TWI659005B - Method for manufacturing solidified slag, solidified slag, method for manufacturing coarse aggregate for concrete, and coarse aggregate for concrete - Google Patents

Method for manufacturing solidified slag, solidified slag, method for manufacturing coarse aggregate for concrete, and coarse aggregate for concrete Download PDF

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TWI659005B
TWI659005B TW106134288A TW106134288A TWI659005B TW I659005 B TWI659005 B TW I659005B TW 106134288 A TW106134288 A TW 106134288A TW 106134288 A TW106134288 A TW 106134288A TW I659005 B TWI659005 B TW I659005B
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slag
solidified
mold
solidified slag
manufacturing
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TW106134288A
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TW201802057A (en
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當房博幸
田恵太
荻尾勇樹
渡辺圭児
桑山道弘
今西大輔
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杰富意鋼鐵股份有限公司
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    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B5/00—Treatment of  metallurgical  slag ; Artificial stone from molten  metallurgical  slag 
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B18/00—Use of agglomerated or waste materials or refuse as fillers for mortars, concrete or artificial stone; Treatment of agglomerated or waste materials or refuse, specially adapted to enhance their filling properties in mortars, concrete or artificial stone
    • C04B18/04—Waste materials; Refuse
    • C04B18/14—Waste materials; Refuse from metallurgical processes
    • C04B18/141—Slags
    • C—CHEMISTRY; METALLURGY
    • C21—METALLURGY OF IRON
    • C21B—MANUFACTURE OF IRON OR STEEL
    • C21B3/00—General features in the manufacture of pig-iron
    • C21B3/04—Recovery of by-products, e.g. slag
    • C21B3/06—Treatment of liquid slag
    • C21B3/08—Cooling slag
    • C—CHEMISTRY; METALLURGY
    • C21—METALLURGY OF IRON
    • C21B—MANUFACTURE OF IRON OR STEEL
    • C21B2400/00—Treatment of slags originating from iron or steel processes
    • C21B2400/02—Physical or chemical treatment of slags
    • C21B2400/022—Methods of cooling or quenching molten slag
    • C21B2400/026—Methods of cooling or quenching molten slag using air, inert gases or removable conductive bodies
    • C—CHEMISTRY; METALLURGY
    • C21—METALLURGY OF IRON
    • C21B—MANUFACTURE OF IRON OR STEEL
    • C21B2400/00—Treatment of slags originating from iron or steel processes
    • C21B2400/04—Specific shape of slag after cooling
    • C21B2400/044—Briquettes or moulded bodies other than sheets
    • C—CHEMISTRY; METALLURGY
    • C21—METALLURGY OF IRON
    • C21B—MANUFACTURE OF IRON OR STEEL
    • C21B2400/00—Treatment of slags originating from iron or steel processes
    • C21B2400/05—Apparatus features
    • C21B2400/052—Apparatus features including rotating parts
    • C21B2400/058—Rotating beds on which slag is cooled
    • Y—GENERAL 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
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
    • Y02W30/00—Technologies for solid waste management
    • Y02W30/50—Reuse, recycling or recovery technologies
    • Y02W30/91—Use of waste materials as fillers for mortars or concrete

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  • Engineering & Computer Science (AREA)
  • Chemical & Material Sciences (AREA)
  • Ceramic Engineering (AREA)
  • Materials Engineering (AREA)
  • Organic Chemistry (AREA)
  • Structural Engineering (AREA)
  • Civil Engineering (AREA)
  • Environmental & Geological Engineering (AREA)
  • Manufacturing & Machinery (AREA)
  • Metallurgy (AREA)
  • Curing Cements, Concrete, And Artificial Stone (AREA)
  • Furnace Details (AREA)
  • Manufacture Of Iron (AREA)

Abstract

提供一種可成為品質優良的混凝土用粗骨材的原料的凝固熔渣的製造方法、由該凝固熔渣的製造方法製造的凝固熔渣、使用該凝固熔渣的混凝土用粗骨材的製造方法、及藉由該混凝土用粗骨材的製造方法製造的混凝土用粗骨材。本發明的凝固熔渣的製造方法包括：熔渣凝固步驟，將熔融狀態的高爐熔渣流入至移動的金屬製的鑄模中進行冷卻，在鑄模內以成為板狀的方式使其凝固；熔渣落下步驟，將鑄模反轉而使在鑄模內已凝固至內部為止的熔渣從鑄模落下；及熔渣溫度保持步驟，將落下的熔渣的熔渣表面的一部分或整個面的表面溫度以900℃以上保持5分鐘以上。Provided are a method for producing a solidified slag that can be used as a raw material for high-quality coarse aggregate for concrete, a method for producing a solidified slag produced by the method for producing a solidified slag, and a method for producing a coarse aggregate for concrete using the solidified slag. And a coarse aggregate for concrete manufactured by the method for producing a coarse aggregate for concrete. The method for producing solidified slag according to the present invention includes a slag solidification step, in which a molten blast furnace slag is poured into a moving metal mold to be cooled, and the plate is solidified in a mold shape in the mold; the slag is solidified; A dropping step of inverting the mold so that the slag which has solidified to the inside of the mold is dropped from the mold; and a slag temperature maintaining step of reducing the surface temperature of a part or the entire surface of the dropped slag to 900 Hold above 5 ° C for 5 minutes.

Description

凝固熔渣的製造方法、凝固熔渣、混凝土用粗骨材的製造方法以及混凝土用粗骨材Method for producing solidified slag, method for producing solid aggregate for concrete, and coarse aggregate for concrete

本發明是有關於一種凝固熔渣的製造方法、利用該凝固熔渣的製造方法製造的凝固熔渣、使用了該凝固熔渣的混凝土用粗骨材（coarse aggregate for concrete）的製造方法、以及藉由該混凝土用粗骨材的製造方法而製造的混凝土用粗骨材，所述凝固熔渣是使熔融狀態的高爐熔渣（blast furnace slag）在金屬製的鑄模上凝固，並使已凝固的凝固熔渣（solidified slag）從鑄模落下而製造板狀的凝固熔渣。The present invention relates to a method for manufacturing a solidified slag, a solidified slag manufactured by the method for manufacturing a solidified slag, a method for manufacturing a coarse aggregate for concrete using the solidified slag, and In the coarse aggregate for concrete manufactured by the method for producing a coarse aggregate for concrete, the solidified slag solidifies a blast furnace slag in a molten state on a metal mold and solidifies the solidified slag. The solidified slag dropped from the mold to produce a plate-like solidified slag.

作為使金屬的提純步驟等中產生的熔融熔渣（molten slag）凝固的方法，如下方法被廣泛使用：將高壓冷卻水向熔融熔渣吹送而進行急冷的方法，或者，將熔融熔渣向乾渣坑（dry pit）或熔渣冷卻場（slag cooling yard）排出且在大氣中進行緩冷的方法。As a method for solidifying molten slag generated in a metal purification step or the like, a method is widely used in which high-pressure cooling water is blown to the molten slag and quenched, or the molten slag is dried to dryness. A method in which a slag cooling pit or a slag cooling yard is discharged and slowly cooled in the atmosphere.

在將熔融熔渣急冷的方法中，因大量吹送高壓冷卻水，故形成具有多個氣孔（pore）的粒徑為5 mm以下的砂狀凝固熔渣（所謂的水淬熔渣（water granulated slag））。另一方面，在使熔融熔渣流向乾渣坑或熔渣冷卻場等使其凝固並緩冷的方法中，形成數m大小的塊，將該塊粉碎而形成塊狀的凝固熔渣（所謂的緩冷熔渣（空冷爐渣（air-cooled slag）））。In the method of quenching molten slag, a large amount of high-pressure cooling water is blown, so that a sand-like solidified slag (so-called water granulated slag) having a plurality of pores with a particle diameter of 5 mm or less is formed. )). On the other hand, in a method in which molten slag flows to a dry slag pit or a slag cooling field to solidify and slowly cool, a block having a size of several m is formed, and the block is pulverized to form a block-like solidified slag (so-called Slow-cooling slag (air-cooled slag)).

最近，實現了代替礫石（gravel）等而在混凝土用粗骨材中應用高爐緩冷熔渣。為了將高爐熔渣應用於混凝土用粗骨材，需要減少熔渣中的氣孔且將熔渣粒徑的最大值調整為20 mm左右。Recently, blast furnace slow-cooling slag has been applied to rough aggregates for concrete instead of gravel. In order to apply the blast furnace slag to the coarse aggregate for concrete, it is necessary to reduce the pores in the slag and adjust the maximum value of the slag particle size to about 20 mm.

因此，在該狀態下，水淬熔渣的氣孔多且粒徑小，因而無法應用於混凝土用粗骨材。另一方面，緩冷熔渣雖無氣孔的問題，但需要將數m大小的塊粉碎為20 mm左右的粒徑，該粉碎需要大量時間，從而效率差。Therefore, in this state, since the water-quenched slag has many pores and a small particle size, it cannot be applied to a coarse aggregate for concrete. On the other hand, although slow-cooling slag does not have the problem of pores, it is necessary to pulverize a block having a size of several m to a particle diameter of about 20 mm. This pulverization requires a lot of time and is inefficient.

因此，作為混凝土用粗骨材，為了獲得氣孔少且容易粉碎的凝固熔渣，而提出多種使用金屬製的鑄模使熔融熔渣凝固的技術。若在金屬製鑄模中使熔融熔渣凝固，則獲得尺寸比水淬熔渣大且比緩冷熔渣小的凝固熔渣，藉由將其粉碎而可容易獲得所需尺寸的熔渣，與緩冷熔渣相比可縮短粉碎的時間，從而可容易獲得粒徑為20 mm左右的所需的凝固熔渣。Therefore, as a coarse aggregate for concrete, in order to obtain a solidified slag with few pores and easy crushing, various techniques have been proposed for solidifying the molten slag using a metal mold. If the molten slag is solidified in a metal mold, a solidified slag having a size larger than that of the water quenching slag and smaller than the slow-cooling slag can be obtained. The slag having a desired size can be easily obtained by crushing the slag, and Compared with the slow-cooling slag, the pulverization time can be shortened, and the required solidified slag having a particle diameter of about 20 mm can be easily obtained.

作為使用金屬製鑄模將熔融熔渣凝固的例，例如有專利文獻1中記載的瀝青路面用骨材（aggregate for asphalt pavement）及其製造方法以及瀝青路面。專利文獻1的熔融熔渣的凝固方法為如下：將熔融狀態的高爐熔渣以成為層厚10 mm～30 mm的板狀的方式在金屬製的移動鑄模上以單層而流動並使其冷卻凝固，從而形成單層板狀的凝固熔渣。將該單層板狀的熔渣粉碎，製造吸水率（water absorption percentage）為1.5%以下、磨損損失率（abrasion loss percentage）為20%以下的瀝青路面用骨材。Examples of the solidification of the molten slag using a metal mold include, for example, an aggregate for asphalt pavement described in Patent Document 1, a method for producing the aggregate for asphalt pavement, and an asphalt pavement. The method of solidifying the molten slag of Patent Document 1 is as follows: The molten blast furnace slag is flowed in a single layer on a metal moving mold to cool it in a plate shape with a layer thickness of 10 mm to 30 mm and allowed to cool. Solidified to form a single-layer plate-like solidified slag. This single-layer plate-shaped slag is pulverized to produce an aggregate for asphalt pavement with a water absorption percentage of 1.5% or less and an abrasion loss percentage of 20% or less.

