WO2023100600A1 - コークスの反応後強度推定モデル作成方法、コークスの反応後強度推定方法及びコークスの製造方法 - Google Patents
コークスの反応後強度推定モデル作成方法、コークスの反応後強度推定方法及びコークスの製造方法 Download PDFInfo
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- 239000000571 coke Substances 0.000 title claims abstract description 217
- 238000006243 chemical reaction Methods 0.000 title claims abstract description 141
- 238000000034 method Methods 0.000 title claims abstract description 50
- 238000004519 manufacturing process Methods 0.000 title claims description 16
- 238000010438 heat treatment Methods 0.000 claims description 26
- 239000003245 coal Substances 0.000 claims description 18
- 238000010238 partial least squares regression Methods 0.000 claims description 15
- 238000002156 mixing Methods 0.000 claims description 9
- 230000008859 change Effects 0.000 claims description 8
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- 230000001419 dependent effect Effects 0.000 abstract 1
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- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 22
- 239000007789 gas Substances 0.000 description 14
- 229910002092 carbon dioxide Inorganic materials 0.000 description 11
- 238000000354 decomposition reaction Methods 0.000 description 7
- 238000005259 measurement Methods 0.000 description 7
- 238000004458 analytical method Methods 0.000 description 5
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- 238000010298 pulverizing process Methods 0.000 description 5
- 230000004580 weight loss Effects 0.000 description 5
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 4
- 239000002245 particle Substances 0.000 description 4
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- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 3
- 229910052799 carbon Inorganic materials 0.000 description 3
- 238000004939 coking Methods 0.000 description 3
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- 229910000805 Pig iron Inorganic materials 0.000 description 2
- 230000006399 behavior Effects 0.000 description 2
- 239000011335 coal coke Substances 0.000 description 2
- 230000000875 corresponding effect Effects 0.000 description 2
- 229910052742 iron Inorganic materials 0.000 description 2
- 238000010801 machine learning Methods 0.000 description 2
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 2
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- 206010049040 Weight fluctuation Diseases 0.000 description 1
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- 230000003197 catalytic effect Effects 0.000 description 1
- 239000003638 chemical reducing agent Substances 0.000 description 1
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10B—DESTRUCTIVE DISTILLATION OF CARBONACEOUS MATERIALS FOR PRODUCTION OF GAS, COKE, TAR, OR SIMILAR MATERIALS
- C10B45/00—Other details
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10B—DESTRUCTIVE DISTILLATION OF CARBONACEOUS MATERIALS FOR PRODUCTION OF GAS, COKE, TAR, OR SIMILAR MATERIALS
- C10B57/00—Other carbonising or coking processes; Features of destructive distillation processes in general
- C10B57/04—Other carbonising or coking processes; Features of destructive distillation processes in general using charges of special composition
-
- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N25/00—Investigating or analyzing materials by the use of thermal means
- G01N25/02—Investigating or analyzing materials by the use of thermal means by investigating changes of state or changes of phase; by investigating sintering
-
- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N33/00—Investigating or analysing materials by specific methods not covered by groups G01N1/00 - G01N31/00
- G01N33/22—Fuels, explosives
-
- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N5/00—Analysing materials by weighing, e.g. weighing small particles separated from a gas or liquid
- G01N5/04—Analysing materials by weighing, e.g. weighing small particles separated from a gas or liquid by removing a component, e.g. by evaporation, and weighing the remainder
Definitions
- the present invention relates to a method for estimating post-reaction strength of coke, a method for estimating post-reaction strength of coke, and a method for producing coke.
- coke is an essential material as a reducing agent for iron ore.
- the reason for this is that coke itself is porous and has air permeability that allows the blown gas from the lower part of the blast furnace to escape to the upper part.
- coke is required to have sufficient strength to prevent crushing.
- strength of coke a numerical value based on test results in air at room temperature, such as rotating drum type strength, is often used.
- the inside of the blast furnace is a high-temperature environment exceeding 1000 ° C that contains gases that are reactive with coke, mainly carbon dioxide. Hard to say it shows.
- CSR Coke Strength after Reaction
- the CSR measurement procedure is specified in the ISO standard "ISO 18894 coal and coke test” and the ASTM standard “ASTM D 5341 coal and coke test” (hereinafter simply referred to as "ASTM standard”) regarding product specifications and test methods.
