CA2123572A1 - Stabilised peracid solutions - Google Patents
Stabilised peracid solutionsInfo
- Publication number
- CA2123572A1 CA2123572A1 CA002123572A CA2123572A CA2123572A1 CA 2123572 A1 CA2123572 A1 CA 2123572A1 CA 002123572 A CA002123572 A CA 002123572A CA 2123572 A CA2123572 A CA 2123572A CA 2123572 A1 CA2123572 A1 CA 2123572A1
- Authority
- CA
- Canada
- Prior art keywords
- peracetic acid
- alcohol ethoxylate
- wetting agent
- aliphatic alcohol
- stabilised
- 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.)
- Abandoned
Links
Classifications
-
- A—HUMAN NECESSITIES
- A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
- A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
- A01N37/00—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom having three bonds to hetero atoms with at the most two bonds to halogen, e.g. carboxylic acids
- A01N37/16—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom having three bonds to hetero atoms with at the most two bonds to halogen, e.g. carboxylic acids containing the group; Thio analogues thereof
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C407/00—Preparation of peroxy compounds
- C07C407/003—Separation; Purification; Stabilisation; Use of additives
- C07C407/006—Stabilisation; Use of additives
Abstract
2123572 9310088 PCTABS00022 Peracetic acid solutions tend to decompose slowly during storage.
The storage stability of the peracetic acid therein can be improved by introduction of an effective amount of an aliphatic alcohol ethoxylate wetting agent which has an EO number of greater than 4 and preferably from 8 to 20. The wetting agent is preferably derived from an alcohol containing from 8 to 18 carbons. Desirably at least 0.1 % and particularly from 0.5 to 5 % alcohol ethoxylate is incorporated.
The storage stability of the peracetic acid therein can be improved by introduction of an effective amount of an aliphatic alcohol ethoxylate wetting agent which has an EO number of greater than 4 and preferably from 8 to 20. The wetting agent is preferably derived from an alcohol containing from 8 to 18 carbons. Desirably at least 0.1 % and particularly from 0.5 to 5 % alcohol ethoxylate is incorporated.
Description
W093/l00~ PCT/GB92/02087 . . .
Stabilised Peracid Solutions The present invention relates to stabilised peracid solutions and their production.
Soluble peracids have a number of attractive 5 propertie~, including oxidati~e and broad spectrum biocidal properties. As a consequence, they have been employed or proposed for use as oxidising agents in chemicsl synthesis reactions, as bleaching agents in the bleaching or cleans~ng of laundry and other substrates 10 and as disinfectants or sterilisers for especially li~uid media or solid surfaces.
One peracid which is widely available and suitable for the above-mentioned uses is peracetic acid which is usually produced in an aqueous solution by reaction between acetic acid and hydrogen peroxide, optionally in the presence of a catalyst such as a strong acid, including sulphuric, phosphoric and/or phosphonic acids.
In a number of cQmmercially a~ailable peracetic acid-containing compositions, the peracetic acid i~ present in equilibrium with the two reactants from which it is produced and water. Although such c~mpositions may be used immediately after their production, they are often stored for considerable periods during their distribution and/or by the end user. During storage there is a tendency for some decomposition of the peroxygen species to occur, thereby progressively impairing the effecti~eness of the composition for its desired purpose .
WO93/10088 PCT~GB92/02087 or reouiring the use of an increased amount to attain a desired concentration of active ingredient. Plainly, therefore, it is desirable to find ways of improving the stability of peracid compositions, by which is meant ways s of ameliorating or inhibiting the rate at which the measured concentration of peroxygen compounds and particularly peracetic acid falls during storage.
One method of apparently improving the peracid stability in peracid compositions is described by Henkel l0 in British Patent Specification no l 580 561, which comprises employing a higher concentration of hydrogen pero~ide relative to the peracetic acid than an e~uilibrium concentration. Essentially the same concept is disclosed in European Patent 0 024 l25 to L'Air Li~uide, but augmented by simultaneously diluting the acid catalyst below a minimal level so as to retard the rate of re-equilibration of the composition. By using excess hydrogen peroxide inventors seek to balance peracetic acid generation arising from slow re-e~uilibration against its rate of decomposition.
Disadvantageously, the use of a considerable excess of one of the reagents inevitably increases the cost of the final product.
An alternative method of improving the storage ~s stability of peracetic acid solutions has been proposed in European Patent 0 147 207 to Albright & Wilson, namely the incorporation of certain C6-C18 alkyl substituted benzene sulphonate wetting agents. In the course of the present investigations, it has been found that certain 30 other wetting agents can be even more effective than alkyl benzene sulphonates at stabilising peracetic acid solutions.
According to one aspect of the present invention, there is provided a process for improving the storage stability 3s of peracetic acid in a solution containing a wetting agent characterised by introducing therein an effective W093/loo~ PCT/GB92/02087 concentration of an aliphatic alcohol ethoxylate wetting agent which has an E0 number of greater than 4.
According to a second aspect of the invention, there are provided peracetic acid solutions having improved 5 storage stability by introduction therein of an effective concentration of an aliphatic alcohol ethoxylate wetting agent which has an EO number of greater than 4.
