WO2014080817A1 - コークスの製造方法 - Google Patents
コークスの製造方法 Download PDFInfo
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- WO2014080817A1 WO2014080817A1 PCT/JP2013/080652 JP2013080652W WO2014080817A1 WO 2014080817 A1 WO2014080817 A1 WO 2014080817A1 JP 2013080652 W JP2013080652 W JP 2013080652W WO 2014080817 A1 WO2014080817 A1 WO 2014080817A1
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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
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G33/00—Dewatering or demulsification of hydrocarbon oils
- C10G33/06—Dewatering or demulsification of hydrocarbon oils with mechanical means, e.g. by filtration
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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
- 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
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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
- C10B47/00—Destructive distillation of solid carbonaceous materials with indirect heating, e.g. by external combustion
- C10B47/02—Destructive distillation of solid carbonaceous materials with indirect heating, e.g. by external combustion with stationary charge
- C10B47/04—Destructive distillation of solid carbonaceous materials with indirect heating, e.g. by external combustion with stationary charge in shaft furnaces
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10K—PURIFYING OR MODIFYING THE CHEMICAL COMPOSITION OF COMBUSTIBLE GASES CONTAINING CARBON MONOXIDE
- C10K1/00—Purifying combustible gases containing carbon monoxide
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10K—PURIFYING OR MODIFYING THE CHEMICAL COMPOSITION OF COMBUSTIBLE GASES CONTAINING CARBON MONOXIDE
- C10K1/00—Purifying combustible gases containing carbon monoxide
- C10K1/08—Purifying combustible gases containing carbon monoxide by washing with liquids; Reviving the used wash liquors
- C10K1/16—Purifying combustible gases containing carbon monoxide by washing with liquids; Reviving the used wash liquors with non-aqueous liquids
- C10K1/18—Purifying combustible gases containing carbon monoxide by washing with liquids; Reviving the used wash liquors with non-aqueous liquids hydrocarbon oils
Definitions
- the present invention relates to a coke production method for producing coke by charging coal blend into a coke oven and subjecting it to dry distillation.
- the mechanism by which “clogging” occurs is as follows.
- the blended coal charged into the carbonization chamber is dry-distilled in order from the furnace wall side by the heat from the combustion chamber adjacent to the carbonization chamber to produce a coke cake.
- a gap hereinafter referred to as clearance
- the discharge (extrusion) of the coke cake to the outside of the furnace becomes easy.
- the water content of the blended coal is positively determined from the water content when it is stacked in the yard (although it varies depending on the weather and weather, it is approximately 8-14% by mass).
- Wet charcoal operation that operates without any significant decrease is widely adopted as the simplest and most effective means.
- Patent Document 1 describes a technique of carbonizing coal blend in a coke oven after adjusting the moisture content of the coal blend using a coal humidity control facility. Specifically, this technique obtains the target moisture content of the blended coal necessary to ensure a desired clearance based on the relationship between the moisture content of the blended coal and the clearance measured in advance. This technology reduces the frequency of “clogging” by controlling the heat input of the coal humidity control equipment so that the total water content of the blended coal at the outlet side of the coal humidity control equipment becomes the target water content.
- Patent Document 2 discloses that water is locally added to coal in a coal tower that supplies coal to a coal-filled car that charges coal into the carbonization chamber, and water-added coal is carbonized via the coal-filled car. It describes the technique of charging the room. According to this technology, coal having a higher water content than other coals is unevenly distributed in a part of the carbonization chamber, thereby increasing the shrinkage of coke in the coal portion having the higher water content and increasing the clearance. The occurrence frequency of “clogging” can be reduced.
- Technologies for improving coke strength can be broadly classified into pretreatment technology, compounding technology, and dry distillation technology. Among them, the pretreatment technology is particularly emphasized because the facility design is possible without increasing the cost of blended coal and without being restricted by the productivity of the coke oven. This pretreatment technology is classified according to the approach to coke strength.
- technology (1) Technology for improving the charging bulk density of coal blend
- technology (2) homogenization of coal blend
- the technology is roughly divided into two technologies (hereinafter referred to as technology (2)).
- the purpose of the technique (1) is to reduce voids between coal particles when blended coal is charged into a coke oven in order to reduce the number of pore defects affecting coke strength.
- a method of the technique (1) there is a method in which blended coal is mechanically consolidated and charged into a coke oven, and a method such as a method of partially charging cast charcoal or a stamping method can be exemplified.
