JPH08198647A - Production of cement clinker - Google Patents

Production of cement clinker

Info

Publication number
JPH08198647A
JPH08198647A JP7005832A JP583295A JPH08198647A JP H08198647 A JPH08198647 A JP H08198647A JP 7005832 A JP7005832 A JP 7005832A JP 583295 A JP583295 A JP 583295A JP H08198647 A JPH08198647 A JP H08198647A
Authority
JP
Japan
Prior art keywords
slag
cement
cement clinker
raw material
weight
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.)
Granted
Application number
JP7005832A
Other languages
Japanese (ja)
Other versions
JP3554389B2 (en
Inventor
Junji Igawa
順司 井川
Motohiro Muta
元弘 牟田
Masayoshi Yokoo
正義 横尾
Shigemori Tanaka
茂守 田中
Ryoichi Oyamada
良一 小山田
Kazuo Sadatsune
一夫 定常
Toyoshige Ogura
豊茂 小椋
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Nippon Steel Corp
Nippon Steel Chemical and Materials Co Ltd
Original Assignee
Nippon Steel Corp
Nippon Steel Chemical Co Ltd
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by Nippon Steel Corp, Nippon Steel Chemical Co Ltd filed Critical Nippon Steel Corp
Priority to JP00583295A priority Critical patent/JP3554389B2/en
Publication of JPH08198647A publication Critical patent/JPH08198647A/en
Application granted granted Critical
Publication of JP3554389B2 publication Critical patent/JP3554389B2/en
Anticipated expiration legal-status Critical
Expired - Lifetime legal-status Critical Current

Links

Classifications

    • CCHEMISTRY; METALLURGY
    • C04CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04BLIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B7/00Hydraulic cements
    • C04B7/36Manufacture of hydraulic cements in general
    • C04B7/38Preparing or treating the raw materials individually or as batches, e.g. mixing with fuel
    • CCHEMISTRY; METALLURGY
    • C04CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04BLIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B2111/00Mortars, concrete or artificial stone or mixtures to prepare them, characterised by specific function, property or use
    • C04B2111/10Compositions or ingredients thereof characterised by the absence or the very low content of a specific material
    • CCHEMISTRY; METALLURGY
    • C04CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04BLIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B2111/00Mortars, concrete or artificial stone or mixtures to prepare them, characterised by specific function, property or use
    • C04B2111/10Compositions or ingredients thereof characterised by the absence or the very low content of a specific material
    • C04B2111/1062Halogen free or very low halogen-content materials
    • YGENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02PCLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P40/00Technologies relating to the processing of minerals
    • Y02P40/10Production of cement, e.g. improving or optimising the production methods; Cement grinding

Abstract

PURPOSE: To effectively utilize a dephosphorized/desulfurized slag which have been difficult conventionally to use as a part of a cement starting material, etc., and have been disposed. CONSTITUTION: 2-5 pts.wt. dephosphorized/desulfurized slag regulated to <=1000ppm in a chlorine content incorporated in the slug and to <=15wt.% in a granular iron amount by controlling a cooling water for a molten slag generating at desulfurizing stage and dephosphorizing stage as a molten iron pretreatment and a magnetic separation/removal treating condition, is compounded with 140 pts.wt. cement clinker starting material and burned. In this way, the dephosphorized and desulfurized slag can be used as a part of the cement clinker starting material hardly causing influence on compression strength and coagulation of the cement.

Description

【発明の詳細な説明】Detailed Description of the Invention

【0001】[0001]

【産業上の利用分野】本発明は、脱燐硫スラグをセメン
トクリンカーの原料として利用するセメントクリンカー
の製造方法に関するものである。
BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for producing cement clinker using dephosphorization slag as a raw material for cement clinker.

【0002】[0002]

【従来の技術】高炉操業時に発生する鉄鋼スラグは、そ
の発生工程によって、徐冷又は急冷処理した高炉スラグ
と、転炉スラグを主とする製鋼スラグが知られている。
これらの発生量は、製鉄業の進展に伴い膨大なものとな
っており、資源化を目指した種々の検討が報告されてい
る。この内高炉スラグの組成は、シリカ約31〜35
%、アルミナ約14〜20%、酸化カルシウム約38〜
42%、酸化第二鉄約0.2〜0.8%程度でありこれ
らは、セメントクリンカーの主成分組成物(CaO、S
iO2、Al23、Fe23等)に類似していることか
ら、現在発生量の約60%程度がセメントクリンカー原
料の一部として又高炉セメント用として、或いは又その
他のセメント混和材として使用されている。また徐冷処
理した高炉スラグは路盤材や土壌改良材としても利用さ
れている。又熔融高炉スラグに遠心力を作用させて製綿
処理しロックウール断熱材を得ることにも利用されてい
る。
2. Description of the Related Art As steel slag generated during operation of a blast furnace, blast furnace slag that is gradually cooled or rapidly cooled and steel-making slag mainly composed of converter slag are known depending on the generation process.
The amount of these generations has become enormous with the progress of the iron manufacturing industry, and various studies aimed at resource recovery have been reported. The composition of this inner blast furnace slag is about 31-35 silica.
%, Alumina about 14 to 20%, calcium oxide about 38 to
42%, about 0.2-0.8% ferric oxide, which are the main components of the cement clinker (CaO, S
Since the iO 2, similar to the Al 2 O 3, Fe 2 O 3 , etc.), or as a blast furnace cement, or alternatively other cement about about 60% of the current generation amount as part of the cement clinker raw material It is used as a material. The slowly cooled blast furnace slag is also used as a roadbed material and soil improvement material. It is also used to obtain a rock wool heat insulating material by subjecting the molten blast furnace slag to centrifugal force to make cotton.

