CN103308475A - Method for simultaneously measuring contents of Pu (IV) and HNO3 in aftertreatment feed liquid - Google Patents
Method for simultaneously measuring contents of Pu (IV) and HNO3 in aftertreatment feed liquid Download PDFInfo
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- CN103308475A CN103308475A CN2013102867261A CN201310286726A CN103308475A CN 103308475 A CN103308475 A CN 103308475A CN 2013102867261 A CN2013102867261 A CN 2013102867261A CN 201310286726 A CN201310286726 A CN 201310286726A CN 103308475 A CN103308475 A CN 103308475A
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Abstract
The invention belongs to the technical field of analytical chemistry, and particularly relates to a method for simultaneously measuring contents of Pu (IV) and HNO3 in an aftertreatment feed liquid. The method comprises the following steps that: (1) a series of Pu (IV)-HNO3 standard solutions with different concentrations are prepared as a sample set, wherein the sample set is divided into a correction set and a verification set; (2) a near infrared spectrum of the sample set is analyzed by a near infrared spectrograph; (3) a mathematical model between spectrum data and the concentrations of Pu (IV) and HNO3 is established by a PLS (Partial Least Squares) method for the spectrum data of the correction set at wave bands of 900-1200nm and 1500-1660nm; and (4) a near infrared spectrum of an unknown sample is measured by keeping consistent with measuring conditions of sample solutions in the correction set, and the contents of Pu (IV) and HNO3 contained in the unknown sample are acquired by utilizing the model established in the step (3). The method can be used for simply, rapidly and simultaneously determining the contents of Pu (IV) and HNO3 in the aftertreatment feed liquid.
Description
Technical field
The invention belongs to technical field of analytical chemistry, be specifically related to a kind of Pu(IV in the aftertreatment feed liquid of measuring simultaneously) and HNO
3The method of content.
Background technology
The spentnuclear fuel reprocessing plant all adopts general rex (PUREX) flow process usually, mainly comprises uranium, plutonium co-decotamination cycle, uranium decontamination cycle and plutonium decontamination cycle.This flow process is utilized TBP to U (VI), Pu(IV) high extractibility realize the extraction of U, Pu, a lot of process point in the flow process all need to monitor the Pu(IV) and HNO
3Content, in order to uranium, plutonium separation case are controlled.
At present, analytical approach Pu(IV) has spectrophotometric method, α counting method, χ ray fluorescence photometry etc.Spectrophotometric method is easy, quick, but is subject to the interference of Coexisting component; The α counting method is highly sensitive, but method is loaded down with trivial details, and sample needs pre-service, and analytical cycle is long.χ ray fluorescence photometry is easy, quick, but [U]/when [Pu] is higher than 50 times, uranium will disturb the mensuration of plutonium.HNO
3Analytical approach density-conductance method, oxalates complexing-Ding pH titrimetry etc. is arranged, density-conductance method precision is relatively poor, and is multiplex in in-line analysis; PH titrimetry precision is high, accuracy good for oxalates complexing-Ding, but analytical cycle is long, and the waste liquid amount of generation is large.And above method all can not be measured the Pu(IV simultaneously) and HNO
3Content.Therefore, set up an energy while, Fast Measurement Pu(IV) and HNO
3Control analysis is very necessary for aftertreatment technology for content and analytical approach easy and simple to handle.
Summary of the invention
(1) goal of the invention
According to the existing problem of prior art, the invention provides a kind of simple, fast and can be simultaneously to Pu(IV in the aftertreatment feed liquid) and HNO
3Content carries out method for measuring.
(2) technical scheme
In order to solve the existing problem of prior art, the invention provides following technical scheme:
A kind ofly measure simultaneously Pu(IV in the aftertreatment feed liquid) and HNO
3The method of content, key be, the method may further comprise the steps:
(1) the Pu(IV of a series of variable concentrations of configuration)-HNO
3Standard solution is as sample sets, and wherein sample sets is divided into calibration set and checking collection two parts, and the ratio of the sample number that calibration set and checking integrate is as 3:1～4:1;
(2) use near infrared spectrometer that the near infrared spectrum of sample sets is analyzed, obtaining the wavelength band that the near infrared spectrum of sample selects is 896.3nm～1701.7nm, and the wavelength coverage that the near infrared spectrum data of analytic sample is selected is 900nm～1200nm and 1500nm～1660nm;
(3) calibration set is set up spectroscopic data and Pu(IV at the spectroscopic data of 900nm～1200nm and 1500nm～1660nm wave band with the PLS method) and HNO
3Mathematical model between the concentration;
(4) measuring condition with the calibration set sample solution is consistent, and measures the near infrared spectrum of unknown sample, and the model that utilizes step (3) to set up obtains the Pu(IV that contains in the unknown sample) and HNO
3Content;
Preferably, the mathematical model of utilizing step (3) to set up is verified the Pu(IV in the collection sample) and HNO
3Then concentration compare with its concentration known value, according to deviation size between the two mathematical model verified;
Preferably, when utilizing near infrared spectrometer that sample is analyzed, be 0.4ms～0.6ms selected integral time;
Preferably, when utilizing near infrared spectrometer that sample is analyzed, the temperature of sample solution is 20 ℃～60 ℃;
Preferably, when utilizing near infrared spectrometer that sample is analyzed, used optical path length is 2mm.
