JP2007037413A - Method for producing alga/coral multiplication member - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a method for producing an alga/coral multiplication member by which the intensive alga/coral multiplication member having high mechanical strength, eluting a small amount of an alkali component, scarcely increasing pH of seawater near the surface, readily compatible with the natural environment, easily establishing spores of the alga and larvae of the coral and having excellent multiplication effects can be produced at a low cost with excellent productivity and wastes can effectively be utilized with excellent resource saving and energy saving properties. <P>SOLUTION: The method for production comprises a mixing step of mixing (a) coal ash with (b) inorganic binding powder such as slaked lime, dolomite or magnesium hydroxide and affording mixed powder, a pressure forming step of pressurizing the mixed powder under a vacuum, carrying out pressure forming of the mixed powder into a prescribed shape and providing a formed product of the coal ash and a carbonating step of housing the formed product of the coal ash in a vessel, bringing the formed product of the coal ash into contact with a gas containing carbon dioxide and introduced into the vessel and carbonating the formed product of the coal ash from the surface thereof toward the interior. <P>COPYRIGHT: (C)2007,JPO&INPIT

Description

  The present invention relates to a method for producing algae and cocoon breeding members that grow algae and cocoons.

  Conventionally, seaweed beds composed of large-scale seaweeds such as the family Kombuaceae and the Amaranthaceae are formed in the ocean coastal area. The seaweed basin plays an important role as a fishing ground for protecting and cultivating seafood or supplying food to algae, and as a foundation for coastal ecosystems. For this reason, algae cultivation, which is one of the fishing grounds aimed at maintaining or increasing aquatic resources, has been carried out in various places, and research on algae breeding members has also been conducted.

In the ocean, coral reefs such as corals are accumulated and consolidated to form coral reefs. Coral reefs create a number of holes, crevasses, etc., and provide a place to live where abundant organisms live, so in the various environments of the sea, the most abundant species and complex species relationships are precious. Forming.
However, along with recent development works such as marine pollution, land reclamation and land improvement, the disappearance of coral reefs has been observed, and the reef corals and fish communities living in the coral reef areas are exhausted. For this reason, techniques aimed at breeding cocoons have been developed.
As a conventional technique, for example, (Patent Document 1) states that “a clinker ash or coal husk is a main material, and a molding material obtained by forming a mixture of clay minerals on this is sintered into a sintered body having a water absorption of 10% or more. A fishing reef formed by stacking sintered ceramic bodies and submerging them in the sea is disclosed.
(Patent Document 2) discloses “a coral reef landscaping method in which rape seedlings grown on a dice-like anchorage base are fitted and fixed in a landscaping block formed of hardened coal ash, concrete, or the like”. .
JP 2000-262179 A JP 11-308939 A

However, the above conventional techniques have the following problems.
(1) Since the technique disclosed in (Patent Document 1) sinters a molding material of clinker ash or a mixture of coal husk and clay mineral, clinker ash, coal husk, clay mineral in the process of sintering Condensation causes the surface energy to decrease and the surface to become denser, so that there is a problem that algae, spore spores and larvae are difficult to settle and lack a proliferation effect.
(2) The molding material has to be heated in order to sinter, and thus has a problem of consuming a great deal of energy and lacking energy savings.
(3) The technology disclosed in (Patent Document 2) is to form a coral reef using the anchoring base on which the seedlings of vines have settled, but the material of the fixing base suitable for the propagation of the coral is not disclosed. Had problems.

  The present invention solves the above-described conventional problems, and has high mechanical strength, low elution amount of alkaline components, hardly raises the pH of seawater in the vicinity of the surface, and is easy to adapt to the natural environment. Can produce algae and cocoon breeding members that are easy to settle and have excellent growth effects at low cost, and are more intensive and more productive. An object of the present invention is to provide a method for producing an algae / soil-growing member that is excellent in the quality.

In order to solve the above-described conventional problems, the method for producing an algae / spoilage-growing member of the present invention has the following configuration.
The method for producing an algae / spider-growing member according to claim 1 of the present invention comprises: a. Coal ash; b. A mixing step of mixing an inorganic binder powder such as slaked lime, dolomite, and magnesium hydroxide to obtain a mixed powder, and pressurizing the mixed powder under reduced pressure to form a coal ash molded body And a carbonization process in which the coal ash compact is accommodated in a container and brought into contact with a carbon dioxide-containing gas introduced into the container, and carbonized from the surface of the coal ash compact toward the inside. And a process.
With this configuration, the following effects can be obtained.
(1) The coal ash molded body obtained in the pressure molding step under reduced pressure has a water-soluble inorganic binder powder such as slaked lime in the coal ash molded body that absorbs carbon dioxide in the air immediately after molding and is water. It becomes a carbonate such as calcium carbonate, which is hardly soluble, and hardens while bonding the particles to each other. For this reason, although the coal ash molded body increases the mechanical strength, it has a carbonation step of carbonating from the surface of the coal ash molded body toward the inside, so that the carbon dioxide to the inorganic binder powder is reduced. Absorption is promoted and the mechanical strength of the coal ash compact can be increased in a short time. As a result, because it does not require a curing place or curing time to leave the coal ash compacts for a long time in order to carbonize with carbon dioxide in the air, it is intensive and excellent in productivity, and in the water where algae and straw are grown. It is possible to manufacture a breeding member that does not collapse even when immersed, and that can enhance the fixing and breeding effect of wrinkles and the like at a low cost.
(2) Since coal ash is used, waste can be used effectively, and coal ash is composed mainly of silica and alumina, like natural silicate clay and diatomaceous earth, so it is easy to adapt to the natural environment. Algae spores and moth larvae are easy to settle and have excellent proliferation effect.
(3) Since it has a carbonation step and the coal ash molded body is hardened with a poorly soluble carbonate, a cutting agent such as water is used when the coal ash molded body is processed such as cutting, cutting, drilling, etc. Even if is used, it does not become muddy and does not collapse, and it is excellent in workability.
(4) Since it has a carbonation step, the water-soluble inorganic binding powder such as slaked lime existing on the surface of the coal ash molded body absorbs carbon dioxide, and the carbonate such as calcium carbonate hardly soluble in water and Since it becomes hardened, it can suppress that alkaline components, such as unreacted slaked lime, elute, can prevent the pH of seawater near the surface from rising, and can improve the fixing and proliferation effect of sea bream. In addition, elution of harmful substances and the like can be suppressed, and the environmental conservation is excellent.
(5) Since it is possible to obtain mechanical strength that does not crack or collapse even if it is submerged in a tidal sea simply by pressure molding without firing, etc., it is excellent in energy saving.
(6) Since it is pressurized under reduced pressure, air hardly remains in the coal ash molded body formed by degassing and molding the mixed powder. Therefore, the air remaining in the coal ash molded body expands and coal ash molding is performed. It is possible to prevent the body from being easily broken and to increase the product yield.

