method to evaluate the thermal plasticity of coals and pie-forming additives

专利摘要:
METHOD FOR EVALUATING THE THERMAL PLASTICITY OF COALS AND PIE FORMING ADDITIVES AND METHOD FOR PRODUCING COKE. The present invention relates to the thermal plasticity of coals and pie formation additives that is measured while simulating the environment that will surround the thermally plastic coals and pie formation additives in a coke oven, so that the thermal plasticity of coals and pie-forming additives can be more accurately evaluated by a simple method. The invention provides a method for evaluating the thermal plasticity of coals and pie-forming additives, and a method for producing coke using the measured values. The invention involves a method for assessing the thermal plasticity of coals and pie-forming additives, which includes packing a coal or pie-forming additive in a container to prepare a sample 1; disposing of a through hole material 2 that has through holes from surfaces greater than inferior on the sample 1; heating sample 1 at a predetermined heating rate while maintaining a constant volume or while applying a constant load on sample 1 and through hole material 2; measure (...).
公开号:BR112013004939B1
申请号:R112013004939-1
申请日:2011-08-31
公开日:2020-11-10
发明作者:Yusuke DOHI；Izumi Shimoyama；Kiyoshi Fukada；Tetsuya Yamamoto；Hiroyuki Sumi
申请人:Jfe Steel Corporation；
IPC主号:

专利说明:

Technique Field
[0001] The present invention relates to a method for evaluating the thermal plasticity of coals and pie formation additives during carbonization. The method is one of the approaches to assess the quality of coke coals and pie formation additives. The invention also relates to a method for producing coke using the evaluation method. Background of the Technique
[0002] In a blast furnace method which is the most common method for producing pig iron, coke plays a number of roles, for example, as a reducing agent for iron ore, as a source of heat and as a spacer. In order to operate a blast furnace in a stable and efficient manner, it is important that gas permeability in the blast furnace is maintained. Thus, there is a need for high-strength coke to be produced. Coke is produced by carbonizing a mixture of coal, which is a mixture of several types of coke coals that have been ground in a coke oven. During carbonization, coking coal softens and melts at temperatures in the range of about 300 ° C to 550 ° C and, at the same time, volatile matter is removed to form a gas that causes expansion, so that the particles are adhered entre di to provide a semi-mass. The semi-coke is subsequently densified when contracted in the course where the temperature is raised to almost 1000 ° C, resulting in a rigid coke (a coke pie). In this way, the adhesiveness of thermally plastic coal greatly influences properties, such as coke strength and particle diameter after carbonization.
[0003] In order to improve the adhesion of coking coal (coal mixture), a coke production method is generally adopted in which a coal mixture is mixed with a pie-forming additive that exhibits high fluidity at temperatures where the coal becomes soft and molten. Here, examples of pie forming additives include tar niches, oil niches, solvent-refined coals and solvent-extracted coals. Similar to coal, the adhesion of these pie-forming additives in a thermally plastic state affects the coke properties after carbonization.
[0004] In the production of coke in a coke oven, the carbonized coke is discharged from the coke oven with a pressure machine. If the degree of shrinkage of the coke pie itself produced is low, the discharge out of the oven becomes difficult. This can lead to "adhesives (or difficult pressure)", that is, a problem in which the coke cannot be discharged from the oven. The structure of a carbonized coke cake is largely affected by changes in the volume of coal and semi-coke during the carbonization process. Semicoke shrinkage is known to have a good correlation with the volatile content of coal (see, for example, Non-Patent Literature 1). In many cases, the volatile contents of coal mixtures are controlled to be substantially constant for operations at the same plant. In this way, the volume change characteristics of plastic coal greatly affect the structure of a carbonized coke cake.
[0005] As mentioned above, the thermal plasticity of coal is very important due to its great influences on the properties of coke and coke pie structures after carbonization. Thus, the methods for measuring these characteristics have been actively studied for a long time. In particular, coke resistance, which is an important coke quality, is greatly affected by the properties of raw material coal, especially coal classification and thermal plasticity. Thermal plasticity is exhibited when coal becomes softened and melted when heated, and is generally measured and evaluated for properties such as fluidity, viscosity, adhesion and the ability to expand thermally plastic coal.
[0006] Of the thermal plasticity of coal, the fluidity of thermally plastic coal is commonly measured by a coal fluidity test method based on a Gieseler plastometer method specified in JIS M 8801. According to a Gieseler plastometer method, the coal that has been ground in sizes of no more than 425 pm is placed in a prescribed crucible and heated at a specified temperature rise rate while the rotational speed of a stirring rod under a specified torque is read on a display and is indicated in terms of ddpm (display division per minute).
[0007] Although a Gieseler plastometer method measures the rotational speed of a stirring rod under constant torque, other methods evaluate torque at a constant rotational speed. For example, Patent Literature 1 describes a method in which torque is measured while rotating a rotor at a constant rotational speed.
[0008] In order to measure viscosity, which is a physically significant thermal plasticity, there are methods to measure viscosity with a dynamic viscoelastometer (see, for example, Patent Literature 2). Dynamic viscoelastometry is a measurement of viscoelastic behaviors observed when a viscoelastic body is subjected to periodic forces. In the method described in Patent Literature 2, the viscosity of the thermally plastic coal is evaluated based on the complex viscosity coefficient between the parameters obtained by the measurement. This method is characterized by the fact that the viscosity of thermally plastic coal is measurable at a given shear rate.
[0009] Furthermore, it has been reported that the thermal plasticity of coal is assessed by measuring the adhesion of thermally plastic coal to activated carbon or glass spheres. In such a method, a small amount of a sample of coal, vertically sandwiched between the activated coals or glass spheres, is heated in thermal plasticity and is subsequently cooled, and the adhesion of the coal in relation to the activated coals or spheres of glass is visually observed.
[00010] A common method for measuring the thermal expansion capacity of thermally plastic coal is a dilatometer method specified in JIS M 8801. In a dilatometer method, coal that has been crushed in sizes no larger than 250 pm is compacted by a method specified, placed in a prescribed crucible and heated to a specified temperature rise rate while the displacement of the coal is measured over time using a detection rod arranged on top of the coal.
[00011] In order to thermally stimulate the plastic behavior of coal in a coke oven, methods of testing coal expansion capacity are known that perform the optimized simulation of permeation behaviors for a gas generated during coal plasticization (see , for example, Patent Literature 3). According to such a method, a permeable material is disposed between a layer of coal and a piston or is disposed between a layer of coal and a piston, as well as at the bottom of the layer of coal, in order to increase the paths through which the volatile matter and liquid substances generated from coal can pass, thus approaching the measurement environment more closely to an environment in which expansion behaviors actually occur in a coke oven. A similar method is also known in which the expansion capacity of coal is measured by placing a material that has a passing path over a layer of coal and microwave heating the coal while applying a load to it (see Patent Literature 4). Citation List Patent Literature
[00012] [PTL 1] unexamined Japanese patent application number 6-347392
[00013] [PTL 2] unexamined Japanese patent application number 2000-304674
[00014] [PTL 3] Japanese patent number 2855728
[00015] [PTL 4] publication of unexamined Japanese patent application number 2009-204609 Non-Patent Literature
[00016] [NPL 1] C. Meyer et al .: "Gluckauf Forshungshefte", Vol. 42, 1981, pp. 233-239
[00017] [NPL 2] Morotomi et al .: "Journal of the Fuel Society of Japan", Vol. 53, 1974, pp. 779-790
[00018] [NPL 3] D. W. van Krevelen: "Coal", 1993, pp. 693-695
[00019] [NPL 4] Miyazu et al .: "Nippon Kokan Gihou (Nippon Kokan Technical Report)", Vol. 67, 1975, pp. 125-137
[00020] [NPL 5] Kamioka et al .: "Tetsu to Hagane (Iron and Steel)", Vol. 93, 2007, pp. 728-735 Problem of the Technique
[00021] In order to evaluate the thermally plastic behavior of the coal in a coke oven, it is necessary that the thermal plasticity of the coal be measured while simulating the environment that will surround the thermally plastic coal in a coke oven. Plasticized coal in a coke oven, as well as an environment surrounding the coal will be described in detail below.
[00022] In a coke oven, thermally plastic coal is constricted between adjacent layers. Due to the fact that the thermal conductivity of coal is low, the coal in a coke oven is not uniformly heated and has different states. That is, it forms a layer of coke, a thermally plastic layer and a layer of coal from the wall side of the oven, that is, the heating face side. Although the coke oven itself is slightly expanded during carbonization, there is substantially no deformation. In this way, thermally plastic coal is constricted between the adjacent coke layer and the coal layer.
[00023] In addition, thermally plastic coal is surrounded by a large number of defective structures, such as voids between coal particles in a coal layer, interparticle voids in thermally plastic coal, large pores formed by the volatilization of gas thermally decomposed, and cracks in an adjacent coke layer. In particular, the cracks that occurred in a layer of coke are considered to be about several hundred micrometers to several millimeters wide, greater than the voids or interparticle pores of coal whose sizes are around several tens several hundred micrometers. In this way, it is likely that not only the thermally decomposed gases and liquid substances that are by-products of coal, but also the thermally plastic coal itself is permeated in such large flaws formed in a layer of coke. In addition, it is expected that the shear rate acting on thermally plastic coal during permeation will be different from brand to brand.
[00024] As mentioned above, the restriction conditions and permeation conditions need to be optimized in order to measure the thermal plasticity of the coal while simulating the environment that will surround the thermally plastic coal in a coke oven. However, existing methods have the following problems.
[00025] In a Gieseler plastometer method, the measurement is performed in relation to the coal placed in a container. Thus, this method presents a problem in which no consideration is given to the restriction conditions or permeation conditions. Furthermore, this method is not suitable for measuring coal that exhibits high fluidity. This is because when the highly fluid coal is measured, a phenomenon occurs where the surroundings of the inner wall of a container become empty (Weissenberg effect) and a stirring rod is rotated at idle and may fail to assess fluidity in a manner need (see, for example, Non-Patent Literature 2).
[00026] Similarly, methods based on measuring torque at a constant speed of revolution are problematic due to the fact that restriction conditions and permeation conditions are not considered. Furthermore, due to the fact that the measurement is carried out at a constant shear rate, such methods cannot accurately compare and evaluate the thermal plasticity of the coals for the reason described above.
[00027] A dynamic viscoelastometer is a device dedicated to measuring viscosity as a thermal plasticity and capable of measuring viscosity at any shear rate. In this way, the viscosity of thermally plastic coal in a coke oven is measurable by adjusting the shear rate in the measurement to a shear value that will act on the coal in a coke oven. However, it is often difficult to measure or estimate the shear rate in a coke oven beforehand for each brand.
[00028] The reproduction of permeation conditions in terms of the presence of a layer of charcoal is attempted in methods that evaluate the thermal plasticity of charcoal by measuring adhesion in relation to activated carbon or glass beads. However, such methods present a problem due to the fact that they do not simulate the presence of a coke layer and major flaws, as well as, due to the fact that the measurement is not restricted.
[00029] The method of testing the expansion capacity of coal in Patent Literature 3, which involves the use of a permeable material considers the movement of gases and liquid substances generated from coal. However, this method is problematic due to the fact that the movement of the thermally plastic coal itself is not met. The reason for this neglect is that the permeability of the permeable material used in Patent Literature 3 is not high enough for thermally plastic coal to permeate the material. The present inventors actually perform a test according to the description in Patent Literature 3 to confirm that thermally plastic charcoal does not permeate the permeable material. Consequently, it is necessary that new conditions are designed to allow thermally plastic coal to permeate the permeable material.
[00030] Patent Literature 4 describes a similar method for measuring the expansion capacity of coal with a material having a passing path over a layer of coal, in consideration of the movements of gases and liquid substances generated from coal . However, this method presents problems due to the fact that the heating method is limited and the literature does not specify the conditions for evaluating a permeation phenomenon in a coke oven. Furthermore, Patent Literature 4 does not clearly describe a relationship between a permeation phenomenon and a thermally plastic coal-melting behavior, and does not indicate a relationship between the coal-melting permeation phenomenon and the quality of coke produced. Thus, this literature does not address the production of high quality coke.
[00031] As described above, existing techniques are unable to measure the thermal plasticity of coals and pie-forming additives, such as flow properties, viscosity, adhesion, permeation, coefficient of expansion during permeation, and pressure during permeation, while sufficiently simulating the environment that will surround the thermally plastic coals and pie-forming additives in a coke oven.
[00032] In order to solve the technical problems mentioned above and perform the measurement of the thermal plasticity of coals and pie formation additives while sufficiently simulating the environment that will surround the thermally plastic coals and pie formation additives in a coke oven, an objective of the present invention is to provide a simple and more accurate method for evaluating the thermal plasticity of coals and pie formation additives.
[00033] Furthermore, the higher precision in the evaluation of thermal plasticity makes it possible to understand the influences of coals and pie formation additives on the coke resistance more precisely. In using these findings, another objective of the invention is to provide a method for producing high-strength coke by setting a new criterion for mixing coals. Solution to the Problem
[00034] The characteristics of the present invention that aim to solve the problems mentioned above are summarized as follows:
[00035] (1) A method for assessing the thermal plasticity of carbons and pie-forming additives, which includes:
[00036] pack a charcoal or pie-forming additive in a container to prepare a sample,
[00037] to dispose of a material that has through holes from superior to inferior surfaces on the sample,
[00038] heat the sample while keeping the sample and through hole material at a constant volume,
[00039] measure the permeation distance with which the melted sample was permeated in the through holes, and
[00040] evaluate the thermal plasticity of the sample using the measured value.
[00041] (2) A method for assessing the thermal plasticity of carbons and pie-forming additives, which includes:
[00042] pack a charcoal or pie-forming additive in a container to prepare a sample,
[00043] dispose of a through hole material that has through holes from upper to lower surfaces on the sample,
[00044] heat the sample while keeping the sample and through hole material at a constant volume,
[00045] measure the pressure of the sample that is transmitted through the through hole material, and
[00046] evaluate the thermal plasticity of the sample using the measured value.
[00047] (3) A method for assessing the thermal plasticity of carbons and pie-forming additives, which includes:
[00048] pack a charcoal or pie-forming additive in a container to prepare a sample,
[00049] dispose of a through-hole material that has holes through from upper to lower surfaces on the sample,
[00050] heat the sample while applying a constant load on the through hole material,
[00051] measure the permeation distance with which the melted sample was permeated in the through holes, and
[00052] evaluate the thermal plasticity of the sample using the measured value.
[00053] (4) A method for assessing the thermal plasticity of carbons and pie-forming additives, which includes:
[00054] pack a charcoal or pie-forming additive in a container to prepare a sample,
[00055] dispose of a through hole material that has through holes from upper to lower surfaces on the sample,
[00056] heat the sample while applying a constant load on the through hole material,
[00057] measure the sample expansion coefficient, and evaluate the sample's thermal plasticity using the measured value.
[00058] (5) The method for assessing the thermal plasticity of coals and pie-forming additives described in any of between (1) and (4), where sample preparation includes grinding a coal or a pie-forming additive pie, so that particles with a particle diameter of no more than 3 mm represent no less than 70% by weight, and pack the coal or crushed pie-forming additive in a container with a packing density of 0.7 to 0.9 g / cm3 and a layer thickness of 5 to 20 mm.
[00059] (6) The method for evaluating the thermal plasticity of coals and pie-forming additives described in (5), in which the coal or pie-forming additive is ground, so that particles with a particle diameter not more than 2 mm represent 100% by mass.
[00060] (7) The method for assessing the thermal plasticity of coals and pie-forming additives described in any of between (1) and (4), wherein the through-hole material is a spherical packed particle layer or a packed non-spherical particle layer.
[00061] (8) The method for assessing the thermal plasticity of coals and pie-forming additives described in (7), wherein the through-hole material is a spherical particle layer.
[00062] (9) The method for assessing the thermal plasticity of coals and pie-forming additives described in (8), wherein the spherical particle layer packaged includes glass spheres.
[00063] (10) The method for assessing the thermal plasticity of carbons and pie-forming additives described in any of between (1) and (4), in which the sample is heated from room temperature to 550 ° C at a heating rate of 2 to 10 ° C / min. in an atmosphere of inert gas.
[00064] (11) The method for evaluating the thermal plasticity of carbons and pie-forming additives described in (10), where the heating rate is 2 to 4 ° C / min.
[00065] (12) The method for assessing the thermal plasticity of carbons and pie-forming additives described in (3) or (4), in which the application of a constant load includes applying such a load in which the pressure on the surface through the through hole material becomes 5 to 80 kPa.
[00066] (13) The method for assessing the thermal plasticity of carbons and pie-forming additives described in (12), in which the application of a load includes applying such a load in which the pressure on the upper surface of the material through hole becomes 15 to 55 kPa.
[00067] (14) The method for assessing the thermal plasticity of carbons and pie-forming additives described in (1) or (2), where
[00068] the arrangement of the through-hole material includes arranging glass spheres having a diameter of 0.2 to 3.5 mm over the sample, in order to obtain a layer thickness of 20 to 100 mm, and
[00069] heating the sample includes heating the sample from room temperature to 550 ° C at a heating rate of 2 to 10 ° C / min. in an inert gas atmosphere while keeping the sample and the glass sphere layer at a constant volume.
[00070] (15) The method for evaluating the thermal plasticity of carbons and pie-forming additives described in (3) or (4), where
[00071] the arrangement of the through-hole material includes arranging glass spheres having a diameter of 0.2 to 3.5 mm over the sample, in order to obtain a layer thickness of 20 to 100 mm, and
[00072] heating the sample includes heating the sample from room temperature to 550 ° C at a heating rate of 2 to 10 ° C / min. in an inert gas atmosphere while applying a charge from above the glass spheres, so that 5 to 80 kPa are obtained.
[00073] (16) The method for evaluating the thermal plasticity of carbons and pie-forming additives described in (1) or (2), where
[00074] Sample preparation includes grinding a coal or a pie-forming additive, so that particles with a particle diameter of no more than 3 mm represent no less than 70% by weight, and conditioning the coal or additive of crushed cake formation in a container with a packing density of 0.7 to 0.9 g / cm3 and a layer thickness of 5 to 20 mm,
[00075] the arrangement of the through-hole material includes arranging glass spheres having a diameter of 0.2 to 3.5 mm over the sample, in order to obtain a layer thickness of 20 to 100 mm, and
[00076] heating the sample includes heating the sample from room temperature to 550 ° C at a heating rate of 2 to 10 ° C / min. in an inert gas atmosphere while keeping the sample and the glass sphere layer at a constant volume.
[00077] (17) The method for assessing the thermal plasticity of carbons and pie-forming additives described in (3) or (4), where
[00078] sample preparation includes grinding a coal or a pie-forming additive, so that particles with a particle diameter of no more than 3 mm represent no less than 70% by weight, and conditioning the coal or additive of crushed cake formation in a container with a packing density of 0.7 to 0.9 g / cm3 and a layer thickness of 5 to 20 mm,
[00079] the arrangement of the through-hole material includes arranging glass spheres having a diameter of 0.2 to 3.5 mm over the sample, in order to obtain a layer thickness of 20 to 100 mm, and
[00080] heating the sample includes heating the sample from room temperature to 550 ° C at a heating rate of 2 to 10 ° C / min. in an inert gas atmosphere while applying a charge from above the glass spheres, so that 5 to 80 kPa are obtained.
[00081] (18) The method for assessing the thermal plasticity of carbons and pie-forming additives described in (1) or (2), where
[00082] sample preparation includes grinding a charcoal or a pie-forming additive, so that particles with a particle diameter of no more than 2 mm represent 100% by weight, and conditioning the coal or pie-forming additive crushed in a container with a packing density of 0.8 g / cm3 and a layer thickness of 10 mm,
[00083] the arrangement of the through-hole material includes arranging glass spheres having a diameter of 2 mm over the sample, in order to obtain a layer thickness of 80 mm, and
[00084] heating the sample includes heating the sample from room temperature to 550 ° C at a heating rate of 3 ° C / min. in an inert gas atmosphere while keeping the sample and the glass sphere layer at a constant volume.
[00085] (19) The method for evaluating the thermal plasticity of carbons and pie-forming additives described in (3) or (4), where
[00086] sample preparation includes grinding a charcoal or a pie-forming additive, so that particles with a particle diameter of no more than 2 mm represent 100% by weight, and conditioning the coal or pie-forming additive crushed in a container with a packing density of 0e8 g / cm3 and a layer thickness of 10 mm,
[00087] the arrangement of the through-hole material includes arranging glass spheres having a diameter of 2 mm over the sample, in order to obtain a layer thickness of 80 mm, and
[00088] heating the sample includes heating the sample from room temperature to 550 ° C at a heating rate of 3 ° C / min. in an inert gas atmosphere while applying a charge from above the glass spheres, so that 50 kPa is obtained.
[00089] (20) A method for producing coke, which includes:
[00090] measure the permeation distance, which is a thermal plasticity of the coal, in relation to the coal or coals to be added in a mixture of coking coal that has a logarithmic value of maximum Gieseler fluidity, logMF, of not less than 3 , 0,
[00091] Based on a weighted average value of the measured permeation distances, determine the mixing ratio of the coals that have a logarithmic value of maximum Gieseler fluidity, logMF, of not less than 3.0, and
[00092] carbonize the coals that have been mixed according to the determined mixing ratio.
[00093] (21) The method for producing coke described in (20), in which
[00094] the permeation distance distance is measured by (1) to (4) below, and
[00095] the mixing ratio is determined by determining the proportions of the coals that have a logarithmic value of maximum Gieseler fluidity, logMF, of not less than 3.0 so that the weighted average value of the measured permeation distances becomes not more than 15 mm,
[00096] (1) a coal or pie-forming additive is crushed, so that particles with a particle diameter of no more than 2 mm represent 100% by weight, and the coal or crushed pie-forming additive is packed in a container with a packing density of 0.8 g / cm3 and a layer thickness of 10 mm, thereby preparing a sample,
[00097] (2) glass spheres having a diameter of 2 mm are placed on the sample in order to obtain a layer thickness of 80 mm,
[00098] (3) the sample is heated from room temperature to 550 ° C at a heating rate of 3 ° C / min. in an inert gas atmosphere while keeping the sample and the glass sphere layer at a constant volume,
[00099] (4) the permeation distance of the molten sample that was permeated in the glass sphere layer is measured.
[000100] (22) The method for producing coke described in (20), wherein
[000101] the permeation distance is measured by (1) to (4) below, and
[000102] the mixing ratio is determined by determining the proportions of the coals that have a logarithmic maximum Gieseler fluidity value, logMF, of not less than 3.0 so that the weighted average value of the measured permeation distances becomes not more than 17 mm,
[000103] (1) a coal or a pie-forming additive is crushed, so that particles with a particle diameter of no more than 2 mm represent 100% by weight, and the crushed coal or pie-forming additive is packed in a container with a packing density of 0.8 g / cm3 and a layer thickness of 10 mm, thus preparing a sample,
[000104] (2) glass spheres having a diameter of 2 mm are placed on the sample in order to obtain a layer thickness of 80 mm,
[000105] (3) the sample is heated from room temperature to 550 ° C at a heating rate of 3 ° C / min. in an inert gas atmosphere while applying a charge from above the glass spheres, so that 50 kPa are obtained,
[000106] (4) the permeation distance of the molten sample that has been permeated in the glass sphere layer is measured.
[000107] (23) A method for producing coke, which includes:
[000108] determine in advance brands of coals or pie formation additives to be added to a coking coal mixture, as well as the total mixing ratio of a coal or coals with logMF of less than 3.0 in relation to coal mixture,
[000109] measure the permeation distance in relation to coal or coals that have a logarithmic maximum Gieseler fluidity value, logMF, of not less than 3.0, between the coals to be added to the coking coal mixture,
[000110] determine a relationship between the permeation distance of weighted average of the coals or pie formation additives with logMF of not less than 3.0 that will be added to the coal mixtures, and the coke resistance obtained with the coal mixtures prepared while changing the proportions of the individual brands of coals, the relationship being obtained by changing the proportions of the individual brands of coals or pie formation additives with the total mixture ratio of the coal or coals with logMF of less than 3, 0 being kept constant in relation to the coal mixture, and
[000111] adjust the weighted average permeation distance by controlling the mark and the proportion of the coals with logMF of not less than 3.0 in order to reach the coke resistance which is not less than a desired value.
[000112] (24) The method for producing coke described in (23), in which the permeation distance is measured under conditions selected from the range described below:
[000113] a coal or a pie-forming additive is crushed, so that particles with a particle diameter of no more than 3 mm represent no less than 70% by weight; the crushed material is packed in a container with a packing density of 0.7 to 0.9 g / cm3 and a layer thickness of 5 to 20 mm, thus preparing a sample; glass spheres having a diameter of 0.2 to 3.5 mm are placed on the sample, in order to obtain a layer thickness of 20 to 100 mm; and the sample is heated from room temperature to 550 ° C at a temperature increase rate of 2 to 10 ° C / min. in an inert gas atmosphere while keeping the sample and the glass sphere layer at a constant volume.
[000114] (25) The method for producing coke described in (23), in which the permeation distance is measured under conditions selected from the range described below:
[000115] a coal or a pie-forming additive is crushed, so that particles with a particle diameter of no more than 3 mm represent no less than 70% by weight; the crushed material is packed in a container with a packing density of 0.7 to 0.9 g / cm3 and a layer thickness of 5 to 20 mm, thus preparing a sample; glass spheres having a diameter of 0.2 to 3.5 mm are placed on the sample, in order to obtain a layer thickness of 20 to 100 mm; and the sample is heated from room temperature to 550 ° C at a temperature increase rate of 2 to 10 ° C / min. in an inert gas atmosphere while applying a charge from above the glass spheres, so that a pressure of 5 to 80 kPa is obtained. Advantageous Effects of the Invention
[000116] According to the present invention, it is possible to evaluate the thermal plasticity of coals and pie formation additives, that is, the permeation distance of a thermal plastic in defective structures, the expansion coefficient during permeation, and the pressure during permeation while simulating the influences of defective structures that will be present around the thermally plastic layer of coals and pie formation additives in a coke oven, in particular, the influence of cracks present in a layer of coke adjacent to the layer thermally plastic, as well as, properly reproduce the restriction conditions that will surround the thermal plastic in a coke oven. In detail, the invention makes it possible to measure the permeation distance of a thermal plastic in defective structures, the expansion coefficient during permeation, and the pressure during permeation while simulating a shear rate at which coals and pie formation additives that were laminated in a coke oven will move and change shapes. With the measured values, the properties of coke and coke pie structures can be estimated with higher precision than that obtained by conventional methods.
[000117] In this way, thermally plastic behaviors of coal in a coke oven can be precisely evaluated, and the data obtained can be used in the production of high-strength coke. Brief Description of Drawings
[000118] Figure 1 is a schematic view illustrating an example of an apparatus for use in the invention to measure thermal plasticity while maintaining a sample and through hole material that has through holes from upper to lower surfaces in one volume constant.
[000119] Figure 2 is a schematic view illustrating an example of an apparatus for use in the invention to measure thermal plasticity while applying a constant load on a sample and through-hole material.
[000120] Figure 3 is a schematic view illustrating a through hole material with circular through holes as an example of the through hole material for use in the invention.
[000121] Figure 4 is a schematic view illustrating a spherical particle layer packaged as an example of through hole materials for use in the invention.
[000122] Figure 5 is a schematic view illustrating a layer packed with cylinder as an example of the through hole materials for use in the invention.
[000123] Figure 6 is a graph showing results of measuring the permeation distance of thermally plastic coals in Example 1.
[000124] Figure 7 is a graph showing results of the measurement of the permeation distance of thermally plastic coals in the Example 2
[000125] Figure 8 is a graph showing the relationship between the measured permeation distance and the weighted average permeation distance of the thermally plastic coal mixtures in Example 3.
[000126] Figure 9 is a graph showing the relationship between the weighted average permeation distance (measured when heating under constant load) of a coal with a logarithmic fluidity maximum logies value of logMF 3.0 that is added to a mixture of coal, and the resistance to the drum measured in Example 4.
[000127] Figure 10 is a graph that shows the relationship between the permeation distance of weighted average (average when heating in a constant volume) of a coal with a logarithmic fluidity maximum logies value of logMF 3.0 that is added to a mixture of coal, and the resistance to the drum measured in Example 4.
[000128] Figure 11 is an image showing a coke structure obtained by carbonizing a mixture of coal A that contained coal A that has an adequate permeation distance.
[000129] Figure 12 is an image showing a coke structure obtained through the carbonization of a mixture of coal F which contained coal F which has an excessively long permeation distance. Description of Modalities
[000130] The exemplary apparatus used in the invention to measure thermal plasticity are illustrated in Figures 1 and 2. The apparatus illustrated in Figure 1 is dedicated to heating a sample of a charcoal or a pie-forming additive while maintaining the sample and a material that has through holes from upper to lower surfaces in a constant volume. The apparatus illustrated in Figure 2 is dedicated to heating a sample of a charcoal or a pie-forming additive while applying a constant load on the sample and a through hole material. A charcoal or pie-forming additive is stored in a lower part of a container 3 to provide a sample 1. A through-hole material 2 is arranged on top of the sample 1. Sample 1 is heated to or above a temperature range in which the sample becomes softened and melted, in order to cause the sample to permeate in the through hole material 2. This permeation distance is measured. The above heating is carried out in an inert gas atmosphere. Here, the term "inert gas" refers to a gas that does not react with coal in the measurement temperature range. Typical gases include argon gas, helium gas and nitrogen gas.
[000131] In the event that sample 1 is heated while holding sample 1 and through hole material 2 at a constant volume, the pressure during sample permeation can be measured through the through hole material 2. As illustrated in Figure 1, a pressure sensing rod 4 is arranged on the upper surface of the through-hole material 2, and a load cell 6 is placed in contact with the upper end of the pressure sensing rod 4 to measure the pressure. In order to maintain a constant volume, the load cell 6 is fixed in order not to move in a vertical direction. Before starting heating, the through hole material 2, the pressure sensing rod 4 and the load cell 6 are placed in close contact with the sample contained in the container 3 to ensure that there is no gap between any one of these elements. In the case where the through hole material 2 is a packed particle layer, the pressure sensing rod 4 can be buried in the packed particle layer. In this way, it is desirable for a plate to be inserted between the through hole material 2 and the pressure sensing rod 4.
[000132] When sample 1 is heated while applying a constant load on sample 1 and through hole material 2, sample 1 is allowed to be expanded or contracted in order to move through hole material 2 in one vertical direction. In this way, the expansion coefficient during sample permeation can be measured through the through hole material 2. For this purpose, as shown in Figure 2, an expansion coefficient detection rod 13 can be arranged on the upper surface of the material through hole 2, a load weight 14 can be placed on the upper end of the expansion coefficient detection rod 13, and a displacement meter 15 can be arranged above the unit to measure the expansion coefficient. The displacement meter 15 may be able to measure the expansion coefficient in a range over which the sample can be expanded (-100% to 3000). Due to the fact that the interior of the heating system needs to be maintained in an inert gas atmosphere, a non-contact type displacement meter is suitable, and an optical displacement meter is desirably used. The inert gas atmosphere is preferably a nitrogen atmosphere. In the case where the through hole material 2 is a packed particle layer, the expansion coefficient detection rod 13 can be buried in the packed particle layer. Thus, it is desirable that a plate be inserted between the through hole material 2 and the expansion coefficient detection rod 13. The load is preferably applied uniformly on the upper surface of the through hole material disposed on the upper surface of the sample. It is desirable that a pressure of 5 to 80 kPa, preferably 15 to 55 kPa and, more preferably, 25 to 50 kPa be applied over the upper surface area of the through hole material. This pressure is preferably adjusted based on the expansion pressure of a thermally plastic layer in a coke oven. The present inventors studied the ability to reproduce measurement results and the power to detect brand differences in relation to different types of coals. As a result, the present inventors have found that a pressure that is slightly higher than the expansion pressure in an oven, in detail, a pressure of about 25 to 50 kPa is more preferable as a measurement condition.
[000133] Desirably, the heating medium is of a type capable of heating the sample at a predetermined rate of temperature increase while measuring the temperature of the sample. Specific examples include an electric oven, an external heating system that is a combination of a conductive and high frequency induction vessel, and an internal heating system, such as a microwave. In the event that an internal heating system is adopted, it is necessary to develop a design that allows the internal temperature of the sample to become uniform. For example, it is preferable to develop a measure that increases the thermal insulation properties of the container.
[000134] In order to simulate the thermally plastic behaviors of coals and pie-forming additives in a coke oven, the heating rate must correspond to a heating rate for coal in a coke oven. The heating rate for coal around softening and melting temperatures in a coke oven is generally 2 to 10 ° C / min., Although it varies depending on the location within the oven and operating conditions and, desirably, 2 to 4 ° C / min. and, more desirably, about 3 ° C / min. in terms of average heating rate. In the case of low-flow coals, such as non-coke coals and slightly coke coals, meanwhile, heating to 3 ° C / min. results in a small permeation distance and small expansion that can be difficult to detect. Generally, it is known that coal is improved in fluidity according to a Gieseler plastometer when it is quickly heated (see, for example, Non-Patent Literature 3). Thus, in the case of a coal with a permeation distance, for example, 1 mm or less, the measurement can be carried out at an increased heating rate of 10 to 1000 ° C / min. in order to increase detection sensitivity.
[000135] Since the measurement aims to assess the thermal plasticity of coals and pie formation additives, heating can be carried out to such an extent that the temperature is increased in softening and melting temperatures of coals and pie formation additives . Due to the softening and melting temperatures of coals and pie formation additives for the production of coke, heating can be carried out at a predetermined heating rate of 0 ° C (room temperature) to 550 ° C and, preferably, of 300 to 550 ° C which is a temperature range in which the coal becomes softened and melted.
[000136] The through hole material is, desirably, the one whose permeability coefficient can be measured or calculated beforehand. Exemplary material configurations include integral materials that have through holes, and conditioned particle layers. Examples of integral materials that have through holes include materials that have circular through holes 16, as shown in Figure 3, materials that have rectangular through holes, and materials that have irregular through holes. The conditioned particle layers are broadly classified into conditioned spherical particle layers and conditioned non-spherical particle layers. Examples of packed spherical particle layers include layers formed of packed particles 17, such as spheres, as shown in Figure 4. Examples of packed non-spherical particle layers include layers of irregular particles and layers formed by conditioned cylinders 18, as illustrated in Figure 5. In order to ensure the reproducibility of the measurement, the permeability coefficient is desirably as uniform as possible throughout the material. For simple measurement, it is desirable that the material allows easy calculation of its permeability coefficient. In this way, a spherical packed particle layer is particularly desired for use as the through hole material in the present invention. The substance forming the through hole material is not particularly specified as long as it is not substantially deformed at or above the softening and melting temperatures of the coal, in detail, up to 600 ° C, and does not react with the coal. The height of the material is not particularly limited as long as the material is high enough to accept coal-melt permeation. In the event that a layer of coal with a thickness of 5 to 20 mm is heated, the height of the through hole material is approximately 20 to 100 mm.
[000137] It is necessary that the permeability coefficient of the through hole material be adjusted assuming that the coefficient of permeability of large flaws is present in a coke layer. The present inventors have studied a particularly preferred permeability coefficient in the invention while considering the factors constituting such large flaws and assuming their sizes. As a result, the present inventors have found that a permeability coefficient of 1 x 108 to 2 x 109 m-2 is more suitable. This permeability coefficient is derived based on Darcy's law represented by Equation (1) below: ΔP / L = K • p • u (1)
[000138] where ΔP is the pressure loss [Pa] within the through hole material, L is the height [m] of the through hole material, K is the permeability coefficient [nr2], p is the viscosity [Pa * s] of the fluid, eu is the velocity [m / s] of the fluid. For example, in the case where a layer of glass spheres with a uniform particle diameter is used as the through hole material, it is desirable to select glass spheres with a diameter of about 0.2 mm to 3.5 mm, most desirably, 2 mm, in order to achieve the appropriate permeability coefficient mentioned above.
[000139] Coals and pie-forming additives for measuring samples are ground beforehand and are packed with a predetermined packing density and a predetermined layer thickness. The crushed particle size can be similar to a coal particle size loaded in a coke oven (particles with a particle diameter of no more than 3 mm that represent about 70 to 80% by weight, relative to the total) . Alternatively, the sample material is preferably crushed, so that particles with a particle diameter of not more than 3 mm represent not less than 70% by weight. Due to the fact that the measurement is carried out with a small device, it is particularly preferable that all the crushed material has a particle diameter of no more than 2 mm. The crushed material can be packed with a density of 0.7 to 0.9 g / cm3 according to a possible packing density in a coke oven. Based on the results of studies on reproducibility and detection power, the present inventors have found that the packing density of 0.8 g / cm3 is preferable. Based on the thickness of a thermally plastic layer in a coke oven, the thickness of the conditioned layer can be from 5 to 20 mm. Studies on reproducibility and detection power carried out by the present inventors have revealed that a layer thickness of 10 mm is preferable.
[000140] It is essentially desirable that the permeation distance of a thermally plastic coal or a thermally plastic pie forming additive is measurable in a constant and continuous manner during heating. However, constant measurement is difficult, for example, due to the influences of the tar generated from the sample. The expansion and permeation of coal through heating are irreversible phenomena. In this way, once the coal has been expanded or permeated, its shape is substantially maintained even if the coal is cooled. Based on this fact, the measurement can be carried out in such a way that after the permeation of a coal melt has ended, the entire vessel is cooled and the extent to which the permeation occurred during heating is determined by measuring a distance permeation after cooling. For example, through-hole material can be removed from the cooled container and the distance can be directly measured with a vernier gauge or ruler. In the case where the through-hole material is particles, the thermal plastic that has been permeated in the interparticle voids connects the particle layer across the permeation distance. Thus, provided that a relationship between the mass and the height of the packed particle layer has been measured beforehand, the permeation distance can be calculated by measuring the mass of particles that are not bonded together after the permeation is completed, and subtracting the measured mass from the initial mass to provide the mass of the bound particles.
[000141] Equation (1) described above includes the viscosity term (11). In this way, the viscosity term of the thermal plastic that was permeated in the through hole material can be derived from the measured parameters, according to the invention. For example, in the case where the sample is heated while the sample and through-hole material are kept at a constant volume, AP corresponds to the pressure during permeation, L to the permeation distance and I to the permeation speed, so that the viscosity term can be derived by substituting the parameters above in Equation (1). Alternatively, in the case where the sample is heated while a constant load is applied to the sample and the through hole material, AP corresponds to the pressure of the applied load, L at the permeation distance and I at the permeation speed, so that the viscosity can be derived in a similar way by replacing the above parameters in Equation (1).
[000142] As shown above, the thermal plasticity of coals and pie formation additives is assessed by measuring a permeation distance, pressure or expansion coefficient of thermally plastic coals and thermally plastic pie formation additives. Here, the phrase "thermal plasticity of a sample (a coal or pie-forming additive) is evaluated" in the invention means that at least the permeation distance, pressure and expansion coefficient are measured and, based on the values measured, indicators to quantitatively assess the coal melting behaviors, as well as the consequent phenomena (for example, properties of coke produced, resistance to coke pressure) are obtained. The measured values of the permeation distance, pressure and expansion coefficient can be used in combination with other property values (for example, MF). Alternatively, one or more of the selected permeation distance, pressure and expansion coefficient can be used alone. In the latter case, the evaluation of thermal plasticity is referred to as being produced when the measured values of permeation distance, pressure and expansion coefficient are obtained. That is, measuring the permeation distance, pressure and expansion coefficient has substantially the same meaning as assessing thermal plasticity. In addition, the permeation distance, pressure and expansion coefficient can be used as parameters in the estimation of coke resistance, so that it becomes possible to produce coke that has adequate strength by mixing coals of numerous brands. The most common indicator of coke resistance is resistance to the drum at normal temperature. In addition to drum resistance, other coke properties, such as CSR (coke resistance after reaction) (resistance after CO2 reaction), tensile strength and micro-resistance can be estimated based on the above parameters, so that make it possible to produce coke that has the desired strength by mixing coals from numerous brands.
[000143] In a conventional coal mixing theory to estimate coke resistance, coke resistance is thought to be determined primarily by an average maximum vitrinite reflectance (Ro) and a logarithmic maximum Gieseler fluidity (MF) value (logMF) of coal (see, for example, Non-Patent Literature 4). Gieseler fluidity is a fluidity indicator displayed when 0 coal is thermally plastic, and is represented in terms of the rotational speed of a stirring rod of a Gieseler plastometer, that is, 0 degree of rotation per 1 minute in ddpm unit (division of dial per minute). The charcoal property used is maximum fluidity (MF). Alternatively, the common ddpm logarithm is sometimes used. Due to the fact that the permeation distance, according to the invention, is thought to be a parameter that indicates fluidity under conditions that simulate thermally plastic behavior in a coke oven, this parameter will be greater than a logarithmic value of maximum logies Gieseler fluidity in estimating coke properties or coke pie structures.
[000144] This superiority of the permeation distance is expected in principle based on the fact that the measurement method simulates an environment in a coke oven, and was confirmed by the results of a study that examined the influences of the permeation distance on the resistance of coke. In fact, it was discovered through the inventive evaluation method that coals with similar logMF have different permeation distances depending on the brands. It was further confirmed that the coke resistance is affected differently when the coals having permeation distances are mixed and produced in the coke. In detail, as will be demonstrated later in the Examples, a relationship occurs so that the coke resistance is decreased after the permeation distance value exceeds a certain limit. The reasons for this are considered as follows.
[000145] When coals that have a long permeation distance are mixed, the proportion of coals that exhibit sufficient melting properties during carbonization is considered high. However, it is assumed that coals that have an excessively long permeation distance permeate between the surrounding coal particles to such a marked extent that the regions where these coal particles were present are left as large cavities, leading to failure. Although a conventional concept based on maximum Gieseler fluidity anticipated the possibility of a reduction in coke resistance in the case of a coal mixture that has very high fluidity (see, for example, Non-Patent Literature 4), it is still impossible clarify behaviors of individual brands that have high fluidity. One reason for this is probably due to the fact that the conventional Gieseler fluidity measurement is unable to accurately measure properties in high fluidity due to the Weissenberg effect mentioned above. The inventive method of measurement allowed for a more accurate assessment of melt properties, particularly at high fluidity. In this way, the present invention has made significant advances by making it possible to clarify the differences in properties between thermal plastics that were difficult to distinguish by conventional methods, as well as by allowing the best assessment of a relationship between thermally plastic behaviors and coke structures.
[000146] The present inventors established suitable measurement conditions in the inventive method, and concluded a method for producing high strength coke using the measurement results. Examples Example 1
[000147] Examples of constant volume heating measurement for coal samples and pie formation additives in combination with a material that has through holes from upper to lower surfaces will be described. The permeation distance and pressure during permeation were measured using 17 types of coals and 4 types of pie forming additives (coals A to Q, pie forming additives R to U) as samples. Table 1 describes the properties (average maximum reflectance: Ro, logarithmic value of maximum Gieseler fluidity: logMF, volatile matter content: VM, ash content: Gray) of the coals and pie-forming additives used. Measuring the fluidity of the pie forming additives used in this document using a Gieseler plastometer method resulted in common logarithmic values of all these maximum Gieseler fluids (logMF) being 4.8, which was the detection limit. Table 1


