TWI457555B - Evaluation method of softening and melting of coal and binder and method for manufacturing coke - Google Patents

Description

Method for evaluating softening and melting characteristics of coal and cement and method for producing coke

The present invention relates to a method for evaluating softening and melting characteristics of coal and a binder during dry distillation of carbon and a binder, and a method for producing coke using the same.

The coke used in the blast furnace method which is most commonly used in the method of producing iron is used as a reducing material, a heat source, a spacer, and the like of iron ore. In order to stabilize the blast furnace and perform work efficiently, it is important to maintain the air permeability in the blast furnace, so high-strength coke production is required. The coke system is prepared by blending coal of various coke-making coals which have been pulverized and adjusted in particle size, and dry-distilling them in a coke oven. The coal for coke production is softened and melted in a temperature range of about 300 ° C to 550 ° C in dry distillation, and foamed and expanded with the occurrence of volatile matter, whereby the respective particles are bonded to each other to form a block-shaped semi-coke. Carbon (semi coke). Thereafter, the semi-coke is shrunk and sintered in the process of raising the temperature to around 1000 ° C to become a hard coke (coke cake). Therefore, the cohesive property of coal during softening and melting has a great influence on the properties such as coke strength or particle size after dry distillation.

In addition, in order to enhance the adhesion of coal (coal blending) for coke production, a method of producing coke by adding a binder having a high fluidity in a temperature region where coal is softened and melted in coal blending is generally performed. Here, the binder is specifically, for example, coal pitch, petroleum pitch, solvent refined carbon, solvent extracted carbon, or the like. As for the above-mentioned cemented materials, as in the case of coal, the adhesive properties during softening and melting have a great influence on the coke properties after carbonization.

On the other hand, in the coke production in the coke oven, the coke after coke distillation is discharged to the outside of the coke oven by the extruder. At this time, if the contraction of the produced coke cake main body is small, it is difficult to discharge it to the outside of the furnace, and as a result, the "crowding" which cannot be discharged to the outside of the furnace may occur. The coke cake structure after dry distillation can be said to be greatly affected by the volume change of coal and semi-coke in the dry distillation process. Among them, it is known that there is a good correlation between the shrinkage of the semi-coke carbon and the volatile matter of the coal (for example, refer to Non-Patent Document 1), and the volatile content of the mixed coal is kept almost constant within the operating range. Therefore, the volume change characteristic of coal during softening and melting can be said to have a great influence on the structure of the coke cake after carbonization.

As described above, since the softening and melting characteristics of coal greatly affect the coke behavior or coke cake structure after carbonization, it is extremely important, and the review of the measurement method has been quite popular since ancient times. In particular, the coke strength which is an important quality of coke is greatly affected by the coal properties of the raw materials, especially the degree of coalification and softening and melting. The softening and melting property refers to a property of softening and melting when coal is heated, and is usually measured and evaluated by softening the fluidity, viscosity, adhesion, and swelling property of the melt.

Among the softening and melting characteristics of coal, a general method for measuring the fluidity at the time of softening and melting is, for example, a coal flowability test method by the Gieseler Plastometer method defined in JIS M 8801. In the Gisele plastometer method, the coal pulverized to 425 μm or less is placed in a predetermined crucible, heated at a prescribed heating rate, and the rotation speed of the stirring rod to which the predetermined torque is applied is read by the scale plate, according to ddpm (dial division) Per minute) The method to be represented.

In comparison with the Gisele plastometer method, the rotation speed of the stirring rod under a fixed torque is measured, and a method of measuring the torque by a fixed rotation method is also proposed. For example, Patent Document 1 describes a method of measuring torque while rotating a rotor at a constant rotation speed.

In addition, there is a method of measuring the viscosity by a dynamic viscoelasticity measuring device for the purpose of measuring the viscosity of a physical property in terms of softening and melting properties (see, for example, Patent Document 2). The so-called dynamic viscoelasticity measurement refers to the measurement of the viscoelastic behavior observed when a force is periodically applied to a viscoelastic body. In the method described in Patent Document 2, the viscosity of the softened molten coal is evaluated by measuring the composite viscosity ratio in the obtained parameters, and the viscosity of the softened molten coal at an arbitrary shear rate can be measured.

Further, as a softening and melting property of coal, an example in which activated carbon or glass beads are used and the adhesion of coal softened melt to the like has been reported. This is a method in which a small amount of coal sample is heated in a state in which activated carbon and glass beads are held in the vertical direction, and then cooled and softened, and the adhesion between coal and activated carbon and glass beads is observed from the appearance.

As a general method for measuring the expandability at the time of softening and melting of coal, for example, a dilatometer prescribed by JIS M 8801 can be mentioned. In the dilatometer method, the coal pulverized to 250 μm or less is molded according to a predetermined method, placed in a predetermined crucible, and heated at a predetermined heating rate, and the time-dependent change of the displacement of the coal is measured by a detection rod disposed on the upper portion of the coal. method.

In addition, in order to simulate the softening and melting behavior of the coal in the coke oven, a coal swelling test method for improving the penetration behavior of the gas generated when the coal is softened and melted is known (for example, see Patent Document 3). This is because the penetrating material is disposed between the coal layer and the piston, or between the coal layer and the piston and below the coal layer, so that the permeability of the volatile matter and the liquid substance generated by the coal is increased, thereby making the determination The environment is closer to the expansion behavior in the coke oven. In the same manner, a method of measuring the swelling property of coal by applying a load to the coal layer and applying a load to the coal to measure the swelling property of the coal is also known (see Patent Document 4).

(Patent Document 1) Japanese Patent Laid-Open No. Hei 6-347392

(Patent Document 2) Japanese Patent Laid-Open Publication No. 2000-304674

(Patent Document 3) Japanese Patent No. 2855728

(Patent Document 4) Japanese Patent Laid-Open Publication No. 2009-204609

(Non-Patent Document 1) C. Meyer et al.: "Gluckauf Forshungshefte", Vol. 42, 1981, p. 233-239

(Non-Patent Document 2) Zhu Fu and others: "Fuel Association", Vo1.53, 1974, p.779-790

(Non-Patent Document 3) D.W. van Krevelen: "Coal", 1993, p.693-695

(Non-Patent Document 4) Miyazu et al.: "Japan Steel Pipe Technology", Vol.67, 1975, p.125-137

(Non-Patent Document 5) Ueoka et al., "Iron and Steel", Vol.93, 2007, p.728-735

In order to evaluate the softening and melting behavior of the coal in the coke oven, it is necessary to measure the softening and melting characteristics of coal in a state simulating the surrounding environment of the softened and melted coal in the coke oven. The coal softened and melted in a coke oven and its surrounding environment are described in detail below.

In the coke oven, the coal which is softened and melted is softened and melted in a state of being restrained by the adjacent layer. Since the thermal conductivity of coal is small, in the coke oven, the coal is not uniformly heated, and the coke layer, the softened molten layer, and the coal layer are in different states from the furnace wall side of the heating surface. Since the coke oven itself is slightly expanded but hardly deformed during dry distillation, the softened and melted coal is restrained by the adjacent coke layer and coal layer.

In addition, around the softened and melted coal, there are voids between coal particles in the coal layer, interparticle voids in the softened molten coal, coarse atmospheric pores generated by volatilization of the pyrolysis gas, and cracks in the adjacent coke layer. Most of the defect structures. In particular, cracks generated in the coke layer are considered to have a width of about several hundred micrometers to several millimeters, and a large gap or pore between coal particles having a size of several tens to several hundreds of micrometers. Therefore, it is considered that not only the thermal decomposition gas or the liquid matter of the by-product produced from the coal penetrates into such coarse defects generated in the coke layer, but also the coal which is softened and melted permeates. Further, when it is infiltrated, it is expected that the shearing speed of the softened and melted coal will vary depending on each brand.

As described above, in order to measure the softening and melting characteristics of coal in a state in which the surrounding environment of the softened and melted coal in the simulated coke oven is measured, it is necessary to appropriately correct the restraining conditions and the infiltration conditions. However, the conventional method has the following problems.

The Gisele plastometer method measures the state in which the coal is filled in the container, so that the problem of restraint and penetration conditions is not considered at all. Moreover, this method is not suitable for the measurement of coal exhibiting high fluidity. The reason for this is that when the coal exhibiting high fluidity is measured, a phenomenon in which the inner wall portion of the container becomes a void (Weissenberg effect) occurs, and the stirring rod is idling, and the fluidity cannot be correctly evaluated (for example, refer to the non-patent literature). 2).

The method of measuring the torque according to the fixed rotation method also does not take into consideration the restraint conditions and the infiltration conditions. Moreover, since the measurement was performed at a fixed shear rate, the softening and melting characteristics of coal could not be accurately evaluated as described above.

The dynamic viscoelasticity measuring device is a device that measures the viscosity at any shear rate by using viscosity as a target for softening and melting properties. Therefore, if the shear rate at the time of measurement is set to the value of the coal in the coke oven, the viscosity of the softened molten coal in the coke oven can be measured. However, it is often difficult to predict or predict the shear rate in each brand's coke oven in advance.

