CN104730266B - The method of a kind of total organic carbon continuous the real time measure Tong Bu with total nitrogen and instrument - Google Patents

The method of a kind of total organic carbon continuous the real time measure Tong Bu with total nitrogen and instrument Download PDF

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CN104730266B
CN104730266B CN201510147252.1A CN201510147252A CN104730266B CN 104730266 B CN104730266 B CN 104730266B CN 201510147252 A CN201510147252 A CN 201510147252A CN 104730266 B CN104730266 B CN 104730266B
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detector
reactor
sampling
reagent
acidification
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CN104730266A (en
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徐惠忠
王东亮
徐成彬
朱燕娟
纳欣叶
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Yantai University
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Yantai University
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Abstract

The present invention relates to instrument and the method for a kind of total organic carbon continuous the real time measure Tong Bu with total nitrogen, it mainly includes sampling head, reagent bottle, oxygen cylinder, acidification reactor, oxidation reactor, semiconductor cooling condenser, ionic absorption device, infrared CO2Detector, ultraviolet NO3 Detector, data processor, automatic controller, LCDs.Sampling head is connected with described acidification reactor by sampling tube, sampling peristaltic pump;……;Oxidation reactor is by appendix and infrared CO2Detector is connected, by liquid delivery tube and ultraviolet NO3 Detector is connected;Described infrared CO2Detector and ultraviolet NO3 Detector is connected with data processor and LCDs by circuit;…….By sharing a set of sampling, being acidified, aoxidize and data handling system and two independent detectors, total organic carbon in water (TOC) and total nitrogen (TN) can be carried out the on-line continuous automatic simultaneous determination of synchronization.Measurement result both can show in the LCDs of instrument in real time, also can be transferred on the master server of environmental monitoring department by remote protocol, show with various diagrammatic forms.

Description

The method of a kind of total organic carbon continuous the real time measure Tong Bu with total nitrogen and instrument
Technical field
The invention belongs to environmental pollution monitoring technical field.Be specifically related to a kind of can be to the total organic carbon (TOC) in water The instrument and the method that carry out synchronize continuous the real time measure on-line automatic with total nitrogen (TN).
Background technology
The organic contamination of water body, is also called eutrophication pollution, has discharged super in water body mainly due to mankind's activity The supernutrition material of water-outlet body self-cleaning ability.Wherein, total organic carbon (TOC), total nitrogen (TN) are commonly used to weigh water body is had The degree that machine pollutes.
Monitoring and the best approach preventing water quality organic contamination are to use online automatic measurement apparatus, TOC, the TN to waste water Continuously measure Deng environmental pollution index and supervise.But, so far, in the on-line automatic determining instrument side of water quality Face remains in following shortcoming and defect: (1) instrumental function is more single.Same instrument is typically only used for measuring a finger Mark, such as AstroTOC UV, Auto TOC1950, the AstroTOC HT of HACH company of the U.S.;The TOC-1000 of STAR company ~ 4000: TOC4100, YANACO Co., Ltd. of TOC-620, SFIMADZU Co., Ltd. of TORAY Co., Ltd. of Japan TOC-3A;The ON-Lime TOC 200 of TOCOR20 and the WTW company of MAIHAK company of Germany;APPLIFEK company of Belgium APPLI TOC;The PRO TOC300 of PPM company of Britain;The TOC2000 of SERES company of France;The XHTOC-of the Hebei China beginning The INSTRUMENT MODEL such as 90 and the WW-050/TOC that reaches of Beijing profit, are only used for measuring mono-index of TOC.TORAY Co., Ltd. of Japan TN-520;The TN-1A type total nitrogen detector etc. of wound gathers in Qingdao in China, only measures mono-index of TN.(2) multiparameter can not be carried out Synchro measure.Though minority instrument can measure multiple index, such as the Quick TOC of Moni TOC/TN, LARge of Germany AJ; The TNC-6200 of Japan TORAY;Germany's WTW TresCon company 6B-2000 multi-parameter water quality Quick testing instrument etc., but it is not to The mensuration of same parameter remains and individually carries out.1200 DEG C of high-temperature combustion methods are used as the TN of Quick TNP aoxidizes, and TP oxidation Then using UV-persulfate resolution method, its operating process is also to separate;And for example Japan's Shimadzu TNP-4110 total phosphorus and total nitrogen is analyzed Instrument all have employed persulfate-Ultraviolet Oxidation resolution method when TN, TP measure, but two systems from sample introduction, be oxidized to detection, whole Individual flow process is all independent operating.This quasi-instrument is the most only by multiple test system in combination to instrument , therefore, it is difficult to accomplish multiparameter Simultaneous Determination.(3) continuous real-time monitoring can not be carried out.Existing TOC, TN, TP analyser Device, often measures a sample, from sample introduction to oxidation again to detection, it is generally required to time-consuming 30min ~ 60min, even if those are referred to as The product of line analyzer, such as Phosphax Sigma, the Tres.Ccon of Germany WTW, the Japan TORAY of U.S. HACH TP800 etc., its mensuration cycle is 20min at least, says from this respect, and these instruments are the most still batch (-type) analyser, METHOD FOR CONTINUOUS DETERMINATION incessantly can not be carried out, also cannot obtain the real-time pollution situation of water quality.
