JP2006304711A - Stone to be installed under water and method for producing the same - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To obtain a stone to be installed under water, on which objective marine algae, coral, etc., efficiently grow without cleaning the surface of a base after underwater installation. <P>SOLUTION: At least a part of the surface of a carbonated solidified product obtained by solidifying a granular non-carbonated Ca-containing raw material through a carbonation reaction is coated with a film composed of a biodegradable plastic. The surface of the carbonated solidified product is coated with the film only in a period from underwater installation to the start of the growth period of an objective organism, the film is degraded and lost according to at the same time with the start of the growth period, the surface of the carbonated solidified product is exposed to water and the objective organism efficiently grows on the surface of the carbonated solidified product. <P>COPYRIGHT: (C)2007,JPO&INPIT

Description

  The present invention relates to a stone for submerging using a carbonized solid obtained by carbonizing a non-carbonized Ca raw material such as slag, and this stone is mainly used for an aquatic base such as seaweed and coral, and a fish reef. Used as such.

As one of the methods for making slag generated in the steel manufacturing process, a method of obtaining a carbonated solidified body by carbonizing powdered slag using uncarbonated Ca contained therein Is known (for example, Patent Document 1). In this method, for example, powdery slag to which moisture is added is filled into a mold, and carbonation gas is blown into the slag filling layer to cause a carbonation reaction in uncarbonated Ca contained in the slag. The slag filling layer is consolidated using calcium carbonate produced by the crystallization reaction as a main binder to obtain an agglomerated carbonated solidified body.
JP-A-11-71160

  Such a carbonate solidified body is not only very useful from the viewpoint of resource recycling because slag and other CaO-containing waste materials can be used as raw materials, but in particular, a seaweed settlement base (artificial alga reef) When used as a material for underwater subsidence such as for seawater and fish reefs, there is no risk of raising the pH of seawater like concrete products, so it has excellent performance that can provide a favorable environment for the growth of seaweeds and the habitat of aquatic organisms. It is attracting attention as a new material for subsidence to replace concrete products.

  In order to efficiently produce the target seaweed and corals such as kombu and hondawala on the artificial seedling base, the zoospores and larvae that hit those species are released into the sea and are limited to the time when they settle on the basement. It is necessary to install a base in the water. Otherwise, other non-target seaweeds and animals will adhere to the base installed in the water, making it impossible for the target seaweed and corals to attach.

  However, since the implementation of offshore construction (sinking work) depends greatly on the weather conditions, it is often impossible to carry out the sinking work at the most suitable time for the foundation installation. For this reason, if a foundation is installed in the water at a time when the subsidence work can be carried out, and other seaweeds or animals other than the target adhere to this foundation, the target seaweed or coral settlement stage (zoospores and larvae) Measures are taken, such as a diver diving in the sea just before the release period, and cleaning work to remove seaweed and animals attached to the surface of the base. However, such a cleaning operation requires a lot of labor and cost, and this operation depends on weather conditions and the like, and may not be performed at an appropriate time.

Further, in a general production process of a solidified carbonic acid product, a metal mold is filled with a granular uncarbonated Ca-containing raw material such as slag, and carbon dioxide gas (carbon dioxide-containing gas) is blown into the raw material packed layer. To solidify the entire raw material packed bed by solidifying the uncarbonated Ca. Then, by removing the solidified raw material packed bed from the mold, a carbonated solid product as a product is obtained.
As described above, in the conventional process for producing a solidified carbonic acid product, a complicated unframed process is required for each product, and there is a problem in terms of production efficiency. In particular, when mass production of small carbonated solids is desired, production efficiency is very poor due to the de-frame process, and the de-frame of plate-type products is particularly troublesome, so the quantity that can be manufactured at one time. Will be limited.

Accordingly, an object of the present invention is to provide a target seaweed without cleaning the base surface after submerging in a submerged stone using a carbonate solid obtained by carbonizing an uncarbonated Ca raw material. The object is to provide a stone for submergence that can efficiently cause the formation of corals and corals.
Another object of the present invention is to provide an underwater sedimentary stone using a carbonate solid obtained by carbonizing an uncarbonated Ca raw material, which can be produced without a complicated deframing step. The purpose is to provide stones for sinking.
Furthermore, the other object of this invention is to provide the manufacturing method which can manufacture the above stones for submergence efficiently.

  As a technique for solving the above problems, the inventors of the present invention (a) coating the surface of the carbonate solidified body with a biodegradable plastic, and the surface of the carbonate solidified body submerged by this coating for a certain period of time. (B) Furthermore, as one form thereof, a mold for filling an uncarbonated Ca-containing raw material is produced with a biodegradable plastic as one form thereof, The idea was obtained that the produced carbonic acid-solidified product was used as a stone for submerging in water while being held in the mold without being removed from the mold, that is, the mold was used as the covering. According to such a method, since the coating made of biodegradable plastic decomposes and disappears after a certain period of time after the carbonated solid body is set in water, the type and composition of the biodegradable plastic and the thickness of the coating are preliminarily determined. By selecting the length, etc., and setting the period of decomposition / disappearance in water, the carbonized solid surface is covered with the coating only from the time it is submerged until the start of the target organism's settlement period. In accordance with the beginning of the same growing season, the coating can be decomposed and disappeared to expose the surface of the carbonate solidified body, so that the target organism can be efficiently grown on the surface of the carbonized solidified body. . In addition, the method of forming a coating using a mold has an advantage that a frame removal step in producing a carbonated solid can be omitted.

