CN106596770A - Low-pressure anion-cation chromatographic-spectrophotometric method for simultaneous online automatic analysis of trace ammonium ions and nitrite ions in water sample - Google Patents

Low-pressure anion-cation chromatographic-spectrophotometric method for simultaneous online automatic analysis of trace ammonium ions and nitrite ions in water sample Download PDF

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CN106596770A
CN106596770A CN201611148465.7A CN201611148465A CN106596770A CN 106596770 A CN106596770 A CN 106596770A CN 201611148465 A CN201611148465 A CN 201611148465A CN 106596770 A CN106596770 A CN 106596770A
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low pressure
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jing
blender
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CN106596770B (en
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张新申
赵正喜
莫珊
高跃昕
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Sichuan University
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Sichuan University
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    • 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
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D15/00—Separating processes involving the treatment of liquids with solid sorbents; Apparatus therefor
    • B01D15/08—Selective adsorption, e.g. chromatography
    • B01D15/10—Selective adsorption, e.g. chromatography characterised by constructional or operational features
    • B01D15/22—Selective adsorption, e.g. chromatography characterised by constructional or operational features relating to the construction of the column
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D15/00—Separating processes involving the treatment of liquids with solid sorbents; Apparatus therefor
    • B01D15/08—Selective adsorption, e.g. chromatography
    • B01D15/26—Selective adsorption, e.g. chromatography characterised by the separation mechanism
    • B01D15/265—Adsorption chromatography
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D15/00—Separating processes involving the treatment of liquids with solid sorbents; Apparatus therefor
    • B01D15/08—Selective adsorption, e.g. chromatography
    • B01D15/26—Selective adsorption, e.g. chromatography characterised by the separation mechanism
    • B01D15/36—Selective adsorption, e.g. chromatography characterised by the separation mechanism involving ionic interaction
    • B01D15/361—Ion-exchange
    • 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
    • G01N21/17—Systems in which incident light is modified in accordance with the properties of the material investigated
    • G01N21/25—Colour; Spectral properties, i.e. comparison of effect of material on the light at two or more different wavelengths or wavelength bands
    • G01N21/31—Investigating relative effect of material at wavelengths characteristic of specific elements or molecules, e.g. atomic absorption spectrometry
    • 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
    • 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
    • G01N30/04—Preparation or injection of sample to be analysed
    • G01N30/16—Injection
    • G01N30/20—Injection using a sampling valve
    • 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
    • G01N2030/143—Preparation by elimination of some components selective absorption
    • 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
    • G01N2030/146—Preparation by elimination of some components using membranes
    • 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
    • G01N30/16—Injection
    • G01N30/20—Injection using a sampling valve
    • G01N2030/201—Injection using a sampling valve multiport valves, i.e. having more than two ports

Abstract

The invention provides a low-pressure anion-cation chromatographic-spectrophotometric method for simultaneous online automatic analysis of trace ammonium ions and nitrite ions in a water sample; the method employs analytical apparatuses, such as a low-pressure pump, a sample injection valve, a sample injection ring, a low-pressure anion exchange column, a low-pressure cation exchange column, an oxidation reactor, a color rendering reactor, an optical flow cell, an optical detector, a computer processing system, a first mixer and a second mixer, and comprises the steps of (1) drawing a baseline; (2) drawing a spectrum of NH4+ and NO2- in a sample; (3) drawing a standard working curve; (4) calculating the concentrations of NH4+ and NO2- to be detected in the sample according to peak height values of the spectrum of NH4+ and NO2- and a regression equation of the standard working curve. It is the first time for the method to provide simultaneous online analysis for trace NH4+ and NO2- in a water sample by the joint use of low-pressure ion chromatography and spectrophotometry, and the method has the advantages of low analytical cost and high analytical efficiency.

Description

Simultaneously in on-line automatic analysis water-like micro ammonium ion and nitrite ion it is low Pressure anions and canons chromatograph-photometry
Technical field
The invention belongs to NH4 +With NO2 -Detection and analysis field, micro NH more particularly in water sample4 +And NO2 -While Line automatic analysis method.
Background technology
Nitrogen-containing compound not only can be polluted to water quality, and totally unfavorable to health.NH4 +、NO2 -And NO3 -It is logical Oxidation, nitrification and the Denitrification for crossing microorganism mutually can be converted.NH4 +Oxidation can substantially reduce dissolved oxygen in water body Concentration, causes deteriorating water quality, causes photosynthetic microorganism to sharply increase, and water body occurs eutrophication.The NH of high concentration4 +Can shadow The hydrobiological permeability of sound, and acute ammonia poisoning can be caused to even result in death.NH4 +It is both the factor for affecting aesthetic water, And the important Con trolling index of industrial wastewater discharge thing, and NO2 -It is a kind of strong carcinogen.Therefore, while different in determining water The nitrogen of valence state, contributes to understanding water pollution and evaluating its self-cleaning situation.For aquaculture, NH4 +And NO2 -Tool There is obvious toxic action, need to pay close attention to, thus it is particularly important to the research and application of the two.
At present, NH of the ion chromatography analysis in water sample4 +And NO2 -When, employing is high-pressure ion chromatograph, and Two kinds of ions of separately sampled, independent detection are needed, i.e., generally uses anion chromatographic column and supporting anion eluent system, conductance Detection and analysis NO2 -, with cation chromatographic column and supporting cation eluent system, separation detection NH4 +, it is impossible to realize NH4 +With NO2 -While analyze.NH in existing analysis water-like4 +And NO2 -The chromatography of ions there is following deficiency：It is separately sampled, single Solely detection has the deficiency that analyze speed is slow and analysis efficiency is low；High-pressure ion chromatograph adopts operation with high pressure, high-pressure ion color The price of spectrometer is high, and matching used chromatographic column belongs to easily-consumed products, its price generally 1～20,000 yuan/root, thus the party The analysis cost of method is high, it is difficult to popularization and application；Meanwhile, the column packing of the matching used chromatographic column of high-pressure ion chromatograph is thin Shell mould ion exchange resin, as its exchange capacity is very low, only 0.01～0.02mmol/g is multiple in analysis leather-making waste water this constituents During miscellaneous waste water, chromatographic column is easily contaminated, cause the service life of chromatographic column shorten and analysis system capacity of resisting disturbance Reduce, therefore, it is difficult to the popularization and application in leather-making waste water analysis industry.Based on the above-mentioned state of the art, if can be based on analysis cost more Low low-voltage ion chromatography develops the NH in water sample4 +And NO2 -While on-line automatic analysis method, for reduce analysis Cost, raising analysis efficiency all will produce positive meaning.
The content of the invention
It is an object of the invention to overcome the deficiencies in the prior art, there is provided while micro ammonium root in on-line automatic analysis water-like The low pressure anions and canons chromatograph-photometry of ion and nitrite ion, to reduce analysis cost, improves analysis efficiency.