In a word, up to the present, no matter home and abroad, the most do not occur can two water quality parameters of TOC, TN being synchronized The on-line automatic determining instrument of the real time measure continuously.
Summary of the invention
For the deficiencies in the prior art, it is an object of the invention to provide one and can synchronize in continuous the real time measure water the most organic Carbon (TOC), the on-line automatic analyzer device of total nitrogen (TN).This instrument can in the case of unmanned long-term always having water sample Machine carbon and total nitrogen carry out continuously synchronous real-time measurement automatically, and measurement result can be shown in real time or with environmental monitoring portion Door master server connects, and is automatically depicted as various statistical graph.
Technical scheme is as follows: total organic carbon continuous the real time measure instrument Tong Bu with total nitrogen, it mainly includes adopting Sample head, reagent bottle, oxygen cylinder, acidification reactor, oxidation reactor, infrared CO2Detector, ultraviolet NO3 -Detector, data process Device, automatic controller, LCDs.Described sampling head is connected with described acidification reactor by sampling tube, sampling peristaltic pump; Described reagent bottle is connected with described acidification reactor by reagent sampling tube, reagent peristaltic pump;Described oxygen cylinder by oxygen hose, Electronic three-way valve is connected with described acidification reactor and described oxidation reactor respectively;Described acidification reactor is carried by fluid Pipe is connected with described oxidation reactor;Described oxidation reactor is by appendix and infrared CO2Detector is connected;Described oxidation is anti- Device is answered to pass through liquid delivery tube and ultraviolet NO3 -Detector is connected;Described infrared CO2Detector and ultraviolet NO3 -Detector is by electricity Road is connected with data processor and LCDs;All thermocouples, flow transducer, three-way electrovalve, peristaltic pump etc. are the most logical Oversampling circuit is connected with automatic controller.
Described total organic carbon continuous the real time measure instrument Tong Bu with total nitrogen, it is preferred that described sampling peristaltic pump and institute The sampling tube stated between acidification reactor is provided with sampling flow transducer.
Described total organic carbon continuous the real time measure instrument Tong Bu with total nitrogen, it is preferred that described reagent peristaltic pump and institute The reagent sampling tube stated between acidification reactor is provided with reagent flow sensor.
Described total organic carbon continuous the real time measure instrument Tong Bu with total nitrogen, it is preferred that described acidification reactor and oxygen The fluid delivery tube changing reactor connected is provided with gas-liquid separator.
Described total organic carbon continuous the real time measure instrument Tong Bu with total nitrogen, it is preferred that described oxidation reactor is with red Outer CO2The appendix that detector is connected is provided with semiconductor cooling condenser and ionic absorption device.
Described total organic carbon continuous the real time measure instrument Tong Bu with total nitrogen, it is preferred that the chamber of described oxidation reactor Body case is the quartz glass tube that outer surface is silver-plated, is inserted with 4 ~ 6 lamps that can launch 180nm-200nm short wave ultraviolet light in cavity Pipe, cavity is divided into upper and lower two parts by waterproof ventilated membrane, and top is air chamber, and is connected with appendix, and bottom is liquid chambers, And be connected with liquid delivery tube;Cavity bottom is provided with thermocouple, and shell surrounding is coated with electric heating cover, and with automatic controller group Become self-feedback ciucuit, so that the temperature of liquid in cavity is maintained at 90 ~ 98 DEG C (preferably 95 DEG C).
Described total organic carbon continuous the real time measure instrument Tong Bu with total nitrogen, it is preferred that described infrared CO2Detector Centre wavelength be 4.26 μm.
