JP5337832B2 - X-ray analysis method and apparatus - Google Patents

Description

  The present invention relates to an X-ray analysis method for determining the content of ignition loss in lime and an apparatus therefor.

In this specification, lime means quick lime (main component is calcium oxide CaO), slaked lime (main component is calcium hydroxide Ca (OH) ₂ ), and limestone (main component is calcium carbonate CaCO ₃ ). Limestone is pyrolyzed to produce quick lime, and it is important to manage the ignition loss in the produced quick lime, which is quantified by the following official method. In the specification of the present application, the loss on ignition means a weight loss caused by the ignition of the sample, and the weight loss (mass%) expressed as the weight loss is referred to as the content of ignition loss.

The official method JIS R9011 2006 "Testing method of lime" specifies lime other than limestone, and the loss on ignition is ignited over time until the lime reaches a constant weight at 1050 ° C. Seeking by About limestone, it is calculated | required similarly by the method prescribed | regulated to JISM88501994 "limestone analysis method" (There is a little difference in the said JIS method and a heating process.). The carbon dioxide content is determined by the infrared absorption method or the volume method. In the case of quicklime, the content of moisture (H ₂ O) that volatilizes during ignition loss is treated as a numerical value indicating the moisture absorption deterioration of quicklime, but the moisture content is determined by the above method. It is obtained by subtracting the carbon dioxide (CO ₂ ) content from the weight loss content. Thus, the content rate of ignition loss is the sum of the content rate of carbon dioxide and the content rate of water that volatilizes during ignition loss. Hereinafter, the water that volatilizes during ignition loss is referred to as moisture during ignition loss. CaO, which is the main component of lime, and MgO, SiO ₂ , Al ₂ O ₃ , Fe ₂ O ₃ , P ₂ O ₅ , S, etc., which are other components, are quantified by a fluorescent X-ray analysis method.

  On the other hand, when producing lime raw material by pyrolyzing limestone or the like to produce lime raw material, in order to manage the firing condition of calcium oxide in the lime raw material being produced, in a short time (less than 10 minutes) in front of the furnace There is a fluorescent X-ray analysis method that measures the content (concentration) of calcium oxide in a lime raw material (Patent Document 1).

  This fluorescent X-ray analysis method irradiates a standard sample made of a lime raw material with a known content of calcium oxide and carbon dioxide as main components, detects the intensity of fluorescent X-rays generated from calcium, Detecting the intensity of the Compton scattered radiation generated from the sample, creating a calibration curve indicating the correlation between the ratio of the fluorescent X-ray intensity and the intensity of the Compton scattered radiation and the content of calcium oxide. Irradiate primary X-ray, detect fluorescent X-ray intensity generated from calcium, detect intensity of Compton scattered radiation generated from sample, and obtain ratio of fluorescent X-ray intensity and intensity of Compton scattered radiation The method for detecting the content of calcium oxide in a lime raw material, wherein the content of calcium oxide is detected using the calibration curve.

JP-A-7-306168

This Patent Document 1 focuses on the fact that the intensity of the Rh-Kα Compton scattered radiation has a very good correlation with the content of carbon dioxide in the sample, and the carbon dioxide in the sample depends on the intensity of the Rh-Kα Compton scattered radiation. The lime raw material is based on the idea that CaO as the main component and CO _{2 as} the second component form a binary system. This Patent Document 1 describes a method for determining carbon dioxide by an X-ray analysis method, but does not describe ignition loss itself or determination of moisture during ignition loss.

  Therefore, as a result of experiments on quick lime (details will be described later) on the ignition loss and the method for determining moisture in ignition loss by the X-ray analysis method, the content of ignition loss in quick lime and Compton scattered rays It was found that there is a good correlation with the intensity of the Rh-Kα Compton scattered radiation. In addition, the intensity of the Rh-Kα Compton scattered radiation has a very good correlation with the carbon dioxide content if the water content in ignition loss is constant, but if the water content varies, the intensity of carbon dioxide It did not correlate with the content rate, and it was found that the content rate of carbon dioxide could not be determined accurately using Rh-Kα Compton scattered radiation. Therefore, with the conventional technique, the content of ignition loss in lime cannot be obtained accurately in a short time.

  This invention is made | formed in view of the said conventional problem, and it aims at providing the X-ray-analysis method and apparatus which can obtain | require the content rate of the ignition loss in lime accurately in a short time. .

  In order to achieve the above object, the X-ray analysis method of the first configuration of the present invention generates a primary X-ray by irradiating a standard sample made of lime with a known loss ratio of ignition loss from the standard sample. Detect the intensity of Compton scattered radiation, create a calibration curve for ignition loss showing the correlation between the detected intensity of Compton scattered radiation and the content of ignition loss, and irradiate unknown samples made of lime with primary X-rays Then, the intensity of the Compton scattered radiation generated from the unknown sample is detected, and the ignition loss content in the unknown sample is determined using the ignition loss calibration curve.

  According to the X-ray analysis method of the first configuration of the present invention, the content of ignition loss of lime can be obtained accurately in a short time.

  The X-ray analysis method according to the second configuration of the present invention irradiates a standard sample made of lime with known loss of ignition and carbon dioxide content with primary X-rays, and the intensity of Compton scattered radiation generated from the standard sample. And a C-Kα ray intensity, a calibration curve for loss on ignition showing the correlation between the intensity of the detected Compton scattered ray and the content of loss on ignition, and the detected C-Kα ray intensity and carbon dioxide A carbon dioxide calibration curve showing a correlation with the content rate is created, and an unknown sample made of lime is irradiated with primary X-rays to detect the intensity of Compton scattered radiation and C-Kα radiation generated from the unknown sample. The ignition loss and the carbon dioxide calibration curve are used to obtain the ignition loss and carbon dioxide content in the unknown sample, respectively, and the carbon dioxide obtained from the obtained ignition loss content. Subtracting the content of Request moisture content in ignition loss of knowledge samples.

  According to the X-ray analysis method of the second configuration of the present invention, in addition to the X-ray analysis method of the first configuration, the carbon dioxide and moisture content in the ignition loss of lime can be obtained accurately in a short time. it can.