As a softening and melting property of coal, activated carbon or glass beads are used to measure the adhesion of the coal. Although the permeation conditions are reproduced for the presence of the coal layer, there are problems of unsimulating the coke layer and coarse defects. . Also, there is insufficient measurement in the case of restraint.

In the coal expansion test method using the penetrating material described in Patent Document 3, the movement of the gas or the liquid substance generated by the coal is considered, but the movement of the softened and melted coal itself is not considered. problem. This is due to the degree of penetration of the penetrating material used in Patent Document 3, which is not sufficiently large to soften the extent to which the molten coal moves. The inventors of the present invention actually conducted the test described in Patent Document 3, and as a result, the penetration of the softened molten coal into the penetrating material did not occur. Therefore, in order for the penetration of the softened molten coal into the penetrating material to occur, new conditions must be considered.

Patent Document 4 similarly discloses a method of measuring a coal swelling property in which a material having a through-passage is disposed on a coal layer, and a gas or a liquid substance generated by coal is considered, except for a problem that the heating method is limited. There are still problems in assessing the conditions of penetration in the coke oven that are still unclear. Further, in Patent Document 4, the relationship between the penetration phenomenon of the coal melt and the softening and melting behavior is still unclear, and the relationship between the penetration phenomenon of the coal melt and the produced coke quality is not taught, and there is no good The record of quality coke production.

In this way, the fluidity, viscosity, adhesion, permeability, and penetration of coal and cement are measured under the condition that the surrounding environment of the softened and melted coal and the binder in the coke oven is fully simulated by the prior art. Softening and melting characteristics such as expansion ratio, pressure at the time of penetration, and the like.

However, an object of the present invention is to solve the problems of the prior art, and to provide a soft-melting property of coal and a binder in a state in which the surrounding environment of the softened and melted coal and the binder is sufficiently simulated in a coke oven. Although it is a simple method, it is more accurate to evaluate the softening and melting characteristics of coal and cement.

Furthermore, by more accurately evaluating the softening and melting characteristics, it is possible to better grasp the influence of the focused carbon intensity of coal and the binder. The present invention utilizes this discovery in order to provide a high strength coke manufacturing process by setting a novel coal blending reference.

In order to solve the above problems, the features of the present invention are as follows.

(1) A method for evaluating the softening and melting characteristics of coal and a cement material, wherein a coal or a cement material is filled in a container to prepare a sample, and a material having a through hole is disposed above the sample above the sample, and the sample and the sample are The material having the through hole in the upper and lower surfaces was held in a fixed volume, and while the sample was heated, the penetration distance of the molten sample permeating the through hole was measured, and the softening and melting characteristics of the sample were evaluated using the measured value.

(2) A method for evaluating the softening and melting characteristics of coal and a cement material, wherein a coal or a cement material is filled in a container to prepare a sample, and a material having a through hole is disposed above the sample above the sample, and the sample and the sample are The material having the through hole in the upper and lower surfaces was held in a fixed volume, and while the sample was heated, the pressure of the sample conveyed through the material having the through hole in the upper and lower surfaces was measured, and the softening and melting characteristics of the sample were evaluated using the measured value.

(3) A method for evaluating softening and melting characteristics of coal and a cement material, wherein a coal or a cement material is filled in a container to prepare a sample, and a material having a through hole is disposed above and below the sample, and the upper and lower sides are The material of the through-hole was subjected to a fixed load, and while the sample was heated, the penetration distance of the molten sample permeating the through-hole was measured, and the softening and melting characteristics of the sample were evaluated using the measured value.

(4) A method for evaluating the softening and melting characteristics of coal and a cement material, wherein a coal or a cement material is filled in a container to prepare a sample, and a material having a through hole in the upper and lower surfaces is disposed above the sample, and the upper and lower sides are The material of the through hole was fixed with a load, and while the sample was heated, the expansion ratio of the sample was measured, and the softening and melting characteristics of the sample were evaluated using the measured value.

(5) The method for evaluating softening and melting characteristics of coal and a binder according to any one of (1) to (4), wherein the preparation of the sample comprises: pulverizing coal or a cement material to a particle diameter of 3 mm or less and 70 mass More than %, the pulverized coal or the binder is filled into the container in a manner of a packing density of 0.7 to 0.9 g/cm ³ and a layer thickness of 5 to 20 mm.

(6) The method for evaluating softening and melting characteristics of coal and a binder according to (5), wherein the pulverization system pulverizes coal or a cement material to have a particle diameter of 2 mm or less and 100% by mass.

(7) The method for evaluating the softening and melting characteristics of coal and a binder according to any one of (1) to (4), wherein the material having the through holes in the upper and lower surfaces is a spherical particle-filled layer or a non-spherical-particle-filled layer.

(8) The method for evaluating softening and melting characteristics of coal and a binder according to (7), wherein the material having the through holes in the upper and lower surfaces is a spherical particle-filled layer.

(9) The method for evaluating softening and melting characteristics of coal and a binder according to (8), wherein the spherical particle-filled layer contains glass beads.

(10) The method for evaluating softening and melting characteristics of coal and a binder according to any one of (1) to (4), wherein the heating system of the sample comprises: a heating rate of 2 to 10 ° C /min, from room temperature Heating to 550 ° C under an inert gas atmosphere.

(11) A method for evaluating softening and melting characteristics of coal and a binder according to (10), wherein the heating rate is 2 to 4 ° C /min.

(12) The method for evaluating softening and melting characteristics of coal and a binder according to (3) or (4), wherein the applying the fixed load comprises applying a load such that the pressure on the material having the through hole becomes 5 to 80 kPa.

(13) The method for evaluating the softening and melting characteristics of coal and a binder according to (12), wherein the load-bearing system comprises: applying a load such that the pressure on the material having the through-hole is 15 to 55 kPa.

(14) The method for evaluating the softening and melting characteristics of coal and a binder according to (1) or (2), wherein the material having the through hole in the upper and lower surfaces comprises: a glass having a diameter of 0.2 to 3.5 mm on the sample. The beads are arranged to have a layer thickness of 20 to 100 mm; the heating system of the sample comprises: maintaining the sample and the glass bead layer at a fixed volume, at a heating rate of 2 to 10 ° C / min, from room temperature to 550 ° C in an inert gas atmosphere Heat up.

(15) The method for evaluating the softening and melting characteristics of coal and a binder according to (3) or (4), wherein the material having the through hole in the upper and lower surfaces comprises: a glass having a diameter of 0.2 to 3.5 mm on the sample. The bead is arranged to have a layer thickness of 20 to 100 mm; the heating system of the sample includes: applying a load to the upper portion of the glass bead to be 5 to 80 kPa, and heating at a temperature of 2 to 10 ° C/min and from room temperature to 550 ° C. Heating is carried out under an inert gas atmosphere.

(16) The method for evaluating softening and melting characteristics of coal and a binder according to (1) or (2), wherein the preparation of the sample comprises: pulverizing coal or a cement material to a particle diameter of 3 mm or less and 70 mass% or more, The pulverized coal or the binder is filled into the container according to a filling density of 0.7 to 0.9 g/cm ³ and a layer thickness of 5 to 20 mm; and the material having the through hole in the upper and lower surfaces is disposed to include a diameter on the sample The glass beads of 0.2 to 3.5 mm are arranged to have a layer thickness of 20 to 100 mm; the heating system of the above sample includes: maintaining the sample and the glass bead layer at a fixed volume, and heating at a rate of 2 to 10 ° C / min, from room temperature to 550 °C is heated under an inert gas atmosphere.

(17) The method for evaluating softening and melting characteristics of coal and a binder according to (3) or (4), wherein the preparation of the sample comprises: pulverizing coal or a cement material to have a particle diameter of 3 mm or less and 70% by mass or more, The pulverized coal or the binder is filled into the container according to a filling density of 0.7 to 0.9 g/cm ³ and a layer thickness of 5 to 20 mm; and the material having the through hole in the upper and lower surfaces is disposed to include a diameter on the sample The glass beads of 0.2 to 3.5 mm are arranged to have a layer thickness of 20 to 100 mm; the heating system of the above sample includes: applying a load to the upper portion of the glass beads in a manner of 5 to 80 kPa, and heating at a rate of 2 to 10 ° C/min. The temperature was raised to 550 ° C under an inert gas atmosphere.

(18) The method for evaluating softening and melting characteristics of coal and a binder according to (1) or (2), wherein the preparation of the sample comprises: pulverizing coal or a binder into a particle diameter of 2 mm or less and 100% by mass; The pulverized coal or the cement material is filled into the container according to a filling density of 0.8 g/cm ³ and a layer thickness of 10 mm; and the material having the through holes in the upper and lower surfaces is disposed to include: the glass beads having a diameter of 2 mm are disposed on the sample The layer thickness is 80 mm; the heating of the sample includes heating the sample and the glass bead layer at a fixed volume while heating at a temperature of 3 ° C/min from room temperature to 550 ° C in an inert gas atmosphere.