Described total organic carbon continuous the real time measure instrument Tong Bu with total nitrogen, it is preferred that described ultraviolet NO3 -Detector master Will be made up of ultraviolet lamp bank, multistage optical filter, flow cell and photoelectric detector, it by the ultraviolet centre wavelength of flow cell is 220nm。
Described total organic carbon continuous the real time measure instrument Tong Bu with total nitrogen, it is preferred that described sampling head is with filtration Net (preferably, the mesh size of drainage screen is 0.125mm), a diameter of 2.0-4.0mm(of sampling head is preferred, sampling head diameter For 3.0mm).
Described total organic carbon continuous the real time measure instrument Tong Bu with total nitrogen, it is preferred that described sampling tube, reagent are sampled Pipe, fluid delivery tube, liquid delivery tube are made by polyfluortetraethylene pipe, and external diameter is that 0.6-1.0mm(is preferably 0.8mm), Internal diameter is that 0.2-0.4mm(is preferably 0.3mm).
Described total organic carbon continuous the real time measure instrument Tong Bu with total nitrogen, it is preferred that described oxygen hose, gas transmission Pipe, exhaustor are made by silicone rubber, and external diameter is that 2-3mm(is preferably 2.5mm), internal diameter is that 1-2mm(is preferably 1.5mm).
Described total organic carbon continuous the real time measure instrument Tong Bu with total nitrogen, it is preferred that the reagent in described reagent bottle Be preferably 1:2-2:1 by sulphuric acid and sodium peroxydisulfate according to mol ratio 1:3-3:1() ratio mix, mass concentration is 20%-30%(is preferably 25%).
Described total organic carbon continuous the real time measure instrument Tong Bu with total nitrogen, it is preferred that the oxygen in described oxygen cylinder For carbon-free, the high purity oxygen gas of nitrogen-free, wherein, CO2Content is less than 0.5 × 10-6(V/V), TOC content is less than 0.4 × 10-6(V/V), TN content is less than 4.0 × 10-6(V/V), pressure low limit value is 0.1MPa.
Present invention also offers and synchronize according to described total organic carbon continuous the real time measure instrument automatic on-line Tong Bu with total nitrogen The real time measure total organic carbon and the method for total nitrogen continuously, its step is.
Sampling head is inserted water body certain depth to be measured;Water sample is under the swabbing action of sampling peristaltic pump, through over-sampled stream Quantity sensor, enters acidification reactor.Meanwhile, reagent peristaltic pump is started, by the reagent in reagent bottle, through reagent flow Sensor is also sent in acidification reactor;Subsequently, open three-way magnetic valve, by the oxygen in oxygen cylinder by oxygen hose respectively In input acidification reactor and in oxidation reactor, the data fed back by gas flow sensor, Reasonable adjustment threeway electronics The gas sendout of valve, to ensure that the liquid in acidification reactor is in micro-fluidized state;In acidification reactor, water sample to be measured In inorganic carbonate and sulphuric acid generation chemical reaction, generate CO2And sulfate.
Gas-liquid-solid mixture after acidification reaction, under the promotion of peristaltic pump and oxygen pressure, along fluid delivery tube stream Enter in vapour liquid separator, acidification reaction the inorganic CO produced2And carrier gas discharged by exhaustor, the fluid section after acidifying is then Move on along fluid delivery tube, flow in oxidation reactor;In oxidation reactor, the Organic substance in water sample, nitrogen Compound, under the synergy of ultraviolet light, sodium peroxydisulfate and temperature, is oxidized to CO2、NO3 -Deng high price state.
Mixed gas after oxidation reaction, is flow to quasiconductor through appendix by oxidation reactor top through waterproof ventilated membrane In condenser, steam therein is discharged from condensate pipe after being condensed into water, and the gas being dried initially enters ionic absorption Device, may interfere with CO to eliminate2The foreign ion of detection, subsequently into infrared CO2Detector, after reading to be detected, waste gas is by red Outer CO2Detector afterbody discharges.
And the mixed liquor body portion after oxidation reaction, then flowed into NO by liquid delivery tube by oxidation reactor bottom3 -Inspection Survey device.
NO3 -Detector is mainly by transformator, ultraviolet lamp bank, optical filter, flow cell, photoelectric detector, signal amplifier group Become.When mixing liquid and flowing through flow cell, the radiant intensity that wavelength is 220nm ultraviolet light can be changed into telecommunications by photoelectric detector Number feeding data processor.After reading, mixing liquid is discharged from flow cell afterbody.
