CN208459337U - A kind of size exclusion chromatograph combination type Nitrogen detector - Google Patents
A kind of size exclusion chromatograph combination type Nitrogen detector Download PDFInfo
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- CN208459337U CN208459337U CN201820562797.8U CN201820562797U CN208459337U CN 208459337 U CN208459337 U CN 208459337U CN 201820562797 U CN201820562797 U CN 201820562797U CN 208459337 U CN208459337 U CN 208459337U
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Abstract
The utility model discloses a kind of size exclusion chromatograph combination type Nitrogen detectors, belong to water analysis detection field.The device of the utility model includes oxidative system, nitrate anion detection system, power-supply system, signal processing and control system；Sample to be tested is entered to the oxidative system oxidation processes first after size exclusion chromatograph separates, the nitrogen in sample is detected after being converted into nitrate anion using ultraviolet absorptivity method nitrate anion detection system；The power-supply system provides power supply for detector；Signal processing and control system are responsible for oxidative system, the signal processing of nitrate anion detection system and control；The utility model can realize the quantitative analysis of total nitrogen, organic nitrogen, nitrate nitrogen and ammonia nitrogen, have many advantages, such as easy to operate and abundant information, effectively prevent in traditional organic nitrogen analysis method because of large error and negative value problem caused by subtractive calculating.
Description
Technical field
The utility model relates to water analysis detection fields, and in particular to a kind of size exclusion chromatograph combination type nitrogen detection
Device.
Background technique
In drinking water and sewage disposal process, dissolved organic matter is main removal object.It is analyzed and characterized dissolubility
The composition and property of organic matter are the important means of water treatment technology mechanism study.Weight distributing characteristic is that dissolubility is organic
One of critical nature of object affects the effect of the materializing strategies technologies such as coagulation, film filtering, advanced oxidation, absorption and ion exchange
Fruit.
The analysis and characterization method of weight distributing characteristic mainly has serial membrane separation process and size exclusion chromatography, Qian Zheshou
The influence of ultrafiltration membrane pore size, molecular weight separate poor accuracy；The latter utilizes size exclusion chromatograph column, different molecular weight size
The substance delivery time it is different, molecular weight good separating effect, but the detector that liquid chromatogram is configured is mainly UV absorption light
Detector, fluorescence spectrum detector and evaporative light scattering detector are composed, it is existing since dissolved organic matter has height heterogeneity
There is detector that can only carry out relative quantification.Dissolved organic carbon is that dissolved organic matter matter total amount in water body is indicated with the content of carbon
Overall target.In recent years, the U.S. GE company organic carbon detector produced based on film conductance detection technique, by with
The combination of size exclusion chromatograph, it is CO that organic carbon, which is merged Ultraviolet Oxidation with acid-mixed,2, to the CO through film2It is measured, from
And the molecular weight distribution of organic carbon is measured.
As water body eutrophication degree constantly deteriorates, nitrogen is as a kind of important nutrient, in water
Become important research contents in the presence of and using form.Dissolubility total nitrogen (total dissolved in water body
Nitrogen, TDN) it include soluble organic nitrogen (dissolved organic nitrogen, DON) and dissolubility inorganic nitrogen
(dissolved inorganic nitrogen, DIN).Wherein, soluble organic nitrogen is from various natural organic
Object, such as protein, humus and amino acid；Inorganic nitrogen mainly includes ammonia nitrogen, nitrate nitrogen and nitrite nitrogen.Soluble organic nitrogen
There is direct or indirect toxic action to human body, in particular, organic nitrogen will form in Chlorination Process for Drinking Water to be had
The nitrogenous disinfection byproducts of higher " three cause effect "；On the other hand, the molecular size range distribution of organic nitrogen material, to biologically effective
Property and its Impacts on ecology and environment also have a major impact.Current organic nitrogen determination method is based primarily upon minusing, i.e., dependent on molten
The measurement of solution property total nitrogen concentration, subtracts the dissolubility inorganic nitrogen (NH measured respectively4 +, NO3 -And NO2 -The sum of concentration).This inter-species
Measurement is connect, there are total nitrogens, NH4 +, NO3 -And NO2 -The add up error of various aspects measurement, it is as a result inevitably inaccurate and reliable, even
It can be because test error calculates negative value.