(19) The method for evaluating softening and melting characteristics of coal and a binder according to (3) or (4), wherein the preparation of the sample comprises: pulverizing coal or a binder into a particle diameter of 2 mm or less and 100% by mass; The pulverized coal or the cement material is filled into the container according to a filling density of 0.8 g/cm ³ and a layer thickness of 10 mm; and the material having the through holes in the upper and lower surfaces is disposed to include: the glass beads having a diameter of 2 mm are disposed on the sample The thickness of the layer was 80 mm. The heating of the sample was carried out by applying a load to the upper portion of the glass bead so as to be 50 kPa, and heating at room temperature to 550 ° C in an inert gas atmosphere at a heating rate of 3 ° C/min.

(20) A method for producing coke, which is a coal having a logarithmic log MF having a maximum fluidity of Giesel contained in a coal blend for coke production of 3.0 or more, and measuring a penetration distance belonging to a softening and melting property of coal; The weighted average of the permeation distances determines the ratio of the coal with a logarithm of the highest fluidity of the above-mentioned Giesel, with a log MF of 3.0 or more, and the coal blended by the determined blending ratio.

(21) The method for producing coke according to (20), wherein the measurement of the permeation distance is performed by the following (1) to (4); and the determination of the ratio is determined by a weighted average of the measured penetration distances. The method of determining the maximum logarithm of the above-mentioned Giesel, with a log MF of 3.0 or more, is set to be 15 mm or less;

(1) The coal or the cement material is pulverized to a particle diameter of 2 mm or less and 100% by mass, and the pulverized coal or the binder is filled into a container in a manner of a packing density of 0.8 g/cm ³ and a layer thickness of 10 mm as a sample;

(2) arranging glass beads having a diameter of 2 mm on the sample to a layer thickness of 80 mm;

(3) while maintaining the sample and the glass bead layer in a fixed volume, heating at room temperature to 550 ° C in an inert gas atmosphere at a heating rate of 3 ° C / min;

(4) The penetration distance of the molten sample permeating to the above glass bead layer was measured.

(22) The method for producing coke according to (20), wherein the measurement of the permeation distance is performed by the following (1) to (4); and the determination of the blending ratio is based on a weighted average of the measured permeation distances. The ratio of the above-mentioned Giesel's highest fluidity log MF of 3.0 or more is determined to be 17 mm or less;

(1) The coal or the cement material is pulverized to a particle diameter of 2 mm or less and 100% by mass, and the pulverized coal or the binder is filled into a container in a manner of a packing density of 0.8 g/cm ³ and a layer thickness of 10 mm as a sample;

(2) arranging glass beads having a diameter of 2 mm on the sample to a layer thickness of 80 mm;

(3) applying a load to the upper portion of the glass beads so as to be 50 kPa, and heating at room temperature to 550 ° C in an inert gas atmosphere at a heating rate of 3 ° C /min;

(4) The penetration distance of the molten sample permeating to the above glass bead layer was measured.

(23) A method for producing coke, which determines in advance a total blending ratio of a brand of coal or a binder contained in a blended coal used in coke production and a coal having a log MF of less than 3.0 in a blended coal; For the coal contained in the blended coal for coke production, the logarithmic log MF of the maximum flow of Giesel is 0.0 or more; the total blending rate of coal with a log MF of less than 3.0 in the blended coal. Under certain conditions, by changing the blending rate of coal or cement of each brand, the weighted average penetration distance of coal or cement with a logMF of 3.0 or more at this time is compared with the coal of each of the above brands. The ratio of the blending rate is changed, and the relationship between the coke strength obtained by the blended coal thus prepared is obtained; and the brand and the blending ratio of the coal having a log MF of 3.0 or more are adjusted in such a manner that the coke carbon strength becomes a desired value or more, and the weighted average penetration is adjusted. distance.

(24) The method for producing coke according to (23), wherein the measurement of the permeation distance is carried out by a condition selected from the group consisting of: pulverizing coal or a cement material to have a particle diameter of 3 mm or less and 70% by mass or more, The pulverized material is filled into a container as a sample according to a packing density of 0.7 to 0.9 g/cm ³ and a layer thickness of 5 to 20 mm; the glass beads having a diameter of 0.2 to 3.5 mm are disposed on the sample to have a layer thickness of 20 to 100 nm; The sample and the glass bead layer were kept at a fixed volume, and heated at room temperature to 550 ° C in an inert gas atmosphere at a temperature increase rate of 2 to 10 ° C /min.

(25) The method for producing coke according to (23), wherein the measurement of the permeation distance is carried out by a condition selected from the group consisting of: pulverizing coal or a cement material to have a particle diameter of 3 mm or less and 70% by mass or more, The pulverized material is filled into a container as a sample according to a packing density of 0.7 to 0.9 g/cm ³ and a layer thickness of 5 to 20 mm; glass beads having a diameter of 0.2 to 3.5 mm are disposed on the sample to have a layer thickness of 20 to 100 mm; The upper part of the glass bead is subjected to a load by a pressure of 5 to 80 kPa, and is heated in an inert gas atmosphere at room temperature to 550 ° C at a temperature increase rate of 2 to 10 ° C /min.

According to the present invention, it is possible to simulate the defect structure existing around the softened molten layer of coal and the cement in the coke oven, especially the crack existing in the coke layer adjacent to the softened molten layer, and suitably The softening and melting characteristics of the coal and the binder are evaluated in a state in which the restraining conditions around the softened melt in the coke oven are reproduced, that is, the penetration distance of the softened melt to the defective structure, the expansion ratio at the time of permeation, and the pressure at the time of permeation. Specifically, by using the present invention, the penetration distance of the softened melt to the defect structure, the expansion ratio at the time of penetration, and the shear rate at the shear rate when the coal and the binder in the coke oven are softened, melted, moved, and deformed can be measured. Pressure when infiltrated. If such measured values are used, the coke trait or coke cake structure can be estimated more accurately than conventionally.

Thereby, the softening and melting behavior of the coal in the coke oven can be correctly evaluated, and it can also be utilized in the manufacture of high-strength coke.

Fig. 1 and Fig. 2 show an example of an apparatus for measuring softening and melting characteristics used in the present invention. Fig. 1 is a view showing a state in which a sample of a coal or a cement material and a material having a through hole in the upper and lower surfaces are held in a fixed volume while heating the sample. Fig. 2 is a view showing a state in which a sample is heated by applying a fixed load to a coal or a cement sample and a material having a through hole in the upper and lower surfaces. The lower portion of the container 3 was filled with coal or a cement as the sample 1, and on the sample 1, the material 2 having the through holes was placed on the upper and lower surfaces. The sample 1 was heated to a temperature higher than the softening melting temperature region, and the sample was allowed to permeate into the material 2 having the through holes in the upper and lower surfaces, and the penetration distance was measured. The heating is carried out under an inert gas atmosphere. Here, the inert gas system refers to a gas that does not react with coal in the measurement temperature region, and representative gases such as argon gas, helium gas, nitrogen gas, and the like.

When the sample 1 is heated while holding the sample 1 and the material 2 having the through holes in the upper and lower surfaces at a fixed volume, the pressure at the time of penetration of the sample can be measured via the material 2 having the through holes in the upper and lower surfaces. As shown in Fig. 1, the pressure detecting rod 4 is placed on the material 2 having the through holes in the upper and lower surfaces, and the load cell 6 is brought into contact with the upper end of the pressure detecting rod 4 to measure the pressure. In order to maintain a fixed volume, the load cell 6 is fixed so as not to move in the up and down direction. Before the heating, the sample filled in the container 3 is adhered to each other so as not to have a gap between the material 2 having the through holes in the upper and lower surfaces, the pressure detecting rod 4, and the force measuring device 6. In the case where the material 2 having the through holes in the upper and lower surfaces is a particle-filled layer, since there is a possibility that the pressure detecting rod 4 is buried in the particle-filled layer, it is preferable to adopt the material 2 having the through-holes in the upper and lower surfaces and the pressure detecting rod 4 Measures to hold the board between.

