JP2012062505A - Method for manufacturing agglomerate - Google Patents
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本発明は、鉄鉱石と炭材を含む混合物の塊成物を炉に装入して加熱し、該塊成物中の鉄鉱石に含まれる酸化鉄を還元することによって還元鉄を製造する方法に関するものである。詳細には、低品位の原料を用いても上記還元の生産性を高めることのできる塊成物を製造する方法に関するものである。 The present invention relates to a method for producing reduced iron by charging an agglomerate of a mixture containing iron ore and carbonaceous material into a furnace and heating, and reducing iron oxide contained in the iron ore in the agglomerate. It is about. More specifically, the present invention relates to a method for producing an agglomerate that can improve the reduction productivity even when a low-grade raw material is used.
鉄鉱石と炭材とを含む混合物から還元鉄を製造する直接還元製鉄法が開発されている。この製鉄法では上記混合物を成形した塊成物を炉に装入し、炉内で加熱バーナーによるガス伝熱や輻射熱で加熱することによって塊成物中の鉄鉱石に含まれる酸化鉄が還元され、還元鉄を製造できる（特許文献１）。 A direct reduction iron manufacturing method for producing reduced iron from a mixture containing iron ore and carbonaceous material has been developed. In this iron making method, the agglomerate formed from the above mixture is charged into a furnace, and the iron oxide contained in the iron ore in the agglomerate is reduced by heating in the furnace with gas heat transfer or radiant heat by a heating burner. And reduced iron can be manufactured (patent document 1).
上記塊成物を加熱する炉（加熱炉）としては移動炉床炉、例えば回転炉床炉を用いることができる。回転炉床炉を用いた場合は、炉床上に装入した上記塊成物は炉内を１０分程度かけて１周する間に加熱され、上記炭材によって塊成物に含まれる酸化鉄が還元され、還元鉄として炉外へ排出される（ＦＡＳＴＭＥＴ法）。また、上記炉内において、加熱還元後に、更に加熱して還元鉄を一旦溶融させ、これを冷却すれば粒状金属鉄を製造できる（ＩＴｍｋ３法）。この炉内は酸化鉄の還元を促進するために、通常１３００〜１５００℃程度に加熱されている。しかし、省エネルギーの観点から還元鉄を１３００℃よりも低い温度で製造することが望まれる。 As the furnace (heating furnace) for heating the agglomerates, a moving hearth furnace, for example, a rotary hearth furnace can be used. When a rotary hearth furnace is used, the agglomerate charged on the hearth is heated while making one round in the furnace over about 10 minutes, and the iron oxide contained in the agglomerate is formed by the carbon material. Reduced and discharged out of the furnace as reduced iron (FASTMET method). Further, after heating and reducing in the furnace, the heated iron is further heated to once melt the reduced iron and then cooled, whereby granular metallic iron can be produced (ITmk3 method). The inside of the furnace is usually heated to about 1300 to 1500 ° C. in order to promote the reduction of iron oxide. However, it is desired to produce reduced iron at a temperature lower than 1300 ° C. from the viewpoint of energy saving.
また、上記塊成物は、上述した移動炉床炉で加熱還元して還元鉄を製造する際に用いる以外に、高炉に装入して銑鉄を製造する際にも用いられる。即ち、高炉には、コークス層と鉄鉱石層が層状に重なるようにコークスと鉄鉱石が装入され、羽口から高温の空気を吹き込んでコークスを燃焼させる。このとき発生した還元性ガスで鉄鉱石中の酸化鉄を還元することによって銑鉄を製造できる。そして上記塊成物を上記鉄鉱石層に配合することによって塊成物内で酸化鉄と炭材の直接還元が起こり、ＦｅＯ−Ｆｅ平衡となる熱保存帯の温度を低下させることができる。そのため高炉で用いる還元剤比（例えば、Ｃ／Ｆｅ比）を低減できる。また、上記塊成物を上記鉄鉱石層に配合することにより、上記塊成物が燃焼して発生する還元性ガスによって鉄鉱石層中の酸化鉄の還元が促進される。更に、塊成物中の鉄成分の触媒作用により、銑鉄の生産効率が向上する。 Moreover, the agglomerate is used not only when the reduced iron is produced by heat reduction in the above-mentioned moving hearth furnace, but also when the pig iron is produced by charging into the blast furnace. That is, coke and iron ore are charged into the blast furnace so that the coke layer and iron ore layer overlap each other, and hot air is blown from the tuyere to burn the coke. Pig iron can be produced by reducing the iron oxide in the iron ore with the reducing gas generated at this time. And by mix | blending the said agglomerate with the said iron ore layer, the direct reduction | restoration of an iron oxide and a carbon material occurs in an agglomerate, and the temperature of the heat preservation zone used as FeO-Fe equilibrium can be reduced. Therefore, the reducing agent ratio (for example, C / Fe ratio) used in the blast furnace can be reduced. Moreover, by mix | blending the said agglomerate with the said iron ore layer, the reduction | restoration of the iron oxide in an iron ore layer is accelerated | stimulated with the reducing gas which the said agglomerate burns and generate | occur | produces. Furthermore, pig iron production efficiency is improved by the catalytic action of the iron component in the agglomerate.
ところで上記塊成物の原料となる上記鉄鉱石や上記炭材の品質は一様ではなく、様々な種類のものが知られている。 By the way, the quality of the iron ore and the carbonaceous material used as the raw material of the agglomerate is not uniform, and various types are known.
上記炭材としては瀝青炭や褐炭が知られている。瀝青炭は炭素含有率が高く、高品位炭と呼ばれており、褐炭は炭素含有率が低く、低品位炭と呼ばれている。近年では高品位炭の枯渇化が進行しており、低品位炭の利用が望まれている。ところが上記褐炭の埋蔵量は豊富であるが、褐炭の含水率は高く、また乾燥させると自然発火し易く、取扱いが難しいという問題がある。 Bituminous coal and lignite are known as the above carbon materials. Bituminous coal has a high carbon content and is called high-grade coal, and lignite has a low carbon content and is called low-grade coal. In recent years, depletion of high-grade coal has progressed, and the use of low-grade coal is desired. However, although the lignite reserves are abundant, the moisture content of the lignite is high, and when dried, there is a problem that it tends to spontaneously ignite and is difficult to handle.
一方、上記鉄鉱石についても、ヘマタイト鉱石のように結晶水を殆ど含有しない高品位の鉄鉱石や、リモナイト鉱石のように、結晶水を多く含有する低品位の鉄鉱石が知られている。高品位鉄鉱石の産出量は近年減少しており、低品位鉄鉱石の利用が検討されている。しかし低品位鉄鉱石は高品位鉄鉱石と比べると、焼結過程において強度低下や生産性の低下を来したり、また酸化鉄の還元に時間がかかり、更には還元に要する炭材量も増加する必要がある。 On the other hand, also about the said iron ore, the high quality iron ore which hardly contains crystal water like a hematite ore, and the low grade iron ore which contains many crystal waters like a limonite ore are known. The production of high-grade iron ore has decreased in recent years, and the use of low-grade iron ore is being considered. However, compared to high-grade iron ore, low-grade iron ore causes a decrease in strength and productivity during the sintering process, and it takes time to reduce iron oxide, and the amount of carbon material required for reduction also increases. There is a need to.
低品位鉄鉱石を製鉄で有効活用する技術として特許文献２の技術が提案されている。この文献では結合水を含有する鉱石を加熱し、結合水を水蒸気として脱水させることにより、シングルナノメートル径の細孔壁を有する多孔質化した特定の元素の酸化物を含有する多孔質鉱石を得ている。そして分子の大きさが前記細孔壁よりも一桁小さいサブナノメートルである有機化合物を含む有機液体又は有機ガスを上記多孔質鉱石に接触させることによって、有機化合物を前記多孔質鉱石の前記シングルナノメートル径の細孔壁に付着させている。この文献には上記有機化合物を含む有機ガスとして乾留ガスを用い、この乾留ガスを前記多孔質鉱石に接触させる事により乾留ガス中に含まれるメタンガスの分解によって生じるカーボンやタール等の有機化合物を上記多孔質鉱石に付着させることが記載されている。これによって、鉱石に含まれる酸化物と有機化合物に含まれる炭素とが接触するため、炭材に接触する鉱石中の酸化鉄の還元が容易になり、脈石成分を多く含む低品質の鉱石であっても精錬用の原料として利用できる。 The technique of Patent Document 2 has been proposed as a technique for effectively utilizing low-grade iron ore in iron making. In this document, a porous ore containing an oxide of a specific element having a porous wall having a single nanometer diameter is heated by heating ore containing bound water and dehydrating the bound water as water vapor. It has gained. Then, by contacting the porous ore with an organic liquid or organic gas containing an organic compound whose molecular size is one nanometer smaller than that of the pore wall, the organic compound is brought into contact with the single nanometer of the porous ore. It is attached to the pore wall of metric diameter. In this document, a dry distillation gas is used as the organic gas containing the organic compound, and the organic compounds such as carbon and tar generated by the decomposition of methane gas contained in the dry distillation gas by bringing the dry distillation gas into contact with the porous ore are described above. It is described that it adheres to porous ores. As a result, the oxide contained in the ore comes into contact with the carbon contained in the organic compound, which facilitates the reduction of iron oxide in the ore in contact with the carbonaceous material, and is a low-quality ore containing a large amount of gangue components. Even if it exists, it can be used as a raw material for refining.