The present invention has been made on the basis of the above idea, and the features thereof are as follows.
(1) Underwater characterized in that a coating made of a biodegradable plastic is applied to at least a part of the surface of a carbonate solidified body obtained by solidifying a granular uncarbonated Ca-containing raw material by a carbonation reaction. Stone for settling.
(2) In the stone material for submerging in (1) above, the biodegradable plastic coating is one or more types of coating materials selected from biodegradable plastic film materials, sheet materials, and plate materials. A stone material for submerging in water, which is formed by being attached to the body surface.
(3) In the stone for submerging in the above (2), irregularities are formed on the surface of the covering material in contact with the carbonate solidified body, and at least a part of the surface of the carbonized solidified body is formed along the irregular surface of the coating material. A stone for submerging in water.
(4) In the stone material for submergence in (1) above, the biodegradable plastic coating is formed by applying a solution of the biodegradable plastic to the surface of the carbonate solidified body and then solidifying it. A characteristic stone for underwater settling.

(5) In the stone for submerging in (1), a mold made of biodegradable plastic and a packed layer of uncarbonated Ca-containing raw material held in the mold are consolidated by a carbonation reaction. The submerged stone material is characterized in that it is composed of a carbonate solid body that is generated by the above-described method and that is retained in the mold as it is, and the mold frame constitutes a coating of the carbonate solidified body.
(6) The underwater sedimentation stone according to (5) above, wherein irregularities are formed on the inner surface of the mold material made of biodegradable plastic.
(7) The underwater subsidence characterized by retaining a coral larval settlement promoting substance in the form of (a) or / and (b) below in the stone for underwater subsidence according to any one of (1) to (6) above Stone material.
(A) The biodegradable plastic composing the coating is made to contain a coral larva settlement promoting substance.
(B) A coral larvae promoting substance is adhered to the inside of the biodegradable plastic coating.
(8) When a carbonated solid is produced using a mold, it is filled with powdered uncarbonated Ca-containing raw material in the mold, and between the inner surface of the mold and the raw material packed layer, and / or raw material filling One or more kinds of coating materials selected from biodegradable plastic film material, sheet material, and plate material are disposed on the upper surface of the layer, and the raw material packed layer is brought into contact with carbon dioxide gas in a state of containing moisture, A method for producing a stone for submergence in water, characterized by obtaining a carbonate solidified body in which at least a part of the surface is coated with the coating material by solidifying by a carbonation reaction.

(9) In the manufacturing method of the above (8), an unevenness is formed on the surface of the coating material in contact with the raw material packed layer, and the manufacturing method of the stone material for submerging in water is characterized by the above.
(10) Applying a biodegradable plastic solution to the surface of the carbonated solidified body obtained by solidifying a powdery uncarbonated Ca-containing raw material by a carbonation reaction, and then solidifying it, so that at least one of the surfaces A method for producing a stone for submergence in water, comprising obtaining a carbonate solidified body having a coating made of biodegradable plastic on the part.
(11) Filling a mold made of biodegradable plastic with a raw material containing powdered uncarbonated Ca, bringing the raw material packed layer into contact with carbon dioxide gas in a state of containing moisture, and solidifying by a carbonation reaction. The underwater settling stone material is characterized in that it comprises the mold and the carbonate solidified body that is held in the mold as it is, and the mold frame obtains the underwater settling stone material that constitutes the coating of the carbonate solidified body. Manufacturing method.

(12) In the manufacturing method of (11) above, a plurality of container-shaped molds made of biodegradable plastic having a plurality of gas passage holes at the top and a plurality of gas through holes at the bottom are used.
By stacking the plurality of molds in which the packed layers of moisture-containing uncarbonated Ca-containing raw materials are held in multiple stages, and supplying carbon dioxide gas from below to the multi-stage stacked form groups, Carbon dioxide gas is sequentially blown into a plurality of raw material packed layers via gas holes at the bottom of each mold,
Each of the raw material filled layers is carbonated by blowing the carbon dioxide gas, thereby comprising the mold and the carbonated solid body held as it is in the mold, and the mold forms a coating of the carbonized solid body. A method for producing an underwater sinking stone characterized by obtaining a stone for underwater sinking.
(13) The stone for submerging in any one of the above (1) to (7) is submerged in the water before the arrival of the egg, zoospore or larvae from the adult organism to be grown on the surface of the stone. And a method for repairing or creating an aquatic organism breeding ground, wherein a coating made of a biodegradable plastic in water is decomposed over time to at least disappear in the release period of the eggs, zoospores or larvae .

According to the stone for submergence of the present invention, by selecting the type / composition of the biodegradable plastic that constitutes the coating, the thickness of the coating, etc., and setting the decomposition / disappearance period in water, The surface of the carbonate solidified body is covered with the coating only during the period from when it is set to the beginning of the target organism's settlement period, and the carbonized solid surface is decomposed and disappeared at the beginning of the same settlement period. It can be made to expose, Thereby, the target organism can be made to grow efficiently on the carbonic acid solidified body surface. For this reason, the degree of freedom in selecting the time when the substrate (stone) is submerged in the water is extremely wide, and cleaning of the surface of the substrate in which the substrate is submerged can be made completely unnecessary. In addition, since biodegradable plastics are decomposed into CO ₂ and water, there is no possibility of adversely affecting the natural environment.