When the sample 1 is heated and applied to the sample 1 and the material 2 having the through holes in the upper and lower surfaces, the sample 1 is expanded or contracted, and the material 2 having the through holes in the upper and lower surfaces is moved in the vertical direction. Therefore, the expansion ratio at the time of penetration of the sample can be measured via the material 2 having the through holes in the upper and lower surfaces. As shown in Fig. 2, the expansion ratio detecting rod 13 is disposed on the material 2 having the through holes in the upper and lower surfaces, and the weight-adding hammer 14 is placed on the upper end of the expansion ratio detecting rod 13, and the displacement gauge 15 is disposed thereon. The expansion ratio was measured. The displacement meter 15 can be used by measuring the expansion range (-100% to 300%) of the expansion ratio of the sample. Since it is necessary to maintain the heating internal system in an inert gas atmosphere, it is suitable for a non-contact type displacement meter, preferably an optical displacement meter. As an inert gas atmosphere, it is preferable to set it as a nitrogen atmosphere. In the case where the material 2 having the through holes in the upper and lower surfaces is a particle-filled layer, since there is a possibility that the expansion ratio detecting rod 13 is buried in the particle-filled layer, it is necessary to adopt the material 2 having the through-holes in the upper and lower surfaces and the expansion ratio detecting rod. 13 measures to hold the board between. The applied load is preferably applied equally to the upper surface of the material having the through holes disposed on the upper and lower surfaces of the sample, and is applied to the upper surface of the material having the through holes in the upper and lower surfaces, and is applied at 5 to 80 kPa. Good 15~55kPa, best 25~50kPa pressure. This pressure is preferably set according to the expansion pressure of the softened molten layer in the coke oven. After reviewing the reproducibility of the measurement results and the detection force of various coal brand differences, it is found that it is preferable to set the measurement conditions to be inflated in the furnace. The pressure is slightly higher than 25~50kPa.

The heating means is preferably a method in which the temperature of the sample can be measured while heating at a predetermined temperature increase rate. Specifically, there is an electric furnace, an external heating type in which a conductive container is combined with high-frequency induction, or an internal heating type in which microwaves are used. In the case of the internal heating type, special care must be taken to make the temperature inside the sample uniform, and it is preferable to take measures such as improving the barrier property of the container.

Regarding the heating rate, since the purpose is to simulate the softening and melting behavior of the coal and the binder in the coke oven, it is necessary to make the heating rate of the coal in the coke oven uniform. The heating rate of coal in the softening and melting temperature range in the coke oven varies depending on the position or working conditions in the furnace, but is about 2 to 10 ° C / min. It is preferable to set the average heating rate to 2 to 4 ° C / min. More preferably around 3 ° C / min. However, in the case of coal which is less fluid than non-micro-bonded carbon, the penetration distance or expansion at 3 ° C / min is small, and there is a possibility that it is difficult to detect. It is generally known that the coal is improved in fluidity detected by a Gisele plastometer by rapid heating (for example, see Non-Patent Document 3). Therefore, for example, in the case of coal having a penetration distance of 1 mm or less, in order to increase the detection sensitivity, the heating rate can be increased to 10 to 1000 ° C / minute for measurement.

The temperature range for heating is determined by the evaluation of the softening and melting characteristics of coal and the binder, so that it can be heated to the softening and melting temperature region of the coal and the binder. Considering the softening and melting temperature range of the coal and the binder for coke production, it is in the range of 0 ° C (room temperature) to 550 ° C, preferably in the range of 300 to 550 ° C of the softening melting temperature of coal. It can be heated at a predetermined heating rate.

The material having the through holes in the upper and lower sides is preferably one in which the penetration coefficient can be measured or calculated in advance. Examples of the material form include a bulk material having a through hole and a particle packed layer. As a material having a through hole, a member having a circular through hole 16 as shown in FIG. 3, a rectangular through hole, and an amorphous through hole can be exemplified. The particle-filled layer is roughly divided into a spherical particle-filled layer and a non-spherical-particle-filled layer. As the spherical particle-filled layer, as illustrated in FIG. 4, the bead-filled particles 17 are used as non-spherical particles. The filling layer may, for example, be composed of amorphous particles or a packed column 18 as shown in Fig. 5 . In order to maintain the reproducibility of the measurement, it is preferable to make the penetration coefficient in the material as uniform as possible, and in order to make the measurement simple, it is preferable to easily calculate the penetration coefficient. Therefore, the material having the through holes in the upper and lower surfaces used in the present invention is particularly preferably a layer filled with spherical particles. The material of the material having the through-holes in the upper and lower surfaces is not particularly specified if it does not change its shape in the coal softening and melting temperature region or more, specifically, 600 ° C, and does not react with coal. Further, the height may be a height sufficient to allow the molten material of the coal to sufficiently penetrate, and may be about 20 to 100 mm when the coal layer having a thickness of 5 to 20 mm is heated.

The penetration coefficient of the material having the through holes in the upper and lower faces must be set by estimating the penetration coefficient of the coarse defects existing in the coke layer. With regard to the particularly good penetration coefficient of the present invention, the inventors of the present invention have repeatedly studied the investigation of the major defect constituent factors or the estimation of the size, and found that the penetration coefficient is 1 × 10 ⁸ to 2 × 10 ⁹ m ^-2 . optimal. This penetration coefficient is derived from the Darcy formula shown by the following formula (1).

ΔP/L=K‧μ‧u......(1)

Here, ΔP is a pressure loss [Pa] in a material having a through hole in the upper and lower surfaces, L is a height [m] of a material having a through hole, K is a penetration coefficient [m ^-2 ], and μ is a fluid viscosity [ Pa‧s], u is the fluid velocity [m/s]. For example, when a glass bead layer having a uniform particle diameter is used as the material having the through holes in the upper and lower surfaces, in order to have the above appropriate penetration coefficient, it is preferred to select glass beads having a diameter of about 0.2 mm to 3.5 mm, more preferably 2mm.

The coal and the cement as the measurement sample are pulverized in advance, and are filled to a predetermined layer thickness according to a predetermined packing density. The pulverization particle size can be set to a particle size of the coal to be charged in the coke oven (the particle ratio of the particle diameter of 3 mm or less is about 70 to 80% by mass), and it is preferably pulverized to have a particle diameter of 3 mm or less and 70% by mass or more. However, in consideration of the measurement by a small device, it is particularly preferable to pulverize the total amount into a pulverized material having a particle diameter of 2 mm or less. The density of the filled pulverized material was set to 0.7 to 0.9 g/cm ^{3 in} accordance with the packing density in the coke oven, and the reproducibility and the detection force were examined. As a result, it was found to be preferably 0.8 g/cm ³ . In addition, the thickness of the layer to be filled can be set to a layer thickness of 5 to 20 mm in accordance with the thickness of the softened molten layer in the coke oven. When the reproducibility and the detection force are examined, it is found that the layer thickness is preferably 10 mm.

The penetration distance of the softened melt of coal and cement is preferably measured continuously in heating. However, the measurement is often difficult due to the influence of the tar generated by the sample or the like. The expansion and permeation of coal caused by heating is irreversible, because once it is expanded and infiltrated, it retains its shape even if it is cooled. Therefore, after the coal softening melt is infiltrated, the entire container can be cooled and measured for cooling. The subsequent penetration distance is used to determine where it penetrates during heating. For example, the material having the through holes in the upper and lower surfaces taken out from the cooled container can be directly measured by a vernier caliper or a ruler. Further, when particles are used as the material having the through holes in the upper and lower surfaces, the softened melt which permeates into the inter-particle voids fixes the entire particle layer of the infiltrated portion. Therefore, if the relationship between the mass and the height of the particle-filled layer is obtained in advance, the mass of the unsolidified particles is measured after the end of the infiltration, and the mass of the solid particles is obtained by subtracting the mass from the initial mass. Calculate the penetration distance.

The viscosity term (μ) is included in the above formula (1). Therefore, by the parameters measured by the present invention, the viscosity term of the softened melt penetrating into the material having the through holes in the upper and lower sides can be derived. For example, when the sample is heated while holding the sample and the material having the through hole in the upper and lower surfaces at a fixed volume, ΔP is the pressure at the time of penetration, L is the penetration distance, and u is the penetration speed, which can be substituted by (1) The viscosity term is derived from the formula. Further, when the sample is heated by applying a fixed load to the sample and the material having the through hole in the upper and lower surfaces, ΔP is the pressure of the applied load, L is the penetration distance, and u is the penetration speed, which can be substituted by (1) The viscosity is derived from the formula.

As described above, the penetration distance, pressure, and expansion ratio of the softened melt of coal and the binder are measured, and the softening and melting characteristics of the coal and the binder are evaluated. Here, the "softening and melting property of the evaluation sample (coal or cement)" in the present invention means at least the penetration distance, the pressure, and the expansion ratio, and the behavior for quantitatively evaluating the coal melt is obtained based on the measured value. And the phenomenon of the phenomenon (for example, the properties of the produced coke, the extrusion resistance of coke, etc.). The measured value may be a combination of a physical property value other than the penetration distance or the pressure and the expansion ratio (for example, MF or the like), or may be selected from one or more selected from the group consisting of a penetration distance, a pressure, and an expansion ratio. At this time, the softening and melting characteristics were evaluated at the stage where the measured values of the permeation distance, the pressure, and the expansion ratio were obtained, and the measurement of the permeation distance, the pressure, and the expansion ratio were substantially synonymous with the evaluation of the softening and melting characteristics. Further, by applying the above-described penetration distance, pressure, and expansion ratio as parameters to the coke strength estimation, by blending a plurality of brands of coal, it is possible to produce coke having a desired strength. As the coke strength index, the most common is the rotational strength at normal temperature; in addition, it can also be applied to the estimated CSR (coke strength after reaction) (heat-induced CO ₂ reaction intensity) or tensile strength, micro strength, etc. In this way, coal of multiple brands is deployed to produce coke with the required strength.