- a method to improve the bulk density of charging by reducing the water content of the blended coal and reducing the adhesion between the coal particles.
- Coal humidity control method, preheated coal charging method, pulverized agglomerated coal blending method (DAPS), next generation coke oven technology (SCOPE-21), etc. can be exemplified (see Non-Patent Document 1).
- the purpose of technology (2) is to raise the strength of the weakest portion of coke.
- coal is composed of various structures having different thermal and mechanical properties, and is extremely heterogeneous. For this reason, the structure of coke produced from heterogeneous coal is also heterogeneous.
- the strength of a brittle material such as coke is generally explained by the weakest link model, and is determined by the strength of the weakest portion existing in the material. Therefore, if the coke structure is homogenized, the strength inside the coke is averaged, the strength of the weakest portion is raised, and the strength of the entire coke can be improved.
- Non-Patent Document 1 is a method of adjusting the particle size of coal (see Non-Patent Document 1).
- the method of adjusting the particle size of the coal has a basic purpose of finely pulverizing the coal to make the coke structure homogeneous.
- a method is known in which coal is processed by a coal blender such as a drum mixer to increase the degree of coal mixing and homogenize the structure of coke (see Non-Patent Document 2).
- a coal blender such as a drum mixer to increase the degree of coal mixing and homogenize the structure of coke
- it has been confirmed by conventional research that the blended coal used in the coke production process is sufficiently mixed by the transfer of a belt conveyor in the middle of conveyance without passing through a coal blender (non- Patent Document 2). For this reason, there are many coke factories that are trying to homogenize the coke structure without using a coal blender.
- Patent Document 1 controls the clearance by controlling the water content of the blended coal with the clearance necessary for suppressing the occurrence of “clogging” as a target value. For this reason, the technique described in Patent Document 1 is effective in suppressing the occurrence of “clogging”, but it cannot suppress the reduction in coke strength. Similarly, since the technique described in Patent Document 2 controls the clearance by controlling the moisture content of the blended coal, the reduction in coke strength cannot be suppressed. On the other hand, although the technique (1) is effective in improving the coke strength, the occurrence of “clogging” cannot be suppressed because the clearance is reduced. In fact, if the water content of the coal blend is reduced in an aging furnace over 40 years old, “clogging” occurs frequently and the coke oven cannot be operated stably. The operation is carried out with the moisture content of charcoal kept high.
- the technique (2) is effective not only for improving the coke strength but also for ensuring the clearance (see Non-Patent Document 3).
- the technique (2) is effective not only for improving the coke strength but also for ensuring the clearance (see Non-Patent Document 3).
- the coal particles are aggregated through water and the particle size is expanded by forming pseudo particles.
- the effect of homogenization by grinding is reduced.
- the behavior of pseudo particles in blended coal and the effect of pseudo particles on coke strength have not been fully elucidated. For this reason, in order to improve the homogenization effect, what kind of pseudo-particles should be destroyed, and a suitable method for destroying the pseudo-particles are not clear.
- the blended coal is mixed using a coal blender mainly intended for convection mixing such as a drum mixer, the coal particles are mixed macroscopically while maintaining the pseudo-particle state.
- the coal blend is mixed in a non-homogeneous manner when viewed microscopically, and the strength inside the coke cannot be averaged.
- the present invention has been made in view of the above problems, and an object of the present invention is to provide a coke production method capable of producing coke having high strength and excellent extrudability from a coke oven. .
- the inventors of the present invention have intensively studied to what extent the blended coal homogeneity affects the coke strength. As a result, the inventors of the present invention have found that there is a high possibility that the homogeneity of the blended coal of the millimeter order has an influence on the coke strength.
- the homogeneity of the blended coal on the order of millimeters is, for example, when focusing on the range of a cube with one side of several millimeters, if the blended coal has the same properties no matter where in the range, the blended coal has high homogeneity. It is a way of thinking.
- the homogeneity of the blended coal will be high, and conversely if the multiple types of coal particles are partly biased, the homogeneity of the blended coal will be Lower.
- the homogeneity of the blended coal becomes low.
- the homogeneity of the blended coal is low unless a plurality of types of coal particles inside the pseudo-particles are well mixed.
