JPS5844640B2 - Gantetsu TI - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention is applicable to the production of a composite fertilizer by blending nitrogenous fertilizers such as ammonia sulfate and urea with basic phosphoric acid fertilizers, potassium fertilizers, or both;
Regarding the fertilizer containing iron-containing Ti-based substances, which is made by mixing each unitary fertilizer known as K) with a non-unitary iron-containing Ti substance (if necessary, further mixing an agricultural chemical active ingredient). Its purpose is to utilize a solid solution of Fe, which has a strong ability to capture hydrogen sulfide, and Ti, which has the ability to catalyze the photochemical nitrification of ammonia nitrogen, in compound fertilizers and in the soil to which it is fertilized. The aim is to obtain a highly fertilizing product that can control the volatilization rate of ammonia and hydrogen sulfide.

S, which is an essential component of plants, is mainly contained in organic matter as a pre-protein in soil, and is approximately one order of magnitude less than N, and the same amount as P can maintain balance as a suitable growing place for crops. However, in recent years, large amounts of fertilizers containing sulfuric acid roots have been applied without causing S deficiency in crops, and on the contrary, roots of paddy rice etc. have become a problem, and this is due to S being reduced. This is due to hydrogen sulfide produced by
In this case, it is known that application of Fe-based substances detoxifies hydrogen sulfide by converting it into iron sulfide, contributing to suitable soil conditions.

The present inventor has developed a magnetic fertilizer (Patent No. 306,711.
2395J, Patent No. 317898, “Special Publication Showa 4O-11
328J, Patent No. 319970゜ “Special Publication Showa 4l-391
5J, British Patent No. 1065864, West German Patent No. 1273403, Italian Patent No. 757751, French Patent No. 970617).

It is also known that ammonia nitrogen applied to the soil and ammonia nitrogen generated by decomposition of organic matter can be absorbed by crops as is, but much of it is oxidized to nitrate nitrogen and absorbed.

By the way, the boiling point of ammonia is 33.4℃, and the boiling point of nitric acid is 123℃.Generally, the more ammonia-based substances are oxidized, the higher their boiling points, so during high summer temperatures or in tropical regions, If the nitrification action (oxidation action) of ammonia nitrogen does not progress, the volatility of nitrogen will increase, resulting in loss, and if the reduction is reversed, gaseous forms such as NOl and N2 will be produced. It becomes nitrogen and dissipates into the air, resulting in a large elemental loss.

The above correlation is shown as follows.

(←Oxidation, reduction) It is known that Ti promotes the action of rhizobia and is important as a catalyst for photochemical nitrification of ammonia nitrogen during high temperatures in summer and in tropical regions.

As a result of many years of research, the present invention has revealed that a solid solution of Ti, which is known as a photochemical nitrification catalyst for ammonia nitrogen, and the above-mentioned Fe-based substance exhibits photochemical nitrification catalyst ability (effect) in compound fertilizers and/or especially in fertilized soil. This was made based on the discovery that this was significantly greater than when using a conventionally known Ti single element system (Ti, T102) material.

The non-mono-component iron-containing Ti material referred to in the present invention is F eT
It refers to i03 alone or a solid solution (mixed crystal, phenocryst) of Fe203 with one or both of TiO2 and FeTio3.

Alternatively, it may be a solid solution of one or both of TiO2 and FeTiO3 and ferrate.

In this case, ferrates refer to ferrites, perferrites, and ferrates containing Fe", Fe"Fe6+, and the metals forming the salts include alkali and alkaline earth metals, silver, lead,
You can choose from cobalt nickel and iron.

In addition, iron nitride (iron nitride salt) or iron phosphide (iron phosphide salt) may be substituted in place of the above iron oxide and ferrate, and the above TiO2, FeTiOs
Alternatively, titanium nitride (titanium iron nitride) or titanium phosphide (titanium iron phosphide) may be substituted.

In addition, titanate ions and Fe-based substances (Fe, Fe01Fe2
03, Fe3O4, general ferrates, iron hydroxide, iron oxyhydroxide, etc.).

In short, it refers to a solid solution consisting of at least one substance of titanium oxide, titanium nitride, and titanium phosphide and at least one substance of iron oxide, iron nitride, and iron phosphide.

Among the above, easily available iron oxides, ferrates, metal nitrides (iron nitride-based materials), metal phosphides (iron phosphide-based materials), and titanium-based materials include Fe2O3, Fe3O4, K2FeO4, S
r2Feo4, BaFe0+, CaFe04
, MgFe04, ZnFe04, TiN1Fe2N.

These include Fe3P2, Ti, TiO2, FeTiO3, and others are indispensable to obtain.
Solution temperatures and techniques for forming mixed crystals between Fe-based materials and Fe-based materials are also known.

In addition, a small amount of Si, Ca, and Mg are added to the above iron-containing Ti-based materials.
, A12, Mn, Cr, V, P, S, etc., does not change the effect to the extent that it affects the effect, so selection of the material is relatively easy.

