A composition for coloring keratin fibers, containing an indoline, an indole, or a derivative thereof in combination with at least one amino acid or oligopeptide. The composition is useful for coloring human hair and restoring grey hair to its natural color. The formulation can be applied with atmospheric oxygen as the sole oxidizing agent.

This invention relates to formulations for coloring keratin fibers, more particularly human hair, which contain special dye precursors of the indole or indoline type and a component for intensifying and/or shading the color, to the use of this component for intensifying and/or shading colors and to corresponding coloring processes.
Among the various products available for the cosmetic treatment of the human body, formulations for modifying or shading the color of the hair occupy a prominent position. Disregarding blonding preparations which lighten the hair oxidatively by degrading the natural hair dyes, two types of colorants have long been of importance in the coloring of hair:
So-called oxidation colorants are used for permanent, intensive colors with corresponding fastness properties. Oxidation colorants normally contain oxidation dye precursors, so-called primary intermediates and secondary intermediates. The primary intermediates form the actual dyes with one another or by coupling with one or more secondary intermediates under the influence of oxidizing agents or atmospheric oxygen. Although oxidation colorants are distinguished by excellent coloring results, they can also be attended by disadvantages for certain narrow circles of people. Thus, certain dye precursors can cause unwanted skin irritation in so-called xe2x80x9cpara-allergicsxe2x80x9d. In addition, oxidation dyes are generally developed with oxidizing agents, more particularly hydrogen peroxide. In the event of frequent application by people with sensitive hair, this can cause harm or even damage to the hair structure which has to be repaired with special hair-care products. It is also important not to underestimate the number of people who, in the context of the popular xe2x80x9cnatural-versus-chemicalxe2x80x9d debate, avoid using chemical products wherever possible because of their personal feelings.
Colorants or tints containing substantive dyes as their coloring component are normally used for temporary colors. Substantive dyes are based on dye molecules which are directly absorbed onto the hair and do not require an oxidative process for developing the color. Dyes such as these include, for example, henna which has been used since ancient times for coloring the body and hair.
However, since in the eyes of many consumers both coloring processes are tainted by a hint of the xe2x80x9cartificialxe2x80x9d with its negative associations, a new coloring process has recently attracted considerable attention. In this process, precursors of the natural hair dye melanin are applied to the hair and, through oxidative processes in the hair, form near- natural dyes. A corresponding process using 5,6-dihydroxyindoline as dye precursor is described in EP-B1 530 229. By application and, more particularly, frequent application of formulations containing 5,6-dihydroxyindoline, grey hair can be restored to its natural color. The color can be developed with atmospheric oxygen as sole oxidizing agent so that there is no need to use other oxidizing agents.
Under the described conditions, however, satisfactory results can only be achieved in people who, before xe2x80x9cgoing greyxe2x80x9d, had medium blond to dark brown hair. Accordingly, there has been no shortage of attempts to modify this known coloring process in such a way that even originally red and, above all, dark to black hair can be restored to its original color.
One method of obtaining dark to black color tones, particularly those described by experts as xe2x80x9cflatxe2x80x9d, is the subject of German patent application 197 32 975.6 to which reference is expressly made, particularly in regard to the prior art literature cited therein. The solution proposed in this patent application is to add conventional secondary intermediates. Although the color can be developed with atmospheric oxygen alone, the use of at least one other oxidizing agent is recommended as a preferred alternative.
However, in view of the above-mentioned reservations of many consumers, there is still a need for a formulation which restores grey hair to its natural color, even in people with originally dark to black hair, without any need for purely synthetic dye components or to use other oxidizing agents than atmospheric oxygen.
It has now surprisingly been found that the problem stated above can be solved by application of a formulation which, besides known dye precursors of the indole or indoline type, contains at least one amino acid or oligopeptide.
Accordingly, the present invention relates to formulations for coloring keratin fibers, more particularly human hair, containing a dye precursor selected from the group consisting of indoline derivatives and indole derivatives, characterized in that it additionally contains at least one amino acid or oligopeptide.
Amino acids in the context of the invention are substances which contain at least one amino group and at least one xe2x80x94COOH or xe2x80x94SO3H group.
Preferred amino acids are aminocarboxylic acids, more particularly xcex1-aminocarboxylic acids and xcfx89-aminocarboxylic acids. Among the xcex1-aminocarboxylic acids, arginine, lysine, ornithine and histidine are particularly preferred.
The amino acids are preferably added to the formulations according to the invention in free form. However, the amino acids may also be used in salt form. Preferred salts are the compounds containing hydrohalic acids, more particularly hydrochlorides and hydrobromides.
A particularly preferred amino acid is arginine used in particular in free form but also as the hydrochloride.
The present invention does of course also encompass formulations containing two or more amino acids or oligopeptides. In this case, combinations of arginine with another amino acid or oligopeptide are preferred.
In addition, the amino acids may also be used in the form of oligopeptides and protein hydrolyzates providing steps are taken to ensure that the necessary quantities of compounds conforming to the definition of amino acids according to the invention are present. Reference is expressly made in this connection to the disclosure of DE-OS 22 15 303.
The formulations according to the invention contain the amino acid or oligopeptide in quantities of preferably 0.1 to 10% by weight and more preferably 1 to 4% by weight, based on the formulation as a whole.
Hair colorants, more particularly those where the color is developed oxidatively with atmospheric oxygen or other oxidizing agents, such as hydrogen peroxide, are normally adjusted to a mildly acidic or alkaline pH value, i.e. to a pH value in the range from about 5 to 11. To this end, the colorants contain alkalizing agents, normally alkali metal or alkaline earth metal hydroxides, ammonia or organic amines.
In one special embodiment of the present invention, the amino acid or the oligopeptide is used not only to promote color development, but also at least partly as an alkalizing agent. Accordingly, amino acids and oligopeptides of which 2.5% by weight solutions in water have a pH value of 9 or higher are preferably used in this embodiment. One such amino acid is the preferred arginine. In this particular embodiment, the other alkalizing agent is selected from the group consisting of monoethanolamine, monoisopropanolamine, 2-amino-2-methylpropanol, 2-amino-2-methyl-1,3-propanediol, 2-amino-2-ethyl-1,3-propanediol, 2-amino-2-methylbutanol and triethanolamine and alkali metal and alkaline earth metal hydroxides. Within this group, monoethanolamine, triethanolamine and 2-amino-2-methylpropanol and 2-amino-2-methyl-1,3-propanediol are particularly preferred. xcfx89-Amino acids, such as xcfx89-aminocaproic acid, are also preferably used as alkalizing agents in this embodiment of the invention.
Particularly advantageous properties are exhibited by formulations in which the amino acid or the oligopeptide and the other alkalizing agent are present in a ratio by weight of 1:5 to 5:1. Quantity ratios of 1:2 to 2:1 have proved to be particularly suitable.
The formulations according to the invention contain a dye precursor of the indole or indoline type as another compulsory component.
According to the invention, preferred indoles and indolines are those which contain at least one hydroxy or amino group, preferably as a substituent on the six-membered ring. These groups may carry other substituents, for example in the form of etherification or esterification of the hydroxy group or alkylation of the amino group. Compounds containing two of these groups, particularly two hydroxy groups, of which one or both may be etherified or esterified are particularly preferred.
According to the invention, particularly preferred dye precursors are derivatives of indoline, such as 5,6-dihydroxyindoline, N-methyl-5,6-dihydroxyindoline, N-ethyl-5,6-dihydroxyindoline, N-propyl-5,6-dihydroxyindoline, N-butyl-5,6-dihydroxyindoline, 5,6-dihydroxyindoline-2-carboxylic acid, 4-, 6- and 7-hydroxyindoline, 6-aminoindoline and 4-amino-indoline.
Most particularly preferred dye precursors are derivatives of 5,6-dihydroxyindoline corresponding to formula (Ia):
in whichxe2x80x94independently of one another
R1 is hydrogen, a C1-4 alkyl group or a C1-4 hydroxyalkyl group,
R2 is hydrogen or a xe2x80x94COOH group which may even be present as a salt
with a physiologically compatible anion,
R3 is hydrogen or a C1-4 alkyl group,
R4 is hydrogen, a C1-4 alkyl group or a group xe2x80x94COxe2x80x94R6 where R6 is a C1-4 alkyl group,
R5 stands for one of the groups mentioned for R4,
or a physiologically compatible salt of these compounds with an organic or inorganic acid.
According to the invention, preferred representatives are 5,6-dihydroxyindoline, N-methyl-5,6-dihydroxyindoline, N-ethyl-5,6-dihydroxy-indoline, N-propyl-5,6-dihydroxyindoline, N-butyl-5,6-dihydroxyindoline. The parent compound, 5,6-dihydroxyindoline, is most particularly preferred.
According to the invention, preferred indoles are 5,6-dihydroxyindole, N-methyl-5,6-dihydroxyindole, N-ethyl-5,6-dihydroxy-indole, N-propyl-5,6-dihydroxyindole, N-butyl-5,6-dihydroxyindole, 5,6-dihydroxyindole-2-carboxylic acid, 4-, 6- and 7-hydroxyindole, 6-amino-indole and 4-aminoindole.
Particular preference is attributed to derivatives of 5,6-dihydroxyindole corresponding to formula (Ib):
in whichxe2x80x94independently of one another
R1 is hydrogen, a C1-4 alkyl group or a C1-4 hydroxyalkyl group,
R2 is hydrogen or a xe2x80x94COOH group which may even be present as a salt with a physiologically compatible anion,
R3 is hydrogen or a C1-4 alkyl group,
R4 is hydrogen, a C1-4 alkyl group or a group xe2x80x94COxe2x80x94R6 where R6 is a C1-4 alkyl group,
R5 stands for one of the groups mentioned for R4,
or a physiologically compatible salt of these compounds with an organic or inorganic acid.
