WO2013145678A1 - 石炭の配合方法及び配合炭、並びに、コークス製造方法 - Google Patents
石炭の配合方法及び配合炭、並びに、コークス製造方法 Download PDFInfo
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- WO2013145678A1 WO2013145678A1 PCT/JP2013/001980 JP2013001980W WO2013145678A1 WO 2013145678 A1 WO2013145678 A1 WO 2013145678A1 JP 2013001980 W JP2013001980 W JP 2013001980W WO 2013145678 A1 WO2013145678 A1 WO 2013145678A1
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- coal
- surface tension
- coke
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- 239000000571 coke Substances 0.000 title claims abstract description 216
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Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
- C10L9/00—Treating solid fuels to improve their combustion
- C10L9/10—Treating solid fuels to improve their combustion by using additives
-
- 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
- C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
- C10L5/00—Solid fuels
- C10L5/02—Solid fuels such as briquettes consisting mainly of carbonaceous materials of mineral or non-mineral origin
- C10L5/04—Raw material of mineral origin to be used; Pretreatment thereof
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
- C10L9/00—Treating solid fuels to improve their combustion
-
- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N13/00—Investigating surface or boundary effects, e.g. wetting power; Investigating diffusion effects; Analysing materials by determining surface, boundary, or diffusion effects
-
- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N33/00—Investigating or analysing materials by specific methods not covered by groups G01N1/00 - G01N31/00
- G01N33/22—Fuels; Explosives
- G01N33/222—Solid fuels, e.g. coal
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
- C10L2290/00—Fuel preparation or upgrading, processes or apparatus therefore, comprising specific process steps or apparatus units
- C10L2290/24—Mixing, stirring of fuel components
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
- C10L2290/00—Fuel preparation or upgrading, processes or apparatus therefore, comprising specific process steps or apparatus units
- C10L2290/60—Measuring or analysing fractions, components or impurities or process conditions during preparation or upgrading of a fuel
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
- C10L2300/00—Mixture of two or more additives covered by the same group of C10L1/00 - C10L1/308
- C10L2300/20—Mixture of two components
Definitions
- the present invention relates to a method for blending coal as a raw material for coke for blast furnace with high strength, a blended coal blended by the blending method, and a method for producing coke produced from the blended coal.
- Blast furnace coke is used in the blast furnace as a reducing material, a heat source, and a support material for maintaining air permeability.
- high strength is required to realize stable operation under the operation of a low reducing material ratio.
- Coke production is oriented.
- When producing coke for blast furnace usually, coal blended with multiple brands (2 to 20 brands) of coal is used. For this reason, conventionally, the strength of coke produced using blended coal as a raw material is used.
- Estimation methods have been studied. For example, the following methods (a) to (c) are known.
- JP 2002-294250 A JP-A-9-255966
- the method (b) focuses on the fluidity and viscosity of coal, and eventually uses an index that improves the detection sensitivity of the maximum fluidity (MF).
- the problem arises. Furthermore, there is a problem that the measuring apparatus is complicated and not a simple method.
- the present invention has been made to solve such problems, and the object of the present invention is to increase the strength of coke produced using blended coal as a raw material by using as an index physical properties that have not been considered in the past. This is to provide a coal blending method capable of suppressing the increase in raw material cost of blended coal and increasing the coke strength. Another object of the present invention is to provide a blended coal blended by this blending method and a method for producing coke by dry distillation of the blended coal.
- the gist of the present invention for solving the above problems is as follows.
- [1] A method for blending coal for producing coke obtained by blending two or more brands of coal, and heating each of the brands by cooling to a temperature in the range of 350 to 800 ° C.
- [2] Each of the two or more kinds of assumed coals obtained by heating and cooling to a temperature in the range of 350 to 800 ° C., assuming that the two or more kinds of coal and the blending ratio of the coals are assumed in advance.
- a surface tension distribution is prepared, and the standard deviation ( ⁇ 1) of the distribution obtained by weighted averaging of the prepared surface tension distribution is calculated by weighting the assumed coal blending ratio, and the standard deviation ( ⁇ 1) is calculated.
- the prepared surface tension distribution is a surface tension distribution of coal obtained by heating to 500 ° C. and then cooling, and the standard deviation ( ⁇ 1) is obtained by changing the presumed coal blending ratio.
- the blending ratio within which the modified standard deviation ( ⁇ 1) falls within the range of 5.5 [mN / m] or less is defined as the coal blending ratio to be determined, and the coal brand assumed in advance is determined.
- the coal to be blended is determined, and the surface tension distribution of each of the coals is the surface tension distribution of coal obtained by heating to 500 ° C. and then cooling, and is obtained by weighted averaging the surface tension distribution.
- the coal blending method according to the above [1], wherein the blending ratio at which the standard deviation ( ⁇ 1) of the distribution falls within the range of 5.5 [mN / m] or less is the determined blending ratio of coal.
- a surface tension distribution is prepared, a standard deviation ( ⁇ 2) of the average value derived from the assumed coal blending ratio and an average value of the prepared surface tension distribution is calculated, and the standard deviation ( ⁇ 2) is calculated as described above.
- the surface tension distribution to be prepared is a surface tension distribution of coal obtained by heating to 500 ° C. and then cooling, and the standard deviation ( ⁇ 2) is obtained by changing the presumed coal blending ratio.
- the blending ratio in which the modified standard deviation ( ⁇ 2) falls within the range of 0.8 [mN / m] or less is set as the blending ratio of the determined coal, and the coal brand assumed in advance is determined.
- the surface tension distribution of each of the coals to be blended is the surface tension distribution of coal obtained by heating to 500 ° C. and then cooling, and the average value derived from the average value of the surface tension distribution
- the coal blending method according to the above [1], wherein the blending ratio at which the standard deviation ( ⁇ 2) falls within a range of 0.8 [mN / m] or less is set as the blending ratio of the coal to be determined.
- the brand of coal constituting the blended coal that is the raw material of coke and the blending ratio of coal of each brand are determined. That is, this invention mix
- the estimation accuracy of the coke strength estimation formula can be increased.
- the increase in the coal property parameter increases the degree of freedom in purchasing the raw material, and the coke strength can be increased without increasing the raw material cost.
- the present invention can be applied to non-finely caking coal with low fluidity, which is difficult to evaluate using a Gisela plastometer, and therefore the degree of freedom of blending raw coal can be further increased.
- FIG. 1 is a diagram showing the principle of surface tension measurement by the film flotation method.
- FIG. 2 is a diagram showing the distribution of surface tension as a frequency distribution curve.
- FIG. 3 is an image diagram of the surface tension distribution of the virtual composite semi-coke.
- FIG. 4 is a diagram for explaining the relationship between the surface tension distribution of the virtual composite semi-coke and the standard deviation of the distribution.
- FIG. 5 is a diagram showing a regression result between the estimated drum strength value and the actually measured drum strength value according to the conventional coke strength estimation method.
- FIG. 6 is a diagram showing a regression result between the estimated drum strength value and the actually measured drum strength value according to the coke strength estimation method of the present invention.
- FIG. 1 is a diagram showing the principle of surface tension measurement by the film flotation method.
- FIG. 2 is a diagram showing the distribution of surface tension as a frequency distribution curve.
- FIG. 3 is an image diagram of the surface tension distribution of the virtual composite semi-coke.
