JP4152286B2 - Granulation method for sintered raw materials for iron making - Google Patents
Granulation method for sintered raw materials for iron making Download PDFInfo
- Publication number
- JP4152286B2 JP4152286B2 JP2003333929A JP2003333929A JP4152286B2 JP 4152286 B2 JP4152286 B2 JP 4152286B2 JP 2003333929 A JP2003333929 A JP 2003333929A JP 2003333929 A JP2003333929 A JP 2003333929A JP 4152286 B2 JP4152286 B2 JP 4152286B2
- Authority
- JP
- Japan
- Prior art keywords
- raw material
- iron
- sintered
- making
- fine particles
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Fee Related
Links
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 title claims description 216
- 239000002994 raw material Substances 0.000 title claims description 177
- 229910052742 iron Inorganic materials 0.000 title claims description 108
- 238000000034 method Methods 0.000 title claims description 79
- 238000005469 granulation Methods 0.000 title claims description 63
- 230000003179 granulation Effects 0.000 title claims description 62
- 238000005245 sintering Methods 0.000 claims description 105
- 239000010419 fine particle Substances 0.000 claims description 104
- 239000000203 mixture Substances 0.000 claims description 91
- 239000002245 particle Substances 0.000 claims description 63
- 238000002156 mixing Methods 0.000 claims description 60
- 239000000178 monomer Substances 0.000 claims description 48
- 229920000642 polymer Polymers 0.000 claims description 45
- 150000001875 compounds Chemical class 0.000 claims description 43
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 claims description 34
- 150000003839 salts Chemical class 0.000 claims description 27
- 230000008569 process Effects 0.000 claims description 26
- 239000000428 dust Substances 0.000 claims description 22
- 229910000019 calcium carbonate Inorganic materials 0.000 claims description 17
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 16
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims description 16
- 239000000463 material Substances 0.000 claims description 15
- 239000000446 fuel Substances 0.000 claims description 13
- 125000000542 sulfonic acid group Chemical group 0.000 claims description 13
- 239000000377 silicon dioxide Substances 0.000 claims description 7
- 239000010881 fly ash Substances 0.000 claims description 6
- 239000010459 dolomite Substances 0.000 claims description 5
- 229910000514 dolomite Inorganic materials 0.000 claims description 5
- 239000002893 slag Substances 0.000 claims description 5
- 239000000440 bentonite Substances 0.000 claims description 4
- 229910000278 bentonite Inorganic materials 0.000 claims description 4
- SVPXDRXYRYOSEX-UHFFFAOYSA-N bentoquatam Chemical compound O.O=[Si]=O.O=[Al]O[Al]=O SVPXDRXYRYOSEX-UHFFFAOYSA-N 0.000 claims description 4
- 239000004927 clay Substances 0.000 claims description 4
- 229910052570 clay Inorganic materials 0.000 claims description 4
- 238000003672 processing method Methods 0.000 claims description 4
- 229910021487 silica fume Inorganic materials 0.000 claims description 4
- 239000005995 Aluminium silicate Substances 0.000 claims description 3
- 235000019738 Limestone Nutrition 0.000 claims description 3
- WYTGDNHDOZPMIW-RCBQFDQVSA-N alstonine Natural products C1=CC2=C3C=CC=CC3=NC2=C2N1C[C@H]1[C@H](C)OC=C(C(=O)OC)[C@H]1C2 WYTGDNHDOZPMIW-RCBQFDQVSA-N 0.000 claims description 3
- 235000012211 aluminium silicate Nutrition 0.000 claims description 3
- OSGAYBCDTDRGGQ-UHFFFAOYSA-L calcium sulfate Chemical compound [Ca+2].[O-]S([O-])(=O)=O OSGAYBCDTDRGGQ-UHFFFAOYSA-L 0.000 claims description 3
- NLYAJNPCOHFWQQ-UHFFFAOYSA-N kaolin Chemical compound O.O.O=[Al]O[Si](=O)O[Si](=O)O[Al]=O NLYAJNPCOHFWQQ-UHFFFAOYSA-N 0.000 claims description 3
- 239000006028 limestone Substances 0.000 claims description 3
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- 238000009628 steelmaking Methods 0.000 claims description 2
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- 229920001495 poly(sodium acrylate) polymer Polymers 0.000 description 23
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- ODINCKMPIJJUCX-UHFFFAOYSA-N Calcium oxide Chemical compound [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 description 18
- 230000000694 effects Effects 0.000 description 18
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- 239000002202 Polyethylene glycol Substances 0.000 description 6
- 239000000571 coke Substances 0.000 description 6
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- 239000003505 polymerization initiator Substances 0.000 description 6
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- 229910000831 Steel Inorganic materials 0.000 description 4
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 description 4
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- 229910019142 PO4 Inorganic materials 0.000 description 3
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- 239000010452 phosphate Substances 0.000 description 3
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 3
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- PQUXFUBNSYCQAL-UHFFFAOYSA-N 1-(2,3-difluorophenyl)ethanone Chemical compound CC(=O)C1=CC=CC(F)=C1F PQUXFUBNSYCQAL-UHFFFAOYSA-N 0.000 description 2
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- 125000003903 2-propenyl group Chemical group [H]C([*])([H])C([H])=C([H])[H] 0.000 description 2
- CIWBSHSKHKDKBQ-JLAZNSOCSA-N Ascorbic acid Chemical compound OC[C@H](O)[C@H]1OC(=O)C(O)=C1O CIWBSHSKHKDKBQ-JLAZNSOCSA-N 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- VZCYOOQTPOCHFL-OWOJBTEDSA-N Fumaric acid Chemical compound OC(=O)\C=C\C(O)=O VZCYOOQTPOCHFL-OWOJBTEDSA-N 0.000 description 2
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- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 2
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 2
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- 229910052783 alkali metal Inorganic materials 0.000 description 2
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Landscapes
- Manufacture And Refinement Of Metals (AREA)
Description
本発明は、製鉄用焼結原料の造粒処理方法に関する。より詳しくは、製銑工程における高炉装入用原料となる焼結鉱の製造において粉鉄鉱石等を造粒するための製鉄用焼結原料の造粒処理方法に関する。 The present invention relates to a method for granulating a sintering raw material for iron making. More specifically, the present invention relates to a method for granulating a sintered raw material for iron making for granulating fine iron ore and the like in the production of sintered ore as a raw material for charging a blast furnace in the iron making process.
製銑工程は、一般に鉄鉱石からなる焼結鉱、塊鉱石、ペレットをコークスと共に高炉へ装入することにより行われている。この焼結鉱は、鉄鉱石、副原料、燃料等を含む焼結原料を事前処理して、焼結機に特定の高さに充填し焼結ベッドを形成した後、表層に点火して焼成することにより製造される。焼結機としては、通常では下方吸引式が採用されており、焼結原料の下側から吸引することによって焼結に必要な空気を流通させると共に、焼結原料の上側から下側へ向かって燃料を燃焼させることにより、焼結原料を焼結するようになっている。このため、焼結原料が微粒子を多く含んでいると、目詰まりを起こす等して通気性が低下し、燃料であるコークスの燃焼速度が遅くなるので、焼結鉱の生産効率が低下することとなる。 The iron making process is generally performed by charging sintered ore made of iron ore, lump ore, and pellets together with coke into a blast furnace. This sintered ore is pre-processed with sintering raw materials including iron ore, auxiliary raw materials, fuel, etc., filled in a sintering machine to a specific height to form a sintering bed, and then fired by firing the surface layer It is manufactured by doing. As the sintering machine, a downward suction type is usually adopted, and air necessary for sintering is circulated by suctioning from the lower side of the sintering raw material, and from the upper side to the lower side of the sintering raw material. By burning the fuel, the sintering raw material is sintered. For this reason, if the sintering raw material contains a large amount of fine particles, the air permeability decreases due to clogging and the like, and the combustion rate of coke, which is the fuel, becomes slow, so the production efficiency of the sintered ore decreases. It becomes.
そこで焼結機における通気性を改善し、生産性を向上させるために、焼結原料を造粒して擬似粒子化する等の事前処理が行われている。例えば、焼結原料となる鉄鉱石、副原料、燃料等を混合し、少量の水を添加して造粒機で攪拌する等の造粒操作が行われている。擬似粒子とは、一般的に、０．５ｍｍ以下の微粒子が１〜３ｍｍの核粒子に付着している粒子である。このような造粒に際して求められる作用は、微粒子が核粒子の周りに付着する擬似粒化性を向上すること、擬似粒子が焼結工程において崩壊しにくくなるようにすること等である。
また最近では、優良塊鉱の枯渇化と共に、粉鉱石の劣質化も激しく、焼結原料の造粒性が以前よりも悪化している傾向にあることから、焼結原料の擬似粒子化を向上する効果の高い技術が切望されている。
Therefore, in order to improve the air permeability in the sintering machine and improve the productivity, a pretreatment such as granulating the sintered raw material to form pseudo particles is performed. For example, granulation operations such as mixing iron ore as a raw material for sintering, auxiliary materials, fuel, and the like, adding a small amount of water, and stirring with a granulator are performed. Pseudo particles are particles in which fine particles of 0.5 mm or less are generally attached to 1 to 3 mm core particles. Actions required for such granulation are to improve the quasi-granulating property that the fine particles adhere to the periphery of the core particles, and to make the quasi-particles difficult to collapse in the sintering process.
Recently, with the depletion of excellent agglomerates, the deterioration of powdered ore has also become severe, and the granulation properties of sintered raw materials tend to be worse than before. Technology that is highly effective is highly desired.
このような焼結原料の事前処理において、水だけを用いる造粒操作では、擬似粒化性を向上させる効果が乏しいため、焼結原料に含まれる微粒子の量をあまり低減することができない。このために、擬似粒化性を向上させる対策として、焼結原料中に粘結剤としての作用を有する造粒添加剤を添加する方法が提案されている。造粒添加剤としては、生石灰が広く用いられている。生石灰は、造粒機内での擬似粒子化の促進を図ることができるうえに、焼結工程において、乾燥、加熱する過程で擬似粒子が崩壊することを防止し、焼結層中の均一な風の流れを保つことができるとされている。 In such a pretreatment of the sintering raw material, the granulation operation using only water has a poor effect of improving the pseudo-granulating property, so that the amount of fine particles contained in the sintering raw material cannot be reduced so much. For this reason, as a countermeasure for improving the pseudo-granulating property, a method of adding a granulating additive having an action as a binder to the sintered raw material has been proposed. Quick lime is widely used as a granulating additive. Quick lime can promote the formation of pseudo-particles in the granulator, and also prevents the pseudo-particles from collapsing during the drying and heating process in the sintering process. It is said that the flow of
しかしながら、生石灰等のバインダーは、一般に比較的高価なものであり、また、生石灰は吸湿しやすく、このとき発熱するため、取り扱いやすいものが求められている。更に、現在使用されている生石灰は、使用量を比較的多くしないと充分な効果が得られないため、この点でもコストが上昇することとなる。生石灰を用いる場合には、その使用量を極力減少させて操業しているのが現状である。そして、生石灰を２質量％以上添加しても、その擬似粒化性の向上効果は頭打ちとなる傾向にある。 However, binders such as quick lime are generally relatively expensive, and quick lime easily absorbs moisture and generates heat at this time, so that easy to handle is required. Furthermore, since quick lime currently used cannot obtain a sufficient effect unless the amount used is relatively large, the cost also increases in this respect. In the case of using quicklime, the current situation is that the amount used is reduced as much as possible. And even if 2 mass% or more of quicklime is added, the improvement effect of the pseudo-granulation property tends to reach a peak.
従来の製鉄用焼結原料の造粒処理方法としては、ポリアクリル酸等の高分子化合物と炭酸カルシウム等の微粒子とを併用し、粉鉄鉱石を含む鉄鉱石を造粒処理する方法が開示されている（例えば、特許文献１参照。）。しかしながら、この方法には改良の余地がある。通常、各々の原料は、それぞれホッパーからベルトコンベア上に切り出される。この際、各々の原料は、充分混合されることなく造粒機に投入され、加水造粒が行われる。しかしながら、該微粒子を上記方法で添加した場合、該微粒子の粒径が細かいために、凝集力が強く、配合原料（製鉄用焼結原料）全体への均一な分散が充分行われず、該微粒子の添加効果が充分得られないとの問題点がある。これはまた、該微粒子を配合原料の大部分に添加して、予備混合した後に、加水し、造粒処理を行うような方法においても、該微粒子と比較して、残りの配合原料があまりにも多く、均一に分散させることが困難であるため、該微粒子の添加効果を充分得ることができない。すなわち造粒処理剤としての作用を有する微粒子を他の配合原料と共に加水造粒する場合等において、微粒子の造粒処理剤としての作用が有効に発揮されるようにし、更に焼結鉱の生産性が向上されるようにするための工夫の余地があった。
本発明は、上記現状に鑑みてなされたものであり、製銑工程における高炉装入用原料となる焼結鉱の製造において粉鉄鉱石等の製鉄用焼結原料の造粒に有効であり、造粒処理剤としての作用を有する微粒子の製鉄用焼結原料への分散性が向上し、有効に作用することにより、焼結鉱の生産性を向上させることができる製鉄用焼結原料の造粒処理方法を提供することを目的とするものである。 The present invention has been made in view of the above situation, and is effective for granulating a sintered raw material for iron making, such as fine iron ore, in the production of sintered ore as a raw material for charging a blast furnace in the iron making process, Production of sintered raw materials for iron making that can improve the productivity of sintered ore by improving the dispersibility of fine particles having an action as a granulating agent in the sintered raw materials for iron making and acting effectively. The object is to provide a grain processing method.
