Title of Invention	A PROCESS FOR PREPARATION OF A COMPOSITION USEFUL AS A NITRIFICATION INHIBITING ADDITIVE FOR AMMONIA PRODUCING FERTILIZERS
Abstract	A process for preparation of composition useful as a nitrification inhibiting additive for ammonium producing fertilizers A process for preparation of a composition useful as a nitrification inhibiting additive for ammonium producing fertilizers which comprises mixing benzotriazole 2.5 to 50% ( by wt% of the ammonium fertilizer) and metal chelating agent 1 to 50% ( by wt% of the ammonium fertilizer) and precursors thereof in a 1:2 proportion to obtain the composition.

Title of Invention

A PROCESS FOR PREPARATION OF A COMPOSITION USEFUL AS A NITRIFICATION INHIBITING ADDITIVE FOR AMMONIA PRODUCING FERTILIZERS

Abstract

A process for preparation of composition useful as a nitrification inhibiting additive for ammonium producing fertilizers A process for preparation of a composition useful as a nitrification inhibiting additive for ammonium producing fertilizers which comprises mixing benzotriazole 2.5 to 50% ( by wt% of the ammonium fertilizer) and metal chelating agent 1 to 50% ( by wt% of the ammonium fertilizer) and precursors thereof in a 1:2 proportion to obtain the composition.

