KR20100105472A - Material for forming iron chelate and method for using the same - Google Patents

Abstract

PURPOSE: An iron chelate generating material and a method for using the same are provided to promote and activate proliferation of marine biology. CONSTITUTION: An iron chelate generating material contains iron, carbonaceous, distilled ethanol residue or citrus residue. The iron and carbonaceous are integrally formed by the distilled ethanol residue or citrus residue. The content of the distilled ethanol residue is 2.5-10 weight%.

Description

Iron chelate generating material and its method of use {MATERIAL FOR FORMING IRON CHELATE AND METHOD FOR USING THE SAME}

The present invention relates to an iron chelate generating material for generating iron chelate in water and a method of using the same.

In rivers, lakes, and beaches, sediments such as slime accumulate and the water quality deteriorates. Under these circumstances, the nutrition necessary for phytoplankton is likely to be insufficient. In particular, when iron is scarce, phytoplankton breeding does not proceed. Phytoplankton are the basis of the plant chain. If propagation of phytoplankton does not progress, the activity of aquatic organisms feeding phytoplankton is impaired, and as a result, the entire aquatic environment is worsened.

The following invention is disclosed for the purpose of improving such a deteriorated water environment.

Japanese Unexamined Patent Application Publication No. 2007-268511 discloses an eluent for use in which a plurality of small agglomerates obtained by mixing particulate iron and carbonaceous materials together with a water-soluble binder such as starch and hardening into a plate shape using a non-aqueous binder such as clay powder. It is. If this iron ion eluate is arrange | positioned in water, iron ion will elute. Phytoplankton are promoted by ingesting eluted iron ions. When phytoplankton propagates, it can promote or promote the activity of other aquatic organisms that feed on phytoplankton. As a result, the water environment is improved.

In addition, it has been reported that phytoplankton grows when phytoplankton such as crude is cultured in a medium containing iron citrate. This is because phytoplankton is easily ingested because iron citrate is present in iron ions as iron chelate.

Eluted iron ions are likely to be oxidized. Oxidized iron ions form poorly soluble iron oxide and the like and aggregate and precipitate in water. Since phytoplankton cannot ingest iron in this state, phytoplankton cannot be sufficiently reproduced under conditions in which iron ions are rapidly oxidized.

If phytoplankton cannot breed sufficiently, the proliferation and activity of other aquatic organisms cannot be expected, so there is a problem that the improvement of the water environment is not achieved.

In addition, there is a problem that the iron citrate can not continuously supply iron ions to phytoplankton over a long period of time.

Iron chelate generating material according to the first aspect of the present invention

Iron and carbonaceous and distilled ethanol residue or citrus residue,

The iron and the carbonaceous are integrally formed by the distilled ethanol dregs or the citrus dregs,

Iron ions are eluted by the iron-carbon contact in water, and iron chelate is produced by a chelating agent contained in the iron ions and the distilled ethanol residue or the citrus residue.

In addition, the distillation ethanol residues are preferably formed by blending 2.5 to 10% by weight.

Method of using the iron chelate generating material according to the second aspect of the present invention

Containing iron, carbonaceous, and distilled ethanol residues or citrus residue, wherein the iron and carbonaceous material is formed by river distillation ethanol residues or citrus residues; By installing in water or on the bottom of the,

Iron ions are eluted by the iron and the carbonaceous contact, and iron chelate is produced by a chelating agent contained in the iron ions and the distilled ethanol residue or citrus residue, thereby promoting phytoplankton growth. do.

Method of using the iron chelate generating material according to the third aspect of the present invention

Rivers and lakes containing iron and carbonaceous substances and distilled ethanol residues or citrus residues, wherein the iron and carbonaceous substances are integrally formed by the distilled ethanol residues or citrus residues. ) Or install it underwater or at the bottom of the sea,

Iron ions are eluted by the contact between the iron and the carbonaceous material, and iron chelate is produced by a chelating agent contained in the iron ions and the distilled ethanol dregs or the citrus dregs.

The iron chelate is ingested in phytoplankton to promote phytoplankton proliferation and improve deteriorated water quality.

The use method of iron chelate generating material according to the fourth aspect of the present invention

An iron chelate generating material containing iron, carbonaceous and distilled ethanol dregs or citrus dregs, the iron and carbonaceous integrally formed by the distilled ethanol dregs or the citrus dregs, are installed on a cultured raft of shellfish;

Iron ions are eluted by the iron-to-carbonaceous contact, and iron chelate is produced by a chelating agent contained in the iron ions and the distilled ethanol residue or citrus residue, thereby promoting phytoplankton growth.

