WO2012029987A1 - 冶金用コークスの製造方法 - Google Patents

冶金用コークスの製造方法 Download PDF

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WO2012029987A1
WO2012029987A1 PCT/JP2011/070319 JP2011070319W WO2012029987A1 WO 2012029987 A1 WO2012029987 A1 WO 2012029987A1 JP 2011070319 W JP2011070319 W JP 2011070319W WO 2012029987 A1 WO2012029987 A1 WO 2012029987A1
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Prior art keywords
coal
sample
coke
log
blended
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PCT/JP2011/070319
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English (en)
French (fr)
Japanese (ja)
Inventor
勇介 土肥
下山　泉
深田　喜代志
山本　哲也
広行 角
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Ｊｆｅスチール株式会社
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Priority to CN201180051089.9A priority Critical patent/CN103180414B/zh
Priority to EP11821997.1A priority patent/EP2612894B1/de
Priority to KR1020137007937A priority patent/KR101461838B1/ko
Publication of WO2012029987A1 publication Critical patent/WO2012029987A1/ja

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    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10B—DESTRUCTIVE DISTILLATION OF CARBONACEOUS MATERIALS FOR PRODUCTION OF GAS, COKE, TAR, OR SIMILAR MATERIALS
    • C10B53/00—Destructive distillation, specially adapted for particular solid raw materials or solid raw materials in special form
    • C10B53/04—Destructive distillation, specially adapted for particular solid raw materials or solid raw materials in special form of powdered coal
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10B—DESTRUCTIVE DISTILLATION OF CARBONACEOUS MATERIALS FOR PRODUCTION OF GAS, COKE, TAR, OR SIMILAR MATERIALS
    • C10B57/00—Other carbonising or coking processes; Features of destructive distillation processes in general
    • C10B57/04—Other carbonising or coking processes; Features of destructive distillation processes in general using charges of special composition
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10B—DESTRUCTIVE DISTILLATION OF CARBONACEOUS MATERIALS FOR PRODUCTION OF GAS, COKE, TAR, OR SIMILAR MATERIALS
    • C10B57/00—Other carbonising or coking processes; Features of destructive distillation processes in general
    • C10B57/04—Other carbonising or coking processes; Features of destructive distillation processes in general using charges of special composition
    • C10B57/06—Other carbonising or coking processes; Features of destructive distillation processes in general using charges of special composition containing additives

Definitions

  • the present invention relates to a method for producing metallurgical coke using a test method for evaluating softening and melting characteristics during coal carbonization.
  • the present invention relates to a method for producing metallurgical coke that can reduce the amount of high-grade coal used while maintaining coke strength, or a method for producing metallurgical coke that can obtain high-strength coke from the same blended coal. .
  • Coke used in the blast furnace method which is most commonly used as a steelmaking method, plays a number of roles such as iron ore reducing material, heat source, spacers, and the like.
  • Coke is produced by dry-distilling blended coal in which various types of coal for coke production, which are pulverized and adjusted in particle size, are blended in a coke oven.
  • Coal-producing coal softens and melts in the temperature range of about 300 ° C to 550 ° C during dry distillation, and at the same time, foams and expands as volatiles are generated, so that the particles adhere to each other, creating a massive semi-coke and Become.
  • Semi-coke is burned by shrinkage in the process of raising the temperature to around 1000 ° C., and becomes robust coke. Therefore, it can be said that the adhesion characteristics during softening and melting of coal have a great influence on properties such as coke strength and particle size after dry distillation.
  • a method of producing coke by adding a caking agent that exhibits high fluidity in the temperature range where coal softens and melts to the blended coal is generally used.
  • the binder is specifically tar pitch, petroleum pitch, solvent refined coal, solvent extracted coal, and the like.
  • these binders, like coal it can be said that the adhesive properties during softening and melting greatly affect the coke properties after dry distillation.
  • the softening and melting characteristics of coal are extremely important because they greatly influence the coke properties and coke cake structure after dry distillation, and the measurement methods have been actively studied for a long time.
  • coke strength which is an important quality of coke, is greatly affected by the properties of coal as the raw material, particularly the degree of coalification and softening and melting characteristics.
  • the softening and melting property is a property of softening and melting when coal is heated, and is usually measured and evaluated by the fluidity, viscosity, adhesiveness, expandability, etc. of the softened melt.
  • a general method for measuring the fluidity at the time of softening and melting includes a coal fluidity test method based on the Gisela plastometer method specified in JIS M8801.
  • Gisela plastometer method coal pulverized to 425 ⁇ m or less is put in a predetermined crucible, heated at a specified temperature increase rate, and the rotation speed of a stirring bar to which a specified torque is applied is read with a scale plate, and ddpm (dial division) per minute).
  • Patent Document 1 describes a method of measuring torque while rotating a rotor at a constant rotational speed.