The X-ray analysis method according to the third configuration of the present invention irradiates a standard sample made of lime whose ignition loss content is known, and detects the intensity of Compton scattered rays generated from the standard sample. ,
For correction of the loss of ignition loss and lime having a known content of at least one of carbon dioxide, MgO, SiO ₂ , Al ₂ O ₃ , Fe ₂ O ₃ , P ₂ O ₅ and S Using a standard sample or a standard sample for virtual correction of lime, for correcting the calibration curve of ignition loss indicating the correlation between the intensity of Compton scattered radiation and the content of ignition loss for the influence of the at least one component A correction calibration curve for loss on ignition is created using the detected Compton scattered radiation intensity and the obtained matrix correction coefficient, and an unknown sample made of lime is irradiated with primary X-rays, Detecting the intensity of Compton scattered radiation generated from the unknown sample and the intensity of fluorescent X-rays corresponding to the at least one component among C, Mg, Si, Al, Fe, P, and S; Determining the content rate of loss on ignition in said unknown sample by using a correction calibration curve of loss on ignition. In the present specification, the lime virtual correction standard sample refers to a virtual sample that assumes a lime composition in order to obtain a theoretical matrix correction coefficient.

  According to the X-ray analysis method of the third configuration of the present invention, the accuracy of the ignition loss calibration curve is improved by performing matrix correction, and the ignition loss content rate is analyzed with better accuracy. Can do.

  The X-ray analysis method according to the fourth configuration of the present invention irradiates a standard sample made of lime with a known loss ratio of ignition loss and carbon dioxide content with a primary X-ray and generates Compton scattering generated from the standard sample. The intensity of the line and the intensity of the C-Kα line are detected, and the correlation between the intensity of Compton scattered radiation and the content of ignition loss is shown for the influence of carbon dioxide using the standard sample or the virtual standard sample of lime. A matrix correction coefficient for correcting the calibration curve for ignition loss is obtained, and a correction calibration curve for ignition loss is created using the intensity of the detected Compton scattered radiation and the obtained matrix correction coefficient, and the detection is performed. A calibration curve of carbon dioxide showing the correlation between the intensity of the C-Kα ray and the carbon dioxide content is prepared, and an unknown sample made of lime is irradiated with primary X-rays, and the Compton powder generated from the unknown sample Detecting the intensity of turbulent lines and the intensity of C-Kα lines, and using the calibration curve for ignition loss and the calibration curve for carbon dioxide, respectively, determine the ignition loss and carbon dioxide content in the unknown sample, By subtracting the carbon dioxide content obtained from the obtained ignition loss content, the moisture content in the ignition loss of the unknown sample is obtained.

  According to the X-ray analysis method of the fourth configuration of the present invention, the accuracy of the calibration curve for loss on ignition is improved by performing matrix correction, and the carbon dioxide and moisture content are analyzed with better accuracy. be able to.

  The X-ray analyzer of the fifth configuration of the present invention includes an X-ray source that irradiates a sample with primary X-rays, and an intensity of secondary X-rays generated from the sample irradiated with primary X-rays from the X-ray source. An X-ray analysis apparatus comprising: a detection means for detecting the primary X-ray from the X-ray source to a standard sample made of lime whose ignition loss is known; A calibration curve creating means for detecting the intensity of the Compton scattered radiation to be detected by the detection means and creating a calibration curve for ignition loss indicating a correlation between the intensity of the detected Compton scattered radiation and the content of ignition loss; and lime Irradiating the unknown sample consisting of primary X-rays from the X-ray source, detecting the intensity of Compton scattered radiation generated from the unknown sample with the detection means, and the ignition loss created by the calibration curve creation means Obtain the content of loss on ignition in the unknown sample using the calibration curve Comprising a quantity means.

  According to the X-ray analyzer of the fifth configuration of the present invention, the content of ignition loss of lime can be obtained accurately in a short time.

  The X-ray analyzer of the sixth configuration of the present invention includes an X-ray source that irradiates a sample with primary X-rays, and an intensity of secondary X-rays generated from the sample irradiated with primary X-rays from the X-ray source. An X-ray analyzer comprising: a standard sample made of lime whose ignition loss and carbon dioxide content are known, and the standard X-ray is irradiated from the X-ray source, A calibration curve for loss on ignition showing the correlation between the intensity of Compton scattered rays and the content of ignition loss detected by the detection means by detecting the intensity of Compton scattered rays and C-Kα rays generated from the sample. And a calibration curve creating means for creating a calibration curve of carbon dioxide showing a correlation between the intensity of the detected C-Kα ray and the carbon dioxide content, and primary X-ray from the X-ray source to an unknown sample made of lime The intensity of Compton scattered radiation generated from the unknown sample and The intensity of C-Kα rays is detected by the detection means, and the ignition loss and carbon dioxide content in the unknown sample is determined by the calibration curve for ignition loss and the calibration curve for carbon dioxide created by the calibration curve creation means. Quantitative means for determining the rate respectively, and moisture for calculating the moisture content in the ignition loss of the unknown sample by subtracting the carbon dioxide content determined from the ignition loss content determined by the quantitative means Calculating means.

  According to the X-ray analyzer of the sixth configuration of the present invention, in addition to the X-ray analyzer of the first configuration, the carbon dioxide and moisture content in the ignition loss of lime can be obtained accurately in a short time. it can.

