CN104764740B - Method and instrument for synchronously, continuously and automatically measuring total organic carbon and total phosphorus - Google Patents
Method and instrument for synchronously, continuously and automatically measuring total organic carbon and total phosphorus Download PDFInfo
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Abstract
The invention relates to an instrument and a method for continuously, synchronously and automatically measuring total organic carbon/total phosphorus on line. The instrument mainly comprises a sampling head, a reagent bottle, a carrier-gas cylinder, an acidifier, an oxidation reactor, a semiconductor condenser, an ion absorber, a CO2 detector, an orthophosphate detector and a data processor. The sampling head is connected with the acidifier by virtue of a sampling pipe, a peristaltic pump and a flow sensor; the reagent bottle is connected with the acidifier by virtue of a sampling pipe, a peristaltic pump and a flow sensor; ...; the CO2 detector and the orthophosphate detector are connected with the data processor by virtue of a circuit; .... A set of sampling, acidifying, oxidizing and data processing system and two independent detectors are shared, so that total organic carbon (TOC) and total phosphorus (TP) in water can be continuously, synchronously and automatically measured on line. The instrument has the characteristics of multi-functionality, compact structure, continuity of measured data, synchronism and real-time property of measurement of different indexes, and the like.
Description
Technical field
The invention belongs to environmental monitoring technology field.Be specifically related to it is a kind of can be to the total organic carbon (TOC) in water and total
Phosphorus (TP) synchronizes the online analytical instrument and method of continuous automatic measurement.
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 excessive Organic substance of water-outlet body self-cleaning ability.Wherein total organic carbon (TOC) and total phosphorus (TP) are often used as measurement water body is had
The index of machine pollution level.
Monitoring and prevent the best approach of water quality organic contamination from being to use on-line automatic analyzer, to TOC, TP of waste water etc.
Environmental pollution index is continuously measured and supervised.However, so far, in terms of water quality on-line automatic analyzer still
Have the disadvantage that and not enough：(1) instrumental function is relatively simple.Same instrument is typically only used for determining an index, such as
The AstroTOC UV of HACH companies of the U.S., Auto TOC1950, AstroTOC HT；TOC-1000～4000 of STAR companies：
The TOC-3A of TOC4100, YANACO Co., Ltd. of TOC-620, SFIMADZU Co., Ltd. of Japanese TORAY Co., Ltd.；
The ON-Lime TOC 200 of the TOCOR20 and WTW companies of German MAIHAK companies；The APPLI of Belgian APPLIFEK companies
TOC；The PRO TOC300 of PPM companies of Britain；The TOC2000 of French SERES companies；The XHTOC-90 of the Hebei China beginning and north
The INSTRUMENT MODELs such as the WW-050/TOC of Jing Lida, are only used for determining mono- index of TOC.The PHOSPHAX of HACH companies of the U.S.；
The TP-800 of Japanese TORAY Co., Ltd.；The TP Analyzer of Australian GREENSPA companies；German WTW companies
The models such as TresCon P511, can only determine mono- index of TP.(2) it is unable to synchro measure.Although minority instrument is known as can survey
Determine multiple indexs, but its multimode design for being adopted only is combined to multiple test systems on one instrument,
Its measure to different parameters remains what is individually carried out, therefore is difficult to reach synchronization when different parameters are determined, such as
The TN oxidations of QuickTNP adopt 1200 DEG C of high-temperature combustion methods, and TP oxidations then adopt UV- persulfate resolution methods, and it was operated
Journey is also detached；Although and for example Japanese Shimadzu TNP-4110 total phosphorus and total nitrogen analyser employs over cure when TN, TP are measured
Hydrochlorate-Ultraviolet Oxidation resolution method, but two systems from sample introduction, be oxidized to detection, whole flow process is also all independent operating；For another example
German WTW TresCon companies 6B-2000 multi-parameter water quality Quick testing instruments, though COD, ammonia nitrogen, total phosphorus, total nitrogen can be determined
Etc. multiple indexs, but this quasi-instrument is multi parameter analysis instrument, and actually simply a suite of racks has been used, by changing
Different measurement system and realize, thus measurement can not be synchronized；(3) it is unable to continuous monitoring.Existing TOC, TP point
Analyzer device, often determines a sample, from sample introduction to oxidation again to detection, generally requires time-consuming 30min～60min, even if those
The referred to as product of on-line determination instrument, the such as Phosphax Sigma of U.S. HACH, the Tres.Ccon of Germany WTW, Japan TORAY
TP800 etc., the measure cycle of each of which data is at least 20min, therefore, say from this respect, these instruments are in itself
It is still batch (-type) analyser.