- ASTM standard the ASTM standard
- CSR is the lump residual rate after rotating 600 times with an I-type drum tester and Normally, a lower limit is set for CSR, and operations are carried out so as not to fall below that lower limit.
- a problem with CSR measurement is the length of time required to obtain CSR results.
- the reaction time between coke and carbon dioxide is 2 hours, but the furnace for carrying out this reaction is large in scale, and the temperature of the furnace is increased or decreased. require even longer time.
- a series of operations such as pre-preparation of coke and measurement with a drum tester after heating in the furnace are combined, it may take nearly one day as the required time.
- Patent Literature 1 discloses a method of estimating CSR using Raman spectroscopy and utilizing the intensity ratio of specific peaks.
- Patent Literature 2 discloses a method of obtaining the CRI of blended coal by weighted average from the CRI of single coal and the total expansion rate, and estimating the CSR from the CRI of the blended coal and the drum strength of the blended coal.
- Patent Document 3 discloses a method of estimating CSR using the abundance ratio of inorganic components in coal and the physical property values of various coking coals.
- JP 2019-163986 A JP-A-2005-232350 JP-A-2001-172643
- Patent Documents 2 and 3 aim to determine the blending ratio of single coal on the premise that blended coal coke is generated from single coal. , and the problem of CSR estimation error cannot be avoided. In addition, it is impossible to estimate the CSR of blended coal coke for which the blending ratio of single coal is unknown.
- the present invention has been made in view of such circumstances, and an object of the present invention is to provide a method for creating a model for estimating post-reaction strength of coke that can quickly estimate post-reaction strength of coke.
- the present invention has the following configurations.
- a coke post-reaction strength estimation model is created using the TG curve obtained in the step of obtaining the coke TG curve as an explanatory variable and the post-reaction strength obtained in the step of obtaining the coke strength after reaction as an objective variable.
- a modeling process A method for creating a post-reaction strength estimation model of coke.
- the step of obtaining a TG curve of the coke is A heating step of heating the pulverized coke to a predetermined temperature range under an inert gas atmosphere and/or a CO2 atmosphere; After the heating step, a holding step of holding for a predetermined time at a holding temperature within the predetermined temperature range in a CO 2 atmosphere; The post-reaction strength estimation model creation method for coke according to [1].
- post-reaction intensity estimation model creation method [4] The post-reaction strength estimation model creation method of coke according to any one of [1] to [3], wherein the model creation step creates the post-reaction strength estimation model of coke by partial least squares regression. [5] Estimating the post-reaction strength of coke by the coke post-reaction strength estimation model created by the coke post-reaction strength estimation model creation method according to any one of [1] to [4] above. post-reaction strength estimation method. [6] Estimate the post-reaction strength of coke by the method for estimating the post-reaction strength of coke described in [5] above, and change the coke production conditions based on the estimated post-reaction strength of coke. Production method. [7] The method for producing coke according to [6], wherein the change in the production conditions is a change in coal blending ratio.
- the present invention it is possible to speed up the estimation of the post-reaction strength of coke and improve the accuracy of estimating the post-reaction strength of coke. As a result, stabilization of blast furnace operation can be achieved. In addition, it is possible to optimize the coal blend based on the estimated post-reaction strength of coke, thereby improving the quality of coke and stabilizing the operation of the coke oven.
- FIG. 1 is a TG curve of general coke obtained when the temperature is raised from room temperature at a rate of 40° C./min in a CO 2 atmosphere and held at 1120° C. for 2 hours.
- FIG. 2 is a graph showing the relationship between the CSR obtained by the method conforming to the ASTM standard and the CSR estimated by the present invention.
- FIG. 1 is a TG curve of general coke obtained when the temperature is raised from room temperature at a rate of 40° C./min in a CO 2 atmosphere and held at 1120° C. for 2 hours. First, fine weight fluctuations are observed during the heating up to 1120°C. This is due to the weight increase due to the absorption of CO 2 by the inorganic substances contained in the coke of about 10% by mass, and the weight decrease due to thermal decomposition of the coke itself.
- the weight starts to decrease rapidly. This is mainly due to the reaction of carbon and CO 2 to form CO and gasify. In other words, it means that the carbon content that forms the skeleton of coke is decomposed, and it is easy to imagine that the strength also decreases accordingly, and this TG curve (weight loss behavior) is considered to be involved in CSR. .