The X-ray analyzer of the seventh configuration of the present invention includes an X-ray source that irradiates a sample with primary X-rays, and an intensity of secondary X-rays generated from the sample irradiated with primary X-rays from the X-ray source. An X-ray analysis apparatus comprising: a detection means for detecting the content of ignition loss, and carbon dioxide, MgO, SiO ₂ , Al ₂ O ₃ , Fe ₂ O ₃ , P ₂ O ₅ , S Using a correction standard sample made of lime whose content of at least one component is known or a virtual correction standard sample of lime, the intensity of Compton scattered radiation and loss on ignition are measured for the influence of the at least one component. A correction coefficient calculating means for calculating a matrix correction coefficient for correcting a calibration curve of ignition loss showing a correlation with the content rate, and a standard sample made of lime with a known ignition loss content rate from the X-ray source Irradiated with primary X-ray and generated from the standard sample A calibration curve for detecting a loss of ignition loss using the detection means and a matrix correction coefficient calculated by the correction coefficient calculation means. An X-ray source that irradiates an unknown sample made of lime with a primary X-ray from an X-ray source, and the intensity of Compton scattered rays generated from the unknown sample; and C, Mg, Si, Al, Fe, P, The intensity of the fluorescent X-ray corresponding to the at least one component of S is detected by the detection means, and the intensity in the unknown sample is detected using the calibration curve for loss on ignition created by the calibration curve creation means. And a quantitative means for obtaining the content of heat loss.

  According to the X-ray analyzer of the seventh configuration of the present invention, by performing matrix correction, the accuracy of the calibration curve for ignition loss is improved, and the content of ignition loss is analyzed with better accuracy. Can do.

  The X-ray analyzer of the eighth configuration of the present invention includes an X-ray source that irradiates a sample with primary X-rays, and an intensity of secondary X-rays generated from the sample irradiated with primary X-rays from the X-ray source. An X-ray analyzer comprising: a standard sample made of lime with a known loss of ignition loss and a known carbon dioxide content or a virtual standard sample of lime. A correction coefficient calculation means for calculating a matrix correction coefficient for correcting a calibration curve for loss on ignition indicating a correlation between the intensity of Compton scattered radiation and the content of ignition loss, and the X-ray A primary X-ray is irradiated from a source, the intensity of Compton scattered radiation and C-Kα radiation generated from the standard sample are detected by the detection means, and the intensity of the detected Compton scattered radiation and the correction coefficient are calculated. Calculated by means A calibration curve creating means for creating a calibration curve for loss on ignition using a Rix correction coefficient and creating a calibration curve for carbon dioxide showing a correlation between the intensity of the detected C-Kα ray and the content of carbon dioxide And comprising.

  The X-ray analyzer of the eighth configuration of the present invention further irradiates an unknown sample made of lime with primary X-rays from the X-ray source, and the intensity of Compton scattered rays generated from the unknown sample and C-Kα rays. Is detected by the detection means, and the ignition loss and the carbon dioxide content in the unknown sample using the calibration curve for ignition loss and the calibration curve for carbon dioxide created by the calibration curve creation means. And a moisture calculation for calculating the moisture content in the ignition loss of the unknown sample by subtracting the carbon dioxide content obtained from the ignition loss content obtained by the quantitative means. Means.

  According to the X-ray analyzer of the eighth configuration of the present invention, the accuracy of the calibration curve for loss on ignition is improved by performing matrix correction, and the carbon dioxide and moisture content are analyzed with better accuracy. be able to.

1 is a schematic diagram showing an X-ray analysis apparatus according to a first embodiment of the present invention. It is a figure which shows the calibration curve for calculating | requiring the content rate of the ignition loss in the same embodiment. It is a figure which shows the calibration curve for calculating | requiring the content rate of the carbon dioxide in the same embodiment. It is a figure which shows the correlation with the content rate of the ignition loss calculated | required by experiment, and the X-ray intensity of a Rh-K (alpha) Compton scattered ray. It is the schematic which shows the X-ray analyzer of the 2nd embodiment. It is a figure which shows the calibration curve created with the theoretical standard sample of ignition loss, and the theoretical X-ray intensity of Rh-Kα Compton scattered radiation. It is a figure which shows the calibration curve created with the theoretical standard sample of ignition loss, and the theoretical X-ray intensity of Rh-Kα Thomson scattered radiation. It is a figure which shows the correlation with the content rate of a carbon dioxide, and the theoretical X-ray intensity of a Rh-K (alpha) Compton scattered ray. It is the schematic which shows the X-ray analyzer of 3rd Embodiment. It is a figure which shows the correction | amendment calibration curve for calculating | requiring the content rate of the ignition loss in the same embodiment. It is a figure which shows the matrix uncorrected calibration curve for calculating | requiring the content rate of the ignition loss in the same embodiment. It is the schematic which shows the X-ray analyzer of 4th Embodiment.

  The analysis method according to the first embodiment of the present invention will be described below. First, the structure of the X-ray analyzer used for this analysis method is demonstrated according to FIG. This apparatus is generated by irradiating a primary S-ray 2 from an X-ray source 1 such as a rhodium (Rh) X-ray tube onto a sample S made of lime such as quick lime placed on a sample stage 8 2 An X-ray analyzer such as a fluorescent X-ray analyzer that measures the intensity of the next X-ray 4 with the detection means 9. The secondary X-ray 4 includes fluorescent X-rays, Compton scattered rays, Thomson scattered rays and the like generated when the sample X is irradiated with the primary X-rays 2. The detection means 9 includes a spectroscopic element 5 such as lithium fluoride (LiF) that receives the secondary X-ray 4 generated from the sample S and diffracts the secondary X-ray 6 to be measured, and the diffracted secondary X-ray. And a detector 7 for measuring the intensity of the line 6. The spectroscopic element 5 and the detector 7 are fixed by a goniometer (not shown) so that the secondary X-ray 6 is incident on the detector 7 while changing the wavelength of the secondary X-ray 6 dispersed by the spectroscopic element 5. It is rotated while maintaining the angular relationship.

