JP5062378B1 - Coke production method - Google Patents
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- 239000003245 coal Substances 0.000 claims abstract description 333
- 239000000463 material Substances 0.000 claims abstract description 106
- 238000002844 melting Methods 0.000 claims abstract description 81
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- Coke Industry (AREA)
Abstract
【課題】コークス炉内において軟化溶融した石炭及び粘結材の周辺の環境を十分に模擬した状態での石炭及び粘結材の軟化溶融特性を測定することで、簡便な方法を用いながら石炭及び粘結材の軟化溶融特性をより正確に評価できる方法を提供し、これにより、新たな石炭の配合基準を設定することによって高強度コークスの製造方法を提供する。
【解決手段】石炭又は粘結材を容器に充填して試料１とし、試料１の上に上下面に貫通孔を有する材料２を配置し、試料１と上下面に貫通孔を有する材料２を一定容積に保ちつつ、あるいは一定の荷重を負荷しつつ、所定の加熱速度で試料１を加熱し、貫通孔へ浸透した溶融試料の浸透距離を測定し、該測定値を用いて試料の軟化溶融特性を評価する石炭及び粘結材の軟化溶融特性の評価方法を用いる。または、試料１と上下面に貫通孔を有する材料２を一定容積に保ちつつ、所定の加熱速度で試料１を加熱して、上下面に貫通孔を有する材料２を介して伝達される試料の圧力を測定し、該測定値を用いて試料の軟化溶融特性を評価する。
【選択図】図１An object of the present invention is to measure the softening and melting characteristics of coal and binder in a coke oven in a state that sufficiently simulates the environment around the coal and binder that has been softened and melted. The present invention provides a method capable of more accurately evaluating the softening and melting characteristics of a binder, thereby providing a method for producing high-strength coke by setting a new coal blending standard.
A container is filled with coal or a caking additive to form a sample 1, a material 2 having through holes on the upper and lower surfaces is arranged on the sample 1, and a material 2 having through holes on the upper and lower surfaces is disposed. While maintaining a constant volume or applying a constant load, the sample 1 is heated at a predetermined heating rate, the permeation distance of the molten sample that has penetrated into the through-hole is measured, and the sample is softened and melted using the measured value The evaluation method of softening and melting properties of coal and caking additive is used. Alternatively, the sample 1 is heated at a predetermined heating rate while keeping the sample 1 and the material 2 having through holes on the upper and lower surfaces at a constant volume, and the sample 1 transmitted through the material 2 having the through holes on the upper and lower surfaces. The pressure is measured, and the softened and melt characteristics of the sample are evaluated using the measured value.
[Selection] Figure 1
Description
この発明はコークス製造用石炭及び粘結材の品質評価法の一つである、石炭及び粘結材乾留時の軟化溶融特性を評価する方法およびその方法を用いたコークスの製造方法に関する。 The present invention relates to a method for evaluating the softening and melting characteristics of coal and caking additive during carbonization, which is one of the quality evaluation methods for coal for coke production and caking additive, and a coke production method using the method.
製銑法として最も一般的に行われている高炉法において使用されるコークスは、鉄鉱石の還元材、熱源、スペーサーなどの数々の役割を担っている。高炉を安定的に効率良く操業するためには、高炉内の通気性を維持することが重要であることから、強度の高いコークスの製造が求められている。コークスは、粉砕し、粒度を調整した種々のコークス製造用石炭を配合した配合炭を、コークス炉内にて乾留することで製造される。コークス製造用石炭は、乾留中約３００℃〜５５０℃の温度域で軟化溶融し、また同時に揮発分の発生に伴い発泡、膨張することで、各々の粒子が互いに接着しあい、塊状のセミコークスとなる。セミコークスは、その後１０００℃付近まで昇温する過程で収縮することで焼きしまり、堅牢なコークス（コークスケーキ）となる。従って、石炭の軟化溶融時の接着特性が、乾留後のコークス強度や粒径等の性状に大きな影響を及ぼす。 Coke used in the blast furnace method, which is most commonly used as a steelmaking method, plays a number of roles, such as iron ore reductant, heat source, and spacer. In order to operate the blast furnace stably and efficiently, it is important to maintain the air permeability in the blast furnace, and therefore production of coke having high strength is required. Coke is produced by dry-distilling blended coal in which various types of coal for coke production, which are pulverized and adjusted in particle size, are blended in a coke oven. Coal-producing coal softens and melts in the temperature range of about 300 ° C to 550 ° C during dry distillation, and at the same time foams and expands with the generation of volatile matter. Become. The semi-coke is then burned by shrinking in the process of raising the temperature to around 1000 ° C., and becomes a solid coke (coke cake). Therefore, the adhesion characteristics during softening and melting of coal greatly affect properties such as coke strength and particle size after dry distillation.
また、コークス製造用石炭（配合炭）の接着を強化する目的で、石炭が軟化溶融する温度域で高い流動性を示す粘結材を配合炭に添加してコークスを製造する方法が一般的に行われている。ここで、粘結材とは、具体的にはタールピッチ、石油系ピッチ、溶剤精製炭、溶剤抽出炭などである。これら粘結材についても石炭と同様に、軟化溶融時の接着特性が、乾留後のコークス性状に大きな影響を及ぼす。 In addition, for the purpose of strengthening the adhesion of coal for coke production (mixed coal), a method of producing coke by adding a caking agent exhibiting high fluidity in the temperature range where the coal is softened and melted to the blended coal Has been done. Here, the binder is specifically tar pitch, petroleum pitch, solvent refined coal, solvent extracted coal, and the like. For these binders, as with coal, the adhesive properties during softening and melting greatly affect the coke properties after dry distillation.
一方、コークス炉におけるコークス製造において、乾留後のコークスは、押し出し機によりコークス炉外へ排出される。このとき、生成したコークスケーキ自体の収縮が小さいと、炉外への排出が困難となり、炉外への排出ができなくなる「押し詰まり」発生のトラブルを招くことがある。乾留後のコークスケーキ構造は、乾留過程における石炭、セミコークスの体積変化に大きく影響を受ける。このうち、セミコークスの収縮は、石炭の揮発分との間に良好な相関関係があることが知られており（例えば、非特許文献１参照。）、また、配合炭の揮発分含有量は同一工場における操業範囲内でほぼ一定に管理されることが多い。従って、石炭の軟化溶融時の体積変化特性が、乾留後のコークスケーキ構造に大きな影響を及ぼす。 On the other hand, in coke production in a coke oven, coke after dry distillation is discharged out of the coke oven by an extruder. At this time, if the shrinkage of the produced coke cake itself is small, it is difficult to discharge the coke cake to the outside of the furnace, which may cause a trouble of “clogging” that cannot be discharged to the outside of the furnace. The coke cake structure after carbonization is greatly affected by changes in the volume of coal and semi-coke during the carbonization process. Among these, the shrinkage of semi-coke is known to have a good correlation with the volatile content of coal (see, for example, Non-Patent Document 1), and the volatile content of blended coal is It is often managed almost uniformly within the operating range of the same factory. Therefore, the volume change characteristic at the time of softening and melting of coal greatly affects the coke cake structure after dry distillation.
上述のとおり、石炭の軟化溶融特性は、乾留後のコークス性状やコークスケーキ構造を大きく左右するため、極めて重要であり、古くからその測定方法の検討が盛んになされてきた。特に、コークスの重要な品質であるコークス強度は、その原料である石炭性状、とりわけ石炭化度と軟化溶融特性に大きく影響される。軟化溶融特性とは、石炭を加熱したときに軟化溶融する性質であり、通常、軟化溶融物の流動性、粘度、接着性、膨張性などにより測定、評価される。 As described above, the softening and melting characteristics of coal are extremely important because they greatly affect the coke properties and coke cake structure after carbonization, and the investigation of the measurement method has been actively conducted for a long time. In particular, coke strength, which is an important quality of coke, is greatly affected by the properties of coal as the raw material, particularly the degree of coalification and softening and melting characteristics. The softening and melting property is a property of softening and melting when coal is heated, and is usually measured and evaluated by the fluidity, viscosity, adhesiveness, expandability, etc. of the softened melt.
石炭の軟化溶融特性のうち、軟化溶融時の流動性を測定する一般的な方法としては、ＪＩＳ Ｍ ８８０１に規定されるギーセラープラストメータ法による石炭流動性試験方法が挙げられる。ギーセラープラストメータ法は、４２５μｍ以下に粉砕した石炭を所定のるつぼに入れ、規定の昇温速度で加熱し、規定のトルクをかけた撹拌棒の回転速度を目盛板で読み取り、ddpm(dial division per minute)で表示する方法である。 Among the softening and melting characteristics of coal, a general method for measuring the fluidity at the time of softening and melting includes a coal fluidity test method by the Gieseler plastometer method defined in JIS M8801. In the Gieseler plastometer method, coal pulverized to 425 μm or less is put in a predetermined crucible, heated at a specified temperature increase rate, and the rotation speed of a stirring rod to which a specified torque is applied is read with a scale plate, and ddpm (dial division per minute).
ギーセラープラストメータ法がトルク一定での撹拌棒の回転速度を測定しているのに対し、定回転方式でトルクを測定する方法も考案されている。例えば、特許文献１では、回転子を一定の回転速度で回転させながらトルクを測定する方法が記載されている。 In contrast to the Gisela plastometer method, which measures the rotational speed of the stirring rod with a constant torque, a method for measuring the torque by the constant rotation method has also been devised. For example, Patent Document 1 describes a method of measuring torque while rotating a rotor at a constant rotational speed.
また、軟化溶融特性として物理的に意味のある粘性を測定することを目的にした、動的粘弾性測定装置による粘度の測定方法がある（例えば、特許文献２参照。）。動的粘弾性測定とは、粘弾性体に周期的に力を加えたときに見られる粘弾性挙動の測定である。特許文献２に記載の方法では、測定で得られるパラメータ中の複素粘性率により軟化溶融石炭の粘性を評価しており、任意のせん断速度における軟化溶融石炭の粘度を測定可能な点が特徴である。 In addition, there is a viscosity measurement method using a dynamic viscoelasticity measuring device for the purpose of measuring a physically meaningful viscosity as a softening and melting characteristic (see, for example, Patent Document 2). Dynamic viscoelasticity measurement is the measurement of viscoelastic behavior seen when a force is applied periodically to a viscoelastic body. The method described in Patent Document 2 is characterized in that the viscosity of the softened molten coal is evaluated by the complex viscosity in the parameters obtained by the measurement, and the viscosity of the softened molten coal at an arbitrary shear rate can be measured. .
さらに、石炭の軟化溶融特性として、活性炭、またはガラスビーズを用い、それらへの石炭軟化溶融物接着性を測定した例が報告されている。少量の石炭試料を活性炭、ガラスビーズで上下方向から挟んだ状態で加熱し、軟化溶融後に冷却を行い、石炭と活性炭、ガラスビーズとの接着性を外観から観察する方法である。 Furthermore, as an example of the softening and melting characteristics of coal, an example in which activated carbon or glass beads was used and the coal softening melt adhesion to them was measured was reported. In this method, a small amount of coal sample is heated while being sandwiched between activated carbon and glass beads from above and below, cooled after softening and melting, and the adhesion between coal, activated carbon and glass beads is observed from the appearance.
石炭の軟化溶融時の膨張性を測定する一般的な方法としては、ＪＩＳ Ｍ ８８０１に規定されているジラトメーター法が挙げられる。ジラトメーター法は、２５０μｍ以下に粉砕した石炭を規定の方法で成型し、所定のるつぼに入れ、規定の昇温速度で加熱し、石炭の上部に配置した検出棒で、石炭の変位の経時変化を測定する方法である。 A general method for measuring the expansibility of coal during soft melting is the dilatometer method defined in JIS M8801. In the dilatometer method, coal pulverized to 250 μm or less is molded by a specified method, placed in a predetermined crucible, heated at a specified rate of temperature rise, and a detection rod placed on the top of the coal is used to measure changes in coal displacement over time. It is a method of measuring.
さらに、コークス炉内での石炭軟化溶融挙動を模擬するため、石炭軟化溶融時に発生するガスの透過挙動を改善した石炭膨張性試験方法も知られている（例えば、特許文献３参照）。これは、石炭層とピストンの間、もしくは石炭層とピストンの間と石炭層の下部に透過性材料を配置し、石炭から発生する揮発分と液状物質の透過経路を増やすことで、測定環境を、よりコークス炉内の膨張挙動に近づけた方法である。同様に、石炭層の上に貫通経路を有する材料を配置し、荷重を負荷しながら石炭をマイクロ波加熱して石炭の膨張性を測定する方法も知られている（特許文献４参照。）。 Furthermore, in order to simulate the behavior of coal softening and melting in a coke oven, a coal expansibility test method that improves the permeation behavior of gas generated during softening and melting of coal is also known (see, for example, Patent Document 3). This is because the permeable material is placed between the coal bed and the piston, or between the coal bed and the piston and below the coal bed, and the passage of volatiles and liquid substances generated from the coal is increased, thereby reducing the measurement environment. This is a method closer to the expansion behavior in the coke oven. Similarly, a method is also known in which a material having a through-passage is disposed on a coal bed, and the coal is microwave-heated while applying a load to measure the expansibility of the coal (see Patent Document 4).
コークス炉内での石炭の軟化溶融挙動を評価するためには、コークス炉内において軟化溶融した石炭の周辺の環境を模擬した状態で、石炭の軟化溶融特性を測定することが必要である。コークス炉内において軟化溶融した石炭とその周辺の環境を、以下に詳述する。 In order to evaluate the softening and melting behavior of coal in a coke oven, it is necessary to measure the softening and melting characteristics of coal in a state simulating the environment around the coal softened and melted in the coke oven. The coal softened and melted in the coke oven and the surrounding environment will be described in detail below.
コークス炉内において、軟化溶融時の石炭は隣接する層に拘束された状態で軟化溶融している。石炭の熱伝導率は小さいため、コークス炉内において石炭は一様に加熱されず、加熱面である炉壁側からコークス層、軟化溶融層、石炭層と状態が異なっている。コークス炉自体は乾留時多少膨張するがほとんど変形しないため、軟化溶融した石炭は隣接するコークス層、石炭層に拘束されている。 In the coke oven, the coal at the time of softening and melting is softened and melted while being constrained by adjacent layers. Since the thermal conductivity of coal is small, the coal is not uniformly heated in the coke oven, and the state differs from the coke layer, the softened molten layer, and the coal layer from the furnace wall side that is the heating surface. Since the coke oven itself expands somewhat during dry distillation but hardly deforms, the softened and melted coal is constrained by the adjacent coke layer and coal layer.