In a word, no matter home and abroad, up to the present, does not still occur to carry out two water pollution indexs of TOC, TP
The on-line determination instrument of synchronous continuous automatic measurement.
The content of the invention
For the deficiencies in the prior art, it is an object of the invention to provide one kind can total organic carbon in synchronous METHOD FOR CONTINUOUS DETERMINATION water
(TOC), the on-line automatic analyzer device of two water pollution indexs of total phosphorus (TP).The instrument can be grown in the case of unmanned
Phase carries out continuously synchronous automatic measurement to the above-mentioned two parameter of water sample, and can be by measurement result and environmental monitoring portion
Door master server connection, is depicted as various statistical graphs automatically.
Technical scheme is as follows：Total organic carbon continuous automatic measurement instrument synchronous with total phosphorus, it is preferred that its master
To include sampling head, reagent bottle, carrier gas bottle, acidifier, oxidation reactor, gas-liquid separator, CO2Detector, orthophosphate inspection
Survey device, data processor, integrated automatic controller；The sampling head is by sampling tube and peristaltic pump, flow transducer and described
Acidifier is connected；The reagent bottle is connected by sampling tube with peristaltic pump, flow transducer and the acidifier；The carrier gas bottle
It is connected with the acidifier and the oxidation reactor respectively by carrier gas pipe, three-way magnetic valve, gas flow sensor；It is described
Acidifier is connected by acidizing fluid delivery pipe with the gas-liquid separator, the oxidation reactor；The oxidation reactor leads to
Air shooter is crossed with the CO2Detector is connected, and is connected with the orthophosphate detector by liquid delivery tube；It is described
CO2Detector and the orthophosphate detector are connected by circuit with data processor；The peristaltic pump, electromagnetic valve and all kinds of
Sensor and external power supply are connected by circuit with integrated automatic controller.
Described total organic carbon continuous automatic measurement instrument synchronous with total phosphorus, it is preferred that the oxidation reactor is main
Including quartz glass tube, ultraviolet lamp tube, water proof ventilated membrane, electric heating cover, temperature sensor, wherein, quartz glass tube outer surface
It is silver-plated；The emission wavelength of ultraviolet lamp tube is 180nm-200nm (preferably 185nm)；Water proof ventilated membrane is empty by quartz glass tube
Chamber is divided into upper and lower two parts, and top is air chamber, and bottom is liquid chambers；Electric heating cover and temperature sensor are automatically controlled with integrated
Device constitutes self-feedback ciucuit, to guarantee the temperature of liquid in oxidation reactor as 90～98 DEG C (preferably 95 DEG C).
Described total organic carbon continuous automatic measurement instrument synchronous with total phosphorus, it is preferred that the oxidation reactor top
Air chamber and CO2The connected air shooter of detector is provided with semiconductor cooling condenser and ionic absorption device.
Described total organic carbon continuous automatic measurement instrument synchronous with total phosphorus, it is preferred that the oxidation reactor bottom
The liquid delivery tube that is connected with orthophosphate detector of liquid chambers be provided with two groups of spiral coils, and rise in every group of spiral coil
It is connected to molybdate solution transfusion bottle and ascorbic acid solution transfusion bottle at beginning respectively.
Described total organic carbon continuous automatic measurement instrument synchronous with total phosphorus, it is preferred that the reagent in the reagent bottle
By sulphuric acid and sodium peroxydisulfate according to mol ratio 1:3-3:1 (preferably 1:2-2:1) ratio is mixed, and mass concentration is
20%-30% (preferably 25%).
Described total organic carbon continuous automatic measurement instrument synchronous with total phosphorus, it is preferred that the carrier gas in the carrier gas bottle
For high purity oxygen gas, air pressure is not less than 0.1MPa.
Described total organic carbon continuous automatic measurement instrument synchronous with total phosphorus, it is preferred that the infrared CO2Detector
Centre wavelength be 4.26 μm.
