Propionic acid, ammonia, propanediol and water solutions and...

Food or edible material: processes – compositions – and products – Inhibiting chemical or physical change of food by contact... – Biocidal or disinfecting chemical agent

Reexamination Certificate

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C426S623000, C426S630000, C426S635000, C426S807000

Reexamination Certificate

active

06183794

ABSTRACT:

The present invention relates to solutions of propionic acid, ammonia, propanediol and water, with or without other auxiliaries, and to their use in livestock nutrition.
The use of propionic acid and its salts or esters as preserving additive to feedstuffs of a wide variety of types has been known for a long time (DE-A 20 19 125, DE-A 20 19 972). It is particularly used to preserve feedstuffs such as compound feeds and cereals, legumes or residues from human food. The effect of propionic acid and its salts derives from their biocidal and long-lasting biostatic effect (Zbl. Bakt. II, 125 (1970) 100).
When pure propionic acid is used as preservative, the storage and use are made difficult by the corrosive effect and the unpleasant odor of the acid. Because of these disadvantages, the pure acid is in many cases replaced by its salts, especially the sodium or calcium salt, or its esters. The disadvantage of using the salts or esters is that a considerable part of the biocidal and biostatic activity of propionic acid is lost.
EP-B-0 122 979 discloses the dehydrating effect of virtually anhydrous propylene glycol in the preservation of fish feed. To prevent moldiness, 0.1% by weight of calcium propionate is also added to the fish feed. The method described for the preservation of fish feed is unsuitable for preserving other livestock feeds because of the large amount of propylene glycol (17 to 50% of the weight of the feed) and the small amount of propionic acid.
DE-A 35 00 187 describes a stable pharmaceutical product for treating ketosis in calving cattle, consisting of calcium propionate, dextrose, propylene glycol and other additives such as vitamins, mineral salts and/or amino acids.
EP-A-0 241 400 discloses aqueous solutions of ammonium propionate, which was prepared by mixing 2 mol of propionic acid with 1 mol of ammonium bicarbonate, and at least 5% by weight of propylene glycol. The disadvantage of these aqueous solutions is that their water content is at least 15% by weight, which is too high for concentrated use of ammonium propionate in feed preservation, which reduces the effectiveness of the propionic acid.
DE-A 26 44 351 describes liquid mixtures of ammonium propionate, propylene glycol and water, where the ammonium propionate:propylene glycol molar ratio is from 1:0.1 to 1:0.7 and the ammonium propionate:water molar ratio is from 1:2.0 to 1:3.5. The water content of the liquid mixture is thus in the range from 20 to 30% by weight and is too high for wide use of the preservative. An increasing residual moisture content of the feedstuff to be preserved means that a distinct increase in the amounts used is necessary.
Owing to this and owing to the high water content, the solutions described in EP-A 0 241 400 and DE-A 26 44 351 can be used reliably for preservation of feedstuffs only if their residual moisture content does not exceed 20%. If the residual moisture content of the feed is higher, spoilage often occurs.
For optimal preservation of the feedstuffs, the preservative should have a number of beneficial properties, such as
1. little or no corrosive effect
2. large and/or long-lasting biocidal and/or biostatic effect
3. preservative easy to use (for example good miscibility with the foodstuffs to be preserved)
4. reduced odor (ie. low vapor pressure of the preservative over the solution)
5. minimal water content (ie. small amount used, high activity)
6. little or no damage to materials (ie. no damage to seals, valves and other items).
7. no freezing of the preservative at low temperatures
8. adequate reduction in the pH of the foodstuff to be preserved.
It is an object of the present invention to provide preservative solutions which have little or no corrosive effect, little or no odor and have a high activity, but, on the other hand, have a freezing point which is sufficiently low for practical purposes.
