CA1061632A - Preservative for use on grain, forage and the like - Google Patents
Preservative for use on grain, forage and the likeInfo
- Publication number
- CA1061632A CA1061632A CA243,811A CA243811A CA1061632A CA 1061632 A CA1061632 A CA 1061632A CA 243811 A CA243811 A CA 243811A CA 1061632 A CA1061632 A CA 1061632A
- Authority
- CA
- Canada
- Prior art keywords
- formaldehyde
- propionic acid
- composition
- methanol
- water
- Prior art date
- Legal status (The legal status 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 status listed.)
- Expired
Links
Abstract
ABSTRACT OF THE DISCLOSURE
A preservative for use on grain, forage and the like, comprising propionic acid, formaldehyde, water and methanol.
A preservative for use on grain, forage and the like, comprising propionic acid, formaldehyde, water and methanol.
Description
~ 0~ 3~ ~
This invention relates to a liquid mixture of propionic acid and formaldehyde, particularly suitable as a preservative for grain of high moisture content and forage. The mixtures of this invention remain stable, and highly effective, on long-term storage at low tempera~ures without phase separation (such as precipitation of solid formaldehyde poly-merization products). When such separation occurs and one attempts to spray material from a storage container ~such as a drum) the sprayed material may be deficient in one of the components, e.g., formaldehyde, -and the desired preservative effect is not attained; this is avoided by the use of the mixtures of this invention.
Accordingly, the present invention provides for a preservative composition consisting essentially of pr~pionic acid, formaldehyde, water and methanol, the weight proportion of propionic acid being at least 50% and the proportion of formaldehyde being about 1/4 to 1 mol of ~
formaldehyde per mol of propionic acid, the water methanol ratio in said ;
composition being greater than 1 and being such that said composition remains a clear solution on aging for a year at -18C.
The present invention also provides a preservative composition consisting essentially of (a) an alkanoic acid selected from the group consisting of propionic acid and mixtures of propionic acid with at least one other lower alkanoic acid of 1 to 4 carbon atoms; (b) formaldehyde;
(c) water; and (d) an alcohol selected from the group consisting of ;
methanol and mixtures of methanol with another alcohol which is a member of the group consisting of ethanolJ the propanols, butanol, and the lower glycols, the weight proportions of alkanoic acid being at least 50%, the water: alcohol mole ratio being greater than 1 and less than 5, and the mole ratio of formaldehyde to the sum of water and alcohol being at least about 0.4.
According to a further aspect the present invention provides a ; process forthe preservation of grain, forage and cellulosic materials which comprises applying to such materials a preservative composition as referred to above.
p~ - 1 - ~ '. ' In particular, accordlng to the in~ention moisture-containing grain or forage can be treated With a uniform liquid blend of propionic acid, formaldehyde, water and methanol. The weight proportion of propionic acid is at least about 50%, such as about 50, 60, 70 or 80%.
It is found thatin the propionic acid, as the solvent medium, the stability of added aqueous fornlaldehyde is adversely affected. Replacement of much of the water by methanol leads, surprisingly, to poorer results (see the Comparative Example, below). It is found, however, that when an intermediate amount of methanol is present (for instance about 20 parts by weight of methanol with 43 parts by weight of water and 37 parts by weight of formaldehyde) a composition of high storage stability is obtained.
Thus the water:me~hanol mol ratio may be more than l, preferably more than 3 ~e.g. 4) and less than 5, and the mol ratio of formaldehyde to the sum of water and methanol may be in the range of about 0.4 to 0.8. The amount of formaldehyde is preferably in the range of about 1/4 to 1 mol (e.g. about lt3 mol) per mol of propionic acid.
The composition is preferably a clear homogeneous liquid. On storage for prolonged periods at low temperature (e.g. -185) it may - la -~J ' ~ `
3~
become slightly turbicl presum~bly due to the formation of stably suspended particles of formaldehyde polymerizltion products therein. This turbid mix~
ture Is still a stable uniform liquid blend and may be used just like the clear solution; e. g. it may be pumped and sprayed onto the grain or forage, giving 5 excellent protection against spoilage.
