JP2000143304A - Artificial stone made from slag as principal raw material and production of the same stone - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide artificial building stone having high strength without adding an industrial product such as cement when producing an artificial stone (a consolidated product) by making slag as a principal raw material become consolidated through carbonation reaction. SOLUTION: When this artificial stone is made from a mixture, as a raw material, of slag from a steel-manufacturing process as a principal raw material with an additive, the slag as a principal raw material comprises at least one kind selected from a group consisting of granule slag, coarse grain-form one and small aggregated one, and at least part of the additive comprises water granulated slag. The mixture of the slag with the additive is made to consolidate and to be aggregated by CaCO3 formed through carbonation reaction as a binder.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an artificial stone material using slag generated in a steel manufacturing process as a main raw material, and more particularly, to an artificial stone material formed by consolidating raw slag by a carbonation reaction. Artificial stones that can be used in various applications, such as civil engineering and building materials such as vegetation stones, road surface laying stones, building stones, etc., and underwater laying stones such as seaweed beds and fish reef stones. It relates to a manufacturing method. In particular, the artificial stone material of the present invention is a stone material for seaweed beds, a stone for a rocky shore, a stone for a fish reef, a stone for a sea bottom mound, a stone for a riverbed, a stone for a fishway, a stone for an artificial riverbed, a stone for the setting of lakes and ponds, and furthermore, It is suitable as an underwater submersion stone, such as a stone submerged or laid in the sea, river, lake, marsh, pond or the like for the main purpose of water purification. In addition, the said "seaweed bed" refers to a community of seaweeds (algae, seaweed, etc.) growing on the sea floor.

[0002]

2. Description of the Related Art Conventionally, as a part of effective utilization of slag (eg, blast furnace slag, converter slag, etc.) generated in a steelmaking process, slag is consolidated by a carbonation reaction to obtain a hardened product. Attempts have been made to use it for building materials and the like. However, when a hardened body is obtained by consolidating slag by a carbonation reaction, the slag alone may not provide sufficient strength, and therefore it is necessary to improve the strength of the hardened body by some method.

As a method for producing a high-strength cured product by subjecting slag to a carbonation reaction, JP-A-52-140535 discloses a method of adding cement to slag.
In this method, powdery converter slag is mixed with 5 to 30 parts by weight of Portland cement, an appropriate amount of water is added, and the mixture is subjected to pressure molding, followed by contact reaction with carbon dioxide gas in a high humidity atmosphere to obtain high strength. Of building materials.

[0004]

However, the use of cement, which is an industrial product, for the purpose of utilizing slag, which is a by-product of steel, as in the prior art, is difficult from the viewpoint of recycling of steel by-product and resource saving. This is not desirable from the viewpoint of using slag as a material, and increases the cost for using the slag as a material.

[0005] Recently, attempts have been made to use slag generated in the steelmaking process as a material for submerging underwater such as stones for seaweed beds and fish reefs. Conventionally, as a main form when slag is used as these materials, there are known a method in which a massive slag of 200 mm or more is used as it is as a stone for seaweed beds and a method in which slag is used as an aggregate such as a concrete fish reef. Have been.

In recent years, there has been a growing trend to improve and improve the natural environment of freshwater water bodies such as rivers and lakes, including the living environment of living organisms such as fish and crustaceans. Attempts have also been made to rehabilitate the environment in which aquatic organisms (fish, crustaceans, aquatic insects, etc.) and aquatic plants (algae, aquatic plants, etc.) can easily live and grow. Taking a river as an example, the so-called life space (biotope) of living and resting space in a river is mostly provided by stones in the riverbed, and therefore, the riverbed generally has many irregularities due to stones and the like. It can be said that the riverbed is in an environment where underwater organisms are more likely to survive. For example, the relatively large space between submerged or semi-submerged large blocks of stone in a river and the small space between small stones laid on the riverbed are both vital spaces for underwater organisms. Becomes Also,
Riverbed stones are also places where aquatic plants such as algae grow, and the presence of stones is also important for growing aquatic plants.

[0007] Therefore, in rehabilitation of a riverbed or the like performed as part of the maintenance and improvement of the natural environment of a river, a stone is laid or laid in an appropriate form on the riverbed (for example, a large stone laying stone, a riverbed). Laying, laying, etc. of medium and small blocks of stone material), and inhabit underwater organisms such as fish and aquatic plants,
It can be an effective means of preparing an environment that is easy to grow. However, rehabilitation of such riverbeds requires an enormous amount of stone materials, and procuring natural stones for use elsewhere may cause new destruction of natural resources. Since it is not cheap, the construction cost also increases. Therefore, the use of slag as described above can be considered as a stone material used for this river.

However, the above-mentioned method using slag as a material for submersion in water has the following problems. First, in a method in which massive slag is used as it is as a stone material for seaweed beds or riverbeds, Ca contained in the slag may be dissolved in water, thereby increasing the pH of seawater, river water, or the like. In addition, the amount of Ca dissolved in water and Mg in water
The reaction with ions may cause precipitation (white precipitation) of Mg (OH) ₂ , which adheres to the slag surface and has a problem of inhibiting the formation and germination of aquatic plants such as algae. Furthermore, the strength of the slag itself is reduced due to the elution of the Ca component, and the slag may be broken down over time or under the action of an external force.

[0009] Further, when the massive slag obtained in the steel making process is used as a stone material for seaweed beds, etc., compared with concrete products, the growth of aquatic plants such as seaweeds and the like can be considered due to the surface properties and the like. Although it can be said that it is suitable for growth, it has only the same function as natural stone (adhesiveness and growth of aquatic plants such as seaweeds) as a stone material for seaweed beds, and can grow aquatic plants such as seaweeds. It is not a stone with a special function that can be promoted.

Further, slag generated in the steel making process contains a large amount of metal (iron such as granular iron). Therefore, usually, the slag is pulverized to a certain size to recover the iron contained in the slag. Recycled to the steel manufacturing process. However, slag used as a stone material for seaweed beds and riverbeds needs a certain size, and slag that has been pulverized for metal recovery can hardly be used. For this reason, when using massive slag as a stone material for seaweed beds or the like, bare metal useful as a steel resource can hardly be recovered.

On the other hand, the method of using slag as an aggregate of a precast concrete body such as a concrete fish reef or the like does not easily cause the above-described problem as when the massive slag is submerged in water as it is. However, since the material obtained by this method is a concrete product whose surface is made of cement mortar, the properties of massive slag (for example, irregular Surface properties, etc.).

Stones used for seaweed beds and fishing reefs need to be functionally suitable for the formation and growth of aquatic plants such as seaweeds. Concrete stones include slag as aggregate. Regardless of whether or not it is functionally unsuitable for the formation and growth of aquatic plants such as seaweeds, and it is said that it promotes the adhesion and propagation of lime algae that cause so-called shore burning, and It is not at all suitable as a submerged stone for fishing or fishing reefs.
Also, concrete has a high pH (usually pH 12).
程度 12.5), the pH of surrounding seawater or river water may be increased, or the growth of aquatic plants such as seaweed may be delayed.

[0013] In recent years, it has been recognized that it is necessary to provide a fishway in a dam or a weir provided in a river so that fish can be moved up or down or run upstream. Has also been implemented in various places. This fishway is provided with a waterway (usually a waterway having a width of about 2 to 5 m) in a part of a dam or a weir in which a flow is formed so that fish can move. And various other types are known. A conventional general fishway is provided by cutting off a part of a dam or a weir in a waterway surrounded by a concrete wall.

[0014] Such a conventional fishway does not hinder the movement of fishes unless there is any particular problem in the flow rate of water, the inclination of the bottom, the step, and the like. However, the fishway made of concrete has a smooth bottom, and it is difficult for aquatic plants such as algae to grow. Therefore, the concrete fishway crawls on a riverbed (projections on the surface of stones or aquatic plants) while crawling or moving. There is a problem that it is difficult for underwater creatures (for example, crustaceans and aquatic insects) that move while catching claws or the like on the riverbed in places where the flow is fast. To solve such a problem, there is a method in which the fishway is made of foamed concrete and fine irregularities are formed at the bottom of the fishway. However, such a fishway has a high construction cost and is not practical. In any case, since concrete has a high pH, a fishway made of concrete is not preferable for underwater organisms moving along a riverbed.

Furthermore, in recent years, from the viewpoint of environmental protection, the sea,
Water purification of rivers, lakes and ponds has become a major issue. One of the methods for water purification is to artificially provide an active food chain environment among living organisms in the water, aiming to utilize the self-cleaning action of the ecosystem of living organisms, mainly bacteria. Attempts have been made to use porous concrete blocks that can inhabit various organisms such as aerobic organisms and anaerobic organisms as materials to be submerged or laid in the water or waterside to provide the environment. I have. However, since such conventional materials for water purification are also concrete products, they have the essential problems as described above.

Accordingly, an object of the present invention is to provide an artificial stone material (hardened body) obtained by consolidating slag as a main raw material by a carbonation reaction without having to add an industrial product such as cement to obtain high strength. To provide artificial stone.

Another object of the present invention is to solve the above-mentioned problem of a material for submersion using slag as a raw material,
Seaweed bed stone, Tsukiiso stone, fish reef, etc., seabed mound stone, riverbed stone, fishway stone, artificial riverbed stone, lakes and marshes
As a stone for pond laying, and as a stone for water purification,
When submerged or laid in water such as the sea, rivers, lakes, marshes, ponds, etc., it does not cause problems such as an increase in pH of seawater or river water and the occurrence of white sinking, and the formation of aquatic plants such as seaweeds. It can exhibit excellent functions in terms of life, breeding, breeding of fish and shellfish, formation of living space for fish, etc., water purification, etc.In addition, artificial structures such as fishways provided in river dams and weirs, and stone floors It is an object of the present invention to provide an artificial stone material for submerged submersion that can exert excellent functions in terms of mobility of aquatic organisms other than fish and growth of aquatic plants when submerged or laid in an artificial riverbed such as. .

Another object of the present invention is to provide a manufacturing method capable of manufacturing the above-mentioned artificial stone at low cost and efficiently. Still another object of the present invention is to provide a method of using the above-mentioned artificial stone material for submersion underwater.