また、軟化溶融した石炭の周囲には、石炭層の石炭粒子間空隙、軟化溶融石炭の粒子間空隙、熱分解ガスの揮発により発生した粗大気孔、隣接するコークス層に生じる亀裂など、多数の欠陥構造が存在する。特に、コークス層に生じる亀裂は、その幅が数百ミクロンから数ミリ程度と考えられ、数十〜数百ミクロン程度の大きさである石炭粒子間空隙や気孔に比較して大きい。従って、このようなコークス層に生じる粗大欠陥へは、石炭から発生する副生物である熱分解ガスや液状物質だけではなく、軟化溶融した石炭自体の浸透も起こると考えられる。また、その浸透時に軟化溶融した石炭に作用するせん断速度は、銘柄毎に異なることが予想される。 In addition, there are many defects around the softened and melted coal, such as voids between coal particles in the coal bed, interparticle voids in the softened molten coal, rough air holes generated by volatilization of the pyrolysis gas, and cracks in the adjacent coke layer. Structure exists. In particular, the crack generated in the coke layer is considered to have a width of several hundred microns to several millimeters, and is larger than the voids and pores between coal particles having a size of about several tens to several hundreds of microns. Therefore, it is considered that coarse defects generated in such a coke layer are not only caused by pyrolysis gas and liquid substances, which are by-products generated from coal, but also permeate softened and melted coal itself. Further, it is expected that the shear rate acting on the softened and melted coal at the time of infiltration varies from brand to brand.
上述したとおり、コークス炉内において軟化溶融した石炭の周辺の環境を模擬した状態で石炭の軟化溶融特性を測定するためには、拘束条件、浸透条件を適正にする必要がある。しかし、従来方法には以下のような問題がある。 As described above, in order to measure the softening and melting characteristics of coal in a state of simulating the environment around the softened and melted coal in a coke oven, it is necessary to make the restraint conditions and infiltration conditions appropriate. However, the conventional method has the following problems.
ギーセラープラストメータ法は、石炭を容器に充填した状態での測定のため、拘束、浸透条件を全く考慮していない点で問題である。また、この方法は、高い流動性を示す石炭の測定には適さない。その理由は、高い流動性を示す石炭を測定する場合、容器内側壁部が空洞となる現象（Ｗｅｉｓｓｅｎｂｅｒｇ効果）が起こり、撹拌棒が空転し、流動性を正しく評価できない場合があるためである（例えば、非特許文献２参照。）。 The Giselaer plastometer method is problematic in that it does not take into account any restraint or infiltration conditions for measurement in a state where coal is filled in a container. Moreover, this method is not suitable for the measurement of coal showing high fluidity. The reason is that, when measuring coal showing high fluidity, a phenomenon that the inner wall of the container becomes hollow (Weissenberg effect) occurs, the stirrer may idle, and the fluidity may not be evaluated correctly ( For example, refer nonpatent literature 2.).
定回転方式でトルクを測定する方法についても同様に、拘束条件、浸透条件を考慮していない点で不備がある。また、せん断速度一定下での測定のため、上記で述べたように石炭の軟化溶融特性を正しく比較評価することができない。 Similarly, the method of measuring the torque by the constant rotation method is deficient in that the constraint condition and the penetration condition are not taken into consideration. In addition, because of the measurement under a constant shear rate, it is impossible to correctly compare and evaluate the softening and melting characteristics of coal as described above.
動的粘弾性測定装置は、軟化溶融特性として粘性を対象とし、任意のせん断速度下で粘度が測定可能な装置である。よって、測定時のせん断速度を、コークス炉内での石炭に作用する値に設定すれば、コークス炉内での軟化溶融石炭の粘度を測定可能である。しかし、各銘柄のコークス炉内でのせん断速度を予め測定、または推定することは通常は困難である。 The dynamic viscoelasticity measuring apparatus is an apparatus that targets viscosity as a softening and melting characteristic and can measure the viscosity under an arbitrary shear rate. Therefore, if the shear rate at the time of measurement is set to a value that acts on the coal in the coke oven, the viscosity of the softened molten coal in the coke oven can be measured. However, it is usually difficult to measure or estimate the shear rate in each coke oven in advance.
石炭の軟化溶融特性として、活性炭、またはガラスビーズを用い、それらへの接着性を測定する方法は、石炭層の存在について浸透条件を再現しようとしているものの、コークス層と粗大欠陥を模擬していない点で問題がある。また、拘束下での測定でない点でも不十分である。 The method of measuring the adhesion to coal using activated carbon or glass beads as the softening and melting characteristics of coal tries to reproduce the infiltration conditions for the presence of coal layer, but does not simulate the coke layer and coarse defects There is a problem in terms. Moreover, the point which is not a measurement under restraint is also insufficient.
特許文献３に記載されている透過性材料を用いた石炭膨張性試験方法においては、石炭から発生するガス、液状物質の移動を考慮しているが、軟化溶融した石炭自体の移動を考慮していない点で問題である。これは特許文献３で用いる透過性材料の透過度が、軟化溶融石炭が移動するほど十分に大きくないためである。本発明者らが実際に特許文献３に記載の試験を行ったところ、軟化溶融石炭の透過性材料への浸透は起こらなかった。したがって、軟化溶融石炭の透過性材料への浸透を起こさせるためには、新たな条件を考慮する必要がある。 In the coal expansibility test method using the permeable material described in Patent Document 3, the movement of gas and liquid substance generated from coal is considered, but the movement of softened and melted coal itself is considered. There is no problem in that. This is because the permeability of the permeable material used in Patent Document 3 is not large enough to move the softened molten coal. When the present inventors actually performed the test described in Patent Document 3, penetration of the softened molten coal into the permeable material did not occur. Therefore, it is necessary to consider new conditions in order to cause the soft molten coal to penetrate into the permeable material.
特許文献４にも同様に石炭層の上に貫通経路を有する材料を配置して石炭から発生するガス、液状物質の移動を考慮した石炭の膨張性測定方法が開示されているが、加熱方法に制約があるという問題点の他、コークス炉内における浸透現象を評価するための条件が明確になっていないという問題がある。さらに特許文献４では、石炭溶融物の浸透現象と軟化溶融挙動の関係が明確になっておらず、石炭溶融物の浸透現象と生成するコークスの品質との関係についての示唆も無く、良好な品質のコークスの製造について記載されているものではない。 Similarly, Patent Document 4 discloses a method for measuring the expansibility of coal in consideration of the movement of gas and liquid substances generated from coal by arranging a material having a through path on the coal bed. In addition to the problem of restrictions, there is a problem that the conditions for evaluating the infiltration phenomenon in the coke oven are not clear. Furthermore, in Patent Document 4, the relationship between the infiltration phenomenon of the coal melt and the softening and melting behavior is not clear, and there is no suggestion about the relationship between the infiltration phenomenon of the coal melt and the quality of the coke to be produced. It does not describe the production of coke.
このように、従来技術ではコークス炉内において軟化溶融した石炭及び粘結材の周辺の環境を十分に模擬した状態で、石炭及び粘結材の流動性、粘性、接着性、浸透性、浸透時膨張率、浸透時圧力などの軟化溶融特性を測定することができない。 As described above, in the prior art, the fluidity, viscosity, adhesiveness, permeability, and penetration of coal and binder are fully simulated in the environment around coal and binder that has been softened and melted in a coke oven. Softening and melting properties such as expansion rate and pressure during penetration cannot be measured.
したがって本発明の目的は、このような従来技術の課題を解決し、コークス炉内において軟化溶融した石炭及び粘結材の周辺の環境を十分に模擬した状態での石炭及び粘結材の軟化溶融特性を測定するため、簡便な方法を用いながら石炭及び粘結材のより正確な軟化溶融特性評価方法を提供することにある。 Therefore, the object of the present invention is to solve such problems of the prior art and soften and melt coal and binder in a state that sufficiently simulates the environment surrounding coal and binder that has been softened and melted in a coke oven. In order to measure properties, it is to provide a more accurate method for evaluating softening and melting properties of coal and caking additive using a simple method.
さらに、軟化溶融特性をより正確に評価することにより、石炭及び粘結材のコークス強度への影響をより精度よく把握することが可能になる。本発明はこうした知見を利用し、新たな石炭の配合基準を設定することによって高強度コークスの製造方法を提供することも目的とする。 Furthermore, by more accurately evaluating the softening and melting characteristics, it becomes possible to grasp the influence on the coke strength of coal and caking additive more accurately. Another object of the present invention is to provide a method for producing high-strength coke by utilizing such knowledge and setting a new coal blending standard.
上述したような課題を解決するための本発明の特徴は以下の通りである。
［１］石炭又は粘結材を容器に充填して試料を作成し、
該試料の上に上下面に貫通孔を有する材料を配置し、
前記試料と前記上下面に貫通孔を有する材料を一定容積に保ちつつ、前記試料を加熱し、
前記貫通孔へ浸透した溶融試料の浸透距離を測定し、
該測定値を用いて試料の軟化溶融特性を評価する、
石炭及び粘結材の軟化溶融特性の評価方法。
［２］石炭又は粘結材を容器に充填して試料を作成し、
該試料の上に上下面に貫通孔を有する材料を配置し、
前記試料と前記上下面に貫通孔を有する材料を一定容積に保ちつつ、前記試料を加熱し、
前記上下面に貫通孔を有する材料を介して伝達される前記試料の圧力を測定し、
該測定値を用いて試料の軟化溶融特性を評価する、
石炭及び粘結材の軟化溶融特性の評価方法。
［３］石炭又は粘結材を容器に充填して試料を作成し、
該試料の上に上下面に貫通孔を有する材料を配置し、
前記上下面に貫通孔を有する材料に一定荷重を負荷しつつ、前記試料を加熱し、
前記貫通孔へ浸透した溶融試料の浸透距離を測定し、
該測定値を用いて試料の軟化溶融特性を評価する、
石炭及び粘結材の軟化溶融特性の評価方法。
［４］石炭又は粘結材を容器に充填して試料を作成し、
該試料の上に上下面に貫通孔を有する材料を配置し、
前記上下面に貫通孔を有する材料に一定荷重を負荷しつつ、前記試料を加熱し、
前記試料の膨張率を測定し、
該測定値を用いて試料の軟化溶融特性を評価する、
石炭及び粘結材の軟化溶融特性の評価方法。
［５］前記試料の作成が、石炭又は粘結材を粒径３ｍｍ以下が７０質量％以上となるように粉砕し、該粉砕された石炭又は粘結材を充填密度０．７〜０．９ｇ／ｃｍ３で、層厚が５〜２０ｍｍとなるように容器に充填することからなる［１］乃至［４］の何れかに記載の石炭及び粘結材の軟化溶融特性の評価方法。
［６］前記粉砕が、石炭又は粘結材を粒径２ｍｍ以下が１００質量％となるように粉砕することからなる［５］に記載の石炭及び粘結材の軟化溶融特性の評価方法。
［７］前記上下面に貫通孔を有する材料が、球形粒子充填層、或いは、非球形粒子充填層である［１］乃至［４］の何れかに記載の石炭及び粘結材の軟化溶融特性の評価方法。
［８］前記試料の加熱が、２〜１０℃／分の加熱速度で室温から５５０℃まで不活性ガス雰囲気下で加熱することからなる［１］乃至［４］の何れかに記載の石炭及び粘結材の軟化溶融特性の評価方法。
［９］前記一定荷重を負荷することが、貫通孔を有する材料の上面における圧力が５〜８０ｋＰａとなるような荷重を負荷することからなる［３］または［４］に記載の石炭及び粘結材の軟化溶融特性の評価方法。
［１０］前記上下面に貫通孔を有する材料を配置することが、該試料の上に直径０．２〜３．５ｍｍのガラスビーズを層厚２０〜１００ｍｍとなるように配置することからなり、
前記試料の加熱が、前記試料とガラスビーズ層を一定容積に保ちつつ、加熱速度２ないし１０℃／分で室温から５５０℃まで不活性ガス雰囲気下で加熱することからなる、
［１］または［２］に記載の石炭及び粘結材の軟化溶融特性の評価方法。
［１１］前記上下面に貫通孔を有する材料を配置することが、該試料の上に直径０．２〜３．５ｍｍのガラスビーズを層厚２０〜１００ｍｍとなるように配置することからなり、
前記試料の加熱が、前記ガラスビーズの上部から５〜８０ｋＰａとなるように荷重を負荷しつつ、加熱速度２〜１０℃／分で室温から５５０℃まで不活性ガス雰囲気下で加熱することからなる、
［３］または［４］に記載の石炭及び粘結材の軟化溶融特性の評価方法。
［１２］前記試料の作成が、石炭又は粘結材を粒径３ｍｍ以下が７０質量％以上となるように粉砕し、該粉砕された石炭又は粘結材を充填密度０．７〜０．９ｇ／ｃｍ３で、層厚が５〜２０ｍｍとなるように容器に充填することからなり、
前記上下面に貫通孔を有する材料を配置することが、該試料の上に直径０．２〜３．５ｍｍのガラスビーズを層厚２０〜１００ｍｍとなるように配置することからなり、
前記試料の加熱が、前記試料とガラスビーズ層を一定容積に保ちつつ、加熱速度２〜 １０℃／分で室温から５５０℃まで不活性ガス雰囲気下で加熱することからなる、
［１］または［２］に記載の石炭及び粘結材の軟化溶融特性の評価方法。
［１３］前記試料の作成が、石炭又は粘結材を粒径３ｍｍ以下が７０質量％以上となるように粉砕し、該粉砕された石炭又は粘結材を充填密度０．７〜０．９ｇ／ｃｍ３で、層厚が５〜２０ｍｍとなるように容器に充填することからなり、
前記上下面に貫通孔を有する材料を配置することが、該試料の上に直径０．２〜３．５ｍｍのガラスビーズを層厚２０〜１００ｍｍとなるように配置することからなり、
前記試料の加熱が、前記ガラスビーズの上部から５〜８０ｋＰａとなるように荷重を負荷しつつ、加熱速度２〜１０℃／分で室温から５５０℃まで不活性ガス雰囲気下で加熱することからなる、
［３］または［４］に記載の石炭及び粘結材の軟化溶融特性の評価方法。
［１４］前記試料の作成が、石炭又は粘結材を粒径２ｍｍ以下が１００質量％となるように粉砕し、該粉砕された石炭又は粘結材を充填密度０．８ｇ／ｃｍ３で、層厚が１０ｍｍとなるように容器に充填することからなり、
前記上下面に貫通孔を有する材料を配置することが、該試料の上に直径２ｍｍのガラスビーズを層厚８０ｍｍとなるように配置することからなり、
前記試料の加熱が、前記試料とガラスビーズ層を一定容積に保ちつつ、加熱速度３℃／分で室温から５５０℃まで不活性ガス雰囲気下で加熱することからなる、
［１］または［２］に記載の石炭及び粘結材の軟化溶融特性の評価方法。
［１５］前記試料の作成が、石炭又は粘結材を粒径２ｍｍ以下が１００質量％となるように粉砕し、該粉砕された石炭又は粘結材を充填密度０．８ｇ／ｃｍ３で、層厚が１０ｍｍとなるように容器に充填することからなり、
前記上下面に貫通孔を有する材料を配置することが、該試料の上に直径２ｍｍのガラスビーズを層厚８０ｍｍとなるように配置することからなり、
前記試料の加熱が、前記ガラスビーズの上部から５０ｋＰａとなるように荷重を負荷しつつ、加熱速度３℃／分で室温から５５０℃まで不活性ガス雰囲気下で加熱することからなる、
［３］または［４］に記載の石炭及び粘結材の軟化溶融特性の評価方法。
［１６］ コークス製造用配合炭に含まれるギーセラー最高流動度の対数値ｌｏｇＭＦが３．０以上の石炭について、石炭の軟化溶融特性である浸透距離を測定し、
測定された浸透距離の加重平均値に基づいて、前記ギーセラー最高流動度の対数値ｌｏｇＭＦが３．０以上の石炭の配合率を決定し、
決定された配合率により配合された石炭を乾留する、
コークスの製造方法。
［１７］前記浸透距離の測定が下記（１）〜（４）により行われ、
前記配合率の決定が、測定された浸透距離の加重平均値が１５ｍｍ以下になるように、前記ギーセラー最高流動度の対数値ｌｏｇＭＦが３．０以上の石炭の配合率を決定する、
［１６］に記載のコークスの製造方法。
（１）石炭又は粘結材を粒径２ｍｍ以下が１００質量％となるように粉砕し、該粉砕された石炭又は粘結材を充填密度０．８ｇ／ｃｍ３で、層厚が１０ｍｍとなるように容器に充填して試料を作成し、
（２）該試料の上に直径２ｍｍのガラスビーズを層厚８０ｍｍとなるように配置し、
（３）前記試料と前記ガラスビーズ層を一定容積に保ちつつ、加熱速度３℃／分で室温から５５０℃まで不活性ガス雰囲気下で加熱し、
（４）前記ガラスビーズ層へ浸透した溶融試料の浸透距離を測定する。
［１８］前記浸透距離の測定が下記（１）〜（４）により行われ、
前記配合率の決定が、測定された浸透距離の加重平均値が１７ｍｍ以下になるように、前記ギーセラー最高流動度の対数値ｌｏｇＭＦが３．０以上の石炭の配合率を決定する、
［１６］に記載のコークスの製造方法。
（１）石炭又は粘結材を粒径２ｍｍ以下が１００質量％となるように粉砕し、該粉砕された石炭又は粘結材を充填密度０．８ｇ／ｃｍ３で、層厚が１０ｍｍとなるように容器に充填して試料を作成し、
（２）該試料の上に直径２ｍｍのガラスビーズを層厚８０ｍｍとなるように配置し、
（３）前記ガラスビーズの上部から５０ｋＰａとなるように荷重を負荷しつつ、加熱速度３℃／分で室温から５５０℃まで不活性ガス雰囲気下で加熱し、
（４）前記ガラスビーズ層へ浸透した溶融試料の浸透距離を測定する。
［１９］コークス製造に用いる配合炭中に含まれる石炭又は粘結材の銘柄と配合炭中に占めるｌｏｇＭＦが３．０未満の石炭の合計配合率を予め決定し、
コークス製造用配合炭に含まれる石炭のうち、ギーセラー最高流動度の対数値ｌｏｇＭＦが３．０以上の石炭の浸透距離を測定し、
配合炭に含まれるｌｏｇＭＦが３．０未満の石炭の合計配合率を一定とした条件下で個々銘柄の石炭又は粘結材の配合率を変化させることでその時の配合炭に含まれるｌｏｇＭＦが３．０以上の石炭又は粘結材の加重平均浸透距離と前記個々銘柄の石炭の配合率を変化させて調製した配合炭から得られるコークス強度の関係を求め、
コークス強度が所望の値以上になるようにｌｏｇＭＦが３．０以上の石炭の銘柄と配合率を調整して加重平均浸透距離を調整する、
コークスの製造方法。
［２０］前記浸透距離の測定が、以下の範囲から選ばれる条件で行なわれる［１９］に記載のコークスの製造方法。
石炭又は粘結材を粒径３ｍｍ以下が７０質量％以上となるように粉砕し、該粉砕物を充填密度０．７〜０．９ｇ／ｃｍ3で、層厚が５〜２０ｍｍとなるように容器に充填して試料とし、該試料の上に直径０．２〜３．５ｍｍのガラスビーズを層厚２０〜１００ｍｍとなるように配置し、前記試料とガラスビーズ層を一定容積に保ちつつ、昇温速度２〜１０℃／分で室温から５５０℃まで不活性ガス雰囲気下で加熱する。
［２１］前記浸透距離の測定が、以下の範囲から選ばれる条件で行なわれる［１９］に記載のコークスの製造方法。
石炭又は粘結材を粒径３ｍｍ以下が７０質量％以上となるように粉砕し、該粉砕物を充填密度０．７〜０．９ｇ／ｃｍ3で、層厚が５〜２０ｍｍとなるように容器に充填して試料とし、該試料の上に直径０．２〜３．５ｍｍのガラスビーズを層厚２０〜１００ｍｍとなるように配置し、ガラスビーズの上部から圧力５〜８０ｋＰａとなるように荷重を負荷しつつ、昇温速度２〜１０℃／分で室温から５５０℃まで不活性ガス雰囲気下で加熱する。