【0003】また、転炉スラグを主とする製鋼スラグ
は、その発生工程によって、熔銑から珪素、燐、硫黄等
の不純物を除去する予備処理工程において発生する脱珪
スラグ、脱燐硫スラグと、転炉工程で発生する転炉スラ
グとに大別できる。製鋼スラグの主成分自体は、含有率
は異なるが高炉スラグと同じようにセメントクリンカー
の主成分組成物と類似しているが、その他に塩素や燐、
フッ素、硫黄等の不純物や、粒鉄等を大量に含んでいる
ためにその有効利用が限られている。
Further, steelmaking slag mainly composed of converter slag includes desiliconization slag and dephosphorization slag produced in a pretreatment process for removing impurities such as silicon, phosphorus and sulfur from hot metal in the generation process. , And converter slag generated in the converter process. The main component of steelmaking slag itself is similar to the main component composition of cement clinker like blast furnace slag, although the content ratio is different, but in addition, chlorine and phosphorus,
Since it contains a large amount of impurities such as fluorine and sulfur and granular iron, its effective use is limited.

【0004】現在は殆どが路盤材や土壌改良材等への用
途が挙げられるが、粒度構成や安定性の点から制約を受
けるため、利用できるスラグの種類が限定され、その処
理量はセメントのみの使用量として約5%程度に留まっ
ている。特に製鋼スラグの中でも熔銑予備処理の脱S、
脱P工程において発生し分離回収される脱燐硫スラグの
如き礫分が極端に少なく、風化、膨張性が著しいものに
ついては、未だ適当な処理方法が見出されておらず、そ
の殆どが埋立等の廃棄処分に付されているに過ぎない。
特に近年、「リサイクル法」によるスラグの副産物指定
により、鉄鋼スラグの資源化の動きは多様化し、これの
安価な有効活用方法が今後益々求められて来ている。
At present, most of them are used as roadbed materials, soil improvement materials, etc., but the types of slag that can be used are limited due to restrictions in terms of particle size composition and stability, and the treatment amount is only cement. The amount used is about 5%. Especially in steelmaking slag, S removal of hot metal pretreatment,
For dephosphorization slag, which is generated and separated and recovered in the de-P process, and which has extremely small amount of gravel and is highly weathered and expandable, an appropriate treatment method has not yet been found and most of it is landfilled. It is only attached to the disposal such as.
Particularly in recent years, the slag by-product designation according to the "recycling law" has diversified the movement of resource utilization of steel slag, and there is an increasing demand for cheap and effective utilization of the slag.

【0005】ところで脱燐硫スラグの利用法として、特
開昭61−275148号公報には、溶融状の脱燐硫ス
ラグに珪酸塩質の改質材を添加し窒素や空気等をバブリ
ングした後、冷却し破砕して磁選処理し、非磁着物をセ
メント原料や路盤材とする技術が開示されている。また
特開平2−267142号公報には、フライアッシュと
製鋼スラグを配合したセメントクリンカー原料を焼成し
て、灰緑色系の色彩を帯びたセメントクリンカーを製造
する方法が記載されているが、脱燐硫スラグを使用する
ことの問題点やその解決方法に関しては特に開示されて
いない。
As a method of utilizing dephosphorization slag, Japanese Patent Laid-Open No. 61-275148 discloses a method in which a siliceous modifier is added to molten dephosphorization slag and nitrogen or air is bubbled. There is disclosed a technology of cooling, crushing and magnetically separating the non-magnetically adhering material into a cement raw material or a roadbed material. Further, JP-A-2-267142 discloses a method for producing a cement clinker having a grayish green color by firing a cement clinker raw material containing fly ash and steelmaking slag. There is no particular disclosure regarding the problems of using sulfur slag and the solution thereof.