Moreover, it is preferable to use the said iron chelate generating material formed by mix | blending 2.5-10 weight% of the residues of the said distilled ethanol.

In the iron chelate generating material of the present invention, iron ions are continuously eluted, and the eluted iron ions are present in the water as iron chelates as they are.

Since iron chelates are present in water, they are easily consumed by phytoplankton and promote the growth of phytoplankton. Proliferation of phytoplankton promotes or activates the proliferation of aquatic organisms, including zooplankton, the first consumer in the plant chain.

Thus, purification of slime and the like, improvement of the water environment, and increase of asset resources can be realized.

In addition, distilled ethanol residues and citrus wastes have been considered as wastes until now, so that the effective use of such wastes and the treatment cost can be reduced.

FIG. 1 shows the dissolution test data of iron in Example 2. FIG.
2 is phytoplankton growth test data in Example 3. FIG.
3 is phytoplankton growth test data in Example 4. FIG.
4 is a layout view of an iron chelate generator and an iron ion eluate in Example 5. FIG.
FIG. 5 is a layout view of the iron chelate generator and the iron ion eluent in Example 5. FIG.

An iron chelate generating material according to the first embodiment of the present invention will be described in detail. The iron chelate generating material according to this embodiment contains iron, carbonaceous and distilled ethanol residues or citrus residues, and has a structure in which iron and carbonaceous substances are integrally formed by distilled ethanol residues or citrus residues.

Iron chelate generating materials can be mainly used in rivers, lakes or in the water or bottom of the sea. When distilled ethanol residues or citrus residues are slowly separated in water, iron and carbonaceous contact and iron having lower electronegativity than carbonaceous are oxidized to elute iron ions. This iron ion then reacts with the chelating agent contained in the distilled ethanol residue or citrus residue to form iron chelate.

Iron chelate generators continue to provide iron ions, an important nutrient for phytoplankton. In addition, the generated iron ions form iron chelate, so that they do not aggregate or precipitate, and remain stable in water as they are. For this reason, phytoplankton, which is the basis of the plant chain, can easily ingest iron ions and promote phytoplankton proliferation. Proliferation of phytoplankton promotes or activates the proliferation of aquatic organisms that feed on it, and consequently improves the water environment.

The carbonaceous material contained in the iron chelate generating material may include carbon, and for example, various carbonaceous materials such as coke, graphite, charcoal, bamboo charcoal, and coal may be used. Carbon has a higher electronegativity than iron, so iron is quickly oxidized and iron ions are eluted when in contact with iron.

Iron contained in the iron chelate generating material may contain iron atoms or may be an alloy or an oxide. Therefore, scrap metal and the like can also be used.

The carbonaceous material and iron contained in the iron chelate generating material are preferably granules having a small particle diameter. By using a granule having a small particle size, the contact area between iron and carbonaceous material is increased and the elution of iron ions is efficiently carried out.

Distilled ethanol residues and citrus residues are viscous and thus function as a binder when forming carbonaceous material and iron. In addition, distilled ethanol residues and citrus residues contain chelating agents, which are components that bind iron ions to form iron chelates.

Distilled ethanol residue is a residue from distilled ethanol production. Distilled ethanol is usually produced through the process of empire, primary fermentation, secondary fermentation, and distillation. First, yeast is added to raw materials such as barley, sweet potato, and rice, and cultured, and yeast is made (empire). The leaven is fermented in a tank or the like (primary fermentation), and the above-described raw materials are again added and fermented (secondary fermentation). The fermentation broth produced in the secondary fermentation is distilled (distilled), and distilled ethanol is prepared. The residue left after distillation is called distilled ethanol residue. Distilled ethanol residue consists of a mixture of liquid and solids from the distillation.

Citrus residues are leftovers from citrus fruits such as tangerines. When processing foods or drinks made from citrus fruits, wastes can be used.

Distilled ethanol residues and citrus residues are disposed of by ocean dumping, incineration, etc., and the wastes are treated as wastes, but these residues can be effectively reused as iron chelate generators. Therefore, the disposal cost of this waste is reduced and contributes to the promotion of the cyclical social formation.

The iron chelate generating material according to the present embodiment can be produced, for example, as follows. First, iron and carbonaceous material and distilled ethanol waste or citrus waste are kneaded. This is molded into a predetermined shape. The iron chelate generating material according to the present embodiment can be produced by placing the molded product in a furnace or the like and firing under predetermined conditions.

In the iron chelate generator according to the present embodiment, the carbonaceous material preferably contains an amount such that iron is sufficiently eluted. The distilled ethanol residue or citrus residue preferably contains an amount that can be kneaded with iron and carbonaceous material.

