CN114264683B - Comparison filter membrane for measuring iron content in water by X-ray fluorescence, preparation method and application thereof, and measuring method for iron content in water of nuclear power station - Google Patents
Comparison filter membrane for measuring iron content in water by X-ray fluorescence, preparation method and application thereof, and measuring method for iron content in water of nuclear power station Download PDFInfo
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- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 title claims abstract description 157
- 239000012528 membrane Substances 0.000 title claims abstract description 146
- 229910052742 iron Inorganic materials 0.000 title claims abstract description 66
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 title claims abstract description 28
- 238000002360 preparation method Methods 0.000 title claims abstract description 22
- 238000004876 x-ray fluorescence Methods 0.000 title claims abstract description 20
- 238000000034 method Methods 0.000 title claims description 42
- 238000001914 filtration Methods 0.000 claims abstract description 32
- 238000005303 weighing Methods 0.000 claims abstract description 20
- 239000000725 suspension Substances 0.000 claims abstract description 19
- 238000001035 drying Methods 0.000 claims abstract description 14
- 238000005070 sampling Methods 0.000 claims abstract description 13
- 238000009681 x-ray fluorescence measurement Methods 0.000 claims abstract description 5
- 238000005259 measurement Methods 0.000 claims description 17
- 230000003595 spectral effect Effects 0.000 claims description 17
- 238000012417 linear regression Methods 0.000 claims description 13
- -1 polytetrafluoroethylene Polymers 0.000 claims description 8
- 229920001343 polytetrafluoroethylene Polymers 0.000 claims description 8
- 239000004810 polytetrafluoroethylene Substances 0.000 claims description 8
- 239000000020 Nitrocellulose Substances 0.000 claims description 7
- 238000001479 atomic absorption spectroscopy Methods 0.000 claims description 7
- 238000001514 detection method Methods 0.000 claims description 7
- SZVJSHCCFOBDDC-UHFFFAOYSA-N ferrosoferric oxide Chemical group O=[Fe]O[Fe]O[Fe]=O SZVJSHCCFOBDDC-UHFFFAOYSA-N 0.000 claims description 7
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N iron oxide Inorganic materials [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 claims description 7
- 239000000463 material Substances 0.000 claims description 7
- 238000000120 microwave digestion Methods 0.000 claims description 7
- 229920001220 nitrocellulos Polymers 0.000 claims description 7
- NDLPOXTZKUMGOV-UHFFFAOYSA-N oxo(oxoferriooxy)iron hydrate Chemical compound O.O=[Fe]O[Fe]=O NDLPOXTZKUMGOV-UHFFFAOYSA-N 0.000 claims description 7
- 239000012498 ultrapure water Substances 0.000 claims description 6
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 claims description 5
- 229910052796 boron Inorganic materials 0.000 claims description 5
- 239000011521 glass Substances 0.000 claims description 5
- 238000010183 spectrum analysis Methods 0.000 claims description 4
- 238000001132 ultrasonic dispersion Methods 0.000 claims description 4
- 238000002604 ultrasonography Methods 0.000 claims description 4
- 239000013078 crystal Substances 0.000 claims description 3
- 239000011148 porous material Substances 0.000 claims description 3
- 239000000126 substance Substances 0.000 claims description 3
- 239000006185 dispersion Substances 0.000 claims description 2
- 238000012795 verification Methods 0.000 claims description 2
- 238000004445 quantitative analysis Methods 0.000 abstract description 7
- 230000008901 benefit Effects 0.000 abstract description 6
- 239000011159 matrix material Substances 0.000 abstract description 4
- 238000004846 x-ray emission Methods 0.000 description 16
- 238000004458 analytical method Methods 0.000 description 9
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 4
- QZPSXPBJTPJTSZ-UHFFFAOYSA-N aqua regia Chemical compound Cl.O[N+]([O-])=O QZPSXPBJTPJTSZ-UHFFFAOYSA-N 0.000 description 4
- 230000007797 corrosion Effects 0.000 description 4
- 238000005260 corrosion Methods 0.000 description 4
- 230000029087 digestion Effects 0.000 description 4
- 238000010812 external standard method Methods 0.000 description 4
- 229910017604 nitric acid Inorganic materials 0.000 description 4
- 239000012080 ambient air Substances 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 230000007613 environmental effect Effects 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 239000002245 particle Substances 0.000 description 3
- 238000010521 absorption reaction Methods 0.000 description 2
- 239000003570 air Substances 0.000 description 2
- 238000004364 calculation method Methods 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 238000001755 magnetron sputter deposition Methods 0.000 description 2
- 238000012544 monitoring process Methods 0.000 description 2
