CN112461945B - Method for simultaneously and rapidly analyzing dibutyl phosphate, monobutyl phosphate, n-butyric acid, NO 3-and NO2- - Google Patents
Method for simultaneously and rapidly analyzing dibutyl phosphate, monobutyl phosphate, n-butyric acid, NO 3-and NO2- Download PDFInfo
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Abstract
The invention discloses a method for simultaneously and rapidly analyzing dibutyl phosphate, monobutyl phosphate, n-butyric acid, NO 3-and NO2-, which comprises the steps of firstly dissolving five substance standards in pure water to prepare a standard stock solution, then preparing sample solutions with different concentrations, obtaining an ion chromatography standard spectrogram and peak areas of corresponding components through ion chromatography analysis, and drawing a standard working curve; taking a sample to be tested, carrying out centrifugal separation, extracting an upper organic phase, carrying out back extraction elution on the organic phase obtained by separation, carrying out centrifugal separation again, extracting a lower aqueous phase, and diluting properly; then carrying out ion chromatography analysis under the same ion chromatography analysis condition to obtain peak areas of corresponding components in the ion chromatogram of the extracting solution of the sample to be detected, and calculating to obtain DBP, MBP and n-C in the organic phase of the sample to be detected by using the standard working curve and the dilution multiple of the sample to be detected 4 H 9 COO ‑ 、NO 3 ‑ And NO 2 ‑ And (4) concentration. The invention adopts the ion chromatography, can simultaneously and rapidly analyze five substances, and has high analysis sensitivity, low detection limit and good repeatability.
Description
Technical Field
The invention relates to an analysis method for simultaneously and rapidly analyzing five ions, in particular to a qualitative and quantitative analysis method for coexistence of ester, organic acid, inorganic acid and inorganic acid salt in a complex phase, belonging to the technical field of analytical chemistry.
Background
In order to solve the problem of serious environmental pollution caused by long-term use of fossil fuels, nuclear power is being vigorously developed in China, and belongs to clean energy. However, the rapid development of nuclear power will produce a large amount of spent fuel. In spent fuel post-treatment, tributyl phosphate (TBP) is irradiated or nitric acid in the system is acted, and is decomposed to generate dibutyl phosphate (DBP), monobutyl phosphate (MBP) and n-butyl alcohol, and the n-butyl alcohol is oxidized into n-butyl acid (n-C) by nitric acid 4 H 9 COOH). In addition, decomposition of nitric acid produces NO 2 - Thus, the system exists DBP, MBP, n-C 4 H 9 COOH、NO 3 - And NO 2 - These substances may interfere with the proper operation of the process, and their concentration needs to be accurately analyzed. In order to rapidly analyze these substances, it is desired to simultaneously analyze them, and since there is no literature report on a method for simultaneously analyzing these substances at home and abroad, it is necessary to establish a method for simultaneously analyzing DBP, MBP and n-C 4 H 9 COOH、NO 3 - And NO 2 - The novel process of (1).
Disclosure of Invention
In order to solve the problems of the prior art, the invention aims to overcome the defects in the prior art and provide a method for simultaneously and rapidly analyzing dibutyl phosphate, monobutyl phosphate, n-butyric acid and NO 3 - And NO 2 - The method of the invention can be adopted to simultaneously and rapidly analyze DBP, MBP and n-C 4 H 9 COO - 、NO 3 - And NO 2 - 。DBP、MBP、n-C 4 H 9 COO - 、NO 3 - And NO 2 - The lowest detection limit of the analysis is 8X 10 respectively -8 、8×10 -7 、4×10 -6 、2×10 -7 And 4X 10 -7 mol/L, the relative standard deviations of the analyses were 0.8%, 2.2%, 1.6%, 1.1% and 1.1%, respectively. The invention adopts ion chromatography, and can simultaneously and rapidly analyze DBP, MBP and n-C 4 H 9 COO - 、NO 3 - And NO 2 - High sensitivity, low detection limit and good repeatability.
