JP7315406B2 - bottom sand - Google Patents

Description

The present invention relates to bottom sand.

Various fertilizers have been proposed for promoting the growth of aquatic plants in aquariums for aquatic organisms (for example, ornamental fish and aquatic plants).
For example, Patent Literature 1 describes a fertilizer for aquatic plants characterized by holding a fertilizer in a base material made of a water-soluble material, and a polyvinyl alcohol resin sheet as the base material, and holding the fertilizer in the sheet. According to the aquatic plant fertilizer, by adjusting the solubility, the durability of the fertilizer can be enhanced.
On the other hand, Patent Document 2 describes a wet vegetation substrate for a vegetation base made of porous concrete blocks, which is characterized by comprising 1 to 5 parts by weight of a water-retentive material, 1 to 10 parts by weight of humic acid or a humic acid compound, 50 to 70 parts by weight of water, and the balance being soil, as a wet vegetation base material that can promote the growth of plants by using it for slopes, riverbeds, road surfaces, bank protection, and the like.

JP-A-9-286686 JP-A-9-65759

The bottom sand (gravel, soil, burnt soil, sand, etc.) used in aquariums for aquatic organisms is required to have the effect of water quality control (for example, the absence of turbidity and the pH being within a specific range) and the effect of growing aquatic plants (good growth).
An object of the present invention is to provide a bottom sand that can continuously supply ammonium nitrogen and ionized minerals (minerals in an ionic state) into water to promote the growth of aquatic plants, does not cause turbidity in the water in an aquarium for aquatic organisms, and can stably maintain the pH within a numerical range suitable for the growth of aquatic plants over a long period of time.

As a result of intensive studies to solve the above problems, the present inventors found that the above objects can be achieved by using bottom sand made of granules composed of a composition containing soil, ammonium humate, and mineral components, and completed the present invention.
That is, the present invention provides the following [1] to [8].
[1] A bottom sand characterized by comprising granules made of a composition containing soil, ammonium humate, and mineral components as constituent materials.
[2] The bottom sand according to [1], wherein the composition contains 0.001 to 20% by mass of the ammonium humate.
[3] The bottom sand according to [1] or [2], wherein the mineral component contains one or more selected from the group consisting of calcium, magnesium, potassium, and iron, and the composition contains the mineral component in a proportion of 0.01 to 15% by mass.
[4] The bottom sand according to any one of [1] to [3], wherein the granules have a particle size of 1 to 5 mm.
[5] The bottom sand according to any one of [1] to [4] above, wherein the granules have a crushing strength of 2.0 N or more as measured according to "JIS Z 8841:1993" (granules - strength test method).

[6] A method for producing the bottom sand according to any one of the above [1] to [5], comprising a composition preparation step of mixing the constituent materials to prepare the composition, and a granulation step of granulating the composition to obtain the granules.
[7] The method for producing bottom sand according to [6] above, including a heat treatment step of heat-treating the granules obtained in the granulation step.
[8] A method for promoting the growth of aquatic plants using the bottom sand according to any one of the above [1] to [5], comprising a bottom sand supplying step of supplying the bottom sand to the water bottom.

According to the bottom sand of the present invention, ammonium nitrogen and ionized minerals (minerals in the state of ions) can be continuously eluted into water and the elution amount can be increased, so that the growth of aquatic plants can be promoted, and furthermore, the water in the water tank for aquatic organisms can be stably maintained within a numerical range suitable for the growth of aquatic plants without causing turbidity for a long period of time.

The bottom sand of the present invention comprises granules of a composition containing soil, ammonium humus, and mineral components as constituent materials.
The soil is not particularly limited, and examples thereof include black soil, volcanic ash soil, silica sand, red soil, Kanuma soil, lawn soil, and silicate clay. Among them, black soil is preferable from the viewpoint of easy availability and keeping the pH of the water in the tank using the bottom sand within the weakly acidic to neutral range most suitable for the growth of aquatic plants.
In addition, the soil may be subjected to particle size adjustment or the like as necessary.