- 239000013618 particulate matter Substances 0.000 description 2
- 238000005507 spraying Methods 0.000 description 2
- 238000004544 sputter deposition Methods 0.000 description 2
- 238000000967 suction filtration Methods 0.000 description 2
- 238000000862 absorption spectrum Methods 0.000 description 1
- 238000009825 accumulation Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 230000001066 destructive effect Effects 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 230000005389 magnetism Effects 0.000 description 1
- 238000000691 measurement method Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 238000003908 quality control method Methods 0.000 description 1
- 230000000717 retained effect Effects 0.000 description 1
- 239000010865 sewage Substances 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 229910021642 ultra pure water Inorganic materials 0.000 description 1
- 238000005145 wavelength dispersive X-ray fluorescence spectroscopy Methods 0.000 description 1
Classifications
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E30/00—Energy generation of nuclear origin
- Y02E30/30—Nuclear fission reactors
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- Analysing Materials By The Use Of Radiation (AREA)
Abstract
The invention discloses a preparation method of a comparison filter membrane for measuring the iron content in water by X-ray fluorescence, which comprises the following steps: drying the filtering membrane and weighing; installing the dried filtering membrane into a filter; dispersing a plurality of sets of oxides in water to form a plurality of sets of suspensions; transferring a plurality of groups of the suspensions into the filters respectively, and filtering respectively; taking out the filtering membrane after the filtering is finished, and weighing after drying; and verifying the filtering membrane, and if the filtering membrane is qualified, quantitatively measuring the iron content in the nuclear power station, namely, comparing the filtering membrane. The preparation method of the comparison filter membrane for the X-ray fluorescence measurement of the iron content in water has the advantages of short preparation time, simple preparation process, good stability of the comparison filter membrane, basically consistent with the matrix of the accumulated sampling filter membrane in the secondary loop of the nuclear power station, and can be used for quantitative analysis of the external standard of the iron content in the filter membrane of the nuclear power station by XRF measurement.
Description
Technical Field
The invention relates to a method for measuring the iron content of feed water in a secondary loop of a nuclear power plant, in particular to a method for preparing a comparison filter membrane used when the iron content of a feed water accumulated sampling filter membrane is measured by an X-ray fluorescence spectrometry, the comparison filter membrane prepared by the preparation method, application of the comparison filter membrane, and a method for measuring the iron content of water in the nuclear power plant by adopting the comparison filter membrane.
Background
The main water supply iron concentration of the secondary loop of the nuclear power station is used as an important parameter for representing corrosion of materials of the secondary loop system, at present, an online sample water accumulation technology is generally adopted to sample suspended iron corrosion products, the iron corrosion products in enough volume of sample water are collected in a nitrocellulose membrane with the aperture of 0.45 mu m, aqua regia is used for dissolving or nitric acid microwave digestion, then the iron concentration is measured by an atomic absorption method, and then the iron corrosion products are converted into the iron content of the sample water. In the implementation process of the method, aqua regia or nitric acid is needed to digest the filter membrane, so that the risk of dangerous chemical operation is increased, the digestion process is long in time consumption and large in workload, in addition, the nitrocellulose filter membrane can not be completely dissolved sometimes, a certain fibrous filiform matters still exist, and a sampling tube and an atomizer of an atomic absorption analysis instrument are blocked, so that equipment is damaged.
The X-ray fluorescence spectrometry (XRF) can realize multi-element, rapid, direct, nondestructive and accurate analysis of filter membrane samples, can accurately acquire the content information of the multiple elements in the samples by one-time measurement without destructive processing of the samples, greatly shortens the analysis period, has lower analysis cost, and has obvious advantages for multi-element qualitative and semi-quantitative measurement of large-batch samples. However, if quantitative analysis is performed, a proper detection method and support for standard samples are required, otherwise the accuracy of measurement is poor.
