CN113993372A - Material for cultivation and manufacturing method thereof - Google Patents

Material for cultivation and manufacturing method thereof Download PDF

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Publication number
CN113993372A
CN113993372A CN202080042964.6A CN202080042964A CN113993372A CN 113993372 A CN113993372 A CN 113993372A CN 202080042964 A CN202080042964 A CN 202080042964A CN 113993372 A CN113993372 A CN 113993372A
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porous
cultivation
mass
slurry
hydrothermal reaction
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千叶彩香
须藤俊吉
坂本好明
神谷隆
阿部信彦
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Taiheiyo Cement Corp
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    • AHUMAN NECESSITIES
    • A01AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01GHORTICULTURE; CULTIVATION OF VEGETABLES, FLOWERS, RICE, FRUIT, VINES, HOPS OR SEAWEED; FORESTRY; WATERING
    • A01G33/00Cultivation of seaweed or algae
    • AHUMAN NECESSITIES
    • A01AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01KANIMAL HUSBANDRY; AVICULTURE; APICULTURE; PISCICULTURE; FISHING; REARING OR BREEDING ANIMALS, NOT OTHERWISE PROVIDED FOR; NEW BREEDS OF ANIMALS
    • A01K63/00Receptacles for live fish, e.g. aquaria; Terraria
    • A01K63/04Arrangements for treating water specially adapted to receptacles for live fish
    • CCHEMISTRY; METALLURGY
    • C12BIOCHEMISTRY; BEER; SPIRITS; WINE; VINEGAR; MICROBIOLOGY; ENZYMOLOGY; MUTATION OR GENETIC ENGINEERING
    • C12NMICROORGANISMS OR ENZYMES; COMPOSITIONS THEREOF; PROPAGATING, PRESERVING, OR MAINTAINING MICROORGANISMS; MUTATION OR GENETIC ENGINEERING; CULTURE MEDIA
    • C12N1/00Microorganisms, e.g. protozoa; Compositions thereof; Processes of propagating, maintaining or preserving microorganisms or compositions thereof; Processes of preparing or isolating a composition containing a microorganism; Culture media therefor
    • C12N1/12Unicellular algae; Culture media therefor
    • YGENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02ATECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE
    • Y02A40/00Adaptation technologies in agriculture, forestry, livestock or agroalimentary production
    • Y02A40/80Adaptation technologies in agriculture, forestry, livestock or agroalimentary production in fisheries management

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  • Marine Sciences & Fisheries (AREA)
  • Genetics & Genomics (AREA)
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  • Virology (AREA)
  • Tropical Medicine & Parasitology (AREA)
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  • Microbiology (AREA)
  • Animal Husbandry (AREA)
  • Biodiversity & Conservation Biology (AREA)
  • Biochemistry (AREA)
  • General Engineering & Computer Science (AREA)
  • General Health & Medical Sciences (AREA)
  • Cell Biology (AREA)
  • Farming Of Fish And Shellfish (AREA)

Abstract

The invention provides a material for aquaculture and a method for producing the same, wherein the propagation of diatoms in water is promoted by supplying silicic acid to the water, thereby inhibiting the deterioration of water quality in aquaculture ponds and the like, improving the growth of aquatic organisms feeding diatoms, and providing a source of calcium for the aquatic organisms and having excellent particle size retention. The material for cultivation comprises a porous solidified granular body containing calcium silicate hydrate which is a reaction product of a silicic acid material and a calcareous material, and an unreacted calcareous material, and the content of calcium carbonate is 0.1-12.0 mass%. The manufacturing method of the breeding material comprises the following steps: a step for preparing a slurry by using a siliceous material, a calcareous material, calcium carbonate, a foaming agent, and water as raw materials; curing the slurry to foam and cure the slurry to obtain a porous cured body; subjecting the porous cured product to a hydrothermal reaction to obtain a porous cured product after the hydrothermal reaction; and granulating the porous solidified body after the hydrothermal reaction to obtain a material for cultivation.

Description

Material for cultivation and manufacturing method thereof
Technical Field
The invention relates to a cultivation material and a manufacturing method thereof.
Background
As a method for improving the growing environment of aquatic organisms, various methods are known.
For example, patent document 1 describes a culture solution for promoting the growth of diatoms, which is capable of promoting the growth of diatoms and promoting the growth of crustaceans, shellfish, animal plankton and the like that feed on diatoms, wherein the culture solution contains water and a particulate siliceous material containing calcium silicate hydrate as a main component, and the amount of the siliceous material is 0.001 to 2 parts by mass per 100 parts by mass of water.
Patent document 2 describes, as a cultivation material that can further promote the propagation of diatoms in water, can suppress the deterioration of water quality in a cultivation pond or a closed water area, and can improve the survival rate of aquatic organisms, a cultivation material containing calcium silicate for supplying to cultivation water of aquatic organisms, characterized in that when the cultivation material is added in an amount of 1g per 1 liter of distilled water, water-soluble SiO is added2The amount of elution is 3mg or more.
Documents of the prior art
Patent document
Patent document 1: japanese patent laid-open publication No. 2015-167538
Patent document 2: japanese patent laid-open publication No. 2016-129512
Disclosure of Invention
Problems to be solved by the invention
An object of the present invention is to provide a material for aquaculture, which can promote the propagation of diatoms in water by supplying silicic acid to water, inhibit the deterioration of water quality in aquaculture ponds and the like, improve the growth of aquatic organisms feeding diatoms, and serve as a source of calcium for the aquatic organisms, and which has excellent particle size retention, and a method for producing the same.