This invention provides a grain- or forage-treating composition that is highly effective and stable even under low temperature winter conditions.
The composition may be sprayed onto, for instance, corn (maize) h~ving a moisture content of about 15% or much higher (such as about 20%, e. g.
10 about 25 to 30 or 35%) which is to be stored and used for cattle feed, the amount of composition applied to corn bein8 in the range of about 0.5 to 2%
(e. g. 0. 8, 1. 0, 1. 2, 1. 5 or 2~o)~ with the larger proportions being used for grain that has higher moisture content and/or is to be stored at higher temperatures (e. g. above 16~C). High local moisture contents such as 25%
1~ may occur In the material being stored (even though the overall moi3ture content of the mass being stored is below 15%) owing to moistu~e mi~ration in the mass which may result from temperature differentials between outer and inner portions of the mass and from convection currents transporting such moisture; the preservative composition of this invention is thus also 20 useful for application to grain or forage having such lo~er overall moisture conterts. The material flows well for application over a wide range of temperatures (e.g. -20 to ~40C).
The mixture may be prepared in any suitable manner, 35 by mixing propionic acid with a fresh aqueous solution of formaldehyde (C~I20) con-? 7 taining methanol.
The following e}~arnples are given to illustrate this invention further.In this application all proportions are by weight unless otherwise indicated.
r ~ :
06~3~ ~
EXI~MPLE
The following compositions are highly effective pre$ervatives and ' are stable on storage for long periods of time (o~er a year) at 0C.
(a) 80% propionic acid, 7.4% CH20, 4.0% methanol, 8.6% H20;
(b) 70% propionic acid, 11.1% CH20, 6.0% methanol, 12.9% H20;
(c) 60% propionic acid, 14.8% CH20, 8.0% methanol, 17.2% H20;
(d) 50% propionic acid, 18.5% CH20, 10% methanol, 21.5% H20;
(e) The composition of Example (b) above is a clear solution having a specific gravity 20/20C of about 1.04, a boiling point of about 100C
and a vapor pressure of about 40 mmHg at 46C, 54 mmHg at 50C, 70 mmHg at 53C, 121 mmHg at 63C and 129 mmHg at 67C. `~
COMPARATIVE EXAMPLE
A composition containing 70% propionic acid, 11.1% CH20, 13.3%
methanol and 2.7% H20, when stored at -18C forms a copious white precipitate ~presumably of a formaldehyde polymer) in less than a month. The formaldehyde, methanol, and water are supplied as a "Formcel" ~registered trademark of the Celanese Corporation) composition of formaldehyde and an alcohol ( in this ~` -case'methanol) containing small quantities of water). ' It is within the broader scope of the invention to use other lower alkanoic àcids of 1 to 4 carbon atoms in place of part of the propionic acid;
for instance, one may substitute acetic acid, butyric acid or isobutyric acid `'' ~or mixtures thereof) for part (e.g. 1/10 or 113) of the propionic acid. It is also within the broader scope of the invention'to'replace part (e.g. 1/10 ~ '-or 1/3) of the methanol by another alcohol such as ethanol, n-propanol, ;' ; ' i-propanol, or butanol, or ethylene glycol, propylene glycols or other lower '''' ;
glycols. "' It is also within the broader scope of the invention to employ the composition for the preservation of other carbohydrate (e.g. cellulosic) '.'.:',,:', :~
: ' ' ~ , "
::
... ..
materi31s such as wood chips, bagasse, citrus pulp, be~t pulp, potato peel-ing s ~ e tc .
For preservation of certain cellulosic materials, such as hay, the composition may be more conveniently diluted with water before it is applied 5 to the cellulosic material; that is the composition may serve as a concen-trate to which may be added 50~10, 1007~o, Z00% or even 300% of its weight of water before spraying to improve the surface distribution.
It is understood that the foregoing detailed descriptiorl is given merely by way of illustration and that variations may be made therein withGut 10 departing from the spirit of the invention. ~he "Abstract" given aboYe is merely for the convenience of technical searchers and is not to be given any weight with respect to the scope of the invention.