- the coke decomposition reaction is caused by a combination of various factors.
- factors such as the structure of the carbon content, the catalytic action of inorganic substances, and the pore structure that affects the reaction surface area.
- the TG curve in Fig. 1 also looks smooth, but it is thought that it is composed of the overlapping of such complicated factors.
- CSR can be estimated with high accuracy by machine learning this TG curve, that is, the relationship between the time from the beginning to the end of the reaction and the weight.
- the method for estimating the post-reaction strength of coke includes the step of acquiring the post-reaction strength of coke, the step of acquiring the TG curve of the coke, and the step of acquiring the TG curve of the coke. and a model creation step of creating a post-reaction strength estimation model of coke using the TG curve of as an explanatory variable and using the post-reaction strength obtained in the step of obtaining the post-reaction strength of coke as an objective variable.
- Step of acquiring post-reaction strength of coke the post-reaction strength (CSR) of coke is actually measured.
- the post-reaction strength of coke is measured according to ASTM standards.
- ASTM standards an example in which the post-reaction strength of coke is actually measured in accordance with the ASTM standard is shown, but the present invention is not limited to this, and the post-reaction strength of coke is measured in accordance with, for example, the above-mentioned ISO standards.
- Step of obtaining TG curve of coke In the step of acquiring the TG curve of coke, the TG curve of the coke is acquired. That is, in this step, in the step of obtaining the post-reaction strength of the coke, the TG curve is obtained for the coke corresponding to (manufactured under the same conditions) as the coke subjected to the actual measurement of the post-reaction strength. Either the step of acquiring the post-reaction strength of coke or the step of acquiring a TG curve of coke may be performed first, or may be performed simultaneously (in parallel).
- thermogravimetry (TG) device is used as a device for thermal decomposition reaction of the coke sample.
- the TG apparatus has the characteristics of excellent atmosphere control and temperature responsiveness, and can rapidly measure the gas reaction rate of coke in a CO 2 atmosphere.
- This step includes a heating step of heating the pulverized coke to a predetermined temperature range under an inert gas atmosphere and/or a CO2 atmosphere, and after the heating step, a CO2 atmosphere within the predetermined temperature range. and a holding step of holding at the holding temperature for a predetermined period of time.
- the atmosphere in the holding step is preferably carbon dioxide (CO 2 ) to simulate the inside of a blast furnace. It is the same environment as the CSR analysis specified by ASTM and ISO.
- the atmosphere of the heating process may be an inert gas atmosphere and/or a CO2 atmosphere. That is, the atmosphere of the heating process may be an atmosphere of an inert gas such as N 2 , Ar, or He, a CO 2 atmosphere, or a mixed gas atmosphere of these.
- coke In this step, it is preferable to use pulverized coke.
- the coke is preferably in the form of uniform fine powder. If the coke is not sufficiently pulverized, there is a risk that the weight loss cannot be measured correctly due to the effects of pores inside the coke and uneven distribution of inorganic substances.
- the particle size of coke after pulverization is preferably 500 ⁇ m or less, more preferably 200 ⁇ m or less.
- the particle size of coke after pulverization can be adjusted by, for example, sieving with a sieve having a predetermined mesh size.
- the amount of coke used in this process can be adjusted according to the capabilities of the TG equipment. As for the amount of coke, it is preferable to use coke of about 50% of the volume of the reaction vessel for the purpose of realizing uniform heating. Specifically, the amount of coke is preferably 20-40 mg.
- Heating process In the TG apparatus, it is preferable to heat the coke to a predetermined temperature range in an inert gas atmosphere such as N 2 , Ar, He, etc. and/or in a CO 2 atmosphere (heating step). That is, in the heating step, it is preferable to heat the coke to a predetermined temperature range under any one of an inert gas atmosphere, a CO 2 (CO 2 gas) atmosphere, and a mixed gas atmosphere thereof. In addition, in the heating step and the holding step described later, it is preferable to supply the atmosphere gas to the TG apparatus at a flow rate of 200 mL/min or more. If the flow rate is smaller than this, the amount of gas supplied will be insufficient for coke, and there is a risk that the weight loss due to the reaction cannot be analyzed correctly.