Means for solving the problems
The present inventors have conducted extensive studies to solve the above problems, and as a result, have found that the above object can be achieved by a material for cultivation comprising a porous solidified material of a calcium silicate hydrate which is a reaction product of a siliceous material and a calcareous material and an unreacted calcareous material, and having a calcium carbonate content of 0.1 to 12.0 mass%.
The present invention provides the following [1] to [6 ].
[1] A material for cultivation, characterized by comprising a porous solidified material of granules containing calcium silicate hydrate as a reaction product of a silicic acid material and a calcareous material and an unreacted calcareous material, and having a calcium carbonate content of 0.1 to 12.0 mass%.
[2] The material for cultivation as described in the above [1], wherein the material for cultivation contains 50 mass% or more of granules having a particle size of 0.5 to 5 mm.
[3] The material for aquaculture according to the above [1] or [2], wherein the porous solidified body is a porous carbonated granular body obtained by carbonating a reaction product of a silicic acid material and a calcareous material.
[4] A method for producing the material for cultivation according to the above [1] or [2], comprising: a slurry preparation step of preparing a slurry using the siliceous material, the calcareous material, calcium carbonate, a foaming agent, and water as raw materials; a curing step of curing the slurry to foam and cure the slurry to obtain a porous cured body; a hydrothermal reaction step of subjecting the porous cured product to a hydrothermal reaction to obtain a porous cured product after the hydrothermal reaction; and a granulation step of granulating the porous solidified body after the hydrothermal reaction to obtain the cultivation material.
[5] A method for producing a material for aquaculture as described in [3], comprising: a slurry preparation step of preparing a slurry using the siliceous material, the calcareous material, a foaming agent, and water as raw materials; a curing step of curing the slurry to foam and cure the slurry to obtain a porous cured body; a hydrothermal reaction step of subjecting the porous cured product to a hydrothermal reaction to obtain a porous cured product after the hydrothermal reaction; and a granulation and carbonation step of obtaining the material for cultivation by using the porous solidified body after the hydrothermal reaction, wherein the granulation and carbonation step is any one of the following methods: (a) a method of obtaining the above-mentioned cultivation material by granulating the above-mentioned porous solidified body to obtain a porous granular material and then carbonating the porous granular material; or (b) carbonating the porous solidified body to obtain a porous carbonated solidified body, and granulating the porous carbonated solidified body to obtain the material for cultivation.
[6] The method for producing a material for livestock breeding according to the above [4] or [5], wherein the siliceous material comprises one or more selected from silica, silica sand and diatomaceous earth, the calcareous material comprises one or more selected from quicklime, slaked lime and cement, and the foaming agent comprises aluminum powder.
Effects of the invention
Since the breeding material of the present invention is porous and contains calcium silicate hydrate, it is possible to supply water-soluble silicic acid to water and promote the propagation of diatoms in water.
Further, since the propagation of diatoms in water is promoted, the occurrence of algal blooms and the like can be suppressed in a culture pond, a closed water area or the like, and as a result, the deterioration of water quality in the culture pond or the like can be suppressed, and the survival rate of aquatic organisms (for example, crustaceans such as shrimps, shellfish, fish) to be cultured can be improved. In addition, the growth of aquatic organisms (for example, crustaceans such as shrimp, shellfish, and fish) feeding on diatoms is improved.
In the material for cultivation according to the present invention, even if calcium silicate contained in the material is dissolved in water, calcium carbonate contained in the material, which is hardly soluble, remains, and thus the particle size retention is excellent. Therefore, the above material can maintain its particle size (size of granules) without disintegration for a long period (for example, 30 days), and as a result, consolidation of the substrate can be prevented, air permeability and water permeability of the substrate can be improved, and the substrate can be inhibited from becoming anoxic.
In addition, the residual calcium carbonate can be used as a calcium supply source for aquatic organisms (for example, crustaceans such as shrimp, shellfish, and fish).
In the present specification, the term "bottom" refers to a surface layer constituting a bottom of a fresh water body, a brackish water body, or a sea water body.
Detailed Description
The material for cultivation of the present invention comprises a porous solidified body of granules containing calcium silicate hydrate which is a reaction product of a siliceous material and a calcareous material and an unreacted calcareous material, and having a calcium carbonate content of 0.1 to 12.0 mass%.
Here, the siliceous material means a silicic acid component (SiO) for forming a hydrated calcium silicate2) The raw materials of (1).
Examples of the siliceous raw material include silica, silica sand, diatomaceous earth, and the like.
As the siliceous material, a material in the form of powder is generally used in order to improve the reaction with the calcareous material.
The calcareous raw material means a raw material for forming calcareous matter (CaO) constituting calcium silicate hydrate.
Examples of the calcareous raw material include quicklime (CaO), hydrated lime (Ca (OH)2) Cement, etc. It should be noted that cement also corresponds to the siliceous material.
As the calcareous material, a material in the form of powder or granules is generally used.
The calcium silicate hydrate refers to CaO-SiO2-H2An O-based compound (for example, tobermorite, which is known as a main component of lightweight cellular concrete).