上記特許文献２には、多孔質鉱石に付着させる炭素の含有量は、多孔質鉱石を乾留ガスに接触させる時間を調整することによって制御できると記載されている。しかしこの乾留ガスに含まれる有機化合物は、メタンのような低分子化合物であるため、多孔質鉱石の細孔壁に吸着させることは困難である。そのため、多孔質鉱石の細孔内に付着した有機化合物による炭素の付着量は、上記特許文献２に記載されているように、４．０４％であり、この炭素量は酸化鉄を完全に還元するための炭素最小必要量（９．２２％）の約半分である。また、酸化鉄の還元率は４１％に留まっており、更なる還元率の向上が望まれる。 Patent Document 2 describes that the content of carbon attached to the porous ore can be controlled by adjusting the time during which the porous ore is brought into contact with the dry distillation gas. However, since the organic compound contained in the dry distillation gas is a low molecular compound such as methane, it is difficult to adsorb it on the pore walls of the porous ore. For this reason, the amount of carbon deposited by the organic compound deposited in the pores of the porous ore is 4.04% as described in Patent Document 2, and this amount of carbon completely reduces iron oxide. About half the minimum carbon requirement (9.22%). Moreover, the reduction rate of iron oxide remains at 41%, and further improvement of the reduction rate is desired.
本発明は、このような状況に鑑みて成されたものであり、その目的は、鉄鉱石と炭材を含む混合物を加熱して還元鉄を製造する際に用いる製鉄用の塊成物であって、低品位の鉄鉱石と低品位の炭材を用いて還元鉄が得られる塊成物を製造する方法を提供することにある。 The present invention has been made in view of such a situation, and an object thereof is an agglomerate for iron making used in producing reduced iron by heating a mixture containing iron ore and a carbonaceous material. An object of the present invention is to provide a method for producing an agglomerate from which reduced iron is obtained using low-grade iron ore and low-grade carbonaceous material.
上記課題を解決することのできた本発明に係る塊成物の製造方法とは、鉄鉱石と炭材を含む混合物を塊成化して製鉄用の塊成物を製造する方法であり、前記鉄鉱石として、結晶水を５質量％以上含有する鉄鉱石を加熱して脱水した脱水鉄鉱石、前記炭材として、沸点が２００〜５００℃の物質を２０質量％以上含む炭材を準備し、これらの混合物を塊成化する点に要旨を有している。 The method for producing an agglomerate according to the present invention capable of solving the above-mentioned problems is a method for producing an agglomerate for iron making by agglomerating a mixture containing iron ore and a carbonaceous material, and said iron ore As a dehydrated iron ore obtained by heating and dehydrating iron ore containing 5% by mass or more of crystal water, a carbon material containing 20% by mass or more of a substance having a boiling point of 200 to 500 ° C. is prepared. The point is that the mixture is agglomerated.
また、本発明に係る塊成物は、前記鉄鉱石として、結晶水を５質量％以上含有する鉄鉱石、前記炭材として、沸点が２００〜５００℃の物質を２０質量％以上含む炭材を準備し、これらを混合しつつ加熱するか、混合した後に加熱してから塊成化しても製造できる。 Moreover, the agglomerate which concerns on this invention is the iron ore containing 5 mass% or more of crystal waters as said iron ore, and the carbon material containing 20 mass% or more of substances whose boiling point is 200-500 degreeC as said carbon material. It can be manufactured by preparing and heating them while mixing them or by agglomerating them after heating them.
前記加熱は、例えば、４００℃以下で行なうことが好ましい。 The heating is preferably performed at 400 ° C. or lower, for example.
更に、上記塊成物は、前記鉄鉱石として、結晶水を５質量％以上含有する鉄鉱石を加熱して脱水した脱水鉄鉱石、前記炭材として、分子量分布を測定したときにピーク強度が最も大きい分子の分子量が２００〜３００である炭材を準備し、これらの混合物を塊成化することによっても製造できる。 Furthermore, the agglomerate has the highest peak intensity when the molecular weight distribution is measured as dehydrated iron ore obtained by heating and dehydrating iron ore containing 5% by mass or more of crystal water as the iron ore. It can also be produced by preparing a carbonaceous material having a large molecular weight of 200 to 300 and agglomerating the mixture.
また、上記塊成物は、前記鉄鉱石として、結晶水を５質量％以上含有する鉄鉱石、前記炭材として、分子量分布を測定したときにピーク強度が最も大きい分子の分子量が２００〜３００である炭材を準備し、これらを混合しつつ加熱するか、混合した後に加熱してから塊成化することによっても製造できる。 In addition, the agglomerate has a molecular weight of 200 to 300 as the iron ore, the iron ore containing 5% by mass or more of crystal water, and the carbonaceous material having the highest peak intensity when the molecular weight distribution is measured. It can also be produced by preparing a certain carbon material and heating it while mixing, or by heating after mixing and then agglomerating.
前記炭材としては、軟化開始温度が３００℃以下の低温軟化炭材を用いることが好ましい。前記点炭材としては、溶剤で原料炭材から抽出した可溶成分を用いることができる。この原料炭材としては、褐炭を用いることができる。 As the carbon material, it is preferable to use a low-temperature softened carbon material having a softening start temperature of 300 ° C. or lower. As the spot carbon material, a soluble component extracted from the raw material carbon material with a solvent can be used. As this raw material carbonaceous material, lignite can be used.
上述した製造方法で得られた塊成物を炉で加熱すれば、還元鉄を製造できる。 Reduced iron can be produced by heating the agglomerate obtained by the above-described production method in a furnace.
本発明では、結晶水を５質量％以上含有する鉄鉱石と、沸点が２００〜５００℃の物質を２０質量％以上含むか、或いは分子量分布を測定したときにピーク強度が最も大きい分子の分子量が２００〜３００である炭材を準備し、前記鉄鉱石を脱水して得られる脱水鉄鉱石の内部に前記炭材を吸着させたものを成形して塊成物を製造している。従って本発明で得られる塊成物は、脱水鉄鉱石と低沸点炭材を密に接触できるだけでなく、脱水後の細孔内に多量の炭材を挿入することができるため、この塊成物を炉で加熱すると良好な還元鉄を製造できる。 In the present invention, an iron ore containing 5% by mass or more of crystal water and a substance having a boiling point of 200 to 500 ° C. contain 20% by mass or more, or the molecular weight of the molecule having the highest peak intensity when the molecular weight distribution is measured. A carbon material of 200 to 300 is prepared, and an agglomerate is produced by molding the carbon material adsorbed in the dehydrated iron ore obtained by dehydrating the iron ore. Therefore, the agglomerate obtained in the present invention can not only make intimate contact between the dehydrated iron ore and the low boiling point carbon material, but also can insert a large amount of carbon material into the pores after dehydration. When heated in a furnace, good reduced iron can be produced.
本発明者らは、低品位の鉄鉱石と低品位の炭材を用いて還元鉄を製造する方法について鋭意検討を重ねてきた。その結果、低品位の鉄鉱石として結晶水を５質量％以上含有する鉄鉱石を準備し、低品位の炭材として沸点が２００〜５００℃の物質を２０質量％以上含む炭材を準備し、前記鉄鉱石を脱水して得られる脱水鉄鉱石と前記炭材を接触させれば、図２に示すように、炭材が脱水鉄鉱石の内部に速やかに浸透することが明らかになった。即ち、結晶水含有鉄鉱石を脱水すると、鉄鉱石には開口直径が理想的には０．８ｎｍ程度（図２には、一例として０．８ｎｍと記載）の空隙が形成される。この空隙に炭材が吸着する。脱水鉄鉱石の内部に炭材が吸着するのは、沸点が２００〜５００℃の物質は比較的低温で軟化溶融しやすく、またガス化しない物質を炭材として残留させることができるからである。このように炭材が吸着することによって脱水鉄鉱石の内部で炭材が鉄鉱石と接触するため、この脱水鉄鉱石と上記炭材を含む混合物を塊成化して得られる塊成物を炉で加熱すれば還元鉄の還元を促進できる。以下、本発明について詳細に説明する。 The present inventors have intensively studied a method for producing reduced iron using a low-grade iron ore and a low-grade carbon material. As a result, iron ore containing 5% by mass or more of crystal water is prepared as low-grade iron ore, and carbon material containing 20% by mass or more of a substance having a boiling point of 200 to 500 ° C. is prepared as a low-grade carbon material, When the dehydrated iron ore obtained by dehydrating the iron ore and the carbon material are brought into contact with each other, as shown in FIG. 2, it has been clarified that the carbon material quickly penetrates into the dehydrated iron ore. That is, when the crystal water-containing iron ore is dehydrated, voids having an opening diameter of about 0.8 nm ideally (described as 0.8 nm as an example in FIG. 2) are formed in the iron ore. Carbonaceous material is adsorbed in the voids. The reason why the carbon material is adsorbed inside the dehydrated iron ore is that a substance having a boiling point of 200 to 500 ° C. is easily softened and melted at a relatively low temperature, and a substance that does not gasify can remain as a carbon material. As the carbon material is adsorbed in this manner, the carbon material comes into contact with the iron ore inside the dehydrated iron ore. Therefore, the agglomerate obtained by agglomerating the mixture containing the dehydrated iron ore and the carbon material is used in the furnace. Heating can promote reduction of reduced iron. Hereinafter, the present invention will be described in detail.