Based on drawbacks described above, many scholars propose to measure again after separating DON with DIN, to improve the standard of concentration mensuration
True property, such as Chinese Patent Application No. CN201010022653.1, publication date discloses use for the application case of 2010.07.21 and receives
Filter membrane isolation technics is measured after separating to DON, but due to needing additional nitrogen to control transmembrane pressure, and energy consumption is high and to test
The demand of water sample is larger.And Chinese Patent Application No. CN201710048270.3, publication date are the application case of 2017.05.31
It discloses and is measured after being separated using dialysis preconditioning technique to DON, it is subsequent due to needing to judge by Preliminary Determination result
Measurement scheme, separation and determination step are complicated, cumbersome.In addition, above soluble organic nitrogen test method is only limitted to determine
Analysis method, can not composition to soluble organic nitrogen and its molecular weight distribution carry out deep qualitative and quantitative analysis.
National Standard of the People's Republic of China " GB 11894-89 ", the measurement of total nitrogen is using potassium peroxydisulfate at 60 DEG C or more
Oxidation resolution is carried out in aqueous solution, then with determined by ultraviolet spectrophotometry NO3 -Concentration.Based on changing to total nitrogen standard method
Into with optimization, the utility model provide a kind of high sensitivity and the good size exclusion chromatograph combination type Nitrogen detector of accuracy and its
Application method, it is intended to solve the qualitative and quantitative analysis detection problem of soluble organic nitrogen.
Summary of the invention
1. to solve the problems, such as
The analyzing detecting method sensitivity of soluble organic nitrogen is low in the prior art, error is big and testing procedure is complicated etc. asks
Topic, the utility model are intended to provide the good size exclusion chromatograph combination type Nitrogen detector of a kind of high sensitivity, accuracy.
2. technical solution
To solve the above-mentioned problems, technical solution used by the utility model is as follows:
The utility model provides a kind of size exclusion chromatograph combination type Nitrogen detector, including the inspection of oxidative system, nitrate anion
Examining system, power-supply system, signal processing and control system；Sample to be tested is entered to institute first after size exclusion chromatograph separates
The oxidative system oxidation processes stated, the nitrogen in sample are detected after being converted into nitrate anion using nitrate anion detection system；The electricity
Source system provides power supply for detector；Signal processing and control system are used at the signal of oxidative system, nitrate anion detection system
Reason and control.
It is further improved as the utility model, the oxidative system includes Ultraviolet Oxidation module and ultraviolet light intensity
Spend monitoring modular.
It is further improved as the utility model, the oxidative system includes leakage monitoring modular and negative pressure of vacuum
Module, the ozone and vacuumize that the negative pressure of vacuum module is used to eliminate in oxidative system.
It is further improved as the utility model, the Ultraviolet Oxidation module includes ultraviolet lamp tube, quartzy spiral
Pipe flow path, quartzy adapter, PEEK pipe, supporting and mounting bracket and quartz ampoule, the supporting and mounting bracket hold Ultraviolet Oxidation module
It holds in the palm and fixes on the base；The ultraviolet lamp tube is located inside quartz ampoule, and quartzy helix tube flow path is helically wound around quartz ampoule
On, the quartzy helix tube flow path both ends are connect with one end of quartzy adapter respectively, it is each quartz the adapter other end with
The connection of PEEK pipe.
It is further improved as the utility model, the nitrate anion detection system is UV detector, including stream
Logical pond module and UV absorption optical detecting module.
It is further improved as the utility model, the power-supply system includes ultraviolet lamp power source special and AC-DC
Power conversion module；The ultraviolet lamp power source special is Ultraviolet Oxidation module for power supply, and the AC-DC power conversion module is
Nitrate anion (NO3 -) detection system, signal processing and control system, the power supply of ultraviolet ray intensity monitoring modular.
Further improved as the utility model, the signal processing and control system include SCM system,
Display screen and communication module；The described SCM system control and processing signal, the signal can be shown by display screen or by
Communication module is transferred to host computer.
It is further improved as the utility model, the ultraviolet ray intensity monitoring modular is deep using gallium nitride aluminium base
Ultraviolet photodiode carries out real-time monitoring to the light intensity of the Ultraviolet Oxidation module.
It is further improved as the utility model, the ultraviolet lamp tube is low pressure mercury lamp, the quartzy spiral
Pipe flow path is the capillary quartz ampoule of 0.5~1.0mm of internal diameter, 1.5~3.0mm of outer diameter.
