JP6007446B2 - Method for producing iron fulvic acid containing soluble silica - Google Patents

Description

The present invention relates to a method for producing an iron-containing fulvic acid-containing material containing soluble silica, and in particular, supplies iron fulvic acid to water areas such as seas, rivers, tidal flats, farms, ponds and lakes, and soils or deserts. Rehabilitation of sand and landslides by decomposition of sediments in estuaries and tidal flats, water purification of farms, ponds, lakes and marshes is improved, and mixed use with soil and desert promotes soil improvement and plant growth, and desert greening The present invention relates to a method for producing an iron fulvic acid-containing material containing soluble silica.

In the natural world, iron fulvic acid forms fulvic acid in the humic substance formed by humming the leaves and stems of the plant, and this is combined with iron dissolved in water in the oxygen-free state of the soil and chelated. Thus, fulvic acid iron is generated (see Patent Documents 1 and 2) . This iron fulvic acid is transported to the sea by rivers and contributes to the growth of phytoplankton and seaweed. Recently, it has been reported that this fulvic acid iron prevents the burning of the sea, decomposes the sediment on the seabed, and purifies the river.

In addition, the effects of silica deficiency, muddy water inflow, iron deficiency, etc. on fishery resources have been pointed out in fish fields (see Non-Patent Documents 1 to 4) .

JP 2005-34140 A Japanese Patent No. 4710036

Satoshi Hatakeyama, forest is a lover of the sea Masatsugu Fukushima, Influence of Humic Substances on Changes in Chemical Forms of Hazardous Chemicals NIRE News September 2000 Muraoka Hiroaki et al., Ministry of Transport, 3rd Port Construction Bureau Laboratory Experiment Results Bottom Soil Purification Method Investigation Survey Report Japan Sea and Sea Breeding Environment Beautification Promotion Organization, FY 2010 Survey report on forestation, such as tree planting activities related to fishery environment and biodiversity conservation

  In nature, the encounter between fulvic acid and iron is governed by chance, and in the methods of Patent Documents 1 and 2, the amount of fulvic acid iron is unknown, and it is difficult to control the amount of fulvic acid. There are problems that iron-acid-containing substances cannot be stably supplied, the production cost is high, and the problem of silica deficiency cannot be solved.

Bacillus bacteria are also said to be effective for water purification and bottom sediment purification. However, this alone had a variation in effect, and it was necessary to use it together with iron fulvic acid.

Therefore, the present invention provides a method for stably and inexpensively producing an iron fulvic acid-containing material containing soluble silica.

The invention of claim 1 of the present invention is to mix and mature a liquid substance made of silica iron into a fermented product produced by fulvic acid by fermentation and sterilization of papermaking sludge or bamboo powder or sludge fertilizer using wood chips. Is a method for producing an iron fulvic acid-containing material containing soluble silica.

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The invention of claim 2 of this application is that 50 mg to 7000 mg of a liquid substance composed of silica iron is used for 1 kg of sludge fertilizer using fermented product or wood waste produced by fulvic acid by fermentation and sterilization treatment of paper sludge or bamboo powder. The method for producing an iron-containing fulvic acid-containing material containing soluble silica according to claim 1, wherein the aging is carried out by mixing within a range of 5%.

Invention of Claim 3 of this application mixes a Bacillus bacterium to the iron fulvic acid containing material containing the soluble silica manufactured by the manufacturing method of the iron fulvic acid containing material containing the soluble silica of Claim 1 or 2. This is a method for producing a bio-fulvic acid iron-containing material.

In the present invention, a liquid substance composed of silica iron is mixed with fermented and sterilized organic waste, and the fulvic acid produced in the fermentation and sterilization process of organic waste during the aging process and the iron component of silica iron are chelated. By reacting, an iron fulvic acid-containing material containing soluble silica is stably and inexpensively produced.

  The organic waste fermented and sterilized product of the present invention can be a commercially available product made from wood chips or bamboo powder during compost manufacture, or can be used in a paper wastewater treatment process using a silica iron-based flocculant. It is possible to effectively use a papermaking sludge produced by mixing a mushroom waste medium as a fermentation accelerator and performing a fermentation treatment. In order to kill or inactivate harmful microorganisms in the fermentation process, fermentation temperature and exposure time are important. For example, compost is produced by exposure to 55 ° C. or more for 3 days or more.

  The liquid substance consisting of silica iron is commercially available. By using a silica iron flocculant (trade name: PSI) based on iron and silica, soluble silica and iron can be easily supplied to the water and soil. Soluble silica and iron fulvic acid are eluted in it, and it works effectively for the environmental improvement effect of the sea and rivers and the growth effect of plants.

  The amount of liquid substance composed of silica iron to fermented and sterilized processed organic waste is 50 mg / kg to 7000 mg / kg per mass (kg) of organic waste, and optimally 500 mg / kg. Add from kg to 5000 mg / kg.