Advantageously, it has been found that the introduction of the specified wetting agent improves the retention of 10 the ~mportant constituent, namely the peracetic acid in solution relative to like compositions containing no wetting agent or an alkyl benzene sulphonate, though it may not improve the retention overall of peroxygen species in the solution during storage. In general, peracetic acid solutions are stored at ambient temperature, which can vary depending upon the locality and the time of year, but is often between about 0 and 35C.
The amount of aliphatic alcohol ethoxylate employed in the processes and compositions of the present invention preferably is at least 0.1%, particularly at least 0.2%
w/w and often at least 0.5% w/w of the peracetic acid solution. In many instances, its concentration in the solution is not greater than 5% w/w. In some embodiments a convenient range of concentrations combining the benefits of wetting and improved stability comprises from about 0.5 to about 2.5% w/w of the solution.
The aliphatic alcohol ethoxylates e~ployed herein preferably have an E0 number of at least 6, often up to about 25, and usually, on average, between about 8 and about 20. It will be recognised though that the E~
number is an average and in individual molecules, the number of ethylene oxide units can be below, within or 35 above the ranges stated above. The alcohol moiety preferably contains at least 6 carbons and often up to about 20 carbons on average. In many alcohol W093/10088 PCTlGB92/02087 2I 235 7~ 4 ethoxylates that are suitable for the present in~ention, the alcohol moiety contains on average a chain length of from 8 to 18 carbons. The alcohol moiety is often either a prim~ry or a secondary alcohol.
5 The alcohol ethoxylate can be introduced into the peracetic acid solution either during its manufacture or when it has been produced. Thus, in one variation, the alcohol ethoxylate is mixed with the reactants which form peracetic acid, viz the acetic acid and a~ueous hydrogen 10 peroxide solution, and the mixture is stored until a desired proportion of the reactants have been con~erted to peracetic acid. Conventional variants in the manufact~-ing process can be employed. Thus, optionally, the manufacture can employ a strong acid 15 catalyst selected at the operator's discretion, often in the range of from 0.1 to 10% w~w and selected from ` sulphuric acid, phosphoric acid and organic phosphonic acids (eg hydroxyethylenediphosphonic acid) or a mixture of mineral acid and organic phosphonic acid. A suitable reaction temperature can be selected at the operator~s discretion at frnm 5 to 95C, and often from 15 to 60C.
Suitable reaction times, which can vary from minutes to days depending upon the reaction temperature and amount of catalyst present, can be calculated from published 25 data, for example broadly as set out in a paper by Y
Sawaki and Y Ogata published in Decem~er 1965 in the Bulletin of the Chemical Society of Japan vol 38 no 12, pp2103/6. Naturally, conventional and appropriate safety precautions are taken during manufacture that are commensurate with the selected reaction conditions, such as the use of an inert atmosphere at ele~ated reaction temperatures and adequate agitation of the mixture.
The concentration of peracetic acid in solution can be selected within a wide range, depending on its intended 35 end use. Its concentration is usually at least 0.01% w/w often at least 0.1% w/w and normally up to about 40% w/w.
In many instances, the peracetic acid concentration is .
` 5 2123~72 from about 0.03% to about 15%; ready to use mixtures conveniently containing from 0.03 to 5% and dilutable concentrates often containing from about 10 to lS~ w~w.
The amounts of reactants can be selected to leave s residual concentrations of them, ~iz hydrogen peroxide and acetic acid within wide ranges, typically each having a selected residual in the range of from about 1 to about 40% w/w. The amounts of reagents to use can be calculated using data on the equilibrium point of the 1~ reaction. For many ready to use mixtures, the reactants concentrations are each often chosen in the range of up to about 15% w/w and for dilutable concentrates they are often chosen in the range of about 1~ to about 30% w/w.
It will be understood, of course, that where the compositions, as made, differ to a significant extent from the corresponding equilibrium mixture, there will be a tendency for further or re-equilibration to occur during sub~equent storage.
The present invention is particularly applicable to peracetic acid compositions in which the peracetic acid, acetic acid, hydrogen peroxide and water therein are approximately in e;~uilibrium.
For some purposes it is desirable to produce a peracetic acid solution which contains a wetting agent, but which also generates relatively little foaming on application. Advantageously, it has been found that the selection of alcohol ethoxylate according to the present in~ention can not only improve peracetic acid storage stability, but also enable a low-foaming wetting agent-30 containing composition to be formed.
The stabilised compositions of the present inventionare especially suitable for spraying onto or otherwise ~ contacting solid surfaces, for example equipment, apparatus, containers, pipework, work surfaces, sanitary 3~ ware and the like for the purposes of disinfecting or sanitising them, the wetting agent promoting contact between the solution and the surface.
21 2 3 5 7 2 6 PCTtGB92/02087 Ha~ing described the invention in general terms, specific embodiments thereof will hereafter be described more explicitly, by way of example only.