[0019]

The inventors of the present invention have conducted experiments and studies to solve the above-mentioned problems, and as a result, have found the following facts. (1) When powdery, coarse, or small slag is carbonized and solidified to obtain a massive artificial stone, the carbonation reaction of only the CaO content of the slag cannot secure sufficient strength of the stone. In order to ensure the strength of a stone material using such slag as a main raw material, a small amount of granulated slag powder (for example, granulated blast furnace slag powder is used industrially and organizationally) as an additive to slag. It is extremely effective to solidify the mixture with carbonic acid after blending with (Easy), whereby a high strength that does not cause cracking or collapse over a long period of time can be stably obtained. The granulated slag fine powder itself is also a steel by-product, and therefore, a high-strength artificial stone material can be obtained by using only slag for both the main raw material and the additive without using industrial products such as cement.

Conventionally, granulated slag, which is a by-product of steel, is often used as a cement admixture. However, since it is vitreous, it has poor CaO dissolving ability unless subjected to alkali stimulus. Is poor in reactivity. The vitreous crushed slag fine powder has a property that a silicate network forming vitreous is broken by alkali. Then, the granulated slag fine powder in which the silicate network is separated by the alkali is in a state in which CaO in the inside is easily dissolved in water, and if carbon dioxide gas is present, a carbonation reaction easily occurs, and slag is generated. To produce CaCO ₃ as a binder for
Therefore, in order to make the granulated slag fine powder into a state in which the silicate network forming the vitreous is divided, the wet slag suitable for the raw slag mixed with the granulated slag fine powder before the carbonation reaction is applied. It is preferable to perform curing.

(2) Powder, coarse or small slag, particularly slag containing a moderate amount of iron (iron originally contained in the slag and / or iron significantly added to the slag), CaO (or C
CaCO generated by the carbonation reaction of aO and MgO)
_{By using 3} (or CaCO ₃ and MgCO ₃ ) as a binder and agglomerated as a stone for submersion in the sea or river, the pH of seawater or river water rises and the occurrence of white settling, etc. It does not cause the problem described above, and exhibits excellent effects in terms of the formation and growth of aquatic plants such as seaweeds, purification of water quality, and the like. Also, when submerged or laid in artificial structures or artificial riverbeds such as fishways provided in river dams and weirs, etc., it also has excellent effects on the mobility of underwater organisms other than fish and the growth of aquatic plants. I do.

(3) In order to obtain a massive artificial stone as described above, a small amount of granulated slag powder is added to powdery, coarse, or small slag, and the slag is brought to a desired density. Piled or filled, and the pile or the packed layer is cured in a wet or dry state by a method that does not lose moisture (for example, by sheeting), and then a slag is consolidated by causing a carbonation reaction in the presence of carbon dioxide gas. The manufacturing method is effective. In addition, according to such a manufacturing method, for example, when trying to obtain a stone material for submersion underwater, the condition of the seabed and riverbed to be applied, the condition of the ocean current and the water current, and also for seaweed beds, fishing reefs, and riverbeds It is possible to manufacture stones of any density and size according to different uses, such as for fishways, for water purification, etc., and it is also very easy to realize large stones.

The present invention has been made based on such findings, and the features thereof are as follows. [1] The main raw material is slag generated in the steel making process.
An artificial stone material using a mixture of the main raw material and the additive as a raw material, wherein the slag serving as the main raw material is at least one of powdery slag, coarse slag, and small slag, and A slag as a main raw material, wherein at least a part of the slag is made of granulated slag fine powder, and a mixture of the slag and the additive is solidified as a binder with CaCO ₃ generated by a carbonation reaction as a binder. And artificial stone.

[2] An artificial stone material using slag generated in a steelmaking process as a main raw material and a mixture of the main raw material and an additive, wherein the slag serving as the main raw material is a powdery slag, a coarse-grained slag. slag, small lumps consists of one or more of the slag, at least a portion of the additional material is made of water-granulated slag, the mixture CaCO ₃ and MgCO that generated by the carbonation reaction of the additive material and the slag ₃ (However, M
gCO ₃ is present as a hydrate, a hydroxide salt or a double salt (including the case where it is present as a hydrate, a hydroxide salt or a double salt) as a binder, and agglomerated.

[3] In the artificial stone material of the above [1] or [2], the blended amount of the granulated slag fine powder in all the raw materials is 2 to 20 w.
An artificial stone material mainly composed of slag, characterized in that it is t%. [4] In the artificial stone material according to any one of the above [1] to [3], the particle size of the granulated slag fine powder is 0.001 to 1.5 mm.
An artificial stone material containing slag as a main raw material.

[5] In the artificial stone material according to any one of the above [1] to [4], the slag as a main raw material is composed of powdery and / or coarse-grained slag that has been subjected to a slag collection process or a slab removal process. An artificial stone material mainly composed of slag. [6] The artificial stone material containing slag as a main raw material, wherein the artificial stone material according to any one of [1] to [5] has a porosity of 10 to 70%.

[7] The artificial stone according to any one of [1] to [6], wherein at least a part of the slag as a main raw material is granulated blast furnace slag, wherein the slag is a main raw material. Artificial stone. [8] In the artificial stone according to any one of the above [1] to [7], a part of the additive is at least one selected from metallic iron, a metal-containing iron material, iron oxide, and an iron oxide-containing material. Characterized by artificial stone made mainly from slag.

[9] The artificial stone according to any one of the above [1] to [7], wherein a part of the additive is soluble silica and / or soluble silica, and the slag is a main raw material. Artificial stone. [10] In the artificial stone according to any one of the above [1] to [7], a part of the additive is CaO, Ca (OH) ₂ , MgO, Mg
(OH) An artificial stone material mainly composed of slag, characterized in that it is at least one selected from ( ₂ ) ₂ . [11] An artificial stone material comprising slag as a main raw material, wherein the artificial stone material is a stone material for submersion underwater in the artificial stone material according to any one of the above [1] to [10].

[12] A method for producing an artificial stone material using slag generated in a steel production process as a main raw material and using a mixture of the main raw material and an additive as raw materials. Slag, slag composed of one or more of small-lumped slag, mixed granulated slag fine powder as at least a part of the additive material, to form a pile by the mixture or a packed layer in any space, A carbonation reaction is caused in the pile or the packed bed in the presence of carbon dioxide gas to consolidate the mixture, thereby obtaining a slag and an additive-agglomerated stone material. Stone manufacturing method.

[13] The production method of the above-mentioned [12], wherein the blended amount of the granulated slag fine powder in all the raw materials is 2 to 20 wt%. Method. [14] The method according to [12] or [13], wherein the granulated slag has a particle size of 0.001 to 1.5 mm. .

[15] In the production method according to any one of the above [12] to [14], after mixing the granulated slag fine powder with the slag as a main raw material, a wet-air curing is performed for 12 to 72 hours. Thereafter, a method for producing an artificial stone material using slag as a main raw material, wherein a carbonation reaction is caused in the presence of carbon dioxide gas. [16] In the production method according to any one of the above [12] to [15],
An artificial slag-based artificial material characterized by blowing carbon dioxide or a carbon dioxide-containing gas into a pile or packed layer of slag, or placing the pile or packed layer under an atmosphere of carbon dioxide or gas containing carbon dioxide. Stone manufacturing method.

[17] In the production method according to any one of the above [12] to [16], as the slag as a main raw material, powdery and / or coarse-grained slag that has undergone a slag collection process or a slab removal process is used. A method for producing an artificial stone material using slag as a main raw material, characterized in that it is used. [18] In the production method according to any one of the above [12] to [17],
A method for producing artificial stone using slag as a main raw material, wherein at least a part of slag as a main raw material is granulated blast furnace slag. [19] In the production method according to any one of the above [12] to [18],
A part of the additive material is one or more selected from iron metal, metal-containing iron material, iron oxide, iron oxide-containing material,
A method for producing artificial stone using slag as a main raw material.

[20] The method according to any one of the above [12] to [18], wherein a part of the additive is soluble silica and / or a soluble silica-containing material. Manufacturing method of artificial stone. [21] In the production method according to any one of the above [12] to [18],
Some of the additives are CaO, Ca (OH) ₂ , MgO, Mg
(OH) _2. A method for producing an artificial stone material using slag as a main raw material, wherein the method is at least one selected from (OH) ₂ .

[22] In the manufacturing method according to any one of the above [12] to [21], the bulk specific gravity / true specific gravity of the pile of slag or the packed layer is in the range of 0.3 to 0.9. And
A method for producing artificial stone using slag as a main raw material. [23] In the production method according to any one of the above [12] to [22],
By passing carbon dioxide or carbon dioxide-containing gas through water,
_A method for producing an artificial stone material containing slag as a main material, characterized by saturating ₂ O and then supplying the slag to a pile or a packed bed of slag for carbonation treatment.

[24] In the production method according to any one of the above [12] to [23], the consolidated pile or packed layer is crushed into a lump having a desired size, and the lump having a fracture surface due to the crushing is crushed. A method for producing an artificial stone using slag as a main raw material, characterized by obtaining a stone. [25] In the production method according to any one of the above [12] to [24],
A method for producing an artificial stone material using slag as a main raw material, wherein the slag is adjusted to an optimum moisture content, and a carbonation reaction is caused in a pile or a packed bed of the slag in the presence of carbon dioxide gas. .

[26] In the production method according to any one of the above [12] to [25], the total amount is 50 mm or less, and the particle size (D30) of 30% by weight from the smaller diameter side of the cumulative particle size distribution (D30) is 80%.
It has a particle size distribution of 0 μm or less and a water content of 3
A method for producing an artificial stone material using slag as a main raw material, wherein a carbonation reaction is caused in a slag pile or a packed bed of 10% to 10% in the presence of carbon dioxide gas.

[27] The method of any of the above-mentioned [12] to [26], wherein the artificial stone to be produced is a stone for submersion in water, wherein the artificial stone is mainly made of slag. Method. [28] A method for using an artificial stone material according to the above [11], wherein the artificial stone material is laid or laid on an artificial structure or an artificial riverbed through which water flows in a river. [29] The use method of the above [28], wherein the artificial stone is laid or laid at least on the bottom of the fishway. [30] The use method of the above-mentioned [28] or [29], wherein the upper surface of the artificial stone material laid or laid is a fractured surface formed by crushing or breaking.

[0038]

BEST MODE FOR CARRYING OUT THE INVENTION The present invention is an artificial stone material mainly made of slag generated in a steel manufacturing process. The slag used as the main material is blast furnace slow cooling slag, blast furnace granulated slag, etc. Decarburized slag, dephosphorized slag, desulfurized slag generated in the process of slag, pretreatment, converter, casting, etc.
Desiliconized slag, steelmaking slag such as cast slag, ore-reduced slag, electric furnace slag, and the like can be mentioned, but are not limited thereto, and a mixture of two or more slags may be used. it can.