Finally, by CO2Detector, NO3 -The electrical signal data that detector is obtained, is sent to data processor in the lump, This, detector the signal of telecommunication obtained with have been stored in data processor being demarcated CO by standard solution2、NO3 -Data compare Relatively, TOC and the TN data of actual measurement water sample are just obtained;Keeping peristaltic pump to run continuously, gas and liquid in instrument can be continuously Flowing, detector will continuously obtain measurement data;Response time according to different indexs is in data processor Timer is adjusted, just can real-time TOC and the TN data of synchronization gain water quality.
The technology used in the present invention route is as shown in Figure 1.
First with fixed support or buoy, the sampling head 1 of band drainage screen is installed in water body to be measured, and uses sampling tube Sampling head 1 is connected by 2 with this instrument.Water sample is under the swabbing action of sampling peristaltic pump 3, through sampling flow transducer 4, enters Acidification reactor 5.Meanwhile, start reagent peristaltic pump 8, by the reagent in reagent bottle 6, send through reagent flow sensor 9 Enter in acidification reactor 5.Subsequently, turn on three-way magnetic valve 11, the oxygen in oxygen cylinder 10 is the most defeated by oxygen hose 12 Enter in acidification reactor 5 and oxidation reactor 17 in.By the data of oxygen flow sensor 13 feedback, use automatic controller The gas sendout of 32 Reasonable adjustment three-way magnetic valves, to ensure that the liquid in acidification reactor 5 is in micro-fluidized state.
Reagent in reagent bottle 6 is mainly mixed by a certain percentage by sodium peroxydisulfate and sulphuric acid.When it is at acidification reaction After mixing with water sample to be measured in device 5, the inorganic carbonate in water sample just with sulphuric acid generation chemical reaction, generation CO2And sulfate.
Gas-liquid-solid mixture after acidification reaction, under the promotion of peristaltic pump 3,8 and oxygen pressure, can carry along fluid Pipe 16 flows in vapour liquid separator 14, the inorganic CO produced by acidification reaction at this2And oxygen discharged by exhaustor 15, and it is acidified After solid-liquid fluid-mixing then flow in oxidation reactor 17.
Oxidation reactor is the quartz glass tubulose cavity 18 that an outer surface is silver-plated, and being inserted with 4 ~ 6 therein can launch The fluorescent tube 20 of 180nm-200nm short wave ultraviolet light, is coated with electric heating cover 21 outside it.When fluid-mixing enters oxidation reactor After, the Organic substance in water sample and various nitrogen-containing compound, in the synergy of ultraviolet light, sodium peroxydisulfate, oxygen and temperature Under, will all be oxidized to CO2、NO3 -Deng high price state.
Mixed gas after oxidation reaction, is flow to half through appendix 23 by oxidation reactor top through waterproof ventilated membrane 22 In conductor condenser 24, steam therein is discharged from condensed water discharge pipe 27 after being condensed into water, and the gas being dried is first Enter ionic absorption device 25, may interfere with CO to eliminate2The Cl of detection-、SO4 2-、PO4 3-Deng foreign ion, subsequently into infrared CO2 Detector 26, after reading to be detected, waste gas is by infrared CO2Detector afterbody discharges, and the mixed liquor body after oxidation reaction Point, then flowed to ultraviolet NO by liquid delivery tube 283 -Detector 28.
NO3 -The structure of detector is as shown in Figure 2.When mixing liquid flows through ultraviolet NO3 -During the flow cell 45 of detector, position Ultraviolet lamp bank 38 in side will send the parallel ultraviolet of 180 ~ 236nm wavelength, after multistage optical filter 39 filters, remaining Wavelength is that the ultraviolet light of 220nm will arrive photoelectric detector 41 by optical channel 44 through flow cell 45.When 220nm ultraviolet light is saturating When crossing flow cell, flow through the NO in the mixing liquid of flow cell3 -The ultraviolet of this wavelength will be absorbed strongly, and meet Lambert-Beer's law, i.e. absorbance (signal of telecommunication) are directly proportional to sample concentration.Therefore, it can the intensity (telecommunications according to ultraviolet Number) situation of change, reflect NO3 -The situation of change of content.
Finally, by infrared CO2Detector, ultraviolet NO3 -The electrical signal data of detector acquisition, is sent to data in the lump and processes Device 31.Here, CO can be reflected by what two detectors obtained2、NO3 -The signal of telecommunication of concentration with have been stored in data processor The signal of telecommunication demarcated by standard solution compares, and just can obtain TOC, TN data of actual measurement water sample;Peristaltic pump is kept to transport continuously OK, gas and liquid in instrument can flow continuously, and detector will continuously obtain measurement data;Refer to according to difference Timer in data processor is adjusted by target response time, just can real-time TOC and the TN data of synchronization gain water quality.
