JPH07280751A - Coal ash estimating method by fluorescent x-ray analysis - Google Patents

Abstract

PURPOSE:To lower the error of coal ash estimation by fluorescent x-ray analysis by computing the coal ash quantity from content of each component obtained by fluorescent x-ray analysis based on a specified equation. CONSTITUTION:Coal is pulverized and a binder is added thereto and press- forming is carried out to give a briquette specimen. X-ray intensity for Si, AQ, P, Ti, Ca, Mg, Fe, Mn, and S is measured by carrying out fluorescent x-ray analysis for the specimen. Based on the working curve at zero intensity of fluorescent x-ray at the time when no element exists, said working curve is set previously based on the x-ray intensity for each element, the content of each component of SiO2, Al2O3, P2O5, TiO2, CaO, MgO, Fe2O3, MnO, and total S is obtained by conversion. The coal ash quantity is computed from the content of each component based on the equation wherein A4=1.116, B4=0.945, C3=1.819, D3= 0.791, E3=0.944, F1=0.546, J4=0.141. Consequently, the number of analysis processes is lessened and labour is saved as compared with chemical analysis by JIS method.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for estimating coal ash content by fluorescent X-ray analysis capable of estimating ash content in coal in a short time and with high accuracy.

[0002]

Blast furnace coke usually has a water content of 8 to 10%.
It is manufactured by blending and pulverizing several types of raw material coal of several types to more than 10 types in a predetermined ratio and with a predetermined particle size to prepare a charging coal, charging it into a carbonization chamber of a chamber furnace type coke oven, and performing high temperature carbonization. . The coke strength and coke ash content of the blast furnace coke are controlled to predetermined values from the viewpoint of stable operation of the blast furnace and heat balance. The management of the coke ash content is performed according to JIS M 8812 by comparing the ash content of each coal brand at the preparation stage of charging coal.
The raw material coal was blended so that the coke ash content would be a predetermined value, as measured by chemical analysis by the industrial analysis method of coals and cokes prescribed in 1.

The ash content in coal is measured by an industrial analysis method for coals and cokes specified in JIS M 8812 described above. After ashing (combusting) coal in air at 815 ° C ± 10 ° C, the coal is cooled and then cooled. Immediately, the mass was measured to obtain the ash amount, and the ash content was obtained by a predetermined calculation formula. However, according to the method specified in JIS M 8812, it takes at least 4 to 5 hours for measurement and is not only inefficient. In addition, in order to prepare charging coal, dozens of brands It is necessary to measure the ash content, and the measurement man-hour is enormous.

As a method of estimating the ash content in coal in a short time, the coal is subjected to fluorescent X-ray analysis to obtain S in the coal.
i, Ca, Al, Fe, Mg are measured, and
A method of calibrating the amount of each component of O ₂ , CaO, Al ₂ O ₃ , Fe ₂ O ₃ , and MgO and estimating the ash content of coal from the total amount of each component (JP-A-51-105888) is proposed. Has been done.

[0005]

DISCLOSURE OF THE INVENTION Problems to be Solved by the Invention
The method disclosed in Japanese Patent No. 5888 discloses a method in which coal is crushed to 60 mesh or less, then the crushed coal is put in a container, and pressure is applied to the container from above for 20 to 35 t / cm ^{2 for} about 5 to 15 seconds for briquette. and Jo samples subjected to the fluorescent X-ray analyzer, SiO ₂ in _{coal, CaO, Al 2 O 3,} Fe
_The amount of each component of ₂ O ₃ and MgO is read from the calibration curve preset based on the X-ray intensity display of Si, Ca, Al, Fe and Mg displayed on the fluorescent X-ray analyzer, and the amount of each component is read. Is estimated as an approximate value of coal ash content. However, in the method disclosed in Japanese Patent Laid-Open No. 51-105888, cracks are likely to occur on the surface when the sample is pressure-molded into a briquette, and as shown in FIGS. X-ray intensity is confirmed even when the content of is zero, and as shown in FIG. 22 (c), when the X-ray intensity in the calibration curve is conversely zero, the phenomenon of element detection occurs and analysis is performed. Accuracy deteriorated, ash estimated value and JIS M
It has a drawback that the estimated ash value cannot be adopted for production control in actual operation because the error with the ash value by the industrial analysis method prescribed in 8812 is large.

The object of the present invention is to obtain the above-mentioned Japanese Patent Laid-Open No. 51-10.
The drawbacks of the method disclosed in Japanese Patent No.
An object of the present invention is to provide a method for estimating coal ash content by fluorescent X-ray analysis, which has an extremely small error from the ash content value according to the industrial analysis method specified in M 8812.