Examples of combinations of siliceous materials and calcareous materials include: (a) the siliceous material is silica or silica sand, and the calcareous material is the combination of quicklime and cement; (b) the siliceous material is silica or silica sand and diatomite, and the calcareous material is the combination of quicklime and cement; (c) the siliceous raw material is silica or silica sand, and the calcareous raw material is the combination of quicklime, hydrated lime and cement; and so on.
Examples of the calcium silicate hydrate include tobermorite, xonotlite, CSH gel, orthosilkite, whinesite, hydrocalumite, wollastonite, and the like.
Toberlite is crystalline calcium silicate hydrate with Ca5·(Si6O18H2)·4H2O (plate-like form), Ca5·(Si6O18H2) (plate-like form), Ca5·(Si6O18H2)·8H2O (fibrous form) and the like.
Xonotlite is a crystalline calcium silicate hydrate having Ca6·(Si6O17)·(OH)2(fibrous form), and the like.
The CSH gel has alpha CaO beta SiO2·γH2O (wherein alpha/beta is 0.7-2.3, and gamma/beta is 1.2-2.7). Specifically, it may be a compound having 3CaO 2SiO2·3H2Calcium silicate hydrate of chemical composition of O, and the like.
The orthorhombic xonotlite has Ca4(SiO3)3(OH)2Etc.
The whitlockite has the formula (NaCa)2)Ca14(Si23Al)O60(OH)8·14H2O, etc.
The hydrocalcite has Ca2SiO3(OH)2Etc.
Wollastonite with CaO and SiO2(fibrous or columnar form) and the like.
Among them, tobermorite is preferable from the viewpoint of ease of production and economy.
The unreacted calcareous raw material is a raw material which does not react with the siliceous raw material and remains as a constituent of the calcium silicate hydrate, among the raw materials for forming calcareous (CaO) constituting the calcium silicate hydrate.
The unreacted calcareous material is usually calcium hydroxide (Ca (OH) as a hydration reaction product of quicklime2) The form of (2) is present in the porous cured body.
From the viewpoint of improving the particle size retention and balancing the supply amount of silicic acid, the content of calcium carbonate in the material for cultivation (granules of a porous solidified body) of the present invention is preferably 0.1 to 12.0 mass%, more preferably 0.5 to 11.0 mass%, even more preferably 1.0 to 10.0 mass%, even more preferably 2.0 to 9.0 mass%, even more preferably 3.0 to 8.5 mass%, even more preferably 4.0 to 8.2 mass%, and particularly preferably 5.0 to 8.0 mass%.
When the content of calcium carbonate is 0.1 mass% or more, the amount of calcium (calcium carbonate remaining in the substrate) taken in by the aquatic organism (particularly, crustacean or shellfish) increases, and the growth or survival rate of the aquatic organism can be further improved. When the content of calcium carbonate is 12.0 mass% or less, the amount of calcium silicate contained in the cultivation material can be relatively increased, and the amount of silicic acid supplied to water can be increased to further promote the propagation of diatoms in water.
The material for cultivation (the porous solidified material granule) of the present invention may be a porous carbonated granule obtained by carbonating a reaction product of a siliceous material and a calcareous material.
From the viewpoint of supplying a larger amount of silicic acid to water when the material for aquaculture of the present invention is used, the proportion of calcium silicate hydrate in the solid phase of the reaction product (porous solidified body) between the silicic acid material and the calcareous material before carbonation treatment is preferably 40 mass% or more, more preferably 50 mass% or more, and particularly preferably 60 mass% or more.
When one or more selected from silica, silica sand, and diatomaceous earth is used as a siliceous material, one or more selected from quicklime, hydrated lime, and cement is used as a calcareous material, and the amount of the calcareous material relative to the amount of the siliceous material satisfies a preferable numerical range (0.1 to 12.0 mass%) of the calcium carbonate content in the porous carbonated granules described below, the proportion of calcium silicate hydrate in the solid phase of the porous cured product before carbonation treatment is 50 mass% or more.
The "carbonation treatment" refers to the generation of calcium carbonate by the reaction of unreacted calcareous raw material (usually calcium hydroxide) contained in the porous solidified body with carbon dioxide (usually carbonic acid gas).
The breeding material (granules of a porous solidified body) of the present invention is a porous material.
Here, "porous" means that voids are present in granules (cured bodies) by foaming with a foaming agent during production, as in the case of the lightweight cellular concrete (ALC).
The void ratio of the material for cultivation (granules of a porous solidified body) of the present invention is preferably 50 to 80 vol%, more preferably 55 to 75 vol%, and particularly preferably 60 to 70 vol%, from the viewpoints of increasing the carbonation degree during production, increasing the supply amount of silicic acid into water during use, and ensuring sufficient strength (e.g., compressive strength) of the material for cultivation.
The porosity is a ratio of a total volume of internal voids to a total volume of a region surrounded by the outer surface of the granules constituting the porous solidified body of the material for cultivation according to the present invention.
Since the material for cultivation of the present invention is porous, the amount of silicic acid eluted from the material for cultivation is further increased, and the propagation of diatoms can be further promoted.
In addition, since the material for cultivation of the present invention is porous, air present in the porous portion (internal voids) of the material for cultivation is taken into the substrate, whereby the dissolved oxygen amount of water present in the substrate can be further increased. In addition, the water permeability and air permeability of the substrate can be further improved.