In the theory of coal blending used to estimate the coke strength, it has always been considered that the coke strength is mainly determined by the average maximum reflectance (Ro) of coal and the logarithm of the maximum fluidity MF of Giselle (logMF). Decision (for example, refer to Non-Patent Document 4). The Gisele fluidity is an index indicating the fluidity at the time of softening and melting of coal, and the rotation speed of the stirring bar of the Gisele plastometer, that is, the amount of rotation per minute is expressed in units of ddpm (dial division per minute). As the characteristic value of coal, the maximum fluidity (MF) is used. Also, the common logarithm of ddpm is sometimes used. The permeation distance of the present invention is considered to be a parameter indicating the fluidity under the condition of softening and melting behavior in a simulated coke oven, so it can be considered that the logarithm of the highest fluidity of Giselle, logMF, would be suitable for estimating the coke trait or The parameters of the coke cake construction.

The superiority of such penetration distance is not only based on the principle of the measurement method using the conditions close to the coke oven, but also the result of investigating the influence of the penetration distance on the intensity of the focused carbon. In fact, according to the evaluation method of the present invention, it can be understood that even coal having the same degree of log MF differs in the penetration distance due to the brand, and the influence of the intensity of the focused carbon when coking of the coal is confirmed. It is also different. Specifically, as shown in the following examples, when the value of the penetration distance exceeds a certain point, the coke strength is lowered. The reason for this is as follows.

It is generally considered that in the case of blending coal having a long penetration distance, the proportion of coal which is sufficiently melted during dry distillation is large. However, the coal whose penetration distance is too long is presumed to be a large defect due to the significant penetration into the surrounding coal particles, and the original portion of the coal particles itself becomes a defect. Although the conventional idea of Giselle's highest fluidity is also expected to be a case where the fluidity of the coal blend is too high, the coke strength is lowered (for example, refer to Non-Patent Document 4), but the brands of high liquidity are not clarified. the behavior of. This case is considered to be one of the reasons why the correct physical properties in the high fluidity region cannot be determined due to the Weissenberg effect described above in the conventional Gisele fluidity measurement. By adopting the measuring method of the present invention, since the physical properties of the molten material in the particularly high fluidity region can be more accurately evaluated, the difference in the physical properties of the softened melt which cannot be distinguished by the conventional method can be made clear. It is better to evaluate the relationship between the softening melt behavior and the coke structure, which is an excellent advancement brought about by the present invention.

The inventors have established suitable measurement conditions in the method of the present invention, and established a method for producing high-strength coke using the measurement results.

[Examples] [Example 1]

A measurement example in which the coal and the binder sample are heated in a fixed volume by a material having a through hole in the upper and lower surfaces. 17 kinds of coal and 4 types of cement (A carbon ~ Q carbon, binder R ~ U) were used as samples to measure the penetration distance and the pressure during the penetration. The properties of the coal and the binder used (average maximum reflectance: Ro, logarithm of Gisele's highest fluidity: logMF, volatiles: VM, ash: Ash) are shown in Table 1. Further, the fluidity of the binder used in the measurement was measured by the Gisele plastometer, and as a result, the common logarithm (logMF) of any of Giselle's highest fluidity showed a detection limit of 4.8.

The penetration distance and the pressure at the time of permeation were measured using the same apparatus as that shown in Fig. 1. Since the heating method is a high-frequency induction heating type, the heating element 8 of Fig. 1 is used as an induction heating coil, and the material of the container 3 is made of dielectric black lead. The container 3 has a diameter of 18 mm and a height of 37 mm, and a glass bead having a diameter of 2 mm is used as the material 2 having through holes in the upper and lower surfaces. The sample which was pulverized to a particle diameter of 2 mm or less and vacuum-dried at room temperature was weighed and loaded into a container, and placed in a container, and the weight of 200 g was dropped five times from the sample by a drop distance of 20 mm, thereby filling the sample ( In this state, the sample layer thickness was 10 mm). Next, a glass bead having a diameter of 2 mm was placed on the packed layer of the sample 1 to have a thickness of 25 mm, and a glass bead-filled layer was used as the material 2 having a through-hole in the upper and lower surfaces. On the glass bead filler layer, a sillimanite disk having a diameter of 17 mm and a thickness of 5 mm was placed, and a quartz rod was placed thereon as a pressure detecting rod 4. Nitrogen gas was used as an inert gas, and was heated from room temperature to 550 ° C at a heating rate of 3 ° C / min. The pressure applied by the pressure detecting rod 4 is measured by the load cell 6 during heating. After the completion of the heating, the mixture was cooled under a nitrogen atmosphere, and the beads which were not fixed to the softened melt were taken out from the cooled container 3 and the mass was measured.

The penetration distance is set to the filling height of the fixed bead layer. The relationship between the filling height and the mass of the glass bead filler layer is obtained in advance, and the glass bead filling height can be derived from the quality of the beads which solidify the softened melt. The result is the following formula (2), and the penetration distance is derived from the formula (2).

L=(G-M)×H...(2)

Here, L is the penetration distance [mm], G is the mass of the filled glass beads [g], M is the mass of the beads [g] which is not adhered to the softened melt, and H represents the glass beads filled into the experimental apparatus. The height of the filling layer per 1 g [mm/g].

When measuring the penetration distance of the binder, a container having the same diameter and a height of 100 mm was used as a sample container, and the thickness of the glass bead filler layer disposed on the upper portion of the sample was set to 80 mm. This is due to the large penetration distance of the bonded material. Further, although the thickness of the sample layer and the thickness of the glass bead filler layer were changed using coal and the thickness of the sample layer to be fixed, if the thickness of the glass bead filler layer was equal to or higher than the penetration distance, the measured values of the permeation distance were the same.

The measurement results of the permeation distance and the maximum pressure at the time of permeation are shown in Table 2. The relationship between the permeation distance measurement result and the logarithm value (logMF) of the highest fluidity of Giselle is shown in Fig. 6 (the adhesion of the MF value is not correctly obtained). The value of the material was not plotted).

According to Fig. 6, it can be confirmed that the penetration distance has a certain degree of correlation with respect to logMF, but also many brands that are out of relevance are also seen. Further, from the measurement results of the bonded material of Table 2, it was also found that the difference in the physical properties of the bonded material which could not be distinguished by the conventional method can be observed. In the measurement of the case where the sample and the material having the through hole in the upper and lower surfaces are heated in a fixed volume, the factor affecting the penetration distance is the viscosity μ of the sample and the expansion pressure ΔP of the sample as shown in the above formula (1). Change with each sample. Therefore, the penetration distance and pressure obtained by the measurement method in which the coal and the binder sample and the material having the through holes in the upper and lower sides are heated by the fixed volume are considered to reflect the value of the molten state in the coke oven. The melting state or pressure of the coal and the binder during softening and melting is presumed to affect the coke structure after the dry distillation, so the estimation of the intensity of the focused carbon is particularly effective.

In addition, the pressure applied to the penetration of the sample is a result of the pressure measurement in the measurement environment simulating the expansion behavior in the coke oven, so it can be effectively applied to the coke oven wall in the dry distillation of coal in the coke oven. The presumption of the applied pressure.

[Embodiment 2]

A measurement example of a case where a sample is heated by applying a fixed load to a material having a through hole in the upper and lower sides of the coal and the binder sample. As in the first embodiment, the penetration distance and the expansion ratio at the time of penetration were measured for the 17 types of coal and the four kinds of the binders (A carbon to Q carbon, the binder R to U) shown in Table 1 above. The penetration distance and the expansion rate at the time of permeation were measured using the same apparatus as shown in Fig. 2. Since the heating method is a high-frequency induction heating type, the heating element 8 of Fig. 2 is used as an induction heating coil, and the material of the container 3 is made of dielectric black lead. The container 3 has a diameter of 18 mm and a height of 37 mm, and a glass bead having a diameter of 2 mm is used as a material having a through hole in the upper and lower surfaces. The sample which was pulverized to a particle diameter of 2 mm or less and vacuum-dried at room temperature was weighed and loaded into a container 3, and the weight of 200 g was dropped five times from the sample by a drop distance of 20 mm, thereby filling the sample. 1. Next, a glass bead having a diameter of 2 mm was placed on the packed layer of the sample 1 to have a thickness of 25 mm, and a glass bead-filled layer was used as the material 2 having a through-hole in the upper and lower surfaces. A disk of a diameter of 17 mm and a thickness of 5 mm was placed on the glass bead filler layer, and a quartz rod was placed thereon as an expansion ratio detecting rod 13, and a 1.3 kg hammer 14 was placed on the upper portion of the quartz rod. Thereby, the pressure applied to the gangue disk was 50 kPa. Nitrogen gas was used as an inert gas and heated to 550 ° C at a heating rate of 3 ° C / min. During heating, the displacement was measured by a laser displacement gauge, and the expansion ratio was calculated from the height at which the sample was filled. After the completion of the heating, the mixture was cooled under a nitrogen atmosphere, and the mass of the beads which were not adhered to the softened melt was measured from the cooled container. The penetration distance is derived from the above formula (2).