[0007]

Means for Solving the Problems The inventors of the present invention have conducted various tests and examinations in order to achieve the above object. As a result, by adding a binder when pressure-molding the sample into a briquette, it is possible to prevent crack generation on the sample surface,
By improving the calibration curve so that the X-ray intensity becomes zero when the element is zero, the detection accuracy of each component amount is improved, and the amount of coal ash based on the predetermined estimation formula from the content ratio of each component obtained from the calibration curve Is calculated according to JIS M 88
The error from the ash value by the industrial analysis method specified in 12 is ± 0.
The inventors have reached the present invention by investigating that it is extremely small at 2% or less.

That is, the first invention of the present application is a method for estimating ash content in coal by fluorescent X-ray analysis, in which coal is crushed, a binder is added and mixed, and pressure molding is performed to form a briquette-like sample, Fluorescent X-ray analyzer for Si, Al, C
a, X-ray intensities of Fe are measured, and when the element is preset to zero based on the measured X-ray intensities of the respective elements, SiO ₂ , Al ₂ O ₃ , CaO, Fe are obtained from the calibration curve of zero fluorescent X-ray intensity. ₂ O ₃
The content of each component is converted, and the amount of coal ash is calculated from the content of each component based on the following ash estimation formula (1). _{Ash (%) = (A 1} × SiO 2 + B 1 × Al 2 O 3 + C 1 × CaO + D 1 × Fe 2 O 3) + J 1 ... (1) _{However, A 1 = 1.117, B 1} = 1. 007, C ₁ =
2.094, D ₁ = 0.830, J ₁ = 0.447

The second invention of the present application is to detect the ash content in coal by fluorescent X
In the method of estimating by line analysis, coal is crushed and bonded.
Mix and mix the mixture, and press-mold it into a briquette-shaped sample.
None, Si, Al, P, Ti, X-ray fluorescence analyzer
The X-ray intensity of Mg was measured, and the measured X-ray intensity of each element
Based on the preset element zero, the fluorescent X-ray intensity is zero.
From the calibration curve SiO₂, Al₂O₃, P₂O_Five, TiO₂, Mg
Converting the content rate of each component of O, the following ash is calculated from the content rate of each component.
To calculate the amount of coal ash based on the minute estimation formula (2)
A method for estimating coal ash content by a characteristic X-ray fluorescence analysis.
It Ash (%) = (A₂× SiO₂+ B₂× Al₂O₃+ P₂O_Five  + E₁× TiO₂+ MgO) + J₂(2) However, A₂= 0.816, B₂= 1.029, E₁=
0.913, J₂= 2.396

The third invention of the present application is to detect the ash content in coal by fluorescent X
In the method of estimating by line analysis, coal is crushed, a binder is added and mixed, and pressure molding is performed to form a briquette-like sample, and Si, Al, Ca, F is subjected to a fluorescent X-ray analyzer.
The X-ray intensities of e, P, Ti and Mg were measured, and when the element was preset to zero based on the measured fluorescent X-ray intensities of the respective elements, SiO ₂ and Al ₂ O were obtained from the calibration curve of zero fluorescent X-ray intensity. ₃ , C
It is characterized in that the content of each component of aO, Fe ₂ O ₃ , P ₂ O ₅ , TiO ₂ , and MgO is converted, and the amount of coal ash is calculated from the content of each component based on the following ash content estimation formula (3). Is a method for estimating coal ash content by fluorescent X-ray analysis. _{Ash (%) = (A 3} × SiO 2 + B 3 × Al 2 O 3 + C 2 × CaO + D 2 × Fe 2 O 3 + P 2 O 5 + E 2 × TiO 2 + MgO) + J 3 ... (3) However, A _{3 = 1.127, B 3 = 0.955,} C 2 =
1.775, D ₂ = 0.869, E ₂ = 0.777, J ₃
= 0.345

The fourth invention of the present application is to detect the ash content in coal by fluorescent X
In a method of estimating by line analysis, coal is crushed, a binder is added and mixed, and pressure molding is performed to form a briquette-like sample, and Si, Al, P, Ti,
The X-ray intensities of Ca, Mg, Fe, Mn, and S were measured, and when the element was preset to zero based on the measured X-ray intensities of the respective elements, SiO ₂ , Al from the calibration curve of zero fluorescent X-ray intensity.
₂ O ₃ , P ₂ O ₅ , TiO ₂ , CaO, MgO, Fe ₂ O ₃ ,
A method for estimating coal ash content by fluorescent X-ray analysis, characterized in that the content of each component of MnO and Total S is converted and the amount of coal ash is calculated from the content of each component based on the following ash content estimation formula (4). is there. _{Ash (%) = (A 4} × SiO 2 + B 4 × Al 2 O 3 + C 3 × CaO + D 3 × Fe 2 O 3 + P 2 O 5 + E 3 × TiO 2 + MgO + MnO + F 1 × Total S) + J 4 ... (4 ) However, A ₄ = 1.116, B ₄ = 0.945, C ₃ =
_{1.819, D 3 = 0.791, E} 3 = 0.944, F 1
= 0.546, J ₄ = 0.141

[0012]