- FIG. 4 is a diagram
- FIG. 7 shows the standard deviation ( ⁇ 1) of the distribution obtained by weighted averaging the surface tension distribution of semi-coke obtained by heat-treating each brand of coal constituting the blended coal with the blending ratio of each coal as a weight. It is a figure which shows the relationship with coke intensity
- FIG. 8 is a diagram showing the relationship between the standard deviation ( ⁇ 2) of the average value of the surface tension distribution of semi-coke obtained by heat-treating each brand of coal constituting the coal blend and the coke strength.
- Coal is softened and melted by carbonization and fused together to produce coke. Considering this phenomenon of fusion, it is considered that the adhesive strength between coal particles has an influence on the coke strength. However, it has not been known what kind of coal physical property affects adhesive strength and how much it affects coke strength. Therefore, the present inventors have clarified the physical properties that affect the adhesion strength between coal particles, and intended to clarify the influence of the physical properties on the coke strength. We focused on interfacial tension.
- Interfacial tension can be considered as free energy existing at the interface, as can be seen from the unit mN / m, and the presence of interfacial tension means that there is free energy that can act as a force at the interface. Means that. If so, it is considered that when the interfacial tension is large, the adhesive interface is easily broken, and when the interfacial tension is small, the adhesive interface is difficult to break. Based on this inference, it is expected that the interfacial tension is used to estimate the adhesive strength.
- the present inventors did not directly measure the interfacial tension, but determined the interfacial tension based on the surface tension of coal obtained by heat-treating the following brands of coal (hereinafter also referred to as “semi-coke” where appropriate).
- the estimation method was adopted, and the method of determining the brand of coal constituting the coal blend and the blending ratio of the coal of the brand using the surface tension of the semi-coke was studied.
- conditions for measuring surface tension suitable for the purpose of coke strength estimation, methods for estimating interfacial tension from surface tension, and their influence on coke strength have not been elucidated.
- semi-coke is coal obtained by heating at a temperature in the range of 350 to 800 ° C. and then cooling.
- the interfacial tension is represented by the surface tension of the substance to be bonded and can be derived from the surface tension of the substance to be bonded.
- the interfacial tension ⁇ AB between the substance A and the substance B can be obtained from the surface tension ⁇ A of the substance A and the surface tension ⁇ B of the substance B.
- ⁇ AB ⁇ A + ⁇ B ⁇ 2 ⁇ ( ⁇ A ⁇ B ) 0.5 (1)
- ⁇ is the interaction coefficient (substance A and substance B).
- the coal heating temperature is the temperature at which the coal is heated and begins to soften and melt, and the coal is bonded and solidified to complete coking. It is appropriate to set the temperature range to the temperature at which the coking is completed, that is, the temperature range of 350 ° C. or higher at which softening and melting starts and up to 800 ° C. where coking is completed. For this reason, semi-coke is preferably obtained by cooling coal after heating it to 350 ° C. or higher in an inert gas while blocking air. At a heating temperature of 350 ° C.
- the temperature particularly contributing to adhesion is the temperature at the time of softening and melting, but the softening and melting temperature range of coal used for coke production is 350 to 550 ° C. Is considered to be determined around 500 ° C., and the heating temperature is preferably 480 to 520 ° C. especially around 500 ° C.
- the reason for cooling coal in inert gas is to suppress surface tension measurement errors. This is because the coal immediately after heating is high in temperature, and when cooled in an oxygen-containing atmosphere, the surface is partially oxidized to cause structural changes, resulting in errors in the measured surface tension.
- the inert gas a rare gas such as helium or argon gas or a nitrogen gas can be used, and a nitrogen gas is usually used.
- the heated coal is cooled rapidly.
- the reason for rapidly cooling the heated coal is to maintain the molecular structure in the softened and melted state, and it is preferable to cool at a cooling rate of 10 ° C./sec or more, which is considered to be the molecular structure is not changed.
- an inert gas such as liquid nitrogen, ice water, water, or nitrogen gas
- gas cooling takes time to cool down to the inside of coal, and the cooling rate is distributed.
- the container holding coal may be immersed in liquid nitrogen.
- the heat treatment method applied to coal in the present invention is as follows.
- (A) The coal is pulverized. In this coal pulverization, it is desirable to pulverize the coal to 250 ⁇ m or less, which is the pulverization particle size in the industrial analysis of coal described in JIS M8812.
- (B) The coal pulverized in step (a) is heated at an appropriate heating rate. It is desirable to determine the heating rate according to the heating rate when the coke to be evaluated by the interfacial tension is manufactured. What is necessary is just to heat coal to the temperature within the range of 350-800 degreeC mentioned above.
- (C) The coal heated in the step (b) is cooled with liquid nitrogen. In this cooling, it is desirable to quench rapidly by the above-described method.
- semi-coke is defined as coal obtained by heating at a temperature in the range of 350 to 800 ° C. and then cooling.
- Measurement methods of surface tension include sessile drop method, capillary rise method, maximum bubble pressure method, hanging drop method, liquid weight method, plate method (Wilhelmy method), expansion / contraction method, ring method, sliding method, retention time measurement method
- a film floatation method is known. Coal is composed of various molecular structures, and its surface tension is expected to be non-uniform, so use the film flotation method (see Non-Patent Document 2) that can be expected to evaluate the surface tension distribution. Is particularly preferred.
- the pulverized sample particle 1 is dropped from the gas phase 2 onto the surface of the liquid 3 and the sample particle 1 is immersed in the liquid 3 (in the case of the right sample particle in FIG. 1).
- This is a technique applying the idea that the surface tension of the sample particles and the surface tension of the liquid are equal when the contact angle is approximately equal to 0 °.
- An arrow 4 in FIG. 1 indicates the surface tension of the sample particle 1.
- the surface tension distribution as shown in FIG. 2 is obtained by dropping the sample particles into various liquids having different surface tensions, obtaining the mass ratio of the suspended sample particles with respect to the respective liquids, and expressing the result in a frequency distribution curve. Can be obtained.
- the film / flotation method can measure the surface tension of a solid, the surface tension of any coal can be measured regardless of the type of coal, such as strongly caking coal, non-slightly caking coal, or anthracite coal.
- the surface tension directly obtained by the film / flotation method is the critical surface tension (liquid surface tension when the contact angle is 0 °), and the surface tension of coal is obtained from this critical surface tension as follows. be able to.
- the surface tension ⁇ L of the liquid, the surface tension ⁇ S of the solid (coal or semi-coke), and the interfacial tension ⁇ SL between the liquid and the solid have the following relational expressions:
- ⁇ SL ⁇ S + ⁇ L ⁇ 2 ⁇ ( ⁇ S ⁇ L ) 0.5
- ⁇ interaction coefficient (solid and liquid).
- the Young's equation the following relationship is established between the surface tension ⁇ L of the liquid, the surface tension ⁇ S of the solid (coal or semi-coke), and the interfacial tension ⁇ SL between the liquid and the solid. Also holds.
- the structure of the liquid used in the film flotation method is significantly different from that of coal and semi-coke, but the difference in structure between coal brands is considered to be small compared to the difference. Since the interaction coefficient ⁇ is a parameter affected by the mutual molecular structure, the surface tension ⁇ S is expressed only by the critical surface tension ⁇ C when the interaction coefficient ⁇ is assumed to be constant regardless of the coal brand. Therefore, it can be said that the surface tension of coal and semi-coke can be evaluated only by the critical surface tension.