- the holding step is preferably in a CO2 atmosphere.
- a gas other than CO 2 is used in the heating step, it is preferable to switch to the CO 2 gas at the same time as transitioning to the holding step.
- the predetermined temperature range is preferably 900° C. or higher and 1150° C. or lower.
- the predetermined temperature range is more preferably 950° C. or higher.
- the predetermined temperature range is more preferably 1125° C. or less. When the temperature range is less than 900°C, the weight loss rate is slow and the difference between the samples becomes difficult to see.
- the rate of temperature increase up to the above temperature range may be appropriately adjusted according to the capability of the TG apparatus.
- the rate of temperature increase is preferably 20° C./min or more and 150° C./min or less. If the heating rate is lower than 20° C./min, it takes a long time to reach the above temperature range, and thus the contribution to speeding up the analysis is small.
- the rate of temperature increase is preferably a rate of temperature increase from room temperature to a holding temperature within the predetermined temperature range.
- room temperature is 25 degreeC as an example.
- the predetermined time is preferably 15 minutes or more and 75 minutes or less in which the sample (coke) introduced into the TG reacts sufficiently. More specifically, in the heating step, it is preferable to wait 15 minutes to 75 minutes after reaching a predetermined temperature (holding temperature) and starting holding at the predetermined temperature. If the predetermined time is shorter than 15 minutes, the decomposition reaction may include thermal decomposition of inorganic components, which may cause analytical errors. On the other hand, if the predetermined time exceeds 75 minutes, the decomposition reaction of coke will proceed sufficiently, making it difficult to see the difference in the TG curves, which may lead to analytical errors.
- the explanatory variables used in machine learning may have a certain correlation with each other, and due to the collinearity based on the correlation, the estimation accuracy may deteriorate with simple multiple regression analysis.
- the explanatory variables may be correlated, so in principle it is desirable to select an analysis method that does not cause the problem of collinearity.
- a typical example is partial least squares regression (PLS).
- the regression analysis is performed with the objective variable. It is convenient when estimating, and high estimation accuracy can be obtained.
- the TG curve obtained in the step of obtaining the TG curve of coke is used as an explanatory variable.
- the explanatory variable is the TG curve obtained by heating coke after pulverization in a specified temperature range for a specified period of time in a CO 2 atmosphere and using thermogravimetric analysis. That is, partial least-squares regression is performed using the post-reaction strength obtained in the step of obtaining the coke strength after reaction as an objective variable and the TG curve obtained in the step of obtaining the coke TG curve as an explanatory variable.
- regression analysis is performed with the post-reaction strength of the coke sample from which the post-reaction strength was obtained as the objective variable, and the TG curve of the corresponding coke sample as the explanatory variable, thereby defining the relationship between the objective variable and the explanatory variable.
- a model formula which is a regression formula, is calculated. Then, for a coke sample with an unknown post-reaction strength, the TG curve obtained from the sample (a coke sample with an unknown post-reaction strength) was substituted as an explanatory variable into the calculated model formula, and the objective variable, the post-reaction Calculate strength. That is, the method for estimating the coke strength after reaction of the present invention uses the model formula (coke strength estimation model after reaction) calculated (created) as described above to estimate the strength after reaction of coke whose strength after reaction is unknown. presume.
- the explanatory variable it is preferable to use the coke TG curve measured during holding at a holding temperature within a prescribed temperature range for a prescribed time in the step of acquiring the coke TG curve.
- the predetermined temperature range is preferably 900° C. or higher and 1150° C. or lower.
- the predetermined temperature range is more preferably 950° C. or higher.
- the predetermined temperature range is more preferably 1125° C. or lower.
- the predetermined time is preferably 15 minutes or more and 75 minutes or less in which the sample (coke) introduced into the TG reacts sufficiently. More specifically, in the heating step, it is preferable to wait 15 minutes to 75 minutes after reaching a predetermined temperature (holding temperature) and starting holding at the predetermined temperature.
- Table 1 shows the measured (acquired) post-reaction strengths of the 13 types of coke samples (No. 1 to 13) used in the partial least squares regression.
- a model formula (Equation 1) based on partial least squares regression was created to derive a post-reaction strength estimation model of coke.
