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WO1999004646A1 - Chemical composition - Google Patents

Chemical composition Download PDF

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Publication number
WO1999004646A1
WO1999004646A1 PCT/EP1998/004918 EP9804918W WO9904646A1 WO 1999004646 A1 WO1999004646 A1 WO 1999004646A1 EP 9804918 W EP9804918 W EP 9804918W WO 9904646 A1 WO9904646 A1 WO 9904646A1
Authority
WO
WIPO (PCT)
Prior art keywords
formic acid
calcium
solution
feed
calcium chloride
Prior art date
Application number
PCT/EP1998/004918
Other languages
French (fr)
Inventor
Johannes Adrianus Cornelis Van Ooijen
Original Assignee
Verdugt B.V.
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Verdugt B.V. filed Critical Verdugt B.V.
Priority to AU88630/98A priority Critical patent/AU8863098A/en
Publication of WO1999004646A1 publication Critical patent/WO1999004646A1/en

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Classifications

    • AHUMAN NECESSITIES
    • A23FOODS OR FOODSTUFFS; TREATMENT THEREOF, NOT COVERED BY OTHER CLASSES
    • A23KFODDER
    • A23K30/00Processes specially adapted for preservation of materials in order to produce animal feeding-stuffs
    • AHUMAN NECESSITIES
    • A23FOODS OR FOODSTUFFS; TREATMENT THEREOF, NOT COVERED BY OTHER CLASSES
    • A23KFODDER
    • A23K20/00Accessory food factors for animal feeding-stuffs
    • A23K20/10Organic substances
    • A23K20/105Aliphatic or alicyclic compounds
    • AHUMAN NECESSITIES
    • A23FOODS OR FOODSTUFFS; TREATMENT THEREOF, NOT COVERED BY OTHER CLASSES
    • A23KFODDER
    • A23K20/00Accessory food factors for animal feeding-stuffs
    • A23K20/20Inorganic substances, e.g. oligoelements
    • A23K20/24Compounds of alkaline earth metals, e.g. magnesium