Among these slags, examples of typical slag compositions are shown below. (1) Decarburized slag ... T. Fe: 17.5%, CaO: 4
_{6.2%, SiO 2: 11.7%} , Al 2 O 3: 1.4
%, MgO: 8.3%, MnO: 6.2%, P: 0.7
6%, S: 0.04% (2) Dephosphorized slag ... Fe: 5.8%, CaO: 5
_{4.9%, SiO 2: 18.4%} , Al 2 O 3: 2.8
%, MgO: 2.3%, MnO: 1.9%, P: 2.8
%, S: 0.03%

(3) Desulfurized slag: T. Fe: 10.5
%, CaO: 50.3%, SiO 2: 10.0%, Al 2
O ₃ : 5.4%, MgO: 1.1%, MnO: 0.4
%, P: 0.13%, S: 1.8% (4) Desiliconized slag ... Fe: 10.5%, CaO: 1
_{3.6%, SiO 2: 43.7%} , Al 2 O 3: 3.8
%, MgO: 0.4%, MnO: 15.8%, P: 0.
10%, S: 0.19% (5) Granulated blast furnace slag: FeO: 0.3%, CaO: 4
2.0%, SiO ₂ : 33.8%, MnO: 0.3%,
MgO: 6.7%, Al ₂ O ₃ : 14.4%

Among the slags generated in the steelmaking process, dephosphorized slag has a high P content, and desiliconized slag has a high MnO content, so that it is difficult to use them as cement raw materials. However, in the present invention, these slags can be used as a main raw material of the stone for submersion underwater without any problem.

The artificial stone of the present invention is mainly made of slag composed of at least one of powdery slag, coarse slag, and small slag. By using such slag as a main raw material and consolidating it by a carbonation reaction, it is possible to obtain a stone material having a porous property as a whole (surface and inside).

The slag serving as a main raw material may be at least one of powdery slag, coarse slag, and small slag, and other conditions are optional. Therefore, the slag may be a slag that has undergone a slag recovery step or a slab removal step as described below, or may be a slag that does not undergo such a step.

The slag generated in the steel making process is relatively large (typically a few weight% to 30%), though the degree is different.
(% By weight) of metal (iron such as grained iron). Generally, metal is recovered from slag in order to recycle such iron to the steelmaking process. Normal,
The slag is pulverized in order to carry out the slag recovery.Thus, the slag that has undergone the slag recovery process, including slag that has originally been pulverized, coarse-grained, or agglomerated, is inevitably powdery, granular, and coarse. It becomes granular or small lumps. Usually, the particle size of the slag particles that have undergone this slag recovery step is on the order of cm or less (for example, 5 cm or less).

Here, the bullion collecting process is a process of collecting bullion from slag for the purpose of recycling bullion contained in slag as described above.
This is different from the processing performed for the purpose of substantially removing the metal in the slag as in the metal removal processing described later.
Generally, slag is not finely crushed in the slag recovery process, and therefore, a considerable amount of slag still remains in the slag after the process.

When the slag is used as the material of the stone for submersion in water, the iron content in the slag generally does not need to be as low as the case where the slag subjected to the later-described metal removal processing is used as the material of the stone. Rather, it is better to contain an appropriate amount of iron (particularly, metallic iron such as granular iron or a metal-containing iron material). this is,
This is because the iron (metallic iron, metal-containing iron material, etc.) contained in the slag in an appropriate amount elutes into the water, whereby iron is replenished as a nutrient in the water, and this effectively acts on the growth of aquatic plants such as seaweeds. . For this reason, usually, it is appropriate that the iron content in the slag is 3% by weight or more.

The iron in the slag may be left without recovering part or all of the metal (such as granular iron) originally contained in the slag, and may be used as it is, or may be used once. After removing substantially all of the metal in the slag (except for metal that cannot be inevitably removed) by metal ingot removal treatment, the metal is secured by adding metallic iron and / or metal-containing iron as an additive. Is also good.

In the latter method, that is, a method in which substantially all of the ingot in the slag is once removed by the ingot removal treatment, and then metallic iron and / or a metal-containing iron material is added as an additive, There are the following advantages. (1) It is difficult to accurately adjust the amount of the slag remaining in the slag by a method in which a portion of the slag originally contained in the slag (granular iron or the like) is left without being collected. That is, the collection of bullion from the slag is performed by magnetic separation, etc., due to the nature of this magnetic separation processing, it is quite difficult to recover the bullion so that a certain amount of bullion remains, Even when this is possible, it is necessary to perform complicated controls and operations in performing the magnetic separation. On the other hand, the latter method removes and collects substantially all of the metal originally contained in the slag, and re-adds metallic iron such as granular iron or a metal-containing iron material. Iron content can be arbitrarily controlled.

(2) For the same reason as described above, the former method, that is, the iron content originally contained in the slag (granular iron etc.)
In the method of leaving a part of the slag without collecting it, the shape and size of the metal to be left in the slag cannot be selected. In general, the iron contained in the slag to be composed of the submerged stone is preferably so-called granular iron, which is metallic iron. Iron does not always remain, but rather granular iron may be collected and removed, leaving large-sized ingots. On the other hand, in the latter method, the shape and size of metallic iron or the like added to the slag can be arbitrarily selected, and a preferable iron source such as granular iron can be contained in the slag.

Therefore, in order to obtain slag containing metallic iron or metallic iron-containing material, it is necessary to first remove substantially all of the slag in the slag (except for the inevitable slag) by the slag removing process. It is most preferable to add metal iron or a metal-containing iron material again. In general, the slag removal process is performed by crushing the slag into powder or coarse particles, and then by magnetic sorting or the like. The slag is necessarily in the form of powder and / or coarse particles (usually 50 m
slag particle size on the order of m or less).

In the above-mentioned slag removal processing, it is preferable to remove as much as possible the slag in the slag except for the inevitably remaining slag component. Usually, the iron content in the slag after the slag removal processing is reduced. The (metal) content is preferably less than 3% by weight. Then, an appropriate amount of metallic iron such as granular iron and / or a metal-containing iron material is added to the slag that has undergone such ingot removal treatment, and a slag having a desired iron content including the metal iron and the metal-containing iron material is obtained. can get.

The metallic iron or metal-containing iron material to be added to the slag is such that a large-sized metal iron or metal-containing iron material does not hinder the molding when the slag is formed, From the viewpoint of increasing the specific surface area of the stones and the like, and increasing the elution property of iron from the stone laid in the water, it is preferable that the particles have a small particle size and a uniform size to some extent. Iron is best.
In addition, as the granular iron, not only the granular iron recovered from the slag but also any other granular iron that can be procured can be used.

In general, slag generated in the steel making process contains a considerable amount (usually 20% to 60% by weight) of Ca.
O is contained, and in the artificial stone material of the present invention, CaO contained in this slag (a slag composed of one or more of granular slag, coarse-grained slag, and small slag) or this CaO is changed. Ca (OH) ₂ is converted into CaCO ₃ by a carbonation reaction, and slag (and additive material particles) particles are consolidated using the CaCO ₃ as a binder to form a mass.

The reaction between CaO and CO ₂ , that is, consolidation using CaCO ₃ generated by a carbonation reaction, is a technique that has been known for a long time. When put down, the CaCO ₃ produced by the following reaction formula, resulting in consolidation phenomenon between the particles of the CaCO ₃ as the binder. CaO + CO ₂ → C
aCO ₃

Conventionally, as a technique utilizing such a carbonation reaction, for example, a method of producing a hardened product such as a building material using a kneaded product of steelmaking crushed slag and water (for example, Japanese Patent Application Laid-Open No. 58-1983) No.-74559), a method for producing a hardened product for high-strength building materials using a mixture of the powdery converter slag and Portland cement as described above (for example, JP-A-52-140535), Pellet production method (for example, JP-A-57-92143, JP-A-5-92143)
8-48642, JP-A-58-133334) and the like. However, these conventional techniques are only intended to produce a hardened product or a non-fired pellet having a required strength in a short time, and carbonize powdery, coarse or small slag. Nothing is shown that the stones obtained by consolidation by the reaction are extremely suitable in terms of their properties and properties as stones for submersion underwater such as for seaweed beds. A technique utilizing the carbonation hardening value of the granulated slag or a technique for activating the carbonation reaction of the granulated slag is not disclosed.

Also, when the particulate matter containing MgO is placed in a carbon dioxide gas atmosphere, MgC is formed by a carbonation reaction.
O ₃ is generated, and a consolidation phenomenon occurs between the particles using the MgCO ₃ as a binder. MgCO ₃ generated by the carbonation reaction of MgO can be used in various forms such as anhydrate, hydrate (eg, dihydrate, trihydrate, pentahydrate, etc.) and hydroxide salt (basic magnesium carbonate). Although, for example, MgCO ₃
Is produced by the following reaction formula. _{MgO + CO 2 + 3H 2 O} → MgCO 3 · 3H 2 O

Most of the slag contains a certain amount of MgO together with CaO. Such slag (a slag composed of at least one of powdery slag, coarse slag, and small slag) is used as a raw material. The artificial stone material of the present invention is MgO or Mg (OH) ₂ in which this MgO is changed.
Is also changed to MgCO ₃ by the above-mentioned carbonation reaction, and slag particles (and additive material particles) are solidified by using MgCO ₃ and CaCO ₃ as binders to form agglomerates.

As described above, MgCO ₃ generated by the carbonation reaction of MgO takes various forms such as anhydrides, hydrates, hydroxide salts and the like. MgCO ₃ contained as a binder may be any of these forms of MgCO ₃ . For example,
The hydrate of _{MgCO 3, MgCO 3 · 2H 2} O, M
gCO ₃ · 3H ₂ O, there is MgCO ₃ · 5H ₂ O, etc., also, M is a hydroxide salt (basic magnesium carbonate)
gCO ₃ · Mg (OH) ₂ · 3H ₂ O, 4MgCO ₃ · Mg
_{(OH) 2 · 4H 2 O} , 4MgCO 3 · Mg (OH) 2 · 5
H ₂ O, there is _{4MgCO 3 · Mg (OH) 2} · 8H 2 O and the like. Further, MgCO ₃ may combine with other salts to form various double salts, and MgCO ₃ existing in the form of such double salts may be used.