In order to achieve the purpose, the invention adopts the following technical scheme:
rapid analysis of dibutyl phosphate, monobutyl phosphate, n-butyric acid and NO simultaneously 3 - And NO 2 - The method adopts ion chromatography to analyze dibutyl phosphate DBP, monobutyl phosphate MBP and n-butyl acid radical ion n-C 4 H 9 COO - 、NO 3 - And NO 2 - The method comprises the following steps:
①DBP、MBP、n-C 4 H 9 COO - 、NO 3 - and NO 2 - Drawing a standard curve:
mixing DBP, MBP, n-C 4 H 9 COOH、KNO 3 And NaNO 2 Respectively dissolving the standard substances in ultrapure water to obtain corresponding standard solutions; then, if necessary, DBP, MBP, n-C are added 4 H 9 COOH、KNO 3 And NaNO 2 The standard solution is diluted into standard test solutions with different concentrations to be respectively used as DBP, MBP and n-C 4 H 9 COOH、KNO 3 And NaNO 2 Characterizing the sample solution by applying different concentrations of DBP, MBP, n-C 4 H 9 COOH、KNO 3 And NaNO 2 Analyzing the characteristic sample solution by ion chromatography to obtain DBP, MBP, n-C 4 H 9 COOH、KNO 3 And NaNO 2 An ion chromatography standard spectrogram of the characteristic sample solution and peak areas of corresponding components; respectively using DBP, MBP and n-C 4 H 9 COO - 、NO 3 - And NO 2 - The concentration is the abscissa, the corresponding peak area is the ordinate, and DBP, MBP and n-C are drawn 4 H 9 COO - 、NO 3 - And NO 2 - Standard working curve:
y = aX + b, wherein: x is DBP, MBP, n-C 4 H 9 COO - 、NO 3 - Or NO 2 - Molar concentration of the solution, Y is the correspondingA and b are dimensionless coefficients;
(2) pretreatment of a sample to be detected:
taking 4mL of a sample to be detected to be placed in a 13mL centrifugal tube, then placing the centrifugal tube into a centrifugal machine, and centrifuging for at least 5min at a rotating speed of not less than 2000 rpm; then taking 1mL of the upper organic phase and putting the upper organic phase into another 13mL centrifuge tube, and adding 5mL of Na with the mass concentration of 1wt.% 2 CO 3 And 1wt.% aqueous NaOH; then, putting the centrifugal tube into a turbine oscillator, oscillating for at least 5min at the rotating speed of not less than 2300rpm so as to fully mix and back-extract; then placing the centrifugal tube into a centrifuge, centrifuging for at least 5min at the rotating speed of not less than 2000rpm, taking the lower-layer water phase for dilution, and taking the diluted lower-layer water phase as a sample extracting solution to be detected;
(3) ion chromatography analysis of the sample extract to be tested:
DBP, MBP, n-C in step (1) 4 H 9 COOH、KNO 3 And NaNO 2 Under the condition of the same characteristic sample solution analysis, carrying out ion chromatography analysis on the extract of the sample to be detected to obtain DBP, MBP and n-C in the extract of the sample to be detected 4 H 9 COO - 、 NO 3 - And NO 2 - Using the peak area of DBP, MBP, n-C obtained in step (1) 4 H 9 COO - 、NO 3 - And NO 2 - Calculating standard working curve to obtain DBP, MBP, n-C in the sample extractive solution 4 H 9 COO - 、NO 3 - And NO 2 - And (4) concentration.
Preferably, in the step (1), DBP, MBP, n-C are rapidly analyzed simultaneously 4 H 9 COO - 、NO 3 - And NO 2 - The method comprises the following analysis conditions by ion chromatography:
a. a chromatographic column: metrosep A supp5-250 (250 mm. Times.4.0 mm);
b. sample introduction amount: 20 mu L of the solution;
c. concentration of the leacheate: 1.8mmol/L Na 2 CO 3 -1.0mmol/L NaHCO 3 ；
d. Flow rate of eluent: 0.8mL/min;
e. column temperature: 30 ℃;
f. a detector: a conductivity detector.
Preferably, the sample to be detected is spent fuel post-treatment fluid TBP and HNO 3 The mixture after the reaction.