本発明に係る製鉄用の塊成物は、
（１）鉄鉱石として、結晶水を含有する鉄鉱石を加熱して脱水した脱水鉄鉱石を準備し、炭材として、沸点が２００〜５００℃の物質を２０質量％以上含む炭材を準備し、これらの混合物を塊成化するか、
（２）鉄鉱石として、結晶水を含有する鉄鉱石を準備し、炭材として、沸点が２００〜５００℃の物質を２０質量％以上含む炭材を準備し、これらを混合しつつ加熱するか、或いは混合した後に加熱してから塊成化する
ことによって製造できる。
The agglomerate for iron making according to the present invention is
(1) A dehydrated iron ore obtained by heating and dehydrating iron ore containing crystal water is prepared as the iron ore, and a carbon material containing 20% by mass or more of a substance having a boiling point of 200 to 500 ° C. is prepared as the carbon material. Agglomerate these mixtures, or
(2) Whether iron ore containing crystal water is prepared as iron ore, carbon material containing 20% by mass or more of a substance having a boiling point of 200 to 500 ° C. is prepared as the carbon material, and is heated while mixing these materials? Alternatively, it can be produced by heating after mixing and agglomerating.
上記（１）の方法では、結晶水を含有する鉄鉱石を予め加熱して脱水し、脱水鉄鉱石を得ている。この脱水鉄鉱石と、沸点が２００〜５００℃の物質を２０質量％以上含む炭材とを混合することによって炭材を脱水鉄鉱石に吸着させることができる。 In the method (1), iron ore containing crystal water is heated in advance and dehydrated to obtain dehydrated iron ore. By mixing the dehydrated iron ore and a carbon material containing 20% by mass or more of a substance having a boiling point of 200 to 500 ° C., the carbon material can be adsorbed on the dehydrated iron ore.
一方、上記（２）の方法では、鉄鉱石と炭材を混合する時点では、鉄鉱石は脱水しておらず結晶水を含有する鉄鉱石をそのまま用いている。この結晶水を含有する鉄鉱石と、沸点が２００〜５００℃の物質を２０質量％以上含む炭材とを混合しながら加熱するか、結晶水含有鉄鉱石と炭材とを混合した後に加熱することによって、上記鉄鉱石は脱水され、脱水後に形成される細孔に上記炭材を吸着させることができる。 On the other hand, in the method (2), at the time when the iron ore and the carbon material are mixed, the iron ore is not dehydrated and the iron ore containing crystal water is used as it is. It heats, mixing iron ore containing this crystal water, and the carbonaceous material containing 20 mass% or more of substances with a boiling point of 200-500 degreeC, or heating after mixing crystal water containing iron ore and carbonaceous material. Thus, the iron ore is dehydrated, and the carbonaceous material can be adsorbed in the pores formed after the dehydration.
このように、上記（１）、（２）の方法は、結晶水を含有する鉄鉱石を加熱して脱水するタイミングが相違している。上記（２）で規定するように鉄鉱石と炭材とを混合しながら加熱するか、混合した後に加熱することによって、上記（１）で規定するように事前に鉄鉱石を脱水するよりも、時間短縮できるため、生産性を向上させることができる。また、鉄鉱石と炭材とを混合しながら加熱するか、混合した後に加熱することによって、加熱に必要な熱エネルギーを削減できる。 Thus, the methods (1) and (2) are different in the timing of heating and dehydrating iron ore containing crystal water. Rather than dehydrating the iron ore in advance as defined in (1) above by heating while mixing the iron ore and carbonaceous material as defined in (2) above, or by heating after mixing, Since time can be shortened, productivity can be improved. Moreover, the heat energy required for a heating can be reduced by heating, mixing iron ore and a carbonaceous material, or heating after mixing.
上記加熱は、４００℃以下で行なうことが好ましい。加熱温度を高くするほど鉄鉱石の脱水を短時間で行なうことができるが、加熱温度が高くなり過ぎると鉄鉱石自体の焼結が起こり、結晶水の脱水時に形成された細孔が閉塞してしまう。そのため上記炭材を鉄鉱石の内部に吸着させることが困難となる。従って上記加熱温度は４００℃以下とすることが好ましく、より好ましくは３５０℃以下、更に好ましくは３００℃以下とするのがよい。加熱温度の下限は、例えば、２００℃である。加熱温度が２００℃を下回ると鉄鉱石に含まれる結晶水の脱水が困難となる。 The heating is preferably performed at 400 ° C. or lower. The higher the heating temperature, the faster the iron ore can be dehydrated. However, if the heating temperature becomes too high, the iron ore itself sinters and pores formed during the dehydration of the crystal water are blocked. End up. Therefore, it becomes difficult to adsorb | suck the said carbonaceous material inside an iron ore. Therefore, the heating temperature is preferably 400 ° C. or lower, more preferably 350 ° C. or lower, and further preferably 300 ° C. or lower. The lower limit of the heating temperature is, for example, 200 ° C. If the heating temperature is below 200 ° C., it becomes difficult to dehydrate the crystal water contained in the iron ore.
一方、上記（１）、（２）の方法は、沸点が２００〜５００℃の物質を２０質量％以上含む炭材を用いている点で一致しており、また加熱により脱水した後に形成される細孔に上記炭材を吸着させ、炭材と鉄鉱石とを接触させている点で一致している。こうした鉄鉱石と炭材を含む混合物の塊成物を炉で加熱することによって、鉄鉱石の還元を促進できる。 On the other hand, the above methods (1) and (2) are identical in that a carbon material containing 20 mass% or more of a substance having a boiling point of 200 to 500 ° C. is used, and is formed after dehydration by heating. It is in agreement that the carbon material is adsorbed in the pores and the carbon material and iron ore are brought into contact with each other. Reduction of iron ore can be promoted by heating an agglomerate of a mixture containing such iron ore and carbonaceous material in a furnace.
上記鉄鉱石としては、結晶水を５質量％以上含有する鉄鉱石を用いる必要がある。結晶水の含有量が５質量％を下回ると、加熱して脱水させたときに鉄鉱石の内部に形成される空隙体積が少なくなり、鉄鉱石に吸着される炭材量が減少し、炭材を吸着させることによる効果を享受できない。 As said iron ore, it is necessary to use the iron ore containing 5 mass% or more of crystal water. When the content of crystallization water is less than 5% by mass, the void volume formed in the iron ore when dehydrated by heating is reduced, and the amount of carbon material adsorbed on the iron ore is reduced. The effect of adsorbing can not be enjoyed.
上記結晶水の含有量の下限値を５質量％と定めたのは、次の理由による。まず、不純物がなく、ＦｅＯ（ＯＨ）またはＦｅ2Ｏ3のみで構成される酸化鉄を、還元率１００％（即ち、全量金属鉄）で還元するために必要な炭材を、ＦｅＯ（ＯＨ）の加熱によって形成される細孔に挿入するとした場合、必要な細孔の体積から結晶水量を計算すると７．９質量％となる。 The reason why the lower limit of the content of crystallization water is set to 5% by mass is as follows. First, a carbonaceous material necessary for reducing iron oxide composed of only FeO (OH) or Fe 2 O 3 without impurities with a reduction rate of 100% (that is, total amount of metallic iron) is FeO (OH). When it is inserted into the pores formed by heating, the amount of water of crystallization is calculated from the necessary volume of pores to be 7.9% by mass.
ところが実際の鉄鉱石は不純物を１０質量％程度含有しており、また還元率の目標値は、通常、８０％以上である。こうした実際の事情を考慮すると下記式から算出されるように鉄鉱石に含まれている結晶水量は５．６９質量％以上であればよい。但し、鉄鉱石は細孔外に存在する炭素によっても還元され、また細孔外に付着する炭材の状態は鉄鉱石の粒度等の性状によって異なるため、こうした事情も考慮して多少の余裕をもって結晶水の下限値は５質量％と定めた。
７．９質量％×０．９×０．８＝５．６９質量％
However, actual iron ore contains about 10% by mass of impurities, and the target value of the reduction rate is usually 80% or more. Considering such actual circumstances, the amount of crystal water contained in the iron ore may be 5.69% by mass or more as calculated from the following formula. However, iron ore is also reduced by carbon existing outside the pores, and the state of the carbonaceous material adhering outside the pores varies depending on the properties such as the particle size of the iron ore. The lower limit of crystal water was set to 5% by mass.
7.9% by mass × 0.9 × 0.8 = 5.69% by mass
なお、ＦｅＯ（ＯＨ）とＦｅ2Ｏ3のうち、結晶水を含んでいるのはＦｅＯ（ＯＨ）であり、このＦｅＯ（ＯＨ）は、加熱によって下記反応式に示されるようにＦｅ2Ｏ3とＨ2Ｏに分解される。
２ＦｅＯ（ＯＨ）→Ｆｅ2Ｏ3＋Ｈ2Ｏ
Of FeO (OH) and Fe 2 O 3 , it is FeO (OH) that contains water of crystallization, and this FeO (OH) is Fe 2 O 3 as shown in the following reaction formula by heating. And H 2 O.
