JPH11319815A - Water quality improving mass and production of water quality improving mass - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide fired and crushed shells which are effectual in purification for a long period without being flushed away by water flow or sea flow by mixing the fired and crushed shells 1 which are formed by pulverizing and firing the shells with a concrete body and solidifying the mixture. SOLUTION: The fired and crushed shells 1 which are fired are mixed at a prescribed ratio with cement, sand, water, etc., by a concrete mixer or mixing machine and the mixture is poured into a form. When the cement solidifies, the water quality improving mass 2 is formed. The setting retarder of the concrete is applied on the inside wall of the form before pouring. The setting rate of the concrete 4 varies from the inside and front surface of the water quality improving mass 2 and the front surface does not solidify and the solidification is retarded, although the inside of the water quality improving mass 2 is already solidified. When the surface of such water quality improving mass 2 is flushed away, only the concrete-component of the surface of the water quality improving mass 2 is removed. As a result, the fired and crushed shells 1 are more exposed on the front surface of the water quality improving mass 2. Consequently, a water quality improving effect is improved.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

TECHNICAL FIELD The present invention relates to a water quality improving mass,
The water quality improvement lump is installed in a water tank, a waterway, a river, a lake, a pond, a bog, or underwater on the sea shore to improve the water quality.

[0002]

BACKGROUND OF THE INVENTION In recent years, marine pollution caused by industrial wastewater or domestic wastewater has become a serious problem. One of the reasons is that the purification ability of rivers that lead these wastewaters to the sea is significantly reduced. Wastewater containing eutrophic substances discharged into rivers is purified by a variety of aquatic organisms such as microorganisms, creatures, crabs, fish and aquatic insects. The aquatic life inhabiting the rocks of these rivers has been deprived of their habitat by seawall protection work, and their types and quantities have been drastically reduced. As a result, the water purification capacity of rivers throughout the country has been significantly reduced.

Further, a water quality improving agent is disclosed in JP-A-8-1320.
No. 72, Japanese Patent Publication No. 64-10279, powders have conventionally been used. However, although such a powdery water quality improving agent is effective in improving water quality, it is washed away by a water current or an ocean current and cannot exert its effect for a long time.

[0004] The present invention has been made to solve the above-mentioned problems, and an object of the present invention is to provide a water quality improvement lump which can exhibit the effect of water quality improvement for a long time.

[0005]

In order to achieve the above object, in the present invention, a crushed shell obtained by crushing and firing a shell is mixed with a concrete body and hardened. Thereby, the fired and crushed shell is not washed away by the water current or the ocean current, and the effect of improving the water quality can be exhibited for a long time.

[0006] Naturally occurring oyster shells have excellent ability to remove phosphoric acid. This phosphoric acid is one of the causative substances of eutrophication. Therefore, in order to provide a habitat for aquatic organisms on the riverbank and recover various types of aquatic organisms that have been drastically reduced, the ground oyster shells are placed in water. In order to maintain the strength of the oyster hull, it is mixed with concrete to produce oyster husk-mixed concrete artificial stones of various shapes and installed in water such as a river.

[0007]

BEST MODE FOR CARRYING OUT THE INVENTION Oyster shells are crushed using a crusher or the like.
Pieces of tens of micrometers, hundreds of micrometers, millimeters to centimeters, preferably 0.
Crushed into small pieces between 01 and 20 millimeters. This crushed oyster shell can be hundreds of degrees, for example 20
The sintering is performed at 0 ° to 600 °, preferably 400 °, using a baking oven or the like. Thus, the fired and crushed shell 1 is manufactured. The fired and crushed shell 1 may be oysters, oyster shells, scallop shells, clams, clams, clams, shells or shells.

By this baking, the oyster shell is sterilized, and the microorganisms and bacteria attached to the oyster shell surface are removed. In addition, the oyster shell is made porous by making many very fine holes by this firing, and the surface area of the fired and crushed shell 1 is increased to improve the water quality improvement effect, and the algae are more likely to adhere to the oyster shell, and the water quality improvement effect is also improved. I do.

FIG. 1 shows a cross section of the water quality improvement lump 2 and the mold 3. The inner surface of the mold 3 has a square shape of 10 cm square.
The fired and crushed shell 1 is mixed with cement, sand, water and the like at a predetermined ratio by a concrete mixer or a mixer, and poured into the mold 3. After a while, when the cement solidifies, a water quality improvement lump 2 is formed, and this is
Drawn from.

Before the pouring, a concrete setting retarder is applied to the inner wall of the formwork 3. As a result, the solidification rate of the concrete 4 differs between the inside and the surface of the water quality improvement lump 2, and although the interior of the water quality improvement lump 2 has already solidified, the surface still does not solidify and the solidification is delayed. You.
When the surface of the water quality improvement lump 2 is washed away, only the concrete on the surface of the water quality improvement lump 2 is removed. The clotting retarder is, for example, ligninsulfonic acid.