而且，作為使用金屬製的鑄模使高爐熔渣凝固而製造混凝土用粗骨材的方法，有專利文獻2中揭示的混凝土用粗骨材。專利文獻2中揭示的包含熔渣的混凝土用粗骨材，使熔融熔渣流入至金屬製鑄模並凝固，將凝固後獲得的熔渣粉碎，並調整為吸水率1.5%以下及粒徑5 mm～20 mm。 [現有技術文獻] [專利文獻]In addition, as a method of manufacturing a coarse aggregate for concrete using a metal mold to solidify the blast furnace slag, there is a coarse aggregate for concrete disclosed in Patent Document 2. The coarse aggregate for concrete containing slag disclosed in Patent Document 2 allows molten slag to flow into a metal mold and solidify. The slag obtained after solidification is pulverized and adjusted to have a water absorption of 1.5% or less and a particle diameter of 5 mm. ~ 20 mm. [Prior Art Literature] [Patent Literature]

專利文獻1：日本專利第3855706號公報 專利文獻2：日本專利特開2004-277191號公報Patent Document 1: Japanese Patent No. 3855706 Patent Document 2: Japanese Patent Laid-Open No. 2004-277191

[發明所欲解決之課題] 專利文獻1所述的熔融熔渣的凝固方法為如下方法，即，將熔融狀態的高爐熔渣以成為凝固厚度10 mm～30 mm的板狀的方式，以單層流入至金屬製的移動鑄模上並冷卻凝固，藉由急速進行冷卻凝固，而抑制在凝固熔渣內部生成的氣孔的成長，從而以低氣孔率製造吸水率低且耐磨損性（abrasion resistance）高的骨材。[Problems to be Solved by the Invention] The method for solidifying the molten slag described in Patent Document 1 is a method in which a molten blast furnace slag is formed into a plate shape with a solidified thickness of 10 mm to 30 mm. The layer flows into a metal moving mold and is cooled and solidified. By rapidly cooling and solidifying, the growth of pores generated in the solidified slag is suppressed, thereby producing a low porosity with low water absorption and abrasion resistance. ) High aggregate.

然而，亦如專利文獻1的實施例中所記載，在使高爐熔渣以板狀而於金屬製鑄模上凝固的情況下，自與金屬製鑄模接觸的下表面算起為1 mm左右的部分為玻璃狀（glassy state）。這是由如下引起，即，熔融熔渣中，與金屬製鑄模的接觸面最急速地得到冷卻而成為玻璃質（glassy state），但因熔融熔渣的導熱率非常小，故熔融熔渣內部的冷卻速度不會增大而是以結晶質的狀態（crystalline state）凝固。However, as described in the example of Patent Document 1, when the blast furnace slag is solidified on a metal mold in a plate shape, the portion from the lower surface in contact with the metal mold is about 1 mm. It is glassy (glassy state). This is caused by the fact that, in the molten slag, the contact surface with the metal mold is most rapidly cooled to become a glassy state, but the thermal conductivity of the molten slag is very small, so the interior of the molten slag is very small. The cooling rate does not increase but solidifies in a crystalline state.

所如述般，專利文獻1的方法中，單面生成玻璃質的板狀凝固熔渣，但在將此種板狀凝固熔渣粉碎而製造骨材的情況下，可形成表面的一部分為玻璃質的粗骨材。在將表面為玻璃質的粗骨材用作混凝土用粗骨材的情況下，存在新拌混凝土（fresh concrete）凝固時容易泌水（bleeding）的問題。泌水為如下現象，即，在新拌混凝土中因固體材料的沈降或分離，而攪拌混合水的一部分游離並上升至表面為止。As described above, in the method of Patent Document 1, glassy plate-shaped solidified slag is generated on one side. However, when such plate-shaped solidified slag is pulverized to produce an aggregate, a part of the surface that can be formed is glass. Rough aggregate. When a coarse aggregate having a glassy surface is used as the coarse aggregate for concrete, there is a problem that bleeding occurs when fresh concrete is solidified. Water bleeding is a phenomenon in which a part of the mixed mixed water is released and rises to the surface due to the sedimentation or separation of the solid material in the fresh concrete.

而且，自與金屬製鑄模接觸的面算起為1 mm左右的玻璃質部分與結晶質部分的邊界容易裂開。因此，亦存在如下問題，即，在進行粉碎而調整為粗骨材粒度時玻璃質部分容易成為細粒，從而粗骨材的良率降低。Furthermore, the boundary between the glassy portion and the crystalline portion, which is about 1 mm from the surface in contact with the metal mold, is liable to crack. Therefore, there is also a problem that the glassy portion is liable to become fine particles when pulverization is performed to adjust the particle size of the coarse aggregate, and the yield of the coarse aggregate is reduced.

專利文獻2的混凝土用粗骨材與專利文獻1同樣地，利用在金屬製的鑄模上凝固的高爐熔渣，且將該高爐熔渣粉碎，而形成吸水率1.5%以下、粒徑5 mm～20 mm的粗骨材。將熔融熔渣流入至金屬製鑄模而凝固成20 mm～30 mm的厚度，從而與專利文獻1同樣地，與金屬製鑄模的接觸面玻璃化的可能性高。專利文獻2的調配了混凝土用粗骨材的混凝土的調配條件（調配比例（mix proportion））、養護期間（curing period）為7日、28日的壓縮強度明瞭，但關於泌水則不清楚。The coarse aggregate for concrete of Patent Document 2 is the same as that of Patent Document 1. Using blast furnace slag solidified on a metal mold, the blast furnace slag is crushed to form a water absorption of 1.5% or less and a particle diameter of 5 mm to 20 mm coarse aggregate. The molten slag flows into a metal mold and solidifies to a thickness of 20 mm to 30 mm. As in Patent Document 1, the contact surface with the metal mold is likely to vitrify. In Patent Document 2, the compressive strength of concrete (mix proportion) and curing period of 7 days and 28 days for concrete prepared with coarse aggregate for concrete is clear, but it is not clear about bleeding.

本發明是為了解決所述問題而完成，目的在於提供可成為品質優良的混凝土用粗骨材的原料的凝固熔渣的製造方法、利用該凝固熔渣的製造方法製造的凝固熔渣、使用了該凝固熔渣的混凝土用粗骨材的製造方法、以及藉由該混凝土用粗骨材的製造方法製造的混凝土用粗骨材。This invention is made in order to solve the said problem, The objective is to provide the manufacturing method of the solidified slag which can be used as the raw material of the coarse aggregate for concrete, the solidified slag manufactured by this manufacturing method of the solidified slag, The method for producing a coarse aggregate for concrete using the solidified slag, and the coarse aggregate for concrete produced by the method for producing a coarse aggregate for concrete.

[解決課題之手段] 用以解決所述課題的本發明的主旨為以下所示。[Means for Solving the Problems] The gist of the present invention for solving the problems is as follows.

[1]一種凝固熔渣的製造方法，包括：熔渣凝固步驟，將熔融狀態的高爐熔渣流入至移動的金屬製的鑄模中進行冷卻，在所述鑄模內以成為板狀的方式使其凝固；熔渣落下步驟，將所述鑄模反轉而使在所述鑄模內已凝固至內部為止的熔渣從鑄模落下；以及熔渣溫度保持步驟，將落下的熔渣的熔渣表面的一部分或整個面的表面溫度以900℃以上保持5分鐘以上。[1] A method for producing a solidified slag, comprising the step of solidifying a slag, flowing the molten blast furnace slag into a moving metal mold to cool it, and making the mold into a plate shape in the mold. Solidification; a slag dropping step of inverting the mold so that the slag which has solidified to the inside of the mold is dropped from the mold; and a slag temperature maintaining step of a part of the slag surface of the dropped slag Or, the surface temperature of the entire surface is maintained at 900 ° C or higher for 5 minutes or longer.

[2]如所述[1]所述的凝固熔渣的製造方法，其特徵在於：在所述鑄模內以成為板狀的方式凝固的高爐熔渣的厚度為20 mm以上且30 mm以下。[2] The method for producing solidified slag according to the above [1], wherein the thickness of the blast furnace slag solidified in a plate shape in the mold is 20 mm or more and 30 mm or less.

[3]如所述[1]或所述[2]所述的凝固熔渣的製造方法，其特徵在於：所述熔渣溫度保持步驟中，對於從所述鑄模落下的凝固熔渣的表面中的凝固時的鑄模接觸面的80面積%以上，將熔渣表面溫度以900℃以上保持5分鐘以上。[3] The method for producing solidified slag according to the above [1] or [2], wherein in the slag temperature maintaining step, a surface of the solidified slag dropped from the mold During the solidification, the mold contact surface was 80% by area or more, and the surface temperature of the slag was maintained at 900 ° C or higher for 5 minutes or more.

[4]如所述[1]至所述[3]中任一項所述的凝固熔渣的製造方法，其特徵在於：所述熔渣溫度保持步驟中，使從所述鑄模落下的凝固熔渣以熔渣厚度方向平均溫度超過900℃而積層。[4] The method for producing a solidified slag according to any one of the above [1] to [3], wherein in the step of maintaining the temperature of the slag, solidification falling from the mold is solidified. The slag is laminated so that the average temperature in the thickness direction of the slag exceeds 900 ° C.

[5]如所述[1]至所述[4]中任一項所述的凝固熔渣的製造方法，其特徵在於：所述熔渣溫度保持步驟中，使從所述鑄模落下的凝固熔渣積層於可從落下位置搬出的保持容器內。[5] The method for producing a solidified slag according to any one of the above [1] to [4], wherein in the slag temperature maintaining step, solidification falling from the mold is solidified. The slag is laminated in a holding container that can be carried out from a dropping position.

[6]一種凝固熔渣，由所述[1]至所述[5]中任一項所述的凝固熔渣的製造方法而製造，在進行將通過孔徑100 mm的篩而未通過孔徑40 mm的篩的熔渣試樣，從2 m的高度落下4次的落下試驗後，以未通過孔徑40 mm的篩的試樣的相對於落下試驗前的試樣的質量比率進行評估的落下強度（碎裂指數（Shatter Index））為70%以上。[6] A solidified slag manufactured by the method for manufacturing a solidified slag according to any one of the above [1] to [5], which is passed through a sieve having a hole diameter of 100 mm without passing through a hole diameter of 40 The slag sample with a sieve of mm mm was dropped four times from a height of 2 m, and the drop strength was evaluated based on the mass ratio of the sample that did not pass through the sieve with a diameter of 40 mm to the sample before the drop test. (Shatter Index) is over 70%.

[7]一種混凝土用粗骨材的製造方法，其包括：凝固熔渣製造步驟，包含如所述[1]至所述[5]中任一項所述的凝固熔渣的製造方法；凝固熔渣粉碎步驟，將所製造的凝固熔渣粉碎；以及篩選步驟，將粉碎的凝固熔渣篩選。[7] A method for producing a coarse aggregate for concrete, comprising: a step for producing a solidified slag, including the method for producing a solidified slag according to any one of the above [1] to [5]; and solidification A slag pulverizing step, which pulverizes the produced solidified slag; and a screening step, which smashes the pulverized solidified slag.

[8]一種混凝土用粗骨材，由如所述[7]所述的混凝土用粗骨材的製造方法製造，平均壓縮強度為100 N/mm2 以上。[8] A coarse aggregate for concrete, produced by the method for producing a coarse aggregate for concrete according to the above [7], with an average compressive strength of 100 N / mm 2 or more.

[發明的效果] 根據本發明的凝固熔渣的製造方法，凝固熔渣的於對金屬製鑄模的接觸面上生成的玻璃質的部分，在將熔渣表面溫度以900℃以上保持5分鐘以上的期間變為結晶質，因而獲得落下強度高的凝固熔渣。而且，將根據本發明的凝固熔渣的製造方法而製造的凝固熔渣進一步粉碎、篩選（screening）製造而成的混凝土用粗骨材，因表面具有玻璃質的部分的比例小，故可穩定地獲得高強度，從而獲得對於製造高強度的混凝土而言較佳的粗骨材。[Effects of the Invention] According to the method for producing a solidified slag according to the present invention, the glassy portion of the solidified slag generated on the contact surface with a metal mold is maintained at a surface temperature of the slag of 900 ° C or higher for 5 minutes or more. During the period of time, it becomes crystalline, and a solidified slag having a high dropping strength is obtained. In addition, the coarse aggregate for concrete manufactured by further pulverizing and screening the solidified slag produced by the method for producing a solidified slag according to the present invention can be stabilized because the proportion of the portion having a glassy surface is small. To obtain high strength, thereby obtaining coarse aggregates that are better for making high strength concrete.