Full Text	The present invention relates to a composition useful as nitrification inhibiting additive for ammonia producing fertilizers. Application of various nitrification inhibitors for economising fertiliser N use in agriculture has been reviewed. (Prasad, R and Power, J. F. 1995. Nitrification inhibitors in agriculture, health and the environment. In Advances in Agronomy 54 : 233-81). Benzotriazole may be used to reduce nitrogen fertilizer use and applied to soils to retard nitrification thereby increasing crop yields and quality, reducing N losses and increasing fertilizer use efficiency but the present invention involves a synergistic effect of benzotriazole and a chelating agent to inhibit nitrification to a greater degree. Me Carty and Bremner (Inhibition of nitrification in soil by heterocyclic nitrogen compounds. Biol Fertil. Soil, 8(3), 204, 1989) screened a number of heterocyclic compounds for inhibition 01 nitrification. They reported that several of these compounds inhibited nitrification in soil and benzotriazole was one of them. Benzotriazole and other nitrification inhibitors showed variable potency in three different soils. The main drawback is that it showed variable potency in different soils. Theoretic considerations suggest that the potency can be very low in some soils high in soluble metal ions. No method is available for increasing the low potency in some soils. The main object of the present invention is to provide a composition useful as nitrification inhibiting additive for ammonia producing fertilizers. Another objective of the present invention is to provide metal ion chelating agents for increasing the potency of benzotriazole as a nitrification inhibitor which obviates the drawbacks as detailed above. Accordingly the present invention provides a process for preparation of a composition useful as a nitrification inhibiting additive for ammonium producing fertilizers which comprises mixing benzotriazole 2.5 to 50% ( by wt% of the ammonium fertilizer) and metal chelating agent 1 to 50% ( by wt% of the ammonium fertilizer) and precursors thereof in a 1:2 proportion (adding this to urea, ammonium salt or ammonium producing fertilizer to obtain the composition. In an embodiment of the present invention the metal ion chelating agent may be selected from salicylaldoxime, ethylene diamine, dimethyl glyoxime, cupferron, thiourea, 1-nitroso-2-naphthol, acetyl acetone or any copper and / or nickel ion binding compounds or there precursors or mixtures of these. In another embodiment of the present invention, the synergistic composition may be added to, coated on mixed with, blended with or incorporated into urea, ammonium salt or any other ammonium producing fertilizers. In yet another embodiment of the invention, the product may be optionally used after changing the physical form as a soil applied fertilizer. In yet another embodiment of the invention the said composition may be optionally used for soil application before, with or after the application of the nitrogen fertilizer for inhibiting nitrification, Benzotriazole at 2.5 to 50% by weight of urea or ammonium salts and 1.0 to 50% salicylaldoxime, ethylene diamine, dimethyl glyoxime, cupferron, thiourea, 1-nitroso-2-naphthol, acetyl acetone, mixtures of these and/or their precursors are added to ammonium producing fertilizer and mixed, coated or blended to produce a fertilizer which can be applied to soils. The fertilizer may optionally be converted to a briquette, super granule etc., before applying. Benzotriazole and the chelating agents may also be applied separately before, during or after the application of the fertilizer. Other compounds such as urease inhibitors may also be included in the fertilizer. Nitrification of fertilizer nitrogen will be retarded more than it would when only benzotriazole is added. Benzotriazole reacts with most of the metal ions to produce insoluble compounds and thus loses, to varying degrees depending on the metal ion and its concentration, its ability to inhibit nitrification. The concentration of different metal ions or their availability in soil varies from soil to soil and thus influences the extent to which nitrification is inhibited by benzotriazole. The chelating agents, which have a low affinity for the generally abundant calcium ions in soil but high affinity for transition metal ions such as copper and nickel bind the transition metal ions so that benzotriazole is not precipitated or otherwise inactivated but remains free and effective. This in turn increases the fertilizer use efficiency. The following examples are given by way of illustration of the present invention