The proportion of soil in the composition is preferably 60 to 99.9% by mass, more preferably 65 to 99.5% by mass, still more preferably 70 to 99.0% by mass, still more preferably 75 to 96% by mass, still more preferably 80 to 95% by mass, particularly preferably 85 to 94% by mass. If the ratio is 60% by mass or more, the bottom sand is less likely to collapse. When the ratio is 99.9% by mass or less, the ratio of ammonium humate and mineral components in the composition increases, and the amount of ammonium nitrogen and ionized minerals eluted into water can be increased.

The proportion of ammonium humate in the composition is preferably 0.001 to 20% by mass, more preferably 0.01 to 18% by mass, still more preferably 0.05 to 16% by mass, still more preferably 0.1 to 15% by mass, still more preferably 0.2 to 14% by mass, still more preferably 0.3 to 13% by mass, still more preferably 0.5 to 12% by mass, still more preferably 1 to 11% by mass, still more preferably 2 to 10% by mass, and even more preferably 2 to 10% by mass. is 3 to 9% by weight, particularly preferably 5 to 8% by weight. When the ratio is 0.001% by mass or more, the amount of ammonium nitrogen eluted into water can be increased. Moreover, the crushing strength of the grains constituting the bottom sand can be increased. Furthermore, the pH of the water in the tank using the bottom sand can be kept within the weakly acidic to neutral range. If the ratio is 20% by mass or less, the granules constituting the bottom sand become more difficult to collapse.

In this specification, "ammonium humate" includes ammonium humate as a humic acid salt (e.g., commercially available ammonium humate), a mixture of humic acid and an ammonium salt (e.g., a mixture of humic acid and ammonium chloride), and a precursor of ammonium humate (a mixture of humic acid and urea; for example, when used as bottom sand, urea becomes ammonium ions by the action of microorganisms.).

As used herein, the term "mineral component" includes both the state of the mineral element itself (e.g., iron) and the state of a compound containing minerals (hereinafter also referred to as "mineral-containing compound").
Minerals include calcium, magnesium, potassium, and iron.
In the present invention, calcium, magnesium, and potassium are not used as simple substances (elements themselves), but are used as compounds.
The composition may contain one mineral, or may contain two or more minerals.
Among them, at least one selected from the group consisting of calcium, magnesium, and potassium is more preferable from the viewpoint of further promoting the growth of aquatic plants.

Examples of mineral-containing compounds include carbonates, oxides, hydroxides, sulfates, and the like, including the minerals mentioned above. These may be natural products or commercially available reagents.
More specific examples of mineral-containing compounds include calcium compounds such as calcium carbonate, calcium oxide, calcium hydroxide, and calcium sulfate; magnesium compounds such as magnesium carbonate, magnesium oxide, magnesium hydroxide, and magnesium sulfate; potassium compounds such as potassium carbonate, potassium oxide, and potassium sulfate; and iron compounds such as iron oxide, iron hydroxide, and iron sulfate.
Examples of natural products containing mineral-containing compounds include biological materials such as shellfish fossils containing calcium carbonate and minerals such as dolomite containing dolomite (CaMg(CO ₃ ) ₂ ).
When natural products such as shellfish fossils and dolomite are used, only mineral-containing compounds contained in the natural products correspond to the "mineral component" of the present invention.
In addition, the composition may contain one kind of mineral-containing compound as a constituent material, or may contain two or more kinds thereof.

The proportion of the mineral component in the composition is preferably 0.001 to 20% by mass, more preferably 0.01 to 18% by mass, still more preferably 0.05 to 16% by mass, still more preferably 0.1 to 15% by mass, still more preferably 0.2 to 14% by mass, still more preferably 0.3 to 13% by mass, still more preferably 0.5 to 12% by mass, still more preferably 1 to 11% by mass, still more preferably 2 to 10% by mass, still more preferably 3 to 3% by mass. to 9% by weight, particularly preferably 5 to 9% by weight. If the ratio is 0.001% by mass or more, the amount of ionized minerals eluted into water can be increased. If the ratio is 20% by mass or less, the granules constituting the bottom sand become more difficult to collapse.

