EP2612894A1 - Herstellungsverfahren für hüttenkoks - Google Patents

Herstellungsverfahren für hüttenkoks Download PDF

Info

Publication number
EP2612894A1
EP2612894A1 EP11821997.1A EP11821997A EP2612894A1 EP 2612894 A1 EP2612894 A1 EP 2612894A1 EP 11821997 A EP11821997 A EP 11821997A EP 2612894 A1 EP2612894 A1 EP 2612894A1
Authority
EP
European Patent Office
Prior art keywords
coals
coal
sample
permeation distance
caking additive
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Granted
Application number
EP11821997.1A
Other languages
English (en)
French (fr)
Other versions
EP2612894A4 (de
EP2612894B1 (de
Inventor
Yusuke Dohi
Izumi Shimoyama
Kiyoshi Fukada
Tetsuya Yamamoto
Hiroyuki Sumi
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
JFE Steel Corp
Original Assignee
JFE Steel Corp
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by JFE Steel Corp filed Critical JFE Steel Corp
Publication of EP2612894A1 publication Critical patent/EP2612894A1/de
Publication of EP2612894A4 publication Critical patent/EP2612894A4/de
Application granted granted Critical
Publication of EP2612894B1 publication Critical patent/EP2612894B1/de
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Images

Classifications

    • 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 a metallurgical coke that uses a test method for evaluating thermal plasticity during carbonization of coal.
  • the present invention relates to a method for producing a metallurgical coke that can reduce the amount of high grade coals used while maintaining the coke strength or a method for producing a metallurgical coke in which a high-strength coke can be obtained from the same coal blend.
  • Coke used in a blast furnace process that is most commonly used as an iron-making process variously serves as a reducing agent for iron ore, a heat source, a spacer, and the like.
  • Coke is produced by carbonizing, in a coke oven, a coal blend produced by blending various coals for coke making which are prepared by being pulverized so as to have an appropriate particle size.
  • the coals for coke making are softened and melted in a temperature range of about 300°C to 550°C during carbonization.
  • the thermal plasticity of coal is extremely important because the thermal plasticity considerably affects the properties of coke and coke cake structures after carbonization.
  • the measurement method of thermal plasticity has been actively studied for a long time.
  • coke strength which is an important quality of coke, is considerably affected by the properties of coal serving as a raw material of coke, namely, coal rank and thermal plasticity.
  • the thermal plasticity is a property of coal that is softened and melted by heating.
  • the thermal plasticity is measured and evaluated using, for example, the fluidity, viscosity, adhesive properties, and swelling properties of a plastic product.
  • a typical method for measuring the fluidity in a plastic phase may be a coal fluidity test method that uses a Gieseler plastometer method specified in JIS M 8801.
  • the Gieseler plastometer method is a method in which a coal pulverized so as to have a particle size of 425 ⁇ m or less is placed into a particular crucible and heated at a predetermined heating rate, and the rotation speed of a stirring rod on which a predetermined torque is exerted is read from a dial plate and given in units of ddpm (dial division per minute).
  • the Gieseler plastometer method is a method in which the rotation speed of a stirring rod at a constant torque is measured, and furthermore a method in which a torque at a constant rotation speed is measured has been developed.
  • Patent Literature 1 discloses a method in which a torque is measured while a rotor is rotated at a constant rotation speed.
  • a method for measuring a viscosity with a dynamic viscoelastometer for the purpose of measuring a viscosity that has a physical significance as the thermal plasticity (e.g., refer to Patent Literature 2).
  • the measurement of dynamic viscoelasticity is a measurement of viscoelastic behavior observed when a force is periodically applied to a viscoelastic body.
  • the viscosity of plastic coal is evaluated using a complex viscosity among parameters obtained in the measurement and thus the viscosity of plastic coal can be measured at a desired shear rate.
  • a typical method for measuring the swelling properties of coal in a plastic phase may be a dilatometer method specified in JIS M 8801.
  • the dilatometer method is a method in which a coal pulverized so as to have a particle size of 250 ⁇ m or less is molded by a prescribed method, inserted into a designated crucible, heated at a predetermined heating rate, and measuring the displacement of the coal over time with a detection rod disposed above the coal.
  • the coke strength is empirically controlled to be higher than or equal to a particular coke strength by setting the target coke strength on the high side in advance in consideration of variations in coke strength resulting from inaccuracies in evaluation of thermal plasticity.
  • the average grade of a coal blend needs to be set on the high side by using relatively expensive coals having so-called excellent thermal plasticity, which increases the cost.
  • coal In a coke oven, coal is softened and melted while being restricted by adjacent layers. Since the thermal conductivity of coal is low, coal is not uniformly heated in the coke oven and a coke layer, a plastic layer, and a coal layer are formed in different states in that order from an oven wall serving as a heating surface. The coke oven itself swells to a degree during carbonization, but substantially does not deform. Thus, the plastic coal is restricted by the adjacent coke layer and coal layer.
  • the cracks formed in the coke layer are believed to have a width of about several hundred micrometers to several millimeters, which are larger than the gaps between coal particles and the large pores each having a size of about several tens of micrometers to several hundred micrometers. Therefore, it is believed that not only the pyrolytic gas and liquid substances, which are by-products generated from the coal, but also the plastic coal itself permeates into the large defects formed in the coke layer. The rate of shear exerted on the plastic coal during the permeation is expected to be different depending on brands.
  • the inventors have considered that the thermal plasticity of coal measured under the conditions that an environment surrounding the above-described coal in a coke oven is simulated needs to be used as an index to more precisely control the coke strength.
  • the inventors have considered that it is important to perform the measurement under the conditions that the plastic coal is restricted and under the conditions that the movement and permeation of plastic products into defect structures around the plastic products are simulated.