[000148] Using a device similar to that illustrated in Figure 1, the permeation distance and pressure during permeation were measured. The heating system was a high frequency induction heating system. That is, a heating element 8 and a container 3 in Figure 1 were an induction heating coil and a dielectric graphite container. Container 3 was 18 mm in diameter and 37 mm high. Glass beads having a diameter of 2 mm were used as a through-hole material 2. The container was loaded with 2.04 g of a sample that was ground to a particle diameter of no more than 2 mm and was dried vacuum at room temperature. A weight weighing 200 g was loosened from the top of the sample five times with a drop distance of 20 mm, thus conditioning the sample. (At this time, the thickness of the sample layer was 10 mm.) Then, the glass spheres with a diameter of 2 mm were placed on the packed layer of the sample 1, in order to reach a thickness of 25 mm, thus preparing In this way, a layer of glass sphere packaged as the through-hole material 2. In the layer of packed glass ball, a silimanite disk with a diameter of 17 mm and a thickness of 5 mm was laid out, and a quartz rod as a pressure sensing rod 4 was additionally disposed thereon. Using nitrogen gas as an inert gas, the sample was heated from room temperature to 550 ° C at a heating rate of 3 ° C / min. During heating, the pressure transmitted through the pressure sensing rod 4 was measured with a load cell 6. Upon completion of the heating, the cooling was carried out in a nitrogen atmosphere. The spheres that did not adhere to the thermal plastic were collected from the cooled container 3, and their mass was measured.
[000149] The permeation distance was determined based on the packing height of the sphere layer that was adhered together. A relationship was obtained beforehand between the packing height and the mass of the packed glass sphere layer, so that it became possible that from the mass of spheres that adhered to each other to the thermal plastic, the packing height of such balls glass was derived, as shown in Equation (2) below. The permeation distance was derived from Equation (2). L = (G - M) x H - (2)
[000150] where L is the permeation distance [mm], G is the mass [g] of the packed glass spheres, M is the mass [g] of the spheres that have not adhered to each other in the thermal plastic, and H is the layer height conditioned by 1 g of the glass spheres conditioned in this experimental apparatus [mm / g].
[000151] For pie formation additives, the permeation distance was measured using a sample container of the same diameter, as described above, however, with a height of 100 mm, and the sphere layer being arranged glass with a thickness of 80 mm over the sample. This configuration was adopted due to the fact that the permeation distance of the pie formation additives was large. Separately, tests were carried out in which a coal was conditioned with a constant sample layer thickness while changing the height of the container and the thickness of the conditioned glass sphere layer. The measured values of the permeation distance are identical as long as the thickness of the packed glass sphere layer is greater than the permeation distance.
[000152] Table 2 describes the measurement results of the permeation distance and the maximum pressure during permeation. Figure 6 shows a relationship between the permeation distance measurement results and the logarithmic values of maximum Gieseler fluidity (logMF). (The graphical representation excluded the values of pie formation additives whose MF value was not accurately measured). Table 2