The method for quantitatively measuring the element content in the filter membrane by XRF has been applied to real-time monitoring and emergency monitoring of atmospheric environmental pollution. The environmental protection department issued two XRF measurement standards for the content of inorganic elements in air in 2017, namely HJ 829 'energy dispersion X-ray fluorescence spectrometry for measuring inorganic elements in environmental air particulate matters'; HJ 830 "determination of inorganic elements in ambient air particulate matter wavelength dispersive X-ray fluorescence Spectroscopy". The two standards prescribe an XRF analysis method for measuring energy scattering and wavelength scattering of inorganic elements in ambient air and the unorganized discharged particulate matters, the standards are suitable for quantitative analysis of the contents of Na-Sb and other elements in the ambient air and the unorganized discharged particulate matters collected by using a filter membrane, the quantitative analysis method is an external standard method, namely a series of standard filter membranes with evidence are used, and element measurement in the filter membranes is carried out after a standard curve is drawn.
But the crystal structure of the oxide in the sampling filter membrane in the secondary loop main water supply of the nuclear power station is ferric oxide, and the ferric oxide of the oxide in the sampling filter membrane in the secondary loop sewage. The particle size of the oxide particles is between 0.5 and 1 mu m. The Fe mass per unit area of the surface of the filter membrane reaches 1000 mug/cm 2 Even up to 4500. Mu.g/cm 2 . This is quite different from the filter membrane standard used in the environmental field for quantitative measurement of elemental content in particulate matter in the atmosphere. In order to ensure the accuracy of quantitative measurement and avoid the deviation of matrix benefit and filter membrane thickness on measurement, the filter membrane standard (or comparison filter membrane) used in the process of carrying out quantitative measurement of the Fe content XRF in the nuclear power filter membrane must be similar to the characteristics of the filter membrane of the power plant. However, no standard filter membrane similar to a nuclear power filter membrane exists in the market at present, in order to accurately measure the Fe content in the filter membrane, the problems of a preparation technology, a process, a flow and the like of a comparison filter membrane sample are solved by aiming at the characteristics of the nuclear power filter membrane, a reasonable comparison filter membrane sample preparation mode is provided, and a series of comparison filter membrane samples which are necessary for quantitative analysis of iron element XRF in a nuclear power station are prepared.
The existing preparation process of the comparative filter membrane sample comprises a flat-plate dropping method, a spray coating method, a magnetron sputtering method, a radio frequency sputtering method and the like, and the method has the following problems:
(1) The unit area and the mass of the comparison filter membrane obtained by the drip method are lower, generally 10 mug/cm 2 The difference between the filter membrane and the nuclear power secondary loop filter membrane is larger;
(2) The methods such as spray coating, magnetron sputtering, radio frequency sputtering and the like have the defects of complex process, high equipment requirement, difficult realization and the like, and the influence of human factors is large, so that the obtained comparison filter membrane has poor stability.
Disclosure of Invention
In view of the above, in order to overcome the defects of the prior art, one of the purposes of the present invention is to provide a method for preparing a comparison filter membrane for measuring the iron content in water by using X-ray fluorescence.
In order to achieve the above purpose, the present invention adopts the following technical scheme:
the preparation method of the comparison filter membrane for the X-ray fluorescence measurement of the iron content in water comprises the following steps:
drying the filtering membrane and weighing; installing the dried filtering membrane into a filter;
dispersing a plurality of sets of oxides in water to form a plurality of sets of suspensions;
transferring a plurality of groups of the suspensions into the filters respectively, and filtering respectively;
taking out the filtering membrane after the filtering is finished, weighing after drying, and converting the ratio of Fe element in the oxide chemical molecule into Fe mass in unit area;
and verifying the filtering membrane, and if the filtering membrane is qualified, quantitatively measuring the iron content in the nuclear power station, namely, comparing the filtering membrane.
According to some preferred embodiments of the invention, the verification comprises the steps of: measuring the net peak height value of the characteristic spectral line of the iron element K alpha 1 by using X-ray fluorescence, and quantifying the mass of iron on the unit area of the filtering membrane;
and drawing a standard curve by taking the net peak height value of the characteristic spectral line of the iron element K alpha 1 as a Y axis and the mass of iron on the unit area of the filtering membrane as an X axis, and calculating a linear regression coefficient, and if the linear regression coefficient reaches a set standard, verifying to be qualified.