本発明者等は、製鉄用焼結原料を造粒する造粒処理方法について種々検討した結果、製鉄用焼結原料を造粒処理するに際し、平均粒径が２００μｍ以下の微粒子を用いると、造粒性の向上や擬似粒子の崩壊防止に有効であることに着目し、平均粒径が２００μｍ以下の微粒子を予め製鉄用焼結原料の０．３〜１０質量％と混合処理した後に、残りの製鉄用焼結原料と混合して造粒処理することにより、著しく焼結鉱の生産性が向上することを見いだし、上記課題をみごとに解決することができることに想到した。
従来の方法で微粒子の作用効果が少ない原因としては、微粒子を他の焼結原料と共に、例えば、造粒処理剤としての作用を有する高分子化合物の存在下で加水造粒する場合、通常では微粒子が全ての焼結原料中に充分に分散されないうちに水がかかってしまうこと等から、微粒子の固まりがほぐれないうちに造粒されたり、微粒子どうしで凝集してしまい、充分に微粒子を分散することができずに、微粒子が造粒処理剤として有効に作用しないためであると推察できる。そこで、本発明においては、予め（予備的に）、微粒子を製鉄用焼結原料の０．３〜１０質量％と混合処理することにより、製鉄用焼結原料等が希釈剤としての作用を発揮し、例えば、炭酸カルシウム等の微粒子どうしが凝集しにくくなり、残りの製鉄用焼結原料と混合して造粒処理する際に、該微粒子の分散性が向上し、該微粒子の造粒処理剤としての作用効果が有効に作用していると考えられる。このとき、微粒子と予備混合する製鉄用焼結原料の割合が増加すると、やはり該微粒子の分散性が低下することが見いだされた。予め（予備的に）、平均粒径が２００μｍ以下の微粒子を製鉄用焼結原料の０．３〜１０質量％と混合処理することにより、該微粒子を造粒処理剤として有効に作用させることができることを見いだし、本発明に到達したものである。
As a result of various investigations on the granulation treatment method for granulating a sintered raw material for iron making, the present inventors have found that, when granulating the sintered raw material for iron making, using fine particles having an average particle diameter of 200 μm or less, Focusing on the fact that it is effective in improving graininess and preventing the collapse of pseudo particles, fine particles having an average particle size of 200 μm or less are previously mixed with 0.3 to 10% by mass of the sintering raw material for iron making, and then the rest It has been found that the productivity of sintered ore can be remarkably improved by mixing with a raw material for iron making and granulating to solve the above problems.
The reason why the effect of the fine particles is small in the conventional method is that the fine particles are usually granulated together with other sintering raw materials in the presence of, for example, a polymer compound having an action as a granulating agent. However, it is granulated before the mass of fine particles is unraveled or agglomerated among the fine particles, so that the fine particles are sufficiently dispersed. It can be assumed that the fine particles do not effectively act as a granulating agent. Therefore, in the present invention, the sintered material for iron making exhibits the action as a diluent by previously (preliminarily) mixing the fine particles with 0.3 to 10% by mass of the sintered material for iron making. For example, the fine particles such as calcium carbonate are less likely to agglomerate, and when mixed with the rest of the sintering raw material for iron making, the dispersibility of the fine particles is improved, and the fine particle granulating agent It is considered that the function and effect are effectively working. At this time, it was found that the dispersibility of the fine particles also decreased as the proportion of the iron-making sintered raw material premixed with the fine particles increased. By preliminarily (preliminarily) mixing the fine particles having an average particle size of 200 μm or less with 0.3 to 10% by mass of the sintering raw material for iron making, the fine particles can be effectively acted as a granulating agent. We have found what we can do and have arrived at the present invention.
すなわち本発明は、製鉄用焼結原料を造粒処理するに際し、平均粒径が２００μｍ以下の微粒子を用いる製鉄用焼結原料の造粒処理方法であって、上記製鉄用焼結原料の造粒処理方法は、上記微粒子を予め製鉄用焼結原料の０．３〜１０質量％と混合処理する工程の後に、上記工程により得られる混合物を残りの製鉄用焼結原料と混合して造粒処理する工程を含んでなる製鉄用焼結原料の造粒処理方法である。
以下に本発明を詳述する。
That is, the present invention is a method for granulating a sintered raw material for iron making using fine particles having an average particle size of 200 μm or less when granulating the sintered raw material for iron making, and granulating the sintered raw material for iron making In the treatment method, after the step of mixing the fine particles with 0.3 to 10% by mass of the iron-making sintered raw material in advance, the mixture obtained by the step is mixed with the remaining iron-made sintering raw material and granulated. It is the granulation processing method of the sintering raw material for iron manufacture which comprises the process to do.
The present invention is described in detail below.
本発明においては、製鉄用焼結原料を造粒処理するに際し、平均粒径が２００μｍ以下の微粒子を予め製鉄用焼結原料の０．３〜１０質量％と混合処理する工程を行うこととなる。混合処理工程における「混合処理」とは、平均粒径が２００μｍ以下の微粒子と製鉄用焼結原料の一部との混合物を調製することを意味し、微粒子を製鉄用焼結原料の一部に充分に分散することが好ましい。 In the present invention, when granulating the sintered raw material for iron making, a step of previously mixing the fine particles having an average particle size of 200 μm or less with 0.3 to 10% by mass of the sintered raw material for iron making is performed. . “Mixing process” in the mixing process means that a mixture of fine particles having an average particle size of 200 μm or less and a part of a sintered raw material for iron making is prepared. It is preferable to disperse sufficiently.
上記混合処理工程における「製鉄用焼結原料の０．３〜１０質量％」とは、製鉄用焼結原料の造粒処理方法において用いられる全ての製鉄用焼結原料のうちの０．３〜１０質量％であればよく、鉄鉱石の一部、燃料の一部、製鉄用副原料の一部若しくは全部、又は、これらを組み合わせた原料が好適である。より好ましくは、製鉄用副原料及び／又は燃料を必須として含むものを用いることである。
上記製鉄用焼結原料の０．３〜１０質量％は、製鉄用焼結原料の造粒処理方法において用いられる全ての焼結原料を１００質量％としたときの数値を意味する。より好ましくは、０．４質量％以上とし、また、８質量％以下とすることである。本発明において、上記微粒子は製鉄用焼結原料に含まれるものとするが、製鉄用焼結原料の０．３〜１０質量％は、該微粒子を含まないものである。
なお、本明細書中において、製鉄用焼結原料、すなわち、製鉄用焼結原料の造粒処理方法において用いられる原料（鉄鉱石、製鉄用副原料、微粒子、造粒処理剤等）の使用量は、これらの原料を乾燥した状態としたときの値（絶乾換算）である。
予備混合する製鉄用焼結原料が１０質量％を超えた場合、上記微粒子の分散状態が悪くなり、生産性が低下する傾向にある。予備混合する製鉄用原料が、０．３質量％未満であった場合、上記微粒子の予備希釈効果が小さくなり、予備混合物を残りの製鉄用原料と共に造粒処理する際に、均一に分散しにくくなり、生産性が低下する傾向にある。
“0.3 to 10% by mass of sintered raw material for iron making” in the above-mentioned mixing process step means 0.3 to 0.3% of all the sintered raw materials for iron making used in the granulation method of the sintered raw material for iron making. It may be 10% by mass, and a part of the iron ore, a part of the fuel, a part or all of the auxiliary raw material for iron making, or a raw material combining these is preferable. More preferably, an iron-making auxiliary material and / or a fuel that essentially contains fuel is used.
0.3-10 mass% of the said iron-making sintered raw material means a numerical value when all the sintering raw materials used in the granulation processing method of the iron-making sintered raw material are 100 mass%. More preferably, the content is 0.4% by mass or more and 8% by mass or less. In the present invention, the fine particles are included in the iron-making sintered raw material, but 0.3 to 10% by mass of the iron-making sintered raw material does not contain the fine particles.
In addition, in this specification, the amount of raw materials (iron ore, secondary materials for iron making, fine particles, granulating agent, etc.) used in the method for granulating the iron making sintered raw material, that is, the iron making sintered raw material. Is a value (absolute dry conversion) when these raw materials are dried.
When the pre-mixed sintering material for iron making exceeds 10% by mass, the dispersion state of the fine particles is deteriorated, and the productivity tends to be lowered. When the raw material for iron making to be premixed is less than 0.3% by mass, the effect of predilution of the fine particles is reduced, and it is difficult to uniformly disperse the premixed product together with the remaining raw material for iron making. Therefore, productivity tends to decrease.
上記混合処理工程において、平均粒径が２００μｍ以下の微粒子を製鉄用焼結原料の０．３〜１０質量％と混合する形態としては特に限定されず、製鉄用焼結原料の一部に一回で添加してもよいし、複数回に分けて添加してもよい。 In the mixing treatment step, the form in which fine particles having an average particle size of 200 μm or less are mixed with 0.3 to 10% by mass of the iron-making sintered raw material is not particularly limited, and once in a part of the iron-making sintered raw material Or may be added in multiple portions.
本発明における平均粒径が２００μｍ以下の微粒子としては、このような平均粒径を有する微細な粒子であればよいが、炭酸カルシウム、カオリンクレー、シリカ、珪砂、タルク、ベントナイト、ドロマイト粉末、ドロマイトプラスタ、炭酸マグネシウム、シリカフューム、無水石膏、セリサイト、モンモリロナイト、シラス、シラスバルーン、珪藻土、焼成珪藻土、シリコンカーバイド、黄色酸化鉄、炭酸ストロンチウム、炭酸バリウム、黒鉛、ワラストナイト、クレカスフェアー、カーボンブラック、べんがら、粉砕蛇紋岩、活性白土、ポルトランドセメント、粉砕珪石、粉砕蛇紋岩、酸化マグネシウム、焼成ヒル石、製鉄所以外のプロセスで発生するダスト、具体的には、フライアッシュや重油灰等の火力発電所で発生するダスト、製銅プロセスで発生するカラミ鉄精鉱や銅スラグ、アルミナ製造工程で排出される赤泥、その他、排煙脱硫石膏やアスベスト粉塵等が好適であり、１種又は２種以上を用いることができる。好ましくは、炭酸カルシウム、フライアッシュ、カオリンクレー、シリカ、タルク、ベントナイト、シリカフューム及び無水石膏からなる群より選択される少なくとも一種のものである。より好ましくは、炭酸カルシウム、フライアッシュ、シリカフュームである。 The fine particles having an average particle size of 200 μm or less in the present invention may be fine particles having such an average particle size, but calcium carbonate, kaolin clay, silica, silica sand, talc, bentonite, dolomite powder, dolomite plaster , Magnesium carbonate, silica fume, anhydrous gypsum, sericite, montmorillonite, shirasu, shirasu balloon, diatomaceous earth, calcined diatomaceous earth, silicon carbide, yellow iron oxide, strontium carbonate, barium carbonate, graphite, wollastonite, crecas sphere, carbon black, Bengala, ground serpentine, activated clay, Portland cement, ground silica, ground serpentine, magnesium oxide, calcined leech stone, dust generated in processes other than steelworks, specifically, thermal power generation such as fly ash and heavy oil ash Dust generated at Karami iron ore concentrate and copper slag generated in the process, red mud discharged by alumina production processes, other a suitable flue gas desulfurization gypsum and asbestos dust, can be used alone or in combination. Preferably, it is at least one selected from the group consisting of calcium carbonate, fly ash, kaolin clay, silica, talc, bentonite, silica fume, and anhydrous gypsum. More preferred are calcium carbonate, fly ash and silica fume.
上記平均粒径が２００μｍ以下の微粒子の平均粒径としては、０．０１μｍ以上であることが好ましく、また、１００μｍ以下であることが好ましい。より好ましくは、０．０２μｍ以上であり、また、５０μｍ以下である。最も好ましくは、０．１μｍ以上であり、また、２０μｍ以下である。
平均粒径が２００μｍを超えた場合、焼結べット等における擬似粒子の崩壊抑制効果のある微粒子の割合に対して、微粒子を付着する粒径の大きな粒子の割合が多くなるため、添加効果は得られにくくなる。一方、０．０１μｍ未満になると、微粒子の凝集力が強くなり、製鉄用原料に分散しにくくなるから、添加効果は得られにくくなる。
The average particle diameter of the fine particles having an average particle diameter of 200 μm or less is preferably 0.01 μm or more, and preferably 100 μm or less. More preferably, it is 0.02 μm or more and 50 μm or less. Most preferably, it is 0.1 μm or more and 20 μm or less.
When the average particle diameter exceeds 200 μm, the ratio of large particles to which the fine particles adhere is larger than the ratio of fine particles having the effect of suppressing the decay of pseudo particles in the sintering bed or the like. It becomes difficult to obtain. On the other hand, when the thickness is less than 0.01 μm, the cohesive force of the fine particles becomes strong and it is difficult to disperse in the raw material for iron making.
上記平均粒径が２００μｍ以下の微粒子の使用量としては、混合処理工程において用いられる製鉄用焼結原料（該微粒子は除く）と該微粒子との質量比（絶乾換算）が、混合処理工程において用いる製鉄用焼結原料：該微粒子＝０．３：１〜５０：１となるようにすることが好ましい。より好ましくは、１：１から２０：１である。
また本発明においては、上記混合処理工程で添加する微粒子が、全製鉄用焼結原料（該微粒子を入れる）に対して、０．０５〜３０質量％であることが好ましい。さらに好ましくは、０．０７〜１０質量％であり、最も好ましくは０．１〜５質量％である。微粒子の添加量が０．０５質量％未満であった場合、擬似粒子の崩れ抑制効果が得られにくくなり、生産性の向上効果が得られにくくなる。３０質量％を超えた場合、細かい粒子が充分に造粒しきれずに、焼結ベッドの通気性が低下し、生産性の向上効果が得られにくくなる。
The amount of fine particles having an average particle size of 200 μm or less is such that the mass ratio (absolutely converted) between the sintered raw material for iron making (excluding the fine particles) used in the mixing treatment step and the fine particles in the mixing treatment step. Sintering raw material for iron making to be used: The fine particles are preferably 0.3: 1 to 50: 1. More preferably, it is 1: 1 to 20: 1.