and should not be construed to limit the scope of the present invention. Example 1 The formulation consists of benzotriazole and chelating agent chosen from salicylaldoxime, dimethylglyoxime, cupferron or thiourea in 1: 2 proportion. The formulations were added to urea to give a benzotriazole concentration equal to 10% of N and were tested as follows : To 50 g of a and benzotriazole were added to obtain 100 g urea-N and 5 g benzotriazole g-1 soil. An aqueous solution or a fine dispersion in finely ground soil of a metal ion chelating agent mentioned above was added to obtain 10 g chelating agent/g soil. Triplicate sets of flasks were prepared in this way and appropriate blanks were included. The flasks were incubated at 30 C and 100% relative humidity for 45 days after adjusting the moisture content to 60% of the maximum water holding capacity of the soil by adding the calculated quantities of distilled water. Sub samples were withdrawn at 15 day intervals and analyzed for ammonium, nitrite and nitrate by phenol hypochlorite (Hinds, A. A. and Lowe, L. E. 1980. Application of Berthlot reaction to the determination of ammonium N in soil extracts and soil digests. Commun. Soil Sci. Plant Anal. 11 : 469-475) sulphanilic acid/N-(l-naphthyl ethylene diamine (Puttanna, K. and Prakasa Rao E.V.S. 1986 Modified method of nitrite determination in soils by sulphanilic acid/N-(l- naphthyl) ethylene diamine Z Pflanzenemaehr. Bodenk. 149 : 517-521) and second derivative UV (Puttanna, K and Prakasa Rao, E.V.S. 1993 Determination of nitrate in soil by second derivative ultraviolet spectrometry. Commun. Soil Sci. Plant Anal. 24 : 737-743.) methods, respectively. The percentage of inhibition of nitrification was calculated as (Equation Removed) (Bundy, L.G. and Bremner, J. M. 1973. Inhibition of nitrification in soils. Soil Sci. Soc. Am. Proc. 37, 396-398). Table 1 shows the results for these dielating agents. Table 1: Effect of treatments on the mineral forms of N in soils at 15 days (Table Removed) Example 2 The formulation consisted of benzotriazole and a chelating agent chosen from ethylenediamine, l-nitroso-2-naphthol, acetyl acetone or mixtures thereof in 1:2 proportions. The formulations were added to urea to give a benzotriazole concentration equal to 10% of N and were tested as in the above example. EDTA and glycine were also tested in the same way. The results are summarized in Table 2. Table 2: Effect of treatments on mineral forms of N in soils at 15 days (Table Removed) Example 3 The formulation consists of benzotriazole and thiourea in the ratio 1:4. The formulation was tested as in the above examples and the results are given in Table 3. Table 3: Effect of thiourea on the mineral forms of N produced in soil from benzotriazole treated urea at 15 days (Benzotriazole : thiourea = 1:4) (Table Removed) These examples show that though EDTA and glycine failed to affect the efficacy of benzotriazole, the other compounds improved the potency of benzotriazole as a nitrification inhibitor. The present inhibition values are presented in Table 4. Table 4: Effect of 10 ppm chelating agents on the nitrification inhibition by 5 ppm benzotriazole (Table Removed) Without benzotriazole, these compounds did not inhibit nitrification. This shows that inhibition of nitrification by benzotriazole was greatly enhanced when a chelating agent is also present signifying the synergistic actions of the composition. The compositions prepared are not mere admixtures but synergistic mixtures in which the aggregate property of the compositions are different from the properties of individual ingredients. The main advantages of the present invention are: i 1. Better inhibiton of nitrification can be achieved which reduces nitrogen losses and economises N use. 2. Lower concentrations of benzotriazole can be used. We claim : 1. A process for preparation of a composition useful as a nitrification inhibiting additive for ammonium producing fertilizers which comprises mixing benzotriazole 2.5 to 50% ( by wt% of the ammonium fertilizer) and metal chelating agent selected from copper/ nickel ion binding compounds and precursors thereof 1 to 50% ( by wt% of the ammonium fertilizer) in 1:2 proportion to obtain the composition. 2. A process for preparation of composition as claimed in claim 1 wherein the metal chelating agent used is selected from salicylaldoxime, ethylenediamine, dimethylglyoxime , cupferron.thiourea, 1-nitroso-2- naptho or acetylacetone. 3. A process for preparation of composition useful as a nitrification inhibiting additive for ammonium producing fertilizers as herein described with reference to the examples.

