibrium condition.
(3). mixed reaction solution flows behind one section pipeline, mix with sodium bicarbonate solution in the sodium bicarbonate pipeline again, sodium bicarbonate consumes remaining hydroxyl radical free radical in the solution rapidly as the trapping agent of hydroxyl radical free radical, because hydroxyl radical free radical can produce chemiluminescence by the oxidation luminol, bring interference for the ozone oxidation luminol.
(4). continue in pipeline, to flow with the mixed solution of sodium bicarbonate, flow behind the segment distance successively with the luminol pipeline in luminol solution and the cobalt ions solution in the cobalt ions solution pipeline mix, stream passes through sensing chamber together, the chemiluminescence signal that residual ozone and luminol produce in the photomultiplier detection solution in the Electro-Optical Sensor Set; Because there is trace metal ion in the water sample, as ferric ion (Fe
2+), cobalt ions (Co
2+), copper ion (Cu
2+) or the like, equal energy catalysis luminol chemiluminescence, in order to eliminate the interference of metallic ion in the potential matrix water sample, the cobalt ions that adopts the high several magnitude of metallic ion in the concentration ratio natural water body is covered the catalytic action of other metallic ions in the water sample as screening agent with stronger cobalt ions catalytic luminescence signal.
(5). the light signal that solution sent that the photomultiplier convection current is passed through is gathered amplification, and convert electric signal to and send into the microcomputer data processing equipment, data processing equipment quantizes signal, calculates the chemical oxygen demand (COD) and the total organic carbon of water sample, and show, printout.
Described ozone solution flow is 0.05-0.10ml/min, and concentration is 8-13mg/L.
Described detected water sample flow is 0.5-1.0ml/min.
Described sodium bicarbonate solution flow is 0.5-1.0ml/min, and concentration is 0.1-0.3mol/L.
Described luminol solution flow is 0.5-1.0ml/min, and concentration is (0.8-1.2) * 10
-4Mol/L.
Described cobalt ions liquid inventory is 0.05-0.10ml/min, and concentration is (1.8-2.2) * 10
-3Mol/L.
The luminous intensity integrated value of 50-150 second after selecting the record chemiluminescence signal stable, difference and the COD of standard method and the corresponding relation of TOC by water sample and redistilled water integrated value, calculate the chemical oxygen demand (COD) and the total organic carbon of water sample, and show, printout.
Described ozone generator is an electrolysis type ozone generator, and 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 reach characteristics such as ozone concentration height, purity height by force.
Described pump is a peristaltic pump, and described pipeline adopts polytetrafluoroethylmaterial material to make.
The light signal that reaction is sent is faint chemiluminescence signal, maximum emission wavelength is at 425nm, faint optical signal 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, is amplified to the certain voltage amplitude and send that the A/D ALT-CH alternate channel of data processing equipment quantizes, Integral Processing.
Utilize the microcomputer data processing equipment, by the calculating of software programming realization to control, signal Processing, chemical oxygen demand (COD) and the total organic carbon of device.
Photomultiplier adopts Japanese shore pine Photosensor Modules H5784 Series.
Adopt ozone solution mobile equilibrium chamber, make ozone produce hydroxyl radical free radical in the effect lower part of uviol lamp, ozone and ultraviolet are collaborative to the oxidation efficiency of organic oxidation efficiency much larger than single-oxidizer.
The inventive method is by integrated portable injection chemiluminescence Photodetection system light, mechanical, electrical, that form, can be divided into four parts by operational module: first is the flow injection part, mainly be to produce ozone solution (concentration known) by electrolysis type ozone generator, ozone solution is moving as one under the promotion of peristaltic pump, the continuous current-carrying of no airspace, detected water sample, sodium bicarbonate solution, luminol solution, cobalt ions (Co
2+) solution is injected in the current-carrying as the peristaltic pump of sample by separately in the very high mode of reappearance successively, travelling forward in the process owing to convection current and diffusion are dispersed into the sample band that has concentration gradient one by one with current-carrying, the sample band respectively with current-carrying in the hydroxyl radical free radical generation chemical reaction that decomposes of ozone molecule and ozone, produce at last can be detected chemiluminescence signal, by carrier band in sensing chamber.Second portion is opto-electronic conversion and amplifier section, mainly adopts the low-light photomultiplier as detecting element, carrier fluid circulation sensing chamber, and the light signal of generation is transformed into electric signal immediately, and by continuous recording.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 the microcomputer data handling system, main being responsible for carried out integration to the continuous signal that obtains, again according to difference and the COD of standard method and the corresponding relation of TOC of signal integration data and blank solution (redistilled water) integrated value, calculate the chemical oxygen demand (COD) (COD) and the total organic carbon (TOC) of water sample, and show, printout.