The features of the present invention for solving the above-described problems are as follows.
[1] A sample is prepared by filling a container with coal or caking additive,
A material having through holes on the upper and lower surfaces is placed on the sample,
While maintaining the sample and the material having through holes on the upper and lower surfaces at a constant volume, heating the sample,
Measure the penetration distance of the molten sample that has penetrated into the through hole,
Using the measured values to evaluate the softening and melting characteristics of the sample,
Evaluation method for softening and melting characteristics of coal and caking additive.
[2] Prepare a sample by filling a container with coal or caking additive,
A material having through holes on the upper and lower surfaces is placed on the sample,
While maintaining the sample and the material having through holes on the upper and lower surfaces at a constant volume, heating the sample,
Measuring the pressure of the sample transmitted through a material having a through hole in the upper and lower surfaces;
Using the measured values to evaluate the softening and melting characteristics of the sample,
Evaluation method for softening and melting characteristics of coal and caking additive.
[3] Fill a container with coal or caking additive to make a sample,
A material having through holes on the upper and lower surfaces is placed on the sample,
While applying a constant load to the material having through holes on the upper and lower surfaces, the sample is heated,
Measure the penetration distance of the molten sample that has penetrated into the through hole,
Using the measured values to evaluate the softening and melting characteristics of the sample,
Evaluation method for softening and melting characteristics of coal and caking additive.
[4] Prepare a sample by filling a container with coal or caking additive,
A material having through holes on the upper and lower surfaces is placed on the sample,
While applying a constant load to the material having through holes on the upper and lower surfaces, the sample is heated,
Measuring the expansion coefficient of the sample,
Using the measured values to evaluate the softening and melting characteristics of the sample,
Evaluation method for softening and melting characteristics of coal and caking additive.
[5] Preparation of the sample is performed by pulverizing coal or a binder so that a particle size of 3 mm or less is 70% by mass or more, and filling the pulverized coal or the binder with a packing density of 0.7 to 0.9 g. The method for evaluating the softening and melting characteristics of coal and caking additive according to any one of [1] to [4], wherein the container is filled so that the layer thickness is 5 to 20 mm at / cm 3 .
[6] The evaluation method for softening and melting characteristics of coal and a binder according to [5], wherein the pulverization includes pulverizing coal or a binder so that a particle size of 2 mm or less is 100% by mass.
[7] Softening and melting characteristics of coal and caking additive according to any one of [1] to [4], wherein the material having through holes on the upper and lower surfaces is a spherical particle packed bed or a non-spherical particle packed bed Evaluation method.
[8] The coal according to any one of [1] to [4], wherein the heating of the sample includes heating in an inert gas atmosphere from room temperature to 550 ° C at a heating rate of 2 to 10 ° C / min. Evaluation method for softening and melting characteristics of binders.
[9] Coal and caking according to [3] or [4], wherein applying the constant load comprises applying a load such that the pressure on the upper surface of the material having a through hole is 5 to 80 kPa. Evaluation method for softening and melting characteristics of materials.
[10] Disposing a material having a through-hole on the upper and lower surfaces comprises disposing glass beads having a diameter of 0.2 to 3.5 mm on the sample so as to have a layer thickness of 20 to 100 mm,
Heating the sample comprises heating from room temperature to 550 ° C. in an inert gas atmosphere at a heating rate of 2 to 10 ° C./min while maintaining the sample and the glass bead layer at a constant volume;
The evaluation method of the softening and melting characteristics of the coal and the binder according to [1] or [2].
[11] Disposing a material having a through-hole on the upper and lower surfaces comprises disposing glass beads having a diameter of 0.2 to 3.5 mm on the sample so as to have a layer thickness of 20 to 100 mm,
The heating of the sample consists of heating from room temperature to 550 ° C. in an inert gas atmosphere at a heating rate of 2 to 10 ° C./min while applying a load so as to be 5 to 80 kPa from the top of the glass beads. ,
The evaluation method of the softening and melting characteristics of the coal and the binder according to [3] or [4].
[12] Preparation of the sample is performed by pulverizing coal or a binder so that a particle diameter of 3 mm or less is 70% by mass or more, and filling the pulverized coal or binder with a packing density of 0.7 to 0.9 g. / Cm 3 and filling the container so that the layer thickness is 5 to 20 mm,
Arranging the material having through holes on the upper and lower surfaces consists of arranging glass beads having a diameter of 0.2 to 3.5 mm on the sample so as to have a layer thickness of 20 to 100 mm,
The heating of the sample consists of heating in an inert gas atmosphere from room temperature to 550 ° C. at a heating rate of 2 to 10 ° C./min while maintaining the sample and the glass bead layer at a constant volume.
The evaluation method of the softening and melting characteristics of the coal and the binder according to [1] or [2].
[13] Preparation of the sample is performed by pulverizing coal or a binder so that a particle size of 3 mm or less is 70% by mass or more, and filling the pulverized coal or binder with a packing density of 0.7 to 0.9 g. / Cm 3 and filling the container so that the layer thickness is 5 to 20 mm,
Arranging the material having through holes on the upper and lower surfaces consists of arranging glass beads having a diameter of 0.2 to 3.5 mm on the sample so as to have a layer thickness of 20 to 100 mm,
The heating of the sample consists of heating from room temperature to 550 ° C. in an inert gas atmosphere at a heating rate of 2 to 10 ° C./min while applying a load so as to be 5 to 80 kPa from the top of the glass beads. ,
The evaluation method of the softening and melting characteristics of the coal and the binder according to [3] or [4].
[14] The preparation of the sample is performed by pulverizing coal or a binder so that a particle size of 2 mm or less is 100% by mass, and the pulverized coal or binder is filled with a packing density of 0.8 g / cm 3 . Consisting of filling the container so that the layer thickness is 10 mm,
Arranging the material having through holes on the upper and lower surfaces consists of arranging glass beads having a diameter of 2 mm on the sample so as to have a layer thickness of 80 mm,
Heating the sample consists of heating in an inert gas atmosphere from room temperature to 550 ° C. at a heating rate of 3 ° C./min while maintaining the sample and the glass bead layer at a constant volume,
The evaluation method of the softening and melting characteristics of the coal and the binder according to [1] or [2].
[15] The preparation of the sample is performed by pulverizing coal or a binder so that a particle size of 2 mm or less is 100% by mass, and the pulverized coal or binder is filled with a packing density of 0.8 g / cm 3 . Consisting of filling the container so that the layer thickness is 10 mm,
Arranging the material having through holes on the upper and lower surfaces consists of arranging glass beads having a diameter of 2 mm on the sample so as to have a layer thickness of 80 mm,
The heating of the sample consists of heating in an inert gas atmosphere from room temperature to 550 ° C. at a heating rate of 3 ° C./min while applying a load so as to be 50 kPa from the top of the glass beads.
The evaluation method of the softening and melting characteristics of the coal and the binder according to [3] or [4].
[16] For coal having logarithm log MF of 3.0 or more of Gieseler maximum fluidity included in the blended coal for coke production, the penetration distance which is the softening and melting characteristic of the coal is measured,
Based on the weighted average value of the measured penetration distance, a blending ratio of coal having a logarithm log MF of 3.0 or more of the Gieseller maximum fluidity is determined,
Carbonizing the coal blended at the determined blending rate,
Coke production method.
[17] The penetration distance is measured by the following (1) to (4),
The determination of the blending ratio determines the blending ratio of coal having a logarithm log MF of 3.0 or more of the Gieseler maximum fluidity so that the weighted average value of the measured penetration distance is 15 mm or less.
The method for producing coke according to [16].
(1) Coal or caking material is pulverized so that the particle size of 2 mm or less is 100% by mass, and the pulverized coal or caking material has a packing density of 0.8 g / cm 3 and a layer thickness of 10 mm. Create a sample by filling the container like
(2) Place glass beads having a diameter of 2 mm on the sample so that the layer thickness is 80 mm,
(3) While maintaining the sample and the glass bead layer at a constant volume, heating in an inert gas atmosphere from room temperature to 550 ° C. at a heating rate of 3 ° C./min,
(4) The penetration distance of the molten sample that has penetrated into the glass bead layer is measured.
[18] The penetration distance is measured by the following (1) to (4),
The determination of the blending ratio determines the blending ratio of coal having a logarithmic value log MF of 3.0 or more of the Gieseler maximum fluidity so that the weighted average value of the measured penetration distance is 17 mm or less.
The method for producing coke according to [16].
(1) Coal or caking material is pulverized so that the particle size of 2 mm or less is 100% by mass, and the pulverized coal or caking material has a packing density of 0.8 g / cm 3 and a layer thickness of 10 mm. Create a sample by filling the container like
(2) Place glass beads having a diameter of 2 mm on the sample so that the layer thickness is 80 mm,
(3) Heating in an inert gas atmosphere from room temperature to 550 ° C. at a heating rate of 3 ° C./min while applying a load from the top of the glass beads to 50 kPa,
(4) The penetration distance of the molten sample that has penetrated into the glass bead layer is measured.
[19] Predetermine the total blending ratio of coal or coal binder used for coke production and coal having a log MF of less than 3.0 in the blended coal,
Measure the penetration distance of coal with logarithm log MF of Max Gieseller's highest fluidity of 3.0 or more among coal contained in coal blend for coke production,
The log MF contained in the blended coal at that time is 3 by changing the blending rate of individual brand coal or caking additive under the condition that the total blending rate of coal having a log MF of less than 3.0 is constant. Find the relationship between the weighted average permeation distance of the coal or caking material of 0 or more and the coke strength obtained from the blended coal prepared by changing the blending ratio of the individual brand coal,
Adjust the weighted average permeation distance by adjusting the coal brand with a log MF of 3.0 or more and the blending ratio so that the coke strength is not less than the desired value.