Described total organic carbon continuous automatic measurement instrument synchronous with total phosphorus, it is preferred that the orthophosphate detector
Central detection wavelengths be 700nm.
Present invention also offers being connected according to described total organic carbon continuous automatic measurement instrument on-line synchronous synchronous with total phosphorus
Continue the method for automatically determining total organic carbon and total phosphorus concentration, its step is.
Sampling head is inserted into water body certain depth to be measured；Water sample under the swabbing action of peristaltic pump, through flow transducer,
Into acidifier, and start the peristaltic pump on Reagent Tube while sampling peristaltic pump is started, the reagent in reagent bottle is passed through
Flow transducer is also sent in acidifier；Subsequently, three-way magnetic valve is opened, the carrier gas in carrier gas bottle is distinguished by carrier gas pipe
In input acidifier and oxidation reactor, the data fed back by gas flow sensor, the gas of Reasonable adjustment three-way magnetic valve
Body sendout, to ensure the liquid in acidifier in micro- fluidized state, and the liquid in oxidation reactor is in stationary flow shape
State；In acidifier, there is chemical reaction in the inorganic carbonate in water sample to be measured with sulphuric acid, generate CO2Gas and fine sulfur
Hydrochlorate solid suspension；Gas-liquid-solid mixture after acidification reaction, under the promotion of peristaltic pump and nebulizer gas pressure, along acidifying
Fluid delivery tube is flowed in vapour liquid separator, the inorganic CO that here is produced by acidification reaction2And carrier gas is discharged by exhaustor, and
Liquid portion after acidifying then moves on, and flows in oxidation reactor；In oxidation reactor, Organic substance in water sample and contain
Phosphorus compound, under the synergy of ultraviolet light, sodium peroxydisulfate and temperature, is oxidized to CO2、PO4 3-Etc. high price state；Oxidation
Reacted mixed gas, through water proof ventilated membrane the air chamber on oxidation reactor top is concentrated on, by air shooter stream
In entering semiconductor cooling condenser, here, the vapor in mixed gas is condensed into after liquid water from condensed water discharge pipe discharge, and
Dry gas initially enters ionic absorption device, eliminates and may interfere with CO2The foreign ion of detection, subsequently into CO2Detector,
After reading to be detected, waste gas is discharged by detector afterbody；And the mixing liquid part after oxidation reaction, then by liquid delivery tube
Flow to two groups of spiral coils；From top to bottom, in the entrance point of every group of spiral coil, molybdate solution is respectively connected to by stilligout
With ascorbic acid solution drop transfusion bottle；PO in spiral coil, in liquid4 3-Show after with molybdate and ascorbic acid reaction
Color, subsequently enters orthophosphate detector, and after reading to be detected, waste liquid is discharged from discharging tube；Finally, by CO2Detector,
PO4 3-The data that detector is obtained, are sent in the lump data processor, the CO that here respectively obtains two detectors2With
PO4 3-Concentration data is compared with the data for having been stored in being demarcated by standard solution in data processor, just obtains actual measurement water sample
Total organic carbon (TOC) and total phosphorus (TP) data；Peristaltic pump is kept continuously to run, the gas and liquid in instrument continuously flows,
Detector will continuously obtain measurement data；According to the response time of different indexs to the timer in data processor
Adjusted, just can synchronization gain water quality real-time TOC and TP data.
The technology used in the present invention route is as shown in Figure 1.
First with fixed support or buoy, the sampling head 1 with drainage screen is installed in water body to be measured, and uses sampling tube
2 are connected sampling head 1 with this instrument.Water sample under the swabbing action of peristaltic pump 3, through flow transducer 4, into acidifier 5.
At the same time, another peristaltic pump is started, the reagent in reagent bottle 6 is also sent in acidifier through flow transducer.With
Afterwards, three-way magnetic valve 8 is turned on, the carrier gas in carrier gas bottle 7 is input into into respectively in acidifier 5 and oxidation reactor by carrier gas pipe 9
In 14.The data fed back by gas flow sensor 10, the gas sendout of Reasonable adjustment three-way magnetic valve, to ensure acidifying
Liquid in device is in micro- fluidized state, and the liquid in oxidation reactor is then in condition of steady flow；Reagent in reagent bottle
Mainly mixed by a certain percentage by sodium peroxydisulfate and sulphuric acid, after it mixes in acidifier with water sample to be measured, in water sample
Inorganic carbonate just there is chemical reaction with sulphuric acid, generate inorganic CO2Gas and fine sulfate solid float；Acidifying
Reacted gas-liquid-solid mixture, under the promotion of peristaltic pump and nebulizer gas pressure, can flow into vapour along acidizing fluid delivery pipe 13
In liquid/gas separator 11, here, the inorganic CO produced by acidification reaction2And carrier gas is discharged by exhaustor 12, and the liquid after being acidified
Part is then flowed in oxidation reactor 14.