2FeO (OH) → Fe 2 O 3 + H 2 O
上記鉄鉱石に含まれる結晶水の量は、ＪＩＳ Ｍ８２１１に基づいて測定できる。 The amount of crystal water contained in the iron ore can be measured based on JIS M8211.
上記炭材としては沸点が２００〜５００℃の物質を含む炭材を用いる必要がある。この炭材は鉄鉱石と混合する時点での温度域で軟化溶融するため、鉄鉱石の脱水により形成された細孔内に容易に吸着させることができる。また、上記特許文献２に記載されている乾留ガスは低分子量の成分であるため、この乾留ガスは鉄鉱石と気体の状態で接触することになり、鉄鉱石中に還元に必要な炭材を挿入させることはできない。一方、本発明によれば、上記炭材の沸点は鉄鉱石と混合時の温度に比べて高いため、鉄鉱石に形成させた細孔内に液体状で浸透させることができるため、鉄鉱石に多量の炭材を吸着させることができる。また、上記炭材は、鉄鉱石同士の接着力を高める作用も有しているため、上記鉄鉱石と上記炭材を混合して塊成物を製造することによって塊成物の強度を高めることができる。 As the carbon material, it is necessary to use a carbon material containing a substance having a boiling point of 200 to 500 ° C. Since this carbon material softens and melts in the temperature range at the time of mixing with iron ore, it can be easily adsorbed in the pores formed by dehydration of iron ore. In addition, since the dry distillation gas described in Patent Document 2 is a low molecular weight component, this dry distillation gas comes into contact with iron ore in a gaseous state, and the carbon material necessary for reduction is contained in the iron ore. It cannot be inserted. On the other hand, according to the present invention, since the boiling point of the carbonaceous material is higher than the temperature at the time of mixing with iron ore, it can be infiltrated in a liquid state into the pores formed in the iron ore. A large amount of carbonaceous material can be adsorbed. Moreover, since the said carbon material also has the effect | action which raises the adhesive force of iron ore, the intensity | strength of an agglomerate is raised by mixing the said iron ore and the said carbon material and manufacturing an agglomerate. Can do.
上記沸点が２００℃を下回ると分子量が小さい化合物が多くなるため、鉄鉱石に形成された細孔に付着する炭材量が減少する。そのため鉄鉱石の還元を促進できない。従って上記炭材の沸点は２００℃以上とする。好ましくは２５０℃以上であり、より好ましくは３００℃以上である。しかし上記炭材の沸点が５００℃を超えると軟化溶融性が低下するため、上記鉄鉱石と混合しても、鉄鉱石の細孔に炭材が吸着しにくくなる。そのため鉄鉱石の還元を促進できなくなる。従って上記炭材の沸点は５００℃以下とする。好ましくは４５０℃以下であり、より好ましくは４００℃以下である。 When the boiling point is lower than 200 ° C., the number of compounds having a small molecular weight increases, so the amount of carbonaceous material attached to the pores formed in the iron ore decreases. Therefore, reduction of iron ore cannot be promoted. Therefore, the boiling point of the carbonaceous material is 200 ° C. or higher. Preferably it is 250 degreeC or more, More preferably, it is 300 degreeC or more. However, when the boiling point of the carbon material exceeds 500 ° C., the softening and melting property is lowered, so that even when mixed with the iron ore, the carbon material is difficult to be adsorbed into the pores of the iron ore. Therefore, the reduction of iron ore cannot be promoted. Therefore, the boiling point of the carbonaceous material is 500 ° C. or less. Preferably it is 450 degrees C or less, More preferably, it is 400 degrees C or less.
本発明で用いる炭材は、上記沸点が２００〜５００℃の物質を２０質量％以上含有している必要がある。含有率が２０質量％を下回ると炭材の吸着量を充分に確保できないからである。上記含有率は５０質量％以上であることが好ましく、より好ましくは８０質量％以上である。上記含有率の上限は１００質量％であってもよいが、沸点が２００〜５００℃の物質からなる炭材を製造するにはコストがかかる。 The carbon material used in the present invention needs to contain 20% by mass or more of the substance having a boiling point of 200 to 500 ° C. This is because if the content is less than 20% by mass, a sufficient amount of carbonaceous material cannot be secured. The content is preferably 50% by mass or more, and more preferably 80% by mass or more. The upper limit of the content may be 100% by mass, but it costs money to produce a carbonaceous material made of a substance having a boiling point of 200 to 500 ° C.
上記炭材に占める上記沸点が２００〜５００℃の物質の含有率は次の手順で測定できる。 The content of the substance having a boiling point of 200 to 500 ° C. in the carbon material can be measured by the following procedure.
まず、ＪＩＳ Ｋ０１２９に規定される熱重量分析（ＴＧ分析）によって上記炭材を加熱し、質量変化を測定する。熱重量分析は、不活性ガス雰囲気（例えば、窒素ガス雰囲気）で、一定の昇温速度（例えば、１０℃／分）で炭材を加熱して行なえばよい。 First, the carbonaceous material is heated by thermogravimetric analysis (TG analysis) defined in JIS K0129, and the mass change is measured. The thermogravimetric analysis may be performed by heating the carbonaceous material in an inert gas atmosphere (for example, a nitrogen gas atmosphere) at a constant rate of temperature increase (for example, 10 ° C./min).
一例として、図１の（ａ）に下記実験例で用いたＬｏｙ Ｙａｎｇ Ｓｏｌｕｂｌｅを熱重量分析した結果を示す。なお、熱重量分析は、Ｎ2ガス雰囲気で、昇温速度を１０℃／分として行なった。横軸は分析時の加熱温度、縦軸は熱重量分析に供した炭材の質量を１としたときの相対質量である。また、図１の（ｂ）に、上記図１の（ａ）に示した結果を１℃あたりの質量減少量に換算した結果を示す。図１の（ｂ）の横軸（下方に示した横軸）は分析時の加熱温度、縦軸は１℃あたりの質量減少量を示している。 As an example, FIG. 1A shows the result of thermogravimetric analysis of Loy Yang Soluble used in the following experimental example. The thermogravimetric analysis was performed in an N 2 gas atmosphere at a heating rate of 10 ° C./min. The horizontal axis is the heating temperature at the time of analysis, and the vertical axis is the relative mass when the mass of the carbonaceous material subjected to thermogravimetric analysis is 1. FIG. 1 (b) shows the result of converting the result shown in FIG. 1 (a) into a mass decrease per 1 ° C. In FIG. 1B, the horizontal axis (the horizontal axis shown below) represents the heating temperature during analysis, and the vertical axis represents the amount of mass reduction per 1 ° C.
次に、上記炭材の沸点を、ＪＩＳ Ｋ２２５４に規定されるガスクロマトグラフ法蒸留試験方法に基づいて測定する。測定は、不活性ガス雰囲気（例えば、窒素ガス雰囲気）で、一定の昇温速度（例えば、１０℃／分）で行い、具体的な測定条件は、上記熱重量分析と同じ条件とする。ガスクロマトグラフ法蒸留試験方法によれば、加熱したときの保持時間と炭材の沸点との関係が得られる。一方、上記図１の（ａ）、（ｂ）に示した横軸（下方に示した横軸）は加熱温度を示しているが、加熱時の昇温速度（ここでは、１０℃／分）に基づいて、この横軸を時間に換算できる。そこで、上記ガスクロマトグラフ法蒸留試験方法によって求めた保持時間と炭材の沸点との関係を、上記図１の（ｂ）の上方の横軸に併せて示す。 Next, the boiling point of the carbonaceous material is measured based on a gas chromatographic distillation test method defined in JIS K2254. The measurement is performed in an inert gas atmosphere (for example, a nitrogen gas atmosphere) at a constant rate of temperature increase (for example, 10 ° C./min), and specific measurement conditions are the same as those in the thermogravimetric analysis. According to the gas chromatographic distillation test method, the relationship between the holding time when heated and the boiling point of the carbonaceous material is obtained. On the other hand, the horizontal axis (the horizontal axis shown below) shown in FIGS. 1A and 1B shows the heating temperature, but the heating rate during heating (here, 10 ° C./min) This horizontal axis can be converted to time based on Therefore, the relationship between the retention time determined by the gas chromatographic distillation test method and the boiling point of the carbonaceous material is shown together with the horizontal axis above (b) in FIG.
上記図１の（ａ）と（ｂ）から炭材中の沸点が２００〜５００℃の物質の含有率を算出できる。即ち、図１の（ｂ）の上方に示した横軸が２００℃と５００℃における炭材の質量を、上記図１の（ａ）から求める。具体的には、沸点が２００℃の物質が揮発した時点の炭材の相対質量は図１の（ａ）から１．０ｋｇ／ｋｇで、沸点が５００℃の物質が揮発した時点の炭材の相対質量は図１の（ａ）から０．６２ｋｇ／ｋｇと読み取れる。従って、炭材に占める沸点が２００〜５００℃の物質の相対含有量は、１．０−０．６２＝０．３８であり、含有率は３８％となる。 From (a) and (b) of FIG. 1 above, the content of a substance having a boiling point of 200 to 500 ° C. in the carbonaceous material can be calculated. That is, the mass of the carbonaceous material with the horizontal axis shown above (b) in FIG. 1 being 200 ° C. and 500 ° C. is obtained from (a) in FIG. Specifically, the relative mass of the carbon material when the substance having a boiling point of 200 ° C. is 1.0 kg / kg from (a) of FIG. 1, and the carbon material when the substance having a boiling point of 500 ° C. is volatilized. The relative mass can be read as 0.62 kg / kg from FIG. Therefore, the relative content of the substance having a boiling point of 200 to 500 ° C. in the carbonaceous material is 1.0−0.62 = 0.38, and the content rate is 38%.