In the present invention, by crushing coal, adding and mixing the binder, and press-molding it into a briquette-like sample, the occurrence of surface cracks during press-molding is prevented,
The analysis accuracy of each element can be improved. First of this application
In the invention, calculated SiO ₂ , Al ₂ O ₃ , Ca
The above ash content estimation formula (1) from the content ratios of O and Fe ₂ O ₃
By calculating the amount of coal ash based on the above, the error between the estimated ash content and the ash content value by the chemical analysis method specified in JIS M 8812 is set to ± 0.2% or less which can be applied to the coke ash management in actual operation. It is possible to measure the ash content in coal used in the actual operation of coke ash management according to JIS M8.
It became possible to replace the chemical analysis method prescribed in 812 with the fluorescent X-ray analysis method. As a result, the number of man-hours required for ash content measurement can be significantly reduced from about 4 hours for one brand to 30 minutes, about 1/8, and labor saving of analysis personnel can be achieved.

In the second invention of the present application, coal ash is calculated from the calculated content ratios of SiO ₂ , Al ₂ O ₃ , P ₂ O ₅ , TiO ₂ and MgO based on the ash estimation formula (2). By calculating the quantity, the ash estimated value and JIS M
The error from the ash value by the chemical analysis method prescribed in 8812 is
It can be set to ± 0.2% or less which can be applied to the coke ash management of the actual operation, and the ash content in the coal used for the coke ash management of the actual operation can be measured by fluorescent X-ray analysis from the chemical analysis method prescribed in JIS M 8812. It became possible to replace it with the law. As a result, the number of man-hours required for ash measurement is from 3 hours per brand to 3 hours.
The time can be reduced to about 1/8, and the labor required for the analysis staff can be reduced.

Further, in the third invention of the present application, calculated SiO ₂ , Al ₂ O ₃ , CaO, Fe ₂ O ₃ , P ₂ O ₅ ,
By calculating the amount of coal ash based on the ash content estimation formula (3) from the content of each component of TiO ₂ and MgO,
The error between the estimated ash value and the ash value according to the chemical analysis method specified in JIS M 8812 can be set to ± 0.2% or less applicable to the coke ash management in the actual operation, and is used for the coke ash management in the actual operation. Measure ash content in coal according to JIS
It has become possible to replace the chemical analysis method specified in M 8812 with the fluorescent X-ray analysis method. As a result, the number of man-hours required for ash content measurement can be significantly reduced from about 4 hours for one brand to 30 minutes, about 1/8, and labor saving of analysis personnel can be achieved.

Furthermore, in the fourth invention of the present application,
SiO _2, Al ₂ O ₃ the _{calculated, P 2 O 5, TiO 2} , Ca
The ash content and JIS M are calculated by calculating the coal ash content based on the ash content estimation formula (4) from the content ratios of O, MgO, Fe ₂ O ₃ , MnO, and Total S.
The error from the ash value by the chemical analysis method prescribed in 8812 is
It can be set to ± 0.2% or less which can be applied to the coke ash management of the actual operation, and the ash content in the coal used for the coke ash management of the actual operation can be measured by fluorescent X-ray analysis from the chemical analysis method prescribed in JIS M 8812. It became possible to replace it with the law. As a result, the number of man-hours required for ash measurement is from 3 hours per brand to 3 hours.
The time can be reduced to about 1/8, and the labor required for the analysis staff can be reduced.

In the present invention, polystyrene maleic acid polymer, starch or the like can be used as the binder to be added to and mixed with the crushed coal during pressure molding. The pressure when press-molding into a briquette sample is 3 t / cm
^{It is 2} or more, preferably 20 to 35 t / cm ² . Since the briquette-like sample needs to have a measuring surface of 20 mm or more in outer diameter, it is desirable to use a ring container having an outer diameter of 25 to 35 mm during pressure molding.

The calculation of the content rate of each component based on the X-ray intensity of Si, Al, Ca, Fe measured by the fluorescent X-ray analyzer in the first invention of the present application is based on the measured X-ray intensity of each element. It can be read from a calibration curve of zero X-ray intensity when the element is preset to zero, but Si, Al, Ca,
Substituting the fluorescent X-ray intensity of each element of Fe into the following formula, SiO
It is also possible to calculate the content of each component of ₂ , Al ₂ O ₃ , CaO, and Fe ₂ O ₃ . _{SiO 2 = 0.144 × I o -0.312} Al 2 O 3 = 0.135 × I 1 -0.061 CaO = 0.023 × I 2 -0.019 Fe 2 O 3 = 0.004 × I ₃ +0.012 where I _{o to} I ₃ are X-ray intensities of each element