When using distilled ethanol waste, it is preferable to mix | blend 2.5 weight% or more of distilled ethanol waste with respect to the total weight of iron, carbonaceous, and distilled ethanol waste, and to form an iron chelate generating material. The iron chelate generating material may be formed at the compounding ratio. More preferably, it is good to mix | blend 2.5-10 weight% of distilled ethanol waste, and to form an iron chelate generating material. By forming it in the said compounding ratio, it can be made into the iron chelate generating material which is high in mechanical strength and is hard to collapse, and is excellent in the handling at the time of carrying and construction to a construction site.

The shape of the iron chelate generating material is not particularly limited and is selected according to the purpose. As a specific shape, a sphere, a cube, a cylinder, etc. are mentioned, for example. Spheres are preferred because iron chelates are generated over the longest possible time as small shapes as possible with a surface area to volume ratio are preferred.

The size of the iron chelate generating material is not particularly limited and is selected according to the purpose. For example, if the shape is the same, the ratio of surface area to size and volume is small, and iron chelate can be generated over a long period of time. In this case, it is preferable that the iron chelate generating material be as large as possible within the range where there is no problem in use.

A method of using the iron chelate generating material according to the present embodiment will be described below. The iron chelate generating material according to the present embodiment can be used, for example, in a river, a lake or in the water or the bottom of the sea. Alternatively, the iron chelate generating material may be added to the water as it is, or may be mounted on a river bottom or on the sea floor.

As an example, the case where an iron chelate generating material is arrange | positioned to a steel bottom etc. is demonstrated. A large number of iron chelate generators are arranged, for example, in the form of a matrix on the bottom of the river in the range where the water quality is to be improved. At this time, the arrangement of the iron chelate generating material is preferable because the work can be facilitated if the steel chelate generating material is disposed at a time when the river bottom or the like is exposed or when the water depth becomes shallow. The spacing of the iron chelate generating material can be appropriately adjusted by the size or shape of the iron chelate generating material. For example, when using a large iron chelate generating material, it may be arranged at a further interval. In addition, the method of arranging the iron chelate generating material is not limited to the above. Within the range in which iron chelate can be sufficiently widespread within the range to improve the water quality, the arrangement of the iron chelate generating material can take various forms.

Distilled ethanol dregs or citrus dregs contained in the iron chelate generator are gradually degraded by contact with water. Then iron and carbonaceous contact and iron with lower electronegativity than carbonaceous are oxidized and iron ions are eluted in water. As the iron chelate generating material according to the present embodiment, as iron and carbonaceous contact are gradually decomposed as distilled ethanol residue or citrus residue is gradually elution of iron ions. For this reason, iron ion by the iron chelate generating material which concerns on a present Example can be supplied continuously in water for a long time.

Since the eluted iron ions are immediately oxidized in water to become iron oxide, iron ions alone cannot be stably present for a long time. Iron oxide aggregates and precipitates in large chunks. In this state, phytoplankton cannot ingest iron. If phytoplankton ingests iron oxide, iron oxide can't cross the cell membrane, so phytoplankton can't absorb iron, a nutrient. Therefore, phytoplankton proliferation cannot be expected only by eluting iron ions in water.

Here, the iron chelate generating material according to the present embodiment is also released into the water by the chelating agent contained in the distilled ethanol residues or citrus residues by separation of distilled ethanol residues or citrus residues. The released chelating agent binds quickly with iron ions and produces iron chelate. Iron chelates are stable in water and are therefore easy to ingest in phytoplankton. When iron chelates are ingested, iron is absorbed into the cells of phytoplankton as nutrients.

Iron is absorbed into the cells of phytoplankton as a nutrient source, thereby promoting the growth of phytoplankton. The growth of phytoplankton promotes the growth and activation of zooplankton and other aquatic organisms, which are the first consumers in the plant chain. As a result, the purification of slime or the like and the increase of fishery resources are promoted, and the water environment is improved.

In addition, the improvement of the water environment promotes the growth of aquatic plants. These aquatic plants and phytoplankton are released from oxygen and carbon dioxide is consumed by photosynthesis. Thus, the iron chelate generating material according to the present embodiment may contribute to the reduction of carbon dioxide, which is mentioned as one of the causes of global warming in the greenhouse gas.

In addition, as another method of using the iron chelate generating material according to the present embodiment, for example, the iron chelate generating material may be used to form shellfish such as oysters and pearl shells, and the like. By placing the iron chelate generating material on aquaculture raft or the like, iron chelate is produced as described above, and phytoplankton can efficiently consume iron as a nutrient source. As a result, the growth of phytoplankton is promoted. Oysters and pearl clams consume this phytoplankton as food. That is, the iron chelate generating material according to the present embodiment can be effectively used in the culture of such shellfish.