In the slag generated in the steelmaking process, some or all of the CaO and MgO contained in the slag absorb Ca over time or other causes due to the absorption of moisture over time or other causes.
H) ₂ or Mg (OH) ₂ , but as described above, there is no problem as a slag used in the present invention.
These Ca (OH) ₂ and Mg (OH) ₂ are also converted into CaCO ₃ and MgCO ₃ respectively by the carbonation reaction, and the artificial stone material of the present invention is obtained.

A small amount of finely ground granulated slag powder is added as at least a part of the additive to the raw slag of the artificial stone material of the present invention, and is produced by the carbonation reaction of CaO contained in the finely ground granulated slag powder. CaCO ₃ contributes to solidification of slag particles as a part of the binder. Granulated slag is, for example, blast furnace granulated slag crushed to 0.1 mm or less.

Usually, the granulated slag fine powder contains about 40 wt% of CaO, which becomes a part of the binder generated by the carbonation reaction, and improves the strength of the stone.
When the CaO source to be a binder in the carbonation reaction is determined only for CaO in the slag, which is the main raw material, a binder (CaCO 2) for binding slag particles with sufficient strength is used.
₃ , the amount of MgCO ₃ ) is insufficient, and the strength as an artificial stone used for various applications (especially, a stone for submersion in water for a long time) cannot be sufficiently secured.

As described above, granulated slag, which is a by-product of steel, is conventionally used as a cement admixture, but since it is vitreous, the CaO dissolving ability is poor unless subjected to alkali stimulation. As such, the carbonation reactivity is poor. The vitreous material of the granulated slag fine powder has a property that a silicate network forming vitreous material is separated by an alkali. When the silicate network is separated by an alkali, the internal CaO becomes water. The carbon dioxide gas is easily dissolved in the slag, and the presence of carbon dioxide gas easily causes a carbonation reaction.
Generate aCO ₃ . Therefore, in order to make the granulated slag fine powder into a state in which the silicate network forming the vitreous is divided, it is preferable to perform appropriate wet-air curing on the raw slag mixed with the granulated slag fine powder. This will be described in detail later.

In order for CaCO ₃ generated by the carbonation reaction of the granulated slag as an additive to function effectively as a binder for the raw material slag particles, the granulated slag must be a fine powder. Those having a particle size of 0.1 mm or less are preferred. Granulated slag having a particle size of more than 0.1 mm can no longer be said to be a fine powder, and cannot sufficiently function as a binder for slag particles as a main raw material.

The mixing amount of the finely ground granulated slag powder is preferably 2 to 20% by weight in the total raw material. When the blended amount of the granulated slag fine powder is less than 2 wt%, the effect of improving the strength is small, and it is difficult to uniformly disperse the granulated slag fine powder throughout the raw material. On the other hand, if the mixing amount of the granulated slag fine powder exceeds 20% by weight, the effect of improving the strength of the stone material by the addition thereof is saturated, and on the contrary, the economic efficiency is impaired.

The artificial stone according to the present invention is optionally used in order to obtain a suitable composition in accordance with various uses, particularly in accordance with the situation in water to be applied when used as a submerged stone. In addition, various additives (powder-granular, coarse-grained or small-lumped additives) other than the granulated slag fine powder can be added to the raw slag. Examples of the additive include powder or coarse particles (soluble silica, soluble silica material) serving as a soluble silica source, and powder or coarse particles (metallic iron, metal-containing metal) serving as an iron source as described above. Iron material, iron oxide, iron oxide-containing material), powdered or coarse-grained CaO, Ca
(OH) ₂ , MgO, Mg (OH) _{2 and the} like.

When the artificial stone is used as a submerged stone, the soluble silica and iron sources (metallic iron and iron oxide) contained in the submerged stone are dissolved in water to produce aquatic plants such as seaweed. Effectively affects growth. In addition, from the viewpoint of dissolution into water and the growth of seaweeds, metallic iron and metal-containing iron materials are particularly preferable among iron sources.

Further, CaO, Ca (OH) ₂ ,
When one or more of MgO and Mg (OH) ₂ are added, they are converted into CaCO ₃ and MgCO ₃ by a carbonation reaction to become a part of the binder, or a part of the binder remains as CaO or the like, It performs the following functions. That is, CaO contained in a small amount in submerged stones adsorbs phosphorus and sulfur that cause red tide and sulfur that causes blue tide when the sea floor contains a large amount of phosphorus and sulfur, causing the generation of red tide and blue tide. It is effective in preventing. As described above, when a large amount of CaO is contained in a stone, there is a problem that the pH of seawater is increased. However, in order to adsorb phosphorus and sulfur, a small amount of CaO that remains after carbonation and solidification is required. Is sufficient if it is included.

The powdery or coarse-grained material serving as the soluble silica source includes powdery or coarse-grained soluble silica and / or a soluble silica-containing material. As the soluble silica material, fly ash, clinker ash, or the like generated by coal combustion in a thermal power plant or the like can be used. Of these, fly ash is 45-75% by weight
To the extent that clinker ash contains about 50 to 65% by weight of soluble silica.

Examples of the powdery or coarse-grained material serving as an iron source include powdery or coarse-grained metal iron or metal-containing iron material such as granular iron, and powdery or coarse-grained iron oxide or iron oxide-containing material. Particularly easily and inexpensively available powder or coarse particles include iron-containing dust and mill scale generated in a steelmaking process. Iron-making dust is generally used as the iron-containing dust, and usually, this dust contains about 75% of iron oxide in terms of Fe. The mill scale also contains about 70% iron oxide in terms of Fe.
In addition, the additives are not limited to those described above, and additives of various components (for example, in a greening block for terrestrial plants, an additive containing a fertilizer component) are added according to the use of stone or the like. be able to.

Since granulated blast furnace slag contains a relatively large amount of soluble silica, part or all of the slag used as the main raw material is converted into granulated blast furnace slag, for example, steelmaking slag and granulated blast furnace slag are used. By mixing and using the same, the same effect as in the case where an additive serving as a soluble silica source is added can be obtained.

Further, as described above, when a stone material having a large specific gravity is laid on the seabed where sludge is deposited, the stone material sinks into the sludge, and serves as a stone material for a seaweed bed or a fish reef. May not be fulfilled. Therefore, it is preferable to use slag having a relatively small specific gravity as a main raw material for submerged stones used in the sea area where such sludge is deposited. It is effective to use crushed slag as at least a part of the main raw material.

The artificial stone material of the present invention, which is mainly made of powdery, coarse or small slag, has relatively porous properties, and when used as a submerged stone, it has the following properties. The effect is obtained. Although the porosity of the stone is not particularly limited, it is usually preferable to set the porosity to about 10 to 70%. This porosity can be easily adjusted by adjusting the bulk density (consolidation density) of the raw material slag at the time of carbonation and solidification.

The artificial stone material of the present invention can be used for various purposes, for example, a civil engineering material for terrestrial plant vegetation, a civil engineering material for laying a road surface, a civil engineering material installed for slopes, cliffs and seawalls, Civil engineering and building materials such as building materials, sea,
It can be used for a wide range of purposes, such as stones for submersion in rivers, lakes, marshes, and ponds. In addition, when used as underwater submersion stone, for example, in the sea, as a seaweed bed stone, rocky shore stone, fish reef stone, seabed mound stone, water purification stone, riverbed stone, fishway in rivers Stones for water purification, stones for water purification, etc.
It is used by being laid or laid in water as a stone material for water purification. In addition, the mode of installing the stone material in water is arbitrary, and it may be not only sunk but also fixedly laid in an appropriate structure or the like.

When the artificial stone of the present invention is used as a stone for submersion in water, a part of the stone is exposed on the water surface,
Alternatively, it is needless to say that the present invention can be used in a mode in which the entirety is temporarily exposed on the water surface due to the fluctuation of the water level. Examples of these include stone materials laid on the shore, riverbank, and the shore of a river, and stone materials laid on a slope for seawall and river protection. In addition, as a mode of laying down or laying, not only a block of stone is randomly placed and laid, but also a mode of laying medium and large blocks of stone, and a step of storing small and medium blocks of stone in a gabion or the like. Such as the mode of stacking, the mode of laying by assembling block-shaped stone materials,
Any mode can be adopted.

The artificial stone material of the present invention is also suitable as an underwater laying stone material laid or laid on an artificial structure or an artificial riverbed, such as a fishway stone material. It is sunk or fixedly laid at the bottom of the car. In addition to the fishway, for example, the upper surface of an artificial structure portion through which water flows (for example, a gentle inclined surface of an artificial structure portion that constitutes a part or all of a head work such as a weir) or a fixedly constructed artificial structure portion It can also be fixedly laid on any structural part such as a riverbed (for example, a riverbed constructed of stone or stonework).

The artificial stone of the present invention can be used in any form (size, shape, etc.) when used as civil engineering / building material, underwater laying stone, or the like.
The order of m or more to the order of several tens of mm may be appropriately selected according to the application. Also, as the shape of the stone, as described later, if the stone is cut out from a pile or a packed bed of carbonated and solidified slag by crushing with a heavy machine, etc. If carbonation is solidified in the packed bed, a massive stone material in the shape of the packed bed is obtained. In the latter case, the shape of the stone can be any shape such as a sphere, a panel, a rectangular parallelepiped or a cubic block, a cylinder, a container, and the like. Grooves, protrusions and the like can be provided.

Further, in the case of fixedly laying in a fishway, another artificial structure, an artificial riverbed, or the like, in order to facilitate the installation and, in some cases, to lay it fixedly with only a stone masonry, It is preferable to use it in a block shape, a panel shape, a tile shape or a shape close to it (a fixed material). However, also in a fishway or the like, an irregular shaped massive stone may be simply laid down at the bottom thereof.

The artificial stone of the present invention has the following advantages as a stone applied to the various uses described above. It is possible to economically obtain high-strength artificial stone using only slag for both main raw materials and additives, without using industrial products such as cement, etc., and realize the use of slag in an ideal form. it can.