According to some preferred implementations of the invention, the set criterion is that the linear regression coefficient of the standard curve reaches 0.99 and above.
According to some preferred embodiments of the invention, the quantitative measurement of iron mass per unit area of the filter membrane is to quantitatively determine iron mass per unit area of the filter membrane by using a weighing method or a microwave digestion and atomic absorption spectrometry method.
According to some preferred embodiments of the invention, the plurality of sets of oxides comprises at least five sets of oxides of different mass, the mass of the oxides being weighed between 0 and 120 mg. And the range settings of the content and gradient need to include the iron content in the final detected sample to get a more accurate result.
According to some preferred embodiments of the invention, the crystal structure of the oxide is ferroferric oxide and ferric oxide, D 50 The grain diameter is 0.5-1 mu m, and the purity is analytically pure or above.
According to some preferred embodiments of the invention, the diameter of the comparison filter membrane is 25-47 mm, so as to ensure that the size of the prepared comparison filter membrane is consistent with that of a filter membrane used in a power plant, and the comparison filter membrane is made of nitrocellulose.
According to some preferred embodiments of the invention, the filter pore size of the alignment filter is in the order of nanometers, preferably below 500 nanometers, to ensure that the majority of the oxide is retained by the filter.
According to some preferred embodiments of the invention, the filter is a sand core filter, and the material is high boron glass or polytetrafluoroethylene; the diameter of the sand core is 25-47 mm and is matched with the diameter of the filter membrane; the volume is 1L to 5L.
According to some preferred embodiments of the invention, the drying is performed at a temperature of 40-55deg.C, and care is taken to control the drying temperature to avoid damage to the filter membrane due to curling caused by high temperature.
According to some preferred embodiments of the invention, the dispersing is carried out under the action of ultrasound, the ultrasound time is 3-5 min, and the power is 1kw.
According to some preferred embodiments of the invention, the suspension is formulated by transferring the oxide in its entirety into a suitable vessel, adding a suitable amount of high purity water to the vessel, and sonicating for a period of time to form a uniform suspension. The material of the container is high boron glass or polytetrafluoroethylene; the volume is 1L to 5L. The addition amount of the high-purity water is 100-1000 mL.
According to some preferred embodiments of the invention, a polytetrafluoroethylene container is used if the oxide type is ferric oxide, and a high boron glass container is used if the oxide type is ferric oxide. Because the ferroferric oxide has magnetism, polytetrafluoroethylene vessels are needed when the ferroferric oxide is used for preparing the suspension, so that the adsorption of suspended oxide particles on the surface of a container is reduced.
In some embodiments of the present invention, the preparation method specifically includes the following steps:
1) Preparing a filtering membrane made of nitrocellulose and having a filtering aperture of nano-scale, accurately weighing the mass after drying, and recording as M 0 ；
2) Installing the filter membrane in a sand core filter matched with the diameter of the filter membrane;
3) Accurately weighing a series of oxides with different mass, and recording the mass as M 1 ；
4) Transferring all the oxides into a proper container, adding a proper amount of high-purity water into the container, and performing ultrasonic dispersion for a certain time to form a uniform suspension;
5) Transferring the suspension into an upper container of the sand core filter, starting a vacuum suction pump, and sucking all the suspension in the upper container of the sand core filter to the surface of a filter membrane;
6) Taking out the filter membrane after the suction is finished, accurately weighing the mass of the filter membrane after the drying, and recording the mass as M 2 ；
7) Measuring net peak height value (cps/mA) of characteristic spectral line of iron element K alpha 1 by X-ray fluorescence, and measuring iron mass (mug/cm) per unit area of filter membrane by using weighing method or microwave digestion and atomic absorption spectrometry 2 ) And (5) accurately determining the value.
The net peak height value (cps/mA) of characteristic spectral line of iron element K alpha 1 is taken as the Y axis, and the unit area iron mass (mug/cm) of the filter membrane is taken as the filter membrane 2 ) And drawing a standard curve for the X axis, and calculating a linear regression coefficient, wherein if the linear regression coefficient reaches 0.99 or more, the prepared series of comparison filter membranes can be used for quantitatively measuring the iron content of the nuclear power station.