(3) beneficial effect
A kind ofly measure simultaneously Pu(IV in the aftertreatment feed liquid) and the method for HNO3 content, the method utilizes near infrared spectrometer at 900nm～1200nm and 1500nm～1660nm wave band sample to be analyzed, and its most significant advantage is can be simultaneously to the Pu(IV) and HNO
3Content is analyzed.This method is utilized Unscrambler software that the spectroscopic data of calibration set is processed in conjunction with the PLS method and is set up mathematical model, and this model is having significant effect aspect the identification of the elimination of background interference and Weak Absorption band.Wherein sample sets is the sample of a series of concentration known, and sample sets is used for setting up mathematical model exactly, and the set of all samples that model accuracy is verified; Calibration set is by a part of sample composition that branches away from sample sets, be used for match, set up mathematical model, modeling process adopts certain chemometrics method exactly, sets up mathematical relation according to the spectroscopic data of calibration set sample and its actual value.The checking collection is by another part sample composition of removing calibration set in the sample sets, be used for the accuracy of the mathematical model set up is carried out evaluation test, its specific practice is the model determination value that can obtain sample after the mathematical model that the spectroscopic data substitution of checking collection is set up, actual value with checking collection sample compares again, from the relative deviation size can judgment models quality.
In addition, the method also has the following advantages: (1) nondestructive analysis, and sample need not pre-service, can directly measure; (2) analytic process is simple, and is fast efficient, in the analytical cycle 3min; (3) antijamming capability is strong, and partial least square method can be eliminated the phase mutual interference of Coexisting component; (4) sampling amount is little, and each analysis only needs the 0.5mL sample.
Description of drawings
Fig. 1 is variable concentrations HNO
3Near-infrared absorption spectrum;
Fig. 2 is variable concentrations Pu(IV) near-infrared absorption spectrum;
Fig. 3 is the mathematical model evaluation map.
Embodiment
Below in conjunction with specification drawings and specific embodiments the present invention is further elaborated.
A kind ofly measure simultaneously Pu(IV in the aftertreatment feed liquid) and HNO
3The method of content, the method may further comprise the steps:
(1) the sample standard solution of a series of variable concentrations of preparation is measured Pu (IV)-U (VI)-HNO as sample sets
3Mixed system or Pu (IV)-HNO
3Pu in the system (IV) and HNO
3Content.
Adopting concentration is Pu (IV) mother liquor of 21.954g/L, U (VI) mother liquor of 245.45g/L, the HNO of 7.34mol/L
3Mother liquor is 34 modeling sample collection of preparation accurately, wherein do not contain U (VI) in 14～No. 28 samples, and 1～No. 26 sample is as calibration set, and 27～No. 34 samples are as the checking collection.Pu in the sample sets (IV) concentration range is 0.53～21.95g/L, HNO
3Concentration range is 0.17～3.97mol/L, specifically prepares the result as shown in table 1:
The configuration of table 1 modeling sample collection
| Sequence number | Acid concentration (mol/L) | Uranium concentration (g/L) | Plutonium concentration (g/L) |
| 1 | 1.30 | 1.47 | 2.01 |
| 2 | 1.30 | 1.47 | 4.00 |
| 3 | 1.00 | 1.47 | 3.00 |
| 4 | 3.00 | 16.84 | 6.28 |
| 5 | 3.97 | 16.84 | 6.28 |
| 6 | 1.26 | 1.47 | 3.00 |
| 7 | 3.50 | 16.84 | 6.28 |
| 8 | 2.14 | 15.92 | 3.14 |
| 9 | 1.03 | 35.74 | 1.50 |
| 10 | 3.04 | 28.42 | 3.14 |
| 11 | 1.75 | 30.74 | 1.50 |
| 12 | 2.73 | 15.74 | 1.50 |
| 13 | 1.65 | 5.74 | 1.50 |
| 14 | 1.13 | 0 | 8.19 |
| 15 | 2.23 | 0 | 9.97 |
| 16 | 1.67 | 0 | 12.10 |
| 17 | 0.64 | 0 | 1.07 |
| 18 | 2.06 | 0 | 14.95 |