Coke production method.
[20] The coke production method according to [19], wherein the permeation distance is measured under conditions selected from the following ranges.
Coal or caking material is pulverized so that the particle size of 3 mm or less is 70% by mass or more, and the pulverized product has a packing density of 0.7 to 0.9 g / cm 3 and a layer thickness of 5 to 20 mm. Fill the container as a sample, place glass beads with a diameter of 0.2 to 3.5 mm on the sample so that the layer thickness is 20 to 100 mm, and keep the sample and the glass bead layer at a constant volume, Heat from room temperature to 550 ° C. in an inert gas atmosphere at a temperature rising rate of 2 to 10 ° C./min.
[21] The coke production method according to [19], wherein the penetration distance is measured under conditions selected from the following ranges.
Coal or caking material is pulverized so that the particle size of 3 mm or less is 70% by mass or more, and the pulverized product has a packing density of 0.7 to 0.9 g / cm 3 and a layer thickness of 5 to 20 mm. Fill the container to make a sample, and place glass beads with a diameter of 0.2 to 3.5 mm on the sample so as to have a layer thickness of 20 to 100 mm so that the pressure is 5 to 80 kPa from the top of the glass beads. While applying a load, heating is performed in an inert gas atmosphere from room temperature to 550 ° C. at a temperature rising rate of 2 to 10 ° C./min.
本発明によれば、コークス炉内での石炭及び粘結材の軟化溶融層周辺に存在する欠陥構造、特に軟化溶融層に隣接するコークス層に存在する亀裂の影響を模擬し、また、コークス炉内での軟化溶融物周辺の拘束条件を適切に再現した状態での石炭及び粘結材の軟化溶融特性、すなわち、欠陥構造への軟化溶融物浸透距離、浸透時膨張率、浸透時圧力の評価が可能である。具体的には、本発明を用いることにより、コークス炉内で石炭及び粘結材が軟化溶融し、移動、変形した時のせん断速度での、欠陥構造への軟化溶融物浸透距離、浸透時膨張率、浸透時圧力が測定可能である。これらの測定値を用いると、コークス性状やコークスケーキ構造の推定を、従来法よりも精度良く行なうことができる。 According to the present invention, a defect structure existing in the vicinity of a softened and molten layer of coal and a binder in a coke oven, particularly an effect of a crack existing in a coke layer adjacent to the softened and molten layer, Evaluation of softening and melting characteristics of coal and binder in the state where the restraint conditions around the softened melt are appropriately reproduced, that is, the penetration distance of softened melt into the defect structure, expansion coefficient during penetration, and pressure during penetration Is possible. Specifically, by using the present invention, the softening melt penetration distance into the defect structure, the expansion during penetration, at the shear rate when the coal and the binder are softened and melted, moved and deformed in the coke oven. The rate and pressure during penetration can be measured. By using these measured values, the estimation of coke properties and coke cake structure can be performed with higher accuracy than the conventional method.
これによりコークス炉内での石炭の軟化溶融挙動を正確に評価することができるようになり、高強度コークスの製造にも利用できる。 This makes it possible to accurately evaluate the softening and melting behavior of coal in a coke oven, and can also be used to produce high-strength coke.
本発明で使用する軟化溶融特性を測定する装置の一例を図１と図２に示す。図１は石炭又は粘結材試料と上下面に貫通孔を有する材料を一定容積に保ちつつ試料を加熱する場合の装置である。図２は石炭又は粘結材試料と上下面に貫通孔を有する材料に一定荷重を負荷して試料を加熱する場合の装置である。容器３下部に石炭又は粘結材を充填して試料１とし、試料１の上に、上下面に貫通孔を有する材料２を配置する。試料１を軟化溶融温度域以上に加熱し、試料を上下面に貫通孔を有する材料２に浸透させ、浸透距離を測定する。加熱は不活性ガス雰囲気下で行なわれる。ここで、不活性ガスとは、測定温度域で石炭と反応しないガスを指し、代表的なガスとしてはアルゴンガス、ヘリウムガス、窒素ガス等である。 An example of an apparatus for measuring the softening and melting characteristics used in the present invention is shown in FIGS. FIG. 1 shows an apparatus for heating a sample while keeping a constant volume of a coal or binder sample and a material having through holes on the upper and lower surfaces. FIG. 2 shows an apparatus for heating a sample by applying a constant load to a coal or binder sample and a material having through holes on the upper and lower surfaces. The lower part of the container 3 is filled with coal or a binder to form a sample 1, and a material 2 having through holes on the upper and lower surfaces is arranged on the sample 1. The sample 1 is heated to the softening and melting temperature range or more, the sample is infiltrated into the material 2 having through holes on the upper and lower surfaces, and the infiltration distance is measured. Heating is performed in an inert gas atmosphere. Here, the inert gas refers to a gas that does not react with coal in the measurement temperature range, and representative gases include argon gas, helium gas, nitrogen gas, and the like.
試料１と上下面に貫通孔を有する材料２を一定容積に保ちつつ試料１を加熱する場合、上下面に貫通孔を有する材料２を介して試料浸透時の圧力を測定することが可能である。図１に示すように、上下面に貫通孔を有する材料２の上面に圧力検出棒４を配置し、圧力検出棒４の上端にロードセル６を接触させ、圧力を測定する。一定容積を保つため、ロードセル６が上下方向に動かないよう固定する。加熱前、容器３に充填された試料に対し、上下面に貫通孔を有する材料２、圧力検出棒４、ロードセル６間に隙間が出来ないよう、それぞれを密着させておく。上下面に貫通孔を有する材料２が粒子充填層の場合は、圧力検出棒４が粒子充填層に埋没する可能性があるため、上下面に貫通孔を有する材料２と圧力検出棒４の間に板を挟む措置を講ずるのが望ましい。 When heating the sample 1 while keeping the sample 1 and the material 2 having through holes on the upper and lower surfaces at a constant volume, it is possible to measure the pressure at the time of sample penetration through the material 2 having the through holes on the upper and lower surfaces. . As shown in FIG. 1, the pressure detection rod 4 is disposed on the upper surface of the material 2 having through holes on the upper and lower surfaces, the load cell 6 is brought into contact with the upper end of the pressure detection rod 4, and the pressure is measured. In order to maintain a constant volume, the load cell 6 is fixed so as not to move up and down. Before heating, the sample filled in the container 3 is brought into close contact with each other so that no gap is formed between the material 2 having a through hole on the upper and lower surfaces, the pressure detection rod 4 and the load cell 6. When the material 2 having through holes on the upper and lower surfaces is a particle packed layer, the pressure detection rod 4 may be buried in the particle packed layer. It is desirable to take measures to sandwich the board.
試料１と上下面に貫通孔を有する材料２に一定荷重を負荷して試料１を加熱する場合、試料１が膨張又は収縮を示し、上下面に貫通孔を有する材料２が上下方向に移動する。よって、上下面に貫通孔を有する材料２を介して試料浸透時の膨張率を測定することが可能である。図２に示すように上下面に貫通孔を有する材料２の上面に膨張率検出棒１３を配置し、膨張率検出棒１３の上端に荷重付加用の錘１４を乗せ、その上に変位計１５を配置し、膨張率を測定する。変位計１５は、試料の膨張率の膨張範囲（−１００％〜３００％）を測定可能なものを用いれば良い。加熱系内を不活性ガス雰囲気に保持する必要があるため、非接触式の変位計が適しており、光学式変位計を用いることが望ましい。不活性ガス雰囲気としては、窒素雰囲気とすることが好ましい。上下面に貫通孔を有する材料２が粒子充填層の場合は、膨張率検出棒１３が粒子充填層に埋没する可能性があるため、上下面に貫通孔を有する材料２と膨張率検出棒１３の間に板を挟む措置を講ずるのが望ましい。負荷させる荷重は、試料上面に配置した上下面に貫通孔を有する材料の上面に対して、均等にかけることが好ましく、上下面に貫通孔を有する材料の上面の面積に対し、５〜８０ｋＰａ、好ましくは１５〜５５ｋＰａ、最も好ましくは２５〜５０ｋＰａの圧力を負荷することが望ましい。この圧力は、コークス炉内における軟化溶融層の膨張圧に基づいて設定することが好ましいが、測定結果の再現性、種々の石炭での銘柄差の検出力を検討した結果、炉内の膨張圧よりはやや高めの２５〜５０ｋＰａ程度が測定条件として最も好ましいことを見出した。 When a constant load is applied to the sample 1 and the material 2 having through holes on the upper and lower surfaces and the sample 1 is heated, the sample 1 expands or contracts, and the material 2 having the through holes on the upper and lower surfaces moves in the vertical direction. . Therefore, it is possible to measure the expansion coefficient at the time of sample penetration through the material 2 having through holes on the upper and lower surfaces. As shown in FIG. 2, an expansion coefficient detection rod 13 is arranged on the upper surface of the material 2 having through holes on the upper and lower surfaces, a weight 14 for applying a load is placed on the upper end of the expansion coefficient detection rod 13, and a displacement meter 15 is placed thereon. And measure the expansion rate. The displacement meter 15 may be one that can measure the expansion range (-100% to 300%) of the expansion coefficient of the sample. Since it is necessary to maintain the inside of the heating system in an inert gas atmosphere, a non-contact type displacement meter is suitable, and it is desirable to use an optical displacement meter. The inert gas atmosphere is preferably a nitrogen atmosphere. In the case where the material 2 having through holes on the upper and lower surfaces is a particle packed layer, the expansion coefficient detecting rod 13 may be buried in the particle packed layer, and therefore the material 2 having the through holes on the upper and lower surfaces and the expansion coefficient detecting rod 13. It is desirable to take measures to sandwich the board between the two. The load to be applied is preferably evenly applied to the upper surface of the material having through holes on the upper and lower surfaces arranged on the upper surface of the sample, and 5 to 80 kPa with respect to the area of the upper surface of the material having the through holes on the upper and lower surfaces, It is desirable to apply a pressure of preferably 15 to 55 kPa, most preferably 25 to 50 kPa. This pressure is preferably set based on the expansion pressure of the softened and molten layer in the coke oven, but as a result of examining the reproducibility of the measurement results and the ability to detect the difference in brands in various coals, It has been found that a slightly higher level of about 25 to 50 kPa is most preferable as a measurement condition.
加熱手段は、試料の温度を測定しつつ、所定の昇温速度で加熱できる方式のものを用いることが望ましい。具体的には、電気炉や、導電性の容器と高周波誘導を組み合わせた外熱式、またはマイクロ波のような内部加熱式である。内部加熱式を採用する場合は、試料内温度を均一にする工夫を施す必要があり、例えば、容器の断熱性を高める措置を講ずることが好ましい。 It is desirable to use a heating means that can heat at a predetermined rate of temperature rise while measuring the temperature of the sample. Specifically, an electric furnace, an external heating type that combines a conductive container and high frequency induction, or an internal heating type such as a microwave. When the internal heating method is adopted, it is necessary to devise a method for making the temperature in the sample uniform, and for example, it is preferable to take measures to increase the heat insulation of the container.
加熱速度については、コークス炉内での石炭及び粘結材の軟化溶融挙動を模擬するという目的から、コークス炉内での石炭の加熱速度に一致させる必要がある。コークス炉内での軟化溶融温度域における石炭の加熱速度は炉内の位置や操業条件によって異なるが概ね２〜１０℃／分であり、平均的な加熱速度として２〜４℃／分とすることが望ましく、もっとも望ましいのは３℃／分程度である。しかし、非微粘結炭のように流動性の低い石炭の場合、３℃／分では浸透距離や膨張が小さく、検出が困難となる可能性がある。石炭は急速加熱することによりギーセラープラストメータによる流動性が向上することが一般的に知られている（例えば、非特許文献３参照。）。従って、例えば浸透距離が１ｍｍ以下の石炭の場合には、検出感度を向上させるために、加熱速度を１０〜１０００℃／分に高めて測定しても良い。 The heating rate needs to match the heating rate of coal in the coke oven for the purpose of simulating the softening and melting behavior of coal and binder in the coke oven. Although the heating rate of coal in the softening and melting temperature range in the coke oven varies depending on the position in the furnace and operating conditions, it is generally 2 to 10 ° C / min, and the average heating rate should be 2 to 4 ° C / min. The most desirable is about 3 ° C./min. However, in the case of coal with low fluidity such as non-slightly caking coal, the permeation distance and expansion are small at 3 ° C./min, which may make detection difficult. It is generally known that coal is improved in fluidity by a Gisela plastometer by rapid heating (see, for example, Non-Patent Document 3). Therefore, for example, in the case of coal with an infiltration distance of 1 mm or less, measurement may be performed with the heating rate increased to 10 to 1000 ° C./min in order to improve detection sensitivity.
加熱を行なう温度範囲については、石炭及び粘結材の軟化溶融特性の評価が目的であるため、石炭及び粘結材の軟化溶融温度域まで加熱できればよい。コークス製造用の石炭及び粘結材の軟化溶融温度域を考慮すると、０℃（室温）〜５５０℃の範囲において、好ましくは石炭の軟化溶融温度である３００〜５５０℃の範囲で所定の加熱速度で加熱すればよい。 About the temperature range which heats, since the objective is evaluation of the softening and melting characteristic of coal and a binder, what is necessary is just to be able to heat to the softening and melting temperature range of coal and a binder. Considering the softening and melting temperature range of coal and caking material for coke production, a predetermined heating rate in the range of 0 ° C (room temperature) to 550 ° C, preferably in the range of 300 to 550 ° C, which is the softening and melting temperature of coal. You can heat with.
