JP2007204629A - Formulation method for coke production raw material - Google Patents

Formulation method for coke production raw material Download PDF

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JP2007204629A
JP2007204629A JP2006025659A JP2006025659A JP2007204629A JP 2007204629 A JP2007204629 A JP 2007204629A JP 2006025659 A JP2006025659 A JP 2006025659A JP 2006025659 A JP2006025659 A JP 2006025659A JP 2007204629 A JP2007204629 A JP 2007204629A
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coke
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strength
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JP4871605B2 (en
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Hiroko Nishihata
裕子 西端
Masaru Nishimura
勝 西村
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Kansai Coke and Chemicals Co Ltd
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Abstract

<P>PROBLEM TO BE SOLVED: To provide a method for formulating coke production raw materials using coking coal and an organic material (material which is not usable ordinarily as a raw material for metallurgical coke), and capable of keeping the strength of the obtained coke to the highest possible level. <P>SOLUTION: The method for the formulation of coking coal and an organic material to form a raw material for producing metallurgical coke. The formulation of the raw materials is carried out by determining the formulation ratio of the organic material based on the correlation data between the quantity of CO<SB>2</SB>generated from a formulated specimen composed of the coking coal and the organic material until the specimen reaches the Giesler maximum fluidity temperature and the coke strength and the correlation data between the weight ratio of the dry-distilled organic material in the produced coke in the coking of a specimen of the formulated coal and the coke strength, and performing the formulation of the raw material based on the determined formulation ratio of the organic material. <P>COPYRIGHT: (C)2007,JPO&INPIT

Description

本発明は、原料炭と有機物を用いて冶金用コークス製造用原料を配合する方法に関するものである。   The present invention relates to a method of blending raw materials for producing metallurgical coke using raw coal and organic matter.

冶金用コークスの原料用の石炭としては、加熱時に軟化溶融し、その後再固化して強固なコークスとなるものが優れた原料炭であるとされており、主に瀝青炭が使用されてきている。従って、軟化溶融性を有さない褐炭などの劣質炭は一般的には使用されていない。しかし、コークス原料として使用することのできる瀝青炭の資源量には限りがあるとともに、瀝青炭は他の石炭に比較してコストが高いという問題がある。そこで、より広範囲の石炭等を用いてコークス原料を配合する試みが行なわれているが、単に瀝青炭を他の褐炭等と配合した場合には、製造されるコークスの強度低下などの問題が生じるため、配合するにあたり熱処理を行なうなどの工夫が要求される。かかる点に鑑みて、下記特許文献1〜3に示されるような処理方法が種々提案されてきている。   As coal for raw materials of metallurgical coke, what is softened and melted when heated and then re-solidified to become strong coke is considered to be an excellent raw coal, and bituminous coal has been mainly used. Therefore, inferior quality coal such as lignite that does not have soft melting property is generally not used. However, the amount of resources of bituminous coal that can be used as a coke raw material is limited, and bituminous coal has a problem that it is more expensive than other coals. Therefore, attempts have been made to blend coke raw materials using a wider range of coal, but when bituminous coal is simply blended with other lignite, problems such as reduced strength of the coke produced arise. Therefore, a device such as heat treatment is required for blending. In view of this point, various processing methods as shown in Patent Documents 1 to 3 below have been proposed.

特許文献1は、冶金用コークスを製造するための中間製品であるチャーの製造方法を開示するものであり、高揮発分非、微粘結炭(高揮発分非粘結炭、褐炭、微粘結炭)から製造するに際して、高揮発分非、微粘結炭を250℃から最高450℃〜600℃の温度範囲で緩速乾留することで最適のチャーを製造することが記載されている。   Patent Document 1 discloses a method for producing char, which is an intermediate product for producing metallurgical coke. Highly volatile matter-free, slightly caking coal (high volatile matter non-caking coal, lignite, slightly caking coal It is described that an optimum char is produced by subjecting a low volatile matter non-fine coking coal to a slow carbonization within a temperature range of 250 ° C. to a maximum of 450 ° C. to 600 ° C. when producing it from coal.

特許文献2は、褐炭のような劣質炭を用いて高炉用コークスを製造する方法を開示するものであり、劣質炭を媒体液中で圧力を1〜20MPa、温度を400℃以下として熱処理した後、さらに熱処理炭と媒体液を分離した後、熱処理炭を配合炭の一部に代えてコークス炉に装入して乾留するものである。   Patent Document 2 discloses a method for producing coke for blast furnace using inferior coal such as lignite, and after heat treating the inferior coal in a medium liquid at a pressure of 1 to 20 MPa and a temperature of 400 ° C. Further, after the heat-treated charcoal and the medium liquid are separated, the heat-treated charcoal is replaced with a part of the blended charcoal and charged into a coke oven for dry distillation.