  • the existing measurement method has the following problems.
  • the Gieseler plastometer method in which the measurement is performed while coal is packed in a vessel poses a problem because the restriction and permeation conditions are not taken into account at all.
  • This method is also not suitable for the measurement of a coal that exhibits high fluidity. This is because, when a coal that exhibits high fluidity is measured, a phenomenon (Weissenberg effect) occurs in which a hollow space is formed in a portion close to the sidewall of the vessel and a stirring rod rotates without making contact, and consequently the fluidity sometimes cannot be accurately evaluated (e.g., refer to Non Patent Literature 1).
  • the dynamic viscoelastometer is a device in which viscosity is targeted as the thermal plasticity and the viscosity can be measured at a desired shear rate.
  • the shear rate in the measurement By setting the shear rate in the measurement to a rate of shear exerted on the coal in a coke oven, the viscosity of plastic coal in the coke oven can be measured.
  • Patent Literature 4 also discloses a coal dilatation measurement method in which the movement of gas and liquid substances generated from coal is taken into account by disposing a material having permeation paths on a coal layer.
  • the method poses problems in that the heating method is restricted and the conditions for evaluating a permeation phenomenon in a coke oven are unclear.
  • Patent Literature 4 the relationship between the permeation phenomenon of plastic coal and the thermoplastic behavior is unclear, the relationship between the permeation phenomenon of plastic coal and the quality of coke produced is not mentioned, and the production of high quality coke is not mentioned.
  • the thermal plasticity such as fluidity, viscosity, adhesive properties, permeation properties, dilatation during permeation, or pressure during permeation of coals and caking additives cannot be measured in a state in which an environment surrounding plastic coals and caking additives in a coke oven is sufficiently simulated.
  • the thermal plasticity of coals used for a coal blend is accurately evaluated by measuring the thermal plasticity of coal in a state in which an environment surrounding plastic coal in a coke oven is simulated, to clarify the effects of the coals on coke strength; and the adverse effects on coke strength are reduced by adjusting the pretreatment conditions of coals that adversely affect coke strength.
  • the present invention is characterized as follows.
  • the thermal plasticity of coals or caking additives can be evaluated in a state in which the effects of defect structures that are present around a plastic layer of coal in a coke oven, which is believed to considerably affect the thermal plasticity of coal in a coke oven, in particular, the effects of cracks that are present in a coke layer adjacent to the plastic layer are simulated and the restriction conditions around a plastic product in a coke oven are properly reproduced.
  • the formation of defects derived from coals or caking additives that exhibit excessively high fluidity which cannot be detected by an existing method for evaluating thermal plasticity, can be estimated and coals or caking additives that adversely affect the coke quality can be specified.
  • the adverse effects on coke quality can be reduced and a high-strength metallurgical coke can be produced.
  • the inventors of the present invention have conducted thorough studies on the relationship between coke strength and "permeation distance" which is the measured thermal plasticity, by enabling the thermal plasticity to be measured in a state in which an environment surrounding plastic coal in a coke oven is simulated. As a result, the inventors have found that even coals that have been reported that they have almost no difference in terms of thermal plasticity have a difference in terms of thermal plasticity measured by a method of the present invention, that is, thermal plasticity measured in a state in which an environment surrounding plastic coal is simulated. The inventors have also found that, when the coals having a difference in terms of thermal plasticity measured by the method of the present invention are blended to produce coke, the coke strengths of the coke are different from each other. Thus, the present invention has been completed by finding that coals that adversely affect coke strength are used as coals for coke making after the particle size is decreased and thus the adverse effects can be reduced.
  • Fig. 1 shows an example of an apparatus for measuring thermal plasticity (permeation distance) used in the present invention.
  • the apparatus in Fig. 1 is an apparatus used when a coal sample is heated while a constant load is imposed on the coal sample and a material having through-holes that connect upper and lower surfaces.
  • a sample 1 is prepared by packing a coal in a lower portion of a vessel 3, and a material 2 having through-holes that connect upper and lower surfaces is disposed on the sample 1.
  • the sample 1 is heated to a temperature higher than or equal to the initial softening temperature of the sample 1, and the sample is caused to permeate into the material 2 having through-holes that connect upper and lower surfaces to measure the permeation distance.
  • the heating is performed in an inert gas atmosphere.
  • the permeation distance may be measured by performing heating while the coal and the material having through-holes are kept at a constant volume.
  • Fig. 14 shows an example of an apparatus for measuring thermal plasticity (permeation distance) used in that case.
  • a dilatation detection rod 13 is disposed on the upper surface of the material 2 having through-holes that connect upper and lower surfaces, a loading weight 14 is placed on the upper end of the dilatation detection rod 13, and a displacement meter 15 is disposed above the loading weight 14 to measure the dilatation.
  • a displacement meter that can measure the range (-100% to 300%) of the dilatation of the sample may be used as the displacement meter 15. Since an inert gas atmosphere needs to be kept in the heating system, a non-contact displacement meter is suitable and an optical displacement meter is desirably used.
  • the inert gas is a gas that does not react with coal in the temperature range of the measurement. Typical examples of the gas include argon gas, helium gas, and nitrogen gas, and the nitrogen gas is preferably used.
  • the dilatation detection rod 13 may be buried in the particle-packed layer and thus a plate is desirably disposed between the dilatation detection rod 13 and the material 2 having through-holes that connect upper and lower surfaces.