【0006】[0006]

【発明が解決しようとする課題】前記した特開昭61−
275148に開示されている脱燐硫スラグの処理方法
は、Na、Cl、及びPを揮化して除去する効果に優れ
ているが、改質材やバブリング設備費用及び加熱熔融エ
ネルギーの補充を要する点などでコストアップが避けら
れず実用化が困難である。従って、本発明の目的は、従
来セメント原料等への利用が困難であり、廃棄処分され
ていた脱燐硫スラグを、コストアップを図ることなく簡
単な調整処理だけによってセメントクリンカー原料の一
部として有効利用する方法を提供することにある。
DISCLOSURE OF THE INVENTION Problems to be Solved by the Invention
The method for treating dephosphorization slag disclosed in 275148 is excellent in the effect of volatilizing and removing Na, Cl, and P, but it requires the cost of a modifier and bubbling equipment and the supplementation of heating and melting energy. As a result, cost increase is unavoidable and practical application is difficult. Therefore, the object of the present invention is difficult to use as a cement raw material conventionally, as a part of the cement clinker raw material, by simply adjusting the dephosphorization slag that has been disposed of, without increasing the cost. It is to provide a method for effective use.

【0007】[0007]

【課題を解決するための手段】本発明者等は、上記事情
に鑑み鋭意研究を行った結果、脱燐硫スラグの塩素含有
量、粒鉄量を特定の数値以下になるよう調整することに
より、セメントクリンカー原料の一部として利用可能と
なること、更には該セメントクリンカーを用いたセメン
トの品質が従来品に比して同等以上のものであることを
見出し、本発明を完成した。すなわち、本発明は、熔銑
予備処理の脱S、脱P工程において発生する熔融スラグ
に対する冷却水と磁選除去処理条件の調整によって、ス
ラグに含まれる塩素分を1000ppm以下、粒鉄量を
15重量%以下に調節した脱燐硫スラグを、セメントク
リンカー原料に配合し、焼成することを特徴とするセメ
ントクリンカーの製造方法である。また、熔融スラグに
対する冷却水として塩素濃度の低い淡水を使用するとと
もに、粉砕と磁選除去処理を複数回繰り返すことによっ
てスラグに含まれる塩素分を1000ppm以下、粒鉄
量を15重量%以下に調整することを特徴とする上記セ
メントクリンカーの製造方法である。
Means for Solving the Problems The inventors of the present invention have conducted extensive studies in view of the above circumstances, and as a result, adjusted the chlorine content and the granular iron content of the dephosphorization slag to be below specific values. The present invention has been completed by finding that it can be used as a part of a raw material for cement clinker, and that the quality of cement using the cement clinker is equal to or higher than that of conventional products. That is, according to the present invention, the chlorine content in the slag is 1000 ppm or less and the amount of granular iron is 15% by weight by adjusting the cooling water and the magnetic separation removal treatment condition for the molten slag generated in the de-S and de-P steps of the hot metal pretreatment. % Of dephosphorization slag is mixed with a cement clinker raw material, and the mixture is fired. Further, while using fresh water having a low chlorine concentration as cooling water for the molten slag, the chlorine content contained in the slag is adjusted to 1000 ppm or less and the amount of granular iron is adjusted to 15% by weight or less by repeating grinding and magnetic separation removal treatment several times. The method for producing the cement clinker is characterized by the above.

【0008】以下、本発明を詳細に説明する。本発明で
言う脱燐硫スラグとは、高炉で発生する熔銑の予備処理
工程において、熔銑に生石灰、フッ化カルシウム等の添
加剤を使用して燐(P)、硫黄(S)等の不純物を取り
除く際に発生する製鋼スラグである。この脱燐硫スラグ
の組成は、シリカ約5〜20%、アルミナ約4〜15
%、酸化カルシウム約40〜60%、酸化第二鉄約10
〜25%であり、これらはセメントクリンカーの主成分
(CaO、SiO2、Al23、Fe23)に類似してい
るが、これら以外にも塩素をClとして約1500〜1
0000ppm、粒鉄約15〜30重量%、五酸化燐約
1〜5%、フッ素約1〜5%等の他酸化マグネシウム、
酸化マンガン、酸化チタン、硫黄等の微量成分も含有す
る。なお、本明細書において%及びppmは特にこだわ
らない限り、重量%、重量ppmを意味する。
The present invention will be described in detail below. The dephosphorization slag referred to in the present invention means that phosphorus (P), sulfur (S) and the like are added to the hot metal in the pretreatment step of hot metal generated in a blast furnace by using additives such as quick lime and calcium fluoride. Steelmaking slag generated when removing impurities. The composition of this dephosphorization slag is about 5 to 20% silica and about 4 to 15 alumina.
%, Calcium oxide about 40-60%, ferric oxide about 10
Was 25%, these are the cement clinker principal components (CaO, SiO 2, Al 2 O 3, Fe 2 O 3) is similar to, but approximately chlorine besides those as Cl from 1,500 to 1
Other magnesium oxide such as 0000 ppm, granular iron about 15 to 30% by weight, phosphorus pentoxide about 1 to 5%, fluorine about 1 to 5%,
It also contains trace components such as manganese oxide, titanium oxide, and sulfur. In this specification,% and ppm mean% by weight and ppm by weight, unless otherwise specified.