- the value of the interaction coefficient ⁇ in coal or semi-coke is estimated to be close to 1
- the value of the surface tension ⁇ S of coal or semi-coke is equal to the critical surface tension ⁇ C. I think.
- the liquid used in the film flotation method has a surface tension value in the range of 20 to 73 mN / m of coal at normal temperature and softened and melted. Use it.
- an organic solvent such as ethanol, methanol, propanol, tert-butanol, or acetone
- a liquid having a surface tension of 20 to 73 mN / m can be prepared from an aqueous solution of these organic solvents.
- the particle size of the sample for measuring the surface tension it is desirable to measure the surface tension when the contact angle is almost equal to 0 ° from the above-mentioned measurement principle, and the contact angle increases as the particle size of the crushed sample particles increases. For this reason, the smaller the particle size, the better.
- the particle size of the sample particles is less than 53 ⁇ m, the sample particles are likely to agglomerate.
- the film flotation method uses the floating phenomenon of a substance (sample particle) due to surface tension, it is necessary to perform measurement under conditions where the gravity of the substance can be ignored. This is because if the density of the substance is high, the contact angle becomes large due to the influence of gravity. Therefore, it is desirable to measure a substance having a density of 2000 kg / m 3 or less, which is considered that gravity does not affect the contact angle. Since various types of coal and semi-coke meet this requirement, all types of coal and semi-coke powder, such as strongly caking coal, non-slightly caking coal, and anthracite coal, can be used for film flotation. Can be employed for sample particles, and the surface tension can be measured by that method. Furthermore, additives such as pitch, oil coke, powder coke, dust, waste plastic, and other biomass can be measured in the same manner.
- one example of a process for processing coal is as follows.
- the heating rate in the step (b ′) is set to 3 ° C./min in accordance with the heating rate when coke is produced in the coke oven.
- C ′ The coal heated in step (b ′) is quenched with liquid nitrogen.
- step (D ′) The coal rapidly cooled in step (c ′) is pulverized to a particle size of 150 ⁇ m or less, and the pulverized coal is dried at 120 ° C. for 2 hours in a dry inert gas stream.
- the drying method in the step (d ′) may be any method as long as it can remove moisture adhering to the surface, in addition to the method of heating to 100 to 200 ° C. in an inert gas such as nitrogen or argon. Alternatively, a method of drying under reduced pressure can be employed.
- the average value of the surface tension distribution (average surface tension) , Standard deviation of surface tension distribution, surface tension of peak value of surface tension distribution, two values of maximum surface tension and minimum surface tension of surface tension distribution, distribution function of surface tension distribution, and the like.
- the average value of the surface tension distribution (average value of ⁇ ) is expressed, for example, by the following equation (8).
- ⁇ with an overline average value of surface tension distribution
- ⁇ surface tension
- f ( ⁇ ) frequency of surface tension distribution.
- the standard deviation ( ⁇ ⁇ ) of the surface tension distribution is expressed, for example, by the following equation (9).
- reference numeral 5 is the peak value of the surface tension distribution
- reference numeral 6 is the surface tension distribution
- the minimum surface tension, symbol 7 is the maximum surface tension of the surface tension distribution.
- Examples of the distribution function of the surface tension include distributions similar in shape to the surface tension distribution, such as normal distribution, lognormal distribution, F distribution, chi-square distribution, exponential distribution, gamma distribution, and beta distribution.
- the weight ratio of each simple coal in blended coal is weighted, and each simple semi-coke obtained from each simple coal is weighted.
- the standard deviation ( ⁇ 1) of the distribution obtained by weighted averaging of the surface tension distribution and the average value derived from the average value of the surface tension distribution of each plain semi-coke and the blending ratio of each simple coal Standard deviation ( ⁇ 2) is adopted.
- the reason for measuring the surface tension of plain semi-coke rather than plain coal is that the surface tension of coal correlates with the strength of coke and can be used to estimate coke strength. This is because it is more correlated with the strength of coke than the surface tension of coal, and it is preferable to use the surface tension of semi-coke for estimating the coke strength rather than the surface tension of coal.
- the coal blending method of the present invention includes the following steps.
- the present inventors have found that the aforementioned standard deviation ( ⁇ 1) and standard deviation ( ⁇ 2) calculated from the surface tension of semi-coke are related to the strength of coke produced by dry distillation of the coal blend. Thus, the present invention using these as management indices has been derived.
- Step (I) preferably further comprises the following steps (Ia) to (Id).
- Step (Ic) The hypothesis that would have been obtained from the virtual blended coal by weighting and averaging the surface tension distribution prepared in the step (Ib) with the coal blending rate assumed in the step (Ia) as a weight Obtain the surface tension distribution of composite semi-coke.
- Step (Ia) Prior to step (II) (preliminary), the brand of the coal composing the blended coal is appropriately selected (assumed), and further, the blending ratio of the coal is assumed, and the virtual blended coal is assumed. . Below, the case where a combination coal is comprised from four types of coal is demonstrated.
- FIG. 3 (a) shows the surface tension distribution of four simple semi-cokes obtained from four brands of coal, and the reference numeral 8 (8a, 8b, 8c, 8d) denotes the single semi-coke of each plain.
- the surface tension distribution curve is shown. Preparing this surface tension distribution means that the surface tension of a simple semi-coke is measured by the above-mentioned film flotation method and prepared as a surface tension distribution. It includes not only the creation of a surface tension distribution based on the surface tension measured by a third party, but also the acquisition of the surface tension distribution from a third party.
- Step (Ic) A weighted average distribution of the surface tension distribution of semi-coke obtained from each coal is obtained by weighting the blending ratio of each coal assumed in step (Ia). This distribution corresponds to the surface tension distribution of the virtual composite semi-coke assumed to be obtained by heat-treating the virtual coal blend assumed in step (Ia).
- FIG. 3B shows the surface tension distribution of the virtual composite semi-coke obtained from the surface tension distribution of each simple semi-coke shown in FIG.
- the weight of the surface tension distribution of each single semi-coke is weighted by the blending ratio of each single coal.
- the distribution of the average value is interpreted as the surface tension distribution of the blended coal in the softened and melted state.
- the standard deviation ( ⁇ 1) of the surface tension distribution of the virtual composite semi-coke can be cited. Since this standard deviation ( ⁇ 1) can be obtained by calculation if the surface tension of plain semi-coke obtained from plain coal is known in advance, it can be a criterion for determining the surface tension distribution of blended coal. Therefore, the present invention is suitable when preparing blended coal composed of multi-brand coal and estimating the strength of coke produced from the blended coal.
- the standard deviation ( ⁇ 1) is used as a management index, assuming a simplified situation, the conditions under which the bond strength between coals constituting the blended coal is maximized are considered. Specifically, for example, assuming that the blended coal consists of two types of coal and the blending ratio of the coal is 1: 1, the surface tension distribution of semi-coke obtained from these coals is compared. 3 cases of a case where there is a large difference (Condition A), a case where there is a relatively small difference (Condition B), and a case where they are completely equal (Condition C), and the standard deviation ( ⁇ 1) of the virtual composite semi-coke required in each case ).
- FIG. 4 (a) on the left side of FIG. 4 represents the surface tension distribution of two semi-coke under conditions A to C, and (b) on the right side of FIG. 4 shows the two semi-coke in each condition.
- a distribution obtained by weighted averaging the surface tension distribution by 1: 1 is schematically shown.