特許文献3は、コークスの製造方法を開示するものであり、予め熱処理された木質系廃棄物を原料炭と共にコークス炉に装入するものである。熱処理は、空気を遮断して350℃〜450℃に加熱することで行われる。   Patent Document 3 discloses a method for producing coke, in which woody waste that has been heat-treated in advance is charged into a coke oven together with raw coal. The heat treatment is performed by heating to 350 ° C. to 450 ° C. while blocking air.

特開昭56−136880号公報JP-A-56-136880 特開2003−55667号公報JP 2003-55667 A 特開2004−307683号公報JP 2004-307683 A

このように、より広範囲の石炭やその他の有機物を使用してコークス原料とする試みがなされているものの、依然として次に説明するような課題を有している。   Thus, although attempts have been made to produce coke raw materials using a wider range of coal and other organic substances, there are still problems as described below.

特許文献1においては、劣質炭を熱処理する際の温度が250℃〜600℃と広範囲にわたっている。しかし、熱処理時の最適温度は石炭の銘柄等により大きく異なると考えられるが、かかる最適温度をいかにして決定するかの条件が開示されていない。   In patent document 1, the temperature at the time of heat-processing an inferior quality coal is 250 to 600 degreeC over a wide range. However, although it is considered that the optimum temperature during the heat treatment varies greatly depending on the brand of coal and the like, the conditions for determining the optimum temperature are not disclosed.

特許文献2にも、劣質炭を加圧・加熱処理することでコークスの品質を改善することが記載されているが、処理条件の違いがコークス強度にどのように影響を及ぼすのかについて開示されていない。   Patent Document 2 also describes that coke quality is improved by pressurizing and heat-treating inferior coal, but it is disclosed how differences in processing conditions affect coke strength. Absent.

特許文献3は、木質系廃棄物を熱処理してコークス原料とする方法が開示されているが、やはり同様に、熱処理における最適温度をいかにして決定するかの条件が開示されていない。また、木質系廃棄物以外の有機物をコークス原料とする点については開示がない。   Patent Document 3 discloses a method of heat treating woody waste to produce a coke raw material, but similarly, the conditions for determining the optimum temperature in heat treatment are not disclosed. In addition, there is no disclosure regarding the use of organic materials other than woody waste as coke raw materials.

本発明は上記実情に鑑みてなされたものであり、その課題は、原料炭と有機物を用いて冶金用コークス製造用原料を配合するに際し、得られるコークスの強度を可能な限り高い水準に維持できるような配合方法を提供することである。   The present invention has been made in view of the above circumstances, and the problem is that when the raw material for producing metallurgical coke is blended using raw coal and organic matter, the strength of the obtained coke can be maintained at the highest possible level. It is to provide such a blending method.

上記課題を解決するため本発明に係るコークス製造用原料の配合方法は、原料炭と劣質炭や木質系廃棄物のような有機物を用いて高炉用コークス製造用原料を配合する方法であって、原料炭と有機物を配合した試料のギースラー最高流動度温度に達するまでに発生するCO2の発生量とコークス強度との相関関係データと、前記試料コークス化時における製造コークス中の有機物乾留物の重量割合とコークス強度との相関関係データに基づいて、有機物の配合率を決定し、この決定された配合率に基づいて、コークス製造用原料の配合を行なうことを特徴とするものである。 In order to solve the above problems, the method for blending raw materials for coke production according to the present invention is a method of blending raw materials for coke production for blast furnace using organic materials such as raw coal and inferior coal or wood waste, Correlation data between CO 2 generation amount and coke strength generated until reaching the maximum Geisler fluidity temperature of the sample containing raw coal and organic matter, and the weight of the organic matter distillate in the production coke at the time of the sample coking Based on the correlation data between the ratio and the coke strength, the blending ratio of the organic matter is determined, and the blending of the raw material for coke production is performed based on the determined blending ratio.