Comparison 1 and 2 and Example 3 s In each of these Comparisons and Example, a commercial equilibrated peracetic acid-containing composition was employed available from Interox Chemicals Ltd. under their trade mark PROXITANE 0510, and containing nominally 5% w/w acetic acid, 10% w~w acetic acid and 20% w/w 10 hydrogen peroxide. In Comparison 2 and Example 3, 1.2 parts by weight of wetting agent were mixed into the peracetic acid composition at laboratory ambient temperature, about 22C. The mixtures were stored at laboratory ambient temperature in translucent polyethylene storage bottles. The peracetic acid and total a~ailable oxygen (A~ox) contents of each composition were determ~ned at intervals during the storsge, and the values obtained after 58 weeks storage are compared with their respective initial values and 20 expressed below as a percentage of PAA and A~ox retained, rounded to the nearest whole number. The total Avox content was measured using a standard ferric iron catalysed thiosulphate/iodine titration, and the peracetic acid content was measured by subtracting from ~s the total A~ox content the hydrogen peroxide content obtained by ferroin-indicated titration with ceric sulphate solution.
Table 1 Wetting agent ~ Retained PAA Avox Comparison 1 No wetting agent 86 90 Comparison 2 Alkylbenzenesulphonic acid 85 95 (Alkyl = C12 approx) Example 3 alcohol ethoxylate 88 91 3s (Alkyl = C9, E0 z 8) From Table 1, it can be seen that the effect of em~loying the alkyl benzene sulphonic acid is to increase WO93/1~ PCT/GB92/02087 `` , 2123~72 the overall A~ox retention of the composition relative to the corresponding composition which did not contain wetting agent, but that the stability of the most active constituent, namely PAA, was actually slightly worse.
5 On the other hand, when the alcohol ethoxylate was employed, the overall effect was to not only increase the stability slightly of the compositions when expressed as total Avox, but more importantly, a significant contribution to this improvement arose from the rather 10 greater increase in stability of the most active constituent, PAA. This demonstrate~ the superiority of the alcohol ethoxylate for PAA stabilisation compared with an alkyLbenzenesulphonic acid.
The compositions produced and tested in the foregoing Comparisons and Example were also tested to show their foaming and wetting properties.
The wetting trial was conducted by obser~in~ how long it took for a standard drop of sample to be absorbed by a piece of cotton (Brunch~eiller).
The foaming trial was conducted by allowing the whole of a sample of 25 mls of composition to flow under gravity from a height of 25 from a wide-tipped burette into a measuring cylinder (100mls) of diameter 28 mms placed underneath. The volume of foam generated initially and still present after 5 minutes is given in Table 2 below.
Table 2 Wetting time (secs) Volume of foam (mls) Initially 5 minutes 30 Comparison 1 >300 0 0 Comparison 2 5 38 36 Example 3 5 32 17 From Table 2, it can be seen that one effect of incorporating the wetting agent is that the ability of 35 the composition to wet a surface is markedly improved, and that when the alcohol ethoxylate is employed the extent of foam generated is detectably less than if an wo g~l~N* ~12 3 5 72 PCT/GB92/02087 acid and 6% hydrogen peroxide. In Comparison 5 and Examples 6 to 8, 2% of commercially available alcohol ethoxylates specified in Table 3 are mixed in at ambient temperature, about 22C, and stored in polyethylene S sample bottles.
The peracetic acid, hydr~gen peroxide and total Avox contents of the compositions were measured at the start of the storage period and at regular intervals thereafter. The results after 8 months storage are also 10 included in Table 3.
Table 3 Wetting Agent % Retained EO number Alkyl chain PAA Avox Comparison 4No wetting agents 82 100 lS Comparison 5 4 C12 80 100 Example 6 6.5 C9 85 100 Example 7 8 C9-11 89 100 Example 8 11 C13/15 92 100 .
~0 From Table 3, it can be seen that although the total Avox retention was the same for all the c,ompositions tested, there was a very significant change in the proportion of peracetic acid retained. When the EO
number was only 4, as in comparison 5, the proportion 25 retained was no better than when no wetting agent was present, but as the EO number increased, the proportion of peracetic acid which was retained increased.
Comparisons 9 and 10 and Examples 11 to 14 In these Comparisons and Examples non-equilibrium 30 solutions containing approximately 300 ppm peracetic acid were obtained by diluting the commercially available peracetic acid composition of Comparison 1, PROXITANE
0510, with demineralised water. In comparison 10 and Examples 13 and 14, the composition was doped with 0.5%
35 w/w sulphuric acid as re-equilibrium catalyst, and in Examples 11 to 14, the composition was mixed with a commercially available alcohol ethoxylate having an EO
number of 7 and a 6?%/33% mixture of C13 and C15 carbon 212357~
were obtained by diluting the commercially available peracetic acid composition of Comparison 1, PROXIT~NE
0510, with demineralised water. In compasison 10 and Examples 13 and 14, the composition was doped with 0.5 s w/w sulphuric acid as re-equilibrium catalyst, and in Examples 11 to 14, the composition was mixed with a commercially available alcohol ethoxylate ha~ing an EO
number of 7 and a 67~/33% mixture of C13 and C15 car~on chain lengths in the alcohol moiety. The compositions 0 were stored in polyethylene bottles at ambient temperat~e, about 22C, and the peracetic acid content measured periodically by a direct method thiosulphate/iodine titration at below -10C in ethane -1,2-diol. The results after 29 hours are listed in Table 4.