Further, the calculation of the content rate of each component based on the X-ray intensities of Si, Al, P, Ti and Mg measured by the fluorescent X-ray analyzer in the second invention of the present application is carried out by measuring the X-ray intensities of the respective elements. It is possible to read from a calibration curve of zero X-ray intensity when the element is zero, which is preset based on
Substituting the X-ray intensities of 1, P, Ti, and Mg into the following formula, Si
It is also possible to calculate the content of each component of O ₂ , Al ₂ O ₃ , P ₂ O ₅ , TiO ₂ , and MgO. SiO ₂ = 0.144 × I _o −0.312 Al ₂ O ₃ = 0.135 × I ₁ −0.061 P ₂ O ₅ = 0.040 × I ₄ +0.001 TiO ₂ = 0.012 × I _{5 -0.019 MgO = 1.185 × I 6} -0.089 _{However, I o ~I 1, I 4} ~I 6 is X-ray intensity of each element

Furthermore, Si, Al, Ca, Fe, P, T measured by the fluorescent X-ray analyzer in the third invention of the present application
The calculation of the content rate of each component based on the X-ray intensity of i and Mg can be read from the calibration curve of zero X-ray intensity when the element is preset to zero based on the measured X-ray intensity of each element. Substituting the X-ray intensities of Si, Al, Ca, Fe, P, Ti, and Mg into the following formula, SiO ₂ , Al ₂ O ₃ , CaO, F
It is also possible to calculate the content of each component of e ₂ O ₃ , P ₂ O ₅ , TiO ₂ , and MgO. _{SiO 2 = 0.144 × I o -0.312} Al 2 O 3 = 0.135 × I 1 -0.061 CaO = 0.023 × I 2 -0.019 Fe 2 O 3 = 0.004 × I _{3 +0.012 P 2 O 5 = 0.040} × I 4 +0.001 TiO 2 = 0.012 × I 5 -0.019 MgO = 1.185 × I 6 -0.089 However, I _o ~I ₆ Is the X-ray intensity of each element

Furthermore, Si, Al, P, Ti, C measured by the fluorescent X-ray analyzer in the fourth invention of the present application
The content of each component based on the X-ray intensity of a, Mg, Fe, Mn, and S is calculated from the calibration curve of zero X-ray intensity when the element is zero, which is preset based on the measured X-ray intensity of each element. Can be read, but Si, Al, P, Ti, Ca, M
Substituting the X-ray intensities of g, Fe, Mn, and S into the following formula, Si
O ₂ , Al ₂ O ₃ , P ₂ O ₅ , TiO ₂ , CaO, MgO, F
It is also possible to calculate the content of each component of e ₂ O ₃ , MnO, and Total S. SiO ₂ = 0.144 × I _o −0.312 Al ₂ O ₃ = 0.135 × I ₁ −0.061 P ₂ O ₅ = 0.040 × I ₂ +0.001 TiO ₂ = 0.012 × I ₃ -0.019 CaO = 0.023 x I ₄ -0.019 MgO = 1.185 x I ₅ -0.089 Fe ₂ O ₃ = 0.004 x I ₆ + 0.012 MnO = 0.003 x I _{7 -0.004 Total S = 0.008 × I} 8 -0.039 However, I _o ~I ₈ is X-ray intensity of each element

In the present invention, the X-ray fluorescence analyzer is linked to a computer to calculate the content rate of each component by the stored calibration curve formula of each component, and the ash content estimation formulas (1) to It is also possible to calculate the ash value in coal by any of (4) and print it as a quantitative value.

[0022]

【Example】

Example 1 Using a standard sample measured by a chemical analysis method defined in JIS M 8812, a standard sample coal pulverized to a total amount of 200 mesh or less in 3 minutes by a disc mill, 6 g of coal and 4 g of styrene-malenic acid polymer were mixed with a V-type mixer. Was mixed for 5 minutes, and the Fe ring having an inner diameter of 35 mm was cut into 5 mm pieces and filled into a ring. The pressure was 30 t / cm ² , and the pressurizing time was 1
A briquette-like sample having an outer diameter of 35 mm and a thickness of 3 mm was prepared by pressure molding for 5 seconds. The obtained briquette-like samples were measured for Si, Al, P, Ti, Ca, Mg, Fe, M under the measurement conditions shown in Table 1 by using a multi-element simultaneous measurement fluorescent X-ray apparatus.
X-ray intensities of n and S were measured, and SiO ₂ , Al ₂ O ₃ and P ₂ O were measured.
₅ , TiO ₂ , CaO, MgO, Fe ₂ O ₃ , MnO, To
A calibration curve with zero X-ray intensity was obtained when the element of each component of tal S was zero. The results are shown in FIGS. Further, Table 2 shows a calibration curve formula in which the X-ray intensity is zero when the element is zero.

[0023]

[Table 1]

[0024]

[Table 2]

As shown in FIGS. 1 to 9, the X-ray intensity of each element becomes zero when each component is zero due to the improvement of the calibration curve, the detection accuracy of each component amount is improved, and each component amount can be accurately detected. Recognize.