The grain size of the material for cultivation of the present invention is preferably 0.1 to 15mm, more preferably 0.3 to 10mm, further preferably 0.5 to 8mm, and particularly preferably 0.5 to 5 mm. When the particle size is 0.1mm or more, the energy required for granulation (e.g., pulverization and cutting) in the production of the material for cultivation can be further reduced, and the consolidation of the substrate can be further suppressed. When the particle size is 15mm or less, the amount of silicic acid to be supplied to water can be further increased.
The material for cultivation according to the present invention preferably has a particle size distribution in which the proportion of the porous carbonated granules having the above-mentioned preferred particle size (for example, 0.5 to 5mm) is 50 mass% or more (preferably 60 mass% or more, more preferably 70 mass% or more).
In the present specification, "particle size" refers to a size corresponding to a mesh size of a sieve. For example, a particle size of 1.0mm or less means a sieve having a mesh of 1.0 mm.
Next, a method for producing the breeding material of the present invention will be described.
An example of the method for producing the breeding material of the present invention includes a method including the steps of: a slurry preparation step of preparing a slurry using a siliceous material, a calcareous material, a foaming agent, and water as raw materials; a curing step of curing the slurry to foam and cure the slurry to obtain a porous cured body; a hydrothermal reaction step of subjecting the obtained porous cured product to a hydrothermal reaction to obtain a porous cured product after the hydrothermal reaction; and granulating and carbonating, and obtaining the cultivation material by using the porous solidified body after the hydrothermal reaction.
Here, the slurry preparation step, the curing step, and the hydrothermal reaction step are the same as those in the general production method of light-weight cellular concrete (ALC), except that the amount of the calcareous material relative to the siliceous material is set so as to be excessive compared with the amount of the calcareous material in the general production method of light-weight cellular concrete (ALC).
In a general method for producing lightweight cellular concrete (porosity: about 80 vol%), the amount of the siliceous material is set so as to be excessive relative to the amount of the calcareous material. Therefore, the solid phase (about 20 vol%) of the lightweight cellular concrete contains 13 to 16 vol% tobermorite and 4 to 7 vol% unreacted silicic acid.
The slurry preparation step is performed by mixing silica (silica sand, diatomaceous earth, etc., which may be used as other siliceous raw materials in combination), cement, quicklime (hydrated lime, etc., which may be used as other calcareous raw materials in combination), a foaming agent (for example, aluminum powder, a surfactant), and water. As the reaction accelerator which can be arbitrarily blended, dihydrate gypsum can be used.
The amount of each raw material (particularly, the amount of the calcareous raw material) may be appropriately set in consideration of the target ratio of calcium hydroxide (which becomes calcium carbonate after the carbonation treatment in the granulation and carbonation steps) in the porous solidified body after the hydrothermal reaction obtained in the hydrothermal reaction step.
In this step, calcium carbonate can be used in order to adjust (further increase) the content of calcium carbonate in the material for cultivation. Calcium carbonate may be industrially produced calcium carbonate or calcium carbonate-containing substances such as natural limestone.
The curing step is performed, for example, by the following operations: the slurry obtained in the slurry preparation step is poured into a template, and then cured at normal temperature (for example, 15 to 35 ℃) and high humidity (for example, 95 to 99% relative humidity) for 4 to 10 hours, and then further cured at high temperature (for example, 75 to 85 ℃) and high humidity (for example, 95 to 99% relative humidity) for 6 to 12 hours, and finally, the mold is removed to obtain a porous cured body.
The inner dimension of the template is not particularly limited, and is, for example, 5 to 40cm (length) × 5 to 15cm (width) × 5 to 15cm (height).
The hydrothermal reaction step is performed by, for example, autoclave curing (high-temperature high-pressure steam curing) of the porous cured body using an autoclave apparatus.
The autoclave curing temperature is preferably 160-210 ℃, more preferably 170-200 ℃, and particularly preferably 180-190 ℃.
The pressure for autoclave curing is preferably 0.9 to 1.2MPa (9 to 12 atm), more preferably 1.0 to 1.1MPa (10 to 11 atm).
The curing time (time for maintaining the above-mentioned preferable temperature) of the autoclave curing is preferably 3 to 10 hours, more preferably 4 to 9 hours, still more preferably 5 to 8 hours, and particularly preferably 5.5 to 7 hours.
The granulation and carbonation steps are carried out by any of the following methods: (a) granulating the porous solidified body after the hydrothermal reaction to obtain a porous granular body, and then carbonating the porous granular body to obtain a material for cultivation; or (b) carbonating the porous solidified substance after the hydrothermal reaction to obtain a porous carbonated solidified substance, and granulating the porous carbonated solidified substance to obtain a material for cultivation.
Examples of the method of granulation (granulation treatment method) include pulverization, cutting, and the like.
Examples of the method of carbonation (carbonation treatment method) include a method in which the porous granules or the porous solidified body is placed in a carbonic acid gas atmosphere (including a case where the porous granules or the porous solidified body is placed in the atmosphere). In this case, the concentration of the carbonic acid gas is preferably 1% by volume or more, more preferably 3% by volume or more, further preferably 4% by volume or more, and particularly preferably 5% by volume or more, from the viewpoint of further promoting carbonation. In addition, from the viewpoint of preventing an excessive increase in cost, the concentration of the carbonic acid gas is preferably 90% by volume or less, more preferably 70% by volume or less, further preferably 50% by volume or less, further preferably 30% by volume or less, further preferably 20% by volume or less, and particularly preferably 10% by volume or less.