  This apparatus includes the following calibration curve creation means 11, quantification means 12, and moisture calculation means 13. The calibration curve creating means 11 irradiates the standard sample S made of lime with known loss of ignition and carbon dioxide content with the primary X-ray 2 from the X-ray source 1 and generates secondary X-rays generated from the standard sample S. The intensity of the Compton scattered line 6A and the intensity of the C-Kα line 6B obtained by separating 4 with the spectroscopic element 5 are detected by the detector 7, and the correlation between the detected intensity of the Compton scattered line 6A and the content of ignition loss is detected. And a calibration curve of carbon dioxide showing a correlation between the intensity of the detected C-Kα line 6B and the content of carbon dioxide, and each of the created calibration curves is stored. The quantification unit 12 irradiates the unknown sample S made of lime with the primary X-ray 2 from the X-ray source 1, and the Compton scattered ray 6 </ b> A obtained by causing the spectroscopic element 5 to split the secondary X-ray 4 generated from the unknown sample S. The detector 7 detects the intensity and the intensity of the C-Kα line 6B, and applies the calibration curve for ignition loss and the calibration curve for carbon dioxide, which are created and stored by the calibration curve creation means 11, respectively. Determine the loss on ignition and the carbon dioxide content. The moisture calculation means 13 calculates the moisture content in the ignition loss of the unknown sample S by subtracting the carbon dioxide content obtained from the ignition loss content obtained by the quantification means 12. That is, the method of the first embodiment is an X-ray analysis method for obtaining the ignition loss in a sample made of lime, carbon dioxide, and the moisture content in the ignition loss.

  In the analysis method of the first embodiment using this apparatus, the intensity of the Compton scattered ray 6A generated from the loss of ignition in the sample S made of lime in FIG. 1, for example, an X-ray source that generates primary X-rays 2 is used. Note that when a rhodium (Rh) X-ray tube is used for 1, the intensity of the Rh-Kα Compton scattering line 6A has a very good correlation with the content of ignition loss in the sample S, Rh-Kα Compton scattering The content of ignition loss in the sample S was determined by the intensity of the line 6A. FIG. 4 shows the correlation between the ignition loss content obtained by the experiment conducted prior to the present invention and the X-ray intensity of the Rh-Kα Compton scattered radiation. According to FIG. 4, it can be seen that the intensity of the Rh-Kα Compton scattered ray 6A and the content of ignition loss are in a linear proportional relationship.

  In the first embodiment, first, as shown in FIG. 1, a plurality of standard samples S made of lime with known ignition loss and carbon dioxide content are used, and the X-ray source 1 is used for these standard samples S. Is irradiated with primary X-rays 2 and the intensity of Rh-Kα Compton scattered radiation 6A generated from ignition loss and fluorescent X-rays generated from carbon (C) which is a constituent element of carbon dioxide, that is, C-Kα rays 6B. Is detected by a detector 7, and a calibration curve for ignition loss showing a correlation between the intensity of the detected Compton scattered ray 6A and the content of ignition loss, and the intensity of the detected C-Kα line 6B A calibration curve for carbon dioxide showing a correlation with the carbon dioxide content is created by the calibration curve creating means 11 and stored. FIG. 2 shows the calibration curve for ignition loss created. The correlation between the intensity of the C-Kα line 6B and the content of carbon (C), which is a constituent element of carbon dioxide, and the correlation between the intensity of the C-Kα line 6B and the content of carbon dioxide are both linearly proportional. Yes, a calibration curve for carbon dioxide is shown in FIG. The standard sample made of lime refers to a sample in which the ignition loss in quicklime, carbon dioxide, and the moisture content in the ignition loss are determined by JIS R9011 2006 “Testing method of lime”.

  Next, as shown in FIG. 1, the unknown sample S is irradiated with the primary X-ray 2 from the X-ray source 1, and the intensity of the Rh-Kα Compton scattered ray 6A generated from ignition loss and the constituent elements of carbon dioxide are The intensity of the C-Kα line 6B generated from a certain carbon is detected by the detector 7, and the corresponding calibration curve (FIGS. 2 and 3) stored by the calibration curve creation means 11 is applied to each detected intensity by the quantification means 12. Thus, ignition loss and carbon dioxide content (mass%) are required.

  Next, the carbon dioxide content is subtracted from the ignition loss content (mass%) obtained by the quantitative means 12, and the moisture content (mass%) in the ignition loss is calculated by the moisture calculation means 13. Calculated.

According to the method of this embodiment, only the intensity of the Rh-Kα Compton scattered ray 6A and the intensity of the C-Kα ray 6B generated from the sample S is detected, and the ignition loss in lime, carbon dioxide, strong Each content rate of the water | moisture content in heat loss can be calculated | required accurately in a short time. Furthermore, CaO, which is the main component of lime, and MgO, SiO ₂ , Al ₂ O ₃ , Fe ₂ O ₃ , P ₂ O ₅ , S, etc., which are other components, have been conventionally quantified by fluorescent X-ray analysis. Therefore, all the components in the lime prescribed | regulated by JISR9011 2006 "the test method of lime" can be quantified by a fluorescent X ray analysis.

  The analysis method according to the second embodiment of the present invention will be described below. First, an apparatus used in this method is shown in FIG. Similar to the X-ray analysis apparatus shown in FIG. 1, this apparatus includes an X-ray source 1, a sample stage 8, a spectroscopic element 5, a detection means 9, a calibration curve creation means 11 and a quantification means 12, but calculates moisture. Means 13 is not provided, but is an X-ray analyzer such as a fluorescent X-ray analyzer for obtaining the content of ignition loss in a sample made of lime.

  Using this apparatus, in the analysis method of the second embodiment, a plurality of standard samples S made of lime with known ignition loss are used, and primary X-rays 2 from the X-ray source 1 are applied to these standard samples S. Irradiation is performed to detect the intensity of the Rh-Kα Compton scattered ray 6A generated from the loss of ignition by the detector 7, and the ignition shows the correlation between the intensity of the detected Compton scattered ray 6A and the content of ignition loss. A calibration curve for weight reduction is created by the calibration curve creating means 11 and stored. FIG. 2 shows the calibration curve for ignition loss created.

  The unknown sample S is irradiated with the primary X-ray 2 from the X-ray source 1, and the intensity of the Rh-Kα Compton scattered ray 6 A generated from the ignition loss is detected by the detector 7. The calibration curve (FIG. 2) stored by the calibration curve creation means 11 is applied to determine the ignition loss content rate (mass%).

  According to the method of this embodiment, the intensity of the Rh-Kα Compton scattered ray 6A generated from the sample S can be detected, and the content of ignition loss in lime can be accurately determined in a short time.