In addition, according to the stone for underwater settling of the invention according to claim 5, since the time-consuming unframed process can be omitted in the manufacturing process, the manufacturing process can be simplified and efficient production can be performed. It is also possible to mass-produce small products such as
Moreover, according to the stone material for submergence of the invention which concerns on Claim 3, 6, the uneven | corrugated formation base surface where seaweed etc. are easy to grow can be easily formed in the carbonate solidified body surface.
Further, according to the stone material for submerging in the invention according to claim 7, when the biodegradable plastic constituting the coating is decomposed / disappeared over time in water, the coral larval growth promoting substance is released into the water. Therefore, it is possible to effectively promote the establishment of coral larvae.
In addition, according to the method for producing an underwater settling stone according to the twelfth aspect of the invention, in particular, a plate type stone for underwater settling can be efficiently produced with high productivity.

The stone for submergence according to the present invention comprises a biodegradable plastic on at least a part of the surface of a carbonized solid body obtained by solidifying a powdery uncarbonated Ca-containing raw material by a carbonation reaction by contact with carbon dioxide gas. A coating made of
The carbonate solidified body is, for example, (a) filling a mold with a granular uncarbonated Ca-containing raw material to form a raw material packed layer, and carbon dioxide gas (usually, A method of solidifying the raw material packed layer by carbonation reaction by blowing carbon dioxide gas), and (b) mixing powdery uncarbonated Ca-containing raw material with a binder such as cement, starch, etc. A preform is formed by molding into a shape, and a preform with a moderate amount of moisture is placed in a container in a carbon dioxide atmosphere, and carbon dioxide is permeated into the interior from the surface of the preform. It can be produced by a method such as a method of solidifying a body by a carbonation reaction.

Here, the biodegradable plastic constituting the coating refers to a plastic that is decomposed by microorganisms when it is placed in an environment such as soil or seawater, and finally becomes water and carbon dioxide. This type of plastic has functions (strength, etc.) equivalent to other general plastics under normal use conditions.
There are no particular restrictions on the type of biodegradable plastic used in the present invention. For example, polylactic acid mainly made from plant starch such as corn, PHB produced by microorganisms, bacterial cellulose, and the like can be used. When these are used, for example, by mixing bacterial cellulose having a high degradation rate and polylactic acid having a slow degradation rate, and adjusting the mixing ratio thereof, the degradation rate of the coating can be adjusted.

The coating made of biodegradable plastic is decomposed over time by microorganisms in the water after the stone material is submerged in water, and eventually disappears, but the type and composition of the biodegradable plastic, the thickness of the coating, etc. By selecting, the decomposition / disappearance period in water can be set.
In general, the biodegradable plastic coating is provided on the surface of the carbonated solid body on which a desired organism (for example, a specific seaweed or coral) is desired to grow or is likely to grow. Of course, the entire surface of the carbonic acid solidified body may be provided with a coating, or all or part of the outer surface that is in contact with water when it is submerged in water (usually the outer surface other than the “bottom surface” that contacts the bottom of the water). A coating may be provided.

  In addition, the coating made of the biodegradable plastic used in the present invention is a mixture in which a substance other than the biodegradable plastic is mixed or physically combined in addition to the one composed entirely of the biodegradable plastic. (That is, a coating mainly composed of a biodegradable plastic). The point is that the main constituent material or constituent biodegradable plastic can be decomposed / disappeared over time, so that most of the coating can disappear from the surface of the carbonated solidified body. A substance or member other than the degradable plastic may partially remain on the surface of the carbonated solid.

Examples of a method for providing a coating made of a biodegradable plastic on the surface of the carbonic acid solidified body include the following.
(A) A coating material made of biodegradable plastic is attached to the surface of the produced carbonate solidified body.
(B) When a carbonated solid is produced using a mold, a biodegradable plastic covering material is disposed between the raw material filling layer and the mold or on the upper surface of the raw material filling layer to cover the raw material filling layer. Carbonate and solidify while holding the material.
(C) A biodegradable plastic solution is applied to the surface of the solidified carbonic acid product and then solidified.

  In the case of the method (a), one or more types of coating materials selected from biodegradable plastic film materials, sheet materials, and plate materials are mounted on the surface of the carbonated solid body produced. The attachment method is arbitrary. For example, (1) a bag-like or box-like covering material is placed on the entire carbonized solidified body, and an appropriate place is fixed to the carbonized solidified body as necessary, (2) the coating material is mechanically Method (for example, fixing bolt, etc.) or a method of fixing to the surface of the carbonated solid with an adhesive such as an underwater bond, (3) a method of winding a coating material (film material, sheet material) around the carbonated solid, (4) coating material A method such as thermocompression bonding to the outer surface of the carbonized solidified body can be employed, and a coating made of a biodegradable plastic is formed on the surface of the carbonized solidified body by the attached covering material.

In the case of the method (c), after applying the resin solution of the biodegradable plastic to the surface of the carbonate solidified body, it is solidified at room temperature or at an appropriate temperature, so that the biodegradable plastic surface of the carbonate solidified body is coated. A coating is formed.
In the case of the above method (b), the biodegradable plastic covering material disposed between the raw material filling layer and the formwork or on the upper surface of the raw material filling layer may be a film material, a sheet material, or a plate material. One or more selected are used. In order to hold the coating material on the surface of the carbonic acid solidified body, an anchor embedded in the raw material filling layer is provided on the coating material surface in contact with the raw material filling layer as necessary.