- the inventors of the present invention indicate that pseudo particles in which a plurality of coal particles aggregate also affect the coke strength. Revealed. Further, the inventors of the present invention investigated the relationship between the moisture content of the blended coal and the formation state of pseudo particles. As a result, the inventors of the present invention, when the water content of the blended coal exceeds 6 [mass%], the weight ratio of pseudo particles having a particle size of 1 [mm] or more increases, and the blended coal of millimeter order is homogeneous. It was found that the sex decreased.
- the inventors of the present invention not only reduce the charging bulk density of the coal blend, but also reduce the coke strength due to the increase in the moisture content of the coal blend in the order of millimeters by increasing the weight ratio of the pseudo particles. It was clarified that the decrease in the homogeneity of the blended coal contributed.
- the method for producing coke according to the present invention conceived on the basis of the above knowledge is a preparation step in which two or more types of coal are blended to prepare blended coal, and the blended coal is agitated and mixed, whereby coal particles are aggregated.
- the coke production method according to the present invention is characterized in that, in the above invention, the preparation step includes a step of pulverizing the two or more types of coal before mixing the two or more types of coal.
- the coke production method according to the present invention is characterized in that, in the above-mentioned invention, the preparation step includes a step of drying the two or more kinds of coal.
- the method for producing coke according to the present invention is characterized in that, in the above-described invention, the stirring and mixing step is performed on blended coal having a water content of 6% by mass or more.
- the coke production method according to the present invention is the coke production method according to the invention, wherein the stirring and mixing step is performed at a level of 0.6 or more after 60 seconds from the start of the stirring and mixing operation as determined by the following mathematical formula (1). It comprises the step of stirring and mixing the blended charcoal using a mixing device having the stirring and mixing performance.
- the degree of attainment is that of a mixture obtained by carrying out a stirring and mixing operation by placing 95% by mass of calcium carbonate having an average particle size of 2.66 ⁇ m and 5% by mass of iron (III) oxide having an average particle size of 0.47 ⁇ m in a mixing apparatus. It is a value calculated from the brightness.
- t is the time since the start of the stirring and mixing operation
- V max is the brightness of calcium carbonate
- V st is the brightness of a mixture in which calcium carbonate and iron (III) are completely mixed
- V (t) Represents the lightness of the mixture at time t.
- the coke production method according to the present invention is the above-described invention, wherein the stirring and mixing step uses a mixing device having a required power per unit mixing volume of 1.0 ⁇ 10 4 W / m 3 or more. And stirring and mixing.
- coke having high strength and excellent extrudability from a coke oven can be produced.
- FIG. 1 is a diagram showing the relationship between the moisture content of the blended coal and the particle size distribution.
- FIG. 2A is a diagram for explaining the homogeneity of the blended coal when simple coals not including pseudo particles are mixed.
- FIG. 2B is a diagram for explaining the homogeneity of the blended coal when the simple coals including pseudo particles are mixed.
- FIG. 3A is a schematic diagram for explaining a clearance evaluation method.
- FIG. 3B is a schematic diagram for explaining a clearance evaluation method.
- FIG. 4 is a diagram showing the relationship between the moisture content of simple coal used for preparation of blended coal and coke strength.
- FIG. 5 is a diagram showing the relationship between the moisture content of the simple coal used for the preparation of the blended coal and the clearance.
- FIG. 6 is a diagram showing the relationship between the weight ratio of particles having a particle size of 1 [mm] or more and the coke strength.
- FIG. 7 is a diagram showing the evaluation results of the optical structure of coke.
- FIG. 8 is a diagram showing the relationship between the stirring and mixing time of the mixer and the degree of achievement.
- FIG. 9 is a diagram showing the relationship between the degree of achievement after 60 seconds and the degree of crushing.
- FIG. 10 is a diagram showing the relationship between the required power per unit mixing volume and the degree of reach after 60 seconds.
- FIG. 11 is a diagram showing the relationship between the moisture content of the blended coal during mixing and the drum strength of the coke.
- the inventors of the present invention have intensively studied to what degree the blended coal homogeneity affects the coke strength, and the millimeter-order blended coal homogeneity may affect the coke strength. Was found to be high.
- the water content of the coal blend exceeds 6 [mass%]
- the inventors of the present invention increase the weight ratio of pseudo particles having a particle size of 1 [mm] or more, and the homogeneity of the millimeter-order coal blend. was found to decrease.