According to the invention, preferred representatives are 5,6-dihydroxyindole, N-methyl-5,6-dihydroxyindole, N-ethyl-5,6-dihydroxyindole, N-propyl-5,6-dihydroxyindole, N-butyl-5,6-dihydroxyindole. The parent compound, 5,6-dihydroxyindole, is most particularly preferred.
The indoline and indole derivatives present in the formulations according to the invention may be used both as free bases and in the form of their physiologically compatible salts with inorganic or organic acids, for example hydrochlorides, sulfates and hydrobromides.
The indole or indoline derivatives are present in the formulations according to the invention in quantities of normally 0.05 to 10% by weight and preferably 0.2 to 5% by weight.
The present invention does of course also encompass formulations which contain more than one indoline or indole derivative or mixtures of indoline or indole derivatives.
In one particularly preferred embodiment, the formulations according to the invention contain no dyes or dye precursors other than the indoles or indolines mentioned.
In principle, however, other dye components or dye precursors could be used.
In the embodiments containing such additional compounds, the following substances are preferred:
Preferred primary intermediates:
p-phenylenediamine, p-toluylenediamine, p-aminophenol, o-aminophenol, 1-(2xe2x80x2-hydroxyethyl)-2,5-diaminobenzene, N,N-bis-(2-hydroxyethyl)-p-phenylenediamine, 2-(2,5-diaminophenoxy)-ethanol, 1-phenyl-3-carboxyamido-4-amino-5-pyrazolone, 4-amino-3-methylphenol, 2,4,5,6-tetraaminopyrimidine, 2-hydroxy-4,5,6-triaminopyrimidine, 4-hydroxy-2,5,6-triaminopyrimidine, 2,4-dihydroxy-5,6-diaminopyrimidine, 2-dimethylamino 4,5,6-triaminopyrimidine, 2-hydroxyethylaminomethyl-4-aminophenol, 4,4xe2x80x2-diaminodiphenylamine, 4-amino-3-fluorophenol, 2-aminomethyl-4-aminophenol, 2-hydroxymethyl-4-aminophenol, bis-(2-hydroxy-5-aminophenyl)-methane, 1,4-bis-(4-aminophenyl)-diazacycloheptane, 1,3-bis-(N-(2-hydroxyethyl)-N-(4-aminophenylamino))-2-propanol, 4-amino-2-(2-hydroxyethoxy)-phenol and 4,5-diaminopyrazole derivatives according to EP 0 740 741 and WO 94/108970 such as, for example, 4,5-diamino-1-(2xe2x80x2-hydroxyethyl)-pyrazole.
Particularly preferred primary intermediates:
p-phenylenediamine, p-toluylenediamine, p-aminophenol, 1-(2xe2x80x2-hydroxyethyl)-2,5-diaminobenzene, 4-amino-3-methylphenol, 4-amino-2-((diethylamino)-methyl)-phenol, 2,4,5,6-tetraaminopyrimidine, 2-hydroxy-4,5,6-triaminopyrimidine and 4-hydroxy-2,5,6-triaminopyrimidine.
Preferred secondary intermediates:
m-aminophenol and derivatives thereof such as, for example, 5-amino-2-methylphenol, 5-(3-hydroxypropylamino)-2-methylphenol, 3-amino-2-chloro-6-methylphenol, 2-hydroxy4-aminophenoxyethanol, 3-amino-6-methoxy-2-methylaminophenol, 2,6-dimethyl-3-aminophenol, 3-trifluoroacetylamino-2-chloro-6-methylphenol, 5-amino4-chloro-2-methylphenol, 5-amino-4-methoxy-2-methylphenol, 5-(2xe2x80x2-hydroxyethyl)-amino-2-methylphenol, 3-(diethylamino)-phenol, N-cyclopentyl-3-aminophenol, 1,3-dihydroxy-5-(methylamino)-benzene, 3-(ethylamino)-4-methylphenol and 2,4-dichloro-3-aminophenol,
o-aminophenol and derivatives thereof,
m-diaminobenzene and derivatives thereof such as, for example, 2,4-diaminophenoxyethanol, 1,3-bis-(2,4-diaminophenoxy)-propane, 1-methoxy-2-amino-4-(2xe2x80x2-hydroxyethylamino)-benzene, 1,3-bis-(2,4-diaminophenyl)-propane, 2,6-bis-(2-hydroxyethylamino)-1-methylbenzene and 1-amino-3-bis-(2xe2x80x2-hydroxyethyl)-aminobenzene,
o-diaminobenzene and derivatives thereof such as, for example, 3,4-diaminobenzoic acid and 2,3-diamino-1-methylbenzene,
di- and trihydroxybenzene derivatives such as, for example, resorcinol, resorcinol monomethyl ether, 2-methyl resorcinol, 5-methyl resorcinol, 2,5-dimethyl resorcinol, 2-chlororesorcinol, 4-chlororesorcinol, pyrogallol and 1,2,4-trihydroxybenzene,
pyridine derivatives such as, for example, 2,6-dihydroxypyridine, 2-amino-3-hydroxypyridine, 2-amino-5-chloro-3-hydroxypyridine, 3-amino-2-methylamino-6-methoxypyridine, 2,6-dihydroxy-3,4-dimethylpyridine, 2,6-dihydroxy-3,4-diaminopyridine, 2,6-dihydroxy-4-methylpyridine, 2,6-diaminopyridine, 2,3-diamino-6-methoxy-pyridine and 3,5-diamino-2,6-dimethoxypyridine,
naphthalene derivatives such as, for example, 1-naphthol, 2-methyl-1-naphthol, 2-hydroxymethyl-1-naphthol, 2-hydroxyethyl-1-naphthol, 1,5-dihydroxynaphthalene, 1,6-dihdroxynaphthalene, 1,7-dihdroxy-naphthalene, 1,8-dihdroxynaphthalene, 2,7-dihdroxynaphthalene and 2,3-dihdroxynaphthalene,
morpholine derivatives such as, for example, 6-hydroxybenzomorpholine and 6-aminobenzomorpholine,
quinoxaline derivatives such as, for example, 6-methyl-1,2,3,4-tetrahydroquinoxaline,
pyrazole derivatives such as, for example, 1-phenyl-3-methylpyrazol-5-one,
indole derivatives such as, for example, 4-hydroxyindole, 6-hydroxyindole and 7-hydroxyindole,
methylenedioxybenzene derivatives such as, for example, 3,4-methylenedioxyphenol, 1-hydroxy-3,4-methylenedioxybenzene, 1-amino-3,4-methylenedioxybenzene and 1-(2xe2x80x2-hydroxyethyl)-amino-3,4-methylenedioxybenzene.
Particularly preferred secondary intermediates:
1-naphthol, 1,5-, 2,7- and 1,7-dihydroxynaphthalene, 3-aminophenol, 5-amino-2-methylphenol, 2-amino-3-hydroxypyridine, resorcinol, 4-chloro-resorcinol, 2-chloro-6-methyl-3-aminophenol, 2-methyl resorcinol, 5-methyl resorcinol, 2,5-dimethyl resorcinol, 2,6-dihydroxy-3,4-diaminopyridine.
Preferred substantive dyes are the compounds known under the International names or commercial names of HC Yellow 2, HC Yellow 4, HC Yellow 5, HC Yellow 6, Basic Yellow 57, Disperse Orange 3, HC Red 3, HC Red BN (4-Hydroxypropylamino-3-Nitrophenol), Basic Red 76, HC Blue 2, HC Blue 12, Disperse Blue 3, Basic Blue 99, HC Violet 1, Disperse Violet 1, Disperse Violet 4, Disperse Black 9, Basic Brown 16 and Basic Brown 17 and also 4-amino-2-nitrodiphenylamine-2xe2x80x2-carboxylic acid, 6-nitro-1,2,3,4-tetrahydroquinoxaline, hydroxyethyl-2-nitrotoluidine, picramic acid, 2-amino-6-chloro-4-nitrophenol, 4-ethylamino-3-nitrobenzoic acid and 2-chloro-6-ethylamino-1-hydroxy-4-nitrobenzene. Other preferred substantive dyes are naturally occurring dyes such as, for example, henna red, henna neutral, henna black, camomile blossom, sandalwood, black tea, black alder bark, sage, logwood, madder root, catechu, sedre and alkanet.
The oxidation dye precursors or the substantive dyes do not have to be single compounds. Instead, the hair colorants according to the inventionxe2x80x94due to the processes used for producing the individual dyesxe2x80x94may contain small quantities of other components providing they do not adversely affect the coloring result or have to be ruled out for other reasons, for example toxicological reasons.
With regard to the dyes suitable for use in the hair coloring and tinting formulations according to the invention, reference is also specifically made to Ch. Zviak""s work The Science of Hair Care, Chapter 7 (pages 248-250; Substantive Dyes) and Chapter 8, pages 264-267; Oxidation Dye Precursors), published as Vol. 7 of the Series xe2x80x9cDermatologyxe2x80x9d (Editors: Ch. Culnan and H. Maibach), Marcel Dekker Inc., New York/Basel, 1986 and to the xe2x80x9cEuropxc3xa4ische Inventar der Kosmetik-Rohstoffexe2x80x9d published by the Europxc3xa4ische Gemeinschaft and available in diskette form from the Bundesverband Deutscher Industrie- und Handelsunternehmen fxc3xcr Arzneimittel, Reformwaren und Kxc3x6rperpflegemittel e.V., Mannheim, Germany.
Both the oxidation dye precursors and the substantive dyes are present in the formulations according to the invention in quantities of preferably 0.01 to 20% by weight and preferably 0.5 to 5% by weight, based on the formulation as a whole.
Preferred formulations containing other dyes or dye precursors are those which do not contain an oxidation dye precursor of the primary intermediate type. In this embodiment of the invention, the corresponding formulations contain an oxidation dye precursor of the secondary intermediate type and, if desired, substantive dyes.