上下面に貫通孔を有する材料は、透過係数をあらかじめ測定または算出できるものが望ましい。材料の形態の例として、貫通孔を持つ一体型の材料、粒子充填層が挙げられる。貫通孔を持つ一体型の材料としては、例えば、図３に示すような円形の貫通孔１６を持つもの、矩形の貫通孔を持つもの、不定形の貫通孔を持つものなどが挙げられる。粒子充填層としては、大きく球形粒子充填層、非球形粒子充填層に分けられ、球形粒子充填層としては図４に示すようなビーズの充填粒子１７からなるもの、非球形粒子充填層としては不定形粒子や、図５に示すような充填円柱１８からなるものなどが挙げられる。測定の再現性を保つため、材料内の透過係数はなるべく均一で、かつ測定を簡便にするため、透過係数の算出が容易なものが望ましい。したがって、本発明で用いる上下面に貫通孔を有する材料には球形粒子充填層の利用が特に望ましい。上下面に貫通孔を有する材料の材質は、石炭軟化溶融温度域以上、具体的には６００℃まで形状がほとんど変化せず、石炭とも反応しないものならば特に指定はない。また、その高さは、石炭の溶融物が浸透するのに十分な高さがあればよく、厚み５〜２０ｍｍの石炭層を加熱する場合には、２０〜１００ｍｍ程度あればよい。 The material having through holes on the upper and lower surfaces is preferably one that can measure or calculate the transmission coefficient in advance. Examples of the form of the material include an integrated material having a through hole and a particle packed layer. Examples of the integrated material having a through hole include a material having a circular through hole 16 as shown in FIG. 3, a material having a rectangular through hole, and a material having an indeterminate shape. The particle packed layer is roughly divided into a spherical particle packed layer and a non-spherical particle packed layer. The spherical particle packed layer is composed of beads packed particles 17 as shown in FIG. 4, and the non-spherical particle packed layer is not suitable. Examples of the particles include regular particles and filled cylinders 18 as shown in FIG. In order to maintain the reproducibility of the measurement, it is desirable that the transmission coefficient in the material is as uniform as possible and that the calculation of the transmission coefficient is easy in order to simplify the measurement. Therefore, the use of a spherical particle packed bed is particularly desirable for the material having through holes on the upper and lower surfaces used in the present invention. The material having the through holes on the upper and lower surfaces is not particularly specified as long as the shape hardly changes to the coal softening and melting temperature range, specifically up to 600 ° C., and does not react with coal. Moreover, the height should just be sufficient height for the melt of coal to osmose | permeate, and what is necessary is just about 20-100 mm when heating a coal layer of thickness 5-20 mm.
上下面に貫通孔を有する材料の透過係数は、コークス層に存在する粗大欠陥の透過係数を推定して設定する必要がある。本発明に特に望ましい透過係数について、粗大欠陥構成因子の考察や大きさの推定など、本発明者らが検討を重ねた結果、透過係数が１×１０8〜２×１０9ｍ-2の場合が最適であることを見出した。この透過係数は、下記（１）式で表されるＤａｒｃｙ則に基づき導出されるものである。
ΔＰ／Ｌ＝Ｋ・μ・ｕ ・・・ （１）
ここで、ΔＰは上下面に貫通孔を有する材料内での圧力損失［Ｐａ］、Ｌは貫通孔を有する材料の高さ［ｍ］、Ｋは透過係数［ｍ-2］、μは流体の粘度［Ｐａ・ｓ］、ｕは流体の速度［ｍ／ｓ］である。例えば上下面に貫通孔を有する材料として均一な粒径のガラスビーズ層を用いる場合、上述の好適な透過係数を持つようにするためには、直径０．２ｍｍから３．５ｍｍ程度のガラスビーズを選択することが望ましく、もっとも望ましいのは２ｍｍである。
The transmission coefficient of the material having through holes on the upper and lower surfaces needs to be set by estimating the transmission coefficient of coarse defects present in the coke layer. In the case where the transmission coefficient is 1 × 10 8 to 2 × 10 9 m −2 as a result of repeated investigations by the present inventors, such as consideration of coarse defect constituent factors and estimation of the size, which are particularly desirable for the present invention. Was found to be optimal. This transmission coefficient is derived based on the Darcy law expressed by the following equation (1).
ΔP / L = K · μ · u (1)
Here, ΔP is the pressure loss [Pa] in the material having through holes on the upper and lower surfaces, L is the height [m] of the material having the through holes, K is the transmission coefficient [m −2 ], μ is the fluid. Viscosity [Pa · s], u is fluid velocity [m / s]. For example, when a glass bead layer having a uniform particle diameter is used as a material having through holes on the upper and lower surfaces, in order to have the above-mentioned preferable transmission coefficient, glass beads having a diameter of about 0.2 mm to 3.5 mm are used. It is desirable to choose, most preferably 2 mm.
測定試料とする石炭および粘結材はあらかじめ粉砕し、所定の充填密度で所定の層厚に充填する。粉砕粒度としては、コークス炉における装入石炭の粒度（粒径３ｍｍ以下の粒子の比率が全体の７０〜８０質量％程度）としてもよく、粒径３ｍｍ以下が７０質量％以上となるように粉砕することが好ましいが、小さい装置での測定であることを考慮して、全量を粒径２ｍｍ以下に粉砕した粉砕物を用いることが特に好ましい。粉砕物を充填する密度はコークス炉内の充填密度に合わせ０．７〜０．９ｇ／ｃｍ3とすることができるが、再現性、検出力を検討した結果、０．８ｇ／ｃｍ3が好ましいことを知見した。また、充填する層厚は、コークス炉内における軟化溶融層の厚みに基づいて層厚５〜２０ｍｍとすることができるが、再現性、検出力を検討した結果、層厚は１０ｍｍとすることが好ましいことを知見した。 The coal and binder used as the measurement sample are pulverized in advance and filled to a predetermined layer thickness with a predetermined packing density. The pulverized particle size may be the particle size of the coal charged in the coke oven (the ratio of particles having a particle size of 3 mm or less is about 70 to 80% by mass), and pulverization is performed so that the particle size of 3 mm or less is 70% by mass or more. However, it is particularly preferable to use a pulverized product in which the total amount is pulverized to a particle size of 2 mm or less in consideration of measurement with a small apparatus. The density for filling the pulverized product can be 0.7 to 0.9 g / cm 3 in accordance with the packing density in the coke oven. As a result of studying reproducibility and detection power, 0.8 g / cm 3 is preferable. I found out. Further, the layer thickness to be filled can be 5 to 20 mm based on the thickness of the softened and melted layer in the coke oven, but as a result of studying reproducibility and detection power, the layer thickness should be 10 mm. I found it preferable.
石炭及び粘結材の軟化溶融物の浸透距離は、加熱中に常時連続的に測定できることが本来望ましい。しかし、常時測定は、試料から発生するタールの影響などにより、困難である。加熱による石炭の膨張、浸透現象は不可逆的であり、一旦膨張、浸透した後は冷却してもほぼその形状が保たれているので、石炭溶融物が浸透終了した後、容器全体を冷却し、冷却後の浸透距離を測定することで加熱中にどこまで浸透したかを測定するようにしてもよい。例えば、冷却後の容器から上下面に貫通孔を有する材料を取り出し、ノギスや定規で直接測定することが可能である。また、上下面に貫通孔を有する材料として粒子を使用した場合には、粒子間空隙に浸透した軟化溶融物は、浸透した部分までの粒子層全体を固着させている。したがって、前もって粒子充填層の質量と高さの関係を求めておけば、浸透終了後、固着していない粒子の質量を測定し、初期質量から差し引くことで、固着している粒子の質量を導出でき、そこから浸透距離を算出することができる。 It is inherently desirable that the penetration distance of the softened melt of coal and caking can be measured continuously during heating. However, continuous measurement is difficult due to the influence of tar generated from the sample. The expansion and infiltration phenomenon of coal by heating is irreversible, and once expanded and infiltrated, the shape is maintained even after cooling, so after the coal melt has been infiltrated, the entire container is cooled, You may make it measure how much it penetrate | infiltrated during the heating by measuring the penetration distance after cooling. For example, it is possible to take out a material having through holes on the upper and lower surfaces from the cooled container and directly measure with a caliper or a ruler. Further, when particles are used as the material having through holes on the upper and lower surfaces, the softened melt that has permeated the interparticle voids fixes the entire particle layer up to the permeated portion. Therefore, if the relationship between the mass and height of the particle packed bed is obtained in advance, the mass of the non-adhered particles is measured after the infiltration, and the mass of the adhering particles is derived by subtracting from the initial mass. And the penetration distance can be calculated therefrom.
上記の（１）式中には粘度項（μ）が含まれている。よって、本発明で測定したパラメータより、上下面に貫通孔を有する材料内に浸透した軟化溶融物の粘度項を導出することが可能である。例えば、試料と上下面に貫通孔を有する材料を一定容積に保ちつつ試料を加熱した場合では、ΔＰは浸透時圧力、Ｌは浸透距離、ｕは浸透速度となり、（１）式に代入することにより粘度項が導出可能である。また、試料と上下面に貫通孔を有する材料に一定荷重を負荷して試料を加熱する場合では、ΔＰは付加した荷重の圧力、Ｌは浸透距離、ｕは浸透速度となり、これも（１）式に代入することにより粘度が導出可能である。 Viscosity term (μ) is included in the above formula (1). Therefore, it is possible to derive the viscosity term of the softened melt that has penetrated into the material having through holes on the upper and lower surfaces from the parameters measured in the present invention. For example, when the sample is heated while maintaining a constant volume of the sample and the material having through holes on the upper and lower surfaces, ΔP is the pressure during penetration, L is the penetration distance, and u is the penetration speed, which is substituted into equation (1). From this, the viscosity term can be derived. In addition, when a sample is heated with a constant load applied to the sample and the material having through holes on the upper and lower surfaces, ΔP is the pressure of the applied load, L is the penetration distance, u is the penetration rate, and this is also (1) Viscosity can be derived by substituting into the equation.
以上のように、石炭及び粘結材の軟化溶融物の浸透距離や、圧力、膨張率を測定して、石炭及び粘結材の軟化溶融特性を評価する。ここで、本発明における「試料（石炭または粘結材）の軟化溶融特性を評価する」とは、少なくとも浸透距離や、圧力、膨張率を測定して、その測定値に基づいて、石炭溶融物の挙動および、それに起因して発生する現象（例えば、生成するコークスの性状、コークスの押し出し抵抗など）を定量的に評価するための指標を得ることを指す。測定値は浸透距離や、圧力、膨張率以外の物性値（例えば、ＭＦ等）を併用することができるが、浸透距離、圧力、膨張率のみから選択された一つ以上を用いることもできる。その場合は、浸透距離や、圧力、膨張率の測定値が得られた段階で軟化溶融特性を評価したことになり、浸透距離や、圧力、膨張率を測定することと軟化溶融特性を評価することとは実質的に同義となる。更に、前記浸透距離や、圧力、膨張率をパラメータとしてコークス強度推定に適用し、これにより複数銘柄の石炭を配合して、所望の強度を有するコークスを製造することができる。コークス強度の指標としては常温における回転強度が最も一般的であるがそれ以外にも、ＣＳＲ(coke strength after reaction)（熱間ＣＯ２反応後強度）や引張強度、ミクロ強度等のコークス性状に対する推定に適用し、これにより複数銘柄の石炭を配合して、所望の強度を有するコークスを製造することができる。
As described above, the penetration distance, pressure, and expansion rate of the softened melt of coal and caking material are measured, and the softening and melting characteristics of coal and caking material are evaluated. Here, “evaluating the softening and melting characteristics of the sample (coal or binder)” in the present invention means that at least the permeation distance, pressure, and expansion coefficient are measured, and the coal melt is measured based on the measured values. This is to obtain an index for quantitatively evaluating the behavior of the material and the phenomenon caused by the behavior (for example, properties of coke to be generated, extrusion resistance of coke). As the measurement value, a physical property value other than the permeation distance, pressure, and expansion rate (for example, MF) can be used in combination, but one or more selected from only the permeation distance, pressure, and expansion rate can also be used. In that case, the softening and melting characteristics were evaluated when the measured values of the penetration distance, pressure, and expansion rate were obtained, and the softening and melting characteristics were evaluated by measuring the penetration distance, pressure, and expansion rate. Is substantially synonymous with this. Furthermore, the coke strength estimation can be applied to the coke strength estimation using the permeation distance, pressure, and expansion rate as parameters, and thereby, a plurality of brands of coal can be blended to produce a coke having a desired strength. As besides that the rotational strength at room temperature is the most common indicator of the coke strength, CSR (coke strength after reaction) ( hot CO 2 strength after reaction) and tensile strength, estimates for coke properties of micro strength, etc. In this way, coke having a desired strength can be produced by blending multiple brands of coal.
従来のコークス強度を推定するための石炭配合理論においては、コークス強度は主に、石炭のビトリニット平均最大反射率（Ｒｏ）と、ギーセラー最高流動度（ＭＦ）の対数値（ｌｏｇＭＦ）により決定されると考えられてきた（例えば、非特許文献４参照。）。ギーセラー流動度は石炭の軟化溶融時における流動性を示す指標であり、ギーセラープラストメータの撹拌棒の回転速度、すなわち、１分間当たりの回転量をｄｄｐｍ（dial division per minute）単位で表したものである。石炭の特性値としては、最高流動度（maximum fluidity：ＭＦ）を用いる。また、ｄｄｐｍの常用対数を使用することもある。本発明による浸透距離は、コークス炉内での軟化溶融挙動を模擬した条件下での流動性を示すパラメータであると考えられるので、ギーセラー最高流動度の対数値ｌｏｇＭＦより、コークス性状やコークスケーキ構造を推定するのに優れたパラメータであると考えられる。 In conventional coal blending theory for estimating coke strength, coke strength is mainly determined by the coal's vitrinite average maximum reflectance (Ro) and logarithmic value (log MF) of the Gieseler maximum fluidity (MF). (For example, refer nonpatent literature 4.). Gieseller fluidity is an index that indicates the fluidity of coal during softening and melting. The rotation speed of the stirring rod of the Gieseller plastometer, that is, the amount of rotation per minute expressed in units of ddpm (dial division per minute) It is. The maximum fluidity (MF) is used as the characteristic value of coal. Also, the common logarithm of ddpm may be used. Since the penetration distance according to the present invention is considered to be a parameter indicating fluidity under conditions simulating softening and melting behavior in a coke oven, the coke properties and coke cake structure are determined from the logarithm log MF of the highest Gieseller fluidity. This is considered to be an excellent parameter for estimating.
このような浸透距離の優位性は、コークス炉内状況に近い測定方法をとることに基づいて原理的に想定されるだけではなく、コークス強度への浸透距離の影響を調査した結果からも明らかとなった。実際、本発明の評価方法により、同程度のｌｏｇＭＦを持つ石炭であっても、銘柄により浸透距離に差があることが明らかとなり、浸透距離の異なる石炭を配合してコークスを製造した場合のコークス強度に対する影響も異なることが確認された。具体的には、以下の実施例で示すように、浸透距離の値がある点を超えるとコークス強度が低下するような関係になっている。この理由は、以下のように考察される。 The superiority of such penetration distance is not only assumed in principle based on the measurement method close to the coke oven conditions, but is also clear from the results of investigating the effect of penetration distance on coke strength. became. In fact, the evaluation method of the present invention reveals that even if the coal has the same log MF, there is a difference in permeation distance depending on the brand, and coke when coke is produced by blending coal with different permeation distances. It was confirmed that the effect on strength was also different. Specifically, as shown in the following examples, the relationship is such that the coke strength decreases when the permeation distance value exceeds a certain point. The reason for this is considered as follows.