Full Text

The present invention relates to a composition useful as nitrification inhibiting additive for
ammonia producing fertilizers.
Application of various nitrification inhibitors for economising fertiliser N use in agriculture has been reviewed. (Prasad, R and Power, J. F. 1995. Nitrification inhibitors in agriculture, health and the environment. In Advances in Agronomy 54 : 233-81). Benzotriazole may be used to reduce nitrogen fertilizer use and applied to soils to retard nitrification thereby increasing crop yields and quality, reducing N losses and increasing fertilizer use efficiency but the present invention involves a synergistic effect of benzotriazole and a chelating agent to inhibit nitrification to a greater degree.
Me Carty and Bremner (Inhibition of nitrification in soil by heterocyclic nitrogen compounds. Biol Fertil. Soil, 8(3), 204, 1989) screened a number of heterocyclic compounds for inhibition 01 nitrification. They reported that several of these compounds inhibited nitrification in soil and benzotriazole was one of them. Benzotriazole and other nitrification inhibitors showed variable potency in three different soils. The main drawback is that it showed variable potency in different soils.
Theoretic considerations suggest that the potency can be very low in some soils high in soluble metal ions. No method is available for increasing the low potency in some soils.
The main object of the present invention is to provide a composition useful as nitrification inhibiting additive for ammonia producing fertilizers.
Another objective of the present invention is to provide metal ion chelating agents for increasing the potency of benzotriazole as a nitrification inhibitor which obviates the drawbacks as detailed above.
Accordingly the present invention provides a process for preparation of a composition useful
as a nitrification inhibiting additive for ammonium producing fertilizers which comprises mixing
benzotriazole 2.5 to 50% ( by wt% of the ammonium fertilizer) and metal chelating agent 1
to 50% ( by wt% of the ammonium fertilizer) and precursors thereof in a 1:2 proportion (adding this to urea, ammonium salt or ammonium producing fertilizer to obtain the composition.
In an embodiment of the present invention the metal ion chelating agent may be selected from salicylaldoxime, ethylene diamine, dimethyl glyoxime, cupferron, thiourea, 1-nitroso-2-naphthol, acetyl acetone or any copper and / or nickel ion binding compounds or there precursors or mixtures of these.
In another embodiment of the present invention, the synergistic composition may be added to, coated on mixed with, blended with or incorporated into urea, ammonium salt or any other ammonium producing fertilizers.
In yet another embodiment of the invention, the product may be optionally used after changing the physical form as a soil applied fertilizer.
In yet another embodiment of the invention the said composition may be optionally used for soil application before, with or after the application of the nitrogen fertilizer for inhibiting nitrification,
Benzotriazole at 2.5 to 50% by weight of urea or ammonium salts and 1.0 to 50% salicylaldoxime, ethylene diamine, dimethyl glyoxime, cupferron, thiourea, 1-nitroso-2-naphthol, acetyl acetone, mixtures of these and/or their precursors are added to ammonium producing fertilizer and mixed, coated or blended to produce a fertilizer which can be applied to soils. The fertilizer may optionally be converted to a briquette, super granule etc., before applying. Benzotriazole and the chelating agents may also be applied separately before, during or after the application of the fertilizer. Other compounds such as urease inhibitors may also be included in the fertilizer. Nitrification of fertilizer nitrogen will be retarded more than it would when only benzotriazole is added.
Benzotriazole reacts with most of the metal ions to produce insoluble compounds and thus loses, to varying degrees depending on the metal ion and its concentration, its ability to inhibit nitrification. The concentration of different metal ions or their availability in soil varies from soil to soil and thus influences the extent to which nitrification is inhibited by benzotriazole. The chelating agents, which have a low affinity for the generally abundant calcium ions in soil but high affinity for transition metal ions such as copper and nickel bind the transition metal ions so that benzotriazole is not precipitated or otherwise inactivated but remains free and effective. This in turn increases the fertilizer use efficiency.
The following examples are given by way of illustration of the present invention and should not be construed to limit the scope of the present invention.
Example 1
The formulation consists of benzotriazole and chelating agent chosen from salicylaldoxime, dimethylglyoxime, cupferron or thiourea in 1: 2 proportion. The formulations were added to urea to give a benzotriazole concentration equal to 10% of N and were tested as follows :
To 50 g of a and benzotriazole were added to obtain 100 g urea-N and 5 g benzotriazole g-1 soil. An aqueous solution or a fine dispersion in finely ground soil of a metal ion chelating agent mentioned above was added to obtain 10 g chelating agent/g soil. Triplicate sets of flasks were prepared in this way and appropriate blanks were included. The flasks were incubated at 30 C and 100% relative humidity for 45 days after adjusting the moisture content to 60% of the maximum water holding capacity of the soil by adding the calculated quantities of distilled water. Sub samples were withdrawn at 15 day intervals and analyzed for ammonium, nitrite and nitrate by phenol hypochlorite (Hinds, A. A. and Lowe, L. E. 1980. Application of Berthlot reaction to the determination of ammonium N in soil extracts and soil digests. Commun. Soil Sci. Plant Anal. 11 : 469-475) sulphanilic acid/N-(l-naphthyl ethylene diamine (Puttanna, K. and Prakasa Rao E.V.S. 1986 Modified method of nitrite determination in soils by sulphanilic acid/N-(l-
naphthyl) ethylene diamine Z Pflanzenemaehr. Bodenk. 149 : 517-521) and second derivative UV (Puttanna, K and Prakasa Rao, E.V.S. 1993 Determination of nitrate in soil by second derivative ultraviolet spectrometry. Commun. Soil Sci. Plant Anal. 24 : 737-743.) methods, respectively. The percentage of inhibition of nitrification was calculated as
(Equation Removed)
(Bundy, L.G. and Bremner, J. M. 1973. Inhibition of nitrification in soils. Soil Sci. Soc. Am. Proc. 37, 396-398).
Table 1 shows the results for these dielating agents.
Table 1: Effect of treatments on the mineral forms of N in soils at 15 days
(Table Removed)
Example 2
The formulation consisted of benzotriazole and a chelating agent chosen from ethylenediamine, l-nitroso-2-naphthol, acetyl acetone or mixtures thereof in 1:2 proportions. The formulations were added to urea to give a benzotriazole concentration equal to 10% of N and were tested as in the above example. EDTA and glycine were also tested in the same way. The results are summarized in Table 2.
Table 2: Effect of treatments on mineral forms of N in soils at 15 days