【0009】上記の熔銑の脱S、脱P予備処理工程で
は、熔銑に添加剤として生石灰、フッ化カルシウム等を
添加し、これらに熔銑中の燐、硫黄を結合させ、脱燐硫
スラグとして分離回収する。通常はこれを水及び空気で
冷却した後、粉砕して残存する粒鉄は大型のリフティン
グマグネットにより磁選除去して回収している。本発明
者等が分析調査した結果によると、かかる脱燐硫スラグ
の塩素の含有量は、主として冷却に用いる工業用水中の
塩素濃度に左右されており、通常約1500〜1000
0ppmにも達していることが判明した。
In the above-described hot metal de-S and de-P pretreatment process, quicklime, calcium fluoride, etc. are added to the hot metal as additives, and phosphorus and sulfur in the hot metal are bonded to these, and dephosphorization is performed. Separated and collected as slag. Usually, this is cooled with water and air, and the granular iron remaining after pulverization is magnetically removed by a large lifting magnet and collected. According to the results of the analysis conducted by the present inventors, the chlorine content of the dephosphorization slag depends mainly on the chlorine concentration in industrial water used for cooling, and is usually about 1500 to 1000.
It was found to have reached 0 ppm.

【0010】また、脱燐硫スラグの粒鉄の含有量は、粉
砕し大型のリフテイングマグネットによる磁選除去処理
を行った後でも約20〜25重量%程度残存しているこ
とも明らかになった。一方、セメントクリンカー中に五
酸化燐やフッ素等が過剰に含まれていると、セメントの
凝結遅延、強度低下を引き起こすことが知られている。
従って、これらの成分を多く含有する脱燐硫スラグは、
セメントクリンカー原料として好ましいものではなく2
%以上の使用はできないものとされて来た。
Further, it has been revealed that the content of granular iron in the dephosphorization slag remains about 20 to 25% by weight even after pulverization and magnetic separation removal treatment by a large lifting magnet. . On the other hand, it is known that excessive inclusion of phosphorus pentoxide, fluorine, etc. in the cement clinker causes a delay in setting of cement and a decrease in strength.
Therefore, the dephosphorization slag containing many of these components is
Not a preferred cement clinker raw material 2
It has been said that it cannot be used in excess of%.

【0011】そこで、本発明では、上記の熔融スラグの
冷却に使用する工業用水として、淡水の如き塩素を含ま
ないか、濃度の低いもの好ましくは1000ppm以
下、より好ましくは500ppm以下のものを選定する
ことによって、脱燐硫スラグの塩素分を1000ppm
以下に調整するものである。これを超える含有量では、
セメント製造プロセス内、とりわけ、キルン内等で塩素
が遊離して循環、濃縮し、クリンカーに含まれるアルカ
リと塩を形成する。これが増加すると焼成原料を凝集さ
せ、閉塞等の原因となる。
Therefore, in the present invention, as the industrial water used for cooling the above-mentioned molten slag, one such as fresh water that does not contain chlorine or has a low concentration is preferably 1000 ppm or less, more preferably 500 ppm or less. As a result, the chlorine content of the dephosphorization slag is 1000 ppm.
It is adjusted as follows. In the content exceeding this,
Chlorine is liberated in the cement production process, especially in the kiln, and circulates and concentrates to form a salt with the alkali contained in the clinker. If this amount increases, the calcining raw material is agglomerated to cause clogging or the like.

【0012】また、粒鉄の磁選除去処理においては、ク
ラッシャーで粉砕し大型のリフテイングマグネットによ
る通常の磁選除去後の脱燐硫スラグを、更にクラッシャ
ーで粉砕し、磁選除去処理する工程を数回繰り返す調整
処理によって、粒鉄量を15重量%以下にまで低減する
ことができる。粒鉄が15重量%を超えて含有されてい
ると、セメント原料として使用した場合、装置が損傷す
る等操業に支障をきたすので好ましくない。そして、こ
のように塩素分や粒鉄量を制限すると、これをセメント
クリンカー原料として得られた以外の圧縮強度等も向上
するという意外な効果も認められる。
Further, in the magnetic separation removal treatment of granular iron, the dephosphorization slag that has been crushed with a crusher and subjected to normal magnetic separation removal with a large lifting magnet is further crushed with a crusher and the magnetic separation removal treatment is performed several times. By repeating the adjustment process, the amount of granular iron can be reduced to 15% by weight or less. If the granular iron content exceeds 15% by weight, when it is used as a cement raw material, the equipment is damaged and the operation is hindered. When the chlorine content and the amount of granular iron are limited in this way, a surprising effect that the compression strength and the like other than those obtained as a cement clinker raw material is also improved is recognized.