Example 2 The estimated ash content in coal by the fluorescent X-ray analysis of the method of the present invention and the comparative example was compared with the ash value of the JIS method measured by the chemical analysis method specified in JISM 8812. The estimation of the ash content in the coal by the fluorescent X-ray analysis of the method of the present invention and the comparative example was performed according to JIS M8810.
0 brand coal was crushed to a total amount of 200 mesh or less in 3 minutes using a disc mill, and 6 g of each coal
And 4 g of styrene-malenic acid polymer were mixed using a V-type mixer for 5 minutes, and a Fe ring having an inner diameter of 35 mm was cut into 5 mm pieces and filled in a container. The pressure was 30 t / cm ² and the pressurizing time was 15 seconds. Outer diameter 35mm, thickness 3mm by pressure molding
The briquette-like sample of was prepared.

Each briquette sample thus obtained was analyzed by a multi-element simultaneous fluorescent X-ray apparatus under the measurement conditions shown in Table 1, Si,
The X-ray intensities of Al, P, Ti, Ca, Mg, Fe, Mn, and S were measured, and based on the measured X-ray intensities of the respective elements, when the preset element was zero, the fluorescent X-ray intensity was zero. Figure 1
From the calibration curve shown in FIG. 9, SiO ₂ , Al ₂ O ₃ , P ₂ O ₅ , T
iO ₂ , CaO, MgO, Fe ₂ O ₃ , MnO, Tota
The ash content estimation formulas (1) to (4) of the present invention and the ash content estimation of the comparative example, which are obtained by converting the content rate of each component of 1 S and determining the content rate of each component by the nonlinear least squares method as shown in Table 3. The amount of coal ash was calculated based on the equations (5) to (10).
The results are shown in Table 4 and FIGS. 10 to 19, the simple correlation regression equation and the correlation coefficient (γ) obtained from the number of samples (n), the JIS method (x) and the estimated value (y).
Is also described.

[0028]

[Table 3]

[0029]

[Table 4]

As shown in Table 4 and FIGS. 10 to 19,
As shown in Table 4 and FIG. 10, FIG. 11, FIG. 13, and FIG. 15, the ash estimation values calculated by the ash estimation formulas (1) to (4) in coal of the present invention are all maximum error rates of estimation accuracy. Was 0.20% or less, and it was possible to use as an ash value in coal in coal blending for coke ash management in actual operation.

Comparative Example 1 Estimated value of ash content in coal by fluorescent X-ray analysis by the method disclosed in JP-A-51-105888 and JIS M
8812 was compared with the ash value of the JIS method measured by the chemical analysis method prescribed in 8812. The results are shown in Table 3 and FIG.
Shown in. To estimate the ash content in coal according to JP-A-51-105888, 20 brands of coal shown in Table 5 sampled according to JIS M 8810 were pulverized to a total amount of 60 mesh or less using a disc mill, and an inner diameter of 35 mm was determined. F
Fill the e-ring into 5 mm slices, and press the pressure 3
Outer diameter of 3 by press molding at 0 t / cm ^{2 for} 15 seconds
A briquette-shaped sample having a thickness of 5 mm and a thickness of 3 mm was prepared. Each of the obtained briquette-like samples was measured for Si, Ca, A under the measurement conditions shown in Table 1 above using a multi-element simultaneous measurement fluorescent X-ray apparatus.
The X-ray intensities of 1, Fe, and Mg were measured, and the method disclosed in JP-A-51-10
From the calibration curve disclosed in No. 5888, SiO2, CaO,
The amount of each component of Al2O3, Fe2O3, and MgO was read, and the total amount of each component was estimated as an approximate value of the coal ash content. The results are shown in Table 5.

[0032]

[Table 5]

As shown in Table 5 and FIG. 20, there is a difference of 0.6 to 1.8% in the ash content in the coal between the value measured by the JIS method and the value estimated by JP-A-51-105888. 20 is said to be applicable to the actual operation, and all of the values are out of the range of ± 0.2% shown by the one-dot chain line, and the estimated value according to JP-A-51-105888 is the ash value in coal blending in the actual operation. It is impossible to apply as.

Example 3 The estimated ash content in coal by fluorescent X-ray analysis according to the method of the present invention was compared with the ash value of JIS method measured by the chemical analysis method specified in JIS M 8812. The result is shown in FIG. For comparison, the above-mentioned JP-A-51-1 is used.
The ash content in coal was estimated by fluorescent X-ray analysis by the method disclosed in No. 05888, and the results are also shown in FIG. The ash content in coal by fluorescent X-ray analysis according to the present invention was sampled according to JIS M 8810 1
Eight brands of coal were pulverized to a total amount of 200 mesh or less in 3 minutes using a disc mill, and 6 g of each coal
And 4 g of styrene-malenic acid polymer were mixed using a V-type mixer for 5 minutes, and a Fe ring having an inner diameter of 35 mm was cut into 5 mm pieces and filled in a container. The pressure was 30 t / cm ² and the pressurizing time was 15 seconds. Outer diameter 35mm, thickness 3mm by pressure molding
The briquette-like sample of was prepared.