The time of the carbonation treatment (for example, the time of placing the porous granular material or the like in a carbonic acid gas atmosphere) varies depending on the size (particle size or dimension) of the porous granular material or the porous solidified material and the target proportion of calcium carbonate in the culture material, and is preferably 3 hours or more, more preferably 4 hours or more, and particularly preferably 5 hours or more. From the viewpoint of the efficiency of the carbonation treatment, the upper limit value of the time is preferably 15 hours, more preferably 12 hours, and particularly preferably 10 hours.
The carbonation treatment may be performed in an autoclave apparatus for performing the hydrothermal reaction, or may be performed using an apparatus different from the autoclave apparatus for performing the hydrothermal reaction.
As a device different from the autoclave device, a carbonation processing device having a high-concentration carbonic acid gas atmosphere can be cited. The porous granular material or the porous solidified material before the carbonation treatment may be placed in the atmosphere (in the air; in a gas containing 0.04 vol% of carbon dioxide) without using an autoclave device or a carbonation treatment device to perform the carbonation treatment.
Another example of the method for producing a material for aquaculture according to the present invention includes a method including the steps of: a slurry preparation step for preparing a slurry from a siliceous material, a calcareous material, calcium carbonate, a foaming agent, and water; a curing step of curing the slurry to foam and cure the slurry to obtain a porous cured body; a hydrothermal reaction step of subjecting the obtained porous cured product to a hydrothermal reaction to obtain a porous cured product after the hydrothermal reaction; and a granulation step for granulating the porous solidified body after the hydrothermal reaction to obtain a material for cultivation.
The slurry preparation step, the solidification step, and the hydrothermal reaction step are the same as the above-described steps except that calcium carbonate is used in the slurry preparation step and the amount of calcium carbonate is appropriately set in consideration of the content of the target calcium carbonate in the breeding material.
The method of granulation in the granulation step is the same as the method of granulation in the granulation and carbonation steps (granulation treatment method) described above.
The water for aquaculture to use the material for aquaculture of the present invention is not particularly limited, and may be any of fresh water, brackish water, and seawater.
Examples of the aquatic organisms include crustaceans, shellfish, and fish which can be cultured in culture water. Among them, aquatic organisms (for example, crustaceans such as shrimp) which feed on diatoms are preferable.
Since calcium carbonate contained in the material for cultivation of the present invention has poor solubility in water, calcium carbonate remains even when calcium silicate hydrate is dissolved in water. Therefore, the material for cultivation of the present invention can maintain its particle size (size of granules) without disintegration, and as a result, can prevent consolidation of the substrate, improve air permeability and water permeability of the substrate, and suppress the substrate from becoming an anoxic state.
In addition, calcium carbonate remaining in the substrate is taken up by aquatic organisms. By allowing the calcium to be taken in by the aquatic organism, for example, the effect of improving the strength of the shell of a juvenile shrimp or the bone of a juvenile fish can be obtained.
Examples
The present invention will be described in more detail with reference to the following examples, but the present invention is not limited to these examples.
[ materials used ]
(1) Quick lime
Proportion of ingredients having a particle size of 2mm or less: 90% by mass or more
Content of CaO: 95% by mass
(2) Silica powder
Pulverizing silica with mill to obtain component
The ratio of components having a particle size in the range of 53 to 150 [ mu ] m: 90% by mass or more
SiO2The content ratio of (A): 98% by mass
(3) Diatomite
SiO2The content ratio of (A): 82% by mass
Content of CaO: 1% by mass
(4) Ordinary Portland cement (manufactured by Pacific Cement Co., Ltd.)
Content of CaO: 63.5% by mass
SiO2The content ratio of (A): 21.5% by mass
(5) Aluminum powder (high purity chemical company, manufactured)
(6) Calcium carbonate powder (manufactured by Kanto chemical Co., Ltd.)
[ production of powdery Material a and evaluation of calcium silicate-containing Material a Using powdery Material a ]
Silica powder, ordinary portland cement, and quicklime were mixed in a mixing ratio such that the content of silica powder, ordinary portland cement, and quicklime in 100 mass% of a powder raw material obtained by mixing silica powder, ordinary portland cement, and quicklime was 65 mass%, 25 mass%, and 10 mass%, respectively, to obtain a powder raw material a.
A calcium silicate-containing material a was prepared using the obtained powder raw material a, and powder X-ray diffraction was performed on the material a.
Specifically, 40 parts by mass of water was added to 100 parts by mass of the "powder raw material a" and kneaded, and then 0.01 part by mass of aluminum powder was further added and kneaded to obtain a slurry.
The resulting slurry was poured into a form having an inner size of 10X 10cm, and cured at 30 ℃ under an atmosphere of 98% relative humidity for 6 hours. Subsequently, the cured product was cured at 80 ℃ and 98% relative humidity for 8 hours, and the porous cured body in the template was released.
The released porous cured product was subjected to hydrothermal curing (hydrothermal reaction) in an autoclave at 180 ℃ and 1.0MPa (10 atm) for 6 hours. Immediately after completion of the hydrothermal curing, the porous cured product was taken out of the autoclave and dried at 105 ℃ for 24 hours.