以下，對本發明進行具體說明。Hereinafter, the present invention will be specifically described.

本實施形態的凝固熔渣的製造方法包括：熔渣凝固步驟，將熔融狀態的高爐熔渣流入至移動的金屬製的鑄模中進行冷卻，在所述鑄模內以成為板狀的方式使其凝固；熔渣落下步驟，將所述鑄模反轉而使在所述鑄模內已凝固至內部為止的熔渣從鑄模落下；以及熔渣溫度保持步驟，將落下的熔渣的熔渣表面的一部分或整個面的表面溫度以900℃以上保持5分鐘以上。The method for producing solidified slag according to this embodiment includes a slag solidification step of flowing a molten blast furnace slag into a moving metal mold to cool it, and solidifying the mold into a plate shape in the mold. A slag dropping step of inverting the mold to cause the slag which has solidified to the inside of the mold to fall from the mold; and a slag temperature maintaining step of a part of the slag surface of the dropped slag or The surface temperature of the entire surface was maintained at 900 ° C. or higher for 5 minutes or longer.

將可實現所述凝固熔渣的製造方法的凝固熔渣製造裝置的一例表示於圖1中。圖1所示的凝固熔渣製造裝置1（圖1）對具有供收容於熔渣鍋23的熔融狀態的高爐熔渣，即，熔融熔渣3流入的凹陷部5a（recessed part）的多個金屬製的鑄模5進行支持以使其可環繞移動，在鑄模5環繞的期間向凹陷部5a流入熔融熔渣3而連續地製造凝固熔渣18。An example of the solidified slag manufacturing apparatus which can implement the manufacturing method of the said solidified slag is shown in FIG. A solidified slag manufacturing apparatus 1 (FIG. 1) shown in FIG. 1 has a plurality of recessed parts 5 a (recessed parts) having molten slag 3 which are accommodated in the molten state and accommodated in the slag pot 23. The mold 5 made of metal is supported so as to be movable around, and the molten slag 3 flows into the recessed portion 5 a while the mold 5 surrounds to continuously manufacture the solidified slag 18.

進行此種動作的凝固熔渣製造裝置1包括環繞移動機構7，該環繞移動機構7以使多個鑄模5接近而進行支持的狀態沿水平方向環繞移動。該環繞移動機構7包括：空冷移動部9，在鑄模環繞1周的期間內，在將所流入的熔融熔渣3保持於所述凹陷部5a的狀態下使鑄模5向環繞方向移動，將熔融熔渣3空冷而使其凝固；反轉排出部11，將鑄模5以其凹陷部5a朝向下方的方式反轉而排出凝固熔渣18；反轉移動部13，使反轉的鑄模5保持反轉的狀態而移動；再反轉部15，將處於反轉狀態的鑄模5以凹陷部5a朝向上方的方式再反轉；再反轉移動部17，使再反轉的鑄模5移動至熔融熔渣3所流入的部位為止；以及冷卻裝置21，將反轉的鑄模5冷卻。再反轉移動部17亦可省略。另外，凝固熔渣製造裝置1為了使熔融熔渣3容易流入至鑄模5而設置流槽20。The solidified slag manufacturing apparatus 1 that performs such an operation includes a surrounding moving mechanism 7 that moves in a horizontal direction in a state where a plurality of molds 5 are approached and supported. The orbiting moving mechanism 7 includes an air-cooled moving portion 9 that moves the casting mold 5 in the orbiting direction while holding the molten slag 3 flowing in the recessed portion 5a during a period of one round of the casting mold to melt the molten mold. The slag 3 is air-cooled to solidify it; the discharge part 11 is reversed, and the mold 5 is inverted so that the recessed part 5a of the mold 5 is directed downward to discharge the solidified slag 18; The reversing part 15 re-reverses the mold 5 in the reversed state with the recessed portion 5a facing upward; the reversing moving part 17 moves the re-reversed mold 5 to the molten state. And a cooling device 21 that cools the reversed mold 5. The reversing moving section 17 may be omitted. In addition, the solidified slag manufacturing apparatus 1 is provided with a flow channel 20 in order to allow the molten slag 3 to easily flow into the mold 5.

而且，凝固熔渣製造裝置1具有設置於反轉排出部11的環繞的鑄模5的下方的坑（pit）19，在坑19配置著可***排出的凝固熔渣18的凝固熔渣保持容器22。Furthermore, the solidified slag manufacturing apparatus 1 has a pit 19 provided below the surrounding mold 5 surrounding the reversing discharge section 11, and a solidified slag holding container capable of containing the discharged solidified slag 18 is disposed in the pit 19. twenty two.

如圖2所示，凝固熔渣保持容器22具有如下容量，即，可保持相當於熔渣鍋23的1杯份熔融熔渣3的量的凝固熔渣18，亦可在收容熔渣鍋23的1杯份凝固熔渣18後，從熔渣落下位置搬出，並與空的凝固熔渣保持容器22進行更換。據此，即便在凝固熔渣保持容器22內以某種程度長時間保持熔渣，亦不會產生等待時間而使生產性降低，繼而可對下一熔渣鍋23的熔融熔渣3進行處理。As shown in FIG. 2, the solidified slag holding container 22 has a capacity that can hold the solidified slag 18 in an amount equivalent to one cup of the molten slag 3 and can also accommodate the slag pot 23. After 1 cup of solidified slag 18 is removed, it is carried out from the slag dropping position and replaced with an empty solidified slag holding container 22. According to this, even if the slag is held in the solidified slag holding container 22 for a certain period of time, there is no waiting time to reduce productivity, and the molten slag 3 of the next slag pot 23 can be processed. .

自保溫性的觀點而言，凝固熔渣保持容器22的底面及側面理想的是至少一部分沿著各面的法線方向包含導熱率為5 W/（m·K）左右以下的低導熱率的耐火物。而且，亦可選擇下述形態等：在收容凝固熔渣18後在凝固熔渣保持容器22上設置蓋；或將燃燒器等簡易加熱源附加而配備於凝固熔渣保持容器22；或者將熔渣落下位置的坑19自身用作凝固熔渣保持容器，在收容凝固熔渣後設置並保持外蓋。From the viewpoint of thermal insulation properties, it is desirable that at least a part of the bottom surface and the side surfaces of the solidified slag holding container 22 include a low thermal conductivity of about 5 W / (m · K) or less along the normal direction of each surface. Refractory. In addition, the following forms may be selected: a cover is provided on the solidified slag holding container 22 after the solidified slag 18 is contained; or a simple heating source such as a burner is attached to the solidified slag holding container 22; The pit 19 at the slag dropping position itself is used as a solidified slag holding container, and an outer cover is installed and held after the solidified slag is received.

將使用如以上般構成的本實施形態的凝固熔渣製造裝置1製造凝固熔渣18的方法的一例，與凝固熔渣製造裝置1的動作一併進行說明。An example of the method of manufacturing the solidified slag 18 using the solidified slag manufacturing apparatus 1 of this embodiment configured as described above will be described together with the operation of the solidified slag manufacturing apparatus 1.

使環繞移動機構7以規定的速度旋轉，在熔融熔渣流入部位，使熔融熔渣3經由流槽20流入至環繞的鑄模5中。已流入熔融熔渣3的鑄模5在空冷移動部9內移動，熔融熔渣3受到空冷而成為凝固熔渣18（熔渣凝固步驟）。The orbiting movement mechanism 7 is rotated at a predetermined speed, and the molten slag 3 is caused to flow into the surrounding mold 5 through the flow channel 20 at the molten slag inflow portion. The mold 5 that has flowed into the molten slag 3 moves inside the air-cooled moving part 9, and the molten slag 3 is subjected to air cooling to become a solidified slag 18 (slag solidification step).

此處，較佳為以凝固熔渣18的厚度為20 mm以上且30 mm以下的方式，對鑄模5的環繞移動速度及/或熔融熔渣3的流入速度進行控制。若凝固熔渣的厚度為20 mm以上，則藉由將該凝固熔渣18粉碎，而可獲得被廣泛使用的適用於普通的粗骨材尺寸即5 mm～20 mm的粗骨材製品的粒度分佈。而且，若凝固熔渣18的厚度為20 mm以上，則如後述般，在凝固熔渣18被裝入至凝固熔渣保持容器22內時，可充分增大平均含熱量（average amount of heat），因而無須追加加熱源而僅將凝固熔渣18進行保溫，便可使鑄模接觸面的熔渣表面溫度上升至900℃以上為止並保持5分鐘以上。Here, it is preferable to control the orbiting speed of the mold 5 and / or the inflow speed of the molten slag 3 so that the thickness of the solidified slag 18 is 20 mm or more and 30 mm or less. If the thickness of the solidified slag is 20 mm or more, by pulverizing the solidified slag 18, it is possible to obtain a widely used coarse aggregate product having a particle size of 5 to 20 mm, which is suitable for ordinary coarse aggregate sizes. distributed. When the thickness of the solidified slag 18 is 20 mm or more, as described later, when the solidified slag 18 is loaded into the solidified slag holding container 22, the average amount of heat can be sufficiently increased. Therefore, the heating of the solidified slag 18 without the need for an additional heating source can increase the surface temperature of the slag at the contact surface of the mold to more than 900 ° C. and maintain it for more than 5 minutes.

另一方面，若凝固熔渣18的厚度為30 mm以下，則熔渣的冷卻速度為適當的範圍，抑制熔渣內部的氣孔生成，因而可將粗骨材製品的吸水率降低至1.5%以下，並且在獲得例如壓縮強度為100 N/mm2 以上的高強度的粗骨材粒子方面較佳。On the other hand, if the thickness of the solidified slag 18 is 30 mm or less, the cooling rate of the slag is in an appropriate range and the generation of pores in the slag is suppressed, so that the water absorption of the coarse aggregate product can be reduced to 1.5% or less. In addition, it is preferable to obtain high-strength coarse aggregate particles having a compressive strength of 100 N / mm 2 or more, for example.

已到達反轉排出部11的鑄模5在反轉排出部11中朝向環繞方向旋轉並反轉，凝固熔渣18被排出至坑19或坑19內的凝固熔渣保持容器22中（熔渣落下步驟）。The mold 5 that has reached the reverse discharge section 11 rotates in the reverse discharge section 11 in a circumferential direction and is reversed, and the solidified slag 18 is discharged into the pit 19 or the solidified slag holding container 22 in the pit 19 (the slag falls step).

排出了凝固熔渣18的鑄模5以反轉狀態在反轉移動部13內移動，在其移動途中藉由冷卻裝置21而冷卻。The mold 5 from which the solidified slag 18 has been discharged moves in the reverse moving part 13 in the reversed state, and is cooled by the cooling device 21 during the movement.

已通過反轉移動部13的鑄模5在再反轉部15中朝向周方向旋轉且以凹陷部5a朝向上方的方式再反轉。已再反轉的鑄模5中，在剛再反轉後或在再反轉移動部17內移動後，再次在熔渣流入部位流入熔融熔渣3。The mold 5 having passed through the reversing moving portion 13 is rotated in the re-reversing portion 15 in the circumferential direction and re-reversed so that the recessed portion 5 a faces upward. In the mold 5 that has been reversed again, immediately after re-reversing or after moving within the re-reversing moving portion 17, the molten slag 3 flows into the slag inflow portion again.