When the addition amount is less than 50 mg / kg, the amount of soluble iron is insufficient and the water purification effect is inferior. Moreover, when it adds exceeding 7000 mg / kg, the pH value of a fulvic acid iron and a silica containing material will fall, it will affect the growth to a plant, and cost will also become high.

In this fulvic acid- silica-containing material, the content ratio of fulvic acid and iron is 1 to 5% by mass of the component ratio of iron / fulvic acid, and fulvic acid is rich. Then, in order to give sustainability, you may mix commercially available iron.

  In addition, when used in combination with Bacillus, Bacillus hybridized with iron fulvic acid can be used to decompose Bacillus subtilis, Bacillus amyloliquefaciens, Bacillus pumilus, Bacillus licheniformis, Bacillus thulienis, etc. A synergistic effect using the decomposition ability and the photo-Fenton reaction of iron fulvic acid can be exhibited.

  As described in Non-Patent Document 2, the photo-Fenton reaction of iron fulvic acid is first performed by photoreaction of fulvic acid with oxygen dissolved in water to produce hydrogen peroxide. Photo-Fenton reaction occurs between hydrogen oxide and divalent iron ions in iron fulvicate, and hydroperoxide radicals are generated. This hydroperoxide radical oxidizes and decomposes organic compounds including sulfides and the like because of its strong oxidizing action. For this reason, sludge etc. of sediments on the sea floor decomposes and turn into sand.

At this time, bivalent iron ions becomes the trivalent iron ions, the fulvic acid and light energy, is reduced, back to divalent iron ions, which stiffness Shi caused repeatedly in water, to decompose the sulfide organic compound , Purify water and bottom quality.

  ADVANTAGE OF THE INVENTION According to this invention, purification | cleaning of water quality and the bottom sediment of a seabed and regeneration of a seaweed bed can be accelerated | stimulated by supplying soluble silica and fulvic acid iron well in water, and water quality environment can be improved.

  In addition, when fermented and sterilized organic waste is used, when used for soil, iron fulvic acid, silica, nitrogen, and phosphorus can be supplied, which is effective in promoting the growth of plants.

The state of evaluation of sludge decomposition in Example 1 is shown.

Hereinafter, embodiments of the present invention will be described. The analysis of iron fulvic acid was carried out by requesting the Japan Food Function Analysis Laboratory. Moreover, the elution component from a fulvic acid iron and a silica containing material was analyzed using the ICP-MS analyzer of Kurume Research Park.

[Example 1]
5 kg of liquid material (PSI-025 manufactured by Taiki Yakuhin Kogyo Co., Ltd.) made of silica iron is spray-mixed with 10 tons of sludge fertilizer using wood chips marketed by Soil Microbiology Research Institute, Inc., and aged in a warehouse for 20 days did.

The obtained fulvic acid-silica-containing material was put into a PET bottle, and the supernatant was filtered through a 5A filter paper after being left at room temperature for 20 days in a place where the mixture was exposed to light at a concentration of 50 (g / 100 ml). Fulvic acid and soluble iron were analyzed at Japan Food Functional Analysis Laboratory. The soluble silica in the supernatant was analyzed with an ICP-MS analyzer. The results are shown in Table 1. As a result, it was found that fulvic acid 2400 (mg / L), soluble iron 39 (mg / L), and soluble silica 105 (mg / L) were produced.

Put 15 kg of this fulvic acid-silica-containing material into a biodegradable bag (Terramac sandbag bag made by Unitika), 7.5 kg of fulvic acid-silica-containing material, and 7.5 kg of sea sand. ) When 5 pieces were installed at an installation area of 100 m2 at intervals of 5 m, the sludge decomposed after 3 months, and the height of the low-quality soil was reduced from 10 cm to 20 cm. Specifically, as shown in Fig. 1, when the fulvic acid-silica-containing material was installed, the sludge was thick, it was impossible to walk with boots alone, and it was impossible to walk without using an auxiliary box, but 3 months have passed since installation Later, the sludge decreased, it became sandy and it became possible to walk with only boots. The evaluation of the decomposition of sludge was conducted by the Department of Social Design, Faculty of Engineering, Fukuoka University, in March 2012. The Western Society of Civil Engineering Research Presentation (Empirical study on sludge purification using iron fulvic acid-in Imari Bay for the recovery of horseshoe crab Efforts ~ Fukuoka University Faculty of Engineering Sayaka Sakata, Yasuyoshi Yamazaki, Ryoichi Watanabe, Hiroki Iokaoka, Sanko Co., Ltd. Yoshiaki Koga) The sludge was decomposed by the optical Fenton reaction with iron fulvic acid, and it was floated, and it was thought that the altitude gradually decreased due to the floating mud being washed away by the tide.

