WO2019218530A1 - 一种同步检测水样分子量分布及有机氮的仪器及方法 - Google Patents

一种同步检测水样分子量分布及有机氮的仪器及方法 Download PDF

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WO2019218530A1
WO2019218530A1 PCT/CN2018/102945 CN2018102945W WO2019218530A1 WO 2019218530 A1 WO2019218530 A1 WO 2019218530A1 CN 2018102945 W CN2018102945 W CN 2018102945W WO 2019218530 A1 WO2019218530 A1 WO 2019218530A1
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injection valve
pump
acid
water
oxygen
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PCT/CN2018/102945
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English (en)
French (fr)
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张文俊
黎雷
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同济大学
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Priority to US17/056,425 priority Critical patent/US11796525B2/en
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    • G—PHYSICS
    • G01—MEASURING; TESTING
    • G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N33/00—Investigating or analysing materials by specific methods not covered by groups G01N1/00 - G01N31/00
    • G01N33/18—Water
    • G01N33/182—Specific anions in water
    • G—PHYSICS
    • G01—MEASURING; TESTING
    • G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N30/00—Investigating or analysing materials by separation into components using adsorption, absorption or similar phenomena or using ion-exchange, e.g. chromatography or field flow fractionation
    • G01N30/02—Column chromatography
    • G01N30/88—Integrated analysis systems specially adapted therefor, not covered by a single one of the groups G01N30/04 - G01N30/86
    • G—PHYSICS
    • G01—MEASURING; TESTING
    • G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N30/00—Investigating or analysing materials by separation into components using adsorption, absorption or similar phenomena or using ion-exchange, e.g. chromatography or field flow fractionation
    • G01N30/02—Column chromatography
    • G01N30/04—Preparation or injection of sample to be analysed
    • G01N30/06—Preparation
    • G01N30/14—Preparation by elimination of some components
    • G—PHYSICS
    • G01—MEASURING; TESTING
    • G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N30/00—Investigating or analysing materials by separation into components using adsorption, absorption or similar phenomena or using ion-exchange, e.g. chromatography or field flow fractionation
    • G01N30/02—Column chromatography
    • G01N30/62—Detectors specially adapted therefor
    • G01N30/64—Electrical detectors
    • G—PHYSICS
    • G01—MEASURING; TESTING
    • G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N30/00—Investigating or analysing materials by separation into components using adsorption, absorption or similar phenomena or using ion-exchange, e.g. chromatography or field flow fractionation
    • G01N30/02—Column chromatography
    • G01N30/04—Preparation or injection of sample to be analysed
    • G01N30/06—Preparation
    • G01N2030/067—Preparation by reaction, e.g. derivatising the sample
    • G—PHYSICS
    • G01—MEASURING; TESTING
    • G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N30/00—Investigating or analysing materials by separation into components using adsorption, absorption or similar phenomena or using ion-exchange, e.g. chromatography or field flow fractionation
    • G01N30/02—Column chromatography
    • G01N30/62—Detectors specially adapted therefor
    • G01N30/64—Electrical detectors
    • G01N2030/645—Electrical detectors electrical conductivity detectors
    • G—PHYSICS
    • G01—MEASURING; TESTING
    • G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N30/00—Investigating or analysing materials by separation into components using adsorption, absorption or similar phenomena or using ion-exchange, e.g. chromatography or field flow fractionation
    • G01N30/02—Column chromatography
    • G01N30/88—Integrated analysis systems specially adapted therefor, not covered by a single one of the groups G01N30/04 - G01N30/86
    • G01N2030/8809—Integrated analysis systems specially adapted therefor, not covered by a single one of the groups G01N30/04 - G01N30/86 analysis specially adapted for the sample
    • G01N2030/884—Integrated analysis systems specially adapted therefor, not covered by a single one of the groups G01N30/04 - G01N30/86 analysis specially adapted for the sample organic compounds
    • G—PHYSICS
    • G01—MEASURING; TESTING
    • G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N21/00—Investigating or analysing materials by the use of optical means, i.e. using sub-millimetre waves, infrared, visible or ultraviolet light
    • G01N21/75—Systems in which material is subjected to a chemical reaction, the progress or the result of the reaction being investigated
    • G01N21/77—Systems in which material is subjected to a chemical reaction, the progress or the result of the reaction being investigated by observing the effect on a chemical indicator
    • G01N21/78—Systems in which material is subjected to a chemical reaction, the progress or the result of the reaction being investigated by observing the effect on a chemical indicator producing a change of colour
    • G—PHYSICS
    • G01—MEASURING; TESTING
    • G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N33/00—Investigating or analysing materials by specific methods not covered by groups G01N1/00 - G01N31/00
    • G01N33/18—Water
    • G01N33/1826—Organic contamination in water
    • G01N33/1846—Total carbon analysis