FIG. 1 shows one embodiment of the method (b), FIG. 1 (A) shows a manufacturing process of a stone for underwater settling, and FIG. 1 (B) shows a stone for underwater settling as a product. ing.
In the manufacturing process shown in FIG. 1 (A), a raw material filling layer A is formed by filling an uncarbonated Ca-containing raw material into a mold 1 and carbon dioxide gas is blown into the raw material filling layer A. 2 shows a state in which the mold 1 forming the raw material filled layer A is longitudinally cross-sectionally shown.
The mold 1 is a mold that can be substantially airtight or semi-airtight. In the present embodiment, the mold 1 includes a container-like main body 100 and a lid 101 that closes the upper portion thereof. A gas supply unit 2 (gas supply space) is provided at the bottom of the main body 100, and a number of gas through holes 20 are formed in the partition wall between the gas supply unit 2 and the main unit 100. Yes. A gas supply pipe 3 is connected to the gas supply section 2, and carbon dioxide gas or carbon dioxide-containing gas (hereinafter collectively referred to as “carbon dioxide gas”) is supplied into the gas supply section 2 through the gas supply pipe 3. Is done. Further, an exhaust pipe 4 for exhausting the gas supplied into the mold is connected to the upper part of the mold 1. In the other drawings, reference numerals 5 and 6 denote on-off valves provided in each piping system.

In this embodiment, a biodegradable plastic covering material C ₁ is disposed in advance along the inner wall (entire circumference) of the side wall of the mold 1, and then an uncarbonated Ca-containing raw material is charged into the mold 1. The raw material filled layer A is formed. Then, the coating material C ₂ is disposed on the upper surface of the raw material packed layer A.
The covering materials C ₁ and C ₂ are composed of at least one selected from a film material, a sheet material, and a plate material made of biodegradable plastic. Incidentally, the coating material C ₂ disposed on the upper surface of the raw material packed layer A, so that the gas passing through the raw material packed layer A can escape upwards, a plurality of gas holes 8 is formed on the entire surface.
The means and structure for allowing the covering material C to be held on the surface of the carbonic acid solidified body are arbitrary. For example, as shown in FIG. 2, the raw material filling layer is placed on the surface of the covering material C in contact with the raw material filling layer A. An anchor 7 embedded in A may be provided, and the covering material C may be held on the surface of the carbonate solidified body by the anchor 7. Further, as another method, the covering material C ₁ and the covering material C ₂ are joined to form a substantial bag shape or box shape so that the entire covering material C is held by the carbonate solidified body. Also good.

  In order for an uncarbonated Ca-containing raw material to come into contact with carbon dioxide gas and solidify by a carbonation reaction, an appropriate amount of water (water adhering to the surface of the raw material particles) is required. Water is added to the raw material. This water addition may be performed before charging into the mold 1 or may be performed after charging. In addition, when performing after the mold is inserted, the mold 1 may be immersed in water in the water tank with the upper part of the mold 1 opened, or a sufficient amount from the upper part of the raw material filling layer A may be used. Water may be sprinkled. Usually, the moisture content of the raw material packed bed A is 3 to 12%, preferably about 5 to 10%.

After forming the raw material filled layer A containing moisture as described above, the lid 101 is attached to the mold so that the carbon dioxide gas blown into the mold 1 penetrates the entire raw material filled layer. The frame 1 is airtight or semi-airtight. In this state, carbon dioxide gas is supplied into the mold 1 to cause a carbonation reaction in the raw material packed bed A. In the case of FIG. 1, the carbon dioxide gas supplied through the gas supply pipe 3 is introduced into the gas supply unit 2 and then blown into the raw material packed bed A from the gas through hole 20. A part of the carbon dioxide gas passing through the raw material packed bed A reacts with Ca ions eluted from the raw material particles to the water adhering to the surface, and CaCO ₃ is precipitated on the surface of the raw material particles. The consolidation of A proceeds. The remainder of the carbon dioxide gas passes through the raw material packed bed A and is discharged out of the mold 1 from the exhaust pipe 4. In some cases, carbon dioxide gas may be supplied into the raw material packed bed A with the on-off valve 6 of the exhaust pipe 4 closed. In that case, the on-off valve 6 is sometimes opened to open the mold. It is preferable to release the gas accumulated in the frame 1 so that the carbon dioxide concentration in the mold 1 is maintained at a predetermined level or higher.
After supplying the carbon dioxide gas as described above for a predetermined time, the consolidated raw material packed layer A is demolded so that the surface is made of the covering materials C ₁ and C ₂ as shown in FIG. Carbonated solid body B covered with coating D is obtained.

Further, in the method (b) as described above, as shown in FIG. 3, by forming irregularities on the coating material surface 9 in contact with the raw material packed layer A, it is formed along the coating material surface 9. The carbonic acid solidified body surface can be an uneven surface that is preferable for the growth of organisms. The shape of the unevenness formed on the covering material surface 9 is arbitrary, and may be an unevenness having the function of the anchor 7 as shown in FIG. 2, for example.
The shape of the carbonate solidified body constituting the stone for submergence according to the present invention is arbitrary. For example, the cross-sectional shape is a circle, an ellipse, a triangle, a polygon more than a quadrangle, a star, or the like, or the overall shape is a spherical shape or an elliptical shape. A tetrahedron or more polyhedron shape, a cone shape, a columnar shape, a tetrapot shape, or the like can be used.

  As another embodiment of the stone for underwater settling of the present invention, the mold used for producing the carbonated solid can be used as a coating as it is. That is, this underwater settling stone is formed by solidifying a formwork in which all or main components are made of biodegradable plastic and a packed layer of uncarbonated Ca-containing raw material held in this formwork by a carbonation reaction. The carbonic acid solidified body produced by the above process and held in the mold as it is. FIG. 4 shows an embodiment of the present invention. FIG. 4 (A) shows a manufacturing process of the underwater settling stone of the present invention, and FIG. 4 (B) shows a product underwater settling stone.