  Here, as coal ash, fly ash, pulverized coal combustion that is included in the combustion gas of combustion devices such as pulverized coal combustion boilers that mainly use coal such as coal-fired power generation, and is collected by dust collectors such as cyclones and filters Cinder ash collected by falling when the combustion gas of a combustion device such as a boiler passes through an air preheater or a economizer, clinker ash or a mixture thereof collected by dropping at the bottom of a combustion device such as a pulverized coal combustion boiler Etc. are used.

  As the inorganic binder powder, a powder that absorbs carbon dioxide in the presence of moisture such as slaked lime, dolomite, magnesium hydroxide and forms a carbonate to be cured is used. These may be used alone or as a mixture of plural kinds.

In the pressure forming step, the mixed powder obtained by mixing coal ash and inorganic binder powder is a mold having a predetermined shape and the inside of which is decompressed to −101 to −80 kPa, preferably −100 to −90 kPa, etc. Is pressure-molded in the mold.
As the pressure under reduced pressure becomes lower than −100 kPa, the vacuum pump used for the pressure reduction becomes larger and it takes time to reduce the pressure, and the productivity tends to decrease. Voids are easily formed inside the ash compact, and the mechanical strength is reduced, and the air remaining in the mixed powder and encapsulated inside the coal ash compact expands after molding and destroys the coal ash compact. There is a tendency to become easier. In particular, if it is higher than -80 kPa, this tendency becomes remarkable, which is not preferable.

The pressure for pressure molding in the pressure molding step is suitably 49 to 200 MPa, preferably 73 to 150 MPa. Since the coal ash compact can be appropriately densified, the mechanical strength of the coal ash compact immediately after pressure molding can be maintained at a certain level, and carbon dioxide can easily penetrate into the compact. This is because, through the carbonation step, the carbonation reaction can proceed to the inside of the molded body, and the mechanical strength can be dramatically increased.
It should be noted that as the pressure of the pressure molding becomes lower than 73 MPa, the coal ash compact does not become densified, so that the mechanical strength of the algae / soot breeding member is low and easily damaged even through the carbonation step, and the wear resistance is also improved. It is difficult to wear early and tends to lack durability, and as it becomes higher than 150 MPa, lamination tends to occur in the coal ash compact and the product yield decreases, and the coal ash compact becomes dense and molded in the carbonation process. Since carbon dioxide does not easily penetrate into the body, the carbonation reaction inside the molded body does not proceed, and the carbonation layer on the surface is thin, so that the mechanical strength of the algae / spider breeding member tends to decrease. In particular, when the pressure is lower than 49 MPa or higher than 200 MPa, these tendencies become remarkable, so that neither is preferable.

In the carbonation step, the container is not particularly limited as long as it can be sealed to some extent so that the coal ash molded body can be placed in a gas atmosphere containing carbon dioxide having a concentration higher than the concentration of carbon dioxide in the air. For example, a simple storage container or the like formed of a sheet, a film, or the like so as to cover a chamber such as a chamber or the periphery of a coal ash molded body can be used.
The carbon dioxide-containing gas can be brought into contact with the coal ash compact under normal pressure, or the pressurized carbon dioxide-containing gas can be brought into contact with the coal ash compact in a pressurized chamber or the like.

  As the carbon dioxide-containing gas, carbon dioxide produced industrially, carbon dioxide obtained as a by-product when producing industrial products, combustion exhaust gas from factories, power plants, and the like are used. In particular, if combustion exhaust gas is used as a carbon dioxide-containing gas and released into the atmosphere after being brought into contact with the coal ash compact, the combustion exhaust gas as a greenhouse gas can be used for the production of algae / soot breeding members. This is preferable because it enables effective utilization of greenhouse gases.

  In the carbonation step, the contact time between the coal ash compact and the carbon dioxide-containing gas depends on the carbon dioxide concentration of the carbon dioxide-containing gas, the thickness of the coal ash compact, etc., but is preferably 2 to 8 hours. 5 hours is preferably used. When the contact time is shorter than 2 hours, the carbonized layer formed by carbonation from the surface of the coal ash molded body toward the inside is thin, so that the mechanical strength is low and the crack is easily broken. As the contact time becomes longer than 5 hours, the rate at which the carbonation layer formed on the coal ash molded body proceeds in the depth direction becomes slower, and the mechanical strength does not increase as compared with the contact time and the productivity tends to decrease. In particular, when the time is longer than 8 hours, this tendency is remarkable, which is not preferable.