  • Dynamic viscoelasticity measurement is the measurement of viscoelastic behavior seen when a force is applied periodically to a viscoelastic body.
  • the method described in Patent Document 2 is characterized in that the viscosity of the softened molten coal is evaluated by the complex viscosity in the parameters obtained by the measurement, and the viscosity of the softened molten coal at an arbitrary shear rate can be measured. .
  • a dilatometer method As a general method for measuring the expansibility during softening and melting of coal, there is a dilatometer method defined in JIS M8801.
  • coal pulverized to 250 ⁇ m or less is molded by a specified method, placed in a predetermined crucible, heated at a specified rate of temperature rise, and a detection rod placed on the top of the coal is used to measure changes in coal displacement over time. It is a method to measure.
  • blended coal that is a mixture of several brands of coal at a specified ratio.
  • the softening and melting characteristics cannot be evaluated correctly, the required coke strength is satisfied.
  • low-strength coke that does not satisfy the specified strength is used in a vertical furnace such as a blast furnace, the amount of powder generated in the vertical furnace is increased, resulting in an increase in pressure loss and the operation of the vertical furnace. May cause troubles such as so-called blow-through, in which the gas flow is locally concentrated.
  • the coke strength is controlled to a certain value or higher by setting the target coke strength higher in advance in consideration of the variation in coke strength resulting from inaccuracy of the evaluation of softening and melting characteristics. Has been done.
  • this method it is necessary to use a relatively expensive coal having excellent softening and melting characteristics, which is generally known, and to set the average quality of the blended coal to be higher, so that the cost is reduced. Incurs an increase.
  • the coal at the time of softening and melting is softened and melted while being constrained by adjacent layers. Since the thermal conductivity of coal is small, the coal is not uniformly heated in the coke oven, and the state differs from the coke layer, the softened molten layer, and the coal layer from the furnace wall side that is the heating surface. Since the coke oven itself expands somewhat during dry distillation but hardly deforms, the softened and melted coal is constrained by the adjacent coke layer and coal layer.
  • the crack generated in the coke layer is considered to have a width of about several hundred microns to several millimeters, and is larger than the voids and pores between coal particles having a size of about several tens to several hundreds of microns. Therefore, it is considered that coarse defects generated in such a coke layer are not only caused by pyrolysis gas and liquid substances, which are by-products generated from coal, but also permeate softened and melted coal itself. Further, it is expected that the shear rate acting on the softened and melted coal at the time of infiltration varies from brand to brand.
  • the inventors need to use the coal softening and melting characteristics measured under conditions simulating the environment in which the coal is placed in the coke oven as an index. I thought. In particular, it was important to measure under conditions where softened and melted coal was constrained, and under conditions simulating the movement and penetration of the melt into the surrounding defect structure.
  • the conventional measuring method has the following problems.
  • the Giselaer plastometer method is problematic in that it does not take into account any restraint or infiltration conditions for measurement in a state where coal is filled in a container. Moreover, this method is not suitable for the measurement of coal showing high fluidity. The reason is that, when measuring coal showing high fluidity, a phenomenon that the inner wall of the container becomes hollow (Weissenberg effect) occurs, the stirrer may idle, and the fluidity may not be evaluated correctly ( For example, refer nonpatent literature 1.).
  • the method of measuring torque by the constant rotation method is deficient in that it does not consider the constraint condition and the penetration condition.
  • the measurement under a constant shear rate it is impossible to correctly compare and evaluate the softening and melting characteristics of coal as described above.
  • the dynamic viscoelasticity measuring device is a device that can measure viscosity under an arbitrary shear rate with viscosity as a softening and melting characteristic. Therefore, if the shear rate at the time of measurement is set to a value that acts on the coal in the coke oven, the viscosity of the softened molten coal in the coke oven can be measured. However, it is usually difficult to measure or estimate the shear rate in each coke oven in advance.
  • the method of measuring the adhesion to coal using activated carbon or glass beads as the softening and melting characteristics of coal tries to reproduce the infiltration conditions for the presence of coal layer, but does not simulate the coke layer and coarse defects There is a problem in terms. Moreover, the point which is not a measurement under restraint is also insufficient.
  • Patent Document 4 discloses a method for measuring the expansibility of coal in consideration of the movement of gas and liquid substances generated from coal by arranging a material having a through path on the coal bed.
  • the conditions for evaluating the infiltration phenomenon in the coke oven are not clear.
  • the relationship between the infiltration phenomenon of the coal melt and the softening and melting behavior is not clear, and there is no suggestion about the relationship between the infiltration phenomenon of the coal melt and the quality of the coke to be produced. It does not describe the production of coke.