かかる構成によるコークス製造用原料の配合方法の作用・効果を説明する。前述したように、コークス製造に使用される石炭としては、加熱時に軟化溶融し、その後再固化する瀝青炭が一般的に使用される。この瀝青炭に、軟化溶融性を示さない褐炭や木材等の有機物を配合すると、コークスの強度が低下することは知られている。本願発明者らは、鋭意検討を重ねた結果、コークスの強度低下には2つの要因が存在することを見出した。   The effect | action and effect of the compounding method of the raw material for coke manufacture by this structure are demonstrated. As described above, as coal used for coke production, bituminous coal that softens and melts when heated and then resolidifies is generally used. It is known that when bituminous coal is blended with an organic material such as lignite or wood that does not exhibit softening and melting properties, the strength of coke decreases. As a result of intensive studies, the inventors of the present application have found that there are two factors in reducing the strength of coke.

その1つは、それら有機物が原料炭に化学的な作用を及ぼして、原料炭が加熱された際に示す軟化溶融時の流動性を低下させるということである。もう1つは、コークス化時におけるこれら有機物と原料炭間の接着不良という物理的な要素である。   One of them is that these organic substances exert a chemical action on the raw coal to reduce the fluidity at the time of softening and melting, which is shown when the raw coal is heated. The other is a physical element of poor adhesion between these organic substances and raw coal during coking.

一般的に、褐炭や木材等の有機物には酸素官能基が多く存在し、通常冶金用コークス製造に使用される原料炭(瀝青炭)に比べるとCO2の発生量が多い。このCO2発生時に生じるラジカルにより、有機物を原料炭に配合した場合、原料炭が加熱された際に示す軟化溶融性が阻害され低下するものと考えられる。しかし、褐炭や木材等の有機物は配合前に適当な温度で熱処理することで、CO2発生量を十分に低下させることができる。そこで、本願発明者らは褐炭や木材等を異なる熱処理温度で処理し、その熱処理物を異なる割合で配合した試料のギースラー最高流動度温度に達するまでに発生するCO2発生量とコークスI型強度との関係を実験的に調査し、CO2発生量とコークスI型強度が相関を示すことを確認した(図2参照)。 In general, organic substances such as lignite and wood have many oxygen functional groups, and the amount of CO 2 generated is larger than that of raw coal (bituminous coal) usually used in the production of metallurgical coke. It is considered that when the organic matter is blended with the raw coal due to radicals generated when CO 2 is generated, the softening and melting properties exhibited when the raw coal is heated are impaired. However, organic substances such as lignite and wood can be sufficiently heat-treated at an appropriate temperature before blending to sufficiently reduce the amount of CO 2 generated. Accordingly, the inventors of the present application treat lignite and wood at different heat treatment temperatures, and the amount of CO 2 generated and the coke I-type strength before reaching the maximum Geisler fluidity temperature of the samples in which the heat treatment products are blended in different proportions. Was experimentally investigated, and it was confirmed that the CO 2 generation amount and the coke type I intensity showed a correlation (see FIG. 2).

一方、CO2発生量を十分に低下させた場合でも、これらの有機物を大量に配合した場合は、コークスI型強度の低下を引き起こす。その原因は、有機物あるいはその熱処理物と原料炭とのコークス化時接着不良及びコークス基質強度の低下によるものと考えられる。すなわち、軟化溶融しない有機物やその熱処理物と石炭粒子表面との接着は弱いと考えられ、配合有機物と原料炭の乾留時の収縮率の差により両者が剥がれやすくなりコークスの強度低下を招く。また、軟化溶融性を示さない有機物は、コークス化した時に異方性組織が発達せず、コークス基質の強度が低下するものと考えられる。従って、コークス中に占める有機物乾留物の割合が高いほど強度低下が起こりやすいと考えられる。そこで、本願発明者らは実験を行い、コークス中に占める有機物乾留物の割合が高いほどコークスI型強度が低下する傾向を確認した(図3参照)。 On the other hand, even when the amount of generated CO 2 is sufficiently reduced, when a large amount of these organic substances are blended, the coke I type strength is lowered. The cause is considered to be due to poor adhesion at the time of coking of the organic substance or the heat-treated product thereof and the raw coal and a decrease in the strength of the coke substrate. That is, the adhesion between the organic matter that is not softened and melted or the heat-treated product thereof and the surface of the coal particles is considered to be weak, and due to the difference in shrinkage ratio during dry distillation between the blended organic matter and the raw coal, both are easily peeled and the strength of the coke is reduced. In addition, it is considered that an organic substance that does not exhibit softening and melting property does not develop an anisotropic structure when coked, and the strength of the coke substrate is reduced. Therefore, it is considered that the strength decreases more easily as the proportion of the organic dry matter in the coke is higher. Therefore, the inventors of the present application conducted an experiment and confirmed that the coke I-type strength tends to decrease as the proportion of the organic dry matter in the coke increases (see FIG. 3).