Utilize the high sensitivity of chemiluminescence reaction to become the desirable means of detection reaction material.Luminol, i.e. the amino phthalylhydrazine of 3-because of its detection sensitivity height, and is reflected at aqueous phase and carries out, so be luminous agent the most frequently used in the chemiluminescence analysis.Can produce the chemiluminescence phenomenon in the middle of ozone and the luminol oxidizing process, utilize this phenomenon, adopt the flow injection technology, by detecting the amount that residual ozone and luminol reaction produce in the solution of flow injection reaction back chemiluminescence intensity calculates the ozone that consumes in the flow injection reaction oxidation reaction process, the amount of the ozone by consumption can reflect the content of chemical oxygen demand (COD) in the water body (COD) and total organic carbon (TOC).The error of bringing for the elimination system, the microcomputer data handling system is selected the signal of gathering and 100 second the luminous intensity integrated value of record chemiluminescence signal after stable, again because deozonize also contains the material that makes luminol luminous outward in the detected water sample, in order to eliminate the interference that background brings, we are by adopting the difference of detected water sample and blank solution (redistilled water) integrated value, be amount and the COD of standard method and the corresponding relation of TOC of the ozone that organism consumed in the water sample, calculate the chemical oxygen demand (COD) (COD) and the total organic carbon (TOC) of water sample.
Because chemiluminescence reaction speed is very fast usually; so must guarantee sample and luminescence reagent can be fast, effectively, highly reproduction mixes; the flow injection technology has satisfied this requirement; therefore combine with the chemiluminescence analysis method of the mode of oxidizing floating injected ozone measurement chemical oxygen demand (COD) that produces and total organic carbon of flow injection is not only highly sensitive; the range of linearity is wide; and fast, favorable reproducibility, automaticity height, can be developed rapidly in fields such as environmental analyses.
, electrooptical device luminous by integrated chemical, data acquisition, software processes are present very effective express-analysis means to the measurement of chemical oxygen demand of water body (COD) and total organic carbon (TOC), are the ideal environment analyzing detecting methods.
Contrast as follows:
Chemical oxygen demand of water body (COD)
| The contrast feature | Classic method | SERES-COD/ France | The oxidizing floating injected ozone method |
| Measurement range (mg/L) | 0.8-1000 | 30-700 | 0.2-1000 |
| The measurement number of times/hour | 1-2 | 4-6 | Continuously |
| Measuring Time/each | 20-30 minute | 10-20 minute | Less than 1 minute |
| Reagent consumption | In a large number | In a large number | Trace |
| Have or not noxious material to form | Have | Have | No |
| Environment for use | Only for the laboratory | The laboratory | Laboratory/scene |
| Measuring accuracy % | 20-30 | 20 | 10 |
Water body total organic carbon (TOC)
| The contrast feature | Classic method | Day island proper Tianjin | U.S.'s Hash | The oxidizing floating injected ozone 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 |
1 |
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 | Chemiluminescence |
| Measuring accuracy % | 20-30 | 20 | 15 | 10 |
The present invention-mode of oxidizing floating injected ozone is measured the method for chemical oxygen demand of water body (COD) and total organic carbon (TOC), have that response speed is fast, reagent consumption is little, good stability, sensitivity and the high characteristics of resolution, can measure chemical oxygen demand of water body (COD) and water body total organic carbon (TOC) accurately, continuously, fast, can be at the medium-term and long-term reliably working of water body environment.
This method produces the ozone solution of concentration known by electrolysis type ozone generator, adopt the ozone solution balance cylinder, the oxidability of ozone solution is strengthened greatly, ozone solution mix with water sample carry out oxidation send out should after, again successively and sodium bicarbonate solution, luminol solution, cobalt ions solution mixes, the chemiluminescence signal that produces is detected by photomultiplier, method solves conventional oxygen or the air high-voltage power produces the ozone poor stability, ozone concentration is low, the shortcoming that energy consumption is big, solved traditional mobile injecting method pipeline complexity, 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, the technology maturity that has with mobile this province of injected chemical luminesceence analysis technology of tradition is low, 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.