上記炭材としては、分子量分布を測定したときにピーク強度が最も大きい分子の分子量が２００〜３００の炭材を用いてもよい。分子量が２００〜３００の炭材は、沸点がほぼ２００〜５００℃になるからである。従って分子量が２００〜３００の化合物は、鉄鉱石の細孔に吸着しやすく、鉄鉱石の還元を促進する作用を有している。 As the carbon material, a carbon material having a molecular weight of 200 to 300 having the highest peak intensity when the molecular weight distribution is measured may be used. This is because a carbon material having a molecular weight of 200 to 300 has a boiling point of approximately 200 to 500 ° C. Therefore, a compound having a molecular weight of 200 to 300 is easily adsorbed on the pores of iron ore and has an action of promoting the reduction of iron ore.
上記炭材の分子量分布は、例えば、ゲル濾過クロマトグラフィー（ＧＦＣ；Ｇｅｌ Ｆｉｌｔｒａｔｉｏｎ Ｃｈｒｏｍａｔｏｇｒａｐｈｙ）により測定できる。 The molecular weight distribution of the carbonaceous material can be measured by, for example, gel filtration chromatography (GFC).
上記炭材のなかでも、軟化開始温度が３００℃以下の低温軟化炭材を用いることが好ましい。軟化開始温度が低いほど鉄鉱石の細孔内に炭材を低温で吸着させることができる。軟化開始温度は、鉄鉱石と炭材を混合する温度にもよるが、より好ましくは２００℃以下であり、更に好ましくは１００℃以下である。軟化開始温度が低いほど鉄鉱石の細孔内への浸透を促進させることができるが、軟化開始温度が０℃を下回る低温軟化炭材を高収率で製造することは炭材製造における回収率が低下するため軟化開始温度の下限値は０℃程度とする。 Among the carbon materials, it is preferable to use a low-temperature softened carbon material having a softening start temperature of 300 ° C. or lower. The lower the softening start temperature, the more carbonaceous material can be adsorbed in the pores of iron ore at a lower temperature. Although softening start temperature is based also on the temperature which mixes iron ore and a carbonaceous material, More preferably, it is 200 degrees C or less, More preferably, it is 100 degrees C or less. The lower the softening start temperature, the more the penetration of iron ore into the pores can be promoted. However, producing a low-temperature softened carbon material with a softening start temperature lower than 0 ° C. in a high yield is a recovery rate in the production of carbon materials. Therefore, the lower limit of the softening start temperature is about 0 ° C.
上記軟化開始温度は、ＪＩＳ Ｍ８８０１に規定される流動性試験により測定できる。流動性試験では、ギーセラープラストメータを用いて軟化開始温度を測定すればよい。 The softening start temperature can be measured by a fluidity test specified in JIS M8801. In the fluidity test, the softening start temperature may be measured using a Gieseller plastometer.
上記炭材は、例えば、溶剤で原料炭材から抽出した可溶成分を用いることができる。 As the carbon material, for example, a soluble component extracted from a raw material carbon material with a solvent can be used.
上記原料炭材としては、高品位炭と低品位炭のいずれを用いてもよいが、入手のしやすさや資源を有効活用する観点から、低品位炭を用いることが好ましい。低品位炭は、産出量が多く、資源としては豊富であるが、揮発分や水分を多く含むため工業的な用途は少ない。一方、溶媒抽出する原料として用いれば、揮発分や水分を多く含んでいても問題にはならない。よって低品位炭を用いることが推奨される。 As the raw material carbon material, either high-grade coal or low-grade coal may be used, but it is preferable to use low-grade coal from the viewpoint of easy availability and effective utilization of resources. Low-grade coal has a large output and is abundant as a resource, but it has few industrial uses because it contains a large amount of volatile matter and moisture. On the other hand, if it is used as a raw material for solvent extraction, it does not matter even if it contains a large amount of volatile matter and moisture. Therefore, it is recommended to use low grade coal.
上記低品位炭としては、例えば、褐炭を用いることができる。 As the low-grade coal, for example, lignite can be used.
上記褐炭の種類は特に限定されないが、例えば、Ｌｏｙ Ｙａｎｇ（ＬＹ）、Ｍａｅ Ｍｏｈ（ＭＭ）、Ｗａｒａ（ＷＡ）、Ｂｅｒａｕ Ｂｉｎｕnｇａｎ（ＢＢ）、Ｍｕｋａｈ Ｂａｌｉｎｇｉａｎ（ＭＢ）、Ｐｈｉｌｉｐｐｉｎｅ Ｌｉｇｎｉｔｅ（ＰＨ）、Ａｄａｒｏ（ＡＤ）、Ｔａｎｉｔｏ Ｈａｒｕｍ（ＴＨ）などを用いることができる。 The type of the lignite is not particularly limited. For example, Loy Yang (LY), Mae Moh (MM), Wara (WA), Berau Binungan (BB), Mukah Balingian (MB), Philippine Lite (PH), ADaro (AD) ), Tanito Harum (TH), etc. can be used.
上記原料炭材は、溶剤で可溶成分を抽出し易くするために、例えば、直径５ｍｍ程度以下（好ましくは３ｍｍ以下）に粉砕しておくことが好ましい。また、可溶成分を抽出する際には、抽出率を高めるために上記原料炭材と溶剤とをスラリー状に混合することが好ましい。この混合物を攪拌しつつ加熱すれば、上記原料炭材に含まれる溶剤に可溶な可溶成分が溶剤中に抽出される。 In order to make it easy to extract soluble components with a solvent, the raw carbon material is preferably pulverized, for example, to a diameter of about 5 mm or less (preferably 3 mm or less). Moreover, when extracting a soluble component, in order to raise an extraction rate, it is preferable to mix the said raw material carbon material and a solvent in a slurry form. If this mixture is heated with stirring, soluble components soluble in the solvent contained in the raw carbon material are extracted into the solvent.
上記原料炭材から溶剤に可溶な成分を抽出するときに用いる溶剤としては、極性溶剤や芳香族溶剤を使用できる。極性溶剤としては、例えば、Ｎ-メチルピロリドンやピリジン等が用いられる。芳香族溶剤としては、一般的には、ベンゼン、トルエン、キシレン等の１環芳香族化合物や、ナフタレン、メチルナフタレン、ジメチルナフタレン、トリメチルナフタレン、テトラヒドロナフタレン（テトラリン；登録商標）等の２環芳香族化合物、アントラセン等の３環以上の芳香族化合物等が用いられる。また、２環芳香族化合物には、その他脂肪族側鎖をもつナフタレン類、また、これにビフェニルや長鎖脂肪族側鎖をもつアルキルベンゼンが含まれる。 As a solvent used when extracting a component soluble in a solvent from the raw material carbonaceous material, a polar solvent or an aromatic solvent can be used. For example, N-methylpyrrolidone or pyridine is used as the polar solvent. The aromatic solvent is generally a one-ring aromatic compound such as benzene, toluene or xylene, or a two-ring aromatic compound such as naphthalene, methylnaphthalene, dimethylnaphthalene, trimethylnaphthalene or tetrahydronaphthalene (tetralin; registered trademark). An aromatic compound having three or more rings such as a compound and anthracene is used. The bicyclic aromatic compound includes other naphthalenes having an aliphatic side chain, and biphenyl and alkylbenzene having a long aliphatic side chain.
上記可溶成分を抽出する温度は、例えば、３００〜４２０℃程度（特に、３３０〜４００℃程度）に設定することが好ましい。抽出温度が低過ぎると上記原料炭材に含まれる易ガス化成分を除去できないうえ、原料炭材を構成する成分の分子間結合力を弱めることが不充分となって可溶成分の抽出率が小さくなる。一方、抽出温度が高過ぎると原料炭材が熱分解して生成したラジカルの再結合が起こるため、可溶成分の抽出率が小さくなる。 The temperature at which the soluble component is extracted is preferably set to, for example, about 300 to 420 ° C. (particularly about 330 to 400 ° C.). If the extraction temperature is too low, the gasification component contained in the raw material carbon material cannot be removed, and it is insufficient to weaken the intermolecular bonding force of the components constituting the raw material carbon material, so that the extraction rate of soluble components is reduced. Get smaller. On the other hand, if the extraction temperature is too high, radical recombination generated by thermal decomposition of the raw carbon material occurs, so that the extraction rate of soluble components becomes small.