Definitions

  • the invention relates to the technical field of environmental detection, in particular to an apparatus and a method for simultaneously detecting molecular weight distribution of water samples and organic nitrogen.
  • the data of different types of water quality are obtained separately, so that the water quality data is targeted.
  • the TOC concentration and the DON concentration of the water sample are independent, and the water quality cannot be more targeted.
  • Shimadzu's TOC analyzer can detect the TOC concentration, but even after adding the total nitrogen (TN) module, the detection path of the two parameters is still independent, and the simultaneous detection of DON concentration is still not possible.
  • the HACH series of multi-parameter water quality analyzers in the United States can detect the parameters such as TN and ammonia nitrogen concentration, but the instrument combines several measurement modules.
  • each module is still independent. Like the Shimadzu TOC Analyzer, it does not allow simultaneous detection of DON concentrations. Different from the above-mentioned detecting instruments, the present invention can realize the synchronous detection of the TOC concentration and the DON concentration by using one oxidation, thereby further improving the pertinence of the water quality data and realizing the full-width multi-dimensional detection of the water quality.
  • DON concentration is currently difficult to accurately detect, but it is critical to the safety of drinking water supply.
  • DON concentration is critical to the safety of drinking water supply.
  • DON because one of the sources of nitrogen-containing disinfection by-products is DON in raw water, understanding the concentration of influent DON is critical to controlling the amount of nitrogen-containing disinfection by-products in the effluent.
  • the detection of DON concentration is also based on the difference method.
  • the TW analyzer of WTW in Germany is actually a combination of three modules.
  • the instrument was also carried out using the above difference method.
  • the invention can realize the detection of the DON concentration by using the separation of the chromatography column, which is convenient, fast and accurate. It makes up for the shortcomings of the current DON concentration detection method.
  • Patent No. 2015101472555 discloses an apparatus and method for simultaneously detecting the concentrations of TOC, TN and TP. Although the apparatus and method can simultaneously detect three indicators, the direct ultraviolet spectrometry is used for the detection of TN concentration.
  • the photometric method that is, DON is oxidized to produce nitrate nitrogen, and then directly irradiated with a 220 nm ultraviolet lamp, and the nitrate nitrogen is detected by the magnitude of the absorbance, thereby converting the concentration of DON, but the detection limit of the method is high, and the ultraviolet signal
  • the interference received by the remaining impurity examples is large, and the accuracy of the experimental results cannot be guaranteed.
  • the above patents still fail to achieve simultaneous detection of DON concentration.
  • Another application No. 201610712720X proposes an instrument for on-line ultraviolet digestion of total nitrogen total phosphorus total organic carbon synchronous detection.
  • the TN concentration of the patent is also irradiated by ultraviolet light at 220 nm, and synchronous detection of DON concentration cannot be achieved.
  • the invention aims to solve the above-mentioned deficiencies of the currently widely detected water quality detection of polluted water bodies, and further provides an apparatus and method for simultaneously detecting the molecular weight distribution of water samples and organic nitrogen.
  • the invention can simultaneously detect the total organic carbon (TOC) concentration and the dissolved organic nitrogen (DON) concentration of the components in the different molecular weight distribution intervals of the water sample to be tested.
  • Qualitative and quantitative detection of the separated molecular weight components is achieved based on the existing molecular weight distribution map.
  • the measurement data can be displayed and stored as a chromatogram on a computer and can be aggregated into a chromatogram for further analysis by the relevant mapping software.
  • An apparatus for simultaneously detecting molecular weight distribution of water samples and organic nitrogen comprising an end injection valve sequentially connected through a pipeline, a chromatography column, a pressure reducing valve, an acid injection valve, an oxygen injection valve, an acid oxygen reaction spiral tube, and a CO 2 Remover, UV digestion device, second gas-water separation membrane, buffer solution injection valve, buffer solution reaction spiral tube, cadmium column, developer injection valve, developer reaction spiral tube, UV detector, the end injection valve
  • the second gas-water separation membrane is connected to a CO 2 conductance detector
  • the UV detector, the CO 2 conductance detector are each connected to a computer for data processing.
  • the end injection valve is connected to the sampling pump and the sample bottle, and the end injection valve is also connected to the mobile phase infusion pump and the mobile phase reagent bottle;
  • the acid addition valve is connected to the acid injection pump and the acid bottle;
  • the oxygenation injection valve is connected to the oxygen liquid injection pump and the oxygen liquid bottle;
  • the buffer solution injection valve is connected to the buffer solution injection pump and the buffer solution reagent bottle;
  • the developer injection valve is connected to the developer injection pump and the developer reagent bottle.
  • the CO 2 remover includes a first gas water separation membrane, a gas collection coil, a purge pump, and a separator, wherein the first gas water separation membrane, the gas collection coil, and the membrane are sequentially connected, and the first gas water
  • the separation membrane is connected to the acid-oxygen reaction spiral tube through a pipeline, the membrane is connected to the transparent quartz spiral tube through an outlet vent pipe and a pipeline, and the purge pump is connected to the gas collection coil, the first gas-water separation membrane
  • the function is to separate the CO 2 produced by the acidification of the IC from the liquid component, and then collect it into the gas collecting coil.
  • the first gas-water separation membrane is preferably a polydimethylsiloxane membrane, which belongs to the oxygen enrichment.
  • the membrane has a good separation effect on CO 2 and is structurally stable.
  • the action of the membrane isolates the CO 2 in the air from the outside and prevents entry into the component to be tested.
  • the function of the purge pump is to provide blow-off power to blow off the CO 2 collected in the gas collection coil.
  • the purge pump is preferably a micro-pneumatic diaphragm pump, which is small in size and can effectively provide blow-off power. ,cheap price.
  • the UV digestor comprises a heating wire, a transparent quartz spiral tube and a UV lamp, the transparent quartz spiral tube being connected between the diaphragm and the second gas-water separation membrane by a pipeline, the UV lamp being located in a transparent quartz spiral tube Above the heating wire is located below the transparent quartz spiral tube.
  • the second gas separation membrane is connected between the water with UV digestion buffer solution injection valve, connected to the second gas-water separation membrane conductance detector CO 2 for CO 2 separation reactor to produce a UV digestion to CO In the conductivity detector, the remaining sample enters the buffer solution injection valve and then enters the UV detector.
  • the second gas-water separation membrane is preferably a polydimethylsiloxane membrane, belonging to an oxygen-rich membrane, for CO 2 It has a good separation effect and is structurally stable.
  • the CO 2 conductivity detector comprises an ultrapure water tank, an ultrapure water pump and a conductivity cell connected in sequence, and the sample oxidized by the UV digestion device passes through a gas-liquid separation membrane, and the generated CO 2 is separated and dissolved and driven by an ultrapure water pump.
  • the ultrapure water purified by the ion-purifying resin is then introduced into the conductivity cell, and the amount of CO 2 is detected by detecting the change of the conductivity of the liquid in the conductivity cell, and the TOC concentration is characterized by a certain conversion relationship.
  • the ultrapure water is made by Milli-Q ultrapure water meter, the resistivity is 18.2M ⁇ , and the ultrapure water pump is a micro infusion pump.
  • the conductivity range of the conductivity cell is 0.01 ⁇ s/cm–300 ⁇ s/cm, and the resolution is 0.01 ⁇ s. /cm conductivity cell flow cell.
  • the column is located in the column oven.
  • the UV detector is connected to a waste liquid tank.
  • the UV detector via data line UV detector and a computer connected to the data processing, the CO 2 by the CO 2 conductance detector conductivity detector and a data line connected to a computer for data processing.
  • the method for simultaneously detecting the molecular weight distribution of water samples and organic nitrogen by using the above instrument comprises the following steps:
  • the sample is collected into the pipeline through the sampling pump, mixed with the mobile phase transported by the infusion pump through the end injection valve, and then separated through the liquid chromatography column in the column oven, and the components in the sample are sequentially discharged according to the molecular weight. Then, the pressure is reduced to about 1 atmosphere by the pressure reducing valve, and the separated molecular weight components of the sample are sequentially passed through the acid addition valve and the oxygen injection valve through the pipeline, and the acid liquid of the acid pipeline at this time.
  • the syringe pump will inject the acid into the acid injection valve according to the set amount.
  • the oxygen injection pump of the oxygen liquid pipeline will inject the oxygen liquid into the oxygen injection valve according to the set amount, and then the components to be tested and flow.
  • phase, acid and oxygen are fully reacted in the acid-oxygen reaction spiral tube; the inorganic carbon (IC) in the component to be tested is acidified by the acid to produce CO 2 , which is blown off into the air through a subsequent CO 2 remover.
  • IC inorganic carbon
  • the test component from which the inorganic carbon has been removed further passes through the pipeline to the UV digester, and the TOC in the component is oxidized to CO 2 under the irradiation of ultraviolet light and heated, and DON is oxidized to nitrate nitrogen, and the oxidized sample after liquid separation, the CO 2 produced is separated into a CO 2 conductivity detector, electric conductivity detector CO 2 amount of CO 2, the TOC concentration and characterized by a certain conversion relationship, then set the remaining free TOC
  • the buffer solution is added to the components through the buffer solution injection valve, and then reduced by the cadmium column to reduce the nitrate nitrogen to nitrite nitrogen, and then the color developer is added through the developer injection valve, and then the reaction reagent is spiraled.
  • the mixing reaction is carried out in the tube, and finally enters the UV detector, the amount of nitrite nitrogen is detected at 540 nm, and the DON concentration is characterized by a certain conversion relationship.
  • the UV detector outlet waste liquid and the CO 2 conductivity detector waste are discarded.
  • the liquid is discharged to the waste liquid tank through the waste liquid pipe.
  • the column adopts a liquid-phase size exclusion chromatography column, and the effective range of the molecular weight distinction can be set according to the needs of the user, and generally can be selected from 500 to 800000 Da.
  • the flow is selected according to the requirements of the column, and is generally selected as a phosphate buffer solution having an ionic strength of 0.1 to 0.4 M and a pH of 6.8 ⁇ 0.2.
  • the flow rate of the mobile phase infusion pump should ensure that each peak of the chromatographic peak is sharp and easy to distinguish, and no tailing phenomenon occurs, and the range of the flow rate allowed by the column is generally 0.4 to 1.0 mL/min.
  • the mobile phase infusion pump pressure should be within the allowable pressure range of the column, and generally can be selected as 1.8 ⁇ 0.2 MPa.
  • the column oven has a heating wire, and the column temperature of the column should be adjusted according to the peak condition of the sample. On the one hand, it is necessary to ensure that each peak has a narrow peak width, and on the other hand, the temperature allowed in the column. In the range, the peak width of a general chromatographic peak is approximately 4 to 10 min, and the temperature is generally set to 30 to 60 °C.