The composition may contain a granulating agent as a constituent material depending on the size of the granules of the composition.
Polyvinyl alcohol etc. are mentioned as a granulating agent.
When a granulating agent is used, the proportion of the granulating agent in the composition varies depending on the type of granulating agent, but is preferably 0.1 to 10% by mass. When the ratio is 0.1% by mass or more, the crushing strength of the grains constituting the bottom sand can be further increased. If the ratio is 10% by mass or less, the cost of materials can be reduced.
The composition may contain other ingredients (eg, fulvic acid, bitumen, etc.) generated during the manufacturing process of ammonium humate.

The particle size of the granules constituting the bottom sand is preferably 1 to 5 mm, more preferably 1 to 4.5 mm, particularly preferably 1 to 4 mm. If the particle size is 1 mm or more, the amount of ammonium humate and mineral components contained in the granules can be increased, and ammonia nitrogen and ionized minerals can be eluted over a long period of time. When the particle size is 5 mm or less, it is possible to prevent the ammonium nitrogen and ionized minerals in the central part of the particles from becoming difficult to elute.
If the particle size is too small (for example, the particle size is about 0.1 to 0.2 mm), the water may be colored yellow or the like.
In addition, the particle size of a particle refers to the size of its maximum dimension (for example, when the cross section is elliptical, the major axis).

The crushing strength of the granules constituting the bottom sand of the present invention measured according to "JIS Z 8841: 1993" (granules-strength test method) is preferably 2.0 N or more, more preferably 2.2 N or more, and particularly preferably 2.4 N or more. When the crushing strength is 2.0 N or more, the granules constituting the bottom sand are less likely to collapse during storage and transportation of the bottom sand. Further, in water, the granules constituting the bottom sand are less likely to disintegrate, and the turbidity of the water due to the disintegration of the granules is less likely to occur.

An example of the method for producing the bottom sand of the present invention includes a composition preparation step of mixing the constituent materials of the composition (specifically, soil, ammonium humate, mineral components, and optionally a granulating agent) to prepare a composition, and a granulation step of granulating the obtained composition to obtain granules.
Examples of granulation methods include tumbling granulation, stirring granulation, compression granulation, and extrusion granulation. Examples of devices used for granulation include pan pelletizers, mixers, disc pelleters, and the like.

From the viewpoint of increasing the strength of the granules, a heat treatment step of heat-treating the obtained granules may be performed after the granulation step.
The temperature at which the heat treatment is performed may be any temperature that can increase the strength of the granules and does not decompose the ammonium humate contained in the granules. The time required for the heat treatment varies depending on the temperature, but is usually 2 to 10 minutes.
Examples of equipment used for heat treatment include dryers, electric furnaces, rotary kilns, and the like.
Moreover, when the surface of the granules is in a wet state, cracks or bursts may occur due to sudden heat treatment, so drying treatment such as air drying may be performed before the heat treatment step.

By supplying the bottom sand of the present invention to the bottom of the water (for example, the bottom portion of a water tank filled with water), ammonia nitrogen and ionized minerals (minerals in an ion state) are eluted from the bottom sand, and the growth of aquatic plants living on the bottom of the water can be promoted.
Moreover, according to the bottom sand of the present invention, the pH of the water in the aquarium can be kept constant over a long period of time. Specifically, the pH in the water tank can be maintained preferably between 4.0 and 8.6, more preferably between 4.5 and 8.3, still more preferably between 5.0 and 8.0, still more preferably between 5.5 and 7.5, and particularly preferably between 5.5 and 7.3. By setting the pH within the above numerical range, the environment in the aquarium can be made suitable for the growth of aquatic plants that prefer weak acidity to neutrality (especially weak acidity).