上記可溶成分を抽出する時間は、例えば、１０〜１２０分程度（特に、３０〜６０分程度）とすればよい。抽出時間が長過ぎると抽出した可溶成分の熱分解反応が進行し、ラジカル重合反応が進むため可溶成分の抽出率が小さくなる。 The time for extracting the soluble component may be, for example, about 10 to 120 minutes (particularly about 30 to 60 minutes). If the extraction time is too long, the thermal decomposition reaction of the extracted soluble component proceeds and the radical polymerization reaction proceeds, so the extraction rate of the soluble component decreases.
上記可溶成分の抽出は、例えば、不活性ガス（例えば、窒素）の存在の下で行なえばよい。なお、抽出工程では、溶剤が沸騰しないように加圧する必要があり、圧力は、通常、０．８〜２．５ＭＰａ程度（特に、１〜２ＭＰａ）の範囲に調整すればよい。 The soluble component may be extracted in the presence of an inert gas (for example, nitrogen), for example. In addition, it is necessary to pressurize so that a solvent may not boil in an extraction process, and what is necessary is just to adjust a pressure to the range of about 0.8-2.5 MPa (especially 1-2 MPa) normally.
上記結晶水を５質量％以上含有する鉄鉱石と上記炭材の混合比は、質量基準で、例えば、９０：１０〜２０：８０とすればよい。 The mixing ratio of the iron ore containing 5% by mass or more of the crystal water and the carbon material may be 90:10 to 20:80, for example, on a mass basis.
上記鉄鉱石と上記炭材を含む混合物には、その他の成分としてＭｇＯ含有物質やＣａＯ含有物質などを配合してもよい。ＭｇＯ含有物質としては、例えば、ＭｇＯ粉末や天然鉱石や海水などから抽出されるＭｇＯ含有物質、或いはドロマイトや炭酸マグネシウム（ＭｇＣＯ3）などを用いることができる。ＣａＯ含有物質としては、例えば、生石灰（ＣａＯ）や石灰石（主成分はＣａＣＯ3）などを用いることができる。なお、軟化溶融した炭材は上記混合物のバインダーとしても作用するため、本発明ではバインダーの配合を省略してもよい。但し、上記混合物を常温で塊成物に成形する場合には、バインダーを添加することが好ましい。バインダーとしては、例えば、多糖類（例えば、小麦粉等の澱粉など）などを用いることができる。 You may mix | blend MgO containing material, CaO containing material, etc. with the mixture containing the said iron ore and the said carbon material as another component. As the MgO-containing substance, for example, an MgO-containing substance extracted from MgO powder, natural ore, seawater, etc., dolomite, magnesium carbonate (MgCO 3 ), or the like can be used. As the CaO-containing substance, for example, quick lime (CaO) or limestone (main component is CaCO 3 ) can be used. In addition, since the softened and melted carbon material also acts as a binder of the above mixture, the blending of the binder may be omitted in the present invention. However, when the mixture is formed into an agglomerate at room temperature, it is preferable to add a binder. As the binder, for example, a polysaccharide (for example, starch such as wheat flour) can be used.
上記混合物の塊成物の形状は特に限定されず、例えば、ペレット状やブリケット状などであればよい。 The shape of the agglomerate of the mixture is not particularly limited, and may be, for example, a pellet shape or a briquette shape.
次に、上記塊成物を炉で加熱して還元鉄を製造する方法について説明する。 Next, a method for producing reduced iron by heating the agglomerate in a furnace will be described.
上記炉としては、加熱炉や高炉を用いることができる。加熱炉としては、移動炉床炉を用いることができる。移動炉床炉とは、炉床がベルトコンベアのように炉内を移動する加熱炉であり、具体的には、回転炉床炉が例示できる。回転炉床炉は、炉床の始点と終点が同じ位置になるように炉床の外観形状が円形（ドーナツ状）に設計されている。従って、回転方向の最上流側には塊成物を炉内に供給する装入手段が配置されると共に、回転方向の最下流側（回転構造であるため、実際には装入手段の直上流側になる）には排出手段が設けられる。 A heating furnace or a blast furnace can be used as the furnace. A moving hearth furnace can be used as the heating furnace. The moving hearth furnace is a heating furnace in which the hearth moves in the furnace like a belt conveyor, and specifically, a rotary hearth furnace can be exemplified. In the rotary hearth furnace, the outer shape of the hearth is designed in a circular shape (donut shape) so that the start point and end point of the hearth are in the same position. Therefore, the charging means for supplying the agglomerate into the furnace is arranged on the most upstream side in the rotation direction, and the most downstream side in the rotation direction (because of the rotating structure, it is actually just upstream of the charging means. A discharge means is provided on the side.
上記炉床上に供給された塊成物は、炉内を一周する間に加熱還元されて還元鉄を生成する。また、炉内で更に加熱して還元鉄を一旦溶融し、これを冷却すれば粒状金属鉄を製造できる。 The agglomerate supplied onto the hearth is reduced by heating while making a round in the furnace to produce reduced iron. Further, if the reduced iron is once melted by further heating in a furnace and then cooled, granular metallic iron can be produced.
上記塊成物中の酸化鉄を加熱炉内で加熱還元するときの条件は特に限定されないが、本発明の塊成物は、脱水鉄鉱石に低融点炭材が吸着するため鉄鉱石の還元が促進される。従って、炉内温度を１３００℃より低くても還元鉄を製造できる。よって炉の加熱に必要な熱量を削減できるため燃料消費量を低減できる。炉内温度は、例えば、９００〜１３００℃とすればよい。炉内の加熱には、バーナーを用い、該バーナーの燃焼条件を制御すれば、塊成物の温度を調整できる。一方、炉内温度を１３００℃よりも高くする場合には、上記塊成物の炉内での移動速度を通常よりも大きくすることができる。従って従来よりも生産性を高めることができる。 The conditions for heating and reducing the iron oxide in the agglomerate in the heating furnace are not particularly limited, but the agglomerate of the present invention can reduce the iron ore because the low melting point carbonaceous material is adsorbed on the dehydrated iron ore. Promoted. Therefore, reduced iron can be produced even when the furnace temperature is lower than 1300 ° C. Therefore, since the amount of heat necessary for heating the furnace can be reduced, fuel consumption can be reduced. The furnace temperature may be, for example, 900 to 1300 ° C. If the burner is used for heating in the furnace and the combustion conditions of the burner are controlled, the temperature of the agglomerate can be adjusted. On the other hand, when the furnace temperature is higher than 1300 ° C., the moving speed of the agglomerate in the furnace can be made higher than usual. Therefore, productivity can be improved as compared with the conventional case.
上記還元鉄を一旦溶融し、粒状金属鉄を製造する場合においても本発明の塊成物を用いれば金属鉄を従来よりも低温で製造でき、鉄の溶融開始以前の炉の加熱に必要な熱量を削減できるため、燃料消費量を低減できる。なお、炉内温度を従来通りとする場合には、上記塊成物の炉内での還元速度を従来よりも大きくできるため生産性を高めることができる。 Even when the reduced iron is once melted to produce granular metallic iron, if the agglomerate of the present invention is used, metallic iron can be produced at a lower temperature than before, and the amount of heat necessary for heating the furnace before starting the melting of iron. Therefore, fuel consumption can be reduced. Note that, when the furnace temperature is set to the conventional value, the reduction rate of the agglomerate in the furnace can be increased as compared with the conventional technique, so that productivity can be increased.
上記塊成物を炉床上に供給するに先立って、炉床上には床敷材として炭材を予め敷いておくことが好ましい。床敷材は、炉床保護材として作用すると共に塊成物に含まれる炭素が不足したときの炭素供給源となる。 Prior to supplying the agglomerate to the hearth, it is preferable to lay a carbon material in advance on the hearth as a flooring material. The flooring material acts as a hearth protection material and becomes a carbon supply source when the carbon contained in the agglomerate is insufficient.
上記床敷材の厚みは特に限定されないが、例えば、３〜３０ｍｍとすることが好ましい。上記床敷材として用いる炭材としては、上記炭素質還元剤として例示したものを用いることができる。上記炭材としては、粒子径が０．５〜３．０ｍｍ程度のものを用いることが推奨される。 The thickness of the floor covering material is not particularly limited, but is preferably 3 to 30 mm, for example. As the carbon material used as the floor covering material, those exemplified as the carbonaceous reducing agent can be used. As the carbon material, it is recommended to use one having a particle diameter of about 0.5 to 3.0 mm.
上記塊成物は、高炉へ装入して銑鉄を製造するための材料として用いてもよい。上記塊成物を鉄鉱石層に配合することによって、鉄鉱石層中の酸化鉄の還元が促進される。そのため高炉へ装入するコークス量を低減できる。 You may use the said agglomerate as a material for charging a blast furnace and manufacturing pig iron. By mix | blending the said agglomerate with an iron ore layer, the reduction | restoration of the iron oxide in an iron ore layer is accelerated | stimulated. Therefore, the amount of coke charged into the blast furnace can be reduced.
以下、実施例を挙げて本発明をより具体的に説明するが、本発明はもとより下記実施例によって制限を受けるものではなく、前・後記の趣旨に適合し得る範囲で適当に変更を加えて実施することも勿論可能であり、それらはいずれも本発明の技術的範囲に包含される。 EXAMPLES Hereinafter, the present invention will be described more specifically with reference to examples. However, the present invention is not limited by the following examples, but may be appropriately modified within a range that can meet the purpose described above and below. Of course, it is possible to implement them, and they are all included in the technical scope of the present invention.