  In the carbonation step, the humidity in the container is 50 to 100%, preferably 55 to 100%. Carbonation reaction is likely to occur when the inorganic binder powder is carbonated in the presence of water, and the inorganic binder powder in the coal ash compact is reliably carbonated from the surface, so the mechanical strength of the coal ash compact is reduced. This is because the product yield can be increased.

Means for setting the humidity in the container to 50 to 100%, preferably 55 to 100%, means for introducing the carbon dioxide-containing gas kept in the above range into the container, means for humidifying the inside of the container to the above range Etc. can be used.
In addition, as the humidity in the container becomes lower than 55%, the reaction rate of the carbonation reaction is slow, and the carbonation of the inorganic binder powder becomes uneven, and some of the coal ash compacts show insufficient carbonation. The product yield tends to decrease. In particular, when the humidity in the container is lower than 50%, this tendency is remarkable, which is not preferable.

  In the carbonation step, when the carbonation reaction is started, water is obtained as a reaction product, and the carbonation reaction proceeds using the generated water. For this reason, the humidity in a container should just be said range at the time of the start of carbonation reaction, and after reaction is started, the humidity in a container can also be made into humidity lower than said range.

In the carbonation step, the coal ash molded body was formed with a carbonized layer having a depth of 2 to 10 mm, or a carbonized layer having a depth of 10 to 50% with respect to the thickness of the coal ash molded body. It becomes an algae and cocoon breeding member.
As a result, since a carbonized layer having an appropriate thickness is formed on the surface of the coal ash molded body, the mechanical strength of the coal ash molded body can be increased, and alkali components such as unreacted slaked lime are added to seawater. Elution can be suppressed and the pH of seawater in the vicinity of the surface can be prevented from rising, and anchoring and propagation effects such as drought can be enhanced.
In addition, as the depth of the carbonation layer becomes shallower than 2 mm, the mechanical strength of the coal ash compact decreases, it tends to crack and lacks workability, and the product yield tends to decrease. Since the contact time with the carbon dioxide containing gas in a process becomes long and the tendency for productivity to fall is seen, neither is preferable.
In addition, as the depth of the carbonized layer becomes shallower than 10% of the thickness from one side of the coal ash molded body, the mechanical strength of the coal ash molded body tends to decrease and the product yield tends to decrease. Therefore, it is not preferable. The carbonation layer having a depth of 50% with respect to the thickness of the coal ash molded body means that the entire cross section in the thickness direction of the coal ash molded body is carbonated.

  Algae and coral breeding members can be formed into a predetermined shape such as flat plate, corrugated plate, uneven plate, etc. by molds, and wave extinction of coral reef rocks, breakwaters, breakwaters, jetty, tetrapots, etc. It can be fixed to a block or the like. Moreover, it can fix to the weight body formed in the shape of blocks, blocks, etc. by the product made from concrete, cast iron, etc., and it can also be used by sinking to the seabed with a weight body. It can also be moored on the seabed or dredging.

Invention of Claim 2 of this invention is a manufacturing method of the algae and cocoon growth member of Claim 1, Comprising: The said mixed powder is the said coal ash 100 weight part, and the said inorganic binding powder 10 It has a constitution containing -100 parts by weight, preferably 25-70 parts by weight.
With this configuration, in addition to the operation obtained in the first aspect, the following operation can be obtained.
(1) Since the mixed powder contains 100 parts by weight of coal ash and 10 to 100 parts by weight of inorganic binder powder, preferably 25 to 70 parts by weight, the inorganic binder powder is carbonated to form coal ash. The body can harden from the surface, increase the mechanical strength and increase the product yield, and even if the coal ash molded body is immersed in water, it can be prevented from collapsing, and further increase the growth effect of algae and straw it can.

  Here, in the mixed powder, as the content of the inorganic binder powder is less than 25 parts by weight with respect to 100 parts by weight of the coal ash, the amount of the inorganic binder powder is small, and the coal ash produced by the carbonation reaction of the inorganic binder powder is reduced. Cohesive strength is low and the mechanical strength of the coal ash compact becomes small, and the product yield tends to decrease, and as the amount exceeds 70 parts by weight, the content of coal ash becomes relatively small and the growth effect of soot There is a tendency to decrease. In particular, when the amount is less than 10 parts by weight or more than 100 parts by weight, these tendencies tend to be remarkable, and neither is preferable.

Invention of Claim 3 of this invention is a manufacturing method of the algae and cocoon growth member of Claim 1 or 2, Comprising: The temperature in the said container in the said carbonation process is 0-90 degreeC, Preferably It has the structure which is 0-50 degreeC.
With this configuration, in addition to the operation obtained in the first or second aspect, the following operation can be obtained.
(1) Since the temperature in the container in the carbonation step is 0 to 90 ° C., preferably 0 to 50 ° C., the reaction rate of the carbonation reaction, which is an exothermic reaction in which the inorganic binder powder is carbonated, is large, and the carbonation In the process, the contact time between the coal ash compact and the carbon dioxide-containing gas can be shortened, and the productivity can be increased.