It is further improved as the utility model, the application side of the size exclusion chromatograph combination type Nitrogen detector
Method, it is characterised in that: the following steps are included:
1) using size exclusion chromatograph column to organic nitrogen, nitrate nitrogen (NO in sample3 -_ N) and ammonia nitrogen (NH4 +_ N) it carries out
Separation, mobile phase use pure water or phosphate buffer, cannot use organic solvent；
2) bypass PEEK pipe is formed in the PEEK pipe of size exclusion chromatograph column both ends parallel connection certain length, passes through testing and debugging
PEEK length of tube, allow to be formed the ratio between bypass PEEK pipe and pressure caused by size exclusion chromatograph column be n:1 (n for 5~
It 15) is, 1:n from there through bypass PEEK pipe is formed with the flow-rate ratio by size exclusion chromatograph column；
3) when autosampler sample introduction, sample introduction sample passes through bypass PEEK pipe and volume exclusion according to the ratio of 1:10 respectively
Then chromatographic column is detected through Nitrogen detector, wherein forming quick appearance, peak area is denoted as since bypass acts on without reserve
Area_TN；To organic nitrogen, NO after the separation of size exclusion chromatograph3 -And NH4 +Appearance integrated respectively, peak area
It is denoted as Area_TON, Area_NO3 -_ N and Area_NH4 +_N；
4) with NO3 -Standard solution establishes the linear relationship between Area_TN peak area and nitrogen content, is bypassed with sample
Area_TN calculates total nitrogen (TN), according to Area_TON, Area_NO3 -_ N and Area_NH4 +_ N accounts for the total peak of size exclusion chromatograph
The ratio of area calculates separately out organic nitrogen in sample (TON), nitrate nitrogen (NO3 -_ N) and ammonia nitrogen (NH4 +_ N) concentration.
3. beneficial effect
Compared with the prior art, the utility model has the following beneficial effects:
(1) a kind of size exclusion chromatograph combination type Nitrogen detector described in the utility model uses oxidative system will first
Nitrogen oxidation in various compounds through size exclusion chromatograph separation is nitrate anion, then is detected to nitrate anion, can be to each
Total nitrogen, nitrate nitrogen, nitrite nitrogen and ammonia nitrogen in class compound etc. carry out accurate quantitative analysis, as a result accurately and reliably；It overcomes
Organic nitrogen test in the prior art measures total nitrogen, nitrate nitrogen, nitrite nitrogen and ammonia nitrogen using distinct methods respectively, so
The difference of total nitrogen and inorganic nitrogen, complex for operation step, the biggish defect of test error, and the detector of the utility model are calculated afterwards
Constant flow pump, autosampler and the size exclusion chromatograph column that can generally purchase with laboratory are combined, low in cost, system
It is integrated convenient, it is conducive to promote.
(2) a kind of size exclusion chromatograph combination type Nitrogen detector described in the utility model, oxidative system includes ultraviolet
Oxidation module and ultraviolet ray intensity monitoring modular, Ultraviolet Oxidation module are used for the nitrogen oxidation in compound into nitrate ion,
Ultraviolet ray intensity monitoring modular is used to carry out real-time monitoring to the ultraviolet ray intensity of Ultraviolet Oxidation module, and two modules mutually match
It closes, guarantees that oxidative system has enough oxidizing intensities, to guarantee to stablize effective oxidation effectiveness.
(3) a kind of size exclusion chromatograph combination type Nitrogen detector described in the utility model, oxidative system are also set up very
Idling die block, the ozone that negative pressure of vacuum module not only generates ultraviolet irradiation air excludes, but also is reduced by vacuumizing
The decaying of ultraviolet light intensity is further ensured that oxidative system stablizes effective oxidation effectiveness to enhance oxidation effectiveness.
(4) a kind of size exclusion chromatograph combination type Nitrogen detector described in the utility model, power-supply system is according to ultraviolet oxygen
Different power supply systems is arranged in the different characteristics for changing module and other modules, advantageously reduces energy consumption, further decrease run at
This.