排出至坑19並裝入至凝固熔渣保持容器22的凝固熔渣18，積層於凝固熔渣保持容器22內，藉由凝固熔渣18自身具有的熱量，凝固時降低的凝固熔渣18的鑄模接觸面的溫度上升。此時，藉由將落下的凝固熔渣18的熔渣表面溫度以900℃以上保持5分鐘以上，而可將凝固熔渣18的鑄模接觸面的玻璃質改質為結晶質（熔渣溫度保持步驟）。如此，在玻璃質改質為結晶質後，將凝固熔渣18從凝固熔渣保持容器22排出至熔渣冷卻床24。The solidified slag 18 discharged to the pit 19 and loaded into the solidified slag holding container 22 is stacked in the solidified slag holding container 22, and the heat of the solidified slag 18 is reduced during solidification by the heat of the solidified slag 18 itself. The temperature at the contact surface of the mold increased. At this time, by maintaining the slag surface temperature of the falling solidified slag 18 at 900 ° C. or higher for 5 minutes or more, the glass quality of the mold contact surface of the solidified slag 18 can be changed to crystalline (the slag temperature is maintained). step). In this manner, after the glassy material is modified to be crystalline, the solidified slag 18 is discharged from the solidified slag holding container 22 to the slag cooling bed 24.

如以上般，本發明的凝固熔渣製造方法具有熔渣凝固步驟、熔渣落下步驟及熔渣溫度保持步驟這3個步驟，該些3個步驟中，尤其熔渣溫度保持步驟具有特徵，因而以下對其進行詳細說明。As described above, the solidified slag manufacturing method of the present invention has three steps: a slag solidification step, a slag dropping step, and a slag temperature maintaining step. Among these three steps, especially the slag temperature maintaining step has characteristics, so This will be described in detail below.

＜需要熔渣溫度保持步驟的理由＞ 若觀察自鑄模5落下的板狀的凝固熔渣18的剖面，則自鑄模接觸面算起為約1 mm左右為止的範圍玻璃化。僅自鑄模接觸面算起為1 mm左右的範圍玻璃化的理由在於冷卻速度僅在該部分加快。即便凝固熔渣18的凝固厚度發生變化，玻璃質的部分仍自鑄模接觸面算起為約1 mm。<Reason why a slag temperature maintaining step is required> When the cross-section of the plate-like solidified slag 18 dropped from the mold 5 is observed, the range from about 1 mm from the mold contact surface is vitrified. The reason for vitrification only in the range of about 1 mm from the mold contact surface is that the cooling rate is accelerated only in this part. Even if the solidified thickness of the solidified slag 18 is changed, the glassy portion is still about 1 mm from the mold contact surface.

使用放射溫度計對凝固熔渣18的大氣側的表面溫度進行測定，並且在鑄模背面設置熱電偶，在凝固熔渣18的厚度為23 mm的情況下，對直至流到鑄模上的熔融熔渣3被冷卻而凝固的過程為止的溫度轉移（temperature transition）進行測定。將測定結果表示於圖3中。圖3中一併表示藉由後述的傳熱解析而求出的、熔渣的厚度方向中心位置及與鑄模5接觸的位置的熔渣溫度的轉移。與鑄模5接觸的位置的熔渣藉由向鑄模的熱傳導而初始冷卻速度顯著增大，以約15秒降低至400℃為止，然後成為大致固定的溫度。熔渣的中心部的溫度的下降慢且2分鐘後僅降低至1150℃左右，大氣側的表面亦在2分鐘後僅降低至900℃左右為止。A radiation thermometer was used to measure the surface temperature on the atmospheric side of the solidified slag 18, and a thermocouple was provided on the back of the mold. When the thickness of the solidified slag 18 was 23 mm, the molten slag 3 flowing up to the mold 3 was measured. The temperature transition until the process of being cooled and solidified is measured. The measurement results are shown in FIG. 3. FIG. 3 also shows the transition of the slag temperature at the center position in the thickness direction of the slag and the position in contact with the mold 5, which are obtained by the heat transfer analysis described later. The slag at the position in contact with the mold 5 increases the initial cooling rate significantly by heat conduction to the mold, decreases to 400 ° C. in about 15 seconds, and then reaches a substantially constant temperature. The temperature of the central part of the slag dropped slowly and only decreased to about 1150 ° C after 2 minutes, and the surface on the atmospheric side also decreased to only about 900 ° C after 2 minutes.

這樣，在主要藉由對鑄模5的熱傳導而將熔融熔渣3冷卻的本方式中，鑄模接觸面受到急冷，熔渣的導熱率小，為2 W/（m·K）以下，因而熔渣內部的熱傳導慢，鑄模接觸面以外的冷卻速度小。因此，僅鑄模接觸面的熔渣受到急冷而玻璃化。將鑄模5反轉，從鑄模5落下後的凝固熔渣18若逐片地分開被搬送，則搬送中冷卻從表面開始進行，因而表面的玻璃質直接殘留。In this way, in the present method in which the molten slag 3 is mainly cooled by heat conduction to the mold 5, the mold contact surface is rapidly cooled, and the thermal conductivity of the slag is small, which is 2 W / (m · K) or less. Internal heat conduction is slow, and the cooling rate outside the mold contact surface is small. Therefore, only the slag on the contact surface of the mold is quenched and vitrified. When the mold 5 is reversed and the solidified slag 18 dropped from the mold 5 is transported separately one by one, the cooling during the transport starts from the surface, so the glass on the surface remains directly.

若玻璃質殘留，則如所述般，在用作混凝土用粗骨材的情況下，產生容易泌水的問題或粗骨材的良率降低的問題，因而需要將玻璃質部分改質為結晶質。 因此，需要將玻璃質部分改質為結晶質的溫度保持步驟。If the glassy substance remains, as described above, when it is used as a coarse aggregate for concrete, there is a problem that it is easy to leak water or a problem that the yield of the coarse aggregate is reduced. Therefore, it is necessary to reform the glassy part into a crystal. quality. Therefore, a temperature-maintaining step of reforming the glassy part to crystalline is required.

＜藉由解析進行的冷卻速度的研究＞ 對應如何將玻璃質部分改質為結晶質進行了研究。在進行研究時，藉由傳熱解析對熔渣內部的冷卻速度進行了研究。本製程將熔渣凝固成板狀，因而亦可認為冷卻、凝固過程中的溫度轉移為單純的平板的非穩態一維熱傳導（unsteady one-dimension heat conduction）。該基礎式為下述（1）式。<Research on Cooling Rate by Analysis> A study has been made on how to change the glassy part to crystalline. During the research, the cooling rate inside the slag was studied by heat transfer analysis. In this process, the slag is solidified into a plate shape, so the temperature during the cooling and solidification process can be considered to be an unsteady one-dimension heat conduction of a flat plate. This basic formula is the following formula (1).

[數式1] [Equation 1]

此處，λ為導熱度（W/（m·K）），ρ為密度（kg/m3 ），Cp為比熱（J/（kg·K）），T為熔渣或鑄模的溫度（K），X為厚度方向的長度（m），t為時間（s）。Here, λ is the thermal conductivity (W / (m · K)), ρ is the density (kg / m 3 ), Cp is the specific heat (J / (kg · K)), and T is the temperature of the slag or mold (K ), X is the length (m) in the thickness direction, and t is the time (s).

圖4（a）、圖4（b）表示解析模型，圖4（a）表示鑄模中收容熔渣的狀態，圖4（b）表示從鑄模落下的凝固熔渣。如圖4（a）、圖4（b）所示，對熔渣、鑄模的厚度方向，將熔渣分為10份、鑄模分為10份而進行計算。在從鑄模落下後僅對凝固熔渣進行計算。4 (a) and 4 (b) show an analytical model, FIG. 4 (a) shows a state where slag is contained in a mold, and FIG. 4 (b) shows a solidified slag dropped from the mold. As shown in FIGS. 4 (a) and 4 (b), the thickness direction of the slag and the mold is calculated by dividing the slag into 10 parts and the mold into 10 parts. Only the solidified slag is calculated after falling from the mold.

此處，將大氣-熔渣的界面（interface）的導熱係數hs、鑄模-大氣界面的導熱係數hm、熔渣-鑄模界面的熱阻R設為參數，以溫度計算值與圖3的實測值相符的方式來決定參數的值。大氣-熔渣界面在初期為1300 K以上的高溫的溫度差，因而考慮熱放射。環境溫度Ta固定為293 K，溫度不會上升。從鑄模落下後，假定為隔熱狀態，並無與熔渣外部的熱移動。設為△t=0.5 sec，藉由顯式解法（explicit solution technique）而進行計算。Here, the thermal conductivity hs of the interface between the atmosphere and the slag, the thermal conductivity hm of the mold-atmosphere interface, and the thermal resistance R of the interface between the slag and the mold are set as parameters. Match the way to determine the value of the parameter. Since the air-slag interface has a high temperature difference of 1300 K or more in the initial stage, heat radiation is considered. The ambient temperature Ta is fixed at 293 K, and the temperature does not rise. After falling from the mold, it is assumed to be in a heat-insulated state, and there is no movement from the heat outside the slag. It is set to Δt = 0.5 sec, and calculation is performed by an explicit solution technique.

熔渣的導熱率λ（W/（m·K））使用根據下述（2）式、（3）式計算的值。 當T＞1400 K時， λ=-5.0×10-3 T＋9.20…（2） 當T≦1400 K時， λ=7.78×10-4 T+1.11…（3） 基於荻野（Ogino）等人的高爐熔渣的熱容量測定結果（K.荻野和J.西脇（K.Ogino and J.Nishiwaki），「鋼鐵物性值手冊」煉鐵編（2006）p.350，日本鐵鋼協會（股），（獨）日本學術振興會 製鐵第54委員會），熔渣的比熱Cp在T＜1443 K時，設為Cp=1039 J/（kg·K），在1443 K≦T＜1673 K時，設為Cp=2242.5 J/（kg·K），在1673 K≦T＜1773 K時設為Cp=1326 J/（kg·K）。The thermal conductivity λ (W / (m · K)) of the slag is a value calculated based on the following expressions (2) and (3). When T> 1400 K, λ = -5.0 × 10 -3 T + 9.20… (2) When T ≦ 1400 K, λ = 7.78 × 10 -4 T + 1.11… (3) Based on Ogino et al. The heat capacity measurement results of blast furnace slag (K. Ogino and J. Nishiwaki), "Steel Physical Property Value Manual" Ironmaking (2006) p.350, Japan Iron and Steel Association (stock), (Independence) The 54th Committee of the Japan Society for the Promotion of Science) The specific heat Cp of the slag is set to Cp = 1039 J / (kg · K) when T <1443 K, and set to 1443 K ≦ T <1673 K. It is Cp = 2242.5 J / (kg · K), and is set to Cp = 1326 J / (kg · K) when 1673 K ≦ T <1773 K.

熔渣表面的導熱率及鑄模背面的導熱率分別設定為hs=30 W/（m2 ·K），hm=10 W/（m2 ·K），熔渣-鑄模界面的熱阻設定為R=9×10-4 m2 ·K/W，藉此可與圖3的溫度的實測值大致一致。The thermal conductivity on the surface of the slag and the thermal conductivity on the back of the mold are set to hs = 30 W / (m 2 · K), hm = 10 W / (m 2 · K), and the thermal resistance at the slag-mold interface is set to R = 9 × 10 -4 m 2 · K / W, which can be approximately consistent with the measured value of temperature in FIG. 3.

藉此，可計算熔渣的溫度變化，並基於該溫度變化來對熔渣溫度保持步驟的溫度條件及保持時間進行研究。With this, the temperature change of the slag can be calculated, and the temperature conditions and the holding time of the slag temperature maintaining step can be studied based on the temperature change.