  Here, since the water | moisture content which a coal ash molded object contains freezes and expands and the coal ash molded object tends to be damaged as the temperature in the container in a carbonation process becomes lower than 0 degreeC, it is unpreferable. As the temperature rises above 50 ° C., the reaction rate of the carbonation reaction decreases, and in the carbonation step, the contact time between the coal ash compact and the carbon dioxide-containing gas tends to increase, and the productivity tends to decrease. In particular, when the temperature is higher than 90 ° C., this tendency is remarkable, which is not preferable.

Invention of Claim 4 of this invention is a manufacturing method of the algae and anther growth member of any one of Claim 1 thru | or 3, Comprising: The moisture content of the said mixed powder is 2-20 weight %, Preferably 2 to 8% by weight.
According to this configuration, in addition to the action obtained in any one of claims 1 to 3, the following action is obtained.
(1) Since the moisture content of the mixed powder is 2 to 20% by weight, preferably 2 to 8% by weight, the adhesion between the particles of the mixed powder is improved, and the formability of the coal ash compact in the pressure molding process is improved. The molded coal ash molded body is hard to break and the product yield can be increased.

Here, the moisture content of the mixed powder is the mass obtained by subtracting the mass in the dry state of the mixed powder from the mass of the mixed powder (the mass of water contained in the mixed powder), and the dry state of the mixed powder. It is a value obtained by dividing the result by the mass and expressing the result as a percentage.
As the water content is less than 2% by weight or more than 8% by weight, the adhesion between the particles of the mixed powder is reduced, and the coal ash compact tends to break and the product yield tends to decrease. In particular, if it exceeds 20% by weight, this tendency becomes remarkable, which is not preferable.

  In addition, when coal ash containing a large amount of anhydrous gypsum components such as fly ash contained in the combustion gas of a pressurized fluidized bed boiler and collected by a dust collector is used, it is mixed with an inorganic binder powder. Before that, water that has been sprayed in advance to form dihydrate gypsum is dried. Thereby, when optimizing the moisture content of the mixed powder in the mixing step, the coal ash and the inorganic binder powder can be uniformly mixed without solidifying the mixed powder.

As described above, according to the method for producing an algae / spider growing member of the present invention, the following advantageous effects can be obtained.
According to the invention of claim 1,
(1) Since a curing place and a curing time for leaving the coal ash compact for a long period of time are unnecessary, it is possible to provide a method for producing an algae / soil growth member that is intensive and excellent in productivity. Also, there is provided a method for producing algae and cocoon breeding members that can be obtained at a low cost without being broken down even when immersed in water for growing algae and cocoons, and capable of obtaining algae and cocoon breeding members that are excellent in anchoring and breeding effects of cocoons and the like. Can be provided.
(2) It is possible to provide a method for producing an algae / soil breeding member that can effectively use waste and is excellent in resource saving. In addition, it is possible to provide a method for producing an algae / spider-growing member that is easily accustomed to the natural environment and is capable of obtaining algae / spider-growing members that are easy to colonize algae spores and spider larvae and have an excellent proliferation effect.
(3) When processing such as cutting, cutting, drilling, etc. to coal ash compacts, even if a cutting agent such as water is used, it is excellent in workability without becoming muddy and disintegrating and increasing the processing speed. Therefore, it is possible to provide a method for producing an algae / spider-growing member having excellent productivity.
(4) Suppressing the elution of alkali components such as unreacted slaked lime to prevent the pH of seawater in the vicinity of the surface from rising, and improving the anchoring and growth effect of drought etc. It is possible to provide a method for producing an algae / cullet breeding member that can suppress elution of substances and the like and obtain an algae / spider breeding member excellent in environmental conservation.
(5) Since it is possible to obtain mechanical strength that does not break or collapse even if it is submerged in the sea simply by pressure molding, it is possible to provide a method for producing an algae / soil growth member that is excellent in energy saving. .
(6) Since it is difficult for air to remain in the coal ash molded body formed by degassing and molding the mixed powder under reduced pressure, the air remaining in the coal ash molded body expands and the coal ash molded body is easily destroyed. It is possible to provide a method for producing an algae / spider-growing member that can prevent the above-described problem and increase the product yield.

According to invention of Claim 2, in addition to the effect of Claim 1,
(1) It is possible to provide a method for producing an algae / soot-growing member, in which the inorganic binder powder is carbonated and the coal ash molded body is cured from the surface, and the mechanical strength is increased and the product yield is increased. In addition, it is possible to provide a method for producing an algae / cocoon breeding member that can be prevented from disintegrating even when immersed in water and obtain an algae / cocoon breeding member having an excellent effect of algae and cocoon multiplication.

According to invention of Claim 3, in addition to the effect of Claim 1 or 2,
(1) To provide a method for producing an algae / soil-growing member that has a high carbonation reaction rate and that can shorten the contact time between the coal ash compact and the carbon dioxide-containing gas in the carbonation step and has excellent productivity. it can.

According to the invention of claim 4, in addition to the effect of any one of claims 1 to 3,
(1) The moldability of the coal ash molded body in the pressure molding process can be improved, and a method for producing an algae / soot breeding member having a high product yield in which the molded coal ash molded body is difficult to break can be provided.