Detailed description of the invention
Fig. 1 is the top view of the size exclusion chromatograph combination type Nitrogen detector of the utility model；
Fig. 2 is the main view of the size exclusion chromatograph combination type Nitrogen detector helix tube oxidation module of the utility model；
Fig. 3 is the top view of the size exclusion chromatograph combination type Nitrogen detector helix tube oxidation module of the utility model；
Fig. 4 is the flow diagram of the application method of the Nitrogen detector of the utility model；
Fig. 5 is NO3 -Standard solution establishes the linear relationship chart between Area_TN peak area and nitrogen content；
Fig. 6 is that the size exclusion chromatograph combination type Nitrogen detector of the utility model detects sewage plant biochemistry secondary effluent water sample
Chromatogram；
Fig. 7 is that the size exclusion chromatograph combination type Nitrogen detector of the utility model detects the chromatogram of the Changjiang river water sample；
Fig. 8 is the test chart of the size exclusion chromatograph combination type Nitrogen detector oxidation efficiency of the utility model.
In figure: 1, oxidative system；2, nitrate anion detection system；3, power-supply system；4, signal processing and control system；5, phosphorus
Hydrochlorate buffer solution；6, ultrapure water；7, constant flow pump；8, autosampler；9, size exclusion chromatograph column；10, bypass PEEK pipe；
11, syringe pump；12, Nitrogen detector；101, Ultraviolet Oxidation module；102, leakage monitoring modular；103, ultraviolet ray intensity monitors mould
Block；104, negative pressure of vacuum module；201, flow cell module；202, UV absorption optical detecting module；301, ultraviolet lamp Special electric
Source；302, AC-DC power conversion module；401, SCM system；402, display screen；403, communication module；111, ultraviolet lamp tube；
112, quartzy helix tube flow path；113, quartzy adapter；114, PEEK pipe fitting；115, supporting and mounting bracket；116, quartz ampoule.
Specific embodiment
The utility model is further described below combined with specific embodiments below.
Embodiment 1
A kind of size exclusion chromatograph combination type Nitrogen detector is present embodiments provided, as shown in Figure 1, the detector includes oxygen
Change system 1, nitrate anion detection system 2, power-supply system 3, signal processing and control system 4；By sample to be tested first through volume
Enter 1 oxidation processes of oxidative system after exclusion chromatography separation, the nitrogen in sample is converted into after nitrate anion using nitrate anion
Detection system 2 detects；The power-supply system 3 provides power supply for detector；Signal processing and control system 4 are used for oxidative system
1, the signal processing of nitrate anion detection system 2 and control.
The detector basic principle of the utility model be using oxidative system 1 will after size exclusion chromatograph separates it is all kinds of
Nitrogen contained by compound is converted into NO3 -, according to NO3 -Molar absorption coefficient or unit mass extinction under specific UV wavelength
Coefficient carries out quantitative detection.
The oxidative system 1 includes Ultraviolet Oxidation module 101 and ultraviolet ray intensity monitoring modular 103, and described is ultraviolet
Oxidation module 101 aoxidizes compound by ultraviolet oxidation mode, converts NO for nitrogen contained by compound3 -；It is ultraviolet
Luminous intensity monitoring modular 103 is for ultraviolet ray intensity caused by real-time monitoring Ultraviolet Oxidation module 101, signal processing and control
System 4 is for controlling the signal of generation, to guarantee that Ultraviolet Oxidation module 101 generates enough oxidizing intensities.
The oxidative system 1 further includes negative pressure of vacuum module 104, and the negative pressure of vacuum module 104 can be ultraviolet
It irradiates the ozone that air generates and detector is discharged, and vacuumize enhancing Ultraviolet Oxidation effect, specifically use minipump, and
It is equipped with active carbon filter core before minipump air entry and removes ozone.
The oxidative system 1 further includes leakage monitoring modular 102, and the leakage monitoring modular 102 is for monitoring system
System leakage situation is simultaneously controlled by signal processing with control system 4；The leakage monitoring modular 102 uses LeaKFilm
Sensing zone, to liquid leakage can fast reaction, can quickly be reset without false alarm, and after leakage cleaning, and enter
Working condition.
As shown in Figure 2 and Figure 3, the nitrogen in the classes of compounds of entrance is converted NO by the Ultraviolet Oxidation module 1013 -,
The leakage monitoring modular 102 is used for the detection of leakage situation, and leakage situation is shown through signal processing and control system 4
Show；The ultraviolet ray intensity monitoring modular 103 shows ultraviolet light intensity through signal processing and control system 4.