,
This invention relates to a liquid mixture of propionic acid and formaldehyde, particularly suitable as a preservative for grain of high moisture content and forage. The mixtures of this invention remain stable, and highly effective, on long-term storage at low tempera~ures without phase separation (such as precipitation of solid formaldehyde poly-merization products). When such separation occurs and one attempts to spray material from a storage container ~such as a drum) the sprayed material may be deficient in one of the components, e.g., formaldehyde, -and the desired preservative effect is not attained; this is avoided by the use of the mixtures of this invention.
Accordingly, the present invention provides for a preservative composition consisting essentially of pr~pionic acid, formaldehyde, water and methanol, the weight proportion of propionic acid being at least 50% and the proportion of formaldehyde being about 1/4 to 1 mol of ~
formaldehyde per mol of propionic acid, the water methanol ratio in said ;
composition being greater than 1 and being such that said composition remains a clear solution on aging for a year at -18C.
The present invention also provides a preservative composition consisting essentially of (a) an alkanoic acid selected from the group consisting of propionic acid and mixtures of propionic acid with at least one other lower alkanoic acid of 1 to 4 carbon atoms; (b) formaldehyde;
(c) water; and (d) an alcohol selected from the group consisting of ;
methanol and mixtures of methanol with another alcohol which is a member of the group consisting of ethanolJ the propanols, butanol, and the lower glycols, the weight proportions of alkanoic acid being at least 50%, the water: alcohol mole ratio being greater than 1 and less than 5, and the mole ratio of formaldehyde to the sum of water and alcohol being at least about 0.4.
According to a further aspect the present invention provides a ; process forthe preservation of grain, forage and cellulosic materials which comprises applying to such materials a preservative composition as referred to above.
p~ - 1 - ~ '. ' In particular, accordlng to the in~ention moisture-containing grain or forage can be treated With a uniform liquid blend of propionic acid, formaldehyde, water and methanol. The weight proportion of propionic acid is at least about 50%, such as about 50, 60, 70 or 80%.
It is found thatin the propionic acid, as the solvent medium, the stability of added aqueous fornlaldehyde is adversely affected. Replacement of much of the water by methanol leads, surprisingly, to poorer results (see the Comparative Example, below). It is found, however, that when an intermediate amount of methanol is present (for instance about 20 parts by weight of methanol with 43 parts by weight of water and 37 parts by weight of formaldehyde) a composition of high storage stability is obtained.
Thus the water:me~hanol mol ratio may be more than l, preferably more than 3 ~e.g. 4) and less than 5, and the mol ratio of formaldehyde to the sum of water and methanol may be in the range of about 0.4 to 0.8. The amount of formaldehyde is preferably in the range of about 1/4 to 1 mol (e.g. about lt3 mol) per mol of propionic acid.
The composition is preferably a clear homogeneous liquid. On storage for prolonged periods at low temperature (e.g. -185) it may - la -~J ' ~ `
3~
become slightly turbicl presum~bly due to the formation of stably suspended particles of formaldehyde polymerizltion products therein. This turbid mix~
ture Is still a stable uniform liquid blend and may be used just like the clear solution; e. g. it may be pumped and sprayed onto the grain or forage, giving 5 excellent protection against spoilage.
This invention provides a grain- or forage-treating composition that is highly effective and stable even under low temperature winter conditions.
The composition may be sprayed onto, for instance, corn (maize) h~ving a moisture content of about 15% or much higher (such as about 20%, e. g.
10 about 25 to 30 or 35%) which is to be stored and used for cattle feed, the amount of composition applied to corn bein8 in the range of about 0.5 to 2%
(e. g. 0. 8, 1. 0, 1. 2, 1. 5 or 2~o)~ with the larger proportions being used for grain that has higher moisture content and/or is to be stored at higher temperatures (e. g. above 16~C). High local moisture contents such as 25%
1~ may occur In the material being stored (even though the overall moi3ture content of the mass being stored is below 15%) owing to moistu~e mi~ration in the mass which may result from temperature differentials between outer and inner portions of the mass and from convection currents transporting such moisture; the preservative composition of this invention is thus also 20 useful for application to grain or forage having such lo~er overall moisture conterts. The material flows well for application over a wide range of temperatures (e.g. -20 to ~40C).