Other preferred formulations are those which do not contain an oxidation dye precursor of the secondary intermediate type. These formulations are also preferably free from oxidation dye precursors of the primary intermediate type, but may contain a substantive dye, preferably from the series of naturally occurring dyes.
To produce the colorants according to the invention, the compulsory and optional constituents mentioned above are incorporated in a suitable water-containing carrier. For coloring hair, such carriers are, for example, cremes, emulsions, gels or even surfactant-containing foaming solutions, for example shampoos, foam aerosols or other formulations suitable for application to the hair.
The hair colorants according to the invention are adjusted to a pH value of preferably 5 to 11 and, more preferably, 7 to 10.
The colorants according to the invention may also contain any of the known active substances, additives and auxiliaries typical of such formulations. In many cases, the colorants contain at least one surfactant, both anionic and zwitterionic, ampholytic, nonionic and cationic surfactants being suitable in principle. In many cases, however, it has been found to be of advantage to select the surfactants from anionic, zwitterionic or nonionic surfactants. Anionic surfactants can be particularly useful.
Suitable anionic surfactants for the hair colorants according to the invention are any anionic surface-active substances suitable for use on the human body. Such substances are characterized by a water-solubilizing anionic group such as, for example, a carboxylate, sulfate, sulfonate or phosphate group and a lipophilic alkyl group containing around 10 to 22 carbon atoms. In addition, glycol or polyglycol ether groups, ether, amide and hydroxyl groups andxe2x80x94generallyxe2x80x94ester groups may also be present in the molecule. The following are examples of suitable anionic surfactantsxe2x80x94in the form of the sodium, potassium and ammonium salts and the mono-, di- and trialkanolammonium salts containing 2 or 3 carbon atoms in the alkanol group:
linear and branched fatty acids containing 8 to 22 carbon atoms (soaps),
ether carboxylic acids corresponding to the formula Rxe2x80x94Oxe2x80x94(CH2xe2x80x94CH2O)xxe2x80x94CH2xe2x80x94COOH, in which R is a linear alkyl group containing 10 to 22 carbon atoms and x=0 or 1 to 16,
acyl sarcosides containing 10 to 18 carbon atoms in the acyl group,
acyl taurides containing 10 to 18 carbon atoms in the acyl group,
acyl isethionates containing 10 to 18 carbon atoms in the acyl group,
sulfosuccinic acid mono- and dialkyl esters containing 8 to 18 carbon atoms in the alkyl group and sulfosuccinic acid monoalkyl polyoxyethyl esters containing 8 to 18 carbon atoms in the alkyl group and 1 to 6 oxyethyl groups,
linear alkane sulfonates containing 12 to 18 carbon atoms,
linear xcex1-olefin sulfonates containing 12 to 18 carbon atoms,
xcex1-sulfofatty acid methyl esters of fatty acids containing 12 to 18 carbon atoms,
alkyl sulfates and alkyl polyglycol ether sulfates corresponding to the formula Rxe2x80x94O(CH2xe2x80x94CH2O)xxe2x80x94SO3H, in which R is a preferably linear alkyl group containing 10 to 18 carbon atoms and x=0 or 1 to 12,
mixtures of surface-active hydroxysulfonates according to DE-A-37 25 030,
sulfated hydroxyalkyl polyethylene and/or hydroxyalkylene propylene glycol ethers according to DE-A-37 23 354,
sulfonates of unsaturated fatty acids containing 12 to 24 carbon atoms and 1 to 6 double bonds according to DE-A-39 26 344,
esters of tartaric acid and citric acid with alcohols in the form of addition products of around 2 to 15 molecules of ethylene oxide and/or propylene oxide with fatty alcohols containing 8 to 22 carbon atoms.
Preferred anionic surfactants are alkyl sulfates, alkyl polyglycol ether sulfates and ether carboxylic acids containing 10 to 18 carbon atoms in the alkyl group and up to 12 glycol ether groups in the molecule and, in particular, salts of saturated and, more particularly, unsaturated C8-22 carboxylic acids, such as oleic acid, stearic acid, isostearic acid and palmitic acid.
In the context of the invention, zwitterionic surfactants are surface-active compounds which contain at least one quaternary ammonium group and at least one xe2x80x94COO(xe2x88x92) or xe2x80x94SO3(xe2x88x92) group in the molecule. Particularly suitable zwitterionic surfactants are the so-called betaines, such as N-alkyl-N,N-dimethyl ammonium glycinates, for example cocoalkyl dimethyl ammonium glycinate, N-acylaminopropyl-N,N-dimethyl ammonium glycinates, for example cocoacylaminopropyl dimethyl ammonium glycinate, and 2-alkyl-3-carboxymethyl-3-hydroxyethyl imidazolines containing 8 to 18 carbon atoms in the alkyl or acyl group and cocoacylaminoethyl hydroxyethyl carboxymethyl glycinate. A preferred zwitterionic surfactant is the fatty acid amide derivative known by the CTFA name of Cocamidopropyl Betaine.
Ampholytic surfactants are surface-active compounds which, in addition to a C8-18 alkyl or acyl group, contain at least one free amino group and at least one xe2x80x94COOH or xe2x80x94SO3H group in the molecule and which are capable of forming inner salts. Examples of suitable ampholytic surfactants are N-alkyl glycines, N-alkyl propionic acids, N-alkyl aminobutyric acids, N-alkyl iminodipropionic acids, N-hydroxyethyl-N-alkyl amidopropyl glycines, N-alkyl taurines, N-alkyl sarcosines, 2-alkyl aminopropionic acids and alkyl aminoacetic acids containing around 8 to 18 carbon atoms in the alkyl group. Particularly preferred ampholytic surfactants are N-cocoalkyl amino-propionate, cocoacyl aminoethyl aminopropionate and C12-18 acyl sarcosine.
Nonionic surfactants contain, for example, a polyol group, a poly-alkylene glycol ether group or a combination of polyol and polyglycol ether groups as the hydrophilic group. Examples of such compounds are
products of the addition of 2 to 30 moles of ethylene oxide and/or 0 to 5 moles of propylene oxide to linear fatty alcohols containing 8 to 22 carbon atoms, to fatty acids containing 12 to 22 carbon atoms and to alkylphenols containing 8 to 15 carbon atoms in the alkyl group,
C12-22 fatty acid monoesters and diesters of products of the addition of 1 to 30 moles of ethylene oxide to glycerol,
C8-22 alkyl mono- and oligoglycosides and ethoxylated analogs thereof,
products of the addition of 5 to 60 moles of ethylene oxide to castor oil and hydrogenated castor oil,
products of the addition of ethylene oxide to sorbitan fatty acid esters,
products of the addition of ethylene oxide to fatty acid alkanolamides.
Examples of cationic surfactants suitable for use in the hair treatment formulations according to the invention are, in particular, quaternary ammonium compounds. Preferred quaternary ammonium compounds are ammonium halides, such as alkyl trimethyl ammonium chlorides, dialkyl dimethyl ammonium chlorides and trialkyl methyl ammonium chlorides, for example cetyl trimethyl ammonium chloride, stearyl trimethyl ammonium chloride, distearyl dimethyl ammonium chloride, lauryl dimethyl ammonium chloride, lauryl dimethyl benzyl ammonium chloride and tricetyl methyl ammonium chloride. Other cationic surfactants suitable for use in accordance with the invention are the quaternized protein hydrolyzates.
Also suitable for use in accordance with the invention are cationic silicone oils such as, for example, the commercially available products Q2-7224 (manufacturer: Dow Corning; a stabilized trimethyl silyl amodimethi-cone), Dow Corning 929 Emulsion (containing a hydroxylamino-modified silicone which is also known as Amodimethicone), SM-2059 (manufacturer: General Electric), SLM-55067 (manufacturer: Wacker) and Abil(copyright)-Quat 3270 and 3272 (manufacturer: Th. Goldschmidt; diquaternary polydimethyl siloxanes, Quaternium-80).
Alkyl amidoamines, particularly fatty acid amidoamines, such as the stearyl amidopropyl dimethyl amine obtainable as Tego Amid(copyright)S 18, are distinguished not only by their favorable conditioning effect, but also and in particular by their ready biodegradability.
Quaternary ester compounds, so-called xe2x80x9cesterquatsxe2x80x9d, such as the methyl hydroxyalkyl dialkoyloxyalkyl ammonium methosulfates marketed under the trade name of Stepantex(copyright) and the corresponding products commercially available as Dehyquart(copyright), are also readily biodegradable.
One example of a quaternary sugar derivative suitable for use as a cationic surfactant is the commercially available product Glucquat(copyright)100 (CTFA name: Lauryl Methyl Gluceth-10 Hydroxypropyl Dimonium Chloride).
The compounds containing alkyl groups used as surfactants may be single compounds. In general, however, these compounds are produced from native vegetable or animal raw materials so that mixtures with different alkyl chain lengths dependent upon the particular raw material are obtained.
The surfactants representing addition products of ethylene and/or propylene oxide with fatty alcohols or derivatives of these addition products may be both products with a xe2x80x9cnormalxe2x80x9d homolog distribution and products with a narrow homolog distribution. Products with a xe2x80x9cnormalxe2x80x9d homolog distribution are mixtures of homologs which are obtained in the reaction of fatty alcohol and alkylene oxide using alkali metals, alkali metal hydroxides or alkali metal alcoholates as catalysts. By contrast, narrow homolog distributions are obtained when, for example, hydrotalcites, alkaline earth metal salts of ether carboxylic acids, alkaline earth metal oxides, hydroxides or alcoholates are used as catalysts. The use of products with a narrow homolog distribution can be of advantage.
