TW201835008A - Process for preparing granular oxamide having high hardness and high anti-disintegration in water or soil to produce a slow-acting function - Google Patents

Abstract

The present invention provides a granular oxamide which has high hardness of the fertilizer granule, and is highly stable in water and has stable slow-acting property, and is capable of reducing the number of top dressing and easing the burden of top dressing work. In the present invention, a mixture containing 0.5 parts by weight or more of polyvinyl alcohol or modified polyvinyl alcohol with respect to 100 parts by weight of oxamide powder is stirred in an inclined mixing pot container, and then is dried for final products.

Description

Method for producing granular grassy amine

The present invention relates to a method for producing a granular grassy melon, and more particularly to a fertilizer having a high hardness and high disintegration resistance in water or soil, and having a stable slow-acting fertilizer effect. A method for producing granular grassy amine.

One of the characteristics of the agricultural structure change from 2010 to 2015 is that the reduction rate of the number of agricultural operators and the number of sales farmers has reached the highest level in history, and the problem of aging of agricultural workers has been continuously advanced. Therefore, at the farmer's work site, slow-acting nitrogen fertilizers that minimize the physical burden caused by fertilization operations and have fewer top dressings are widely used. It is one of the representative examples of grassy amine [(CONH ₂ ) ₂ ], and it is used as a slow-acting nitrogen fertilizer, which is a powder which is odorless white, has low solubility in water, and is excellent in no harm to crops. However, the powder of phytonylamine is relatively rapidly inorganicized by microorganisms in the soil (the form in which the phytosterol is decomposed until it is absorbed by the plant), and the inorganic nitrogen component is combined with ammonium sulfate, urea, ammonium chloride and ammonium nitrate. In the same manner, nitrogen-soluble fertilizers which are easily soluble in water are liable to cause loss due to loss, etc., and therefore, the characteristics of the slow-acting properties of the herbicide can not be fully exerted. Further, even if the chemically treated fertilizer is kneaded and contains grassy amine, the fertilizer particles will quickly disintegrate under the conditions of the water, so that the microorganisms involved in the decomposition rapidly decompose and the slow-acting fertilizer cannot be exerted. In general, by controlling the incorporation of phytosamine into the water or soil, the contact between the phytosamine and the microorganism decomposing the phytosamine can be inhibited, thereby reducing the rate of mineralization of the phytonamine and slowing down the fertilizer effect of the physic amine. In order to control the herbicide in the water or the soil, it is necessary to form a granular material having a high particle strength and being difficult to disintegrate in water or soil. As a granulation accelerator (adhesive) in the granulation of fertilizer, it is known to use: bentonite, red molasses, lignosulfonate, starch, strontium powder, sodium sulphate, carboxymethyl cellulose (CMC), Polyvinyl alcohol (PVA), polypropylene decylamine (PAM), gypsum, sodium humate, etc. (Non-Patent Document 1). It is disclosed that a fertilizer can be produced by using the above method to increase the particle strength of the herbicide-containing fertilizer particles and the characteristics that the particles do not disintegrate in water to maintain their shape (water shape stability), and control the dissolution and inhibit the grass. The contact between the guanamine and the microorganism associated with the decomposition thereof is carried out by extrusion molding into a rod shape by a polyvinyl alcohol-bonded oxalylamine powder (Patent Document 1); After the polyvinyl alcohol-bonded oxalylamine powder is extruded into a rod shape and then formed into pellets, the pellet-shaped molded product is deformed into a spherical shape by a high-speed rotary granulator (Patent Document 2); And a composition of an iron compound such as iron sulfate, iron chloride or iron nitrate, and an ammonium phosphate such as monoammonium phosphate, which is granulated by a dish granulator or an extrusion granulator (Patent Document 3); A composition of a grass amide and a gypsum and an aluminum compound such as aluminum sulfate, aluminum chloride or aluminum nitrate, and an ammonium phosphate salt such as ammonium phosphate is granulated by a dish granulator or an extrusion granulator (Patent Document 4); Containing grassy amine and ammonium chloride, diammonium phosphate, gypsum, Granulation (Patent Document 5) by a dish granulator, extrusion granulator. Further, Patent Document 6 discloses an invention which provides a polyvinyl alcohol having a degree of polymerization of 1800 or less and a degree of saponification of 90 mol% or less and a raw material fertilizer (specifically, a processed slag phosphate fertilizer, slag citrate fertilizer) , mixed with phosphate fertilizer, chemically treated fertilizer) and granulated by a dish-shaped granulator, the particle strength is high, especially in granular fertilizer with excellent disintegration in water at low temperature. However, in the method of Patent Document 1, the hardness of the granular grassy amine is 2 kgf or less, and the problem of pulverization occurs in the bag after the formation. In the method of Patent Document 2, the hardness of the globular sulphonamide is 3 kgf or less, and in order to form a spherical shape, it is necessary to manufacture by using two or more types of devices: after mixing by a twin-shaft rotor type mixer, After extrusion molding, a spherical granulator manufactured by Fuji Paudal Co., Ltd. was used as a high-speed rotary granulator. Further, in the methods of Patent Documents 3, 4, and 5, there are disadvantages in that the hardness of the granular fertilizer is 5 to 9 kgf, but the granular fertilizer is higher because the ratio of the additive to the powdery grassy amine is higher. The amount of nitrogen from grassy amines is reduced. Further, the shape stability in water which is directly related to the slow-acting fertilizer effect of the granulated phytosamine is also a result in a short period of time, and is 2 weeks in Patent Document 1, and 1 in Patent Documents 3 and 4. The hour is 10 hours in Patent Document 5, and the slow-acting fertilizer effect in water or soil under the condition of water is insufficient. Further, Patent Document 6 provides a technique for a granular fertilizer which is excellent in disintegration in water, which is different from granular physicoside which is hard to disintegrate in water, for the purpose of the present invention. Patent Document 7 is a coated nitrification inhibitor formulated to produce a coated nitrification inhibitor containing a nitrification inhibitor coated with a coating material and a fertilizer containing ammonia nitrogen and/or urea nitrogen. An example of the granulation method is a method in which a powder such as a nitrification inhibitor or a fertilizer is introduced into a tilting pot type granulator, and an aqueous solution of lignin sulfonate or red molasses is used as a binder, and the squeezing method is used. A method of pressing a granulator, a method of using a mixing granulator such as an Ehrlich mixer, or the like. In Patent Document 8, it is mixed and granulated as a chemical treatment fertilizer and urea which are coated with a film material to cover a nitrification inhibitor and a diluent (however, a form containing a nitrogenous nitrogen and an ammonia nitrogen as a nitrogen component) An example of a granulation method in which a nitrification inhibitor is formed by a granular nitrification inhibitor is described as an example of a granulation method, in which a nitrification inhibitor is introduced into a tilting pot type granulator, and chemical treatment is performed. A powder such as a fertilizer, a method of granulating an aqueous solution of lignosulfonate, red molasses or the like as a binder, a method using an extrusion granulator, a method using a mixing granulator such as an Ehrlich mixer, or the like. However, there is no case where the smear-forming production of oxalidamide is carried out using a tilt-type Ehrlich mixer. [Prior Art Document] [Patent Document 1] Japanese Patent Laid-Open No. Hei 59-169527 (Patent Document 2) Japanese Patent Laid-Open No. Hei 2-145493 (Patent Document 3) Japanese Patent Special Fair 6-2628 Japanese Patent Publication No. Hei 6-2630 [Patent Document 5] Japanese Patent Laid-Open Publication No. Hei 6-2630 [Patent Document 6] Japanese Patent Laid-Open Publication No. Hei No. 2006-21968 [Patent Document 7] Japan Japanese Laid-Open Patent Publication No. 2000-53481 (Patent No. 1, paragraph 0011, Manufacturing Examples 1 and 2) [Non-Patent Document] [Non-Patent Document 1] "Fertilizer Processing" Granulation Accelerator (Binder) BSI Bioscience Research Institute