Calculated the measured value obtained by data processor, can show in real time in the LCDs 33 of instrument, also may be used It is transferred on the master server of environmental monitoring department by remote protocol, shows with various diagrammatic forms.
Various temperature sensors in instrument, flow transducer, electronic valve, peristaltic pump, power supply etc., without exception by circuit by Automatically control 32 to automatically control.
The technical characterstic of the present invention is as follows with advantage.
1. multi-functional.Two water pollution indexs of TOC, TN can be measured with an instrument.
2. the compactedness of apparatus structure.This instrument is by the mensuration system of TOC, TN two indices, by sharing a set of adopting Sample, it is acidified, aoxidizes and data handling system, simplify technological process and component number.
3. the seriality of measurement data.The instrument of the present invention, due to from sample introduction to detection, whole gas flow path and liquid Stream is all to run continuously, the most once starts equipment, after first response phase terminates, as long as data-handling capacity is enough Powerful, just can continuously obtain detection data.
4. the synchronicity of different index measurements and real-time.Owing to as above 2 index systems use same flow process to carry out even Continuous mensuration, as long as being deducted on timer according to the response time of different detectors, just can be to the TOC of any time water quality Carry out synchronizing to monitor in real time with TN situation.
5. ease-to-operate.This instrument is installed in place after, except monthly change a medicament and be carrier gas bottle aerating with Outward, long-term unmanned can be realized.Detection data can show in real time on instrument, also can by remote transfer protocol with Connect on the master server of environmental monitoring department.
Accompanying drawing explanation
Fig. 1 is total organic carbon continuous the real time measure apparatus structure schematic diagram Tong Bu with total nitrogen.Wherein, 1-sampling head;2-adopts Sample pipe;3-samples peristaltic pump;4-sampling flow transducer;5-acidification reactor;6-reagent bottle;7-reagent sampling tube;8-reagent Peristaltic pump;9-reagent flow sensor;10-oxygen cylinder;11-three-way magnetic valve;12-oxygen hose;13-oxygen flow sensor; 14-gas-liquid separator;15-exhaustor;16-fluid delivery tube;17-oxidation reactor;18-quartz glass tube;19-ultra-violet lamp Pipe;20-external power supply;21-electric heating cover;22-waterproof ventilated membrane;23-appendix;24-semiconductor cooling condenser;25-ion is inhaled Receive device;The infrared CO of 26-2Detector;27-condensed water discharge pipe;28-liquid delivery tube;29-ultraviolet NO3 -Detector;30-thermoelectricity Even;31-data processor;32-automatic controller;33-LCDs;34-liquid flow direction;35-gas flow direction.
Fig. 2 is ultraviolet NO3 -The structural representation of detector.Wherein, 36-external power supply;37-transformator;38-uviol lamp Row;The multistage optical filter of 39-;40-flow cell shell;41-photoelectric detector;42-signal amplifier;43-external data processor; 44-optical channel;45-flow cell.
Detailed description of the invention
Below in conjunction with embodiment, the present invention made detailed description, but protection domain is not limited by this.