- 4A to 4C show the cases of conditions A to C.
- condition A the surface tension distribution 10 of semi-coke obtained from coal x is significantly different from the surface tension distribution 11 of semi-coke obtained from coal a, and the distribution 12 obtained by weighted average of these has two peaks. And spread.
- Condition B the difference between the surface tension distribution 10 of semi-coke obtained from coal x and the surface tension distribution 13 of semi-coke obtained from coal b is smaller than in the case of FIG.
- the width of the distribution 14 obtained by weighted average of these is relatively narrow.
- condition C the surface tension distribution 10 of semi-coke obtained from coal x and the surface tension distribution 15 of semi-coke obtained from coal c are the same.
- the width of the distribution 16 obtained by weighted average of these is narrower than the width of the distribution 14 in the condition B.
- the spread of the weighted average distribution is (condition A)> (condition B)> (condition C), and the value of the standard deviation ( ⁇ 1) of the distribution is also (condition A)> (condition B)> (Condition C).
- condition A)> (condition B)> (Condition C) the coal particles constituting the blended coal have a higher probability of coming into contact with particles having different surface tensions in the softened and melted state. Therefore, it is considered that a large number of contact interfaces with high interfacial tension and low adhesive strength are generated in the soft and molten blended coal, and the strength of coke obtained from this blended coal is also lowered. Thereby, it is desirable to obtain the blending ratio of coal so that the spread of the distribution obtained by weighted averaging of the surface tension distribution of the simple semi-coke is small, that is, the standard deviation ( ⁇ 1) is small. Recognize.
- Step (Id) In the step (Id), the standard deviation ( ⁇ 1) of the surface tension distribution of the virtual composite semi-coke determined in the step (Ic) is changed by changing the coal blending rate assumed in the step (Ia). Steps (Ia) to (Ic) are performed once or a plurality of times to obtain a blending ratio such that the standard deviation ( ⁇ 1) is within a predetermined value or less. Two or more types of coal assumed in the step (Ia) and the obtained blending ratio are determined as the brand of each simple coal and the blending ratio of each simple coal in the above step (I).
- the step (Ib) semi-coke obtained by heat treatment up to 500 ° C. is used, and the above steps (Ia) to (Ic) are performed once or a plurality of times, and the standard deviation ( ⁇ 1) is 5.5 [mN / M]
- the blending ratio that falls within the following range is preferably the blending ratio of coal to be determined. That is, the surface tension distribution prepared in the step (Ib) is a semi-coke surface tension distribution obtained by heat treatment up to 500 ° C. It is preferable that the blending ratio at which the standard deviation ( ⁇ 1) calculated based on the prepared surface tension distribution is in the range of 5.5 or less is the determined coal blending ratio. Since the standard deviation ( ⁇ 1) only needs to have a value, it may be larger than 0.
- the step ((1) calculated based on a plurality of semi-cokes obtained by heat treatment up to 500 ° C. is preferably 5.5 [mN / m] or less.
- the blending ratio of each simple coal in I) is determined.
- the step (I) preferably further comprises the following steps (Ie) and (If).
- Step (Ie) First, two or more types of coal to be blended are determined. There exists semi-coke obtained from these coals, and the semi-coke has a surface tension distribution. This surface tension distribution corresponds to the surface tension distribution of coal obtained by heating to 500 ° C. and then cooling, and it is not always necessary to heat treat coal to obtain semi-coke and to measure the surface tension of the semi-coke. Absent.
- Step (If) The standard deviation ( ⁇ 1) of the distribution obtained by weighted averaging the surface tension distribution of the semi-coke obtained from each of the coals determined in the step (Ie) is calculated, and the standard deviation ( ⁇ 1) is 5.5 [mN / m]
- the blending ratio within the following range is defined as the blending ratio of coal to be determined. That is, in step (If), first, the blending ratio of each of the coals determined in step (Ie) is set to an appropriate value, and the appropriate value is weighted, and the surface tension distribution of semi-coke obtained from the determined coal The standard deviation ( ⁇ 1) of the distribution obtained by weighted averaging is calculated.
- the blending ratio at which the standard deviation ( ⁇ 1) is 5.5 [mN / m] or less is the blending ratio of each simple coal determined in the step (I).
- the coal defined by process (Ie) is each simple coal determined by process (I).
- Step (I) In the second embodiment, in the step (I), the following steps (Ic ′) and (Id ′) are preferably performed after the steps (Ia) and (Ib) described above.
- the average value of the surface tension distribution of the semi-coke obtained in the step (Ib) means the average surface tension of the semi-coke.
- the steps (Ic ′) and (Id ′) will be described in detail.
- Step (Ic ′) To describe the example of FIG. 3, it is calculated 8a in FIG. 3 (a), 8b, 8c, average gamma 8a in each of the surface tension distribution 8d, gamma 8b, gamma 8c, the gamma 8d.
- the standard deviation ( ⁇ 2) Is calculated.
- the standard deviation ( ⁇ 2) is calculated by the following formula (10) as the square root of the variance.
- Step (Id ′) In step (Id ′), steps (Ia) to (Ic) are changed so that the standard deviation ( ⁇ 2) obtained in step (Ic ′) is changed by changing the coal blending rate assumed in step (Ia). ') Is performed once or a plurality of times to obtain a blending ratio such that the standard deviation ( ⁇ 2) is within a predetermined value or less. Next, two or more types of coal assumed in the step (Ia) and the obtained blending ratio are determined as the coal brand and the blending ratio of the branded coal in the step (I).
- the semi-coke obtained by heat treatment up to 500 ° C. in the step (Ib) is used, and the steps (Ia) to (Ic ′) described above are performed once or a plurality of times. It is preferable that the blending ratio at which the standard deviation ( ⁇ 2) falls within the range of 0.8 [mN / m] or less is determined as the coal blending ratio to be determined. That is, the surface tension distribution prepared in the step (Ib) is a semi-coke surface tension distribution obtained by heat treatment up to 500 ° C.
- the blending ratio in which the standard deviation ( ⁇ 2) calculated based on the prepared surface tension distribution is in the range of 0.8 or less becomes the determined blending ratio of coal. Note that the standard deviation ( ⁇ 2) only needs to have a value, and therefore should be larger than zero.
- the process ((2) is preferably performed by utilizing the point that the standard deviation ( ⁇ 2) calculated based on a plurality of semi-coke obtained by heat treatment up to 500 ° C. is 0.8 [mN / m] or less.
- the blending ratio of each simple coal in I) is determined.
- the step (I) further includes a step (Ie) of another form of the first embodiment and the following (If ′).
- Step (If ′) The standard deviation ( ⁇ 2) of the distribution obtained by weighted averaging the surface tension distribution of the semi-coke obtained from each of the coals determined in the step (Ie) is calculated, and the standard deviation ( ⁇ 2) is 0.8 [mN / m]
- the blending ratio within the following range is defined as the blending ratio of coal to be determined. That is, in step (If ′), first, the blending ratio of each of the coals determined in step (Ie) is set to an appropriate value, and the appropriate value is used as a weight to determine the surface tension of semi-coke obtained from the determined coal. A standard deviation ( ⁇ 2) of the distribution obtained by weighted averaging of the distribution is calculated.
- the blending ratio at which the standard deviation ( ⁇ 2) is 0.8 [mN / m] or less is the blending ratio of each simple coal determined in the step (I).