Hereinafter, the best mode for carrying out the present invention will be described with reference to the drawings.
(Embodiment 1)
FIG. 1 is a schematic diagram of a pressure molding apparatus for a coal ash molded body of an algae / spoil breeding member used in the pressure molding process, and FIG. 2 is a container used in a carbonation process in which the coal ash molded body is housed. FIG. 3 is a schematic view, FIG. 3 is a perspective view of a coal ash molded body (algae / soot breeding member) after undergoing a carbonation step, FIG. 4 is a cross-sectional photograph taken along line AA in FIG. FIG. 5 is a schematic view of a cross-section of the algae / spider breeding member shown in FIG.
In FIG. 1, 1 is a pressure molding apparatus, 2 is a frame of the pressure molding apparatus 1, 3 is a lower mold disposed under the frame 2, 3 a is a recess formed in the lower mold 3, 4 is a hydraulic lifting cylinder disposed at the top of the frame 2, 5 is a cylinder rod disposed with its tip facing downward from the lifting cylinder 4, and 6 is a lifting cylinder connected to the tip of the cylinder rod 5. 4 is an upper mold formed so as to freely enter and exit the recess 3a of the lower mold 3, and a cylinder rod 5 is fitted in the upper hole so that the upper mold at the tip of the lower mold 3 and the cylinder rod 5 is inserted. A decompression chamber that surrounds the mold 6, 7 a is a packing that keeps an airtight space between the upper hole of the decompression chamber 7 and the cylinder rod 5, 8 is a vacuum pump that communicates with the decompression chamber 7, and 9 communicates with the elevating cylinder 4. A hydraulic pump 10 is a hydraulic operation panel.

In FIG. 2, 11 is a chamber such as a chamber, a simple storage container formed of a sheet or a film, etc., and a container formed so as to be sealed to some extent, and 12 is an industrially produced carbon dioxide, combustion exhaust gas, etc. An inlet for introducing the carbon dioxide-containing gas into the container 11, 13 is an exhaust outlet for exhausting the carbon dioxide-containing gas from the container 11 to the outside, and 14 is a coal ash molding housed in the container 11 at a predetermined interval. Is the body.
3, 4, and 5, 14 is a carbonated coal ash molded body, 15 is a carbon dioxide-containing gas, and the inorganic bound powder in the coal ash molded body 14 is carbonated by contact with the carbon dioxide-containing gas. A carbonation layer formed at a predetermined depth (a portion that looks black in FIG. 4), 16 is an inside of the coal ash compact 14 in which the carbon dioxide-containing gas does not penetrate and an unreacted inorganic binder powder remains. It is an unreacted layer (a portion that looks whitish in FIG. 4). In the present embodiment, the depth d of the carbonation layer 15 is 2 to 10 mm, or 20 to 40% of the thickness t of the coal ash molded body 14.

A method for producing an algae / soil growth member using the pressure molding apparatus and container configured as described above will be described below.
First, in the mixing step, 100 parts by weight of coal ash and 10 to 100 parts by weight, preferably 25 to 70 parts by weight of inorganic binder powder such as slaked lime are mixed to obtain a mixed powder. At this time, the moisture content is adjusted by adding water using an Eirich mixer or the like so that the moisture content of the mixed powder is 2 to 20 wt%, preferably 2 to 8 wt%.
Next, in the pressure molding step, a predetermined amount of the mixed powder is put into the recess 3 a of the lower mold 3 of the pressure molding apparatus 1. Next, after the inside of the decompression chamber 7 is decompressed to −101 to −80 kPa, preferably −100 to −90 kPa, using the vacuum pump 8, the lifting / lowering cylinder 4 is lowered by the hydraulic pressure of the hydraulic pump 9 by operating the hydraulic operation panel 10. Then, the mixed powder placed in the recess 3a of the lower mold 3 is pressed by the upper mold 6 at the tip of the cylinder rod 5 with a pressure of 49 to 200 MPa, preferably 73 to 150 MPa to form a coal ash molded body of a predetermined shape. To do. In the present embodiment, a flat coal ash compact is manufactured. After the molding of the coal ash compact is finished, the elevating cylinder 4 is raised to remove the upper die 6 at the tip of the cylinder rod 5 from the recess 3a of the lower die 3 and introduce air into the decompression chamber 7 to reduce the pressure. The inside of the chamber 7 is returned to atmospheric pressure. Next, the molded coal ash compact is taken out from the recess 3 a of the lower mold 3.
Next, in the carbonation step, after the coal ash molded body 14 formed in the container 11 is accommodated at a predetermined interval, a carbon dioxide-containing gas such as combustion exhaust gas is introduced into the container 11 from the introduction port 12. The inside of the container 11 is adjusted so that the humidity is 50 to 100%, preferably 55 to 100%, and the temperature is 0 to 90 ° C, preferably 0 to 50 ° C.
Carbon dioxide-containing gas is brought into contact with the coal ash molded body 14 accommodated in the container 11 for 2 to 8 hours, preferably 2 to 5 hours, and carbonized from the surface of the coal ash molded body 14 toward the inside. As a result, an algae / soot breeding member in which the carbonized layer 15 having a predetermined depth is formed on the coal ash compact 14 is manufactured.