As shown in Fig. 2 wherein, 32 is the silver-plated quartz glass tube of an outer surface to the structure of oxidation reactor；Interpolation master sends out
Six strands of ultraviolet lamp tubes 33 of bended that spectrum is 185nm are penetrated, electric heating cover 34 is coated with outside it, it is ensured that in quartz glass tube
Liquid maintain 95 DEG C or so.In oxidation reactor, the Organic substance and phosphorus-containing compound in water sample, in ultraviolet light, over cure
Under the synergy of sour sodium and temperature, CO will be all oxidized to2、PO4 3-Etc. high price state.
Mixed gas after oxidation reaction, through water proof ventilated membrane 35 oxidation reactor top is focused on, defeated by gas
The stream of pipe 15 is sent to enter in semiconductor cooling condenser 16, the vapor in this mixed gas is discharged after being condensed into liquid water from condensed water
Pipe 19 is discharged, and the gas being dried initially enters ionic absorption device 17, eliminates and may interfere with CO2The foreign ion of detection, then
Into CO2Detector 18, after reading to be detected, waste gas is discharged by detector afterbody.
And the mixing liquid part after oxidation reaction, then two groups of spiral coils 21 are flowed to by liquid delivery tube 20；On to
Under, in the entrance point of every group of spiral coil, molybdate solution drop transfusion bottle 22 is respectively connected to by stilligout and ascorbic acid is molten
Liquid drop transfusion bottle 23；PO in spiral coil, in liquid4 3-Develop the color after with molybdate and ascorbic acid reaction, subsequently enter
Orthophosphate detector 24, after reading to be detected, waste liquid is discharged from discharging tube 25.
Finally, by CO2The data that detector 18, orthophosphate detector 24 are obtained, are sent in the lump data processor
27；Here, the CO that two detectors are obtained2、PO4 3-Concentration data with have been stored in data processor by standard solution
The data of demarcation are compared, and just can obtain the total organic carbon (TOC) and total phosphorus (TP) data of actual measurement water sample.
The measured value of acquisition is calculated by data processor 27, can in real time be shown in the LCDs 28 of instrument, also
Can be transferred on the master server of environmental monitoring department by remote protocol, be shown with various diagrammatic forms.
By feedback circuit and programme-control, once sampling head is blocked, or the medicament in reagent bottle, carrier gas bottle or carrier gas
Use up, flow transducer 4 and gas flow sensor 10 can perceptual signal, instrument is by automatic alarm；The air-liquid stream of each pipeline
The parameters such as amount, temperature, can be turned by integrated automatic controller by the feedback signal of each sensor by automatically controlling peristaltic pump
Speed, electromagnetic valve flux, source current etc. are realized.
When sampling head 1 is blocked, can automatically be cleaned by peristaltic pump reversion.When accidental power failure is run into or need
When wanting maintenance shut-downs, the liquid that waste liquid discharge pipe 26 empties in advance remaining in machine can be passed through.
As long as peristaltic pump continuously runs, the gas and liquid in instrument continuously flows, and detector will be obtained continuously
Measurement data is obtained, as long as being adjusted to the timer in data processor according to the response time of different indexs, just can be synchronous
Obtain the real-time TOC and TP data of water quality.
The technical characterstic of the present invention is as follows with advantage.
1. multi-functional, can determine two water pollution indexs of TOC, TP with an instrument.
2. the compactedness of apparatus structure, the instrument of the present invention by the measure of TOC, TP two indices, by sharing a set of adopting
Sample, acidifying, oxidation and data handling system, can enormously 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 flow
Road is all continuous operation, once therefore start equipment, after first response phase terminates, as long as data-handling capacity is sufficiently strong
Greatly, detection data just can continuously be obtained.