Iron mass per unit area (mug/cm) of filter membrane is measured by adopting weighing method 2 ) When accurate value determination is carried out, the unit area iron mass of the filter membrane is= (M) 2 -M 0 ) X (X is 0.72 if ferroferric oxide is used and 0.7 if ferric oxide is used). M is M 1 Only data is recorded and no calculation is participated.
According to some preferred embodiments of the invention, the parameters detected by X-ray fluorescence spectroscopy are: the voltage of the X-ray light tube is not lower than 40kV, the tube current is not lower than 1mA, the measurement time is not lower than 60s, and the diameter of the X-ray light spot is not lower than 30mm.
According to some preferred embodiments of the invention, the mass of iron per unit area in the plurality of aligned filters of different iron content is in the range of 0 to 4500 μg/cm 2 。
According to some preferred embodiments of the invention, the alignment filter and the sampling filter in the nuclear power plant are of the same specification.
According to some preferred embodiments of the present invention, the characteristic spectral line of the iron element is a kα1 spectral line when subjected to X-ray fluorescence spectrometry detection. The K alpha 1 spectral line has high intensity, is suitable for being used as a characteristic spectral line, and is beneficial to detection.
The invention also aims to provide an alignment filter membrane prepared by the preparation method.
It is a further object of the present invention to provide the use of an alignment filter as described above for the measurement of iron content in secondary water of a nuclear power plant.
The invention further provides a method for measuring the iron content in secondary circuit water of a nuclear power station, which comprises the following steps:
preparing a plurality of comparison filter membranes with different iron contents by adopting the preparation method, performing X-ray fluorescence spectrum analysis and detection on the comparison filter membranes, and obtaining a standard curve equation according to detection results;
and measuring the net peak height value of the characteristic spectral line of the iron element in the secondary water accumulated sampling filter membrane by using an X-ray fluorescence spectrum analysis method, and substituting the net peak height value into the standard curve equation to obtain the iron content in the sampling filter membrane.
Due to the adoption of the technical scheme, compared with the prior art, the invention has the following advantages: the preparation method of the comparison filter membrane for measuring the iron content in the water by using the X-ray fluorescence has the advantages of short preparation time, simple preparation process, good stability of the comparison filter membrane, and basically consistent with the matrix of the accumulated sampling filter membrane in the secondary loop of the nuclear power station, can be used for quantitative analysis of an external standard method for measuring the iron content in the filter membrane of the nuclear power station by using XRF, achieves the measurement accuracy of the existing digestion atomic absorption spectrometry of the power station, greatly shortens the analysis time of the power station, and avoids the industrial safety risk brought by using nitric acid or aqua regia.
Drawings
In order to more clearly illustrate the technical solutions of the embodiments of the present invention, the drawings required for the description of the embodiments will be briefly described below, and it is apparent that the drawings in the following description are only some embodiments of the present invention, and other drawings may be obtained according to these drawings without inventive effort for a person skilled in the art.
FIG. 1 is a flow chart of a method for preparing an alignment filter in a preferred embodiment of the invention;
FIG. 2 is a standard curve in the preferred embodiment 1 of the present invention.
Detailed Description
In order to make the technical solution of the present invention better understood by those skilled in the art, the technical solution of the present invention will be clearly and completely described below with reference to the accompanying drawings in the embodiments of the present invention, and it is apparent that the described embodiments are only some embodiments of the present invention, not all embodiments. All other embodiments, which can be made by those skilled in the art based on the embodiments of the present invention without making any inventive effort, shall fall within the scope of the present invention.