Embodiment total organic carbon continuous the real time measure instrument Tong Bu with total nitrogen, its mainly include sampling head 1, reagent bottle 6, Oxygen cylinder 10, acidification reactor 5, oxidation reactor 17, infrared CO2Detector 26, ultraviolet NO3 -Detector 29, data processor 31, automatic controller 32, LCDs 33.Described sampling head 1 is by sampling tube 2, sampling peristaltic pump 3 and described acidification reaction Device 5 is connected;Described reagent bottle 6 is connected 5 by reagent sampling tube 7, reagent peristaltic pump 8 with described acidification reactor;Described oxygen Bottle 10 is connected with described acidification reactor 5 and described oxidation reactor 17 respectively by oxygen hose 12, electronic three-way valve 11;Described Acidification reactor 5 is connected with described oxidation reactor 17 by fluid delivery tube 16;Described oxidation reactor 17 passes through appendix 23 and infrared CO2Detector 26 is connected;Described oxidation reactor 17 is by liquid delivery tube 28 and ultraviolet NO3 -Detector 29 phase Even;Described infrared CO2Detector 26 and ultraviolet NO3 -Detector 29 is by circuit and data processor 31 and LCDs 33 phase Even;All thermocouples such as 30, flow transducer such as 4, electronic valve such as 11, peristaltic pump such as 3 etc. are all by circuit and automatic controller 32 are connected;Sampling tube between described sampling peristaltic pump 3 and described acidification reactor 5 is provided with sampling flow transducer 4;Described Reagent sampling tube 7 between reagent peristaltic pump 8 and described acidification reactor 5 is provided with reagent flow sensor 9;Described acidifying is anti- The fluid delivery tube 16 answering device 5 to be connected with oxidation reactor 17 is provided with gas-liquid separator 14;Described oxidation reactor 17 is with red Outer CO2The appendix 23 that detector 26 is connected is provided with semiconductor cooling condenser 24 and ionic absorption device 25;Described oxidation reactor Shell cavity be the silver-plated quartz glass tube 18 of outer surface, be inserted with ultraviolet tube 19 in cavity, shell surrounding is coated with electricity Heating mantle 21, portion is provided with thermocouple 30 under the cavity;Described sampling head 1 is with drainage screen (preferably, the mesh size of drainage screen For 0.125mm);The described a diameter of 2.0-4.0mm(of sampling head 1 is preferred, a diameter of 3.0mm of sampling head);Described sampling tube 2, Reagent sampling tube 7, fluid delivery tube 16, liquid delivery tube 28 are made by polyfluortetraethylene pipe, and external diameter is that 0.6-1.0mm(is excellent Choosing for 0.8mm), internal diameter is that 0.2-0.4mm(is preferably 0.3mm);Described oxygen hose 12, appendix 23, exhaustor 15 Being made by silicone rubber, external diameter is that 2-3mm(is preferably 2.5mm), internal diameter is that 1-2mm(is preferably 1.5mm);Described reagent Bottle 6 in reagent be preferably 1:2-2:1 by sulphuric acid and sodium peroxydisulfate according to mol ratio 1:3-3:1() ratio mix, Mass concentration is that 20%-30%(is preferably 25%);In described oxidation reactor 17, the emission wavelength of ultraviolet lamp tube is 180nm- 200nm(is preferably 185nm);Described infrared CO2The centre wavelength of detector 26 is 4.26 μm;Described ultraviolet NO3 -Detector 29 are mainly made up of ultraviolet lamp bank 38, multistage optical filter 39, flow cell 45 and photoelectric detector 41, and it is by the ultraviolet of flow cell Line centre wavelength is 220nm;In described oxidation reactor 17, the temperature of liquid is 90 ~ 98 DEG C (preferably 95 DEG C).
Continuous the real time measure is synchronized according to described total organic carbon continuous the real time measure instrument automatic on-line Tong Bu with total nitrogen The method of total organic carbon and total nitrogen is.
First at middle fixed support to be monitored or buoy, the sampling head 1 of one band drainage screen is deep into below the water surface not At 100mm.A diameter of 3.0mm of sampling head, the mesh size of drainage screen is 0.125mm.With sampling water pipe 4 by sampling head 1 is connected with this instrument.Sampling tube is made by polyfluortetraethylene pipe, and external diameter is 0.8mm, and internal diameter is 0.3mm.Water sample is wriggled in sampling Under the swabbing action of pump 3, through flow transducer 4, enter acidification reactor 5.Acidification reactor is formed by potash glass blowing, whole In elliposoidal on body.While starting sampling peristaltic pump 3, start reagent peristaltic pump 8, by the reagent in reagent bottle 6, Jing Guoliu Quantity sensor 9 is sent in acidification reactor 5.Reagent in reagent bottle by sulphuric acid and sodium peroxydisulfate according to 1:1(mol ratio) Ratio mixes, and mass concentration is 25%.Subsequently, open three-way magnetic valve 11, the oxygen in oxygen cylinder 10 is passed through oxygen hose 12 respectively input acidification reactor in 5 and oxidation reactor 17 in.Oxygen hose is made by silicone rubber, and external diameter is 2.5mm, and internal diameter is 1.5mm.Oxygen pressure is 0.1MPa.By the data of oxygen flow sensor 13 feedback, the gas of Reasonable adjustment three-way magnetic valve Sendout, to ensure that the liquid of 5 is in micro-fluidized state in acidification reactor.
In acidification reactor 5, the inorganic carbonate in water sample to be measured generates CO with sulphuric acid generation chemical reaction2And sulphuric acid Salt.