Other active substances, auxiliaries and additives are, for example,
nonionic polymers such as, for example, vinyl pyrrolidone/vinyl acrylate copolymers, polyvinyl pyrrolidone and vinyl pyrrolidone/vinyl acetate copolymers and polysiloxanes,
cationic polymers, such as quaternized cellulose ethers, polysiloxanes containing quaternary groups, dimethyl diallyl ammonium chloride polymers, acrylamide/dimethyl diallyl ammonium chloride copolymers, dimethyl aminoethyl methacrylate/vinyl pyrrolidone copolymers quaternized with diethyl sulfate, vinyl pyrrolidone/imidazolinium methochloride copolymers and quaternized polyvinyl alcohol,
zwitterionic and amphoteric polymers such as, for example, acrylamido-propyl/trimethyl ammonium chloride/acrylate copolymers and octyl acrylamide/methyl methacrylate/tert.butyl aminoethyl methacrylate/2-hydroxypropyl methacrylate copolymers,
anionic polymers such as, for example, polyacrylic acids, crosslinked polyacrylic acids, vinyl acetate/crotonic acid copolymers, vinyl pyrrolidone/ vinyl acrylate copolymers, vinyl acetate/butyl maleate/isobornyl acrylate copolymers, methyl vinyl ether/maleic anhydride copolymers and acrylic acid/ethyl acrylate/N-tert.butyl acrylamide terpolymers,
thickeners, such as agar agar, guar gum, alginates, xanthan gum, gum arabic, karaya gum, carob bean flour, linseed gums, dextrans, cellulose derivatives, for example methyl cellulose, hydroxyalkyl cellulose and carboxymethyl cellulose, starch fractions and derivatives, such as amylose, amylopectin and dextrins, clays such as, for example, bentonite or fully synthetic hydrocolloids such as, for example, polyvinyl alcohol,
structurants, such as glucose, maleic acid and lactic acid,
hair-conditioning compounds, such as phospholipids, for example soya lecithin, egg lecithin and kephalins, and also silicone oils,
protein hydrolyzates, more particularly elastin, collagen, keratin, milk protein, soya protein and wheat protein hydrolyzates, condensation products thereof with fatty acids and quaternized protein hydrolyzates,
perfume oils, dimethyl isosorbide and cyclodextrins,
solvents and solubilizers, such as ethanol, isopropanol, ethylene glycol, propylene glycol, glycerol and diethylene glycol,
antidandruff agents, such as Piroctone Olamine and Zinc Omadine,
other substances for adjusting the pH value, for example xcex1- and xcex2-hydroxycarboxylic acids,
active substances, such as panthenol, pantothenic acid, allantoin, pyrrolidone carboxylic acids and salts thereof, plant extracts and vitamins,
cholesterol,
UV filters,
consistency promoters, such as sugar esters, polyol esters or polyol alkyl ethers,
fats and waxes, such as spermaceti, beeswax, montan wax, paraffins, fatty alcohols and fatty acid esters,
fatty acid alkanolamides,
complexing agents, such as EDTA, NTA and phosphonic acids,
swelling and penetration agents, such as glycerol, propylene glycol monoethyl ether, carbonates, hydrogen carbonates, guanidines, ureas and primary, secondary and tertiary phosphates,
opacifiers, such as latex,
pearlescers, such as ethylene glycol mono- and distearate,
propellents, such as propane/butane mixtures, N2O, dimethyl ether, CO2 and air and
antioxidants.
To produce the colorants according to the invention, the constituents of the water-containing carrier are used in the usual quantities for this purpose. For example, emulsifiers are used in concentrations of 0.5 to 30% by weight while thickeners are used in concentrations of 0.1 to 25% by weight, based on the colorant as a whole.
In one preferred embodiment, the color is developed with atmospheric oxygen as sole oxidizing agent.
In principle, however, a chemical oxidizing agent may also be used, particularly in cases where the formulations additionally contain oxidation dye precursors of the primary intermediate and secondary intermediate type. The same applies when human hair is to be not only colored, but also lightened. Particularly suitable oxidizing agents are hydrogen peroxide or addition products thereof with urea, melamine or sodium borate. Oxidation may also be carried out with enzymes. In this case, the enzymes may be used both to produce oxidizing per compounds and to enhance the effect of an oxidizing agent present in small quantities. One example of an enzymatic process is the procedure whereby the effect of small quantities (for example 1% and less, based on the formulation as a whole) of hydrogen peroxide is enhanced by peroxidases.
The preparation of the oxidizing agent is preferably mixed with the preparation of the oxidation dye precursors immediately before coloring of the hair. The ready-to-use hair coloring preparation formed should have a pH value in the range from 6 to 10. In a particularly preferred embodiment, the hair colorant is used in a mildly alkaline medium. The application temperatures may be in the range from 15 to 40xc2x0 C. but are preferably at the temperature of the scalp. After a contact time of about 5 to 45 and preferably 15 to 30 minutes, the hair colorant is removed from the hair to be colored by rinsing. There is no need for the hair to be washed with a shampoo where a carrier of high surfactant content, for example a coloring shampoo, has been used.
In the particular case of hair which is difficult to color, the preparation containing the oxidation dye precursors may be applied to the hair without preliminary mixing with the oxidation component. The oxidation component is applied after a contact time of 20 to 30 minutes, optionally after rinsing. After another contact time of 10 to 20 minutes, the hair is rinsed and, if desired, shampooed. In a first variant of this embodiment where the preliminary application of the dye precursors is intended to improve penetration into the hair, the corresponding formulation is adjusted to a pH value of about 4 to 7. In a second variant, oxidation with air is initially carried out, the formulation applied preferably having a pH value of 7 to 10. In the subsequent accelerated post-oxidation phase, it can be of advantage to use acidified peroxydisulfate solutions as the oxidizing agent.
Whichever of the processes mentioned above is used to apply the colorant according to the invention, development of the color may be supported and enhanced by adding certain metal ions to the colorant. Examples of such metal ions are Zn2+, Cu2+, Fe2+, Fe3+, Mn2+, Mn4+, Li+, Mg2+, Ca2+ and Al3+. Zn2+, Cu2+ and Mn2+ are particularly suitable. Basically, the metal ions may be used in the form of a physiologically compatible salt. Preferred salts are the acetates, sulfates, halides, lactates and tartrates. Zinc sulfate is a particularly preferred metal salt. Development of the hair color can be accelerated and the color tone can be influenced as required through the use of these metal salts.
The present invention also relates to the use of an amino acid or oligopeptide for intensifying and/or shading the colors in the coloring of keratin fibers with formulations containing an indoline derivative or an indole derivative as dye precursors.
The present invention also relates to a process for coloring human hair in which one of the formulations mentioned above is applied to the hair and the color is subsequently developed. In a preferred embodiment, the color is developed with atmospheric oxygen.
In one particular embodiment of this process, the final color is developed by repeated application of the formulation, followed after each application by oxidation with air. The formulation is preferably applied at intervals of about 1 day to about 2 weeks. Special tones can be selectively obtained in this way.
The following Examples are intended to illustrate the invention.


A method of applying liquid anhydrous ammonia to soil is disclosed as including the step of pressurizing anhydrous ammonia received from a source. The pressurized anhydrous ammonia is conducted to a plurality of terminal outlets, wherein each of the outlets is configured to maintain a back pressure and thereby the liquid state of the anhydrous ammonia. The anhydrous ammonia is discharged from the plurality of terminal outlets to thereby contact the soil.

This invention relates to the accurate application of NH3 on agricultural fields.
NH3 or anhydrous ammonia is a low cost and a physically difficult material to comprehend. It is out of sight and out of mind and seldom understood. The pressure increasing direct injection system requires reverse thinking for the designer and user. The new method and application system applies NH3 without freezing the fines. This is opposite the old pressure reducing system since the unfrozen or melted lines mean no NH3 is being applied. In fact a frozen line on the new pressure increasing system is the visual indication of a partially plugged line.
Anhydrous ammonia expands almost 100 times its stored volume as a gas. When it boils at xe2x88x9228 degrees F approximately 85% remains liquid and the balance is given off as a gas. Yet it looks like water when observed in its liquid state. NH3 has a flow resistance of 0.85 X""s water. NH3 superheats when combined with water to form aqueous ammonia at 24% nitrogen. A tremendous amount of heat is given off when NH3 converts to NH4 and thus vapor is often observed on high humidity days. This vapor is quite insignificant and is said to be less than 0.01% (100 PPM) of the material applied with the NH3 applicator. NH3 is lighter than air and has a specific gravity of 0.590 as a gas and a specific gravity of 0.662 as a liquid.
The NH3 molecule becomes NH4 by attracting the hydrogen atom from the H20 molecule producing beat and releasing hydrogen and oxygen back into the atmosphere. By weight NH3 is 82.5% nitrogen as applied into the soil. This is the highest analysis of any commercial fertilizer. The material is the source for other types of fertilizer whether liquid or dry. It is the most economical material to transport from the natural gas production fields of the world.
NH3 is also used as a refrigerant as it is highly compressible and low cost. Most of the ice found at grocery stores comes from centrally located ice companies that use compressors and NH3 as the refrigerant.
Small doses of the material are medicinally used to revive the unconscious person. However, the material is lethal and can maim anyone who comes in contact with the material. Safety concerns are well documented and goggles, protective clothing, gloves and water are mandatory when working with the material.
Anhydrous ammonia or NH3 has been widespread use in agricultural crop production since the early 1950""s. NH3 was initially priced quite low and by the 1960""s was adapted so broadly that it became a major component in the cost of production for all major cereal crops. The price of the material dropped to 2 to 3 cents per lb. of Nitrogen in 1963 and 64 as several new plants went on line utilizing train compressors. This new technology was so efficient that the cost of producing NH3 was reduced to all time lows. The NH3 production plants, which typically produced 250 tons per day, were now capable of up to 1,500 tons per day. Thus a significant oversupply occurred. Today the industry contributes up $2 billion annually to the economy. No new plants are under construction due to high initial cost of erection and startup. Most NH3 plants are simply upgraded to improve efficiency. Almost all NH3 plants operating today use train compressors developed by Kellogg Corporation.