Definitions

  • This invention relates to a chemical composition enriched in calcium and free carboxylic acid which is used as a feed component in animal feeds.
  • acids and salts are an important component of animal feeds due to their inherent fungicidal, bactericidal and other preservative properties.
  • Two such components are an organic carboxylic acid such as eg formic acid which has fungicidal and bactericidal activity and calcium which enhances the bone strength of the animals fed.
  • Hitherto animal feeds have been prepared in which the calcium is introduced as solid calcium carbonate or slaked lime, along with the other feed components comprising grains/cereals, protein, animal/fish meal, vitamins and carboxylic acids.
  • industry has more recently preferred the use of liquid animal feeds and preservatives which are easier to measure, mix and dispense than a diverse mixture of solid and liquid components.
  • the amount of carboxylic (eg formic) acid can be about 10-80% by weight but the amount of calcium is only about 4-0.5% w/w. This is due to the low solubility of calcium carboxylates and the basic salts of calcium in the acids, such as eg formic acid, used in animal feeds. In the prior art combinations of acids and salts have been disclosed but not in the context of the present invention.
  • JP-A-91032993 describes the use of a preservative which is prepared by combining chitosan in a solution containing a chelate compound formed from (a) at least one of alkali earth metal, aluminium, iron and copper salts and (b) at least one organic acid which may be acetic and propionic acid. It is reported that chitosan decreases the polarity of the preservative used and increases the permeability thereof through the cellular membranes of microbes. The claimed preservative is said to be used in an amount of 0.8-3% in processed foods. There is no mention of formic acid or the use of acidifiers in animal feeds nor the more efficient use of acid values.
  • JP-A- 60130346 describes a chitosan treatment process in which chitosan is immersed in aqueous solutions of salts of alkaline or alkaline earth metals and salts of organic acids including formic acid in order to form chitosan into a pulverised shape.
  • a chitosan treatment process in which chitosan is immersed in aqueous solutions of salts of alkaline or alkaline earth metals and salts of organic acids including formic acid in order to form chitosan into a pulverised shape.
  • the present invention is a composition suitable for use as an acidifier component of an animal feed, said composition comprising a solution of calcium chloride in formic acid such that the amount of calcium in said solution is greater than 5% by weight and the pH value of the solution (10% w/w) admixed with water (90% w/w) is ⁇ 2.5.
  • the calcium salt is calcium chloride which may be used as such or in its hydrated form such as eg a dihydrate.
  • Formic acid and the calcium chloride are mixed together in the appropriate proportions as desired in the animal feed. These components can be simply mixed by bringing into contact an amount of calcium chloride - which is wholly soluble in water - with formic acid and mixing the two components by eg stirring under ambient conditions.
  • Formic acid is usually sold commercially as an 85% w/w aqueous solution.
  • the advantage of the compositions of the present invention is that formic acid has a much lower dissociation constant and a much higher pK value than the corresponding inorganic acids such as carbonic, hydrochloric, sulphuric and ortho-phosphoric acids.
  • the formate ion cannot be displaced by the chloride ion from calcium chloride being of a much higher dissociation constant (K) and a much lower pK value.
  • the chloride of calcium chloride does not consume or adversely affect the formate ions in the solution thereby enabling them to perform their respective functions in the animal feed.
  • a liquid formic acid is used to acidify a feed.
  • a calcium compound such as limestone as a source of calcium in the animal feed.
  • the liquid formic acid contains calcium ions and therefore a lesser amount of limestone can be used, if desired, in the animal feed.
  • formic acid is capable of having its full effect when added to such animal feeds.
  • Examples of typical acidified piglet diet will have the following components in % by weight;
  • Soya beans (heated) 5.0
  • B-value represents buffering capacity of the feed and is the amount mis of 0. IN HC1 that is needed to reduce the pH of 10 g of feed in 100 Ml of water at pH 5.
  • the B- value is reduced to 8.0 ml.
  • a liquid composition was prepared by dissolving 5 grams of calcium chloride dihydrate in 7 grams of an aqueous solution of formic acid (85% w/w).
  • the pH value of a 10% w/w aqueous solution of the composition described above was 1.6.
  • the calcium content of the composition was 11.35% w/w.
  • the calcium remained in solution in the composition at temperatures below 10°C.
  • Example 2
  • a liquid composition was prepared by dissolving 5 grams of calcium chloride dihydrate in 6 grams of an aqueous solution of formic acid (85% w/w) and 1 gram of propionic acid (99.7% w/w).
  • the pH value of a 10% w/w aqueous solution of the composition described above was 1.6.
  • the calcium content of the composition was 11.35% w/w.
  • the calcium remained in solution in the composition at temperatures below 10°C.

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  • Chemical & Material Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Polymers & Plastics (AREA)
  • Animal Husbandry (AREA)
  • Zoology (AREA)
  • Engineering & Computer Science (AREA)
  • Food Science & Technology (AREA)
  • Inorganic Chemistry (AREA)
  • Fodder In General (AREA)

Abstract

This invention relates to a composition suitable for use as an acidifier component of an animal feed, and comprises a solution of calcium chloride in formic acid such that the amount of calcium in said solution is greater than 5 % by weight and the pH value of the solution (10 % w/w) admixed with water (90 % w/w) is < 2.5. The present invention uses a relatively lower amount of acidifier such as formic acid than would otherwise be the case if a basic salt of calcium is used.