As a result, as shown in FIG. 2, more baked and crushed shells 1 are exposed on the surface of the water quality improving mass 2. Therefore, the surface area of the baked and crushed shell 1 is increased, and the effect of improving the water quality is improved, and the algae are more likely to adhere, and the effect of improving the water quality is also improved.

The concrete 4 on the surface of the water quality improving mass 2
If not removed, the baked and crushed shell 1 is not much exposed.
This is because the particle size of the baked and crushed shell 1 is larger than the particle size of the cement, so that most of the surface of the water quality improving mass 2 is covered with the cement particles.

The concrete 4 may be a solidifying resin, a solidifying adhesive, artificial stone or solidifying lime. The solidifying resin is, for example, an epoxy resin, a urethane resin, or the like. The shape of the water quality improvement lump 2 may be a cube, a cuboid, a sphere, a pyramid, a cone, a truncated pyramid, a truncated cone, a cylinder, a prism, a four-legged block, a six-legged block, or the like. It may be a block body or the like, and one or many through holes may be formed in the center.

It is to be noted that a coagulation accelerator may be contained in the central part of the water quality improving mass 2. In this case, the fired and crushed shell 1 containing no coagulant and cement etc. are first poured into the mold 3 and then the calcined and crushed shell 1 with cement is added using a thin pipe or the like. Is injected, and finally, the baked and crushed shell 1 containing no coagulation accelerator, cement, and the like are extended so as to cover and put on the top. Such coagulation accelerators are urethane resins,
Epoxy resin and the like.

Further, only the baked and crushed shell 1 containing no coagulation accelerator or coagulation retarder and cement may be poured into the mold 3. In this case, a jet stream is sprayed on the surface of the water quality improvement lump 2 that has been solidified and taken out, and the concrete 4 is removed.

FIGS. 3 and 4 show a block box 8 in which the water quality improving lump 2 is stored. The block box 8 is box-shaped, and eight water quality improving lump 2 are accommodated in the block box 8 with a gap. The space between the bottom surface of the water quality improvement lump 2 and the inner bottom surface of the block box 8 is installed and fixed with an epoxy resin adhesive. The gap between the stored water quality improving lumps 2 is left as it is or is filled with soil, gravel, fired and crushed shell 1 or other materials.

In some cases, through holes 9 are formed vertically at the center of each water quality improvement lump 2 with a drill or the like. Eels pass or live in this through hole 9 and water flows,
In some cases, algae may proliferate. In some cases, fixing holes 10 are provided at four corners of the outer bottom surface of the block box 8. Anchors are attached to the fixing holes 10, and the block box 8 is fixed to a slope or a vertical surface.

The block box 8 may be made of reinforced concrete, may be made only of concrete, or may have a wire mesh built therein. Further, the block box 8 may be a frame or a container such as a cube or a rectangular parallelepiped, and the water quality improving lump 2 is stored and fixed in such a frame.

The fired and crushed shells 1 and concrete 4 of the water quality improvement lump 2 are gradually dissolved in water, and the water quality improvement lump 2 is gradually reduced in size, but does not flow into the water stream. In this case, even if the fired and crushed shell 1 is melted or peeled, and the concrete 4 is exposed, the concrete 4 is immediately shaved by a water flow or the like.

This is because the amount of the concrete 4 is smaller than the amount of the fired and crushed shell 1 and the strength of the concrete 4 itself is weaker than the strength of the fired and crushed shell 1. Therefore, even if the size of the water quality improvement lump 2 is reduced, the concrete 4 on the surface of the water quality improvement lump 2 is immediately removed, and the fired and crushed shell 1 is always exposed to a large amount on the surface of the water quality improvement lump 2.

The water quality improving lump 2 may be installed in water as it is, or may be housed in a gabion and installed in water. Gabions are spherical, matte, cuboid,
Futon baskets, Daruma baskets and Sazanami baskets.

Experimental results and effects of the water quality improvement of the water quality improvement lump 2 will be described below. As for the measuring method, “phosphoric acid phosphorus” is used for the “ascorbic acid method (Murohy, L. an.
dRiley, J .; P. Anal. Chim. Act
a, 27, 31, 1962), and "N- (1-naphthyl) -ethylenediamine method (Bendschneider, K. and R)
obinson, R .; J. : J. Mar. Res. , 1
1,87 1952) ”and“ ammonia nitrogen ”
About the Indophenol method (Solorzan
o, L. Limnol. Oceanogr. , 14,
789, 1969) ". The following “raw oyster shell” refers to an unfired oyster shell, and “baked oyster shell” refers to a baked oyster shell.