In FIG. 4 (A), 10 is a mold made of biodegradable plastic, A is a packed layer of granular uncarbonated Ca-containing raw material held in this mold 10, and 11 is a mold 10. A gas supply means 12 for blowing carbon dioxide gas into the interior from the bottom, 12 is a lid of the mold 10.
The mold 10 is composed of a container body having an open top, and a large number of gas through holes 13 are formed at the bottom thereof. The gas supply means 11 includes a casing 15 for forming a gas supply chamber 14 under the mold 10 by placing the mold 10, and a gas for supplying carbon dioxide gas into the casing 15. And a supply pipe 16.

As shown in FIG. 4A, the packed layer A of uncarbonated Ca-containing raw material held in the mold 10 has an appropriate amount of moisture as described above in order to efficiently generate a carbonation reaction. Is included. With the lid 12 attached to the upper end of the mold 10, carbon dioxide gas is supplied from the gas supply means 11, and carbon dioxide gas is blown into the raw material packed bed A through the gas supply chamber 14 → the gas through hole 13. The raw material packed layer A, the CaCO ₃ generated by non-carbonated Ca and carbon dioxide are reacted through the water, the CaCO ₃ whole material packed layer is consolidated as the binder, the carbonated solid.
As shown in FIG. 4 (B), the underwater sedimentation stone is a product in a state where the carbonized solid B is held in the mold 10 as it is without being removed from the biodegradable plastic mold 10. Become. Therefore, the underwater sedimentation stone of the present embodiment is one in which the entire surface of the carbonated solid B is covered with the mold 10 (that is, the biodegradable plastic coating D) except for one surface.

In the case of the underwater sinking block of the embodiment shown in FIG. 4, for example, the block is submerged in the form as shown in FIG. In this state, most of the surface of the carbonated solid B is covered with the biodegradable plastic mold 10 (coating D).
After the mold 10 is submerged in water, it is decomposed with time by microorganisms in the water and eventually disappears. However, the type / composition of the biodegradable plastic, the thickness of the mold material, etc. should be selected. Can set the decomposition / disappearance period in water.

5 and 6 show another embodiment of the present invention, and particularly show an embodiment suitable for a plate-type underwater settling stone. FIG. 5 shows a manufacturing process of the underwater settling stone according to the present invention, and FIG. 6 shows the underwater settling stone as a product.
In this embodiment, a plurality of molds having a shallower bottom than that of the embodiment of FIG. 4 are used. In FIG. 5, 10a is a plurality of molds made of biodegradable plastic, 11a is a gas supply means for blowing carbon dioxide into the inside from the lower part of the mold 10a, and 12a is a lid of the mold 10a. .
Each mold 10a is constituted by a shallow container body having an open top, and a plurality of gas through holes 13a are formed at the bottom. The gas supply means 11a includes a casing 15a for forming a gas supply chamber 14a in the lower part of the lowermost mold 10a by placing a plurality of stacked mold groups, and the casing 15a. And a supply pipe 16a for supplying carbon dioxide gas.

  In this embodiment, a plurality of molds 10a holding a packed bed A of uncarbonated Ca-containing raw material containing an appropriate amount of water are stacked in multiple stages, and the multistage stacked mold groups are placed on the gas supply means 11a. To do. A lid 12a is attached to the uppermost mold 10a. Carbon dioxide gas (usually carbon dioxide-containing gas) is supplied from the gas supply means 11a, passes through the gas supply chamber 14a, and the gas passage hole 13a in the lower side mold frame → the raw material packed bed A → the gas through hole 13a in the upper side mold frame. → As the raw material packed layer A, carbon dioxide gas is blown into the raw material packed layer A of each mold 10a in order from the lower side, and the raw material packed layer A of each mold 10a is consolidated to form a carbonate solidified body. Then, as shown in FIG. 6, the carbonate solidified product B becomes a product in a state where it is held in the mold 10a without being removed from the biodegradable plastic mold 10a. Therefore, the underwater sedimentation stone of the present embodiment is also the one in which the entire surface of the carbonized solid body B is covered with the mold 10a (the biodegradable plastic coating D) except for one surface.

According to the above method for producing submerged stones, small stones such as plate molds can be produced in large quantities at the same time, and there is no need to remove the formwork. Can be mass-produced.
FIG. 6 shows an example of an installation form of the stone for underwater subsidence according to the present embodiment, which is bonded and fixed on a natural reef with an underwater bond so that the bottom of the mold 10a is on the top.
5 and 6 can easily produce a plate body having a thickness t of about 10 to 100 mm as the size of the carbonate solidified body in the mold, as shown in FIG. If the manufacturing method of this embodiment is used, it is possible to mass-produce such plate-type stones for submerging underwater with high productivity. In addition, such a plate-type stone for underwater settling can be prevented from being damaged during transportation because the outer side of the carbonized solid body is protected by a form of biodegradable plastic.