すなわち、原料炭に配合する有機物からのCO2発生量低下のためには、有機物の事前熱処理温度を高くすればCO2発生量を低下させることができるが、あまり熱処理温度を高くすると、有機物熱処理物の残留揮発分の低下に伴い、コークス中に占める有機物乾留物の割合が増えるため、逆にコークスI型強度が低下する傾向となる。従って、熱処理温度に関しては、単に高ければよいのではなく、最適な熱処理温度が存在することが確認できた。 That is, for CO 2 emissions reduction from organic matter to be blended to the raw material coal, which can reduce the CO 2 emissions when high pre heat treatment temperature of the organic material, the higher the less the heat treatment temperature, organic heat treatment As the residual volatile content of the product decreases, the proportion of the organic dry distillate in the coke increases, and conversely, the coke I type strength tends to decrease. Accordingly, it was confirmed that the heat treatment temperature is not simply high but an optimum heat treatment temperature exists.

以上のように、原料炭と有機物を用いてコークス製造用原料を配合するに際し、原料炭と有機物を配合した試料のギースラー最高流動度温度に達するまでに発生するCO2の発生量とコークス強度との相関関係データと、試料コークス化時における製造コークス中の有機物乾留物の重量割合とコークス強度との相関関係データに基づいて、有機物の熱処理温度や配合率の最適な条件を決定することができ、コークス強度を可能な限り高い水準に維持できるような配合方法を提供することができる。 As described above, when blending raw materials for coke production using raw coal and organic matter, the amount of CO 2 generated and coke strength generated until the maximum Geisler fluidity temperature of the sample containing raw coal and organic matter is reached. The optimum conditions for the heat treatment temperature and blending ratio of organic matter can be determined based on the correlation data of the organic matter and the correlation data between the weight ratio of the dry matter of organic matter in the coke produced during sample coking and the coke strength. Therefore, it is possible to provide a blending method capable of maintaining the coke strength at the highest possible level.

本発明において、前記CO2発生量を配合炭の試料1gあたり2mg以下とし、コークス化時の有機物乾留物の重量割合を11%以下とすることが好ましい。 In the present invention, the CO 2 generation amount is preferably 2 mg or less per 1 g of the blended coal sample, and the weight ratio of the organic dry distillation product during coking is preferably 11% or less.

詳細な実験データについては後述するが、かかる数値となるように熱処理温度や有機物あるいは有機物熱処理物の配合率を決定することで、コークス強度を高い水準に維持することができる。   Although detailed experimental data will be described later, the coke strength can be maintained at a high level by determining the heat treatment temperature and the blending ratio of the organic material or the organic heat treated product so as to obtain such numerical values.

本発明に係る冶金用コークス製造用原料の配合方法の好適な実施形態について説明する。   A preferred embodiment of the method for blending raw materials for producing metallurgical coke according to the present invention will be described.

前述したように、コークス製造に使用される石炭としては、加熱時に軟化溶融し、その後再固化する瀝青炭が使用される。この瀝青炭に代わり、軟化溶融性を示さない褐炭や木材等の有機物を配合すると、コークスの強度が低下する。このコークスの強度低下には2つの要因が存在する。   As described above, as coal used for coke production, bituminous coal that softens and melts when heated and then resolidifies is used. If an organic substance such as lignite or wood that does not exhibit softening and melting properties is blended in place of this bituminous coal, the strength of the coke decreases. There are two factors in reducing the strength of the coke.

その1つは、それら有機物が原料炭に化学的な作用を及ぼして、原料炭が加熱された際に示す軟化溶融時の流動性を低下させるということである。もう1つは、コークス化時におけるこれら有機物と原料炭間の接着不良という物理的な要素である。   One of them is that these organic substances exert a chemical action on the raw coal to reduce the fluidity at the time of softening and melting, which is shown when the raw coal is heated. The other is a physical element of poor adhesion between these organic substances and raw coal during coking.