Description

CHEMICAL COMPOSITION
This invention relates to a chemical composition enriched in calcium and free carboxylic acid which is used as a feed component in animal feeds.
It is well known that acids and salts are an important component of animal feeds due to their inherent fungicidal, bactericidal and other preservative properties. Two such components are an organic carboxylic acid such as eg formic acid which has fungicidal and bactericidal activity and calcium which enhances the bone strength of the animals fed. Hitherto animal feeds have been prepared in which the calcium is introduced as solid calcium carbonate or slaked lime, along with the other feed components comprising grains/cereals, protein, animal/fish meal, vitamins and carboxylic acids. However, industry has more recently preferred the use of liquid animal feeds and preservatives which are easier to measure, mix and dispense than a diverse mixture of solid and liquid components. One of the problems with the latter is that such a feed does not retain sufficient amount of the carboxylic acid such as eg formic acid values in the feed for the desired anti-salmonella, fungicidal or bactericidal activity nor does it retain enough of the calcium in solution due to the relatively low solubility of such calcium salts. For instance, if a basic salt such as eg calcium carbonate or calcium hydroxide is dissolved in formic acid, the basic nature of the calcium compound neutralises the acid values of the composition and the inherent insolubility of the compound in water further diminishes the amount of calcium that can be incorporated in the animal feed. Thus, in conventional liquids produced by the above method, the amount of carboxylic (eg formic) acid can be about 10-80% by weight but the amount of calcium is only about 4-0.5% w/w. This is due to the low solubility of calcium carboxylates and the basic salts of calcium in the acids, such as eg formic acid, used in animal feeds. In the prior art combinations of acids and salts have been disclosed but not in the context of the present invention. For instance, JP-A-91032993 describes the use of a preservative which is prepared by combining chitosan in a solution containing a chelate compound formed from (a) at least one of alkali earth metal, aluminium, iron and copper salts and (b) at least one organic acid which may be acetic and propionic acid. It is reported that chitosan decreases the polarity of the preservative used and increases the permeability thereof through the cellular membranes of microbes. The claimed preservative is said to be used in an amount of 0.8-3% in processed foods. There is no mention of formic acid or the use of acidifiers in animal feeds nor the more efficient use of acid values. Similarly, JP-A- 60130346 describes a chitosan treatment process in which chitosan is immersed in aqueous solutions of salts of alkaline or alkaline earth metals and salts of organic acids including formic acid in order to form chitosan into a pulverised shape. There is no mention of using a combination of a calcium chloride with formic acid nor indeed the objectives, problems or solutions contemplated by the present invention.
It has now been found that such problems may be overcome by pre-forming a solution of a calcium compound in the carboxylic acid and using this preformed solution as a liquid feed component thereby enhancing the amount of acid as well calcium in the feed.
Accordingly, the present invention is a composition suitable for use as an acidifier component of an animal feed, said composition comprising a solution of calcium chloride in formic acid such that the amount of calcium in said solution is greater than 5% by weight and the pH value of the solution (10% w/w) admixed with water (90% w/w) is < 2.5.
The calcium salt is calcium chloride which may be used as such or in its hydrated form such as eg a dihydrate.
Formic acid and the calcium chloride are mixed together in the appropriate proportions as desired in the animal feed. These components can be simply mixed by bringing into contact an amount of calcium chloride - which is wholly soluble in water - with formic acid and mixing the two components by eg stirring under ambient conditions. Formic acid is usually sold commercially as an 85% w/w aqueous solution. The advantage of the compositions of the present invention is that formic acid has a much lower dissociation constant and a much higher pK value than the corresponding inorganic acids such as carbonic, hydrochloric, sulphuric and ortho-phosphoric acids. Thus, the formate ion cannot be displaced by the chloride ion from calcium chloride being of a much higher dissociation constant (K) and a much lower pK value. Hence, the chloride of calcium chloride does not consume or adversely affect the formate ions in the solution thereby enabling them to perform their respective functions in the animal feed. Thus, it is possible to generate formulations containing greater than 10% w/w of calcium and yet retaining a high formic acid value than hitherto possible.
To acidify a feed, normally a liquid formic acid is used. However, its effectiveness is decreased when this is used in conjunction with a calcium compound such as limestone as a source of calcium in the animal feed. In the present invention the liquid formic acid contains calcium ions and therefore a lesser amount of limestone can be used, if desired, in the animal feed. By adopting this method, formic acid is capable of having its full effect when added to such animal feeds. Examples of typical acidified piglet diet will have the following components in % by weight;
Barley meal 42.3
Wheat feed 19.1
Maize 10.0 Soya protein (45% CP) 15.3
Fish meal 2
Soya beans (heated) 5.0
DL Methionine 0.10
Dicalcium phosphate 1.2 Limestone 0.6
Animal fat 3.0
Vitamins Premix 0.5
Salt 0.25
Formic Acid (85%) 0.6 B-value* 11.5 ml
* B-value represents buffering capacity of the feed and is the amount mis of 0. IN HC1 that is needed to reduce the pH of 10 g of feed in 100 Ml of water at pH 5. When a solution of calcium in formic acid according to the present invention is used, the B- value is reduced to 8.0 ml. The present invention is illustrated with reference to the following Examples: Example 1:
A liquid composition was prepared by dissolving 5 grams of calcium chloride dihydrate in 7 grams of an aqueous solution of formic acid (85% w/w). The pH value of a 10% w/w aqueous solution of the composition described above was 1.6. The calcium content of the composition was 11.35% w/w. The calcium remained in solution in the composition at temperatures below 10°C. Example 2:
A liquid composition was prepared by dissolving 5 grams of calcium chloride dihydrate in 6 grams of an aqueous solution of formic acid (85% w/w) and 1 gram of propionic acid (99.7% w/w). The pH value of a 10% w/w aqueous solution of the composition described above was 1.6. The calcium content of the composition was 11.35% w/w. The calcium remained in solution in the composition at temperatures below 10°C. Example 3:
A typical composition was prepared according to the invention and compared with a conventional (control) feed composition (both in % w/w) for its acidity using the same amount of formic acid. The results are tabulated below:
Figure imgf000006_0001
The above results show that the formulations of the present invention have greater acidity for the same amount of acid if a solution of calcium chloride in the carboxylic acid is used instead of acid and limestone.