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. second distillation water collector; 2. electrolysis type ozone generator; 3. distilled water feeder; 4. cool cycles hydrophone; 5. ultraviolet lamp tube; 6. ozone mobile equilibrium pipe; 7. ozone solution peristaltic pump; 8. water sample peristaltic pump; 9. water sample; 10. sodium bicarbonate peristaltic pump; 11. sodium bicarbonate solution; 12. luminol peristaltic pump; 13. luminol solution; 14. cobalt ions solution peristaltic pump; 15. cobalt ions solution; 16. sensing chamber; 17. data processing section; 18. control section; 19. photodetection part; 20. water sample gatherer; 21. ozone solution balance cylinder.
Embodiment
The inventive method comprises following step:
(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 21 of circulating under the 0.05ml/min flow.
(2). ozone solution at first mixes with the water sample 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 0.5ml/min.
(3). mixed reaction solution is behind the one section pipeline that flows, mix with the sodium bicarbonate solution that peristaltic pump 10 is carried again, sodium bicarbonate consumes remaining hydroxyl radical free radical in the solution rapidly as the trapping agent of hydroxyl radical free radical, because hydroxyl radical free radical can produce chemiluminescence by the oxidation luminol, bring interference for the ozone oxidation luminol.The sodium bicarbonate solution flow is 0.5ml/min, and concentration is 0.2mol/L.
(4). continue in pipeline, to flow the luminol solution and the cobalt ions (Co that successively carry with peristaltic pump 12 and peristaltic pump 14 behind the segment distance that flows with the mixed solution of sodium bicarbonate
2+) the solution mixing, stream passes through sensing chamber 16 together, the chemiluminescence signal that residual ozone and luminol produce in the photomultiplier detection record solution.Because there is trace metal ion in the water sample, as ferric ion (Fe
2+), cobalt ions (Co
2+), copper ion (Cu
2+) or the like, equal energy catalysis luminol chemiluminescence, in order to eliminate the interference of metallic ion in the potential matrix water sample, the cobalt ions that adopts the high several magnitude of metallic ion in the concentration ratio natural water body is covered the catalytic action of other metallic ions in the water sample as screening agent with stronger cobalt ions catalytic luminescence signal.The luminol solution flow is 0.5ml/min, and concentration is 1 * 10
-4Mol/L.The cobalt ions liquid inventory is 0.05ml/min, and concentration is 2 * 10
-3Mol/L.
(5). the light signal that solution sent that the photomultiplier convection current of photodetection 19 is passed through is gathered amplification, and convert electric signal to and send into the microcomputer data handling system, data handling system quantizes signal, and 100 seconds luminous intensity integrated value after selecting the record chemiluminescence signal stable, difference and the COD of standard method and the corresponding relation of TOC by water sample and blank solution (redistilled water) integrated value, calculate the chemical oxygen demand (COD) (COD) and the total organic carbon (TOC) of water sample, and show, printout.
The light signal that reaction is sent is faint chemiluminescence signal, maximum emission wavelength is at 425nm, faint optical signal 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, is amplified to the certain voltage amplitude and send the A/D ALT-CH alternate channel of data processing section to quantize Integral Processing.
Utilize the microcomputer data handling system, realize control and signal Processing, aspect data processing, adopt standard substance can cause that to optical system gain, sample turbidity the factor of systematic error carries out data correction and handle system by software programming.
Described electrolysis type ozone generator 2 adopts the electrode film treatment technology, and the ozone solution concentration height that is produced is stable.