Compared with the prior art, the invention has the following obvious substantive characteristics and remarkable advantages:
1. the invention adopts ion chromatography and can carry out ion chromatography on DBP, MBP and n-C in complex phases 4 H 9 COO - 、NO 3 - And NO 2 - Performing simultaneous and rapid analysis;
2. the method has the advantages of high analysis speed, low detection limit, high sensitivity and good repeatability.
Drawings
FIG. 1 shows a schematic view of 8X 10 -4 mol/L DBP、MBP、n-C 4 H 9 COO - 、NO 3 - And NO 2 - And (5) ion chromatogram of the characteristic sample mixed solution. In the figure, the abscissa is time (min), and the ordinate is peak height (mv). DBP, MBP, n-C 4 H 9 COO - 、NO 3 - And NO 2 - The retention time of (A) is 10.51min, 33.96min, 7.71min, 18.17min and 12.17min respectively.
Fig. 2 is an operation curve of a DBP plotted in example 2 of the present invention. The abscissa is the DBP concentration (10) -5 mol/L) and the ordinate is the peak area of DBP (mv. Multidot.s). Working curve: y =49.411X-8.418; coefficient of correlation (R) 2 )：R 2 ＝0.9994。
FIG. 3 is a graph of the MBP operation plotted in example 2 of the present invention. The abscissa is MBP concentration (10) -6 mol/L) and the ordinate is the peak area of MBP (mv. Multidot.s). Working curve: y =5.3243X +0.5958; r 2 ＝0.9986。
FIG. 4 is a drawing of n-C according to example 2 of the present invention 4 H 9 COO - The operating curve of (c). The abscissa is n-C 4 H 9 COO - Concentration (10) -6 mol/L), longitudinal seatMarked n-C 4 H 9 COO - Peak area (mv · s). Working curve: y =1.4036X +0.0394; r 2 ＝0.9997。
FIG. 5 is a graphic representation of NO according to example 2 of the present invention 3 - The operating curve of (c). On the abscissa of NO 3 - Concentration (10) -4 mol/L), ordinate is NO 3 - Peak area (mv · s). Working curve: y =11.451X-12.434; r is 2 ＝0.9990。
FIG. 6 is a drawing of NO according to example 2 of the present invention 2 - The operating curve of (c). On the abscissa of NO 2 - Concentration (10) -5 mol/L), ordinate is NO 2 - Peak area (mv · s). Working curve: y =67.591X-11.894; r 2 ＝0.9991。
FIG. 7 shows TBP-and 2mol/L and HNO in example 2 of the present invention 3 Mixing according to a volume ratio of 1. In the figure, the abscissa is time (min) and the ordinate is peak height (mv).
Detailed Description
The above-described embodiments are further illustrated below with reference to specific examples, in which preferred embodiments of the invention are detailed below:
example 1:
in this example, a rapid simultaneous analysis of dibutyl phosphate, monobutyl phosphate, n-butyric acid, NO 3 - And NO 2 - The method adopts ion chromatography to analyze dibutyl phosphate DBP, monobutyl phosphate MBP and n-butyl acid radical ion n-C 4 H 9 COO - 、 NO 3 - And NO 2 - The method comprises the following steps:
①DBP、MBP、n-C 4 H 9 COO - 、NO 3 - and NO 2 - Drawing a standard curve:
mixing DBP, MBP, n-C 4 H 9 COOH、KNO 3 And NaNO 2 Respectively dissolving the standard substances in ultrapure water to obtain corresponding standard solutions; then DB is combined as requiredP、MBP、n-C 4 H 9 COOH、KNO 3 And NaNO 2 The standard solution is diluted into standard test solutions with different concentrations to be respectively used as DBP, MBP and n-C 4 H 9 COOH、KNO 3 And NaNO 2 Characterizing the sample solution by applying different concentrations of DBP, MBP, n-C 4 H 9 COOH、KNO 3 And NaNO 2 Analyzing the characteristic sample solution by ion chromatography to obtain DBP, MBP, n-C 4 H 9 COOH、KNO 3 And NaNO 2 Ion chromatography standard spectrogram of the characteristic sample solution and peak areas of corresponding components; respectively using DBP, MBP and n-C 4 H 9 COO - 、NO 3 - And NO 2 - The concentration is the abscissa, the corresponding peak area is the ordinate, and DBP, MBP and n-C are drawn 4 H 9 COO - 、NO 3 - And NO 2 - Standard working curve:
y = aX + b, wherein: x is DBP, MBP, n-C 4 H 9 COO - 、NO 3 - Or NO 2 - The molar concentration of the solution, Y is the corresponding peak area, and a and b are dimensionless coefficients;
(2) pretreatment of a sample to be detected:
taking 4mL of a sample to be detected, putting the sample into a 13mL centrifugal tube, putting the centrifugal tube into a centrifugal machine, and centrifuging for 5min at the rotating speed of 2000 rpm; then taking 1mL of the upper organic phase and putting the upper organic phase into another 13mL centrifuge tube, and adding 5mL of Na with the mass concentration of 1wt.% 2 CO 3 And 1wt.% aqueous NaOH; then, putting the centrifugal tube into a turbine oscillator, oscillating for 5min at the rotating speed of 2300rpm so as to fully mix and back-extract; then placing the centrifugal tube into a centrifugal machine, centrifuging for 5min at the rotating speed of 2000rpm, taking the lower-layer water phase for dilution, and taking the diluted lower-layer water phase as a sample extracting solution to be detected;
(3) ion chromatography analysis of the sample extract to be tested:
DBP, MBP, n-C in step (1) 4 H 9 COOH、KNO 3 And NaNO 2 Separating the extract of the sample to be tested under the condition of the same analysis of the characteristic sample solutionAnalyzing by sub-chromatography to obtain DBP, MBP, n-C in the extractive solution of the sample to be detected 4 H 9 COO - 、 NO 3 - And NO 2 - The peak area of (2) is determined by using DBP, MBP, n-C obtained in step (1) 4 H 9 COO - 、NO 3 - And NO 2 - The standard working curve can be calculated to obtain DBP, MBP and n-C in the extract of the sample to be detected 4 H 9 COO - 、NO 3 - And NO 2 - And (4) concentration.
The invention adopts ion chromatography, and can simultaneously and rapidly analyze DBP, MBP and n-C 4 H 9 COO - 、NO 3 - And NO 2 - High sensitivity, low detection limit and good repeatability.
Example 2:
this embodiment is substantially the same as embodiment 1, and is characterized in that:
in this example, ion chromatography was used to simultaneously analyze DBP, MBP, n-C, see FIGS. 1-7 4 H 9 COO - 、NO 3 - And NO 2 - The method comprises the following steps:
(1) Preparation of standard solution: 0.173g of DBP, 0.250g of MBP, and 0.066g of n-C were weighed out separately 4 H 9 COOH、0.082 g KNO 3 And 0.056g NaNO 2 Adding ultrapure water into a 10mL volumetric flask for dissolving and diluting to scale marks, shaking uniformly, and respectively preparing into 8 × 10 -2 mol/L DBP、MBP、n-C 4 H 9 COO - 、NO 3 - And NO 2 - Diluting the standard solution into standard solutions with different concentrations according to the needs;
(2) Pretreatment of a reaction sample: tributyl phosphate (TBP) and 2mol/L HNO at 75 DEG C 3 And reacting for 8 hours, wherein the volume ratio of the organic phase to the aqueous phase is 1:1; then taking a 4mL mixture sample as a sample to be detected, putting the sample to be detected in a 13mL centrifuge tube, putting the centrifuge tube in a centrifuge, and centrifuging for 5min at the rotating speed of 2000 rpm; taking 1mL of the upper organic phase and putting the upper organic phase into another 13mL centrifuge tube, adding 5mL of the organic phaseThe mass concentration of Na is 1 wt% 2 CO 3 And 1wt.% aqueous NaOH; placing the centrifuge tube into a turbine oscillator, oscillating at 2300rpm for 5min to mix thoroughly and perform back extraction; then, placing the centrifugal tube into a centrifuge, centrifuging for 5min at the rotating speed of 2000rpm to separate an organic phase from a water phase, taking the lower-layer water phase, and properly diluting the lower-layer water phase to obtain a sample extracting solution to be detected;