一般的に、褐炭や木材等の有機物には酸素官能基が多く存在し、通常冶金用コークス製造に使用される原料炭(瀝青炭)に比べるとCO2の発生量が多い。このCO2発生時に生じるラジカルにより、有機物を原料炭に配合した場合、原料炭が加熱された際に示す軟化溶融性が阻害され低下するものと考えられる。しかし、褐炭や木材等の有機物は配合前に適当な温度で熱処理することで、CO2発生量を十分に低下させることができる。そこで、本願発明者らは褐炭や木材等を異なる熱処理温度で処理し、その熱処理物を異なる割合で配合した試料のギースラー最高流動度温度に達するまでに発生するCO2発生量とコークスI型強度との関係を実験的に調査し、CO2発生量とコークスI型強度が相関を示すことを確認した(図2参照)。 In general, organic substances such as lignite and wood have many oxygen functional groups, and the amount of CO 2 generated is larger than that of raw coal (bituminous coal) usually used in the production of metallurgical coke. It is considered that when the organic matter is blended with the raw coal due to radicals generated when CO 2 is generated, the softening and melting properties exhibited when the raw coal is heated are impaired. However, organic substances such as lignite and wood can be sufficiently heat-treated at an appropriate temperature before blending to sufficiently reduce the amount of CO 2 generated. Accordingly, the inventors of the present application treat lignite and wood at different heat treatment temperatures, and the amount of CO 2 generated and the coke I-type strength before reaching the maximum Geisler fluidity temperature of the samples in which the heat treatment products are blended in different proportions. Was experimentally investigated, and it was confirmed that the CO 2 generation amount and the coke type I intensity showed a correlation (see FIG. 2).

一方、CO2発生量を十分に低下させた場合でも、これらの有機物を大量に配合した場合は、コークスI型強度の低下を引き起こす。その原因は、有機物あるいはその熱処理物と原料炭とのコークス化時接着不良及びコークス基質強度の低下によるものと考えられる。すなわち、軟化溶融しない有機物やその熱処理物と石炭粒子表面との接着は弱いと考えられ、配合有機物と原料炭の乾留時の収縮率の差により両者が剥がれやすくなり強度低下を招く。また、軟化溶融性を示さない有機物は、コークス化した時に異方性組織が発達せず、コークス基質の強度が低下するものと考えられる。従って、コークス中に占める有機物乾留物の割合が高いほど強度低下が起こりやすいと考えられる。そこで、本願発明者らはコークス中に占める有機物乾留物の割合と、コークスI型強度の関係を実験的に調査した(図3参照)。 On the other hand, even when the amount of generated CO 2 is sufficiently reduced, when a large amount of these organic substances are blended, the coke I type strength is lowered. The cause is considered to be due to poor adhesion at the time of coking of the organic substance or the heat-treated product thereof and the raw coal and a decrease in the strength of the coke substrate. That is, it is considered that the adhesion between the organic matter not softened and melted or the heat-treated product thereof and the surface of the coal particles is weak, and due to the difference in shrinkage ratio between the blended organic matter and the raw coal, the two tend to be peeled and the strength is reduced. In addition, it is considered that an organic substance that does not exhibit softening and melting property does not develop an anisotropic structure when coked, and the strength of the coke substrate is reduced. Therefore, it is considered that the strength decreases more easily as the proportion of the organic dry matter in the coke is higher. Therefore, the inventors of the present application experimentally investigated the relationship between the ratio of the organic dry matter in the coke and the coke I type strength (see FIG. 3).

上記の2種類の実験を行うための実験装置の構成を図1に示す。熱天秤1は、試料を加熱したときの重量変化を測定する機械であり、この熱天秤1を用いて試料を900℃まで乾留したときの石炭及び有機物乾留物の歩留まりを測定することで、コークス中に占める有機物乾留物の重量割合を算出することができる。試料は図1の図番3で示される位置にセットされ、加熱部4により試料を不活性ガス雰囲気中で加熱していくことができる。   FIG. 1 shows the configuration of an experimental apparatus for performing the above two types of experiments. The thermobalance 1 is a machine that measures a change in weight when a sample is heated. By measuring the yield of coal and organic dry matter when the sample is dry-distilled to 900 ° C. using the thermobalance 1, coke is measured. It is possible to calculate the weight ratio of the organic dry matter occupying the inside. The sample is set at a position indicated by a number 3 in FIG. 1, and the sample can be heated in an inert gas atmosphere by the heating unit 4.

また、試料を加熱することで発生する反応ガスについては、図示するようにガスクロマトグラフ2の方向に導くように構成し、試料から発生したガスの種類(ガス中に含まれるCO2等の成分)及び量を測定することができる。発生するガスについては、一定時間ごとにサンプリングしてガスクロマトグラフ2により分析することができる。 In addition, the reaction gas generated by heating the sample is configured to be guided in the direction of the gas chromatograph 2 as shown, and the type of gas generated from the sample (components such as CO 2 contained in the gas) And the amount can be measured. The generated gas can be sampled at regular intervals and analyzed by the gas chromatograph 2.