  • the sampling pump collects the sample into the pipeline and mixes it with the mobile phase through the end injection valve.
  • the sampling pump uses a micro-injection pump, the working pressure of the pump should be higher than 1500 psi, the highest precision should be less than 0.1%, no pulse delivery, uniform delivery, and the injection volume from very small to very large can be accurately distributed.
  • the sampling volume should ensure that the peaks of the chromatographic peaks are sharp and easy to distinguish, and can be selected according to the separation effect of the column.
  • the general setting is 50-500 uL.
  • the acid bottle is used for the acid solution, and the acid solution should be selected according to the sample, but it is necessary to ensure that the IC is fully acidified into CO 2 , and generally 15% to 30% phosphoric acid can be selected.
  • the oxygen liquid bottle is used for oxygen storage, and the oxygen liquid should be selected according to different samples.
  • the oxygen liquid should ensure that all TOC is oxidized to CO 2 , and generally 10% to 20% ammonium persulfate can be selected. Solution.
  • the acid liquid injection pump and the oxygen liquid injection pump should be capable of injecting the acid liquid and the oxygen liquid into the main flow path according to a certain flow rate, and does not affect the flow rate and pressure of the main flow path.
  • micro-injection pump, pump working pressure should be higher than 1500 psi, the highest precision is less than 0.1%, no pulse delivery, accurate distribution from very small to very large injection volume, acid-added oxygen pipeline and sample pipeline Injection valve connection.
  • the flow rate of the acid oxygen injection pump should ensure that the acid oxygen solution is excessive, and can be selected according to the concentration of the sample and the acid oxygen solution, and generally can be selected as 1.0 to 4.0 ⁇ L/min.
  • the end injection valve, the acid injection valve, the oxygen injection valve, the buffer solution injection valve, and the developer injection valve are all configured to stably and slowly mix a liquid into another liquid, and No back suction will occur.
  • the injection valve is provided with a shut-off plate that prevents liquid from flowing back and the cushion pad helps to stably and slowly inject the liquid into the other liquid.
  • the acid oxygen reaction spiral tube is disposed between the UV digestion device and the oxygen injection valve to ensure that the IC is sufficiently acidified to CO 2 , preferably: a stainless steel PEEK tube is spiraled.
  • a stainless steel PEEK tube is spiraled.
  • the cost is reduced; on the other hand, the stainless steel PEEK tube can effectively prevent the corrosion of the medicament and ensure that the separated components to be tested are not mixed again.
  • the buffer solution reagent bottle is used for loading a buffer solution, and the buffer solution is prepared by using an ammonium chloride buffer solution, and is dissolved in 800 mL of water through 85.0 g of ammonium chloride and 1.0 g of disodium ethylenediaminetetraacetate dihydrate, and the volume is adjusted to 1000 mL. Mix well.
  • the pH of the solution is preferably 8.5.
  • the developer is prepared as follows. 100 mL of phosphoric acid is dissolved in 600 mL of water, then 40 g of sulfonamide and 1 g of naphthylethylenediamine hydrochloride are added, and the mixture is diluted with water to 1000 mL, and the phosphoric acid is selected for analytical purity.
  • the purpose of the cadmium column is to reduce the oxidized nitrate nitrogen to nitrite nitrogen.
  • the reduction efficiency of the cadmium column should be higher than 98%, and the cadmium column loading is convenient and not easy to damage.
  • the buffer solution reaction spiral tube and the color developer reaction spiral tube are preferably formed by spiraling a stainless steel PEEK tube.
  • the cost is reduced; on the other hand, the stainless steel PEEK tube can effectively prevent the corrosion of the medicament and ensure that the separated components to be tested are not mixed again.
  • the amount of the buffer solution is determined based on the actual water sample.
  • the flow rate of the developer injection pump is such that an excess of the added developer is ensured, and generally it can be selected from 1.0 to 4.0 ⁇ L/min.
  • the UV digestor includes a transparent quartz reaction spiral tube, a UV lamp, and a heating wire.
  • the transparent quartz reaction spiral tube provides a sufficient reaction space, and under the irradiation of the UV lamp and the heating condition, the oxidizing active substance persulfate radical generated by the oxidizing agent will fully oxidize the component to be tested.
  • the UV lamp has a wavelength of 190 nm and the heating temperature is set to (95 ⁇ 2 ° C).
  • the UV detector satisfies the change in on-line detection of absorbance, is equipped with a flow through sample cell, and stores the results and outputs to a computer for further analysis.
  • the UV detector is provided with a PEEK pipe joint, an ultraviolet detector capable of detecting on-line, and automatically drawing a chromatogram using software.
  • the internal sample line material of the instrument is preferably a stainless steel PEEK tube in order to avoid corrosion of the sample.
  • the flow rate of the main flow channel is the flow rate of the mobile phase infusion pump, which can be selected from 0.4 to 1.0 mL/min.
  • the pressure liquid chromatography column was 1.8 ⁇ 0.2 MPa before, and the liquid chromatography column was passed through a pressure reducing valve with a pressure of 1 bar, and the flow state was free flowing.
  • the invention can synchronously detect the TOC concentration and the DON concentration of the components of the water sample to be tested in different molecular weight distribution intervals.
  • the specific detection principle is:
  • the sample is passed through a size exclusion chromatography column, and the sample components in the effluent are arranged according to the molecular weight within the range of the selected column separation, and then the TOC concentration and the DON concentration of the two most common water quality parameters in the different molecular weight distribution intervals are detected.
  • the invention utilizes the different molecular weight components in the water sample separated by size exclusion chromatography to sequentially flow out according to the molecular weight, and the detection of the TOC concentration in the present invention can accurately understand the different molecular weight distributions and determine the difference. TOC concentration within the molecular weight distribution interval.
  • DON is discharged out of the column within a certain residence time, and the detection of DON is carried out in accordance with the present invention, so that the water sample to be tested is conveniently, efficiently and accurately determined. DON concentration.
  • the present invention can provide a TOC concentration and a DON concentration for simultaneously detecting components of a water sample to be tested in different molecular weight distribution intervals.
  • the analysis time is greatly shortened, and more importantly, the present invention can realize the synchronous collection of the polluted water quality data in a complete sense.
  • the technical route of the present invention is:
  • the sample in the vial is transferred by the sampling pump, reaches the line, and is injected into the mobile phase line by the end injection valve.
  • the mobile phase in the mobile phase reagent bottle is transported to the main flow path by the mobile phase infusion pump and is mixed with the sample after reaching the end injection valve.
  • the mobile phase carries the sample separated through a column in the column oven. After separation by the column, the sample to be tested flows out in order according to the molecular weight of the components, and passes through a pressure reducing valve, and the pressure is reduced to one atmosphere, and the flow state is a free outflow.
  • the component to be tested reaches the acid injection valve and the oxygen injection valve in the main flow path, and is mixed with the acid liquid and the oxygen liquid which are transmitted through the acid liquid injection pump and the oxygen liquid injection pump, and further reaches the acid oxygen reaction spiral tube.
  • the mobile phase, the component to be tested, the acid solution and the oxygen solution are thoroughly mixed in the acid-oxygen reaction helix.
  • the inorganic carbon (IC) in the component to be tested is acidified by the acid, and the generated CO 2 is mixed in the pipeline, enters the CO 2 remover, and the generated CO 2 is separated from the liquid phase and discharged into the air.
  • the structure of the CO 2 remover is as described above: wherein the generated CO 2 is immediately separated from the liquid phase by the first gas-water separation membrane, enters the gas collection coil, and is transported through the purge pump to pass the CO 2 through the separator. After blowing off, it enters the air, and the CO 2 in the air is blocked by the diaphragm and does not enter the liquid phase.
  • the remaining components and mobile phase from which the IC has been removed continue to advance into the UV digestor.
  • the structure of the UV digestor is as follows: a transparent quartz reaction spiral tube provides a reaction space, and the component to be tested, the mobile phase, the oxygen liquid, and the acid liquid are sufficiently mixed and spiraled therein, under the irradiation of the UV lamp and the heating wire heating condition, Oxidation of TOC to CO 2 oxidizes DON to nitrate ions (Reactions 2, 3).
  • the CO 2 generated by the oxidation of the TOC enters the second gas-water separation membrane, is separated from the liquid phase, and enters the CO 2 conductance detector.
  • the CO 2 conductance detector structure is as described above, in which the separated CO 2 enters the CO 2 conductance detector from another flow path and is dissolved in the ultrapure water line.
  • the ultrapure water is driven by an ultrapure water pump, which is taken from the ultrapure water tank, enters the conductivity cell after dissolving CO 2 , and detects the CO 2 content by the change of the conductance to indicate the TOC concentration.
  • the components of the TOC are removed to reach the buffer solution injection valve, and then mixed with the buffer solution delivered by the buffer solution injection pump, and after reaching the buffer solution, the reaction spiral tube is further mixed and then enters the cadmium column to reduce the nitrate nitrogen produced by the oxidation to the sub- Nitrate nitrogen, which is then mixed with the developer delivered by the developer injection pump and the developer pump, and further reacted in the developer reaction spiral tube, using nitrite nitrogen and sulfonamide under acidic medium.
  • the nitridation reaction is then coupled with naphthylethylenediamine hydrochloride to form a purplish red material.
  • the UV detector is used to generate absorption under the ultraviolet light of nm by nitrite nitrogen, and the absorption amount conforms to Beer's law. After obtaining the signal through the photoelectric sensor, the amount of nitrite nitrogen is obtained after treatment, according to a certain conversion relationship. Further, the DON concentration was further characterized.
  • the conductivity cell outlet wastewater and the UV detector outlet wastewater are combined and collected into a waste liquid tank.
  • the data of the sum is transmitted by the data transmission line and transmitted to the computer for further storage and processing.
  • the export wastewater is collected and collected into the waste liquid tank.
  • the UV detector is connected to the computer for data processing via the UV detector data line
  • the CO 2 conductance detector is connected to the computer for data processing via the CO 2 conductance detector data line, and the computer performs further storage and processing.
  • An instrument can synchronously detect the components of the contaminated water sample in different molecular weight distribution intervals, and the TOC and DON concentrations of the components in different molecular weight distribution intervals.
  • the instrument of the invention is capable of detecting the TOC and DON concentrations of the pollutant components in different molecular weight distribution intervals after the sample to be tested is separated by the chromatographic column, and the water quality data is more targeted, and the research on the nitrogen-containing disinfection by-products in the future. It has important supporting significance.