(3) Preparation of an ion chromatograph: the anion chromatographic column was correctly loaded into an ion chromatograph, and 1.8mmol/L Na was added 2 CO 3 -1.0mmol/L NaHCO 3 Pouring the solution into a washing bottle correctly;
(4) Turning on the power supply of the instrument, and lighting an indicator light; opening the computer and starting the IC NET 2.3 software; a System for opening a main window; opening a system method site; clicking Open, starting a pump and starting operation; setting the flow of the leaching solution: 0.8mL/min; column temperature: 30 ℃; sample introduction amount: 20 mu L of the solution; pressure: 13.5MPa; a base line is taken;
(5) Placing the solution to be tested in a sample tray;
(6) When the baseline is stable, selecting Start determination in a Control menu in a system window, continuously recording a white window of the baseline, starting sample injection when the color of the window is changed from white to green, and simultaneously starting data recording;
(7) After the analysis is finished, selecting Stop determination in a Control menu in a system window; then entering a qualitative analysis stage and a quantitative analysis stage; using retention time comparison, i.e. comparing DBP, MBP, n-C 4 H 9 COO - 、NO 3 - And NO 2 - Determining the retention time of each substance in the standard sample spectrogram and the mixed standard sample solution spectrogram, and determining the peak corresponding to each substance in the mixed solution; comparison of DBP, MBP, n-C 4 H 9 COO - 、NO 3 - And NO 2 - Determining the retention time of each peak of the standard sample spectrogram and the spectrogram of the sample to be detected, and determining whether DBP, MBP and n-C corresponding to the sample exist or not 4 H 9 COO - 、NO 3 - And NO 2 - Peak, thereby determining the presence or absence of DBP, MBP, n-C in the sample 4 H 9 COO - 、NO 3 - And NO 2 - (ii) a The quantitative analysis adopts an external standard method, namely a quantitative sample introduction-working curve method; the quantitative sample introduction-working curve method comprises the following steps: under the same operation conditions, a series of DBP, MBP and n-C with different concentrations are respectively injected into the sample by an automatic sample injector in a quantitative mode 4 H 9 COO - 、NO 3 - And NO 2 - Obtaining the peak area of each component, and then respectively drawing a DBP peak area-DBP concentration diagram, an MBP peak area-MBP concentration diagram and n-C 4 H 9 COO - Peak area-n-C 4 H 9 COO - Concentration profile, NO 3 - Peak area-NO 3 - Concentration profile and NO 2 - Peak area-NO 2 - Concentration patterns, i.e. DBP, MBP, n-C 4 H 9 COO - 、NO 3 - And NO 2 - The working curve of (a); under the same analysis conditions, quantitatively injecting a sample to be analyzed; if the sample contains DBP, MBP, n-C 4 H 9 COO - 、 NO 3 - And NO 2 - DBP, MBP, n-C appeared at about 10.55min, 33.96min, 7.71min, 18.17min and 12.17min, respectively 4 H 9 COO - 、NO 3 - And NO 2 - A peak; according to DBP, MBP, n-C 4 H 9 COO - 、NO 3 - And NO 2 - The DBP, MBP and n-C in the sample to be measured can be calculated by utilizing the working curve and the dilution multiple of the sample 4 H 9 COO - 、NO 3 - And NO 2 - The concentration of (c).