[000153] From Figure 6, the permeation distance showed a certain extent of correlation with the logMF, although numerous marks have deviated from the correlation. In addition, the measurement results for the pie formation additives in Table 2 showed that the differences in the properties of pie formation additives were successfully observed. Such discrimination was impossible with conventional methods. In a measurement in which a sample and through hole material are heated to a constant volume, the factors that will affect the permeation distance are, as shown in Equation (1), the sample viscosity p and the expansion pressure AP sample, which vary from sample to sample. In this way, the permeation distances and the pressures measured while heating the samples of coals and pie forming additives in combination with the through hole material in a constant volume are considered opposed to reflect the state of the melt in a coke oven. Due to the fact that the melting condition and the pressure of thermally plastic coals and thermally plastic pie formation additives are supposed to affect the coke structure after carbonization, it can be said that such parameters are particularly effective in estimating the resistance of coke.
[000154] Furthermore, due to the fact that the pressure exerted during the permeation of the sample is the result of the pressure measurement performed in a measurement environment that simulates the expansion behaviors in a coke oven, it can be said that this parameter is effectively used to estimate the pressure applied to the wall of a coke oven during carbonization of coal in a coke oven. Example 2
[000155] The measurement examples will be described in which the coals and pie formation additives as samples have been heated while applying a constant load to the sample and a material that has through holes from upper to lower surfaces. The permeation distance and the expansion coefficient during permeation were measured in relation to the same coals and pie-forming additives as in Example 1, that is, 17 types of coals and 4 types of pie-forming additives (coals A to Q, pie formation additives R to U) shown in Table 1. Using a device similar to that illustrated in Figure 2, the permeation distance and the expansion coefficient during permeation were measured. The heating system was a high frequency induction heating system. That is, a heating element 8 and a container 3 in Figure 2 were an induction heating coil and a dielectric graphite container. Container 3 was 18 mm in diameter and 37 mm high. Glass spheres having a diameter of 2 mm were used as a through hole material. Container 3 was loaded with 2.04 g of a sample which was ground to a particle diameter of no more than 2 mm and was vacuum dried at room temperature. A weight weighing 200 g was released from the top of the sample five times with a drop distance of 20 mm, thus packing sample 1. Next, the glass spheres with a diameter of 2 mm were placed in the layer of sample 1, in order to reach a thickness of 25 mm, thus preparing a layer of glass sphere packaged as the through-hole material 2. In the layer of packed glass sphere, a silimanite disk with a diameter of 17 mm and a thickness of 5 mm was disposed, and a quartz rod as an expansion coefficient detection rod 13 was additionally disposed on it. In addition, a weight 14 weighing 1.3 kg has been placed on top of the quartz rod. As a result, the pressure applied to the silimanite disk was 50 kPa. Using nitrogen gas as an inert gas, the sample was heated to 550 ° C at a heating rate of 3 ° C / min. During heating, a displacement was measured with a displacement laser, and the expansion coefficient was calculated from the height at which the sample was stored. After heating was completed, cooling was carried out in a nitrogen atmosphere. The spheres that did not adhere to the thermal plastic were collected from the cooled container, and their mass was measured. The permeation distance was derived from Equation (2).
[000156] In measuring the permeation distance of the pie formation additives, in this example too, the tests were performed by using a larger container and increasing the thickness of the glass sphere layer packaged in a similar manner in Example 1. Confirmed it was noted that the thickness of the conditioned glass sphere layer did not affect the measured values of the permeation distance under the conditions of Example 2.
[000157] Table 3 describes the results of measurement of the permeation distance and the final expansion coefficient. Figure 7 shows the relationship between the permeation distance measurement results and the logarithmic values of the maximum Gieseler fluidity (logMF). (The graphical representation excluded the values of pie-forming additives whose MF value was not accurately measured). Table 3