Mixed solution circulation sensing chamber 16, the chemiluminescence that remaining ozone solution and luminol produce is by the Electro-Optical Sensor Set 19-photomultiplier of sensing chamber's 16 sidewalls, adopt Japanese shore pine PhotosensorModules H5784 Series, gather amplification, and convert electric signal to and send into the microcomputer data handling system.Utilize the microcomputer data handling system, realize signal is handled by software programming, integration, again by water sample and the difference of blank solution (redistilled water) integrated value and the corresponding relation of standard method COD and TOC, calculate the chemical oxygen demand (COD) (COD) and the total organic carbon (TOC) of water sample, 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 COD and 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 (5)
1. a mode of oxidizing floating injected ozone is measured the method for chemical oxygen demand (COD) and total organic carbon, it is characterized in that this method adopts pick-up unit, pick-up unit comprises the pump of electrolysis type ozone generator, distilled water feeder, ozone solution balance cylinder, sensing chamber, Electro-Optical Sensor Set, control device, data processing equipment and delivery of ozone solution and other liquid, connect by pipeline between electrolysis type ozone generator, ozone solution balance cylinder, 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, be provided with uviol lamp in its side, when ozone solution circulation mobile equilibrium pipe, ozone solution is through the irradiation of uviol lamp;
(2). ozone solution is after flowing through ozone solution mobile equilibrium pipe, water sample first and in the detected water sample pipeline mixes, oxidation reaction takes place in organism in mixing back ozone solution and the water sample under the non-mobile equilibrium condition that flows, described ozone solution flow is 0.05-0.10ml/min, and concentration is 8-13mg/L;
(3). mixed reaction solution flows behind one section pipeline, mixes with sodium bicarbonate solution in the sodium bicarbonate pipeline again;
(4). continue in pipeline, to flow with the mixed solution of sodium bicarbonate, flow behind the segment distance successively with the luminol pipeline in luminol solution and the cobalt ions solution in the cobalt ions solution pipeline mix, stream passes through sensing chamber together, the chemiluminescence signal that residual ozone and luminol produce in the photomultiplier detection solution in the Electro-Optical Sensor Set;
(5). the light signal that solution sent that the photomultiplier convection current is passed through is gathered amplification, and convert electric signal to and send into the microcomputer data processing equipment, data processing equipment quantizes signal, calculates the chemical oxygen demand (COD) and the total organic carbon of water sample, and show, printout;
The detected water sample flow is 0.5-1.0ml/min;
The sodium bicarbonate solution flow is 0.5-1.0ml/min, and concentration is 0.1-0.3mol/L;
The luminol solution flow is 0.5-1.0ml/min, and concentration is (0.8-1.2) * 10
-4Mol/L;
The cobalt ions liquid inventory is 0.05-0.10ml/min, and concentration is (1.8-2.2) * 10
-3Mol/L.
2. method according to claim 1, it is characterized in that selecting writing down the chemiluminescence signal luminous intensity integrated value of the 50-150 second after stable, difference and the chemical oxygen demand (COD) of standard method and the corresponding relation of total organic charcoal by water sample and distilled water integrated value, calculate the chemical oxygen demand (COD) and the total organic carbon of water sample, and show, printout.
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, it is characterized in that reacting the light signal that is sent is faint chemiluminescence signal, maximum emission wavelength is at 425nm, faint optical signal is through the optical lens cumulative, import photomultiplier, light signal is electric signal output through the photomultiplier treatment conversion, and the output electric signal is changed through the feeble signal amplifying circuit, is amplified to the certain voltage amplitude and send that the A/D ALT-CH alternate channel of data processing equipment quantizes, Integral Processing.