After drying, the porous cured product was pulverized to obtain a calcium silicate-containing material a. The calcium silicate-containing material a was identified by powder X-ray diffraction, and the formation of tobermorite was confirmed. The formation of calcium hydroxide and calcium carbonate was not confirmed.
[ production of powdery raw material b and evaluation of calcium silicate-containing Material b Using powdery raw material b ]
Diatomaceous earth, silica powder, ordinary portland cement, and quicklime were mixed in a mixing ratio such that the contents of diatomaceous earth, silica powder, ordinary portland cement, and quicklime were 35 mass%, 25 mass%, and 15 mass%, respectively, in 100 mass% of the powder raw material obtained by mixing these materials, to obtain a powder raw material b. A calcium silicate-containing material b was obtained in the same manner as in the above-described method for producing a calcium silicate-containing material a except that the obtained powdery raw material b was used instead of the powdery raw material a.
The calcium silicate-containing material b was identified by powder X-ray diffraction, and the formation of tobermorite was confirmed. The formation of calcium hydroxide and calcium carbonate was not confirmed.
[ examples 1 to 6]
The powdery raw material a and quicklime were mixed so that the content of each raw material (quicklime, silica powder, cement) in 100 mass% of a raw material mixture obtained by mixing the powdery raw material a and quicklime was the content shown in table 1, respectively, to obtain a raw material mixture.
Specifically, the powdery raw material a and the quicklime were mixed so that the amounts of the quicklime in 100 mass% of the total amount of the powdery raw material a (including the quicklime) and the quicklime were 0 mass% (comparative example 1), 0.5 mass% (example 1), 1.0 mass% (example 2), 2.0 mass% (example 3), 4.0 mass% (example 4), 6.0 mass% (example 5), and 8.0 mass% (example 6). The content of quicklime in the obtained raw material mixture (shown as "raw material for breeding material" in table 1) includes quicklime derived from the powdery raw material a.
To 100 parts by mass of the obtained raw material mixture, 40 parts by mass of water was added and kneaded, and then 0.01 part by mass of aluminum powder was further added and kneaded to obtain a slurry.
The resulting slurry was poured into a form having an inner size of 10X 10cm, and cured at 30 ℃ under an atmosphere of 98% relative humidity for 6 hours. Subsequently, the cured product was cured at 80 ℃ and 98% relative humidity for 8 hours, and the porous cured body in the template was released.
The released porous cured product was subjected to hydrothermal curing (hydrothermal reaction) in an autoclave at 180 ℃ and 1.0MPa (10 atm) for 6 hours. Immediately after completion of the hydrothermal curing, the cured product was taken out from the autoclave and dried at 105 ℃ for 24 hours.
The obtained porous cured body contains calcium silicate (tobermorite) and calcium hydroxide.
After drying, the porous cured body was cut so that each cut piece became a cube of about 2 × 2 × 2 cm. The obtained cubic porous solidified body was allowed to stand still for 6 hours in a closed vessel having a carbonic acid gas concentration of 5 vol%, and thereby subjected to carbonation treatment, thereby obtaining a cubic porous carbonated solidified body containing calcium silicate (tobermorite) and calcium carbonate.
[ measurement of calcium carbonate content in porous carbonated solidified body ]
The above cubic porous carbonated solidified body was pulverized and then sieved with a sieve having a mesh of 1 mm. The powder of the cultivation material having a particle size of 1mm or less passing through the sieve is heated at 650 ℃ and then further heated at 900 ℃. The calcium carbonate content in the cultivation material is calculated from the decrease in powder mass (due to the desorption of carbon dioxide) when the material is heated at 650 to 900 ℃.
The results are shown in Table 1.
[ measurement of elution amount of Water-soluble silicic acid from porous carbonated solidified body ]
The above cubic porous carbonated solidified body was pulverized and then sieved with a sieve having a mesh of 1 mm. 1g of a powder of a porous carbonated solidified body having a particle size of 1mm or less which has passed through a sieve was added to 1 liter of distilled water, and the mixture was shaken at 70rpm and then shaken at 24-hour intervalsThe distilled water was replaced at that time. The concentration of Si dissolved in the distilled water after replacement was measured using an ICP emission spectrometer, and water-soluble silicic acid (SiO) was calculated from the powder addition time of the breeding material until 7 days elapsed2) The amount eluted per day (mg/liter/day).
The results are shown in Table 2.
[ evaluation of particle size Retention (relative evaluation to comparative example) ]
After the cubic porous carbonated solidified body is crushed, a sieve with 5mm meshes and a sieve with 0.5mm meshes are used to obtain the breeding material with the granularity of 0.5-5 mm. 50g of the cultivation material was placed in a water-permeable bag made of polyethylene (bag through which water would not pass but cultivation material would pass), and was set on the bottom of the shrimp cultivation pond.
After 30 days from the time of installation, the bag was collected from the culture pond, and soil, diatoms, or the like attached to the bag was removed with water, followed by drying at 105 ℃. After drying, the breeding materials are taken out from the bag and screened by a screen with 0.5mm mesh.
Then, the mass of the breeding materials passing through the sieve and the mass of the breeding materials remaining on the sieve are measured. From the obtained mass, the ratio of the breeding material remaining on the sieve was calculated using the following formula (1).