  Next, experiments and theoretical verification conducted prior to the present invention will be described. The correlation between the intensity of the Rh-Kα Compton scattered radiation and the content of ignition loss was examined using a standard sample whose ignition loss, carbon dioxide, and moisture content in ignition loss were known. FIG. 4 shows a calibration curve in which the intensity of the measured Rh-Kα Compton scattered radiation is plotted using a plurality of standard samples whose ignition loss is in the range of 0.63 to 10.07 mass%. As shown in FIG. 4, the intensity of Rh-Kα Compton scattered radiation had a very good linear relationship with the content of ignition loss, and the accuracy was 0.33 mass%.

  A theoretical verification was performed to verify the experimental results. Software based on the X-ray fluorescence analysis FP method with a loss of ignition in the range of 1.0 to 11.0 mass%, with the elements uniformly distributed and considering the influence of coexisting elements as the theoretical standard sample 6 and 7 show calibration curves created by using the theoretical X-ray intensities of the Rh-Kα Compton scattered ray and the Rh-Kα Thomson scattered ray. FIG. 6 is a calibration curve of Rh-Kα Compton scattered radiation, and FIG. 7 is a calibration curve of Rh-Kα Thomson scattering radiation. The correlation coefficient of the calibration curve of Rh-Kα Compton scattered radiation is 0.9993, and the correlation coefficient of the calibration curve of Rh-Kα Thomson scattered radiation is 0.9988. The calibration curve of the Rh-Kα Compton scattering line has a higher gradient than the calibration curve of the Rh-Kα Thomson scattering line, and the calibration curve of the Rh-Kα Compton scattering line is preferable.

  Next, FIG. 8 shows the result of obtaining the correlation with the theoretical X-ray intensity of the Rh-Kα Compton scattered radiation for the theoretical standard sample having the carbon dioxide content in the range of 0 to 10 mss% in the same manner as described above. When the moisture content during ignition loss is constant and 1.0 mass%, the carbon dioxide content and the theoretical X-ray intensity of Rh-Kα Compton scattered radiation show a good correlation. The plot point of the vertical axis | shaft direction of the position of the carbon dioxide content rate of 2 mass% in FIG. 8 is the theoretical X-ray intensity of the Rh-Kα Compton scattered ray from the carbon dioxide content of 2.0 mass%. In order from 0, 0.5, 1.0, 1.5, 2.0, 2.5 mass%). That is, if the moisture content during ignition loss is constant, the carbon dioxide content and the theoretical X-ray intensity of the Rh-Kα Compton scattered radiation show a good correlation, but if the moisture content changes, it is good. No significant correlation. Therefore, the carbon dioxide content cannot be determined accurately using Rh-Kα Compton scattered radiation.

  Therefore, in the present invention, in order to determine the content of carbon dioxide, the content of carbon, which is a constituent element of carbon dioxide, is determined using C-Kα rays without using Rh-Kα Compton scattered radiation. The carbon dioxide content is calculated by converting the rate.

  Patent Document 1 describes that the content (concentration) of carbon dioxide in a sample is determined based on the intensity of Rh-Kα Compton scattered radiation, but this document does not describe the moisture content. This is because the water adhering to the surface of the raw limestone has already volatilized at the stage where the temperature exceeds 100 ° C, there is no moisture brought in from the raw material, the quick lime in front of the furnace becomes a sample that does not contain water, and contains carbon dioxide The rate and the intensity of Rh-Kα Compton scattered radiation seem to show a good correlation.

  The analysis method according to the third embodiment of the present invention will be described below. First, an apparatus used for this method is shown in FIG. Similar to the X-ray analyzer shown in FIG. 1, this apparatus includes an X-ray source 1, a sample stage 8, a spectroscopic element 5, a detection means 9, a calibration curve creation means 11, a quantification means 12, and a moisture calculation means 13. The X-ray fluorescence analyzer further includes a correction coefficient calculation means 14 and calculates the loss of ignition in the sample S made of lime, carbon dioxide, and the moisture content in the loss of ignition by performing matrix correction.

The correction coefficient calculation means 14 has a content ratio of ignition loss and a content ratio of at least one component of carbon dioxide, MgO, SiO ₂ , Al ₂ O ₃ , Fe ₂ O ₃ , P ₂ O ₅ , and S. Carbon dioxide, MgO, SiO ₂ , Al ₂ O ₃ , Fe ₂ O ₃ , P ₂ O ₅ using the intensity of the Compton scattering line 4 of a known standard sample for correction made of lime or a standard sample for virtual correction of lime. A matrix correction coefficient is calculated for correcting the calibration curve of ignition loss indicating the correlation between the intensity of Compton scattered radiation and the content of ignition loss with respect to the influence of at least one component of S.

  The calibration curve creating means 11 irradiates the standard sample S made of lime with a known loss ratio of ignition loss and carbon dioxide content with the primary X-ray 2 from the X-ray source 1 and generates from the standard sample S. The detection means 9 detects the intensity of the Compton scattered ray 6A and the intensity of the C-Kα line 6B, creates a calibration curve for ignition loss using the matrix correction coefficient calculated by the correction coefficient calculation means 14, The calibration curve for ignition loss and the calibration curve for carbon dioxide created by creating a calibration curve for carbon dioxide showing the correlation between the intensity of the detected C-Kα line and the content of carbon dioxide are stored.

  The quantification unit 12 irradiates the unknown sample S made of lime with the primary X-ray 2 from the X-ray source 1 and detects the intensity of the Compton scattered ray 6A and the intensity of the C-Kα ray 6B generated from the unknown sample S. The calibration loss curve for ignition loss and the calibration curve for carbon dioxide created by the calibration curve creating means 11 are applied respectively to obtain the ignition loss and carbon dioxide content in the unknown sample S. . The moisture calculation means 13 calculates the moisture content in the ignition loss of the unknown sample S as in the first embodiment.