5. method according to claim 4 is characterized in that utilizing the microcomputer data processing equipment, by the calculating of software programming realization to control, signal Processing, chemical oxygen demand (COD) and the total organic carbon of device.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB2007100131652A CN100541181C (en) | 2007-01-15 | 2007-01-15 | Mode of oxidizing floating injected ozone is measured the method for chemical oxygen demand (COD) and total organic carbon |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB2007100131652A CN100541181C (en) | 2007-01-15 | 2007-01-15 | Mode of oxidizing floating injected ozone is measured the method for chemical oxygen demand (COD) and total organic carbon |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN101004386A CN101004386A (en) | 2007-07-25 |
| CN100541181C true CN100541181C (en) | 2009-09-16 |
Family
ID=38703671
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CNB2007100131652A Expired - Fee Related CN100541181C (en) | 2007-01-15 | 2007-01-15 | Mode of oxidizing floating injected ozone is measured the method for chemical oxygen demand (COD) and total organic carbon |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN100541181C (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102788782A (en) * | 2012-08-15 | 2012-11-21 | 山东省科学院海洋仪器仪表研究所 | Method for measuring dissolved oxygen of water body by flow-injection chemiluminiscence mode |
| CN102798629A (en) * | 2012-08-15 | 2012-11-28 | 山东省科学院海洋仪器仪表研究所 | Method for measuring water sulfide concentration through flow injection chemiluminescence |
| CN102809558A (en) * | 2012-08-15 | 2012-12-05 | 山东省科学院海洋仪器仪表研究所 | Method for measuring polycyclic aromatic hydrocarbons (PAHs) of sea water in flow injection chemiluminescence way |
Families Citing this family (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
| CN100543455C (en) * | 2007-08-01 | 2009-09-23 | 山东省科学院海洋仪器仪表研究所 | Ozone oxidation and ultraviolet scanning spectrum integral way is measured the method for total organic carbon |
| CN100541171C (en) * | 2007-08-01 | 2009-09-16 | 山东省科学院海洋仪器仪表研究所 | The method of ultraviolet cooperating with ozone measuring water body total nitrogen and total phosphorous by digestion spectrophotometry |
| 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 |
| CN101915723B (en) * | 2010-07-21 | 2012-09-05 | 山东省科学院海洋仪器仪表研究所 | Method and device for measuring total organic carbon in waterbody |
| CN103499569B (en) * | 2013-10-14 | 2015-05-13 | 山东省科学院海洋仪器仪表研究所 | Detecting device and method for detecting flow injection chemiluminescence water inorganic mercury by inhibiting |
| CN103575869B (en) * | 2013-10-31 | 2015-04-22 | 江南大学 | Method and device for detecting COD (chemical oxygen demand) of water body through synergy of ozone and ultraviolet |
| CN103698321A (en) * | 2014-01-10 | 2014-04-02 | 山东京鲁水务集团有限公司 | Rapid chemical oxygen demand (COD) detection method |
| ES2830390T3 (en) | 2014-11-24 | 2021-06-03 | Sabic Global Technologies Bv | Optical analysis method and system |
| CN107449686A (en) * | 2017-08-30 | 2017-12-08 | 北京建筑大学 | A kind of ozone concentration detection method and device |
| CN112924439A (en) * | 2021-01-29 | 2021-06-08 | 山东省科学院海洋仪器仪表研究所 | Method for measuring total organic carbon content in water body |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1670509A (en) * | 2005-04-28 | 2005-09-21 | 国家海洋局第一海洋研究所 | Device for detecting chemical oxygen demand in water mass through ozone oxidation-chemoluminescence method |
| CN2741968Y (en) * | 2004-11-22 | 2005-11-23 | 袁红玲 | Hydroxy negative ion water generator |
| CN1737542A (en) * | 2005-08-29 | 2006-02-22 | 山东省科学院海洋仪器仪表研究所 | The method of chemical oxygen consumption (COC) and total organic carbon is measured in ultrasound wave and ozone cooperative effect |
| 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 |
-
2007
- 2007-01-15 CN CNB2007100131652A patent/CN100541181C/en not_active Expired - Fee Related
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN2741968Y (en) * | 2004-11-22 | 2005-11-23 | 袁红玲 | Hydroxy negative ion water generator |
| CN1670509A (en) * | 2005-04-28 | 2005-09-21 | 国家海洋局第一海洋研究所 | Device for detecting chemical oxygen demand in water mass through ozone oxidation-chemoluminescence method |
| CN1737542A (en) * | 2005-08-29 | 2006-02-22 | 山东省科学院海洋仪器仪表研究所 | The method of chemical oxygen consumption (COC) and total organic carbon is measured in ultrasound wave and ozone cooperative effect |
| 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 |
Non-Patent Citations (3)
| Title |
|---|
| 分析化学手册 第三分册 光谱分析. 柯以侃等，1300，化学工业出版社. 1998 * |
| 利用臭氧化学发光法测量水体中有机物含量的可行性研究. 张喜验，高杨，刘岩，孟庆明.气象水文海洋仪器，第4期. 2003 * |