- the inventors of the present invention improve the coke strength even with the same blended coal by applying a stirring and mixing operation to the blended coal that can improve the homogeneity of the millimeter-order blended coal.
- the present invention has been completed by conceiving what can be done.
- a method for producing coke which is an embodiment of the present invention, will be described.
- the inventors of the present invention investigated the relationship between the moisture content of blended coal and the formation state of pseudo particles.
- the blended coal a blended coal having general properties used for the production of metallurgical coke was used. Properties of four types of simple coal (A charcoal to D charcoal) constituting the blended charcoal (average maximum reflectance Ro [%], Gieseller fluidity log MF [log ddpm], volatile content VM [mass%], ash content Ash [ Mass%]) and blending ratio [mass%] and the average properties of the blended coal are shown in Table 1 and Table 2 below, respectively.
- the average maximum reflectance was measured based on JIS M8816, the maximum Gieseller fluidity was measured based on JIS M8801, and the volatile content and ash content were measured based on JIS M8812. Volatile and ash values are dry base values.
- the blended charcoal has a particle size distribution assuming actual operation (3 [mm] or less: 75 [%], 3 to 6 [mm]: 15 [%], 6 [mm] or more: 10 [%]. %). After heating the blended charcoal to 107 [° C.] to bring the moisture content to 0 [mass%], the moisture was added to acclimate all day and night, and the eight patterns shown in Table 3 below (0, 4, 6, 7, 8, 9, 10, 12 [mass%]) blended charcoal was prepared. Thereafter, each blended coal was sieved with a sieve shaker for 5 minutes, and the particle size distribution was measured.
- FIG. 1 shows the relationship between the moisture content of the blended coal and the particle size distribution.
- the inventors of the present invention investigated the relationship between blended coal homogeneity, coke strength, and clearance in consideration of the presence of pseudo particles.
- the homogeneity of the blended coal it is necessary to consider the coal brand in the quasi-particles contained in the blended coal and its particle size. That is, the quasi-particles made before preparing the blended coal are composed of a single coal brand.
- plural kinds of coal brands exist inside the pseudo particles formed after the preparation, and plural kinds of coal brands are mixed to some extent.
- blended pseudo-particles composed of a single coal brand are prepared and obtained from the blended coal. It is necessary to evaluate the strength of coke produced. In order to perform this evaluation ideally, it is necessary to make the particle sizes of the single particles or pseudo particles constituting the coal uniform. However, coal is inhomogeneous and the grindability is different for each structure, so it is difficult to make the particle sizes uniform.
- the coke strength was evaluated by the following procedure.
- the furnace was filled with 17.1 [kg] of coal blend in a dry distillation can so that the bulk density (dry weight basis) was 725 [kg / m 3 ] and a weight of 10 [kg] was placed on the dry distillation can.
- the 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 having a particle size of 15 mm or more after 150 rotations at a rotation speed of 15 rpm and The mass ratio ⁇ 100 was calculated as the drum strength DI (150/15).
- the clearance was evaluated according to the following procedure.
- a small simulated retort 1 for clearance measurement shown in FIGS. 3A and 3B is charged with 2.244 [kg] of coal blend so as to have a bulk density (dry weight basis) of 775 [kg / m 3 ], and a furnace wall temperature of 1050 [ C.] in an electric furnace for 4 hours and 20 minutes, and then taken out of the furnace and cooled with nitrogen to obtain a coke cake.
- the gap between one side of the obtained coke cake and the furnace wall was measured with a laser distance meter, and the average value of the gap was calculated. And the sum of both sides of the average value of the gap was defined as clearance.
- the small simulated retort 1 shown in FIGS. 3A and 3B is disposed on a bottom plate 11 made of bricks, a pair of metal side plates 12a and 12b erected on the bottom plate 11, and a pair of side plates 12a and 12b. And a top plate 13 formed of bricks.
- the blended coal 2 is filled in a space formed by a plate constituting the small simulated retort 1, and as shown in FIG. 3B, a coke cake 3 obtained by dry distillation and a pair of side plates 12a, A gap D with respect to 12b is measured using a laser distance meter.
- the small simulated retort 1 has a length L: 114 [mm] ⁇ width W: 190 [mm] ⁇ height H: 120 [mm].
- FIG. 4 shows the relationship between the moisture content of the simple coal used for the preparation of the blended coal and the coke strength
- FIG. 5 shows the relationship between the moisture content of the simple coal and the clearance.