Moreover, in this invention, it is preferable that the microparticles | fine-particles added at the said mixing process process are 0.05-30 mass% with respect to all the sintering raw materials for iron manufacture (it puts this microparticles | fine-particles). More preferably, it is 0.07-10 mass%, Most preferably, it is 0.1-5 mass%. When the addition amount of the fine particles is less than 0.05% by mass, it becomes difficult to obtain the effect of suppressing the breakage of the pseudo particles, and it becomes difficult to obtain the effect of improving productivity. When it exceeds 30% by mass, fine particles cannot be sufficiently granulated, the air permeability of the sintered bed is lowered, and the productivity improvement effect is hardly obtained.
本発明における製鉄用焼結原料とは、鉄鉱石、製鉄用副原料、燃料、上記微粒子、造粒処理剤を意味し、製鉄用副原料とは、鉄鉱石や燃料等と共に焼結される製鉄用焼結原料であり、石灰石、ドロマイト、蛇紋岩、珪石、スラグ、ダスト、返し鉱等である。本発明においては、製鉄用副原料及び／又はコークス等の燃料であることが好ましく、石灰石、ドロマイト、蛇紋岩、珪石、スラグ、ダスト、返し鉱、粉コークス、無煙炭が特に好ましい。 In the present invention, the iron-making sintered raw material means iron ore, iron-making auxiliary materials, fuel, the fine particles, and the granulating agent, and the iron-making auxiliary material means iron-making sintered together with iron ore and fuel. Sintering raw materials for limestone, dolomite, serpentinite, silica, slag, dust, ore, etc. In this invention, it is preferable that it is fuel, such as an auxiliary raw material for iron manufacture, and / or coke, and limestone, dolomite, serpentinite, quartzite, slag, dust, reverse minerals, pulverized coke, and anthracite are especially preferable.
上記製鉄用副原料において、ダストとは、製鉄所において製鉄のプロセスにおける各工程で、発生する微粒子廃棄物の総称であり、例えば、焼結プロセスで発生する焼結ダスト、高炉プロセスで発生する高炉ダスト、転炉プロセスで発生する転炉ダストや転炉グラファイト、冷延工場で発生する酸洗ダスト、その他、コークス消化沈殿粉、圧延戻り水ダスト、ラグーンダスト等が挙げられる。これらは１種又は２種以上を用いることができる。また、製鉄以外のプロセスで発生するダストも使用可能である。具体的には、火力発電所で発生するダスト、例えば、フライアッシュや重油灰、製銅プロセスで発生するカラミ鉄精鉱や銅スラグ等のスラッジ、アルミナ製造工程で排出される赤泥、その他、排煙脱硫石膏やアスベスト粉塵等であってもよい。 In the iron making auxiliary material, dust is a general term for fine particle waste generated at each step in the iron making process at the ironworks, for example, sintered dust generated in the sintering process, blast furnace generated in the blast furnace process, etc. Examples include dust, converter dust and converter graphite generated in the converter process, pickling dust generated in a cold rolling mill, coke digested sediment powder, rolled return water dust, lagoon dust, and the like. These can use 1 type (s) or 2 or more types. Also, dust generated in processes other than iron making can be used. Specifically, dust generated in thermal power plants, such as fly ash and heavy oil ash, sludge such as calami iron concentrate and copper slag generated in the copper making process, red mud discharged in the alumina manufacturing process, etc. It may be flue gas desulfurization gypsum or asbestos dust.
上記混合処理工程においては、平均粒径が２００μｍ以下の微粒子が水分量の少ないものであることが好ましく、また、該微粒子と混合される製鉄用焼結原料の０．３〜１０質量％も水分量の少ないものであることが好ましい。これにより、混合処理工程で調製される混合物において、造粒されにくくなり、残りの製鉄用焼結原料と混合して造粒処理する際に、該微粒子の分散性が向上し、該微粒子の造粒処理剤としての作用効果がより有効に作用することとなる。好ましくは、平均粒径が２００μｍ以下の微粒子１００質量％中に含有する水分量としては、２０質量％以下である。より好ましくは、５質量％以下である。また、該微粒子と混合される製鉄用焼結原料１００質量％中に含有する水分量としては、２０質量％以下である。より好ましくは、１２質量％以下、最も好ましくは、８質量％以下である。 In the mixing treatment step, it is preferable that fine particles having an average particle size of 200 μm or less have a small water content, and 0.3 to 10% by mass of the sintering raw material for iron making mixed with the fine particles is also water. It is preferable that the amount is small. As a result, the mixture prepared in the mixing treatment step is less likely to be granulated, and when mixed with the remaining sintering raw material for iron making, the dispersibility of the fine particles is improved, and the fine particles are formed. The effect as a grain processing agent will act more effectively. Preferably, the amount of water contained in 100% by mass of fine particles having an average particle size of 200 μm or less is 20% by mass or less. More preferably, it is 5 mass% or less. The amount of water contained in 100% by mass of the iron-making sintered raw material mixed with the fine particles is 20% by mass or less. More preferably, it is 12 mass% or less, Most preferably, it is 8 mass% or less.
また混合処理工程においては、混合物の水分量の調整を行ってもよく、造粒処理工程においては、水が添加されてもよく、添加されなくてもよいが、造粒性を向上するために水が添加されることが好ましい。混合処理工程において調製される混合物１００質量％中に含有する水分量としては、０質量％以上とし、また、１５質量％以下とすることが好ましい。より好ましくは、０質量％以上とし、また、８質量％以下とすることである。なお、造粒処理工程において水が添加される場合、混合処理工程により得られた混合物や後述する造粒処理剤を残りの製鉄用焼結原料と混合するに際し、微粒子が混合されている製鉄用焼結原料の分散性を向上させるためには、これらの造粒機に投入した後にもできるだけ充分に混合してから水を添加することが望ましく、投入口付近に水がかからないようにすることが好ましい。 In the mixing treatment step, the water content of the mixture may be adjusted. In the granulation treatment step, water may or may not be added, but in order to improve granulation properties. It is preferred that water is added. The amount of water contained in 100% by mass of the mixture prepared in the mixing treatment step is preferably 0% by mass or more, and preferably 15% by mass or less. More preferably, the content is 0% by mass or more and 8% by mass or less. In addition, when water is added in the granulation treatment step, when mixing the mixture obtained in the mixing treatment step and the granulation treatment agent described later with the remaining sintering raw material for iron making, for iron production in which fine particles are mixed In order to improve the dispersibility of the sintering raw material, it is desirable to add water after mixing as much as possible after charging into these granulators, so that water is not applied near the charging port. preferable.
本発明においては、上記混合処理する工程の後に、該工程により得られる混合物を残りの製鉄用焼結原料と混合して造粒処理する工程を行うこととなる。すなわち本発明の製鉄用焼結原料の造粒処理方法において用いられる製鉄用焼結原料のうち、一部を混合処理工程において混合物を調製するために用い、残りを該混合物と混合して造粒処理することになる。これにより、該混合物中の平均粒径が２００μｍ以下の微粒子が造粒処理工程において有効に作用し、造粒性が向上し、充分な焼結鉱の生産性が実現できることとなる。 In the present invention, after the mixing treatment step, the mixture obtained by the step is mixed with the remaining sintering raw material for iron making and granulated. That is, among the sintering raw materials for iron making used in the method for granulating a sintering raw material for iron making according to the present invention, a part is used for preparing a mixture in the mixing treatment step, and the rest is mixed with the mixture for granulation. Will be processed. As a result, fine particles having an average particle diameter of 200 μm or less in the mixture effectively act in the granulation treatment step, improve granulation, and realize sufficient productivity of sintered ore.
上記造粒処理工程においては、造粒処理剤を用いて造粒処理してもよく、造粒処理剤を用いないで造粒処理してもよいが、造粒処理剤を用いることが好ましい。造粒処理剤とは、製鉄用焼結原料を造粒する際に、造粒性を向上させるために用いる化合物等を意味する。
なお、混合処理工程により得られる混合物を残りの製鉄用焼結原料と混合する方法や造粒処理剤を用いる方法としては特に限定されず、造粒処理工程における製鉄用焼結原料及び製鉄用副原料に一回で添加してもよいし、複数回に分けて添加してもよい。
In the granulation treatment step, a granulation treatment may be performed using a granulation treatment agent, or a granulation treatment may be performed without using a granulation treatment agent, but a granulation treatment agent is preferably used. The granulation treatment agent means a compound or the like used for improving the granulation property when granulating a sintered raw material for iron making.
In addition, it does not specifically limit as a method of mixing the mixture obtained by a mixing process process with the remaining sintering raw materials for iron manufacture, or a method using a granulation processing agent, The sintering raw material for iron manufacture in the granulation process process, and the subordinate for iron manufacture You may add to a raw material at once and may add in multiple times.
上記造粒処理剤としては、カルボキシル基、スルホン酸基及びこれらの塩からなる群より選択される少なくとも１種の基を有する高分子化合物（以下高分子化合物Ａとする）を用いることが好ましい。これにより、平均粒径が２００μｍ以下の微粒子が焼結中の擬似粒子の崩壊を抑制する作用効果が充分に発揮されると共に、該高分子化合物（高分子化合物Ａ）による造粒性が効果的に発揮され、これらの作用効果が相乗的に発揮されて造粒性が向上することとなる。
また造粒処理剤としては、上記高分子化合物と共に、又は、上記高分子化合物に代えて、生石灰、ベントナイト、リグニン亜硫酸塩（パルプ廃液）、澱粉、砂糖、糖蜜、水ガラス、セメント、ゼラチン、コーンスターチ等を用いることができる。
As the granulating agent, it is preferable to use a polymer compound having at least one group selected from the group consisting of a carboxyl group, a sulfonic acid group, and a salt thereof (hereinafter referred to as polymer compound A). As a result, fine particles having an average particle size of 200 μm or less can sufficiently exhibit the effect of suppressing the collapse of pseudo particles during sintering, and the granulation property by the polymer compound (polymer compound A) is effective. These functions and effects are exhibited synergistically to improve granulation.
In addition, as a granulation treatment agent, quick lime, bentonite, lignin sulfite (pulp waste liquor), starch, sugar, molasses, water glass, cement, gelatin, corn starch together with or in place of the above polymer compound Etc. can be used.
上記高分子化合物Ａの使用量としては、焼結原料の造粒性や、該高分子化合物の種類、使用する装置の種類等に応じて適宜設定すればよいが、製鉄用焼結原料の造粒処理方法において用いられる全ての製鉄用焼結原料（鉄鉱石、副原料、燃料等）１００重量部に対して高分子化合物が０．００１重量部以上となるようにすることが好ましく、また、２重量部以下となるようにすることが好ましい。０．００１重量部未満であると、本発明の作用効果を充分に発揮することができなくなるおそれがあり、２重量部を超えると、製鉄用焼結原料等に対する高分子化合物の添加量が多くなりすぎ、製鉄用焼結原料の大きな固まりができ、焼結されにくくなる等の問題が生じるおそれがある。より好ましくは、高分子化合物が０．００３重量部以上となるようにすることであり、また、１重量部以下となるようにすることである。 The amount of the polymer compound A used may be set as appropriate depending on the granulation properties of the sintering raw material, the type of the polymer compound, the type of equipment used, and the like. It is preferable to make the polymer compound 0.001 part by weight or more with respect to 100 parts by weight of all the iron-making sintering raw materials (iron ore, auxiliary materials, fuel, etc.) used in the grain treatment method, It is preferable to be 2 parts by weight or less. If the amount is less than 0.001 part by weight, the effects of the present invention may not be fully exhibited. If the amount exceeds 2 parts by weight, the amount of the polymer compound added to the sintered raw material for iron making is large. If it becomes too much, a large mass of the sintering raw material for iron making may be formed, which may cause problems such as difficulty in sintering. More preferably, the polymer compound is made 0.003 part by weight or more, and is made to be 1 part by weight or less.
上記高分子化合物Ａを添加するタイミングとしては、造粒処理前、造粒処理中の何れでもよいが、該微粒子と製鉄用焼結原料の０．３〜１０質量％とを混合処理した後に添加することが好ましく、該微粒子と製鉄用焼結原料の０．３〜１０質量％との混合物と、残りの製鉄用焼結原料を造粒処理しながら添加することがより好ましい。該微粒子と製鉄用焼結原料の０．３〜１０質量％とを混合処理しながら添加することも可能であるが、その場合、該微粒子と製鉄用焼結原料の０．３〜１０質量％とが混合時に造粒して、該微粒子が取り込まれることがあり、該微粒子と製鉄用焼結原料の０．３〜１０質量％との混合物と、残りの製鉄用焼結原料を造粒処理する工程で該微粒子が偏在してしまい、擬似粒子の崩れ抑制効果が低減することがある。
本発明においてはまた、高分子化合物の添加量が、全製鉄用焼結原料に対して０．００１〜１質量％であり、微粒子の添加量が、全製鉄用焼結原料に対して０．０５〜３０質量％であることも好ましい形態である。
The timing of adding the polymer compound A may be before the granulation treatment or during the granulation treatment, but is added after mixing the fine particles and 0.3 to 10% by mass of the sintering raw material for iron making. It is preferable to add the mixture of the fine particles and 0.3 to 10% by mass of the iron-making sintering raw material and the remaining iron-making sintering raw material while granulating. It is possible to add the fine particles and 0.3 to 10% by mass of the sintering raw material for iron making while mixing, in which case 0.3 to 10% by mass of the fine particles and the sintering raw material for iron making is possible. May be granulated at the time of mixing, and the fine particles may be taken in. The mixture of the fine particles and 0.3 to 10% by mass of the sintering raw material for iron making and the remaining sintering raw material for iron making are granulated. In the process, the fine particles are unevenly distributed, and the effect of suppressing the collapse of the pseudo particles may be reduced.
In the present invention, the addition amount of the polymer compound is 0.001 to 1% by mass with respect to all the iron-making sintering raw materials, and the addition amount of fine particles is 0.000 with respect to all the iron-making sintering raw materials. It is also a preferable form that it is 05-30 mass%.