While the present invention is provided in on-line automatic analysis water-like the low pressure of micro ammonium ion and nitrite ion it is cloudy, Cation chromatography-photometry, using includes that low-lift pump, injection valve, injection annulus, low pressure anion-exchange column, low pressure cation are handed over Change post, oxidation reactor, chromogenic reaction device, optical flow cell, fluorescence detector, computer processing system, the first blender, Two blenders, sample flow path, the analytical tool for promoting liquid stream, oxidation solution stream and nitrite ion stream, step are as follows：
1. analytical tool is set to into sample introduction state, under the driving of low-lift pump, blank sample Jing sample flow paths, injection valve Into in injection annulus；Then analytical tool is set to into analysis state, under the driving of low-lift pump, the oxidized liquid stream of oxidation solution Into the first blender, nitrite ion Jing nitrite ions stream enters the second blender, promotes liquid Jing to promote liquid stream, injection valve to enter Injection annulus, the blank sample in injection annulus under the promotion for promoting liquid, hand over successively by Jing low pressure anion-exchange column, low pressure cation Change Jing oxidation reactors after post is mixed with oxidation solution in the first blender to enter in the second blender, in the second blender After mixing with nitrite ion, Jing chromogenic reactions device enters optical flow cell, and Jing fluorescence detectors transmit a signal to computer disposal system System process, obtains baseline；
2. analytical tool is set to into sample introduction state, under the driving of low-lift pump, sample Jing sample flow paths, injection valve are entered In injection annulus；Then analytical tool is set to into analysis state, under the driving of low-lift pump, the oxidized liquid stream of oxidation solution is entered First blender, nitrite ion Jing nitrite ions stream enter the second blender, promote liquid Jing to promote liquid stream, injection valve to enter sample introduction The ring sample in promoting injection annulus is sequentially entered in low pressure anion-exchange column, low pressure cation exchange column, the NH in sample4 + And NO2 -After being separated in low pressure anion-exchange column, low pressure cation exchange column, NH4 +And NO2 -In the presence of liquid is promoted First mixed liquor and second mixed liquor are mixed to form in the first blender with oxidation solution successively, the first mixed liquor and second is mixed It is taken up in order of priority in the second blender after closing the oxidized reactor of liquid and be mixed to form with nitrite ion the 3rd mixed liquor and the 4th mixed Close liquid, the 3rd mixed liquor and the 4th mixed liquor successively enter chromogenic reaction device and chromogenic reaction occurs and form the first reactant liquor and the Two reactant liquors, the first reactant liquor and the second reactant liquor successively enter optical flow cell, and Jing fluorescence detectors transmit a signal to meter The process of calculation machine processing system, obtains NH in sample4 +And NO2 -Spectrogram；
3. use a series of NH known to concentration4 +And NO2 -Standard specimen replaces sample, repeat step operation 1. and 2. to obtain A series of NH4 +And NO2 -The spectrogram of standard specimen, with NH in standard specimen4 +And NO2 -Concentration be abscissa, with NH in standard specimen4 +And NO2 -Spectrum The peak height of figure is that vertical coordinate draws standard working curve；
4. respectively by NH in sample4 +And NO2 -The peak height value of spectrogram substitutes into the recurrence side of step 3. gained standard working curve Cheng Zhong, calculates NH in sample4 +And NO2 -Concentration；
The pH value of the sample and standard specimen adopts sodium hydroxide or hydrochloric acid to adjust to 6.9～7.1, blank sample for go from Sub- water, the promotion liquid are the mixed liquors being configured to by Sodium Chloride, potassium chloride and deionized water, and the oxidation solution is by bromination The mixed liquor that potassium, Potassium bromate., hydrochloric acid, sodium hydroxide and deionized water are configured to, the nitrite ion are by sulfanilamide, hydrochloric acid, hydrochloric acid The mixed liquor that naphthodiamide and deionized water are configured to, the column packing of the low pressure anion-exchange column is that strong alkaline quaternary ammonium type is cloudy Ion exchange resin, the column packing of the low pressure cation exchange column is sulfonic acid ion exchange resin and styrene-diethyl The mixture of alkenyl benzene copolymer.
In promotion liquid described in said method, the concentration of Sodium Chloride is 10～15g/L, and the concentration of potassium chloride is 1～5g/L.
In oxidation solution described in said method, the concentration of potassium bromide is 0.05～0.06g/L, and the concentration of Potassium bromate. is 0.005～0.0075g/L, the concentration of hydrochloric acid is 0.040～0.048mol/L, and the concentration of sodium hydroxide is 0.20～0.25mol/ L。
In nitrite ion described in said method, the concentration of hydrochloric acid is 0.1～0.6mol/L, and the concentration of hydrochloride naphthodiamide is 0.20～0.25g/L, the concentration of sulfanilamide is 2.0～2.5g/L.
In said method, the particle diameter of the strong alkaline quaternary ammonium type anion exchange resin is preferably 30～35 μm, exchanges and hold Amount is preferably 3～4mmol/g, and strong alkaline quaternary ammonium type anion exchange resin is prepared according to existing method, and concrete preparation method can With reference to ion exchange and adsorbent resin [M], 1995, p43～51, He Ping Lin, Huang Wenqiang chief editor, the publication of education of science and technology of Shanghai society. In the mixture of the sulfonic acid ion exchange resin and styrene diethylene benzene copoly mer, sulfonic acid type cation is exchanged Resin is 1 with the mass ratio of styrene diethylene benzene copoly mer:(0.95～1.05)；Preferably, the sulfonic acid type cation The particle diameter of exchanger resin is 30～35 μm, exchange capacity is 0.1～0.5mmol/g, and sulfonic acid ion exchange resin is according to existing There is method to prepare, concrete preparation method can refer to ion exchange and adsorbent resin [M], 1995, p37～43, He Ping Lin, Huang Wenqiang Chief editor, the publication of education of science and technology of Shanghai society；Preferably, the particle diameter of the styrene diethylene benzene copoly mer is 80～100 μm, Styrene diethylene benzene copoly mer can be bought by market.
In said method, the Detection wavelength of fluorescence detector is 530nm.
In said method, the light path of optical flow cell is 20～30mm.
In said method, sample first passes through filtering with microporous membrane, absorption with macroporous adsorbent resin process before into low-lift pump, Microporous filter membrane can eliminate aminoacid, polypeptide and protein to NH4 +The impact of measure, absorption with macroporous adsorbent resin process substantially can be gone Except organic substance and colourity are to NH4 +The interference of measure, this is conducive to improving the capacity of resisting disturbance of analysis system and protecting chromatographic column.
The method of the invention being capable of simultaneously NH in on-line automatic analysis water-like4 +And NO2 -Principle it is as follows：
The NH contained in sample4 +And NO2 -After low pressure anion-exchange column and low pressure cation exchange column, NH4 +With NO2 -It is separated and successively enters in oxidation reactor, in oxidation reactor, NH4 +It is oxidized to NO2 -, by NH4 +Oxidation life Into NO2 -With the NO for containing in sample originally2 -Chromogenic reaction device, the NO in chromogenic reaction device are entered successively2 -Occur with nitrite ion The product formed after chromogenic reaction successively carries out photometric detection, that is, realize NH4 +And NO2 -While on-line automatic analysis.
Compared with prior art, the invention has the advantages that：
1. the invention provides micro NH in a kind of on-line analyses water sample simultaneously4 +With NO2 -New method, the method will be low The pressure chromatography of ions is combined with photometry, realizes NH using combination type low voltage anion and low pressure cation chromatography4 +With NO2 -Separation, then through on-line oxidation is derivative and chromogenic reaction after, NH is capable of achieving by photometry4 +And NO2 -While On-line analyses, compared with existing high-pressure ion chromatography, the price of the analytical tool that low-voltage ion chromatography is adopted is substantially more It is low, with the advantage for significantly reducing analysis cost, meanwhile, it is separately sampled, single that the method for the invention also solves existing method Solely determine the cumbersome problem brought, with analyze speed it is fast, analysis efficiency is high the characteristics of, these are all conducive to the present invention The popularization and application of methods described.
2. as this law methods described employs the higher low pressure anion-exchange column of exchange capacity and low pressure cation is handed over Post column packing is changed, the antipollution and capacity of resisting disturbance of chromatographic column is effectively increased, is conducive to extending the service life of chromatographic column, together When, the method for the invention using the mixture of sulfonic acid ion exchange resin and styrene diethylene benzene copoly mer as The column packing of low pressure cation exchange column, the two ratio are appropriate, then the eluent that gradation composition and concentration are appropriate so that chromatograph system Can first there is obvious plateau behind peak in system, then occur quasi-molecular ions to be measured again, and this can significantly reduce high salt and color in water sample Degree is to determining NH4 +With NO2 -Interference (see embodiment 1).Factors above causes the method for the invention to can be used in analyzing process hides The waste water of this kind of complicated component of waste water, is conducive to the popularization and application in leather-making waste water analysis industry.
3. the method for the invention first passes through filtering with microporous membrane, macroporous adsorbent resin before into low-lift pump in sample and inhales Attached process, microporous filter membrane can eliminate aminoacid, polypeptide and protein to NH4 +The impact of measure, absorption with macroporous adsorbent resin process The obvious organics removal matter of energy and colourity are to NH4 +The interference of measure, this is also beneficial to the capacity of resisting disturbance of raising analysis system simultaneously Protection chromatographic column.