【0013】このようにして得られた脱燐硫スラグを、
セメントクリンカー原料の一部とし、他のクリンカー原
料と混合し、粉砕、焼成する。クリンカー原料として
は、通常石灰石等の酸化カルシウム原料、粘土、軟珪
石、水砕スラグ等のシリカ、アルミナ原料、及びパイラ
イトシンダー、銅がらみ、焼鉱、転炉スラグ、平炉スラ
グ等の酸化第二鉄原料等を適宜組み合わせ配合調整した
ものである。脱燐硫スラグの、かかるセメントクリンカ
ー原料への配合量としては、セメントクリンカー原料1
40重量部中に2〜5重量部、好ましくは2〜4重量部
の範囲内である。なお、セメントクリンカー原料140
重量部は、得られるセメントクリンカー100重量部に
ほぼ相当する。かかる程度に限定することによって特に
焼成して得られるセメントクリンカー中に含有される五
酸化燐やフッ素は0.2%以下となりセメントの凝結遅
延、強度低下を引き起こすことがなく、むしろ強度につ
いては向上する傾向がみられるので好ましい。脱燐硫ス
ラグの配合量が5重量部を超えると、セメントクリンカ
ー中の五酸化燐、フッ素の含有量が過剰となり、モルタ
ル圧縮強さ比や凝結時間が延びる等セメントの品質が悪
化するので好ましくない。
The dephosphorization slag thus obtained is
It is used as a part of cement clinker raw material, mixed with other clinker raw material, crushed and fired. As clinker raw materials, calcium oxide raw materials such as limestone, silica, silica such as clay, soft silica, and granulated slag, alumina raw materials, and ferric oxide such as pyrite cinder, copper slag, calciner, converter slag, open hearth slag, etc. The raw materials and the like are appropriately combined and adjusted. The amount of dephosphorized slag to be added to the cement clinker raw material is cement clinker raw material 1
It is in the range of 2 to 5 parts by weight, preferably 2 to 4 parts by weight in 40 parts by weight. The cement clinker raw material 140
The parts by weight correspond approximately to 100 parts by weight of the obtained cement clinker. By limiting the content to such a range, the phosphorus pentoxide and fluorine contained in the cement clinker obtained by firing will be 0.2% or less, and the setting of cement will not be delayed and the strength will not decrease, but rather the strength will improve. It is preferable because it tends to occur. If the content of dephosphorized slag exceeds 5 parts by weight, the content of phosphorus pentoxide and fluorine in the cement clinker becomes excessive, and the quality of the cement deteriorates, such as the mortar compressive strength ratio and setting time, which is preferable. Absent.

【0014】本発明で脱燐硫スラグを配合したセメント
クリンカー原料は、通常のロータリーキルン、電気炉の
ような焼成窯を用いて1450℃程度で焼成し、空気で
急冷してセメントクリンカーとする。このセメントクリ
ンカーは、適宜石膏を添加して、ブレーン比表面積が3
500〜6000cm2/g程度に粉砕してポルトランド
セメントとして利用出来る。或いはこのポルトランドセ
メントに急冷高炉スラグを粉砕した微粉末を適宜配合し
て各種高炉セメントとして利用することも出来る。従っ
て、本発明で得られるセメントクリンカーを用いたセメ
ントの品質は従来品に比して同等以上のものである。
The cement clinker raw material in which the dephosphorization slag is blended according to the present invention is fired at about 1450 ° C. using a firing kiln such as an ordinary rotary kiln and an electric furnace, and rapidly cooled with air to obtain a cement clinker. This cement clinker has a Blaine specific surface area of 3 by appropriately adding gypsum.
It can be used as Portland cement by crushing to about 500 to 6000 cm 2 / g. Alternatively, fine powder obtained by crushing rapidly cooled blast furnace slag may be appropriately mixed with this Portland cement and used as various blast furnace cements. Therefore, the quality of the cement using the cement clinker obtained in the present invention is equal to or higher than that of the conventional cement.

【0015】[0015]