The ratio (%) of the cultivation material remaining on the sieve (mass of the cultivation material remaining on the sieve) × 100/(mass of the cultivation material remaining on the sieve + mass of the cultivation material passing through the sieve) · (1)
Then, the ratio of the breeding material remaining on the sieve after 30 days in comparative example 1 (described later) was calculated in the same manner as described above. The ratio of the cultivation material remaining on the sieve in each example (examples 1 to 6) is numerically expressed by using the following formula (2) based on the ratio (100) of the cultivation material remaining on the sieve in comparative example 1.
(relative evaluation value of each example with respect to comparative example 1) × 100 (ratio of culture material remaining on the sieve in each example) × 100/(ratio of culture material remaining on the sieve in comparative example 1) · (2)
The larger the relative evaluation value of example to comparative example 1, the more excellent the particle size retention.
The results are shown in Table 2.
[ evaluation of particle size Retention (Absolute evaluation) ]
After the cubic porous carbonated solidified body is crushed, a cultivation material with the granularity of 0.5-5 mm is obtained by using a sieve with 5mm meshes and a sieve with 0.5mm meshes. After the image of 50g of the cultivation material was taken, the cultivation material was put into a water-permeable bag made of polyethylene (bag through which water would not pass but cultivation material would pass), and set on the bottom of the cultivation pond for shrimps.
After 30 days from the time of installation, the bag was collected from the culture pond, and soil, diatoms, or the like attached to the bag was removed with water, followed by drying at 105 ℃. After drying, the breeding materials are taken out from the bag, and images of the breeding materials are shot.
The image of the material for cultivation before being set in the pond for cultivation and the image of the material for cultivation after being recovered from the pond for cultivation are subjected to image analysis using "area measurement software" provided by "Vector" (online software distribution site), and the ratio (%) of the planar area of the material for cultivation before being set and the planar area of the material for cultivation after being recovered (after 30 days) by the image analysis is calculated using the following formula (3).
The ratio of the planar area (%) (planar area of cultivation material after 30 days) x 100/(planar area of cultivation material before installation) · (3)
The larger the planar area ratio (%) is, the more excellent the particle size retention is.
Comparative example 1
A porous cured product was obtained in the same manner as in example 1 except that the porous cured product after the hydrothermal reaction was cut so that each block became a cube of about 2X 2cm, and then dried at 105 ℃ for 3 hours without carbonation treatment.
The calcium carbonate content of the obtained porous cured product was measured in the same manner as in example 1. Furthermore, a breeding material was obtained using the porous solidified body in the same manner as in example 1, and the particle size retention was evaluated.
[ examples 7 to 13]
A porous carbonated solidified body was obtained in the same manner as in example 1, except that the powdery raw material b was used instead of the powdery raw material a, and the powdery raw material b and quicklime were mixed so that the content of each raw material (quicklime, silica powder, diatomaceous earth, cement) in 100 mass% of the raw material mixture obtained by mixing the powdery raw material b and quicklime was the content shown in table 1.
Specifically, the powder raw material b (containing quicklime) and quicklime were mixed so that the amounts of quicklime were 0 mass% (comparative example 2), 0.5 mass% (example 7), 1.0 mass% (example 8), 3.0 mass% (example 9), 5.0 mass% (example 10), 7.0 mass% (example 11), 9.0 mass% (example 12), and 10.0 mass% (example 13) in the total 100 mass% of the powder raw material b and quicklime. The content of the quick lime in the obtained raw material mixture includes quick lime derived from the powder raw material b.
The calcium carbonate content of the obtained porous carbonated solidified body was measured in the same manner as in example 1. In addition, a material for cultivation was obtained using the porous carbonated solidified body in the same manner as in example 1, and the particle size retention was evaluated.
Comparative example 2
A porous cured body was obtained in the same manner as in comparative example 1, except that the powder material b was used instead of the powder material a.
The calcium carbonate content of the obtained porous cured product was measured in the same manner as in example 1. In addition, breeding materials were obtained using the porous solidified bodies in the same manner as in example 1, and the particle size retention was evaluated.
[ examples 14 to 16]
The powder raw material a, quicklime, and calcium carbonate powder were mixed so that the content of each raw material (quicklime, silica powder, cement, and calcium carbonate powder) was the content shown in table 1, respectively, in 100 mass% of the mixed raw material mixture, to obtain a raw material mixture.
Specifically, the powdery raw material a, the quicklime, and the calcium carbonate powder were mixed so that the amounts of the calcium carbonate powder were 1.0 mass% (example 14), 2.0 mass% (example 15), and 4.0 mass% (example 16), respectively, in 100 mass% of a raw material mixture in which the powdery raw material a (containing the quicklime, the silica powder, and the ordinary portland cement), the quicklime, and the calcium carbonate powder were mixed. The amount of quicklime is the same as that of the calcium carbonate powder. The quicklime is added so that the amount of the calcareous material is larger than that of the siliceous material in a general production method of lightweight cellular concrete (ALC). The content of the quicklime in the obtained raw material mixture includes quicklime derived from the powder raw material a.
Using the obtained raw material mixture, a porous cured body was obtained in the same manner as in example 1. The porous cured body contains calcium silicate (tobermorite) and calcium hydroxide.