In the analysis method of the third embodiment, first, a standard sample S made of lime whose ignition loss and carbon dioxide content is known is irradiated with primary X-rays 2 from the X-ray source 1 and the standard sample. The detection means 9 detects the intensity of the Compton scattered radiation 6A generated from S and the intensity of the C-Kα radiation 6B. Next, the theoretical matrix correction coefficient is calculated by the correction coefficient calculation means 14 of the apparatus shown in FIG. 9 using the lime virtual correction standard sample assuming the lime composition as follows. For example, a lime sample is considered to be a binary system of H ₂ O and CaO, and the coexisting components MgO, SiO ₂ , Al ₂ O ₃ , Fe ₂ O ₃ , P are based on an ignition loss of 6 mass%. _The correction coefficient calculation means 14 calculates the theoretical matrix correction coefficient by changing the contents of ₂ O ₅ , S and carbon dioxide. Table 1 shows theoretical matrix correction coefficients obtained by calculation.

  For example, the following equation (1) is used to calculate the theoretical matrix correction coefficient.

  The calibration curve creation means 11 creates a correction calibration curve for ignition loss using the intensity of the Compton scattered ray 6A detected by the detection means 9 and the theoretical matrix correction coefficient calculated by the correction coefficient calculation means 14, and also detects the calibration curve. A calibration curve for carbon dioxide is created and stored using the intensity of the C-Kα line 6B detected by the means 9. FIG. 10 shows the created calibration curve for loss on ignition. In the calibration curve for ignition loss in FIG. 10, the horizontal axis represents the ignition loss content (mass%), and the vertical axis represents the Rh-Kα Compton scattered radiation intensity. The accuracy of the calibration curve for the loss on ignition is 0.146 mass%.

The quantification unit 12 irradiates the unknown sample S made of lime with the primary X-ray 2 from the X-ray source 1, and the Compton scattered ray 6 </ b> A obtained by causing the spectroscopic element 5 to split the secondary X-ray 4 generated from the unknown sample S. The intensity, the intensity of the C-Kα ray 6B, and the intensity of fluorescent X-rays of Mg, Si, Al, Fe, P, and S are detected by the detector 7, and the ignition is created and stored by the calibration curve creating means 11 The weight loss correction calibration curve and the carbon dioxide calibration curve are respectively applied to determine the ignition loss in the unknown sample S and the carbon dioxide content. The moisture calculation means 13 calculates the moisture content in the ignition loss of the unknown sample S by subtracting the carbon dioxide content obtained from the ignition loss content obtained by the quantification means 12. That is, according to the method of the third embodiment, the content of ignition loss in a sample made of lime is determined by coexisting components MgO, SiO ₂ , Al ₂ O ₃ , Fe ₂ O ₃ , P ₂ O ₅ , S and This is an X-ray analysis method for obtaining a carbon dioxide matrix correction and obtaining the content of carbon dioxide and moisture in ignition loss.

In order to evaluate the correction calibration curve for the loss on ignition shown in FIG. 10, matrix correction of coexisting components MgO, SiO ₂ , Al ₂ O ₃ , Fe ₂ O ₃ , P ₂ O ₅ , S and carbon dioxide was performed. A calibration curve of no ignition loss was created and compared. Using the lime standard sample S in which the contents of MgO, SiO ₂ , Al ₂ O ₃ , Fe ₂ O ₃ , P ₂ O ₅ , S and carbon dioxide are in the ranges shown in Table 2 below, a calibration curve creation means 11 A calibration curve for loss on ignition was created. The prepared matrix uncorrected calibration curve for ignition loss is shown in FIG. The accuracy of this matrix uncorrected calibration curve was 0.172 mass%. The accuracy of the matrix correction calibration curve of FIG. 10 obtained above is 0.146 mass%, and it was found that the accuracy of the calibration curve is improved by performing matrix correction. As described above, according to the analysis method of the third embodiment, by performing matrix correction, the accuracy of the calibration curve for ignition loss is improved, and the ignition loss, carbon dioxide and moisture content ratios are more excellent and accurate. Now you can analyze.

In the analysis method of the third embodiment, matrix correction of MgO, SiO ₂ , Al ₂ O ₃ , Fe ₂ O ₃ , P ₂ O ₅ , S and carbon dioxide was performed, but at least one of these components For example, matrix correction may be performed only for carbon dioxide.

  The analysis method according to the fourth embodiment of the present invention will be described below. First, an apparatus used for this method is shown in FIG. Similar to the X-ray analyzer shown in FIG. 9, this apparatus includes an X-ray source 1, a sample stage 8, a spectroscopic element 5, a detecting means 9, a calibration curve creating means 11, a quantifying means 12 and a correction coefficient calculating means 14. However, it is a fluorescent X-ray analyzer that does not include the moisture calculation means 13 and calculates the content of ignition loss in the sample S made of lime.

In the analysis method of the fourth embodiment, first, Compton scattering generated from the standard sample S by irradiating the standard sample S made of lime with a known loss ratio of ignition loss with the primary X-ray 2 from the X-ray source 1. The detection means 9 detects the intensity of the line 6A. Next, in the same manner as in the third embodiment, the correction coefficient calculation means 14 has a matrix correction coefficient of coexisting components MgO, SiO ₂ , Al ₂ O ₃ , Fe ₂ O ₃ , P ₂ O ₅ , S and carbon dioxide. Is calculated. The calibration curve creation means 11 creates and stores a correction calibration curve for ignition loss using the intensity of the Compton scattered ray 6A detected by the detection means 9 and the theoretical matrix correction coefficient calculated by the correction coefficient calculation means 14. . The quantification unit 12 obtains the content of ignition loss in the unknown sample S by using the calibration curve for ignition loss created and stored by the calibration curve creation unit 11. That is, the method of the fourth embodiment is an X-ray analysis method for obtaining the content of ignition loss in a sample made of lime by performing matrix correction.

  According to the method of the fourth embodiment, the accuracy of the calibration curve for ignition loss is improved by performing matrix correction, and the content of ignition loss can be analyzed with better accuracy.