【実施例】以下、実施例により本発明を具体的に説明す
るが、本発明はこれら実施例により何ら限定されるもの
ではない。脱燐硫スラグの製造は、以下のようにして行
った。熔銑予備処理の脱S、脱P工程において発生する
熔融状の脱燐硫スラグが入っているノロ鍋の中に塩素濃
度が100ppmの淡水を注入して水冷した。これを乾
燥し、リフテイングマグネットを用いた通常の磁選除去
処理によって粒径100mm以上の比較的大型の粒鉄を
除去後の粒鉄含有量は25重量%であった。このものを
クラッシャーで粉砕し、ベルトコンベアー移送ライン上
の固定磁石による磁選除去工程を3回繰り返し行った。
得られた脱燐硫スラグの組成は、シリカ12.5%、ア
ルミナ7.3%、酸化カルシウム41.2%、酸化第二
鉄10.8%、塩素150ppm、酸化マンガン1.6
%、五酸化燐3.5%、フッ素2.6%、粒鉄10重量
%、水分8.5%であった。また、この脱燐硫スラグの
粒度分布は、粒径13mm以上25mm以下のものが3
%、5mm以上13mm未満のものが10.1%、5m
m未満のものが86.9%であった。
EXAMPLES The present invention will be described in detail below with reference to examples, but the present invention is not limited to these examples. The dephosphorization slag was manufactured as follows. Fresh water having a chlorine concentration of 100 ppm was poured into a Noro pot containing molten dephosphorization slag generated in the de-S and de-P steps of the hot metal pretreatment and water cooling was performed. The iron content was 25% by weight after the material was dried and the relatively large iron particles having a particle diameter of 100 mm or more were removed by an ordinary magnetic separation removal treatment using a lifting magnet. This product was crushed with a crusher, and the magnetic separation removal process using a fixed magnet on the belt conveyor transfer line was repeated 3 times.
The composition of the obtained dephosphorization slag was as follows: silica 12.5%, alumina 7.3%, calcium oxide 41.2%, ferric oxide 10.8%, chlorine 150 ppm, manganese oxide 1.6.
%, Phosphorus pentaoxide 3.5%, fluorine 2.6%, granular iron 10% by weight, and water content 8.5%. The particle size distribution of this dephosphorization slag is 3 mm or more and 25 mm or less.
%, 5% or more and less than 13 mm 10.1%, 5m
The value of less than m was 86.9%.

【0016】実施例1 上記の調整した脱燐硫スラグを石灰石、軟珪石、水砕ス
ラグ、焼鉱等を組み合わせたクリンカー原料に混合し
て、粉砕して90μmのふるい残分が20%程度のセメ
ントクリンカー原料を調整した。ここで、脱燐硫スラグ
の配合量は、セメントクリンカー原料140重量部あた
り3重量部となるようにした。次いで、該セメントクリ
ンカー原料を電気炉にて1450℃で焼成し、空気で急
冷してセメントクリンカーを製造した。得られたセメン
トクリンカーに適当量の石膏を添加し、ポットミルで粉
砕してブレーン比表面積が3800cm2 /gのポルト
ランドセメントを得た。該ポルトランドセメントに同重
量の水砕スラグ微粉末を配合し、V型ブレンダーで混合
して高炉セメントB種を得た。該高炉セメントB種の三
酸化硫黄含有量は、約2.0%となるように調整した。
上記の高炉セメントB種について、JIS R−520
1に従い、モルタルの圧縮強さ試験及び凝結試験を行っ
た結果を表1に示す。
Example 1 The prepared dephosphorization slag was mixed with a clinker raw material in which limestone, soft silica stone, granulated slag, calcined ore, etc. were combined and ground to obtain a 90 μm sieve residue of about 20%. A cement clinker raw material was prepared. Here, the compounding amount of the dephosphorization slag was set to 3 parts by weight per 140 parts by weight of the cement clinker raw material. Next, the cement clinker raw material was fired at 1450 ° C. in an electric furnace and rapidly cooled with air to produce a cement clinker. An appropriate amount of gypsum was added to the obtained cement clinker, and the mixture was ground in a pot mill to obtain Portland cement having a Blaine specific surface area of 3800 cm 2 / g. Granulated slag fine powder of the same weight was mixed with the Portland cement and mixed with a V-type blender to obtain blast furnace cement type B. The sulfur trioxide content of the blast furnace cement type B was adjusted to about 2.0%.
Regarding the above-mentioned blast furnace cement class B, JIS R-520
Table 1 shows the results of the mortar compressive strength test and coagulation test according to 1.

【0017】実施例2 脱燐硫スラグの配合量は、セメントクリンカー原料14
0重量部あたり5重量部となるようにした以外は実施例
1と同様にして得た高炉セメントB種について、JIS
R−5201に従い、モルタルの圧縮強さ試験及び凝
結試験を行った結果を表1に示す。
Example 2 The amount of dephosphorization slag mixed was the amount of cement clinker raw material 14
Regarding blast furnace cement type B obtained in the same manner as in Example 1 except that the amount was 5 parts by weight per 0 parts by weight, JIS
The results of compression strength test and setting test of mortar according to R-5201 are shown in Table 1.

【0018】比較例1 脱燐硫スラグの配合量を、セメントクリンカー原料14
0重量部あたり6重量部となるようにした以外は、実施
例1と同様にして得た高炉セメントB種について、JI
S R−5201に従い、モルタルの圧縮強さ試験及び
凝結試験を行った結果を表1に示す。
Comparative Example 1 Cement clinker raw material 14
A blast furnace cement type B obtained in the same manner as in Example 1 except that 6 parts by weight per 0 parts by weight was used
Table 1 shows the results of the compression strength test and the setting test of the mortar according to SR-5201.

【0019】比較例2 脱燐硫スラグを配合しない以外は、実施例1と同様にし
て得た高炉セメントB種について、JIS R−520
1に従い、モルタルの圧縮強さ試験及び凝結試験を行っ
た結果を表1に示す。
Comparative Example 2 Blast furnace cement type B obtained in the same manner as in Example 1 except that dephosphorization slag was not mixed, JIS R-520
Table 1 shows the results of the mortar compressive strength test and coagulation test according to 1.