  • the present invention accurately evaluates the softening and melting characteristics of the coal used in the blended coal by measuring the softening and melting characteristics of the coal while simulating the surrounding environment of the softened and melted coal in the coke oven, After clarifying the effect of coal on coke strength, the adverse effect is reduced by adjusting the pre-treatment conditions of coal that adversely affect the coke strength.
  • the object is to provide a method for producing
  • a method for producing coke by dry distillation of two or more kinds of coal or a blended coal comprising two or more kinds of coal containing a binder Filling a container with each coal and caking additive constituting the blended coal as a sample, placing a material having through holes on the upper and lower surfaces on the sample, heating the sample, and penetrating into the through hole Measure the penetration distance of the sample, At least a part of the coal and caking material having a permeation distance higher than a predetermined control value is blended after being pulverized to be finer than a predetermined particle size
  • a method for producing metallurgical coke characterized in that: [2] A method for producing coke by dry distillation of two or more kinds of coal or a blended coal comprising two or more kinds of coal containing a binder, Filling a container with each coal and caking additive constituting the blended coal as a sample, placing a material having through holes on the upper and lower surfaces on the sample
  • a method for producing metallurgical coke characterized in that: [3] A method for producing coke by dry distillation of two or more kinds of coal or a blended coal comprising two or more kinds of coal containing a binder, Filling a container with each coal and caking additive constituting the blended coal as a sample, placing a material having through holes on the upper and lower surfaces on the sample, heating the sample, and penetrating into the through hole Measure the penetration distance of the sample in advance, When coal and a caking additive having a permeation distance higher than a predetermined control value are blended with the blended coal, all the coal and caking additive constituting the blended coal are pulverized to be finer than a predetermined particle size.
  • a method for producing metallurgical coke characterized in that: [4] The metallurgy according to (1) or (3), wherein the predetermined particle size is a particle size distribution having a particle size distribution such that a ratio of particles of 6 mm or more to the whole is 5 mass% or less. Coke production method. [5] The method for producing metallurgical coke according to any one of [1] to [4], wherein the predetermined control value of the permeation distance is defined by the following formula (1).
  • Penetration distance 1.3 x a x log MF
  • a measures the penetration value and logMF of at least 1 sort (s) or more of coal in the range of logMF ⁇ 2.5 among coal and caking additive which constitute blended coal, and the measured value is A constant in the range of 0.7 to 1.0 times the log MF coefficient when the regression line passing through the origin is used.
  • log MF is a common logarithm value of the Geeseeller maximum fluidity MF.
  • Permeation distance a ′ ⁇ log MF + b (2)
  • b is a constant that is not less than the average value of the standard deviation when the sample used for preparing the regression line is measured a plurality of times and not more than 5 times the average value;
  • log MF is a common logarithm value of the Geeseeller maximum fluidity MF.
  • the brand of coal or caking additive contained in the blended coal used for coke production and the blending ratio of coal or caking additive of each brand are determined in advance, Measure the penetration distance and log MF of each brand of coal or binder, and calculate the weighted average calculated from the penetration distance and blend ratio of each brand of coal or binder with a log MF of less than 3.0 A value more than twice the penetration distance is used as the management value of the penetration distance.
  • log MF is a common logarithmic value of the Geeseeller maximum fluidity MF.
  • a sample of coal or a binder is pulverized so that a particle size of 2 mm or less is 100 mass%, the pulverized sample is packed at a density of 0.8 g / cm 3 and a layer thickness is 10 mm.
  • the metallurgy according to any one of [1] to [4], characterized in that the measured value when heated in an inert gas atmosphere from room temperature to 550 ° C. at a temperature rising rate of 3 ° C./min is 15 mm or more.
  • Coke production method [11] The penetration distance fills a container with each coal and caking material constituting the blended coal as a sample, and a material having through holes on the upper and lower surfaces is disposed on the sample, and penetrates the upper and lower surfaces.
  • Any one of [1] to [9] is performed by heating the sample while applying a constant load to the material having holes and measuring the penetration distance of the sample that has penetrated into the through-hole.
  • a method for producing metallurgical coke as described in 1. [12] The penetration distance fills a container with each coal and caking material constituting the blended coal as a sample, and a material having through holes on the upper and lower surfaces is disposed on the sample, and penetrates the upper and lower surfaces.
  • Any one of [1] to [9] wherein the measurement is performed by heating the sample while keeping the material having holes at a constant volume, and measuring the penetration distance of the sample that has penetrated the through-hole.
  • the manufacturing method of the metallurgical coke as described.
  • the defect structure existing around the coal softening and melting layer in the coke oven particularly the coke layer adjacent to the softening and melting layer, which is considered to have a great influence on the coal softening and melting characteristics in the coke oven. It is possible to evaluate the softening and melting characteristics of coal or binder in the state of simulating the effect of existing cracks and appropriately reproducing the restraint conditions around the softened melt in the coke oven. As a result, it is possible to predict the generation of defects derived from coal or caking material exhibiting excessive fluidity, which could not be detected by conventional methods for evaluating softening and melting properties, and to adversely affect coke quality.