＜溫度條件＞ 對將玻璃質部分結晶化所需的表面溫度進行了研究。剛進行熔渣落下步驟後的凝固熔渣的表面溫度，根據熔渣凝固厚度、將鑄模反轉直至剝離熔渣為止的熔渣的冷卻時間而發生變化。因此，藉由對熔渣凝固厚度與所述冷卻時間進行多種變更而使凝固熔渣表面溫度發生變化，將使表面溫度發生了多種變化的凝固熔渣保持於凝固熔渣保持容器中24小時，對凝固熔渣的鑄模接觸面的最高溫度與玻璃質部分的面積比率的關係進行調查。結果，確認為了將玻璃質部分結晶化，有效的是將表面溫度上升至900℃以上。<Temperature conditions> The surface temperature required for crystallizing a glassy part was examined. The surface temperature of the solidified slag immediately after the slag dropping step is changed according to the solidified thickness of the slag and the cooling time of the slag until the mold is inverted until the slag is peeled. Therefore, by changing the solidification thickness of the slag and the cooling time in various ways, the surface temperature of the solidified slag is changed, and the solidified slag having various changes in surface temperature is held in the solidified slag holding container for 24 hours. The relationship between the maximum temperature of the mold contact surface of the solidified slag and the area ratio of the glassy part was investigated. As a result, it was confirmed that in order to crystallize the vitreous part, it was effective to raise the surface temperature to 900 ° C or higher.

＜保持時間＞ 然後，在將熔渣的凝固厚度與將鑄模反轉直至剝離熔渣為止的熔渣的冷卻時間設為固定的條件下，變更凝固熔渣保持容器內的保持時間，對自凝固熔渣的鑄模接觸面側的表面溫度上升至900℃的時間點算起的保持時間，即，熔渣表面溫度保持為900℃以上的時間，與凝固熔渣的鑄模接觸面的玻璃質部分的面積比率的關係進行了調查。<Holding time> Then, under the condition that the solidification thickness of the slag and the cooling time of the slag until the mold is reversed until the slag is peeled off are fixed, the holding time in the solidified slag holding container is changed, and self-solidification is performed. The retention time from the point when the surface temperature of the mold contact surface side of the slag rises to 900 ° C, that is, the time when the surface temperature of the slag is maintained at 900 ° C or more, the glassy part of the surface in contact with the mold of the solidified slag The relationship of area ratio was investigated.

具體而言，在後述實施例所示的凝固熔渣製造裝置中，將金屬製鑄模5的環繞重複2周而在6分鐘內連續地處理12噸的熔融熔渣3，在凝固熔渣18向凝固熔渣保持容器22的收容結束之後保持規定時間，且在成為規定的保持時間的時間點立即將凝固熔渣18向熔渣冷卻床24排出並擴散，且在大氣中進行冷卻，其中所述凝固熔渣保持容器22配置於將鑄模5反轉時的熔渣落下位置。Specifically, in the solidified slag manufacturing apparatus shown in the examples described later, the surrounding of the metal mold 5 was repeated for 2 weeks, and 12 tons of the molten slag 3 was continuously processed in 6 minutes. After the storage of the solidified slag holding container 22 is completed for a predetermined time, the solidified slag 18 is immediately discharged and diffused to the slag cooling bed 24 at a time point that becomes the predetermined holding time, and is cooled in the atmosphere. The solidified slag holding container 22 is arranged at a slag dropping position when the mold 5 is inverted.

為了計算900℃以上的保持時間，需要特別指定熔渣的鑄模接觸面側的表面溫度上升至900℃的時間點、與下降至小於900℃的時間點。因此，熔渣的鑄模接觸面側的表面溫度上升至900℃的時間點，設為最後的凝固熔渣向凝固熔渣保持容器的收容結束、且該熔渣的鑄模接觸面側的表面溫度達到900℃的時間點，利用所述傳熱解析假定凝固熔渣保持容器內熔渣表面為絕熱邊界條件（adiabatic boundary condition）而求出該時間點。而且，表面溫度降低至小於900℃的時間點，設為將凝固熔渣從凝固熔渣保持容器向熔渣冷卻床排出並擴散的時間點。這基於如下的假定而得出，即，在將凝固熔渣從凝固熔渣保持容器向熔渣冷卻床排出並擴散的時間點，凝固熔渣的表面溫度立即降低至小於900℃。In order to calculate the holding time of 900 ° C or higher, it is necessary to specify a time point when the surface temperature of the mold contact surface side of the slag rises to 900 ° C and a time point when the surface temperature decreases to less than 900 ° C. Therefore, when the surface temperature of the mold contact surface side of the slag rises to 900 ° C., it is assumed that the storage of the last solidified slag in the solidified slag holding container is completed and the surface temperature of the mold contact surface side of the slag reaches At the time point of 900 ° C, the time point was obtained by assuming that the surface of the slag in the solidified slag holding container was an adiabatic boundary condition using the heat transfer analysis. The time point at which the surface temperature is lowered to less than 900 ° C. is the time point at which the solidified slag is discharged from the solidified slag holding container to the slag cooling bed and diffused. This is based on the assumption that at the time point when the solidified slag is discharged from the solidified slag holding container to the slag cooling bed and diffused, the surface temperature of the solidified slag is immediately lowered to less than 900 ° C.

圖5是表示玻璃質面積比率（%）與保持為900℃以上的時間（min）的關係的曲線圖。如圖5的曲線圖所示可知，藉由以900℃以上保持5分鐘，而鑄模接觸面的玻璃質部分的面積比率大致降低至10%左右為止，即便進一步增加保持時間，玻璃質部分的面積比率亦不會大幅變化。據此可確認：為了將鑄模接觸面的玻璃質部分結晶化，有效的是將凝固熔渣的表面溫度以900℃以上保持5分鐘以上。FIG. 5 is a graph showing a relationship between a glassy area ratio (%) and a time (min) for holding at 900 ° C. or higher. As shown in the graph of FIG. 5, it can be seen that the area ratio of the glassy part of the mold contact surface is reduced to about 10% by holding at 900 ° C. for 5 minutes. Even if the holding time is further increased, the area of the glassy part The ratio will not change significantly. From this, it was confirmed that in order to crystallize the vitreous portion of the mold contact surface, it is effective to maintain the surface temperature of the solidified slag at 900 ° C. or higher for 5 minutes or more.

另外，關於即便將圖5中900℃以上的保持時間較5分鐘延長，玻璃質部分的面積比率亦不會大幅低於10%左右的理由，認為基於如下而得出：對於在積層並堆積於熔渣保持容器內的凝固熔渣的最表層部分中，鑄模接觸面朝向上方的凝固熔渣而言，即便延長保持時間，溫度亦不會上升至900℃以上從而不會結晶化。因此，若在熔渣保持容器上，在熔渣收容後設置蓋，或使用燃燒器等簡易加熱源而進行再加熱，則可進一步降低玻璃質部分的面積比率。In addition, even if the holding time of 900 ° C. or higher in FIG. 5 is longer than 5 minutes, the area ratio of the glassy portion is not significantly lower than about 10%. It is considered to be based on the following: In the outermost part of the solidified slag in the slag holding container, the solidified slag with the mold contact surface facing upwards will not rise to a temperature of 900 ° C or higher even if the holding time is extended, and will not crystallize. Therefore, if a lid is provided on the slag holding container after the slag is stored, or a simple heating source such as a burner is used for reheating, the area ratio of the glassy portion can be further reduced.

而且，關於圖5中900℃以上的保持時間的計算值即便為零，而一部分玻璃質熔渣亦結晶化的理由，認為基於如下而得出：對於在熔渣處理的初期收容於熔渣保持容器內的堆積層內下部的凝固熔渣而言，在直至收容最終的凝固熔渣為止的時間內，表面溫度上升，且以900℃以上保持了5分鐘以上。即，認為在熔渣處理的初期收容於熔渣保持容器內的凝固熔渣滿足結晶化的條件而進行結晶化。In addition, even if the calculated value of the holding time at 900 ° C. or higher in FIG. 5 is zero, the reason why a part of the glassy slag is crystallized is considered to be based on the following: In the solidified slag in the lower part of the buildup layer in the container, the surface temperature rose during the time until the final solidified slag was stored, and it was maintained at 900 ° C or higher for 5 minutes or more. That is, it is considered that the solidified slag contained in the slag holding container at the initial stage of the slag treatment satisfies the conditions for crystallization and is crystallized.

然後，對是否可藉由使經熔渣落下步驟而落下的凝固熔渣積層而確保所述溫度條件與保持時間進行了研究。Then, it was examined whether the temperature condition and the retention time can be secured by laminating the solidified slag that has been dropped through the slag dropping step.

＜保溫狀態的熔渣溫度＞ 對熔渣厚度為25 mm的凝固熔渣，計算即將從鑄模落下前的溫度分佈。作為一例，圖6中表示在將熔融熔渣3注入至鑄模後的120秒後的凝固熔渣18內部的溫度分佈的計算結果。凝固熔渣內部的溫度分佈例如為圖6的實線曲線圖。認為剛從鑄模排出後的凝固熔渣的溫度與即將從鑄模落下前的凝固熔渣的溫度大致相同，因而圖6中表述為「剛從鑄模排出後」。<Slag temperature in the heat preservation state> For solidified slag with a thickness of 25 mm, calculate the temperature distribution immediately before falling from the mold. As an example, FIG. 6 shows a calculation result of the temperature distribution inside the solidified slag 18 120 seconds after the molten slag 3 is injected into the mold. The temperature distribution inside the solidified slag is, for example, a solid line graph of FIG. 6. The temperature of the solidified slag immediately after being discharged from the mold is considered to be approximately the same as the temperature of the solidified slag immediately before being dropped from the mold. Therefore, it is expressed as "immediately after being discharged from the mold" in FIG. 6.

剛從鑄模排出後的凝固熔渣中，鑄模接觸面、大氣面的溫度下降，成為內部的溫度高的狀態。若該狀態下使凝固熔渣落下至保持容器內，並不斷地積層而堆積，則堆積層內部的熔渣成為保溫狀態，因而隨時間經過而熔渣內部的熱傳導至凝固時的鑄模接觸面側及大氣側，熔渣整體接近均勻的溫度分佈。由圖6的虛線表示3分鐘後的溫度分佈計算結果。本條件中，暫時降低的鑄模接觸面的溫度亦上升而成為1000℃左右的溫度。In the solidified slag immediately after being discharged from the mold, the temperature of the mold contact surface and the atmospheric surface decreased, and the internal temperature became high. If the solidified slag is dropped into the holding container in this state and continuously stacked and stacked, the slag inside the stacked layer becomes a heat-preserving state, so that the heat in the slag is conducted to the contact surface side of the mold during solidification with time. And the atmosphere, the slag as a whole has a nearly uniform temperature distribution. The calculation result of the temperature distribution after 3 minutes is shown by the dotted line in FIG. 6. In this condition, the temperature of the mold contact surface that is temporarily lowered also rises to a temperature of about 1000 ° C.

本發明的凝固熔渣的製造方法中，在使凝固熔渣從鑄模落下、排出後，需要使包含鑄模接觸面的凝固熔渣的熔渣表面的一部分或整個面的表面溫度上升至900℃以上並保持5分鐘以上。確認使從鑄模排出的凝固熔渣的熔渣厚度方向平均溫度超過900℃，且使該凝固熔渣在坑19或凝固熔渣保持容器內積層，藉此無須使用新的加熱源便可實施所述步驟。In the method for producing solidified slag of the present invention, after the solidified slag is dropped and discharged from the mold, it is necessary to raise the surface temperature of a part or the entire surface of the slag including the solidified slag at the mold contact surface to 900 ° C or higher. And hold for more than 5 minutes. By confirming that the average temperature in the thickness direction of the solidified slag discharged from the mold exceeds 900 ° C. and that the solidified slag is laminated in the pit 19 or the solidified slag holding container, it can be implemented without using a new heating source. Mentioned steps.

＜熔渣積層的溫度＞ 藉由凝固熔渣自身的含熱量使熔渣表面溫度上升至900℃以上的情況，可藉由適當地選擇凝固熔渣的凝固厚度、將鑄模反轉直至使凝固熔渣落下為止的熔渣的冷卻時間及凝固熔渣保持容器內的保持時間等條件來實現。以下對該點進行具體說明。<Temperature of slag stacking> When the surface temperature of the slag rises to 900 ° C or higher due to the heat content of the solidified slag itself, the solidification thickness of the solidified slag can be appropriately selected, and the mold can be inverted until the solidification melts. Conditions such as the cooling time of the slag until the slag falls and the holding time in the solidified slag holding container are realized. This point will be specifically described below.