また上記生石灰等の高分子化合物Ａ以外の造粒処理剤を使用する場合、該使用量としては、製鉄用焼結原料の造粒処理方法において用いられる全ての製鉄用焼結原料１００重量部に対して、０．０５重量部以上とすることが好ましく、また、２．５重量部以下とすることが好ましい。より好ましくは、０．１重量部以上であり、また、２．０重量部以下である。 When a granulating agent other than the polymer compound A such as quicklime is used, the amount used is 100 parts by weight of all the iron-making sintered raw materials used in the method of granulating a steel-making sintered raw material. On the other hand, it is preferable to set it as 0.05 weight part or more, and it is preferable to set it as 2.5 weight part or less. More preferably, it is 0.1 parts by weight or more and 2.0 parts by weight or less.
上記混合処理工程において、混合方法としては、アイリッヒミキサー、レーディゲミキサー、ローラーミル、ロッドミル、ボールミル等により混合する方法が好適であり、これらの中でも、アイリッヒミキサー、レーディゲミキサーを用いる方法が好ましい。
上記造粒処理工程において、造粒方法としては、パンペレタイザー、マルメライザー、ドラムミキサー、アイリッヒミキサー、レーディゲミキサー等を用いることが好適であり、これらの中でも、ドラムミキサー、パンペレタイザーを用いることが好ましい。
In the above-mentioned mixing treatment step, as a mixing method, a method of mixing by an Eirich mixer, a Ladige mixer, a roller mill, a rod mill, a ball mill, or the like is preferable, and among these, an Eirich mixer or a Ladige mixer is used. The method is preferred.
In the granulation process, it is preferable to use a pan pelletizer, a malmerizer, a drum mixer, an Eirich mixer, a Laedige mixer, etc., among these, a drum mixer and a pan pelletizer are used. It is preferable.
本発明の製鉄用焼結原料の造粒処理方法により得られる造粒物は、焼結機により焼結処理されて焼結鉱とすることができるものである。このような本発明の製鉄用焼結原料の造粒処理方法により得られる造粒物から製造されてなる焼結鉱もまた、本発明の好ましい実施形態の一つである。このような焼結鉱は、本発明の製鉄用焼結原料の造粒処理方法において得られる造粒物、すなわち平均粒径が２００μｍ以下の微粒子の分散性が向上し、該微粒子の添加による焼結層の水分凝縮帯や、乾燥帯における造粒物（擬似粒子）の崩れ抑制作用効果が有効に作用し、充分な焼結鉱の生産性が実現できる造粒物から製造されてなる有用なものである。 The granulated product obtained by the granulation treatment method for the iron-making sintered raw material of the present invention can be sintered by a sintering machine to form a sintered ore. A sintered ore produced from such a granulated product obtained by the method for granulating a sintering raw material for iron making according to the present invention is also one preferred embodiment of the present invention. Such a sintered ore is improved in the dispersibility of the granulated product obtained in the method for granulating a sintering raw material for iron making according to the present invention, that is, fine particles having an average particle size of 200 μm or less, and is sintered by adding the fine particles. It is useful to be produced from a granulated product that effectively acts to suppress the collapse of the granulated product (pseudoparticles) in the moisture condensation zone of the stratified layer and the dry zone, and realizes sufficient sintered ore productivity. Is.
本発明における焼結鉱製造の生産性は、焼結鉱の成品歩留、生産率により計測することが可能であり、例えば、成品歩留は、焼結鍋試験において、焼結後の焼結鉱（シンターケーキ）５０ｋｇを２ｍの高さから鉄板上に５回落下させたときの、粒径５ｍｍ以上の粒度を有する粒子の割合を測定することにより評価することができる。また、生産率は、以下の式により算出することができる。
生産率（ｔ／ｄａｙ／ｍ２）＝成品歩留評価後の粒径５ｍｍ以上の粒度を有する粒子の総質量（ｔ）／焼結時間（ｄａｙ）／焼結機（鍋）の表面積（ｍ２）
The productivity of the sinter production in the present invention can be measured by the product yield and the production rate of the sinter. For example, the product yield can be measured after sintering in the sintering pot test. It can be evaluated by measuring the ratio of particles having a particle size of 5 mm or more when 50 kg of ore (sinter cake) is dropped five times on a steel plate from a height of 2 m. The production rate can be calculated by the following equation.
Production rate (t / day / m 2 ) = total mass of particles having a particle size of 5 mm or more after product yield evaluation (t) / sintering time (day) / surface area of sintering machine (pan) (m 2 )
以下では、本発明におけるカルボキシル基、スルホン酸基及びこれらの塩からなる群より選択される少なくとも一種の基を有する高分子化合物（以下高分子化合物Ａ）について説明する。なお、高分子化合物において、カルボキシル基やスルホン酸基の塩とは、カルボキシル基やスルホン酸基における水素原子が金属原子等で置き換わった構造を有する基であり、塩の形態となった基を意味する。 Below, the high molecular compound (henceforth high molecular compound A) which has at least 1 type of group selected from the group which consists of a carboxyl group in this invention, a sulfonic acid group, and these salts is demonstrated. In the polymer compound, a salt of a carboxyl group or a sulfonic acid group is a group having a structure in which a hydrogen atom in a carboxyl group or a sulfonic acid group is replaced with a metal atom or the like, and means a group in the form of a salt. To do.
上記高分子化合物としては、（１）カルボキシル基及び／又はその塩を有する高分子化合物、（２）スルホン酸基及び／又はその塩を有する高分子化合物、（３）カルボキシル基及び／又はその塩、並びに、スルホン酸基及び／又はその塩を有する高分子化合物のいずれか１種又は２種以上が挙げられる。このような高分子化合物としては、カルボキシル基を有する単量体、スルホン酸基を有する単量体及びこれらの塩を有する単量体からなる群より選択される少なくとも１種の単量体を必須とする単量体組成で重合することにより得ることができるものが好ましい。このような単量体としては１種又は２種以上用いることができるが、より好ましくは、全単量体組成１００モル％に対して、カルボキシル基を有する単量体及び／又はその塩を有する単量体を１０モル％以上含有する単量体組成で重合してなるものである。単量体組成物におけるカルボキシル基を有する単量体及び／又はその塩を有する単量体の含有量が１０モル％未満であると、造粒効果を充分には得られないおそれがある。更に好ましくは、３０モル％以上であり、特に好ましくは、５０モル％以上である。 Examples of the polymer compound include (1) a polymer compound having a carboxyl group and / or a salt thereof, (2) a polymer compound having a sulfonic acid group and / or a salt thereof, and (3) a carboxyl group and / or a salt thereof. And any one or two or more polymer compounds having a sulfonic acid group and / or a salt thereof. As such a polymer compound, at least one monomer selected from the group consisting of a monomer having a carboxyl group, a monomer having a sulfonic acid group, and a monomer having a salt thereof is essential. What can be obtained by superposing | polymerizing with the monomer composition made into is preferable. Such monomers can be used singly or in combination of two or more, but more preferably have a monomer having a carboxyl group and / or a salt thereof with respect to 100 mol% of the total monomer composition. It is formed by polymerization with a monomer composition containing 10 mol% or more of monomers. If the content of the monomer having a carboxyl group and / or the monomer having a salt thereof in the monomer composition is less than 10 mol%, the granulation effect may not be sufficiently obtained. More preferably, it is 30 mol% or more, and particularly preferably 50 mol% or more.
上記カルボキシル基を有する単量体やその塩を有する単量体としては、（メタ）アクリル酸、マレイン酸、無水マレイン酸、イタコン酸、フマル酸、クロトン酸、アクリルアミドグリコール酸等のカルボキシル基を有する単量体やその塩等が好適である。これらは単独で用いてもよく、２種以上を併用してもよい。これらの中でも、（メタ）アクリル酸及び／又はその塩がより好ましい。すなわち本発明におけるカルボキシル基及び／又はその塩を有する高分子化合物としては、（メタ）アクリル酸及び／又はその塩を主成分とする単量体組成で重合してなるものが好ましい。より好ましくは、アクリル酸及び／又はその塩である。また、塩としては、ナトリウム、カリウム等のアルカリ金属塩；カルシウム、マグネシウム等のアルカリ土類金属塩；アンモニウム塩；モノエタノールアミン、トリエタノールアミン等の有機アミシ塩が好適である。これらの中でも、ナトリウム、カリウム等のアルカリ金属塩、アンモニウム塩が好ましく、ナトリウム塩がより好ましい。 The monomer having a carboxyl group or a salt thereof has a carboxyl group such as (meth) acrylic acid, maleic acid, maleic anhydride, itaconic acid, fumaric acid, crotonic acid, acrylamide glycolic acid, etc. Monomers and their salts are preferred. These may be used alone or in combination of two or more. Among these, (meth) acrylic acid and / or a salt thereof is more preferable. That is, the polymer compound having a carboxyl group and / or a salt thereof in the present invention is preferably a polymer obtained by polymerization with a monomer composition mainly composed of (meth) acrylic acid and / or a salt thereof. More preferred is acrylic acid and / or a salt thereof. As the salt, alkali metal salts such as sodium and potassium; alkaline earth metal salts such as calcium and magnesium; ammonium salts; Among these, alkali metal salts such as sodium and potassium, and ammonium salts are preferable, and sodium salts are more preferable.
上記スルホン酸基を有する単量体やその塩を有する単量体としては、ビニルスルホン酸、スチレンスルホン酸、スルホエチル（メタ）アクリレート、２−アクリルアミド−２−メチルプロパンスルホン酸等のスルホン酸基を有する単量体やその塩等が好適である。これらは単独で用いてもよく、２種以上を併用してもよい。 Examples of the monomer having a sulfonic acid group or a salt thereof include sulfonic acid groups such as vinyl sulfonic acid, styrene sulfonic acid, sulfoethyl (meth) acrylate, and 2-acrylamido-2-methylpropane sulfonic acid. Preferred are monomers having a salt thereof and salts thereof. These may be used alone or in combination of two or more.
上記高分子化合物は、カルボキシル基を有する単量体、スルホン酸基を有する単量体やこれらの塩を有する単量体と、これらの単量体と共重合可能な他の共重合性単量体１種又は２種以上とを共重合して得られるものであってもよい。
上記他の共重合性単量体としては、２−（メタ）アクリロイルオキシエチルアシッドホスフェート、２−（メタ）アクリロイルオキシプロピルアシッドホスフェート、２−（メタ）アクリロイルオキシ−３−クロロプロピルアシッドホスフェート、２−（メタ）アクリロイルオキシエチルフェニルホスフェート等の酸性リン酸エステル基を有する単量体；ビニルフェノール等の石炭酸系単量体等の酸基を有する単量体及びその塩等が好適である。
The polymer compound includes a monomer having a carboxyl group, a monomer having a sulfonic acid group and a monomer having a salt thereof, and other copolymerizable monomers that can be copolymerized with these monomers. It may be obtained by copolymerizing one kind or two or more bodies.
Examples of the other copolymerizable monomers include 2- (meth) acryloyloxyethyl acid phosphate, 2- (meth) acryloyloxypropyl acid phosphate, 2- (meth) acryloyloxy-3-chloropropyl acid phosphate, 2 -Monomers having an acidic phosphate group such as (meth) acryloyloxyethylphenyl phosphate; monomers having an acid group such as a vinyl acid monomer such as vinylphenol, and salts thereof are preferred.
上記他の共重合性単量体としてはまた、ポリエチレングリコールモノメタアクリル酸エステル、メトキシポリエチレングリコールモノメタクリル酸エステル、メトキシポリエチレングリコールモノアクリル酸エステル等のポリアルキレングリコール（メタ）アクリル酸エステル；３−メチル−３−ブテン−１−オールにエチレンオキサイドを付加してなるポリアルキレングリコールモノアルケニルエーテル単量体；アリルアルコールにエチレンオキサイドを付加してなるポリエチレングリコールモノエテニルエーテル単量体；無水マレイン酸にポリエチレングリコールを付加させたマレイン酸ポリエチレングリコールハーフエステル等のポリアルキレングリコール鎖を有する単量体等が好適である。これらのポリアルキレングリコール鎖を有する単量体の中でも、エチレンオキサイド換算で５モル以上、１００モル以下の鎖長のポリアルキレングリコール鎖を有する単量体が、入手が容易であり、また、擬似粒化性の向上、重合性の点から好ましい。より好ましくは、エチレンオキサイド換算で１０モル以上、また、１００モル以下の鎖長のポリアルキレングリコール鎖を有する単量体である。 Examples of the other copolymerizable monomers also include polyalkylene glycol (meth) acrylates such as polyethylene glycol monomethacrylate, methoxypolyethylene glycol monomethacrylate, and methoxypolyethyleneglycol monoacrylate; Polyalkylene glycol monoalkenyl ether monomer formed by adding ethylene oxide to methyl-3-buten-1-ol; polyethylene glycol monoethenyl ether monomer formed by adding ethylene oxide to allyl alcohol; A monomer having a polyalkylene glycol chain such as maleic acid polyethylene glycol half ester to which polyethylene glycol has been added is preferred. Among these monomers having a polyalkylene glycol chain, a monomer having a polyalkylene glycol chain having a chain length of 5 mol or more and 100 mol or less in terms of ethylene oxide is easy to obtain, It is preferable from the viewpoints of improvement in polymerization and polymerization. More preferably, it is a monomer having a polyalkylene glycol chain having a chain length of 10 mol or more and 100 mol or less in terms of ethylene oxide.