4. the synchronicity and real-time of different index measurements.Because as above 2 index systems are connected using same flow process
It is continuous to determine, as long as being deducted on timer according to the response time of different detectors, just can be to the water quality feelings of any time
Condition synchronizes real-time monitoring.
5. ease-to-operate.By the instrument install it is in place after, except monthly change a medicament and for carrier gas bottle aerating in addition to,
Long-term unmanned is capable of achieving, detection data can in real time show in the LCDs of this instrument, also can be by long-range association
View transmission is displayed in real time on the master server of environmental monitoring department, is shown with various diagrammatic forms.
Description of the drawings
Fig. 1 is total organic carbon continuous automatic measurement apparatus structure schematic diagram synchronous with total phosphorus.Wherein, 1- sampling heads；2- is adopted
Sample pipe；3- peristaltic pumps；4- flow transducers；5- acidifiers；6- reagent bottle；7- carrier gas bottles；8- three-way magnetic valves；9- carrier gas pipes；
10- gas flow sensors；11- gas-liquid separators；12- exhaustors；13- acidizing fluid delivery pipes；14- oxidation reactors；15-
Air shooter；16- semiconductor cooling condensers；17- ionic absorption devices；18-CO2Detector；19- condensed water discharge pipes；20- liquid
Delivery pipe；21- spiral coils；22- molybdate solution transfusion bottles；23- ascorbic acid solution transfusion bottles；24- orthophosphate detectors；
25- discharging tubes；26- waste liquid discharge pipes；27- data processors；28- LCDs；The integrated automatic controllers of 29-；30- liquid
Flow direction；31- gas flow directions.
Fig. 2 is oxidation reactor structural representation.Wherein, 32- quartz glass tubes；33- ultraviolet lamp tubes；34- electric heating covers；
35- water proof ventilated membranes；36- temperature sensors；37- external power supplys；38- ambient temperature controllers；39- waste liquid discharge pipes.
Specific embodiment
Make detailed description to the present invention with reference to embodiment, but protection domain is not limited by this.
Embodiment total organic carbon continuous automatic measurement instrument synchronous with total phosphorus, it mainly includes sampling head 1, reagent bottle 6, carries
Gas cylinder 7, acidifier 5, oxidation reactor 14, gas-liquid separator 11, semiconductor cooling condenser 16, ionic absorption device 17, CO2Detector
18th, orthophosphate detector 24, data processor 27 and integrated automatic controller 29；The sampling head 1 by sampling tube 2 with it is compacted
Dynamic pump 3, flow transducer 4 and the acidifier 5 are connected；The reagent bottle 6 is by sampling tube 2 and peristaltic pump 3, flow transducer
4 and the acidifier 5 be connected；The carrier gas bottle 7 by carrier gas pipe 9, three-way magnetic valve 8, gas flow sensor 10 respectively with
The acidifier 5 is connected with the oxidation reactor 14；The acidifier 5 is by acidizing fluid delivery pipe 13 and the gas-liquid point
It is connected from device 11, the oxidation reactor 14；The oxidation reactor 14 is by air shooter 15 and the semi-conductor condensation
Device 16, the ionic absorption device 17, the CO2Detector 18 is connected, and is examined with the orthophosphate by liquid delivery tube 20
Survey device 24 to be connected；The CO2Detector 18 and the orthophosphate detector 24 are connected by circuit with data processor 27；Institute
Peristaltic pump 3, electromagnetic valve 8, various kinds of sensors such as 4,10,26 and various external power supplys such as 37,38 are stated, it is automatic with integrated by circuit
Control 29 connects.
The oxidation reactor mainly includes quartz glass tube 32, ultraviolet lamp tube 33, water proof ventilated membrane 35, electric heating cover
34th, temperature sensor 36, wherein, the outer surface of quartz glass tube 32 is silver-plated；The main light emission wavelength of ultraviolet lamp tube 33 is 185nm；Every
Quartz glass tube cavity is divided into upper and lower two parts by water ventilated membrane 35, and top is air chamber, and bottom is liquid chambers；Electric heating cover 34
Self-feedback ciucuit is constituted with temperature sensor 36 and integrated automatic controller 29, to guarantee that the temperature of liquid in oxidation reactor is
95℃。
Set on the liquid delivery tube 20 that the liquid chambers of the bottom of the oxidation reactor 14 are connected with orthophosphate detector 24
There are two groups of spiral coils 21, and molybdate solution transfusion bottle 22 and ascorbic acid solution are connected to respectively in every group of spiral coil section start
Transfusion bottle 23.