In particular, stones for submersion underwater have the following advantages. Since most of CaO (or Ca (OH) ₂ generated from CaO) contained in the slag changes to CaCO ₃ , an increase in pH of seawater due to CaO can be prevented. Generally, the pH of natural stone (limestone) is about 9.3, and the pH of concrete is about 12 to 12.5. However, the artificial stone of the present invention has a pH of about 10 which is equivalent to that of natural stone due to the neutralization reaction at the time of production. be able to. Further, it is possible to prevent the occurrence of white precipitation due to the reaction between the Ca component and the Mg ions in the water. On the other hand, an appropriate amount of iron (especially metallic iron, metal-containing iron material) in slag
Is contained, the iron content elutes into the water, so that the iron content is replenished as a nutrient in the water, and this effectively acts on the growth of aquatic plants such as seaweeds.

A mass obtained by carbonating and solidifying a slag composed of at least one of a granular slag, a coarse slag, and a small slag has a porous property as a whole (surface and inside), For this reason, seaweeds easily adhere to the surface of the stone, and the inside of the stone is porous, which is a component effective in promoting the growth of aquatic plants such as seaweed contained in the stone (for example, soluble silica and iron). Easily elutes in water. Therefore, the growth of aquatic plants such as seaweeds can be effectively promoted as compared with the case where the massive slag is used as it is as a stone for submersion underwater or as compared with a concrete fish reef using slag as an aggregate.

In particular, in order to effectively promote the growth and growth of seaweed on a stone laid in a seaweed bed formation site or the like, it is necessary to promote the growth of larvae of seaweed on the surface of the stone. In this regard, the active ingredient eluted into water from the artificial stone of the present invention is more effective for growing seaweed larvae, since the individual of the seaweed acts more effectively as the stone is closer to the stone. The growth of the young body can be effectively promoted.

When the massive slag itself is used as a stone for submersion in water, the size of the molten slag is generally limited by the cooling method and conditions of the molten slag (usually at most 8 mm).
(Approximately 00 mm), and it is difficult to obtain large blocks of stone having a uniform size. On the other hand, stones obtained by carbonating and solidifying a slag composed of at least one of powdery granular slag, coarse granular slag, and small slag are selected from shapes selected when carbonated or solidified, and cut shapes after carbonized. The size can be adjusted arbitrarily, and a large block of stone, which is particularly preferable as a seaweed bed stone or a fish reef, can be easily obtained. In addition, stones for rivers, lakes, marshes, ponds, etc. can be any stones such as large stones for standing stones, medium stones laid or laid on riverbeds and water bottoms, small stones (split stones), etc. Stones of the size can be easily obtained.

The stone for submersion underwater is the condition of the seabed and riverbed,
It is preferable to use a material having an optimum density (specific gravity) according to the current and the current of the current. For example, when a high-density stone is laid on the seabed where sludge is deposited, the stone sinks into the sludge. As a result, it can no longer serve as seaweed bed stone or fish reef. In this regard, stone materials obtained by carbonating and solidifying slag composed of at least one of powdery and granular slag, coarse-grained slag, and small slag are obtained by appropriately adjusting the bulk density (pressure density) of the slag when carbonating and solidifying. , Its density can be adjusted arbitrarily.

The artificial stone of the present invention also has an excellent function as a stone for water purification. That is, as described above, the artificial stone of the present invention has a porous property throughout the stone (surface and inside), and therefore has an excellent microbial carrier function (stably inhabits various organisms, particularly microorganisms). Function) to fix various microorganisms and efficiently promote decomposition of organic pollutants and nitrification of nitrogen compounds by the microorganisms. Furthermore, the excellent function as the vegetation base of aquatic plants as described above provides a growth environment for aquatic plants such as algae, and further, a humid plant, and promotes the absorption of eutrophic nutrients by the plant, thereby improving natural water quality. Improve purification ability. In addition, the aquatic plants cultivated with this stone provide food and habitat for aquatic organisms, thereby securing the environment of the food chain among various living organisms and promoting the ecological system of living organisms and the self-cleaning action of water by the food chain. Let it. By combining such a microbial carrier function and a function as a vegetation base, an excellent water purification action that cannot be obtained with a conventional water purification block made of concrete can be obtained.

Usually, since the artificial stone material of the present invention has a rocky and rugged form by being cut out from a solid pile or a packed bed, when the artificial stone material is laid or laid on a riverbed, a lake or marsh, etc. Larger spaces between stones and between stones and the riverbed are more likely to be created than natural stones of cobblestones or similar shapes found in rivers of the U.S.A. Cheap.

Further, as described above, the artificial stone material of the present invention is particularly suitable for artificial structures such as fishways and water for artificial riverbeds, especially for rivers (hereinafter, stone materials for fishways). In the case where the stone is used for such a purpose, it has the following advantages in addition to the above points.

The surface of a lump obtained by carbonating and solidifying a slag composed of at least one of powdery slag, coarse slag, and small lump slag is porous and has numerous indentations When this is laid or laid at the bottom of a fishway, riverbeds (projections on the surface of stones or aquatic plants)
Even underwater creatures (for example, crustaceans and aquatic insects) that move while hooking on claws or the like can easily move in the fishway. Particularly, the artificial stone material of the present invention has a porous and uneven surface as described above, has a pH similar to that of natural stone, and has a property of easily eluting an active ingredient. It is easy to attach and grow, and the attachment and growth of such aquatic plants makes it easier for the underwater organisms to move in the fishway.

When a stone is used for the fishway, it is only necessary to simply sink the massive stone in the fishway. However, in order to prevent the stone from flowing out due to the water flow, a stone formed into a block or panel shape is used. It is preferable to lay it fixedly on the bottom of a fishway or the like. In this regard, the stone obtained by solidifying the slag by carbonation can be formed into an arbitrary shape at the time of production, so that a block-shaped or panel-shaped one can be easily obtained. By using, it is easy to perform the work of laying fixedly on the bottom of the fishway or the like, and it is possible to lay it securely.

Next, a method for producing the artificial stone material of the present invention will be described. In the method for producing an artificial stone material according to the present invention, granulated slag fine powder as at least a part of an additive is mixed with slag composed of at least one of powdery and granular slag, coarse-grained slag and small-lumped slag, which are main raw materials. Preferably, after the mixture is wet-cured and cured, a pile is formed by the mixture or in a space in any space, or after a mixture is formed in a pile of the mixture or in a space of any shape. Then, the mixture is consolidated by causing a carbonation reaction in the presence of carbon dioxide on the pile or the packed bed after curing under wet and dry conditions to obtain a stone material in which the slag and the additive are aggregated.

FIG. 1 shows an example of a manufacturing flow according to the method of the present invention, and FIG. 2 shows an example of a manufacturing process according to this manufacturing flow. Regarding slag generated in the steel making process, slag is generally collected in the slag, and a considerable proportion of the slag contained in the slag is removed. Normal,
In the slag collection process, the slag is crushed by a crusher or the like to a particle size of cm order or smaller (for example, 5 cm or less) to obtain a granular, coarse or small slag, and then the slag is collected. . The slag only needs to have a particle size capable of recovering the slag.Therefore, if the slag can be recovered even if the particle size is relatively coarse due to the properties of the slag, etc. May be crushed.

In the above-mentioned slag recovery, the slag content rate in the slag after the collection process does not have to be as low as after the slag removal process described later, and an appropriate amount of the slag may be left. This is because when artificial stone is used as submerged stone, iron contained in slag in an appropriate amount (particularly metallic iron, metal-containing iron)
Is dissolved in water, so that iron is replenished in the water as a nutrient, which effectively acts on the growth of aquatic plants such as seaweeds. For this reason, especially in the case of stones for submersion underwater, it is usually sufficient to recover the slag to the extent that 3% by weight or more of the ingot remains in the slag after the recovery treatment.

Further, some slags are carried in a state of spontaneously disintegrating to a particle size capable of recovering the metal (that is, in a state of spontaneously disintegrating into a granular form, a coarse-grained form, or a small lump). In some cases, the above-mentioned pulverizing treatment is not necessary for a fine slag. For example, after the unslagged CaO contained in the slag is cooled and solidified, the slag reacts with moisture or rainwater in the air, water spray during cooling, etc., to cause Ca (O).
H) ₂ is produced, during which the slag expands and collapses,
When powdered or in a slag having a basicity (CaO / SiO ₂ ) close to 2, 2CaO · SiO ₂ (C ₂ S) is generated, and this C ₂ S undergoes transformation expansion in the slag cooling process, and the slag is formed. The slag may be disintegrated, powdered, or the like, and the slag that has been powdered, granulated, or compacted to a particle size that is already capable of recovering the slag can be directly subjected to the slag recovery. .

Normally, the slag is recovered by magnetic separation using a magnetic separator (a method of removing the metal in the slag using a magnet). However, the present invention is not limited to this. It is also possible to use a specific gravity selection method such as a wind power separation utilizing a specific gravity difference between the gold component and the slag component. By this metal recovery, a considerable amount of metal components contained in the slag are recovered. In FIG. 2, 1 is a crusher,
Reference numeral 2 denotes a magnetic separator.

In general, most of the slag that has passed through the slag recovery process contains powder slag particles or coarse slag particles at a certain ratio or more, although the degree of the slag varies to a certain degree. Even if small slag particles with large diameters are mixed, the gaps between the small slag particles are filled with powdery or coarse slag particles. There is almost no risk of disruption. However, when the slag is substantially composed of only small slag particles or when the ratio of the small slag particles in the slag is relatively large, the contact area between the slag particles becomes small. There is a possibility that a problem may occur when carbonation is solidified to have a predetermined strength. Therefore, in such a case,
It is preferable to perform particle size adjustment such as increasing the ratio of powdery or coarse slag particles.

[0095] The iron in the slag may be left without recovering part or all of the metal (granular iron or the like) originally contained in the slag as described above. As described above, the content of iron contained in the slag is arbitrarily controlled, and the shape and size of the iron contained in the slag are arbitrarily selected, and a preferred iron source such as granular iron is slag. In order to be contained in the slag, once the slag is substantially all of the metal (except for unavoidable slag)
It is more preferable to adopt a method of removing metallic iron and / or a metallic iron-containing material as an additive after removing the metallic iron by a metal removal treatment.

Generally, this slag removal treatment is performed in a state where the slag is crushed by a crusher or the like to a particle size of mm order or smaller (for example, 5 mm or less). However,
The slag only needs to have a particle size capable of removing the slag.Therefore, if the slag can be removed even if it is relatively coarse-grained due to the properties of the slag, etc. It may be crushed. For slag that has already been granulated or coarsened due to natural powdering,
In some cases, the above-mentioned pulverizing treatment is not necessary. In the ingot removal process, it is preferable that the ingot in the slag is removed as much as possible except for the inevitable remaining ingot component. Usually, the ingot content rate in the slag after the ingot removal process is 3%. weight%
It is preferred to be less than.