According to the method for producing an algae / spider-growing member in Embodiment 1 of the present invention as described above, the following effects are obtained.
(1) The coal ash molded body obtained in the pressure molding step under reduced pressure has a water-soluble inorganic binder powder such as slaked lime in the coal ash molded body that absorbs carbon dioxide in the air immediately after molding and is water. Hardens as a carbonate such as calcium carbonate, which is hardly soluble. For this reason, although a coal ash molded object increases mechanical strength, since it has the carbonation process which accommodates a coal ash molded object in the container 11 and forcibly carbonizes, it is to inorganic binding powder. By promoting the absorption of carbon dioxide, the mechanical strength of the coal ash compact can be increased in a short time. As a result, because it does not require a curing place or curing time to leave the coal ash compacts for a long time in order to carbonize with carbon dioxide in the air, it is intensive and excellent in productivity, and in the water where algae and straw are grown. Even if immersed, it does not disintegrate, and it is possible to produce algae and cocoon breeding members with high effect of colonization and growth of cocoons at a low cost.
(2) Since coal ash is used as a raw material, waste can be used effectively, and coal ash contains silica and alumina as the main components in the same way as natural silicate white clay and diatomaceous earth. It is easy to get familiar with, and the algae spores and cocoon larvae are easy to settle and have an excellent proliferation effect.
(3) Since it has a carbonation step and the coal ash molded body is hardened with a poorly soluble carbonate, a cutting agent such as water is used when the coal ash molded body is processed such as cutting, cutting, drilling, etc. Even if is used, it does not become muddy and does not collapse, and it is excellent in workability.
(4) Since it has a carbonation step, the water-soluble inorganic binding powder such as slaked lime existing on the surface of the coal ash molded body absorbs carbon dioxide, and the carbonate such as calcium carbonate hardly soluble in water and Since it becomes hardened, it is possible to prevent alkaline components such as unreacted slaked lime from eluting into seawater, and to prevent the pH of seawater near the surface from rising, and to enhance the fixation and proliferation effect of sea bream etc. .
(5) Since the coal ash molded body can obtain a predetermined mechanical strength simply by pressure molding without firing, etc., it is excellent in energy saving.
(6) Since the water content of the mixed powder is 2 to 20% by weight, preferably 2 to 8% by weight, the adhesion between the particles of the mixed powder is improved, and the formability of the coal ash compact in the pressure molding process is improved. The molded coal ash molded body is hard to break and the product yield can be increased.
(7) Since the mixed powder contains 100 parts by weight of coal ash and 10 to 100 parts by weight of inorganic binder powder, preferably 25 to 70 parts by weight, the inorganic binder powder is carbonated to form coal ash. The body can harden from the surface, increase the mechanical strength and increase the product yield, and even if the coal ash molded body is immersed in water, it can be prevented from collapsing, and further increase the growth effect of algae and straw it can.
(8) In the pressure molding step, the mixed powder is pressure-molded in a mold whose pressure is reduced to −101 to −80 kPa, preferably −100 to −90 kPa, so that the pressure can be reduced in a short time and the productivity is excellent. In addition, since it is difficult for air to remain in the coal ash molded body, it is possible to prevent the remaining air from expanding and easily destroying the coal ash molded body, and to increase the product yield.
(9) In the pressure molding step, since the pressure of the pressure molding is 49 to 200 MPa, preferably 73 to 150 MPa, the coal ash molded body can be appropriately densified. The mechanical strength can be maintained at a certain level, and carbon dioxide can easily penetrate into the molded body, so that the carbonation reaction can proceed to the inside of the molded body through the carbonation process. Strength can be dramatically increased.
(10) In the carbonation step, the coal ash compact is brought into contact with the carbon dioxide-containing gas for 2 to 8 hours, preferably 2 to 5 hours, so that it is excellent in productivity and forms a carbonation layer with an appropriate depth. The mechanical strength can be increased and the product yield can be increased.
(11) Since the humidity in the container in the carbonation step is 50 to 100%, preferably 55 to 100%, the reaction rate of the carbonation reaction in which the inorganic binder powder is carbonated in the presence of water is high, Since the inorganic binder powder in the coal ash compact is reliably carbonated from the surface, the mechanical strength of the coal ash compact can be increased and the product yield can be increased.
(12) Since the temperature in the container in the carbonation step is 0 to 90 ° C., preferably 0 to 50 ° C., the reaction rate of the carbonation reaction, which is an exothermic reaction in which the inorganic binder powder is carbonated, is large, and carbonation In the process, the contact time between the coal ash compact and the carbon dioxide-containing gas can be shortened, and the productivity can be increased.
(13) In the carbonation step, a carbonized layer having a depth of 2 to 10 mm or a carbonized layer having a depth of 20 to 40% of the thickness of the coal ash molded body is formed on the coal ash molded body. As a result, the mechanical strength of the coal ash molded body can be increased, and the pH of seawater near the surface of the coal ash molded body is increased by suppressing the dissolution of alkaline components such as unreacted slaked lime into the seawater. Can be prevented, and the fixing and proliferation effect of wrinkles and the like can be enhanced. Moreover, it is possible to prevent toxic substances from leaching into seawater, which is excellent in environmental conservation.

Hereinafter, the present invention will be specifically described by way of examples. The present invention is not limited to these examples.
Example 1
A mixed powder obtained by mixing 100 parts by weight of fly ash as coal ash (particles having a particle size of 0.1 mm or less of 90% by weight or more) and 25 parts by weight of slaked lime as an inorganic binding powder is reduced in pressure from −100 to −90 kPa. Under pressure molding at a pressure of 150 MPa, a plate-shaped coal ash compact having a length of 10 cm, a width of 10 cm, and a thickness of 1.6 cm was obtained. The obtained coal ash compact is accommodated in a container, and a combustion exhaust gas having a carbon dioxide concentration of 20 to 30% is introduced into the container as a carbon dioxide-containing gas for 3 hours, and then carbonized from the surface of the coal ash compact toward the inside. Turned into. In addition, the total volume of the coal ash molded object accommodated in the container was about 6% of the volume of the container. The humidity inside the container was 97% and the temperature was 27 ° C. As described above, a plate-like algae / spider-growing member of Example 1 was obtained.
In addition, the depth of the carbonation layer was 3-4 mm from the result of cross-sectional observation of the algae / spider breeding member of Example 1.
Moreover, it was found that the compressive strength of the algae / spider growing member of Example 1 was 35 N / mm ^{2 as} measured by a method according to JIS. This is higher in compressive strength than bricks (2 types, 3 types, 4 types) specified by JIS (standard values of 2 types of bricks are 14.71 N / mm ² or more, 3 types are 19.61 N / mm ² or more) 4 types were found to be 29.42 N / mm ² or more.)