[Problem to be Solved by the Invention] An object of the present invention is to provide a granular phytochemical which has a high hardness of a fertilizer and which has high disintegration resistance in water or soil and has a stable slow-acting effect. [Means for Solving the Problems] The inventors of the present invention have conducted intensive studies to solve the above problems, and as a result, found that grassy amine contains polyvinyl alcohol or modified polyvinyl alcohol, and is rapidly stirred in a tilt type mixing pot container. The granules are dried and dried to maintain a high hardness of the fertilizer, and the particle shape stability can be kept high under conditions of water or field conditions, so that the present invention can be completed. That is, the gist of the present invention is as follows. (1) A method for producing a granular grassy amine, which comprises a mixture of 0.5 parts by weight or more of a polyvinyl alcohol or a modified polyvinyl alcohol in an inclined type with respect to 100 parts by weight of the mesaconamine powder. After mixing and granulating in a mixing pot container, it is dried. (2) The production method according to the above (1), wherein a mixing pot having a rotation and a mixing tool disposed at a position eccentric from a center position of the mixing pot and rotating independently from the mixing pot are used, and The high-speed stirring mixer of the squeegee disposed inside the mixing pot is subjected to high-speed stirring granulation. (3) The production method according to (2) above, wherein the time of high-speed stirring granulation after adding polyvinyl alcohol or modified polyvinyl alcohol and water is 13 to 60 minutes. [Effects of the Invention] According to the present invention, there is provided a granular phytochemical which has a high hardness of a fertilizer and a high disintegration resistance in water or soil, and which can exert a stable slow-acting effect, thereby reducing crops The number of top dressings in cultivation reduces the burden on fertilization work brought about by the aging of agricultural workers in recent years.