Table 4 % wetting Agent % H2SO4 % P
Comparison 9 None 70 Comparison 10 None 0.5 56 Example 11 0.2 None 80 Example 12 1.0 None 100 Example 13 0.2 0.5 60 ~xample 14 1.0 0.5 100 From Table 4, it can be seen that the presence of the alcohol ethoxyla~e increased the proportion of peracetic acid retained in the composition, and that the effect was greater at the higher concentration of the wetting agent. This shows that the useful life of diluted non-equilibrium peracetic acid compositions can be extended by incorporating the selected alcohol ethoxylates according to tha present in~ention.
Stabilised Peracid Solutions The present invention relates to stabilised peracid solutions and their production.
Soluble peracids have a number of attractive 5 propertie~, including oxidati~e and broad spectrum biocidal properties. As a consequence, they have been employed or proposed for use as oxidising agents in chemicsl synthesis reactions, as bleaching agents in the bleaching or cleans~ng of laundry and other substrates 10 and as disinfectants or sterilisers for especially li~uid media or solid surfaces.
One peracid which is widely available and suitable for the above-mentioned uses is peracetic acid which is usually produced in an aqueous solution by reaction between acetic acid and hydrogen peroxide, optionally in the presence of a catalyst such as a strong acid, including sulphuric, phosphoric and/or phosphonic acids.
In a number of cQmmercially a~ailable peracetic acid-containing compositions, the peracetic acid i~ present in equilibrium with the two reactants from which it is produced and water. Although such c~mpositions may be used immediately after their production, they are often stored for considerable periods during their distribution and/or by the end user. During storage there is a tendency for some decomposition of the peroxygen species to occur, thereby progressively impairing the effecti~eness of the composition for its desired purpose .
WO93/10088 PCT~GB92/02087 or reouiring the use of an increased amount to attain a desired concentration of active ingredient. Plainly, therefore, it is desirable to find ways of improving the stability of peracid compositions, by which is meant ways s of ameliorating or inhibiting the rate at which the measured concentration of peroxygen compounds and particularly peracetic acid falls during storage.
One method of apparently improving the peracid stability in peracid compositions is described by Henkel l0 in British Patent Specification no l 580 561, which comprises employing a higher concentration of hydrogen pero~ide relative to the peracetic acid than an e~uilibrium concentration. Essentially the same concept is disclosed in European Patent 0 024 l25 to L'Air Li~uide, but augmented by simultaneously diluting the acid catalyst below a minimal level so as to retard the rate of re-equilibration of the composition. By using excess hydrogen peroxide inventors seek to balance peracetic acid generation arising from slow re-e~uilibration against its rate of decomposition.
Disadvantageously, the use of a considerable excess of one of the reagents inevitably increases the cost of the final product.
An alternative method of improving the storage ~s stability of peracetic acid solutions has been proposed in European Patent 0 147 207 to Albright & Wilson, namely the incorporation of certain C6-C18 alkyl substituted benzene sulphonate wetting agents. In the course of the present investigations, it has been found that certain 30 other wetting agents can be even more effective than alkyl benzene sulphonates at stabilising peracetic acid solutions.
According to one aspect of the present invention, there is provided a process for improving the storage stability 3s of peracetic acid in a solution containing a wetting agent characterised by introducing therein an effective W093/loo~ PCT/GB92/02087 concentration of an aliphatic alcohol ethoxylate wetting agent which has an E0 number of greater than 4.
According to a second aspect of the invention, there are provided peracetic acid solutions having improved 5 storage stability by introduction therein of an effective concentration of an aliphatic alcohol ethoxylate wetting agent which has an EO number of greater than 4.
Advantageously, it has been found that the introduction of the specified wetting agent improves the retention of 10 the ~mportant constituent, namely the peracetic acid in solution relative to like compositions containing no wetting agent or an alkyl benzene sulphonate, though it may not improve the retention overall of peroxygen species in the solution during storage. In general, peracetic acid solutions are stored at ambient temperature, which can vary depending upon the locality and the time of year, but is often between about 0 and 35C.
The amount of aliphatic alcohol ethoxylate employed in the processes and compositions of the present invention preferably is at least 0.1%, particularly at least 0.2%
w/w and often at least 0.5% w/w of the peracetic acid solution. In many instances, its concentration in the solution is not greater than 5% w/w. In some embodiments a convenient range of concentrations combining the benefits of wetting and improved stability comprises from about 0.5 to about 2.5% w/w of the solution.
The aliphatic alcohol ethoxylates e~ployed herein preferably have an E0 number of at least 6, often up to about 25, and usually, on average, between about 8 and about 20. It will be recognised though that the E~
number is an average and in individual molecules, the number of ethylene oxide units can be below, within or 35 above the ranges stated above. The alcohol moiety preferably contains at least 6 carbons and often up to about 20 carbons on average. In many alcohol W093/10088 PCTlGB92/02087 2I 235 7~ 4 ethoxylates that are suitable for the present in~ention, the alcohol moiety contains on average a chain length of from 8 to 18 carbons. The alcohol moiety is often either a prim~ry or a secondary alcohol.