Claims

Claims :
1. A composition suitable for use as an acidifier component of an animal feed, said composition comprising a solution of calcium chloride in formic acid such that the amount of calcium in said solution is greater than 5% by weight and the pH value of the solution (10% w/w) admixed with water (90% w/w) is < 2.5.
2. A composition according to Claim 1 wherein formic acid is used as an aqueous solution thereof.
3. A composition according to any one of the preceding Claims wherein calcium chloride is used as such or in its hydrated form.
4. A composition according to any one of the preceding Claims wherein formic acid and the calcium chloride are mixed together in the appropriate proportions as desired in the animal feed.
5. A composition according to any one of the preceding Claims wherein formic acid and calcium chloride are mixed by bringing into contact an amount of calcium chloride with an aqueous solution of formic acid and mixing the two by stirring under ambient conditions.
6. A composition according to any one of the preceding Claims wherein formic acid is used as an 85% w/w aqueous solution.
7. An animal feed composition comprising as diet the following components in % by weight: Barley meal 42.3
Wheat feed 19.1
Maize 10.0
Soya protein (45% CP) 15.3
Fish meal 2 Soya beans (heated) 5.0 DL Methionine 0.10
Dicalcium phosphate 1.2
Limestone 0.6
Animal fat 3.0
Vitamins Premix 0.5
Salt 0.25
Formic Acid (85%) 0.6
B-value 11.5 ml wherein B-value represents buffering capacity of the feed and is the amount in mis of 0. IN HCl that is needed to reduce the pH of 10 g of feed in 100 ml of water at pH 5.
PCT/EP1998/004918 1997-07-28 1998-07-17 Chemical composition WO1999004646A1 (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
AU88630/98A AU8863098A (en) 1997-07-28 1998-07-17 Chemical composition

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
GBGB9715908.1A GB9715908D0 (en) 1997-07-28 1997-07-28 Chemical composition
GB9715908.1 1997-07-28

Publications (1)

Publication Number Publication Date
WO1999004646A1 true WO1999004646A1 (en) 1999-02-04

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ID=10816590

Family Applications (1)

Application Number Title Priority Date Filing Date
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GB (1) GB9715908D0 (en)
WO (1) WO1999004646A1 (en)

Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2004019683A3 (en) * 2002-08-30 2004-04-15 Novus Int Inc Antimicrobial compositions
US7232514B2 (en) 2001-03-14 2007-06-19 Applied Materials, Inc. Method and composition for polishing a substrate
US7465471B2 (en) 2003-03-21 2008-12-16 Novus International, Inc. Palatability of aquaculture feed
US8465761B2 (en) 2007-07-03 2013-06-18 Novus International, Inc. Piglet feed rations having low levels of fermentable carbohydrates
US8691843B2 (en) 2006-07-12 2014-04-08 Novus International, Inc. Antioxidant combinations for use in ruminant feed rations
CN105379965A (en) * 2015-12-28 2016-03-09 上海美农生物科技股份有限公司 Production method for protective feed acidifier

Citations (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3901976A (en) * 1972-03-20 1975-08-26 Dow Chemical Co Thixotropic liquid feed supplements for ruminants of carbohydrates, npn and clay
GB1515487A (en) * 1976-03-30 1978-06-28 Degussa Process for the preparation of silage
EP0009366A1 (en) * 1978-09-14 1980-04-02 Bp Nutrition Limited Milk containing animal feed compositions and aqueous feeds based on them
JPS60130346A (en) * 1983-12-20 1985-07-11 Nippon Soda Co Ltd Treatment of chitosan
JPS6254201A (en) * 1985-09-03 1987-03-09 Mitsubishi Chem Ind Ltd Polarizing film and its manufacturing method
EP0219997A1 (en) * 1985-10-10 1987-04-29 BP Chemicals Limited Antimicrobial additives for compound animal feedstuffs
DE3733080A1 (en) * 1986-10-02 1988-04-14 Anton Kahlbacher Liquid thawing substance for combating compacted snow and sheet ice (black ice)
JPH09263477A (en) * 1996-01-23 1997-10-07 Daiichi Seimo Kk Liquid calcium fertilizer

Patent Citations (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3901976A (en) * 1972-03-20 1975-08-26 Dow Chemical Co Thixotropic liquid feed supplements for ruminants of carbohydrates, npn and clay
GB1515487A (en) * 1976-03-30 1978-06-28 Degussa Process for the preparation of silage
EP0009366A1 (en) * 1978-09-14 1980-04-02 Bp Nutrition Limited Milk containing animal feed compositions and aqueous feeds based on them
JPS60130346A (en) * 1983-12-20 1985-07-11 Nippon Soda Co Ltd Treatment of chitosan
JPS6254201A (en) * 1985-09-03 1987-03-09 Mitsubishi Chem Ind Ltd Polarizing film and its manufacturing method
EP0219997A1 (en) * 1985-10-10 1987-04-29 BP Chemicals Limited Antimicrobial additives for compound animal feedstuffs
DE3733080A1 (en) * 1986-10-02 1988-04-14 Anton Kahlbacher Liquid thawing substance for combating compacted snow and sheet ice (black ice)
JPH09263477A (en) * 1996-01-23 1997-10-07 Daiichi Seimo Kk Liquid calcium fertilizer

Non-Patent Citations (3)

* Cited by examiner, † Cited by third party
Title
DATABASE WPI Section Ch Week 8534, Derwent World Patents Index; Class C03, AN 85-206512, XP002085814 *
DATABASE WPI Section Ch Week 8715, Derwent World Patents Index; Class A23, AN 87-105939, XP002085815 *
PATENT ABSTRACTS OF JAPAN vol. 098, no. 002 30 January 1998 (1998-01-30) *

Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US7232514B2 (en) 2001-03-14 2007-06-19 Applied Materials, Inc. Method and composition for polishing a substrate
WO2004019683A3 (en) * 2002-08-30 2004-04-15 Novus Int Inc Antimicrobial compositions
US7465471B2 (en) 2003-03-21 2008-12-16 Novus International, Inc. Palatability of aquaculture feed
US8691843B2 (en) 2006-07-12 2014-04-08 Novus International, Inc. Antioxidant combinations for use in ruminant feed rations
US8465761B2 (en) 2007-07-03 2013-06-18 Novus International, Inc. Piglet feed rations having low levels of fermentable carbohydrates
CN105379965A (en) * 2015-12-28 2016-03-09 上海美农生物科技股份有限公司 Production method for protective feed acidifier

Also Published As

Publication number Publication date
GB9715908D0 (en) 1997-10-01
AU8863098A (en) 1999-02-16

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