浸透距離が長い石炭を配合した場合、乾留時に十分な溶融を示す石炭の割合は多いと考えられる。しかし、浸透距離が長すぎる石炭は、周囲の石炭粒子間に顕著に浸透することで、その石炭粒子が存在していた部分自体が大きな空洞となり、欠陥となると推測される。従来のギーセラー最高流動度に基づく考え方でも配合炭の流動性が高すぎるとコークス強度が低下する場合があることは予想されてはいたが（例えば、非特許文献４参照。）、高流動性の個別銘柄の挙動までは明らかになっていなかった。これは、従来のギーセラー流動性測定においては、前述のＷｅｉｓｓｅｎｂｅｒｇ効果のために高流動度域での正しい物性が測定できなかったことも原因のひとつと考えられる。本発明の測定方法を採用することにより、特に流動性の高い領域における溶融物の物性をより正確に評価できるようになったため、従来の方法では区別できなかった軟化溶融物の物性の差が明確になり、軟化溶融挙動とコークス構造の関係をよりよく評価できるようになった点が、本発明により大きく進歩した点である。 When coal with a long permeation distance is blended, the proportion of coal that exhibits sufficient melting during dry distillation is considered to be large. However, it is presumed that coal having a too long permeation distance permeates remarkably between surrounding coal particles, so that the portion where the coal particles existed itself becomes a large cavity and becomes a defect. Although it has been predicted that coke strength may be reduced if the flowability of the blended coal is too high even in the conventional idea based on the maximum Gieseller fluidity (for example, refer to Non-Patent Document 4), the high fluidity. The behavior of individual brands was not clarified. This is considered to be one of the causes in the conventional measurement of the Gieseller fluidity that correct physical properties in the high fluidity range could not be measured due to the above-mentioned Weissenberg effect. By adopting the measurement method of the present invention, it has become possible to more accurately evaluate the physical properties of the melt, particularly in regions with high fluidity, so the difference in physical properties of the softened melt that could not be distinguished by conventional methods is clear. Thus, the fact that the relationship between the softening and melting behavior and the coke structure can be better evaluated is a significant advancement of the present invention.
発明者らは、本発明の方法における好適な測定条件を確立し、その測定結果を用いて高強度のコークスを製造する方法を確立した。 The inventors established suitable measurement conditions in the method of the present invention, and established a method for producing high-strength coke using the measurement results.
石炭及び粘結材試料と上下面に貫通孔を有する材料を一定容積で加熱した場合の測定例を示す。１７種類の石炭及び４種類の粘結材（Ａ炭〜Ｑ炭、粘結材Ｒ〜Ｕ）を試料として、浸透距離と浸透時圧力の測定を行った。使用した石炭及び粘結材の性状（平均最大反射率：Ｒｏ、ギーセラー最高流動度の対数値：ｌｏｇＭＦ、揮発分：ＶＭ、灰分：Ａｓｈ）を表１に示す。なお、測定に使用した粘結材の流動性をギーセラープラストメータ法で測定したところ、いずれもギーセラー最高流動度の常用対数値（ｌｏｇＭＦ）が、検出限界である４．８を示した。 The measurement example at the time of heating coal and a binder material and the material which has a through-hole in an up-and-down surface by a fixed volume is shown. Using 17 types of coal and 4 types of caking materials (A charcoal to Q charcoal, caking materials R to U) as samples, the penetration distance and the pressure during penetration were measured. Table 1 shows the properties of coal and binder used (average maximum reflectance: Ro, logarithmic value of Gieseller maximum fluidity: log MF, volatile content: VM, ash content: Ash). In addition, when the fluidity | liquidity of the caking additive used for the measurement was measured by the Gieseller plastometer method, all showed the common logarithm value (logMF) of the highest Gieseller fluidity 4.8 which is a detection limit.
図１に示したものと同様の装置を用い、浸透距離と浸透時圧力の測定を行った。加熱方式を高周波誘導加熱式としたため、図１の発熱体８は誘導加熱コイルとし、容器３の素材は誘電体である黒鉛とした。容器３の直径は１８ｍｍ、高さ３７ｍｍとし、上下面に貫通孔を有する材料２として直径２ｍｍのガラスビーズを用いた。粒径２ｍｍ以下に粉砕し室温で真空乾燥した試料２．０４ｇを容器に装入し、試料の上から重さ２００ｇの錘を落下距離２０ｍｍで５回落下させることにより試料を充填した（この状態で試料層厚は１０ｍｍとなった。）。次に直径２ｍｍのガラスビーズを試料１の充填層の上に２５ｍｍの厚さとなるように配置して、ガラスビーズ充填層を上下面に貫通孔を有する材料２とした。ガラスビーズ充填層の上に直径１７ｍｍ、厚さ５ｍｍのシリマナイト製円盤を、その上に圧力検出棒４として石英製の棒を配置した。不活性ガスとして窒素ガスを使用し、加熱速度３℃／分で室温から５５０℃まで加熱した。加熱中はロードセル６により圧力検出棒４から付加される圧力を測定した。加熱終了後、窒素雰囲気で冷却を行い、冷却後の容器３から、軟化溶融物に固着していないビーズを取り出してその質量を計測した。 Using a device similar to that shown in FIG. 1, the permeation distance and the pressure during permeation were measured. Since the heating method is a high frequency induction heating type, the heating element 8 of FIG. 1 is an induction heating coil, and the material of the container 3 is a dielectric graphite. The diameter of the container 3 was 18 mm, the height was 37 mm, and glass beads having a diameter of 2 mm were used as the material 2 having through holes on the upper and lower surfaces. 2.04 g of a sample pulverized to a particle size of 2 mm or less and vacuum-dried at room temperature was charged into a container, and a sample having a weight of 200 g was dropped from the top of the sample 5 times at a drop distance of 20 mm to fill the sample (this state) The sample layer thickness was 10 mm.) Next, glass beads having a diameter of 2 mm were arranged on the packing layer of Sample 1 so as to have a thickness of 25 mm, and the glass bead packing layer was used as material 2 having through holes on the upper and lower surfaces. A sillimanite disk having a diameter of 17 mm and a thickness of 5 mm was disposed on the glass bead packed layer, and a quartz rod was disposed thereon as the pressure detection rod 4. Nitrogen gas was used as an inert gas, and the mixture was heated from room temperature to 550 ° C. at a heating rate of 3 ° C./min. During heating, the pressure applied from the pressure detection rod 4 by the load cell 6 was measured. After completion of the heating, cooling was performed in a nitrogen atmosphere, and beads not fixed to the softened melt were taken out from the cooled container 3 and the mass thereof was measured.
浸透距離は固着したビーズ層の充填高さとした。ガラスビーズ充填層の充填高さと質量の関係をあらかじめ求め、軟化溶融物が固着したビーズの質量よりガラスビーズ充填高さを導出できるようにした。その結果が下記（２）式であり、（２）式より浸透距離を導出した。
Ｌ＝（Ｇ−Ｍ）×Ｈ ・・・ （２）
ここで、Ｌは浸透距離［ｍｍ］、Ｇは充填したガラスビーズ質量［ｇ］、Ｍは軟化溶融物と固着していないビーズ質量［ｇ］、Ｈは本実験装置に充填されたガラスビーズの１ｇあたりの充填層高さ［ｍｍ／ｇ］を表す。
The penetration distance was the filling height of the fixed bead layer. The relationship between the filling height and the mass of the glass bead packed layer was determined in advance so that the glass bead filling height could be derived from the mass of the beads to which the softened melt was fixed. The result is the following formula (2), and the penetration distance was derived from the formula (2).
L = (GM) × H (2)
Here, L is the penetration distance [mm], G is the mass of the filled glass beads [g], M is the mass of the beads not fixed to the softened melt [g], and H is the glass beads filled in this experimental apparatus. It represents the height of the packed bed per gram [mm / g].
粘結材の浸透距離を測定する際には、試料容器として、同一の径を持ち、高さ１００ｍｍの容器を用い、試料上部に配置するガラスビーズ充填層の厚さを８０ｍｍとした。これは、粘結材の浸透距離が大きいためである。なお、石炭を用い、一定の試料層厚で、容器高さとガラスビーズ充填層の厚さを変更した試験を行なったが、ガラスビーズ充填層厚さが浸透距離以上であれば、浸透距離の測定値は同じであった。 When measuring the penetration distance of the binder, a sample container having the same diameter and a height of 100 mm was used, and the thickness of the glass bead packed layer disposed on the upper part of the sample was 80 mm. This is because the penetration distance of the binder is large. In addition, a test was performed using coal and changing the height of the container and the thickness of the glass bead packed layer at a constant sample layer thickness. The value was the same.
浸透距離ならびに浸透時の最大圧力の測定結果を表２に、浸透距離測定結果とギーセラー最高流動度の対数値（ｌｏｇＭＦ）の関係を図６に示す（ＭＦ値が正しく求められなかった粘結材の値はプロットしていない。）。 Table 2 shows the measurement results of the permeation distance and the maximum pressure during permeation, and FIG. 6 shows the relationship between the measurement results of the permeation distance and the logarithmic value (log MF) of the Gieseler maximum fluidity. Values are not plotted.)
図６によれば、浸透距離はｌｏｇＭＦに対しある程度の相関は認められるが、相関から外れている銘柄も多く見られる。また、表２の粘結材の測定結果でも、従来の方法では区別できなかった粘結材物性の違いが観測できていることがわかる。試料と上下面に貫通孔を有する材料を一定容積で加熱した場合の測定において、浸透距離に影響する因子は、上記（１）式が示すとおり試料の粘度μと試料の膨張圧ΔＰであり、試料毎に変わる。従って、石炭及び粘結材試料と上下面に貫通孔を有する材料を一定容積で加熱する測定法で得られた浸透距離と圧力は、コークス炉内での溶融物の状態を反映した値であると考えられる。軟化溶融時の石炭及び粘結材の溶融状況や圧力は、乾留後のコークス構造に影響を及ぼすと推測されることから、コークス強度を推定するのに特に有効であるといえる。 According to FIG. 6, the penetration distance has a certain degree of correlation with logMF, but many brands are out of the correlation. Moreover, it can be seen from the measurement results of the binder in Table 2 that the difference in the physical properties of the binder, which could not be distinguished by the conventional method, can be observed. In the measurement when the sample and the material having through-holes on the upper and lower surfaces are heated at a constant volume, the factors affecting the permeation distance are the viscosity μ of the sample and the expansion pressure ΔP of the sample as shown in the above equation (1). Change from sample to sample. Therefore, the penetration distance and pressure obtained by the measurement method in which the coal and the binder sample and the material having through holes on the upper and lower surfaces are heated at a constant volume are values reflecting the state of the melt in the coke oven. it is conceivable that. It can be said that it is particularly effective for estimating the coke strength because it is presumed that the melting state and pressure of coal and binder during softening and melting affect the coke structure after dry distillation.
また、試料の浸透時に作用する圧力は、コークス炉内での膨張挙動を模擬した測定環境での圧力測定結果であるため、コークス炉で石炭の乾留中にコークス炉壁にかかる圧力の推定への適用にも有効であるといえる。 In addition, since the pressure acting when the sample penetrates is the result of pressure measurement in a measurement environment that simulates the expansion behavior in the coke oven, it is necessary to estimate the pressure applied to the coke oven wall during coal carbonization in the coke oven. It can be said that it is effective for application.
石炭及び粘結材試料と上下面に貫通孔を有する材料に一定荷重を負荷して試料を加熱した場合の測定例を示す。実施例１と同じ、上記表１に示す１７種類の石炭及び４種類の粘結材（Ａ炭〜Ｑ炭、粘結材Ｒ〜Ｕ）について、浸透距離と浸透時膨張率の測定を行った。図２に示したものと同様の装置を用い、浸透距離と浸透時膨張率の測定を行った。加熱方式は高周波誘導加熱式としたため、図２の発熱体８を誘導加熱コイルとし、容器３の素材は誘電体である黒鉛とした。容器３の直径は１８ｍｍ、高さ３７ｍｍとし、上下面に貫通孔を有する材料として直径２ｍｍのガラスビーズを用いた。粒径２ｍｍ以下に粉砕し室温で真空乾燥した試料２．０４ｇを容器３に装入し、試料の上から重さ２００ｇの錘を落下距離２０ｍｍで５回落下させることにより試料１を充填した。次に直径２ｍｍのガラスビーズを試料１の充填層の上に２５ｍｍの厚さとなるように配置してガラスビーズ充填層を上下面に貫通孔を有する材料２とした。ガラスビーズ充填層の上に直径１７ｍｍ、厚さ５ｍｍのシリマナイト製円盤を配置し、その上に膨張率検出棒１３として石英製の棒を置き、さらに石英棒の上部に１．３ｋｇの錘１４を置いた。これにより、シリマナイト円盤上にかかる圧力は５０ｋＰａとなる。不活性ガスとして窒素ガスを使用し、加熱速度３℃／分で５５０℃まで加熱した。加熱中はレーザー変位計により変位を測定し、試料充填時の高さから膨張率を算出した。加熱終了後、窒素雰囲気で冷却を行い、冷却後の容器から、軟化溶融物と固着していないビーズ質量を計測した。浸透距離は、上記（２）式により導出した。 An example of measurement when a sample is heated by applying a constant load to a coal and a binder sample and a material having through holes on the upper and lower surfaces is shown. About 17 types of coal and 4 types of caking materials (A charcoal-Q charcoal, caking materials RU) shown in the said Table 1 same as Example 1, the penetration distance and the expansion coefficient at the time of penetration were measured. . Using a device similar to that shown in FIG. 2, the permeation distance and the expansion coefficient during permeation were measured. Since the heating method was a high frequency induction heating type, the heating element 8 in FIG. 2 was an induction heating coil, and the material of the container 3 was a dielectric graphite. The diameter of the container 3 was 18 mm, the height was 37 mm, and glass beads having a diameter of 2 mm were used as materials having through holes on the upper and lower surfaces. The sample 1 was filled by loading 2.04 g of the sample pulverized to a particle size of 2 mm or less and vacuum-dried at room temperature into the container 3 and dropping a weight of 200 g from the sample 5 times at a drop distance of 20 mm. Next, glass beads having a diameter of 2 mm were arranged on the packing layer of Sample 1 so as to have a thickness of 25 mm, and the glass bead packing layer was used as material 2 having through holes on the upper and lower surfaces. A sillimanite disk having a diameter of 17 mm and a thickness of 5 mm is placed on the glass bead packed layer, a quartz rod is placed thereon as the expansion coefficient detecting rod 13, and a weight of 1.3 kg is placed on the quartz rod. placed. Thereby, the pressure applied on the sillimanite disk becomes 50 kPa. Nitrogen gas was used as the inert gas, and the mixture was heated to 550 ° C. at a heating rate of 3 ° C./min. During heating, the displacement was measured with a laser displacement meter, and the expansion coefficient was calculated from the height at the time of sample filling. After the heating, cooling was performed in a nitrogen atmosphere, and the mass of beads not fixed to the softened melt was measured from the cooled container. The permeation distance was derived from the above equation (2).