NH3 is priced at about {fraction (1/2+L )} the cost of the liquid and dry sources of nitrogen. Commercial fertilizer manufacturers utilize NH3 as a base material to build urea, ammonium nitrate, ammoniated phosphate, and ammonium sulfate. Utilizing NH3 as the primary source of nitrogen results in the lowest cost of production historically.
Approximately 85% of the NH3 is consumed in the Midwestern cornbelt at 4,000,000 tons annually. The Pacific states consume about 220,000 tons annually.
Terms
Nonaberrant: No boiling or expansion of the material from the liquid pressurized state to the gaseous pressurized state. This wandering or errant flow is difficult to meter and the NH3 gas will flow in an irregular path. Previous pressure reducing systems have aberrant flow.
Transitional flow: At a given pressure and temperature NH3 will begin to convert from a liquid state to a gas state. This will occur when distribution or injection line pressure begins to drop below tank pressure. The pressure increasing system of direct injection denies transitional flow. Pressure reducing systems common to the fertilizer systems of today allow transitional flow to occur immediately after the metering pump, the pressure reducing valve, or the meter.
Tank pressure: The pressure observed at the NH3 pressure vessel or the tank varies with the ambient temperature.
Manifold Pressure: The pressure observed in the distribution cavity of the manifold. Pressure reducing systems always have manifold pressures below the tank pressure. The new direct injection pressure increasing system meters NH3 very accurately at the manifold since the manifold pressure is below the tank pressure, at the tank pressure or above the tank pressure at normal seeding speed.
Line Pressure: Varies significantly with pressure reducing systems and line pressure is lower than manifold pressure due to expansion of NH3 in the oversized lines. This is primarily due to the extra volume found in the lines. Thus external freezing of the lines is observed since line pressure is below tank pressure. The lines accumulate dew. The lines are operating well below freezing to xe2x88x9228 degrees F. The unique pressure increasing system has line pressures at or above tank pressure and the lines do not freeze or collect frozen dew.
Terminal Expansion Point: Ideally is located at the point of injection of the material into the ground. A final orifice located at this point allows for precise metering and uneven line lengths. Pressures are elevated above tank pressure at this injection point allowing for a solid non-gaseous stream flow and less vaporization. Pressure reducing systems require equal line lengths. The final injection point with pressure reducing systems is about 15% NH3 gas and 85% is a nonuniform NH3 liquid since injection pressure is well below vapor or tank pressure.
In Line Orifice or Range Orifice: The range orifice is located after the manifold and is inserted into the injection line at the high-pressure adapter. This orifice is selected by picking the maximum rate in the band at the maximum ground speed. For maximum accuracy line lengths must be equal if no terminal expansion orifice is used. This system set up is easier to use for changing orifices but it does have some aberrant flow if the terminal expansion orifice is not used. However, temperature drop is seldom significant enough to observe line freezing or dew accumulation.
Terminal Injection Orifice: The orifice is located at the end of the small inside diameter black nylon line by inserting it into the line and clamping it with a stainless steel compression clamp. The terminal injection orifice is designed to allow for a solid stream flow. Unequal line lengths can be used. Port to port variance can be a little as 1% if precision calibrated orifices are used. The range orifice is not required, but should be utilized to support the high pressure clamping aspect of the ferrule. Terminal expansion orifices can be utilized as range orifices. The terminal expansion orifices can also be sized one size larger than the range orifices which allows stream particulate escapes to plug the smaller range orifice which is more serviceable at the manifold. The range orifices and terminal expansion orifices are identical by design. Only the location of the part is different.
The orifices are selected by (1) Band spacing, (2) Ground speed, (3) above tank pressure desired at application speed, (4) Gallons per acre to be applied. Generally speaking once the correct orifice size has been selected it will not be necessary to change orifices due to the wide range of operating pressures.
Distribution Manifold: A captious component in the regulation of NH3 is the manifold. The pressure increasing direct injection manifold is designed with a minimum volume for a quick site specific, variable rate, GPS response and to prevent aberrant flow. The manifold is mounted at or near the pump so that the material is instantly placed in the soil. The system stores very little material and this feature is critical to prevent gassing at corners and start and stop response with the applicator.
Accumulator: The accumulator is critical to prevent aberrant flow since the pump is delivering liquid NH3 in metered surges. This means that the pressure increases and decreases during each revolution and the pump piston never travels at the same speed. A nitrogen spring or accumulator acts as a flywheel, storing energy and the giving it back to the system. This means that the accumulator piston moves up and down with each pump revolution. As pressure increases the accumulator piston moves up. As system pressure drops the accumulator piston moves down. The accumulator piston does not move when the system pressure is below the preset nitrogen charge in the accumulator gas charge chamber.
Accumulator Pressure Settings: The accumulator is charged with nitrogen gas. The accumulator is charged to {fraction (1/2+L )} the maximum system operating pressure. The accumulator can also be charged at the tank pressure or {fraction (1/2+L )} to {fraction (2/3+L )} of the tank pressure. If rates are being adjusted constantly with a variable rate, site specific, GPS system charge the accumulator at {fraction (1/2+L )} tank pressure. The manifold NH3 pressure gauge should be steady (5 psi movement) at normal application speed. Pressure reducing NH3 systems do not use an accumulator.
Safety Shield: The shield slides up and down on the accumulator tie bolts. The shield contains and protects liquid NH3 from being haphazardly sprayed on the machine or operators if the line adapter assemblies are improperly installed when orifices are inspected or changed. Pressure reducing systems do not use a safety shield.
Maximum Design Pressures:
Pressure reducing systems use translucent EVA (Ethyl Vinyl Acetate) lines at the manifold distribution point that are rated at 75 psi. Pressure reducing systems must meet the pressure standards set by various states prior to the pressure reducing valve. The supply lines must have a 300-psi operating pressure rating as specified by the State of Indiana.
System Filters: The new pressure increasing system has two filters. The system primary filter is located prior to the pump. The screen is normally 100 mesh. A second 100 mesh final safety filter is installed after the pump and prior to the manifold to catch any failed parts or rust that may have collected in the pump during storage or pump service.
System Relief Valve: When operating at high ambient temperatures, above 80 degrees F, or with a remote mounted manifold utilizing an on/off Gromo(trademark) valve. It is recommended that two 300-psi relief valves be installed to protect the pump.
The Pump: The Dempster(copyright) E-5 and E-6 positive displacement pumps have been developed. The pumps are positive displacement and are uniquely different from previous pressure reducing pumps. Several recent improvements have been incorporated into the pump to allow for a 300 psi direct injection system pressure. Dempster has built pressure reducing pumps for NH3 since 1958 and their pressure reducing B-3 and B-4 pumps are well known in the fertilizer industry. John Blue/Thurston also offers a pressure reducing pump. No beat exchanger or super cooler is used in the direct injection pressure increasing system. E-6:0.1236 gallons per stroke, 350 rpm, Range @ 8 mph, 40 to 195 lbs. N @ 52.5 ft. E-6:0.0515 gallons per stroke, 350 mm, Range @ 8 mph, 40 to 195 lbs. N @ 32.5 ft.
Global Positioning, Variable Rate Technology: The pump can be driven hydraulically or electrically, fully stroked and in combination with the accumulator setting can apply rates per acre of NH3 from virtually nil to the maximum rate with within a {fraction (1/4+L )} second. Pressure reducing systems require 14 seconds to respond to a full rate signal change. Site specific farming can be achieved within 3 feet of travel verse 200 feet of travel with the pressure reducing systems. This is a unique feature of the pressure increasing system.
Two basic systems are used to apply NH3 to agricultural soils. Both systems require a shank type tool to apply the material below the ground line. The method has always been to reduce pressure from the supply tank. The material becomes gaseous dropping below vapor pressure as it leaves the supply tank. NH3 will expand almost 100 times its stored volume as it is applied to the soil. Both of these systems in widespread use are referred to as pressure reducing systems. NH3 has always been metered and applied previously to agricultural soils at a pressure below vapor pressure or tank pressure.
The inventor made an accidental discovery in the first field trials with an electronic pressure reducing system. At the time of the trial the wiring to the pressure-reducing valve had been reverse wired after the pressure reducing valve had been changed. The result was the injection lines began to melt the frozen ice that bad clung to the lines from the previous pass. The gallons per acre were applied at such a rate that maximum system flow occurred resulting in above freezing temperature ammonia being applied. The applied per acre rate was in excess of 200 gallons per acre. Having never forgotten this observation the inventor began investigating in later years a means to meter and place liquid ammonia with no line freezing. Several approaches were tried. Compressors were even considered to capture the vapor and place it back into the tank. All approaches appeared unfeasible either due to complexity, maintenance or cost. Given more time and an opportunity to investigate in a more leisurely manner produced a new discovery of increasing pressure above vapor pressure and keeping NH3 temperature at close to ambient. Three unplanned discoveries resulted; improved accuracy, improved rate change response and no line freezing.
The first pressure reducing system uses a throttle or meter to reduce pressure. These can be mechanical or electromechanical units that utilize a pressure reducing manifold. Dempster Industries Inc. of Beatrice, Nebr., developed the second pressure reducing system. This system uses a pump to reduce pressure below tank pressure and therefore deliver metered amounts through a discharge valve. As the material eaves the discharge valve pressure is reduced and the distribution manifold receives a mix of liquid and vapor.
The first known placement of NH3 occurred in 1930 at the Delta Branch, Mississippi Agricultural Experiment Station, by J. O. Smith. A small cylinder of compressed anhydrous ammonia was adapted to a one-row cultivator and was drawn by white mule. This was the first pressure reducing system as reported in The History of the U. S. Fertilizer Industry. Lewis B. Nelson, Tennessee Valley Authority, 1990.
