JP2005067996A - Orthosilicic acid-containing liquid fertilizer - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a liquid fertilizer containing orthosilicic acid (Si(OH)<SB>4</SB>)which is easily absorbed by vegetables. <P>SOLUTION: This orthosilicic acid-containing liquid fertilizer is obtained by adding an orthosilicic acid alkyl (tetraalkoxysilane) into water or an aqueous solution containing an inorganic material and/or an organic material and hydrolyzing the orthosilicic acid alkyl (tetraalkoxysilane) under an acidic state. <P>COPYRIGHT: (C)2005,JPO&NCIPI

Description

Detailed Description of the Invention

  This invention provides the liquid fertilizer containing the water-soluble normal silicic acid obtained by hydrolyzing a normal alkyl silicate (tetraalkoxysilane).

Conventional technology

  Silicic acid exhibits physiological effects such as strengthening crop foliage, increasing disease resistance and insect resistance, promoting root growth, and substituting part of the physiological function of phosphorus, especially in rice plants. However, siliceous fertilizers are indispensable for increasing disease resistance and insect resistance, and for increasing the size of the foliage and preventing lodging.

Currently, most of the siliceous fertilizers used are slag siliceous fertilizers made from slag generated during the production of pig iron and steel. The main component of this mineral siliceous fertilizer is calcium metasilicate (CaSiO ₃ ), which is sparingly soluble in water.

Despite the fact that this siliceous siliceous fertilizer is extremely difficult to dissolve, it is used for paddy rice, and the effects of disease resistance, increased yield, etc. are expressed in the special environment of paddy rice fields, that is, in the presence of water. As a result of being placed in a reduced state, the following reaction is caused by carbon dioxide generated by the respiration of anaerobic microorganisms and roots, and low-molecular-weight water-soluble This is thought to be due to the change to normal silica.
CaSiO ₃ + H ₂ CO ₃ + H ₂ O → Si (OH) ₄ + CaCO ₃

In this way, the effect of silicic acid in paddy rice is recognized, and it is partly used in field crops and golf courses, but mineral silicic acid fertilizer is poorly soluble as mentioned above, so the effect of paddy rice is not expected and a soil conditioner It is only used as.

  Under such circumstances, liquid silicate fertilizers using potassium silicate as a raw material that can be used in field crops and golf courses have been developed. For example, in Japanese Patent Publication No. 2-2837, a potassium silicate liquid fertilizer mainly composed of an aqueous solution of potassium silicate citrate is used, and in Japanese Patent Application Laid-Open No. 5-78189, an aqueous solution in which potassium silicate and ethylenediaminetetraacetate magnesium are dissolved. A liquid potassium silicate fertilizer is proposed, and JP-A-7-101792 proposes a liquid silicate fertilizer containing an alkali metal silicate and gluconic acid or a salt thereof.

However, the form of dissolved silicic acid in the liquid potassium silicate manure varies depending on the hydrogen ion concentration (PH), and when PH is 6 or less, 100% of H ₄ SiO ₄ (Si (OH) ₄ ) is contained, but PH 9.6. In this state, H ₄ SiO ₄ (Si (OH) ₄ ) is 50%, H ₃ SiO ₄ ⁻ is 50%, and in the PH11 state, H ₄ SiO ₄ (Si (OH) ₄ ) is 4%, H ₃ SiO ₄ ⁻ + H ₂ SiO ₄ ⁻⁻ changes to 96%. The form of silicic acid that is most easily absorbed by crops has the structure of H ₄ SiO ₄ (Si (OH) ₄ ) (Eiichi Takahashi: “Nippon Soil Fertilizer Science Journal” Vol. 49, No. 5, 357, published in 1978). Although it is normal silicic acid, in the above-mentioned method using potassium silicate as a raw material, so far, silicic acid is precipitated, so PH cannot be made to be an acidic side of 6 or less, and normal silicic acid having a PH of 9 or more. Alkaline solution with low content.
Thus, the liquid silicic acid fertilizer that has been developed so far is a concentrated alkaline aqueous solution made of potassium silicate silicate as a raw material, so it is safe in handling, and because there are few normal silicic acids with small molecules, Difficult to be absorbed, and it cannot be absorbed by the crop unless it is converted to normal silicic acid by the root acid of the crop and the organic acid secreted from the root. was there.
For this reason, if an aqueous solution containing normal silicic acid in a form that can be easily absorbed by crops can be developed, it can be applied to the symptoms of silicic acid deficiency as a fast-acting silicate liquid fertilizer that can be absorbed from the foliage and roots of crops. It is thought to bring.