- the TG curve of each coke sample used as an explanatory variable is the time of 3601 points measured at 1-second intervals from 15 minutes to 75 minutes after the start of holding at the holding temperature (here, 1120 ° C.) and weight data.
- Y c0 + c1 * X1 + c2 * X2 +...+ cn * Xn (Equation 1) here, Y: CSR X 1 to X n : explanatory variables (TG measurement data) c 0 to c n : Regression coefficients obtained by expanding latent variables. Latent variables are defined and weighted for the regression coefficients c 0 to c n . The relationship between the latent variables and the regression equation is as follows.
- T 1 w 11 ⁇ X 1 +w 12 ⁇ X 2 + . . .
- FIG. 2 shows the relationship between the post-reaction strength of coke estimated by substituting the TG curve of the coke sample shown in Table 1 into the model formula and the measured post-reaction strength of coke.
- the horizontal axis indicates the measured strength of coke after reaction (hereinafter referred to as “measured strength after reaction”), and the vertical axis indicates the estimated strength of coke after reaction (hereinafter referred to as “estimated strength after reaction”).
- the coefficient of determination (R 2 ) is 0.9999, indicating that there is a very high correlation between the two. Therefore, the model formula based on the partial least squares regression can predict the post-reaction strength of coke with higher accuracy.
- post-reaction strength of coke actually measured here is a numerical value obtained by a method according to the ASTM standard as described above.
- the post-reaction strength estimated by the post-reaction strength estimation model of coke deviates from the allowable range of post-reaction strength for operation, the injection of coke into the blast furnace can be promptly stopped. It becomes possible, and stabilization of blast furnace operation can be achieved.
- mixing ratio management such as changing the coke-to-coal mixing ratio can be efficiently performed, and the coal mixing ratio can be optimized.
- changing the coke production conditions based on the estimated post-reaction strength of coke corresponds to the "coke production method" in the present invention.
- changing the coke production conditions includes changing the coal blending ratio based on the estimated post-reaction strength of the coke.
- the TG curve of coke obtained in the step of obtaining the TG curve of coke is used as an explanatory variable, and the strength after reaction obtained in the step of obtaining the strength after reaction of coke is used as an objective variable,
- a post-reaction strength estimation model of coke is created in advance by a technique such as partial least squares regression. Then, even during operation of the blast furnace, the TG curve is acquired for coke whose post-reaction strength is unknown, and the acquired TG curve of coke is simply substituted into the previously created coke post-reaction strength estimation model.
- the post-reaction strength of coke can be quickly estimated, and it is possible to quickly determine whether or not the coke strength after reaction deviates from the permissible range for operation.
- the post-reaction strength of coke can be predicted with higher accuracy.
- the estimation of post-reaction strength of coke using the post-reaction strength estimation model of coke corresponds to the "post-reaction strength estimation method of coke" in the present invention.
- CSR can be estimated within about 2 to 3 hours, so it is possible to grasp CSR in real time even in coke oven operation.
- Two types of coke were prepared as samples. 20 g of each coke was taken out, and the whole amount was ground and sieved to a particle size of 150 ⁇ m or less. After air drying, 30 mg was weighed.
- As the TG device Thermo Plus 2 TG8120 manufactured by Rigaku was used. A platinum vessel attached to the device was filled with weighed coke and introduced into the device. The atmospheric gas was CO 2 and the flow rate was 300 mL/min. When the device was stabilized, the temperature was raised from room temperature to 1120°C at 40°C/min, held at 1120°C for 120 minutes, and naturally cooled to room temperature to measure the TG curve.
- two types of coke (A, B) are added to the coke strength estimation model after reaction, which is the result of partial least squares regression performed based on the strength after reaction of 13 types of coke shown in Table 1 and the TG curve.
- Estimate the post-reaction strength of the cokes (A, B) by applying the TG curve of, and measure the post-reaction strengths of the cokes (A, B) according to the ASTM standard, and estimate the post-reaction strength and the measured reaction After strength comparisons were made.
- the cross-validation method was applied using "OriginPro2017" (registered trademark).
- the TG curves of the cokes (A, B) used for post-reaction strength estimation were in the range of 60 minutes from 15 minutes to 75 minutes after starting holding at the holding temperature (1120 ° C.). .
- Table 2 shows the results of the estimated post-reaction strength and the measured post-reaction strength for the cokes (A, B).