4. experiment shows that the method for the invention has good precision, 100 μ g/L NH of replication4 +With 25 μ g/L NO2 -Mixed sample 10 times, NH4 +The relative standard deviation of spectrogram peak height is 3.37%, NO2 -The relative standard of spectrogram peak height is inclined Difference is 2.17%.
5. the method for the invention is to NH4 +And NO2 -Quantitative detection limit be respectively 5.77 μ g/L and 1.25 μ g/L, NH4 +It is dense Degree is in 20～500 μ g/L and NO2 -The standard working curve obtained in the range of 5～50 μ g/L by concentration have it is good linear, It is particularly suited for NH in leather-making waste water4 +And NO2 -The detection of content.
6. the response rate of the method for the invention is can reach in the range of 84%～117%, with national standard method measured value And recovery of standard addition is close to.
7. instrument and equipment needed for the method for the invention is simple, simple operation, analyze speed are fast, strong antijamming capability, can Online automatic detection is realized, is conducive to popularization and application.
Description of the drawings
Fig. 1 is process chart of the method for the invention in sample introduction state, is also the structure of supporting analytical tool Schematic diagram.
Fig. 2 is process chart of the method for the invention in analysis state, is also the structure of supporting analytical tool Schematic diagram.
In figure, 1-low-lift pump, 2-injection valve, 3-injection annulus, 4-low pressure anion-exchange column, 5-low pressure cation Exchange column, 6-oxidation reactor, 7-chromogenic reaction device, 8-optical flow cell, 9-fluorescence detector, 10-computer disposal System, the 11-the first blender, the 12-the second blender, C-promotion liquid, O-oxidation solution, R-nitrite ion, S0- blank examination Sample, S1- sample, S2- standard specimen, W-waste liquid.
Fig. 3 be in embodiment 1 using 1# column packings when the NH that surveys and draws4 +And NO2 -Spectrogram.
Fig. 4 be in embodiment 1 using 2# column packings when the NH that surveys and draws4 +And NO2 -Spectrogram.
Fig. 5 is the NH of the mapping of embodiment 24 +And NO2 -The precision spectrogram of standard specimen.
Fig. 6 is the NH that embodiment 3 is drawn4 +The standard working curve of standard specimen.
Fig. 7 is the NO that embodiment 3 is drawn2 -The standard working curve of standard specimen.
Specific embodiment
Below by embodiment to of the present invention while micro ammonium ion and nitrous acid in on-line automatic analysis water-like The low pressure anions and canons chromatograph-photometry of radical ion, is described further.
Embodiment 1
In the present embodiment, the column packing composition for investigating low pressure cation exchange column determines NH to the method for the invention4 +With NO2 -Impact.
1. prepare containing NH4 +And NO2 -Standard specimen
NH4 +Standard reserving solution (1000mg/L)：It is placed in exsiccator after ammonium sulfate is dried 1h at 110 DEG C and is cooled to room temperature, Weigh 0.4716g and be dried ammonium sulfate, move in 100mL volumetric flasks, deionized water is settled to graticule, shakes up, in 4 DEG C of refrigerators Preserve, stably can preserve six months.Measure during use in right amount, deionized water is diluted to desired concn.
NO2 -Standard reserving solution (1000mg/L)：It is placed in exsiccator after sodium nitrite is dried 1h at 110 DEG C and is cooled to room Temperature, weighs 0.4929g and is dried sodium nitrite, move in 100mL volumetric flasks, and deionized water is settled to graticule, shakes up, and stores in palm fibre In color bottle, keep in dark place in 4 DEG C of refrigerators.Take during use in right amount, deionized water is diluted to desired concn.
100μg/L NH4 +With 25 μ g/L NO2 -Mixed sample：Pipette 0.01mL NH4 +Standard Stock solutions and 0.025mLNO2 -During Standard Stock solutions add 100mL volumetric flasks, deionized water is settled to graticule.
2. oxidation solution O is prepared
Oxidation storing solution：Precise 2.00g potassium bromide, 0.25g Potassium bromate .s, move in 100mL brown volumetric flasks, spend Ionized water is settled to graticule, keeps in dark place in 4 DEG C of refrigerators, stably can preserve more than 1 year.
Oxidation solution O：3.0mL oxidation storing solutions are measured, is moved in 1000mL brown volumetric flasks, is added 200mL deionized waters Afterwards, shake up, add the hydrochloric acid that 8mL concentration is 6mol/L, cover rapidly bottle stopper and reaction at least 5min is aggressively shaken in dark place, plus It is 5mol/L sodium hydroxide solutions to enter 50mL concentration, is shaken up, and deionized water is settled to graticule.
3. nitrite ion R is prepared
2.50g sulfanilamide is weighed, is moved in 1000mL volumetric flasks, is added about 600mL water, it is not necessary to wait to be dissolved, add 100mL dense The hydrochloric acid for 6mol/L is spent, after shaking up, adds 0.25g hydrochloride naphthodiamides, deionized water to be settled to graticule.
4. prepare and promote liquid C
15g Sodium Chloride, 5g potassium chloride are weighed, is moved in 1000mL volumetric flasks, deionized water is settled to graticule.
5. blank sample S0For deionized water.
6. the column packing composition of low pressure cation exchange column is to separating NH4 +With NO2 -Impact
In the present embodiment, the column packing of low pressure cation exchange column has two kinds, is denoted as 1# and 2# column packings respectively, wherein, 1# column packings are sulfonic acid ion exchange resin, and its particle diameter is 30～35 μm, exchange capacity is 0.1～0.5mmol/g；2# posts Filler is the mixture of aforementioned 1# column packings and styrene diethylene benzene copoly mer (being commonly called as Archon), 1# column packings and benzene second The mass ratio of alkene-divinyl benzene copolymer is 1:1, the particle diameter of styrene diethylene benzene copoly mer is 80～100 μm.