  • the binding material can be specified. Then, by blending the coal and binder after making the particle size fine, adverse effects on coke quality can be reduced, and high strength metallurgical coke can be produced.
  • FIG. 1 It is the schematic which shows an example of the apparatus which measures a softening-melting characteristic, applying a fixed load to the coal thru
  • FIG. 3 is a schematic diagram showing the generation state of a defect structure when coking coal corresponding to (A) to (D) or a coal blended with a binder.
  • A Coal filling status before coking.
  • B Defect generation status after coking.
  • FIG. 3 is a schematic diagram showing the generation state of a defect structure when coking coal that does not correspond to (A) to (D) or a coal blend obtained by blending a binder.
  • A Coal filling status before coking.
  • B Defect generation status after coking.
  • FIG. 3 is a schematic diagram showing the generation state of a defect structure when coking coal that is obtained by finely pulverizing coal or caking material corresponding to (A) to (D).
  • A Coal filling status before coking.
  • FIG. 6 It is the schematic which shows an example of the apparatus which measures a softening-melting characteristic, keeping the coal sample used by this invention, and the material which has a through-hole in an upper and lower surface at a fixed volume.
  • the present inventors have made it possible to measure the softening and melting characteristics while simulating the surrounding environment of the softened and melted coal in the coke oven, and eagerly researched the relationship between the measured softening and melting characteristics “penetration distance” and coke strength.
  • the softening and melting characteristics obtained by the method of the present invention measured in a state simulating the surrounding environment of the softened and melted coal, even for coal that has little difference in the softening and melting characteristics reported so far, Found that there was a difference.
  • FIG. 1 shows an example of a measuring device for softening and melting characteristics (penetration distance) used in the present invention.
  • FIG. 1 shows an apparatus for heating a coal sample by applying a constant load to the coal sample and a material having through holes on the upper and lower surfaces.
  • the lower part of the container 3 is filled with coal to form a sample 1, and a material 2 having through holes on the upper and lower surfaces is arranged on the sample 1.
  • the sample 1 is heated to the softening and melting start temperature or higher, the sample is infiltrated into the material 2 having through holes on the upper and lower surfaces, and the infiltration distance is measured. Heating is performed in an inert gas atmosphere. Note that the penetration distance may be measured by heating the material having coal and the through-holes while maintaining a constant volume.
  • An example of a measuring device for softening and melting characteristics (penetration distance) used in that case is shown in FIG.
  • an expansion coefficient detecting rod 13 is arranged on the upper surface of a material 2 having through holes on the upper and lower surfaces, a weight 14 for applying a load is placed on the upper end of the expansion coefficient detecting rod 13, and a displacement meter 15 is placed thereon. And measure the expansion rate.
  • a displacement meter 15 that can measure the expansion range ( ⁇ 100% to 300%) of the expansion coefficient of the sample may be used. Since it is necessary to maintain the inside of the heating system in an inert gas atmosphere, a non-contact type displacement meter is suitable, and it is desirable to use an optical displacement meter.
  • the inert gas refers to a gas that does not react with coal in the measurement temperature range, and typical gases include argon gas, helium gas, nitrogen gas, and the like, but it is preferable to use nitrogen gas.
  • the expansion coefficient detecting rod 13 may be buried in the particle packed layer, and therefore the material 2 having the through holes on the upper and lower surfaces and the expansion coefficient detecting rod 13.
  • the load to be applied is preferably uniformly applied to the upper surface of the material having through holes on the upper and lower surfaces arranged on the upper surface of the sample, and 5 to 80 kPa with respect to the area of the upper surface of the material having the through holes on the upper and lower surfaces, It is desirable to apply a pressure of preferably 15 to 55 kPa, most preferably 25 to 50 kPa.
  • This pressure is preferably set based on the expansion pressure of the softened and molten layer in the coke oven, but as a result of examining the reproducibility of the measurement results and the ability to detect the difference in brands in various coals, It has been found that a slightly higher value of about 25 to 50 kPa is most preferable as a measurement condition.
  • a heating means that can be heated at a predetermined rate of temperature while measuring the temperature of the sample.
  • a heating means that can be heated at a predetermined rate of temperature while measuring the temperature of the sample.
  • an electric furnace an external heating type that combines a conductive container and high frequency induction, or an internal heating type such as a microwave.
  • the internal heating method it is necessary to devise a method for making the temperature in the sample uniform, and for example, it is preferable to take measures to increase the heat insulation of the container.
  • the heating rate is set to match the heating rate of the coal in the coke oven for the purpose of simulating the softening and melting behavior of the coal and binder in the coke oven.