- the TG curve of coke can be measured without measuring the post-reaction strength of coke based on the ASTM standard each time. It is possible to estimate the post-reaction strength of coke only by In addition, by using partial least squares regression as a method of multivariate analysis, it is possible to estimate the post-reaction strength of coke with higher accuracy.
Abstract
Description
[1]コークスの反応後強度を取得する工程と、
前記コークスのTG曲線を取得する工程と、
前記コークスのTG曲線を取得する工程で取得したTG曲線を説明変数とし、前記コークスの反応後強度を取得する工程で取得した反応後強度を目的変数として、コークスの反応後強度推定モデルを作成するモデル作成工程と、
を有する、コークスの反応後強度推定モデル作成方法。
[2]前記コークスのTG曲線を取得する工程が、
粉砕後のコークスを、不活性ガス雰囲気下及び/又はCO2雰囲気下で所定の温度域に加熱する加熱工程と、
前記加熱工程後、CO2雰囲気下で前記所定の温度域内の保持温度で所定時間保持する保持工程と、
を有する、[1]に記載のコークスの反応後強度推定モデル作成方法。
[3]前記加熱工程では、前記粉砕後のコークスを、昇温速度20℃/min以上150℃/min以下で、900℃以上1150℃以下の温度域に加熱する、[2]に記載のコークスの反応後強度推定モデル作成方法。
[4]前記モデル作成工程は、部分最小二乗回帰により前記コークスの反応後強度推定モデルを作成する、[1]~[3]のいずれかに記載のコークスの反応後強度推定モデル作成方法。
[5]前記[1]~[4]のいずれかに記載されたコークスの反応後強度推定モデル作成方法により作成されたコークスの反応後強度推定モデルにより、コークスの反応後強度を推定する、コークスの反応後強度推定方法。
[6]前記[5]に記載されたコークスの反応後強度推定方法によりコークスの反応後強度を推定し、前記推定されたコークスの反応後強度に基づいてコークスの製造条件を変更する、コークスの製造方法。
[7]前記製造条件の変更は、石炭配合比の変更である[6]に記載のコークスの製造方法。
コークスの反応後強度を取得する工程では、コークスの反応後強度(CSR)を実測する。具体的には、コークスの反応後強度をASTM規格に準じて実測する。なお、本実施形態では、コークスの反応後強度をASTM規格に準じて実測する例を示すが、これに限定されず、コークスの反応後強度を、例えば、上述のISO規格等に準じて実測してもよい。
コークスのTG曲線を取得する工程では、前記コークスのTG曲線を取得する。すなわち、本工程では、前記コークスの反応後強度を取得する工程で、反応後強度の実測に供したコークスと対応する(同じ条件で製造された)コークスについて、TG曲線を取得する。なお、コークスの反応後強度を取得する工程と、コークスのTG曲線を取得する工程は、どちらの工程を先に実施してもよいし、同時に(並行して)実施してもよい。
本工程では、粉砕後のコークスを用いることが好ましい。前記コークスは、均一な微粉状であることが好ましい。コークスの粉砕が不十分であると、コークス内部の気孔や無機物の分布ムラの影響により正しく重量減少を測定出来ない恐れがある。粉砕後のコークスの粒径は、好ましくは500μm以下であり、より好ましくは200μm以下である。粉砕後のコークスの粒径は、例えば、所定の目開きの篩で篩い分けることで調整できる。
TG装置では、N2、Ar、Heなどの不活性ガス雰囲気下及び/又はCO2雰囲気下で所定の温度域に前記コークスを加熱することが好ましい(加熱工程)。すなわち、加熱工程では、不活性ガス雰囲気下、CO2(CO2ガス)雰囲気下、これらの混合ガス雰囲気下のいずれかの雰囲気下で所定の温度域に前記コークスを加熱することが好ましい。なお、加熱工程と後述する保持工程では、雰囲気となるガスを、200mL/min以上の流量でTG装置に供給することが好ましい。これよりも小さい流量であると、ガスの供給量がコークスに対して不足状態となり、反応による重量減少を正しく分析出来ない恐れがある。