  • the instrument of the invention pioneered the method for measuring the DON concentration by liquid chromatography separation method, and the accuracy of the method is greatly improved compared with the traditional difference method.
  • the method of the invention is a pioneering method for measuring the DON concentration by liquid chromatography, which is simpler and more convenient than the common dialysis membrane, ion exchange column, preconcentration and catalytic reduction method at home and abroad, and greatly improves the water quality detection. s efficiency.
  • FIG. 1 is a schematic view showing the structure of an apparatus for simultaneously detecting molecular weight distribution of water samples and organic nitrogen according to the present invention
  • FIG. 2 is a schematic structural view of a CO 2 remover
  • Figure 3 is a schematic view showing the structure of a UV digestor.
  • the label 1-mobile phase reagent bottle; 2-mobile phase infusion pump; 3-terminal injection valve; 4-sampling pump; 5-vial; 6-column; 7-column column thermostat; Pressure valve; 9-acid injection valve; 10-acid injection pump; 11-acid bottle; 12-oxygen injection valve; 13-oxygen injection pump; 14-oxygen bottle; 15-acid-oxygen reaction coil ; 16-UV digester; 17-buffer solution syringe pump; 18-buffer solution reagent bottle; 19-buffer solution injection valve; 20-buffer solution reaction spiral tube; 21-cadmium column; 22-chromogen injection valve; - developer injection pump; 24 - developer reagent bottle; 25 - developer reaction spiral tube; 26-UV detector; 27 - waste liquid barrel; 28 - computer; 29 - heating wire; 30 - transparent quartz spiral Tube; 31-UV lamp; 32-CO 2 remover; 33-second gas-water separation membrane; 34-CO 2 conductivity detector; 35-ultra-pure water tank
  • an apparatus for simultaneously detecting the molecular weight distribution of water samples and organic nitrogen includes an end injection valve 3, a column 6, a pressure reducing valve 8, an acid injection valve 9, and an oxygen injection valve 12 which are sequentially connected by a pipeline. , acid oxygen reaction spiral tube 15, CO 2 remover 32, UV digestion device 16, second gas water separation membrane 33, buffer solution injection valve 19, buffer solution reaction coil 20, cadmium column 21, developer injection valve 22 a developer reaction spiral tube 25, a UV detector 26 for receiving a mobile phase and a sample, and a second gas-water separation membrane 33 connected to a CO 2 conductance detector 34, the UV detector 26, CO 2 conductance detector 34 is connected to the computer 28 for data processing.
  • the end injection valve 3 is connected to the sampling pump 4 and the sample vial 5, and the end injection valve 3 is also connected to the mobile phase infusion pump 2 and the mobile phase reagent bottle 1; the acid injection valve 9 and the acid injection
  • the pump 10 and the acid bottle 11 are connected;
  • the oxygen injection valve 12 is connected to the oxygen liquid injection pump 13 and the oxygen liquid bottle 14;
  • the buffer solution injection valve 19 is connected to the buffer solution injection pump 17 and the buffer solution reagent bottle 18;
  • the developer injection valve 22 is connected to the developer injection pump 23 and the developer reagent bottle 24.
  • the column 6 is located in the column oven 7 of the column.
  • the UV detector 26 is connected to the waste liquid tank 27.
  • the UV detector is connected to the computer 264 328 for data processing by the data line UV detector, the CO 2 34 CO 2 conductance detector conductivity detector 44 connected to the data line for the computer 28 through the data processing.
  • the CO 2 remover 32 includes a first gas-water separation membrane 38, a gas collection coil 39, a purge pump 40, and a separator 41, the first gas-water separation membrane 38, the gas collection coil 39, and The diaphragms 41 are sequentially connected, and the first gas-water separation membrane 38 is connected to the acid-oxygen reaction spiral tube 15 through a pipe, and the diaphragm 41 is connected to the transparent quartz spiral pipe 30 through the outlet vent pipe 42 and the pipe, the blowing The pumping unit 40 is connected to the gas collecting coil 39.
  • the function of the first gas-water separation membrane 38 is to separate the CO 2 generated by acidification of the IC from the liquid component, and then collect it into the gas collecting coil, the first
  • the gas-water separation membrane 38 is preferably a polydimethylsiloxane membrane which is an oxygen-rich membrane, has a good separation effect on CO 2 , and is structurally stable.
  • the action of the diaphragm 41 isolates the CO 2 in the air from the outside to prevent entry into the component to be tested.
  • the function of the purge pump 40 is to provide blow-off power to blow off the CO 2 collected in the gas collection coil 39.
  • the purge pump 40 is preferably a micro-pneumatic diaphragm pump, which is small in size and can be effectively provided. Blow off power, the price is cheap.
  • the UV sterilizer 16 includes a heating wire 29, a transparent quartz spiral tube 30, and a UV lamp 31.
  • the transparent quartz spiral tube 30 is connected to the diaphragm 41 and the second gas-water separation membrane 33 through a pipeline.
  • the UV lamp 31 is located above the transparent quartz spiral tube 30, and the heating wire 29 is located below the transparent quartz spiral tube 30.
  • the second gas-water separation membrane 33 is connected between the UV digestor 16 and the buffer solution injection valve 19, and the second gas-water separation membrane 33 is connected to the CO 2 conductance detector 34 for generating the UV digestor 16 of CO 2 to CO 2 separation conductance detector 34, the remainder of the sample into the buffer solution injection valve 19, which can then enter the UV detector, the second gas-water separation membrane 33 is preferably a polydimethylsiloxane membrane It is an oxygen-rich membrane with good separation effect on CO 2 and stable structure.
  • the CO 2 conductance detector 34 includes an ultrapure water tank 35, an ultrapure water pump 36, and a conductivity cell 37 that are sequentially connected.
  • the sample oxidized by the UV digestor 16 passes through the gas-liquid separation membrane 19 to separate and dissolve the generated CO 2 .
  • the amount of CO 2 is detected by detecting the change of the conductivity of the liquid in the conductivity cell, and a certain conversion relationship is passed. Characterize TOC concentration.
  • the ultrapure water is made by Milli-Q ultrapure water meter, the resistivity is 18.2M ⁇ , and the ultrapure water pump is a micro infusion pump.
  • the conductivity range of the conductivity cell is 0.01 ⁇ s/cm–300 ⁇ s/cm, and the resolution is 0.01 ⁇ s. /cm conductivity cell flow cell.
  • the sample in the vial 5 is transferred by the sampling pump 4, reaches the line, and is injected into the mobile phase line by the end injection valve 3.
  • the mobile phase in the mobile phase reagent bottle 1 is transferred to the main flow path by the mobile phase infusion pump 2, and after the end injection valve 3 is reached, the sample is mixed.
  • the mobile phase carries the sample separated by column 6 in the column oven 7 of the column. After separation by the chromatography column 6, the sample to be tested flows out in order according to the molecular weight of the components, and passes through the pressure reducing valve 8, the pressure is reduced to one atmosphere, and the flow state is a free outflow.
  • the component to be tested reaches the acid addition valve 9 and the oxygen injection valve 12 in the main flow path, and is mixed with the acid liquid and the oxygen liquid which are transmitted through the acid injection pump 10 and the oxygen liquid injection pump 13, and further reaches the acid oxygen reaction spiral.
  • tube 15 The mobile phase, the component to be tested, the acid solution and the oxygen solution are thoroughly mixed in the acid oxygen reaction coil 15.
  • the inorganic carbon (IC) in the component to be tested is acidified by the acid, and the generated CO 2 is mixed in the pipeline, enters the CO 2 remover 16, and the generated CO 2 is separated from the liquid phase and discharged into the air. .
  • the structure of the CO 2 remover 16 is as shown in Fig. 2, in which the generated CO 2 is immediately separated from the liquid phase by the first gas-water separation membrane 38, enters the gas collection coil 39, and is transported through the purge pump 40. The CO 2 is blown off the separator 41 and then enters the air, and the CO 2 in the air is blocked by the separator 41 and does not enter the liquid phase.
  • the remaining components and mobile phase from which the IC has been removed continue to advance into the UV digestor.
  • the structure of the UV digestor 16 is as shown in FIG. 3: a transparent quartz reaction spiral tube provides a reaction space, a component to be tested, a mobile phase, an oxygen liquid, and an acid solution in which the spiral is sufficiently mixed, the irradiation of the UV lamp 31, and the heating wire. Under heating, TOC is oxidized to CO 2 and DON is oxidized to nitrate ions (Reactions 2, 3).
  • CO 2 generated by the oxidation of the TOC enters the second gas-water separation membrane 33, is separated from the liquid phase, and enters the CO 2 conductance detector 34.
  • the CO 2 conductance detector 34 is constructed as shown by the dashed box in Figure 1 in which the separated CO 2 is passed from another flow path into the CO 2 conductance detector and dissolved in the ultrapure water line.
  • the ultrapure water is driven by an ultrapure water pump, which is taken from the ultrapure water tank, enters the conductivity cell after dissolving CO 2 , and detects the CO 2 content by the change of the conductance to indicate the TOC concentration.
  • the components of the TOC are removed to the buffer solution injection valve 19, at this time, mixed with the buffer solution delivered by the buffer solution injection pump 17, and after reaching the buffer solution, the reaction coil 20 is further mixed, and then enters the cadmium column 21 to oxidize the nitrate produced.
  • the nitrogen is reduced to nitrite nitrogen, and then mixed with the developer conveyed by the developer injection pump 23 at the developer injection valve 22, and further reacted in the developer reaction spiral tube 25, using an acidic medium, Nitrate nitrogen is diazotized with sulfonamide and then coupled with naphthylethylenediamine hydrochloride to form a purplish red material.
  • the UV detector 26 After obtaining the signal through the photoelectric sensor, the amount of nitrite nitrogen is obtained after treatment, according to a certain conversion relationship. Further characterizing the DON concentration.
  • the outlet wastewater of the conductivity cell 37 and the outlet wastewater of the UV detector 26 are combined and collected into the waste liquid tank 27.
  • the data of 23 and 33 are transmitted to the computer terminal 36 by data transmission lines 35 and 34, respectively, for further storage and processing.
  • the outlet wastewater is collected and collected into the waste liquid tank 27.
  • the UV detector 26 is coupled via a UV detector data line 43 to a computer 28 for data processing
  • the CO 2 conductance detector 34 is coupled to a computer 28 for data processing via a CO 2 conductance detector data line 44, the computer 28 proceeds further Storage and processing.
  • the instrument is turned on and the computer 28 is turned on.
  • the mobile phase was subjected to ultrasonic degassing for 20 minutes to eliminate bubbles in the mobile phase to avoid interference with the detection results.
  • the sample was passed through a 0.45 ⁇ m membrane to remove particulate impurities to avoid clogging of the instrument.
  • the UV detector 26 was turned on and the detection wavelength was set to 540 nm.
  • the ultrapure water pump 36 is turned on to allow the ultrapure water in the CO 2 detector to start flowing. Empty the waste container 27.
  • the mobile phase infusion pump 2 is turned on, and the flow rate and pressure are set.
  • the baseline of the computer 28 is stabilized (generally 1 ⁇ 2h)
  • the liquid injection pump 13, the buffer solution injection pump 17, and the developer injection pump 23 is open.
  • the sample is injected into the mobile phase through the end injection valve 3, and the acid and oxygen are injected into the mobile phase, after which the data results are awaited.
  • the residence time of different molecular weight standards obtained from the TOC concentration peaks is as follows:
  • the method provided by the present invention has a detection range of TOC concentration of 0.03 ⁇ g/L to 50 mg/L;
  • Detection of DON concentration When the detection optical path of the ultraviolet detector is 10 mm, the method provided by the present invention measures the DON concentration in the range of 0.12 mg/L to 10 mg/L.