Moreover, the stone material for submergence as shown in FIGS. 4-6 uses the molds 10 and 10a by which the unevenness | corrugation was formed in the inner surface of the mold material which consists of biodegradable plastics, and the carbonic acid solidified body surface is the Since it is formed along the concavo-convex surface, it is possible to form a concavo-convex formation base surface on which seaweed or the like is likely to grow. The shape of the unevenness formed on the inner surface of the mold material is arbitrary, and may be, for example, a coating material surface 9 shown in FIG.
In addition, the molds 10 and 10a made of biodegradable plastic used in the present invention may be mixed with a substance other than biodegradable plastic, in addition to those made entirely of biodegradable plastic, or physically. (That is, a mold mainly composed of biodegradable plastic). For example, a metal reinforcing material or the like for ensuring the strength of the molds 10 and 10a may be used in part. The point is that the main component or component biodegradable plastic can be decomposed and disappeared over time, so that most of the formwork (coating) can disappear from the carbonated solid surface. Depending on the case, a substance or member other than the biodegradable plastic may partially remain on the surface of the carbonated solid.

When the underwater sedimentation stone of the present invention is used as a coral settlement base, it is preferable to retain a coral larval settlement promoting substance in the form of (a) or / and (b) below, whereby the coating is submerged in water. Since the coral larva settlement promoting substance is released into the water when it decomposes and disappears over time, it is possible to effectively promote the coral larva settlement.
(A) The biodegradable plastic constituting the coating (in the case of the embodiment shown in FIGS. 4 to 6, the molds 10 and 10 a) is made to contain a coral larva settlement promoting substance.
(B) A coral larva growth promoting substance is adhered to the inside of the biodegradable plastic coating (in the case of the embodiment shown in FIGS. 4 to 6, the molds 10 and 10a).
As a specific form of the above (b), it is conceivable to apply a coral larva settlement promoting substance to the inside of the coating. As a coral larvae accretion promoting substance to be included in or attached to biodegradable plastic, the algae Peyssonnelia
sp. (Authentic red algae Cacridae Ivanokawaceae), Hydrolithon reinboldii (Authentic red algae Cacridae Coralaceae; lime red algae), or an extract thereof. In addition, the biodegradable plastic can contain a substance that is repelled by seaweeds and predators.

  By using the stone for underwater subsidence according to the present invention as described above, it is possible to repair or create an aquatic breeding ground (eg, algae ground, coral reef) in the following manner. That is, “an egg from an adult, a zoospore” of a living organism (for example, a specific useful seaweed such as kombu, arame, sword, etc., coral, etc.) to be grown on the surface of the stone of the present invention. Or larvae release period ”(= the egg, zoospore or larvae settlement stage on the settlement base), and then submerged in water and covered with water D (form 10 in FIG. 4 to FIG. 6). , 10a) is decomposed over time to at least disappear in the “egg, zoospore or larval release period” of the organism to be grown on the stone surface. In order to do this, the type, composition, thickness, etc. of the biodegradable plastic constituting the coating D are selected in advance to set the decomposition / disappearance period in water. As a result, the surface of the carbonized solid B is covered with the coating D only during the period from the time when it is submerged in the water as described above until the start of the “release period of eggs, zoospores or larvae” of the target organism. In accordance with the beginning of the period, the coating D can be decomposed and disappeared to expose the surface of the carbonated solid B, so that the target organism can be efficiently grown on the surface of the carbonated solid.

As a result of the above, the freedom of selection of the timing for laying the substrate (stone) in the water is extremely wide, and cleaning work for the surface of the substrate set in the water can be completely eliminated. Further, since the biodegradable plastic is only decomposed into CO ₂ and water, there is no possibility of adversely affecting the natural environment such as water quality.
In addition, when the stone material for submerging in the present invention is submerged in water, organisms may temporarily adhere to the surface of the coating made of biodegradable plastic, but this coating sequentially decomposes and disappears from the surface side. Therefore, the organism cannot maintain the attached state.

Hereinafter, basic production conditions for the carbonated solid will be described.
Carbonated solids are produced by bringing powdered, uncarbonated Ca-containing raw material into contact with carbon dioxide in the presence of water, and generating calcium carbonate by the reaction (carbonation reaction) between uncarbonated Ca and carbon dioxide through water. And the raw material is solidified (consolidated) using this calcium carbonate as a binder.
The uncarbonated Ca contained in the uncarbonated Ca-containing raw material, that is, CaO and / or Ca (OH) ₂ suffices to be contained at least as a part of the composition of the solid particles, and therefore CaO as a mineral. In addition to Ca (OH) ₂ , 2CaO · SiO ₂ , 3CaO · SiO ₂ , glass, and the like that are present in solid particles as part of the composition are also included.

Although there is no special restriction | limiting in the kind of the granular uncarbonated Ca containing raw material to be used, For example, steelmaking, such as decarburization slag, dephosphorization slag, desulfurization slag, desiliconization slag, etc. generated in the steel manufacturing process Slag), concrete (for example, concrete waste material), mortar, glass, alumina cement, CaO-containing refractory, and the like, and one or more of these can be used alone or in combination. These materials are crushed into powder as necessary and used as raw materials.
The uncarbonated Ca-containing raw material does not need to be solid particles whose entire amount contains uncarbonated Ca. That is, if the carbonation of the uncarbonated Ca contained in the uncarbonated Ca-containing raw material produces a sufficient amount of CaCO ₃ as a binder of the carbonate solidified body, the uncarbonated Ca-containing raw material is converted into the uncarbonated Ca-containing raw material. Solid particles not containing may be contained. Examples of such solid particles include natural stone, sand, soluble silica, metal (for example, metallic iron, iron oxide) and the like.