In JP-A-7-69964, an ammonium salt or alkali metal salt such as hydrochloric acid, phosphoric acid or sulfuric acid and a silicate such as sodium metasilicate or calcium metasilicate are reacted in an aqueous medium in the range of PH6-9. It is proposed that a solid composition containing orthosilicic acid having a Si (OH) ₄ structure that is easily absorbed by crops is obtained. However, this method has a problem that when the concentration of normal silicic acid is 300 ppm or more in terms of SiO ₂ , silicic acid is precipitated, so that the concentration cannot be increased to a higher level, and an aqueous solution containing normal silicic acid is used as a foliar spray agent. When used as, there is a manufacturing disadvantage that solids in the reaction solution must be separated and removed after completion of the reaction.

Problems to be solved by the invention

An object of the present invention is to provide a normal silicic acid-containing liquid fertilizer having a structure of Si (OH) ₄ that is easily absorbed by crops in an industrially advantageous manner.

Means for solving the problem

As a result of intensive studies to solve the above problems, the present inventor has a general formula Si (OR) ₄ (R represents an alkyl group having 1 to 3 carbon atoms) in water or an aqueous solution containing an inorganic substance and / or an organic substance. A liquid fertilizer containing a stable water-soluble normal silicic acid can be obtained by adding a normal alkyl silicate (tetraalkoxysilane) represented by the formula (II) and hydrolyzing the normal alkyl silicate (tetraalkoxysilane) in an acidic state. The inventor has completed the present invention. In addition, according to the present invention, nitrogen, phosphoric acid, potassium plant three major nutrients and / or trace elements necessary for plant growth such as calcium, magnesium, manganese, boron and / or which could not be easily achieved by the prior art and / or An arbitrary amount of water-soluble orthosilicic acid can be introduced into an aqueous solution containing chitosan having an effect of suppressing the generation of pathogenic bacteria on soil and plants and / or an aqueous extract of chicken manure fermented product useful as an organically grown fertilizer.

Hereinafter, the liquid fertilizer containing orthosilicic acid of the present invention will be described in detail.
The water used in the present invention is not particularly limited, but acidic ion water is preferably used.

  In the present invention, the aqueous solution containing an inorganic substance used is phosphoric acid, potassium dihydrogen phosphate, ammonium dihydrogen phosphate, ammonium chloride, ammonium chloride, an aqueous solution containing an inorganic substance containing phosphorus, potassium, and the like, and It is an inorganic aqueous solution containing metals necessary for the growth of plants such as zinc sulfate, magnesium chloride, calcium chloride, copper sulfate, manganese sulfate, magnesium sulfate, ferric chloride, ferric sulfate, and boric acid.

  In the present invention, the aqueous solution containing an organic substance is urea and / or calcium citrate, magnesium acetate, manganese acetate, calcium lactate, calcium gluconate, magnesium lactate, ethylenediaminetetraacetate disodium magnesium, ethylenediaminetetraacetate dinatrium calcium acetate An aqueous solution of an organic substance containing a metal necessary for the growth of a plant and / or an aqueous solution containing an extract of water or hydrous alcohol of a plant or a fermentation product, a natural polymer, an amino acid, a nucleic acid, an organic acid, etc. . For example, spiruna extract as plant water or hydrous alcohol extract, tomorrow leaf extract, fermented water or fermented water extract as alcohol extract, chitosan as natural polymer, Examples include alginic acid.

  The normal alkyl silicate (tetraalkoxysilane) used in the present invention is normal methyl silicate (tetramethoxysilane), normal ethyl silicate (tetraethoxysilane), and normal propyl silicate (tetrapropoxysilane). Those sold by the company can be applied.