- the coke strength hardly changes until the moisture content of the simple coal reaches 6 [mass%], but when the moisture content of the simple coal exceeds 6 [mass%], the coke strength rapidly increases. To drop.
- FIG. 1 showing the relationship between the moisture content of the coal blend and the pseudo particles was compared with FIG. 4 showing the relationship between the moisture content of the simple coal used for the preparation of the coal blend and the coke strength.
- FIG. 6 shows the relationship between the weight ratio of particles having a particle diameter of 1 [mm] or more in the blended coal shown in FIG. 1 and the coke strength.
- a good correlation is established between the weight ratio of particles having a particle size of 1 [mm] or more in the blended coal and the coke strength.
- Non-Patent Document 4 describes a report that a defect having a dimension on the order of millimeters causes surface breakage based on the investigation result of the defect that causes coke surface breakage.
- Non-Patent Document 5 describes the size of an inert causing a reduction in coke strength based on the investigation result of the relationship between the size of the inert (coal structure that does not soften and melt by heating) and the coke strength.
- a report that the critical point is 1.5 [mm] or more is described.
- the reason why the homogeneity on the millimeter order affects the coke strength is that the low-grade coal particles such as non-slightly caking coal, which has poor meltability when coking, are agglomerated in the millimeter order, that is, pseudo particles. If so, the pseudo-particle portion behaves like a coarse-grained inert, and is considered to form a millimeter-order portion that is not well-cured in coke, in other words, a defect having a dimension of millimeter order.
- the optical structure of the obtained coke was evaluated.
- the evaluation results are shown in FIG.
- a mosaic structure is developed in blended coal with high homogeneity on the order of millimeters with a moisture content of 6 [% by mass] or less. It is said that the optical structure has a strong relationship with the strength of the coke substrate, and the strength of the isotropic tissue or mosaic structure derived from the active ingredient is high (see Non-Patent Document 6). Therefore, it is considered that not only the effect of reducing defects of dimensions on the order of millimeters but also the effect of developing a mosaic structure contributes to the improvement of coke strength accompanying the homogenization of blended coal.
- the reason why the mosaic structure develops with the homogenization (mixing strengthening) of the blended coal including the interior of the quasi-particles is mainly due to the coal that forms a relatively anisotropic structure (coal with a high degree of carbonization). It is thought that this is because the mosaic structure formed at the contact interface with coal (generally having a low degree of carbonization) forming an isotropic structure increases as the contact interface increases.
- the inventors of the present invention performed an operation for improving homogeneity on the order of millimeters, specifically a stirring and mixing operation even for a coal blend having a water content of 6 [% by mass] or more. It was thought that the decrease in coke strength caused by the decrease in the homogeneity of the blended coal can be suppressed by crushing the pseudo particles. Accordingly, the inventors of the present invention can perform a stirring and mixing operation (shear mixing) in which pseudo particles having a particle size of 1 [mm] or more formed with a moisture content of 6 [% by mass] or more are crushed and uniformly dispersed. The stirring and mixing device and its stirring and mixing performance were evaluated.
- the inventors of the present invention have made extensive studies and devised a method of crushing pseudo particles having a particle size of 1 [mm] or more and indexing the degree of uniform dispersion as follows.
- Coal coated with powdered fluorescent paint (FX-305, manufactured by Sinloihi Co., Ltd.) is prepared as a tracer.
- the tracer emits light under ultraviolet irradiation. Therefore, by adding a tracer and mixing and mixing the mixture, the mixed coal is photographed with a digital camera under ultraviolet irradiation, and the resulting image is processed to obtain the size and dispersion state of the tracer in the blended coal. Can be indexed.
- the tracer can be easily extracted on the image by setting an appropriate threshold with image data such as luminance and brightness. The inventors of the present invention set the luminance threshold and extracted the tracer portion.
- the above method is a method that allows direct observation of whether or not the pseudo particles made of coal coated with a fluorescent paint are being crushed, and rather than simply measuring the particle size distribution of the pseudo particles. Can be evaluated accurately. In general, in the presence of moisture, coal easily becomes pseudo-particles, so that the structure of the pseudo-particles may be changed by handling or sieving after mixing. Therefore, the above method was adopted for evaluation of the degree of crushing.