(Experiment-1)-"Purification of water quality of oyster shell powder"
-KH2 so that the final concentration of phosphoric acid phosphorus is 6 ppm.
PO4 or NaNO2 is dissolved in distilled water to make a 1 liter solution. Raw oyster shell powder or baked oyster shell powder was added to each solution to a concentration of 5,000 ppm, and the mixture was allowed to stand at 25 ° C. for 2 weeks, after which the concentration of remaining phosphoric acid phosphorus was measured. The results are shown in [Table 1].

[Table 1] Phosphorus Phosphorus Phosphorus (ppm) Control Section (Only Basic Composition) 5.56 Raw Oyster Shell Section (Basic Composition Tofu Oyster Shell Powder) 1.41 Baked Oyster Shell Section (Basic Composition Toyaki Oyster) (Powder powder) 0.33 (Result-1) As shown in [Table 1], phosphoric acid phosphorus did not decrease so much in the control group, but 7 in the raw oyster shell group.
7% and 94% in the baked oyster shells were removed. Thus, both the raw oyster shell and the baked oyster shell had the ability to adsorb and remove phosphoric acid dissolved in water. The adsorption capacity of phosphoric acid was about four times higher for baked oyster shells than for raw oyster shells.

(Experiment 2)-"Purification of water quality in the goldfish tank"-
17 liters of tap water were placed in two water tanks (25 cm × 39 cm × 27 cm), one water tank (water tank A) was set as a control, and the other water tank (water tank B) was filled with oyster shell mixed mortar (8).
× 16 × 4 cm; 1,045 g). In each of these aquariums, ten goldfish having a body length of 3 to 4 cm were bred, and the concentrations of remaining phosphoric acid phosphorus and nitrite nitrogen were measured over time. The results are shown in [Table 2].

[0026] (Result-2) As shown in [Table 2], both the phosphate nitrogen and the nitrite nitrogen decreased in the water tank to which the mortar mixed with oyster shells was added.

(Experiment-3)-"Purification of water quality using oyster husk-concrete concrete"-Raw oyster husk concrete block and baked oyster husk concrete block prepared by mixing crushed oyster husk and concrete at various ratios The effect on water purification was investigated.

(Experimental Materials) KH 2 PO 4, NaNO 2, NaNO 3, NH 4 Cl were dissolved in distilled water so that the final concentrations of phosphoric acid phosphorus, nitrite nitrogen, and ammonia nitrogen became 10 ppm, and a 15 liter solution was prepared. I do.

(Basic Composition of Test Aqueous Solution) Each final concentration of phosphoric acid phosphorus, nitrite nitrogen, and ammonia nitrogen is 10
KH2PO4, NaNO2, NaNO
3. Dissolve NH4Cl in distilled water to make a 15 liter solution.

(Preparation of oyster shell concrete block)
The oyster shell raw or burned oyster shell burned at 400 ° C. is mixed with concrete in various proportions to produce a cylindrical oyster shell concrete block having a size of about 10 × 10 × 10 cm (about 2 kg). did.

(Oyster shell concrete block) B: Raw oyster shells B20, B50, B70 C: Roasted oyster shells C20, C50, C70 (Experimental method) Three types of raw oyster shells (B20, B50, B)
70) and three types of baked oyster shells (C20, C50, C7)
The water quality of the test aqueous solution into which the concrete block composed of the above (0) was added and the test aqueous solution not containing the block were changed over a period of 64 days from September 30 to December 3 over a period of 64 days.
The measurement was performed 11 times in total.

(Result 3-1)-"pH and temperature"-The test aqueous solution was 23 ° C on September 30 of the experiment start date.
Thereafter, the temperature gradually decreased, and decreased to 12 ° C. on December 3 ([Table 3-1] in FIG. 5). PH of the aqueous solution at the start of the experiment
Was 7.01 and neutral. In the control group, the pH was set at day 21
It showed a pH of 7.20, but gradually decreased thereafter, and showed pH 5.80 on the 64th day. The aqueous solution into which the raw oyster shell block and the baked oyster shell block were added showed an alkaline pH of 9.06 to 9.49 in one case after one day. Thereafter, although a slight change was observed, the alkalinity at around pH 9 was maintained ([Table 3-1] in FIG. 5).

(Result 3-2)-"Daily change of phosphoric acid" As shown in [Table 3-2] in FIG.
In the control group with ppm phosphoric acid concentration, 11.04 p even after 7 days
pm and only 12.1%. On the other hand,
7 in the test plot with raw and baked oyster shell blocks
By day 60, a sharp decrease in phosphoric acid concentration by 60-80% was observed.