  In the present invention, in order to obtain the normal silicic acid-containing liquid fertilizer, first, phosphoric acid, polyphosphoric acid, sulfuric acid, nitric acid hydrochloric acid, hydroxyacetic acid, lactic acid, citric acid, malic acid is added to an aqueous solution containing water or inorganic and / or organic substances as described above. Then, one or more acids such as gluconic acid and acetic acid are added to adjust the pH to a range of 1 to 4. Above PH4, the hydrolysis rate of the normal alkyl silicate is slow, and a gelled product obtained by condensation polymerization of the normal silicic acid is likely to be produced, which is not preferable in terms of storage stability.

  In the present invention, a normal alkyl silicate (tetraalkoxysilane) is then added and stirred at 30 to 80 ° C. for 0.5 to 5 hours to cause hydrolysis of the normal alkyl silicate (tetraalkoxysilane) and contain water-soluble normal silicic acid. Liquid fertilizer is obtained. The addition amount of the normal alkyl silicate (tetraalkoxysilane) is in the range of 0.005 to 15%, preferably 0.01 to 10% with respect to the aqueous solution containing water or inorganic and / or organic matter. If it is 0.005% or less, the concentration of normal silicic acid in the liquid fertilizer containing normal silicic acid is low, so that it is not possible to expect silicic acid fertilization effect on crops. If it is 15% or more, normal silicic acid undergoes polycondensation during hydrolysis or storage. , Because the liquid fertilizer containing orthosilicic acid becomes a non-flowable gelled product

EXAMPLES Hereinafter, although an Example demonstrates this invention in detail, this invention is not limited to these at all.
Example 1
To 320 g of acidic ionized water, 3.3 g of 85% phosphoric acid is added (PH = 1.3), and then 18.9 g of ethyl silicate (tetraethoxysilane) manufactured by Tama Chemical Industry Co., Ltd. is added at 50 to 60 ° C. By stirring for 1 hour, a liquid fertilizer containing 2.6% concentration of normal silicic acid (Si (OH) ₄ was obtained. This aqueous solution was stable with no gelation even after standing at room temperature for 3 months. there were.

Example 2
3.2 g of 50% gluconic acid and 1.5 g of 85% phosphoric acid are added to 320 g of acidic ionized water (PH = 1.4), and 18.9 g of methyl silicate (tetramethoxysilane) manufactured by Tama Chemical Industry Co., Ltd. is added. The mixture was added and stirred at 50 to 60 ° C. for 1 hour to obtain a liquid fertilizer containing 3.4% concentration of normal silicic acid (Si (OH) ₄ ). This aqueous solution was stable with no gelation even when left at room temperature for 3 months.

Example 3
After dispersing 0.47 kg of Kyowa Technos Co., Ltd. low molecular weight chitosan (trade name Flornac C) in 14.9 kg of acidic ionized water at 63 ° C., 2.2 kg of brewed vinegar and 2.46 kg of 70% hydroxyacetic acid solution And stirred for 30 minutes to dissolve the chitosan. To this aqueous chitosan solution (chitosan concentration 2.2%, PH = 2.2), 0.47 kg of the same normal ethyl silicate (tetraethoxysilane) as in Example 1 was added and stirred at 50-60 ° C. for 1 hour to 0 A liquid fertilizer containing 9% strength orthosilicic acid (Si (OH) ₄ ) was obtained. This aqueous solution was stable with no gelation even when left at room temperature for 3 months.

Example 4
Extraction of fermented chicken manure containing 2% active ingredient after adding 0.7 kg of fermented chicken manure (manufactured by Marumashi Sangyo, trade name: Takarafune) to 5 kg of acidic ionized water and stirring for 30 minutes at 60-70 ° C 4.4 kg of liquid was obtained. To 564 g of this fermented chicken manure extract, 51 g of 85% phosphoric acid was added, and at 40-50 ° C., 18.6 g of calcium citrate tetrahydrate, 24.4 g of magnesium acetate tetrahydrate, 10.3 g of boric acid, manganese acetate 4 3.1 g of hydrate was added and dissolved to obtain an aqueous extract of trace element-containing fermented chicken manure (Ca content was 0.6%, Mg content was 0.4%, B content was 0.7%, Mn The content is 0.1%). To this trace element-containing fermented chicken manure extract (PH = 2.8), 25.6 g of the same normal ethyl silicate (tetraethoxysilane) as in Example 1 was added, stirred at 50-60 ° C. for 1 hour, and 1.8%. A liquid fertilizer containing% concentration of orthosilicic acid (Si (OH) ₄ ) was obtained. This aqueous solution was stable with no gelation even when left at room temperature for 3 months.