- Equation (3) parameter t is the elapsed time from the start of stirring and mixing, V max is the brightness of calcium carbonate, V st is the brightness of a mixture in which calcium carbonate and iron (III) are completely mixed, and V (t) is The brightness of the mixture at time t is shown.
- Non-Patent Document 7 the above evaluation is performed with various mixers, and the mixers are classified into three patterns from the shape of the curve of the mixing time and the degree of achievement.
- the curve becomes a downward convex curve.
- the curve becomes a convex curve.
- the curve is an intermediate curve between the curve of the A type mixer and the curve of the B type mixer. The shape of this curve is obtained by stirring and mixing for a long time, and the degree of achievement is low in the stirring and mixing operation of about 60 seconds.
- the result is a B type mixer, and the middle is a C type mixer.
- FIG. 8 shows the relationship between the stirring and mixing time of the mixer and the degree of achievement.
- the mixer A shown in FIG. 8 is a conventional drum mixer, and is classified into the A type.
- the mixer B is a C type mixer, and the mixers C to E are B type mixers.
- FIG. 9 shows the relationship between the degree of achievement after 60 seconds and the degree of disintegration.
- the degree of pulverization varies greatly within the range of reach of 0.4 to 0.6. That is, the mixing performance necessary for homogenization of the blended coal on the millimeter order has a reach of 60 or more after 60 seconds, preferably 0.7 or more.
- a suitable mixer having such mixing performance is shear mixing. It became clear that this is a B type mixer.
- FIG. 8 in the conventional drum mixer type coal blender (A type mixer) employed in the conventional coke factory, it was confirmed that the pseudo particles were hardly crushed.
- the inventors of the present invention tried to organize the mixer from a mechanical point of view and evaluate the relationship with the achievement after 60 seconds. In principle, it is necessary to apply a force higher than the breaking strength of the aggregate to break down the aggregate of Bengala.
- a force higher than the breaking strength of the aggregate to break down the aggregate of Bengala.
- there are various ways of applying forces such as compressive force and shear force to the agglomerates, and systematically evaluating the mixer with the force applied to the agglomerates is not possible. It takes a lot of effort. Therefore, the inventors of the present invention considered that the force applied to the agglomerate has a correlation with the input energy (power) to the mixer, and tried to arrange the mixer by the input energy.
- the input energy is converted not only to the breaking energy of the aggregates but also to the transport energy and frictional heat of the mixture, and the respective conversion ratios are considered to be different for each mixer.
- FIG. 10 when the relationship between the required power per unit mixing volume and the degree of achievement after 60 seconds is simply evaluated, a generally good correlation is established. From the correlation shown in FIG. 10, the degree of achievement after 60 seconds is 0.6 or more because the required power per unit mixing volume is 1.0 ⁇ 10 4 [W / m 3 ] or more, 0.7 It became clear that the required power per unit mixing volume is 3.0 ⁇ 10 4 [W / m 3 ] or more.
- a suitable mixer having a stirring and mixing performance necessary for homogenization of blended coal in the millimeter order by crushing pseudo particles has a required power per unit mixer volume of 1.0 ⁇ 10 4 [W / m 3 ] or more. Preferably, it is 3.0 ⁇ 10 4 [W / m 3 ] or more. That is, a suitable mixer can be easily selected from the required power and the unit mixing volume without measuring the reach.
- the homogeneity of the blended coal after the stirring and mixing treatment by the mixer is also affected by the homogeneity before the stirring and mixing treatment by the mixer. That is, when the homogeneity before the stirring and mixing process by the mixer is high, the stirring and mixing time required to obtain the target homogeneity can be shortened, which is efficient.
- a coke production line includes a pulverization process, a mixing process, a drying process (including partial drying process), etc., and the blended coal is mixed and homogenized in the course of processing and conveyance in each process. move on. Accordingly, it is desirable that the stirring and mixing process by the mixer is performed as much as possible immediately before charging into the coke oven as much as possible.
- the effect of improving the homogeneity of the blended coal is increased, which is particularly effective. Further, from the result of investigating the relationship between the water content at the time of mixing and the coke strength, the effect of stirring and mixing is effective when the water content of the blended coal is 6 [% by mass] or more. Therefore, even in a coke production line having a step of drying the blended coal, if the moisture content of the blended coal after drying is 6% by mass or more, the effect of improving the coke strength by the stirring and mixing treatment by the mixer Can be obtained.