We have found that this object is achieved by a solution consisting essentially of
78.0-93.0% by weight propionic acid,
0.5-5.0% by weight ammonia,
1.0-6.0% by weight propanediol,
0.1-10.0% by weight water,
where the amounts of individual components add up to 100% by weight.
A preferred embodiment is a solution consisting essentially of
a) 92% by weight propionic acid,
3% by weight ammonia,
4% by weight propanediol and
1% by weight water
b) with or without other auxiliaries.
Another preferred embodiment is a solution consisting essentially of
a) 90% by weight propionic acid,
3% by weight ammonia,
4% by weight propanediol and
1% by weight water and
2% by weight surface-active substance
b) with or without other auxiliaries.
Another preferred embodiment is a solution consisting essentially of
a) 93% by weight propionic acid,
3% by weight ammonia,
4% by weight propanediol
b) with or without other auxiliaries.
The solutions according to the invention contain 78-93% by weight propionic acid, preferably 85-93% by weight, particularly preferably 87-92% by weight.
The ammonia is present in the solutions in the range from 0.5 to 5.0% by weight, preferably between 2.0 to 4.0% by weight.
Propanediol means propylene glycol and trimethylene glycol, which are advantageously present in the solution in the range from 1 to 6% by weight, preferably between 1 to 4% by weight, particularly preferably between 2 to 4% by weight.
For high biological activity of the solutions, their water content is advantageously 10% by weight or less, and can even be 0% by weight, preferably 0.1 to 6% by weight, particularly preferably 1 to 3% by weight.
The solutions according to the invention may additionally contain surface-active substances and/or at least one other C
1
-C
8
-carboxylic acid such as formic acid, acetic, isobutyric, n-butyric, n-valeric, 2-methylbutyric, levulinic, sorbic, benzoic, acrylic and methacrylic acids, and the alkali metal or alkaline earth metal salts thereof customary in agriculture, and the ammonium salts thereof or mixtures thereof, advantageously using as other acid formic acid or acetic acid and/or salts thereof.
Examples of suitable surface-active substances are all anionic, cationic, amphoteric or non-ionic surfactants or mixtures thereof, as long as they are suitable for livestock nutrition, such as polyglycol esters, polyglycerol ethers of fatty alcohols, sugar esters (esters of, for example, sucrose and edible fatty acids), sugar glycerides (mixtures of sucrose esters and mono- and diglycerides of sucrose), polyoxyethylene/polyoxypropylene copolymers (average molecular weight from 6800 to 9000), glycerol mono-, di- or triesters such as mono- and diglycerides of edible fatty acids with lower carboxylic acids such as citric acid, acetic acid, lactic acid, monoacethyl- and diacetyltartaric acid, tartaric acid or mono- and diglycerides with edible fatty acids, sorbitan esters or ethoxylates, fatty acid ester ethoxylates, ethoxylated alkyl ethers of higher fatty acids or lecithin.
Examples of surface-active substances which may be mentioned are substances such as the various Brij® types, ie. cetyl, lauryl, oleyl or stearyl ethers with 2 to 100 polyoxyethylene units, the various Myrj® types [lacuna] stearin esters with 8 to 100 polyoxyethylene units (=POE), the various Span® types such as Span 20 (sorbitan monolaurate), Span 40 (sorbitan monopalmitate), Span 60 (sorbitan monostearate) or Span 80 (sorbitan monooleate), the various Tween® types such as Tween 20 (POE(20) sorbitan monolaurate), Tween 40 (POE(20) sorbitan monopalmitate), Tween 60 (POE(20) sorbitan monostearate) or Tween 80 (POE(20) sorbitan monooleate), the various Triton® types (octylphenol ethoxylates) such as Triton X-15, X-35, X-100 CG, X-305 (70%), X-405 (70%), X-705 (70%), the ethoxylated castor oils such as polyoxyethylene glycerol triricinoleate 35 (Cremophor® EL) or polyoxyethylene glycerol trihydroxystearate 40 (Cremophor® RH40), the ethoxylated 12-hydroxystearic acids such as polyoxyethylene 660 12′-hydroxystearate (Solutol® HS15) or sodium lauryl sulfate. Preference is given to polyoxyethylene 20 sorbitan monopalimitate, polyoxyethylene 20 sorbitan monostearate, polyoxyet

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