The degree of polymerization of the polyvinyl alcohol or the modified polyvinyl alcohol used in the present invention is 1300 to 2400, the viscosity (mPa·S) is 15 to 50, and the degree of saponification (mol%) is 90 or more, preferably the degree of polymerization. The viscosity is 1700 to 1800, the viscosity (mPa·S) is 20 to 30, and the degree of saponification (mol%) is 98.0 to 99.7, but is not limited to this range. The modified polyvinyl alcohol is not particularly limited, and for example, an acid-modified polyvinyl alcohol (hereinafter also referred to as "acid-modified PVA"), an ethylene-modified polyvinyl alcohol, or the like can be used. The acid-modified PVA is a vinyl alcohol-based polymer containing a specific amount of a carboxyl group or a sulfonic acid group, the former being referred to as a carboxylic acid-modified PVA, and the latter being referred to as a sulfonic acid-modified PVA. The carboxylic acid-modified PVA can be produced by introducing a compound having a carboxyl group into a polyvinyl alcohol by a conventionally known method. Examples of the compound having a carboxyl group include fumaric acid, maleic acid, itaconic acid, maleic anhydride, phthalic anhydride, trimellitic anhydride, acrylic acid, and the like. The sulfonic acid-modified PVA can be produced by introducing a compound having a sulfonic acid group into a polyvinyl alcohol by a conventionally known method. Examples of the compound having a sulfonic acid group include ethylenesulfonic acid, propylenesulfonic acid, methacrylic acid, 2-propenylamine-2-methylpropanesulfonic acid, and the like. The ethylene-modified polyvinyl alcohol can be obtained by saponifying a copolymer of vinyl ester and ethylene. Examples of the vinyl ester include vinyl formate, vinyl acetate, vinyl propionate, and vinyl pivalate. The content of the polyvinyl alcohol or the modified polyvinyl alcohol in the granular grass phthalamide of the present invention is 0.5 parts by weight or more based on 100 parts by weight of the grass amide powder, from the viewpoint of ensuring the hardness of the particles and the shape stability in the water. It is preferably 1 to 10 parts by weight, more preferably 1 to 2 parts by weight. When the content of the polyvinyl alcohol or the modified polyvinyl alcohol is less than 0.5 part by weight, the effect as a binder at the time of granulation is weakened, and the effect of improving the hardness of the particles after granulation is lowered. On the other hand, if it exceeds 10 parts by weight, The nitrogen component of the granular grassy amine is reduced, and the quality of the component is lowered. Hereinafter, preferred aspects of the method for producing the granular grassy amine of the present invention will be described. First, polyvinyl alcohol or modified polyvinyl alcohol is dissolved in the following points. While stirring the normal temperature water, the polyvinyl alcohol or the modified polyvinyl alcohol which was measured was slowly introduced, and heating was started while maintaining the stirring. After the liquid temperature reached 90 to 95 ° C, stirring was continued for 1 to 2 hours while maintaining the temperature. Thereafter, the heat source is turned off, the stirring force is decreased, and the mixture is slowly cooled to prepare a certain concentration of polyvinyl alcohol or a modified polyvinyl alcohol aqueous solution. The concentration of the polyvinyl alcohol or the modified polyvinyl alcohol liquid is not particularly limited, and is preferably 10 to 15% liquid as an operational viscosity or a fertilizer. Next, the polyvinyl alcohol or the modified polyvinyl alcohol liquid prepared by dissolving is slowly added in a weight ratio of 0.5 parts by weight or more with respect to 100 parts by weight of the grass amide powder added to the granulator, in a tilt type mixing pot. The container was subjected to high-speed stirring granulation to dry the granules. In order to make the bonding force between the raw material powders uniform, it is preferable to add the polyvinyl alcohol or the modified polyvinyl alcohol added to the grassy amine powder in a liquid form, but in the case where the amount of addition is small, the powder may also be used. Add it. Further, in addition to the grass amide powder, mineral powder or the like may be added in order to adjust the bulk specific gravity or prevent suspension in water. The granulator used for the granulation is a high-speed stirring granulator (hereinafter referred to as a slant-type Alpha mixer) manufactured by Eirich Co., Ltd. of Japan, which has a slanting type mixing pot container, and the details thereof are described in Japanese Patent No. 4406328. Bulletin, granulation by the high-performance mixer featuring precision and high-efficiency production "Basic and application of powder technology" Chemical device September issue, Industrial Communications Agency, 2005. Fig. 1 is a schematic perspective view showing an example of a high-speed stirring mixer used in the practice of the present invention. As shown in