MeCO3 + H2SO4 →MeSO4+ H2O + CO2
Gas-liquid-solid mixture after acidification reaction, under the promotion of peristaltic pump 3,8 and oxygen pressure, along fluid delivery tube 16 flow in vapour liquid separator 14, acidification reaction the inorganic CO produced2And carrier gas discharged by exhaustor 15, and the liquid after being acidified Body portion then moves on, and flows in oxidation reactor 17.
Oxidation reactor is the quartz glass tubulose cavity 18 that an outer surface is silver-plated, and being inserted with 4 ~ 6 therein can launch The fluorescent tube 20 of 180nm-200nm short wave ultraviolet light, is coated with electric heating cover 21 outside it.When fluid-mixing enters oxidation reactor After, the Organic substance in water sample and various nitrogen-containing compound, in the synergy of ultraviolet light, sodium peroxydisulfate, oxygen and temperature Under, will all be oxidized to CO2、NO3 -Deng high price state.
Mixed gas after oxidation reaction, is flow to half through appendix 23 by oxidation reactor top through waterproof ventilated membrane 22 In conductor condenser 24, steam therein is discharged from condensed water discharge pipe 27 after being condensed into water, and the gas being dried is first Enter ionic absorption device 25, may interfere with CO to eliminate2The Cl of detection-、SO4 2-、PO4 3-Deng foreign ion, subsequently into infrared CO2 Detector 26, after reading to be detected, waste gas is by infrared CO2Detector afterbody discharges.
Mixed liquor body portion after oxidation reaction, then flowed to ultraviolet NO by liquid delivery tube 283 -Detector 28.Work as mixed liquor Body flows through ultraviolet NO3 -During the flow cell 45 of detector, the ultraviolet lamp bank 38 being positioned at side will send the parallel of 180 ~ 236nm wavelength Ultraviolet light, after multistage optical filter 39 filters, remaining wavelength is that the ultraviolet light of 220nm will be by optical channel 44 through flow cell 45 arrive photoelectric detector 41.When 220nm UV light permeability flow cell, flow through the NO in the mixing liquid of flow cell3 -By right The ultraviolet of this wavelength absorbs strongly, and meets Lambert-Beer's law, i.e. absorbance (signal of telecommunication) becomes with sample concentration Direct ratio.Therefore, it can intensity (signal of telecommunication) situation of change according to ultraviolet, reflect NO3 -The situation of change of content.
Finally, by infrared CO2Detector, ultraviolet NO3 -The electrical signal data of detector acquisition, is sent to data in the lump and processes Device 31.Here, CO can be reflected by what two detectors obtained2、NO3 -The signal of telecommunication of concentration with have been stored in data processor The signal of telecommunication demarcated by standard solution compares, and just can obtain TOC, TN, TP data of actual measurement water sample, keeps peristaltic pump continuous Running, gas and liquid in instrument can flow continuously, and detector will continuously obtain measurement data;According to difference Timer in data processor is adjusted by the response time of index, just can real-time TOC and the TN number of synchronization gain water quality According to.
Calculated the measured value obtained by data processor, can show in real time in the LCDs 33 of instrument, also may be used It is transferred on the master server of environmental monitoring department by remote protocol, shows with various diagrammatic forms.
Various temperature sensors in instrument, flow transducer, electronic valve, peristaltic pump, power supply etc., without exception by circuit by Automatically control 32 to automatically control.
Instrument performance.
Repeatability error ± 3.8%, null offset ± 2%, span drift ± 5%, rectilinearity ± 4%, TOC response time is 5min, TN response time is 8min, Mean stream time 1200h/ time, with the experimental error of actual water sample comparison ± 5%, sample 33 times/min of the frequency.