Embodiment 2
The present embodiment is substantially same as Example 1, the difference is that:
The nitrate anion detection system 2 is UV detector, including flow cell module 201 and UV absorption optical detection
Module 202；Its working principle is that using the ultraviolet light of the continuous light sources such as deuterium lamp or UV_LED lamp transmitting specific wavelength, and detect body
Exclusion chromatography mobile phase is accumulated in the ultraviolet absorptivity of 215~230nm wave-length coverage and 10~40mm light path flow cell, and according to it
NO under corresponding wavelength3 -Molar absorption coefficient or unit mass absorptivity to NO3 -It is quantified.
The nitrate anion detection system 2 is the exit of flow path, wherein the flow cell module 201 is according to NO3 -?
The molar absorption coefficient or unit mass absorptivity of specific UV wavelength carry out the concurrent optical signals of quantitative detection, the purple
Outer absorption optical detecting module 202 converts optical signal into electric signal and input signal is handled and control system 4.
201 light path of flow cell module selects 10mm, using the ultraviolet absorptivity of 220nm wavelength to NO3 -Determined
Amount detection, unit mass absorptivity use 0.25L/ (mg*cm).
The signal processing and control system 4 includes SCM system 401, display screen 402 and communication module 403；Institute
The control of SCM system 401 and processing signal, the signal stated can be shown by display screen 402 or be passed by communication module 403
It is defeated to arrive host computer.
Electric signal caused by the UV absorption optical detecting module 202 is produced through amplifying circuit and analog to digital conversion circuit
Raw digital signal, is transported to SCM system 401；Digital signal is stored into single-chip microcontroller by SCM system 401；The display
The basic status of device 403 real-time display digital signal and device.
The 401 outputting communication signal oxidizing system 1 of SCM system controls the Ultraviolet Oxidation in oxidative system 1
Module 101 is worked with conitnuous forms.
Embodiment 3
The present embodiment is substantially same as Example 1, the difference is that:
The ultraviolet ray intensity monitoring modular 103 is using gallium nitride aluminium base deep ultraviolet light electric diode to the ultraviolet oxygen
The light intensity for changing module 101 carries out real-time monitoring, only responds to the ultraviolet generation of UVC wave band.
The power-supply system 3 includes ultraviolet lamp power source special 301 and AC-DC power conversion module 302；Described is ultraviolet
Lamp power source special 301 is the power supply of Ultraviolet Oxidation module 101, and the AC-DC power conversion module 302 is nitrate anion (NO3 -) inspection
Examining system 2, signal processing and control system 4, ultraviolet ray intensity monitoring modular 103 are powered.
The reason of Ultraviolet Oxidation module 101 and other modules are powered using different power supplys is: Ultraviolet Oxidation mould
The ultraviolet lamp used in block 101 belongs to cold-cathode lamp, and power is small, therefore AC to DC, direct current is selected to become the power supply of exchange
Mode；And the hot cathode lamp output power that other modules need is big, therefore connects standard electric alternating current using variable-frequency variable-voltage, therefore will
The power supply system of Ultraviolet Oxidation module 101 and other modules, which distinguishes, to be conducive to save power supply, further decreases operating cost.
Embodiment 4
The present embodiment is substantially same as Example 1, the difference is that:
The Ultraviolet Oxidation module 101 include ultraviolet lamp tube 111, quartzy helix tube flow path 112, quartzy adapter 113,
PEEK pipe fitting 114, supporting and mounting bracket 115 and quartz ampoule 116, Fig. 2 are the main view of the present embodiment Ultraviolet Oxidation module 101；
Fig. 3 is the top view of the present embodiment Ultraviolet Oxidation module 101, such as Fig. 2, shown in Fig. 3, in the use of supporting and mounting bracket 115
The plastic buckle that diameter is 25mm is by 101 support of Ultraviolet Oxidation module and fixes on the base；The ultraviolet lamp tube 111 is located at stone
Inside English pipe 116, quartz ampoule 116 plays the role of protecting ultraviolet lamp tube 111 and fixed quartzy helix tube 112.The quartz
Helix tube flow path 112 uses the capillary quartz ampoule of internal diameter 1.0mm, outer diameter 3.0mm to be wound on quartz ampoule 116 with melting,
Capillary quartz ampoule both ends pass through one end that melting is connected to two quartzy adapters 113 respectively, and quartzy adapter 113 is another
End has 1/4-28 specification internal screw thread, can connect with the PEEK connector 114 of same size；The PEEK connector 114 connects therewith
The PEEK pipe connect only plays the role of transporting liquid.