上記他の共重合性単量体としては、上述したものの他にも、下記の化合物を用いることができる。
（メタ）アクリル酸メチル、（メタ）アクリル酸エチル、（メタ）アクリル酸ヒドロキシエチル、（メタ）アクリル酸（Ｎ，Ｎ−ジメチルアミノエチル）、（メタ）アクリル酸（Ｎ，Ｎ−ジエチルアミノエチル）、（メタ）アクリル酸アミノエチル等の炭素数１〜１８の（メタ）アクリル酸アルキルエステル；（メタ）アクリルアミド、Ｎ−メチル（メタ）アクリルアミド、Ｎ−エチル（メタ）アクリルアミド、Ｎ，Ｎ−ジメチル（メタ）アクリルアミド等の（メタ）アクリルアミド及びその誘導体；酢酸ビニル；スチレン；（メタ）アクリロニトリル；Ｎ−ビニル−２−ピロリドン、ビニルピリジン、ビニルイミダゾール等の塩基含有単量体；Ｎ−メチロール（メタ）アクリルアミド、Ｎ−ブトキシメチル（メタ）アクリルアミド等の架橋性を有する（メタ）アクリルアミド系単量体；ビニルトリメトキシシラン、ビニルトリエトキシシラン、γ−（メタ）アクリロイルプロピルトリメトキシシラン、ビニルトリス（２−メトキシエトキシ）シラン、アリルトリエトキシシラン等の加水分解性を有する基がケイ素原子に直結しているシラン系単量体；グリシジル（メタ）アクリレート、グリシジルエーテル（メタ）アクリレート等のエポキシ基を有する単量体；２−イソプロペニル−２−オキサゾリン、２−ビニル−２−オキサゾリン等のオキサゾリン基を有する単量体；２−アジリジニルエチル（メタ）アクリレート、（メタ）アクリロイルアジリジン等のアジリジン基を有する単量体；フッ化ビニル、フッ化ビニリデン、塩化ビニル、塩化ビニリデン等のハロゲン基を有する単量体；（メタ）アクリル酸と、エチレングリコール、ジエチレングリコール、プロピレングリコール、１，３−ブチレングリコール、ネオペンチルグリコール、１，６−ヘキサンジオール、トリメチロールプロパン、ペンタエリスリトール、ジペンタエリスリトール等の多価アルコールとのエステル化物等の分子内に不飽和基を複数有する多官能（メタ）アクリル酸エステル；メチレンビス（メタ）アクリルアミド等の分子内に不飽和基を複数有する多官能（メタ）アクリルアミド；ジアリルフタレート、ジアリルマレエート、ジアリルフマレート等の分子内に不飽和基を複数有する多官能アリル化合物；アリル（メタ）アクリレート；ジビニルベンゼン。
As said other copolymerizable monomer, the following compound can be used besides the thing mentioned above.
Methyl (meth) acrylate, ethyl (meth) acrylate, hydroxyethyl (meth) acrylate, (meth) acrylic acid (N, N-dimethylaminoethyl), (meth) acrylic acid (N, N-diethylaminoethyl) C1-C18 (meth) acrylic acid alkyl esters such as aminoethyl (meth) acrylate; (meth) acrylamide, N-methyl (meth) acrylamide, N-ethyl (meth) acrylamide, N, N-dimethyl (Meth) acrylamide and its derivatives such as (meth) acrylamide; vinyl acetate; styrene; (meth) acrylonitrile; base-containing monomers such as N-vinyl-2-pyrrolidone, vinylpyridine, vinylimidazole; N-methylol (meta ) Crosslinking of acrylamide, N-butoxymethyl (meth) acrylamide, etc. (Meth) acrylamide monomer having hydrolyzability such as vinyltrimethoxysilane, vinyltriethoxysilane, γ- (meth) acryloylpropyltrimethoxysilane, vinyltris (2-methoxyethoxy) silane, allyltriethoxysilane A silane-based monomer in which a group having a direct bond to a silicon atom; a monomer having an epoxy group such as glycidyl (meth) acrylate and glycidyl ether (meth) acrylate; 2-isopropenyl-2-oxazoline, 2- Monomers having an oxazoline group such as vinyl-2-oxazoline; monomers having an aziridin group such as 2-aziridinylethyl (meth) acrylate and (meth) acryloylaziridine; vinyl fluoride, vinylidene fluoride, chloride Single unit having halogen groups such as vinyl and vinylidene chloride (Meth) acrylic acid and polyvalent such as ethylene glycol, diethylene glycol, propylene glycol, 1,3-butylene glycol, neopentyl glycol, 1,6-hexanediol, trimethylolpropane, pentaerythritol, dipentaerythritol Multifunctional (meth) acrylic acid ester having a plurality of unsaturated groups in the molecule such as esterified product with alcohol; Multifunctional (meth) acrylamide having a plurality of unsaturated groups in the molecule such as methylenebis (meth) acrylamide; Diallyl phthalate , Diallyl maleate, diallyl fumarate and the like, polyfunctional allyl compounds having a plurality of unsaturated groups in the molecule; allyl (meth) acrylate; divinylbenzene.
上記高分子化合物の原料である単量体を（共）重合する際には、分子量の調節を目的として、連鎖移動剤を用いることもできる。連鎖移動剤としては、メルカプトエタノール、メルカプトプロピオン酸、ｔ−ドデシルメルカプタン等のメルカプト基を有する化合物；四塩化炭素；イソプロピルアルコール；トルエン；次亜リン酸、次亜リン酸ナトリウム、亜硫酸水素ナトリウム等の連鎖移動係数の高い化合物等が好適である。これらは単独で用いてもよく、２種以上を併用してもよい。連鎖移動剤の使用量としては、全単量体組成物１モルに対し、０．００５〜０．１５モルとすることが好ましい。 When (co) polymerizing the monomer that is a raw material of the polymer compound, a chain transfer agent may be used for the purpose of adjusting the molecular weight. Examples of the chain transfer agent include compounds having a mercapto group such as mercaptoethanol, mercaptopropionic acid, t-dodecyl mercaptan; carbon tetrachloride; isopropyl alcohol; toluene; hypophosphorous acid, sodium hypophosphite, sodium bisulfite, etc. A compound having a high chain transfer coefficient is preferred. These may be used alone or in combination of two or more. The amount of the chain transfer agent used is preferably 0.005 to 0.15 mol per 1 mol of the total monomer composition.
上記高分子化合物を得る方法としては、従来公知の種々の重合法、例えば、水中油型乳化重合法、油中水型乳化重合法、懸濁重合法、分散重合法、沈澱重合法、溶液重合法、水溶液重合法、塊状重合法等を採用することができる。これらの中でも、重合コスト（生産コスト）の低減及び安全性等の観点から、水溶液重合法が好ましい。 Methods for obtaining the polymer compound include various conventionally known polymerization methods such as oil-in-water emulsion polymerization, water-in-oil emulsion polymerization, suspension polymerization, dispersion polymerization, precipitation polymerization, solution weight A combination method, an aqueous solution polymerization method, a bulk polymerization method, or the like can be employed. Among these, the aqueous solution polymerization method is preferable from the viewpoint of reduction in polymerization cost (production cost) and safety.
上記重合に用いられる重合開始剤としては、熱又は酸化還元反応によって分解し、ラジカル分子を発生させる化合物であればよい。また、水溶液重合法により重合を行う場合には、水溶性を備えた重合開始剤を用いることが好ましい。重合開始剤としては、過硫酸ナトリウム、過硫酸カリウム、過硫酸アンモニウム等の過硫酸塩類；２，２′−アゾビス−（２−アミジノプロパン）二塩酸塩、４，４′−アゾビス−（４−シアノペンタン酸）等の水溶性アゾ化合物；過酸化水素等の熱分解性開始剤；過酸化水素及びアスコルビン酸、ｔ−ブチルハイドロパーオキサイド及びロンガリット、過硫酸カリウム及び金属塩、過硫酸アンモニウム及び亜硫酸水素ナトリウム等の組み合わせからなるレドックス系重合開始剤が好適である。これらは単独で用いてもよく、２種以上を併用してもよい。重合開始剤の使用量としては、上記高分子化合物の原料である単量体組成や重合条件等に応じて適宜設定すればよい。 The polymerization initiator used for the polymerization may be a compound that decomposes by heat or a redox reaction to generate radical molecules. Moreover, when performing superposition | polymerization by aqueous solution polymerization method, it is preferable to use the polymerization initiator provided with water solubility. Examples of the polymerization initiator include persulfates such as sodium persulfate, potassium persulfate, and ammonium persulfate; 2,2′-azobis- (2-amidinopropane) dihydrochloride, 4,4′-azobis- (4-cyano Water-soluble azo compounds such as pentanoic acid; thermal decomposable initiators such as hydrogen peroxide; hydrogen peroxide and ascorbic acid, t-butyl hydroperoxide and Rongalite, potassium persulfate and metal salts, ammonium persulfate and sodium bisulfite A redox polymerization initiator comprising a combination of the above is preferred. These may be used alone or in combination of two or more. What is necessary is just to set suitably the usage-amount of a polymerization initiator according to the monomer composition which is the raw material of the said high molecular compound, polymerization conditions, etc.
上記重合における反応温度や反応時間等の重合条件としては、単量体組成物の組成や、重合開始剤の種類等に応じて適宜設定すればよいが、反応温度としては、０〜１５０℃とすることが好ましく、４０〜１０５℃とすることがより好ましい。また、反応時間としては、３〜１５時間程度が好適である。水溶液重合法により重合を行う場合における単量体組成物の反応系への供給方法としては、一括添加法、分割添加法、成分滴下法、パワーフィード法、多段滴下法により行うことができる。また、重合は常圧下、減圧下、加圧下の何れで行ってもよい。 The polymerization conditions such as the reaction temperature and reaction time in the above polymerization may be appropriately set according to the composition of the monomer composition, the type of polymerization initiator, etc. The reaction temperature is from 0 to 150 ° C. It is preferable to set it to 40 to 105 ° C. The reaction time is preferably about 3 to 15 hours. As a method for supplying the monomer composition to the reaction system in the case of performing polymerization by an aqueous solution polymerization method, a batch addition method, a divided addition method, a component dropping method, a power feed method, or a multistage dropping method can be used. The polymerization may be performed under normal pressure, reduced pressure, or increased pressure.
上記高分子化合物の製造において、水溶液重合法を採用した場合に得られる高分子化合物水溶液中に含まれる、高分子化合物を含む不揮発分の濃度としては、７０質量％以下であることが好ましい。７０質量％を超えると、粘度が高くなり過ぎるおそれがある。 In the production of the polymer compound, the concentration of the non-volatile component containing the polymer compound contained in the polymer compound aqueous solution obtained when the aqueous solution polymerization method is adopted is preferably 70% by mass or less. When it exceeds 70 mass%, there exists a possibility that a viscosity may become high too much.
上記スルホン酸基及び／又はその塩を有する好ましい高分子化合物として、β−ナフタレンスルホン酸塩ホルマリン縮合物、メラミンスルホン酸塩ホルマリン縮合物、芳香族アミノスルホン酸ポリマー等が挙げられる。 Preferable polymer compounds having the sulfonic acid group and / or salt thereof include β-naphthalene sulfonate formalin condensate, melamine sulfonate formalin condensate, aromatic amino sulfonic acid polymer and the like.
本発明におけるカルボキシル基、スルホン酸基及びこれらの塩からなる群より選択される少なくとも一種の基を有する高分子化合物としては、重量平均分子量が１０００〜１００００００であることが好ましい。重量平均分子量が１０００未満であると、分散剤としての作用が低下するおそれがある。１００００００を超えると、高分子化合物の粘度が高くなり過ぎて分散剤としての作用が充分に発揮されるように混合しにくいものとなるおそれがある。より好ましくは、３０００以上であり、また、１０００００以下である。なお、本明細書中、重量平均分子量は、以下の測定条件で測定される値である。 The polymer compound having at least one group selected from the group consisting of carboxyl groups, sulfonic acid groups and salts thereof in the present invention preferably has a weight average molecular weight of 1,000 to 1,000,000. If the weight average molecular weight is less than 1000, the action as a dispersant may be reduced. If it exceeds 1,000,000, the viscosity of the polymer compound becomes too high, and it may be difficult to mix so that the action as a dispersant is sufficiently exhibited. More preferably, it is 3000 or more and 100000 or less. In the present specification, the weight average molecular weight is a value measured under the following measurement conditions.
（重量平均分子量測定条件）
カラム：水系ＧＰＣカラム「ＧＦ−７ＭＨＱ」（商品名、昭和電工社製）１本
キャリア液：リン酸水素二ナトリウム十二水和物３４．５ｇ及びリン酸二水素ナトリウム二水和物４６．２ｇに超純水を加えて全量を５０００ｇとする。
水溶液流速：０．５ｍｌ／ｍｉｎ
ポンプ：「Ｌ−７１１０」（商品名、日立製作所社製）
検出器：紫外線（ＵＶ）検出器「Ｌ−７４００」（商品名、日立製作所社製）、波長２１４ｎｍ
分子量標準サンプル：ポリアクリル酸ナトリウム（創和科学社より入手可能な重量平均分子量１３００〜１３６００００のポリアクリル酸ナトリウム）
分析サンプルは、高分子化合物が固形分で０．１質量％となるように上記キャリア液で希釈することにより調製する。
ただし、上記測定条件で測定ができない高分子化合物については、以下の測定条件を適用する。
機種：Ｗａｔｅｒｓ ＬＣＭ１
キャリア液：水１０９９９ｇ、アセトニトリル６００１ｇの混合液に酢酸ナトリウム三水和物１１５．６ｇを溶解し、更に３０％水酸化ナトリウム水溶液でｐＨ６．０に調節した水溶液
流速：０．８ｍｌ／ｍｉｎ
カラム：水系ＧＰＣカラム「ＴＳＫｇｅｌ ＧｕａｒｄＣｏｌｕｍｎＳＷＸＬ＋Ｇ４０００ＳＷＸＬ＋Ｇ３０００ＳＷＸＬ＋Ｇ２０００ＳＷＸＬ」（東ソー社製）
カラム温度：３５℃
検出器：Ｗａｔｅｒｓ ４１０示差屈折検出器
分子量標準サンプル：ポリエチレングリコール
分析サンプルは、高分子化合物が固形分で０．１％となるように上記キャリア液で希釈することにより調製する。
(Weight average molecular weight measurement conditions)
Column: Aqueous GPC column “GF-7MHQ” (trade name, manufactured by Showa Denko KK) One carrier liquid: 34.5 g of disodium hydrogen phosphate dodecahydrate and 46.2 g of sodium dihydrogen phosphate dihydrate Ultrapure water is added to make the total amount 5000 g.