下記予備実験では、鉄鉱石としてγ−ＦｅＯ（ＯＨ）の純試薬を用い、炭材の代わりに軟化溶融性を示すイオン交換樹脂を用いて塊成物を製造し、これを加熱したときの様子を調べた。下記実験例では、鉄鉱石と炭材を用いて塊成物を製造するか、鉄鉱石と、溶剤で炭材から抽出した可溶成分とを用いて塊成物を製造し、これを加熱したときの様子を調べた。 In the following preliminary experiment, using a pure reagent of γ-FeO (OH) as an iron ore, an agglomerate is produced using an ion exchange resin showing softening and melting properties instead of a carbonaceous material, and this is heated I investigated. In the following experimental example, an agglomerate is produced using iron ore and a carbonaceous material, or an agglomerate is produced using iron ore and a soluble component extracted from the carbonaceous material with a solvent, and this is heated. I looked at the situation.
［予備実験］
γ−ＦｅＯ（ＯＨ）の純試薬は、Ａｌｆａ Ａｅｓａｒから入手した。この平均粒径は２５０μｍであった。上記純試薬に含まれる結晶水の量は、１０．２質量％であった。一方、軟化溶融性を示すイオン交換樹脂としては、三菱化学製のレジン「ＷＫ１１」を用いた。
[Preliminary experiment]
The pure reagent for γ-FeO (OH) was obtained from Alfa Aesar. The average particle size was 250 μm. The amount of crystallization water contained in the pure reagent was 10.2% by mass. On the other hand, resin “WK11” manufactured by Mitsubishi Chemical was used as an ion exchange resin exhibiting softening and melting properties.
上記純試薬と上記レジンを、質量比で、１５：８５の割合で混合した試料約２０ｍｇを、熱天秤（島津製作所、ＴＧ−５０Ｈ）にてＨｅ雰囲気下で１３５０℃まで加熱し、質量変化を測定するとともに、熱天秤の出口から排出される排ガスの成分組成をマイクロガスクロマトグラフ（Ｍｉｃｒｏ ＧＣ ＣＰ４９００、 ＧＬサイエンス）で分析した。加熱時の昇温速度は、１０℃／分とした。上記排ガス、および上記純試薬に含まれるＯ（酸素）の収支から還元率（ＲＲ）を算出した。 About 20 mg of a sample prepared by mixing the pure reagent and the resin at a mass ratio of 15:85 was heated to 1350 ° C. in a He atmosphere with a thermobalance (Shimadzu Corporation, TG-50H), and the change in mass was measured. While measuring, the component composition of the exhaust gas discharged from the outlet of the thermobalance was analyzed with a micro gas chromatograph (Micro GC CP4900, GL Science). The heating rate during heating was 10 ° C./min. The reduction rate (RR) was calculated from the balance of O (oxygen) contained in the exhaust gas and the pure reagent.
加熱温度に対する還元率の変化を図３に（ａ）の曲線で示す。なお、図３に（ｂ）〜（ｄ）で示した曲線は、後記する実験例の結果を示している。 The change of the reduction rate with respect to the heating temperature is shown in FIG. In addition, the curve shown by (b)-(d) in FIG. 3 has shown the result of the experimental example mentioned later.
次に、還元の様子を直接観察するために高速測定可能なＸＲＤ装置（ＲＩＧＡＫＵ製のＵｌｔｉｍａ ＩＶ）を用いてＸＲＤ回折測定を行った。測定は上記試料約１００ｍｇをステージ上で加熱しながら行なった。上記加熱はＨｅ雰囲気で行い、加熱時の昇温速度は１０℃／分とした。 Next, in order to directly observe the state of reduction, XRD diffraction measurement was performed using an XRD apparatus capable of high-speed measurement (Ultima IV manufactured by RIGAKU). The measurement was performed while heating about 100 mg of the sample on the stage. The above heating was performed in a He atmosphere, and the heating rate during heating was 10 ° C./min.
また、加熱途中の試料を取り出し、透過型電子顕微鏡（ＪＥＯＬ製のＪＥＭ−１０１０）による観察を行った。３００℃または４００℃で取り出した試料のＴＥＭ写真を図４に示す。また、加熱前の室温における試料（上記純試薬と上記レジンを混合した試料）のＴＥＭ写真を図４に示す。 Moreover, the sample in the middle of heating was taken out and observed with the transmission electron microscope (JEM-1010 made from JEOL). A TEM photograph of the sample taken out at 300 ° C. or 400 ° C. is shown in FIG. FIG. 4 shows a TEM photograph of a sample at room temperature before heating (a sample in which the pure reagent and the resin are mixed).
図４から明らかなように、上記純試薬と上記レジンを混合した試料にはレジンの侵入は認められなかった。一方、３００℃に加熱した試料、および４００℃に加熱した試料については、上記純試薬に含まれる結晶水が脱水されて形成された細孔に上記レジンが侵入していることが分かった。 As is clear from FIG. 4, no penetration of the resin was observed in the sample in which the pure reagent and the resin were mixed. On the other hand, for the sample heated to 300 ° C. and the sample heated to 400 ° C., it was found that the resin penetrated into the pores formed by dehydration of the crystal water contained in the pure reagent.
次に、加熱途中で取り出した試料の表面積をＢＥＴ法で測定した。その結果、上記純試薬と上記レジンを混合した試料の表面積は、６８．６ｍ2／ｇ−ＦｅＯ（ＯＨ）、３００℃に加熱した試料の表面積は、１３３．６ｍ2／ｇ−ＦｅＯ（ＯＨ）、４００℃に加熱した試料の表面積は、２１．４ｍ2／ｇ−ＦｅＯ（ＯＨ）であった。 Next, the surface area of the sample taken out during heating was measured by the BET method. As a result, the surface area of the sample in which the pure reagent and the resin were mixed was 68.6 m 2 / g-FeO (OH), and the surface area of the sample heated to 300 ° C. was 133.6 m 2 / g-FeO (OH). The surface area of the sample heated to 400 ° C. was 21.4 m 2 / g-FeO (OH).
４００℃に加熱することによってγ−ＦｅＯ（ＯＨ）の焼結が進行したため、比表面積がやや減少したと考えられる。そのため上記純試薬に侵入するレジン量は、３００℃に加熱した試料よりも少なくなると考えられる。 Since the sintering of γ-FeO (OH) has progressed by heating to 400 ° C., it is considered that the specific surface area has slightly decreased. Therefore, it is considered that the amount of resin entering the pure reagent is smaller than that of the sample heated to 300 ° C.
［実験例］
下記表１に示す成分組成の鉄鉱石粉と、下記表２に示す成分組成の炭材（Ｌｏｙ Ｙａｎｇ）または溶剤で炭材から抽出した可溶成分（Ｌｏｙ Ｙａｎｇ Ｓｏｌｕｂｌｅ）を、下記表４に示す配合比で混合して試料を調製した。各鉄鉱石粉の粒径を下記表１に併せて示す。また、下記表２において水分は、炭材に含まれる水分を示しており、灰分と揮発分は、炭材を乾燥させて測定した値を示している。
[Experimental example]
The composition shown in the following Table 4 includes the iron ore powder having the component composition shown in the following Table 1 and the soluble component extracted from the carbonaceous material (Loy Yang) or the solvent having the component composition shown in the following Table 2. Samples were prepared by mixing at a ratio. The particle size of each iron ore powder is also shown in Table 1 below. Moreover, in Table 2 below, moisture indicates moisture contained in the carbonaceous material, and ash and volatile components indicate values measured by drying the carbonaceous material.
下記表１に示したＳＦ．ローブリバーは、ＦｅＯ（ＯＨ）を約９０質量％以上含有する低品位鉄鉱石である。下記表１に示したＰＦ．ツバロンは、ＦｅＯ（ＯＨ）を殆ど含まない高品位鉄鉱石である。 SF. Shown in Table 1 below. Robber is a low-grade iron ore containing about 90% by mass or more of FeO (OH). The PF. Tubaron is a high-grade iron ore that contains almost no FeO (OH).
下記表２に示したＬｏｙ Ｙａｎｇは豪州褐炭である。下記表３にｄ．ａ．ｆ．の元素分析を行った結果を示す。なお、ｄ．ａ．ｆ．とは、炭材から水分と灰分を除いた有機質の質量を意味している。 Loy Yang shown in Table 2 below is Australian brown coal. In Table 3 below, d. a. f. The results of elemental analysis are shown. D. a. f. The term “organic” refers to the mass of an organic substance obtained by removing moisture and ash from a carbonaceous material.
下記表２に示したＬｏｙ Ｙａｎｇ Ｓｏｌｕｂｌｅは次の手順で調製した。即ち、下記表２に示したＬｏｙ Ｙａｎｇ（１５ｇ−ｄ．ａ．ｆ．）を容量３５０ｃｍ3のＳＵＳ製オートクレーブに充填した後、溶剤として濃度が１ｍｏｌ／Ｌのメチルナフタレンを約３００ｃｍ3供給し、これを３５０℃で３時間保持して加熱した。また、オートクレーブの下部には、開口径０．５μｍのフィルターを設けた。 Loy Yang Soluble shown in Table 2 below was prepared by the following procedure. That is, Loy Yang (15 gdaf) shown in Table 2 below was filled into a 350 cm 3 SUS autoclave and then about 300 cm 3 of methylnaphthalene having a concentration of 1 mol / L was supplied as a solvent. This was heated at 350 ° C. for 3 hours. A filter having an opening diameter of 0.5 μm was provided at the bottom of the autoclave.