Shell Chemical Co. of Pittsburgh Calif. bad progressed to a point in 1934 whereby NH3 could be a commercial operation handled by distributors. They introduced the NH3 primarily into irrigation water. In order to reduce production costs by producing in higher volumes Shell engineers looked at other uses for crops by injecting NH3 into the soil. Commercial application began in 1942 and spread to the three Pacific States.
Meanwhile in 1944 W. B. Andrews at the Mississippi Experiment Station began developing the principles of NH3 injection. The published results and principles were released in 1947. The developed equipment consisted of a tractor; a supply tank or pressure vessel; a flow meter which measured the flow out of the NH3 tank; a knife like applicator shank with an iron pipe and a rubber tube for injecting the NH3 5 to 6 inches into the soil; and covering equipment such as disc hillers to prevent gaseous loss from the application channel. The project was support by the TVA in part from 1944 to 1948. By 1947 the market was ready and several pressure reducing flowmeters went into service. Steel was now available to build the pressure vessels, as swords now became plowshares with the end of the WWII.
By 1955 NH3 accounted for 25% of all the applied nitrogen types. By 1965 NH3 accounted for 40% of the nitrogen market. By 1980 60% of the applied nitrogen in the Midwest was NH3. NH3 has evolved into an annual two billion-dollar industry.
The most popular application system today is the low cost regulator method that uses a pressure-reducing valve called a meter to throttle the flow after the tank and prior to the manifold. For example U.S. Pat. No. 5,170,820, Dec. 15, 1992, Management System For The Application Of Anhydrous Ammonia, James S. Jones describes a new apparatus for applying NH3. This apparatus utilizes the vapor pressure of the system to propel the NH3. The rate per acre is regulated by a throttling device. This system uses a pressure reducing multiport manifold. This allows vapor and liquid to pass to individual ports. The manifold pressure at application speed is below tank pressure. This system requires applicator injection lines of a equal length to each row or band of NH3. This helps to even out the pressure differences between each row. The resistance to flow is the same for each line due to equal line length. Unfortunately well over 1,600 feet of line is used for a 48 foot applicator.
Another disadvantage of the pressure reducing system is that vapor and liquid is mixed in the flow. This problem is discussed in U.S. Pat. No. 4,432,651: Feb. 21, 1984, Apparatus For Mixing Vapor And Liquid Phases Of Anhydrous Ammonia, David M. McLeod. The pressure reducing manifold is distributing the NH3 to the individual applicator lines as 90% vapor and 10% liquid by volume. The drop In pressure can be between 5 and 30 psig resulting in a temperature drop. The flow is aberrant creating irregular flow patbs in the manifold ports.
As the flow enters the applicator injection lines it surges. Line pulsing or vibration is often observed. Pressure reducing systems have port to port rate variance, as measured on 12 inch bands, up to four times greater from one port to another.
Wider 30-inch band spacings have measured variances between 30 and 34%. Specially modified Vertical Dam manifolds can achieve variances port to port of 15% on 30 inch band spacing. Considerable research has been carried out at the University of Nebraska and Iowa State which is reported in the September 1997 again in November 1997, and the September 1998 issue of Successful Farming. Rich Fee, Crops and Soils Editor reports results from tests that verify the tremendous variance port to port of pressure reducing systems.
The specially modified pressure reducing Vertical Dam manifolds do not regulate as effectively at very low ground speeds. Up to six individual pressure reducing manifolds are installed on one machine to meter more effectively. The observed and measured regulation varies from low speed to normal seeding speed (5 to 7 mph). This is a problem for No-till drills and Airseeders since they must travel at very slow speeds (2 to 3 mph) when residue levels are high. The residue must be given more time to weave through the shanks that are applying seed and the NH3. Residue plug ups can occur which require the operator to stop the machine. The operator may also elect to loop around and deposit the plugged residue outside the seeding area. The machine maybe backed up and restarted several times. The start and stop requires a large volume recharge of the 1,600 feet of applicator line. NH3 is highly compressible and the pressure reducing method will often take 14 to 15 seconds to restabilize.
The applicator injection lines leaving the pressure reducing manifold ports to the soil knives or shanks are normally {fraction (1/2+L )} inch inside diameter lines. These ethyl vinyl acetate lines are large to allow for the continued reduction of pressure from the manifold. The eva lines have a maximum 75-psi rating indicating a low pressure reducing system. The stored volume of 1,600 feet of line is 16.2 gallons. This is 3,763 cubic inches. This is the equivalent to the displacement of twelve V-8 engines. The NH3 expands almost 100 times from the liquid phase to the vapor phase. Each change in either ground speed: start, or stop results in a time delay to establish a new equilibrium of pressure and concentration of liquid and vapor.
NH3 is also used as a commercial refrigerant. It is highly compressible. Pressure reducing NH3 application systems use vapor pressure of the supply tank to force the material through the supply lines, coolers, flowmeters, regulating valves, manifold and the applicator lines. Each component reduction in pressure results in boiling, a temperature drop, and errant flow. Only the tank pressure can be used to recompress the vapor phase in the lines.
Compression of NH3 takes valuable time when only tank pressure is available. With variable rate, site specific, GPS application systems the response is immediate ({fraction (1/4+L )} to 1 second) using liquid and dry fertilizer systems. The pressure reducing aberrant flow NH3 systems require about 14 seconds to reach a stabilized new rate. At normal seeding speed this can be over 200 feet of travel ({fraction (1/4+L )} acre @ a 50 foot width). This is not desirable and results in NH3 being noncompetitive with other fertilizer choices for site specific, variable rate application of this critical input.
Creeper speeds (1 to 2 mph) are often utilized to calibrate the Airseeders and No-till drills. It is observed that the machine will creep up to 10% of the time. The vapor phase is significantly higher at low speeds. The liquid phase is discharged in small surging volumes as the NH3 boils. Pressure reducing systems have an optimum ground speed for best regulation.
Designs to improve mixing of liquid and vapor phase NH3 with additive materials have been implemented. See U.S. Pat. No. 4,448,540 May 15, 1984, Apparatus For Mixing A Liquid Additive Compound with Vapor And Liquid Phases Of Anhydrous Ammonia, David M. McLeod. Thus it has been proven that pressure reducing systems offer serious problems for mixing of additives. The reduction in pressure causing aberrant flow results in irregular paths of flow.
Manifolds with up to 72 ports for very wide Airseeders on narrow 7.5 to 12 inch band spacing have very low concentration of NH3 in each port. Port to port regulation on steep slopes and rolling land is poor since the liquid phase is very sensitive to the slope angle of the manifold. The vapor phase is highly compressible. The uphill side of the applicator receives less material than the downhill side of the applicator. To overcome some this problem the manifold supply ports are sequenced in alternating hookups. The lines are sized to equal lengths. The uphill side of the manifold then directs half of the flow to the uphill side of the applicator outlets and half of the flow to the downhill applicator ports. The downhill side of the manifold is plumbed in the same manner of alternating hookups to the uphill and downhill side of the applicator. The uphill side and downhill side of the applicator still deliver the selected per acre rate. However every other band will have as much as a four times variance port to port across the full width of the machine. This has been a temporary solution to a permanent problem. The liquid phase and vapor phase together in the same cavity produce irregular flow paths that are subject to slope angle, inertia, ground speed, band concentration and ambient temperature.
Transitional flow begins as the liquid material leaves the tank. Each valve, filter, fitting and supply line length produces compounding resistance. NH3 is applied at ambient freezing temperatures and pressure drops do occur prior to the regulating pressure reducing meter. Tank pressure is considered low when the temperature is below 50 degrees F. The cold temperature results in a higher percentage of pressure drops. If the supply side of the system is properly designed from the tank to the meter this pressure drop can still be significant at freezing ambient temperatures. Coolers are used in pressure reducing systems to alleviate some of this problem. Thus true transitional flow begins at the pressure reducing valve. Wider applicators traveling at higher speeds need better system designs to handle higher flows. The temperature of the NH3 is flow critical to the resistance of the system.
The pressure reducing valves are discussed in U.S. Pat. No. 4,364,409, Dec. 21, 1982 Fluid Flow Control Device, James S. Jones and in U.S. Pat. No. 4,657,568 Apr. 14, 1987, Apparatus for Volumetrically Controlling the flow of a Gas and a Liquid Mixture, James S. Jones. Both of these inventions are dependent on pressure reduction to facilitate metering and to organize a flow of gas and vapor. Both inventions produce a temperature drop and aberrant flow through a manifold and lines.
Pressure reducing systems use coolers to stabilize the flow of NH3 to the meter. The coolers are simple heat exchangers that bleed off about 2% of the material through the heat exchanger. The bleed off material is directed into the ground via an extra line. The extra line can be directed to a soil knife or through the manifold to all the knives.
Continental an active patent holder in the field of NH3 refers to the cooler as an equalizer. Continental states the equalizer is xe2x80x9cA simple compact device which employs refrigeration of xc2xd-21/2% of the liquid in the system to super cool the remaining 97xc2xd-99% of the liquid. Accurate metering of super cooled liquid ammonia becomes as easy as metering water since both behave as true liquids.xe2x80x9d
The coolers add expense to the system and can plug when additives are premixed with the NH3. The cooler is required for electronic pressure reducing systems and mechanical pressure reducing systems too assure a nonaberrant flow to the measuring flow meter and the regulating valve. Following the regulating valve and prior to the manifold the NH3 becomes aberrant.
Ravens(copyright) Industries states in their ACCU-FLOW ATTACHMENT sales document form FCD5M497. xe2x80x9cCooler can be disassembled for cleaning and preventive maintenance.xe2x80x9d My invention requires no coolers and thus is simpler. Although coolers can be used with the direct injection system they offer no major economic advantage. The goal is to deliver ambient or warm pressurized liquid NH3 throughout the metering system.