(Example 2)
100 parts by weight of clinker ash (50% by weight of particles having a particle size of 0.1 to 1 mm and 50% by weight of particles having a particle size of 1 to 2 mm or more) as coal ash and 25 parts by weight of slaked lime as an inorganic binder powder Except for using the mixed powder thus obtained, the algae / spider-growing member of Example 2 was obtained in the same manner as Example 1.

(Comparative Example 1)
A plate made of Amakusa pottery stone having a length of 10 cm, a width of 10 cm, and a thickness of 1.6 cm was used as Comparative Example 1. Amakusa porcelain stone plates are the most excellent algae / spider-growing members in the present situation where it has been confirmed that juveniles are almost the same as or more than coral reef limestone based on the results of previous tests.

(Creation of specimen)
Specimens were prepared using the algae / spider-growing members of Example 1, Example 2, and Comparative Example 1, and were actually immersed in the sea to conduct algae / spear fixing test.
FIG. 6 is a perspective view of a specimen prepared for the algae / salach fixation test.
In FIG. 6, 20 is a specimen prepared for investigation, 14 is a carbonated coal ash molded body (algae / soot breeding member), 21 is a weight body made of concrete or the like and formed into a block shape, 22 Is a bar-shaped member such as a reinforcing bar, a steel bar, a pipe, or a bolt that is erected at a predetermined location of the sink body 21. The algae / spider breeding member 14 has two through-holes formed at predetermined locations, the rod-shaped member 22 is inserted therethrough, and two algae / spider-growing members 14 are arranged at a predetermined interval. Reference numeral 23 denotes a spacer between which the rod-shaped member 22 is inserted and the weight body 21 and the algae / spider-growing member 14 are spaced apart, and the algae / spider-growing members 14, 14 are maintained at a distance of 10 mm. It is a fixing member such as a nut that prevents the algae / sallet breeding member 14 from being detached from the rod-shaped member 22.

(Familiar fixation test)
The juvenile fixation test using the above-mentioned specimens was conducted at the Margu (World Geodetic System WGS) located at the center of Sekisei Lagoon, Japan's largest coral reef spreading between Ishigakijima and Ishigakijima, Okinawa Prefecture. -84: 24 ° 17.241'N, 124 ° 02.046'E).
The algae / spoilage-growing members of Example 1 and Example 2 (30 sheets per example) and the plate-like body of Comparative Example 1 (30 sheets) were previously set on the sand bottom 5 m deep in the leaf. The above-mentioned specimen 20 was formed by arranging and fixing on the upper surface of the sink body 21 of the concrete block using a rod-like member 22 or the like. That is, a through-hole portion having an inner diameter of 10 mm is formed in the algae / spider breeding member of Example 1, Example 2, and Comparative Example 1, and a plurality of bolts erected on the upper surface of the sink body 21 in the through-hole portion. A rod-shaped member 22 having a diameter of 6 mm and a length of 9 cm was inserted, and two algae / spider-growing members 14 were arranged at a distance of 10 mm for each place of the weight body 21. The water temperature at this time was 25 degreeC.
In the surrounding sea area, it was confirmed that spiders laid eggs the day after the algae / spider breeding member was installed. In the next day, so-called slicks in which eggs were concentrated and floated were observed in various places. That is, the algae / cocoon breeding members of Example 1, Example 2, and Comparative Example 1 were installed immediately before the cocoon larvae settled. This state was left for 3.5 months.

After 3.5 months, the algae / spider breeding members installed were collected. The collected algae and cocoon breeding members were sun-dried for 2 days and then transferred to the experimental facility. The water temperature at the time of recovery was 29 ° C.
The algae / spider-growing members transferred to the experimental facility were observed with a stereomicroscope, and the number of each kind of juvenile settled on the lower surface (surface on the side of the mass 21), the upper surface, and the side surface was counted. The results are shown in (Table 1).

Most of the settled juveniles belonged to the genus Midorii, followed by the genus Coralidae, and the rest were the genus Coralaceae. Both are the dominant species in this area.
The number of young pods fixed on the algae / spider growing members of Examples 1 and 2 was 1.5 to 2.5 times the number of young shoots fixed on the plate-like body of Comparative Example 1.