  • the load is preferably uniformly imposed on the upper surface of the material having through-holes that connect upper and lower surfaces, the material being disposed on the upper surface of the sample.
  • the applied pressure is 5 to 80 kPa, preferably 15 to 55 kPa, and most preferably 25 to 50 kPa relative to the area of the upper surface of the material having through-holes that connect upper and lower surfaces.
  • the pressure is preferably set in accordance with the swelling pressure of a plastic layer in a coke oven.
  • the heating means is desirably a device that can perform heating at a predetermined temperature-increasing rate while monitoring the temperature of a sample.
  • the heating means include an electric furnace, external heating means that uses a conductive vessel and high-frequency induction in a combined manner, and internal heating means such as a microwave.
  • the inside temperature of the sample needs to be made uniform and, for example, a measure of improving the heat-insulating properties of the vessel is preferably taken.
  • the heating rate is set so as to correspond to the heating rate of coals in a coke oven in order to simulate the thermoplastic behavior of coals and caking additives in a coke oven.
  • the heating rate of coals in a plastic temperature range in the coke oven is dependent on the position in the oven and the operation conditions, but is about 2 to 10 °C/min.
  • the heating rate on average is desirably 2 to 4 °C/min and more desirably about 3 °C/min.
  • the permeation distance and dilatation are small at a heating rate of 3 °C/min, which may cause difficulty in detection.
  • the fluidity of coal measured with a Gieseler plastometer is improved by rapidly heating the coal. Therefore, in the case of coals whose permeation distance is 1 mm or less, the heating rate may be increased to 10 to 1000 °C/min to improve the detection sensitivity.
  • coals and caking additives may be heated to their plastic temperature ranges because the purpose is to evaluate the thermal plasticity of the coals and caking additives.
  • the heating may be performed at a predetermined heating rate in a range of 0°C (room temperature) to 550°C and preferably 300°C to 550°C, which is the plastic temperature of coal.
  • the material having through-holes that connect upper and lower surfaces is desirably a material whose permeability coefficient can be measured or calculated in advance.
  • the material is, for example, a unified material having through-holes or a particle-packed layer.
  • Examples of the unified material having through-holes include a material having circular through-holes 16 shown in Fig. 2 , a material having rectangular through-holes , and a material having irregularly shaped through-holes.
  • the particle-packed layer is generally classified into a spherical particle-packed layer and a non-spherical particle-packed layer.
  • An example of the spherical particle-packed layer is a layer composed of packing particles 17 such as beads as shown in Fig. 3 .
  • non-spherical particle-packed layer examples include a layer composed of irregularly shaped particles and a layer composed of packing cylinders 18 as shown in Fig. 4 . It is desirable that the permeability coefficient in the material be as constant as possible to maintain the reproducibility of the measurement and the permeability coefficient be easily calculated to simplify the measurement. Therefore, it is particularly desirable to use a spherical particle-packed layer for the material having through-holes that connect upper and lower surfaces in the present invention. Any material having through-holes that connect upper and lower surfaces may be used as long as the shape of the material substantially does not change at a temperature higher than or equal to the plastic temperature range of coal, specifically, up to 600°C and the material does not react with coal.
  • the material may have a height sufficiently larger than the height of the permeation of a plastic coal. When a coal layer having a thickness of 5 to 20 mm is heated, the height may be about 20 to 100 mm.
  • the permeability coefficient of the material having through-holes that connect upper and lower surfaces needs to be set in consideration of the permeability coefficient of large defects in a coke layer.
  • the permeability coefficient particularly desirable in the present invention is 1 x 10 8 to 2 ⁇ 10 9 m -2 .
  • ⁇ P / L K ⁇ ⁇ ⁇ u
  • ⁇ P represents the pressure loss [Pa] in the material having through-holes that connect upper and lower surfaces
  • L represents the height [m] of the material having through-holes
  • K represents the permeability coefficient [m -2 ]
  • ⁇ represents the viscosity [Pa ⁇ s] of a fluid
  • u represents the velocity [m/s] of a fluid.
  • the diameter of the glass beads selected to provide the above-described suitable permeability coefficient is desirably about 0.2 to 3.5 mm and most desirably 2 mm.
  • a coal or a caking additive to be used as a measurement sample is pulverized in advance and packed at a predetermined packing density with a predetermined layer thickness.
  • the particle size after the pulverization may be a particle size of coals charged into a coke oven (the ratio of particles having a particle size of 3 mm or less to all particles is about 70% to 80% by mass).
  • the coal or caking additive is preferably pulverized so that the ratio of particles having a particle size of 3 mm or less is 70% by mass or more.
  • all particles are particularly preferably pulverized so as to have a particle size of 2 mm or less.
  • the packing density of the pulverized product may be 0.7 to 0.9 g/cm 3 , which corresponds to the packing density in a coke oven. As a result of studies on the reproducibility and detection power, it has been found that the packing density is preferably 0.8 g/cm 3 .
  • the packed layer may have a thickness of 5 to 20 mm on the basis of the thickness of a plastic layer in a coke oven. As a result of studies on the reproducibility and detection power, it has been found that the packed layer preferably has a thickness of 10 mm.
  • the permeation distance of the plastic coal and plastic caking additive can be desirably measured continuously during the heating.
  • a continuous measurement is difficult because of, for example, tar generated from the sample.
  • the swelling and permeation of coal by heating are irreversible phenomena. Once coal is subjected to swelling and permeation, the shape is substantially kept even after cooling. Therefore, after the completion of the permeation of the plastic coal, the entire vessel is cooled and the permeation distance after cooling is measured, whereby the permeation distance during the heating may be measured.
  • the material having through-holes that connect upper and lower surfaces is taken out of the vessel after cooling, and the permeation distance can be directly measured using a vernier caliper or a ruler.