The coexisting components MgO, SiO ₂ , Al ₂ O ₃ , Fe ₂ O ₃ , P ₂ O ₅ and S may be analyzed simultaneously with ignition loss and carbon dioxide. The analysis method is known in that the content of ignition loss and the content of at least one component of carbon dioxide, MgO, SiO ₂ , Al ₂ O ₃ , Fe ₂ O ₃ , P ₂ O ₅ , S are known. A standard sample made of lime is irradiated with primary X-rays, and the intensity of Compton scattered radiation generated from the standard sample and the at least one component among C, Mg, Si, Al, Fe, P, and S The intensity of the Compton scattered ray is detected with respect to the influence of the at least one component by detecting the intensity of the corresponding fluorescent X-ray and using the Compton scattered ray intensity of the correction standard sample made of lime or the virtual correction standard sample of lime. The matrix correction coefficient for correcting the calibration curve for ignition loss indicating the correlation between the content of ignition loss and the ignition loss is obtained, and the intensity of the detected Compton scattered ray and the obtained matrix correction factor are obtained. Is used to create a calibration curve for the at least one component using the corrected calibration curve for loss on ignition and the intensity of the fluorescent X-ray corresponding to the detected at least one component. Irradiating a line, detecting the intensity of Compton scattered radiation generated from the unknown sample, and the intensity of fluorescent X-rays corresponding to the at least one component, and correcting the ignition loss calibration curve and the at least one component Is used to determine the content of ignition loss and the content of the at least one component in the unknown sample.

Furthermore, together with ignition loss, carbon dioxide and moisture in ignition loss, the main component CaO, coexisting components MgO, SiO ₂ , Al ₂ O ₃ , Fe ₂ O ₃ , P ₂ O ₅ and S are analyzed simultaneously. May be.

Along with ignition loss, carbon dioxide and moisture in ignition loss, the main component CaO, coexisting components MgO, SiO ₂ , Al ₂ O ₃ , Fe ₂ O ₃ , P ₂ O ₅ and S are as described above. By analyzing simultaneously, all components required in the lime analysis can be accurately quantified with a fluorescent X-ray analyzer.

  In the third embodiment, the above formula (1) is used as a calculation formula to obtain the theoretical matrix correction coefficient. However, another known calculation formula may be used, or a correction standard sample made of lime is used. Alternatively, the correction coefficient calculation unit 14 may calculate the matrix correction coefficient by regression calculation. Further, the theoretical X-ray intensity is calculated separately without using the correction coefficient calculating means 14, and the theoretical matrix correction coefficient is obtained by a manual calculation method from the relationship with the content rate of the set lime virtual correction standard sample. Also good.

  The apparatus used in the methods of the first to fourth embodiments has been described as a wavelength dispersive fluorescent X-ray analyzer, but may be an energy dispersive fluorescent X-ray analyzer.

  In the present embodiment, a rhodium X-ray tube is used as the X-ray source 1 that generates the primary X-ray 2. However, in the present invention, the target is not limited to the rhodium X-ray tube, and the target is formed of molybdenum, palladium, or the like. An X-ray tube can be used.

  Moreover, although quick lime was demonstrated as a sample in this embodiment, this invention is applicable also to limestone, slaked lime, tancal (calcium carbonate), etc.

DESCRIPTION OF SYMBOLS 1 X-ray source 2 Primary X-ray 4, 6 Secondary X-ray 9 Detection means 11 Calibration curve creation means 12 Determination means 13 Moisture calculation means 14 Correction coefficient calculation means S Sample

Claims (8)