Fig. 1, the high-speed agitating mixer 1 used in the present invention includes a mixing pot 2 that accommodates a stirred object and rotates in a state of accommodating a stirred object; a mixing tool (also referred to as an "aggitator") 3, which is located inside the mixing pot 2 and disposed at a position eccentric from the center position of the mixing pot 2, rotates independently of the mixing pot 2, and a squeegee 4 which is fixed and disposed inside the mixing pot 2. The mixing pot 2 and the mixing tool 3 can independently set the rotation direction and the number of revolutions, and the rotation direction of the mixing pot 2 and the mixing tool 3 can be set to the opposite direction, and the mixing pot 2 and the mixing tool 3 can be rotated. The two stirring methods in the case where the directions are set to the same direction are stirred. The outline of the operation sequence is as follows. After the fertilizer raw material is put into the apparatus, the peripheral speed of the rotor (usually 1 to 10 m/s, preferably 2 to 6 m/s) is increased and mixed to homogenize the raw material. Next, polyvinyl alcohol or modified polyvinyl alcohol solution and water are added. The peripheral speed of the rotor (usually 10 to 40 m/s, preferably 15 to 35 m/s) is increased to carry out dispersion and granulation. The time for the high-speed stirring granulation after the addition of the polyvinyl alcohol, the modified polyvinyl alcohol, and the water is preferably 13 minutes or longer from the viewpoint of the production rate of the target particle diameter, and prevents the particles from adhering to each other. In terms of a larger block state, it is preferably 60 minutes or less. The time for the above high-speed stirring granulation is further preferably from 15 to 45 minutes, more preferably from 20 to 45 minutes. Thereafter, the peripheral speed of the rotor is lowered by 1 to 10 m/s, preferably 2 to 6 m/s, and finally discharged from the mixer. The obtained granules were dried by heating in a drier to produce granulated grass amide. The drying temperature is usually 65 to 130 ° C, preferably 90 to 120 ° C. The shape and size of the granular grassy amine of the present invention are not particularly limited, and are usually in the form of particles having a particle diameter in the range of 1 to 10 mm. In particular, in the range of the particle diameter of 2 to 4 mm, workability such as scattering during fertilization can be reduced, and the workability is good and preferable. Further, in the case where the granulated composition of the present invention is blended with other chemically treated fertilizers, it may be less classified and more preferably. [Examples] Hereinafter, the present invention will be described in detail by way of Examples and Comparative Examples, but the present invention is not limited to the Examples. Polyvinyl alcohol (PVA) or modified polyvinyl alcohol (modified PVA) uses a purity of 94.00% or more. The amount (%) added is expressed by a weight ratio with respect to the herbamine powder. (Example 1) A granulated phytosine containing modified PVA of 1% was produced by a tilt-type Ehrlich mixer. A 5 L beaker to which 2.7 parts by weight of water was added was immersed in a hot water bath at normal temperature, and stirring was set. The motor was slowly added with 0.3 parts by weight of modified polyvinyl alcohol (manufactured by Kuraray Co., Ltd., degree of polymerization 1300, degree of saponification 92 to 98) while stirring the water. The mixture was heated while stirring, and after reaching 95 ° C, the mixture was stirred for 2 hours while maintaining the temperature. It was confirmed that the modified PVA was completely dissolved, the stirring strength was reduced, and the cooling was slowly performed to prepare a 10% liquid. 20 parts by weight of the herbicide powder was placed in a mixing pot container of a tilt-type Ehrlich mixer (manufactured by Eirich Co., Ltd., Wanmauli mixer R02; the same applies hereinafter), and 2 parts by weight of the prepared modified PVA10 was added. % liquid, mixed for 1 minute and 15 seconds at a rotor speed of 6 m/s (900 rpm). Next, add 3.53 parts by weight of water, disperse and granulate at a peripheral speed of 19 m/s (3000 rpm) of the rotor for 23 minutes, and reduce the peripheral speed of the rotor to 6 m/s (900 rpm) for 1 minute and 30 seconds. After that, let it drain. The discharged granules were dried by a drier at 105 ° C for 4 hours, and then sieved to a particle diameter of 2 to 4 mm to obtain a granulated phytoestramine having a modified PVA of 1%. (Example 2) Production of PVA 2% granular physicamine by a tilt-type Ehrlich mixer A 10 L beaker to which 5.4 parts by weight of water was added was immersed in a hot water bath at normal temperature, and a stirring motor was provided. 