  • the plastic product that has permeated into the gaps of the particles fixes the entire particle layer into which the plastic product has permeated. Therefore, the relationship between the mass and height of the particle-packed layer is determined in advance, and then the mass of unfixed particles is measured after the completion of permeation and the mass is subtracted from the initial mass, whereby the mass of fixed particles can be derived and the permeation distance can be calculated.
  • (A) The range of permeation distance is specified by formula (4).
  • a is a constant that is 0.7 to 1.0 times the coefficient of log MF obtained by measuring the permeation distance and log MF of at least one of coals and a caking additive that satisfy log MF ⁇ 2.5 among the coals and the caking additive that constitute the coal blend and making a regression line that passes through the origin using the measured values.
  • the permeation distance is two times or more the weighted average permeation distance calculated from the permeation distances and blending ratio of brands of coals and caking additives that are included in the coal blend and satisfy log MF ⁇ 3.0.
  • the average permeation distance is preferably determined by employing a weighted average in consideration of blending ratio, but may also be determined by employing a simple average.
  • the methods for determining the four control values (A) to (D) above are described because the permeation distance varies depending on the set measurement conditions such as a load, a temperature-increasing rate, the type of material having through-holes , and the structure of an apparatus. This is based on the finding that the methods for determining the control values (A) to (C) are effective as a result of studies conducted in consideration of the cases where measurement conditions different from those described above may be employed.
  • the constants a and a' in the formulae (4) and (5) respectively used when the ranges (A) and (B) are determined are each determined so as to be 0.7 to 1.0 times the coefficient of log MF obtained by measuring the permeation distance and maximum fluidity of at least one of coals that satisfy log MF ⁇ 2.5 and making a regression line that passes through the origin using the measured values. This is because, although a substantially positive correlation is seen between the maximum fluidity and permeation distance of coal in the range of log MF ⁇ 2.5, the brand that decreases the strength is a brand whose permeation distance considerably deviates from the correlation in a positive direction.
  • the inventors of the present invention have found that the brand whose permeation distance is 1.3 or more times the permeation distance determined in accordance with the log MF of coal using the above-described regression line decreases the strength, and thus have specified the range of the formula (4). Furthermore, to detect the brand which deviates from the regression equation in a positive direction beyond measurement errors, the inventors have found that the brand whose permeation distance is higher than or equal to a value obtained by adding 5 times the standard deviation obtained when the same sample is measured multiple times to the regression equation decreases the strength, and thus have specified the range of the formula (5). Therefore, the constant b may be 5 times the standard deviation obtained when the same sample is measured multiple times.
  • the constant b is about 3.0 mm.
  • the formulae (4) and (5) specify, in accordance with the log MF of the coal, the ranges of permeation distance that causes a decrease in the strength. This is because, since the permeation distance generally increases as the MF increases, the degree of the deviation from the correlation is important.
  • the regression line may be made by a linear regression method that uses a publicly known least squares method. The number of coals used for regression is preferably as large as possible because the magnitude of the errors in regression is reduced. In particular, a brand having a low MF has a small permeation distance and thus the magnitude of the errors tends to increase. Therefore, the regression line is particularly preferably determined using at least one coal in the range of 1.75 ⁇ log MF ⁇ 2.50.
  • a and a' are preferably 0.7 to 1.0 times the slope of the regression line and b is preferably 1 to 5 times the standard deviation obtained when the same sample is measured multiple times.
  • Coals or caking additives used for a coal blend are normally used after various properties are measured for each brand.
  • the permeation distance may also be measured for each lot of brands in advance.
  • the average permeation distance of a coal blend may be obtained by measuring the permeation distances of brands in advance and averaging the permeation distances in accordance with the blending ratio or may be obtained by producing a coal blend and measuring the permeation distance of the coal blend.
  • a coal blend used in the production of coke may include oils, coke breeze, petroleum coke, resins, and wastes, in addition to coals and caking additives.
  • coals and caking additives that satisfy the above-described ranges (A) to (D) are used as coals for coke making after subjected to a normal pretreatment, large defects are left and a microstructure having a thin pore wall is formed in the production of coke, resulting in a decrease in the coke strength. Therefore, a measure of restricting the blending ratio of the brands and caking additives is simple and effective means for maintaining the coke strength. In the current production of coke in which many brands from various sources are intended to be blended in terms of stable raw material procurement, even the coals or caking additives that satisfy the above-described ranges (A) to (D) often needs to be used.
  • the inventors of the present invention have found that, even if a coal blend obtained by blending the coals or caking additives that satisfy the above-described ranges (A) to (D) is used as a coal for coke making, a decrease in the strength can be suppressed by changing the particle size of the coal blend.
  • the process of the consideration is described below with reference to the schematic views.
  • Fig. 5 schematically shows the state of formation of defect structures when a coke is produced from a coal blend obtained by blending the coals or caking additives that satisfy the ranges (A) to (D). Particles 19 of the coals or caking additives that satisfy the ranges (A) to (D) considerably permeate into gaps between packed particles and large defects in the production of coke. Therefore, thin pore walls are formed and large defects 22 are left in places in which the particles have been originally present, resulting in the decrease in the coke strength ( Fig. 5(b) ).