Reagent in the reagent bottle 6 is by sulphuric acid and sodium peroxydisulfate according to mol ratio 1:1 ratio is mixed, and quality is dense
Spend for 25%.
Carrier gas in the carrier gas bottle 7 is high purity oxygen gas, and air pressure is not less than 0.1MPa.
The infrared CO2The centre wavelength of detector 18 is 4.26 μm.
The central detection wavelengths of the orthophosphate detector 24 are 700nm.
Always had according to described total organic carbon continuous automatic measurement instrument on-line synchronous continuous automatic measurement synchronous with total phosphorus
The method of machine carbon and total phosphorus is.
First with fixed support or buoy, the sampling head 1 with drainage screen is installed in water body to be measured, and uses sampling tube
2 are connected sampling head 1 with this instrument.Water sample under the swabbing action of peristaltic pump 3, through flow transducer 4, into acidifier 5.
At the same time, another peristaltic pump is started, the reagent in reagent bottle 6 is also sent in acidifier through gas flow sensor.
Subsequently, three-way magnetic valve 8 is turned on, the carrier gas in carrier gas bottle 7 is input into into respectively in acidifier 5 and oxidation reaction by carrier gas pipe 9
In device 14.The data fed back by gas flow sensor 10, the gas sendout of Reasonable adjustment three-way magnetic valve, to ensure acid
Change the liquid in device and be in micro- fluidized state, and the liquid in oxidation reactor is then in condition of steady flow.
Reagent in reagent bottle is mainly mixed by a certain percentage by sodium peroxydisulfate and sulphuric acid, when its in acidifier with
After water sample mixing to be measured, just there is chemical reaction in the inorganic carbonate in water sample, generate inorganic CO with sulphuric acid2Gas and fine
Sulfate solid float.
Gas-liquid-solid mixture after acidification reaction, under the promotion of peristaltic pump and nebulizer gas pressure, can be defeated along acidizing fluid
Pipe 13 is sent to flow in vapour liquid separator 11, here, the inorganic CO produced by acidification reaction2And carrier gas is discharged by exhaustor 12, and
Liquid portion after acidifying is then flowed in oxidation reactor 14.
As shown in Fig. 2 wherein, 32 is the silver-plated quartz glass tube of an outer surface to the structure of oxidation reactor；Interpolation master sends out
Six strands of ultraviolet lamp tubes 33 of bended that spectrum is 185nm are penetrated, electric heating cover 34 is coated with outside it, it is ensured that in quartz glass tube
Liquid maintain 95 DEG C or so.In oxidation reactor, the Organic substance and phosphorus-containing compound in water sample, in ultraviolet light, over cure
Under the synergy of sour sodium and temperature, CO will be all oxidized to2、PO4 3-Etc. high price state.
Mixed gas after oxidation reaction, through water proof ventilated membrane 35 air chamber on oxidation reactor top is focused on, and is led to
Cross the stream of air shooter 15 to enter in semiconductor cooling condenser 16, the vapor in this mixed gas be condensed into liquid water after from cold
Solidifying water discharge pipe 19 is discharged, and the gas being dried initially enters ionic absorption device 17, eliminates and may interfere with CO2The impurity of detection from
Son, subsequently into CO2Detector 18, after reading to be detected, waste gas is discharged by detector afterbody.
And the mixing liquid part after oxidation reaction, then two groups of spiral coils 21 are flowed to by liquid delivery tube 20；On to
Under, in the entrance point of every group of spiral coil, molybdate solution drop transfusion bottle 22 is respectively connected to by stilligout and ascorbic acid is molten
Liquid drop transfusion bottle 23；PO in spiral coil, in liquid4 3-Develop the color after with molybdate and ascorbic acid reaction, subsequently enter
Orthophosphate detector 24, after reading to be detected, waste liquid is discharged from discharging tube 25.