0.6 parts by weight of PVA was slowly added while stirring the water. The mixture was heated while stirring, and after reaching 95 ° C, the mixture was stirred for 2 hours while maintaining the temperature. It was confirmed that the PVA was completely dissolved, and the stirring strength was slowed down to prepare a 10% liquid. After 20 parts by weight of the herbicide powder was placed in the mixing pot container of the inclined Ehrlich mixer, 4 parts by weight of the prepared PVA 10% liquid was added, and the rotor was mixed at a peripheral speed of 6 m/s (900 rpm). minute. Further, 1.66 parts by weight of water was added, and the rotor was dispersed at a peripheral speed of 19 m/s (3000 rpm) for 21 minutes, and the peripheral speed of the rotor was lowered to 6 m/s (900 rpm) for 2 minutes. It is discharged. The discharged granules were dried in a drier at 105 ° C for 4 hours, and sieved to a particle diameter of 2 to 4 mm to obtain a granulated physicamine added with 2% of PVA. (Example 3) Production of PVA 1% granulated grass phthalamide by a tilt-type Ehrlich mixer 20 parts by weight of oxalidamide powder was placed in a mixing pot container of a tilt-type Ehrlich mixer, and 2 parts by weight was added. The PVA 10% liquid prepared in Example 2 was mixed at a peripheral speed of 6 m/s (900 rpm) of the rotor for 1 minute. Further, 3.63 parts by weight of water was added, and the rotor was dispersed and granulated at a peripheral speed of 19 m/s (3000 rpm) for 22 minutes, and the peripheral speed of the rotor was lowered to 6 m/s (900 rpm) for 2 minutes. discharge. The discharged granules were dried in a drier at 105 ° C for 4 hours, and then sieved to a particle diameter of 2 to 4 mm to obtain a granulated physicamine added with 1% of PVA. (Example 4) Manufacture of granular physicamine added with modified PVA by a tilt-type Ehrlich mixer. A 10 L beaker to which 4.8 parts by weight of water was added was immersed in a hot water bath at normal temperature, and stirring was set. The motor was slowly added with 1.2 parts by weight of the modified polyvinyl alcohol while stirring the water. The mixture was heated while stirring, and after reaching 95 ° C, the mixture was stirred for 2 hours while maintaining the temperature. It was confirmed that the modified PVA was completely dissolved, the stirring strength was reduced, and the cooling was slowly performed to prepare a 20% liquid. After 20 parts by weight of the herbicide powder was put into the mixing pot container of the inclined Ehrlich mixer, 4 parts by weight of the prepared modified PVA 20% liquid was added, and the rotor was mixed at a peripheral speed of 6 m/s (900 rpm). 1 minute. Further, 2.3 parts by weight of water was added, and the rotor was dispersed at a peripheral speed of 19 m/s (3000 rpm) for 18 minutes, and the peripheral speed of the rotor was lowered to 6 m/s (900 rpm) for 2 minutes. discharge. The discharged granules were dried in a drier at 105 ° C for 4 hours, and then sieved to a particle diameter of 2 to 4 mm to obtain a granulated physicamine having a modified PVA of 4%. (Example 5) Manufacture of 20 parts by weight of phytonylamine powder added with modified PVA by adding a modified PVA 0.5% granules to a mixing pot container of an inclined Ehrlich mixer, and adding 1 part by weight of the modified PVA 10% liquid prepared in Example 1 was mixed at a peripheral speed of 6 m/s (900 rpm) of the rotor for 1 minute and 15 seconds. Next, add 4.4 parts by weight of water, disperse and granulate at a peripheral speed of 19 m/s (3000 rpm) for 23 minutes, and reduce the peripheral speed of the rotor to 6 m/s (900 rpm) for 1 minute and 30 seconds. Let it drain. The discharged granules were dried in a drier at 105 ° C for 4 hours, and then sieved to a particle diameter of 2 to 4 mm to obtain a granular physicamine having a modified PVA of 0.5%. (Example 6) Production of PVA 0.5% of granulated physicamine by a tilted Ehrlich mixer 20 parts by weight of phytonamide powder was placed in a mixing pot container of a tilted Ehrlich mixer, and 1 weight was added. The PVA 10% liquid prepared in Example 2 was mixed at a peripheral speed of 6 m/s (900 rpm) for 1 minute and 15 seconds. Next, add 4.4 parts by weight of water, disperse and granulate at a peripheral speed of 19 m/s (3000 rpm) for 23 minutes, and reduce the peripheral speed of the rotor to 6 m/s (900 rpm) for 1 minute and 30 seconds. Let it drain. The discharged granules were dried in a drier at 105 ° C for 4 hours, and then sieved to a particle diameter of 2 to 4 mm to obtain a granular phytoestramine having a PVA of 0.5%. (Comparative Example 1) Manufacture of 20 parts by weight of phytonylamine powder by adding a modified PVA of 1% by adding a modified PVA to a horizontal type Ai's mixer (manufactured by Eirich Co., Ltd., Wan Mali, Japan) After mixing the pot container of the mixer type DE14), 2 parts by weight of the modified PVA 10% liquid prepared in Example 1 was added, and the mixture was mixed at a peripheral speed of 13 m/s (600 rpm) for 1 minute. Further, 3.65 parts by weight of water was added, and the rotor was dispersed at a peripheral speed of 31 m/s (1500 rpm) for 25 minutes, and the peripheral speed of the rotor was lowered to 13 m/s (600 rpm) for 2 minutes, and then