[000158] From Figure 7, the permeation distance measured in this example is shown to have a certain extent of correlation with logMF. However, it was also found that some brands exhibited different permeation distances even though their logMF values were similar. In particular, this trend was observed in a higher logMF region. Due to the fact that the permeation distance measurement error with this apparatus was found to be 0.6 in terms of standard error by repeating a test three times under the same conditions, a significant difference in the permeation distance was shown in relation to coal H and coal K which logMF train substantially equal. Based only on the relationship represented by Equation (I), it can be assumed that the marks with the same logMF will have a similar viscosity p in a melted state and, thus, the permeation distances will be identical. The reasons for this assumption are that AP and K are constant in this measurement regardless of the samples to be analyzed, as well as the fact that the logMF of a coal is substantially correlated to the temperatures at which the coal exhibits melting properties (in the present document, such temperatures correspond to the melting time) and, therefore, the term u can be considered substantially constant. During the carbonization of coal, however, the phenomena of gas generation and expansion are observed simultaneously with the coal melting due to the removal of volatile materials. Thus, it is assumed that the permeation distance values obtained in this measurement reflect the combined influences of the fusion permeation in the packed sphere layer and the generation of gas from the fusion in the sphere layer. Due to the fact that these values are supposed to be factors that determine the coke structure after carbonization, it can be said that such parameters are particularly effective in estimating coke resistance.
[000159] Furthermore, the final expansion coefficients described in Table 3 are expansion coefficient values at 550 ° C. Due to the fact that the results in Table 3 arise from the measurement of the expansion coefficient in a measurement environment that simulates the expansion behaviors in a coke oven, it can be said that the data are effective for estimating coke resistance , as well as, to estimate a gap between the wall of a coke oven and a coke mass. Example 3
[000160] If there was an additivity of the permeation distance, it was investigated according to the same measurement method as in Example 2.
[000161] Two brands were selected from 4 types of coals (coals V to Y) and were mixed in various mixing ratios to provide mixtures of coal as samples. The samples were subjected to measurement of the permeation distance. Table 4 describes the coals used and properties (Ro, logMF, VM, Gray) of the coal mixtures. Here, the properties of coal mixtures are weighted average values of properties of individual coals measured according to the mixing ratios. The permeation distance measurement results are also described in Table 4. Figure 8 shows a relationship between the weighted average permeation distances and the measured permeation distances of the coal mixtures.