  • Fig. 6 schematically shows the state of formation of defect structures when a coke is produced from a coal blend obtained by blending coals or caking additives 20 that do not satisfy the ranges (A) to (D).
  • Particles 20 of the coals or caking additives that do not satisfy the ranges (A) to (D) do not considerably permeate into gaps between packed particles and large defects in the production of coke. Therefore, thick pore walls are formed and large defects are not left in places in which the particles have been originally present. Consequently, the decrease in the coke strength is not caused ( Fig. 6(b) ).
  • Fig. 7 schematically shows the state of formation of defect structures when a coke is produced from a coal blend obtained by performing blending after the coals or caking additives 19 that satisfy the ranges (A) to (D) are pulverized into fine particles.
  • particles of the coals or caking additives 19 that satisfy the ranges (A) to (D) considerably permeate into gaps between packed particles and large defects in the production of coke.
  • the size of defects formed in places in which the particles have been originally present is decreased, and thus the decrease in the coke strength can be suppressed ( Fig. 7(b) ).
  • Fig. 8 schematically shows the state of formation of defect structures when a coke is produced from a coal blend obtained by performing blending after the coals or caking additives 20 other than the coals or caking additives that satisfy the ranges (A) to (D) are pulverized into fine particles.
  • the spaces around the particles of the coals or caking additives 19 that satisfy the ranges (A) to (D) are occupied by the fine particles and defects, which decreases the permeability coefficient. Therefore, the particles of the coals or caking additives 19 cannot considerably permeate into gaps between packed particles and large defects in the production of coke. Consequently, thick pore walls are formed and large defects are not left in places in which the particles have been originally present, which can suppress the decrease in the coke strength ( Fig. 8(b) ).
  • the permeation distance of coal can be decreased, the number of large defects can be reduced, and the decrease in the coke strength after carbonization can be suppressed.
  • the particle size of a coal blend decreases, the specific surface of coal particles increases and the distance between particles increases. It is generally said that, to maintain the coke strength, the thermal plasticity of the entire coal blend needs to be improved.
  • the permeation distance was measured with the apparatus shown in Fig. 1 . Since a high-frequency induction heating system was employed, a heating element 8 in Fig. 1 was an induction heating coil and a vessel 3 was made of graphite serving as a dielectric. The vessel had a diameter of 18 mm and a height of 37 mm. Glass beads having a diameter of 2 mm were used as a material having through-holes that connect upper and lower surfaces. Into the vessel 3, 2.04 g of a coal sample that was pulverized so as to have a particle size of 2 mm or less and vacuum-dried at room temperature was charged.
  • a weight of 200 g was dropped from 20 mm above the coal sample five times to pack a sample 1 (the thickness of the sample was 10 mm in this state). Subsequently, the glass beads having a diameter of 2 mm were disposed on the packed layer of the sample 1 so as to have a thickness of 25 mm.
  • a sillimanite disc having a diameter of 17 mm and a thickness of 5 mm was disposed on the glass bead-packed layer.
  • a quartz rod serving as a dilatation detection rod 13 was placed on the sillimanite disc.
  • a weight 14 of 1.3 kg was placed on the quartz rod. Consequently, the pressure applied onto the sillimanite disc was 50 kPa.
  • Heating was performed to 550°C at a heating rate of 3 °C/min using a nitrogen gas as an inert gas. After the completion of the heating, cooling was performed in a nitrogen atmosphere. The mass of beads that were not fixed by the plastic coal in the cooled vessel was measured.
  • the above measurement conditions were determined as preferable measurement conditions for permeation distance by the inventors of the present invention through the comparison of the measurement results under various conditions.
  • the method for measuring the permeation distance is not limited to the above method.
  • the glass bead layer may be disposed so as to have a thickness larger than or equal to the permeation distance.
  • a plastic product permeated to the uppermost portion of the glass bead layer during the measurement the amount of glass beads was increased and the measurement was performed again.
  • the inventors of the present invention have confirmed that, as long as the thickness of the glass bead layer is larger than or equal to the permeation distance, the measurement value of the permeation distance of the same sample is the same.
  • a caking additive having a large permeation distance was measured, a larger vessel was used and the amount of glass beads packed was also increased.
  • the height of the fixed bead-packed layer was defined as the permeation distance.
  • the relationship between the height and mass of the glass bead-packed layer was determined in advance so that the height of the fixed bead-packed layer could be derived from the mass of the beads fixed by the plastic coal. This is represented by formula (6) and the permeation distance was derived from the formula (6).
  • L G - M ⁇ H
  • L represents the permeation distance [mm]
  • G represents the mass [g] of the packed glass beads
  • M represents the mass [g] of the beads not fixed by a plastic product
  • H represents the height of the packed layer per gram of glass beads packed in the experimental apparatus [mm/g].
  • Fig. 9 shows the relationship between the measurement results of the permeation distance and the logarithm (log MF) of the Gieseler maximum fluidity (MF). It is confirmed from Fig. 9 that the permeation distance measured in this Example has a correlation with the maximum fluidity, but there is a difference in permeation distance even at the same MF. For example, as a result of the study on the measurement error of the permeation distance in this apparatus, the standard deviation of three tests under the same conditions was 0.6. In consideration of the standard deviation, a significant difference in permeation distance was recognized between the coal A and coal C having substantially the same maximum fluidity.
  • the coal A and coal F were pulverized so that the ratio of particles having a particle size of less than 1 mm was 100 mass%, the ratio of particles having a particle size of less than 3 mm was 100 mass%, and the ratio of particles having a particle size of less than 6 mm was 100 mass%.
  • Coals other than the coal A and coal F were pulverized so that the ratio of particles having a particle size of less than 3 mm was 100 mass%.