Usually, the metal removal processing is performed by magnetic separation (a method of removing metal in slag by a magnet) using a magnetic separator or the like, but is not necessarily limited to this. A specific gravity selection method such as a wind power separation utilizing a specific gravity difference between the component and the slag component can also be used.

[0098] The slag that has undergone the above-mentioned slag recovery or slag removal is a slag composed of at least one of powdery slag, coarse slag, and small slag.
However, the raw material slag may be at least one of powdery and granular slag, coarse-grained slag, and small-lumped slag. Absent.

As described above, a small amount of finely ground granulated slag is added to the raw material slag as an additive, and if necessary, other additives are added and mixed with the raw material slag. At this stage, the slag can also be adjusted for moisture as needed. This moisture adjustment will be described later in detail. The mixing amount of the granulated slag fine powder is preferably 2 to 20 wt% in the total raw material, and the particle size of the granulated slag fine powder is preferably 0.1 mm or less. These reasons are as described above.

The slag (mixture of the raw material slag and the additive) to which the finely ground granulated slag powder has been added and mixed as described above is preferably subjected to wet-air curing before the carbonation treatment. As described above, the granulated slag fine powder is vitreous, and therefore has poor CaO dissolving ability unless subjected to alkali stimulation, and has poor carbonation reactivity as it is. In order to improve the carbonation reactivity of the granulated slag fine powder, it is necessary to break the silicate network that forms vitreous by alkali, and thus the granulated slag In the slag fine powder, the CaO inside is easily dissolved in water, and the carbonation reactivity is greatly improved.

In order to divide the silicate network forming the glassy of the granulated slag fine powder with alkali and to enhance the carbonation reactivity, the slag mixed with the granulated slag fine powder is appropriately used. It was found that effective moisture curing was effective. That is, the carbonation reactivity is improved by dissolving the granulated slag fine powder in alkali by this wet air curing. Since a certain amount of time is required for this alkali dissolution, if the carbonation treatment is performed immediately after mixing the raw slag and the granulated slag fine powder, the alkalinity of the water around the granulated slag fine powder decreases, and the alkali dissolution occurs. Effect cannot be obtained.

In this wet curing, for example, a mixture of raw material slag and granulated slag fine powder (other additives as necessary) is kneaded in the presence of appropriate moisture, and the mixture is covered with a vinyl sheet. For example, a simple method of preventing water from drying may be used. Further, this wet air curing may be performed before the formation of the pile or the packed bed of the raw material for the carbonation treatment, or may be performed in the state where the raw material is formed into the pile or the packed bed for the carbonation treatment. Good. Further, when the moisture in the raw material becomes insufficient during the curing under moist air, the moisture can be added and kneaded again with a mixer or the like.

As described above, the wet and air curing conditions for dissolving the granulated slag fine powder in alkali and improving the carbonation reactivity thereof were investigated and examined.
It has been found that the carbonation reactivity improvement effect can be sufficiently obtained by securing 2 hours or more. On the other hand, even if the wet-air curing time is lengthened, the strength of the stone material that has been attached does not increase so much, the production takes time, and it is uneconomical.
It is preferable to set the time as the upper limit.

Examples of the additives other than the granulated slag fine powder include powder or coarse particles (soluble silica, soluble silica material) serving as a soluble silica source, and powder particles or coarse particles (soluble silica material) serving as an iron source. Metal iron, metal-containing iron material, iron oxide, iron oxide-containing material), CaO, Ca (OH) ₂ , MgO, Mg (OH) ₂
And the like can be added, and specific examples thereof are as described above. In addition, as the metallic iron or metallic iron-containing material to be added to the slag, granular iron is optimal for the above-mentioned reason. As the granular iron, not only the granular iron recovered from the slag but also any other granular iron that can be procured can be used.

Among these, soluble silica and iron sources (metallic iron and iron oxide) are used when artificial stones are used as submerged stones. Acts effectively on the growth of. In addition, from the viewpoint of dissolution into water and the growth of aquatic plants such as seaweed, metallic iron and metallic iron-containing materials are particularly preferable among iron sources.

The raw material slag and the additive can be mixed by any method, for example, a method of mixing with a kneading machine such as a mortar mixer or a concrete mixer, a method of mixing in a hopper, a slag recovery facility Alternatively, any method can be adopted, such as a method of adding and mixing an additive to the slag that has been subjected to bullion recovery or bullion removal processing in a bullion removal processing facility, or a method of mixing with a heavy machine such as a shovel.

As described above, the granulated slag fine powder is added as an additive (and other additives are added as necessary), and the slag that has been subjected to wet and air curing for a predetermined time is piled up for carbonation treatment. Or it is filled in any space. In addition,
As described above, the wet and air curing may be performed in a state where the raw material is in a pile or a packed layer. Further, after curing in wet air and before filling in a pile or an arbitrary space for carbonation treatment, the moisture of the slag may be adjusted as required.

Here, piles of slag may be piled up in a pile. However, in order to allow the blown carbon dioxide gas to sufficiently flow through the pile, and to prevent the slag from scattering or flowing out due to rainwater, the pile is piled. Is preferably covered with a sheet or the like.

For pile-up or filling of slag, for example, a pit surrounded by partition walls on three sides, a formwork or a container surrounded by partition walls on four sides, or the like can be used. Also in the case where slag is piled or filled in the pits, it is preferable to cover the pile or the filled layer with a sheet or the like, as in the case of the above-mentioned open stacking. Also, when using a mold or a container, it is preferable to cover the slag filling layer with a sheet or to provide a lid. FIG. 2 shows a state where the filling layer A is formed inside the mold 3.

The pile amount or filling amount of the slag is not particularly limited, and may be, for example, a pile amount or filling amount of several to several hundred tons, or a pile amount or filling amount corresponding to about one to several tens of stone materials. It may be the filling amount,
The amount is arbitrary. However, even if the pile amount or the filling amount of the slag is large, the pile or the packed bed after carbonation can be easily cut out by crushing the pile or the packed bed with a heavy machine or the like. When used as a stone for submersion in water, the lump-shaped massive stone has an advantage of having an uneven fracture surface which is advantageous for attachment of aquatic plants such as seaweeds. Therefore, when the stone is used as a submerged stone, it is preferable that the pile amount or filling amount of the slag is somewhat large from the viewpoint of productivity and functions as a stone for a seaweed bed and a fish reef.

It is preferable to adjust the pile of slag or the bulk density (pressure density) of the packed bed according to the density of the stone to be produced. That is, when the stone is used as a submerged stone, the density of the stone is preferably adjusted according to the state of the seabed or the like.For example, when the seabed is muddy or sludge, the stone is mud or sludge. It is preferable to use relatively low-density stones so that they do not sink into the interior.On the other hand, if the seabed is a rocky reef, use relatively high-density stones to prevent the stones from flowing into the ocean currents. Is preferred. Also, depending on the degree of porosity (porosity) of the stone, the degree of adhesion and growth of aquatic plants such as seaweed and the degree of elution of the active ingredient from the inside of the stone also differ.
In some cases, it is preferable to adjust the degree of porosity of the stone according to the condition of the water area to which the stone is applied.

The density of the artificial stone material produced by the method of the present invention depends on the pile density of the slag or the bulk density (consolidation density) of the packed bed. The density of the stone can be easily adjusted by adjusting the degree of compaction of the layer and adjusting the bulk density. The degree of compaction of the pile of slag or the packed bed is arbitrary, but usually the bulk specific gravity / true specific gravity is in the range of 0.3 to 0.9, that is, the porosity in the pile or packed bed is 70 to 10%. % Is compacted.

The slag pile or the packed bed can be compacted by pressing the pile or the packed bed from above with a heavy machine or the like, or by applying vibration to the pile or the packed bed. Can be adopted, and the bulk density of the pile or the packed layer is adjusted by adjusting the degree of compaction when performing these. Further, in the case of producing a low-density stone material, carbonization can be carried out while slag is piled up or filled without compaction.

As a specific method of compaction, for example, when compaction is performed on a pile or a packed layer in a pit, a mold or a container as described above, the target is placed inside the pit, the mold or the container. A weighing line indicating the volume of the slag is displayed, slag of a known weight is put in the slag, and then compaction is performed until the top of the pile or the packed layer reaches the height of the weighing line.

After the adjustment of the bulk specific gravity of the pile of slag or the packed bed as described above is completed, a carbonation reaction is caused in the pile or the packed bed in the presence of carbon dioxide gas to solidify the slag with carbon dioxide. Specifically, a carbon dioxide gas or a carbon dioxide-containing gas is blown into a pile or a packed bed of slag,
Alternatively, the pile or the packed layer is placed under a carbon dioxide gas or a carbon dioxide-containing gas atmosphere, and the slag is carbonized and solidified.

The method of blowing carbon dioxide gas or carbon dioxide-containing gas into the pile or packed bed is not particularly limited.
Gas blowing means is provided at the bottom of the pile or packed bed,
It is most effective to blow gas through this gas blowing means. Specifically, gas supply pipes or hoses are arranged at an appropriate arrangement density at the bottom of the pile or the packed layer (when using pits, formwork or containers, etc., their floors). A carbon dioxide gas or a carbon dioxide-containing gas can be blown out from a gas blowout hole provided in a pipe or a hose at an appropriate pitch (for example, a pitch of 30 to 300 mm × 40 to 400 mm).

As a method for placing a pile or a packed layer in a carbon dioxide gas or a carbon dioxide-containing gas atmosphere, the pile or a packed layer is placed in an airtight space (including a container or the like).
A method of supplying a carbon dioxide gas or a carbon dioxide-containing gas into this space in an arbitrary mode can be adopted. As the carbon dioxide-containing gas used, for example, a lime burning plant exhaust gas (usually, CO ₂ : about 25%) or a heating furnace exhaust gas (usually, CO ₂ : about 6.5%) discharged in an integrated steel mill is used. Suitable, but not limited to. In addition, if the concentration of carbon dioxide in the carbon dioxide-containing gas is too low, there is a problem that the processing efficiency is reduced, but other problems are not particularly significant. Therefore, the concentration of carbon dioxide is not particularly limited, but is preferably 3% or more for efficient processing.