EXAMPLES The present invention will be specifically described below by way of examples, but the present invention is not limited to these examples.
[Materials used]
（１）土壌；黒土（２）腐植酸アンモニウム含有肥料；テルナイト社製、商品名「テルアン」、腐植酸アンモニウム含有肥料の乾燥質量１００質量％中、腐植酸アンモニウム（ニトロフミン酸アンモニウム）の割合が６３質量％であり、フルボ酸の割合が１７質量％であり、ビチューメンの割合が６質量％であり、その他の成分の割合が１４質量％であり、また、腐植酸アンモニウム含有肥料１００質量％中の水分の割合が９質量％であるもの（３）ミネラル成分１：炭酸カルシウム（ＣａＣＯ _３ ）、関東化学社製、試薬、特級（４）ミネラル成分２：酸化マグネシウム（ＭｇＯ）；関東化学社製、試薬、特級（５）ミネラル成分３：炭酸カリウム（Ｋ _２ ＣＯ _３ ）；関東化学社製、試薬、特級

[Examples 1 to 5, Comparative Examples 1 to 11]
The above materials were placed in a synthetic resin flexible bag at the mixing ratio shown in Table 1, and each material was mixed in the bag by hand. After mixing, the resulting mixture was granulated using a pan pelletizer while spraying water using a sprayer, and then the resulting granules (granules) were fired in an electric furnace at 270 ° C. for 5 minutes.
When the surface of the granules (granules) was wet, they were dried at 45°C for 24 hours before firing at 270°C.
As evaluation of properties of the obtained bottom sand, pH and crushing strength were obtained by the following methods.
(1) pH
The obtained bottom sand and water were mixed in a container so that the mass ratio of bottom sand:water was 1:5. The pH of the resulting mixture was measured using a pH meter.
(2) Crushing strength From the obtained bottom sand, 30 granules arbitrarily selected were measured for their crushing strength using a product name: "Force Gauge" manufactured by Aikoh Engineering Co., Ltd. according to "JIS Z 8841: 1993" (granules - strength test method), and the average value was calculated.
Table 1 shows the results.

Next, 5 g of the obtained bottom sand and 500 mL of distilled water were placed in a plastic container and continuously shaken at a speed of 70 rpm.
1 hour, 3 hours, 1 day, 2 days, 3 days, 4 days, 8 days, and 14 days after the start of shaking, the pH of the water in the container, the concentration of ammonia nitrogen (mg/liter), and the concentration of calcium (mg/liter) were measured.
Further, for Comparative Examples 1, 3 to 4, magnesium concentration (mg/liter) and potassium concentration (mg/liter) were measured.
The concentration of ammonium nitrogen was measured using a measuring device manufactured by Kyoritsu Scientific Research Institute Co., Ltd. under the trade name of "PACKTEST". The limit of detection is 0.2 mg/liter.
Calcium concentration, magnesium concentration, and potassium concentration were measured by ICP emission spectrometry.
In addition, after measuring ammonia nitrogen and the like in the water in the container, all the water in the plastic container was replaced.
The results are shown in Tables 2-4 and 6-9.
In Tables 3 and 7, "<0.20" means below the detection limit.
Further, 11 days after the start of shaking, the shaking was terminated, and the presence or absence of collapse of granules constituting the bottom sand and the presence or absence of turbidity in the water were visually confirmed. As a result, in Examples 1 to 5 and Comparative Examples 1 to 11, no disintegration of the granules and turbidity of the water were observed.

[Examples 6 to 7, Comparative Example 12]
Bottom sand having a particle size of 1 to 4 mm was obtained in the same manner as in Example 1, except that the above materials were mixed in the proportions shown in Table 5.
In the same manner as in Example 1, pH and crushing strength were obtained as evaluations of the properties of the obtained bottom sand. Table 5 shows the results.
Next, the obtained bottom sand was shaken in the same manner as in Example 1, and the pH of the water in the container, the concentration of ammonia nitrogen (mg/liter), and the concentration of magnesium (mg/liter) were measured 1 hour, 3 hours, 1 day, 2 days, 3 days, 4 days, 8 days, and 14 days after the start of shaking.
The results are shown in Tables 6-8.
Further, 11 days after the start of shaking, the shaking was terminated, and the presence or absence of collapse of granules constituting the bottom sand and the presence or absence of turbidity in the water were visually confirmed. As a result, in Examples 6 to 7 and Comparative Example 12, no disintegration of the granules and turbidity of the water were observed.