(Table Removed)
Example 3
The formulation consists of benzotriazole and thiourea in the ratio 1:4. The formulation was tested as in the above examples and the results are given in Table 3.
Table 3: Effect of thiourea on the mineral forms of N produced in soil from benzotriazole treated urea at 15 days (Benzotriazole : thiourea = 1:4)

(Table Removed)
These examples show that though EDTA and glycine failed to affect the efficacy of benzotriazole, the other compounds improved the potency of benzotriazole as a nitrification inhibitor. The present inhibition values are presented in Table 4.
Table 4: Effect of 10 ppm chelating agents on the nitrification inhibition by 5 ppm benzotriazole
(Table Removed)
Without benzotriazole, these compounds did not inhibit nitrification. This shows that inhibition of nitrification by benzotriazole was greatly enhanced when a chelating agent is also present signifying the synergistic actions of the composition.
The compositions prepared are not mere admixtures but synergistic mixtures in which the aggregate property of the compositions are different from the properties of individual ingredients.
The main advantages of the present invention are:
i
1. Better inhibiton of nitrification can be achieved which reduces nitrogen losses and
economises N use.
2. Lower concentrations of benzotriazole can be used.

We claim :
1. A process for preparation of a composition useful as a nitrification
inhibiting additive for ammonium producing fertilizers which comprises
mixing benzotriazole 2.5 to 50% ( by wt% of the ammonium fertilizer)
and metal chelating agent selected from copper/ nickel ion binding
compounds and precursors thereof 1 to 50% ( by wt% of the
ammonium fertilizer) in 1:2 proportion to obtain the composition.
2. A process for preparation of composition as claimed in claim 1 wherein
the metal chelating agent used is selected from salicylaldoxime,
ethylenediamine, dimethylglyoxime , cupferron.thiourea, 1-nitroso-2-
naptho or acetylacetone.
3. A process for preparation of composition useful as a nitrification
inhibiting additive for ammonium producing fertilizers as herein described
with reference to the examples.

Documents:

232-del-1999-abstract.pdf

232-del-1999-claims.pdf

232-del-1999-correspondence-others.pdf

232-del-1999-correspondence-po.pdf

232-del-1999-description (complete).pdf

232-del-1999-form-1.pdf

232-del-1999-form-19.pdf

232-del-1999-form-2.pdf

232-del-1999-form-3.pdf

232-del-1999-petition-137.pdf

232-del-1999-petition-138.pdf

« Previous Patent

Next Patent »

Patent Number

232846

Indian Patent Application Number

232/DEL/1999

PG Journal Number

13/2009

Publication Date

27-Mar-2009

Grant Date

21-Mar-2009

Date of Filing

12-Feb-1999

Name of Patentee

COUNCIL OF SCIENTIFIC AND INDUSTRIAL RESEARCH

Applicant Address

RAFI MARG, NEW DELHI-110001, INDIA.

Inventors:

#	Inventor's Name	Inventor's Address
1	KRISHNAMURTHY PUTTANNA	CENTRAL INSTITUTE OF MEDICINAL AND AROMATIC PLANTS, FIELD STATION, BANGALORE- 560065
2	NADUR MUDDANNA NANJE GOWDA	PROFESSOR, DEPT. OF CHEMISTRY, BANGALORE UNIVERSITY, CENTRAL COLLEGE CAMPUS, BANGALORE-560001
3	ERANKI VENKATA SURYA PRAKASA RAO	CENTRAL INSTITUTE OF MEDICINAL & AROMATIC PLANTS, FIELD STATION, BANGALORE- 560065
4	SUSHIL KUMAR	DIRECTOR, CENTRAL INSTITUTE OF MEDICINAL & AROMATIC PLANTS, LUCKNOW- 226015

PCT International Classification Number

C05C 5/00

PCT International Application Number

N/A

PCT International Filing date

PCT Conventions:

#	PCT Application Number	Date of Convention	Priority Country
1			NA