例如，圖7中表示：在將熔融熔渣注入鑄模後的冷卻時間設為2分鐘，自最後的凝固熔渣落下而收容後算起的凝固熔渣保持容器內的保持時間設為3分鐘（180秒）的情況下，熔渣厚度的平均值與凝固熔渣保持容器內的熔渣堆積層內的熔渣表面溫度的關係。For example, FIG. 7 shows that the cooling time after the molten slag is poured into the mold is 2 minutes, and the holding time in the solidified slag holding container after the last solidified slag is dropped and stored is set to 3 minutes ( 180 seconds), the relationship between the average slag thickness and the slag surface temperature in the slag accumulation layer in the solidified slag holding container.

使用紅外線熱成像法（infrared thermography），從凝固熔渣保持容器上部測定凝固熔渣的溫度，並將從表層的凝固熔渣的間隙測定的凝固熔渣（以下有時亦稱作「表層下的凝固熔渣」）的表面溫度標示於圖7中，所述凝固熔渣為非表層的凝固熔渣且位於表層的凝固熔渣的下方。存在於該表層下的經試驗的平均厚度為22 mm以上的凝固熔渣的表面溫度的任一測定值均超過了900℃。圖7的橫軸的熔渣厚度為冷卻後測定表層附近的熔渣的厚度所得的值的平均值。Using infrared thermography, the temperature of the solidified slag is measured from the upper part of the solidified slag holding container, and the solidified slag (hereinafter sometimes referred to as "under the surface layer" The surface temperature of the solidified slag ") is indicated in FIG. 7. The solidified slag is a non-surface solidified slag and is located below the surface solidified slag. Any measured value of the surface temperature of the solidified slag having an average thickness of 22 mm or more tested under the surface layer exceeded 900 ° C. The slag thickness on the horizontal axis in FIG. 7 is an average of values obtained by measuring the thickness of the slag near the surface layer after cooling.

另一方面，實線所示的是凝固熔渣的鑄模接觸面的溫度的計算值，且是剛從鑄模排出後的溫度、與凝固熔渣保持容器內作為表層下的凝固熔渣而保持3分鐘（180秒）後的溫度。如圖7所示，可知只要平均厚度為20 mm以上，則保持了3分鐘後的凝固熔渣的鑄模接觸面的溫度計算值超過900℃，平均厚度越大，則鑄模接觸面的溫度越高。On the other hand, the solid line indicates the calculated value of the temperature of the mold contact surface of the solidified slag, and it is the temperature immediately after being discharged from the mold, and is held in the solidified slag holding container as the solidified slag under the surface 3 Temperature after minutes (180 seconds). As shown in FIG. 7, as long as the average thickness is 20 mm or more, the temperature of the mold contact surface of the solidified slag after being held for 3 minutes exceeds 900 ° C. The larger the average thickness, the higher the temperature of the mold contact surface. .

保持容器內積層的表層下的凝固熔渣的表面溫度的測定值與計算結果同樣地存在熔渣厚度越大則越高的傾向，試驗後的平均厚度為22 mm以上的凝固熔渣均在3分鐘後為900℃以上。即，確認表層下的凝固熔渣的表面溫度測定值良好地與計算結果保持一致，根據計算結果及實測值，使平均厚度為20 mm以上的凝固熔渣積層，藉此3分鐘後可使凝固熔渣的表面溫度為900℃以上。The measured value of the surface temperature of the solidified slag under the surface layer held in the container is the same as the calculation result. The larger the thickness of the slag, the higher the tendency. The solidified slag with an average thickness of 22 mm or more after the test is 3. 900 minutes or more after minutes. That is, it is confirmed that the measured surface temperature of the solidified slag under the surface layer is in good agreement with the calculated result. Based on the calculated result and the measured value, the solidified slag having an average thickness of 20 mm or more is laminated, and the solidification can be achieved after 3 minutes The surface temperature of the slag is 900 ° C or higher.

另外，在用以使凝固熔渣的表面溫度上升的熱源僅為凝固熔渣自身的含熱量的情況下，為了減小散熱對外部的影響，而需要將積層並收容於凝固熔渣保持容器內的凝固熔渣的量確保為某種程度的量。具體而言，較佳為將5噸以上、更理想的是10噸以上的凝固熔渣積層為1 m以上的厚度而收容。In addition, when the heat source for increasing the surface temperature of the solidified slag is only the heat content of the solidified slag itself, in order to reduce the external influence of heat radiation, it is necessary to laminate and store the solidified slag holding container. The amount of solidified slag is ensured to some extent. Specifically, it is preferable that the solidified slag which is 5 ton or more, and more preferably 10 ton or more is stacked to a thickness of 1 m or more to be accommodated.

由金屬製的鑄模鑄造的板狀凝固熔渣與緩冷熔渣相比，平均的凝固速度大，因而存在結晶粒小的傾向，而且，如後述般，可緩和、消除鑄模接觸面附近的殘留應力（residual stress），藉此獲得強度特性比緩冷熔渣優異的材質。Compared with slow-cooled slag, plate-like solidified slag casted from a metal mold tends to have a higher average solidification rate, so that crystal grains tend to be smaller, and, as will be described later, residuals near the contact surface of the mold can be eased and eliminated Residual stress to obtain a material with superior strength characteristics than slow-cooled slag.

而且，藉由本發明的凝固熔渣的製造方法製造的凝固熔渣中，以下定義的落下強度（Shatter Index）為70%以上，藉由本發明的凝固熔渣的製造方法，獲得落下強度（Shatter Index）為70%以上的高強度的板狀的凝固熔渣。而且，藉由使用落下強度為70%以上、且由金屬製鑄模鑄造的板狀的凝固熔渣，將該凝固熔渣進行粉碎、篩選而製造混凝土用粗骨材等熔渣製品時的製品良率提高。Further, in the solidified slag manufactured by the method for manufacturing a solidified slag according to the present invention, the drop strength (Shatter Index) defined below is 70% or more, and by the method for manufacturing the solidified slag according to the present invention, the drop strength (Shatter Index) is obtained. ) Is a plate-like solidified slag with a high strength of 70% or more. Furthermore, by using a plate-shaped solidified slag having a drop strength of 70% or more and cast from a metal mold, the solidified slag is crushed and screened to produce slag products such as coarse aggregates for concrete. Rate increases.

進而，在將藉由本發明的凝固熔渣的製造方法製造的凝固熔渣進行粉碎、篩選而獲得的粗骨材中，獲得利用後述方法測定的平均壓縮強度為100 N/mm2 以上的混凝土用粗骨材，從而適合作為製造高強度混凝土時的粗骨材原料。 [實施例]Furthermore, the coarse aggregate obtained by pulverizing and screening the solidified slag produced by the method for producing a solidified slag of the present invention is used for concrete having an average compressive strength of 100 N / mm 2 or more measured by a method described later. Coarse aggregate is suitable as a raw material for coarse aggregate in the production of high-strength concrete. [Example]

根據具體實施例對本發明的作用效果進行說明。The effects of the present invention will be described based on specific embodiments.

本實施例中，使用圖1所示的裝置來製造凝固熔渣。鑄模5為俯視時為梯形形狀的鑄鋼製，其厚度設為45 mm，將相當於梯形的上底的鑄模的外部尺寸（outer dimension）設為0.7 m，將相當於梯形的下底的鑄模的外部尺寸設為1.0 m，將相當於梯形的高度的鑄模的外部尺寸設為2.7 m。而且，流入熔融熔渣的鑄模5的凹陷部5a的深度設為100 mm。藉由環繞移動機構7將鑄模5環繞搬送，環繞搬送的搬送速度在鑄模中心設為14 m/min。In this embodiment, the apparatus shown in FIG. 1 is used to manufacture solidified slag. The mold 5 is made of cast steel having a trapezoidal shape in plan view, the thickness is set to 45 mm, the outer dimension of the mold corresponding to the trapezoidal upper bottom is set to 0.7 m, and the mold corresponding to the bottom of the trapezoidal shape is set. The external dimensions of the mold are set to 1.0 m, and the external dimensions of the mold having a trapezoidal height are set to 2.7 m. The depth of the recessed portion 5 a of the mold 5 flowing into the molten slag was set to 100 mm. The mold 5 is orbitally conveyed by the orbiting mechanism 7. The conveying speed of the orbital conveyance is set to 14 m / min at the center of the mold.

在熔渣流入部位，使1360℃以上且1410℃以下的熔融狀態的高爐熔渣以約2 ton/min流入至鑄模5中。流入了熔融熔渣3的鑄模5在空冷移動部9內以約120秒｛空冷移動部的長度為全周的2/3（240度）｝進行搬送，藉由空冷使熔融熔渣3成為凝固熔渣18。In the slag inflow portion, the blast furnace slag in a molten state of 1360 ° C. to 1410 ° C. is caused to flow into the mold 5 at about 2 ton / min. The mold 5 that has flowed into the molten slag 3 is transported in the air-cooled moving part 9 in about 120 seconds (the length of the air-cooled moving part is 2/3 (240 degrees) of the entire circumference), and the molten slag 3 is solidified by air cooling. Slag 18.

在反轉排出部11中將鑄模5反轉，使已從鑄模剝離的凝固熔渣18落下至配置於坑19的凝固熔渣保持容器22中。使已排出凝固熔渣18的鑄模5在反轉移動部13內保持反轉狀態而移動，且在設置著冷卻裝置21的部位從上下兩面噴射冷卻水而進行急冷。The mold 5 is inverted in the reversing discharge part 11, and the solidified slag 18 that has been peeled from the mold is dropped into the solidified slag holding container 22 disposed in the pit 19. The mold 5 from which the solidified slag 18 has been discharged is moved while maintaining the reversed state in the reversing moving portion 13, and the cooling device 21 is sprayed with cooling water from both the upper and lower sides to perform rapid cooling.

繼而，藉由再反轉部15將反轉狀態的鑄模5再反轉，原來的凹陷部5a再次恢復為朝向上方的狀態。然後，再次向恢復的鑄模流入熔融熔渣。對1次的熔渣鍋將以上的步驟重複進行5周，在15分鐘內連續地處理30噸的熔融熔渣。Then, the mold 5 in the reversed state is reversed again by the re-reverse portion 15, and the original recessed portion 5a is restored to the upward state again. Then, molten slag was again poured into the restored mold. The above steps were repeated for a single slag pot for 5 weeks, and 30 tons of molten slag was continuously processed within 15 minutes.

當所有凝固熔渣從鑄模落下後，在凝固熔渣保持容器內保持規定時間，然後，將凝固熔渣從凝固熔渣保持容器向熔渣冷卻床排出並擴散，且在大氣中冷卻。After all the solidified slag is dropped from the mold, it is held in the solidified slag holding container for a predetermined time. Then, the solidified slag is discharged from the solidified slag holding container to the slag cooling bed and diffused, and cooled in the atmosphere.

本發明例中，設為如下條件，即，熔融熔渣溫度為1385℃，凝固熔渣保持容器內的熔渣收容結束後的保持時間為10分鐘，凝固熔渣的平均厚度為25 mm，從而在規定的保持時間後立即將凝固熔渣從凝固熔渣保持容器向熔渣冷卻床排出並擴散，且在大氣中冷卻。In the example of the present invention, the conditions are as follows: the molten slag temperature is 1385 ° C, the holding time after the slag storage in the solidified slag holding container is 10 minutes, and the average thickness of the solidified slag is 25 mm, so that Immediately after a predetermined holding time, the solidified slag is discharged from the solidified slag holding container to the slag cooling bed and diffused, and cooled in the atmosphere.