5 The alcohol ethoxylate can be introduced into the peracetic acid solution either during its manufacture or when it has been produced. Thus, in one variation, the alcohol ethoxylate is mixed with the reactants which form peracetic acid, viz the acetic acid and a~ueous hydrogen 10 peroxide solution, and the mixture is stored until a desired proportion of the reactants have been con~erted to peracetic acid. Conventional variants in the manufact~-ing process can be employed. Thus, optionally, the manufacture can employ a strong acid 15 catalyst selected at the operator's discretion, often in the range of from 0.1 to 10% w~w and selected from ` sulphuric acid, phosphoric acid and organic phosphonic acids (eg hydroxyethylenediphosphonic acid) or a mixture of mineral acid and organic phosphonic acid. A suitable reaction temperature can be selected at the operator~s discretion at frnm 5 to 95C, and often from 15 to 60C.
Suitable reaction times, which can vary from minutes to days depending upon the reaction temperature and amount of catalyst present, can be calculated from published 25 data, for example broadly as set out in a paper by Y
Sawaki and Y Ogata published in Decem~er 1965 in the Bulletin of the Chemical Society of Japan vol 38 no 12, pp2103/6. Naturally, conventional and appropriate safety precautions are taken during manufacture that are commensurate with the selected reaction conditions, such as the use of an inert atmosphere at ele~ated reaction temperatures and adequate agitation of the mixture.
The concentration of peracetic acid in solution can be selected within a wide range, depending on its intended 35 end use. Its concentration is usually at least 0.01% w/w often at least 0.1% w/w and normally up to about 40% w/w.
In many instances, the peracetic acid concentration is .
` 5 2123~72 from about 0.03% to about 15%; ready to use mixtures conveniently containing from 0.03 to 5% and dilutable concentrates often containing from about 10 to lS~ w~w.
The amounts of reactants can be selected to leave s residual concentrations of them, ~iz hydrogen peroxide and acetic acid within wide ranges, typically each having a selected residual in the range of from about 1 to about 40% w/w. The amounts of reagents to use can be calculated using data on the equilibrium point of the 1~ reaction. For many ready to use mixtures, the reactants concentrations are each often chosen in the range of up to about 15% w/w and for dilutable concentrates they are often chosen in the range of about 1~ to about 30% w/w.
It will be understood, of course, that where the compositions, as made, differ to a significant extent from the corresponding equilibrium mixture, there will be a tendency for further or re-equilibration to occur during sub~equent storage.
The present invention is particularly applicable to peracetic acid compositions in which the peracetic acid, acetic acid, hydrogen peroxide and water therein are approximately in e;~uilibrium.
For some purposes it is desirable to produce a peracetic acid solution which contains a wetting agent, but which also generates relatively little foaming on application. Advantageously, it has been found that the selection of alcohol ethoxylate according to the present in~ention can not only improve peracetic acid storage stability, but also enable a low-foaming wetting agent-30 containing composition to be formed.
The stabilised compositions of the present inventionare especially suitable for spraying onto or otherwise ~ contacting solid surfaces, for example equipment, apparatus, containers, pipework, work surfaces, sanitary 3~ ware and the like for the purposes of disinfecting or sanitising them, the wetting agent promoting contact between the solution and the surface.
21 2 3 5 7 2 6 PCTtGB92/02087 Ha~ing described the invention in general terms, specific embodiments thereof will hereafter be described more explicitly, by way of example only.
Comparison 1 and 2 and Example 3 s In each of these Comparisons and Example, a commercial equilibrated peracetic acid-containing composition was employed available from Interox Chemicals Ltd. under their trade mark PROXITANE 0510, and containing nominally 5% w/w acetic acid, 10% w~w acetic acid and 20% w/w 10 hydrogen peroxide. In Comparison 2 and Example 3, 1.2 parts by weight of wetting agent were mixed into the peracetic acid composition at laboratory ambient temperature, about 22C. The mixtures were stored at laboratory ambient temperature in translucent polyethylene storage bottles. The peracetic acid and total a~ailable oxygen (A~ox) contents of each composition were determ~ned at intervals during the storsge, and the values obtained after 58 weeks storage are compared with their respective initial values and 20 expressed below as a percentage of PAA and A~ox retained, rounded to the nearest whole number. The total Avox content was measured using a standard ferric iron catalysed thiosulphate/iodine titration, and the peracetic acid content was measured by subtracting from ~s the total A~ox content the hydrogen peroxide content obtained by ferroin-indicated titration with ceric sulphate solution.
Table 1 Wetting agent ~ Retained PAA Avox Comparison 1 No wetting agent 86 90 Comparison 2 Alkylbenzenesulphonic acid 85 95 (Alkyl = C12 approx) Example 3 alcohol ethoxylate 88 91 3s (Alkyl = C9, E0 z 8) From Table 1, it can be seen that the effect of em~loying the alkyl benzene sulphonic acid is to increase WO93/1~ PCT/GB92/02087 `` , 2123~72 the overall A~ox retention of the composition relative to the corresponding composition which did not contain wetting agent, but that the stability of the most active constituent, namely PAA, was actually slightly worse.
5 On the other hand, when the alcohol ethoxylate was employed, the overall effect was to not only increase the stability slightly of the compositions when expressed as total Avox, but more importantly, a significant contribution to this improvement arose from the rather 10 greater increase in stability of the most active constituent, PAA. This demonstrate~ the superiority of the alcohol ethoxylate for PAA stabilisation compared with an alkyLbenzenesulphonic acid.
The compositions produced and tested in the foregoing Comparisons and Example were also tested to show their foaming and wetting properties.