Using this porous solidified body, a porous carbonated granular material (material for cultivation) in a cubic shape containing calcium silicate (tobermorite) and calcium carbonate was obtained by carbonation treatment in the same manner as in example 1.
The obtained cultivation material was measured for the calcium carbonate content in the same manner as in example 1.
[ examples 17 to 19]
The powder raw material a and the calcium carbonate powder were mixed so that the content of each raw material (quicklime, silica powder, cement, calcium carbonate powder) in 100 mass% of the raw material mixture obtained by mixing was the content shown in table 1, respectively, to obtain a raw material mixture.
Specifically, the powder raw material a and the calcium carbonate powder were mixed so that the amounts of the calcium carbonate powder were 2.0 mass% (example 17), 5.0 mass% (example 18), and 10.0 mass% (example 19), respectively, in 100 mass% of a raw material mixture in which the powder raw material a (containing quicklime, silica powder, and ordinary portland cement) and the calcium carbonate powder were mixed. The content of the quick lime in the obtained raw material mixture includes quick lime derived from the powder raw material a.
A granular material (material for cultivation) of the porous solidified body was obtained in the same manner as in example 1, except that the obtained porous solidified body was cut and then subjected to no carbonation treatment. The porous cured body contains calcium silicate (tobermorite) and calcium hydroxide.
The obtained cultivation material was measured for the calcium carbonate content in the same manner as in example 1.
The results are shown in Table 2.
[ Table 1]
Figure BDA0003404055030000141
Figure BDA0003404055030000151
[ Table 2]
Figure BDA0003404055030000152
Figure BDA0003404055030000161
As is clear from Table 2, according to the breeding material of the present invention (examples 1 to 19), the amount of water-soluble silicic acid eluted per 1 day was maintained at 0.8 mg/liter or more even after 7 days, after 1g of the breeding material was added to 1 liter of distilled water.
It is understood from the comparison of examples 1 to 6 with comparative example 1, the comparison of examples 7 to 13 with comparative example 2, the comparison of examples 14 to 16, and the comparison of examples 17 to 19 that the elution amount of the water-soluble silicic acid per 1 day tends to increase as the content of calcium carbonate is smaller (conversely, as the content of calcium silicate is larger).
Further, as for the evaluation of the particle size retention (relative evaluation and absolute evaluation), it is understood from the comparison between examples 1 to 19 and comparative examples 1 to 2 that the material for cultivation of the present invention (examples 1 to 19) is superior in particle size retention to the material for cultivation (comparative examples 1 to 2) having a calcium carbonate content of 0 mass%.
In particular, the particle size retention properties of examples 3 to 5 (calcium carbonate content: 2.4 to 8.0 mass%), examples 9 to 11 (calcium carbonate content: 2.9 to 7.8 mass%), examples 14 to 16 (calcium carbonate content: 2.1 to 9.5 mass%), and examples 18 to 19 (calcium carbonate content: 4.3 to 9.1 mass%) were particularly excellent.

Claims (6)

1. A material for cultivation, characterized by comprising a porous solidified material of granules containing calcium silicate hydrate which is a reaction product of a siliceous material and a calcareous material and an unreacted calcareous material, and having a calcium carbonate content of 0.1 to 12.0% by mass.
2. The material for cultivation according to claim 1, wherein the material for cultivation comprises granules having a particle size of 0.5mm to 5mm in a proportion of 50% by mass or more.
3. The material for cultivation according to claim 1 or 2, wherein the porous solidified material is a porous carbonated material obtained by carbonating a reaction product of a silicic acid material and a calcareous material.
4. A method for producing the material for aquaculture according to claim 1 or 2, comprising the steps of:
a slurry preparation step of preparing a slurry using the siliceous material, the calcareous material, calcium carbonate, a foaming agent, and water as raw materials;
a curing step of curing the slurry to foam and cure the slurry to obtain a porous cured body;
a hydrothermal reaction step of subjecting the porous cured product to a hydrothermal reaction to obtain a porous cured product after the hydrothermal reaction; and
a granulation step of granulating the porous solidified body after the hydrothermal reaction to obtain the cultivation material.
5. A method for manufacturing the material for cultivation according to claim 3, wherein the material for cultivation is a material for cultivation,
the method comprises the following steps:
a slurry preparation step of preparing a slurry using the siliceous material, the calcareous material, a foaming agent, and water as raw materials;
a curing step of curing the slurry to foam and cure the slurry to obtain a porous cured body;
a hydrothermal reaction step of subjecting the porous cured product to a hydrothermal reaction to obtain a porous cured product after the hydrothermal reaction; and
granulating and carbonating, wherein the cultivation material is obtained by using the porous solidified body after the hydrothermal reaction,
and the granulating and carbonating step is any one of the following methods: (a) a method of obtaining the above-mentioned cultivation material by granulating the above-mentioned porous solidified body to obtain a porous granular material and then carbonating the porous granular material; or (b) carbonating the porous solidified body to obtain a porous carbonated solidified body, and granulating the porous carbonated solidified body to obtain the material for cultivation.
6. The method for producing a material for aquaculture according to claim 4 or 5, wherein the siliceous material comprises one or more selected from silica, silica sand and diatomaceous earth, the calcareous material comprises one or more selected from quicklime, slaked lime and cement, and the foaming agent comprises aluminum powder.
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