Aqueous solution flow rate: 0.5 ml / min
Pump: “L-7110” (trade name, manufactured by Hitachi, Ltd.)
Detector: Ultraviolet (UV) detector “L-7400” (trade name, manufactured by Hitachi, Ltd.), wavelength 214 nm
Molecular weight standard sample: sodium polyacrylate (sodium polyacrylate having a weight average molecular weight of 1300 to 1360000 available from Soka Kagaku)
The analytical sample is prepared by diluting with the carrier liquid so that the polymer compound has a solid content of 0.1% by mass.
However, the following measurement conditions are applied to polymer compounds that cannot be measured under the above measurement conditions.
Model: Waters LCM1
Carrier solution: 115.6 g of sodium acetate trihydrate dissolved in a mixture of 10999 g of water and 6001 g of acetonitrile, and further adjusted to pH 6.0 with 30% aqueous sodium hydroxide solution Flow rate: 0.8 ml / min
Column: Water-based GPC column “TSKgel GuardColumnSWXL + G4000SWXL + G3000SWXL + G2000SWXL” (manufactured by Tosoh Corporation)
Column temperature: 35 ° C
Detector: Waters 410 Differential refraction detector Molecular weight standard sample: Polyethylene glycol The analytical sample is prepared by diluting with the carrier solution so that the polymer compound is 0.1% in solid content.
上記高分子化合物としてはまた、分散度が１２以下であることが好ましい。分散度が１２を超えると、粉鉄鉱石を分散する作用が小さくなることに起因して、擬似粒子化させる作用が低下する傾向にある。より好ましくは、１０以下である。分散度とは、重量平均分子量（Ｍｗ）と数平均分子量（Ｍｎ）との比（Ｍｗ／Ｍｎ）であり、分子量分布を表すものである。数平均分子量は、重量平均分子量と同様の方法で測定される。
これらの高分子化合物は、固形のまま添加しても構わないが、固形分濃度０．１〜７０％の水溶液の形態で添加することが好ましい。
The polymer compound preferably has a dispersity of 12 or less. If the degree of dispersion exceeds 12, the action of dispersing fine iron ore tends to be small, and the action of making pseudo particles tends to decrease. More preferably, it is 10 or less. The degree of dispersion is the ratio (Mw / Mn) of the weight average molecular weight (Mw) and the number average molecular weight (Mn), and represents the molecular weight distribution. The number average molecular weight is measured by the same method as the weight average molecular weight.
These polymer compounds may be added in a solid form, but are preferably added in the form of an aqueous solution having a solid content concentration of 0.1 to 70%.
本発明の製鉄用焼結原料の造粒処理方法は、上述の構成よりなり、製銑工程における高炉装入用原料となる焼結鉱の製造において粉鉄鉱石等の焼結原料の造粒に有効であり、これにより、造粒処理剤としての作用を有する微粒子の製鉄用焼結原料への分散性が向上し、有効に作用することにより、焼結鉱の生産性を向上させることとなる。 The method for granulating a sintered raw material for iron making according to the present invention comprises the above-described configuration, and is used for granulating a sintered raw material such as fine iron ore in the production of sintered ore as a raw material for charging a blast furnace in the iron making process It is effective, thereby improving the dispersibility of fine particles having an action as a granulating agent in a sintering raw material for iron making, and improving the productivity of sintered ore by acting effectively. .
以下に実施例を掲げて本発明を更に詳細に説明するが、本発明はこれらの実施例のみに限定されるものではない。なお、特に断りのない限り、「部」は「重量部」を、「％」は「質量％」を意味するものとする。 The present invention will be described in more detail with reference to the following examples. However, the present invention is not limited to these examples. Unless otherwise specified, “part” means “part by weight” and “%” means “mass%”.
実施例及び比較例における擬似粒子の平均粒径及びＧＩ指数、製鉄用焼結原料に対する微粒子量、焼結鉱強度、生産率、成品歩留は、下記方法により測定した。
（擬似粒子の平均粒径、ＧＩ指数）
造粒操作を行って得られた擬似粒子を８０℃で１時間乾燥後、ふるいを用いて分級することにより、その粒度（擬似粒度）を求めた。造粒された擬似粒子のＧＩ指数とは、製鉄研究第２８８号（１９７６）９頁に開示されている評価方法の一つであり、核粒子の周りに付着する微粒子粒子の割合を示す。なお、ＧＩ指数の測定は、製鉄研究第２８８号（１９７６）９頁に記載の方法に準じて行った。
以下の各実施例及び比較例の測定においては、何れも、造粒後の粒径が０．２５ｍｍ以下の擬似粒子のＧＩ指数を求めた。
また、０．２５ｍｍ以下の擬似粒子のＧＩ指数（擬似粒化指数）は以下の式により計算した。
ＧＩ指数＝｛（造粒前の０．２５ｍｍ以下の原料の比率−造粒後の０．２５ｍｍ以下の原料の比率）／（造粒前の０．２５ｍｍ以下の原料の比率）｝×１００
The average particle diameter and GI index of the pseudo particles in Examples and Comparative Examples, the amount of fine particles relative to the sintering raw material for iron making, the strength of the sintered ore, the production rate, and the product yield were measured by the following methods.
(Average particle size of pseudo particles, GI index)
The pseudo particles obtained by the granulation operation were dried at 80 ° C. for 1 hour and classified using a sieve to obtain the particle size (pseudo particle size). The GI index of the granulated pseudo particles is one of the evaluation methods disclosed in Steel Manufacturing Research No. 288 (1976), page 9, and indicates the ratio of fine particles adhering around the core particles. The GI index was measured according to the method described in Steel Manufacturing Research No. 288 (1976), page 9.
In the measurement of each of the following Examples and Comparative Examples, the GI index of pseudo particles having a particle diameter after granulation of 0.25 mm or less was determined.
Moreover, the GI index (pseudo graining index) of pseudo particles of 0.25 mm or less was calculated by the following formula.
GI index = {(ratio of raw material of 0.25 mm or less before granulation−ratio of raw material of 0.25 mm or less after granulation) / (ratio of raw material of 0.25 mm or less before granulation)} × 100
以下に記載の実施例及び比較例における焼結原料は、全て、絶乾状態のものを使用した。また、ポリマー水溶液中のポリマーの重量平均分子量測定には、ＧＰＣ（ゲルパーミエーションクロマトグラフィー）によるポリエチレングリコール換算を用いた。
（成品歩留、生産率）
成品歩留は、焼結鍋試験において、焼結後の焼結鉱（シンターケーキ）５０ｋｇを２ｍの高さから鉄板上に５回落下させたときの、粒径５ｍｍ以上の粒度を有する粒子の割合を測定することにより評価した。生産率は、以下の式により算出した。
生産率（ｔ／ｄａｙ／ｍ２）＝成品歩留評価後の粒径５ｍｍ以上の粒度を有する粒子の総質量（ｔ）／焼結時間（ｄａｙ）／焼結機（鍋）の表面積（ｍ２）
The sintering raw materials in the examples and comparative examples described below were all in an absolutely dry state. The weight average molecular weight of the polymer in the polymer aqueous solution was measured by polyethylene glycol conversion by GPC (gel permeation chromatography).
(Product yield, production rate)
In the product yield, in the sintering pot test, 50 kg of sintered ore after sintering (sinter cake) was dropped 5 times on a steel plate from a height of 2 m. The ratio was evaluated by measuring. The production rate was calculated by the following formula.
Production rate (t / day / m 2 ) = total mass of particles having a particle size of 5 mm or more after product yield evaluation (t) / sintering time (day) / surface area of sintering machine (pan) (m 2 )
実施例１
アイリッヒミキサーに、ダストと平均粒径７μｍの重質炭酸カルシウムを質量比で３：０．５（絶乾換算）になるように投入し６０秒混合を行った。混合後の水分量が、１０％になるように水分調整することにより、微粒子混合物１を得た。一方、表１の配合Ａに示す組成を有する焼結原料（製鉄用原料）を調製した。
Example 1
Dust and heavy calcium carbonate with an average particle diameter of 7 μm were charged into an Eirich mixer so that the mass ratio was 3: 0.5 (absolutely dry conversion) and mixed for 60 seconds. The fine particle mixture 1 was obtained by adjusting the water content so that the water content after mixing was 10%. On the other hand, a sintering raw material (raw material for iron making) having the composition shown in Formulation A of Table 1 was prepared.
上記の焼結原料６９６５０部（絶乾換算）に水を添加し、７４４９２部（水分量６．５％）に調整した。該焼結原料７４４９２部（水分量６．５％）、微粒子混合物１を２７２２部（水分量１０％）をドラムミキサーに投入し、回転速度２４ｍｉｎ−１で混合しながら、該組成物（焼結原料）に、製鉄用造粒処理剤として、予め不揮発分６．３％に調製した重量平均分子量６０００のポリアクリル酸ナトリウム水溶液３３６部を約１．５分間で噴霧（添加）した。焼結原料に対するポリアクリル酸ナトリウムの割合は０．０３％であった。噴霧後、分散剤が添加された上記の組成物（造粒処理用最終組成物）を更に回転速度２４ｍｉｎ−１で３分間攪拌することにより、造粒処理（擬似粒化）を行った。また、得られた擬似粒子を５０ｋｇスケールの鍋試験にて焼結を行ない、焼結鉱を得た。該試験の条件は、焼結鍋は直径３００ｍｍ、高さ６００ｍｍ、層厚５５０ｍｍとし、吸引負圧を９．８ｋＰａ（一定）とした。得られた焼結鉱の生産性を測定した。これらの結果をまとめて表２に示す。 Water was added to 69650 parts (absolute dry conversion) of the above-mentioned sintered raw material to adjust it to 74492 parts (water content 6.5%). 74492 parts (water content 6.5%) of the sintering raw material and 2722 parts (water content 10%) of the fine particle mixture 1 were put into a drum mixer and the composition (sintered) was mixed while mixing at a rotational speed of 24 min −1. The raw material) was sprayed (added) as a granulating agent for iron making in about 1.5 minutes with an aqueous solution of sodium polyacrylate having a weight average molecular weight of 6000, which was prepared in advance with a nonvolatile content of 6.3%. The ratio of sodium polyacrylate to the sintering raw material was 0.03%. After spraying, the above-mentioned composition to which the dispersant was added (final composition for granulation treatment) was further stirred for 3 minutes at a rotational speed of 24 min −1 to perform granulation treatment (pseudo granulation). The obtained pseudo particles were sintered in a 50 kg scale pan test to obtain a sintered ore. The test conditions were as follows: the sintering pot had a diameter of 300 mm, a height of 600 mm, a layer thickness of 550 mm, and a suction negative pressure of 9.8 kPa (constant). The productivity of the obtained sintered ore was measured. These results are summarized in Table 2.
実施例２
アイリッヒミキサーに、ダストと平均粒径７μｍの重質炭酸カルシウムを質量比で３：０．３（絶乾換算）になるように投入し、６０秒混合を行った。混合後の水分量が、１０％になるように水分調整することにより、微粒子混合物２を得た。一方、表１の配合Ｂに示す組成を有する焼結原料（製鉄用原料）を調製した。上記の原料６９７９０部（絶乾状態）に水を添加し、７４６４２部（水分量６．５％）に調製した。
配合Ａ７４４９２部（水分量６．５％）の代わりに、配合Ｂを７４６４２部（水分量６．５％）使用し、微粒子混合物１を２７２２部（水分量１０％）用いる代わりに、微粒子混合物２を２５６７部（水分量１０％）使用し、予め不揮発分６．３％に調製した重量平均分子量６０００のポリアクリル酸ナトリウム水溶液３３６部の代わりに、予め不揮発分６．２％に調製した重量平均分子量６０００のポリアクリル酸ナトリウム水溶液３４１部を使用する以外は実施例１と同様にして焼結鉱の生産性を測定した。これらの結果をまとめて表２に示す。
Example 2
Dust and heavy calcium carbonate with an average particle diameter of 7 μm were charged into an Eirich mixer so that the mass ratio was 3: 0.3 (absolutely dry conversion), and mixing was performed for 60 seconds. The fine particle mixture 2 was obtained by adjusting the water content so that the water content after mixing was 10%. On the other hand, a sintering raw material (iron-making raw material) having the composition shown in Formulation B of Table 1 was prepared. Water was added to 69790 parts (absolutely dry) of the above raw material to prepare 74642 parts (water content 6.5%).
Instead of using 74642 parts (water content 6.5%) of Formulation B instead of 74492 parts (water content 6.5%), the fine particle mixture 2 instead of using 2722 parts (water content 10%) of the fine particle mixture 1 2567 parts (water content 10%), and instead of 336 parts of an aqueous solution of sodium polyacrylate having a weight average molecular weight of 6000, which was previously prepared to have a nonvolatile content of 6.3%, a weight average which was previously prepared to have a nonvolatile content of 6.2% The productivity of sintered ore was measured in the same manner as in Example 1 except that 341 parts of an aqueous sodium polyacrylate solution having a molecular weight of 6000 was used. These results are summarized in Table 2.