The preparation method specifically comprises the following steps:
1) Preparing a filtering membrane made of nitrocellulose and having a filtering aperture of nano-scale, accurately weighing the mass after drying, and recording as M 0 ；
2) Installing the filter membrane in a sand core filter matched with the diameter of the filter membrane;
3) Accurately weighing a series of oxides with different mass, and recording the mass as M 1 ；
4) Transferring all the oxides into a proper container, adding a proper amount of high-purity water into the container, and performing ultrasonic dispersion for a certain time to form a uniform suspension;
5) Transferring the suspension into an upper container of the sand core filter, starting a vacuum suction pump, and sucking all the suspension in the upper container of the sand core filter to the surface of a filter membrane;
6) Taking out the filter membrane after the suction is finished, accurately weighing the mass of the filter membrane after the drying, and recording the mass as M 2 ；
7) Measuring net peak height value (cps/mA) of characteristic spectral line of iron element K alpha 1 by X-ray fluorescence, and measuring iron mass (mug/cm) per unit area of filter membrane by using weighing method or microwave digestion and atomic absorption spectrometry 2 ) And (5) accurately determining the value.
The net peak height value (cps/mA) of characteristic spectral line of iron element K alpha 1 is taken as the Y axis, and the unit area iron mass (mug/cm) of the filter membrane is taken as the filter membrane 2 ) And drawing a standard curve for the X axis, and calculating a linear regression coefficient, wherein if the linear regression coefficient reaches 0.99 or more, the prepared series of comparison filter membranes can be used for quantitatively measuring the iron content of the nuclear power station.
The following specific implementation data illustrate the technical scheme of the invention:
example 1
The preparation method of the comparison filter membrane for measuring the iron content X-ray fluorescence in the water in the embodiment specifically comprises the following steps:
1) 5 filter membranes made of nitrocellulose material and having a filter pore diameter of 0.45 μm and a diameter of 47mm were prepared, and the mass of each filter membrane was accurately measured and set in a sand core filter after the measurement was completed, respectively, to 101.1mg,102.0mg,101.5mg,102.6mg and 99.8 mg.
2) A sand core filter with a sand core diameter of 47mm was prepared, the filter material was polytetrafluoroethylene, and the volume was 1L.
3) Accurately weighing 1.1mg, 4.6mg, 9.1mg, 13.7mg and 22.8mg of analytically pure grade ferroferric oxide, transferring the accurately weighed ferroferric oxide into a beaker made of polytetrafluoroethylene with the capacity of 1L, adding 100mL of ultrapure water, and performing ultrasonic dispersion for 3 minutes to form a uniform suspension.
4) And (3) carrying out reduced pressure suction filtration on the suspension into the filter membrane to finish the manufacture of the comparison filter membrane, and accurately weighing the mass after drying at 50 ℃. The mass of the dried powder is accurately weighed to be 101.9mg, 106.0mg, 110.1mg, 115.9mg and 122.2mg respectively.
5) Using XRF analyzer, setting the X-ray tube voltage as 40kV, tube current as 1mA, measuring time as 60s, and measuring the net peak height values of characteristic spectral lines of iron element Kα1 in the comparison filter film as 289.81cps/mA, 978.08cps/mA, 2204.6cps/mA, 3121.2cps/mA, 4573.6cps/mA.
6) After the measurement is completed, the unit area iron mass (mug/cm) of the filter membrane is measured by using a microwave digestion and atomic absorption spectrometry 2 ) Accurately determining the value to obtain a series of filter membranes with iron weights of 82.3 mug/cm in unit area 2 、330.27μg/cm 2 、721.79μg/cm 2 、997.14μg/cm 2 、1575.7μg/cm 2 。
7) The net peak height value (cps/mA) of characteristic spectral line of iron element K alpha 1 is taken as the Y axis, and the unit area iron mass (mug/cm) of the filter membrane is taken as the filter membrane 2 ) For the X axis, a standard curve is drawn, as shown in FIG. 2, and a linear regression coefficient is calculated, wherein the linear regression equation is: y=2.914x+73.60, and the obtained linear regression coefficient reaches 0.99, which shows that the prepared series of comparison filter membranes can be used for quantitative measurement of iron content in the filter membranes of the nuclear power station.
Example 2
The method for measuring the Fe content in the power plant filter membrane by using the X-ray fluorescence specifically comprises the following steps:
1) Standard curve and fitting formulas were used in example 1.