【0020】[0020]

【表1】 [Table 1]

【0021】実施例3 脱燐硫スラグ中の粒鉄量を変化させ、セメントクリンカ
ー粉砕用原料ミルの操業性との関係を調査した結果を表
2に示す。なお、表2の原料ミル振動振幅は、圧電型ピ
ックアップを用いて振動加速度を検出し、これを振幅に
変換したものであり、これが高いほど原料ミルの粉砕効
率が低下する。表2から、脱燐硫スラグ中の粒鉄量が多
いと原料ミルの粉砕効率が低下している。
Example 3 Table 2 shows the results of investigating the relationship between the amount of granular iron in the dephosphorization slag and the operability of the raw material mill for crushing cement clinker. The vibration amplitude of the raw material mill in Table 2 is obtained by detecting the vibration acceleration using a piezoelectric pickup and converting it into the amplitude. The higher this is, the lower the grinding efficiency of the raw material mill is. From Table 2, the pulverization efficiency of the raw material mill decreases when the amount of granular iron in the dephosphorization slag is large.

【0022】[0022]

【表2】 [Table 2]

【0023】実施例4 脱燐硫スラグの配合量をセメントクリンカー原料140
重量部あたり3重量部となるようにしたセメントクリン
カー原料を使用した際の、脱燐硫スラグの塩素分と、セ
メント焼成装置内の下段サイクロン出口における塩素濃
縮部位におけるセメント材料中の塩素濃度との関係を、
図1に示す。セメント焼成装置内の下段サイクロン出口
における塩素濃縮部位において、セメント材料中の塩素
濃度が増加した場合、閉塞等のトラブルを発生する。こ
の場合の該部位での、セメントクリンカー原料中の塩素
濃度の許容濃度を調査した結果によれば、5000pp
m程度であることが分かった。脱燐硫スラグ中の塩素濃
度の増加に伴い、該部位のセメント材料中の塩素濃度は
比例的に増加することが明らかである。従って脱燐硫ス
ラグ中の塩素濃度が約1000ppmを越えると、該部
位のセメントクリンカー原料中の塩素濃度が許容限界の
5000ppmを超過するのがわかる。
Example 4 The cement clinker raw material 140
The chlorine content of the dephosphorization slag and the chlorine concentration in the cement material at the chlorine concentration site at the lower cyclone outlet in the cement calcination device when the cement clinker raw material was adjusted to 3 parts by weight Relationship
As shown in FIG. If the chlorine concentration in the cement material increases at the chlorine concentration site at the outlet of the lower cyclone in the cement firing device, problems such as clogging will occur. In this case, the result of the investigation of the allowable chlorine concentration in the cement clinker raw material at the site showed that it was 5000 pp.
It was found to be about m. It is clear that as the chlorine concentration in the dephosphorized slag increases, the chlorine concentration in the cement material at the site increases proportionally. Therefore, it can be seen that when the chlorine concentration in the dephosphorized slag exceeds about 1000 ppm, the chlorine concentration in the cement clinker raw material at the site exceeds the allowable limit of 5000 ppm.

【0024】[0024]

【発明の効果】本発明によれば、従来有効活用が困難で
あった脱燐硫スラグを粒鉄量、塩素分を簡単な処理条件
の調整により低減することで、セメントの圧縮強さを向
上させ、凝結に殆ど影響を与えないセメントクリンカー
原料の一部として有効利用できる。またセメント製造設
備の負担を低減し、操業性の向上も図ることもできる。
EFFECTS OF THE INVENTION According to the present invention, the compressive strength of cement is improved by reducing the amount of granular iron and chlorine content of dephosphorization slag, which has been difficult to be effectively utilized in the past, by simply adjusting the treatment conditions. Therefore, it can be effectively used as a part of the raw material for cement clinker which hardly affects the setting. In addition, it is possible to reduce the burden on the cement manufacturing facility and improve operability.

【図面の簡単な説明】[Brief description of drawings]

【図1】脱燐硫スラグの塩素分と、セメント焼成装置内
の下段サイクロン出口におけるセメントクリンカー原料
中の塩素濃度との関係を示す図である。
FIG. 1 is a diagram showing a relationship between a chlorine content of dephosphorization slag and a chlorine concentration in a cement clinker raw material at a lower cyclone outlet in a cement baking device.