treated. discharge. The discharged granules were dried in a drier at 105 ° C for 4 hours, and then sieved to a particle diameter of 2 to 4 mm to obtain a granulated phytoestramine having a modified PVA of 1%. (Comparative Example 2) Production of 20 parts by weight of phytonylamine powder by adding a modified PVA 1% by adding a modified PVA to a dish-shaped granulator (motor drive manufactured by Sumitomo Heavy Industries, Ltd.) After the pot container of the self-made pot granulator, 2 parts by weight of the modified PVA 10% liquid prepared in Example 1 was added, and the mixture was mixed at a peripheral speed of 1.6 m/s (40 rpm) for 15 minutes. Further, while adding 8.02 parts by weight of water slowly, the pellet was granulated at a peripheral speed of 1.6 m/s (40 rpm) for 30 minutes. The granulated granules were dried in a drier at 105 ° C for 4 hours, and sieved into a particle size of 2 to 4 mm to obtain a granulated phytoestramine having a modified PVA of 1%. (Comparative Example 3) Manufacture of 20 parts by weight of powdered oxalidamide by adding a modified PVA of 1% by weight to a biaxial rotor type mixer (manufactured by Fuji Paudal Co., Ltd.) by an extrusion granulator 2 parts by weight of the modified PVA 10% liquid prepared in Example 1 and 6.46 parts by weight of water were sufficiently kneaded. The kneaded product was added to a screw extrusion granulator (manufactured by Fuji Paudal Co., Ltd., screen mesh 1.2 mm), and subjected to extrusion granulation. The granules extruded from the sieve mesh were dried in a drier at 105 ° C for 24 hours, and then cut into a length of 0.5 to 1 cm to obtain granulated grass-like oxaloin having a modified PVA of 1%. (Comparative Example 4) Production of granular grass amide by a tilt-type Ehrlich mixer (no granulation accelerator added) 20 parts by weight of oxalic acid powder was placed in a mixing pot container of a tilt-type Ehrlich mixer, and then added 3.81 parts by weight of water was mixed for 1 minute at a rotor peripheral speed of 6 m/s (900 rpm). Further, 1.82 parts by weight of water was added, dispersed and granulated at a peripheral speed of 19 m/s (3000 rpm) of the rotor for 32 minutes, and the peripheral speed of the rotor was lowered to 6 m/s (900 rpm) for 2 minutes, and then treated. discharge. The discharged granules were dried in a dryer at 105 ° C for 4 hours, and sieved into a particle size of 2 to 4 mm to obtain granulated grass amide. (Comparative Example 5) Production of 25% of granulated grass amide by adding an amylose mixture by tilting an Ehrlich mixer 20 parts by weight of physic acid amine powder and 0.4 part by weight of starch into a mixing pot container of a tilt type Ehrlich mixer Thereafter, the mixture was mixed at a peripheral speed of 6 m/s (900 rpm) for 1 minute. Next, 5.1 parts by weight of water was added and mixed at a peripheral speed of 6 m/s (900 rpm) of the rotor for 1 minute. Further, the rotor was dispersed and granulated at a peripheral speed of 19 m/s (3000 rpm) for 25 minutes, and the peripheral speed of the rotor was lowered to 6 m/s (900 rpm) for 2 minutes, and then discharged. The discharged granules were dried in a drier at 105 ° C for 4 hours, and then sieved to a particle diameter of 2 to 4 mm to obtain 2 g of granulated grass amide. (Comparative Example 6) Production of 20 parts by weight of phytonamide powder and 0.4 part by weight of CMC added to slanted AI by adding carboxymethylcellulose (CMC) 2% granules of grassy amine by a tilt-type Ehrlich mixer After mixing the pots of the mixer, the rotor was mixed at a peripheral speed of 6 m/s (900 rpm) for 1 minute. Next, 5.1 parts by weight of water was added and mixed at a peripheral speed of 6 m/s (900 rpm) of the rotor for 1 minute. Further, the rotor was dispersed and granulated at a peripheral speed of 19 m/s (3000 rpm) for 23 minutes, and the peripheral speed of the rotor was lowered to 6 m/s (900 rpm) for 2 minutes, and then discharged. The discharged granules were dried in a drier at 105 ° C for 4 hours, and then sieved to a particle diameter of 2 to 4 mm to obtain a granulated grass amide which was added with 2% of CMC. (Comparative Example 7) 20 parts by weight of oxaloin powder and 1.25 parts by weight of mineral (basalt powder), 0.42 parts by weight, of mineral, ferric sulfate, and phosphoric acid granules were produced by a tilted Ehrlich mixer. The iron sulfate and 2.5 parts by weight of the phosphoric acid liquid were placed in a mixing pot container of a tilt-type Alpha mixer, and then mixed at a peripheral speed of 6 m/s (900 rpm) for 1 minute. Next, 3.11 parts by weight of water was added and mixed at a peripheral speed of 6 m/s (900 rpm) of the rotor for 1 minute. Further, the rotor was dispersed and granulated at a peripheral speed of 19 m/s (3000 rpm) for 15.5 minutes, and the peripheral speed of the rotor was lowered to 6 m/s (900 rpm) for 2.75 minutes, and then discharged. The discharged granules were dried in a dryer at 105 ° C for 4 hours, and then sieved to a particle diameter of 2 to 4 mm to obtain granulated