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Abstract

本发明涉及一种同步检测水样分子量分布及有机氮的仪器及方法，该仪器包括通过管路顺序连接的末端注入阀、色谱柱、减压阀、加酸注入阀、加氧注入阀、酸氧反应螺旋管、CO 2去除器、UV消解器、第二气水分离膜、缓冲溶液注入阀、缓冲溶液反应螺旋管、镉柱、显色剂注入阀、显色剂反应螺旋管、UV检测器，所述末端注入阀用于接收流动相与样品，所述第二气水分离膜连接CO 2电导检测器，所述UV检测器、CO 2电导检测器均与用于数据处理的计算机连接。本发明实现了待测样品在不同分子量分布区间的TOC浓度、DON浓度的同步检测，为水厂进出水水质分析、含氮消毒副产物检测与控制等水质检测领域提供了可靠便捷的检测手段。

Description

一种同步检测水样分子量分布及有机氮的仪器及方法 技术领域
本发明涉及环境检测技术领域，尤其是涉及一种同步检测水样分子量分布及有机氮的仪器及方法。
背景技术
目前我国由于国土面积的广大，淡水资源总量较高，位居世界第4位，占全球水资源总量的6％。但由于人口众多，淡水资源人均占有量仅在世界上名列121位，这样来看，中国仍是一个缺水严重的国家。尽管淡水资源人均占有量严重不足，各种水环境污染情况在全国各地仍多次出现，比如有机农药、个人护理用品、含磷洗衣粉等的滥用，工业废水未经处理乱排乱放，农业、畜牧业污水排入水体等行为。这些行为正进一步污染着我们仅有的、稀缺的水资源。对水环境污染的治理需要“预防”+“治理”齐头并进：首先要从源头抓起，杜绝污染物质不经处理达标后直接排放到水体中这一类污染水环境现象的发生。其次，在减少污染物排入水体的同时，我们还需要对已经污染的水体进行综合有效的治理。
如何能在治理水环境污染时实现“对症下药”一直是从事水污染治理学者研究的热点。人们提出了类似于高级氧化法，膜分离法等治理方法。这些方法虽然能有效的将污染水体中的污染物质降解到较低水平，但是都不可避免的出现加药量大、不能“对症下药”的问题。这也就出现了治理时易发生由于药剂过量引起的二次污染，处理工艺不经济等问题。解决这些问题的关键是要在治理之前掌握更全面更精准的水质数据，只有彻底了解了受污染水体的最全面精准的水质数据，才能对水处理工艺的提升提供依据，从而提出更加准确的治理方案。
受污染水体水质数据的采集依赖更好的水质检测技术，传统意义上的水质检测是从受污染水体中取得水样，然后运输到实验室内，利用一系列的水质分析仪器， 对污染水体的水质进行表征，从而得出水质数据。但是这样的水质检测有以下不足：
1、检测过程中，不同种类的水质数据的获得都是分开的，从而水质数据的针对性降低。举个例子说明：分析水样所含TOC浓度时，无法做到同时分析DON含量，那么这一时刻此种水样的TOC浓度和DON浓度是独立的，不能更加有针对性的对水质进行表征。例如岛津的TOC分析仪虽能实现TOC浓度的检测，但即使在增加了总氮(TN)模块之后，两个参数的检测路程依然是独立运行的，而且仍不能做到DON浓度的同步检测。美国HACH公司的系列多参数水质分析仪，虽能够实现对TN、氨氮浓度等参数的检测，但是该仪器就是将几个测量模块组合到一起，实际上各个模块的运行依然是独立的，另外和岛津TOC分析仪一样，其也不能实现对DON浓度的同步检测。与以上提到的检测仪器不同的是，本发明利用一次氧化，能够实现对TOC浓度、DON浓度的同步检测，从而进一步提高了水质数据的针对性，实现对水质进行全幅多维检测。
2、DON浓度目前很难做到精确检测，但其对饮用水供水安全至关重要。例如，在水厂中新型含氮消毒副产物的研究领域，为了保证水厂出水中消毒副产物特别是目前新型的含氮消毒副产物的量，需要根据进水水质的不同严格控制消毒剂的量，因为含氮消毒副产物的其中一个来源就是原水中的DON，了解了进水DON浓度的大小，对于控制出水含氮消毒副产物的量至关重要。哈尔滨工业大学张靓的硕士论文《基于渗析加电原理的有机氮浓度检测预处理方法研究》论述了目前国内外有关DON浓度检测方法的不足，并且提出了渗析加电法检测DON浓度的方法。此法对于DON浓度检测的准确性确有提高，但是耗费的检测时间长，检测效率低，检测过程中的操作复杂，这些不足也是大部分检测DON浓度方法的通病。实验室检测DON常用的差值法有总氮减去无机氮和总凯氏氮减去氨氮两种，这两种方法需要多次检测，这样累积的系统误差较大，对结果的影响也较大。目前市场上大部 分的仪器只能检测TN、氨氮浓度，对DON浓度的检测也都是基于差值法，例如：德国的WTW的TN分析仪，其实就是三个模块的组合，对于DON浓度的检测，该仪器也是利用了上述差值法进行。与以上提到的检测仪器不同的是，本发明利用色谱柱的分离即可以实现对DON浓度的检测，方便快捷准确。弥补了目前对于DON浓度检测方法的不足。
以上提到的水质检测的不足对目前污染水体水质数据的采集带来困难，也就不能提供更加精确的治理措施。目前的水环境污染的治理亟需一种能够同步检测出不同污染物在不同分子量区间内的TOC浓度以及DON浓度。专利号为2015101472555的专利公布了一种能同步检测TOC、TN和TP浓度的仪器和方法，该仪器和方法虽然能够实现三种指标的同步检测，但是对于TN浓度的检测采用的是直接紫外分光光度法，即DON被氧化后产生硝酸盐氮，然后直接使用220nm紫外灯照射，通过吸光度的大小来检测硝酸盐氮，从而换算得到DON的浓度，但是该方法的检测限较高，而且紫外信号收到其余杂质例子的干扰较大，实验结果的准确性不能保证。另外，上述专利仍不能实现对DON浓度的同步检测。另一项申请号为201610712720X的专利提出一种在线紫外消解总氮总磷总有机碳同步检测的仪器，该专利的TN浓度也是采用220nm处紫外灯照射法，并且无法实现DON浓度的同步检测。
总之，目前国内外还没有任何一种能够同步检测出不同污染物在不同分子量区间内的TOC浓度以及DON浓度的仪器或者方便、准确的检测方法。
发明内容
本发明致力于解决上述提到的目前广泛存在的污染水体水质检测的不足，进而提供一种同步检测水样分子量分布及有机氮的仪器及方法。本发明能同步检测待测水样在不同分子量分布区间内组分的总有机碳(TOC)浓度、溶解性有机氮(DON)浓度。根据已有的分子量分布图谱，实现对分离出来的不同分子量组分 的定性以及定量检测。测量数据能够在电脑上以色谱图的形式显示并储存，且可以通过相关作图软件汇总到一张色谱图上进行进一步的分析。
本发明的目的可以通过以下技术方案来实现：
一种同步检测水样分子量分布及有机氮的仪器，包括通过管路顺序连接的末端注入阀、色谱柱、减压阀、加酸注入阀、加氧注入阀、酸氧反应螺旋管、CO 2去除器、UV消解器、第二气水分离膜、缓冲溶液注入阀、缓冲溶液反应螺旋管、镉柱、显色剂注入阀、显色剂反应螺旋管、UV检测器，所述末端注入阀用于接收流动相与样品，所述第二气水分离膜连接CO 2电导检测器，所述UV检测器、CO 2电导检测器均与用于数据处理的计算机连接。
所述末端注入阀与采样泵及样品瓶连接，所述末端注入阀还与流动相输液泵及流动相试剂瓶连接；
所述加酸注入阀与酸液注射泵及酸液瓶连接；
所述加氧注入阀与氧液注射泵及氧液瓶连接；
所述缓冲溶液注入阀与缓冲溶液注射泵及缓冲溶液试剂瓶连接；
所述显色剂注入阀与显色剂注射泵及显色剂试剂瓶连接。
所述CO 2去除器包括第一气水分离膜、集气盘管、吹脱泵及隔膜，所述第一气水分离膜、集气盘管及隔膜顺序相连，且所述第一气水分离膜通过管路与酸氧反应螺旋管连接，所述隔膜通过出口通气管及管路与透明石英螺旋管连接，所述吹脱泵与集气盘管连接，所述第一气水分离膜的作用是将IC酸化产生的CO 2与液体组分分开，进而进入集气盘管中收集起来，所述第一气水分离膜优选的是聚二甲基硅氧烷膜，其属于富氧膜，对CO 2有很好的分离效果，而且结构稳定。所述隔膜的作用将空气中的CO 2隔离在外面，防止进入待测组分中。所述吹脱泵的作用是提供吹脱动力，将集气盘管中收集的CO 2吹脱出去，所述吹脱泵优选的是微型气动隔膜泵，体积小巧，能有效的提供吹脱动力，价格便宜。
所述UV消解器包括加热丝、透明石英螺旋管及UV灯，所述透明石英螺旋管通过管路连接在所述隔膜与第二气水分离膜之间，所述UV灯位于透明石英螺旋管的上方，所述加热丝位于透明石英螺旋管的下方。
所述第二气水分离膜连接在UV消解器与缓冲溶液注入阀之间，所述第二气水分离膜连接CO 2电导检测器，用于将UV消解器中产生的CO 2分离至CO 2电导检测器中，其余样品进入缓冲溶液注入阀，进而再进入UV检测器中，所述第二气水 分离膜优选的是聚二甲基硅氧烷膜，属于富氧膜，对CO 2有很好的分离效果，而且结构稳定。
所述CO 2电导检测器包括顺序连接的超纯水箱、超纯水泵及电导池，UV消解器氧化后的样品经过气液分离膜，将产生的CO 2分离出来溶解在经过超纯水泵带动的，经过离子净化树脂净化过的超纯水里面，然后通入电导池中，通过检测电导池液体电导率的变化来检测CO 2的量，并通过一定的换算关系表征TOC浓度。
作为优选，超纯水选用Milli-Q超纯水仪制作，电阻率为18.2MΩ，超纯水泵选用微型输液泵，电导池选用测量范围为0.01μs/cm–300μs/cm，分辨率为0.01μs/cm的电导率电极流通池。
所述色谱柱位于色谱柱柱温箱内。
所述UV检测器与废液桶连接。
所述UV检测器通过UV检测器数据线与用于数据处理的计算机连接，所述CO 2电导检测器通过CO 2电导检测器数据线与用于数据处理的计算机连接。
采用上述仪器同步检测水样分子量分布及有机氮的方法，包括以下步骤：