───────────────────────────────────────────────────── フロントページの続き (72)発明者 横尾 正義 福岡県北九州市戸畑区飛幡町1−1 新日 本製鐵株式会社八幡製鐵所内 (72)発明者 田中 茂守 福岡県北九州市八幡西区熊西2丁目1−13 (72)発明者 小山田 良一 福岡県宗像市自由が丘7丁目9−17 (72)発明者 定常 一夫 福岡県北九州市小倉北区中井4丁目7−5 −303 (72)発明者 小椋 豊茂 福岡県北九州市小倉北区中井4丁目10−3 ─────────────────────────────────────────────────── ─── Continuation of the front page (72) Masayoshi Yokoo, 1-1 Tobata-cho, Tobata-ku, Kitakyushu, Kitakyushu, Fukuoka Inside the Nippon Steel Corporation Hachiman Works (72) Inventor, Shigemori Tanaka, Hachiman-nishi-ku, Kitakyushu, Fukuoka Kumasai 2-chome 1-13 (72) Inventor Ryoichi Oyamada 7-9-17, Jiyugaoka, Munakata-shi, Fukuoka (72) Inventor Kazuo Steady 4-chome, Nakai-ku, Kitakyushu, Fukuoka 7-3-303 (72) Toyomoge Ogura 4-10-3 Nakai, Kokurakita-ku, Kitakyushu, Fukuoka

Claims (2)

【特許請求の範囲】[Claims] 【請求項1】 熔銑予備処理としての脱S、脱P工程に
おいて発生する熔融スラグに対する冷却水と磁選除去処
理条件の調節によって、スラグに含まれる塩素分を10
00ppm以下、粒鉄量を15重量%以下に調整した脱
燐硫スラグをセメントクリンカー原料の一部として、セ
メントクリンカー原料140重量部あたり2〜5重量部
配合し、焼成することを特徴とするセメントクリンカー
の製造方法。
1. The chlorine content contained in the slag is adjusted to 10 by adjusting the cooling water and the magnetic separation removal treatment conditions for the molten slag generated in the de-S and de-P steps as the hot metal pretreatment.
Cement characterized by mixing 2 to 5 parts by weight per 140 parts by weight of the cement clinker raw material as a part of the cement clinker raw material, the dephosphorization slag having a granular iron amount adjusted to 15 ppm by weight or less and not more than 00 ppm, and then firing. Method for producing clinker.
【請求項2】 熔融スラグに対する冷却水として塩素濃
度が1000ppm以下の水を使用するとともに、粉砕
と磁選除去処理を複数回繰り返すことによって脱燐硫ス
ラグに含まれる塩素分を1000ppm以下、粒鉄量を
15重量%以下に調整する請求項1記載のセメントクリ
ンカーの製造方法。
2. The water having a chlorine concentration of 1000 ppm or less is used as cooling water for the molten slag, and the chlorine content contained in the dephosphorization slag is 1000 ppm or less and the amount of granular iron is obtained by repeating pulverization and magnetic separation removal treatment a plurality of times. The method for producing a cement clinker according to claim 1, wherein the content is adjusted to 15% by weight or less.
JP00583295A 1995-01-18 1995-01-18 Manufacturing method of cement clinker Expired - Lifetime JP3554389B2 (en)

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Cited By (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2006045060A (en) * 2005-10-24 2006-02-16 Sumitomo Osaka Cement Co Ltd Cement composition and its manufacturing method
KR100732606B1 (en) * 2006-04-04 2007-06-28 호남석회공업(주) The method of cement activator used by sintering desulphurization dust and cement product having the activator
JP2012197197A (en) * 2011-03-22 2012-10-18 Dc Co Ltd Method for producing cement clinker
WO2013137114A1 (en) * 2012-03-15 2013-09-19 株式会社トクヤマ Method for producing portland cement clinker
JP2013189329A (en) * 2012-03-13 2013-09-26 Ube Industries Ltd METHOD FOR CONTROLLING b-VALUE OF CEMENT CLINKER AND METHOD FOR PRODUCING CEMENT CLINKER
JP2013193926A (en) * 2012-03-21 2013-09-30 Ube Industries Ltd Cement clinker and method for producing cement clinker
JP2014076919A (en) * 2012-10-11 2014-05-01 Tokuyama Corp Method of manufacturing portland cement clinker

Cited By (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2006045060A (en) * 2005-10-24 2006-02-16 Sumitomo Osaka Cement Co Ltd Cement composition and its manufacturing method
KR100732606B1 (en) * 2006-04-04 2007-06-28 호남석회공업(주) The method of cement activator used by sintering desulphurization dust and cement product having the activator
JP2012197197A (en) * 2011-03-22 2012-10-18 Dc Co Ltd Method for producing cement clinker
JP2013189329A (en) * 2012-03-13 2013-09-26 Ube Industries Ltd METHOD FOR CONTROLLING b-VALUE OF CEMENT CLINKER AND METHOD FOR PRODUCING CEMENT CLINKER
WO2013137114A1 (en) * 2012-03-15 2013-09-19 株式会社トクヤマ Method for producing portland cement clinker
JP2013193926A (en) * 2012-03-21 2013-09-30 Ube Industries Ltd Cement clinker and method for producing cement clinker
JP2014076919A (en) * 2012-10-11 2014-05-01 Tokuyama Corp Method of manufacturing portland cement clinker

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