(1) tested using 1# column packings
Tested using the analyser of technical flow design shown in Fig. 1 and Fig. 2.In the analytical tool, low-lift pump 1 is four Passage constant flow peristaltic pump, pump discharge are 0.4～1.0mL/min, and operating pressure is 2 × 105～3 × 105Pa；Injection valve 2 is clematis stem Automatic sampling valve, the sample introduction state of clematis stem automatic sampling valve are adjusted by the time relay；Injection annulus 3 are by polyfluortetraethylene pipe It is entwined, the volume of injection annulus can be adjusted by the adjustment of internal diameter and length；The column length of low pressure anion-exchange column 4 is 5cm, column packing are strong alkaline quaternary ammonium type anion exchange resin, and the particle diameter of column packing is 30～35 μm, and the exchange of column packing is held Measure as 3～4mmol/g；The column length of low pressure cation exchange column 5 is 2.5cm, and column packing is 1# column packings；Oxidation reactor 6 is Coiled structure, is entwined by polyfluortetraethylene pipe of the internal diameter for 0.5mm, and length is 3.0m；Chromogenic reaction device 7 is coiled Structure, is entwined by polyfluortetraethylene pipe of the internal diameter for 0.5mm is crossed, and length is 3.0m；The light path of optical flow cell 8 is 28mm；The Detection wavelength for adjusting fluorescence detector 9 is 530nm；Computer processing system 10 works to be mounted with HW-2000 chromatographs The personal computer stood (compose softcom limited in Shanghai thousand)；The optical flow cell of the analytical tool is connected with spent liquor solution, sample Product are entered in waste fluid container after flowing through optical flow cell.Step is as follows：
1. analytical tool is set to into sample introduction state, under the driving of low-lift pump 1, blank sample S0Jing sample flow paths, enter Sample valve 2 enters injection annulus 3 and is full of injection annulus, unnecessary blank sample S0Entered in the form of waste liquid W in waste fluid container, aoxidized The oxidized liquid streams of liquid O enter the first blender 11, and nitrite ion R Jing nitrite ions stream enters the second blender 12, promotes liquid C Jing Promote liquid stream, injection valve 2, low pressure anion-exchange column 4, low pressure cation exchange column 5 enter the first blender 11 in oxygen After changing liquid O mixing, Jing oxidation reactors 6 are entered in the second blender 12, Jing after mixing with nitrite ion R in the second blender 12 Chromogenic reaction device 7 enters optical flow cell 8, is entered in waste fluid container then；Then analytical tool is set to into analysis state, Under the driving of low-lift pump 1, blank sample S0Entered in waste fluid container in the form of waste liquid W Jing after sample flow path, injection valve, aoxidized The oxidized liquid streams of liquid O enter the first blender 11, and nitrite ion R Jing nitrite ions stream enters the second blender 12, promotes liquid C Jing Liquid stream, injection valve 2 is promoted to enter injection annulus 3, Jing low pressure is cloudy successively under the promotion for promoting liquid for the blank sample in injection annulus After ion exchange column 4, low pressure cation exchange column 5 are mixed with oxidation solution O in the first blender 11, Jing oxidation reactors 6 enter Enter in the second blender 12, after mixing with nitrite ion R in the second blender 12, Jing chromogenic reactions device 7 enters optical flow cell 8, Jing fluorescence detectors 8 transmit a signal to computer processing system 10 and process, and obtain baseline；
2. analytical tool is set to into sample introduction state, under the driving of low-lift pump 1, standard specimen S2Jing sample flow paths, injection valve 2 Into injection annulus 3 and full of injection annulus, unnecessary standard specimen S2Entered in the form of waste liquid W in waste fluid container, oxidation solution O is oxidized Liquid stream enters the first blender 11, and nitrite ion R Jing nitrite ions stream enters the second blender 12, promotes liquid C Jing to promote liquid stream Road, injection valve 2, low pressure anion-exchange column 4, low pressure cation exchange column 5 are entered and are mixed with oxidation solution O in the first blender 11 Enter in the second blender 12 by oxidation reactor 6, Jing chromogenic reaction devices after mixing with nitrite ion R in the second blender 12 7 enter optical flow cell 8, are entered in waste fluid container then；Then analytical tool is set to into analysis state, in low-lift pump 1 Under driving, standard specimen S2Entered in waste fluid container in the form of waste liquid W Jing after sample flow path, injection valve, the oxidized liquid streams of oxidation solution O Road enters the first blender 11, and nitrite ion R Jing nitrite ions stream enters the second blender 12, promotes liquid C Jing to promote liquid stream, enter Sample valve 2 enters injection annulus 3 and promotes standard specimen S in injection annulus2Sequentially enter low pressure anion-exchange column 4, low pressure cation to hand over Change in post 5, standard specimen S2In NH4 +And NO2 -After being separated in low pressure anion-exchange column 4, low pressure cation exchange column 5, NH4 +And NO2 -Successively the first mixed liquor and second are mixed to form with oxidation solution in the first blender 11 in the presence of liquid is promoted It is taken up in order of priority in the second blender 12 and colour developing after mixed liquor, the first mixed liquor and the oxidized reactor of the second mixed liquor 6 Liquid is mixed to form the 3rd mixed liquor and the 4th mixed liquor, and the 3rd mixed liquor and the 4th mixed liquor successively enter chromogenic reaction device 7 simultaneously Generation chromogenic reaction forms the first reactant liquor and the second reactant liquor, and the first reactant liquor and the second reactant liquor successively circulate into optics Pond 8, Jing fluorescence detectors 9 transmit a signal to computer processing system 10 and process, and obtain standard specimen S2Middle NH4 +And NO2 -Spectrogram, As shown in Figure 3.
(2) tested using 2# column packings
The operation of the step is essentially identical with step (1), the difference is that only and hands over the low pressure cation in step (1) The column packing for changing post replaces with 2# column packings and is tested, and obtained spectrogram is as shown in Figure 4.
Relatively Fig. 3 and Fig. 4 understands that low pressure cation exchange column separates NH using 2# column packings4 +With NO2 -When, chromatograph system Can first there is obvious plateau behind peak in system, then occur quasi-molecular ions to be measured again, and this can significantly reduce high salt and color in water sample Degree is to determining NH4 +With NO2 -Interference.
Embodiment 2
The present embodiment is tested to standard specimen, and to investigate the precision of the method for the invention, step is as follows：
1. prepare containing NH4 +With NO2 -Standard specimen
NH4 +Standard reserving solution (1000mg/L)：It is placed in exsiccator after ammonium sulfate is dried 1h at 110 DEG C and is cooled to room temperature, Weigh 0.4716g and be dried ammonium sulfate, move in 100mL volumetric flasks, deionized water is settled to graticule, shakes up, in 4 DEG C of refrigerators Preserve, stably can preserve six months.Measure during use in right amount, deionized water is diluted to desired concn.
NO2 -Standard reserving solution (1000mg/L)：It is placed in exsiccator after sodium nitrite is dried 1h at 110 DEG C and is cooled to room Temperature, weighs 0.4929g and is dried sodium nitrite, move in 100mL volumetric flasks, and deionized water is settled to graticule, shakes up, and stores in palm fibre In color bottle, keep in dark place in 4 DEG C of refrigerators.Take during use in right amount, deionized water is diluted to desired concn.
100μg/L NH4 +With 25 μ g/L NO2 -Mixed sample：Pipette 0.01mL NH4 +Standard Stock solutions and 0.025mLNO2 -During Standard Stock solutions add 100mL volumetric flasks, deionized water is settled to graticule.
2. oxidation solution O is prepared
Oxidation storing solution：Precise 2.00g potassium bromide, 0.25g Potassium bromate .s, move in 100mL brown volumetric flasks, spend Ionized water is settled to graticule, keeps in dark place in 4 DEG C of refrigerators, stably can preserve more than 1 year.
Oxidation solution O：3.0mL oxidation storing solutions are measured, is moved in 1000mL brown volumetric flasks, is added 200mL deionized waters Afterwards, shake up, add the hydrochloric acid that 8mL concentration is 6mol/L, cover rapidly bottle stopper and reaction at least 5min is aggressively shaken in dark place, plus It is 5mol/L sodium hydroxide solutions to enter 50mL concentration, is shaken up, and deionized water is settled to graticule.
3. nitrite ion R is prepared
2.50g sulfanilamide is weighed, is moved in 1000mL volumetric flasks, is added about 600mL water, it is not necessary to wait to be dissolved, add 100mL dense The hydrochloric acid for 6mol/L is spent, after shaking up, adds 0.25g hydrochloride naphthodiamides, deionized water to be settled to graticule.
4. prepare and promote liquid C
15g Sodium Chloride, 5g potassium chloride are weighed, is moved in 1000mL volumetric flasks, deionized water is settled to graticule.
5. blank sample S0For deionized water.