比較例中，設為熔融熔渣溫度為1380℃、凝固熔渣的平均厚度為23 mm的條件，使凝固熔渣從鑄模向坑落下，在所有凝固熔渣從鑄模落下後，立即利用鏟車（shovel car）將凝固熔渣從坑中搬出並在熔渣冷卻床中冷卻，以備下一次熔渣鍋內的熔融熔渣的處理。比較例中，若冷卻後測定凝固熔渣的凝固，則厚度為20 mm～26 mm，平均厚度為23 mm。凝固厚度對鑄模接觸面的玻璃質的存在率的影響並非為20 mm～26 mm的範圍。In the comparative example, the conditions were that the molten slag temperature was 1380 ° C and the average thickness of the solidified slag was 23 mm. The solidified slag was dropped from the mold to the pit. After all the solidified slag was dropped from the mold, the forklift was used immediately. (Shovel car) The solidified slag is removed from the pit and cooled in a slag cooling bed to prepare for the next treatment of the molten slag in the slag pot. In the comparative example, when the solidification of the solidified slag was measured after cooling, the thickness was 20 mm to 26 mm, and the average thickness was 23 mm. The influence of the solidification thickness on the existence rate of glassy on the contact surface of the mold is not in the range of 20 mm to 26 mm.

冷卻後的凝固熔渣中，對凝固時的鑄模接觸面的玻璃質部分的比率進行評估，並且對熔渣的落下強度進行評估。In the solidified slag after cooling, the ratio of the glassy part of the mold contact surface at the time of solidification was evaluated, and the drop strength of the slag was evaluated.

首先，藉由目視從由本發明例製造的凝固熔渣中分選出鑄模接觸面無玻璃質的凝固熔渣（結晶質凝固熔渣），另一方面，藉由目視而從由比較例製造的凝固熔渣中分選出鑄模接觸面為玻璃質的凝固熔渣，並進行落下試驗。First, the glass-free solidified slag (crystalline solidified slag) having a contact surface with a mold is selected from the solidified slag produced in the example of the present invention by visual inspection. On the other hand, the solidified slag produced by the comparative example is visually selected. From the slag, a solidified slag having a contact surface with a mold of glass is sorted and subjected to a drop test.

圖8（a）、圖8（b）、圖9（a）、圖9（b）為表示試驗結果的照片，圖8（a）表示本發明例的試驗前的狀態，圖8（b）表示本發明例的落下試驗後的狀態，圖9（a）表示比較例的試驗前的狀態，圖9（b）表示比較例的落下試驗後的狀態。Fig. 8 (a), Fig. 8 (b), Fig. 9 (a), and Fig. 9 (b) are photographs showing test results, Fig. 8 (a) shows a state before the test of the present invention example, and Fig. 8 (b) Fig. 9 (a) shows the state after the drop test of the comparative example, and Fig. 9 (b) shows the state after the drop test of the comparative example.

在凝固熔渣的鑄模接觸面部分為玻璃質的比較例的凝固熔渣中，如圖9（b）所示，藉由落下而整體微細地粉碎。這是因為，在凝固時為大的溫度梯度的表面附近產生大的殘留應力，因而即便為1 m落下程度的相對小的衝擊亦容易斷裂。As shown in FIG. 9 (b), the solidified slag of the comparative example in which the contact surface portion of the mold of the solidified slag was classified as glassy was finely pulverized as a whole as shown in FIG. 9 (b). This is because a large residual stress is generated in the vicinity of the surface having a large temperature gradient during solidification, and therefore it is easy to break even a relatively small impact of a drop of 1 m.

另一方面，藉由本發明的凝固熔渣的製造方法製造的凝固熔渣中，如圖8（b）所示，幾乎不會有整體發生因落下而端部缺損的程度的破碎的情況，從而形成高強度的板狀的凝固熔渣。這是因為，在鑄模接觸面的玻璃質部分結晶化時，表面附近的殘留應力得到緩和或者消除。On the other hand, in the solidified slag produced by the method for producing a solidified slag of the present invention, as shown in FIG. A high-strength plate-like solidified slag is formed. This is because when the glassy part of the mold contact surface is crystallized, residual stress near the surface is relaxed or eliminated.

利用以下說明的方法測定落下強度（Shatter Index）。落下強度試驗的裝置使用日本工業標準（Japanese Industrial Standards，JIS） M8711鐵礦石燒結礦-落下強度試驗方法中記載的裝置。使用40 mm～100 mm的板狀凝固熔渣的樣本（通過孔徑（sieve opening）100 mm的篩、而未通過孔徑40 mm的篩的板狀凝固熔渣的試樣；約3 kg），實施從2 m的高度落下4次的落下試驗。落下試驗後，求出未粉碎為40 mm以下的比率（未通過孔徑40 mm的篩的試樣的質量比率），將該比率設為落下強度（Shatter Index）。關於其他試驗條件，依據作為燒結礦的試驗方法的JIS M8711鐵礦石燒結礦-落下強度測定方法。The drop strength (Shatter Index) was measured by the method described below. As a device for the drop strength test, the device described in the Japanese Industrial Standards (JIS) M8711 iron sintered ore-fall strength test method was used. A sample of plate-shaped solidified slag with a diameter of 40 mm to 100 mm (a sample of plate-shaped solidified slag that passed through a sieve opening of 100 mm and a plate-shaped solidified slag that did not pass through a sieve with a diameter of 40 mm; about 3 kg) was implemented. Drop test 4 times from a height of 2 m. After the drop test, a ratio (mass ratio of a sample that did not pass through a sieve with a pore size of 40 mm) that was not pulverized to 40 mm or less was determined, and this ratio was set as the drop strength (Shatter Index). Regarding other test conditions, the JIS M8711 iron ore sinter ore-fall strength measurement method as a test method for sinter ore was used.

板狀熔渣的落下強度（Shatter Index）藉由下述（4）式而算出。 S（%）：A/B×100…（4） S：判定為40 mm以上的板狀熔渣的落下強度（Shatter Index） A：試驗後的40 mm以上的質量（kg） B：試驗前的40 mm～100 mm的試樣的質量（kg） 將鑄模接觸面的玻璃質部分的比率與落下強度S的關係在本發明例與比較例中進行比較的結果表示於圖10。本發明例中，玻璃質部分的比率從比較例的52面積%降低至9面積%，落下強度S從比較例的46%提高至89%。The drop strength (Shatter Index) of the plate-like slag is calculated by the following formula (4). S (%): A / B × 100 ... (4) S: Drop strength of plate-shaped slag judged to be 40 mm or more (Shatter Index) A: Mass of 40 mm or more after test (kg) B: Before test The mass (kg) of a sample of 40 mm to 100 mm (kg). The relationship between the ratio of the glassy part of the mold contact surface and the drop strength S is shown in FIG. 10 as a result of comparison between the present invention example and the comparative example. In the example of the present invention, the ratio of the glassy portion was reduced from 52 area% to 9 area% of the comparative example, and the drop strength S was increased from 46% to 89% of the comparative example.

根據所述結果，為了有效地藉由玻璃質部分的結晶化而進行凝固熔渣的強度改善，可以說較佳為對於凝固熔渣的表面中的凝固時的鑄模接觸面的80面積%以上、更理想的是90面積%以上，將熔渣表面溫度以900℃以上保持5分鐘以上。即，較佳為將凝固熔渣凝固時的鑄模接觸面的80面積%以上、更理想的是90面積%以上設為結晶質，換言之，將凝固熔渣的鑄模接觸面的玻璃質部分的面積比率設為小於20面積%、更理想的是設為小於10面積%。Based on the results, in order to effectively improve the strength of the solidified slag by crystallization of the vitreous part, it can be said that it is preferably 80% or more of the area of the mold contact surface during solidification on the surface of the solidified slag, More preferably, it is 90% by area or more, and the surface temperature of the slag is maintained at 900 ° C or higher for 5 minutes or more. That is, it is preferable that the area of the mold contact surface of the solidified slag during solidification is 80% by area or more, and more preferably 90% by area or more of the crystalline material. In other words, the area of the glassy portion of the surface of the mold contact surface of the solidified slag is solidified. The ratio is set to less than 20 area%, and more preferably set to less than 10 area%.

然後，為了使如所述般製造的本發明例及比較例的凝固熔渣成為混凝土粗骨材，而使用撞擊粉碎機（impact crusher）將10噸板狀的凝固熔渣粉碎。然後，將經粉碎的熔渣以20 mm、5 mm的篩進行篩選。藉此，製造出20 mm～5 mm的混凝土用粗骨材。Then, in order to make the solidified slags of the examples of the present invention and the comparative examples manufactured as described above into coarse concrete aggregates, a 10-ton plate-shaped solidified slag was crushed using an impact crusher. Then, the crushed slag is sieved with a sieve of 20 mm and 5 mm. Thereby, a coarse aggregate for concrete of 20 mm to 5 mm was manufactured.

將20 mm～5 mm的粗骨材製品相對於成為原料的凝固熔渣的良率的結果在本發明例與比較例中進行比較並表示於圖11中。本發明例的粗骨材製品的良率為71%，比較例為65%。即，比起比較例的粗骨材製品的良率，本發明例高出6%。The result of comparing the yield of the coarse aggregate product of 20 mm to 5 mm with respect to the solidified slag used as the raw material is compared in the present invention example and the comparative example and is shown in FIG. 11. The yield of the coarse aggregate product of the example of the present invention was 71%, and that of the comparative example was 65%. That is, the yield of the coarse aggregate product of the comparative example is 6% higher than that of the present invention.

測定本發明例的粗骨材的吸水率為0.9%，與現有的高爐緩冷熔渣粗骨材的吸水率即3%～4%相比明顯減小，從而獲得與天然骨材同等的吸水率。The water absorption of the coarse aggregate of the example of the present invention was measured to be 0.9%, which was significantly reduced compared with the existing water absorption of the blast furnace slow-cooled slag coarse aggregate, which is 3% to 4%, thereby obtaining the same water absorption as the natural aggregate. rate.

而且，對本發明例及比較例的熔渣粗骨材的壓縮強度進行比較。關於壓縮強度測定用的樣本，從包含平坦面的稍大的粗骨材粒子中，以該平坦面作為底面而利用金剛石切割器切出10 mm×10 mm×10 mm的尺寸，且使用安思來型壓縮試驗機（萬能式壓縮試驗機（Universal testing machine））對各6個試樣測定壓縮強度。Furthermore, the compressive strength of the slag rough aggregates of the examples of the present invention and the comparative examples was compared. For a sample for measuring the compressive strength, a size of 10 mm × 10 mm × 10 mm was cut out using a diamond cutter from a slightly larger coarse aggregate particle including a flat surface with the flat surface as a bottom surface. A compression tester (universal testing machine) measured the compression strength of each of the six samples.

自比較例的粗骨材採取的試樣的壓縮強度的平均值為50 N/mm2 ，最低值為10 N/mm2 ，存在不均非常大、且強度非常低的粗骨材試樣。與此相對，自本發明例的粗骨材採取的試樣的壓縮強度的平均值為167 N/mm2 ，最低值為80 N/mm2 ，從而穩定地獲得高壓縮強度。The average value of the compressive strength of the sample taken from the coarse aggregate of the comparative example was 50 N / mm 2 , and the lowest value was 10 N / mm 2. There were coarse aggregate samples with very large unevenness and very low strength. In contrast, the average value of the compressive strength of the sample taken from the coarse aggregate of the example of the present invention was 167 N / mm 2 , and the minimum value was 80 N / mm 2 , so that high compressive strength was stably obtained.