Example

Hereinafter, the present invention will be described in detail with reference to examples. In addition, these embodiments disclose very suitable examples of the present invention, and the scope of the present invention is not limited thereto.

≪ Example 1 >

Distilled ethanol residue was blended with the carbonaceous powder and iron powder in various ratios to form iron chelate generating materials, and the respective compressive strengths were measured.

Earth rich powder type (manufactured by Hinomaru Industrial Co., Ltd.) was used as a powder of carbonaceous and iron. The earth rich type is a mixed powder having an iron powder and a carbonaceous powder in a weight ratio of 1: 1.

Distilled ethanol waste was added to the granular material of carbonaceous and iron, and formed into a cylinder, and then fired. The cylinders formed a total of six cylinders 1 to 6 by changing the blending amount of the distilled ethanol residues. Each cylinder is 5 cm in diameter, 5 cm in height, and 100 g in weight. The compounding quantity of distillation ethanol waste is 0 weight%, 2.5 weight%, 3.75 weight%, 5 weight%, 7.5 weight%, and 10 weight% with respect to carbonaceous, iron, and distillation ethanol waste whole quantity.

Each cylindrical body was placed on the ground, and the compressive strength of each cylindrical body was measured by placing a weight on the upper surface of the cylindrical body. The results are shown in Table 1.

Distillation Ethanol Residue Compounding Amount (wt%) Compressive strength Weight (kg) of the weight Pressure (㎏ / ㎡) Cylindrical body 1 0 - - Cylindrical body 2 2.5 15 0.76 × 10⁴ Cylindrical body 3 3.75 20 1.02 × 10⁴ Cylindrical body 4 5 31 1.58 × 10⁴ Cylindrical body 5 7.5 22 1.12 × 10⁴ Cylindrical body 6 10 19 0.97 × 10⁴

In the cylindrical body 1, in which distilled ethanol residue was not added, the weight was not raised and spontaneously collapsed by its own weight. On the other hand, in the cylinder 2-cylinder 6 to which distilled ethanol residue was added, it did not spontaneously decay, and it did not collapse even if it raised all to the weight of 15 kg. Thus, by forming 2.5 to 10% by weight of distilled ethanol residue in the granular material of carbonaceous and iron, it can be seen that an iron chelate generating material having excellent mechanical strength and excellent handleability can be obtained. Moreover, when 5 weight% of distillation ethanol waste is added to the granular material of carbonaceous material and iron, it turns out that the iron chelate generating material with the highest mechanical strength can be obtained.

<Example 2>

(Iron Dissolution Test)

The iron chelate generating material according to the present example was put in water, and the leaching test of iron ions was performed.

The carbonaceous powder of iron and iron and distilled ethanol residues are kneaded, molded and calcined to obtain an iron chelate generating material. Earth-rich powder type (manufactured by Hinomaru Industrial Co., Ltd.) was used as a powder of carbonaceous and iron. In addition, in the earth rich powder type, the iron powder and the carbonaceous powder will be mixed in a weight ratio of 1: 1. Distilled ethanol residue was used as the residue remaining during the distillation of the potato distillation ethanol manufacturing process. Distilled ethanol residue is added to 900 g of Earthrich's powder type at a rate of 100 g. The iron chelate generating material has a cylindrical shape of about 17.5 cm in diameter and about 11.5 cm in height, and weighs 3 kg.

One iron chelate generating material was put in a bucket, and 5 liters of distilled water was added thereto to elute iron ions. A total of three identical ones were prepared and the experiment was conducted under the same conditions.

The elution experiment was started and surface water was taken from the bucket every predetermined time passed. The collected surface water was filtered and the concentration of iron ions (dissolved iron) present in the filtered liquid was measured by a phenanthroline method or the like.

The phenanthrosine method (O-phenanthrosine method) is a method of comparing the red color of the complex salt formed by the reaction of ferrous ions with O-phenanthrosine by spectrophotometer and determining the concentration. In addition, ferric ions were added to the sample to reduce the ferric ions and reduced to ferrous ions. In addition, dissolved iron was determined by a combination of pretreatment such as filtration and boiling in hydrochloric acid.

The specific measurement procedure is shown below. First, 12.5 ml of surface water was collected from a bucket. This was filtered through a filter of 0.45 탆 in pore size, and 5.0 ml of 3N HCl was added immediately. After heating and boiling for 5 minutes, it cooled at room temperature for 30 minutes. After washing three times with a small amount of distilled water, it was transferred to a 50 ml volumetric flask.