There is no particular limitation on the amount of carbon dioxide gas or gas containing carbon dioxide gas to be blown, and the gas may be blown to such an extent that the pile of slag or the packed bed does not flow. 0.004-0.5m ³ / m
It suffices if a gas blowing amount of about int can be secured. There is no particular restriction on the gas blowing time (carbonation time), but as a guide, the time when the amount of carbon dioxide gas (CO ₂ ) blows becomes 3% or more of the weight of the slag, that is, converted into the gas amount. Then, it is preferable to perform gas blowing until carbon dioxide (CO ₂ ) of 15 m ³ or more per 1 t of material is supplied.

The carbon dioxide gas or the carbon dioxide-containing gas blown into the pile of slag or the packed bed may be at room temperature. However, if the gas is at a higher temperature than room temperature, it is advantageous because the reactivity increases accordingly. However, if the gas temperature is excessively high, CaC
O ₃ is decomposed into CaO and CO ₂ , and MgCO ₃ is also converted into MgO
Because the will decompose into CO _2, it is necessary to use the temperature of the gas to the extent that even does not cause such degradation when using a hot gas.

[0120] Further, moisture is necessary to solidify the slag with carbon dioxide by utilizing the reaction between CaO and MgO and carbon dioxide gas, and the optimum moisture content varies depending on the particle size of the slag. Water content of 3-10%
It is appropriate to set the range. This is Ca
This is because the carbonation reaction is promoted by dissolving O, MgO and carbon dioxide gas. Therefore, it is preferable to adjust the water content of the slag to an optimum water content as needed, and then to cause a carbonation reaction in the presence of carbon dioxide gas.
For this reason, if the water content of the slag is too low, for example,
It is preferable to add water to the slag in the mixing process or the like shown in the production flow of FIG. 1 to perform water adjustment such as increasing the water content of the slag.

The optimum water content (moisture content) of the slag means, for example, the form of water present in the pile of the slag or the inside of the packed bed. A thin water film is formed on the surface of each slag particle. And a state in which water films of adjacent slag particles are partially in contact with each other, and a gas flow path for supplying carbon dioxide to the water film surface of each slag particle surface is secured. It is considered to be.

The optimum moisture content (moisture content) of the raw material slag to be used can be determined, for example, as follows. Water absorption (JIS A)
A raw material slag sample of three or more levels is prepared by adding an arbitrary amount of water equal to or greater than the fine aggregate or coarse aggregate specified in 1109 or A1110), and each raw material slag sample is subjected to drying pores. Fill the mold so that the rate is constant. After humidifying a carbon dioxide gas at a predetermined temperature in the range of 10 to 40 ° C. through a water bath or the like, the slag is blown into the slag packed bed at a constant supply amount and supply time from the bottom in the formwork to carbonate and cure the slag. And solidify. Thereafter, the compressive strength of each solidified massive slag (stone block) is measured, and for example, the relationship between the water content of the raw material slag and the compressive strength as shown in FIG. 3 is obtained, and the maximum value of the compressive strength is obtained. The water content of the raw material slag is set as the optimum water content of the raw material slag, and the water content of the raw material slag is adjusted.

FIG. 3 shows the relationship between the water content of the raw material slag and the compressive strength of the produced massive slag (stone) based on the results of an experiment conducted to examine the effect of the water content of the raw material slag. . In this experiment, the basicity (CaO / S
iO ₂ ): Grind 2.8 steelmaking slag to 5 mm or less,
To this slag, 10 wt% of finely ground granulated slag powder was added, and water was added to adjust the water content to several levels. Each of the slags having these several levels of water content was filled in a mold, and carbon dioxide gas was supplied to the slag packed bed from the bottom of the mold at a supply rate of 0.5 L / min · kg to solidify the slag with carbon dioxide. .

The size of 1 m ×
As a result of measuring the compressive strength of a 1 m × 1 m stone block (mass slag), a relationship between the water content of the raw material slag and the compressive strength of the stone block as shown in FIG. 3 was obtained. Among Although raw slag stone blocks obtained by dampening water content a ₁ two tone has the highest compressive strength, stone blocks obtained raw slag dampening water content a ₂ two-tone is a leaving When I tried to move by grabbing with a bucket after the frame, it collapsed relatively easily.

When supplying carbon dioxide or a carbon dioxide-containing gas to the pile or packed bed of slag, carbon dioxide gas or a carbon dioxide-containing gas is blown into water once to saturate H ₂ O, and By blowing the slag into the mountain or the packed bed, the slag can be prevented from drying and the carbonation reaction can be promoted.

By supplying a carbon dioxide gas or a carbon dioxide-containing gas into the pile of slag or the packed bed as described above, CaO (or Ca (O (O)) as described above is supplied.
H) ₂ ), the reaction of MgO (or Mg (OH) ₂ ) with carbon dioxide produces CaCO ₃ and MgCO ₃ ,
ACO ₃ or CaCO ₃ and MgCO ₃ slag particles becomes binder (and additive particles) are consolidated.

After the completion of carbonation solidification, the pile or the packed bed is crushed to an appropriate size by a heavy machine or the like, if necessary, and a massive underwater stone is cut out. Therefore, a stone material of any size can be obtained depending on the size at the time of cutting. Usually, massive stones are 80-15
It is cut out to a size of 00 mm. In addition, the crushing at the time of cutting causes a rough surface having irregularities on which the seaweeds easily adhere to the stone. In the method of the present invention, by sufficiently reducing the volume of the packed bed, it can be used as a stone as it is without cutting out as described above.

The manufacturing method of the present invention has the following advantages. In order to perform carbonation and solidification in a state where the slag is a pile or a packed bed, by adjusting the degree of compaction of the pile or packed bed and adjusting its bulk specific gravity, for example, a stone used as a stone for submersion in water Can easily be adjusted. As described above, it is preferable to adjust the density and porosity of the stone for submersion underwater according to the conditions of the seabed and riverbed, the ocean current and the water current, etc., and perform such adjustment arbitrarily and extremely easily. What you can do is
In particular, it is a great advantage as a method for manufacturing a stone for submersion in water.
As a conventional technique, a technique of carbonizing and solidifying granulated pellets or the like is known, but it is difficult to adjust the density of the untreated material in a wide range by such a granulation method.

According to the method of the present invention, carbonization and solidification is performed in a state where the slag is formed into a pile or a packed bed, and after completion of carbonation and solidification, the pile or the packed bed is crushed into an appropriate size and a massive stone material having a desired size is cut out. Alternatively, since the packed layer is used as it is as a massive stone material, a stone material having an arbitrary size (for example, 80 to 1500 mm) can be obtained by appropriately selecting the size of the cut stone material and the size of the packed layer. When used as a submerged stone, a large block of stone, which is particularly preferable as a seaweed bed stone or a fish reef, can be easily obtained. In the above-described conventional technology for carbonizing and solidifying the granulated pellets and the like, the size of the obtained lump is limited to about 30 to 50 mm at most, and the lump inevitably also has a small size. Therefore,
The fact that large blocks of stone can be obtained as in the method of the present invention is a great advantage particularly as a method of manufacturing stones for submersion underwater.

After carbonation and solidification, a pile of slag or a packed bed is crushed by a heavy machine or the like, and a method of cutting out massive stones is used. When the stones are used as submerged stones, aquatic plants such as seaweeds adhere to them. It is possible to obtain a massive stone having an easily uneven surface (fracture surface).

When the stone is used as a civil engineering or building material or as a stone fixedly laid on an artificial structure such as a fishway or an artificial riverbed, the stone to be used must be in a block shape or a panel shape. However, in the method of the present invention, a stone having such a shape can be easily obtained by appropriately selecting the size and shape of the packed bed.
Also, when obtaining this block-shaped or panel-shaped stone,
By crushing or breaking a block-shaped stone obtained by carbonation and solidification, a block-shaped or panel-shaped stone having a broken surface on its upper surface can be obtained.

[0132]

[Example 1] Slag having a particle size distribution of not more than 5 mm (decarburized slag, iron content: 20 wt%)
Granulated slag fine powder (particle size: Blaine specific surface area 4000 cm ² / g) at a blending amount of 5 wt% and 10 wt% respectively
Was added and mixed with a mortar mixer. The slag was filled in a container and compacted appropriately, and then wet-cured with a vinyl sheet over the container for various times. Thereafter, a carbon dioxide gas was blown in at a supply rate of 0.2 Nm ³ / hr for 48 hours to solidify the slag with carbon dioxide to form a 200 m
An artificial stone material having a size of mx 200 mm x 200 mm was manufactured. FIG. 4 shows the relationship between the moist air curing time and the compressive strength of the artificial stone thus obtained. According to the figure, it is understood that the stone obtained by securing the wet-air curing time for 12 hours or more has significantly increased strength as compared with the stone having the wet-air curing time of less than 8 hours. On the other hand, if the humid curing time exceeds 100 hours, the increase in strength is small and the production time is long, which is uneconomical.

Example 2 Slag having a particle size distribution of not more than 5 mm (dephosphorized slag, iron content: 6 wt%)
Granulated slag fine powder (particle size: Blaine specific surface area 4000 cm ² / g) was added in various amounts to the mixture and mixed with a mortar mixer. did. After filling this slag in a container and compacting it appropriately, carbon dioxide gas was blown in at a supply rate of 0.4 Nm ³ / hr for 48 hours, and the slag was carbonated and solidified to 400 mm × 400 mm × 400 mm
Size artificial stone was manufactured. FIG. 5 shows the relationship between the blended amount of the granulated slag fine powder and the compressive strength of the artificial stone thus obtained. According to the figure, it can be seen that the strength of the stone having a granulated slag fine powder content of 2 wt% or more is significantly increased as compared with the stone having a granulated slag fine powder content of less than 2 wt%. The granulated slag fine powder content is 20 wt.
%, The effect of improving strength is saturated.

Example 3 Slag having a particle size distribution of 30 mm or less (decarburized slag, iron content: 18 wt.
%) In various amounts, and then mixed with a concrete mixer with a granulated slag fine powder (particle size: Blaine specific surface area 6000 cm ² / g). The container was left outdoors and wet-cured for 48 hours while sprinkling water. Thereafter, a carbon dioxide gas is blown in at a supply rate of 1.8 Nm ³ / hr for 96 hours, and the slag is solidified with carbon dioxide to form 2.0 mm × 2.0 mm.
An artificial stone material having a size of 2.0 mm was manufactured. FIG. 6 shows the relationship between the granulated slag fine powder content of the artificial stone material thus obtained and the compressive strength. According to the figure, it can be seen that the strength of the stone having a granulated slag fine powder content of 2 wt% or more is significantly increased as compared with the stone having a granulated slag fine powder content of less than 2 wt%. Also, it can be seen that when the blended amount of the granulated slag fine powder exceeds 20 wt%, the effect of improving the strength is saturated.