- the coal defined by process (Ie) is each simple coal determined by process (I).
- the surface tension distribution of the coal or semi-coke obtained from the coal is measured, and the surface tension of the semi-coke, for example, the standard deviation of the surface tension distribution of the virtual composite semi-coke ( ⁇ 1 ) And standard deviation ( ⁇ 2) of the average surface tension of semi-coke is introduced as a parameter of the coke strength estimation formula used for blending control, thereby improving the accuracy of the coke strength estimation formula and estimating with the conventional coal property parameters
- the coal that cannot be evaluated can be evaluated, and the coke strength can be improved.
- the standard deviation of the surface tension distribution takes a certain optimum value, it is possible to improve the coke strength that cannot be estimated by the conventional coal property parameters.
- the present inventors investigated the correlation between the surface tension of semi-coke obtained from coal and the conventional coal property parameter, but the vitrinite average maximum reflectance (the average value of Ro) used as the conventional coal property parameter. ), Maximum fluidity (MF), inert amount (TI), average reflectance distribution ( ⁇ Ro), ash content (Ash), elemental analysis results, etc., and the surface tension was not significantly correlated. Therefore, the surface tension of semi-coke is a completely new independent parameter.
- the method of the present invention can be applied not only to the blending of ordinary coal but also to the blending of coal.
- additives such as non-coking coal, anthracite, pitch, oil coke, dust coke, dust, waste plastics, and other biomass may be bonded to softened and melted coal.
- the method of the present invention can be applied.
- Coke was produced using simple coal and blended coal, and its strength was measured.
- Five types of coal (A to E) are used as simple coal, and the blending ratio of the two kinds selected from simple coal is 75%: 25%, 50%: Three types of 50% and 25%: 75% were blended.
- the brands to be blended were selected so that the difference in the surface tension of semi-coke obtained from each plain coal was different.
- coal is pulverized to a particle size of 200 ⁇ m or less and charged into a graphite vessel at 3 ° C./min in an inert gas (nitrogen) atmosphere. After heating to 500 ° C. with an electric furnace and immersing the whole vessel in liquid nitrogen and rapidly cooling to produce semi-coke, it was pulverized to 150 ⁇ m or less and dried at 120 ° C. in a dry inert gas stream for 2 hours.
- the surface tension distribution of the prepared semi-coke was measured by a film flotation method.
- As the liquid used for the surface tension measurement by the film flotation method ethanol and water, which are inexpensive and easy to handle, were used.
- the standard deviation ( ⁇ 1) of the surface tension distribution of the virtual composite semi-coke was used as a management index.
- This standard deviation ( ⁇ 1) is a distribution obtained by a weighted average of the surface tension distribution of each plain semi-coke with the blending ratio of each solid coal as a weight (corresponding to the surface tension distribution of the virtual composite semi-coke). Is the standard deviation.
- the strength of the coke was determined by a drum strength test (DI150 / 15). For 5 types of coal (A to E) and 5 types of blended coal (3 types of blending ratio for each combination of coals), 16kg of coal with a grain size of 3mm or less adjusted to 100% by mass and moisture to 8% by mass was packed to a bulk density of 750 kg / m 3 and dry-distilled in an electric furnace. After dry distillation at a furnace wall temperature of 1100 ° C. for 6 hours, nitrogen cooling was performed, and drum strength was measured.
- Drum strength DI150 / 15 is a drum strength obtained by measuring the mass ratio of coke having a particle size of 15 mm or more after charging coke into a predetermined drum and rotating it at a drum rotation speed of 15 rpm by JIS K2151. It is. Table 1 also shows the results of the coal properties and the drum strength test.
- the conventional coke strength estimation formula was derived as follows. Three parameters, vitrinite average maximum reflectance (average value of Ro), Gieseler maximum fluidity (logMF), and inert amount (TI), are adopted as parameters of a conventional coke strength estimation formula.
- these properties of the plain coal shown in Table 1 are calculated as a weighted average with the blending ratio of each coal as a weight, It is set as the representative value of the above properties of each blended coal.
- the coke strength estimation formula for deriving the drum strength using the representative values of the three properties of each blended coal and the measured values of the drum strength as the independent variables was derived from the multiple regression analysis. . Ro and TI were measured according to JIS M8816, and MF was measured according to JIS M8801.
- the coke strength estimation formula of the present invention uses the above-mentioned Ro, log MF, and TI as conventional parameters, and newly adds a standard deviation ( ⁇ 1) to the parameters, and performs multiple regression analysis in the same manner as the derivation of the conventional coke strength estimation formula. Derived by.
- FIG. 5 shows the relationship between the estimated value based on the conventional coke strength estimation equation and the actually measured strength
- FIG. 6 shows the relationship between the estimated value based on the coke strength estimating equation of the present invention and the actually measured strength.
- the correlation coefficient between the estimated value of coke strength and the measured value in FIG. 5 was 0.777, and the correlation coefficient between the estimated value of coke strength and the measured value in FIG. 6 was 0.849. From these results, it is clear that the surface tension of coal is measured and the accuracy of the coke strength estimation formula is improved by using the surface tension as an index, and high strength coke that cannot be estimated by conventional coal property parameters can be produced. It was.
- the Ro and log MF of the blended coal in Table 2 are average values obtained by weighted averaging of the property characteristics of plain coal with the blending ratio of each coal as a weight.
- the standard deviation ( ⁇ 1) in Table 2 is a standard deviation of a distribution obtained by weighted average of the surface tension distribution of semi-coke obtained from each coal with the blending ratio of each coal as a weight. This semi-coke is obtained by heating each coal to 500 ° C. and then cooling.
- the standard deviation ( ⁇ 2) in Table 2 is a standard deviation obtained by the equation (10) from the average value of the surface tension distribution of semi-coke obtained from each coal and the blending ratio of each coal.
- CSR is the strength after CO 2 reaction of coke obtained according to ISO18894.
- FIG. 7 and FIG. 8 show the relationship between the coke strength DI 150/15 and the standard deviation ( ⁇ 1 and ⁇ 2), respectively. 7 and 8, it can be seen that when the distribution of surface tension is wide (standard deviation ( ⁇ 1 and ⁇ 2) is large), the coke strength decreases. In these blended coals, since the average Ro and logMF of the blended coal were adjusted to be constant, the coke strength is estimated to be the same value based on the conventional blending theory. However, from the results of this example, it is clear that the surface tension and its distribution influence the coke strength in addition to the conventional parameters. It can also be seen that if the surface tension distribution ⁇ is less than a certain value, the influence on the coke strength is reduced.
- the standard deviation ( ⁇ 1) is preferably 5.5 [mN / m] or less
- the standard deviation ( ⁇ 2) is preferably 0.8 [mN / m] or less.
- the standard deviation ⁇ 1 includes the standard deviation of the surface tension distribution of simple semi-coke. This is because the smallest value of the above becomes the lower limit value, and the influence of the surface tension distribution of the virtual composite semi-coke on the coke strength becomes smaller as the standard deviation ⁇ 1 approaches the lower limit value.
- the standard deviation ⁇ 2 the smaller the standard deviation ⁇ 2, the closer to the surface tension distribution of the semi-coke obtained from plain coal. Therefore, when the influence of the surface tension distribution of the virtual composite semi-coke on the coke strength decreases. Conceivable.