In the present example, also when the penetration distance of the bonded material was measured, the thickness of the glass bead filler layer was increased by using a container as large as that of Example 1. Further, it was confirmed under the conditions of Example 2 that the thickness of the glass bead filler layer did not affect the measured value of the penetration distance.

The measurement results of the penetration distance and the final expansion ratio are shown in Table 3. The relationship between the measurement result of the penetration distance and the logarithm value (logMF) of the highest fluidity of Giselle is shown in Fig. 7 (the adhesive material of the MF value is not correctly obtained). The value is not plotted).

According to Fig. 7, it was confirmed that the penetration distance measured in the present example has a certain degree of correlation with logMF, but even if it is the same level of log MF, it is confirmed that there are brands having different penetration distances. In particular, this tendency can be seen in the high log MF region. If the measurement error of the penetration distance of the device is considered to be 0.6 based on the results of the three tests under the same conditions, a meaningful difference in the penetration distance can be confirmed for the coal H and the coal K which are almost equal in logMF. It is presumed only by the relationship of the above formula (1) that if it is the brand of the same log MF, since the viscosity μ at the time of melting is also considered, the penetration distance should be the same. The reason is that ΔP and K are not fixed depending on the measurement sample in the measurement, and it is confirmed that the log MF of coal is almost correlated with the temperature region (corresponding to the melting time) in which the coal exhibits meltability, so that u is almost Fixed. However, in the coal in the dry distillation, the foaming and expansion phenomena accompanying the occurrence of the volatile matter are observed while being melted. Therefore, the value of the permeation distance obtained by the present measurement is estimated to indicate the influence of the infiltration of the combined melt on the bead filling layer and the foaming of the molten material in the bead layer. These values are presumed to be factors determining the coke structure after dry distillation, so the estimation of the intensity of the focused carbon is particularly effective.

Further, the final expansion ratio shown in Table 3 is a value of the expansion ratio at 550 °C. Since the result of Table 3 is the measurement result of the expansion ratio in the measurement environment simulating the expansion behavior in the coke oven, the coke strength or the gap between the coke oven wall and the coke block can be effectively estimated.

[Example 3]

The establishment of the penetration distance of the penetration distance was investigated by the same measurement method as in Example 2.

Two brands of four types of coal (V-carbon to Y-carbon) were selected, and various blending ratios were used to produce mixed coal as a sample, and the penetration distance was measured. The properties of coal and coal blended (Ro, logMF, VM, Ash) are shown in Table 4. Here, the trait of the coal blending is a weighted average of the average carbon traits according to the blending ratio. The measurement results of the penetration distance are shown together in Table 4. Further, the relationship between the weighted average penetration distance of the blended coal and the measured penetration distance is shown in Fig. 8.

According to Fig. 8, it is understood that the penetration distance measured in the present embodiment has an excellent addition property. Therefore, when the penetration distance value of the blended coal obtained by blending two or more types of coal is obtained, the actual mixed coal can be used as a sample to measure the penetration distance, and the penetration distance of the single carbon constituting the mixed coal can be measured in advance. The weighted average is calculated again and estimated.

The coal used in the coal blending is usually used by measuring the various qualities of each brand in advance. Therefore, if the penetration distance is measured in advance for each brand batch, the penetration distance of the coal blend can be quickly calculated, which is practically preferable.

[Example 4]

The softening and melting property values of the coal obtained by the present invention are applied to the coke strength estimation, and the effectiveness thereof is reviewed.

As described above, the permeation distance obtained by the present invention can be considered to be a parameter log MF of the highest fluidity of Giselle, and is suitable for estimating the parameters of the coke property or the coke cake structure, so that the logMF is almost equal in use and the permeation distance is different. In the case of coal production of coke, the influence of the intensity of the focused carbon was investigated, and the dry distillation test and the strength test of coke after dry distillation were carried out in the following manner.

In Table 1 used in the above-mentioned Examples 1 and 2, coal A, coal F, and coal G (logMF of 3.5 or more) were selected as "the same degree of MF carbon", and 20% by mass were respectively allocated, so that the weight of the coal blend as a whole was adjusted. The average Ro and the weighted average logMF are equalized, and various coals are prepared as the remaining part to prepare the blended coal (mixed coal A, F, G). Coal A, coal F, and coal G are coals of high MF type used in the production of coke, and are coals that are often used to improve the adhesion of coal particles in coke production. In addition, as a test in the case of mixing such high MF carbon, it is prepared to use a mixed brand of mixed coal (log coal AF, mixed coal FG, mixed coal FGK) of log MF 3.0 at the same time. Moreover, the average quality of the blended coal is modulated to Ro = 0.99 to 1.05 and log MF = 2.0 to 2.3. The weighted averaged penetration distance (calculated from Table 2) and the weighted average constant pressure penetration distance of the coal used in each coal blending and its blending rate, and the logMF≧3.0 coal in the blended coal (by Table 3) The values are calculated. The generated coke strength is shown in Table 5.

Here, each of the coals used in Table 5 was pulverized to have a particle diameter of 3 mm or less and 100% by mass, and the water content of the entire coal blend was adjusted to 8 mass%. The 16 kg of the mixed coal was filled into a dry distillation tank according to a bulk density of 750 kg/cm ³ , and after being subjected to a hammer of 10 kg on the surface thereof, it was retorted in an electric furnace at a furnace wall temperature of 1050 ° C for 6 hours, and then taken out by the furnace and given The nitrogen is cooled to obtain coke. The coke strength of the obtained coke is determined according to the rotation strength test method of JIS K 2151, and the mass ratio of coke having a particle diameter of 15 mm or more after 15 rpm and 150 rotation is measured, and the mass ratio before rotation is adjusted according to the drum strength DI150/15. Calculated. Further, the results of measurement of CRI (hot CO ₂ reactivity), CSR (intensity after heat CO ₂ reaction, measured according to ISO 18894 method), and micro strength (MSI+65) are also shown.

For each coal blend, the maximum pressure of the Giesel contained in the blended coal is the logarithmic penetration distance of the log of the log MF ≧ 3.0 of the coal (the coal sample measured in Example 2 and the material having the through holes in the upper and lower surfaces) The relationship between the weighted average value of the permeation distance obtained by applying the fixed load and the measurement of the heating of the coal sample, and the drum strength of the coke after the dry distillation of each mixed coal is shown in Fig. 9. When the strengths of 20% by mass of coal A, coal F, and coal G are blended as coal blending A, blended coal F, and blended coal G of the same degree of MF carbon, the shorter the penetration distance of MF carbon is, the higher the display is. Drum strength. Furthermore, as a result of the drum strength of the blended coal A, the blended coal F, and the blended coal AF, it is understood that the addition property is established between the penetration distance of the MF carbon of the same degree and the drum strength. In addition to this example, if the results of blending FG and blended coal FGK are also combined, it can be seen that if the maximum flow of Giesel contained in the blended coal is the logarithmic mean value of the constant pressure penetration distance of the log of log ≧ 3.0, the coal exceeds 17mm, the coke strength is reduced. Therefore, high-strength coke can be produced by setting the weighted average value of the constant pressure permeation distance of the coal having the logarithm of the maximum flow of Giesel contained in the coal blended log MF ≧ 3.0 to 17 mm or less.

Next, for each coal blend, the maximum penetration of the Gisele contained in the blended coal is the logarithmic penetration distance of the coal of the log MF ≧ 3.0 (the coal sample measured in Example 1 has a through hole in the upper and lower surfaces) The relationship between the weighted average of the permeation distance measured by heating the material according to the fixed volume and the drum strength of the coke after the dry distillation of each coal is shown in Fig. 10.