样品经过采样泵采集到管路中，通过末端注入阀与由输液泵输送的流动相混合，然后经过色谱柱温箱内的液相色谱柱分离，样品中的组分按照分子量的不同依次流出，然后经过减压阀减压，将压力降低到约为1个大气压，分离出的样品不同分子量组分经过管路依次经过加酸注入阀和加氧注入阀，此时酸液管路的酸液注射泵会按照设定的量向加酸注入阀注入酸液，此时氧液管路的加氧注射泵会按照设定的量向加氧注入阀注入氧液，然后待测组分、流动相、酸液和氧液在酸氧反应螺旋管中充分反应；待测组分中无机碳(IC)会被酸液酸化产生CO 2，经过后面的CO 2去除器吹脱到空气中。已去除无机碳的待测组分经过管路进一步到达UV消解器中，在紫外灯照射以及加热条件下会将组分中的TOC氧化为CO 2，DON氧化为硝酸盐氮，氧化后的样品经过气液分离膜，将产生的CO 2分离出来进入到CO 2电导检测器中，CO 2电导检测器检测CO 2的量，并通过一定的换算关系表征TOC浓度，此后剩余不含TOC的组分通过缓冲溶液注入阀向组分中加入缓冲溶液，然后经过镉柱还原，将硝酸盐氮还原为亚硝酸盐氮，然后通过显色剂注入阀加入显色剂，然后在显色剂反应螺旋管内进行混合反应，最后进入UV检测器中，在540nm处检测亚硝酸盐氮的量，并通过一定的换算关系表征DON浓度，检测完毕后，UV检测器出口废液以及CO 2电导检测器废液经过废液管排出到废液桶。
所述色谱柱采用液相尺寸排阻色谱柱，分子量区分的有效区间可以根据用户的需要自行设置，一般可以选择为500～800000Da。
所述流动相应根据色谱柱的要求进行选择，一般选择为磷酸盐缓冲溶液，离子强度为0.1～0.4M，pH为6.8±0.2。
所述流动相输液泵泵流速应保证每一个色谱峰出峰尖锐易区分，不发生拖尾现象，并且要在色谱柱允许的流速范围内，一般的可以选择为0.4～1.0mL/min。所述流动相输液泵压力要在色谱柱允许的压力范围内，一般可选择为1.8±0.2MPa。
所述色谱柱柱温箱带加热丝，柱温箱柱温应该根据样品的出峰情况进行调整，一方面要保证每一个色谱峰峰宽较窄，另一方面还要在色谱柱允许的温度范围内，一般的色谱峰的峰宽大致为4～10min，温度一般设置为30～60℃。
所述采样泵要将样品采集到管路中，经过末端注入阀和流动相混合。
所述采样泵选用微量注射泵，泵工作压力应高于1500psi，最高精度应小于0.1％，无脉冲式输送，输送均匀，从非常小到非常大的注射量均可精确分配。采样体积应该保证色谱峰出峰尖锐且易区分，可以根据色谱柱分离的效果进行选择，一般的设置在50～500uL。
所述酸液瓶用于装酸液，酸液应根据样品的不同选择，但是都要保证将IC全部酸化为CO 2，一般的可以选为15％～30％的磷酸。
所述氧液瓶用于装氧液，所述氧液应根据样品的不同选择，所述氧液要保证将TOC全部氧化为CO 2，一般的可以选为10％～20％的过硫酸铵溶液。
所述酸液注射泵与氧液注射泵应能按照一定的流速向主流路中注射入酸液和氧液，且不会对主流路的流速和压力产生影响。优选的是：微量注射泵，泵工作压力应高于1500psi，最高精度小于0.1％，无脉冲式输送，从非常小到非常大的注射量均可精确分配，加酸加氧管道和样品管道采用注入阀连接。酸氧注射泵流速应保证酸氧溶液过量，可根据样品以及酸氧溶液的浓度选择，一般的可以选择为1.0～4.0μL/min。
所述末端注入阀、加酸注入阀、加氧注入阀、缓冲溶液注入阀、显色剂注入阀都是满足能稳定的将一种液体缓慢，稳定的加入到另一种液体中混合，而且不会产生倒吸。优选的是：带截止板和缓冲垫的注入阀，截止板防止液体回流倒吸，缓存垫有助于将液体稳定缓慢注入到另一种液体中。
所述酸氧反应螺旋管设置在UV消解器和加氧注入阀之间，以保证IC充分酸化为CO 2，优选的是：采用不锈钢PEEK管螺旋而成。一方面成本降低；另一方面不锈钢PEEK管能有效的防止药剂腐蚀以及保证分离出来的待测组分不会在其中再次混合。
所述缓冲溶液试剂瓶用于装缓冲溶液，所述缓冲溶液采用氯化铵缓冲溶液，通过85.0g氯化铵和1.0g二水合乙二胺四乙酸二钠溶于800mL水中，定容到1000mL混匀即可。溶液的pH值优选为8.5。
所述显色剂制备如下，采用100mL磷酸溶于600mL水中，然后加入40g磺胺和1g的盐酸萘乙二胺，用水稀释到1000mL混匀即可，所述磷酸选用分析纯。
所述镉柱的目的是将氧化后的硝酸盐氮还原为亚硝酸盐氮，镉柱的还原效率应该高于98％，镉柱装填要方便，且不易损坏。
所述缓冲溶液反应螺旋管以及显色剂反应螺旋管优选的是：采用不锈钢PEEK管螺旋而成。一方面成本降低；另一方面不锈钢PEEK管能有效的防止药剂腐蚀以及保证分离出来的待测组分不会在其中再次混合。
所述缓冲溶液的量要根据实际水样来确定。所述显色剂注射泵的流速要保证加入的显色剂过量，一般的可以选择为1.0～4.0μL/min。
所述UV消解器包括透明石英反应螺旋管，UV灯以及加热丝。透明石英反应螺旋管提供足够反应的空间，在UV灯照射以及加热条件下，氧化剂产生的氧化活性物质过硫酸根自由基会将待测组分充分氧化。作为优选，UV灯波长为190nm，加热温度设置为(95±2℃)。
所述UV检测器满足在线检测吸光度的变化，配备有流通样品池，并将结果储存以及输出到计算机进行进一步分析。作为优选的是，所述UV检测器带PEEK管接头，能在线检测，利用软件自动绘制色谱图的紫外检测仪。
所述仪器内部样品管路材料为了避免样品腐蚀，优选的是不锈钢PEEK管。主流路的流速为流动相输液泵泵流速，可选择为0.4～1.0mL/min。压力液相色谱柱之前为1.8±0.2MPa，液相色谱柱之后通过减压阀压力为1bar，流态为自由流动。
本发明能同步检测待测水样在不同分子量分布区间内的组分的TOC浓度，DON浓度。具体的检测原理是：
将样品经过尺寸排阻色谱柱，出水中样品组分按照选择色谱柱分离的范围内的 分子量大小排布，然后检测不同分子量分布区间内的最常见的两个水质参数TOC浓度和DON浓度。此发明利用经过尺寸排阻色谱分离的水样中的不同分子量组分按照分子量大小依次流出，结合本发明中的对TOC浓度的检测，既能精确的了解到不同分子量分布情况，又能确定不同分子量分布区间内的TOC浓度。根据对大量含氮标准样品进行反复实验，得到在某个确定的停留时间内，流出色谱柱的是DON，配合本发明对DON的检测，这样就方便快捷高效准确的确定了待测水样中的DON浓度。
也就是说，本发明可以提供同步检测待测水样在不同分子量分布区间内的组分的TOC浓度，DON浓度。分析时间大大缩短，更加重要的是，本发明能够完全意义上实现污染水体水质数据的同步采集。
本发明的技术路线为：
首先，样品瓶中的样品经过采样泵的传输，到达管路中，并且由末端注入阀注入到流动相管路中。流动相试剂瓶中的流动相在流动相输液泵的作用下，传输到主流路中，到达末端注入阀后和样品混合。流动相携带着样品经过色谱柱柱温箱中的色谱柱分离。经过色谱柱分离后，待测样品按照其组分分子量大小依次流出，并经过减压阀，压力降低为一个大气压，流态为自由出流。随后待测组分在主流路中到达加酸注入阀和加氧注入阀，与经过酸液注射泵和氧液注射泵传输的酸液、氧液混合，进一步到达酸氧反应螺旋管中。流动相，待测组分，酸液和氧液在酸氧反应螺旋中充分混合反应。
酸氧反应螺旋中，IC被彻底酸化为CO 2(反应1)
Figure PCTCN2018102945-appb-000001
待测组分中的无机碳(IC)被酸液酸化，产生的CO 2混合在管路中，进入CO 2去除器，将产生的CO 2从液相中分离出来，并排放到空气中。CO 2去除器的结构如上所述：其中，产生的CO 2立即由第一气水分离膜从液相中分离开，进入到集气盘管中，经过吹脱泵传输，将CO 2经过隔膜吹脱后进入空气中，而空气中的CO 2由隔膜阻断，不会进入液相中。
剩下去除了IC的待测组分和流动相继续前进，进入UV消解器中。UV消解器的结构如上所述：透明石英反应螺旋管提供反应空间，待测组分，流动相，氧液以及酸液在其中充分混合螺旋前进，在UV灯的照射以及电热丝加热条件下，将 TOC氧化为CO 2，将DON氧化为硝酸根离子(反应2，3)。
Figure PCTCN2018102945-appb-000002
Figure PCTCN2018102945-appb-000003
此时TOC氧化产生的CO 2进入第二气水分离膜中，与液相分离开，进入CO 2电导检测器中。CO 2电导检测器结构如上所述，其中，分离开的CO 2由另一条流路进入CO 2电导检测器中，溶解在超纯水管路中。超纯水由超纯水泵驱动，从超纯水箱中吸取而来，在溶解了CO 2后进入电导池中，通过电导的变化来检测出CO 2的含量进而表示出TOC浓度。
之后去除了TOC的组分到达缓冲溶液注入阀，此时和缓冲溶液注射泵输送的缓冲溶液混合，到达缓冲溶液反应螺旋管进一步混合之后进入镉柱中，将氧化产生的硝酸盐氮还原为亚硝酸盐氮，之后在显色剂注入阀处和显色剂注射泵输送的显色剂混合，并在显色剂反应螺旋管中进一步反应，利用酸性介质下，亚硝酸盐氮与磺胺进行重氮化反应，然后与盐酸萘乙二胺偶联生成紫红色物质。
Figure PCTCN2018102945-appb-000004
最后进入UV检测器中，利用亚硝酸盐氮在nm紫外光下产生吸收，且吸收量符合比尔定律，通过光电感应器获得信号之后经过处理得到亚硝酸盐氮的量，根据一定的换算关系，进而进一步表征出DON浓度。
电导池出口废水和UV检测器出口废水汇合后收集入废液桶中。和的数据分别有数据传输线路和传送至电脑端，进行进一步的储存和处理。
出口废水汇合后收集入废液桶中。UV检测器通过UV检测器数据线与用于数据处理的计算机连接，CO 2电导检测器通过CO 2电导检测器数据线与用于数据处理的计算机连接，计算机进行进一步的储存和处理。
与现有技术相比，本发明的技术特点以及优势如下：
1、同步性。一台仪器，可以同步定性检测出污染水体样品在不同的分子量分布区间内组分种类，以及同步定量检测出的不同的分子量分布区间内组分的TOC和DON浓度。
2、全面性。仪器所获得的数据打破了以往只能一个样品一个数据点的检测模式，实现了样品数据从点到面的突破。
3、针对性。本发明仪器开创性的将待测样品通过色谱柱分离之后，检测不同分子量分布区间内的污染物组分的TOC以及DON浓度，水质数据更加具有针对性，对以后的含氮消毒副产物的研究具有重要支撑意义。
4、准确性。本发明仪器开创性的提出液相色谱分离法测DON浓度的方法，此方法相较于传统的差值法，准确性大大提高。
5、简便性。本发明仪器开创性的提出液相色谱分离法测DON浓度的方法，相较于国内外常见的渗析膜，离子交换柱，预浓缩以及催化还原法，操作简便，自动进行，大大提高了水质检测的效率。