6. the testing and drawing of standard specimen spectrogram
Tested using the analyser of technical flow design shown in Fig. 1 and Fig. 2.In the analytical tool, low-lift pump 1 is four Passage constant flow peristaltic pump, pump discharge are 0.4～1.0mL/min, and operating pressure is 2 × 105～3 × 105Pa；Injection valve 2 is clematis stem Automatic sampling valve, the sample introduction state of clematis stem automatic sampling valve are adjusted by the time relay；Injection annulus 3 are by polyfluortetraethylene pipe It is entwined, the volume of injection annulus can be adjusted by the adjustment of internal diameter and length；The column length of low pressure anion-exchange column 4 is 5cm, column packing are strong alkaline quaternary ammonium type anion exchange resin, and the particle diameter of column packing is 30～35 μm, and the exchange of column packing is held Measure as 3～4mmol/g；The column length of low pressure cation exchange column 5 be 2.5cm, column packing be sulfonic acid ion exchange resin with The mixture of styrene diethylene benzene copoly mer (being commonly called as Archon), the sulfonic acid ion exchange resin and styrene-two The mass ratio of divinylbenzene copolymer is 1:1, the particle diameter of sulfonic acid ion exchange resin is 30～35 μm, exchange capacity is 0.1～0.5mmol/g, the particle diameter of styrene diethylene benzene copoly mer is 80～100 μm；Oxidation reactor 6 is tied for coiled Structure, is entwined by polyfluortetraethylene pipe of the internal diameter for 0.5mm, and length is 3.0m；Chromogenic reaction device 7 is coiled structure, by Cross the polyfluortetraethylene pipe that internal diameter is 0.5mm to be entwined, length is 3.0m；The light path of optical flow cell 8 is 28mm；Adjust light The Detection wavelength for learning detector 9 is 530nm；Computer processing system 10 is to be mounted with that HW-2000 chromatographic work stations (are composed in Shanghai thousand Softcom limited) personal computer；The optical flow cell of the analytical tool is connected with spent liquor solution, and sample flows through optical flow Enter in waste fluid container behind logical pond.Step is as follows：
1. analytical tool is set to into sample introduction state, under the driving of low-lift pump 1, blank sample S0Jing sample flow paths, enter Sample valve 2 enters injection annulus 3 and is full of injection annulus, unnecessary blank sample S0Entered in the form of waste liquid W in waste fluid container, aoxidized The oxidized liquid streams of liquid O enter the first blender 11, and nitrite ion R Jing nitrite ions stream enters the second blender 12, promotes liquid C Jing Promote liquid stream, injection valve 2, low pressure anion-exchange column 4, low pressure cation exchange column 5 enter the first blender 11 in oxygen After changing liquid O mixing, Jing oxidation reactors 6 are entered in the second blender 12, Jing after mixing with nitrite ion R in the second blender 12 Chromogenic reaction device 7 enters optical flow cell 8, is entered in waste fluid container then；Then analytical tool is set to into analysis state, Under the driving of low-lift pump 1, blank sample S0Entered in waste fluid container in the form of waste liquid W Jing after sample flow path, injection valve, aoxidized The oxidized liquid streams of liquid O enter the first blender 11, and nitrite ion R Jing nitrite ions stream enters the second blender 12, promotes liquid C Jing Liquid stream, injection valve 2 is promoted to enter injection annulus 3, Jing low pressure is cloudy successively under the promotion for promoting liquid for the blank sample in injection annulus After ion exchange column 4, low pressure cation exchange column 5 are mixed with oxidation solution O in the first blender 11, Jing oxidation reactors 6 enter Enter in the second blender 12, after mixing with nitrite ion R in the second blender 12, Jing chromogenic reactions device 7 enters optical flow cell 8, Jing fluorescence detectors 8 transmit a signal to computer processing system 10 and process, and obtain baseline；
2. analytical tool is set to into sample introduction state, under the driving of low-lift pump 1, standard specimen S2Jing sample flow paths, injection valve 2 Into injection annulus 3 and full of injection annulus, unnecessary standard specimen S2Entered in the form of waste liquid W in waste fluid container, oxidation solution O is oxidized Liquid stream enters the first blender 11, and nitrite ion R Jing nitrite ions stream enters the second blender 12, promotes liquid C Jing to promote liquid stream Road, injection valve 2, low pressure anion-exchange column 4, low pressure cation exchange column 5 are entered and are mixed with oxidation solution O in the first blender 11 Enter in the second blender 12 by oxidation reactor 6, Jing chromogenic reaction devices after mixing with nitrite ion R in the second blender 12 7 enter optical flow cell 8, are entered in waste fluid container then；Then analytical tool is set to into analysis state, in low-lift pump 1 Under driving, standard specimen S2Entered in waste fluid container in the form of waste liquid W Jing after sample flow path, injection valve, the oxidized liquid streams of oxidation solution O Road enters the first blender 11, and nitrite ion R Jing nitrite ions stream enters the second blender 12, promotes liquid C Jing to promote liquid stream, enter Sample valve 2 enters injection annulus 3 and promotes standard specimen S in injection annulus2Sequentially enter low pressure anion-exchange column 4, low pressure cation to hand over Change in post 5, standard specimen S2In NH4 +And NO2 -After being separated in low pressure anion-exchange column 4, low pressure cation exchange column 5, NH4 +And NO2 -Successively the first mixed liquor and second are mixed to form with oxidation solution in the first blender 11 in the presence of liquid is promoted It is taken up in order of priority in the second blender 12 and colour developing after mixed liquor, the first mixed liquor and the oxidized reactor of the second mixed liquor 6 Liquid is mixed to form the 3rd mixed liquor and the 4th mixed liquor, and the 3rd mixed liquor and the 4th mixed liquor successively enter chromogenic reaction device 7 simultaneously Generation chromogenic reaction forms the first reactant liquor and the second reactant liquor, and the first reactant liquor and the second reactant liquor successively circulate into optics Pond 8, Jing fluorescence detectors 9 transmit a signal to computer processing system 10 and process, and obtain standard specimen S2Middle NH4 +And NO2 -Spectrogram；
According to the above-mentioned standard specimen of step operation replication 1. 2. 10 times, obtained spectrogram is as shown in figure 5, this method is determined 100μg/LNH4 +With 25 μ g/L NO2 -Mixed sample when, NH4 +The relative standard deviation of spectrogram peak height is 3.37%, NO2 -Spectrogram The relative standard deviation of peak height is 2.17%, illustrates that the precision of the method for the invention is good.
Embodiment 3
In the present embodiment, standard working curve is drawn, step is as follows：
1. standard specimen is prepared
(1)NH4 +Standard reserving solution (1000mg/L)：It is placed in exsiccator after ammonium sulfate is dried 1h at 110 DEG C and is cooled to room Temperature, weighs 0.4716g and is dried ammonium sulfate, move in 100mL volumetric flasks, and deionized water is settled to graticule, shakes up, in 4 DEG C of ice Preserve in case, stably can preserve six months.Measure during use in right amount, deionized water is diluted to desired concn.
(2)NO2 -Standard reserving solution (1000mg/L)：It is placed in exsiccator after sodium nitrite is dried 1h at 110 DEG C and is cooled to Room temperature, weighs 0.4929g and is dried sodium nitrite, move in 100mL volumetric flasks, and deionized water is settled to graticule, shakes up, and stores in In brown bottle, keep in dark place in 4 DEG C of refrigerators.Take during use in right amount, deionized water is diluted to desired concn.
(3) prepare NH4 +Serial standard specimen：Step (1) is prepared standard reserving solution deionized water dilution, be configured to 1#～ 14# standard specimens, NH in 1#～14# standard specimens4 +Concentration be followed successively by 0 μ g/L, 20 μ g/L, 40 μ g/L, 50 μ g/L, 75 μ g/L, 100 μ g/ L、150μg/L、200μg/L、250μg/L、300μg/L、350μg/L、400μg/L、450μg/L、500μg/L。
(4) prepare NO2 -Serial standard specimen：The standard reserving solution deionized water dilution that step (2) is prepared, is configured to 15# ～21# standard specimens, NO in 15#～21# standard specimens2 -Concentration be followed successively by 0 μ g/L, 5 μ g/L, 10 μ g/L, 20 μ g/L, 25 μ g/L, 40 μ g/ L、50μg/L。
2. prepare and promote liquid C
15g Sodium Chloride, 5g potassium chloride are weighed, is moved in 1000mL volumetric flasks, deionized water is settled to graticule.
3. oxidation solution O is prepared
Oxidation storing solution：Precise 2.00g potassium bromide, 0.25g Potassium bromate .s, move in 100mL brown volumetric flasks, spend Ionized water is settled to graticule, keeps in dark place in 4 DEG C of refrigerators, stably can preserve more than 1 year.
Oxidation solution O：3.0mL oxidation storing solutions are measured, is moved in 1000mL brown volumetric flasks, is added 200mL deionized waters Afterwards, shake up, add the hydrochloric acid that 8mL concentration is 6mol/L, cover rapidly bottle stopper and reaction at least 5min is aggressively shaken in dark place, plus It is 5mol/L sodium hydroxide solutions to enter 50mL concentration, is shaken up, and deionized water is settled to graticule.
4. nitrite ion R is prepared
2.50g sulfanilamide is weighed, is moved in 1000mL volumetric flasks, is added about 600mL water, it is not necessary to wait to be dissolved, add 100mL dense The hydrochloric acid for 6mol/L is spent, after shaking up, adds 0.25g hydrochloride naphthodiamides, deionized water to be settled to graticule.
5. blank sample S0For deionized water.