2) After the power plant filter membrane is obtained, an XRF analyzer is used, the voltage of an X-ray light tube is set to be 40kV, the tube current is set to be 1mA, the measuring time is set to be 60s, the net peak height value (cps/mA) of the characteristic spectral line of the iron element K alpha 1 in the power plant filter membrane is measured to be 1729.7, and the net peak height value is substituted into the fitting equation of the standard curve to obtain the measured value of the iron content in the filter membrane to be 568 mug/cm 2 。
3) Digesting the power plant filter membrane by using a microwave digestion method, and measuring the Fe content in the digestion solution by using an atomic absorption spectrum to obtain a value of 541 mug/cm 2 。
4) The relative deviation of the Fe content values obtained by the two measuring methods is 4.8 percent through calculation, and meets the quality control standard of a power plant.
The XRF method is an instrument analysis technology for element analysis, and can be used for directly analyzing the element content in filter membrane samples. After the sample to be measured is irradiated by high-energy X-rays, inner-layer electrons of atoms of the element to be measured are knocked out to form holes, and outer-layer electrons are leaved toward the inner layer and radiate redundant energy in the form of X-rays, namely X-ray fluorescence. The intensity of the X-ray fluorescence is in direct proportion to the content of the element to be detected, the characteristic X-ray fluorescence intensity of the filter membrane can be compared by measuring the characteristic X-ray fluorescence intensity of a series of known iron masses per unit area, a standard curve of the iron mass per unit area and the X-ray fluorescence intensity can be established, and when the linear correlation coefficient of the standard curve reaches more than 0.99, the content of the element in the filter membrane sample of the nuclear power station can be quantitatively analyzed through an external standard method. The invention provides a method for preparing a comparison filter membrane by using a reduced pressure suction filtration method, which aims to solve the problem that no suitable comparison sample exists in the prior art for measuring the iron content in the filter membrane by using an XRF method, so as to establish a rapid quantitative measurement method for the iron content in the filter membrane of a nuclear power station.
Compared with the prior art, the invention has the following advantages: the manufacturing time of the series comparison filter membrane sample only needs 3 hours, the manufacturing process is simple, the stability of the comparison filter membrane is good, and the series comparison filter membrane sample is basically consistent with the matrix of the accumulated sampling filter membrane in the secondary loop of the nuclear power station. Net peak height value (cps/mA) plotted against iron mass per unit area (μg/cm) of filter membrane using a series of alignment filters 2 ) The linear correlation coefficient of the standard curve can reach more than 0.99, and the method can be used for quantitative analysis of an external standard method for measuring the iron content in a filter membrane of a nuclear power station by XRF, so that the accuracy of measurement with the existing digestion atomic absorption spectrometry of the power station is achieved, the analysis time of the power station is greatly shortened, and the industrial safety risk brought by using nitric acid or aqua regia is avoided.
The above embodiments are provided to illustrate the technical concept and features of the present invention and are intended to enable those skilled in the art to understand the content of the present invention and implement the same, and are not intended to limit the scope of the present invention. All equivalent changes or modifications made in accordance with the spirit of the present invention should be construed to be included in the scope of the present invention.
Claims (6)
1. The preparation method of the comparison filter membrane for the X-ray fluorescence measurement of the iron content in water is characterized by comprising the following steps:
drying the filtering membrane and weighing; installing the dried filtering membrane into a filter;
dispersing a plurality of sets of oxides in water to form a plurality of sets of suspensions;
transferring a plurality of groups of the suspensions into the filters respectively, and filtering respectively;
taking out the filtering membrane after the filtering is finished, weighing after drying, and converting the ratio of Fe element in the oxide chemical molecule into Fe mass in unit area; the mass of iron in unit area of the comparison filter membrane with a plurality of different iron contents is in the range of 0-4500 mug/cm 2 ；
Verifying the filtering membrane, and if the filtering membrane is qualified, quantitatively measuring the iron content in the nuclear power station, namely, comparing the filtering membrane;
the crystal structure of the oxide is ferroferric oxide and/or ferric oxide;
the verification includes the steps of: measuring the net peak height value of the characteristic spectral line of the iron element K alpha 1 by using X-ray fluorescence, and quantifying the mass of iron on the unit area of the filtering membrane;
drawing a standard curve by taking the net peak height value of the characteristic spectral line of the iron element K alpha 1 as a Y axis and the mass of iron on the unit area of the filtering membrane as an X axis, and calculating a linear regression coefficient, and if the linear regression coefficient reaches a set standard, verifying to be qualified; the linear regression coefficient of the standard curve of the set standard reaches 0.99 or above;
the material of the comparison filter membrane is nitrocellulose; the filter pore diameter of the comparison filter membrane is below 500 nanometers; the drying is carried out at the temperature of 40-55 ℃; the dispersion is carried out under the action of ultrasound, and the ultrasound time is 3-5 min;
the multiple groups of oxides at least comprise five groups of oxides with different mass, and the weighing mass of the oxides is between 0 and 120 mg; and the range settings of the content and gradient need to include the iron content in the final detected sample;
when preparing suspension, transferring all the oxide into a proper container, adding proper amount of high-purity water into the container, and performing ultrasonic dispersion for a certain time to form uniform suspension; the material of the container is high boron glass or polytetrafluoroethylene;
the filter is a sand core filter, and is made of high boron glass or polytetrafluoroethylene; the diameter of the sand core is matched with the diameter of the filter membrane;
and the specification of the comparison filter membrane is the same as that of the sampling filter membrane in the nuclear power station.