In Fig. 10, it is also confirmed that the value is slightly weaker than that of Fig. 9, and it is understood that the value of the permeation distance obtained by the measurement is obtained in the measurement by heating in a fixed volume or by applying a fixed load. The conditions obtained in the measurement are all affected by the intensity of the carbon. In addition, in the case where the permeation distance is used as an index, it is judged that the weighted average of the set penetration distance of the coal of the logarithm of the maximum flow of Giesel contained in the coal blended log MF ≧ 3.0 is set to 15 mm. the following. The measurement results of the penetration distance are different depending on the measurement conditions used even if they are the same coal. Therefore, the evaluation of each coal must be carried out under substantially the same conditions. If the product of the layer thickness and the packing density of the sample is in the range of ±20%, the form of the material having the through holes (the spherical particle-filled layer or the cylindrical packed layer, etc.) is the same so that the diameter of the sphere or the cylinder is within ±20%. When the heating rate is in the range of ±20%, it can be used practically without problems, so that the range is substantially the same. Using the values measured under such conditions, as shown in Figs. 9 and 10, if the penetration distance of the high MF carbon contained in the coal blend is obtained in advance, and the correlation with the coke strength obtained by dry distillation of the coal blend is obtained, The penetration distance of high MF carbon can be modulated to some extent to achieve the desired coke strength. Further, CSR was also measured for coke produced from coal blended FG and blended coal FGK. As a result, the coke system CSR of the mixed coal FG was 55.4 (reactive CRI = 29.7), and the coke system CSR of the coal blended FGK was 59.5 (reactive CRI = 29.5), and the JIS drum strength was confirmed. The same tendency. It is known that generally, if the reactivity CRI of coke is the same, CSR and JIS drum strength show a good correlation, and this tendency is also confirmed in the samples in the examples. Further, in the case of the micro strength and the indirect tensile strength, the same tendency as the JIS drum strength was observed.

As described above, it can be understood that the penetration distance of high MF carbon has a great influence on the intensity of the focused carbon. As a reason why the influence of the penetration distance in the high MF carbon is particularly remarkable, as shown in FIGS. 6 and 7, it is considered that the higher the MF carbon, the larger the difference in the penetration distance. The brand difference of the penetration distance at low MF carbon is not too large, and there is a possibility that it is difficult to express the influence of the penetration distance. Further, since the Weissenberg effect or the upper limit of the measurable upper limit is present in the high MF carbon, there is a possibility that the softening and melting characteristics cannot be sufficiently evaluated by the Gisele plastometer method. By the method of the present invention, since the disadvantages of the conventional method can be improved, it is considered that a new insight into the effect of the softening and melting characteristics on the intensity of the focused carbon can be obtained.

Secondly, in order to confirm the reason why the penetration distance affects the coke strength, the coke with a blended coal A of 20% by mass of coal A which is considered to have a suitable penetration distance is subjected to dry distillation, and the penetration distance is adjusted. It is considered that the excessively long coal F of 20% by mass of coal is subjected to dry distillation of coke for observation of the structure. A photograph of the coal A taken at a magnification of 100 times is shown in Fig. 11, and a photograph of the coal F is shown in Fig. 12.

Comparing the photographs shown in Fig. 11 and Fig. 12, it can be seen that compared with the coke which is dry-distilled with the blended coal A of the coal A having the appropriate penetration distance, the blended coal F of the coal F having an excessively long penetration distance is blended for dry distillation. The pore walls 20 of the coke are thin, and the pores are connected to each other to form a thick atmospheric pore 21 having a meandering shape. It has been reported that the thicker the pore wall of the coke strength system, the higher the roundness of the pores (see, for example, Non-Patent Document 5). Therefore, the penetration distance of coal affects the formation of the coke structure at the time of dry distillation, and as a result, the influence of the intensity of the focused carbon can be confirmed.

According to the present embodiment, the measurement is carried out by applying a fixed load to the coal sample and the material having the through hole in the upper and lower surfaces, and heating the coal sample, and measuring the coal sample and the material having the through hole in the upper and lower surfaces according to the fixed volume. The penetration distance is a factor that affects the strength of the generated coke, and is a factor that cannot be explained by a conventional factor. Therefore, by combining the conventional coke strength estimation, high-precision strength estimation can be performed. It can be seen that high-strength coke can be produced by coal blending according to the permeation distance measured under better conditions.

1. . . Sample

2. . . Material with through holes on the upper and lower sides

3. . . container

4. . . Pressure test stick

5. . . Sleeve

6. . . Force measurer

7. . . thermometer

8. . . heating stuff

9. . . Temperature detector

10. . . temperature regulator

11. . . Gas inlet

12. . . Gas discharge

13. . . Expansion rate test rod

14. . . hammer

15. . . Displacement gauge

16. . . Round through hole

17. . . Filled particle

18. . . Filled cylinder

20. . . Stoma wall

twenty one. . . Stomata

1 is a schematic view showing an example of an apparatus for measuring softening and melting characteristics while holding a sample used in the present invention and a material having a through hole in the upper and lower surfaces in a fixed volume.

2 is a schematic view showing an example of an apparatus for measuring softening and melting characteristics while applying a fixed load to a sample used in the present invention and a material having a through hole in the upper and lower surfaces.

3 is a schematic view showing an example of a material having a through-hole in the upper and lower surfaces of the present invention and having a circular through-hole.

4 is a schematic view showing an example of a spherical particle-filled layer in a material having a through-hole in the upper and lower surfaces used in the present invention.

Fig. 5 is a schematic view showing an example of a cylindrical packed bed in a material having a through hole in the upper and lower surfaces used in the present invention.

Fig. 6 is a graph showing the results of measurement of the penetration distance of the coal softened melt measured in Example 1.

Fig. 7 is a graph showing the results of measurement of the penetration distance of the coal softened melt measured in Example 2.

Fig. 8 is a graph showing the relationship between the measured penetration distance of the softened melt of the coal blend measured in Example 3 and the weighted average penetration distance.

Figure 9 is a graph showing the weighted average penetration distance of the coal of the highest logarithm of the Gisele contained in the coal blended log MF ≧ 3.0 (measurement of applying a fixed load and heating), and the drum strength measured in Example 4. The chart of the relationship.

Figure 10 is a graph showing the weighted average penetration distance (measured by heating according to a fixed volume) of the log of the maximum flow of Giesel contained in the coal blend, which is the logarithm of the highest fluidity, and the drum strength measured in Example 4. Relationship chart.

Fig. 11 is a structural observation photograph of coke subjected to dry distillation of blended coal A in which coal A having a suitable penetration distance is prepared.

Fig. 12 is a structural observation photograph of coke subjected to dry distillation of blended coal F in which coal F having a too long penetration distance is prepared.

1. . . Sample

2. . . Material with through holes on the upper and lower sides

3. . . container

4. . . Pressure test stick

5. . . Sleeve

6. . . Force measurer

7. . . thermometer

8. . . heating stuff

9. . . Temperature detector

10. . . temperature regulator

11. . . Gas inlet

12. . . Gas discharge

Claims (25)