以上のように、熱天秤1により測定された重量減少データからコークス化時における歩留まりを測定することができ、ガスクロマトグラフ2の測定結果から原料炭のギースラー最高流動度温度に達するまでに発生する配合炭のCO2発生量を算出することができる。 As described above, the yield at the time of coking can be measured from the weight loss data measured by the thermobalance 1, and the mixture generated from the measurement result of the gas chromatograph 2 until reaching the maximum flow rate temperature of coking coal. The amount of CO 2 generated from charcoal can be calculated.

<実験結果>
次に、実験結果について説明する。表1は、褐炭aの原炭またはその熱処理物を原料炭b(瀝青炭)に配合して乾留した場合のデータを示すものである。表1に示すように7種類の試料により実験を行い、熱処理温度、配合率、コークス中に占める褐炭aの乾留物が占める重量割合、配合炭のCO2発生量、コークスI型強度についてのデータをまとめたものである。
<Experimental result>
Next, experimental results will be described. Table 1 shows data in the case of blending raw coal of lignite a or a heat-treated product thereof into raw coal b (bituminous coal) and dry distillation. As shown in Table 1, the experiment was conducted with seven types of samples, and data on heat treatment temperature, blending ratio, weight ratio of dry coal of lignite a in coke, CO 2 generation amount of blended coal, and coke I type strength. Is a summary.

ここでCO2発生量は、ギースラー最高流動度温度に達するまでに発生する配合炭の試料1gからの発生量を示している。また、コークスI型強度I600 9.5は、コークス強度を表す指標の1つであり、この数値が高いほどコークス強度は高いといえる。具体的な測定方法であるが、コークスを19〜21mmに整粒し、これをφ132mm×L720mmの円筒状のI型強度試験機に入れ、毎分20回転で30分、計600回回転させた後、試験機からコークスを取り出し、9.5mmの篩にかけ、篩上に残存したコークス重量%をもってI型強度指標とする。

Figure 2007204629
Here, the CO 2 generation amount indicates the generation amount from the 1 g sample of the blended coal that is generated before reaching the Geeseler maximum fluidity temperature. Further, coke type I intensity I 600 9.5 is one indicator of the coke strength, coke strength can be said higher this number is high. Although it is a specific measuring method, the coke is sized to 19 to 21 mm, and this is put into a cylindrical type I strength tester of φ132 mm × L720 mm, and rotated at 60 rpm for 30 minutes for a total of 600 times. Thereafter, the coke is taken out from the testing machine, passed through a 9.5 mm sieve, and the weight percentage of coke remaining on the sieve is used as the I-type strength index.
Figure 2007204629

実験No.1の褐炭a無配合の試料に比べて、熱処理を行なわない褐炭aを10wt%配合したコークス(No.2)のコークスI型強度が低下していることが分かる。これは褐炭aを配合したことにより加熱時のCO2発生量が多くなり、流動性が阻害されたためと考えられる。従って、予め褐炭aを適当な温度で熱処理して、CO2発生量を低下させることで、コークスI型強度の低下は抑制される(No.3〜5)。 Experiment No. It can be seen that the coke I type strength of coke (No. 2) containing 10 wt% of lignite a that is not subjected to heat treatment is lower than that of the 1 lignite a-free sample. This is probably because the amount of CO 2 generated during heating increased due to the blending of lignite a, and the fluidity was hindered. Therefore, the lignite a is heat-treated in advance at an appropriate temperature to reduce the CO 2 generation amount, thereby suppressing the reduction in coke I type strength (No. 3 to 5).

熱処理温度を高くすることにより、CO2発生量はコークスI型強度の低下を抑制するに十分な程度まで低下させられる。しかしながら、熱処理温度をあまり高くしすぎると、褐炭a熱処理物の残留揮発分が低下し、乾留した場合に、褐炭a乾留物のコークス中に占める割合が高くなり、コークスI型強度の低下は大きくなる(No.6)。 By increasing the heat treatment temperature, the amount of CO 2 generated can be reduced to a level sufficient to suppress the decrease in coke I type strength. However, if the heat treatment temperature is too high, the residual volatile content of the lignite a heat-treated product will decrease, and when dry distillation, the proportion of the lignite a dry product in the coke will increase, and the reduction in coke I type strength will be large. (No. 6).