2. The preparation method according to claim 1, wherein the quantitative measurement of the iron mass per unit area of the filter membrane is to quantitatively determine the iron mass per unit area of the filter membrane by a weighing method or a microwave digestion and atomic absorption spectrometry method.
3. The method of claim 1, wherein the oxide D 50 The grain diameter is 0.5-1 mu m, and the purity is analytically pure or above.
4. An aligned filter membrane prepared by the method of any one of claims 1-3.
5. Use of an alignment filter according to any one of claims 1-3 for measuring iron content in secondary water of a nuclear power plant.
6. The method for measuring the iron content in the secondary circuit water of the nuclear power station is characterized by comprising the following steps of:
preparing a plurality of comparison filter membranes with different iron contents by adopting the preparation method according to any one of claims 1-3, performing X-ray fluorescence spectrum analysis and detection on the comparison filter membranes, and obtaining a standard curve equation according to the detection result;
and measuring the net peak height value of the characteristic spectral line of the iron element in the secondary water accumulated sampling filter membrane by using an X-ray fluorescence spectrum analysis method, and substituting the net peak height value into the standard curve equation to obtain the iron content in the sampling filter membrane.
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Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH1183767A (en) * | 1997-09-09 | 1999-03-26 | Kansai Electric Power Co Inc:The | Density measurement device for specified element in fluid |
| CN112697829A (en) * | 2020-11-18 | 2021-04-23 | 中国地质调查局西安地质调查中心(西北地质科技创新中心) | Method for measuring various elements in atmospheric particulates by taking actual sample as standard sample |
-
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- 2021-12-28 CN CN202111621631.1A patent/CN114264683B/en active Active
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH1183767A (en) * | 1997-09-09 | 1999-03-26 | Kansai Electric Power Co Inc:The | Density measurement device for specified element in fluid |
| CN112697829A (en) * | 2020-11-18 | 2021-04-23 | 中国地质调查局西安地质调查中心(西北地质科技创新中心) | Method for measuring various elements in atmospheric particulates by taking actual sample as standard sample |
Non-Patent Citations (6)
| Title |
|---|
| A method of examining iron oxides speciation and transport to steam generators during nuclear power reactor startups;Jerzy A. Sawicki等;Journal of Nuclear Materials;第407卷;第157-164页 * |
| G. LEGREID.Characterization of reactor coolant by XRF.ETDEWeb.2003,第1-13页. * |
| X-RAY FLUORESCENCE DETERMINATION OF TRACES OF DISSOLVED AND SUSPENDED METALS IN WATER;C. J. TOUSSAINT等;Analytica Chimica Acto.;第88卷;第193-196页 * |
| 杜祯宇等.Announcement .冶金分析.2020,40(11),第1-7页. * |
| 杨凯等.核电站二回路给水腐蚀产物取样技术的研究与应用.科技创新导报.2016,(10),第71-72页. * |
| 郝慧慧.西安市大气颗粒物中无机元素的污染特征及XRF标准滤膜的制备.中国优秀硕士学位论文全文数据库 工程科技Ⅰ辑.2019,(12),第38页. * |
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