The mixture may be prepared in any suitable manner, 35 by mixing propionic acid with a fresh aqueous solution of formaldehyde (C~I20) con-? 7 taining methanol.
The following e}~arnples are given to illustrate this invention further.In this application all proportions are by weight unless otherwise indicated.
r ~ :
06~3~ ~
EXI~MPLE
The following compositions are highly effective pre$ervatives and ' are stable on storage for long periods of time (o~er a year) at 0C.
(a) 80% propionic acid, 7.4% CH20, 4.0% methanol, 8.6% H20;
(b) 70% propionic acid, 11.1% CH20, 6.0% methanol, 12.9% H20;
(c) 60% propionic acid, 14.8% CH20, 8.0% methanol, 17.2% H20;
(d) 50% propionic acid, 18.5% CH20, 10% methanol, 21.5% H20;
(e) The composition of Example (b) above is a clear solution having a specific gravity 20/20C of about 1.04, a boiling point of about 100C
and a vapor pressure of about 40 mmHg at 46C, 54 mmHg at 50C, 70 mmHg at 53C, 121 mmHg at 63C and 129 mmHg at 67C. `~
COMPARATIVE EXAMPLE
A composition containing 70% propionic acid, 11.1% CH20, 13.3%
methanol and 2.7% H20, when stored at -18C forms a copious white precipitate ~presumably of a formaldehyde polymer) in less than a month. The formaldehyde, methanol, and water are supplied as a "Formcel" ~registered trademark of the Celanese Corporation) composition of formaldehyde and an alcohol ( in this ~` -case'methanol) containing small quantities of water). ' It is within the broader scope of the invention to use other lower alkanoic àcids of 1 to 4 carbon atoms in place of part of the propionic acid;
for instance, one may substitute acetic acid, butyric acid or isobutyric acid `'' ~or mixtures thereof) for part (e.g. 1/10 or 113) of the propionic acid. It is also within the broader scope of the invention'to'replace part (e.g. 1/10 ~ '-or 1/3) of the methanol by another alcohol such as ethanol, n-propanol, ;' ; ' i-propanol, or butanol, or ethylene glycol, propylene glycols or other lower '''' ;
glycols. "' It is also within the broader scope of the invention to employ the composition for the preservation of other carbohydrate (e.g. cellulosic) '.'.:',,:', :~
: ' ' ~ , "
::
... ..
materi31s such as wood chips, bagasse, citrus pulp, be~t pulp, potato peel-ing s ~ e tc .
For preservation of certain cellulosic materials, such as hay, the composition may be more conveniently diluted with water before it is applied 5 to the cellulosic material; that is the composition may serve as a concen-trate to which may be added 50~10, 1007~o, Z00% or even 300% of its weight of water before spraying to improve the surface distribution.
It is understood that the foregoing detailed descriptiorl is given merely by way of illustration and that variations may be made therein withGut 10 departing from the spirit of the invention. ~he "Abstract" given aboYe is merely for the convenience of technical searchers and is not to be given any weight with respect to the scope of the invention.
,
Claims (9)
PROPERTY OR PRIVILEGE IS CLAIMED ARE DEFINED AS FOLLOWS:
1. Preservative composition consisting essentially of propionic acid, formaldehyde, water and methanol, the weight proportion of propionic acid being at least 50% and the proportion of formaldehyde being about 1/4 to 1 mol of formaldehyde per mol of propionic acid, the water:methanol ratio in said composition being greater than 1 and being such that said composition remains a clear solution on aging for a year at -18°C.