Finally, by CO2The data that detector 18, orthophosphate detector 24 are obtained, are sent in the lump data processor
27；Here, the CO that two detectors are obtained2、PO4 3-Concentration data with have been stored in data processor by standard solution
The data of demarcation are compared, and just can obtain the total organic carbon (TOC) and total phosphorus (TP) data of actual measurement water sample.
The measured value of acquisition is calculated by data processor 27, can in real time be shown in the LCDs 28 of instrument, also
Can be transferred on the master server of environmental monitoring department by remote protocol, be shown with various diagrammatic forms.
By feedback circuit and programme-control, once sampling head is blocked, or the medicament in reagent bottle, carrier gas bottle or carrier gas
Use up, flow transducer 4,10 can perceptual signal, instrument is by automatic alarm；The parameters such as air-liquid flow, the temperature of each pipeline, can
By the feedback signal of each sensor, by integrated automatic controller by automatically controlling wriggling revolution speed, electromagnetic valve flux, power supply
Electric current etc. is realized.
When sampling head 1 is blocked, can automatically be cleaned by peristaltic pump reversion.When accidental power failure is run into or need
When wanting maintenance shut-downs, the liquid that waste liquid discharge pipe 26 empties in advance remaining in machine can be passed through.
Peristaltic pump is kept continuously to run, the gas and liquid in instrument continuously flows, and detector will be obtained continuously
Measurement data is obtained, the timer in data processor is adjusted according to the response time of different indexs, just can synchronization gain
The real-time TOC and TP data of water quality.
Instrument performance.
Repeatability error ± 3.8%, null offset ± 2%, span drift ± 5%, rectilinearity ± 4%, TOC response times
For 15min, TP response times are 25min, Mean stream time 1200h/ time, the experiment compared with actual water sample
Error is ± 5%, and sample 33 times/min of the frequency.
Claims (3)
1. total organic carbon continuous automatic measurement instrument synchronous with total phosphorus, is characterized in that, mainly including sampling head, reagent bottle, carrier gas
Bottle, acidifier, oxidation reactor, gas-liquid separator, CO2Detector, orthophosphate detector, data processor, it is integrated automatically
Controller, wherein the sampling head is connected by sampling tube with peristaltic pump, flow transducer and the acidifier；The reagent bottle
It is connected with peristaltic pump, flow transducer and the acidifier by sampling tube；The carrier gas bottle passes through carrier gas pipe, threeway electromagnetism
Valve, gas flow sensor are connected respectively with the acidifier and the oxidation reactor；The acidifier passes through acidizing fluid
Delivery pipe is connected with the gas-liquid separator, the oxidation reactor；The oxidation reactor by air shooter with it is described
CO2Detector is connected, and is connected with the orthophosphate detector by liquid delivery tube；The CO2Detector and the positive phosphorus
Hydrochlorate detector is connected by circuit with data processor；The peristaltic pump, electromagnetic valve and various kinds of sensors and external power supply are logical
Oversampling circuit is connected with integrated automatic controller；Total organic carbon continuous automatic measurement instrument on-line synchronous synchronous with total phosphorus are continuous
The method for automatically determining total organic carbon and total phosphorus, is characterized in that, sampling head is inserted into water body certain depth to be measured；Water sample is being wriggled
Under the swabbing action of pump, through flow transducer, into acidifier, and start on Reagent Tube while sampling peristaltic pump is started
Peristaltic pump, the reagent in reagent bottle is also sent in acidifier through flow transducer；Subsequently, three-way magnetic valve is opened,
Carrier gas in carrier gas bottle is input into respectively in acidifier and oxidation reactor by carrier gas pipe, is fed back by gas flow sensor
Data, the gas sendout of Reasonable adjustment three-way magnetic valve, to ensure the liquid in acidifier in micro- fluidized state, and oxygen
The liquid changed in reactor is in condition of steady flow；In acidifier, the inorganic carbonate in water sample to be measured and sulphuric acid
Reaction is learned, CO is generated2Gas and fine sulfate solid float；Gas-liquid-solid mixture after acidification reaction, in peristaltic pump
And under the promotion of nebulizer gas pressure, flow in gas-liquid separator along acidizing fluid delivery pipe, the nothing that here is produced by acidification reaction