Sample reconsolidates after size exclusion chromatograph 9 and bypass PEEK pipe 10 as all the way, later in oxidation module
Influent enters quartzy helix tube flow path 112 through PEEK connector through walls and quartzy adapter 113, is aoxidized in this section,
Enter nitrate anion detection system 2 through quartzy adapter 113, PEEK pipe fitting 114, PEEK pipe again, in detector after detecting
Effluent mouthfuls of outflow detectors, are discharged through sewer pipe.
The ultraviolet lamp tube 111 uses low pressure cold cathode mercury lamp, diameter 15mm, length 150mm；The ultraviolet lamp
It include two ultraviolet rays of 184.9nm and 253.7nm, the wherein ultraviolet rays of 184.9nm in the ultraviolet spectra that pipe 111 generates
It plays a major role in the oxidation process of nitrogen.
Embodiment 5
The process that size exclusion chromatograph combination type Nitrogen detector in embodiment 1 carries out sample detection is present embodiments provided,
Fig. 4 is flow diagram.As shown in figure 4, the step of whole flow process, is as follows:
A) sample injection is entered in the mobile phase phosphate buffer 5 that constant flow pump 7 drives using autosampler 8；
B) sample is respectively through size exclusion chromatograph 9 and bypass 10 two kinds of flow path Nitrogen detectors 12 of PEEK pipe；The volume
Exclusion chromatography 9 is 250mm long, internal diameter 20mm, and filler uses the gel resin of Toyopearl HW-50S.
C) potassium persulfate solution that mass concentration is 1% is added by syringe pump 11 before Nitrogen detector 12 and is used as oxidation
Agent, effect are can to play the role of enhancing oxidation for high concentration water sample.
D) after the completion of detecting, using 6 detergent line of ultrapure water.
The present embodiment additionally provides the application that size exclusion chromatograph combination type Nitrogen detector in embodiment 1 carries out sample detection
Method, comprising the following steps:
1) using size exclusion chromatograph column 9 to organic nitrogen, NO in sample3 -And NH4 +It is separated, mobile phase uses phosphoric acid
Salt buffer solution 5, the phosphate buffer use 2.5g/L KH2PO4With 1.5g/L Na2HPO4·2H2The mixing of O is molten
Liquid；
2) bypass is formed by threeway one section of bypass PEEK pipe 10 in parallel at 9 both ends of size exclusion chromatograph column, passes through test
PEEK length of tube is adjusted, makes to bypass the ratio between pressure caused by PEEK pipe 10 and size exclusion chromatograph column 9 for 10:1, thus leads to
It is 1:10 that bypass PEEK pipe 10, which is crossed, with the flow-rate ratio by size exclusion chromatograph column 9；
3) sample introduction sample is derived from sewage plant biochemistry secondary effluent, and 500 μ L of volume passes through respectively also according to the ratio of 1:10
PEEK pipe 10 and size exclusion chromatograph column 9 are bypassed, is then detected through Nitrogen detector 12, wherein since bypass acts on without reserve, shape
At quick appearance, peak area is denoted as Area_TN；It, can be to organic nitrogen, NO due to the centrifugation of size exclusion chromatograph3 -And NH4 +Appearance integrated respectively, peak area is denoted as Area_TON, Area_NO3 -_ N and Area_NH4 +_ N, unit AU
(Arbitrary Units)；
4) with NO3 -Standard solution establishes the linear relationship between Area_TN peak area and nitrogen content, is bypassed with sample
Area_TN calculates total nitrogen (TN), according to Area_TON, Area_NO3 -_ N and Area_NH4 +_ N accounts for the total peak of size exclusion chromatograph
The ratio of area calculates separately out organic nitrogen (TON), nitrate anion (NO3 -_ N) and ammonium root (NH4 +_N)。
When establishing linear relationship, the NO in terms of N of 1mg/L, 500 μ g/L, 100 μ g/L, 10 μ g/L, 5 μ g/L are prepared respectively3 -
Standard solution and sample introduction, establish the linear relationship of Area_TN peak area and nitrogen content, Fig. 5 NO3 -Standard solution establishes Area_
Linear relationship chart between TN peak area and nitrogen content, as shown in Figure 5, the linear side between Area_TN peak area and nitrogen content
R in journey2=0.9995, meet linear criterion.