加熱後、その温度のままフィルターの下に設けられたバルブを開放して抽出液と抽出されない成分をろ過分離した。取り出した抽出液を常温まで冷却し、更にろ過することによって常温で析出する成分と常温でも溶剤に可溶な成分を分離した。この常温でも溶剤に可溶な成分からロータリーエバポレータによって溶剤を除去し、固体（Ｌｏｙ Ｙａｎｇ Ｓｏｌｕｂｌｅ）を得た。 After heating, the valve provided under the filter was opened at that temperature to separate the extract and the components that were not extracted by filtration. The extracted liquid was cooled to room temperature and further filtered to separate components that were precipitated at room temperature and components that were soluble in the solvent at room temperature. The solvent was removed from the component soluble in the solvent even at room temperature by a rotary evaporator to obtain a solid (Loy Yang Soluble).
得られたＬｏｙ Ｙａｎｇ Ｓｏｌｕｂｌｅの元素分析を行った結果を下記表３に示す。 Table 3 below shows the results of elemental analysis of the obtained Loy Yang Soluble.
次に、得られたＬｏｙ Ｙａｎｇ Ｓｏｌｕｂｌｅに占める沸点が２００〜５００℃の物質の割合を上述した手順で測定した。その結果、沸点が２００〜５００℃の物質の割合は３８質量％であった。 Next, the ratio of the substance having a boiling point of 200 to 500 ° C. in the obtained Loy Yang Soluble was measured by the procedure described above. As a result, the ratio of the substance having a boiling point of 200 to 500 ° C. was 38% by mass.
また、得られたＬｏｙ Ｙａｎｇ Ｓｏｌｕｂｌｅの軟化開始温度はギーセラープラストメータを用いて測定した。その結果、軟化開始温度は、５０〜８０℃であった。なお、Ｌｏｙ Ｙａｎｇは、沸点を測定できなかった。 Moreover, the softening start temperature of the obtained Loy Yang Soluble was measured using a Gieseler plastometer. As a result, the softening start temperature was 50 to 80 ° C. In addition, Loy Yang could not measure the boiling point.
次に、Ｌｏｙ Ｙａｎｇ Ｓｏｌｕｂｌｅの分子量分布をＧＰＣにて測定した。その結果を図５に示す。図５から明らかなように、ピーク強度が最も大きい分子の分子量は、２８０であった。 Next, the molecular weight distribution of Loy Yang Soluble was measured by GPC. The result is shown in FIG. As is apparent from FIG. 5, the molecular weight of the molecule having the highest peak intensity was 280.
次に、得られた試料約２０ｍｇを上記予備実験と同じ条件で加熱し、質量変化を測定すると共に熱天秤の出口から排出される排ガスの成分組成を分析した。加熱温度に対する還元率の変化を上記図３に合せて示す。図３において、曲線（ｂ）は下記表４に示したＮｏ．１の結果、曲線（ｃ）は下記表４に示したＮｏ．２の結果、曲線（ｄ）は下記表４に示したＮｏ．３の結果を夫々示している。 Next, about 20 mg of the obtained sample was heated under the same conditions as in the preliminary experiment, the mass change was measured, and the component composition of the exhaust gas discharged from the outlet of the thermobalance was analyzed. The change of the reduction rate with respect to the heating temperature is also shown in FIG. In FIG. 3, the curve (b) is No. shown in Table 4 below. As a result, curve (c) is No. shown in Table 4 below. As a result of No. 2, the curve (d) is No. shown in Table 4 below. The results of 3 are shown respectively.
表４および図３から次のように考察できる。Ｎｏ．１［曲線（ｂ）］は、本発明で規定する要件を満足している例であり、約９００℃に加熱することによって、ほぼ完全に還元できることが分かる。即ち、比較的低温の加熱で還元できることが分かる。一方、Ｎｏ．２［曲線（ｃ）］、およびＮｏ．３［曲線（ｄ）］は、１１００℃に加熱しても還元できなかった。また、１３００℃に加熱した場合でも還元が完全に終わらなかったことを確認している。 The following can be considered from Table 4 and FIG. No. 1 [curve (b)] is an example satisfying the requirements defined in the present invention, and it can be seen that the film can be reduced almost completely by heating to about 900 ° C. That is, it can be seen that the reduction can be achieved by heating at a relatively low temperature. On the other hand, no. 2 [curve (c)], and No. 2 3 [curve (d)] could not be reduced by heating to 1100 ° C. It was also confirmed that the reduction was not completely completed even when heated to 1300 ° C.
次に、Ｎｏ．１について加熱を５００℃で停止したとき、９００℃に加熱した直後、および加熱後に冷却した時点においてＸ線回折測定を行った。Ｘ線回折の測定結果を図６に示す。その結果、加熱温度が５００℃の場合には、充分に還元されておらずＦｅ3Ｏ4が一部残っていた。一方、９００℃に加熱すると還元が完了し、Ｆｅのピークのみが検出された。このＦｅのピークは冷却後も検出された。 Next, no. When heating was stopped at 500 ° C. for No. 1, X-ray diffraction measurement was performed immediately after heating to 900 ° C. and immediately after cooling after heating. The measurement result of X-ray diffraction is shown in FIG. As a result, when the heating temperature was 500 ° C., it was not fully reduced and a part of Fe 3 O 4 remained. On the other hand, when heated to 900 ° C., the reduction was completed and only the Fe peak was detected. This Fe peak was detected even after cooling.
次に、加熱を５００℃で停止して得られた塊成物の断面を、透過型電子顕微鏡を用いて写真撮影した。撮影した図面代用写真を図７に示す。図７から鉄鉱石の細孔の間に、炭材が侵入していることが分かる。 Next, the cross section of the agglomerate obtained by stopping the heating at 500 ° C. was photographed using a transmission electron microscope. FIG. 7 shows a photograph substituted for a drawing. It can be seen from FIG. 7 that the carbonaceous material has entered between the pores of the iron ore.
Claims (9)
前記鉄鉱石として、結晶水を５質量％以上含有する鉄鉱石を加熱して脱水した脱水鉄鉱石、
前記炭材として、沸点が２００〜５００℃の物質を２０質量％以上含む炭材を準備し、
これらの混合物を塊成化することを特徴とする塊成物の製造方法。 A method of agglomerating a mixture containing iron ore and carbonaceous material to produce an agglomerate for iron making,
As the iron ore, dehydrated iron ore obtained by heating and dehydrating iron ore containing 5% by mass or more of crystal water,
As the carbon material, a carbon material containing 20% by mass or more of a substance having a boiling point of 200 to 500 ° C. is prepared,
A method for producing an agglomerate, comprising agglomerating the mixture.
前記鉄鉱石として、結晶水を５質量％以上含有する鉄鉱石、
前記炭材として、沸点が２００〜５００℃の物質を２０質量％以上含む炭材を準備し、
これらを混合しつつ加熱するか、混合した後に加熱してから塊成化することを特徴とする塊成物の製造方法。 A method of agglomerating a mixture containing iron ore and carbonaceous material to produce an agglomerate for iron making,
As the iron ore, an iron ore containing 5% by mass or more of crystal water,
As the carbon material, a carbon material containing 20% by mass or more of a substance having a boiling point of 200 to 500 ° C. is prepared,
A method for producing an agglomerated product, characterized in that the agglomerated material is heated while being mixed or heated after being mixed.
前記鉄鉱石として、結晶水を５質量％以上含有する鉄鉱石を加熱して脱水した脱水鉄鉱石、
前記炭材として、分子量分布を測定したときにピーク強度が最も大きい分子の分子量が２００〜３００である炭材を準備し、
これらの混合物を塊成化することを特徴とする塊成物の製造方法。 A method of agglomerating a mixture containing iron ore and carbonaceous material to produce an agglomerate for iron making,
As the iron ore, dehydrated iron ore obtained by heating and dehydrating iron ore containing 5% by mass or more of crystal water,
As the carbon material, preparing a carbon material having a molecular weight of 200-300 having the largest peak intensity when the molecular weight distribution is measured,
A method for producing an agglomerate, comprising agglomerating the mixture.
前記鉄鉱石として、結晶水を５質量％以上含有する鉄鉱石、
前記炭材として、分子量分布を測定したときにピーク強度が最も大きい分子の分子量が２００〜３００である炭材を準備し、
これらを混合しつつ加熱するか、混合した後に加熱してから塊成化することを特徴とする塊成物の製造方法。 A method of agglomerating a mixture containing iron ore and carbonaceous material to produce an agglomerate for iron making,
As the iron ore, an iron ore containing 5% by mass or more of crystal water,
As the carbon material, preparing a carbon material having a molecular weight of 200-300 having the largest peak intensity when the molecular weight distribution is measured,
A method for producing an agglomerated product, characterized in that the agglomerated material is heated while being mixed or heated after being mixed.
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