All electronic NH3 metering systems use rate controlled pressure reducing valves in combination with electronic encoded flowmeters. Raven(copyright) Industries in their sales pamphlet SCS 440, SPRAYER CONTROL SYSTEMS, show a GPS compatible controller that applies NH3 accurately on a per acre basis using a pressure reducing system. Their pressure reducing Accu-Flow attachment is adaptable to their SCS440 Automatic Sprayer Control system. No reference is made to port to port accuracy of NH3 or instant response to the variable rate signal. Spraying Systems Co.(copyright) in their catalog 802 SPRAY CONTROL SOLUTIONS, page 25 show their pressure reducing NH3 system. DICKEY-john(trademark) in their publication PCS(trademark) Precision Control System catalog number 11071-0231 shows a pressure reducing system utilizing a cooler to reduce pressure. Injection line freezing is illustrated in their front cover color picture. MICRO-TRAK(copyright) SYSTEMS, Inc. in their publication NH3 KIT shows a pressure reducing heat exchanger. No NH3 application systems whether mechanical or electromechanical raise pressure above tank pressure.
Another disadvantage of the pressure reducing system is line freezing. The temperature of the applied NH3 drops well below 32 degrees F. Frost begins to accumulate on the lines. The exterior of the injection lines becomes heavily laden with frost gathered from the humid atmosphere. The shank also begins to freeze and ride out of the soil. This is a serious problem for No-till drills and Airseeders that simultaneously deep band NH13 and apply seed with the same opener.
A non-frozen application line indicates a plugged line with a pressure reducing system. A partially plugged line remains frozen on a pressure reducing system. The new pressure increasing direct injection system has the unique feature; the lines do not freeze in normal operation. A partially plugged line will freeze with a pressure increasing system. The NH3 is injected into the soil at temperatures well above 32 degrees F.
Several inventors have developed openers that allow for line freezing and loss of ammonia vapor. U.S. Pat. No. 4,116,139, Sep. 26, 1978, Cold Flow Liquid Vapor Shoe, Clement J Sauer, discusses the problems of dispensing liquid and vapor NH3 into the soil. Sauer states xe2x80x9cIt is the general object of the present invention to provide field plowing and field fertilizing apparatus which will dispense both ammonia liquid and ammonia vapor in a plowed field trench, and which will accomplish this dispensing action in a way which will encourage retention to the ammonia in the field soil.xe2x80x9d Retention of NH3 can be improved if the material is discharged as a liquid. The vapor is difficult to control and seal in the soil.
The use of pressure reducing NH3 systems with airseeders has prompted many large fertilizer companies to publish information about the peculiar aspects of the NH3 material. Westco Fertilizers, Calgary, Alberta. John Harapiak, Thom Weir in their publication, Westco Guidelines, Applying NH3 at Seeding, confirm xe2x80x9cThe conversion of liquid NH3 to a gas results in considerable chilling of any metal parts it contacts. The line carrying the NH3 must be isolated or insulated from the opener to prevent the opener from building with frozen soil. This problem is aggravated by cold soil, high N application rates and wet soil. Accumulation of frozen soil on the opener increases the width of the furrow being created and reduces the ability of the soil to flow around the opener to seal the NH3 into the soil. The NH3 that escapes from the band could cause damage to the germinating seeds or could be lost to the atmosphere.xe2x80x9d
Harapiak and Weir make further note about the uniform distribution of NH3. xe2x80x9cUniform distribution of NH3 to all the openers is critical to avoid the risk of germination damage associated with excessive rates of NH3. Select a non-gravity based distribution system for best results.xe2x80x9d
The problem of placing seed and NH3 at time seeding is also complicated by the use of dry fertilizer materials such ammoniated phosphate and potassium chloride dry prills. The NH3 as it is chilled collects dew and frost and requires very special opener designs. These designs disturb and fracture the soil and require extra horsepower. Poor seedbeds result from such deep placement. Thus the chance of No-till seed and fertilizer system is dramatically reduced. It is often not possible to place NH3 and dry fertilizer with these improved openers without constant attention by the operator. In very wet cold conditions the NH13 observed vapor is actually water vapor from the air combining with a very small amount of NH3 (less than 200 PPM). The water vapor collects on the steel openers and blocking the flow of dry materials. A special opener design is observed in U.S. Pat. No. 3,854,429, Dec. 17, 1974, Fertilizer Dispenser Calvin B. Blair.
Fracturing and cracking of the seed bed is further discussed in U.S. Pat. No. 5,140,917, Aug. 19, 1992. Method and Apparatus for Fertilizing Agricultural Crops, Guy J. Swanson and U.S. Pat. No. 5,752,453, May 19, 1998 Apparatus for Use in Applying Fertilizer, Lee F. Nikkel. Present opener designs for placing NH3 must have wide shanks to accommodate the large NH13 injection tube. These shanks fracture the seedbed up to 6 inches in width. The large NH3 lines make opener design and accurate targeting of the NH3 difficult.
Deep banding NH3 with dry or liquid ammonium phosphate has special chemical and physical issues. The freezing action of the pressure reducing NH3 injection line will often freeze liquid orthophosphate lines and stop the injection of the material. The chemical availability for the plant to take up the placed phosphate is also dramatically affected in spring wheat production if the band becomes too concentrated with NH3. As reported in Bumper Times, January/February, 1991 Volume 16, Guy J. Swanson, author, page 6 states, Producers should switch to nitrate nitrogen if band concentration exceeds 55 lbs of N on 20-inch band spacing. xe2x80x9cHot bandsxe2x80x9d and even localized in the band hot spots can occur with pressure reducing systems since the flow into the band is in surges and never consistent. The pressure reducing manifolds also have band concentration variance as great as tour times. Some band may have 50 lbs of placed nitrogen and other bands will have 200 lbs of placed nitrogen in the form of NH3. The per acre rate maybe 100 lbs of placed nitrogen on the average but half of the crop is starving for nitrogen and the other half is starving for phosphate because of the xe2x80x9cHot bandsxe2x80x9d or nitrogen interference by the NH3.
A typical gravity based system is shown in U.S. Pat. No. 4,196,677, Apr. 8, 1980, Anhydrous Converter and Implement for Applying Ammonia to the Ground, Louis P. Siebert. A gravity based system is also discussed in U.S. Pat. No. 4,060,029, Jan. 17, 1978, Process and Apparatus for Producing and Using Cold Ammonia, John Wilham Hudson. It is also discussed in U.S. Pat. No. 3,978,681, Sep. 7, 1976, Method and Apparatus for the Adiabatic Expansion of Liquid Anhydrous Ammonia, William L. Kjelgaard and Paul M. Anderson. All the above patents discuss reducing pressure either before or after the distribution manifold. Cold liquid (@-28 degrees F) ammonia and cold liquid vapor is delivered to the openers. The ammonia delivered is about 85% liquid and 15% vapor. The ground-engaging opener readily freezes and collects frozen mud. The opener depth is hard to control. The machine pulls harder because of the frozen shanks.
U.S. Pat. No. 4,196,677, Apr. 8, 1980, Anhydrous Converter and Implement for Applying Ammonia to the Ground, Louie P. Siebert is a pressure reducing system invention. Siebert states in his summary that, xe2x80x9cOrdinarily, it is not desirable to pressurize the ammonia as it is being applied to the soil and thus the vents are provided for relieving this vapor pressurexe2x80x9d. This invention cannot deliver accurate rates port to port or allow for a quick response required for variable rate GPS systems in use today.
The specific gravity of liquid NH3 is 0.662. The specific gravity of NH3 gas is 0.690. If NH3 is applied just below vapor pressure gravity and resistance will affect flow pattern and rate. For NH3 to be applied accurately port to port it is required that the NH3 material be applied as a gas only or as a liquid only. No previous system has utilized either approach.
Thus pressure reduction chills the anhydrous ammonia, producing irregular flow patterns and which makes the mix liquid and vapor NH3 slope and inertia sensitive. The above systems have been used by the inventor and found to be unsatisfactory in meeting the variable rate, site specific, GPS requirements. Port to port regulation cannot be controlled in a dynamic field wide application of NH3. Severe freezing of manifolds openers, and lines occurs.
Furthermore the respected inventors in U.S. Pat. No. 4,900,339, Feb. 13, 1990, Ammonia Flow Divider. David P. Ward and James S. Jones discuss the challenge of separating liquid from gas in NH3 placement. Their device improves the depth of placement of NH3 by placing the chilled vapor separately from the chilled liquid ammonia. The result is shallow placement for sidedressing of growing row crops and placing the vapor away from the plant to avoid leaf burn. This system complicates the design of the machine. The cold temperature of the NH3 freezes openers. The NH3 is not in a pressurized state above vapor pressure to assure accurate timed placement for GPS, variable rate, site specific application.
Pressure reducing systems have errant, boiling flow of liquid and vapor NH3. The port to port variations can be as great as four times. A major problem results with wide airseeders since the time period to change flow rate is related to gravity flow or pressure reduction. The rate change is not instantaneous since highly compressible vapor and liquid NH3 is in a mixed state not in a pressurized liquid state.
Accuracy of NH3 placement was recently implemented by Continental NH3 Products Inc. of Dallas, Tex. Airseeders and No-till drills have up to 72 ports to place NH3 in small grain production. Sand centers are common at 7.5 inch, 10 inch, and 12 inch. The machines can be up to 60 feet in width as noted in the Case/Concord sales bulletin AE-170086. Continental has developed a Vertical Dam manifold to improve the port to port variances commonly found on these machines. U.S. Pat. No. 4,807,663, Feb. 28, 1989, Manifold for the Application of Agricultural Ammonia, James S. Jones discusses an advanced manifold which is commercially referred to as the Vertical Dam manifold.