6. the testing and drawing of standard specimen spectrogram
Tested using the analyser of technical flow design shown in Fig. 1 and Fig. 2.In the analytical tool, low-lift pump 1 is four Passage constant flow peristaltic pump, pump discharge are 0.4～1.0mL/min, and operating pressure is 2 × 105～3 × 105Pa；Injection valve 2 is clematis stem Automatic sampling valve, the sample introduction state of clematis stem automatic sampling valve are adjusted by the time relay；Injection annulus 3 are by polyfluortetraethylene pipe It is entwined, the volume of injection annulus can be adjusted by the adjustment of internal diameter and length；The column length of low pressure anion-exchange column 4 is 5cm, column packing are strong alkaline quaternary ammonium type anion exchange resin, and the particle diameter of column packing is 30～35 μm, and the exchange of column packing is held Measure as 3～4mmol/g；The column length of low pressure cation exchange column 5 be 2.5cm, column packing be sulfonic acid ion exchange resin with The mixture of styrene diethylene benzene copoly mer (being commonly called as Archon), the sulfonic acid ion exchange resin and styrene-two The mass ratio of divinylbenzene copolymer is 1:1, the particle diameter of sulfonic acid ion exchange resin is 30～35 μm, exchange capacity is 0.1～0.5mmol/g, the particle diameter of styrene diethylene benzene copoly mer is 80～100 μm；Oxidation reactor 6 is tied for coiled Structure, is entwined by polyfluortetraethylene pipe of the internal diameter for 0.5mm, and length is 3.0m；Chromogenic reaction device 7 is coiled structure, by Cross the polyfluortetraethylene pipe that internal diameter is 0.5mm to be entwined, length is 3.0m；The light path of optical flow cell 8 is 28mm；Adjust light The Detection wavelength for learning detector 9 is 530nm；Computer processing system 10 is to be mounted with that HW-2000 chromatographic work stations (are composed in Shanghai thousand Softcom limited) personal computer；The optical flow cell of the analytical tool is connected with spent liquor solution, and sample flows through optical flow Enter in waste fluid container behind logical pond.Step is as follows：
1. analytical tool is set to into sample introduction state, under the driving of low-lift pump 1, blank sample S0Jing sample flow paths, enter Sample valve 2 enters injection annulus 3 and is full of injection annulus, unnecessary blank sample S0Entered in the form of waste liquid W in waste fluid container, aoxidized The oxidized liquid streams of liquid O enter the first blender 11, and nitrite ion R Jing nitrite ions stream enters the second blender 12, promotes liquid C Jing Promote liquid stream, injection valve 2, low pressure anion-exchange column 4, low pressure cation exchange column 5 enter the first blender 11 in oxygen After changing liquid O mixing, Jing oxidation reactors 6 are entered in the second blender 12, Jing after mixing with nitrite ion R in the second blender 12 Chromogenic reaction device 7 enters optical flow cell 8, is entered in waste fluid container then；Then analytical tool is set to into analysis state, Under the driving of low-lift pump 1, blank sample S0Entered in waste fluid container in the form of waste liquid W Jing after sample flow path, injection valve, aoxidized The oxidized liquid streams of liquid O enter the first blender 11, and nitrite ion R Jing nitrite ions stream enters the second blender 12, promotes liquid C Jing Liquid stream, injection valve 2 is promoted to enter injection annulus 3, Jing low pressure is cloudy successively under the promotion for promoting liquid for the blank sample in injection annulus After ion exchange column 4, low pressure cation exchange column 5 are mixed with oxidation solution O in the first blender 11, Jing oxidation reactors 6 enter Enter in the second blender 12, after mixing with nitrite ion R in the second blender 12, Jing chromogenic reactions device 7 enters optical flow cell 8, Jing fluorescence detectors 8 transmit a signal to computer processing system 10 and process, and obtain baseline；
2. analytical tool is set to into sample introduction state, under the driving of low-lift pump 1,1# standard specimen S2Jing sample flow paths, sample introduction Valve 2 enters injection annulus 3 and is full of injection annulus, unnecessary 1# standard specimen S2Entered in the form of waste liquid W in waste fluid container, oxidation solution O Oxidized liquid stream enters the first blender 11, and nitrite ion R Jing nitrite ions stream enters the second blender 12, promotes liquid C Jing to push away Hydrodynamic stream, injection valve 2, low pressure anion-exchange column 4, low pressure cation exchange column 5 enter the first blender 11 in oxidation After liquid O mixing, Jing oxidation reactors 6 are entered in the second blender 12, and after mixing with nitrite ion R in the second blender 12, Jing shows Colour response device 7 enters optical flow cell 8, is entered in waste fluid container then；Then analytical tool is set to into analysis state, low Under the driving of press pump 1,1# standard specimen S2Entered in waste fluid container in the form of waste liquid W Jing after sample flow path, injection valve, oxidation solution O Oxidized liquid stream enters the first blender 11, and nitrite ion R Jing nitrite ions stream enters the second blender 12, promotes liquid C Jing to push away Hydrodynamic stream, injection valve 2 enter injection annulus 3 and promote 1# standard specimen S in injection annulus2Sequentially enter low pressure anion-exchange column 4, In low pressure cation exchange column 5,1# standard specimen S2In NH4 +And NO2 -In low pressure anion-exchange column 4, low pressure cation exchange column 5 It is middle separated after, NH4 +And NO2 -The is mixed to form in the presence of liquid is promoted in the first blender 11 with oxidation solution successively It is taken up in order of priority after one mixed liquor and the second mixed liquor, the first mixed liquor and the oxidized reactor of the second mixed liquor 6 mixed into second The 3rd mixed liquor and the 4th mixed liquor are mixed to form in clutch 12 with nitrite ion, the 3rd mixed liquor and the 4th mixed liquor are successively entered Simultaneously there is chromogenic reaction the first reactant liquor of formation and the second reactant liquor, the first reactant liquor and the second reactant liquor elder generation in chromogenic reaction device 7 Optical flow cell 8 is entered afterwards, and Jing fluorescence detectors 9 transmit a signal to computer processing system 10 and process, and obtain 1# standard specimen S2 Middle NH4 +And NO2 -Spectrogram；
3. 1# standard specimens, repeat step operation 2. is replaced to obtain a series of NH successively with 2#～21# standard specimens4 +And NO2 -Mark The spectrogram of sample, with NH in standard specimen4 +Concentration (mg/L) be abscissa, with NH in standard specimen4 +The peak height (mV) of spectrogram is painted for vertical coordinate NH processed4 +Standard working curve, with NO in standard specimen2 -Concentration (mg/L) be abscissa, with NO in standard specimen2 -The peak height of spectrogram (mV) NO is drawn for vertical coordinate2 -Standard working curve.NH4 +Concentration is in 20～500 μ g/L and NO2 -Concentration is in 5～50 μ g/L lines Standard working curve in the range of property as shown in Figure 6 and Figure 7, NH4 +Standard working curve regression equation be H=0.205C- 3.96, R2=0.998, NO2 -Standard working curve regression equation be H=0.173C+0.254, R2=0.999, R2= 0.998 (in formula, H is peak height, unit mV；C is testing concentration in standard specimen, unit μ g/L).Made an uproar according to the baseline of analytical tool Sound, using 3 times of signal to noise ratios as quantitative detection limit, calculates the method for the invention to NH4 +And NO2 -Quantitative detection limit difference For 5.77 μ g/L and 1.25 μ g/L.
Embodiment 4
In the present embodiment, the NH in actual environment water sample is analyzed using indophenol blue National Standard Method GB17378.2-20074 +, adopt NO in hydrochloride naphthodiamide National Standard Method GB/T7493-1987 point analysis actual environment water sample2 -, using the method for the invention point NH in analysis actual environment water sample4 +With NO2 -.Actual environment water sample is 5, and numbering is A#, B#, C#, D# and E# examination respectively Sample.
NH in actual environment water sample is analyzed using the method for the invention4 +With NO2 -Step is as follows：
1. prepare and promote liquid C
15g Sodium Chloride, 5g potassium chloride are weighed, is moved in 1000mL volumetric flasks, deionized water is settled to graticule.
2. oxidation solution O is prepared
Oxidation storing solution：Precise 2.00g potassium bromide, 0.25g Potassium bromate .s, move in 100mL brown volumetric flasks, spend Ionized water is settled to graticule, keeps in dark place in 4 DEG C of refrigerators, stably can preserve more than 1 year.