Irradiate a standard sample made of lime with a known loss of ignition loss with primary X-rays,
Detecting the intensity of Compton scattered radiation generated from the standard sample,
Create a calibration curve for ignition loss showing the correlation between the intensity of the detected Compton scattered radiation and the content of ignition loss,
Irradiating an unknown sample made of lime with primary X-rays, detecting the intensity of Compton scattered radiation generated from the unknown sample,
An X-ray analysis method for obtaining a content of ignition loss in the unknown sample by using the calibration curve for ignition loss. Irradiate primary X-rays to a standard sample made of lime with known loss on ignition and carbon dioxide content,
Detecting the intensity of Compton scattered radiation and C-Kα radiation generated from the standard sample,
A calibration curve for ignition loss showing the correlation between the intensity of the detected Compton scattered radiation and the content of ignition loss, and a calibration of carbon dioxide showing the correlation between the intensity of the detected C-Kα ray and the content of carbon dioxide Create a line
Irradiating an unknown sample made of lime with primary X-rays to detect the intensity of Compton scattered rays and C-Kα rays generated from the unknown sample,
Using the calibration curve for ignition loss and the calibration curve for carbon dioxide, the ignition loss and the carbon dioxide content in the unknown sample were determined, respectively.
An X-ray analysis method for obtaining a moisture content in ignition loss of the unknown sample by subtracting the obtained carbon dioxide content from the obtained ignition loss content. An X-ray source for irradiating the sample with primary X-rays;
Detection means for detecting the intensity of secondary X-rays generated from a sample irradiated with primary X-rays from the X-ray source;
An X-ray analyzer comprising:
A standard sample made of lime with a known loss ratio of ignition loss was irradiated with primary X-rays from the X-ray source, and the intensity of Compton scattered rays generated from the standard sample was detected by the detection means, and detected. A calibration curve creation means for creating a calibration curve for ignition loss showing a correlation between the intensity of Compton scattered radiation and the content of ignition loss;
An intense sample created by the calibration curve creating means by irradiating an unknown sample made of lime with primary X-rays from the X-ray source, detecting the intensity of Compton scattered radiation generated from the unknown sample with the detecting means A quantitative means for determining the content of ignition loss in the unknown sample by a calibration curve for weight loss;
An X-ray analyzer comprising: An X-ray source for irradiating the sample with primary X-rays;
Detection means for detecting the intensity of secondary X-rays generated from a sample irradiated with primary X-rays from the X-ray source;
An X-ray analyzer comprising:
A standard sample made of lime with known loss on ignition and carbon dioxide content is irradiated with primary X-rays from the X-ray source, and the intensity of Compton scattered radiation and the intensity of C-Kα rays generated from the standard sample are measured. A calibration curve for loss on ignition showing a correlation between the intensity of the Compton scattered ray detected and the content of loss on ignition detected by the detection means, and the intensity of the detected C-Kα ray and the content of carbon dioxide A calibration curve creation means for creating a calibration curve of carbon dioxide showing the correlation of
A calibration curve is created by irradiating an unknown sample made of lime with primary X-rays from the X-ray source, and detecting the intensity of Compton scattered rays and C-Kα rays generated from the unknown sample with the detection means. Quantification means for determining the ignition loss and carbon dioxide content in the unknown sample by the calibration curve for ignition loss and the calibration curve for carbon dioxide created by the means,
Moisture calculating means for calculating the moisture content in ignition loss of the unknown sample by subtracting the carbon dioxide content determined from the ignition loss content determined by the quantitative means;
An X-ray analyzer comprising: Irradiate a standard sample made of lime with a known loss of ignition loss with primary X-rays,
Detecting the intensity of Compton scattered radiation generated from the standard sample,
For correction of the loss of ignition loss and lime having a known content of at least one of carbon dioxide, MgO, SiO ₂ , Al ₂ O ₃ , Fe ₂ O ₃ , P ₂ O ₅ and S Using a standard sample or a standard sample for virtual correction of lime, for correcting the calibration curve of ignition loss indicating the correlation between the intensity of Compton scattered radiation and the content of ignition loss for the influence of the at least one component Find the matrix correction factor of
Create a calibration curve for loss on ignition using the intensity of the detected Compton scattered radiation and the matrix correction factor obtained,
Irradiate an unknown sample made of lime with primary X-rays, corresponding to the intensity of Compton scattered radiation generated from the unknown sample and the at least one component of C, Mg, Si, Al, Fe, P, S Detecting the intensity of fluorescent X-rays
An X-ray analysis method for obtaining the content of ignition loss in the unknown sample using the calibration curve for ignition loss. Irradiate a standard sample made of lime with a known loss of ignition loss and carbon dioxide content with primary X-rays,
Detecting the intensity of Compton scattered radiation and C-Kα radiation generated from the standard sample,
Matrix correction factor for correction of ignition loss calibration curve showing correlation between Compton scattered radiation intensity and ignition loss content for the effect of carbon dioxide using said standard sample or lime virtual reference sample Seeking
A correction calibration curve for ignition loss is created using the intensity of the detected Compton scattered radiation and the obtained matrix correction coefficient, and the correlation between the intensity of the detected C-Kα ray and the carbon dioxide content is shown. Create a calibration curve for carbon dioxide,
Irradiating an unknown sample made of lime with primary X-rays to detect the intensity of Compton scattered rays and C-Kα rays generated from the unknown sample,
Using the corrected calibration curve for ignition loss and the calibration curve for carbon dioxide, the ignition loss and carbon dioxide content in the unknown sample were determined,
An X-ray analysis method for obtaining a moisture content in ignition loss of the unknown sample by subtracting the obtained carbon dioxide content from the obtained ignition loss content. An X-ray source for irradiating the sample with primary X-rays;
Detection means for detecting the intensity of secondary X-rays generated from a sample irradiated with primary X-rays from the X-ray source;
An X-ray analyzer comprising:
For correction of the loss of ignition loss and lime having a known content of at least one of carbon dioxide, MgO, SiO ₂ , Al ₂ O ₃ , Fe ₂ O ₃ , P ₂ O ₅ and S Using a standard sample or a standard sample for virtual correction of lime, for correcting the calibration curve of ignition loss indicating the correlation between the intensity of Compton scattered radiation and the content of ignition loss for the influence of the at least one component Correction coefficient calculation means for calculating the matrix correction coefficient of
A standard sample made of lime whose ignition loss content is known is irradiated with primary X-rays from the X-ray source, and the intensity of Compton scattered radiation generated from the standard sample is detected by the detection means, and the detection is performed. Calibration curve creation means for creating a corrected calibration curve for loss on ignition using the intensity of the Compton scattered radiation and the matrix correction coefficient calculated by the correction coefficient calculation means;
Irradiating an unknown sample made of lime with primary X-rays from the X-ray source, the intensity of Compton scattered rays generated from the unknown sample, and at least one of C, Mg, Si, Al, Fe, P, and S The intensity of fluorescent X-rays corresponding to one component is detected by the detection means, and the ignition loss content in the unknown sample using the calibration curve for ignition loss created by the calibration curve creation means Quantification means for obtaining
An X-ray analyzer comprising: An X-ray source for irradiating the sample with primary X-rays;
Detection means for detecting the intensity of secondary X-rays generated from a sample irradiated with primary X-rays from the X-ray source;
An X-ray analyzer comprising:
Using a standard sample of lime with known loss of ignition loss and carbon dioxide or a virtual reference sample of lime, the effect of carbon dioxide on the intensity of Compton scattered radiation and the loss of ignition loss A correction coefficient calculating means for calculating a matrix correction coefficient for correcting the calibration curve of ignition loss indicating correlation;
The standard sample is irradiated with primary X-rays from the X-ray source, the intensity of Compton scattered radiation and C-Kα radiation generated from the standard sample is detected by the detection means, and the detected Compton scattered radiation is detected. A correction calibration curve for ignition loss is created using the matrix correction coefficient calculated by the intensity and the correction coefficient calculation means, and the correlation between the detected C-Kα line intensity and the carbon dioxide content is shown. A calibration curve creation means for creating a calibration curve for carbon dioxide;
A calibration curve is created by irradiating an unknown sample made of lime with primary X-rays from the X-ray source, and detecting the intensity of Compton scattered rays and C-Kα rays generated from the unknown sample with the detection means. Quantification means for determining the ignition loss and carbon dioxide content in the unknown sample using the calibration loss curve and the carbon dioxide calibration curve created by the means,
Moisture calculating means for calculating the moisture content in ignition loss of the unknown sample by subtracting the carbon dioxide content determined from the ignition loss content determined by the quantitative means;
An X-ray analyzer comprising:

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