  • Six different coal blends shown in Table 2 were produced using these coals.
  • Table 2 also shows the weighted average permeation distance of the coal blends including coals other than the A coal and F coal, that is, the weighted average permeation distance of coals which are included in the coal blends and whose log MF is less than 3.0.
  • the weighted average permeation distance of coal blends not including the A coal in the coal blends A1 to A3 is 4.7 mm whereas the permeation distance of the A coal is 8.0 mm, which is less than two times the weighted average permeation distance. Therefore, the A coal does not satisfy the ranges (C) and (D).
  • the weighted average permeation distance of coal blends not including the F coal in the coal blends F1 to F3 is 5.0 mm whereas the permeation distance of the F coal is 19.5 mm, which is two times or more the weighted average permeation distance. Therefore, the F coal satisfies the range (C) and also obviously satisfies the range (D).
  • Figs. 10 and 11 show the respective positional relationships between the above ranges (A) and (B) and the permeation distance and maximum fluidity of the caking additive used in this Example, the positional relationships being investigated based on the formulae above. As shown in Figs. 10 and 11 , the F coal satisfies both the ranges (A) and (B).
  • the moisture of all the coal blends shown in Table 2 was adjusted to be 8 mass%. Sixteen kilograms of each of the coal blends was charged into a carbonization can at a bulk density of 750 kg/m 3 and a weight of 10 kg was placed thereon. The coal blend was carbonized in an electric oven whose oven wall temperature was 1050°C for six hours. The carbonization can was taken out of the electric oven and cooled using nitrogen to obtain coke. The mass content of coke having a particle size of 15 mm or more after 150 revolutions at 15 rpm was measured in conformity with the drum strength test method of JIS K 2151. The coke strength of the obtained coke was calculated as drum strength DI 150/15, which was the mass ratio between before and after the revolutions. The CSR (coke strength after reaction with CO 2 measured in conformity with ISO 18894) and the micro strength (MSI +65) were also measured.
  • Table 2 also shows the measurement results of the drum strength.
  • Fig. 12 shows the relationship between the drum strength and the maximum particle size of the coal A and coal F. It has been confirmed that the coal blend obtained by blending the coal F that satisfies the ranges (A) to (D) has lower strength than the coal blend obtained by blending the coal A that does not satisfy the ranges (A) to (D). Therefore, it has been confirmed that the permeation distance measured in the present invention is a factor that affects the strength and cannot be explained using known factors.
  • the strength of any coal blend obtained by blending the coal A that does not satisfy the ranges (A) to (D) and the coal F that satisfies the ranges (A) to (D) is improved by decreasing the particle size of the coals.
  • the strength of the coal blend obtained by blending the coal F that satisfies the ranges (A) to (D) is considerably improved by decreasing the particle size of the coal.
  • the decrease in the strength can be suppressed by performing blending after the particle size of the coal F is decreased to a particle size smaller than that of coals that do not satisfy the ranges (A) to (D) (coal blend F1).
  • the maximum particle size or average particle size of the coals may be decreased.
  • the content of particles whose particle size is larger than a particular sieve opening may be decreased (that is, the content of particles whose particle size is smaller than a particular sieve opening is increased).
  • the particle size of a coal blend is generally controlled using the mass ratio of oversize or undersize relative to the total mass when the coal blend is passed through a sieve with a predetermined opening. Therefore, it is difficult to adjust the particle size of each brand that constitutes the coal blend.
  • a coal blend obtained by blending the coals or caking additives that satisfy the ranges (A) to (D) is carbonized in an actual coke oven, an operation in which the particle size of all the coals or caking additives that constitute the coal blend is decreased is believed to be a practical and effective operation.
  • the inventors of the present invention investigated the relationship between the coke strength and the ratio of coals having a particle size of 6 mm or more in the coal blend by carbonizing the coal blends produced by variously changing the blending ratio of the coals or caking additives that satisfy the ranges (A) to (D) and measuring the drum strength DI 150/15 serving as the coke strength after carbonization.
  • Table 3 shows the average properties of the coal blends used, the carbonization temperature, and the coke temperature at the center of coke oven chamber after carbonization. The ranges of fluctuation in the average properties of a coal blend, the carbonization temperature, and the coke temperature at the center of coke oven chamber after carbonization were reduced so that the effects of these factors on the coke strength were minimized.
  • Fig. 13 shows the relationship between the coke strength and the ratio of coals having a particle size of 6 mm or more in the coal blend. As shown in Fig. 13 , the following has been confirmed. In the case where the blending ratio of the coals or caking additives that satisfy at least one of the ranges (A) to (D) is relatively high, for example, 8 mass% to 12 mass%, the ratio of particles having a particle size of 6 mm or more increases, which means that the coke strength decreases as the coal particle size increases.
  • the relationship between particle size and strength is determined for each blending ratio and an operation is conducted in accordance with the control value of particle size which is expected to achieve the control value of strength, whereby the decrease in the strength can be suppressed.
  • the coke strength decreased, a large amount of relatively expensive strongly caking coal needed to be blended to increase the strength, which increased the production cost.
  • the decrease in the strength can be suppressed by the control of pretreatment conditions of coals before charged into a coke oven and thus the increase in the cost due to the blending of strongly caking coal can be prevented.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Materials Engineering (AREA)
  • Organic Chemistry (AREA)
  • Coke Industry (AREA)
EP11821997.1A 2010-09-01 2011-08-31 Herstellungsverfahren für hüttenkoks Active EP2612894B1 (de)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
JP2010195619 2010-09-01
PCT/JP2011/070319 WO2012029987A1 (ja) 2010-09-01 2011-08-31 冶金用コークスの製造方法