Oxidation solution O：3.0mL oxidation storing solutions are measured, is moved in 1000mL brown volumetric flasks, is added 200mL deionized waters Afterwards, shake up, add the hydrochloric acid that 8mL concentration is 6mol/L, cover rapidly bottle stopper and reaction at least 5min is aggressively shaken in dark place, plus It is 5mol/L sodium hydroxide solutions to enter 50mL concentration, is shaken up, and deionized water is settled to graticule.
3. nitrite ion R is prepared
2.50g sulfanilamide is weighed, is moved in 1000mL volumetric flasks, is added about 600mL water, it is not necessary to wait to be dissolved, add 100mL dense The hydrochloric acid for 6mol/L is spent, after shaking up, adds 0.25g hydrochloride naphthodiamides, deionized water to be settled to graticule.
4. the preparation of sample
A#, B#, C#, D# and E# sample is filtered using Medium speed filter paper before being analyzed, 0.2 μm of aqueouss microporous filter membrane Filter, cross macroporous adsorptive resins and alumina particulate post organics removal matter and decolourize, then adjusted with nitric acid or sodium hydroxide Section sample pH value is to 6.9～7.1 and determines rapidly.
5. blank sample S0For deionized water.
6. the testing and drawing of sample spectrogram
Tested using the analyser of technical flow design shown in Fig. 1 and Fig. 2.In the analytical tool, low-lift pump 1 is four Passage constant flow peristaltic pump, pump discharge are 0.4～1.0mL/min, and operating pressure is 2 × 105～3 × 105Pa；Injection valve 2 is clematis stem Automatic sampling valve, the sample introduction state of clematis stem automatic sampling valve are adjusted by the time relay；Injection annulus 3 are by polyfluortetraethylene pipe It is entwined, the volume of injection annulus can be adjusted by the adjustment of internal diameter and length；The column length of low pressure anion-exchange column 4 is 5cm, column packing are strong alkaline quaternary ammonium type anion exchange resin, and the particle diameter of column packing is 30～35 μm, and the exchange of column packing is held Measure as 3～4mmol/g；The column length of low pressure cation exchange column 5 be 2.5cm, column packing be sulfonic acid ion exchange resin with The mixture of styrene diethylene benzene copoly mer (being commonly called as Archon), the sulfonic acid ion exchange resin and styrene-two The mass ratio of divinylbenzene copolymer is 1:1, the particle diameter of sulfonic acid ion exchange resin is 30～35 μm, exchange capacity is 0.1～0.5mmol/g, the particle diameter of styrene diethylene benzene copoly mer is 80～100 μm；Oxidation reactor 6 is tied for coiled Structure, is entwined by polyfluortetraethylene pipe of the internal diameter for 0.5mm, and length is 3.0m；Chromogenic reaction device 7 is coiled structure, by Cross the polyfluortetraethylene pipe that internal diameter is 0.5mm to be entwined, length is 3.0m；The light path of optical flow cell 8 is 28mm；Adjust light The Detection wavelength for learning detector 9 is 530nm；Computer processing system 10 is to be mounted with that HW-2000 chromatographic work stations (are composed in Shanghai thousand Softcom limited) personal computer；The optical flow cell of the analytical tool is connected with spent liquor solution, and sample flows through optical flow Enter in waste fluid container behind logical pond.Operation is as follows：
1. analytical tool is set to into sample introduction state, under the driving of low-lift pump 1, blank sample S0Jing sample flow paths, enter Sample valve 2 enters injection annulus 3 and is full of injection annulus, unnecessary blank sample S0Entered in the form of waste liquid W in waste fluid container, aoxidized The oxidized liquid streams of liquid O enter the first blender 11, and nitrite ion R Jing nitrite ions stream enters the second blender 12, promotes liquid C Jing Promote liquid stream, injection valve 2, low pressure anion-exchange column 4, low pressure cation exchange column 5 enter the first blender 11 in oxygen After changing liquid O mixing, Jing oxidation reactors 6 are entered in the second blender 12, Jing after mixing with nitrite ion R in the second blender 12 Chromogenic reaction device 7 enters optical flow cell 8, is entered in waste fluid container then；Then analytical tool is set to into analysis state, Under the driving of low-lift pump 1, blank sample S0Entered in waste fluid container in the form of waste liquid W Jing after sample flow path, injection valve, aoxidized The oxidized liquid streams of liquid O enter the first blender 11, and nitrite ion R Jing nitrite ions stream enters the second blender 12, promotes liquid C Jing Liquid stream, injection valve 2 is promoted to enter injection annulus 3, Jing low pressure is cloudy successively under the promotion for promoting liquid for the blank sample in injection annulus After ion exchange column 4, low pressure cation exchange column 5 are mixed with oxidation solution O in the first blender 11, Jing oxidation reactors 6 enter Enter in the second blender 12, after mixing with nitrite ion R in the second blender 12, Jing chromogenic reactions device 7 enters optical flow cell 8, Jing fluorescence detectors 8 transmit a signal to computer processing system 10 and process, and obtain baseline；
2. analytical tool is set to into sample introduction state, under the driving of low-lift pump 1, A# sample S1Jing sample flow paths, sample introduction Valve 2 enters injection annulus 3 and is full of injection annulus, and unnecessary A# samples are entered in waste fluid container in the form of waste liquid W, oxidation solution O Jing Oxidation solution stream enters the first blender 11, and nitrite ion R Jing nitrite ions stream enters the second blender 12, promotes liquid C Jing to promote Liquid stream, injection valve 2, low pressure anion-exchange column 4, low pressure cation exchange column 5 enter the first blender 11 in oxidation solution O After mixing, Jing oxidation reactors 6 are entered in the second blender 12, and after mixing with nitrite ion R in the second blender 12, Jing colour developings are anti- Answer device 7 to enter optical flow cell 8, entered in waste fluid container then；Then analytical tool is set to into analysis state, in low-lift pump Under 1 driving, A# samples are entered in waste fluid container Jing after sample flow path, injection valve in the form of waste liquid W, and oxidation solution O is oxidized Liquid stream enters the first blender 11, and nitrite ion R Jing nitrite ions stream enters the second blender 12, promotes liquid C Jing to promote liquid stream Road, injection valve 2 into injection annulus 3 and promote the A# samples in injection annulus sequentially enter low pressure anion-exchange column 4, low pressure sun from NH in sub- exchange column 5, in A# samples4 +And NO2 -Separated in low pressure anion-exchange column 4, low pressure cation exchange column 5 Afterwards, NH4 +And NO2 -Successively the first mixed liquor is mixed to form with oxidation solution in the first blender 11 in the presence of liquid is promoted With the second mixed liquor, it is taken up in order of priority in the second blender 12 after the first mixed liquor and the oxidized reactor of the second mixed liquor 6 The 3rd mixed liquor and the 4th mixed liquor are mixed to form with nitrite ion, the 3rd mixed liquor and the 4th mixed liquor successively enter chromogenic reaction Simultaneously there is chromogenic reaction the first reactant liquor of formation and the second reactant liquor in device 7, the first reactant liquor and the second reactant liquor successively enter light Flow cell 8 is learned, Jing fluorescence detectors 9 transmit a signal to computer processing system 10 and process, and obtain NH in A# samples4 +And NO2 - Spectrogram；
Successively by step 2. in A# samples be changed to B#, C#, D# and E# sample, repeat abovementioned steps behaviour 1. and 2. Make, obtain NH in B#, C#, D# and E# sample4 +And NO2 -Spectrogram.
7. test result
NH in each sample that respectively step 6 is drawn4 +And NO2 -The peak height value of spectrogram substitutes into 3 gained NH of embodiment4 +And NO2 - In the regression equation of standard working curve, you can calculate NH in each sample4 +And NO2 -Concentration, test result and mark-on reclaims Rate is as shown in Table 1 and Table 2.