Fig. 6 is that the utility model, that is, size exclusion chromatograph combination type Nitrogen detector detects sewage plant biochemistry secondary effluent water sample
Chromatogram, wherein Bypass represent bypass TN appearance；TON,Area_NO3 -_N、Area_NH4 +_ N is represented to be arranged by volume
Hinder TON, NO of chromatographic column3 -_N、NH4 +The appearance of _ N.
Wherein, TN, TON, NO3 -_N、NH4 +The calculating process of _ N concentration is as follows:
The concentration of TN are as follows: the ÷ of 0.367AU × 1.1mL/min × 3.911mgcm/L × 11 0.5mL=34.735mg/L
The concentration of TON are as follows: 34.735mg/L × (0.261 ÷ 0.367) ÷ 10=2.470mg/L
NO3 -The concentration of _ N are as follows: 34.735mg/L × (1.338 ÷ 0.367) ÷ 10=12.636mg/L
NH4 +The concentration of _ N are as follows: 34.735mg/L × (2.069 ÷ 0.367) ÷ 10=19.582mg/L
Table 1 is final testing result statistics.
1 test result of table
Embodiment 6
The present embodiment is substantially same as Example 5, the difference is that: surveyed water sample is the Changjiang river water sample, 500 μ of sampling amount
L, mode of oxidizing are oxidant to be added without using syringe pump 11, by nitrate anion (NO only with Ultraviolet Oxidation3 -_ N) and ammonium root (NH4 +_ N) the sum of be denoted as Total inorganic nitrogrn (TIN), obtained result, wherein TN, TON, NO3 -_N、NH4 +The calculating process of _ N concentration with
Embodiment 5 is identical, and table 2 is the test result statistics in the present embodiment.
2 test result of table
Embodiment 7
The present embodiment is substantially same as Example 5, the difference is that: size exclusion chromatograph column is not used in the present embodiment
9 and bypass PEEK pipe 10, using 25 μ L of bovine serum albumin aqueous solution sample introduction of 100mg/L, 50 μ L, 12.5 μ L, 6.25 μ L each two
It is secondary, it is therefore intended that judge that oxidation efficiency, Fig. 8 are the utility model, that is, size exclusion chromatograph combination type Nitrogen detector oxidation efficiency
Test chart illustrates that sample volume is super as shown in figure 8, wherein sampling volume is to occur fork peak among the chromatographic peak of 25 μ L and 50 μ L
The oxidability of ultraviolet helix tube out, and under 12.5 μ L and 6.25 μ L sampling volumes, peak type is preferable, and peak area is therebetween
2 times of relationships, Ultraviolet Oxidation module 101 can be fully oxidized by organic nitrogen TON under the conditions of showing the sample volume.
Embodiment 8
The present embodiment is substantially same as Example 5, the difference is that: size exclusion chromatograph column is not used in the present embodiment
9 and bypass PEEK pipe 10, using bovine serum albumin, NaNO3、NH4Cl prepares TON_N, NO in terms of N3 -_N、NH4 +_ N solution
10mg/L, sample introduction 5 times respectively, relative standard deviation is respectively less than 2%, meets accuracy requirement.Table 3 is test result statistics.
3 test result of table
Arithemetic unit is mg/L in addition to relative standard deviation in this table.
Meanwhile according to the method in embodiment 6, using size exclusion chromatograph column 9 and bypass PEEK pipe 10, to above-mentioned preparation
TON_N, NO in terms of N3 -_N、NH4 +_ N solution 10mg/L sample introduction, relative standard deviation are respectively less than 2%, meet accuracy and want
It asks.Table 4 is to count according to the method testing result of the utility model.
4 test result of table
As shown in Table 4, the method for the utility model is accurate and reliable.
Embodiment 9
The present embodiment is substantially same as Example 5, the difference is that: it bypasses PEEK pipe 10 and passes through size exclusion chromatograph
The flow-rate ratio of column 9 is 1:5.
The quartzy helix tube flow path 112 uses the capillary quartz ampoule of internal diameter 0.5mm, outer diameter 1.5mm.
Embodiment 10
The present embodiment is substantially same as Example 5, the difference is that: it bypasses PEEK pipe 10 and passes through size exclusion chromatograph
The flow-rate ratio of column 9 is 1:15.
The quartzy helix tube flow path 112 is the capillary quartz ampoule of internal diameter 0.8mm, outer diameter 2.0mm.