- the drying process it is not necessary to evaporate all the moisture of the coal, and the drying process includes partial drying and humidity control operations that reduce the moisture content.
- the blended coal may include additives such as caking additive, oils, powdered coke, petroleum coke, resins, and waste.
- Example ⁇ In this example, four types of simple coals (moisture amounts 3, 4, 6, 8, 10 [mass%]) shown in Table 1 that differ only in the amount of water are prepared, and mixers A to E having different stirring and mixing forms are prepared. 4 types of simple charcoal were stirred and mixed for 60 seconds so that the blending ratio shown in Table 2 was used. The prepared coal blend was subjected to dry distillation under the above-mentioned conditions, and the drum strength DI (150/15) and clearance of the obtained coke were measured.
- the mixer A is a conventional drum mixer (Comparative Example 1)
- the mixers C to E are B type mixers (Invention Examples 1 to 3) mainly composed of shear mixing
- the mixer B is an intermediate mixing performance between the conventional type and the invention examples.
- C type mixer (Comparative Example 2) having
- FIG. 11 shows the relationship between the water content of the blended coal during mixing and the drum strength DI (150/15) of the coke.
- Table 5 and FIG. 11 it was confirmed that the coke strength was improved by mixing with a mixer for the blended coal having a water content of 6 [% by mass] or more at the time of mixing.
- the effect of improving the coke strength varied greatly depending on the type of mixer. That is, in the B type mixer, the effect of improving the coke strength is great, and even when the water content of the blended coal at the time of mixing is 10 [mass%], the coke strength when the water content is 6 [mass%] or less is obtained. The coke strength recovered to a comparable level.
- the effect of improving the coke strength was small in the A type and C type mixers. Regarding the clearance, there was almost no difference in any mixing operation.
- the strength of the obtained coke after CO 2 reaction (measured in accordance with CSR, ISO18894 method) also showed the same tendency as the drum strength DI (150/15). That is, in the conditions of Comparative Example 1, when the moisture content during mixing was 4, 6, and 8 [mass%], the CSR was 59.2 [%], 59.0 [%], and 57.5 [%], respectively. While the strength tended to decrease with increasing water content, in Invention Example 3, the CSR was 59.8 [%], 59 when the water content during mixing was 4, 6, and 8 [mass%], respectively. .7 [%] and 59.4 [%] showed almost no decrease.
- pseudo particles having a particle size of 1 [mm] or more are formed with a blended coal having a moisture content of 6 [% by mass] or more.
- the coke strength is improved by mixing the blended coal having a water content of 6 [% by mass] or more under the condition that the pulverization degree is high in the B type mixer which is the invention example.
- the coke strength is equivalent to the coke strength in the case where the moisture content is 4 [% by mass] or less in which pseudo particles are hardly formed. From the above, it is considered that the effect of improving the coke strength according to the present invention was brought about by pulverizing the pseudo particles contained in the blended coal by the mixing operation by the mixer.
- the conventional type can be obtained by stirring and mixing using a B-type mixer mainly composed of shear mixing. It became clear that the decrease in coke strength caused by the decrease in the homogeneity of the blended coal, which cannot be achieved with this mixer, can be suppressed. In addition, since the clearance can be maintained by the agitation and mixing operation, it has been clarified that the present invention is effective as a means for improving the coke strength by the wet coal operation in an aging coke oven.
- the reach during stirring for 60 seconds is 0.6 or more
- the reach is 0.4 or more even when the stirring and mixing time is 10 seconds, and a partial solution of pseudo particles is obtained.
- the effect of improving coke strength by crushing can be expected.
- a mixer for example, mixer E
- the degree of achievement at the time of 60 seconds of agitation and mixing is 0.6 or more because the degree of achievement at the time of stirring and mixing is 10 seconds. It is preferable to stir and mix the blended charcoal for 10 seconds or more with a mixer.