本実施例においても粘結材の浸透距離測定の際には、実施例１と同様に大きい容器を用い、ガラスビーズ充填層の厚さを増やして試験を行なった。なお、実施例２の条件においてもガラスビーズ充填層の厚さは浸透距離の測定値に影響しないことを確認した。 Also in this example, when measuring the penetration distance of the binder, a test was conducted using a large container as in Example 1 and increasing the thickness of the glass bead packed layer. Note that it was confirmed that the thickness of the glass bead packed layer did not affect the measured value of the penetration distance even under the conditions of Example 2.
浸透距離および最終膨張率の測定結果を表３に、浸透距離測定結果とギーセラー最高流動度の対数値（ｌｏｇＭＦ）の関係を図７に示す（ＭＦ値が正しく求められなかった粘結材の値はプロットしていない。）。 Table 3 shows the measurement results of the penetration distance and final expansion rate, and Fig. 7 shows the relationship between the measurement results of the penetration distance and the logarithmic value (log MF) of the Gieseler maximum fluidity (value of the binder whose MF value was not correctly determined). Is not plotted.)
図７によれば、本実施例で測定した浸透距離はｌｏｇＭＦとある程度の相関は認められるが、同程度のｌｏｇＭＦであっても、浸透距離の異なる銘柄が存在することが確認できた。特にその傾向は、ｌｏｇＭＦが高い領域で見られた。本装置での浸透距離の測定誤差が、同一条件で３回試験を行った結果、標準偏差０．６であったことを考慮すると、ｌｏｇＭＦがほぼ等しい石炭Ｈと石炭Ｋに対して、浸透距離に有意な差が認められた。上記（１）式の関係のみから推測すれば、同じｌｏｇＭＦの銘柄であれば溶融時粘度μも同様と考えられるため、浸透距離は同じになると考えられる。その理由は、本測定ではΔＰ、Ｋは測定する試料によらず一定であり、また、石炭のｌｏｇＭＦとその石炭が溶融性を示す温度域（溶融時間に相当）とはほぼ相関が認められるため、ｕもほぼ一定とみなせるからである。しかし、乾留中の石炭は、溶融すると同時期に、揮発分の発生に伴う発泡・膨張現象が見られる。従って、本測定によって得られた浸透距離の値とは、溶融物のビーズ充填層への浸透と、ビーズ層内での溶融物の発泡とを併せた影響を表したものであると推測される。これらの値は、乾留後のコークスの構造を決定付ける因子であると推測されることから、コークス強度を推定するのに特に有効であるといえる。 According to FIG. 7, the penetration distance measured in the present example has a certain degree of correlation with the log MF, but it was confirmed that there were brands with different penetration distances even with the same log MF. In particular, this tendency was observed in a region where log MF was high. Considering that the measurement error of the penetration distance in this device was 3 times under the same conditions, and the standard deviation was 0.6, the penetration distance for coal H and coal K with almost equal log MF A significant difference was observed. Assuming only from the relationship of the above formula (1), it is thought that the penetration distance is the same because the viscosity μ at the time of melting is the same for brands of the same log MF. The reason is that, in this measurement, ΔP and K are constant regardless of the sample to be measured, and the log MF of coal and the temperature range (corresponding to the melting time) in which the coal exhibits melting properties are almost correlated. , U can be regarded as almost constant. However, coal during dry distillation shows foaming / expansion phenomenon accompanying the generation of volatile matter at the same time as melting. Therefore, the value of the penetration distance obtained by this measurement is presumed to represent the combined effect of the penetration of the melt into the bead packed layer and the foaming of the melt in the bead layer. . Since these values are presumed to be factors determining the structure of coke after carbonization, it can be said that it is particularly effective for estimating the coke strength.
また、表３に示す最終膨張率は、５５０℃での膨張率の値である。表３の結果は、コークス炉内での膨張挙動を模擬した測定環境での膨張率測定結果であるため、コークス強度推定や、コークス炉壁とコークス塊の隙間の推定に有効であるといえる。 Moreover, the final expansion coefficient shown in Table 3 is a value of the expansion coefficient at 550 ° C. The results in Table 3 are expansion coefficient measurement results in a measurement environment simulating expansion behavior in a coke oven, and can be said to be effective for estimating coke strength and estimating the gap between the coke oven wall and the coke lump.
実施例２と同じ測定方法で浸透距離の加成性の成立状況を調査した。 The state of establishment of additivity of the permeation distance was investigated by the same measurement method as in Example 2.
４種類の石炭（Ｖ炭〜Ｙ炭）のうちから２銘柄を選び、種々配合率を変えて作製した配合炭を試料として、浸透距離の測定を行った。使用した石炭ならびに配合炭の性状（Ｒｏ、ｌｏｇＭＦ、ＶＭ、Ａｓｈ）を表４に示す。ここで、配合炭の性状は単味炭の性状を配合割合で平均した加重平均値である。浸透距離の測定結果を表４に併せて示す。また、配合炭の加重平均浸透距離と実測浸透距離の関係を図８に示す。 Two brands were selected from four types of coal (V charcoal to Y charcoal), and the penetration distance was measured using blended coal produced by changing various blending ratios as samples. Table 4 shows the properties of the coal used and the blended coal (Ro, logMF, VM, Ash). Here, the property of blended coal is a weighted average value obtained by averaging the properties of plain coal by blending ratio. The measurement results of the penetration distance are also shown in Table 4. FIG. 8 shows the relationship between the weighted average penetration distance and the actually measured penetration distance of the blended coal.
図８によれば、本実施例で測定した浸透距離は極めて良好な加成性が成立することが分かる。従って、2種類以上の石炭を配合してなる配合炭の浸透距離の値を求めるには、実際に作製した配合炭を試料として浸透距離を測定しても良いし、配合炭を構成する単味炭の浸透距離を予め測定しておき、加重平均値を計算して推定することもできる。 According to FIG. 8, it can be seen that the penetration distance measured in the present example is very good additivity. Therefore, in order to obtain the value of the penetration distance of the blended coal formed by blending two or more types of coal, the penetration distance may be measured using the actually prepared blended coal as a sample, or the simple coal constituting the blended coal The penetration distance of charcoal can be measured in advance, and a weighted average value can be calculated and estimated.
配合炭に使用する石炭は、通常、銘柄ごとに様々な品位を予め測定して使用している。従って、浸透距離についても同様に予め銘柄のロット毎に測定しておけば、配合炭の浸透距離を速やかに算出することが可能となるため、実用上好ましい。 Coal used for blended coal is usually used by measuring various grades for each brand in advance. Accordingly, if the permeation distance is similarly measured in advance for each brand lot, the permeation distance of the blended coal can be calculated quickly, which is practically preferable.
本発明で得られた石炭の軟化溶融特性値をコークス強度推定に適用し、その有効性を検討した。 The softening and melting characteristics of the coal obtained in the present invention were applied to the estimation of coke strength, and the effectiveness was examined.
上記のように、本発明による浸透距離は、ギーセラー最高流動度の対数値ｌｏｇＭＦより、コークス性状やコークスケーキ構造を推定するのに優れたパラメータであると考えられるので、ｌｏｇＭＦがほぼ等しく、浸透距離の異なる石炭を用いてコークスを製造した場合のコークス強度への影響を調査するために、以下の要領で乾留試験ならびに乾留後コークスの強度試験を実施した。 As described above, the penetration distance according to the present invention is considered to be an excellent parameter for estimating the coke properties and the coke cake structure from the logarithmic value log MF of the maximum Gieseller fluidity. In order to investigate the effect on coke strength when coke was produced using different coals, a carbonization test and a strength test of coke after carbonization were conducted as follows.
上記実施例１、２で用いた表１において、石炭Ａ、石炭Ｆ、石炭Ｇ（ｌｏｇＭＦが３．５以上）を「同程度ＭＦ炭」として選択し、それぞれを２０ｍａｓｓ%配合し、配合炭全体の加重平均Ｒｏ、加重平均ｌｏｇＭＦは等しくなるように、種々の石炭を残部として配合した配合炭（配合炭Ａ、Ｆ、Ｇ）を準備した。石炭Ａ、石炭Ｆ、石炭Ｇは、コークス製造において用いられる石炭のなかでもＭＦが高い種類の石炭であって、コークス製造において、石炭粒子の接着性を向上させることを意図して用いられることが多い石炭である。さらに、こうした高ＭＦ炭を混合して使用した場合の試験として、ｌｏｇＭＦ≧３．０の複数の銘柄を同時に用いた配合炭（配合炭ＡＦ、配合炭ＦＧ、配合炭ＦＧＫ）を準備した。なお、配合炭の平均品位は、Ｒｏ＝０．９９〜１．０５、ｌｏｇＭＦ＝２．０〜２．３となるように調製した。それぞれの配合炭で用いた石炭の銘柄とその配合率、および配合炭中におけるｌｏｇＭＦ≧３．０の石炭の加重平均定積浸透距離（表２の値から計算）、加重平均定圧浸透距離（表３の値から計算）、生成したコークスの強度を表５に示す。 In Table 1 used in Examples 1 and 2 above, Coal A, Coal F, and Coal G (log MF is 3.5 or more) are selected as “same MF coal”, and each is blended by 20 mass%, and the entire blended coal The blended coals (mixed coals A, F, and G) blended with various coals as the balance were prepared so that the weighted average Ro and the weighted average log MF were equal. Coal A, coal F, and coal G are types of coal having a high MF among the coals used in coke production, and may be used with the intention of improving the adhesion of coal particles in coke production. A lot of coal. Furthermore, as a test in the case where such high MF coal was mixed and used, blended coal (mixed coal AF, blended coal FG, blended coal FGK) using a plurality of brands having logMF ≧ 3.0 at the same time was prepared. The average quality of the blended coal was prepared so that Ro = 0.99 to 1.05 and logMF = 2.0 to 2.3. Brands of coal used in each blended coal and their blending ratio, weighted average constant volume penetration distance (calculated from the values in Table 2) of coal with logMF ≧ 3.0 in the blended coal, weighted average constant pressure penetration distance (table Table 5 shows the strength of the generated coke.
ここで、表５で用いる各石炭は、粒径３ｍｍ以下１００ｍａｓｓ％に粉砕したものを使用し、配合炭全体の水分が８ｍａｓｓ％になるように調整した。この配合炭１６ｋｇを、嵩密度７５０ｋｇ／ｍ3となるように乾留缶に充填し、その上に１０ｋｇの錘を乗せた状態で、炉壁温度１０５０℃の電気炉内で６時間乾留後、炉から取り出し窒素冷却し、コークスを得た。得られたコークスのコークス強度は、ＪＩＳ Ｋ ２１５１の回転強度試験法に基づき、１５ｒｐｍ、１５０回転後の粒径１５ｍｍ以上のコークスの質量割合を測定し、回転前との質量比をドラム強度指数ＤＩ１５０／１５として算出した。さらにＣＲＩ（熱間ＣＯ２反応性）、ＣＳＲ（熱間ＣＯ２反応後強度、いずれもＩＳＯ１８８９４法に準拠して測定）、マイクロ強度（ＭＳＩ＋６５）の測定結果も示した。 Here, the coal used in Table 5 was pulverized to a particle size of 3 mm or less and 100 mass%, and adjusted so that the water content of the entire blended coal became 8 mass%. 16 kg of this blended charcoal was filled in a dry distillation can so that the bulk density was 750 kg / m 3, and 10 kg of weight was placed on the can, and after carbonization in an electric furnace with a furnace wall temperature of 1050 ° C., And then cooled with nitrogen to obtain coke. The coke strength of the obtained coke was measured based on the rotational strength test method of JIS K 2151. The mass ratio of coke with a particle size of 15 mm or more after 15 rpm and 150 revolutions was measured, and the mass ratio before the revolution was determined as the drum strength index DI150. / 15. Furthermore, the measurement results of CRI (hot CO 2 reactivity), CSR (strength after hot CO 2 reaction, both measured according to ISO 18894 method), and micro strength (MSI + 65) are also shown.
各配合炭について、配合炭中に含まれるギーセラー最高流動度の対数値ｌｏｇＭＦ≧３．０の石炭の定圧浸透距離（実施例２で測定した、石炭試料と上下面に貫通孔を有する材料に一定荷重を負荷して石炭試料を加熱した測定で得られた浸透距離）の加重平均値と、各配合炭の乾留後コークスのドラム強度との関係を図９に示す。同程度ＭＦ炭として石炭Ａ、石炭Ｆ、石炭Ｇを２０ｍａｓｓ％配合した配合炭Ａ、配合炭Ｆ、配合炭Ｇの強度を比較すると、同程度ＭＦ炭の浸透距離が短いほど高いドラム強度を示した。更には、配合炭Ａ、配合炭Ｆ、配合炭ＡＦのドラム強度の結果から、同程度ＭＦ炭の浸透距離とドラム強度との間には、加成性が成立することがわかる。この例に加えて、配合炭ＦＧおよび配合炭ＦＧＫの結果も合わせると、配合炭中に含まれるギーセラー最高流動度の対数値ｌｏｇＭＦ≧３．０の石炭の定圧浸透距離の加重平均値が１７ｍｍを超えるとコークス強度が低下することがわかる。したがって、配合炭中に含まれるギーセラー最高流動度の対数値ｌｏｇＭＦ≧３．０の石炭の定圧浸透距離の加重平均値を１７ｍｍ以下にすることによって、高強度のコークスの製造が可能になる。 For each blended coal, constant pressure penetration distance of coal with logarithm log MF ≧ 3.0 of the Gieseler maximum fluidity contained in the blended coal (constant to the coal sample and the material having through holes on the upper and lower surfaces as measured in Example 2) FIG. 9 shows the relationship between the weighted average value of the permeation distance obtained by heating a coal sample under a load and the drum strength of coke after dry distillation of each blended coal. Comparing the strengths of blended coal A, blended coal F, blended coal G containing 20 mass% of coal A, coal F, and coal G as MF coal, the higher the MF coal penetration distance, the higher the drum strength. It was. Furthermore, it can be seen from the results of the drum strengths of blended coal A, blended coal F, and blended coal AF that additivity is established between the penetration distance of MF coal and the drum strength. In addition to this example, when the results of blended coal FG and blended coal FGK are also combined, the weighted average value of constant pressure penetration distance of coal with log MF ≧ 3.0 of the maximum Gieseller flow rate contained in the blended coal is 17 mm. When it exceeds, it turns out that coke intensity | strength falls. Therefore, high strength coke can be produced by setting the weighted average value of the constant pressure permeation distance of coal with logarithm log MF ≧ 3.0 of the Gieseler maximum fluidity contained in the blended coal to 17 mm or less.