physicamine added with iron sulfate or phosphoric acid. (Comparative Example 8) Manufacture of 20 parts by weight of phytonylamine powder added with modified PVA by adding a modified PVA of 0.2% to the mixing pot container of the inclined Ehrlich mixer, and adding 0.4 parts by weight of the modified PVA 10% liquid prepared in Example 1 was mixed at a peripheral speed of 6 m/s (900 rpm) of the rotor for 1 minute and 15 seconds. Next, add 4.88 parts by weight of water, disperse and granulate at a peripheral speed of 19 m/s (3000 rpm) for 23 minutes, and reduce the peripheral speed of the rotor to 6 m/s (900 rpm) for 1 minute and 30 seconds. Let it drain. The discharged granules were dried in a drier at 105 ° C for 4 hours, and then sieved to a particle diameter of 2 to 4 mm to obtain a granular phytoestramine having a modified PVA of 0.2%. (Comparative Example 9) Production of 20 parts by weight of phytonylamine powder by adding a PVA of 0.2% to the mixing pot container of the inclined Ehrlich mixer by a tilt type Ehrlich mixer The PVA 10% liquid prepared in Example 2 was mixed at a peripheral speed of 6 m/s (900 rpm) for 1 minute and 15 seconds. Next, add 4.88 parts by weight of water, disperse and granulate at a peripheral speed of 19 m/s (3000 rpm) for 23 minutes, and reduce the peripheral speed of the rotor to 6 m/s (900 rpm) for 1 minute and 30 seconds. Let it drain. The discharged granules were dried in a drier at 105 ° C for 4 hours, and then sieved to a particle diameter of 2 to 4 mm to obtain a granular physicamine having a PVA of 0.2%. (Evaluation Test 1) Each of the granulated physicosides obtained in Examples 1 to 6 and Comparative Examples 1 to 9 was investigated for hardness and water shape stability as evaluation of a slow-acting nitrogen fertilizer. The test methods are as follows. Further, in the test described below, among the obtained granular fertilizers, those having a particle diameter of 2.85 to 3.50 mm are used. Moisture: The obtained granulated grass amide is pulverized by a pulverizer, and about 5 g of all the powder passing through the 0.5 mm sieve is accurately measured, and dried in a dryer at 105 ° C for 3 hours, and the weight of the reduction is divided by the weight of the sample. And multiply by 100. The results are shown in Table 1, Table 2, and Table 3. Hardness: The particle hardness of 20 granules of phytochlorin was measured using a house-type hardness tester, and the results are shown in Table 1, Table 2, and Table 3. Shape stability in water: 20 granules of phytoylamine were added to a differentiation tube containing 50 ml of water, and then placed in a thermostat at 25 ° C to observe the water injection, 3 days, 14 days, 28 days. The state of disintegration of the grain surface after 56 days. The disintegration state is recorded as: 0: no disintegration, 1: disintegration of the surface of the particle is 10% or less, 2: disintegration of the surface of the particle is 11 to 30%, and 3: disintegration of the surface of the particle is 31 to 50%, 4: The disintegration of the surface of the granules is 51 to 70%, the disintegration of the surface of the granules is 71 to 90%, and the disintegration of the surface of the granules is 91 to 100%, as shown in Table 1, Table 2, and Table 3. [Table 1] As shown in the results shown in Table 1, in the method using the granulation apparatus of Comparative Examples 1 to 3, the hardness of the fertilizer particles was 3.1 kgf or less, whereas in the first embodiment, it was 6.3 kgf, by the method of the present invention, Granular grass amide can be produced with higher hardness. Further, regarding the shape stability in water, in Comparative Examples 1 to 3, the surface of the particles began to disintegrate after water injection, and 31% or more of the surface of the particles disintegrated after 56 days, whereas in Example 1, even after 56 days. Found disintegration. [Table 2] The results of comparing the granulation accelerator using a tilt type Ehrlich mixer are shown in Table 2. In Comparative Example 4, the hardness of the fertilizer particles to which the granulation accelerator was not added was 3 kgf or less. In Comparative Examples 5 and 6, it was 5.3 and 4.5 kgf, which was lower than that of Example 2. In Comparative Example 7, it was 6.6 kgf, which was not significantly different from Example 2. However, regarding the shape stability in water, no disintegration of the particle surface was observed immediately after the water injection in Comparative Example 4, but it continued to disintegrate after 3 days, and 51% or more of the particle surface disintegrated after 56 days. In Comparative Examples 5, 6, and 7, although the hardness was higher than that of Comparative Example 4, the surface of the granules began to disintegrate immediately after the water injection, and 51% or more of the surface of the granules disintegrated after 56 days. On the other hand, in Example 2, no disintegration was observed even after 56 days. [table 3] As shown by the results shown in Table 3, the addition amount