Publications (3)

Publication Number Publication Date
EP2612894A1 true EP2612894A1 (de) 2013-07-10
EP2612894A4 EP2612894A4 (de) 2017-04-19
EP2612894B1 EP2612894B1 (de) 2018-05-02

Family

ID=45773055

Family Applications (1)

Application Number Title Priority Date Filing Date
EP11821997.1A Active EP2612894B1 (de) 2010-09-01 2011-08-31 Herstellungsverfahren für hüttenkoks

Country Status (5)

Country Link
EP (1) EP2612894B1 (de)
JP (1) JP5152378B2 (de)
KR (1) KR101461838B1 (de)
CN (1) CN103180414B (de)
WO (1) WO2012029987A1 (de)

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP2821774A4 (de) * 2012-02-29 2015-03-11 Jfe Steel Corp Verfahren zur herstellung von kohle bei der verwendung zur herstellung von koks
CN104419434A (zh) * 2013-09-05 2015-03-18 鞍钢股份有限公司 一种烧结用半焦的制造方法
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

Families Citing this family (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2015086301A (ja) * 2013-10-31 2015-05-07 Ｊｆｅスチール株式会社 コークスの製造方法
CN106133116A (zh) * 2014-03-28 2016-11-16 杰富意钢铁株式会社 煤混合物、煤混合物的制造方法、以及焦炭的制造方法
JP6590155B2 (ja) * 2014-08-15 2019-10-16 Ｊｆｅスチール株式会社 冶金用コークスおよびその製造方法
KR102516994B1 (ko) * 2014-12-31 2023-03-31 선코크 테크놀러지 앤드 디벨로프먼트 엘엘씨 코킹 재료의 다중 모달 베드
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
AU2021326589B2 (en) * 2020-08-17 2024-01-11 Jfe Steel Corporation Method for preparing coal or caking additive and method for producing coke
JP7255766B1 (ja) * 2021-12-09 2023-04-11 Ｊｆｅスチール株式会社 石炭の粉砕方法および粉砕設備
WO2023106090A1 (ja) * 2021-12-09 2023-06-15 Ｊｆｅスチール株式会社 石炭の粉砕方法および粉砕設備

Family Cites Families (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1133716C (zh) * 1998-07-29 2004-01-07 川崎制铁株式会社 冶金用焦炭的制造方法
JP4048756B2 (ja) * 2001-10-19 2008-02-20 住友金属工業株式会社 品質を均一化したコークスの製造方法
JP2007262296A (ja) * 2006-03-29 2007-10-11 Jfe Steel Kk 冶金用コークスの製造方法
CN100480694C (zh) * 2006-07-06 2009-04-22 西北工业大学 真空负压浸渗制备金属基复合材料渗流特性测量方法
JP2010043196A (ja) * 2008-08-13 2010-02-25 Jfe Steel Corp 高強度コークスの製造方法
JP2010190761A (ja) * 2009-02-19 2010-09-02 Jfe Steel Corp 石炭の軟化溶融特性評価方法

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
See references of WO2012029987A1 *

Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP2821774A4 (de) * 2012-02-29 2015-03-11 Jfe Steel Corp Verfahren zur herstellung von kohle bei der verwendung zur herstellung von koks
EP2977429A1 (de) * 2012-02-29 2016-01-27 JFE Steel Corporation Verfahren zur herstellung von kohle zur koksherstellung
US9708558B2 (en) 2012-02-29 2017-07-18 Jfe Steel Corporation Method for preparing coal for coke making
CN104419434A (zh) * 2013-09-05 2015-03-18 鞍钢股份有限公司 一种烧结用半焦的制造方法
CN104419434B (zh) * 2013-09-05 2017-04-26 鞍钢股份有限公司 一种烧结用半焦的制造方法
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