On the 64th day, the control group showed 9.68 ppm and 2
Although only 3% was reduced, all block inputs had 80-90% of the starting phosphoric acid removed. Also, 64
On the day, 1/4 of the control plots in any block input plots
Phosphoric acid concentration decreased to 1/5.

From the above results, it was found that both the raw oyster shell and the baked oyster shell block adsorb and reduce phosphoric acid in water.

(Result 3-3)-"Daily change of nitrite nitrogen"-As shown in [Table 3-3] in Fig. 7, even after 42 days, the concentration of nitrite nitrogen was not changed in the control group. There was almost no change in the block input area.

(Result 3-4)-"Daily change of ammonia nitrogen"-As shown in [Table 3-4] in Fig. 8, ammonia nitrogen was increased by 21 days in both the control group and the block input group. Considerably reduced. That is, 51% in the control plot,
64% to 77% of ammonia was removed in the raw oyster shell block input section, and 91 to 96% of ammonia was removed in the baked oyster shell input section.
On the 64th day, the control group was removed by 84%, whereas almost 100% was removed by any of the block administration groups.

The present invention is not limited to the above embodiment, but can be variously modified without departing from the spirit of the present invention. For example, as the fired and crushed shell 1, in addition to shells, fish bones, fish gala, bones of aquatic organisms, animal bones, and the like may be used. In addition, the present water quality improvement lump 2 can be used as a nest of underwater creatures such as a fish farm or a natural reef. Furthermore, the baked and crushed shell 1 may be mixed with the water quality improvement lump 2 and hardened, or may be sown or sprayed in water as it is.

[0039]

As described above in detail, according to the present invention, a crushed shell obtained by crushing and firing a shell is mixed with a concrete body and hardened. Therefore, the fired and crushed shell is not washed away by the water current or the ocean current, and the effect of improving the water quality can be exhibited for a long time.

Also, by mixing oyster shell powder and concrete to produce artificial stones of various shapes and installing them in rivers, crabs and various freshwater fish and aquatic insects, which have lost their habitat during revetment works. Habitats for aquatic organisms can be constructed. In addition, oyster shell powder is mixed with concrete to provide a habitat for microorganisms useful for water purification because it has the ability to remove phosphoric acid dissolved in water and is porous. It can also be effective for purification. The use of calcined oyster shell powder makes it possible to produce aseptic artificial stones, which is suitable for purifying aquaculture ponds. In addition, by installing this product in coastal waters with few rocks, seaweed spores can easily adhere to the surface with fine irregularities caused by mixing oyster shell powder into concrete, and the foundation for seaweed bed creation It is also useful as a stone.

[Brief description of the drawings]

FIG. 1 shows a cross section of a water quality improvement lump 2 and a mold 3.

FIG. 2 shows a cross section of the surface of the water quality improvement lump 2 from which the concrete 4 has been removed.

FIG. 3 shows a plan view of a block box 8 in which the water quality improvement lump 2 is stored.

FIG. 4 shows a side surface of a block box 8 in which the water quality improvement lump 2 is stored.

FIG. 5 shows the results of experiments on the pH and temperature of water using the water quality improvement lump 2.

FIG. 6 shows an experimental result of a daily change of phosphoric acid in water by the water quality improvement lump 2.

7 shows the results of an experiment on the daily change of nitrite nitrogen in water by the water quality improvement lump 2. FIG.

FIG. 8 shows an experimental result of a daily change of ammonia nitrogen in water by the water quality improvement lump 2.

[Explanation of symbols]

DESCRIPTION OF SYMBOLS 1 ... Fired and crushed shell, 2 ... Water quality improvement lump, 3 ... Formwork, 4 ... Concrete, 8 ... Block box, 9 ... Through hole, 10 ... Fixed hole.

Claims (5)

[Claims] 1. A water quality improving lump characterized by mixing and hardening a baked and crushed shell obtained by crushing and firing a shell. 2. A water quality improving lump characterized by comprising a step of crushing a shell, a step of firing the crushed shell, and a step of mixing the baked shell with a concrete body and solidifying it. Production method. 3. The concrete body on the surface of the water quality improvement lump is removed, the fired and crushed shell is largely exposed on the surface of the water quality improvement lump, and the solidification rate of the concrete body is within the water quality improvement lump. The water quality improvement lump according to claim 1, wherein the water quality improvement lump differs from the surface. 4. The amount of the concrete body is smaller than the amount of the fired and crushed shell, and the strength of the concrete body itself is weaker than the strength of the fired and crushed shell. The mass for improving water quality according to claim 1, wherein the mass is an adhesive, artificial stone, or solidifying lime. 5. The shell according to claim 1, wherein said shell is oyster, oyster, scallop, clam, clam, clam, shrimp or shell. The firing temperature of the shell is 200 to 600 degrees. 4. A mass for improving water quality according to item 4.