  • the heating rate of coal in the softening and melting temperature range in the coke oven varies depending on the location and operating conditions in the oven, it is generally 2 to 10 ° C / min.
  • the average heating rate should be 2 to 4 ° C / min. The most desirable is about 3 ° C./min.
  • coal is improved in fluidity by a Gisela plastometer by rapid heating. Therefore, for example, in the case of coal with an infiltration distance of 1 mm or less, measurement may be performed with the heating rate increased to 10 to 1000 ° C./min in order to improve detection sensitivity.
  • a predetermined heating rate in the range of 0 ° C (room temperature) to 550 ° C, preferably in the range of 300 to 550 ° C, which is the softening and melting temperature of coal. You can heat with.
  • the material having the through holes on the upper and lower surfaces can measure or calculate the transmission coefficient in advance.
  • Examples of the form of the material include an integrated material having a through hole and a particle packed layer.
  • Examples of the integrated material having a through hole include a material having a circular through hole 16 as shown in FIG. 2, a material having a rectangular through hole, and a material having an indeterminate shape.
  • the particle packed layer is roughly divided into a spherical particle packed layer and a non-spherical particle packed layer.
  • the spherical particle packed layer is composed of beads packed particles 17 as shown in FIG. 3, and the non-spherical particle packed layer is not suitable. Examples thereof include regular particles and those made of filled cylinders 18 as shown in FIG.
  • the transmission coefficient in the material is as uniform as possible and that the calculation of the transmission coefficient is easy in order to simplify the measurement. Therefore, the use of a spherical particle packed bed is particularly desirable for the material having through holes on the upper and lower surfaces used in the present invention.
  • the material having the through holes on the upper and lower surfaces is not particularly specified as long as the shape hardly changes to the coal softening and melting temperature range, specifically up to 600 ° C., and does not react with coal. Further, the height is sufficient if it is sufficient for the coal melt to permeate, and when the coal layer having a thickness of 5 to 20 mm is heated, it may be about 20 to 100 mm.
  • the transmission coefficient of the material having through holes on the upper and lower surfaces needs to be set by estimating the transmission coefficient of coarse defects present in the coke layer.
  • the transmission coefficient is 1 ⁇ 10 8 to 2 ⁇ 10 9 m ⁇ 2 as a result of repeated studies by the present inventors, such as consideration of coarse defect constituent factors and estimation of the size, which are particularly desirable for the present invention. Was found to be optimal.
  • This transmission coefficient is derived based on the Darcy rule expressed by the following equation (3).
  • ⁇ P the pressure loss [Pa] in the material having through holes on the upper and lower surfaces
  • L the height [m] of the material having the through holes
  • K the transmission coefficient [m ⁇ 2 ]
  • ⁇ the fluid.
  • u fluid velocity [m / s].
  • glass beads having a diameter of about 0.2 mm to 3.5 mm are used. It is desirable to choose, most preferably 2 mm.
  • the coal and binder used as the measurement sample are pulverized in advance and filled to a predetermined layer thickness with a predetermined packing density.
  • the pulverized particle size may be the particle size of the coal charged in the coke oven (the ratio of particles having a particle size of 3 mm or less is about 70 to 80% by mass), and pulverized so that the particle size of 3 mm or less is 70% by mass or more.
  • the density for filling the pulverized product can be 0.7 to 0.9 g / cm 3 in accordance with the packing density in the coke oven, but as a result of studying reproducibility and detection power, 0.8 g / cm 3 is preferable. I found out.
  • the layer thickness to be filled can be 5 to 20 mm based on the thickness of the softened and melted layer in the coke oven. As a result of studying reproducibility and detection power, the layer thickness should be 10 mm. I found it preferable.
  • Coal or caking material is pulverized so that the particle size of 2 mm or less is 100% by mass, and the pulverized coal or caking material has a packing density of 0.8 g / cm 3 and a layer thickness of 10 mm.
  • Create a sample by filling the container like (2) A glass bead having a diameter of 2 mm is arranged on the sample so as to have a layer thickness of an infiltration distance or more, (3) Heating in an inert gas atmosphere from room temperature to 550 ° C. at a heating rate of 3 ° C./min while applying a load from the top of the glass beads to 50 kPa, (4) The penetration distance of the molten sample that has penetrated into the glass bead layer is measured.
  • the penetration distance of the softened melt of coal and binder can be measured continuously during heating.
  • continuous measurement is difficult due to the influence of tar generated from the sample.
  • the expansion and infiltration phenomenon of coal by heating is irreversible, and once expanded and infiltrated, the shape is maintained even after cooling, so after the coal melt has been infiltrated, the entire container is cooled, You may make it measure how much it penetrate
  • the softened melt that has permeated the interparticle voids fixes the entire particle layer up to the permeated portion. Therefore, if the relationship between the mass and height of the particle packed bed is obtained in advance, the mass of the non-adhered particles is measured after the infiltration, and the mass of the adhering particles is derived by subtracting from the initial mass. And the penetration distance can be calculated therefrom.