Machine CO2And carrier gas is discharged by exhaustor, and the liquid portion after being acidified then moves on, and flows in oxidation reactor；In oxygen
Change in reactor, the Organic substance and phosphorus-containing compound in water sample, under the synergy of ultraviolet light, sodium peroxydisulfate and temperature, quilt
It is oxidized to the CO of high price state2、PO4 3-；Mixed gas after oxidation reaction, through water proof ventilated membrane oxidation reactor is concentrated on
The air chamber on top, is entered in semiconductor cooling condenser by air shooter stream, here, the vapor in mixed gas is condensed into
Discharge from condensed water discharge pipe after liquid water, and the gas being dried initially enters ionic absorption device, eliminates and may interfere with CO2Detection
Foreign ion, subsequently into CO2Detector, after reading to be detected, waste gas is discharged by detector afterbody；And after oxidation reaction
Mixing liquid part, then two groups of spiral coils are flowed to by liquid delivery tube；From top to bottom, in the import of every group of spiral coil
End, by stilligout molybdate solution and ascorbic acid solution drop transfusion bottle are respectively connected to；In spiral coil, in liquid
PO4 3-Develop the color after with molybdate and ascorbic acid reaction, subsequently enter orthophosphate detector, after reading to be detected, waste liquid
Discharge from discharging tube；Finally, by CO2Detector, PO4 3-The data that detector is obtained, are sent in the lump data processor,
This CO for respectively obtaining two detectors2And PO4 3-Concentration data with have been stored in data processor by standard solution demarcate
Data be compared, just obtain actual measurement water sample total organic carbon (TOC) and total phosphorus (TP) data, holding peristaltic pump continuously transport
OK, the gas and liquid in instrument continuously flows, and detector will continuously obtain measurement data, according to different indexs
Response time is adjusted to the timer in data processor, just can synchronization gain water quality real-time TOC and TP data.
2. total organic carbon according to claim 1 continuous automatic measurement instrument synchronous with total phosphorus, is characterized in that, the oxidation
Reactor mainly includes quartz glass tube, ultraviolet lamp tube, water proof ventilated membrane, electric heating cover, temperature sensor, wherein, quartzy glass
Glass tube outer surface is silver-plated；The emission wavelength of ultraviolet lamp tube is 180nm-200nm；Water proof ventilated membrane is divided into quartz glass tube cavity
Upper and lower two parts, top is air chamber, and bottom is liquid chambers；Electric heating cover and temperature sensor are constituted with integrated automatic controller
Self-feedback ciucuit, to guarantee the temperature of liquid in oxidation reactor as 90～98 DEG C.
3. total organic carbon according to claim 1 continuous automatic measurement instrument synchronous with total phosphorus, is characterized in that, the oxidation
The air chamber and CO on reactor top2The connected air shooter of detector is provided with semiconductor cooling condenser and ionic absorption device,
And the liquid delivery tube that the liquid chambers of bottom are connected with orthophosphate detector is provided with two groups of spiral coils, and in every group of spiral
Coil pipe section start is connected to respectively molybdate solution transfusion bottle and ascorbic acid solution transfusion bottle.
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| CN105675831A (en) * | 2015-11-08 | 2016-06-15 | 张开航 | Apparatus and method for measuring chlorine ion and total organic carbon in water |
| CN105675832A (en) * | 2015-12-05 | 2016-06-15 | 张开航 | Apparatus and method for measuring total organic carbon (TOC) |
| CN105675763A (en) * | 2016-03-01 | 2016-06-15 | 张开航 | Multifunctional chromatographic apparatus and method for measuring chloridion and total organic carbon |
| DE102016005604A1 (en) * | 2016-05-10 | 2017-11-16 | Elementar Analysensysteme Gmbh | Method for determining the TOC in a liquid sample and determination of the TN and / or the TP and apparatus for carrying out this method |
| CN106124499A (en) * | 2016-08-24 | 2016-11-16 | 徐滋秋 | Online ultraviolet digestion total phosphorus and total nitrogen total organic carbon synchronizes continuous monitor |
| CN109557037A (en) * | 2018-12-27 | 2019-04-02 | 南京理工大学 | Applied to the system and method for continuously monitoring mercury concentration in oxygen-enriching device |
| CN111913420B (en) * | 2020-07-27 | 2022-08-02 | 安徽华速达电子科技有限公司 | Intelligent control method and device for solution microparticle signal acquisition and server |
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