2. A preservative composition consisting essentially of (a) an alkanoic acid selected from the group consisting of propionic acid and mixtures of propionic acid with at least one other lower alkanoic acid of 1 to 4 carbon atoms: (b) formaldehyde; (c) water; and (d) an alcohol selected from the group consisting of methanol and mixtures of methanol with another alcohol which is a member of the group consisting of ethanol, the propanols, butanol, and the lower glycols, the weight proportion of alkanoic acid being at least 50%, the water: alcohol mole ratio being greater than 1 and less than 5, and the mole ratio of formaldehyde to the sum of Water and alcohol being at least about 0.4.
3. A preservative composition as in claim 2 in which said mole ratio of formaldehyde is about 0.4 to 0.8 and in which the alkanoic acid is propionic acid and the alcohol is methanol.
4. Preservative composition as in claim 3 in which there is about 1/4 to 1 mol of formaldehyde per mol of propionic acid.
5. Process for the preservation of grain, forage, and cellulosic material which comprises applying to such material a composition as in claim 2 in amount of 0.5 to 2% by weight.
6. A preservative composition as in claim 2 wherein the alkanoic acid is propionic acid.
7. A preservative composition as in claim 6 in which said mole ratio of formaldehyde is about 0.4 to 0.8.
8. A preservative composition as in claim 7 in which there is about 1/4 to 1 mole of formaldehyde per mol of propionic acid.
9. Process for the preservation of grain, forage and cellulosic materials which comprises applying to such material a composition as in claim 6 in an amount of 0.5 to 2% by weight.
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US55592775A | 1975-03-06 | 1975-03-06 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA1061632A true CA1061632A (en) | 1979-09-04 |
Family
ID=24219168
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA243,811A Expired CA1061632A (en) | 1975-03-06 | 1976-01-20 | Preservative for use on grain, forage and the like |
Country Status (1)
| Country | Link |
|---|---|
| CA (1) | CA1061632A (en) |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5096718A (en) * | 1982-09-17 | 1992-03-17 | The State Of Oregon Acting By And Through The Oregon State Board Of Higher Education On Behalf Of Oregon State University | Preserving foods using metabolites of propionibacteria other than propionic acid |
| EP0605287A1 (en) * | 1992-12-30 | 1994-07-06 | Anitox Corporation | Contamination-resistant animal feedstuffs |
| US5635484A (en) * | 1982-09-17 | 1997-06-03 | The State Of Oregon Acting By And Through The Oregon State Board Of Higher Education On Behalf Of Oregon State University | Propionibacteria peptide microcin |
| WO1999048382A1 (en) * | 1998-03-24 | 1999-09-30 | Stichting Dienst Landbouwkundig Onderzoek | Preservation by higher alcohols |
-
1976
- 1976-01-20 CA CA243,811A patent/CA1061632A/en not_active Expired
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5096718A (en) * | 1982-09-17 | 1992-03-17 | The State Of Oregon Acting By And Through The Oregon State Board Of Higher Education On Behalf Of Oregon State University | Preserving foods using metabolites of propionibacteria other than propionic acid |
| US5260061A (en) * | 1982-09-17 | 1993-11-09 | The State Of Oregon Acting By And Through The State Board Of Higher Education On Behalf Of Oregon State University | Propionibacteria metabolites inhibit spoilage yeast in foods |
| US5635484A (en) * | 1982-09-17 | 1997-06-03 | The State Of Oregon Acting By And Through The Oregon State Board Of Higher Education On Behalf Of Oregon State University | Propionibacteria peptide microcin |
| EP0605287A1 (en) * | 1992-12-30 | 1994-07-06 | Anitox Corporation | Contamination-resistant animal feedstuffs |
| US5505976A (en) * | 1992-12-30 | 1996-04-09 | Anitox Corporation | Contamination-resistant animal feedstuffs |
| WO1999048382A1 (en) * | 1998-03-24 | 1999-09-30 | Stichting Dienst Landbouwkundig Onderzoek | Preservation by higher alcohols |
| EP0958749A1 (en) * | 1998-03-24 | 1999-11-24 | Stichting Instituut voor Dierhouderij en Diergezondheid (ID-DLO) | Preservation by higher alcohols |
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