  • the range of penetration distance is defined by the following formula (4).
  • a measures the penetration distance and logMF of at least 1 sort (s) of coal in the range of logMF ⁇ 2.5 among each coal and caking additive which comprise blended coal, and the measured value. Is a constant in the range of 0.7 to 1.0 times the coefficient of log MF when a regression line passing through the origin is created.
  • the range of the penetration distance is defined by the following formula (5).
  • b is a constant that is not less than the average value of the standard deviation when measuring one or more types of the same sample selected from the brands used for creating the regression line, and not more than 5 times the average value.
  • a coal sample prepared to have a particle size of 2 mm or less and a particle size of 100 mass% is filled into a container at a packing density of 0.8 g / cm 3 to a thickness of 10 mm, and glass beads having a diameter of 2 mm are used as materials having through holes.
  • the permeation distance is 15 mm or more.
  • the four types of management values (A) to (D) described above were determined because the value of the penetration distance depends on the set measurement conditions, for example, the load, the heating rate, and the material having a through hole.
  • the management values as shown in (A) to (C) This is based on the finding that it is.
  • the constants a and a ′ in the formulas (4) and (5) used in determining the ranges of (A) and (B) are at least one penetration of coal in the range of logMF ⁇ 2.5.
  • the distance and maximum fluidity are measured, and the measured values are used to determine a range of 0.7 to 1.0 times the log MF coefficient when a regression line passing through the origin is created. This is because, in the range of log MF ⁇ 2.5, there is an almost positive correlation between the maximum coal flow rate and the penetration distance. This is because the brand is biased.
  • the present inventors have a brand that falls within a range of 1.3 times or more the penetration distance determined according to the log MF value of coal according to the above regression equation, which leads to a decrease in strength.
  • the range was decided to define the range by the equation (4).
  • the above regression equation in order to detect brands that deviate positively beyond the measurement error, it falls within the range above the value obtained by adding 5 times the standard deviation when the same sample is measured multiple times to the above regression equation It was determined that the brand to be used is a brand that causes a decrease in strength, and the range was defined by Equation (5).
  • the constant b may be a value that is five times the standard deviation when the same sample is measured a plurality of times, and is about 3.0 mm under the measurement conditions described in the present invention.
  • both the equations (4) and (5) define the range of the penetration distance that causes the strength to decrease based on the log MF value of the coal. This is because, as the MF increases, the penetration distance generally increases, so how much deviation is important from the correlation.
  • both the constants a and a ′ and b define the range is that by reducing these values, it is possible to more reliably detect coal that causes a decrease in strength. Can be adjusted according to operational requirements. However, if this value is too small, too much coal is estimated to have an adverse effect on coke strength, and it may be misunderstood that even if it does not cause strength reduction, it will cause strength reduction. Therefore, a and a ′ are preferably 0.7 to 1.0 times the slope of the regression line, and b is 1 to 1 of the standard deviation when the same sample is measured a plurality of times. 5 times is preferable.
  • Coal or caking additive used in blended coal is usually used by measuring various grades for each brand in advance. Similarly, the penetration distance may be measured in advance for each brand lot. The average penetration distance of the blended coal is measured in advance for each brand, and the value may be averaged according to the blending ratio, or the blended coal may be measured to measure the penetration distance. . This makes it possible to select a brand having an extremely large penetration distance with respect to the average penetration distance of the blended coal.
  • the blended coal used for coke production may contain oils, powdered coke, petroleum coke, resins, waste, etc. in addition to coal or caking additive.
  • the present inventors change the particle size of the blended coal even when blended coal obtained by blending coal or caking material corresponding to (A) to (D) is used as a coke raw material. Thus, it was found that the strength reduction can be suppressed.
  • the process of the discussion will be described below using schematic diagrams.
  • FIG. 5 schematically shows the state of defect structure generation when coking coal blended with coals or binders corresponding to (A) to (D).
  • the coal or caking additive particles 19 corresponding to (A) to (D) greatly penetrate into the voids between the filler particles and coarse defects during coking, so that a thin pore wall is formed, and the particles Coarse defects 22 remain in the original place, leading to a decrease in coke strength (FIG. 5B).
  • FIG. 6 schematically shows the generation state of the defect structure when coking coal not formed in (A) to (D) or blended coal obtained by blending the binder 20.
  • the coal or caking additive particles 20 not corresponding to (A) to (D) do not permeate the voids between the filler particles or coarse defects during coking, so that they form a thick pore wall, and the particles There is no coarse defect left in the original place, and no reduction in coke strength is caused (FIG. 6B).
  • FIG. 7 schematically shows the generation state of the defect structure when the coal or coal binder corresponding to (A) to (D) is pulverized and then blended into coke.