附图说明
图1为本发明同步检测水样分子量分布及有机氮的仪器结构示意图；
图2为CO 2去除器结构示意图；
图3为UV消解器结构示意图。
图中标号：1-流动相试剂瓶；2-流动相输液泵；3-末端注入阀；4-采样泵；5-样品瓶；6-色谱柱；7-色谱柱柱温箱；8-减压阀；9-加酸注入阀；10-酸液注射泵；11-酸液瓶；12-加氧注入阀；13-氧液注射泵；14-氧液瓶；15-酸氧反应螺旋管；16-UV消解器；17-缓冲溶液注射泵；18-缓冲溶液试剂瓶；19-缓冲溶液注入阀；20-缓冲溶液反应螺旋管；21-镉柱；22-显色剂注入阀；23-显色剂注射泵；24-显色剂试剂瓶；25-显色剂反应螺旋管；26-UV检测器；27-废液桶；28-计算机；29-加热丝；30-透明石英螺旋管；31-UV灯；32-CO 2去除器；33-第二气水分离膜；34-CO 2电导检测器；35-超纯水箱；36-超纯水泵；37-电导池；38-第一气水分离膜；39-集气盘管；40-吹脱泵；41-隔膜；42-出口通气管；43-UV检测器数据线；44-CO 2电导检测器数据线。
具体实施方式
参考图1，一种同步检测水样分子量分布及有机氮的仪器，包括通过管路顺序连接的末端注入阀3、色谱柱6、减压阀8、加酸注入阀9、加氧注入阀12、酸氧反应螺旋管15、CO 2去除器32、UV消解器16、第二气水分离膜33、缓冲溶液注入阀19、缓冲溶液反应螺旋管20、镉柱21、显色剂注入阀22、显色剂反应螺旋管25、UV检测器26，所述末端注入阀3用于接收流动相与样品，所述第二气水分离膜33连接CO 2电导检测器34，所述UV检测器26、CO 2电导检测器34均与用于数据处理的计算机28连接。
其中，所述末端注入阀3与采样泵4及样品瓶5连接，所述末端注入阀3还与流动相输液泵2及流动相试剂瓶1连接；所述加酸注入阀9与酸液注射泵10及酸液瓶11连接；所述加氧注入阀12与氧液注射泵13及氧液瓶14连接；所述缓冲溶液注入阀19与缓冲溶液注射泵17及缓冲溶液试剂瓶18连接；所述显色剂注入阀22与显色剂注射泵23及显色剂试剂瓶24连接。所述色谱柱6位于色谱柱柱温箱7内。所述UV检测器26与废液桶27连接。所述UV检测器26通过UV检测器数据线43与用于数据处理的计算机28连接，所述CO 2电导检测器34通过CO 2电导检测器数据线44与用于数据处理的计算机28连接。
参考图2，所述CO 2去除器32包括第一气水分离膜38、集气盘管39、吹脱泵40及隔膜41，所述第一气水分离膜38、集气盘管39及隔膜41顺序相连，且所述第一气水分离膜38通过管路与酸氧反应螺旋管15连接，所述隔膜41通过出口通气管42及管路与透明石英螺旋管30连接，所述吹脱泵40与集气盘管39连接，所述第一气水分离膜38的作用是将IC酸化产生的CO 2与液体组分分开，进而进入集气盘管中收集起来，所述第一气水分离膜38优选的是聚二甲基硅氧烷膜，其属于富氧膜，对CO 2有很好的分离效果，而且结构稳定。所述隔膜41的作用将空气中的CO 2隔离在外面，防止进入待测组分中。所述吹脱泵40的作用是提供吹脱动力，将集气盘管39中收集的CO 2吹脱出去，所述吹脱泵40优选的是微型气动隔膜泵，体积小巧，能有效的提供吹脱动力，价格便宜。
参考图3，所述UV消解器16包括加热丝29、透明石英螺旋管30及UV灯31，所述透明石英螺旋管30通过管路连接在所述隔膜41与第二气水分离膜33之间，，所述UV灯31位于透明石英螺旋管30的上方，所述加热丝29位于透明石英螺旋管30的下方。
所述第二气水分离膜33连接在UV消解器16与缓冲溶液注入阀19之间，所 述第二气水分离膜33连接CO 2电导检测器34，用于将UV消解器16中产生的CO 2分离至CO 2电导检测器34中，其余样品进入缓冲溶液注入阀19，进而再进入UV检测器中，所述第二气水分离膜33优选的是聚二甲基硅氧烷膜，属于富氧膜，对CO 2有很好的分离效果，而且结构稳定。
所述CO 2电导检测器34包括顺序连接的超纯水箱35、超纯水泵36及电导池37，UV消解器16氧化后的样品经过气液分离膜19，将产生的CO 2分离出来溶解在经过超纯水泵36带动的，经过离子净化树脂净化过的超纯水里面，然后通入电导池中，通过检测电导池液体电导率的变化来检测CO 2的量，并通过一定的换算关系表征TOC浓度。
作为优选，超纯水选用Milli-Q超纯水仪制作，电阻率为18.2MΩ，超纯水泵选用微型输液泵，电导池选用测量范围为0.01μs/cm–300μs/cm，分辨率为0.01μs/cm的电导率电极流通池。
本发明的技术路线如图1所示：
首先，样品瓶5中的样品经过采样泵4的传输，到达管路中，并且由末端注入阀3注入到流动相管路中。流动相试剂瓶1中的流动相在流动相输液泵2的作用下，传输到主流路中，到达末端注入阀3后和样品混合。流动相携带着样品经过色谱柱柱温箱7中的色谱柱6分离。经过色谱柱6分离后，待测样品按照其组分分子量大小依次流出，并经过减压阀8，压力降低为一个大气压，流态为自由出流。随后待测组分在主流路中到达加酸注入阀9和加氧注入阀12，与经过酸液注射泵10和氧液注射泵13传输的酸液、氧液混合，进一步到达酸氧反应螺旋管15中。流动相，待测组分，酸液和氧液在酸氧反应螺旋15中充分混合反应。
酸氧反应螺旋15中，IC被彻底酸化为CO 2(反应1)
Figure PCTCN2018102945-appb-000005
待测组分中的无机碳(IC)被酸液酸化，产生的CO 2混合在管路中，进入CO 2去除器16，将产生的CO 2从液相中分离出来，并排放到空气中。CO 2去除器16的结构如图2所示：其中，产生的CO 2立即由第一气水分离膜38从液相中分离开，进入到集气盘管39中，经过吹脱泵40传输，将CO 2经过隔膜41吹脱后进入空气中，而空气中的CO 2由隔膜41阻断，不会进入液相中。
剩下去除了IC的待测组分和流动相继续前进，进入UV消解器中。UV消解 器16的结构如图3所示：透明石英反应螺旋管提供反应空间，待测组分，流动相，氧液以及酸液在其中充分混合螺旋前进，在UV灯31的照射以及电热丝29加热条件下，将TOC氧化为CO 2，将DON氧化为硝酸根离子(反应2，3)。
Figure PCTCN2018102945-appb-000006
Figure PCTCN2018102945-appb-000007
此时TOC氧化产生的CO 2进入第二气水分离膜33中，与液相分离开，进入CO 2电导检测器34中。CO 2电导检测器34结构如图1中虚线框所示：其中，分离开的CO 2由另一条流路进入CO 2电导检测器中，溶解在超纯水管路中。超纯水由超纯水泵驱动，从超纯水箱中吸取而来，在溶解了CO 2后进入电导池中，通过电导的变化来检测出CO 2的含量进而表示出TOC浓度。
之后去除了TOC的组分到达缓冲溶液注入阀19，此时和缓冲溶液注射泵17输送的缓冲溶液混合，到达缓冲溶液反应螺旋管20进一步混合之后进入镉柱21中，将氧化产生的硝酸盐氮还原为亚硝酸盐氮，之后在显色剂注入阀22处和显色剂注射泵23输送的显色剂混合，并在显色剂反应螺旋管25中进一步反应，利用酸性介质下，亚硝酸盐氮与磺胺进行重氮化反应，然后与盐酸萘乙二胺偶联生成紫红色物质。
Figure PCTCN2018102945-appb-000008
最后进入UV检测器26中，利用亚硝酸盐氮在540nm紫外光下产生吸收，且吸收量符合比尔定律，通过光电感应器获得信号之后经过处理得到亚硝酸盐氮的量，根据一定的换算关系，进而进一步表征出DON浓度。
电导池37出口废水和UV检测器26出口废水汇合后收集入废液桶27中。23和33的数据分别有数据传输线路35和34传送至电脑端36，进行进一步的储存和处理。
出口废水汇合后收集入废液桶27中。UV检测器26通过UV检测器数据线43与用于数据处理的计算机28连接，CO 2电导检测器34通过CO 2电导检测器数据线44与用于数据处理的计算机28连接，计算机28进行进一步的储存和处理。
下面结合附图和具体实施例对本发明进行详细说明。
实施例
准备工作：
仪器开机，打开计算机28。将流动相进行20min的超声脱气处理，以消除流动相中的气泡，以免干扰检测结果。将样品过0.45μm膜，以去除颗粒杂质，以免造成仪器堵塞。设置好色谱柱柱温箱的温度。UV消解器16中，UV灯波长设置为190nm，加热温度设置为95℃。打开UV检测器26，检测波长设置为540nm。打开超纯水泵36，让CO 2检测器中超纯水开始流动。清空废液桶27。
操作步骤：
等准备工作结束后，打开流动相输液泵2，设置好流速以及压力。等计算机28基线稳定后(一般1～2h)，设置好采样泵的采样体积，酸氧注射泵、缓冲溶液注射泵、显色剂注射泵流速后打开采样泵4、酸液注射泵10、氧液注射泵13，缓冲溶液注射泵17、显色剂注射泵23。将样品经过末端注入阀3注射入流动相中，将酸液和氧液注射到流动相中，之后等待数据结果。
本实施例主要色谱条件区间如下：
Figure PCTCN2018102945-appb-000009
Figure PCTCN2018102945-appb-000010
根据TOC浓度色谱峰得到的不同分子量标样停留时间如下：
Figure PCTCN2018102945-appb-000011
采用牛血清蛋白作为DON浓度检测样品，结果如下：
TOC浓度的检测：本发明提供的方法对于TOC浓度检出范围为0.03μg/L～50mg/L；
DON浓度的检测：当紫外检测器的检测光程为10mm时，本发明提供的方法对于DON浓度测定范围为0.12mg/L～10mg/L。
上述的对实施例的描述是为便于该技术领域的普通技术人员能理解和使用发明。熟悉本领域技术的人员显然可以容易地对这些实施例做出各种修改，并把在此说明的一般原理应用到其他实施例中而不必经过创造性的劳动。因此，本发明不限于上述实施例，本领域技术人员根据本发明的揭示，不脱离本发明范畴所做出的改进和修改都应该在本发明的保护范围之内。