Next, 1.0 ml of hydrochloric acid hydroxylamine solution was added. This hydroxylamine hydroxylamine solution was prepared by dissolving 10 g of NH ₂ OH.HCl in 100 ml of distilled water.

Next, 2.5 ml of 1,10-phenanthrosine solution was added and mixed sufficiently. The 1,10-phenanthrosine solution was prepared by dissolving 0.12 g of 1,10-phenanthrosine (C ₁₂ H ₈ N _{2 ·} HCl) in 100 ml of distilled water.

Next, about 2-3 ml of 6N NH ₄ OH was added and neutralized until the pH test paper turned yellow.

Next, 2.5 ml of buffer was added. This buffer was prepared by dissolving 6.8 g of sodium acetate (CH ₃ COONa) in about 50 ml of distilled water, adding 2.88 ml of acetic acid (CH ₃ COOH), and adding distilled water to 100 ml.

Next, distilled water was added to make 50 ml. After it is sufficiently stirred, it is transferred to a plastic container. Allow to color for 30 minutes.

The absorbance at 520 nm was measured using a spectrophotometer. The concentration of iron contained in the reaction solution was calculated based on the calibration curve prepared separately. All three samples were measured in the same order, and the average dissolved iron concentration was computed. This is described below as Sample 1.

As a reference example, the same experiment was also performed with respect to the molded object of the iron and carbonaceous powder which does not contain the distillation ethanol waste (hereinafter referred to as iron ion eluting body), and the dissolved iron concentration was calculated. The iron ion eluting body used the earth-rich briquette type (made by Hinomaru Industry Co., Ltd.) as it is. The size and the like of the iron ion eluate are the same as those of the iron chelate generator. This is described below as Sample 2.

Experimental results when Sample 1 and Sample 2 are used in FIG. 1 are shown. The horizontal axis shows the dissolution test days, and the vertical axis shows the dissolved iron concentration (ppm). It can be seen that iron is continuously eluted in both sample 1 and sample 2.

A large difference between sample 1 and sample 2 of dissolved iron concentration 49 days after the dissolution test began is not noticeable. However, from the beginning of the experiment to 30 days, sample 1 has a higher dissolved iron concentration than sample 2 and shows a stable value.

From this result, it was confirmed that Sample 1 containing the distilled ethanol residue, which is the chelate generating material according to the present embodiment, eluted iron faster than Sample 2 containing no distilled ethanol residue and also had a stable dissolved iron concentration over a longer period than Sample 2. It was.

<Example 3>

(Proliferation Experiment 1 of Phytoplankton)

Next, phytoplankton growth experiments were conducted using the iron ion eluate obtained in Example 2.

First, a liquid culture medium for phytoplankton was prepared. In this example, an iron-free f / 2 liquid culture paper (hereinafter referred to as an iron-free liquid culture paper) from which iron was removed from a f / 2 liquid culture paper, which is a general phytoplankton liquid culture paper, was used. The composition of this iron-free liquid culture medium is obtained by removing FeCl _{3 ·} 6H ₂ O (3.15 mg / l), which is iron, from artificial seawater having the composition shown in Table 1.

NaNO ₃ 75 µg / l NaH ₂ PO _{4 ·} H ₂ O 5 μg / l CuSO _{4 ·} 5H ₂ O 9.8 μg / l ZnSO _{4 ·} 7H ₂ O 22 μg / l CoCl _{2 ·} 6H ₂ O 10 μg / l MnCl _{2 ·} 4H ₂ O 180 µg / l Na ₂ MoO _{4 ·} 2H ₂ O 6.3 μg / l FeCl _{3 ·} 6H ₂ O 3.15 mg / l Na _{2 ·} EDTA 4.36 mg / l ThiaminHCl 0.1mg / l Biotin 0.5 μg / l Vitamin B ₁₂ 0.5 μg / l

The bucket surface water (the dissolved iron concentration of about 21 ppm) of the sample 1 in Example 2 was added to the iron free culture medium so that the last concentration of the dissolved iron might be 0.53 ppm. This is described below as Sample 3.

Separately from the sample 3, the bucket surface water (the dissolved iron concentration of about 19 ppm) of the second day of the sample 2 in Example 2 was added to the nonferrous liquid culture paper so that the final concentration of the dissolved iron was 0.65 ppm. This is described below as Sample 4.

Apart from the samples 3 and 4, ferric chloride (FeCl ₃ ) was added to the iron-free liquid culture so that the final concentration of dissolved iron was 0.65 ppm. This is described below as Sample 5.