次に、各配合炭について、配合炭中に含まれるギーセラー最高流動度の対数値ｌｏｇＭＦ≧３．０の石炭の定積浸透距離（実施例１で測定した、石炭試料と上下面に貫通孔を有する材料を一定容積で加熱した測定で得られた浸透距離）の加重平均値と、各配合炭の乾留後コークスのドラム強度との関係を図１０に示す。 Next, for each blended coal, coal constant volume penetration distance of logarithm log MF ≧ 3.0 of the Gieseler maximum fluidity contained in the blended coal (through holes in the upper and lower surfaces of the coal sample measured in Example 1). FIG. 10 shows the relationship between the weighted average value of the permeation distance obtained by heating a material having a constant volume and the drum strength of coke after dry distillation of each blended coal.
図１０においても図９よりもやや弱いながら同様の傾向が認められ、本測定で得られた浸透距離の値は、一定容積で加熱した測定で得られた場合にも、一定荷重を負荷して加熱した測定で得られた場合にも、コークス強度に対して影響を及ぼしていることが分かる。なお、定積浸透距離を指標とする場合、配合炭中に含まれるギーセラー最高流動度の対数値ｌｏｇＭＦ≧３．０の石炭の定積浸透距離の加重平均値は１５ｍｍ以下とすることが好ましいと判断される。浸透距離の測定結果は、同じ石炭であっても用いる測定条件によって異なるため、各石炭の評価は実質的に同一の条件で行なう必要がある。試料の層厚と充填密度の積が±２０％の範囲であり、貫通孔を有する材料の形式（球形粒子充填層または円柱充填層等）は同一として球形または円柱の径が±２０％の範囲であり、加熱速度が±２０％の範囲であれば実用上は問題なく使用できるので、その範囲を実質的に同一であるとする。このような条件で測定した値を用いて、図９、１０のように、配合炭に含まれる高ＭＦ炭の浸透距離と、その配合炭を乾留して得られるコークス強度の相関を予め得ておけば、所望のコークス強度を得るために高ＭＦ炭の浸透距離をどの程度に調製すればよいかを知ることができる。なお、配合炭ＦＧおよび、配合炭ＦＧＫから製造したコークスについてはＣＳＲの測定も行なった。その結果、配合炭ＦＧからのコークスではＣＳＲ＝５５．４（反応性ＣＲＩ＝２９．７）、配合炭ＦＧＫから製造したコークスではＣＳＲ＝５９．５（反応性ＣＲＩ＝２９．５）となり、ＪＩＳドラム強度と同様の傾向が確認された。一般にコークスの反応性ＣＲＩが同程度であれば、ＣＳＲはＪＩＳドラム強度と良好な相関を示すことが知られており、この傾向は実施例における試料でも確認できた。なお、マイクロ強度、間接引張強度においてもＪＩＳドラム強度と同様の傾向が確認された。 In FIG. 10, the same tendency is recognized although slightly weaker than in FIG. 9, and the value of the penetration distance obtained in this measurement is a constant load even when obtained by measurement with heating at a constant volume. It can also be seen that it has an effect on coke strength when obtained by heating measurements. In addition, when the fixed volume penetration distance is used as an index, it is preferable that the weighted average value of the fixed volume penetration distance of coal with logarithm logMF ≧ 3.0 of the Gieseler maximum fluidity contained in the blended coal is 15 mm or less. To be judged. Since the measurement results of the penetration distance vary depending on the measurement conditions used even for the same coal, it is necessary to evaluate each coal under substantially the same conditions. The product of the layer thickness and the packing density of the sample is in the range of ± 20%, and the type of the material having the through hole (spherical particle packed layer or cylindrical packed layer, etc.) is the same, and the spherical or cylindrical diameter is in the range of ± 20%. If the heating rate is within a range of ± 20%, it can be used practically without any problem, and the range is assumed to be substantially the same. Using the values measured under such conditions, as shown in FIGS. 9 and 10, a correlation between the penetration distance of the high MF coal contained in the blended coal and the coke strength obtained by dry distillation of the blended coal is obtained in advance. If so, it is possible to know how much the permeation distance of the high MF coal should be adjusted in order to obtain a desired coke strength. In addition, CSR was also measured about the coking coal FG and the coke manufactured from the mixing coal FGK. As a result, coke from blended coal FG has CSR = 55.4 (reactive CRI = 29.7), coke produced from blended coal FGK has CSR = 59.5 (reactive CRI = 29.5), and JIS. A tendency similar to drum strength was confirmed. In general, it is known that CSR has a good correlation with JIS drum strength when the coke reactivity CRI is comparable, and this tendency can be confirmed also in the samples in the examples. The same tendency as the JIS drum strength was confirmed in the micro strength and the indirect tensile strength.
以上のように、高ＭＦ炭の浸透距離がコークス強度に大きく影響を及ぼすことが明らかとなった。特に高ＭＦ炭で浸透距離の影響が顕著な理由としては、図６、図７に示すように、高ＭＦ炭ほど浸透距離の差が大きくなることが考えられる。低ＭＦ炭では浸透距離の銘柄差はあまり大きくなく、浸透距離の影響が現れにくかった可能性がある。また、高ＭＦ炭では前述のＷｅｉｓｓｅｎｂｅｒｇ効果や測定可能上限の存在によって、ギーセラープラストメーター法では軟化溶融特性が十分に評価できていなかった可能性がある。本発明の方法により、従来法の欠点を改善することができたため、軟化溶融特性のコークス強度への影響に関する新たな知見を得ることが可能になったものと考えられる。 As described above, it has been clarified that the penetration distance of high MF coal greatly affects the coke strength. Particularly, the reason why the influence of the penetration distance is remarkable in the high MF coal is considered to be that the difference in the penetration distance becomes larger as the high MF coal, as shown in FIGS. With low MF charcoal, the brand difference in the penetration distance is not so large, and the influence of the penetration distance may be difficult to appear. Moreover, in the high MF coal, the softening and melting characteristics may not be sufficiently evaluated by the Giesser plastometer method due to the above-mentioned Weissenberg effect and the existence of the upper limit of measurement. Since the method of the present invention has improved the drawbacks of the conventional method, it is considered that it has become possible to obtain new knowledge regarding the influence of the softening and melting characteristics on the coke strength.
次に、浸透距離がコークス強度に影響する理由を確認するために、光学顕微鏡を用い、浸透距離が好適であると考えられる石炭Ａを２０ｍａｓｓ％配合した配合炭Ａを乾留したコークスと、浸透距離が長すぎると考えられる石炭Ｆを２０ｍａｓｓ％配合した配合炭Ｆを乾留したコークスの組織観察を行った。倍率１００倍で撮影した石炭Ａの写真を図１１に、石炭Ｆの写真を図１２に示す。 Next, in order to confirm the reason why the permeation distance affects the coke strength, coke obtained by dry distillation of blended coal A containing 20 mass% of coal A, which is considered to be suitable for the permeation distance, using an optical microscope, and the permeation distance The structure of the coke obtained by carbonizing coal blend F containing 20 mass% of coal F, which is considered to be too long, was observed. A photograph of coal A taken at a magnification of 100 is shown in FIG. 11, and a photograph of coal F is shown in FIG.
図１１及び図１２に示す写真を比較すると、浸透距離が長すぎる石炭Ｆを配合した配合炭Ｆを乾留したコークスは、浸透距離が好適な石炭Ａを配合した配合炭Ａを乾留したコークスに比べて気孔壁２０が薄く、また、気孔同士が連結し、歪な形状の粗大な気孔２１を形成していることがわかった。コークス強度は、気孔壁が厚いほど、気孔の真円度が高いほど高くなることが報告されている（例えば、非特許文献５参照。）。従って、石炭の浸透距離が、乾留時のコークス構造の形成に影響を及ぼし、その結果、コークス強度に影響することが確認できた。 Comparing the photographs shown in FIG. 11 and FIG. 12, the coke obtained by dry distillation of coal blend F containing coal F whose penetration distance is too long is compared with the coke obtained by dry distillation of coal blend A containing coal A having a suitable penetration distance. It was found that the pore wall 20 was thin and the pores were connected to form a coarse pore 21 having a distorted shape. It has been reported that the coke strength increases as the pore walls become thicker and the roundness of the pores becomes higher (see, for example, Non-Patent Document 5). Therefore, it was confirmed that the permeation distance of coal has an effect on the formation of coke structure during dry distillation and, as a result, has an influence on coke strength.
本実施例から、石炭試料と上下面に貫通孔を有する材料に一定荷重を負荷して石炭試料を加熱した測定および石炭試料と上下面に貫通孔を有する材料を一定容積で加熱した測定で得られた浸透距離は、生成するコークスの強度に影響を及ぼす因子であり、かつ、従来因子では説明できない因子であることから、従来のコークス強度推定に組み合わせることで、高精度の強度推定が可能となることが分かる。さらに好ましい条件において測定された浸透距離に基づいて石炭の配合を行うことで、高強度コークスの製造が可能になることが分かる。 From this example, the measurement was performed by applying a constant load to the coal sample and the material having the through holes on the upper and lower surfaces and heating the coal sample and measuring the coal sample and the material having the through holes on the upper and lower surfaces with a constant volume. The penetration distance obtained is a factor that affects the strength of the coke to be generated, and is a factor that cannot be explained by the conventional factors. I understand that Furthermore, it turns out that manufacture of a high intensity | strength coke is attained by mix | blending coal based on the penetration distance measured on preferable conditions.
１ 試料
２ 上下面に貫通孔を有する材料
３ 容器
４ 圧力検出棒
５ スリーブ
６ ロードセル
７ 温度計
８ 発熱体
９ 温度検出器
１０ 温度調節器
１１ ガス導入口
１２ ガス排出口
１３ 膨張率検出棒
１４ 錘
１５ 変位計
１６ 円形貫通孔
１７ 充填粒子
１８ 充填円柱
２０ 気孔壁
２１ 気孔
DESCRIPTION OF SYMBOLS 1 Sample 2 Material which has a through-hole in the upper and lower surfaces 3 Container 4 Pressure detection rod 5 Sleeve 6 Load cell 7 Thermometer 8 Heating element 9 Temperature detector 10 Temperature controller 11 Gas inlet 12 Gas outlet 13 Expansion coefficient detection rod 14 Weight DESCRIPTION OF SYMBOLS 15 Displacement meter 16 Circular through-hole 17 Packing particle 18 Packing cylinder 20 Porous wall 21 Porous
Claims (3)
測定された浸透距離の加重平均値に基づいて、前記ギーセラー最高流動度の対数値ｌｏｇＭＦが３．０以上の石炭の配合率を決定し、
決定された配合率により配合された石炭を乾留する、
コークスの製造方法。 For coal with logarithm log MF of Max Gieseller included in coal blend for coke production of 3.0 or more, measure the penetration distance, which is the softening and melting characteristic of coal,
Based on the weighted average value of the measured penetration distance, a blending ratio of coal having a logarithm log MF of 3.0 or more of the Gieseller maximum fluidity is determined,
Carbonizing the coal blended at the determined blending rate,
Coke production method.
前記配合率の決定が、測定された浸透距離の加重平均値が１５ｍｍ以下になるように、前記ギーセラー最高流動度の対数値ｌｏｇＭＦが３．０以上の石炭の配合率を決定する、
請求項１に記載のコークスの製造方法。
（１）石炭又は粘結材を粒径２ｍｍ以下が１００質量％となるように粉砕し、該粉砕された石炭又は粘結材を充填密度０．８ｇ／ｃｍ３で、層厚が１０ｍｍとなるように容器に充填して試料を作成し、
（２）該試料の上に直径２ｍｍのガラスビーズを層厚８０ｍｍとなるように配置し、
（３）前記試料と前記ガラスビーズ層を一定容積に保ちつつ、加熱速度３℃／分で室温から５５０℃まで不活性ガス雰囲気下で加熱し、
（４）前記ガラスビーズ層へ浸透した溶融試料の浸透距離を測定する。 The measurement of the penetration distance is performed by the following (1) to (4),
The determination of the blending ratio determines the blending ratio of coal having a logarithm log MF of 3.0 or more of the Gieseler maximum fluidity so that the weighted average value of the measured penetration distance is 15 mm or less.
The method for producing coke according to claim 1.
(1) Coal or caking material is pulverized so that the particle size of 2 mm or less is 100% by mass, and the pulverized coal or caking material has a packing density of 0.8 g / cm 3 and a layer thickness of 10 mm. Create a sample by filling the container like
(2) Place glass beads having a diameter of 2 mm on the sample so that the layer thickness is 80 mm,
(3) While maintaining the sample and the glass bead layer at a constant volume, heating in an inert gas atmosphere from room temperature to 550 ° C. at a heating rate of 3 ° C./min,
(4) The penetration distance of the molten sample that has penetrated into the glass bead layer is measured.
前記配合率の決定が、測定された浸透距離の加重平均値が１７ｍｍ以下になるように、前記ギーセラー最高流動度の対数値ｌｏｇＭＦが３．０以上の石炭の配合率を決定する、
請求項１に記載のコークスの製造方法。
（１）石炭又は粘結材を粒径２ｍｍ以下が１００質量％となるように粉砕し、該粉砕された石炭又は粘結材を充填密度０．８ｇ／ｃｍ３で、層厚が１０ｍｍとなるように容器に充填して試料を作成し、
（２）該試料の上に直径２ｍｍのガラスビーズを層厚８０ｍｍとなるように配置し、
（３）前記ガラスビーズの上部から５０ｋＰａとなるように荷重を負荷しつつ、加熱速度３℃／分で室温から５５０℃まで不活性ガス雰囲気下で加熱し、
（４）前記ガラスビーズ層へ浸透した溶融試料の浸透距離を測定する。 The measurement of the penetration distance is performed by the following (1) to (4),
The determination of the blending ratio determines the blending ratio of coal having a logarithmic value log MF of 3.0 or more of the Gieseler maximum fluidity so that the weighted average value of the measured penetration distance is 17 mm or less.
The method for producing coke according to claim 1.
(1) Coal or caking material is pulverized so that the particle size of 2 mm or less is 100% by mass, and the pulverized coal or caking material has a packing density of 0.8 g / cm 3 and a layer thickness of 10 mm. Create a sample by filling the container like
(2) Place glass beads having a diameter of 2 mm on the sample so that the layer thickness is 80 mm,
(3) Heating in an inert gas atmosphere from room temperature to 550 ° C. at a heating rate of 3 ° C./min while applying a load from the top of the glass beads to 50 kPa,
(4) The penetration distance of the molten sample that has penetrated into the glass bead layer is measured.
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