  • the coal or caking additive 19 particles corresponding to (A) to (D) greatly penetrate into the voids between the filler particles and coarse defects during coking.
  • the defect formed at the place where the particles were originally formed becomes small, a decrease in coke strength can be suppressed (FIG. 7B).
  • Defect structure generation status when coking coal blend formed by pulverizing the remaining coal or binder 20 excluding coal or binder corresponding to (A) to (D) Is schematically shown in FIG.
  • the surroundings of the particles of coal or caking additive 19 corresponding to (A) to (D) are occupied by fine particles or defects, and the permeability coefficient is lowered. Therefore, during coking, the voids between the packed particles and coarse defects cannot be penetrated so much that a thick pore wall is formed, leaving no coarse defects where the particles were originally located, and reducing the coke strength. Can be suppressed (FIG. 8B).
  • coal or caking additive corresponding to (A) to (D)
  • the coal or caking additive, or the remaining coal or caking additive excluding the coal or caking additive By taking measures to reduce the particle size, it is possible to reduce the coal permeation distance, reduce coarse defects, and suppress the strength reduction of coke after dry distillation.
  • the blended coal particle size becomes finer, it is necessary to increase the meltability of the entire blended coal in order to maintain the coke strength due to the increase in the specific surface area of the coal particles and the increase in the interparticle distance. It is generally said that there is.
  • the penetration distance was measured for 18 types of coal (coal A to R) and one type of caking additive (caking agent S).
  • Table 1 shows the properties of the used coal or binder.
  • Ro is the maximum vitrinite average reflectance of JIS M 8816 coal
  • log MF is the common logarithm of the maximum fluidity (Maximum Fluidity: MF) measured by the Gieseler plastometer method
  • volatile matter (VM) volatile matter (Ash)
  • VM volatile matter
  • Ash ash
  • the penetration distance was measured using the apparatus shown in FIG. Since the heating method was a high frequency induction heating type, the heating element 8 in FIG. 1 was an induction heating coil, and the material of the container 3 was graphite, which is a dielectric.
  • the diameter of the container was 18 mm, the height was 37 mm, and glass beads with a diameter of 2 mm were used as materials having through holes on the upper and lower surfaces.
  • the sample 1 was filled by loading 2.04 g of a coal sample pulverized to a particle size of 2 mm or less and vacuum-dried at room temperature into the container 3 and dropping a weight of 200 g from the top of the coal sample 5 times at a fall distance of 20 mm. (In this state, the sample layer thickness was 10 mm).
  • glass beads having a diameter of 2 mm were placed on the packed layer of Sample 1 so as to have a thickness of 25 mm.
  • a sillimanite disk having a diameter of 17 mm and a thickness of 5 mm is placed on the glass bead packed layer, a quartz rod is placed thereon as the expansion coefficient detecting rod 13, and a weight of 1.3 kg is placed on the quartz rod. placed. Thereby, the pressure applied on the sillimanite disk becomes 50 kPa. Nitrogen gas was used as the inert gas, and the mixture was heated to 550 ° C. at a heating rate of 3 ° C./min.
  • the penetration distance was the filling height of the fixed bead layer.
  • the relationship between the filling height and the mass of the glass bead packed bed was obtained in advance, and the glass bead filling height could be derived from the mass of the beads to which the softened and melted coal was fixed.
  • the result is equation (6), and the penetration distance was derived from equation (6).
  • L (GM) ⁇ H (6)
  • L is the penetration distance [mm]
  • G is the mass of the filled glass beads [g]
  • M is the mass of the beads not fixed to the softened melt [g]
  • H is the glass beads filled in this experimental apparatus. It represents the height of the packed bed per gram [mm / g].
  • FIG. 9 shows the relationship between the measurement results of the penetration distance and the logarithmic value (log MF) of the maximum fluidity (Maximum Fluidity: MF).
  • log MF logarithmic value of the maximum fluidity
  • Table 2 also shows the weighted average penetration distance of blended coal excluding A coal and F coal, that is, the weighted average penetration distance of coal having a log MF of less than 3.0 contained in the blended coal.
  • the blended coals A1 to A3, excluding coal A have a weighted average penetration distance of 4.7 mm, while the penetration distance of coal A is 8.0 mm, less than twice the average.
  • the weighted average penetration distance of blended coal excluding F coal of blended coals F1 to F3 is 5.0 mm
  • the penetration distance of F coal is 19.5 mm, which is more than twice the average ( Corresponding to C).
  • F charcoal also corresponds to (D).
  • the constants a and a ′ of the formulas (1) and (2) are calculated based on the penetration distance and the maximum fluidity value of coal in the range of logMF ⁇ 2.5 among the coals constituting the blended coal. Then, the slope of the regression line was calculated and determined to be 2.70 which coincided with the slope.