The wetting trial was conducted by obser~in~ how long it took for a standard drop of sample to be absorbed by a piece of cotton (Brunch~eiller).
The foaming trial was conducted by allowing the whole of a sample of 25 mls of composition to flow under gravity from a height of 25 from a wide-tipped burette into a measuring cylinder (100mls) of diameter 28 mms placed underneath. The volume of foam generated initially and still present after 5 minutes is given in Table 2 below.
Table 2 Wetting time (secs) Volume of foam (mls) Initially 5 minutes 30 Comparison 1 >300 0 0 Comparison 2 5 38 36 Example 3 5 32 17 From Table 2, it can be seen that one effect of incorporating the wetting agent is that the ability of 35 the composition to wet a surface is markedly improved, and that when the alcohol ethoxylate is employed the extent of foam generated is detectably less than if an wo g~l~N* ~12 3 5 72 PCT/GB92/02087 acid and 6% hydrogen peroxide. In Comparison 5 and Examples 6 to 8, 2% of commercially available alcohol ethoxylates specified in Table 3 are mixed in at ambient temperature, about 22C, and stored in polyethylene S sample bottles.
The peracetic acid, hydr~gen peroxide and total Avox contents of the compositions were measured at the start of the storage period and at regular intervals thereafter. The results after 8 months storage are also 10 included in Table 3.
Table 3 Wetting Agent % Retained EO number Alkyl chain PAA Avox Comparison 4No wetting agents 82 100 lS Comparison 5 4 C12 80 100 Example 6 6.5 C9 85 100 Example 7 8 C9-11 89 100 Example 8 11 C13/15 92 100 .
~0 From Table 3, it can be seen that although the total Avox retention was the same for all the c,ompositions tested, there was a very significant change in the proportion of peracetic acid retained. When the EO
number was only 4, as in comparison 5, the proportion 25 retained was no better than when no wetting agent was present, but as the EO number increased, the proportion of peracetic acid which was retained increased.
Comparisons 9 and 10 and Examples 11 to 14 In these Comparisons and Examples non-equilibrium 30 solutions containing approximately 300 ppm peracetic acid were obtained by diluting the commercially available peracetic acid composition of Comparison 1, PROXITANE
0510, with demineralised water. In comparison 10 and Examples 13 and 14, the composition was doped with 0.5%
35 w/w sulphuric acid as re-equilibrium catalyst, and in Examples 11 to 14, the composition was mixed with a commercially available alcohol ethoxylate having an EO
number of 7 and a 6?%/33% mixture of C13 and C15 carbon 212357~
were obtained by diluting the commercially available peracetic acid composition of Comparison 1, PROXIT~NE
0510, with demineralised water. In compasison 10 and Examples 13 and 14, the composition was doped with 0.5 s w/w sulphuric acid as re-equilibrium catalyst, and in Examples 11 to 14, the composition was mixed with a commercially available alcohol ethoxylate ha~ing an EO
number of 7 and a 67~/33% mixture of C13 and C15 car~on chain lengths in the alcohol moiety. The compositions 0 were stored in polyethylene bottles at ambient temperat~e, about 22C, and the peracetic acid content measured periodically by a direct method thiosulphate/iodine titration at below -10C in ethane -1,2-diol. The results after 29 hours are listed in Table 4.
Table 4 % wetting Agent % H2SO4 % P
Comparison 9 None 70 Comparison 10 None 0.5 56 Example 11 0.2 None 80 Example 12 1.0 None 100 Example 13 0.2 0.5 60 ~xample 14 1.0 0.5 100 From Table 4, it can be seen that the presence of the alcohol ethoxyla~e increased the proportion of peracetic acid retained in the composition, and that the effect was greater at the higher concentration of the wetting agent. This shows that the useful life of diluted non-equilibrium peracetic acid compositions can be extended by incorporating the selected alcohol ethoxylates according to tha present in~ention.
Claims (9)
1 A process for improving the storage stability of peracetic acid in a solution containing a wetting agent characterised by introducing therein an effective concentration of an aliphatic alcohol ethoxylate wetting agent which has an EO number of greater than 4.
2 Peracetic acid solutions having improved storage stability by introduction therein of an effective concentration of an aliphatic alcohol ethoxylate wetting agent which has an EO number of greater than 4.
3. A process or composition according to claim 1 or 2 characterised in that from 0.1 to 5% w/w and preferably from 0.5 to 5% w/w of aliphatic alcohol ethoxylate is employed.
4. A process or composition according to any preceding claim characterised in that the aliphatic alcohol ethoxylate has an EO number of at least 6 and preferably from about 8 to about 20.
A process or composition according to any preceding claim characterised in that the alcohol moiety in the aliphatic alcohol ethoxylate contains at least 6 and preferably from 8 to 18 carbons.
6 A process or composition according to any preceding claim characterised in that the aliphatic alcohol ethoxylate is introduced into the mixture of reactants during the manufacture of the peracetic acid solution.
7 A process or composition according to any preceding claim characterised in that the solution to be stabilised contains from about 0.03 to about 15% w/w peracetic acid.
8 A process for stabilising peracid-containing solutions or stabilised peracid compositions themselves substantially as described herein with respect to Example 3.