A method for evaluating the softening and melting characteristics of coal and a cement material, wherein a coal or a cement material is filled in a container to prepare a sample, and a material having a through hole is disposed above the sample above the sample, and the sample and the upper and lower sides are provided The material of the through hole was kept at a fixed volume, and while the sample was heated, the penetration distance of the molten sample permeated into the through hole was measured, and the softening and melting characteristics of the sample were evaluated using the measured penetration distance. A method for evaluating the softening and melting characteristics of coal and a cement material, wherein a coal or a cement material is filled in a container to prepare a sample, and a material having a through hole is disposed above the sample above the sample, and the sample and the upper and lower sides are provided The material of the through hole was held in a fixed volume, and while the sample was heated, the pressure of the sample conveyed through the material having the through hole in the upper and lower surfaces was measured, and the softening and melting characteristics of the sample were evaluated using the measured pressure. The method for evaluating the softening and melting characteristics of coal and a binder according to claim 1 or 2, wherein the material having the through hole in the upper and lower surfaces comprises: arranging the glass beads having a diameter of 0.2 to 3.5 mm on the sample. The thickness of the layer is 20 to 100 mm; the heating of the sample includes maintaining the sample and the glass bead layer at a fixed volume, at a heating rate of 2 to 10 ° C / min, from room temperature to Heating at 550 ° C under an inert gas atmosphere. The method for evaluating softening and melting characteristics of coal and a binder according to claim 1 or 2, wherein the preparation of the sample comprises: pulverizing coal or a cement material to have a particle diameter of 3 mm or less and 70% by mass or more. The pulverized coal or the binder is filled into the container according to a filling density of 0.7 to 0.9 g/cm ³ and a layer thickness of 5 to 20 mm; and the material having the through holes in the upper and lower surfaces is included: the diameter is 0.2~ on the sample. The 3.5 mm glass beads are arranged to have a layer thickness of 20 to 100 mm; the heating system of the above sample comprises: maintaining the sample and the glass bead layer at a fixed volume, at a heating rate of 2 to 10 ° C / min, from room temperature to 550 ° C Heating is carried out under an inert gas atmosphere. The method for evaluating softening and melting characteristics of coal and a binder according to claim 1 or 2, wherein the preparation of the sample comprises: pulverizing coal or a binder into a particle diameter of 2 mm or less to 100% by mass, and pulverizing the sample. The coal or the cement material is filled into the container according to a filling density of 0.8 g/cm ³ and a layer thickness of 10 mm; and the material having the through holes in the upper and lower surfaces is configured to: arrange the glass beads having a diameter of 2 mm into a layer thickness on the sample. 80 mm; The heating of the sample includes heating the sample and the glass bead layer at a fixed volume while heating at a temperature of 3 ° C/min from room temperature to 550 ° C in an inert gas atmosphere. Method for evaluating softening and melting characteristics of coal and cement, which is coal Or the adhesive material is filled in the container to form a sample, and the material having the through hole is disposed above the sample, and the sample is heated while applying a fixed load to the material having the through hole in the upper and lower surfaces, and the sample is permeated to the above. The penetration distance of the molten sample of the through-hole, and the softening and melting characteristics of the sample were evaluated using the measured penetration distance. A method for evaluating softening and melting characteristics of coal and a cement material, wherein a coal or a cement material is filled in a container to prepare a sample, and a material having a through hole in the upper and lower surfaces is disposed above the sample, and a through hole is formed in the upper and lower surfaces. The material was subjected to a fixed load, and while the sample was heated, the expansion ratio of the sample was measured, and the softening and melting characteristics of the sample were evaluated using the measured expansion ratio. The method for evaluating softening and melting characteristics of coal and a viscous material according to any one of claims 1, 2, 6 and 7, wherein the preparation of the sample comprises: pulverizing coal or a cement material into a particle diameter of 3 mm or less 70% by mass or more, the pulverized coal or the binder is filled into the container in a manner of a packing density of 0.7 to 0.9 g/cm ³ and a layer thickness of 5 to 20 mm. The method for evaluating the softening and melting characteristics of coal and a viscous material according to the eighth aspect of the invention, wherein the pulverizing system pulverizes the coal or the viscous material to a particle diameter of 2 mm or less and 100% by mass. Such as applying for coal in any of the scopes 1, 2, 6 and 7 of the patent A method for evaluating softening and melting characteristics of a binder, wherein the material having the through holes in the upper and lower surfaces is a spherical particle-filled layer or a non-spherical-particle-filled layer. The method for evaluating the softening and melting characteristics of coal and a binder according to claim 10, wherein the material having the through holes in the upper and lower surfaces is a spherical particle-filled layer. The method for evaluating the softening and melting characteristics of coal and a binder according to claim 11, wherein the spherical particle-filled layer contains glass beads. The method for evaluating softening and melting characteristics of coal and a binder according to any one of claims 1, 2, 6 and 7, wherein the heating system of the sample comprises: a heating rate of 2 to 10 ° C /min, Heating is carried out under an inert gas atmosphere at room temperature to 550 °C. The method for evaluating the softening and melting characteristics of coal and a binder according to claim 13 of the patent application, wherein the heating rate is 2 to 4 ° C / min. The method for evaluating the softening and melting characteristics of coal and a binder according to claim 6 or 7, wherein the applying the fixed load comprises applying a load such that the pressure on the material having the through hole becomes 5 to 80 kPa. The method for evaluating softening and melting characteristics of coal and a cement material according to claim 15 wherein the load bearing unit comprises: applying a load according to a pressure of 15 to 55 kPa on a material having a through hole. The method for evaluating the softening and melting characteristics of coal and a binder according to claim 6 or 7, wherein the material having the through hole in the upper and lower surfaces comprises: arranging the glass beads having a diameter of 0.2 to 3.5 mm on the sample. to make The layer thickness is 20 to 100 mm; the heating of the sample includes: applying a load to the upper portion of the glass bead to be 5 to 80 kPa, and heating at a temperature of 2 to 10 ° C/min, from room temperature to 550 ° C in an inert gas atmosphere. Heat it down. The method for evaluating softening and melting characteristics of coal and a binder according to claim 6 or 7, wherein the preparation of the sample comprises: pulverizing coal or a cement material to a particle diameter of 3 mm or less and 70 mass% or more. The pulverized coal or the binder is filled into the container according to a filling density of 0.7 to 0.9 g/cm ³ and a layer thickness of 5 to 20 mm; and the material having the through holes in the upper and lower surfaces is included: the diameter is 0.2~ on the sample. The 3.5 mm glass beads are arranged to have a layer thickness of 20 to 100 mm; the heating system of the above sample comprises: applying a load by the upper portion of the glass beads to be 5 to 80 kPa, and heating at a temperature of 2 to 10 ° C / min, from room temperature to Heating at 550 ° C under an inert gas atmosphere. The method for evaluating softening and melting characteristics of coal and a binder according to claim 6 or 7, wherein the preparation of the sample comprises: pulverizing coal or a cement into a particle size of 2 mm or less and 100% by mass, and pulverizing the sample. The coal or the cement material is filled into the container according to a filling density of 0.8 g/cm ³ and a layer thickness of 10 mm; and the material having the through holes in the upper and lower surfaces is configured to: arrange the glass beads having a diameter of 2 mm into a layer thickness on the sample. 80 mm; The heating of the sample includes heating with a weight of 50 kPa from the upper portion of the glass beads, and heating at room temperature to 550 ° C in an inert gas atmosphere at a heating rate of 3 ° C /min. A method for producing coke, which is a coal having a logarithmic log MF having a maximum fluidity of Giesel contained in a coal blend for coke production of carbon of 3.0 or more, and a permeation distance belonging to a softening and melting property of coal; The weighted average value determines the blending rate of the above-mentioned Giesel's highest liquidity log MF of 3.0 or more; and the dry blending of the coal blended by the determined blending ratio. The method for producing coke according to claim 20, wherein the measurement of the permeation distance is performed by the following (1) to (4); and the determination of the ratio is determined by a weighted average of the measured penetration distances. In the method of 15 mm or less, the ratio of the logarithm of the highest fluidity of the above Gisele is set to a coal ratio of 3.0 or more; (1) the coal or the binder is pulverized to have a particle diameter of 2 mm or less and 100% by mass. The coal or the cement is filled into the container as a sample according to a packing density of 0.8 g/cm ³ and a layer thickness of 10 mm; (2) a glass bead having a diameter of 2 mm is placed on the sample to have a layer thickness of 80 mm; The sample and the glass bead layer are maintained in a fixed volume, and heated at room temperature to 550 ° C in an inert gas atmosphere at a heating rate of 3 ° C / min; (4) measuring the penetration distance of the molten sample permeating the glass bead layer . The method for producing coke according to claim 20, wherein the measurement of the permeation distance is performed by the following (1) to (4); and the determination of the ratio is determined by a weighted average of the measured penetration distances. When the ratio is 17 mm or less, the ratio of the logarithm of the highest fluidity of Giesel to the log ratio of coal of 3.0 or more is determined. (1) The coal or the binder is pulverized to have a particle diameter of 2 mm or less and 100% by mass. The coal or the cement is filled into the container as a sample according to a packing density of 0.8 g/cm ³ and a layer thickness of 10 mm; (2) a glass bead having a diameter of 2 mm is placed on the sample to have a layer thickness of 80 mm; The upper part of the glass bead is applied with a load of 50 kPa, and is heated at room temperature to 550 ° C in an inert gas atmosphere at a heating rate of 3 ° C / min; (4) The penetration distance of the molten sample permeating the glass bead layer is measured. . A method for producing coke, which is to determine in advance a total blending ratio of a brand of coal or a binder contained in a blended coal used in coke production and a coal having a log MF of less than 3.0 in a blended coal; In the coal contained in the blended coal for manufacturing, the logarithm of the maximum logarithm of the Giesel's logarithm log MF is 3.0 or more; the total blending rate of the coal containing the logMF of less than 3.0 in the blended coal is set to a certain value. Under the condition of changing the coal blending rate of each brand, the weighted average penetration distance of coal or cement with a logMF of 3.0 or higher and the coal blending rate of the above brands Changing to determine the relationship between the coke strength obtained from the blended coal thus prepared; Adjust the weighted average penetration distance by adjusting the brand and blending rate of coal with a logMF of 3.0 or more in such a manner that the coke carbon strength is more than the desired value. The method for producing coke according to claim 23, wherein the measurement of the permeation distance is carried out by a condition selected from the group consisting of: crushing coal or a cement material into a particle diameter of 3 mm or less and 70 mass% or more, The pulverized material is filled into the container as a sample according to a packing density of 0.7 to 0.9 g/cm ³ and a layer thickness of 5 to 20 mm; the glass beads having a diameter of 0.2 to 3.5 mm are disposed on the sample to have a layer thickness of 20 to 100 mm; The sample and the glass bead layer were kept at a fixed volume, and heated at room temperature to 550 ° C in an inert gas atmosphere at a temperature increase rate of 2 to 10 ° C /min. The method for producing coke according to claim 23, wherein the measurement of the permeation distance is carried out by a condition selected from the group consisting of: crushing coal or a cement material into a particle diameter of 3 mm or less and 70 mass% or more, The pulverized material is filled into a container as a sample according to a packing density of 0.7 to 0.9 g/cm ³ and a layer thickness of 5 to 20 mm; glass beads having a diameter of 0.2 to 3.5 mm are disposed on the sample to have a layer thickness of 20 to 100 mm; The upper part of the glass bead is subjected to a load by a pressure of 5 to 80 kPa, and is heated in an inert gas atmosphere at room temperature to 550 ° C at a temperature increase rate of 2 to 10 ° C /min.