Schematically the utility model and embodiments thereof are described above, description is not limiting, attached drawing
Shown in be also one of the embodiments of the present invention, actual process is not limited thereto.So if this field
Those of ordinary skill enlightened by it, without deviating from the purpose of the present invention, not inventively design
Frame mode similar with the technical solution and embodiment, all should belong to the protection range of the utility model.
Claims (9)
1. a kind of size exclusion chromatograph combination type Nitrogen detector, it is characterised in that: including oxidative system (1), nitrate anion detection system
System (2), power-supply system (3), signal processing and control system (4)；By sample to be tested first after size exclusion chromatograph separates
Into described oxidative system (1) oxidation processes, the nitrogen in sample is examined after being converted into nitrate anion using nitrate anion detection system (2)
It surveys；The power-supply system (3) provides power supply for detector；Signal processing and control system (4) are used for oxidative system (1), nitre
The signal processing of acid group detection system (2) and control.
2. size exclusion chromatograph combination type Nitrogen detector according to claim 1, it is characterised in that: the oxidative system
It (1) include Ultraviolet Oxidation module (101) and ultraviolet ray intensity monitoring modular (103).
3. size exclusion chromatograph combination type Nitrogen detector according to claim 1 or 2, it is characterised in that: the oxidation
System (1) includes leakage monitoring modular (102) and negative pressure of vacuum module (104), and the negative pressure of vacuum module (104) is for disappearing
Except the ozone in oxidative system (1) and vacuumize.
4. size exclusion chromatograph combination type Nitrogen detector according to claim 2, it is characterised in that: the Ultraviolet Oxidation
Module (101) includes ultraviolet lamp tube (111), quartzy helix tube flow path (112), quartzy adapter (113), PEEK pipe fitting
(114), supporting and mounting bracket (115) and quartz ampoule (116), the supporting and mounting bracket (115) hold Ultraviolet Oxidation module (101)
It holds in the palm and fixes on the base；The ultraviolet lamp tube (111) is located at quartz ampoule (116) inside, quartzy helix tube flow path (112) spiral shell
Rotation be wound on quartz ampoule (116), quartzy helix tube flow path (112) both ends respectively with quartzy adapter (113) one
End connection, each quartz adapter (113) other end are connect with PEEK pipe fitting (114).
5. size exclusion chromatograph combination type Nitrogen detector according to claim 4, it is characterised in that: the nitrate anion inspection
Examining system (2) is UV detector, including flow cell module (201) and UV absorption optical detecting module (202).
6. size exclusion chromatograph combination type Nitrogen detector according to claim 2, it is characterised in that: the power-supply system
It (3) include ultraviolet lamp power source special (301) and AC-DC power conversion module (302)；The ultraviolet lamp power source special (301)
For Ultraviolet Oxidation module (101) power supply, the AC-DC power conversion module (302) is nitrate anion (NO3 -) detection system (2),
Signal processing and control system (4), ultraviolet ray intensity monitoring modular (103) are powered.
7. size exclusion chromatograph combination type Nitrogen detector according to claim 4 or 5, it is characterised in that: the signal
Processing and control system (4) include SCM system (401), display screen (402) and communication module (403)；The single-chip microcontroller
System (401) control and processing signal, the signal can be shown by display screen (402) or be transferred to by communication module (403)
Host computer.
8. size exclusion chromatograph combination type Nitrogen detector according to claim 2, it is characterised in that: the ultraviolet light intensity
Spend monitoring modular (103) using gallium nitride aluminium base deep ultraviolet light electric diode to the light intensity of the Ultraviolet Oxidation module (101) into
Row real-time monitoring.
9. size exclusion chromatograph combination type Nitrogen detector according to claim 4 or 5, it is characterised in that: described is ultraviolet
Fluorescent tube (111) is low pressure mercury lamp, and the quartzy helix tube flow path (112) is 0.5~1.0mm of internal diameter, 1.5~3.0mm of outer diameter
Capillary quartz ampoule.
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| CN108414645A (en) * | 2018-04-19 | 2018-08-17 | 南京大学 | A kind of size exclusion chromatograph combination type Nitrogen detector and application process |
| WO2019201086A1 (en) * | 2018-04-19 | 2019-10-24 | 南京大学 | Size exclusion chromatography-combined nitrogen detector and application method |
| CN108414645B (en) * | 2018-04-19 | 2023-05-23 | 南京大学 | Volume exclusion chromatography combined nitrogen detector and application method |
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