[Examples 8 to 9, Comparative Example 13]
Bottom sand having a particle size of 1 to 4 mm was obtained in the same manner as in Example 1, except that the above materials were mixed in the proportions shown in Table 5.
In the same manner as in Example 1, pH and crushing strength were obtained as evaluations of the properties of the obtained bottom sand. Table 5 shows the results.
Next, the obtained bottom sand was shaken in the same manner as in Example 1, and the pH of the water in the container, the concentration of ammonia nitrogen (mg/liter), and the concentration of potassium (mg/liter) were measured 1 hour, 3 hours, 1 day, 2 days, 3 days, 4 days, 8 days, and 14 days after the start of shaking.
The results are shown in Tables 6-7 and 9.
Further, 11 days after the start of shaking, the shaking was terminated, and the presence or absence of collapse of granules constituting the bottom sand and the presence or absence of turbidity in the water were visually confirmed. As a result, in Examples 8 to 9 and Comparative Example 13, no disintegration of the granules and turbidity of the water were confirmed.

From Tables 2 and 6, it can be seen that the pH of the water in Examples 1 to 9 using the bottom sand of the present invention (after 1 hour to 14 days) is 6.4 to 8.4, indicating that the pH is stable.
From Table 3, when Examples 1 and 2 (containing 0.063 to 0.32% by mass of ammonium corrosive acid and 0.1 to 0.5% by mass of calcium carbonate (mineral component)) are compared with Comparative Examples 2 and 3 (containing 0.063 to 0.32% by mass of ammonium corrosive acid and not containing calcium carbonate), it can be seen that the concentration of ammonia nitrogen in Examples 1 and 2 is approximately the same as the concentration of ammonia nitrogen in Comparative Examples 2 and 3.
Further, when Examples 3 and 4 (containing 0.63 to 2.8% by mass of ammonium corrosive acid and 1.0 to 4.5% by mass of calcium carbonate) are compared with Comparative Examples 4 and 5 (containing 0.63 to 3.0% by mass of ammonium corrosive acid and not containing calcium carbonate), it can be seen that the concentration of ammonia nitrogen in Examples 3 and 4 is higher than the concentration of ammonia nitrogen in Comparative Examples 4 and 5.
Further, when comparing Example 5 (containing 5.2% by mass of ammonium corrosive acid and 8.3% by mass of calcium carbonate) and Comparative Example 6 (containing 5.7% by mass of ammonium corrosive acid and not containing calcium carbonate), it can be seen that although the concentration of ammonia nitrogen in Example 5 is higher than that in Comparative Example 6 after 2 days, and the concentration of ammonia nitrogen after 3 to 8 days is lower than that in Comparative Example 6, elution continues.

From Table 4, when Examples 1 and 2 (containing 0.063 to 0.32% by mass of ammonium etchant and 0.1 to 0.5% by mass of calcium carbonate) are compared with Comparative Examples 7 and 8 (containing 0.1 to 0.5% by mass of calcium carbonate and not containing ammonium etchant), it can be seen that the calcium concentrations of Examples 1 and 2 are approximately the same as those of Comparative Examples 7 and 8.
Further, when Examples 3 to 5 (containing 0.63 to 5.2% by mass of ammonium etchant and 1.0 to 8.3% by mass of calcium carbonate) are compared with Comparative Examples 9 to 11 (containing 1.0 to 9.1% by mass of calcium carbonate and not containing ammonium etchant), it can be seen that the concentration of calcium after 3 hours in Examples 3 to 5 tends to be lower than the concentration of calcium in Comparative Examples 9 to 11.
Further, in Examples 1 to 5 and Comparative Examples 7 to 11, the higher the ratio of calcium carbonate, the higher the concentration of eluted calcium. From this, it can be seen that in Examples, a large amount of calcium is not eluted in a short period of time, and calcium can be continuously eluted over a long period of time.