  • the constant b in the formula (2) was determined to be 3.0 from 5 times the value of the standard deviation 0.6 under the measurement conditions of the example of the present invention. Based on these equations, the results of examining the positional relationship between the permeation distance and maximum fluidity of the binder used in this example and the above ranges (A) and (B) are shown in FIGS. Each is shown. From FIG. 10, FIG. 11, F charcoal corresponds to any conditions of the range of (A) and (B).
  • the moisture content of the entire blended coal described in Table 2 was adjusted to 8 mass%, and 16 kg of the blended coal was filled into a dry distillation can so that the bulk density was 750 kg / m 3, and a 10 kg weight was placed thereon.
  • the product was taken out from the furnace and cooled with nitrogen to obtain coke.
  • the coke strength of the obtained coke was measured based on the rotational strength test method of JIS K 2151 by measuring the mass ratio of coke with a particle size of 15 mm or more after 15 rpm and 150 revolutions, and the mass ratio with the pre-rotation drum strength DI150 / Calculated as 15.
  • CSR compressngth after hot CO 2 reaction, measured in accordance with ISO18894 method
  • MSI + 65 microintensity
  • the drum strength measurement results are also shown in Table 2. Moreover, the relationship between the maximum particle size of coal A and coal F and drum strength is shown in FIG. At any particle size, blended coal blended with coal F corresponding to the above (A) to (D) has lower strength than blended coal blended with coal A not corresponding to (A) to (D). It was confirmed. Therefore, it was confirmed that the value of the penetration distance measured in the present invention is a factor affecting the strength and cannot be explained by the conventional factor. Also, in any case of blended coal blended with coal A not corresponding to the above (A) to (D) and blended coal blended with coal F corresponding to (A) to (D), the coal granularity should be made finer. It was confirmed that the strength improved. In particular, in the case of blended coal blended with coal F corresponding to the above (A) to (D), the improvement in strength due to the finer particle size of the coal was noticeable.
  • the decrease in strength can be suppressed by blending the coal F with a finer particle size than coal not corresponding to the above (A) to (D) (mixed coal F1).
  • the maximum particle size of the coal may be reduced or the average particle size may be reduced.
  • the content of particles larger than a specific mesh may be reduced (that is, the content of particles smaller than a specific mesh may be increased).
  • the particle size of the blended coal is controlled by the mass ratio of the above or below the sieve to the total mass when the blended coal is passed through a specified sieve. Therefore, it is difficult to adjust the particle size for each brand constituting the blended coal. Therefore, when coal blends formed by blending coal or binders corresponding to the above (A) to (D) are carbonized in an actual coke oven, the particle sizes of all coals or binders constituting the blended coals It is considered realistic and effective to carry out operations to make the details fine.
  • the present inventors dry-distilled blended coal produced by variously changing the blending ratio of coal or binder corresponding to the above (A) to (D) in an actual coke oven, and drum strength as coke strength after dry distillation. DI150 / 15 was measured, and the relationship between the ratio of the coal blend particle size of 6 mm or more and the coke strength was investigated.
  • Table 3 shows the average properties of the blended coal used, the carbonization temperature, and the coal temperature after carbonization. The variation of the average properties of coal blend, the carbonization temperature, and the temperature in the coal after carbonization was reduced to eliminate the influence of these factors on the coke strength as much as possible.
  • FIG. 13 shows the relationship between the ratio of the coal blend particle size of 6 mm or more and the measured coke strength.
  • the blending ratio of coal or caking material corresponding to at least one of the above (A) to (D) is relatively large as 8 mass% to 12 mass%, the ratio of the particle size of 6 mm or more is obtained. It has been confirmed that the coke strength decreases as the coal particle size increases as the particle size increases.
  • the particle size and strength are different for each blending ratio.
  • a decrease in strength can be suppressed.
  • strength reduction can be suppressed by controlling the coal pretreatment conditions before charging into the coke oven, so that it is possible to avoid an increase in cost due to blending of strong caking coal.

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RU2592598C2 (ru) * 2014-10-23 2016-07-27 Открытое акционерное общество "ЕВРАЗ Нижнетагильский металлургический комбинат" (ОАО "ЕВРАЗ НТМК") Способ получения модифицированного металлургического кокса для высокоинтенсивной выплавки ванадиевого чугуна
WO2016109704A1 (en) * 2014-12-31 2016-07-07 Suncoke Technology And Development Llc Multi-modal beds of coking material
CN111253961B (zh) * 2020-01-21 2021-05-28 鞍钢股份有限公司 一种提高焦炭平均粒度及改善焦炭粒度分布的炼焦配煤方法
CN116194772A (zh) * 2020-08-17 2023-05-30 杰富意钢铁株式会社 煤或粘合材料的制备方法和焦炭的制造方法
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