- the method of the present invention is particularly effective if the heat treatment temperature when preparing semi-coke is in the range of 350 ° C. to 800 ° C. It is. In consideration of the dependency of the surface tension on the heat treatment temperature, it is desirable to evaluate the surface tension by treating all coals used for blending at substantially the same heat treatment temperature.
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Abstract
Description
石炭の性状としてビトリニット平均最大反射率(Roの平均値)とギーセラープラストメーターの最高流動度(MF)との2つの指標をパラメータとしてコークスの強度を推定する配合理論であり、現在一般的に使用されている。
NMRにより測定した石炭の粘結成分量を示す指標と石炭の粘結成分の粘度を示す指標とを用いたコークス強度推定法である(例えば、特許文献1を参照)。
上記の(イ)、(ロ)などで用いている通常のコークス強度推定式では、複数の銘柄の石炭が配合された配合炭を乾留して得られるコークスの強度は、配合された各石炭の物性値の加重平均値で推定される。しかし、単一銘柄の石炭(以下、適宜「単味炭」とも呼ぶ)から得られるコークスの強度と、複数の銘柄の石炭から得られるコークスの強度の間には、加成性が成立しない場合があることが知られている。加成性が成立しない理由は石炭間の相互作用によると考えられているが、上記の(イ)及び(ロ)のコークス強度推定式には、相互作用による強度向上ないしは低下効果、つまり配合効果が考慮されていない場合が多い。これに対して、配合効果を推定する方法として、複数の銘柄の石炭からなる配合炭のコークス特性を各石炭の2種類の組み合わせの集合として、そのコークス特性と各単味炭コークス特性の加重平均からのずれを配合効果係数としてコークス強度推定式を作成する方法が知られている(例えば、特許文献2を参照)。配合効果係数は実測または推測して求めることができる。
[1]2種以上の銘柄の石炭を配合して得られる、コークス製造用の石炭の配合方法であって、350~800℃の範囲の温度まで加熱した後冷却して得られる各銘柄の石炭の表面張力を管理指標に用いて、前記石炭の銘柄と該銘柄の石炭の配合率とを決定する石炭の配合方法。
[2]予め、前記2種以上の銘柄の石炭及び該石炭の配合率を仮定し、350~800℃の範囲の温度まで加熱した後冷却して得られる2種以上の仮定した石炭の各々の表面張力分布を準備し、仮定した石炭の配合率を重みにして、準備した表面張力分布を加重平均して求めた分布の標準偏差(σ1)を算出しておき、該標準偏差(σ1)を前記管理指標に用いる上記[1]に記載の石炭の配合方法。
[3]準備される表面張力分布が、500℃まで加熱した後冷却して得られる石炭の表面張力分布であって、予め仮定される石炭の配合率を変更することで前記標準偏差(σ1)を変更し、変更した標準偏差(σ1)が5.5[mN/m]以下の範囲内になる配合率を、決定される石炭の配合率とし、予め仮定される石炭の銘柄を、決定される石炭の銘柄とする上記[2]に記載の石炭の配合方法。
[4]配合される石炭を定め、該石炭の各々の表面張力分布が、500℃まで加熱した後冷却して得られる石炭の表面張力分布であって、前記表面張力分布を加重平均して求まる分布の標準偏差(σ1)が5.5[mN/m]以下の範囲内になる配合率を、決定される石炭の配合率とする上記[1]に記載の石炭の配合方法。
[5]予め、前記2種以上の銘柄の石炭及び該石炭の配合率を仮定し、350~800℃の範囲の温度まで加熱した後冷却して得られる2種以上の仮定した石炭の各々の表面張力分布を準備し、仮定した石炭の配合率と準備した表面張力分布の平均値とから導出される該平均値の標準偏差(σ2)を算出しておき、該標準偏差(σ2)を前記管理指標に用いる上記[1]に記載の石炭の配合方法。
[6]準備される表面張力分布は、500℃まで加熱した後冷却して得られる石炭の表面張力分布であって、予め仮定される石炭の配合率を変更することで前記標準偏差(σ2)を変更し、変更した標準偏差(σ2)が0.8[mN/m]以下の範囲内になる配合率を、決定される石炭の配合率とし、予め仮定される石炭の銘柄を、決定される石炭の銘柄とする上記[5]に記載の石炭の配合方法。
[7]配合される石炭の各々の表面張力分布が、500℃まで加熱した後冷却して得られる石炭の表面張力分布であって、前記表面張力分布の平均値から導出される該平均値の標準偏差(σ2)が、0.8[mN/m]以下の範囲内になる配合率を、決定される石炭の配合率とする上記[1]に記載の石炭の配合方法。
[8]前記表面張力は、フィルム・フローテーション法によって測定される上記[1]~[7]のいずれかに記載の石炭の配合方法。
[9]上記[1]~上記[8]のいずれかに記載の石炭の配合方法によって配合された配合炭。
[10]上記[9]に記載の配合炭を乾留してコークスを製造するコークスの製造方法。
γAB=γA+γB-2φ(γAγB)0.5 …(1)
但し、φは、(物質Aと物質Bとの)相互作用係数である。
γAB=(γA 0.5-γB 0.5)2 …(2)
この(2)式に基づくと、2種類の物質の表面張力の差が大きいほど、物質間の界面張力は大きくなる。
(A)石炭は均質な物質ではなく、同じ銘柄の石炭でも、局部的に分子構造が異なるので、表面張力の値は同じではない。
(B)石炭が乾留によってコークスになる過程では、化学変化が生じ、表面張力をはじめとする物性が変化する。
従って、石炭間の接着強度に及ぼす表面張力の影響を考察する際には、配合に使用する各銘柄の石炭の、表面張力の差の大きさに着目するとともに表面張力の分布や、その加熱による変化を考慮する必要があるといえる。
(a)石炭を粉砕する。この石炭の粉砕では、JIS M8812に記載されている石炭の工業分析における粉砕粒度である250μm以下に石炭を粉砕することが望ましい。
(b)工程(a)で粉砕した石炭を適当な加熱速度で加熱する。界面張力による評価の対象となるコークスが製造されるときの加熱速度に応じて、この加熱速度を決めることが望ましい。前述の350~800℃の範囲内の温度まで石炭を加熱すればよい。
(c)工程(b)で加熱した石炭を液体窒素で冷却する。この冷却では、上述の方法で急冷することが望ましい。
ここで、セミコークスとは、350~800℃の範囲の温度で加熱した後に冷却して得られる石炭と定義する。
γSL=γS+γL-2φ(γSγL)0.5 …(3)
ここで、φ:(固体と液体との)相互作用係数である。
また、ヤング(Young)の式から、液体の表面張力γLと固体(石炭やセミコークス)の表面張力γSと、液体と固体との間の界面張力γSLとには、次の関係式も成立する。
γS=γLcosθ+γSL …(4)
ここで、θ:液体に対する固体の接触角である。
上記(3)式及び(4)式から次の式が導出される。