Of these, metallic iron, iron oxide, soluble silica and the like effectively act as a sulfur and phosphorus fixing agent in the sea, and as a nutrient source for aquatic plants such as seaweeds. In addition to these, an arbitrary component (particle) can be contained in an appropriate amount, that is, as long as the strength of the carbonated solid is not reduced.
The particle size of the granular uncarbonated Ca-containing raw material is not particularly limited, but it is preferable that the particle size is fine to some extent in order to secure the contact area with CO ₂ and increase the reactivity. In addition, if the particle size of the uncarbonated Ca-containing raw material is too large, Ca that cannot be carbonated remains inside the raw material particles, so that the raw material particles in the produced carbonate solidified body expand and collapse, causing cracks and the like. In some cases.

Examples of the carbon dioxide gas or carbon dioxide-containing gas used for causing the carbonation reaction include exhaust gas from a lime calcining factory (usually around CO ₂ : around 25%) and heating furnace exhaust gas (usually around 25%). , CO ₂ : around 6.5%) is preferable, but is not limited thereto. In addition, if the CO ₂ concentration in the gas is too low, there arises a problem that the processing efficiency is lowered, but other problems are not exceptional. Therefore, the CO ₂ concentration is not particularly limited, but it is preferable to set the CO ₂ concentration to 3% or more for efficient treatment.

Moreover, there is no special restriction | limiting in the supply amount of a carbon dioxide gas, However, As a general guideline, the gas supply amount of about 0.004-0.5m < ³ > / min * t (raw material ton) should just be ensured. Further, there is no special restriction on the gas supply time (carbonation treatment time), but as a guideline, the time when the supply amount of carbon dioxide gas becomes 3% or more of the weight of the uncarbonated Ca-containing raw material, that is, the gas amount Convert to the raw material 1t per 15 m ³ or more, preferably it is preferable to carry out the gas supply to 200 meters ³ or more carbon dioxide is supplied.

[Example 1]
A steelmaking slag with a moisture content of 9% (particle size of 3 mm or less) is charged into the mold, and is vibrated with a pressure vibration molding machine to form a raw material packed layer. A gas with a carbon dioxide concentration of 30% is formed in this raw material packed layer Was blown for 4 days at a blowing rate of 7 Nm ³ / hr to produce a cubic carbonate solidified body having a side of 1 m. A sheet of biodegradable plastic (plastic type: mixture of bacterial cellulose and polylactic acid) is placed on the top surface of the carbonate solidified body, and the central portion and surrounding four sides of the sheet material are bonded to the carbonate solidified surface with an underwater bond. The stone material of the example of the present invention was manufactured. The biodegradable plastic sheet material (thickness 20 mm) was designed such that bacterial cellulose and polylactic acid were mixed and decomposed and disappeared in about 3 months in the sea.

The above-mentioned stone material of the present invention and the stone material of the comparative example in which the carbonized solid body is not provided with a sheet material made of biodegradable plastic, aiming at the growth and growth of larvae and kajime, the release period of larvae of larvae and kajime Was installed on the bottom of the water near the algae ground three months ago. The subsidence time of 3 months before the release period of the larvae of Alame and Kajime was selected as a time when the marine conditions were relatively good and the subsidence work was easy. Four months after the installation of each stone, the state of growth and growth of alame and kajime was investigated (submerged and observed visually). The results are shown below.
Example of the present invention Alame Kajime: about 410 / m ²
Other seaweeds: 3 / m ²
Comparative Example Alame Kajime: 5 / m ²
Other seaweeds: Approximately 80 / m ²

[Example 2]
By the method shown in FIG. 5, 100 plates each having a square shape of 300 mm × 300 mm and a thickness of 10 mm were manufactured at a time. The mold used was a biodegradable plastic mold with a size of 300 mm × 300 mm inside, a depth of 10 mm, and a side wall and a bottom thickness of 10 mm (plastic type: a mixture of bacterial cellulose and polylactic acid). ) And gas through holes having a hole diameter of 5 mm are formed at intervals of 15 mm at the bottom. 100 molds were used.
A steelmaking slag having a moisture content of 9% (particle size of 3 mm or less) was charged into each mold and vibrated with a pressure vibration molding machine to form a raw material packed layer having a thickness of about 10 mm. The 100 molds thus formed with the raw material packed layers were stacked as shown in FIG. 5 and subjected to carbonation treatment by blowing carbon dioxide gas. In this carbonation treatment, a gas having a carbon dioxide gas concentration of 30% was blown in at a blow rate of 5 Nm ³ / hr for 48 hours. As described above, a large number of plate-shaped stones for underwater subsidence composed of a mold made of biodegradable plastic and a carbonate solidified body held in the mold can be manufactured simultaneously.

[Example 3]
According to the same method and production conditions as in Example 2, 100 mg / kg of a pulverized product of Peyssonnelia sp. (Authentic red algae class Icanoceae), which is a coral larval growth promoting substance, in the biodegradable plastic constituting the mold. A stone material (Invention Example 1) to which L was added and a stone material (Invention Example 2) to which the same component was not added in the biodegradable plastic constituting the mold were manufactured. For comparison, a solidified carbonic acid product (comparative example) having no biodegradable plastic mold was manufactured by a conventional method. The biodegradable plastic (thickness 10 mm) used in the examples of the present invention was designed so that it decomposes and disappears in about two months in the sea by mixing bacterial cellulose and polylactic acid.
Three pieces of each stone were placed on the coral own dough two months before the coral spawning season. The settling time of two months before the coral spawning season was selected as a time when the marine conditions were relatively good and the setting work was easy. After 6 months from the installation of each stone material, the state of coral settlement (the number of coral larvae per 10 cm × 10 cm) was investigated (submerged and observed visually). The results are shown below.
Invention Example 1: 20 to 30 Invention Example 2: 5 to 10 Comparative Example: 0 to 1