| 19 | 0.59 | 0 | 4.27 |
| 20 | 3.52 | 0 | 6.05 |
| 21 | 2.94 | 0 | 21.95 |
| 22 | 0.17 | 0 | 0.53 |
| 23 | 0.44 | 0 | 1.42 |
| 24 | 0.42 | 0 | 3.07 |
| 25 | 0.62 | 0 | 4.49 |
| 26 | 0.77 | 0 | 5.61 |
| 27 | 2.20 | 0 | 7.12 |
| 28 | 1.71 | 0 | 8.90 |
| 29 | 1.30 | 1.47 | 3.00 |
| 30 | 2.00 | 1.47 | 3.00 |
| 31 | 3.50 | 16.84 | 6.28 |
| 32 | 3.50 | 16.84 | 5.00 |
| 33 | 2.05 | 23.24 | 2.00 |
| 34 | 2.10 | 0.74 | 12.48 |
(2) use near infrared spectrometer that the sample sets sample is analyzed, and utilize spectroscopic data and Pu (IV), the HNO of calibration set
3The concentration known value carry out modeling
Under 25 ℃ of room temperatures, take water as reference, the characteristic absorption peak of Pu (IV) is positioned at the 900nm-1200nm place, such as Fig. 1, because HNO
3Have absorption at 1500nm～1660nm place, such as Fig. 2, and there be strong the absorption in water at 1400nm～1500nm place.Therefore, the wavelength of selecting during to the sample sets analytic sample is selected 900nm～1200nm and 1500nm～1660nm, reduces the interference of water absorption peak.Scanning integral time is 0.52ms, and the scanning average time is 500 times, and light path is 2mm, and the temperature of sample solution is 20 ℃.
Adopt the spectroscopic data of calibration set to set up spectroscopic data and Pu(IV with the PLS method) and HNO
3Mathematical model between the concentration, 125 of modeling wavelength points data bit are used the PLS modeling, and the modeling result figure is reported as shown in Figure 3, has comprised principal component scores, regression coefficient, modeling factor number and the matched curve of actual value VS predicted value.
The parameters of model is as shown in table 2, and calibration standard deviation SEC and checking collection standard deviation S EP are smaller, coefficient R
2All near 1.0, have good linear dependence, near infrared spectroscopy Rapid Simultaneous Determination Pu (IV) and HNO are described
3The mathematical model of content is comparatively desirable.
Table 2 model evaluation parameter list
| ? | SEC | SEP | R 2 | The main cause subnumber |
| Pu(Ⅳ) | 0.0908 | 0.0960 | 0.9996 | 4 |
| HNO 3 | 0.0875 | 0.0922 | 0.9934 | 4 |
(3) checking collection checking mathematical model
With the near infrared spectrum data substitution model of checking collection sample, with Pu (IV) and HNO in the model prediction sample
3Content, the difference of contrast model measured value and chemical reference value, the accuracy of investigation model the results are shown in table 3.
Table 3 model determination result
(4) applied mathematical model working sample
Under the measuring condition identical with modeling sample, gather the near infrared spectrum of unknown sample, utilize the content of the mathematical model working sample of having set up.
(5) maintenance of mathematical model
When carrying out conventional analysis, when the contained information of sample exceeded model scope, the reply model safeguarded to guarantee the accuracy of model.Model maintenance method commonly used is to add fresh sample and adjust built model slope/intercept.
The result shows, uses Pu (IV) and HNO in simultaneously express-analysis of the near infrared spectroscopy aftertreatment technology
3The method of content is simple, accurate, practical reliable.
Method, the step used with embodiment 1 are identical, and different is used scanning integral time, the temperature of sample was different during from analytic sample, such as following table:
The scanning integral time that table 4 is different and analytic sample thermometer
| ? | Scan integral | Sample temperature | |
| 1 | 0.4ms | 40 |
|
| 2 | 0.6ms | 60℃ |
Utilize above parameter, adopt method and step among the embodiment 1 that sample is analyzed, the result shows, uses Pu (IV) and HNO in simultaneously express-analysis of the near infrared spectroscopy aftertreatment technology
3The method of content is simple, accurate, practical reliable.