9. A process for stabilising peracid-containing solutions or stabilised peracid compositions themselves substantially as described herein with respect to any novel feature or novel combination of features.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| GB9124160.4 | 1991-11-14 | ||
| GB919124160A GB9124160D0 (en) | 1991-11-14 | 1991-11-14 | Stabilised peracid solutions |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA2123572A1 true CA2123572A1 (en) | 1993-05-27 |
Family
ID=10704597
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA002123572A Abandoned CA2123572A1 (en) | 1991-11-14 | 1992-11-11 | Stabilised peracid solutions |
Country Status (15)
| Country | Link |
|---|---|
| US (1) | US5489706A (en) |
| EP (1) | EP0613464B1 (en) |
| AT (1) | ATE133406T1 (en) |
| AU (1) | AU663127B2 (en) |
| BR (1) | BR9206754A (en) |
| CA (1) | CA2123572A1 (en) |
| DE (1) | DE69207920T2 (en) |
| DK (1) | DK0613464T3 (en) |
| ES (1) | ES2085652T3 (en) |
| FI (1) | FI106121B (en) |
| GB (1) | GB9124160D0 (en) |
| GR (1) | GR3019712T3 (en) |
| NO (1) | NO305281B1 (en) |
| NZ (1) | NZ245105A (en) |
| WO (1) | WO1993010088A1 (en) |
Families Citing this family (34)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB9425882D0 (en) * | 1994-12-21 | 1995-02-22 | Solvay Interox Ltd | Thickened peracid compositions |
| GB9425881D0 (en) * | 1994-12-21 | 1995-02-22 | Solvay Interox Ltd | Thickened peracid compositions |
| DE69805697T3 (en) * | 1997-04-24 | 2006-11-30 | Chemoxal S.A. | Disinfecting and fungicidal composition based on peracetic acid and an amine oxide |
| DE19812588C1 (en) * | 1998-03-23 | 1999-04-22 | Degussa | Scale-inhibiting per:carboxylic acid solutions |
| US6010729A (en) | 1998-08-20 | 2000-01-04 | Ecolab Inc. | Treatment of animal carcasses |
| US7150884B1 (en) | 2000-07-12 | 2006-12-19 | Ecolab Inc. | Composition for inhibition of microbial growth |
| US6514556B2 (en) * | 2000-12-15 | 2003-02-04 | Ecolab Inc. | Method and composition for washing poultry during processing |
| US7316824B2 (en) * | 2000-12-15 | 2008-01-08 | Ecolab Inc. | Method and composition for washing poultry during processing |
| US6635286B2 (en) * | 2001-06-29 | 2003-10-21 | Ecolab Inc. | Peroxy acid treatment to control pathogenic organisms on growing plants |
| US20030129254A1 (en) * | 2001-07-13 | 2003-07-10 | Saraya Co., Ltd., A Japanese Corporation | Bactericidal/disinfectant peracetic and acid composition |
| US7507429B2 (en) * | 2004-01-09 | 2009-03-24 | Ecolab Inc. | Methods for washing carcasses, meat, or meat products with medium chain peroxycarboxylic acid compositions |
| EP1703791B1 (en) * | 2004-01-09 | 2014-07-23 | Ecolab Inc. | Medium chain peroxycarboxylic acid compositions |
| US7887641B2 (en) * | 2004-01-09 | 2011-02-15 | Ecolab Usa Inc. | Neutral or alkaline medium chain peroxycarboxylic acid compositions and methods employing them |
| US20050161636A1 (en) * | 2004-01-09 | 2005-07-28 | Ecolab Inc. | Methods for washing and processing fruits, vegetables, and other produce with medium chain peroxycarboxylic acid compositions |
| US7504123B2 (en) * | 2004-01-09 | 2009-03-17 | Ecolab Inc. | Methods for washing poultry during processing with medium chain peroxycarboxylic acid compositions |
| US7771737B2 (en) * | 2004-01-09 | 2010-08-10 | Ecolab Inc. | Medium chain peroxycarboxylic acid compositions |
| US8999175B2 (en) * | 2004-01-09 | 2015-04-07 | Ecolab Usa Inc. | Methods for washing and processing fruits, vegetables, and other produce with medium chain peroxycarboxylic acid compositions |
| US7754670B2 (en) | 2005-07-06 | 2010-07-13 | Ecolab Inc. | Surfactant peroxycarboxylic acid compositions |
| US9034390B2 (en) * | 2006-05-02 | 2015-05-19 | Bioneutral Laboratories Corporation | Anti-microbial composition and method for making and using same |
| US20090074881A1 (en) * | 2006-05-02 | 2009-03-19 | Bioneutral Laboratories Corporation Usa | Antimicrobial cidality formulations with residual efficacy, uses thereof, and the preparation thereof |
| US20070264356A1 (en) * | 2006-05-09 | 2007-11-15 | Kelly Ann Ames | Process for the preparation of a ready-to-use disinfectant |