実施例３
アイリッヒミキサーに、ダストと平均粒径１７μｍのフライアッシュを質量比で３：０．３（絶乾換算）になるように投入し６０秒混合を行った。混合後の水分量が１０％になるように水分調整することにより、微粒子混合物３を得た。一方、表１の配合Ｃに示す組成を有する焼結原料（製鉄用原料）を調製した。上記の原料６９８８０部（絶乾状態）に水を添加し、７４７３８部（水分量６．５％）に調製した。
該焼結原料の７４７３８部（水分量６．５％）と、微粒子混合物３の２５６７部（水分量１０％）とをドラムミキサーに投入し、回転速度２４ｍｉｎ−１で混合しながら、該組成物（焼結原料）に、製鉄用造粒処理剤として、予め不揮発分６．２％に調製した重量平均分子量６０００のポリアクリル酸ナトリウム水溶液３４１部を約１．５分間で噴霧（添加）した。焼結原料に対するポリアクリル酸ナトリウムの割合は０．０３％であった。噴霧後、分散剤が添加された上記の組成物（造粒処理用最終組成物）を更に回転速度２４ｍｉｎ−１で３分間攪拌することにより、造粒処理（擬似粒化）を行った。引き続き、実施例１と同様にして焼結鉱の生産性を測定した。これらの結果をまとめて表２に示す。
Example 3
Dust and fly ash having an average particle diameter of 17 μm were added to an Eirich mixer so that the mass ratio was 3: 0.3 (converted to absolute dryness) and mixed for 60 seconds. The fine particle mixture 3 was obtained by adjusting the water content so that the water content after mixing was 10%. On the other hand, a sintering raw material (raw material for iron making) having a composition shown in Formulation C of Table 1 was prepared. Water was added to 69880 parts (absolutely dried) of the above raw material to prepare 74738 parts (water content 6.5%).
74738 parts (water content 6.5%) of the sintering raw material and 2567 parts (water content 10%) of the fine particle mixture 3 were put into a drum mixer, and the composition was mixed while mixing at a rotational speed of 24 min −1 . 341 parts of a sodium polyacrylate aqueous solution having a weight average molecular weight of 6000, which was prepared in advance to a non-volatile content of 6.2%, was sprayed (added) to the (sintered raw material) in about 1.5 minutes as a granulating agent for iron making. The ratio of sodium polyacrylate to the sintering raw material was 0.03%. After spraying, the above-mentioned composition to which the dispersant was added (final composition for granulation treatment) was further stirred for 3 minutes at a rotational speed of 24 min −1 to perform granulation treatment (pseudo granulation). Subsequently, the productivity of the sintered ore was measured in the same manner as in Example 1. These results are summarized in Table 2.
実施例４
アイリッヒミキサーに、粉コークスと平均粒径７μｍの重質炭酸カルシウムを質量比で０．５：０．５（絶乾換算）になるように投入し６０秒混合を行った。混合後の水分量が、７％になるように水分調整することにより、微粒子混合物４を得た。一方、表１の配合Ｄに示す組成を有する焼結原料（製鉄用原料）を調製した。上記の原料７１４００部（絶乾状態）に水を添加し、７６３６４部（水分量６．５％）に調製した。
該焼結原料の７６３６４部（水分量６．５％）と、微粒子混合物４の７５３部（水分量７％）とをドラムミキサーに投入し、回転速度２４ｍｉｎ−１で混合しながら、該組成物（焼結原料）に、製鉄用造粒処理剤として、予め不揮発分４．８％に調整した重量平均分子量６０００のポリアクリル酸ナトリウム水溶液４３３部を約１．５分間で噴霧（添加）した。焼結原料に対するポリアクリル酸ナトリウムの割合は０．０３％であった。噴霧後、分散剤が添加された上記の組成物（造粒処理用最終組成物）を更に回転速度２４ｍｉｎ−１で３分間攪拌することにより、造粒処理（擬似粒化）を行った。引き続き、実施例１と同様にして焼結鉱の生産性を測定した。これらの結果をまとめて表２に示す。
Example 4
Powdered coke and heavy calcium carbonate having an average particle diameter of 7 μm were added to an Eirich mixer so that the mass ratio was 0.5: 0.5 (converted to absolute dryness) and mixed for 60 seconds. The fine particle mixture 4 was obtained by adjusting the water content so that the water content after mixing was 7%. On the other hand, a sintering raw material (raw material for iron making) having a composition shown in Formulation D of Table 1 was prepared. Water was added to 71400 parts (absolutely dry) of the above raw material to prepare 76364 parts (water content 6.5%).
76364 parts (water content 6.5%) of the sintered raw material and 753 parts (water content 7%) of the fine particle mixture 4 were put into a drum mixer, and the composition was mixed while mixing at a rotational speed of 24 min −1 . 433 parts of a sodium polyacrylate aqueous solution having a weight average molecular weight of 6000, which was previously adjusted to a non-volatile content of 4.8%, was sprayed (added) to the (sintered raw material) in about 1.5 minutes. The ratio of sodium polyacrylate to the sintering raw material was 0.03%. After spraying, the above-mentioned composition to which the dispersant was added (final composition for granulation treatment) was further stirred for 3 minutes at a rotational speed of 24 min −1 to perform granulation treatment (pseudo granulation). Subsequently, the productivity of the sintered ore was measured in the same manner as in Example 1. These results are summarized in Table 2.
実施例５
アイリッヒミキサーに、返し鉱と平均粒径７μｍの重質炭酸カルシウムを質量比で３：０．５（絶乾換算）になるように投入し６０秒混合を行った。混合後の水分量が、７％になるように水分調整することにより、微粒子混合物５を得た。一方、表１の配合Ｅに示す組成を有する焼結原料（製鉄用原料）を調製した。上記の原料Ｅ６９６５０部（絶乾状態）に水を添加し、７４４９２部（水分量６．５％）に調製した。
該焼結原料の７４４９２部（水分量６．５％）と、微粒子混合物５の２６３４部（水分量７％）とをドラムミキサーに投入し、回転速度２４ｍｉｎ−１で混合しながら、該組成物（焼結原料）に、製鉄用造粒処理剤として、予め不揮発分４．９％に調整した重量平均分子量６０００のポリアクリル酸ナトリウム水溶液４２５部を約１．５分間で噴霧（添加）した。焼結原料に対するポリアクリル酸ナトリウムの割合は０．０３％であった。噴霧後、分散剤が添加された上記の組成物（造粒処理用最終組成物）を更に回転速度２４ｍｉｎ−１で３分間攪拌することにより、造粒処理（擬似粒化）を行った。引き続き、実施例１と同様にして焼結鉱の生産性を測定した。これらの結果をまとめて表２に示す。
Example 5
Into an Eirich mixer, reverse ore and heavy calcium carbonate having an average particle diameter of 7 μm were added at a mass ratio of 3: 0.5 (conversion to absolute dryness) and mixed for 60 seconds. The fine particle mixture 5 was obtained by adjusting the water content so that the water content after mixing was 7%. On the other hand, a sintering raw material (raw material for iron making) having a composition shown in Formulation E of Table 1 was prepared. Water was added to the above raw material E69650 parts (absolutely dry state) to prepare 74492 parts (water content 6.5%).
74492 parts (water content 6.5%) of the sintering raw material and 2634 parts (water content 7%) of the fine particle mixture 5 were put into a drum mixer, and the composition was mixed while mixing at a rotational speed of 24 min −1 . 425 parts of a sodium polyacrylate aqueous solution having a weight average molecular weight of 6000, previously adjusted to a non-volatile content of 4.9%, was sprayed (added) to the (sintered raw material) for about 1.5 minutes. The ratio of sodium polyacrylate to the sintering raw material was 0.03%. After spraying, the above-mentioned composition to which the dispersant was added (final composition for granulation treatment) was further stirred for 3 minutes at a rotational speed of 24 min −1 to perform granulation treatment (pseudo granulation). Subsequently, the productivity of the sintered ore was measured in the same manner as in Example 1. These results are summarized in Table 2.
比較例１
表１の配合Ｆに示す組成を有する焼結原料（製鉄用原料）を調製した。上記の焼結原料Ｆの７１７５０部（絶乾状態）に水を添加し、７６７３８部（水分量６．５％）に調整した。該焼結原料７６７３８部（水分量６．５％）をドラムミキサーに投入し、回転速度２４ｍｉｎ−１で混合しながら、該組成物（焼結原料）に、予め不揮発分４．５％に調製した重量平均分子量６０００のポリアクリル酸ナトリウム水溶液４６２部を約１．５分間で噴霧（添加）した。焼結原料に対するポリアクリル酸ナトリウムの割合は０．０３％であった。噴霧後、分散剤が添加された上記の組成物（造粒処理用最終組成物）を更に回転速度２４ｍｉｎ−１で３分間攪拌することにより、造粒処理（擬似粒化）を行った。引き続き、実施例１と同様にして焼結鉱の生産性を測定した。これらの結果をまとめて表２に示す。
Comparative Example 1
Sintering raw materials (iron-making raw materials) having the composition shown in Formulation F of Table 1 were prepared. Water was added to 71750 parts (absolute dry state) of the above-mentioned sintered raw material F to adjust to 76738 parts (water content 6.5%). 76738 parts of the sintering raw material (water content 6.5%) is charged into a drum mixer and mixed at a rotational speed of 24 min −1 to prepare a non-volatile content of 4.5% in advance in the composition (sintering raw material). 462 parts of an aqueous sodium polyacrylate solution having a weight average molecular weight of 6000 was sprayed (added) in about 1.5 minutes. The ratio of sodium polyacrylate to the sintering raw material was 0.03%. After spraying, the above-mentioned composition to which the dispersant was added (final composition for granulation treatment) was further stirred for 3 minutes at a rotational speed of 24 min −1 to perform granulation treatment (pseudo granulation). Subsequently, the productivity of the sintered ore was measured in the same manner as in Example 1. These results are summarized in Table 2.
参考例１
アイリッヒミキサーに、ダストと平均粒径７μｍの重質炭酸カルシウムを質量比で０．１：０．５（絶乾換算）になるように投入し６０秒混合を行った。混合後の水分量が、１０％になるように水分調整することにより、微粒子混合物６を得た。一方、表１の配合Ｈに示す組成を有する焼結原料を調整した。
上記の焼結原料７１６８０部（絶乾換算）に水を添加し、７６６６３部（水分量６．５％）に調整した。該焼結原料７６６６３部（水分量６．５％）、微粒子混合物６を４６７部（水分量１０％）をドラムミキサーに投入し、回転速度２４ｍｉｎ−１で混合しながら、該組成物（焼結原料）に、製鉄用造粒処理剤として、予め不揮発分５．１％に調整した重量平均分子量６０００のポリアクリル酸ナトリウム水溶液４１９部を約１．５分間で噴霧（添加）した。焼結原料に対するポリアクリル酸ナトリウムの割合は０．０３％であった。噴霧後、分散剤が添加された上記の組成物を更に回転速度２４ｍｉｎ−１で３分間混合することにより造粒処理を行った。引き続き、実施例１と同様にして焼結鉱の生産性を測定した。この結果を表２に示す。
Reference example 1
Dust and heavy calcium carbonate having an average particle size of 7 μm were added to an Eirich mixer so that the mass ratio was 0.1: 0.5 (conversion to absolute dryness), and mixing was performed for 60 seconds. The fine particle mixture 6 was obtained by adjusting the water content so that the water content after mixing was 10%. On the other hand, the sintering raw material which has a composition shown to the mixing | blending H of Table 1 was adjusted.
Water was added to the above-mentioned sintered raw material 71680 parts (absolutely dry conversion) to adjust to 76663 parts (water content 6.5%). The composition (sintering) was performed while charging 76663 parts (water content 6.5%) and fine particle mixture 6 (467 parts) (water content 10%) into a drum mixer and mixing at a rotational speed of 24 min −1. 419 parts of an aqueous sodium polyacrylate solution having a weight average molecular weight of 6000, which was previously adjusted to a non-volatile content of 5.1%, was sprayed (added) to the raw material for about 1.5 minutes. The ratio of sodium polyacrylate to the sintering raw material was 0.03%. After spraying, the above-mentioned composition to which the dispersant was added was further granulated by mixing for 3 minutes at a rotational speed of 24 min −1 . Subsequently, the productivity of the sintered ore was measured in the same manner as in Example 1. The results are shown in Table 2.
表１及び表２において、「炭カル」とは、重質炭酸カルシウムである。表１における各値の単位は、重量部であり、「注１）」は、製鉄用焼結原料の一部と混合せずに添加したことを意味する。 In Tables 1 and 2, “charcoal cal” is heavy calcium carbonate. The unit of each value in Table 1 is parts by weight, and “Note 1” means that it was added without being mixed with a part of the sintering raw material for iron making.
実施例６
実施例５において、平均粒径７μｍの重質炭酸カルシウムに代えて、平均粒径１２μｍの重質炭酸カルシウムを使用し（得られた微粒子混合物を微粒子混合物７とする）、予め不揮発分４．９％に調整した重量平均分子量６０００のポリアクリル酸ナトリウム水溶液４２５部を代えて、予め不揮発分１５．２％に調整したβ−ナフタレンスルホン酸塩ホルマリン縮合物であるマイティ１５０（商品名；花王社製）水溶液４７６部を用いる他は実施例５と同様にして、焼結鉱の生産性を測定した。焼結原料に対するβ−ナフタレンスルホン酸ホルマリン縮合物の割合は０．１％であった。この結果を表３に示す。
Example 6
In Example 5, heavy calcium carbonate having an average particle diameter of 12 μm was used in place of heavy calcium carbonate having an average particle diameter of 7 μm (the obtained fine particle mixture is referred to as a fine particle mixture 7), and the nonvolatile content was 4.9 in advance. Instead of 425 parts of an aqueous sodium polyacrylate solution having a weight average molecular weight of 6000 adjusted to%, Mighty 150 (trade name; manufactured by Kao Corporation), a β-naphthalenesulfonate formalin condensate previously adjusted to a non-volatile content of 15.2% ) The productivity of sintered ore was measured in the same manner as in Example 5 except that 476 parts of the aqueous solution was used. The ratio of β-naphthalenesulfonic acid formalin condensate to the sintering raw material was 0.1%. The results are shown in Table 3.