使用本發明例及比較例的熔渣粗骨材調配混凝土且對特性進行了評估。在調配了本發明例的粗骨材的新拌混凝土與調配了比較例的粗骨材的新拌混凝土中對泌水量進行比較。將調查結果表示於圖12中。玻璃質表面少的本發明例的泌水量比玻璃質表面多的比較例小。Concrete was prepared using the slag coarse aggregate of the examples and comparative examples, and the characteristics were evaluated. The amount of bleeding was compared between freshly mixed concrete prepared with the coarse aggregate of the example of the present invention and freshly mixed concrete prepared with the coarse aggregate of the comparative example. The investigation results are shown in FIG. 12. The example of the present invention with a small glassy surface has a smaller amount of bleeding than the comparative example with a larger glassy surface.

其次，使用各個粗骨材，以追求高強度的水灰比（water-cement ratio）為35%的調配來對混凝土進行攪拌，從而製作壓縮強度測定用的供測試體，且對28日強度進行比較。為了進行比較，亦同樣地製作將市售的天然石灰石用於粗骨材而成的供測試體並進行評估。Next, using various coarse aggregates, mixing the concrete with a water-cement ratio of 35% in pursuit of high strength to mix the concrete to produce a test body for measuring the compressive strength, and the 28-day strength was measured. Compare. For comparison, a test body prepared by using commercially available natural limestone for coarse aggregate was also produced and evaluated.

使用了比較例的粗骨材的混凝土中，28日強度為53 N/mm2 ，與此相對，使用了本發明例的粗骨材的混凝土中，28日強度為75 N/mm2 。使用了天然石灰石的粗骨材的混凝土的28日強度為72 N/mm2 ，使用了本發明例的粗骨材的混凝土獲得了比使用了天然石灰石的粗骨材的混凝土高的壓縮強度。因此，可以說本發明例的粗骨材為適合作為高強度混凝土用的粗骨材的材料。The 28-day strength of the concrete using the coarse aggregate of the comparative example was 53 N / mm 2 , while the 28-day strength of the concrete using the coarse aggregate of the example of the present invention was 75 N / mm 2 . The 28-day strength of the concrete using the coarse aggregate of natural limestone was 72 N / mm 2 , and the concrete using the coarse aggregate of the example of the present invention achieved higher compressive strength than the concrete using the coarse aggregate of natural limestone. Therefore, it can be said that the coarse aggregate of the example of this invention is a material suitable as a coarse aggregate for high-strength concrete.

1‧‧‧凝固熔渣製造裝置1‧‧‧Solidified slag manufacturing device

3‧‧‧熔融熔渣3‧‧‧ molten slag

5‧‧‧鑄模5‧‧‧mould

5a‧‧‧凹陷部5a‧‧‧ Depression

7‧‧‧環繞移動機構7‧‧‧Circular movement mechanism

9‧‧‧空冷移動部9‧‧‧Air-cooled mobile unit

11‧‧‧反轉排出部11‧‧‧ reverse discharge

13‧‧‧反轉移動部13‧‧‧Reverse moving part

15‧‧‧再反轉部15‧‧‧ Reversal Department

17‧‧‧再反轉移動部17‧‧‧Reverse moving part

18‧‧‧凝固熔渣18‧‧‧ solidified slag

19‧‧‧坑19‧‧‧ pit

20‧‧‧流槽:20‧‧‧ flume:

21‧‧‧冷卻裝置21‧‧‧cooling device

22‧‧‧凝固熔渣保持容器22‧‧‧ solidified slag holding container

23‧‧‧熔渣鍋23‧‧‧Slag Pot

24‧‧‧熔渣冷卻床24‧‧‧ Slag Cooling Bed

圖1是示意性地表示實現本發明的凝固熔渣製造方法的凝固熔渣製造裝置的一實施形態的構成的示意圖。 圖2是示意性地表示圖1所示的凝固熔渣製造裝置的凝固熔渣保持容器的示意圖。 圖3是表示在金屬製的鑄模上將熔渣冷卻時的各測定位置的溫度轉移的曲線圖。 圖4（a）、圖4（b）是表示熔渣及鑄模的一維傳熱解析模型的示意圖。 圖5是表示熔渣的表面溫度為900℃以上的保持時間與佔據凝固時的鑄模接觸面的玻璃表面積比率的關係的曲線圖。 圖6是表示凝固熔渣的厚度方向的溫度分佈的計算結果的曲線圖。 圖7是表示熔渣的表面溫度測定值及熔渣溫度的計算值與熔渣厚度的關係的曲線圖，所述熔渣的表面溫度測定值是熔渣收容3分鐘後的堆積於凝固熔渣保持容器內的表層的凝固熔渣下方的熔渣的表面溫度測定值，所述熔渣溫度的計算值是凝固熔渣的鑄模接觸面的剛從鑄模排出後及凝固熔渣保持容器內作為表層下的凝固熔渣而保持3分鐘後的熔渣溫度的計算值。 圖8（a）、圖8（b）是表示凝固時的鑄模接觸面為結晶質的情況下的落下強度試驗前後的熔渣的外觀的照片。 圖9（a）、圖9（b）是表示凝固時的鑄模接觸面為玻璃質的情況下的落下強度試驗前後的熔渣的外觀的照片。 圖10是表示落下強度與佔據凝固時的鑄模接觸面的玻璃質部分比率的關係的曲線圖。 圖11是將20 mm～5 mm粗骨材製造時的製品良率在本發明例與比較例中加以比較而表示的曲線圖。 圖12是將本發明例及比較例的各自在使用了粗骨材的混凝土中的泌水量加以比較而表示的曲線圖。FIG. 1 is a schematic diagram schematically showing the configuration of an embodiment of a solidified slag manufacturing apparatus that realizes the solidified slag manufacturing method of the present invention. FIG. 2 is a schematic view showing a solidified slag holding container of the solidified slag manufacturing apparatus shown in FIG. 1. FIG. 3 is a graph showing temperature transitions at each measurement position when the slag is cooled on a metal mold. 4 (a) and 4 (b) are schematic diagrams showing a one-dimensional heat transfer analysis model of slag and a mold. FIG. 5 is a graph showing the relationship between the retention time at which the surface temperature of the slag is 900 ° C. or higher and the ratio of the surface area of the glass which occupies the mold contact surface during solidification. FIG. 6 is a graph showing a calculation result of a temperature distribution in the thickness direction of the solidified slag. FIG. 7 is a graph showing the relationship between the measured surface temperature of the slag, the calculated value of the slag temperature, and the thickness of the slag, and the measured value of the surface temperature of the slag is accumulated in the solidified slag after 3 minutes of storage The measured surface temperature of the slag below the solidified slag in the surface layer of the holding container. The calculated value of the slag temperature is the surface layer of the solidified slag immediately after being discharged from the mold and in the solidified slag holding container as the surface layer. The calculated value of the slag temperature after holding the solidified slag for 3 minutes. FIGS. 8 (a) and 8 (b) are photographs showing the appearance of slag before and after a drop strength test when the mold contact surface is crystalline during solidification. FIGS. 9 (a) and 9 (b) are photographs showing the appearance of slag before and after a drop strength test when the mold contact surface during the solidification is glassy. FIG. 10 is a graph showing the relationship between the drop strength and the ratio of the glassy portion occupying the mold contact surface during solidification. FIG. 11 is a graph showing a product yield when manufacturing a coarse aggregate of 20 mm to 5 mm in comparison with an example of the present invention and a comparative example. FIG. 12 is a graph showing a comparison between the amount of water bleeding in concrete using coarse aggregates in the examples of the present invention and the comparative example.

Claims (8)

一種凝固熔渣的製造方法，包括： 熔渣凝固步驟，將熔融狀態的高爐熔渣流入至移動的金屬製的鑄模中進行冷卻，且以在所述鑄模內成為板狀的方式使其凝固； 熔渣落下步驟，將所述鑄模反轉而使在所述鑄模內已凝固至內部為止的熔渣從鑄模落下；以及 熔渣溫度保持步驟，將落下的熔渣的熔渣表面的一部分或整個面的表面溫度以900℃以上保持5分鐘以上。A manufacturing method of solidified slag, comprising: a slag solidification step of flowing a molten blast furnace slag into a moving metal mold to cool it, and solidifying it in a plate shape in the mold; A slag dropping step of inverting the mold so that the slag which has solidified to the inside of the mold is dropped from the mold; and a slag temperature maintaining step of a part or the entire slag surface of the dropped slag The surface temperature of the surface was maintained at 900 ° C or higher for 5 minutes or longer. 如申請專利範圍第1項所述的凝固熔渣的製造方法，其中在所述鑄模內以成為板狀的方式凝固的高爐熔渣的厚度為20 mm以上且30 mm以下。The method for manufacturing solidified slag according to item 1 of the scope of the patent application, wherein the thickness of the blast furnace slag solidified in a plate-like manner in the mold is 20 mm or more and 30 mm or less. 如申請專利範圍第1項或第2項所述的凝固熔渣的製造方法，其中所述熔渣溫度保持步驟中，對於從所述鑄模落下的凝固熔渣的表面中的凝固時的鑄模接觸面的80面積%以上，將熔渣表面溫度以900℃以上保持5分鐘以上。The method for manufacturing solidified slag according to item 1 or 2 of the scope of application for a patent, wherein in the slag temperature maintaining step, a mold contact during solidification in the surface of the solidified slag dropped from the mold is contacted. The surface area is 80% by area or more, and the surface temperature of the slag is maintained at 900 ° C or more for 5 minutes or more. 如申請專利範圍第1項或第2項所述的凝固熔渣的製造方法，其中所述熔渣溫度保持步驟中，使從所述鑄模落下的凝固熔渣以熔渣厚度方向平均溫度超過900℃而積層。The method for manufacturing solidified slag according to item 1 or 2 of the scope of patent application, wherein in the slag temperature maintaining step, the average temperature of the solidified slag dropped from the mold in the thickness direction of the slag exceeds 900 ℃ and laminated. 如申請專利範圍第1項或第2項所述的凝固熔渣的製造方法，其中所述熔渣溫度保持步驟中，使從所述鑄模落下的凝固熔渣積層於可從落下位置搬出的保持容器內。The method for manufacturing solidified slag according to item 1 or 2 of the scope of application for a patent, wherein in the slag temperature maintaining step, the solidified slag dropped from the mold is laminated and held at a position where the solidified slag can be removed from the dropping position. Inside the container. 一種凝固熔渣，為由如申請專利範圍第1項至第5項中任一項所述的凝固熔渣的製造方法而製造的凝固熔渣，在進行將通過孔徑100 mm的篩而未通過孔徑40 mm的篩的熔渣試樣，從2 m的高度落下4次的落下試驗後，以未通過孔徑40 mm的篩的試樣的相對於落下試驗前的試樣的質量比率進行評估的落下強度（碎裂指數）為70%以上。A solidified slag, which is a solidified slag manufactured by the method for manufacturing a solidified slag according to any one of claims 1 to 5 in a patent application, which is passed through a sieve with a diameter of 100 mm without passing The slag sample with a sieve with a diameter of 40 mm was evaluated by the mass ratio of the sample that did not pass through the sieve with a pore size of 40 mm relative to the sample before the drop test. The drop strength (fragmentation index) is 70% or more. 一種混凝土用粗骨材的製造方法，其包括： 凝固熔渣製造步驟，包含如申請專利範圍第1項至第5項中任一項所述的凝固熔渣的製造方法； 凝固熔渣粉碎步驟，將所製造的凝固熔渣粉碎；以及 篩選步驟，將經粉碎的凝固熔渣篩選。A method for manufacturing coarse aggregate for concrete, comprising: a method for manufacturing solidified slag, comprising the method for manufacturing a solidified slag according to any one of claims 1 to 5 in the scope of patent application; , Crushing the produced solidified slag; and a screening step of screening the crushed solidified slag. 一種混凝土用粗骨材，由如申請專利範圍第7項所述的混凝土用粗骨材的製造方法而製造，平均壓縮強度為100 N/mm2以上。A coarse aggregate for concrete is manufactured by the method for manufacturing a coarse aggregate for concrete described in item 7 of the scope of patent application, and has an average compressive strength of 100 N / mm 2 or more.
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