To 5 ml of each sample placed in the screw cap test tube, 200 µl of phytoplankton culture solution previously washed with an iron-free liquid medium was added. For each sample, the fluorescence intensity (chlorophyll a fluorescence intensity) was measured once daily using a fluorescence photometer. Diatom (Thalassiosira weissflogii) was used as phytoplankton. Iron was not added during the experiment.

The results are shown in FIG. 2 represents the chlorophyll a fluorescence intensity and indicates the relative amount of phytoplankton. That is, phytoplankton is actively growing as the chlorophyll a fluorescence intensity is higher than the initial value, indicating that phytoplankton's growth promoting effect is high.

Although sample 3 had a slightly lower initial dissolved iron concentration compared to sample 4 or sample 5, a significant phytoplankton growth promoting effect was found. Sample 3 uses water in which iron was eluted by the iron chelate generating material according to the present example. It was confirmed that the iron chelate generating material according to this example has a high effect on promoting growth of phytoplankton.

Sample 3 contained water in which iron was eluted by an iron chelate generator containing distilled ethanol residue. In the water of Sample 3, it is thought that the chelating agent contained in the iron ions and the distilled ethanol residue produces iron chelate. Iron chelates can be stably present in water for a long time compared to iron ions that do not form chelates. For this reason, iron contained in the water of Sample 3 is easily ingested into phytoplankton and easily absorbed into phytoplankton cells. As a result, it can be seen that Sample 3 significantly promoted the growth of phytoplankton.

On the other hand, although sample 4 and sample 5 had higher initial iron concentration than sample 3, phytoplankton had a low growth promoting effect. This also includes iron chelators (Na _{2 ·} EDTA) in samples 4 and 5, but the amount is not sufficient to form iron chelates, and it can be considered that a part of dissolved iron is changed to iron oxide. As mentioned above, it is difficult for phytoplankton to ingest iron oxide because iron oxide is likely to aggregate or precipitate. If phytoplankton consumed iron oxide, phytoplankton could not use it as a nutrient because it could not cross the cell membrane. In samples 4 and 5, phytoplankton can be considered to be less active than in sample 3 because iron ions capable of ingesting phytoplankton are small.

<Example 4>

(Proliferation Experiment 2 of Phytoplankton)

The iron-free liquid culture used in Example 3 contains Na _{2 ·} EDTA, which is an artificial iron chelator, so the influence of Na _{2 ·} EDTA cannot be ignored. Here, the effect of the presence or absence of the chelating agent was verified by adjusting the medium without the iron chelator and using this to perform phytoplankton growth experiments.

Liquid cultures prepared by adding ferric chloride, citric acid, and ferric chloride + citric acid were used respectively, and the effects of citric acid and iron ions on the growth of phytoplankton were examined. As the chelating agent, citric acid (sodium citrate), which is thought to be contained in distilled ethanol residue and citrus residue, was used.

From the non-ferrous liquid culture paper in Example 3, a "liquid culture paper without iron chelator" was prepared. This `` liquid culture without iron chelator '' removes Na _{2 ·} EDTA (4.36 mg / l), an artificial iron chelator that does not exist in nature, from ferrous liquid culture.

Ferric chloride was added to a liquid culture without iron chelator so that the final concentration of dissolved iron was 0.65 ppm. This is described as Sample 6 below.

Sodium citrate was added to a liquid culture without iron chelator to a final concentration of 3.4 g / l. This is described below as Sample 7. The concentration of sodium citrate is equivalent to a sodium citrate mucheol liquid Na _{2 ·} EDTA concentrations with (4.36mg / l) equal chakhyeong (錯形) and performance were included in baeyangji when thought of as iron chelator in nature. That is _, it was added to verify whether sodium citrate functions as a substitute for artificial iron chelator Na _{2 ·} EDTA.

Ferric chloride and sodium citrate were added to the liquid culture without iron chelator. At this time, the final concentration of dissolved iron was prepared in sample 6 and sodium citrate in the same concentration as in sample 7. This is described below as Sample 8.

0.5 ml of phytoplankton culture was added to 5 ml of each sample placed in the screw cap test tube. After phytoplankton was incubated in f / 2 liquid culture medium, the cells were collected by centrifugation (8,000 rpm, 5 min) and washed three times with an iron-free liquid culture medium. Diatom (Thalassiosira weissflogii) was used as phytoplankton.

Each sample was incubated in a constant temperature room of 24 degreeC in 12 hours of light conditions _and 12 hours of dark conditions. For each sample, the fluorescence intensity (chlorophyll a fluorescence intensity) was measured once daily using a fluorescence photometer. The screw cap test tube was not opened and no iron source or chelator was added.