| 液相臭氧化流动注射化学发光法测定水体化学耗氧量(COD)的研究:苯酚溶液COD测定. 靳保辉，何鹰，庄峙厦，王小如，Frank，S.C.Lee.厦门大学学报(自然科学版)，第44卷第2期. 2005 * |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102788782A (en) * | 2012-08-15 | 2012-11-21 | 山东省科学院海洋仪器仪表研究所 | Method for measuring dissolved oxygen of water body by flow-injection chemiluminiscence mode |
| CN102798629A (en) * | 2012-08-15 | 2012-11-28 | 山东省科学院海洋仪器仪表研究所 | Method for measuring water sulfide concentration through flow injection chemiluminescence |
| CN102809558A (en) * | 2012-08-15 | 2012-12-05 | 山东省科学院海洋仪器仪表研究所 | Method for measuring polycyclic aromatic hydrocarbons (PAHs) of sea water in flow injection chemiluminescence way |
| CN102788782B (en) * | 2012-08-15 | 2014-06-18 | 山东省科学院海洋仪器仪表研究所 | Method for measuring dissolved oxygen of water body by flow-injection chemiluminiscence mode |
| CN102798629B (en) * | 2012-08-15 | 2014-07-02 | 山东省科学院海洋仪器仪表研究所 | Method for measuring water sulfide concentration through flow injection chemiluminescence |
| CN102809558B (en) * | 2012-08-15 | 2014-09-10 | 山东省科学院海洋仪器仪表研究所 | Method for measuring polycyclic aromatic hydrocarbons (PAHs) of sea water in flow injection chemiluminescence way |
Also Published As
| Publication number | Publication date |
|---|---|
| CN101004386A (en) | 2007-07-25 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN100541181C (en) | Mode of oxidizing floating injected ozone is measured the method for chemical oxygen demand (COD) and total organic carbon | |
| CN100541171C (en) | The method of ultraviolet cooperating with ozone measuring water body total nitrogen and total phosphorous by digestion spectrophotometry | |
| CN100476409C (en) | Method for measuring total organic carbon in water body by chemiluminescence in ozone oxidizing process | |
| CN100454004C (en) | Method for cooperative detection of chemical oxygen consumption and total organic carbon by using ozone and hydrogen peroxide | |
| Takeda et al. | Determination of nitrate in natural waters with the photo-induced conversion of nitrate to nitrite | |
| Frankovich et al. | A rapid, precise and sensitive method for the determination of total nitrogen in natural waters | |
| CN101004385A (en) | Method for measuring concentration of liquid phase ozone by mode of oxidizing floating injected ozone | |
| CN100543455C (en) | Ozone oxidation and ultraviolet scanning spectrum integral way is measured the method for total organic carbon | |
| CN104777108A (en) | Detection apparatus and method for content of chlorophyll | |
| CN103499569B (en) | Detecting device and method for detecting flow injection chemiluminescence water inorganic mercury by inhibiting | |
| Tai et al. | A review of measurement methods of dissolved oxygen in water | |
| CN100504358C (en) | Method for measuring chemical oxygen consumption and total organic carbon by cooperation of ultrasonic wave and ozone | |
| CN102788782B (en) | Method for measuring dissolved oxygen of water body by flow-injection chemiluminiscence mode | |
| CN100412530C (en) | Method for analyzing water body organism kinds by using ozone chemiluminescence spectrum | |
| CN101294940B (en) | Method for measuring heavy metal in sea water by ion color spectrum flow injection chemiluminescence restraint method | |
| CN103336045A (en) | Device for on-line detection and automatic alarm of toxic substances and detection method of toxic substances | |
| CN103616365B (en) | Flow injection Fluorimetric Quenching Method measures pick-up unit plumbous in water and method | |
| CN102798629B (en) | Method for measuring water sulfide concentration through flow injection chemiluminescence | |
| CN100454005C (en) | Method for examining deposit or organic matter content in soil by ozone oxidation | |
| Chivulescu et al. | Determination of amoxicillin, ampicillin, and penicillin G using a flow injection analysis method with chemiluminescence detection | |
| CN103499570B (en) | Portable injection chemiluminescence measures pick-up unit and the method for water body inorganic mercury | |
| Nakano et al. | Flow-injection simultaneous determination of selenium (IV) and selenium (IV+ VI) using photooxidative coupling of p-hydrazinobensenesulfonic acid with N-(1-naphthyl) ethylenediamine | |
| Su et al. | A high-throughput atomic emission analyzer for simultaneous field detection of dissolved inorganic and organic carbon in seawater and lake water | |
| CN206627444U (en) | A kind of Nitrogen dioxide testing instrument based on fluorescent nano material | |
| Kang et al. | Capillary electrophoresis with indirect electrochemiluminescence detection |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| C17 | Cessation of patent right | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20090916 Termination date: 20120115 |