[000162] From Figure 8, it was shown that there is a very good additivity for the permeation distances measured in this example. Consequently, the permeation distance value of a coal mixture formed by two or more types of coals can be determined by actually measuring the permeation distance of a sample of the coal mixture, or by previously measuring the permeation distances of individual coals to be mixed and estimate the permeation distance by calculating the weighted average value.
[000163] Regarding the coals used for coal mixtures, different qualities and grades are usually measured beforehand in relation to each brand, and the data obtained are used in the coal mix. Consequently, it is preferable from a practical point of view that the permeation distance is measured beforehand in relation to each batch of brand, thus allowing easy calculation of the permeation distance of a coal mixture. Example 4
[000164] The coals thermal plasticity values obtained in the present invention were applied to the estimation of coke resistance and their effectiveness was examined.
[000165] As described above, the permeation distance, according to the invention, is considered to be a parameter greater than a logarithmic value of maximum Gieseler fluidity logMF in the estimation of coke properties and coke pie structures. Accordingly, a carbonization test and a coke strength test after carbonization were performed as described below, in order to examine how coke resistance can be affected when coke has been produced using coals that have substantially the same logMF and different permeation distances.
[000166] Referring to Table 1 used in Examples 1 and 2, coal A, coal Feo coal G (each with a logMF of not less than 3.5) were selected as "similar MF coals". Each of these coals was mixed at 20% by mass along with several coals as the equilibrium, so that the weighted average Ro values and the weighted average logMF values of the coal mixtures as a whole can be the same preparing, in this way , coal mixtures (mixtures of coal A, F and G). Coal A, coal F and coal G are such types of coals that have an MF between coals used in coke production and are often used to improve the adhesion of coal particles in coke production. In addition, coal mixtures that include numerous brands with logMF> 3.0 at the same time (AF coal mixture, FG coal mixture and FGK coal mixture) were prepared in order to test the properties of coal mixtures that contain such high MF coals. These coal mixtures were prepared so that the average grades and grades can be Ro = 0.99 to 1.05 and logMF = 2.0 to 2.3. Table 5 describes the marks and proportions of the coals used in the respective coal mixtures, the weighted average constant volume permeation distances (calculated from the values in Table 2) and the weighted average constant pressure permeation distances (calculated from the values in Table 3) of coals with logMF> 3.0 in coal mixtures, and the strength of the coke produced.