次いで、所定の温度域内の保持温度(均熱温度)で所定時間保持することが好ましい(保持工程)。保持工程は、CO2雰囲気とすることが好ましい。加熱工程でCO2以外のガスを用いる場合は、保持工程に移行すると同時にCO2ガスに切り替えることが好ましい。前記所定の温度域としては、900℃以上1150℃以下が好ましい。前記所定の温度域としては950℃以上がより好ましい。また、前記所定の温度域としては1125℃以下がより好ましい。前記温度域が900℃未満の場合、重量減少速度が緩やかで、サンプル間の差が見えにくくなる。また、前記温度域が1150℃超の場合、急激に分解反応が進行するため、分析誤差が生じる恐れもある。前記温度域までの昇温速度(室温から前記温度域までの昇温速度)は、TG装置の能力に準じて適宜調整すれば良い。前記昇温速度は、好ましくは20℃/min以上150℃/min以下である。20℃/minよりも昇温速度が遅い場合、前記温度域に到達するまでに長時間を要することになるため、分析の迅速化に与える寄与が小さくなる。一方、150℃/minよりも昇温速度を速く設定すると、急激な温度変化により、低温領域で生じる無機分の分解反応とコークスの分解反応が重複する影響でコークスの分解反応に起因するTG曲線を正しく求める事が困難となる恐れがある。前記昇温速度は、好ましくは、室温から前記所定の温度域内の保持温度までの昇温速度である。なお、室温は、一例として、25℃である。
コークスの反応後強度推定モデルを作成するモデル作成工程では、前記コークスのTG曲線を取得する工程で取得したTG曲線を説明変数とし、前記コークスの反応後強度を取得する工程で取得した反応後強度を目的変数として、コークスの反応後強度推定モデルを作成する。
ここで、
Y:CSR
X1~Xn:説明変数(TG測定データ)
c0~cn:潜在変数を展開して得られる回帰係数
である。なお、c0~cnに示す回帰係数には、潜在変数を規定し、重み付けを加味する。潜在変数と、回帰式との関係は以下の通りである。
ここで、
Y:CSR
T1~Tr:潜在変数
b0~br:潜在変数にかかる回帰係数
ただし、第1潜在変数:T1=w11×X1+w12×X2+・・・+w1n×Xn
第2潜在変数:T2=w21×X1+w22×X2+・・・+w2n×Xn
第r潜在変数:Tr=wr1×X1+wr2×X2+・・・+wrn×Xn
であり、w11~wrn:潜在変数の入力変数に対する重み付け
である。
(参考文献)第54回自動制御連合講演会講演論文集 2K305(2011)
Claims (7)
- コークスの反応後強度を取得する工程と、
前記コークスのTG曲線を取得する工程と、
前記コークスのTG曲線を取得する工程で取得したTG曲線を説明変数とし、前記コークスの反応後強度を取得する工程で取得した反応後強度を目的変数として、コークスの反応後強度推定モデルを作成するモデル作成工程と、
を有する、コークスの反応後強度推定モデル作成方法。 - 前記コークスのTG曲線を取得する工程が、
粉砕後のコークスを、不活性ガス雰囲気下及び/又はCO2雰囲気下で所定の温度域に加熱する加熱工程と、
前記加熱工程後、CO2雰囲気下で前記所定の温度域内の保持温度で所定時間保持する保持工程と、
を有する、請求項1に記載のコークスの反応後強度推定モデル作成方法。 - 前記加熱工程では、前記粉砕後のコークスを、昇温速度20℃/min以上150℃/min以下で、900℃以上1150℃以下の温度域に加熱する、請求項2に記載のコークスの反応後強度推定モデル作成方法。
- 前記モデル作成工程は、部分最小二乗回帰により前記コークスの反応後強度推定モデルを作成する、請求項1~3のいずれか一項に記載のコークスの反応後強度推定モデル作成方法。
- 請求項1~4のいずれか一項に記載されたコークスの反応後強度推定モデル作成方法により作成されたコークスの反応後強度推定モデルにより、コークスの反応後強度を推定する、コークスの反応後強度推定方法。
- 請求項5に記載されたコークスの反応後強度推定方法によりコークスの反応後強度を推定し、前記推定されたコークスの反応後強度に基づいてコークスの製造条件を変更する、コークスの製造方法。
- 前記製造条件の変更は、石炭配合比の変更である、請求項6に記載のコークスの製造方法。
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