1+cosθ=2φ(γS/γL)0.5 …(5)
この(5)式にθ=0°、γL=γC(γC:臨界表面張力)を代入すると、次の関係式が導かれる。
1+1=2φ(γS/γC)0.5 …(6)
この(6)式の両辺を2乗すると、固体の表面張力γSと臨界表面張力γCとには次の関係が成立する。
φ2γS=γC …(7)
この(7)式によって、臨界表面張力γCと相互作用係数φとから石炭やセミコークスの表面張力γSを求めることができる。
(a’)石炭を粒径200μm以下に粉砕する。
(b’)工程(a’)で粉砕した石炭を3℃/minで500℃まで不活性ガス気流中で加熱する。コークス炉においてコークスが製造されるときの加熱速度に合わせて、上記工程(b’)における加熱速度を3℃/minとしている。
(c’)工程(b’)で加熱した石炭を液体窒素で急冷する。
(d’)工程(c’)で急冷された石炭を粒径150μm以下に粉砕し、粉砕した石炭を乾燥された不活性ガス気流中120℃で2時間乾燥する。工程(d’)における乾燥方法は、表面に付着した水分を除去できる方法ならばどのような方法でも構わず、窒素、アルゴンなどの不活性ガス中で100~200℃に加熱する方法の他にも、減圧下で乾燥する方法なども採用できる。
表面張力分布の標準偏差(σγ)については、例えば下記(9)式のように表される。
工程(I):上記の指標、すなわち、セミコークスの表面張力を管理指標に用いて、各単味炭の銘柄及び各単味炭の配合率を決定する。
工程(II):工程(I)で決定した銘柄の石炭及びその石炭の配合率に基づいて、2種以上の銘柄の石炭を配合する
なお、本発明のコークスの製造方法は、上記工程(I)及び(II)を含み、更に、上記工程(II)で配合して得られた配合炭を乾留する工程(III)からなる。
この管理指標として、前述の標準偏差(σ1)(第1実施形態)または標準偏差(σ2)(第2実施形態)を用いることが好ましい。本発明者らは、セミコークスの表面張力から算出される前述の標準偏差(σ1)及び標準偏差(σ2)が、配合炭を乾留して製造されるコークスの強度に関連していることを見出し、これらを管理指標とする本発明を導いた。
前述の標準偏差(σ1)を、上記工程(I)における管理指標に用いる方法を説明する。工程(I)は、更に次に示す工程(Ia)~(Id)からなることが好ましい。
工程(Ia):配合炭を構成する2種以上の銘柄の石炭及び該石炭の配合率を仮定して、仮想配合炭を想定する。
工程(Ib):工程(Ia)で仮定した石炭を熱処理してセミコークスを得て、このセミコークスの各々の表面張力分布を準備する。
工程(Ic):工程(Ia)で仮定した石炭の配合率を重みにして、上記工程(Ib)で準備した表面張力分布を加重平均することで、仮想配合炭から得られたであろう仮想複合セミコークスの表面張力分布を求める。
工程(Id):工程(Ic)で求めた仮想複合セミコークスの表面張力分布の標準偏差(σ1)を管理指標に用い、この管理指標の値が良好であれば、工程(Ia)で仮定した石炭を工程(II)で配合する石炭と決定するとともに、工程(Ia)で仮定した石炭の配合率を工程(II)での石炭の配合率を決定する。
工程(II)に先立って(予め)、この配合炭を構成する石炭の銘柄を適宜選択(仮定)しておき、更に、その石炭の配合率を仮定して、仮想配合炭を想定しておく。以下では、4種の銘柄の石炭から配合炭が構成される場合を説明する。
図3(a)は、4種の銘柄の石炭から得られる4種の単味のセミコークスの表面張力分布を示し、符号8(8a、8b、8c、8d)は各単味のセミコークスの表面張力分布曲線を示している。この表面張力分布を準備することは、単味のセミコークスの表面張力を、前述のフィルム・フローテーション法で測定して、それを表面張力分布にして準備することや、フィルム・フローテーション法に限らず第三者が測定した表面張力に基づき表面張力分布を作成することや、第三者から表面張力分布を取得することを包含する。
工程(Ia)で仮定した各石炭の配合率を重みにして、この各石炭から得られるセミコークスの表面張力分布を加重平均した分布を求める。この分布は、工程(Ia)で想定した仮想配合炭を熱処理すると得られると想定される仮想複合セミコークスの表面張力分布に相当する。図3(b)は、図3(a)に示した各単味のセミコークスの表面張力分布から得られる、仮想複合セミコークスの表面張力分布を示している。本発明においては、例えば、表面張力分布の異なる4種類の単味炭の配合を考える場合、各単味のセミコークスの表面張力分布の頻度を、各単味炭の配合率を重みにした加重平均値の分布が、軟化溶融した状態の配合炭の表面張力分布と解釈する。
条件Bの場合には、石炭xから得られるセミコークスの表面張力分布10と、石炭bから得られるセミコークスの表面張力分布13との差は、図4(A)の場合よりも小さい。これらを加重平均した分布14の幅は、比較的に狭い。
条件Cの場合には、石炭xから得られるセミコークスの表面張力分布10と、石炭cから得られるセミコークスの表面張力分布15とは同じである。これらを加重平均した分布16の幅は、条件Bにおける分布14の幅より狭い。
工程(Id)では、工程(Ia)で仮定する石炭の配合率を変更することで、工程(Ic)で求められる仮想複合セミコークスの表面張力分布の標準偏差(σ1)を変更するように、工程(Ia)~(Ic)を1回または複数回行なって、標準偏差(σ1)が所定値以下の範囲となるような配合率を求める。工程(Ia)で仮定した2種以上の銘柄の石炭、及び、求めた配合率を、上記工程(I)での各単味炭の銘柄及び各単味炭の配合率と決定する。
本形態では、500℃まで熱処理して得られる複数のセミコークスに基づいて算出された標準偏差(σ1)が5.5[mN/m]以下であることが好ましい点を利用して、工程(I)における、各単味炭の配合率を決定する。本形態において、工程(I)は、更に次に示す工程(Ie)及び(If)からなることが好ましい。
まず、配合される2種以上の石炭を定める。これらの石炭から得られるセミコークスが存在し、そのセミコークスには表面張力分布がある。この表面張力分布は、500℃まで加熱した後冷却して得られる石炭の表面張力分布に相当し、必ずしも、石炭を熱処理してセミコークスを得て、そのセミコークスの表面張力を測定する必要はない。
工程(Ie)で定めた石炭の各々から得られるセミコークスの表面張力分布を、加重平均して求まる分布の標準偏差(σ1)を算出し、その標準偏差(σ1)が5.5[mN/m]以下の範囲内になる配合率を、決定される石炭の配合率とする。すなわち、工程(If)では、まず、工程(Ie)で定めた石炭の各々の配合率を適切な値とし、その適切な値を重みにして、定めた石炭から得られるセミコークスの表面張力分布を加重平均することで求まる分布の標準偏差(σ1)を算出する。次いで、標準偏差(σ1)が5.5[mN/m]以下となる配合率が、工程(I)で決定される各単味の石炭の配合率である。なお、工程(Ie)で定めた石炭が、工程(I)で決定される各単味の石炭である。
前述の標準偏差(σ2)を、前述の工程(I)における管理指標に用いる方法を説明する。第1実施形態では、標準偏差(σ1)を管理指標に用いており、この標準偏差(σ1)を算出する工程は、工程(Ic)及び(Id)である。第2実施形態は、これら以外の工程(Ia)及び(Ib)が第1実施形態と共通しており、工程(Ic)及び(Id)の代わりに、下記の工程(Ic’)及び(Id’)を行うことが好ましい。以下の説明では、第1実施形態と共通している部分は説明を省略する。