Each briquette-like sample thus obtained was analyzed by a multi-element simultaneous measurement fluorescent X-ray apparatus under the measurement conditions shown in Table 1, Si,
The X-ray intensities of Al, P, Ti, Ca, Mg, Fe, Mn, and S were measured, and based on the measured X-ray intensities of the respective elements, when the preset element was zero, the fluorescent X-ray intensity was zero. Figure 1
From the calibration curve shown in FIG. 9, SiO ₂ , Al ₂ O ₃ , P ₂ O ₅ , T
iO ₂ , CaO, MgO, Fe ₂ O ₃ , MnO, Tota
The content of each component of 1 S was calculated, and the amount of coal ash was calculated from the content of each component based on the ash estimation formula (4).
Further, the estimation of the ash content in coal according to JP-A-51-105888 is carried out by grinding each of the above 18 brands of coal into a total of 60 mesh or less by using a disc mill, and Fe having an inner diameter of 35 mm.
Fill the container with the ring sliced into 5 mm and apply pressure 30
t / cm ² , pressure time 15 seconds, pressure molding, outer diameter 35
A briquette sample having a thickness of 3 mm and a thickness of 3 mm was prepared. Each of the obtained briquette-shaped samples was measured for Si, Ca, Al, F under the measurement conditions shown in Table 1 by using a multi-element simultaneous measurement fluorescent X-ray apparatus.
e, the X-ray intensity of Mg was measured,
From the calibration curve disclosed in No. 8, SiO2, CaO, Al2
The amount of each component of O3, Fe2O3, and MgO was read, and the total amount of each component was estimated as an approximate value of the coal ash content.

As shown in FIG. 21, the estimated ash content according to the method of the present invention is approximately similar to the value measured by the JIS method, and it is said that it can be applied to actual operation.
It is within the range of 0.2%. On the other hand, the estimated ash content according to JP-A-51-105888 of the comparative example is shown by the one-dot chain line in FIG. 21, which is said to be applicable to the actual operation.
All brands are significantly out of the 0.2% range.
On the other hand, the ash content estimation formulas (5) to (1) in coal of Comparative Example
The ash estimated value calculated in 0) is shown in Table 6, FIG. 12, and FIG.
4. As shown in FIGS. 16 to 19, the maximum error of the estimation accuracy exceeds 0.20%, and the maximum error between the JIS method and the estimated value is 0.18% and 1.49% at the maximum. Therefore, it was not possible to use it as the ash value in coal in the coal blending for coke ash management in actual operation.

Example 4 Tables 6 to 9 sampled according to JIS M 8810
The method of the present invention was applied to coal of 77 samples of 41 brands shown in Table 8.
Of ash content in coal by X-ray fluorescence analysis with JI,
J measured by the chemical analysis method specified in S M 8812
A comparison was made with the ash value of the IS method. The results are shown in Table 6 to Table
8 shows. In each coal by X-ray fluorescence analysis according to the present invention
The ash content is estimated in 3 minutes using a disc mill.
6g of each coal and styrene
Mix 4 g of maleic acid polymer for 5 minutes using a V-type mixer.
And cut the Fe ring with an inner diameter of 35mm into 5mm.
Filled in a container, pressure 30t / cm², Pressurizing time 15 seconds
It is pressure-molded with a briquette with an outer diameter of 35 mm and a thickness of 3 mm.
A scaly sample was prepared. Each briquette sample obtained was
Simultaneous measurement of elements Using a fluorescent X-ray device, the measurement shown in Table 1 above
Si, Al, P, Ti, Ca, Mg, Fe, M under the conditions
The X-ray intensity of n and S was measured, and the X-ray intensity of each element measured
X-ray intensity when the element is preset to zero based on
From the calibration curve shown in FIGS.₂, Al₂O
₃, P₂O _Five, TiO₂, CaO, MgO, Fe₂O₃, Mn
The content rate of each component of O and Total S was calculated, and the content of each component was calculated.
Coal ash content based on the above ash content estimation formula (4) from the content rate
Was calculated. Table 6 to Table 8 show the content of each component (fluorescent X-ray analysis
Value (%)), JIS method ash content (%), estimated ash content (%), J
IS method-shows estimated value (%).

[0038]

[Table 6]

[0039]

[Table 7]

[0040]

[Table 8]

As shown in Tables 6 to 8, the estimated ash values of coal of 77 brands of 41 brands by fluorescent X-ray analysis according to the present invention are all ash content of JIS method measured by the chemical analysis method specified in JIS M 8812. The difference from the value is ± 0.2% or less, which shows the accuracy that can be used as the ash value in coal in the coal blend for coke ash management in actual operation.

[0042]

As described above, according to the method of the present invention, as an ash value in coal in coal blending for coke ash management in actual operation by fluorescent X-ray analysis, very quickly and with high accuracy. The usable ash value can be estimated. As a result, compared with the conventional chemical analysis by the JIS method, the analysis man-hours can be significantly reduced, and the labor of the workers can be saved.