[Example 2]
It was produced in the same manner as in Example 1 except that 12.5 kg of a liquid substance composed of silica iron was sprayed. A supernatant was prepared in the same manner except that the iron-silica fulvic acid content was changed to a solid content concentration of 20 (g / 100 mL). The analysis results are shown in Table 1. They were fulvic acid 980 (mg / L), soluble iron 32 (mg / L), and soluble silica 78 (mg / L). When 10 kg of this fulvic acid / silica iron-containing material was put in a hemp sack and installed in a place where Imari Bay's seabed sediment (sludge) was found, it was found that sludge decomposed and became sandy in 3 months.

[Example 3]
It was produced in the same manner as in Example 1 except that 25 kg of a liquid substance made of silica iron was used. The obtained fulvic acid-silica-containing material was prepared in the same concentration as in Example 2 to prepare a supernatant. The analysis results are shown in Table 1. They were fulvic acid 990 (mg / L), soluble iron 45 (mg / L), and soluble silica 84 (mg / L). When 10 kg of this fulvic acid-containing material was put in a hemp sack and installed in a place where there was an underwater sediment (sludge) in Imari Bay, it was found that the sludge decomposed and became sandy after 3 months.

[Example 4]
After pulverizing bamboo, liquid material consisting of shea silica iron bamboo powder 10kg it was aged at room temperature for 20 days (Taikiyakuhinkogyo manufactured PSI-025) were 50g mixed (5000 ppm), placed in a plastic bag, cold aged for 30 days Fermentation was carried out to produce a substance containing iron fulvic acid and silica . As a result of measuring fulvic acid and iron in the obtained fulvic acid -silica-containing material at Japan Food Functional Analysis Laboratory, fulvic acid 59 (g / kg) and soluble iron 410 (mg / kg) are produced. I understood that. Soluble silica was obtained by immersing 20 g of the obtained fulvic acid-silica-containing material in 200 ml of tap water for 16 days at room temperature, and measuring the silica concentration of the extracted solution with an ICP- MS analyzer. As a result, the soluble silica concentration was 22 (mg / L). The measurement results are shown in Table 2. 100 g of sample containing fulvic acid iron / silica is put into a biodegradable bag in 10 L of water that is generated by aquatic river water. When submerged in the flow, the turbidity of the water drops from 20 to 10 or less. The occurrence of blue sea bream is no longer seen.

[Example 5]
Three types of Bacillus bacteria (1 × 10 ⁸ cfu / g) spore bacteria previously mixed with the iron-containing fulvic acid / silica-containing material produced in the same manner as in Example 4, 1 g was added, and the mixture was placed in a plastic bag. For 30 days. As a result of measuring the concentration of fulvic acid, iron and silica in the obtained fulvic acid -silica-containing material, it was found that fulvic acid 58 (g / kg) and soluble iron 360 (mg / kg) were produced. It was. Moreover, the soluble silica was 20 (mg / L). The measurement results are shown in Table 2. The effect on river water was the same as in Example 4.

[Comparative Example 1]
Table 1 shows the results of analyzing and analyzing the supernatant of the wood sludge fermented sludge fertilizer used in Example 1 at a solid content concentration of 30 (g / 100 mL). As a result, 510 (mg / L) fulvic acid was produced, but only 1.6 (mg / L) soluble iron brought in from sludge could be detected. Although 10 kg of this iron-containing fulvic acid was put in a hemp sack and installed in a place where there was a seabed deposit (sludge) in Imari Bay, the sludge was not decomposed.

[Comparative Example 2]
As a result of analyzing the fermented and matured bamboo powder of Example 4 at the Japan Food Functional Analysis Laboratory, fulvic acid was 48 (g / kg · dry) and soluble iron was 4 (mg / kg · dry). . The result of fermentation treatment of only this bamboo powder was allowed to stand at room temperature for 16 days at a solid content concentration of 10 (g / 100 ml), and as a result of analyzing the soluble silica in the extracted supernatant, it was 23 (mg / L). The results are shown in Table 2.

Claims (3)

Contains soluble silica characterized by mixing and aging liquid fermented fertilizer using fermented fermented fertilizer or wood sludge fermented fertilizer produced by fermenting and sterilizing paper sludge or bamboo powder. A method for producing iron-containing fulvic acid. A liquid substance consisting of silica iron is mixed in a range of 50 mg to 7000 mg and aged for 1 kg of fermented fertilizer using sulphated fertilizer produced by fermentation and sterilization of paper sludge or bamboo powder, or wood waste. The manufacturing method of the iron fulvic acid containing material containing the soluble silica of Claim 1 characterized by the above-mentioned. Include soluble silica characterized by mixing bacillus to claim 1 or fulvic iron inclusions containing soluble silica produced by the production method of fulvic iron inclusions containing soluble silica described in 2 A method for producing iron-containing fulvic acid.