The results are shown in FIG. Almost no proliferation was found in sample 7 of sodium citrate alone. It was confirmed that phytoplankton proliferation did not occur in the absence of iron.

In sample 6 to which ferric chloride was added, phytoplankton grew to some extent. It is possible to ask that phytoplankton take up iron ions and multiply before iron ions aggregate and precipitate.

Meanwhile, as shown in FIG. 3, in sample 8 to which ferric chloride and sodium citrate were added, significant proliferation of phytoplankton was found in comparison with sample 7. It was confirmed that the addition of ferric chloride and sodium citrate can effectively promote the growth of phytoplankton.

From the results of Example 3 and this example, it can be seen that iron ions are present in the medium as iron chelates in the ionic state by the chelating agent, and these iron ions are taken up in phytoplankton as nutrients to promote phytoplankton growth.

In addition, as a chelating agent contained in the distilled ethanol waste, citric acid, which is usually contained in the distilled ethanol waste, is assumed to function as one of the chelating agents.

<Example 5>

(Water Quality Improvement Experiment)

The prepared iron chelate generating material was placed in the river and conducted a water quality improvement experiment. The experiment was conducted at Kyobashi River, a tributary of Otakawa, Hiroshima Prefecture.

At the low tide on October 27, 2008, when the water level of Kyobashi River was lowered and the bottom was exposed, the iron chelate generating material and the iron ion eluent were disposed respectively.

4 shows an arrangement place of the iron chelate generating material and the iron ion eluting material. The iron chelate generating material was disposed in a 14m * 30m rectangular section (hereinafter referred to as section A1) at a point about 250m from the Tokiwa Bridge constructed in Kyobashi River. In addition, an iron ion eluting body was disposed in a 14m * 30m rectangular section (compartment A2) about 200m from the Tokiwa Bridge.

The iron chelate generating material was obtained by kneading by adding distilled ethanol residue to the carbonaceous and iron granules, and molding and baking two kinds of shapes. Earth rich powder type (manufactured by Hinomaru Industrial Co., Ltd.) was used as a powder of carbonaceous and iron. As the distilled ethanol residue, the residue remaining after distillation in the preparation of potato distillation ethanol was used. Distilled ethanol residue was added at a rate of 100 g relative to 900 g of the earth rich powder type. In addition, the earth powder type is a mixed powder in which the powder of iron and the powder of carbon are 1: 1 by weight.

The iron chelate generating material has a cylindrical shape having a diameter of about 17.5 cm and a height of about 11.5 cm, and weighs 3 kg (hereinafter referred to as iron chelate generating material L (11L)), length of about 5 cm, width of about 5 cm, and maximum thickness. It was assumed to be two kinds of weight of 100 g (hereinafter referred to as iron chelate generating material S (11S)) in the form of briquettes of a partial 4 cm.

As shown in FIG. 5, 44 iron chelate generating materials L (11L) were arranged on the outer circumference of the section A1 at 2m intervals. And 300 iron chelate generating materials S (11S) were arrange | positioned evenly inside the division A1.

The iron ion eluting body has a cylindrical shape having a diameter of about 17.5 cm and a height of about 11.5 cm and an earth-rich briquette type of 3 kg in weight (manufactured by Hinomaru Industrial Co., Ltd., hereinafter referred to as iron ion eluting agent L (12L)) and about 5 cm in length. And earth-rich briquette type (hereinafter referred to as iron ion eluting agent S (12S)) weighing 100 g in a shell shape having a width of about 5 cm and a maximum thickness of 4 cm. In addition, the earth rich briquette type and the earth rich briquette type contain iron and carbonaceous materials in a weight ratio of 1: 1.

The iron ion eluate is the same as the iron chelate generating material, and as shown in parentheses in FIG. 5, 44 iron ion eluates L (12L) are arranged at intervals of 2 m on the outer circumference of the section A2, and the iron ions are located inside the section A2. Eluent S (12S) was arrange | positioned evenly 300 pieces.

As described above, the compartment A1 (iron chelate generation relocation site) and the compartment A2 (iron ion eluent disposition site) are spaced apart so that the effect of the iron chelate generating material in the compartment A1) is too large when the two compartments are too close. This is because there is a possibility that it will occur. In addition, when the iron chelate generating material is disposed downstream and the iron ion eluting material is arranged upstream, the iron chelate generating material is placed upstream and the iron ion eluating material is placed downstream, whereby It is because there exists a possibility that an effect may show up also in the place which arrange | positioned the iron ion eluate of a downstream side.