また、同様に熱処理温度が適切でCO2発生量が低くても、褐炭aの配合率が高く褐炭a乾留物のコークス中に占める割合が高くなった場合は、コークスI型強度の低下が大きくなる(No.7)。従って、褐炭aを配合する場合の事前の熱処理温度と、配合率については最適な条件が存在することが分かる。 Similarly, even if the heat treatment temperature is appropriate and the amount of CO 2 generated is low, when the blending ratio of lignite a is high and the proportion of lignite a dry fraction in the coke is high, the reduction in coke I type strength is large. (No. 7). Therefore, it turns out that the optimal conditions exist about the prior heat processing temperature in the case of mix | blending lignite a, and a compounding rate.

次に、褐炭cとその熱処理物を原料炭dに10wt%配合した場合の実験結果を表2に示す。

Figure 2007204629
Next, Table 2 shows the experimental results when 10 wt% of lignite c and its heat-treated product are blended in raw coal d.
Figure 2007204629

褐炭cを無配合のコークス(No.8)に比べて、熱処理を行なわない褐炭cを10wt%配合したコークス(No.9)のコークスI型強度は大きく低下している。これはCO2発生量が多く、流動性が阻害されたためと考えられる。褐炭cを予め適切な温度で熱処理してCO2発生量を抑制した場合は、先ほどと同様にコークスI型強度の低下を抑制することができる(No.10)。 Compared with coke without blending lignite c (No. 8), coke I type strength of coke (No. 9) blended with 10 wt% of lignite c without heat treatment is greatly reduced. This is thought to be due to the large amount of CO 2 generated and the fluidity being inhibited. When the brown coal c is heat-treated in advance at an appropriate temperature to suppress the amount of CO 2 generated, the decrease in coke I type strength can be suppressed in the same manner as before (No. 10).

次に、木材eを原料炭fに配合した場合の実験結果を表3に示す。

Figure 2007204629
Next, Table 3 shows experimental results when wood e is blended with raw coal f.
Figure 2007204629

木材eを無配合のコークス(No.11)に比べて、熱処理を行なわない木材eを1wt%配合した場合(No.12)は、木材eの配合率が低いためコークスI型強度の低下は起こらなかった。熱処理を行なわない木材eの配合率が高くなると、CO2発生量が多くなるのでコークスI型強度の低下は大きくなる(No.13,14)。一方、木材eを熱処理することでCO2発生量を低下させ、コークス中での木材e乾留物の割合が高くならないような割合で配合した場合、コークスI型強度の低下を抑制することができた(No.15,16)。 When 1 wt% of wood e not subjected to heat treatment is blended (No. 12), compared with coke without blending wood e (No. 11), the blending ratio of wood e is low, so the decrease in coke I type strength is Did not happen. When the blending ratio of the wood e that is not heat-treated increases, the amount of CO 2 generated increases, so that the decrease in the coke I type strength increases (No. 13, 14). On the other hand, when heat treatment is performed on wood e, the amount of CO 2 generated is reduced, and if the proportion of wood e dry distillate in coke is not increased, reduction in coke I type strength can be suppressed. (No. 15, 16).

図2、図3は、以上の実験結果をまとめたものをグラフ化したものである。図2は、ギースラー最高流動度温度に達するまでに配合炭の試料1gあたりから発生するCO2発生量とコークスI型強度の相関関係を表すグラフであり、図3は、有機物乾留物のコークス中に占める割合とコークスI型強度の相関関係を表すグラフである。 FIG. 2 and FIG. 3 are graphs that summarize the above experimental results. FIG. 2 is a graph showing the correlation between the amount of CO 2 generated from 1 gram of coal blended before reaching the maximum flow rate temperature of Geeseler and the coke I type strength, and FIG. It is a graph showing the correlation with the ratio for which it occupies, and coke I type | mold intensity | strength.

以上の実験結果からも分かるように、原料炭のギースラー最高流動度温度に達するまでに発生する配合炭の試料1gあたりからのCO2発生量を2mg以下とし、配合炭試料コークス化時における製造コークス中の有機物乾留物の重量割合を11%以下にすることがコークス強度の低下を抑制する上で好ましいことが分かった。 As can be seen from the above experimental results, the amount of CO 2 generated from 1 g of the coal blend generated before reaching the maximum Geeseler fluidity temperature of the coking coal is 2 mg or less, and the coke produced at the time of coking coal sample is made into coke. It turned out that it is preferable in order to suppress the fall of coke intensity | strength to make the weight ratio of an organic substance dry distillation thing into 11% or less.

本発明による配合方法を採用すれば、コークス製造までの工程は図4に示すようなフローで示すことができる。   If the blending method according to the present invention is employed, the process up to coke production can be shown by a flow as shown in FIG.