[000167] Each of the coals in Table 5 was used after being ground so that particles with a particle diameter of no more than 3 mm represented 100% by weight. In addition, the water content has been adjusted so that the water content in the entire coal mixture can be 8% by weight. The coal mixture that weighs 16 kg was packed in a carbonization box, so that the apparent density can be 750 kg / m3, and a weight of 10 kg has been placed in it. The coal mixture was then charred in an electric oven at an oven wall temperature of 1050 ° C for 6 hours, removed from the oven, and cooled in an atmosphere of nitrogen to provide a coke. The coke resistance of the coke obtained was determined based on a drum resistance test method according to JIS K 2151, in which the drum was spun at 15 rpm and the mass proportion of coke particles that had a particle diameter of not less than 15 mm after 150 rotation was calculated. The mass ratio of this to the proportion of mass before rotations was calculated to provide a drum resistance index of Dl 150/15. In addition, the results of the measurements of CRI (CO2 reactivity), CSR (resistance after CO2 reaction, all measured according to an ISO 18894 method), and micro-resistance (MSI + 65) are also described.
[000168] Figure 9 shows a relationship between the weighted average value of the constant pressure permeation distance of the coal in each coal mixture with a logarithmic fluidity maximum logies GF value of logMF 3.0 (the permeation distance measured in the Example 2 by heating the coal sample while applying a constant load on the coal sample and the through hole material), and the resistance to the carbonized coke drum from each coal mixture. By comparing the resistances of coal mixture A, coal mixture F and coal mixture G that contained coal A, coal F and coal G, respectively, in 20% by mass as coal of similar MF , the resistance to the drum was shown to be higher as the permeation distance of the similar MF coal was shorter. Furthermore, the results of resistance to the drum of coal mixture A, coal mixture F and coal mixture AF show that there is an additivity between the permeation distance and drum resistance of similar MF coals. These results, in combination with the results of the FG coal mixture and the FGK coal mixture, show that the coke resistance decreases when the weighted average value of the constant pressure permeation distance of the coal in the coal mixture with a logarithmic value of maximum Gieseler fluidity of logMF 3.0 exceeds 17 mm. In this way, the production of high-strength coke can be accomplished by regulating the weighted average value of the constant pressure permeation distance of the coal in the coal mixture with a logarithmic fluidity Gieseler maximum value of logMF> 3.0 to be not more than 17 mm.
[000169] Next, Figure 10 shows a relationship between the weighted average value of the constant volume permeation distance of the coal in each coal mixture with a logarithmic fluidity Gieseler maximum value of logMF> 3.0 (the distance of permeation measured in Example 1 by heating the coal sample in combination with the through hole material in a constant volume), and the resistance to carbonized coke drum from each coal mixture.
[000170] A similar trend, although slightly weaker than in Figure 9, was also confirmed in Figure 10. Thus, it was shown that the permeation distance values obtained in this measurement affect the coke resistance in both cases. where such values are determined by measuring constant volume heating and measuring constant load heating. It was determined that when the permeation distance of constant volume is adopted as an indicator, the weighted average value of the permeation distance of constant volume of coal in the coal mixture with a logarithmic value of maximum Gieseler fluidity of logMF> 3 , 0 is preferably set to be no more than 15 mm. Due to the fact that the measurement of the permeation distance in relation to an identical coal gives different results depending on the measurement conditions used, it is necessary that the coals be evaluated under substantially identical conditions. Here, the term "substantially identical" means that the products of the sample layer thickness and packing density are within ± 20%, the types of through hole materials (for example, packed spherical particle layers or packed layers) with cylinder) are the same, however, the diameters of the balls or cylinders are within ± 20%, and the heating rates are within ± 20p. The measurement conditions can be used in a practical way without any problem as long as the differences are within the above ranges. Obtaining previously, based on the values measured under such conditions, as defined above, the correlations, as shown in Figures 9 and 10, between the permeation distance of a high MF coal in a coal mixture and the coke resistance obtained through the carbonization of the coal mixture, it becomes possible to determine the extent to which the permeation distance of the high MF coal must be adjusted in order to obtain a desired coke resistance. Furthermore, CSR was measured in relation to the coke produced from the mixture of FG coal and the mixture of FGK coal. As a result, a similar trend to resistance to the JIS drum was observed, with CSR of coke from the coal mixture FG being 55.4 (CRI reactivity = 29.7) and CSR of coke from the coal mixture FGK being 59.5 (CRI reactivity = 29.5). In general, it is known that when the CRI reactivities of coke are similar, CSR shows a good correlation with the resistance to the JIS drum. This trend was also confirmed with the samples in the Examples. Trends similar to JIS drum resistance were also observed for micro-resistance and indirect tensile strength.
[000171] As shown above, it was revealed that the permeation distance of a high MF coal greatly affected the coke resistance. In particular, the reason why the permeation distance of a high MF coal probably has marked effects is probably because the differences in permeation distance become larger as the coals have a higher MF, as shown in Figure 6 and Figure 7. Low MF coals have limited differences in permeation distance between brands and, therefore, it is likely that their permeation distances do not have significant influences. In addition, it is likely that the evaluation of the thermal plasticity of high MF coals using a Gieseler plastometer method was insufficient due to the Weissenberg effect mentioned above and the presence of the measurable upper limit. The inventive method improves the flaws possessed by conventional methods, and makes it possible to obtain a new discovery that concerns the influences of thermal plasticity on coke resistance.
[000172] Next, the reasons why the permeation distance affected the coke resistance were examined by observing with a light microscope the structure of coke obtained by carbonizing the mixture of coal A which contained 20% by mass of coal A whose permeation distance was imagined as appropriate, as well as the coke structure obtained by carbonizing the mixture of coal F which contained 20% by mass of coal F whose permeation distance was thought to be excessively long. Figure 11 and Figure 12 show images of the mixture of coal A and mixture of coal F, respectively, taken in 100 increments.
[000173] From the comparison between the images shown in Figure 11 and Figure 12, it was shown that the coke from the carbonization of the coal mixture F that contained the coal F with an excessively long permeation distance had more pore walls fine 20 and large distorted pores 21 as a result of the bond between the pores, compared to coke from the carbonization of the mixture of coal A containing coal A with an appropriate permeation distance. Coke resistance has been reported to become higher as the pore walls are thicker and the pores have a higher circularity (see, for example, Non-Patent Literature 5). Consequently, it was confirmed that the permeation distance of the coal affects the formation of a coke structure during carbonization and, consequently, affects the strength of the coke.
[000174] The results in the Examples show that the permeation distance, which is measured by heating the coal sample while applying a constant load on the coal sample and through hole material or by heating the coal sample while if the sample and the through-hole material are kept at a constant volume, it is a factor that affects the coke resistance produced from coal and that cannot be responsible for conventional factors, as well as showing that the use of permeation distance in combination with other conventional parameters in the estimation of coke resistance will allow highly accurate resistance estimation. Furthermore, it is now apparent that the production of high-strength coke is possible by mixing coals based on the permeation distances measured under preferred conditions. Numerical Reference List Sample Through hole material that has through holes from upper to lower surfaces Container Pressure sensing rod Jacket Load cell Thermometer Heating element Temperature detector Temperature controller Gas inlet Gas outlet Detection rod expansion coefficient Weight Displacement gauge Circular through hole Packed particle Packed cylinder Pore wall Pore