The Vertical Dam manifold is a pressure-reducing manifold as discussed in the patent summary. xe2x80x9cA manifold for receiving metered anhydrous ammonia that is a variable combination of liquid and vapor routes the ammonia to the outlets of an applicator for proper injection into the soil by continually accelerating the ammonia as it approaches a discharge member having a plurality of discharge ports evenly spaced and retained between a body member and a bonnet member to form a restriction of equal value for each discharge point.xe2x80x9d Even though the manifold is better than previous manifold designs as pointed out in the Iowa State study that appears in the September, 97 and September, 98 issue of Successful Farming as reported by Rich Fee, it is complicated system.
All of the previous discussed problems are still apparent. They are: Up to six manifolds are required for a 60 foot Case/Concord Airseeder. An additional flow divider is required. An additional 120 feet of 1 inch reinforced eva 150-psi hose is required further increasing the distribution line displacement to 4,520 cubic inches (20 gallons). The manifold freezes. The lines freeze supplying the manifold. The lines freeze that supply the openers. Port to port accuracy is at best 15%. Tremendous time is required to respond to the variable rate GPS signal change. All lines from the manifold to the knives must be of equal lengths. Continental NH3 Products in their Installation Instructions for the Vertical Dam manifold state, xe2x80x9cThe higher the manifold pressures (up to 65% of tank pressure) the better. Manifold efficiency peaks at 65% of tank pressure. Surpassing 65% will not produce any better results.xe2x80x9d
Of further concern is safety since more components mean more chance of failure. Troubleshooting and maintenance is further complicated since all the eva lines must be replaced every five years by law (See State of Indiana Regulations).
Changing band spacings on the applicator is difficult on the Vertical Dam manifold since each manifold and group of manifolds is specifically built for the applicator. The manifold ports cannot be simply blocked off and accuracy maintained. The flow of liquid and vapor NH3 must be sequence through each balanced port.
The second pressure reducing system uses a pressure decreasing pump with a discharge valve originally patented by Dempster Industries Inc.(copyright) U.S. Pat. No. 2,968,255, Jan. 17, 1961, Pumps, Herman M. Loeber. Clearly the inventor designed the pump to decrease pressure from the tank supply pressure. The reduced pressure material was metered at ground speed and thus was insensitive to variable ground speed, which often results in hillside farming. The pump was widely applied in the western U.S. and became a standard for farmers that needed to constantly change ground speed. Some of initial testing and evaluation was carried out with unmodified Dempster pumps, however the pumps were not able to elevate pressure above tank due to design of the pump. Many of the pump components could not meter the material without failure in the pressure increasing system. Additional components were added and altered components were installed. The pump predelivery testing procedure was developed around higher pressures with NH3.
Dempster Industries publishes several owners manual for their pressure decreasing pumps. In the owner""s manual for the model B-4 pump Form 3018 the author discusses troubleshooting, High Operating Pressure, and the possible cause being restricted delivery lines. Obviously this would indicate that elevated pressures is considered a defective system.
Another pressure decreasing pump that has been modified to meter NH3 in a pressure decreasing system is the Thurston/John Blue BLU-JET pump. As stated in their sales bulletin BLU-JET(copyright)GD1 200(trademark) it is obvious the pressure decreasing pump reduces pressure since they use a cooler. No high-pressure lines are represented at the manifold. Although the John Blue pump could be modified similar to the Dempster pump to elevate pressure it would not be consistent to share valuable development information with two pump manufactures. A confidential relationship exists with Dempster and much of Dempsters development work may be patentable.
In the initial development stage several state and federal plant nutrient and soil scientists along with agricultural engineers were contacted about their experience and knowledge in raising pressure of the NH3 above the tank pressure. All scientists reported back it had never been done and could not be done. Further reference was made by one scientist referring to the Spraying Systems Co. catalog 45 A, Agricultural Spray Products Catalog xe2x80x9cstating that if raising NH3 pressure above tank pressure was doable Spraying Systems would have offered it. No reference is made in their catalog nor are orifice charts available for application of NH3. On page 3 of their catalog they discuss specific gravity and conversion factors for liquids weighing from 7 lbs. per gallon to 14 lbs per gallon. NH3 weighs 6.2 lbs. per gallon. No presentation is ever made that NH3 can be applied on agricultural fields using their flow regulators for liquid fertilizers or soil fumigants, page 40 and 41 or using their solid stream spray nozzles page 43 for banding liquid fertilizers.
Spraying Systems Co. orifice charts indicate application pressures to 60 psi. Pressure increasing systems require orifice charts to 300 psi. Special in line range and terminal orifices were developed for the pressure increasing system. The new unique orifice designs were required to handle high pressures and also very low volumes of liquid NH3. The high concentration of nitrogen in very narrow bands dictated new manufacturing techniques not commonly found in the agricultural machinery business. The technical manual 998A for the pressure increasing direct injection system from EXACTRIX GLOBAL SYSTEMS L.L.C. which markets the new method and apparatus shows special orifice charts and troubleshooting techniques required for the superior system.
Pressure increasing direct injection NH3 systems have not been used previously in the application of NH3 to agricultural crops. A review of various suppliers from the 1998 Parts and Sales Catalog for Horvick Manufacturing of Fargo, N.D., pages 161 to 200 indicates several pressure decreasing systems are available. Squibb-Taylor in their catalog AA-98, Anhydrous Ammonia (NH3) Equipment shows only mechanical or electromechanical pressure reducing systems available. John Blue in their Catalog 100 CAT 9/94 page 43-47 show only pressure reducing manifolds and flow meters for sale.
Accordingly, several objects and advantages of my invention are benefits of increasing the pressure above tank pressure to meter NH3 more accurately. Safety is improved with a simpler system with components that exceed safety requirements by a minimum factor of 2. No manifold or line freezing occurs in operation since the NH3 is delivered and placed at a pressure above vapor pressure. Critical seed and fertilizer openers do not freeze and ball up with mud, Germination damage from escaping NH3 is reduced. NH3 can be placed closer to the seed. Improved opener designs can be used. The pressure increasing injection tubes are 3 times smaller and yet durable. The terminal expansion orfices can direct liquid NH3 to a much smaller area in the soil. Dry fertilizer can be more easily placed with the direct injection system. Injection line lengths do not need to be cut to equal lengths. Liquid orthophosphate fertilizer can be placed in the direct proximity of the NH3 terminal expansion orifice without freezing.
The pressure increasing system uses a maximum system pressure of 300 psi. The orifices once installed are seldom changed due to a much broader rate change. This is ideal for variable rate, site specific farming since the system handles a much greater dynamic range based on field speed or band placed rate of NH3.
The placement of NH3 in each band is accomplished with an even uninterrupted flow. This improves crop uptake of nutrients since each band is an even exact lineal band of nitrogen fertilizer. Each plant feeds equally and evenly with a strong competitive effort against weeds. This results in higher crop yields and less loss of nitrogen due to leaching. Nitrogen use efficiency goes up and nitrogen application rates can be reduced about 10%.
The economic impact and utilization of placed phosphate in the band with NH3 is substantially improved. Spring crops can utilize banded phosphate with NH3 more efficiently since phosphate uptake by the plant occurs without the xe2x80x9chot bandxe2x80x9d effect of irregular and overconcentrated bands of NH3.
The growing crop can more fully utilize all of the placed pressure increasing direct injection NH3. Over application of NH3 is critical to protect the environment. Even exact rates of NH3 improve the environment by decreasing leaching of nitrate. Additives such as N-serve can be more effectively added and mixed to Liquid NH3. This additive further reduces the chance of mobile nitrate leaching through the soil and into the drinking water.
Another critical advantage is the quick response to variable rate site specific, GPS controllers. Since the material is a noncompressible liquid with pressure above vapor pressure and lines have up to 15 times less displacement the applicator is immediately responsive to a rate change. The pressure increasing direct injection system can respond to a lull rate change in less than 3 feet of travel.
The positive displacement pump becomes a flowmeter delivering liquid NH3 to the manifold in metered amounts. Thus the pump can be sensed with an encoder and controlled hydraulically with an electronic comparator circuit. This eliminates coolers, electronic in line NH3 flow meters, and control valves that reduce pressure. The result is a much simpler system with very little maintenance and troubleshooting. The operator can stay in the tractor seat and cover substantially more acres in a day.
The versatile pressure increasing direct injection manifold can be connected to lines and openers without regard to sequence arrangement. Since no vapor is present only nonaberrant liquid NH3 follows the path of least resistance. Applicators with uneven number of openers or a short odd number of openers can utilized one common multiport manifold by blocking off any port outlet. Airseeders can be easily changed from a narrow band spacing to a much wider band spacing by disconnecting the lines and capping off the unused ports. Certain crops require wider NH3 band spacing such as sunflowers while cereal crops such as wheat require narrow NH3 band spacing. The same manifold works for both band spacings with a minimum of lost time in changing band spacing.
The cost savings are significant and NH3 can be placed shallow or deep. Airseeder operators can add the system to compliment to their dry fertilizer system lowering their cost over dry nitrogen sources by $5.00 per acre. They can often double their time between fills. With the onset of cold weather the applicator will continue to apply NH3 at accurate rates even with low tank pressure. This often results in two to three weeks of additional fall banding for corn production. The operators can operate much earlier in the day and extend their application of NH3 into freezing nights if necessary. This new system assures the long-term use of NH3 because it is safer and more economical to use.
Previous inventors and developers found it obvious to work only with pressure decreasing NH3 designs. The pressure increasing system is unique and novel to the industry. It has never been considered as an economic and safe approach to the application of NH3.
Further objects and advantage of my invention will become apparent from a consideration of the drawings and ensuing description.

Method for applying liquid nonaberrant NH3 in deep bands for agricultural crops using a process of direct high pressure injection