Next, it was compared to which part of the algae and cocoon breeding member the juveniles settled.
FIG. 7 is a diagram showing the site-specific density of the algae / spider-growing member in the specimen 20 and the juveniles grown on the algae / spider-growing member in Example 1, Example 2, and Comparative Example 1. Bars indicate 95% confidence intervals.
In FIG. 7, A to F indicate the site of the algae / spider growth member (or plate-like body) in the specimen 20, and as shown in FIG. The bottom surface of the algae / spider breeding member, B is the side surface of the bottom algae / spear breeding member, C is the top surface of the bottom algae / spider breeding member, and D is the bottom surface of the upper algae / spear breeding member , E indicates the side surface of the upper algae / spider breeding member, and F indicates the top surface of the upper algae / spider breeding member.
As is clear from FIGS. 7B, 7C, and 7D, there is a tendency for young juveniles to settle on the lower surface (A, D) of the algae / spider breeding member, and the density of Examples 1 and 2 Compared with Comparative Example 1, it was 1.5 to 2 times. Moreover, the density of the juveniles on the side surfaces (B, E) of the algae / spider breeding members of Examples 1 and 2 is more than twice the density of the side surfaces of Comparative Example 1, and according to this example, It became clear that the kindergarten's fixing effect was also high.
In addition, the young pod did not settle at all on the upper surface (F) of the upper algae / spider breeding member. This is presumed to be due to the fact that small seaweeds are likely to grow on site F, silt and the like are easily accumulated, and sea urchin glazing is more likely to occur. In fact, it was confirmed that the algae were fixed on the upper surface (F) of the algae / spider growing member of Example 1 and Example 2.
As apparent from FIG. 7, the largest number of young shoots settled on the algae / spider breeding member of Example 1 prepared with fly ash, and then the young algae on the algae / spider breeding member of Example 2 prepared with clinker ash. Was found to settle. Significant differences were observed with Comparative Example 1.
It was visually confirmed that the algae and cocoon growth members of Example 1 and Example 2 did not cause any abnormalities in appearance such as cracks and cracks even if they were submerged in a tidal current for 3.5 months. .

  As described above, according to this example, algal spores and moth larvae are much easier to settle and proliferate compared to Amakusa pottery stone, which is said to have the best fixability of juveniles. Along with being effective, it is possible to obtain algae and cocoon breeding members with high mechanical strength without disintegrating even when immersed in the sea for a long period of time. It has been clarified that a method for producing algae and anther-growing members that are excellent in resource saving and energy saving can be provided.

(PH measurement of seawater in which algae and cocoon breeding members are immersed)
In order to measure the pH of the seawater in which the algae and cocoon breeding members were immersed, a test solution was prepared in accordance with Environmental Agency Notification No. 48 of 1973. First, the algae / cocoon growth member of Example 1 was crushed and further pulverized to a particle size of about 0.2 to 0.5 mm. Next, 100 g of the crushed algae / soil propagation member added with 1 L of seawater was shaken continuously at 200 times / min for 6 hours. This was filtered (filter paper: GS25), and the filtrate was collected and its pH was measured as a test solution. As a result, the pH of the test solution was 10.
Similarly, when the pH of seawater in which slaked lime was immersed and the pH of seawater in which a pulverized plate-like body formed of Portland cement was measured were measured, the pH of the test solution in which slaked lime was immersed was 12. .4, pH of the test solution in which Portland cement was immersed was 12.8. The pH of the seawater was 8.
As described above, according to the present invention, alkali components such as unreacted slaked lime can be prevented from eluting into seawater, and the pH of seawater near the surface of the algae / soil growth member can be prevented from increasing. It became clear that the colonization and proliferation effect can be enhanced.

  TECHNICAL FIELD The present invention relates to a method for producing algae / spider-growing members, which has high mechanical strength, has little alkaline component elution, can prevent the pH of seawater in the vicinity of the surface from rising, and is easy to adapt to the natural environment, and is an algae spore. Algae and cocoon breeding members that are easy to settle larvae and cocoons can be manufactured at low cost, and are more intensive and productive. Also, waste can be used effectively and resources are excellent. At the same time, it is possible to provide a method for producing an algae / spider breeding member that is excellent in energy saving.

Schematic diagram of the pressure molding device for coal ash moldings of algae and cocoon breeding members used in the pressure molding process Schematic diagram of container used in carbonation process with coal ash compact contained inside Perspective view of a coal ash molded body (algae / kite breeding member) after undergoing a carbonation step Cross-sectional photograph taken along line AA in FIG. Schematic diagram of the cross section of the algae / spider breeding member shown in FIG. Perspective view of specimens prepared for algae and cocoon fixation test Figure showing the density of each part of the algae / spider-growing member in the specimen and the juveniles that have settled on the algae / spear-growing member

Explanation of symbols

DESCRIPTION OF SYMBOLS 1 Pressure molding apparatus 2 Frame 3 Lower die 3a Concave 4 Elevating cylinder 5 Cylinder rod 6 Upper die 7 Decompression chamber 7a Packing 8 Vacuum pump 9 Hydraulic pump 10 Hydraulic operation panel 11 Container 12 Inlet 13 Exhaust port 14 Coal ash Molded body 15 Carbonated layer 16 Unreacted layer 20 Specimen 21 Sedimentation body 22 Bar-shaped member 23 Spacer 24 Fixing member

Claims (4)

a. Coal ash; b. A mixing step of obtaining a mixed powder by mixing inorganic binding powder such as slaked lime, dolomite, magnesium hydroxide, and the like;
A pressure forming step of pressing the mixed powder under reduced pressure to form a coal ash compact by pressure forming into a predetermined shape;
A carbonation step in which the coal ash compact is accommodated in a container and brought into contact with a carbon dioxide-containing gas introduced into the container to be carbonized from the surface of the coal ash compact toward the inside;
A method for producing an algae / sallet breeding member, comprising:   The algae according to claim 1, wherein the mixed powder contains 100 parts by weight of the coal ash and 10 to 100 parts by weight, preferably 25 to 70 parts by weight of the inorganic binding powder. -Manufacturing method of a soot breeding member.   The temperature in the container in the carbonation step is 0 to 90 ° C, preferably 0 to 50 ° C.   4. The method for producing an algae / grass-growing member according to claim 1, wherein a moisture content of the mixed powder is 2 to 20 wt%, preferably 2 to 8 wt%.