In the present invention, the agrochemical active ingredients that can be mixed together as necessary refer to so-called agrochemical fertilizers containing active ingredients such as insecticides, fungicides, and herbicides, or essentially fertilizers and agrochemicals. It means that it encompasses what is imaged.

More specifically, fertilizer adjuvants, agricultural pesticide active ingredients,
Examples of pesticide adjuvants include bentonite, sericite, diatomaceous earth, Oya stone, polyvinyl alcohol, krillium, pentachlorphenol, heptachlor,
These include aldrin, benzene hexachloride, β-indole acetic acid, and surfactants.

It is also the gist that the effect can be further enhanced by applying excitation treatment if necessary.

Next, the present invention will be explained with reference to experimental examples.

Experimental Example 1 As a control, an experiment was conducted to compare the effects of a single titanium material such as Ti1TiO2 and the iron-containing Ti material according to the present invention. The results are as follows: (A) Ti (control) (B) T
lO2 (above) (C) FeTiO3 (solid solution) (D) TiO2-Fe304 (above) (E) TiO2-FeTi03-Fe203 (above)
V) TiN-Fe2N (above) (G) TiO2-FeTi03-Fe3P2 (above) Each of the seven types of compositions was applied alone, and each of these seven types of composition was added with 0.05P per container of nitrogen fertilizer. 0.04
P, phosphate fertilizer 0.071? , and potassium fertilizer 0.145' were applied together with the triad.

Each 401 pieces of air-dried paddy soil was used as the test soil, and this was placed in a long and narrow cylinder with a bottom (inner diameter 3.2Cr, height 10CrIL).
Add water, stir well, remove foam, add more water to make the clean water 1. After leaving it at 40℃ for 3 weeks while supplementing the evaporated water, measure the ammonia nitrogen and nitrate nitrogen produced. The results are shown in Table 1.

As is clear from Table 1 above, when the composition of the present invention shown in Experimental Example 4.5.6.7.8 was applied, the nitrate nitrogen conversion rate was lower than that in Experimental Example 2.3. This will give you an advantage.

Also, as is clear from the comparison with Experimental Example 10.11°, the fertilizer of the present invention also has Experimental Examples 12.13.14.15.
16, it was confirmed that this effect was exhibited.

Experimental example 2 Ammonium sulfate (N, 20%) 46.12 and lime superphosphate (2205
16%) 38.51 and potassium sulfate (K2048%) 15
．． Compound fertilizer containing 41 (N:P: value 3:2:2)
．． 4) (A) applied to 100 gr in Experimental Example 1,
Mix (B), (C), (D), (6), and (G) to 20g each to make a blended fertilizer with 20g of mixed mulch and 100g of gourd, and at a temperature of 3.
Table 2 shows the results of a follow-up comparative experiment of changes in the amount of nitrogen over time under conditions of 0°C and 80% humidity.

As is clear from Table 2 above, compared to Experimental Example 2.3, nitrogen volatilization was suppressed in the case of the compound fertilizer containing the composition of the present invention shown in Experimental Example 4.5.6.7.8. We have an advantage in this area.

The iron-containing Ti-based solid solution material used in this experimental example and the examples described below was manufactured by the following method.

That is, (C) FeTiO3 270 parts of TiO made into as fine a powder as possible and 30 parts of FeO were mixed homogeneously and heated at 1880°C in an electric furnace in a helium atmosphere.
The mixture was heated and melted for 1 hour to obtain a phenocryst-like FeTiO3 lump, which was then crushed using a crusher and a ball mill, and the powder particle size was adjusted so that it could pass through a 50 mesh sieve.

(D) Ti02-Fe3O4 275 parts of TiO made into as fine a powder as possible and Fe3o4
25 parts were mixed homogeneously, and the following steps were produced by the same method as above (Q).

(E) TiO2-FeTi03-Fe203 as fine powder as possible, 280 parts of Ti0, 1033 parts of FeT, Fe
20317 parts were mixed homogeneously, and the subsequent steps were performed using the upper Wiff.
It was produced by the same method as iC1.

(F) TiN-Fe2N Metal Ti and metal Fe are used as raw materials, and these are made into fine powder TiN and Fe2N by the Ishibashi method (Japanese Patent Publication No. 43-28305, Technology), and both are mixed at a ratio of 8:2. Mix the proportions homogeneously, and the subsequent steps follow the above (q and 1 method).
However, only the heat treatment temperature in the electric furnace was 3020°C.

(G) Ti02-FeTi03-Fe3P2 Fes produced by heat treating ferrous phosphate to remove crystallization water and then subjecting it to reduction treatment with carbon as shown in the following chemical reaction formula.
P 2 fine powder and Fe3 (PO4)2 + 8 C
=Fe3P2+8 c.

Fine powders of TiO2 and FeTiO3 were homogeneously mixed at a ratio of 2:1, and the subsequent steps were carried out using the same method as above (q).

Next, several embodiments showing the excellent effects of the fertilizer and iron-containing Ti-based solid solution material of the present invention will be described in more detail.