本発明によれば、加熱時にCO2が多量に発生するため、通常はコークス原料として使用しないような褐炭や木材等の有機物を事前に熱処理し、乾留時のCO2発生量を抑制することで、コークス原料として用いるように改質することができる。 According to the present invention, since a large amount of CO 2 is generated during heating, organic substances such as lignite and wood that are not normally used as coke raw materials are heat-treated in advance to suppress the amount of CO 2 generated during dry distillation. It can be modified to be used as a coke raw material.

CO2発生量は熱天秤を用いて試料を加熱することで調査することができ、そのときに発生するガスはガスクロマトグラフを用いて分析することができる。よって、簡単な方法で熱処理条件を決定することができる。 The amount of CO 2 generated can be investigated by heating the sample using a thermobalance, and the gas generated at that time can be analyzed using a gas chromatograph. Therefore, the heat treatment conditions can be determined by a simple method.

実験装置の構成を示す図Diagram showing the configuration of the experimental apparatus ギースラー最高流動度温度に達するまでに配合炭試料1gあたりから発生するCO2発生量[mg]とコークスI型強度の相関関係を表すグラフGraph showing the correlation between CO 2 generation [mg] generated from 1 g of blended coal sample and the coke I type strength until reaching the maximum flow rate temperature 有機物乾留物のコークス中に占める割合[%]とコークスI型強度の相関関係を表すグラフA graph showing the correlation between the percentage of organic distillate in coke and the strength of coke I type コークス製造までの工程を示すフローチャートFlow chart showing the process up to coke production

符号の説明Explanation of symbols

1 熱天秤
2 ガスクロマトグラフ
3 試料
4 加熱部
1 Thermobalance 2 Gas chromatograph 3 Sample 4 Heating part

Claims (2)

原料炭と有機物(通常冶金用コークス原料として使用しないものをいう。以下同じ)を用いてコークス製造用原料を配合する方法であって、
原料炭と有機物を配合した試料のギースラー最高流動度温度に達するまでに発生するCO2の発生量とコークス強度との相関関係データと、前記試料コークス化時における製造コークス中の有機物乾留物の重量割合とコークス強度との相関関係データに基づいて、有機物の配合率を決定し、この決定された配合率に基づいて、コークス製造用原料の配合を行なうことを特徴とする冶金用コークス製造用原料の配合方法。
It is a method of blending raw materials for coke production using raw coal and organic matter (referring to those not normally used as metallurgical coke raw materials; the same applies hereinafter),
Correlation data between CO 2 generation amount and coke strength generated until reaching the maximum Geisler fluidity temperature of the sample containing raw coal and organic matter, and the weight of the organic matter distillate in the production coke at the time of the sample coking Based on the correlation data between the ratio and the coke strength, the compounding rate of the organic substance is determined, and the coke manufacturing material is mixed based on the determined mixing rate. The blending method.
前記CO2発生量を配合炭の試料1gあたり2mg以下とし、コークス化時の有機物乾留物の重量割合を11%以下とすることを特徴とする請求項1に記載の冶金用コークス製造用原料の配合方法。 2. The raw material for producing metallurgical coke according to claim 1, wherein the CO 2 generation amount is 2 mg or less per 1 g of the blended coal sample, and the weight ratio of the organic dry distillation product during coking is 11% or less. Formulation method.
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Publication number Priority date Publication date Assignee Title
CN108865199A (en) * 2018-07-11 2018-11-23 安徽工业大学 A kind of method and its application of lignite modifying process
CN113969178A (en) * 2020-07-23 2022-01-25 上海梅山钢铁股份有限公司 High-strength coke and coking method

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JP2003055668A (en) * 2001-08-17 2003-02-26 Sumitomo Metal Ind Ltd Production method for blast furnace coke
JP2003055667A (en) * 2001-08-17 2003-02-26 Sumitomo Metal Ind Ltd Production method for blast furnace coke

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JP2003055668A (en) * 2001-08-17 2003-02-26 Sumitomo Metal Ind Ltd Production method for blast furnace coke
JP2003055667A (en) * 2001-08-17 2003-02-26 Sumitomo Metal Ind Ltd Production method for blast furnace coke

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Publication number Priority date Publication date Assignee Title
CN108865199A (en) * 2018-07-11 2018-11-23 安徽工业大学 A kind of method and its application of lignite modifying process
CN113969178A (en) * 2020-07-23 2022-01-25 上海梅山钢铁股份有限公司 High-strength coke and coking method
CN113969178B (en) * 2020-07-23 2023-05-09 上海梅山钢铁股份有限公司 High-strength coke and coking method

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