This water quality improvement experiment was conducted in the river, and since water is always flowing, the effects of water quality improvement cannot be evaluated even if the water is collected and analyzed. Here, whether or not the water quality was improved by the iron chelate generating material according to the present embodiment was carried out by evaluating the degree of improvement of the quality (journey) of each compartment.

Improvements in low quality were obtained by taking the squirrel, calculating the Ignition Loss (IL), and changing the ignition loss. Ignition loss IL is computed according to the following formula.

IL (%) = {(A-B) / A} * 100

In the above formula, A represents the weight (g) measured after heating (?) For 3 hours at 600 ° C and burning the organic matter.

Intensifying a low quality burns the organic substance contained in a low quality. For this reason, the lower quality containing much organic substance etc. shows a big weight reduction. This loss ratio (%) is the loss of ignition, and it is an index that can know at the same time the ratio of all organic matter contained in the low quality. Generally, when the water environment deteriorates, the loss of ignition increases because organic matter or sediment contained in the low quality increases. On the contrary, if the water environment is improved, the loss of ignition decreases because organic matter or sediment contained in the low quality is reduced.

On the installation date of the iron chelate generating material and the iron ion eluent (October 27, 2008), the central portion of each of the compartments A1 and A2 was collected and the ignition loss was calculated.

After 80 days (January 17, 2009), the centers of each of the compartments A1 and A2 were collected in the same way, and the ignition loss was calculated.

Table 3 shows the loss of ignition of each joule after the installation date and 80 days have elapsed.

Ignition loss (%) Block A1 Block A2 Installation date
(2008/10/27) 6.06 1.08 After 80 days
(2009/1/17) 5.34 3.00

As can be seen from Table 3, the loss of ignition of the journey after 80 days from the installation date in the section A2 in which the iron ion eluent is arranged was increased compared with the installation date. This indicates that the organic matter or precipitate is increased in the section A2, and the slime and the like are not purified. In other words, it was found that the water quality was not improved in the section A2 in which the iron ion eluent was disposed.

On the other hand, the loss of ignition decreases compared with the installation date from the jersey after 80 days in the division A1 which used the iron chelate generating material. The decrease in ignition loss means that organic matter or sediment is reduced, that is, slime and the like have been reduced. Thus, according to the iron chelate generating material according to the present embodiment, it was confirmed that the improvement of the water environment was realized.

11L: Iron Chelate Generator L 11S: Iron Chelate Generator S
12L: iron ion eluent L 12S: iron ion eluent S

Claims (6)

Containing iron and carbonaceous and distilled ethanol residue or citrus residue,
The iron and the carbonaceous are integrally formed by the distilled ethanol dregs or the citrus dregs,
Iron chelate generation, characterized in that iron ions are eluted by the contact of the iron with the carbonaceous water, and iron chelate is produced by a chelating agent contained in the iron ions and the distilled ethanol residue or the citrus residue. ashes. The method according to claim 1,
Iron chelate generating material, characterized in that formed by mixing 2.5 to 10% by weight of the distilled ethanol residue. It contains iron, carbonaceous, distilled ethanol residues or citrus residues, and the iron and carbonaceous materials are formed by river distillation ethanol residues or the citrus residues. Installed in the water or on the bottom,
Iron ions are eluted by the contact of iron with the carbonaceous material, and chelating agents are contained in the iron ions and the distilled ethanol residues or the citrus residues. How to use iron chelate generating material. Rivers and appeals containing iron, carbonaceous, distilled ethanol residues or citrus residues, and iron and the carbonaceous material formed integrally with the distilled ethanol residues or citrus residues.湖沼) installed in the water or bottom of the sea,
Iron ions are eluted by the contact between the iron and the carbonaceous material, and iron chelate is produced by a chelating agent contained in the iron ions and the distilled ethanol dregs or the citrus dregs.
The iron chelate is ingested in phytoplankton to promote the proliferation of the phytoplankton and improve the deteriorated water quality. An iron chelate generating material containing iron, carbonaceous and distilled ethanol dregs or citrus dregs, the iron and carbonaceous integrally formed by the distilled ethanol dregs or the citrus dregs, are installed on a cultured raft of shellfish;
Iron ions are eluted by the iron-to-carbonaceous contact, and iron chelates are formed by chelating agents contained in the iron ions and the distilled ethanol residues or the citrus residues, thereby promoting phytoplankton growth. How to use iron chelate generating material. The method according to any one of claims 3 to 5,
Method for using an iron chelate generating material characterized in that for using the iron chelate generating material formed by mixing 2.5 to 10% by weight of the residue of the distilled ethanol.

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