of PVA or modified PVA was 0.2%. The hardness of the fertilizer of Comparative Examples 8 and 9 was 2.8 kgf, and no disintegration was observed from the water injection after the water injection. On the other hand, the hardness of Examples 1 to 6 in which the amount of PVA or modified PVA added was 0.5% or more was 4.5 kgf or more, and the shape stability in water was also high. As described above, by the method of the present invention, it is possible to produce a granular grassy amine which has a high hardness, particularly, which is difficult to disintegrate in water and has high shape stability. (Evaluation test 2: Inorganic test at 25 ° C under paddy field conditions) (1) Objective To study the addition of modified PVA 1% granular physicamine (Example 1) and borrowed by a tilt-type Ehrlich mixer Mineralization of mineral, ferric sulfate, and phosphoric acid granules (Comparative Example 7) produced by a tilt-type Ehrlich mixer under water-field conditions. (2) Test method The tested herbicide-containing fertilizer granules (24 mg of nitrogen equivalent to 4 capsules) were mixed in 60 g of dry soil [Jupbo paddy soil (sand loam soil)], and added to a 200 ml beaker. Further, regarding phosphoric acid and potassium, monopotassium phosphate and potassium chloride were added as ingredients to add 12 mg per 60 g of dry soil. Next, deionized water was added so as to be 140% of the maximum water capacity of the test soil, and after covering with a polyethylene film, it was allowed to stand in a constant temperature library at 25 ° C for a specific period of time. After a certain period of time, the sample in the beaker was shaken and filtered with 300 ml of a 10% potassium chloride aqueous solution, and inorganic nitrogen (the total amount of NH ₄ and NO ₃ ) was quantified by Conway diffusion method to calculate the inorganicization rate. (3) Results The results are shown in Table 4 and Figure 2. [Table 4] As can be seen from Table 4 and Figure 2, the addition of modified PVA 1% granular phytosamine produced by a tilted Ehrlich mixer is compared to the addition of minerals, ferric sulphate, and phosphoric acid produced by a tilted Ehrlich mixer. Granular grass amide, which is slower in mineralization, exerts a slow-acting fertilizer effect. That is, it is clear that the added modified PVA of the product of the present invention has a hardness of no greater than that of the added mineral, ferric sulfate, and phosphoric acid granules produced by the inclined Ehrlich mixer. The difference is, but the shape stability in the water is high, and the slow-acting fertilizer effect is exerted. (Example 7) Comparison of granulation time 20 parts by weight of phytonamide powder was placed in a mixing pot container of a tilt-type Ehrlich mixer (manufactured by Eirich Co., Ltd., Wanmauli Mixer R02 type), and 2 parts by weight was added. The modified PVA 10% liquid prepared in Example 1 was mixed at a peripheral speed of 6 m/s (900 rpm) of the rotor for 1 minute. Next, add 3.20 parts by weight of water, disperse and granulate at a peripheral speed of 19 m/s (3000 rpm) of the rotor for 5 minutes, 10 minutes or 15 minutes, and reduce the peripheral speed of the rotor to 6 m/s (900 rpm). After 30 seconds, let it drain. The discharged granules were dried in a dryer at 105 ° C for 4 hours, and then the particle size distribution was measured. The measurement results of the particle size distribution (the weight of the 1 mm sieve and the 1 mm, 2 mm, and 4 mm sieves divided by the total weight, expressed as a percentage) are shown in Table 5. [table 5] As shown in Table 5, when the granulation time after adding the modified PVA and water was 5 minutes and 10 minutes, the granular phytosamine was 2 mm to 4 mm, whereas the granulation was 15 minutes. 50% or more of 2 mm to 4 mm of granular grassy amine can be obtained.

1‧‧‧High speed mixing mixer

2‧‧‧ mixing pot

3‧‧‧Mixed tools

4‧‧‧Scraper

Fig. 1 is a schematic perspective view showing an example of a high-speed stirring mixer used in the practice of the present invention. Fig. 2 is a graph showing the results of an inorganication test at 25 ° C under paddy conditions.

Claims (3)

A method for producing a granulated phytoestramine, which comprises containing a mixture of 0.5 parts by weight or more of polyvinyl alcohol or modified polyvinyl alcohol in a tilt type mixing pot container with respect to 100 parts by weight of the grass amide powder. After high speed stirring granulation, it is dried. The manufacturing method of claim 1, wherein the high-speed agitating mixer is equipped with a high-speed stirring and mixing machine, and the high-speed stirring mixer has a rotating mixing pot and is disposed at an eccentric position from a center of the mixing pot and independently of the mixing pot. A rotating mixing tool and a squeegee fixed and disposed inside the mixing pot. The production method of claim 2, wherein the high-speed stirring granulation after adding polyvinyl alcohol or modified polyvinyl alcohol and water is carried out for 13 to 60 minutes.