1 shows an embodiment of the present invention, FIG. 1 (A) is an explanatory view showing a manufacturing process, and FIG. 1 (B) is an explanatory view showing a stone for submerging in the present invention manufactured in the manufacturing process. Sectional drawing which shows one Embodiment of the coating | covering material which should comprise the coating | cover of biodegradable plastics Sectional drawing which shows other embodiment of the coating | covering material which should comprise the coating | cover of biodegradable plastics FIG. 4A shows another embodiment of the present invention, FIG. 4A is an explanatory view showing a manufacturing process, and FIG. 4B is an explanatory view showing a stone for underwater settling of the present invention manufactured in the manufacturing process. Explanatory drawing which shows the manufacturing process in other embodiment of this invention. Explanatory drawing which shows the stone material for underwater settling of this invention manufactured by the manufacturing process of FIG.

Explanation of symbols

DESCRIPTION OF SYMBOLS 1 Mold 2 Gas supply part 3 Gas supply pipe 4 Exhaust pipe 5, 6 On-off valve 7 Anchor 8 Gas through-hole 9 Cover material surface 10,10a Formwork 11, 11a Gas supply means 12, 12a Lid 13,13a Gas hole 14,14a gas supply chamber 15,16a casing 16,16a gas supply pipe 20 gas holes 100 Formwork body 101 lid A raw material packed layer B carbonated solid _C 1, _{C 2} dressing D coated

Claims (13)

  A stone material for submergence in water, characterized in that at least a part of the surface of a carbonated solid body obtained by solidifying a powdery uncarbonated Ca-containing raw material by a carbonation reaction is coated with a biodegradable plastic. .   The biodegradable plastic coating is formed by mounting one or more types of coating materials selected from biodegradable plastic film materials, sheet materials, and plate materials on the surface of the carbonate solidified body. The stone for underwater settling according to claim 1, wherein:   The surface of the covering material in contact with the carbonate solidified body is uneven, and at least a part of the surface of the carbonate solidified body is formed along the uneven surface of the coating material. Stone material.   2. The stone for submersion in water according to claim 1, wherein the biodegradable plastic coating is formed by applying a solution of the biodegradable plastic to the surface of the carbonated solidified body and then solidifying.   A carbonic acid produced by solidifying by a carbonation reaction a mold made of biodegradable plastic and a packed layer of uncarbonated Ca-containing raw material held in the mold and held in the mold as it is The stone for underwater subsidence according to claim 1, comprising a solidified body, wherein the mold frame constitutes a coating of the carbonized solidified body.   6. The stone material for submerging in water according to claim 5, wherein irregularities are formed on the inner surface of the formwork made of biodegradable plastic. The coral larva settlement promoting substance is retained in the form of the following (a) or / and (b), the stone for underwater subsidence according to any one of claims 1 to 6.
(A) The biodegradable plastic composing the coating is made to contain a coral larva settlement promoting substance.
(B) A coral larvae promoting substance is adhered to the inside of the biodegradable plastic coating.   When producing a carbonated solid using a mold, the mold is filled with powdered uncarbonated Ca-containing raw material, and between the inner surface of the mold and the raw material packed layer and / or the upper surface of the raw material packed layer One or more types of coating materials selected from biodegradable plastic film materials, sheet materials, and plate materials are disposed on the base material, and the raw material packed layer is brought into contact with carbon dioxide gas in a state of containing moisture, and a carbonation reaction is performed. A method for producing a stone material for submerged subsidence, characterized in that a solidified carbonic acid product is obtained in which at least a part of the surface is coated with the coating material.   9. The method for producing a stone material for underwater settling according to claim 8, wherein irregularities are formed on the surface of the covering material in contact with the raw material packed layer.   A biodegradable plastic solution is applied to the surface of a carbonate solidified body obtained by solidifying a powdered uncarbonated Ca-containing raw material by a carbonation reaction, and then solidified to produce at least part of the surface. A method for producing a submerged stone material, characterized in that a carbonated solid body coated with a decomposable plastic is obtained.   Filling a mold made of biodegradable plastic with a raw material containing uncarbonated Ca in granular form, bringing the raw material packed layer into contact with carbon dioxide gas in a state containing moisture, and solidifying by a carbonation reaction, A method for producing an underwater settling stone comprising the formwork and a carbonate solidified body that is held in the mold as it is, wherein the formwork forms a stone for underwater settling that forms a coating of the carbonate solidified body. . Using a plurality of container-shaped molds made of biodegradable plastic, with the top open and a plurality of gas holes at the bottom,
By stacking the plurality of molds in which the packed layers of moisture-containing uncarbonated Ca-containing raw materials are held in multiple stages, and supplying carbon dioxide gas from below to the multi-stage stacked form groups, Carbon dioxide gas is sequentially blown into a plurality of raw material packed layers via gas holes at the bottom of each mold,
Each of the raw material filled layers is carbonated by blowing the carbon dioxide gas, thereby comprising the mold and the carbonated solid body held as it is in the mold, and the mold forms a coating of the carbonized solid body. The method for producing a stone for underwater settling according to claim 11, wherein the stone for underwater settling is obtained.   The stone material for submerged in water according to any one of claims 1 to 7, is submerged in water before the arrival of the release period of eggs, zoospores or larvae from an adult organism to be grown on the surface of the stone, A method for repairing or creating an aquatic breeding ground characterized in that a biodegradable plastic coating is decomposed over time to be in a disappeared state at least in the release period of the eggs, zoospores or larvae.

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