[Brief description of drawings]

1 is a graph showing the relationship between the SiO ₂ (%) and X-ray intensity of the peak indicating SiO ₂ of the calibration curve (Si).

2 is a graph showing the relationship between, Al ₂ O _3, based on showing the calibration curve of Al ₂ O ₃ (%) and X-ray intensity (Al).

3 is a graph showing the relationship between the _{P 2 O P 2 O 5 (} %) showing a calibration curve of ₅ and X-ray intensity (P).

4 is a graph showing the relationship between the TiO ₂ illustrating the TiO ₂ of the calibration curve (%) and X-ray intensity (Ti).

FIG. 5 is a graph showing a relationship between CaO (%) showing a calibration curve of CaO and X-ray intensity (Ca).

FIG. 6 is a graph showing a relationship between MgO (%) showing a calibration curve of MgO and X-ray intensity (Mg).

7 is a graph showing the relationship between the Fe ₂ Fe ₂ O _3, which shows the calibration curve of the O ₃ (%) and X-ray intensity (Fe).

FIG. 8 is a graph showing a relationship between MnO (%) showing a calibration curve of MnO and X-ray intensity (Mn).

FIG. 9: Total S showing a calibration curve of Total S
It is a graph which shows the relationship between (%) and X-ray intensity (S).

FIG. 10 is a graph showing the relationship between the ash value of the JIS method and the ash value estimated by the ash estimation formula (1) of the present invention.

FIG. 11 is a graph showing the relationship between the ash value of the JIS method and the ash value estimated by the ash estimation formula (2) of the present invention.

FIG. 12 is a graph showing the relationship between the ash value of the JIS method and the ash value estimated by the ash estimation formula (5) of the comparative example.

FIG. 13 is a graph showing the relationship between the ash value of the JIS method and the ash value estimated by the ash estimation formula (3) of the present invention.

FIG. 14 is a graph showing the relationship between the ash value of the JIS method and the ash value estimated by the ash estimation formula (6) of the comparative example.

FIG. 15 is a graph showing the relationship between the ash value of the JIS method and the ash value estimated by the ash estimation formula (4) of the present invention.

FIG. 16 is a graph showing the relationship between the ash value of the JIS method and the ash value estimated by the ash estimation formula (7) of the comparative example.

FIG. 17 is a graph showing the relationship between the ash value of the JIS method and the ash value estimated by the ash estimation formula (8) of the comparative example.

FIG. 18 is a graph showing the relationship between the ash value of the JIS method and the ash value estimated by the ash estimation formula (9) of the comparative example.

FIG. 19: Ash value of JIS method and ash estimation formula (1
It is a graph which shows the relationship with the estimated ash value by 0).

FIG. 20: JIS method ash value and JP-A-51-10588
8 is a graph showing the relationship with the estimated ash value by the method disclosed in No. 8.

FIG. 21 is a ash value of JIS method and an ash value estimated by the ash estimation formula (4) of the present invention, and a comparative example of JP-A-51-51.
It is a graph which shows the relationship with the estimated ash value by the method disclosed in -1088888.

FIG. 22: SiO disclosed in JP-A-51-105888
Fig. ₂ shows calibration curves of ₂ , CaO, and Al ₂ O ₃ , where (a) is a graph showing the relationship between SiO ₂ content and X-ray intensity (Si), and (b) is a CaO content and X-ray. A graph showing the relationship with the intensity (Ca), and a diagram (c) is a graph showing the relationship between the Al ₂ O ₃ content and the X-ray intensity (Ca).

 ─────────────────────────────────────────────────── ─── Continuation of the front page (72) Masatsugu Takenaka, 3 Oza, Oshima, Kashima-machi, Kashima-gun, Ibaraki Prefecture Sumitomo Metal Industries, Ltd. Kashima Steel Works (72) Kiichiro Shimura, Otsuka, Oshima, Kashima-machi, Kashima-gun, Ibaraki Prefecture Address Sumitomo Metal Industries Co., Ltd. Kashima Steel Works

Claims (5)