In this example, the data is obtained by applying DBP, MBP, n-C 4 H 9 COO - 、NO 3 - And NO 2 - Analyzing the mixed characteristic sample solution by ion chromatography to obtain DBP, MBP, n-C 4 H 9 COO - 、NO 3 - And NO 2 - See fig. 1. By measuring the ionic color of the extract of the sampleAnd (4) performing spectrum analysis to obtain an ion chromatogram of the mixture to be detected sample extract, which is shown in figure 7. Comparing the chromatogram of the graph with that of a standard mixed sample, the following can be found: the sample contains DBP, MBP, n-C 4 H 9 COO - And NO 3 - But does not contain NO 2 - . And (3) drawing a DBP standard working curve by taking the DBP concentration as an abscissa and the corresponding peak area as an ordinate: y =49.411X-8.418, correlation coefficient (R) 2 )：R 2 =0.9994, see fig. 2; and (3) drawing an MBP standard working curve by taking the concentration of the MBP as an abscissa and the corresponding peak area as an ordinate: y =5.3243X +0.5958 2 =0.9986, see fig. 3; with n-C 4 H 9 COO - The concentration is the abscissa, the corresponding peak area is the ordinate, and n-C is drawn 4 H 9 COO - Standard working curve: y =1.4036X +0.0394 2 =0.9997, see fig. 4; with NO 3 - The concentration is plotted as abscissa and the corresponding peak area is plotted as ordinate 3 - Standard working curve: y =11.451X-12.434 2 =0.9990, see fig. 5; wherein X is DBP, MBP, n-C 4 H 9 COO - And NO 3 - The concentration of the solution is 10 -5 、10 -6 、10 -6 And 10 -4 mol/L; y is the corresponding peak area in mv s. DBP, MBP, n-C contained in the sample to be detected can be obtained through the ion chromatogram map (figure 7) of the sample to be detected 4 H 9 COO - And NO 3 - Peak area of (a). Then, based on DBP, MBP, n-C 4 H 9 COO - And NO 3 - The standard curve and the dilution multiple of the sample are used for calculating DBP, MBP and n-C in the sample to be detected 4 H 9 COO - And NO 3 - The concentration of (c). The results are shown in table 1 below:
TABLE 1 DBP, MBP, n-C in the samples to be tested 4 H 9 COO - And NO 3 - Retention time, peak area and concentration of
| Retention time (min) | Peak area (mv. S) | Concentration (mol/L) | |
| n-C 4 H 9 COO - | 7.69 | 3.05 | 0.001 |
| DBP | 10.72 | 412.70 | 0.043 |
| NO 3 - | 18.15 | 18087.26 | 0.790 |
| MBP | 34.18 | 12.76 | 0.001 |
The method of the embodiment can realize the DBP, MBP and n-C in the complex phase 4 H 9 COO - 、NO 3 - And NO 2 - Simultaneously, quickly and accuratelyAnd (5) performing qualitative and quantitative analysis.
As described above, the above examples simultaneously and rapidly analyze dibutyl phosphate (DBP), monobutyl phosphate (MBP), and n-C 4 H 9 COO - 、NO 3 - And NO 2 - The method of (1) is that DBP, MBP, n-C are first mixed 4 H 9 COOH、KNO 3 And NaNO 2 Dissolving the standard substance in pure water to obtain standard stock solution, preparing sample solutions with different concentrations, analyzing by ion chromatography to obtain ion chromatography standard spectrogram and peak area of corresponding component, and drawing DBP, MBP, n-C 4 H 9 COO - 、NO 3 - And NO 2 - A standard working curve; centrifuging the sample to be tested, extracting the upper organic phase, and using a quantitative 1wt.% Na 2 Carrying out back extraction elution on a certain amount of organic phase obtained by separation by using CO and 1wt.% of NaOH aqueous solution, then carrying out centrifugal separation, extracting a lower-layer aqueous phase, and properly diluting; then carrying out ion chromatography analysis under the same analysis conditions of the ion chromatography to obtain peak areas of corresponding components in the ion chromatogram of the extracting solution of the sample to be detected, and calculating to obtain DBP, MBP and n-C in the organic phase of the sample to be detected by using the standard working curve and the dilution multiple of the sample to be detected 4 H 9 COO - 、NO 3 - And NO 2 - And (4) concentration. The invention adopts ion chromatography, and can simultaneously and rapidly analyze DBP, MBP and n-C 4 H 9 COO - 、NO 3 - And NO 2 - High sensitivity, low detection limit and good repeatability.
The embodiments of the present invention have been described with reference to the accompanying drawings, but the present invention is not limited to the embodiments, and various changes and modifications can be made according to the purpose of the invention, and any changes, modifications, substitutions, combinations or simplifications made according to the spirit and principle of the technical solution of the present invention shall be equivalent substitutions, as long as the purpose of the present invention is met, and the present invention shall fall within the protection scope of the present invention without departing from the technical principle and inventive concept of the present invention.