参考例２
アイリッヒミキサーに、返し鉱と平均粒径１２μｍの重質炭酸カルシウムを質量比で１２．６：０．５（絶乾換算）になるように投入し６０秒混合を行った。混合後の水分量が、７％になるように水分調整することにより、微粒子混合物８を得た。一方、表１の配合Ｉに示す組成を有する焼結原料を調整した。
上記の焼結原料６２９２６部（絶乾換算）に水を添加し、６７３０１部（水分量６．５％）に調整した。該焼結原料６７３０１部（水分量６．５％）、微粒子混合物８を９８６５部（水分量７％）をドラムミキサーに投入し、回転速度２４ｍｉｎ−１で混合しながら、該組成物（焼結原料）に、製鉄用造粒処理剤として、予め不揮発分１１．２％に調整したβ−ナフタレンスルホン酸塩ホルマリン縮合物であるマイティ１５０（商品名；花王社製）水溶液６４４部を１．５分かけて噴霧した。焼結原料に対するβ−ナフタレンスルホン酸ホルマリン縮合物の割合は０．１％であった。噴霧後、分散剤が添加された上記の組成物を更に回転速度２４ｍｉｎ−１で３分間混合することにより造粒処理を行った。引き続き、実施例１と同様にして焼結鉱の生産性を測定した。この結果を表３に示す。
Reference example 2
Into the Eirich mixer, the reverse ore and heavy calcium carbonate having an average particle size of 12 μm were added in a mass ratio of 12.6: 0.5 (conversion to absolute dryness) and mixed for 60 seconds. The fine particle mixture 8 was obtained by adjusting the water content so that the water content after mixing was 7%. On the other hand, the sintering raw material which has a composition shown to the mixing | blending I of Table 1 was adjusted.
Water was added to 62926 parts of the above-mentioned sintered raw materials (absolutely dry conversion) to adjust 67301 parts (water content 6.5%). 67301 parts (water content 6.5%) of the sintering raw material and 9865 parts (water content 7%) of the fine particle mixture 8 were put into a drum mixer, and the composition (sintered) was mixed while mixing at a rotational speed of 24 min −1. As a granulating agent for iron making, 1.54 of an aqueous solution of 644 parts of Mighty 150 (trade name; manufactured by Kao Corporation), which is a β-naphthalene sulfonate formalin condensate previously adjusted to a non-volatile content of 11.2%. Sprayed over a minute. The ratio of β-naphthalenesulfonic acid formalin condensate to the sintering raw material was 0.1%. After spraying, the above-mentioned composition to which the dispersant was added was further granulated by mixing for 3 minutes at a rotational speed of 24 min −1 . Subsequently, the productivity of the sintered ore was measured in the same manner as in Example 1. The results are shown in Table 3.
実施例７
アイリッヒミキサーに、ダストと平均粒径７μｍの重質炭酸カルシウムを質量比で０．５：０．２（絶乾換算）になるように投入し６０秒混合を行った。混合後の水分量が、１０％になるように水分調整することにより、微粒子混合物９を得た。一方、表１の配合Ｇに示す組成を有する焼結原料を調整した。
上記の焼結原料６９８６０部（絶乾換算）に水を添加し、７４７１７部（水分量６．５％）に調整した。該焼結原料７４７１７部（水分量６．５％）、微粒子混合物９を２４８９部（水分量１０％）をドラムミキサーに投入し、回転速度２４ｍｉｎ−１で混合しながら、該組成物（焼結原料）に、製鉄用造粒処理剤として、予め不揮発分４．３％に調整した重量平均分子量６０００のポリアクリル酸ナトリウム水溶液３３６部を約１．５分間で噴霧（添加）した。焼結原料に対するポリアクリル酸ナトリウムの割合は０．０２％であった。噴霧後、分散剤が添加された上記の組成物を更に回転速度２４ｍｉｎ−１で３分間混合することにより造粒処理を行った。引き続き、実施例１と同様にして焼結鉱の生産性を測定した。この結果を表３に示す。
Example 7
Dust and heavy calcium carbonate having an average particle size of 7 μm were charged into an Eirich mixer so that the mass ratio was 0.5: 0.2 (converted to absolute dryness) and mixed for 60 seconds. The fine particle mixture 9 was obtained by adjusting the water content so that the water content after mixing was 10%. On the other hand, the sintering raw material which has a composition shown to the mixing | blending G of Table 1 was adjusted.
Water was added to 69860 parts (absolute dry conversion) of the above-mentioned sintered raw material to adjust it to 74717 parts (water content 6.5%). The composition (sintered) was charged with 74717 parts of the sintering raw material (water content 6.5%) and 2489 parts of the fine particle mixture 9 (water content 10%) in a drum mixer and mixed at a rotational speed of 24 min −1. The raw material) was sprayed (added) as an iron-making granulation agent in about 1.5 minutes with a sodium polyacrylate aqueous solution having a weight average molecular weight of 6000, which was previously adjusted to a non-volatile content of 4.3%. The ratio of sodium polyacrylate to the sintering raw material was 0.02%. After spraying, the above-mentioned composition to which the dispersant was added was further granulated by mixing for 3 minutes at a rotational speed of 24 min −1 . Subsequently, the productivity of the sintered ore was measured in the same manner as in Example 1. The results are shown in Table 3.
実施例８
国際公開第０２／０６６６８８号に記載の方法で、重量平均分子量３３０００のアクリル酸ナトリウム／アクリル酸メチル共重合体（アクリル酸ナトリウムの組成比が７８．７ｍｏｌ％、共重合体１とする）を得た。実施例１において、予め不揮発分４．８％に調整した重量平均分子量６０００のポリアクリル酸ナトリウム水溶液１８１部にかえて、予め６．３％に調整した重量平均分子量６０００のポリアクリル酸ナトリウム水溶液３３６部に代えて、予め６．３％に調整した上記共重合体１の水溶液３３６部を用いる他は、実施例１と同様にして、焼結鉱の生産性を測定した。この結果を表３に示す。
Example 8
By the method described in WO 02/066688, a sodium acrylate / methyl acrylate copolymer having a weight average molecular weight of 33000 (composition ratio of sodium acrylate is 78.7 mol%, copolymer 1) is obtained. It was. In Example 1, the sodium polyacrylate aqueous solution 336 having a weight average molecular weight of 6000 previously adjusted to 6.3% was replaced with 181 parts of the sodium polyacrylate aqueous solution having a weight average molecular weight of 6000 previously adjusted to a non-volatile content of 4.8%. The productivity of the sintered ore was measured in the same manner as in Example 1 except that 336 parts of the aqueous solution of the copolymer 1 previously adjusted to 6.3% was used instead of the parts. The results are shown in Table 3.
実施例９
アイリッヒミキサーに、ダストと平均粒径７μｍの重質炭酸カルシウムを質量比で３：３（絶乾換算）になるように投入し、６０秒混合を行った。混合後の水分量が、７％になるように水分調整することにより、微粒子混合物１０を得た。一方、表１の配合Ｊに示す組成を有する焼結原料（製鉄用原料）を調整した。
上記の焼結原料６７９００部（絶乾換算）に水を添加し、７２６２０部（水分量６．５％）に調整した。該焼結原料７２６２０部（水分量６．５％）、微粒子混合物１０を４５１６部（水分量７％）をドラムミキサーに投入し、回転速度２４ｍｉｎ−１で混合しながら、該組成物（焼結原料）に、製鉄用造粒処理剤として、予め不揮発分６．３％に調整した重量平均分子量６０００のポリアクリル酸ナトリウム水溶液３３６部を約１．５分間で噴霧（添加）した。焼結原料に対するポリアクリル酸ナトリウムの割合は０．０３％であった。噴霧後、分散剤が添加された上記の組成物（造粒処理用最終組成物）を更に回転速度２４ｍｉｎ−１で３分間混合することにより造粒処理（擬似粒化）を行った。その後、実施例１と同様にして生産率を測定した。この結果を表２に示す。
Example 9
Dust and heavy calcium carbonate having an average particle size of 7 μm were charged into an Eirich mixer so that the mass ratio was 3: 3 (absolute dry conversion), and mixing was performed for 60 seconds. The fine particle mixture 10 was obtained by adjusting the water content so that the water content after mixing was 7%. On the other hand, the sintering raw material (raw material for iron making) having the composition shown in Formulation J of Table 1 was prepared.
Water was added to 67900 parts (absolute dry conversion) of the above-mentioned sintered raw material to adjust to 72620 parts (water content 6.5%). 72620 parts (water content 6.5%) of the sintering raw material and 4516 parts (water content 7%) of the fine particle mixture 10 were put into a drum mixer, and the composition (sintered) was mixed while mixing at a rotational speed of 24 min −1. The raw material) was sprayed (added) as a granulating agent for iron making in about 1.5 minutes with 336 parts of a sodium polyacrylate aqueous solution having a weight average molecular weight of 6000, which had been adjusted to 6.3% nonvolatile content in advance. The ratio of sodium polyacrylate to the sintering raw material was 0.03%. After spraying, the above-mentioned composition to which the dispersant was added (final composition for granulation treatment) was further mixed for 3 minutes at a rotational speed of 24 min −1 to perform granulation treatment (pseudo granulation). Thereafter, the production rate was measured in the same manner as in Example 1. The results are shown in Table 2.
（高分子化合物水溶液における不揮発分の測定方法）
予め秤量したアルミ皿に５ｇの高分子化合物水溶液をサンプリングし、該水溶液を皿上で薄く広げた後、窒素雰囲気下１３０℃で３時間乾燥した。吸湿しないようにデシケータ内で室温まで冷却した後、秤量することにより、不揮発分を算出した。
(Measurement method of nonvolatile content in polymer compound aqueous solution)
5 g of the polymer compound aqueous solution was sampled on a pre-weighed aluminum dish, the aqueous solution was spread thinly on the dish, and then dried at 130 ° C. for 3 hours in a nitrogen atmosphere. After cooling to room temperature in a desiccator so as not to absorb moisture, the nonvolatile content was calculated by weighing.
Claims (6)
該製鉄用焼結原料の造粒処理方法は、該微粒子を予め、製鉄用焼結原料における微粒子を除いた量の０．３〜１０質量％と混合処理する工程の後に、該工程により得られる混合物を残りの製鉄用焼結原料と混合して造粒処理する工程を含んでなり、
該平均粒径が２００μｍ以下の微粒子は、炭酸カルシウム、フライアッシュ、カオリンクレー、シリカ、タルク、ベントナイト、シリカフューム及び無水石膏からなる群より選択される少なくとも一種のものである
ことを特徴とする製鉄用焼結原料の造粒処理方法。 When granulating the sintered raw material for iron making, a method for granulating the sintered raw material for iron making using fine particles having an average particle size of 200 μm or less,
The method of granulating the sintered material for iron making is obtained by the step after the step of mixing the fine particles with 0.3 to 10% by mass of the amount excluding the fine particles in the sintered material for iron making in advance . Ri Na include a step of granulation process mixing the mixture with the remaining iron for sintering the raw material,
The fine particles having an average particle size of 200 μm or less are at least one selected from the group consisting of calcium carbonate, fly ash, kaolin clay, silica, talc, bentonite, silica fume, and anhydrous gypsum. A method for granulating a sintered raw material for iron making.
該製鉄用副原料は、鉄鉱石及び／又は燃料と共に焼結される製鉄用焼結原料であって、石灰石、ドロマイト、蛇紋岩、珪石、スラグ、ダスト及び／又は返し鉱を含むものである
ことを特徴とする請求項１記載の製鉄用焼結原料の造粒処理方法。 Wherein 0.3 to 10% by weight of iron for the sintering raw material state, and are intended to include adjuncts and / or fuel for iron as essential,
The iron-making auxiliary material is a iron-making sintering material that is sintered together with iron ore and / or fuel, and includes limestone, dolomite, serpentine, silica stone, slag, dust, and / or return ore <br / The method for granulating a sintered raw material for iron making according to claim 1.
ことを特徴とする請求項１又は２記載の製鉄用焼結原料の造粒処理方法。 The method for granulating a sintered raw material for iron making according to claim 1 or 2, wherein the addition amount of the fine particles is 0.05 to 30% by mass with respect to the sintered raw material for iron making.
ことを特徴とする請求項１、２又は３記載の製鉄用焼結原料の造粒処理方法。 The granulation step is a carboxyl group, a sulfonic acid group and according to claim 1, characterized in that it is carried out in the presence of a polymer compound having at least one group selected from the group consisting of salts 4. A method for granulating a sintering raw material for iron making according to 3 .
ことを特徴とする請求項４記載の製鉄用焼結原料の造粒処理方法。 The addition amount of the polymer compound is 0.001 to 1% by mass with respect to all the iron-making sintering raw materials, and the addition amount of the fine particles is 0.05 to 30 masses with respect to all the iron-making sintering raw materials. The method for granulating a sintered raw material for iron making according to claim 4, wherein
ことを特徴とする請求項４又は５記載の製鉄用焼結原料の造粒処理方法。 The polymer compound polymerizes a monomer composition containing 10 mol% or more of a monomer having a carboxyl group and / or a salt thereof with respect to 100 mol% of the total monomer composition. granulation processing method for steelmaking sintered material according to claim 4 or 5, wherein the composed Te.
Priority Applications (1)
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN104232883A (en) * | 2013-06-19 | 2014-12-24 | 宝山钢铁股份有限公司 | Mineral material usage method for increasing usage amount and production rate of sintered iron concentrate |
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| JP4772290B2 (en) * | 2004-03-26 | 2011-09-14 | Ｊｆｅスチール株式会社 | Method for producing sintered ore and sintered ore |
| JP5066352B2 (en) * | 2006-08-30 | 2012-11-07 | 株式会社日本触媒 | Granulating agent for iron making |
| DE102009023928A1 (en) * | 2009-06-04 | 2010-12-09 | Rheinkalk Gmbh | Process for producing an agglomerate |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN104232883A (en) * | 2013-06-19 | 2014-12-24 | 宝山钢铁股份有限公司 | Mineral material usage method for increasing usage amount and production rate of sintered iron concentrate |
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