Example 5
39 g of low molecular weight chitosan similar to Example 3 was dispersed in 2.39 kg of acidic ionized water, and 49 g of 70% hydroxyacetic acid, 35 g of 90% lactic acid, 35 g of acetic acid, and 70 g of citric acid monohydrate were added to dissolve chitosan. I let you. Next, 2.49 kg of the fermented chicken manure extract of Example 4 was added to and mixed with the 1.5% chitosan aqueous solution, and then 553 g of 85% phosphoric acid was added, and then 196 g of calcium citrate tetrahydrate and MgSO 4 Hydrate 406 g, potassium dihydrogen phosphate 182 g, boric acid 280 g, urea 147 g, potassium chloride 84 g were added and dissolved, respectively, 1% total nitrogen, water-soluble phosphoric acid 6.3%, water-soluble potassium 1.7%, A fermented chicken manure extract-chitosan aqueous solution containing 1.0% water-soluble clay, 0.1% water-soluble manganese, 0.6% water-soluble calcium, and 2.0% water-soluble boron was obtained. To this aqueous solution (PH = 3.0), 130 g of normal ethyl silicate (tetraethoxysilane) similar to that in Example 1 was added and stirred at 50-60 ° C. for 1 hour to obtain 0.9% concentration of normal silicic acid (Si (OH ₄ ) A liquid fertilizer containing ₄ ) was obtained. This aqueous solution was stable with no gelation even when left at room temperature for 3 months.

[Crop evaluation test]
After spraying a 500-fold dilution of the normal silicic acid-containing liquid fertilizer of Example 3 on the soil at a rate of 1000 liters per 10a, cultivation and then tomato planting were carried out. Thereafter, foliar spraying was performed every 7 to 10 days with a 1000-fold dilution of the normal silicic acid-containing liquid fertilizer of Example 5 at a rate of 100 to 200 liters per 10a. No illness such as ash fungus was observed, and the color, fragrance, fruit, firmness, sugar content of 5 or more, and yield increased by 20% compared to unused tomatoes. In addition, there were few whiteflies and aphids for the pests in the use zone. In addition, in the target area where the normal silicic acid-containing liquid fertilizer of the present invention was not used, pathogenic bacteria and pests such as hip rot, ring rot, and aphids were frequently generated, and the taste, freshness, color, and aroma of tomato were not good. .

The invention's effect

  The normal silicic acid-containing liquid fertilizer of the present invention is diluted by 50 to 2000 times with water and used in methods such as soil irrigation, hydroponics, and foliar application to paddy rice, vegetables, fruit trees, lawn, etc. In addition to orthosilicic acid, which has effects such as promotion of geopower, promotion of photosynthesis, increase in lodging resistance and disease resistance, chitosan aqueous solution effective to suppress the generation of plant pathogens and soil pathogens and / or increase yield of agricultural products Water extract of chicken manure fermented product that has the effect of improving the color of fruits and fruits, aroma, sugar content, and / or nitrogen, phosphorus, potash and / or calcium essential for plant growth, which are the three major nutrients of plants, Since it contains an aqueous solution containing trace elements such as magnesium, manganese, boron, etc., it is suitable not only for conventional farming methods, but also for organic farming methods that are particularly pesticide-free and low pesticides.

Claims (1)

The following general formula (1) is added to water or an aqueous solution containing inorganic and / or organic substances.
Si (OR) ₄ ......... (1)
(Wherein R represents an alkyl group having 1 to 3 carbon atoms)
A normal silicic acid characterized by containing a water-soluble normal silicic acid obtained by adding a normal alkyl silicate (tetraalkoxysilane) represented by the formula (II) and hydrolyzing the normal alkyl silicate (tetraalkoxysilane) in an acidic state. Contains liquid fertilizer.