Example 1 Bikuni soybean was used as a crop in which the effectiveness of nitrogenous fertilizer significantly affects the activation of rhizobia, and the following: (A) Ti (control) (B) Ti
O2 (above) (C) FeTi03 (solid solution) (
D) T102 Fe3O4 (above) (E) T i 02 F eT i03 F e
203 (above) *(F) T i N −F e
2N (solid solution) (G) Ti02-
Seven types of compositions of FeTiO3-Fe3P2 (above) mixed with nitrogen, phosphoric acid, and potassium fertilizers were applied.

Kanto volcanic ash field deep soil was used as the test soil, and 1/50,000
Pot cultivation trials were conducted using anti-Wagner pots.

-Per pot, J, (B), (Q, (D), (E)
, (F), and (G) 0.25 P of nitrogen fertilizer, 0.5 g of phosphoric acid fertilizer, and 1.0 g of potassium fertilizer for each 0.35 y'. OOP
Fertilize with a mixture of (mix) and mix evenly throughout the entire layer.
Table 3 shows the results of outdoor cultivation with two plants per pot.

Example 2 Using Norin No. 24 upland rice, (8) and (8) described in Example 1, (
B), (Q, (Di, (6), (F″)), and (Q) were applied to seven types of composition** for soil cultivation.

The results of the germination rate of the seeds are shown in Table 4 below.

As is clear from Table 3 above, compared to the fertilizer effect in test plot 2.3, when the fertilizer of the present invention (containing iron-containing Ti solid solution substance) was applied, test plot 4.5.6.7 As seen in 8 and 8, there is a significant difference in advantage.

Also, as is clear from Table 4, compared to test plot 1.2, soils to which the present invention iron-containing Ti solid solution substances in test plots 3.4, 5.6, and 7 were applied had lower effects on germination and growth of young plants. It has been found that this material tends to support this, and exhibits an effect that cannot be obtained with conventional titanium monomer materials.

Example 3 In paddy field soil, where over 80% of "root blight" occurs when a fertilizer consisting only of the three elements N-P is applied, 50% of the ferrous Ti-based solid solution substance of the present invention is added to the applied fertilizer. It was confirmed that the application of the compound containing 5% of the above-mentioned compound had a remarkable effect in suppressing the onset of the disease to 5% or less.

Although the present invention has been described above with reference to Examples, the present invention is not limited to these Examples.

It is well known that the availability of nitrogen in fertilizer compositions depends not only on water solubility but also on microbiological decomposition, and iron-based substances have a high magnetic susceptibility and are oriented according to the earth's magnetic field. Therefore, it brings about the so-called M-E effect on the liquid crystal substance of microorganisms, activating the raw colloid, and thus increasing the decomposition power.

As described above, such aspects are also involved in the application of the present invention.

From this point of view, it goes without saying that the nitrogenous fertilizer referred to in the present invention has a total nitrogen content of 20 to 30% or more, and includes the above-mentioned microbiologically related fertilizer.

Urban sewage treated materials contain 30% or more of nitrogen, and can be said to be an effective material with little cadmium in terms of phosphorus, so sludge treated materials from sewage treatment are suitable for removal, and the present invention It can be used primarily as a nitrogenous fertilizer or as a phosphorous fertilizer with low cadmium content.

In addition, the method for producing the iron-containing Ti-based material can be made by using at least one of the well-known AI slag and Ti slag as a raw material, and mixing Na salt or acid radical, or both raw materials, and subjecting the material to thermal drying treatment.
(Preparation before and after P and H7 is also optional).

Alternatively, it can also be made by using at least one of A1 slag and Ti slag as a raw material and drying and sintering it with thermal power in a normal air flow or in a reducing atmosphere, or at least one of Al slag and Ti slag. It can also be made by using Na salt or acid radical as a raw material, or by mixing both raw materials and drying and sintering the mixture in a post-reducing atmosphere.

(P, H, about 7 and above) Also, the composition ratio of the iron-containing Ti solid solution material and the mixing (blending) ratio of this with N, P, etc. may be variously changed without departing from the scope of the claims. is possible.

Conventional urban sewage treatment had no use, and heavy oil was often incinerated and discarded, and fertilization of soil had a slow effect.

When the present invention is applied, the consumption of heavy oil, etc. can be significantly reduced by mixing it with the dehydrated cake-like product or the pre-cake step in the manufacturing process of the above product, and it can also help alleviate pollution. It is not difficult to infer from the effects of iron-based substances that the effect of iron-based substances is that the slow-acting effect can be changed when fertilizer is applied.

In experiments, we were able to reduce the amount of heavy oil used by 30 to 40%.

Also, from 2 weeks after administration (amount), available nitrogen in the soil increased by 25% compared to the control.

Claims (1)

[Claims] 1. When producing a composite fertilizer by blending a basic phosphate fertilizer or a weighted fertilizer or both with a nitrogenous fertilizer, and when applying each unit fertilizer known as the three elements (N, P, K), iron-containing Ti is added to the fertilizer. By mixing system (non-unit system) substances (and further mixing pesticide active ingredients if necessary), it becomes possible to control the volatilization rate of ammonia in fertilizers and the soil to which fertilizer is applied, as well as the hydrogen sulfide in the soil. A fertilizer containing iron-containing Ti-based substances.