[0135]

As described above, the artificial stone of the present invention is
High strength can be ensured by using only slag for both main raw materials and additives without using industrial products such as cement, and from the viewpoint of recycling of steel by-products and resource saving, It can be said that this is an ideal technology for chemical conversion.

In particular, when used as a submerged stone, there is no problem such as an increase in the pH of seawater or river water and the occurrence of white sinking. Underwater such as sea, river, lake, marsh, pond, etc. When submerged or laid, it has excellent effects on breeding aquatic plants such as seaweeds, breeding fish and shellfish, forming living spaces for fish, etc., purifying water quality, and also dams and weirs on rivers, etc. When laid or laid on artificial riverbeds or other artificial riverbeds such as stone-clad riverbeds, it can exert excellent effects on the mobility of aquatic organisms other than fish and the growth of aquatic plants. it can.

Further, according to the production method of the present invention, since carbonation and solidification are performed in a state where the slag is formed as a pile or a packed layer, the degree of compaction of the pile or the packed layer is adjusted, and the stone material cut out after carbonation and solidification is formed. By appropriately selecting the size, the size of the packed bed, and the like, it is possible to easily and inexpensively produce a stone material for submersion having an arbitrary density and size.

Further, some slag contains γ generated during cooling.
-Transformation expansion of dicalcium silicate and free CaO
Some of them have the property of powdering due to expansion etc. caused by hydration of conventional slag.Conventionally, such powdered slag has no way to be used as a raw material except for part of it being used as a cement raw material, etc. Although it has been discarded, in the present invention, such powdered slag can also be used as a raw material, and it is difficult to use it as a cement raw material or the like due to compositional restrictions, and it is difficult to use slag effectively ( For example, dephosphorized slag, desiliconized slag, and the like can be used as a raw material, and this is a very useful invention in terms of effective use of slag generated in a steel manufacturing process.

[Brief description of the drawings]

FIG. 1 is an explanatory diagram showing an example of a production flow of the present invention.

FIG. 2 is an explanatory view showing a specific example of a manufacturing process of the present invention according to the manufacturing flow of FIG.

FIG. 3 is a graph schematically showing the relationship between the water content of raw material slag and the compressive strength of manufactured stone.

FIG. 4 is a graph showing the relationship between the wet-air curing time of raw slag to which granulated slag fine powder is added and the compressive strength of manufactured stone.

FIG. 5 is a graph showing the relationship between the amount of finely ground granulated slag powder in the raw material and the compressive strength of the manufactured stone.

FIG. 6 is a graph showing the relationship between the amount of finely ground granulated slag powder in the raw material and the compressive strength of the stone produced.

[Explanation of symbols]

 1 ... Pulverizer, 2 ... Magnetic separator, 3 ... Form, A ... Filled bed

Claims (30)

[Claims] 1. An artificial stone material using slag generated in a steel manufacturing process as a main raw material and a mixture of the main raw material and an additive as a raw material, wherein the slag as the main raw material is a powdery granular slag, a coarse granular slag. And at least a part of the additive is made of granulated slag fine powder, and a mixture of the slag and the additive is generated by a carbonation reaction, and CaCO ₃ is used as a binder. An artificial stone material mainly composed of slag, characterized by being consolidated and agglomerated. 2. An artificial stone material using slag generated in a steelmaking process as a main raw material, and a mixture of the main raw material and an additive as a raw material, wherein the main raw material slag is a powdery granular slag, a coarse granular slag. CaCO ₃ and MgCO _3, which are composed of at least one of small-lumped slag, wherein at least a part of the additive is made of granulated slag fine powder, and a mixture of the slag and the additive is formed by a carbonation reaction. (However, Mg
An artificial stone material containing slag as a main raw material, which is obtained by consolidating as a binder (including the case where CO ₃ exists as a hydrate, a hydroxide salt or a double salt) as a binder. 3. The artificial stone material comprising slag as a main raw material according to claim 1, wherein the amount of the finely ground granulated slag powder in all raw materials is 2 to 20 wt%. 4. The artificial stone material using slag as a main raw material according to claim 1, wherein the granulated slag fine powder has a particle size of 0.1 mm or less. 5. The slag as a main raw material is formed of powdery and / or coarse-grained slag that has been subjected to a slag collection process or a slab removal process. Artificial stone made mainly from slag. 6. The artificial stone material comprising slag as a main material according to claim 1, wherein the porosity is 10 to 70%. 7. The blast furnace slag according to claim 1, wherein at least a part of the slag as a main raw material is granulated blast furnace slag.
An artificial stone material mainly comprising the slag according to 3, 4, 5 or 6. 8. The method according to claim 1, wherein a part of the additive is at least one selected from metallic iron, metallic iron-containing material, iron oxide, and iron oxide-containing material. An artificial stone material comprising the slag according to any one of claims 6 to 7 as a main raw material. 9. The slag according to claim 1, 2, 3, 4, 5, 6, or 7, wherein a part of the additive is soluble silica and / or a soluble silica-containing material. Artificial stone. 10. Part of the additive is CaO, Ca (OH)
_The artificial stone material mainly comprising slag according to claim 1, 2, 3, 4, 5, 6, or 7, wherein the slag is at least one selected from the group consisting of ₂ , MgO, and Mg (OH) _2. . 11. The artificial stone according to claim 1, wherein the artificial stone is a stone for submersion underwater.
An artificial stone material mainly comprising the slag according to 9 or 10. 12. A method for producing an artificial stone material using slag generated in a steel production process as a main raw material and using a mixture of the main raw material and an additive as raw materials, wherein the main raw material is a granular slag or a coarse slag. Mixing slag consisting of one or more of small-lumpy slag with granulated slag fine powder as at least a part of an additive, forming a pile by the mixture or a packed layer in an arbitrary space, An artificial stone material comprising slag as a main raw material, wherein the mixture is consolidated by causing a carbonation reaction in the presence of carbon dioxide on a pile or a packed bed to obtain a stone material in which slag and additives are aggregated. Manufacturing method. 13. The method for producing an artificial stone material using slag as a main raw material according to claim 12, wherein the blended amount of the granulated slag fine powder in all raw materials is 2 to 20 wt%. 14. The granulated slag fine powder has a particle size of 0.1 mm.
The method for producing an artificial stone material using slag as a main raw material according to claim 12 or 13, characterized in that: 15. A method comprising mixing granulated slag fine powder with slag as a main raw material, performing wet-air curing for 12 to 100 hours, and then causing a carbonation reaction in the presence of carbon dioxide gas. A method for producing an artificial stone material using the slag according to claim 12, 13 or 14 as a main raw material. 16. The method according to claim 12, wherein a carbon dioxide gas or a carbon dioxide-containing gas is blown into the pile or the packed layer of the slag, or the pile or the packed layer is placed under a carbon dioxide or a carbon dioxide-containing gas atmosphere. , 13,
A method for producing an artificial stone material comprising the slag according to 14 or 15 as a main raw material. 17. A slag as a main raw material, wherein powdery and / or coarse-grained slag that has been subjected to a slag collection process or a slab removal process is used.
A method for producing an artificial stone material using the slag according to 3, 14, 15 or 16 as a main raw material. 18. The blast furnace slag according to claim 12, wherein at least a part of the main raw material slag is granulated blast furnace slag.
A method for producing an artificial stone material using the slag according to 13, 14, 15, 16 or 17 as a main raw material. 19. A part of the additive material is metallic iron, metallic iron-containing material,
An iron oxide or at least one selected from iron oxide-containing materials.
19. A method for producing an artificial stone using the slag according to 17 or 18 as a main raw material. 20. A part of the additive is soluble silica and / or
The method for producing an artificial stone material using slag as a main raw material according to claim 12, which is a soluble silica material. 21. A part of the additive is CaO, Ca (OH)
₂ , ₁₂ , MgO, or at least one selected from Mg (OH) ₂ .
19. A method for producing an artificial stone material using the slag according to 16, 17, or 18 as a main raw material. 22. The slag pile or the packed bed has a bulk specific gravity / true specific gravity in the range of 0.3 to 0.9. ,
22. A method for producing an artificial stone material using the slag according to claim 19, 20 or 21 as a main raw material. 23. A method of saturating H ₂ O by passing carbon dioxide gas or a carbon dioxide-containing gas through water, and then supplying the slag to a pile or a packed bed of slag for carbonation treatment. Terms 12, 13, 14, 15, 16, 1
A method for producing an artificial stone material using the slag according to 7, 18, 19, 20, 21 or 22 as a main raw material. 24. The consolidated pile or packed layer is crushed into a block of a desired size to obtain a block of stone having a fractured surface due to the crushing.
4, 15, 16, 17, 18, 19, 20, 21, 22
Or a method for producing an artificial stone material using the slag according to 23 as a main raw material. 25. The method according to claim 1, wherein the slag is adjusted to the optimum moisture content, and a carbonation reaction is caused in the pile or the packed bed of the slag in the presence of carbon dioxide gas.
2, 13, 14, 15, 16, 17, 18, 19, 2,
A method for producing an artificial stone material comprising the slag according to 0, 21, 22, 23 or 24 as a main raw material. 26. The total amount is 50 mm or less in particle size, the particle size distribution of 30% by weight (D30) from the smaller diameter side of the cumulative particle size distribution is 800 μm or less, and the water content is 3 to 10%. The carbonation reaction is caused to occur in a pile or a packed bed of a certain slag in the presence of carbon dioxide gas.
9. A method for producing an artificial stone material using the slag according to 9, 20, 21, 22, 23, 24, or 25 as a main raw material. 27. The artificial stone material to be manufactured is a stone material for submersion underwater.
5, 16, 17, 18, 19, 20, 21, 22, 2,
A method for producing an artificial stone material using the slag according to 3, 24, 25 or 26 as a main raw material. 28. A method of using an artificial stone material according to claim 11, wherein the artificial stone material according to claim 11 is laid or laid on an artificial structure or an artificial riverbed through which water flows in a river. 29. The method according to claim 28, wherein the artificial stone is laid or laid at least at the bottom of the fishway. 30. The method according to claim 28, wherein an upper surface of the artificial stone laid or laid is a fractured surface formed by crushing or breaking.