Claims (2)

1. total organic carbon continuous the real time measure instrument Tong Bu with total nitrogen, is characterized in that, mainly include sampling head, reagent bottle, oxygen Bottle, acidification reactor, oxidation reactor, infrared CO2Detector, ultraviolet NO3 -Detector, data processor, automatic controller, liquid Crystal display screen, wherein, described sampling head is connected with described acidification reactor by sampling tube, sampling peristaltic pump;Described reagent bottle It is connected with described acidification reactor by reagent sampling tube, reagent peristaltic pump;Described oxygen cylinder passes through oxygen hose, electronic three-way valve It is connected with described acidification reactor and described oxidation reactor respectively;Described acidification reactor is by fluid delivery tube and described oxygen Change reactor to be connected;Described oxidation reactor is by appendix and infrared CO2Detector is connected;Described oxidation reactor passes through liquid Body conveying pipe and ultraviolet NO3 -Detector is connected;Described infrared CO2Detector and ultraviolet NO3 -Detector passes through at circuit and data Reason device and LCDs are connected;Thermocouple in described instrument, flow transducer, three-way electrovalve, peristaltic pump pass through circuit It is connected with automatic controller;Sampling tube between described sampling peristaltic pump and described acidification reactor is provided with sampling flow sensing Device;Reagent sampling tube between described reagent peristaltic pump and described acidification reactor is provided with reagent flow sensor;Described acid The fluid delivery tube that change reactor is connected with oxidation reactor is provided with gas-liquid separator;Described oxidation reactor and infrared CO2 The appendix that detector is connected is provided with semiconductor cooling condenser and ionic absorption device;Described total organic carbon is Tong Bu with total nitrogen the most real Time determining instrument automatic on-line to synchronize the method for continuous the real time measure total organic carbon and total nitrogen be that sampling head inserts water body to be measured Certain depth;Water sample is under the swabbing action of sampling peristaltic pump, through sampling flow transducer, enters acidification reactor, with this Meanwhile, start reagent peristaltic pump, by the reagent in reagent bottle, be also sent in acidification reactor through reagent flow sensor, Subsequently, open three-way magnetic valve, the oxygen in oxygen cylinder is passed through in oxygen hose inputs acidification reactor respectively and oxidation reaction In device, the data fed back by gas flow sensor, the gas sendout of Reasonable adjustment three-way electrovalve, to ensure that acidifying is anti- The liquid in device is answered to be in micro-fluidized state;In acidification reactor, the inorganic carbonate in water sample to be measured and sulphuric acid Learn reaction, generate CO2And sulfate;Gas-liquid-solid mixture after acidification reaction, under the promotion of peristaltic pump and oxygen pressure, edge Fluid delivery tube and flow in gas-liquid separator, acidification reaction the inorganic CO produced2And carrier gas discharged by exhaustor, and it is acidified After fluid section then move on along fluid delivery tube, flow in oxidation reactor;In oxidation reactor, in water sample Organic substance, nitrogen-containing compound, under the synergy of ultraviolet light, sodium peroxydisulfate and temperature, be oxidized to CO2、NO3 -Deng high price shape State;Mixed gas after oxidation reaction, is flow to semi-conductor condensation through appendix by oxidation reactor top through waterproof ventilated membrane In device, steam therein is discharged from condensate pipe after being condensed into water, and the gas being dried initially enters ionic absorption device, with Elimination may interfere with CO2The foreign ion of detection, subsequently into infrared CO2Detector, after reading to be detected, waste gas is by infrared CO2 Detector afterbody discharges;And the mixed liquor body portion after oxidation reaction, then flowed by oxidation reactor bottom by liquid delivery tube Enter NO3 -Detector, NO3 -Detector is mainly amplified by transformator, ultraviolet lamp bank, optical filter, flow cell, photoelectric detector, signal Device forms, and when mixing liquid and flowing through flow cell, the radiant intensity that wavelength is 220nm ultraviolet light can be changed into by photoelectric detector The signal of telecommunication sends into data processor, and after reading, mixing liquid is discharged from flow cell afterbody;Finally, by CO2Detector, NO3 -Inspection Survey the electrical signal data that obtained of device, be sent to data processor in the lump, here, the signal of telecommunication obtained by detector with store CO is demarcated in a data processor by standard solution2、NO3 -Data compare, and just obtain TOC and the TN data of actual measurement water sample; Keeping peristaltic pump to run continuously, gas and liquid in instrument can flow continuously, and detector will continuously obtain survey Amount data;Timer in data processor is adjusted by the response time according to different indexs, just can synchronization gain water quality Real-time TOC and TN data.
Total organic carbon the most according to claim 1 continuous the real time measure instrument Tong Bu with total nitrogen, is characterized in that, described oxidation The shell cavity of reactor is the quartz glass tube that outer surface is silver-plated, is inserted with 4 ~ 6 and can launch 180nm-200nm shortwave in cavity The fluorescent tube of ultraviolet light, cavity is divided into upper and lower two parts by waterproof ventilated membrane, and top is air chamber, and is connected with appendix, under Portion is liquid chambers, and is connected with liquid delivery tube;Cavity bottom is provided with thermocouple, and shell surrounding is coated with electric heating cover, and with Automatic controller composition self-feedback ciucuit, so that the temperature of liquid in cavity is maintained at 90 ~ 98 DEG C.
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