Claims (2)
1. Rapid analysis of dibutyl phosphate, monobutyl phosphate, n-butyric acid and NO simultaneously 3 - And NO 2 - The method is characterized in that: analyzing dibutyl phosphate DBP, monobutyl phosphate MBP and n-butyl acid radical ion n-C by ion chromatography 4 H 9 COO - 、NO 3 - And NO 2 - The method comprises the following steps:
①DBP、MBP、n-C 4 H 9 COO - 、NO 3 - and NO 2 - Drawing a standard curve:
mixing DBP, MBP, n-C 4 H 9 COOH、KNO 3 And NaNO 2 Respectively dissolving the standard substances in ultrapure water to obtain corresponding standard solutions; then, if necessary, DBP, MBP, n-C are added 4 H 9 COOH、KNO 3 And NaNO 2 The standard solution is diluted into standard test solutions with different concentrations to be respectively used as DBP, MBP and n-C 4 H 9 COOH、KNO 3 And NaNO 2 Characterizing the sample solution by applying different concentrations of DBP, MBP, n-C 4 H 9 COOH、KNO 3 And NaNO 2 Analyzing the characteristic sample solution by ion chromatography to obtain DBP, MBP, n-C 4 H 9 COOH、KNO 3 And NaNO 2 Ion chromatography standard spectrogram of the characteristic sample solution and peak areas of corresponding components; respectively with DBP, MBP, n-C 4 H 9 COO - 、NO 3 - And NO 2 - The concentration is the abscissa, the corresponding peak area is the ordinate, and DBP, MBP and n-C are drawn 4 H 9 COO - 、NO 3 - And NO 2 - Standard working curve:
y = aX + b, wherein: x is DBP, MBP, n-C 4 H 9 COO - 、NO 3 - Or NO 2 - The molar concentration of the solution, Y is the corresponding peak area, and a and b are dimensionless coefficients;
(2) pretreatment of a sample to be detected:
taking 4mL of sample to be tested in a 13mL centrifuge tube, then,placing the centrifugal tube into a centrifuge, and centrifuging for at least 5min at the rotating speed of not less than 2000 rpm; then taking 1mL of the upper organic phase to be put into another 13mL centrifuge tube, and adding 5mL of Na with the mass concentration of 1wt.% 2 CO 3 And 1wt.% aqueous NaOH; then, putting the centrifugal tube into a turbine oscillator, oscillating for at least 5min at the rotating speed of not less than 2300rpm so as to fully mix and back-extract; then placing the centrifugal tube into a centrifuge, centrifuging for at least 5min at the rotating speed of not less than 2000rpm, taking the lower-layer water phase for diluting, and taking the diluted lower-layer water phase as a sample extracting solution to be detected;
(3) ion chromatography analysis of the sample extract to be tested:
DBP, MBP, n-C in step (1) 4 H 9 COOH、KNO 3 And NaNO 2 Under the condition of the same analysis of characteristic sample solution, carrying out ion chromatography analysis on the extract of the sample to be detected to obtain DBP, MBP and n-C in the extract of the sample to be detected 4 H 9 COO - 、NO 3 - And NO 2 - Using the peak area of DBP, MBP, n-C obtained in step (1) 4 H 9 COO - 、NO 3 - And NO 2 - The standard working curve can be calculated to obtain DBP, MBP and n-C in the extract of the sample to be detected 4 H 9 COO - 、NO 3 - And NO 2 - Concentration;
in the step (1), DBP, MBP, n-C are rapidly analyzed simultaneously 4 H 9 COO - 、NO 3 - And NO 2 - The analysis conditions of the ion chromatography of the method are as follows:
a. a chromatographic column: metrosepAsuppp 5-250, 250 mm. Times.4.0 mm;
b. sample injection amount: 20 mu L of the solution;
c. concentration of the leacheate: 1.8mmol/LNa 2 CO 3 -1.0mmol/LNaHCO 3 ；
d. Flow rate of eluent: 0.8mL/min;
e. column temperature: 30 ℃;
f. a detector: a conductivity detector.
2. The method of claim 1 for simultaneously and rapidly analyzing dibutyl phosphate, monobutyl phosphate, n-butyric acid and NO 3 - And NO 2 - The method of (2), characterized by: the sample to be detected is spent fuel post-treatment fluid TBP and HNO 3 The mixture after the reaction.
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