权利要求:
Claims (13)
[0001]
1. Method for evaluating the thermal plasticity of coals and pie formation additives, characterized by the fact that it comprises: placing a coal or pie formation additive in a container to prepare a sample, disposing of a through hole material that has through holes from higher to lower surfaces on the sample, heat the sample while keeping the sample and through hole material at a constant volume, measure the permeation distance with which the melted sample was permeated through the through holes, and evaluate the thermal plasticity of the sample using the measured value, where sample preparation includes grinding a coal or a pie-forming additive, so that particles with a particle diameter of no more than 3 mm represent no less than 70 % by mass, and pack the coal or crushed pie formation additive in a container with a packing density of 0.7 to 0.9 g / cm3 and a thickness 5 to 20 mm layer, where the through hole material is a spherical packed particle layer or a packed non-spherical particle layer, where the through hole material is a packed spherical particle layer, in which the layer Spherical particle size includes glass spheres, in which the sample is heated from room temperature to 550 ° C at a heating rate of 2 to 10 ° C / min. in an atmosphere of inert gas.
[0002]
2. Method for evaluating the thermal plasticity of coals and pie-forming additives, characterized by the fact that it comprises: placing a coal or pie-forming additive in a container to prepare a sample, disposing of a through hole material that has through holes through upper and lower surfaces on the sample, heat the sample while keeping the sample and through hole material at a constant volume, measure the sample pressure that is transmitted through the through hole material, and evaluate the thermal plasticity of the sample using the measured value, where the sample preparation includes grinding a coal or a pie-forming additive, so that particles with a particle diameter of no more than 3 mm represent no less than 70% in put the coal or crushed pie formation additive in a container with a packing density of 0.7 to 0.9 g / cm3 and a layer thickness of 5 to 20 mm, wherein the through hole material is a spherical packed particle layer or a packed non-spherical particle layer, where the through hole material is a packed spherical particle layer, where the spherical particle layer packaged includes glass beads, in which the sample is heated from room temperature to 550 ° C at a heating rate of 2 to 10 ° C / min. in an atmosphere of inert gas.
[0003]
3. Method for assessing the thermal plasticity of coals and pie-forming additives, characterized by the fact that it comprises: placing a coal or pie-forming additive in a container to prepare a sample, disposing of a through hole material that has through holes from higher to lower surfaces on the sample, heat the sample while applying a constant load on the through hole material, measure the permeation distance with which the melted sample was permeated in the through holes, and evaluate the thermal plasticity of the sample using the measured value, where sample preparation includes grinding a coal or a pie-forming additive, so that particles with a particle diameter of no more than 3 mm represent no less than 70% by weight , and pack the coal or crushed pie-forming additive in a container with a packing density of 0.7 to 0.9 g / cm3 and a layer thickness 5 to 20 mm, where the through hole material is a spherical packed particle layer or a packed non-spherical particle layer, where the through hole material is a packed spherical particle layer, where the particle layer Spherical packaging includes glass spheres, in which the sample is heated from room temperature to 550 ° C at a heating rate of 2 to 10 ° C / min. in an inert gas atmosphere, where applying a constant charge includes applying such a charge in which the pressure on the upper surface of the through hole material becomes 5 to 80 kPa.
[0004]
4. Method for evaluating the thermal plasticity of coals and pie-forming additives, characterized by the fact that it comprises: placing a coal or pie-forming additive in a container to prepare a sample, disposing of a through hole material that has through holes from higher to lower surfaces on the sample, heat the sample while applying a constant load on the through hole material, measure the sample expansion coefficient, and evaluate the sample's thermal plasticity using the measured value, where sample preparation includes grinding a coal or a pie-forming additive, so that particles with a particle diameter of no more than 3 mm represent no less than 70% by weight, and conditioning the coal or forming additive of crushed cake in a container with a packing density of 0.7 to 0.9 g / cm3 and a layer thickness of 5 to 20 mm, in which the through-hole material is a packaged spherical particle layer or a packaged non-spherical particle layer, wherein the through hole material is a packaged spherical particle layer, wherein the packaged spherical particle layer includes glass beads, where the sample is heated to from room temperature to 550 ° C at a heating rate of 2 to 10 ° C / min. in an inert gas atmosphere, where applying a constant charge includes applying such a charge in which the pressure on the upper surface of the through hole material becomes 5 to 80 kPa.
[0005]
5. Method for evaluating the thermal plasticity of coals and pie-forming additives, according to any one of claims 1 to 4, characterized by the fact that the coal or pie-forming additive is crushed, so that particles with a particle diameter of no more than 2 mm represent 100% by mass.
[0006]
6. Method for evaluating the thermal plasticity of coals and pie-forming additives, according to any one of claims 1 to 4, characterized by the fact that the heating rate is 2 to 4 ° C / min.
[0007]
7. Method for evaluating the thermal plasticity of coals and pie-forming additives, according to any of claims 3 or 4, characterized by the fact that the application of a load includes applying such a load in which the pressure on the surface through the through hole material becomes 15 to 55 kPa.
[0008]
8. Method for assessing the thermal plasticity of coals and pie-forming additives according to claim 1 or 2, characterized in that the arrangement of the through-hole material includes arranging glass spheres having a diameter of 0, 2 to 3.5 mm over the sample, to obtain a layer thickness of 20 to 100 mm, and heating the sample includes heating the sample from room temperature to 550 ° C at a heating rate of 2 to 10 ° C / min. in an inert gas atmosphere while keeping the sample and the glass sphere layer at a constant volume.
[0009]
9. Method for assessing the thermal plasticity of coals and pie-forming additives according to claim 3 or 4, characterized in that the arrangement of the through-hole material includes arranging glass spheres having a diameter of 0, 2 to 3.5 mm over the sample, to obtain a layer thickness of 20 to 100 mm, and heating the sample includes heating the sample from room temperature to 550 ° C at a heating rate of 2 to 10 ° C / min. in an inert gas atmosphere while applying a charge from above the glass spheres, so that 5 to 80 kPa are obtained.
[0010]
10. Method for evaluating the thermal plasticity of coals and pie-forming additives according to claim 1 or 2, characterized in that the sample preparation includes grinding a coal or pie-forming additive, so that particles with a particle diameter of no more than 3 mm represent no less than 70% by weight, and pack the coal or crushed pie formation additive in a container with a packing density of 0.7 to 0.9 g / cm3 and a layer thickness of 5 to 20 mm, the arrangement of the through hole material includes arranging glass spheres having a diameter of 0.2 to 3.5 mm over the sample, in order to obtain a layer thickness of 20 to 100 mm, and heating the sample includes heating the sample from room temperature to 550 ° C at a heating rate of 2 to 10 ° C / min. in an inert gas atmosphere while keeping the sample and the glass sphere layer at a constant volume.
[0011]
11. Method for assessing the thermal plasticity of coals and pie-forming additives according to claim 3 or 4, characterized in that the sample preparation includes grinding a coal or pie-forming additive, so that particles with a particle diameter of no more than 3 mm represent no less than 70% by weight, and pack the coal or crushed pie formation additive in a container with a packing density of 0.7 to 0.9 g / cm3 and a layer thickness of 5 to 20 mm, the arrangement of the through hole material includes arranging glass spheres having a diameter of 0.2 to 3.5 mm over the sample, in order to obtain a layer thickness of 20 to 100 mm, and heating the sample includes heating the sample from room temperature to 550 ° C at a heating rate of 2 to 10 ° C / min. in an inert gas atmosphere while applying a charge from above the glass spheres, so that 5 to 80 kPa are obtained.
[0012]
12. Method for evaluating the thermal plasticity of coals and pie-forming additives, according to claim 1 or 2, characterized in that the sample preparation includes grinding a coal or pie-forming additive, so that particles with a particle diameter of no more than 2 mm represent 100% by mass, and pack the coal or crushed pie formation additive in a container with a packing density of 0.8 g / cm3 and a layer thickness of 10 mm, the arrangement of the through-hole material includes arranging glass spheres that have a diameter of 2 mm over the sample, in order to obtain a layer thickness of 80 mm, and heating the sample includes heating the sample from the room temperature up to 550 ° C at a heating rate of 3 ° C / min. in an inert gas atmosphere while keeping the sample and the glass sphere layer at a constant volume.
[0013]
13. Method for assessing the thermal plasticity of coals and pie-forming additives according to claim 3 or 4, characterized in that the sample preparation includes grinding a coal or pie-forming additive, so that particles with a particle diameter of no more than 2 mm represent 100% by mass, and pack the coal or crushed pie formation additive in a container with a packing density of 0.8 g / cm3 and a layer thickness of 10 mm, the arrangement of the through-hole material includes arranging glass spheres that have a diameter of 2 mm over the sample, in order to obtain a layer thickness of 80 mm, and heating the sample includes heating the sample from the room temperature up to 550 ° C at a heating rate of 3 ° C / min. in an inert gas atmosphere while applying a charge from above the glass spheres, so that 50 kPa is obtained.

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法律状态:
2018-12-26| B06F| Objections, documents and/or translations needed after an examination request according [chapter 6.6 patent gazette]|

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2019-08-20| B06U| Preliminary requirement: requests with searches performed by other patent offices: procedure suspended [chapter 6.21 patent gazette]|

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2020-02-11| B06A| Patent application procedure suspended [chapter 6.1 patent gazette]|

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2020-06-23| B09A| Decision: intention to grant [chapter 9.1 patent gazette]|

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2020-11-10| B16A| Patent or certificate of addition of invention granted [chapter 16.1 patent gazette]|Free format text: PRAZO DE VALIDADE: 20 (VINTE) ANOS CONTADOS A PARTIR DE 31/08/2011, OBSERVADAS AS CONDICOES LEGAIS. |

优先权:

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申请号 | 申请日 | 专利标题

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JPPCT/JP2010/065351|2010-09-01|

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JP2010-195622|2010-09-01|

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JP2010065351|2010-09-01|

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JP2010195622|2010-09-01|

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PCT/JP2011/070316|WO2012029985A1|2010-09-01|2011-08-31|Method for evaluating thermal plasticities of coal and caking additive and method for producing coke|

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