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Abstract
Description
本発明の発明者らは、配合炭の水分量と擬似粒子の形成状況との関係を調査した。配合炭としては、冶金用コークスの製造に用いられる一般的な性状の配合炭を使用した。配合炭を構成する4種類の単味炭(A炭乃至D炭)の性状(平均最大反射率Ro[%]、ギーセラー流動度logMF[log ddpm]、揮発分VM[質量%]、灰分Ash[質量%])及び配合率[質量%]と配合炭の平均性状とをそれぞれ以下の表1及び表2に示す。平均最大反射率はJIS M8816に基づき、ギーセラー最高流動度はJIS M8801に基づき、揮発分及び灰分はJIS M8812に基づきそれぞれ測定した。揮発分及び灰分はドライベースの値である。
本発明の発明者らは、以上の調査及び考察より、水分量が6[質量%]以上である配合炭であってもミリメートルオーダーの均質性を向上させる操作、具体的には攪拌混合操作を施すことによって擬似粒子を解砕することにより、配合炭の均質性の低下に起因するコークス強度の低下を抑止できると考えた。そこで、本発明の発明者らは、水分量6[質量%]以上で形成される粒径1[mm]以上の擬似粒子を解砕して均一分散させる攪拌混合操作(剪断混合)が可能な攪拌混合装置及びその攪拌混合性能を評価した。
本実施例では、水分量のみが異なる表1に示す4種の単味炭(水分量3,4,6,8,10[質量%])を用意し、攪拌混合形態が異なるミキサーA乃至Eを用いて表2に示す配合率になるように4種の単味炭を60秒間攪拌混合して配合炭を調製した。調製された配合炭を上述の条件で乾留し、得られたコークスのドラム強度DI(150/15)及びクリアランスを測定した。ミキサーAは従来型のドラムミキサー(比較例1)、ミキサーC乃至Eは剪断混合が主体のBタイプのミキサー(発明例1乃至3)、ミキサーBは従来型と発明例との中間の混合性能を有するCタイプのミキサー(比較例2)である。
上記実施例では、水分量が高いと擬似粒子の解砕が不十分である場合、コークス強度が低下することが確認された。そこで、本比較例では、コークス強度に対する水分量の影響を調べるために、ミキサーAを用いて水分量を変更した試験を実施した。水分量以外の条件は実施例1の条件と同じである。試験結果を以下の表6に示す。表6に示すように、水分量が6.0[質量%]以上になるとコークス強度が低下する。これに対して、上記実施例では、水分量が8[質量%]になってもコークス強度はほとんど低下しなかった。以上のことから、本発明の効果は水分量が6[質量%]以上の条件において顕著に現れることが明らかになった。
2 配合炭
3 コークスケーキ
11 底板
12a,12b 側板
13 天板
Claims (6)
- 2種以上の石炭を配合して配合炭を調製する調製ステップと、
前記配合炭を攪拌混合することによって、石炭粒子が凝集することにより形成された配合炭中の擬似粒子の少なくとも一部を解砕する攪拌混合ステップと、
攪拌混合後の配合炭をコークス炉に装入して乾留することによってコークスを製造する乾留ステップと、
を含むことを特徴とするコークスの製造方法。 - 前記調製ステップは、2種以上の石炭を配合する前に該2種以上の石炭を粉砕するステップを含むことを特徴とする請求項1に記載のコークスの製造方法。
- 前記調製ステップは、前記2種以上の石炭を乾燥させるステップを含むことを特徴とする請求項1又は2に記載のコークスの製造方法。
- 水分量が6質量%以上である配合炭に対して前記攪拌混合ステップを行うことを特徴とする請求項1乃至3のうち、いずれか1項に記載のコークスの製造方法。
- 前記攪拌混合ステップは、以下に示す数式(1)によって求められる到達度が攪拌混合操作を開始してから60秒後に0.6以上になる攪拌混合性能を有する混合装置を用いて配合炭を攪拌混合するステップを含むことを特徴とする請求項1乃至4のうち、いずれか1項に記載のコークスの製造方法。
- 前記攪拌混合ステップは、単位混合容積あたりの所要動力が1.0×104W/m3以上である混合装置を用いて配合炭を攪拌混合するステップを含むことを特徴とする請求項1乃至5のうち、いずれか1項に記載のコークスの製造方法。
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JP2014548530A JP5783338B2 (ja) | 2012-11-22 | 2013-11-13 | コークスの製造方法 |
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WO2015177998A1 (ja) * | 2014-05-19 | 2015-11-26 | Jfeスチール株式会社 | コークスの製造方法およびコークスならびに配合炭の均質性の評価方法 |
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JP6070628B2 (ja) * | 2014-05-15 | 2017-02-01 | Jfeスチール株式会社 | コークスの製造方法 |
JP6094622B2 (ja) * | 2014-05-15 | 2017-03-15 | Jfeスチール株式会社 | コークスの製造方法 |
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