Claims (5)
1. measure simultaneously Pu(IV in the aftertreatment feed liquid for one kind) and HNO
3The method of content, key be, the method may further comprise the steps:
(1) the Pu(IV of a series of variable concentrations of configuration)-HNO
3Standard solution is as sample sets, and wherein sample sets is divided into calibration set and checking collection two parts, and the ratio of the sample number that calibration set and checking integrate is as 3:1～4:1;
(2) use near infrared spectrometer that the near infrared spectrum of sample sets is analyzed, obtaining the wavelength band that the near infrared spectrum of sample selects is 896.3nm～1701.7nm, and the wavelength coverage that the near infrared spectrum data of analytic sample is selected is 900nm～1200nm and 1500nm～1660nm;
(3) calibration set is set up spectroscopic data and Pu(IV at the spectroscopic data of 900nm～1200nm and 1500nm～1660nm wave band with the PLS method) and HNO
3Mathematical model between the concentration;
(4) measuring condition with the calibration set sample solution is consistent, and measures the near infrared spectrum of unknown sample, and the model that utilizes step (3) to set up obtains the Pu(IV that contains in the unknown sample) and HNO
3Content.
A kind of Pu(IV in the aftertreatment feed liquid of measuring simultaneously according to claim 1) and HNO 2.
3The method of content is characterized in that, the mathematical model of utilizing step (3) to set up is verified the Pu(IV in the collection sample) and HNO
3Concentration, then the concentration known value with checking collection sample compares, and according to deviation size between the two mathematical model is verified.
A kind of Pu(IV in the aftertreatment feed liquid of measuring simultaneously according to claim 1) and HNO 3.
3The method of content is characterized in that, when utilizing near infrared spectrometer that sample is analyzed, be 0.4ms～0.6ms selected integral time.
A kind of Pu(IV in the aftertreatment feed liquid of measuring simultaneously according to claim 1) and HNO 4.
3The method of content is characterized in that, when utilizing near infrared spectrometer that sample is analyzed, the temperature of sample solution is 20 ℃～60 ℃.
A kind of Pu(IV in the aftertreatment feed liquid of measuring simultaneously according to claim 1) and HNO 5.
3The method of content is characterized in that, when utilizing near infrared spectrometer that sample is analyzed, used optical path length is 2mm.
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Cited By (6)
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| CN104316510A (en) * | 2014-10-29 | 2015-01-28 | 中国原子能科学研究院 | Raman spectrum analysis method of sexivalent uranium |
| CN110530906A (en) * | 2019-08-14 | 2019-12-03 | 中国原子能科学研究院 | The measuring method of plutonium concentration in a kind of spent fuel solution |
| CN112630177A (en) * | 2020-12-31 | 2021-04-09 | 中国原子能科学研究院 | Method for analyzing content of uranium, plutonium and nitric acid in organic phase |
| CN112763449A (en) * | 2020-12-14 | 2021-05-07 | 中国原子能科学研究院 | Method for simultaneously determining neptunium and plutonium concentrations in nitric acid-containing solution |
| CN113092404A (en) * | 2021-03-16 | 2021-07-09 | 中国原子能科学研究院 | Method for measuring concentration of crown ether |
| CN113324929A (en) * | 2021-05-14 | 2021-08-31 | 中国原子能科学研究院 | Uranium concentration analysis method, analysis system, analysis model and construction method |
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| CN102252980A (en) * | 2011-04-19 | 2011-11-23 | 中国原子能科学研究院 | Direct determination U, HNO3、HNO2Method for mixing component concentrations |
| CN102445428A (en) * | 2011-09-19 | 2012-05-09 | 中国原子能科学研究院 | Analytical method of tetravalent uranium |
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Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104316510A (en) * | 2014-10-29 | 2015-01-28 | 中国原子能科学研究院 | Raman spectrum analysis method of sexivalent uranium |
| CN110530906A (en) * | 2019-08-14 | 2019-12-03 | 中国原子能科学研究院 | The measuring method of plutonium concentration in a kind of spent fuel solution |
| CN112763449A (en) * | 2020-12-14 | 2021-05-07 | 中国原子能科学研究院 | Method for simultaneously determining neptunium and plutonium concentrations in nitric acid-containing solution |
| CN112630177A (en) * | 2020-12-31 | 2021-04-09 | 中国原子能科学研究院 | Method for analyzing content of uranium, plutonium and nitric acid in organic phase |
| CN113092404A (en) * | 2021-03-16 | 2021-07-09 | 中国原子能科学研究院 | Method for measuring concentration of crown ether |
| CN113324929A (en) * | 2021-05-14 | 2021-08-31 | 中国原子能科学研究院 | Uranium concentration analysis method, analysis system, analysis model and construction method |
| CN113324929B (en) * | 2021-05-14 | 2023-03-07 | 中国原子能科学研究院 | Uranium concentration analysis method, analysis system, analysis model and construction method |
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Application publication date: 20130918 |