Claims (10)

  1. 一种同步检测水样分子量分布及有机氮的仪器，其特征在于，包括通过管路顺序连接的末端注入阀(3)、色谱柱(6)、减压阀(8)、加酸注入阀(9)、加氧注入阀(12)、酸氧反应螺旋管(15)、CO 2去除器(32)、UV消解器(16)、第二气水分离膜(33)、缓冲溶液注入阀(19)、缓冲溶液反应螺旋管(20)、镉柱(21)、显色剂注入阀(22)、显色剂反应螺旋管(25)、UV检测器(26)，所述末端注入阀(3)用于接收流动相与样品，所述第二气水分离膜(33)连接CO 2电导检测器(34)，所述UV检测器(26)、CO 2电导检测器(34)均与用于数据处理的计算机(28)连接。
  2. 根据权利要求1所述的一种同步检测水样分子量分布及有机氮的仪器，其特征在于，所述末端注入阀(3)与采样泵(4)及样品瓶(5)连接，所述末端注入阀(3)还与流动相输液泵(2)及流动相试剂瓶(1)连接；
    所述加酸注入阀(9)与酸液注射泵(10)及酸液瓶(11)连接；
    所述加氧注入阀(12)与氧液注射泵(13)及氧液瓶(14)连接；
    所述缓冲溶液注入阀(19)与缓冲溶液注射泵(17)及缓冲溶液试剂瓶(18)连接；
    所述显色剂注入阀(22)与显色剂注射泵(23)及显色剂试剂瓶(24)连接。
  3. 根据权利要求1所述的一种同步检测水样分子量分布及有机氮的仪器，其特征在于，所述CO 2去除器(32)包括第一气水分离膜(38)、集气盘管(39)、吹脱泵(40)及隔膜(41)，所述第一气水分离膜(38)、集气盘管(39)及隔膜(41)顺序相连，且所述第一气水分离膜(38)通过管路与酸氧反应螺旋管(15)连接，所述隔膜(41)通过管路与UV消解器(16)连接，所述吹脱泵(40)与集气盘管(39)连接。
  4. 根据权利要求3所述的一种同步检测水样分子量分布及有机氮的仪器，其特征在于，所述UV消解器(16)包括加热丝(29)、透明石英螺旋管(30)及UV灯(31)，所述透明石英螺旋管(30)通过管路连接在所述隔膜(41)与第二气水分离膜(33)之间，所述UV灯(31)位于透明石英螺旋管(30)的上方，所述加热丝(29)位于透明石英螺旋管(30)的下方。
  5. 根据权利要求1所述的一种同步检测水样分子量分布及有机氮的仪器，其 特征在于，所述CO 2电导检测器(34)包括顺序连接的超纯水箱(35)、超纯水泵(36)及电导池(37)，UV消解器(16)氧化后的样品经过气液分离膜(19)后将产生的CO 2溶解在经过超纯水泵(36)带动的超纯水中，通入电导池中，通过检测电导池液体电导率的变化来检测CO 2的量。
  6. 采用权利要求1所述仪器同步检测水样分子量分布及有机氮的方法，其特征在于，包括以下步骤：
    样品采集到管路中，与流动相混合，然后经过色谱柱分离，样品中的组分按照分子量的不同依次流出，然后经过减压阀减压，分离出的样品不同分子量组分经过管路依次经过加酸注入阀和加氧注入阀，向加酸注入阀注入酸液，向加氧注入阀注入氧液，然后待测组分、流动相、酸液和氧液在酸氧反应螺旋管中充分反应；待测组分中无机碳(IC)会被酸液酸化产生CO 2，经过后面的CO 2去除器吹脱到空气中。已去除无机碳的待测组分经过管路进一步到达UV消解器中，会将组分中的TOC氧化为CO 2，DON氧化为硝酸盐氮，氧化后的样品经过气液分离膜，将产生的CO 2分离出来进入到CO 2电导检测器中，CO 2电导检测器检测CO 2的量，并通过一定的换算关系表征TOC浓度，此后剩余不含TOC的组分通过缓冲溶液注入阀加入缓冲溶液，然后经过镉柱还原，将硝酸盐氮还原为亚硝酸盐氮，然后通过显色剂注入阀加入显色剂，然后在显色剂反应螺旋管内进行混合反应，最后进入UV检测器中，在540nm处检测亚硝酸盐氮的量，并通过换算关系表征DON浓度。
  7. 根据权利要求6所述的方法，其特征在于，所述流动相选择为磷酸盐缓冲溶液，离子强度为0.1～0.4M，pH为6.8±0.2，所述流动相输液泵泵流速选择为0.4～1.0mL/min，所述流动相输液泵压力选择为1.8±0.2MPa，所述色谱柱维持温度为30～60℃，压力在色谱柱之前为1.8±0.2MPa，色谱柱之后通过减压阀压力为1bar，流态为自由流动，所述UV消解器中，UV灯波长为190nm，加热温度设置为95±2℃。
  8. 根据权利要求6所述的方法，其特征在于，所述采样泵选用微量注射泵，泵工作压力高于1500psi，最高精度小于0.1％，采样体积在50～500uL，所述酸液注射泵与氧液注射泵选择微量注射泵，泵工作压力高于1500psi，最高精度小于0.1％，无脉冲式输送，所述酸液注射泵与氧液注射泵流速选择为1.0～4.0μL/min，所述显色剂注射泵的流速选择为1.0～4.0μL/min。
  9. 根据权利要求6所述的方法，其特征在于，所述末端注入阀、加酸注入阀、 加氧注入阀、缓冲溶液注入阀、显色剂注入阀都是满足：能稳定的将一种液体缓慢，稳定的加入到另一种液体中混合，而且不会产生倒吸。
  10. 根据权利要求6所述的方法，其特征在于，所述酸氧反应螺旋管、缓冲溶液反应螺旋管、显色剂反应螺旋管均采用不锈钢PEEK管螺旋而成，仪器内部样品管路选用不锈钢PEEK管。
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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN109406705A (zh) * 2018-11-29 2019-03-01 南京大学 一种液相色谱联用型有机碳检测器及其使用方法
CN113189230A (zh) * 2021-04-27 2021-07-30 浙江大学中原研究院 一种验证液态CO2中是否含有苯并(a)芘的检测方法

Families Citing this family (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN108918746A (zh) * 2018-05-18 2018-11-30 同济大学 一种同步检测水样分子量分布及有机氮的仪器及方法
CN109358128B (zh) * 2018-12-03 2024-04-09 南京大学 一种有机氮-有机碳串联式在线检测方法与装置
CN109709057B (zh) * 2018-12-29 2021-12-07 四川碧朗科技有限公司 水质指标预测模型构建方法及水质指标监测方法
CN110082447B (zh) * 2019-05-09 2024-05-31 同济大学 同步表征水样溶解性有机质结构/理化/浓度特性的仪器
CN111707744B (zh) * 2020-06-11 2023-11-24 同济大学 同步表征待测有机质理化/光学特性的仪器及方法

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH09281099A (ja) * 1996-04-12 1997-10-31 Akira Fujishima 水中化合物の分析方法及び装置
US20040043499A1 (en) * 2002-08-27 2004-03-04 Maria Lee-Alvarez Dissolved carbon measurement
US20120178175A1 (en) * 2011-01-12 2012-07-12 Jay Clifford Crosman CWB conductivity monitor
CN104730266A (zh) * 2015-03-31 2015-06-24 烟台大学 一种总有机碳与总氮同步连续实时测定的方法与仪器
CN108918746A (zh) * 2018-05-18 2018-11-30 同济大学 一种同步检测水样分子量分布及有机氮的仪器及方法

Family Cites Families (14)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20080220533A1 (en) * 2005-05-26 2008-09-11 Shimadzu Corporation Measuring Method for Total Organic Carbon, Measuring Method for Total Nitrogen and Measuring Apparatus for the Methods
CN100541171C (zh) * 2007-08-01 2009-09-16 山东省科学院海洋仪器仪表研究所 紫外光协同臭氧消解光度法测量水体总氮总磷的方法
CN101655501B (zh) * 2009-09-30 2012-02-01 河北科技大学 海水中总氮及总磷的在线自动监测系统及监测方法
AT509275B1 (de) * 2009-12-30 2011-12-15 Ipus Mineral & Umwelttechnologie Gmbh Verfahren zur bestimmung von bodenproben
CN201662575U (zh) * 2010-04-22 2010-12-01 马三剑 水质总氮在线自动监测装置
CN104730267B (zh) 2015-03-31 2016-10-05 烟台大学 Toc、tn、tp浓度及总量连续同步在线监测方法与仪器
CN106124499A (zh) * 2016-08-24 2016-11-16 徐滋秋 在线紫外消解总磷总氮总有机碳同步连续监测仪
CN107024570A (zh) * 2017-03-20 2017-08-08 河北科技大学 一种总氮、磷在线自动监测仪及其清洗方法
CN107655842B (zh) * 2017-09-19 2019-11-05 南京大学 一种基于静态培养的污水生物可降解溶解性有机氮测定方法
CN109406705B (zh) * 2018-11-29 2024-04-09 南京大学 一种液相色谱联用型有机碳检测器及其使用方法
CN109709057B (zh) * 2018-12-29 2021-12-07 四川碧朗科技有限公司 水质指标预测模型构建方法及水质指标监测方法
CN211955227U (zh) * 2020-04-22 2020-11-17 苏州科特环保股份有限公司 总氮在线监测装置
CN111707744B (zh) * 2020-06-11 2023-11-24 同济大学 同步表征待测有机质理化/光学特性的仪器及方法
CN113189230B (zh) * 2021-04-27 2023-05-12 浙江大学中原研究院 一种验证液态CO2中是否含有苯并(a)芘的检测方法

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH09281099A (ja) * 1996-04-12 1997-10-31 Akira Fujishima 水中化合物の分析方法及び装置
US20040043499A1 (en) * 2002-08-27 2004-03-04 Maria Lee-Alvarez Dissolved carbon measurement
US20120178175A1 (en) * 2011-01-12 2012-07-12 Jay Clifford Crosman CWB conductivity monitor
CN104730266A (zh) * 2015-03-31 2015-06-24 烟台大学 一种总有机碳与总氮同步连续实时测定的方法与仪器
CN108918746A (zh) * 2018-05-18 2018-11-30 同济大学 一种同步检测水样分子量分布及有机氮的仪器及方法

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN109406705A (zh) * 2018-11-29 2019-03-01 南京大学 一种液相色谱联用型有机碳检测器及其使用方法
CN109406705B (zh) * 2018-11-29 2024-04-09 南京大学 一种液相色谱联用型有机碳检测器及其使用方法
CN113189230A (zh) * 2021-04-27 2021-07-30 浙江大学中原研究院 一种验证液态CO2中是否含有苯并(a)芘的检测方法

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