| US20080033227A1 (en) * | 2006-08-03 | 2008-02-07 | David Campbell Graves | Recovery of sulfur value in an alkylation process |
| US20080087390A1 (en) * | 2006-10-11 | 2008-04-17 | Fort James Corporation | Multi-step pulp bleaching |
| US8075857B2 (en) | 2006-10-18 | 2011-12-13 | Ecolab Usa Inc. | Apparatus and method for making a peroxycarboxylic acid |
| US7547421B2 (en) * | 2006-10-18 | 2009-06-16 | Ecolab Inc. | Apparatus and method for making a peroxycarboxylic acid |
| US9752105B2 (en) | 2012-09-13 | 2017-09-05 | Ecolab Usa Inc. | Two step method of cleaning, sanitizing, and rinsing a surface |
| US20140308162A1 (en) | 2013-04-15 | 2014-10-16 | Ecolab Usa Inc. | Peroxycarboxylic acid based sanitizing rinse additives for use in ware washing |
| CA2890831C (en) | 2012-11-08 | 2020-04-21 | Evonik Industries Ag | Method for producing equilibrium peracetic acid and equilibrium peracetic acid obtainable by the method |
| US9789216B2 (en) | 2012-12-14 | 2017-10-17 | Saban Ventures Pty Limited | Synergistic disinfection enhancement |
| AU2013359956B2 (en) | 2012-12-14 | 2017-08-10 | Saban Ventures Pty Limited | Disinfectant |
| US11439151B2 (en) * | 2017-10-20 | 2022-09-13 | Biosafe Systems Llc | Process for treating an agricultural medium |
| BR112020016430A2 (en) | 2018-02-14 | 2020-12-15 | Ecolab Usa Inc. | METHODS TO CLEAN AND DISINFECT A MEMBRANE ELEMENT WITHIN A MEMBRANE SYSTEM AND TO REDUCE THE FORMATION OF BIOFILM AND BACTERIAL SPORES IN A MEMBRANE. |
| GB2572364B (en) | 2018-03-27 | 2023-04-12 | Selden Res Ltd | Improved Bleaching Compositions |
| KR102520527B1 (en) | 2020-12-24 | 2023-04-11 | 군산대학교산학협력단 | Stability Enhanced Low Concentration Peracetic Acid Disinfectant Compositions |
Family Cites Families (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB978437A (en) * | 1960-05-02 | 1964-12-23 | Lloyd Dynamowerke G.M.B.H. | |
| FR2578332B1 (en) * | 1985-01-30 | 1989-03-31 | Air Liquide | ASEPTISAN COMPOSITION FOR CONTACT LENSES |
| EP0412599B1 (en) * | 1989-08-08 | 1995-12-13 | Akzo Nobel N.V. | Aqueous peroxide compositions with improved safety profile |
-
1991
- 1991-11-14 GB GB919124160A patent/GB9124160D0/en active Pending
-
1992
- 1992-11-11 DK DK92922821.1T patent/DK0613464T3/en active
- 1992-11-11 WO PCT/GB1992/002087 patent/WO1993010088A1/en active IP Right Grant
- 1992-11-11 DE DE69207920T patent/DE69207920T2/en not_active Expired - Lifetime
- 1992-11-11 US US08/244,026 patent/US5489706A/en not_active Expired - Lifetime
- 1992-11-11 AU AU28954/92A patent/AU663127B2/en not_active Ceased
- 1992-11-11 BR BR9206754A patent/BR9206754A/en not_active IP Right Cessation
- 1992-11-11 AT AT92922821T patent/ATE133406T1/en not_active IP Right Cessation
- 1992-11-11 CA CA002123572A patent/CA2123572A1/en not_active Abandoned
- 1992-11-11 ES ES92922821T patent/ES2085652T3/en not_active Expired - Lifetime
- 1992-11-11 EP EP92922821A patent/EP0613464B1/en not_active Expired - Lifetime
- 1992-11-12 NZ NZ245105A patent/NZ245105A/en unknown
-
1994
- 1994-05-13 NO NO941814A patent/NO305281B1/en not_active IP Right Cessation
- 1994-05-13 FI FI942220A patent/FI106121B/en not_active IP Right Cessation
-
1996
- 1996-04-23 GR GR960401096T patent/GR3019712T3/en unknown
Also Published As
| Publication number | Publication date |
|---|---|
| AU663127B2 (en) | 1995-09-28 |
| EP0613464B1 (en) | 1996-01-24 |
| BR9206754A (en) | 1995-11-21 |
| DE69207920T2 (en) | 1996-08-08 |
| NZ245105A (en) | 1994-08-26 |
| ES2085652T3 (en) | 1996-06-01 |
| FI942220A0 (en) | 1994-05-13 |
| WO1993010088A1 (en) | 1993-05-27 |
| EP0613464A1 (en) | 1994-09-07 |
| FI942220A (en) | 1994-06-23 |
| AU2895492A (en) | 1993-06-15 |
| GB9124160D0 (en) | 1992-01-08 |
| FI106121B (en) | 2000-11-30 |
| NO305281B1 (en) | 1999-05-03 |
| US5489706A (en) | 1996-02-06 |
| NO941814L (en) | 1994-05-13 |
| DE69207920D1 (en) | 1996-03-07 |
| GR3019712T3 (en) | 1996-07-31 |
| ATE133406T1 (en) | 1996-02-15 |
| DK0613464T3 (en) | 1996-06-03 |
| NO941814D0 (en) | 1994-05-13 |
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Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| EEER | Examination request | ||
| FZDE | Discontinued |