Table 1
Table 2

Claims (10)

1. simultaneously in on-line automatic analysis water-like micro ammonium ion and nitrite ion low pressure anions and canons chromatograph-light Degree method, it is characterised in that using includes low-lift pump (1), injection valve (2), injection annulus (3), low pressure anion-exchange column (4), low pressure Cation exchange column (5), oxidation reactor (6), chromogenic reaction device (7), optical flow cell (8), fluorescence detector (9), calculating Machine processing system (10), the first blender (11), the second blender (12), sample flow path, promote liquid stream, oxidation solution stream and The analytical tool of nitrite ion stream, step are as follows：
1. analytical tool is set to into sample introduction state, under the driving of low-lift pump (1), blank sample (S0) Jing sample flow paths, sample introduction Valve (2) is in injection annulus (3)；Then analytical tool is set to into analysis state, under the driving of low-lift pump (1), oxidation solution (O) oxidized liquid stream enters the first blender (11), and nitrite ion (R) Jing nitrite ions stream enters the second blender (12), pushes away Hydrodynamic (C) Jing promotes liquid stream, injection valve (2) into injection annulus (3), and the blank sample in injection annulus is under the promotion for promoting liquid Successively Jing low pressure anion-exchange column (4), low pressure cation exchange column (5) in the first blender (11) with oxidation solution (O) After mixing, Jing oxidation reactors (6) are in the second blender (12), after mixing with nitrite ion (R) in the second blender (12) Jing chromogenic reaction devices (7) transmits a signal to computer processing system into optical flow cell (8), Jing fluorescence detectors (8) (10) process, obtain baseline；
2. analytical tool is set to into sample introduction state, under the driving of low-lift pump (1), sample (S1) Jing sample flow paths, injection valve (2) in injection annulus (3)；Then analytical tool is set to into analysis state, under the driving of low-lift pump (1), oxidation solution (O) Oxidized liquid stream enters the first blender (11), and nitrite ion (R) Jing nitrite ions stream enters the second blender (12), promotes liquid (C) Jing promotes liquid stream, injection valve (2) into injection annulus (3) and promotes the sample (S in injection annulus1) sequentially enter low pressure the moon In ion exchange column (4), low pressure cation exchange column (5), the NH in sample4 +And NO2 -In low pressure anion-exchange column (4), low After being separated in pressure cation exchange column (5), NH4 +And NO2 -Successively enter in the first blender (11) in the presence of liquid is promoted The first mixed liquor and the second mixed liquor, the first mixed liquor and the oxidized reactor of the second mixed liquor (6) are mixed to form with oxidation solution After be taken up in order of priority in the second blender (12), the 3rd mixing Liquid and the 4th mixed liquor successively enter chromogenic reaction device (7) and chromogenic reaction occur and form the first reactant liquor and the second reactant liquor, First reactant liquor and the second reactant liquor successively enter optical flow cell (8), and Jing fluorescence detectors (9) transmit a signal to computer Processing system (10) process, obtains sample (S1) in NH4 +And NO2 -Spectrogram；
3. use a series of NH known to concentration4 +And NO2 -Standard specimen (S2) replace sample (S1), repeat step operation 1. and 2., Obtain a series of NH4 +And NO2 -The spectrogram of standard specimen, with NH in standard specimen4 +And NO2 -Concentration be abscissa, with NH in standard specimen4 +With NO2 -The peak height of spectrogram is that vertical coordinate draws standard working curve；
4. respectively by sample (S1) in NH4 +And NO2 -The peak height value of spectrogram substitutes into the recurrence side of step 3. gained standard working curve Cheng Zhong, calculates sample (S1) in NH4 +And NO2 -Concentration；
Sample (the S1) and standard specimen (S2) pH value adopt sodium hydroxide or hydrochloric acid to adjust to 6.9～7.1, blank sample (S0) for deionized water, the promotion liquid is the mixed liquor being configured to by Sodium Chloride, potassium chloride and deionized water, the oxidation solution It is the mixed liquor being configured to by potassium bromide, Potassium bromate., hydrochloric acid, sodium hydroxide and deionized water, the nitrite ion is by sulfanilamide, salt The mixed liquor that acid, hydrochloride naphthodiamide and deionized water are configured to, the column packing of the low pressure anion-exchange column (4) is highly basic Property quaternary amine type anion exchange resin, the column packing of the low pressure cation exchange column (5) is sulfonic acid ion exchange resin With the mixture of styrene diethylene benzene copoly mer.
2. according to claim 1 simultaneously in on-line automatic analysis water-like micro ammonium ion and nitrite ion low pressure Anions and canons chromatograph-photometry, it is characterised in that in the promotion liquid (C), the concentration of Sodium Chloride is 10～15g/L, potassium chloride Concentration be 1～5g/L.
3. according to claim 1 or claim 2 while micro ammonium ion and nitrite ion in on-line automatic analysis water-like Low pressure anions and canons chromatograph-photometry, it is characterised in that in the oxidation solution (O), the concentration of potassium bromide is 0.05～0.06g/ L, the concentration of Potassium bromate. is 0.005～0.0075g/L, and the concentration of hydrochloric acid is 0.040～0.048mol/L, the concentration of sodium hydroxide For 0.20～0.25mol/L.
4. according to claim 1 or claim 2 while micro ammonium ion and nitrite ion in on-line automatic analysis water-like Low pressure anions and canons chromatograph-photometry, it is characterised in that in the nitrite ion (R), the concentration of hydrochloric acid is 0.1～0.6mol/L, The concentration of hydrochloride naphthodiamide is 0.20～0.25g/L, and the concentration of sulfanilamide is 2.0～2.5g/L.
5. according to claim 3 simultaneously in on-line automatic analysis water-like micro ammonium ion and nitrite ion low pressure Anions and canons chromatograph-photometry, it is characterised in that in the nitrite ion (R), the concentration of hydrochloric acid is 0.1～0.6mol/L, hydrochloric acid The concentration of naphthodiamide is 0.20～0.25g/L, and the concentration of sulfanilamide is 2.0～2.5g/L.
6. according to claim 1 or claim 2 while micro ammonium ion and nitrite ion in on-line automatic analysis water-like Low pressure anions and canons chromatograph-photometry, it is characterised in that the sulfonic acid ion exchange resin and stryrene divinyl base In the mixture of benzene copolymer, sulfonic acid ion exchange resin is 1 with the mass ratio of styrene diethylene benzene copoly mer: (0.95～1.05), the exchange capacity of sulfonic acid ion exchange resin is 0.1～0.5mmol/g；The strong alkaline quaternary ammonium type The exchange capacity of anion exchange resin is 3～4mmol/g.
7. according to claim 3 simultaneously in on-line automatic analysis water-like micro ammonium ion and nitrite ion low pressure Anions and canons chromatograph-photometry, it is characterised in that the sulfonic acid ion exchange resin is with styrene-divinylbenzene altogether In the mixture of polymers, sulfonic acid ion exchange resin is 1 with the mass ratio of styrene diethylene benzene copoly mer:(0.95 ～1.05), the exchange capacity of sulfonic acid ion exchange resin is 0.1～0.5mmol/g；The strong alkaline quaternary ammonium type anion The exchange capacity of exchanger resin is 3～4mmol/g.
8. according to claim 4 simultaneously in on-line automatic analysis water-like micro ammonium ion and nitrite ion low pressure Anions and canons chromatograph-photometry, it is characterised in that the sulfonic acid ion exchange resin is with styrene-divinylbenzene altogether In the mixture of polymers, sulfonic acid ion exchange resin is 1 with the mass ratio of styrene diethylene benzene copoly mer:(0.95 ～1.05), the exchange capacity of sulfonic acid ion exchange resin is 0.1～0.5mmol/g；The strong alkaline quaternary ammonium type anion The exchange capacity of exchanger resin is 3～4mmol/g.
9. according to claim 1 or claim 2 while micro ammonium ion and nitrite ion in on-line automatic analysis water-like Low pressure anions and canons chromatograph-photometry, it is characterised in that the Detection wavelength of fluorescence detector is 530nm.
10. according to claim 1 or claim 2 while micro ammonium ion and nitrite ion in on-line automatic analysis water-like Low pressure anions and canons chromatograph-photometry, it is characterised in that sample (S1) microporous filter membrane mistake is first passed through before into low-lift pump (1) Filter, absorption with macroporous adsorbent resin process.
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