From Table 7, when Examples 6 to 7 (containing 0.32 to 0.63% by mass of ammonium etchate and 0.5 to 1.0% by mass of magnesium oxide (mineral component)) are compared with Comparative Example 12 (containing 0.5% by mass of magnesium oxide and not containing ammonium etchant), it can be seen that the concentration of ammonia nitrogen in Examples 6 to 7 is higher than the concentration of ammonia nitrogen in Comparative Example 12.
Further, when Examples 6-7 (containing 0.32-0.63% by mass of ammonium corrosive acid and 0.5-1.0% by mass of magnesium oxide) are compared with Comparative Examples 3-4 (containing 0.32-0.63% by mass of ammonium corrosive acid and not containing calcium carbonate), it can be seen that ammonia nitrogen was not detected after 4 days in Comparative Examples 3-4, whereas ammonia nitrogen was detected even after 4 days in Examples 6-7.
That is, it can be seen that Examples 6-7 can continuously elute ammonium nitrogen over a longer period of time than Comparative Examples 3-4.

From Table 8, when Examples 6 to 7 (containing 0.32 to 0.63% by mass of ammonium etchate and 0.5 to 1.0% by mass of magnesium oxide) are compared with Comparative Example 12 (containing 0.5% by mass of magnesium oxide and not containing ammonium etchant), it can be seen that the concentration of magnesium in Example 6 is approximately the same as that in Comparative Example 12, and the concentration of magnesium in Example 7 is higher than that in Comparative Example 12.

From Table 7, when Examples 8 to 9 (containing 0.32 to 0.63% by mass of ammonium etchant and 0.5 to 1.0% by mass of potassium carbonate (mineral component)) are compared with Comparative Example 13 (containing 0.5% by mass of potassium carbonate and not containing ammonium etchant), it can be seen that the concentration of ammonia nitrogen in Examples 8 to 9 is higher than the concentration of ammonia nitrogen in Comparative Example 13.
Further, when Examples 8-9 (containing 0.32-0.63% by mass of ammonium corrosive acid and 0.5-1.0% by mass of potassium carbonate) are compared with Comparative Examples 3-4 (containing 0.32-0.63% by mass of ammonium corrosive acid and not containing calcium carbonate), it can be seen that ammonia nitrogen was not detected after 4 days in Comparative Examples 3-4, whereas ammonia nitrogen was detected even after 4 days in Examples 8-9.
That is, it can be seen that Examples 8-9 can continuously elute ammonium nitrogen over a longer period of time than Comparative Examples 3-4.

From Table 9, when comparing Example 8 (containing 0.32% by mass of ammonium etchant and 0.5% by mass of potassium carbonate) with Comparative Example 13 (containing 0.5% by mass of potassium carbonate and not containing ammonium etchant), it can be seen that the concentration of potassium in Example 8 is about the same as or higher than the concentration of potassium in Comparative Example 12. In particular, in Example 8, even after 4 days, the concentration of potassium was high at 0.82 to 1.77 mg/liter.
Further, when comparing Example 9 (containing 0.63% by mass of ammonium etchant and 1.0% by mass of potassium carbonate) with Comparative Example 13 (containing 0.5% by mass of potassium carbonate and not containing ammonium etchant), it can be seen that the concentration of potassium in Example 8 is higher than the concentration of potassium in Comparative Example 13.

Claims (6)

Consists of a composition containing soil, ammonium humus, and mineral components as constituent materials,
The mineral component contains potassium,
The bottom sand characterized by comprising granules in which the proportion of the soil is 85 to 99.5% by mass, the proportion of the ammonium humate is 0.1 to 8% by mass, and the proportion of the mineral component is 0.1 to 9% by mass in the composition. The bottom sand according to claim 1 , wherein the granular material has a particle size of 1 to 5 mm. The bottom sand according to claim 1 or 2 , wherein the granules have a crushing strength of 2.0 N or more as measured according to "JIS Z 8841:1993" (granules - strength test method). A method for producing bottom sand according to any one of claims 1 to 3 ,
A composition preparation step of mixing the constituent materials to prepare the composition;
a granulation step of granulating the composition to obtain the granules;
A method for producing bottom sand, comprising: The method for producing bottom sand according to claim 4 , further comprising a heat treatment step of heat-treating the granules obtained in the granulation step. The method for promoting growth of aquatic plants using the bottom sand according to any one of claims 1 to 3 , comprising a bottom sand supply step of supplying the bottom sand to the water bottom.