[Claims] 1. A method for estimating the ash content in coal by fluorescent X-ray analysis, wherein coal is crushed, a binder is added and mixed, and pressure molding is performed to form a briquette-like sample, which is then subjected to a fluorescent X-ray spectrometer. The X-ray intensity of Si, Al, Ca, Fe was measured, and when the element preset based on the measured X-ray intensity of Si, Al, Ca, Fe was zero, from the calibration curve of zero X-ray intensity, SiO ₂ , A fluorescent X-ray characterized by converting the content of each component of Al ₂ O ₃ , CaO and Fe ₂ O ₃ and calculating the amount of coal ash from the content of each component based on the following ash estimation formula (1). Method for estimating coal ash content by analysis. _{Ash (%) = (A 1} × SiO 2 + B 1 × Al 2 O 3 + C 1 × CaO + D 1 × Fe 2 O 3) + J 1 ... (1) _{However, A 1 = 1.117, B 1} = 1. 007, C ₁ =
2.094, D ₁ = 0.830, J ₁ = 0.447 2. A method for estimating ash content in coal by fluorescent X-ray analysis, wherein coal is crushed, a binder is added and mixed, and pressure molding is performed to form a briquette-like sample, which is then subjected to a fluorescent X-ray analyzer. The X-ray intensities of Si, Al, P, Ti, and Mg were measured, and when the element was preset to zero based on the measured X-ray intensities of the respective elements, the fluorescence X-ray intensity was zero.
The content ratio of each component of O ₂ , Al ₂ O ₃ , P ₂ O ₅ , TiO ₂ , and MgO is converted, and the ash content estimation formula (2) below is calculated from the content ratio of each component.
A method for estimating coal ash content by fluorescent X-ray analysis, characterized in that the amount of coal ash content is calculated based on. Ash (%) = (A ₂ × SiO ₂ + B ₂ × Al ₂ O ₃ + P ₂ O ₅ + E ₁ × TiO ₂ + MgO) + J ₂ (2) where A ₂ = 0.816, B ₂ = 1.029 , E ₁ =
0.913, J ₂ = 2.396 3. A method for estimating the ash content in coal by fluorescent X-ray analysis, wherein the coal is crushed, a binder is added and mixed, and pressure molding is performed to form a briquette-like sample, which is then subjected to a fluorescent X-ray spectrometer. Si, Al, Ca, Fe, P, Ti, M
X-ray intensity of g was measured and measured Si, Al, Ca, F
Based on the X-ray intensities of e, P, Ti, and Mg, when a preset element is zero, the calibration curve of zero X-ray intensity is used for SiO ₂ , Al ₂
The content of each component of O ₃ , CaO, Fe ₂ O ₃ , P ₂ O ₅ , TiO ₂ , and MgO is converted, and the amount of coal ash is calculated from the content of each component based on the following ash estimation formula (3). A method for estimating coal ash content by fluorescent X-ray analysis, which is characterized in that _{Ash (%) = (A 3} × SiO 2 + B 3 × Al 2 O 3 + C 2 × CaO + D 2 × Fe 2 O 3 + P 2 O 5 + E 2 × TiO 2 + MgO) + J 3 ... (3) However, A _{3 = 1.127, B 3 = 0.955,} C 2 =
1.775, D ₂ = 0.869, E ₂ = 0.777, J ₃
= 0.345 4. A method for estimating ash content in coal by fluorescent X-ray analysis, which comprises pulverizing coal, adding and mixing a binder, and press-molding to form a briquette-like sample, which is then subjected to a fluorescent X-ray analyzer. Si, Al, P, Ti, Ca, Mg, F
The X-ray intensity of e, Mn, and S was measured, and the measured Si and A were measured.
Based on the X-ray intensities of 1, P, Ti, Ca, Mg, Fe, Mn, and S, when a preset element is zero, SiO ₂ , Al ₂ O ₃ , and P ₂ O ₅ are obtained from a calibration curve of zero X-ray intensity. , TiO ₂ , Ca
Fluorescence characterized by converting the content of each component of O, MgO, Fe ₂ O ₃ , MnO, and Total S, and calculating the amount of coal ash from the content of each component based on the following ash estimation formula (4) A method for estimating coal ash content by X-ray analysis. Ash (%) = (A ₄ × SiO ₂ + B ₄ × Al ₂ O ₃ + C ₃
× CaO + D ₃ × Fe ₂ O ₃ + P ₂ O ₅ + E ₃ × TiO ₂ + M
gO + MnO + F ₁ × Total S) + J ₄ (4) However, A ₄ = 1.116, B ₄ = 0.945, C ₃ =
_{1.819, D 3 = 0.791, E} 3 = 0.944, F 1
= 0.546, J ₄ = 0.141 5. Si and A measured by a fluorescent X-ray analyzer
Substituting the X-ray intensity of a predetermined element among 1, P, Ti, Ca, Mg, Fe, Mn, and S into the following formula, SiO ₂ , Al ₂ O
₃ , P ₂ O ₅ , TiO ₂ , CaO, MgO, Fe ₂ O ₃ , Mn
The method for estimating coal ash by fluorescent X-ray analysis according to any one of claims 1 to 4, wherein the content ratio of a predetermined component of O and Total S is calculated. _{SiO 2 = 0.144 × I o -0.312} Al 2 O 3 = 0.135 × I 1 -0.061 CaO = 0.023 × I 2 -0.019 Fe 2 O 3 = 0.004 × I ₃ +0.012 P ₂ O ₅ = 0.040 × I ₄ +0.001 TiO ₂ = 0.012 × I ₅ −0.019 MgO = 1.185 × I ₆ −0.089 MnO = 0.003 × I _{7 -0.004 Total S = 0.008 × I} 8 -0.039 However, I _o ~I ₈ is X-ray intensity of each element