工程(Ic’):前述の工程(Ib)で準備された複数の表面張力分布において、各表面張力分布の平均値を複数算出する。前述の工程(Ia)で仮定した石炭の配合率と、複数の平均値と、から導出される該平均値の標準偏差(σ2)を求める。なお、工程(Ib)で得たセミコークスの表面張力分布の平均値は、そのセミコークスの平均表面張力を意味する。
工程(Id’):上記の工程(Ic’)で求めた標準偏差(σ2)を管理指標に用いて、配合炭を構成する石炭の銘柄及び該石炭の配合率を決定する。以下、工程(Ic’)及び(Id’)を詳細に説明する。
図3の例で説明すれば、図3(a)の8a、8b、8c、8dのそれぞれの表面張力分布における平均値γ8a、γ8b、γ8c、γ8dを算出する。次いで、その算出した平均値γ8a、γ8b、γ8c、γ8dと、それらのセミコークスの元となる石炭から構成される配合炭における各石炭の配合率と、から、標準偏差(σ2)を算出する。具体的には、n種の銘柄の石炭から配合炭が調製されるとして、n種の銘柄の石炭iから得られるセミコークスの表面張力分布の平均値をγi、それぞれの配合率をwiとすると、標準偏差(σ2)は、分散の平方根として、次の式(10)で算出される。
工程(Id’)では、工程(Ia)で仮定する石炭の配合率を変更することで、工程(Ic’)で求められる標準偏差(σ2)を変更するように、工程(Ia)~(Ic’)を1回または複数回行なって、標準偏差(σ2)が所定値以下の範囲となるような配合率を求める。次いで、工程(Ia)で仮定した2種以上の銘柄の石炭、及び、求めた配合率を、上記工程(I)での石炭の銘柄及び該銘柄の石炭の配合率と決定する。
本形態では、500℃まで熱処理して得られる複数のセミコークスに基づいて算出された標準偏差(σ2)が0.8[mN/m]以下であることが好ましい点を利用して、工程(I)における、各単味炭の配合率を決定する。本形態において、工程(I)は、更に、第1実施形態の別形態の工程(Ie)、及び、次に示す(If’)からなることが好ましい。
工程(Ie)で定めた石炭の各々から得られるセミコークスの表面張力分布を、加重平均して求まる分布の標準偏差(σ2)を算出し、その標準偏差(σ2)が0.8[mN/m]以下の範囲内になる配合率を、決定される石炭の配合率とする。すなわち、工程(If’)では、まず、工程(Ie)で定めた石炭の各々の配合率を適切な値とし、その適切な値を重みにして、定めた石炭から得られるセミコークスの表面張力分布を加重平均することで求まる分布の標準偏差(σ2)を算出する。次いで、標準偏差(σ2)が0.8[mN/m]以下となる配合率が、工程(I)で決定される各単味の石炭の配合率である。なお、工程(Ie)で定めた石炭が、工程(I)で決定される各単味の石炭である。
従来のコークス強度推定式のパラメータとして、ビトリニット平均最大反射率(Roの平均値)、ギーセラー最高流動度(logMF)、イナート量(TI)の3つの性状を採用する。
表1に示される2種の石炭の組み合わせからなる配合炭につき、表1に示される単味炭のこれらの性状を、各石炭の配合率を重みとした加重平均して算出される値を、各配合炭の上記性状の代表値とする。
各配合炭の3つの性状の代表値とドラム強度の実測値を重回帰分析して、各配合炭の3つの性状の代表値を独立変数としたドラム強度を推定するコークス強度推定式を導出した。なお、RoとTIはJIS M8816、MFはJIS M8801に準拠して測定した。
2 気相
3 液体
4 表面張力
5 表面張力分布のピーク値
6 表面張力分布の最小表面張力
7 表面張力分布の最大表面張力
8(8a、8b、8c、8d) 単味のセミコークスの表面張力分布曲線
9 単味のセミコークスの表面張力分布を、配合率を重みとして加重平均した分布曲線
10 石炭xから得られるセミコークスの表面張力分布
11 石炭aから得られるセミコークスの表面張力分布
12 表面張力分布10及び11を加重平均した分布
13 石炭bから得られるセミコークスの表面張力分布
14 表面張力分布10及び13を加重平均した分布
15 石炭cから得られるセミコークスの表面張力分布
16 表面張力分布10及び15を加重平均した分布
Claims (10)
- 2種以上の銘柄の石炭を配合して得られる、コークス製造用の石炭の配合方法であって、
350~800℃の範囲の温度まで加熱した後冷却して得られる各銘柄の石炭の表面張力を管理指標に用いて、前記石炭の銘柄と該銘柄の石炭の配合率とを決定する石炭の配合方法。 - 予め、前記2種以上の銘柄の石炭及び該石炭の配合率を仮定し、
350~800℃の範囲の温度まで加熱した後冷却して得られる2種以上の仮定した石炭の各々の表面張力分布を準備し、
仮定した石炭の配合率を重みにして、準備した表面張力分布を加重平均して求めた分布の標準偏差(σ1)を算出しておき、
該標準偏差(σ1)を前記管理指標に用いる請求項1に記載の石炭の配合方法。 - 準備される表面張力分布が、500℃まで加熱した後冷却して得られる石炭の表面張力分布であって、
予め仮定される石炭の配合率を変更することで前記標準偏差(σ1)を変更し、変更した標準偏差(σ1)が5.5[mN/m]以下の範囲内になる配合率を、決定される石炭の配合率とし、予め仮定される石炭の銘柄を、決定される石炭の銘柄とする請求項2に記載の石炭の配合方法。 - 配合される石炭を定め、該石炭の各々の表面張力分布が、500℃まで加熱した後冷却して得られる石炭の表面張力分布であって、
前記表面張力分布を加重平均して求まる分布の標準偏差(σ1)が5.5[mN/m]以下の範囲内になる配合率を、決定される石炭の配合率とする請求項1に記載の石炭の配合方法。 - 予め、前記2種以上の銘柄の石炭及び該石炭の配合率を仮定し、
350~800℃の範囲の温度まで加熱した後冷却して得られる2種以上の仮定した石炭の各々の表面張力分布を準備し、
仮定した石炭の配合率と準備した表面張力分布の平均値とから導出される該平均値の標準偏差(σ2)を算出しておき、
該標準偏差(σ2)を前記管理指標に用いる請求項1に記載の石炭の配合方法。 - 準備される表面張力分布は、500℃まで加熱した後冷却して得られる石炭の表面張力分布であって、
予め仮定される石炭の配合率を変更することで前記標準偏差(σ2)を変更し、変更した標準偏差(σ2)が0.8[mN/m]以下の範囲内になる配合率を、決定される石炭の配合率とし、予め仮定される石炭の銘柄を、決定される石炭の銘柄とする請求項5に記載の石炭の配合方法。 - 配合される石炭の各々の表面張力分布が、500℃まで加熱した後冷却して得られる石炭の表面張力分布であって、
前記表面張力分布の平均値から導出される該平均値の標準偏差(σ2)が、0.8[mN/m]以下の範囲内になる配合率を、決定される石炭の配合率とする請求項1に記載の石炭の配合方法。 - 前記表面張力は、フィルム・フローテーション法によって測定される請求項1~7のいずれかに記載の石炭の配合方法。
- 請求項1~8のいずれかに記載の石炭の配合方法によって配合された配合炭。
- 請求項9に記載の配合炭を乾留してコークスを製造するコークスの製造方法。
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