Also Published As

Publication number Publication date
EP2612894A4 (de) 2017-04-19
KR101461838B1 (ko) 2014-11-13
JP5152378B2 (ja) 2013-02-27
KR20130081702A (ko) 2013-07-17
JP2012072388A (ja) 2012-04-12
CN103180414A (zh) 2013-06-26
WO2012029987A1 (ja) 2012-03-08
EP2612894B1 (de) 2018-05-02
CN103180414B (zh) 2014-12-17

Similar Documents

Publication Publication Date Title
EP2612894B1 (de) Herstellungsverfahren für hüttenkoks
EP2613136B1 (de) Verfahren zur auswertung von wärmeplastizitäten von kohle und anbackende zusatzstoffe sowie verfahren zur herstellung von koks
KR101451050B1 (ko) 야금용 코크스의 제조 방법
EP3124575B1 (de) Verfahren zur vorbereitung von kohle zur herstellung von koks
JP6056157B2 (ja) コークス用配合炭組成決定方法及びコークス製造方法
JP5062379B1 (ja) コークスの製造方法
JP5067495B2 (ja) 冶金用コークスの製造方法

Legal Events

Date Code Title Description
PUAI Public reference made under article 153(3) epc to a published international application that has entered the european phase

Free format text: ORIGINAL CODE: 0009012

17P Request for examination filed

Effective date: 20130315

AK Designated contracting states

Kind code of ref document: A1

Designated state(s): AL AT BE BG CH CY CZ DE DK EE ES FI FR GB GR HR HU IE IS IT LI LT LU LV MC MK MT NL NO PL PT RO RS SE SI SK SM TR

DAX Request for extension of the european patent (deleted)
RA4 Supplementary search report drawn up and despatched (corrected)

Effective date: 20170317

RIC1 Information provided on ipc code assigned before grant

Ipc: C10B 57/04 20060101AFI20170313BHEP

Ipc: C10B 57/08 20060101ALI20170313BHEP

GRAP Despatch of communication of intention to grant a patent

Free format text: ORIGINAL CODE: EPIDOSNIGR1

INTG Intention to grant announced

Effective date: 20180103

GRAS Grant fee paid

Free format text: ORIGINAL CODE: EPIDOSNIGR3

GRAA (expected) grant

Free format text: ORIGINAL CODE: 0009210

AK Designated contracting states

Kind code of ref document: B1

Designated state(s): AL AT BE BG CH CY CZ DE DK EE ES FI FR GB GR HR HU IE IS IT LI LT LU LV MC MK MT NL NO PL PT RO RS SE SI SK SM TR

REG Reference to a national code

Ref country code: GB

Ref legal event code: FG4D

REG Reference to a national code

Ref country code: CH

Ref legal event code: EP

Ref country code: AT

Ref legal event code: REF

Ref document number: 995240

Country of ref document: AT

Kind code of ref document: T

Effective date: 20180515

REG Reference to a national code

Ref country code: DE

Ref legal event code: R096

Ref document number: 602011048109

Country of ref document: DE

Ref country code: IE

Ref legal event code: FG4D

REG Reference to a national code

Ref country code: FR

Ref legal event code: PLFP

Year of fee payment: 8

REG Reference to a national code

Ref country code: NL

Ref legal event code: MP

Effective date: 20180502

REG Reference to a national code

Ref country code: LT

Ref legal event code: MG4D

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: SE

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20180502

Ref country code: ES

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20180502

Ref country code: BG

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20180802

Ref country code: FI

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20180502

Ref country code: LT

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20180502

Ref country code: NO

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20180802

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: HR

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20180502

Ref country code: GR

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20180803

Ref country code: NL

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20180502

Ref country code: LV

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20180502

Ref country code: RS

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20180502

REG Reference to a national code

Ref country code: AT

Ref legal event code: MK05

Ref document number: 995240

Country of ref document: AT

Kind code of ref document: T

Effective date: 20180502

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: RO

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20180502

Ref country code: CZ

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20180502

Ref country code: EE

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20180502

Ref country code: PL

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20180502

Ref country code: AT

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20180502

Ref country code: SK

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20180502

Ref country code: DK

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20180502

REG Reference to a national code

Ref country code: DE

Ref legal event code: R097

Ref document number: 602011048109

Country of ref document: DE

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: IT

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20180502

Ref country code: SM

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20180502

PLBE No opposition filed within time limit

Free format text: ORIGINAL CODE: 0009261

STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: NO OPPOSITION FILED WITHIN TIME LIMIT

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: MC

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20180502

REG Reference to a national code

Ref country code: CH

Ref legal event code: PL

26N No opposition filed

Effective date: 20190205

GBPC Gb: european patent ceased through non-payment of renewal fee

Effective date: 20180831

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: LU

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20180831

Ref country code: LI

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20180831

Ref country code: CH

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20180831

REG Reference to a national code

Ref country code: BE

Ref legal event code: MM

Effective date: 20180831

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: SI

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20180502

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: BE

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20180831

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: GB

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20180831

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: AL

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20180502

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: MT

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20180831

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: TR

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20180502

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: HU

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT; INVALID AB INITIO

Effective date: 20110831

Ref country code: PT

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20180502

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: CY

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20180502

Ref country code: IE

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20180831

Ref country code: MK

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20180502

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: IS

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20180902

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: FR

Payment date: 20230703

Year of fee payment: 13

Ref country code: DE

Payment date: 20230705

Year of fee payment: 13