CA2236160C - Method and composition for inhibiting growth of microorganisms including peracetic acid and a non-oxidizing biocide - Google Patents
Method and composition for inhibiting growth of microorganisms including peracetic acid and a non-oxidizing biocide Download PDFInfo
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- CA2236160C CA2236160C CA002236160A CA2236160A CA2236160C CA 2236160 C CA2236160 C CA 2236160C CA 002236160 A CA002236160 A CA 002236160A CA 2236160 A CA2236160 A CA 2236160A CA 2236160 C CA2236160 C CA 2236160C
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Classifications
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/50—Treatment of water, waste water, or sewage by addition or application of a germicide or by oligodynamic treatment
-
- 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
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/72—Treatment of water, waste water, or sewage by oxidation
- C02F1/722—Oxidation by peroxides
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2103/00—Nature of the water, waste water, sewage or sludge to be treated
- C02F2103/02—Non-contaminated water, e.g. for industrial water supply
- C02F2103/023—Water in cooling circuits
Abstract
The present invention provides a composition and method of administering same for inhibiting the growth of microorganisms. The composition of the present invention includes sufficient amounts of a peracetic acid or peracetic acid/peracid blend and a non-oxidizing biocide. The method of the present invention includes the step of adding sufficient amounts of the peracetic acid or peracetic acid/peracid blend and the non-oxidizing biocide to industrial process waters.
Description
Field of the Invention The present invention relates generally to controlling the growth of microorganisms. More specifically, the present invention relates to inhibiting the growth of microorganisms in industrial waters.
Background of the Invention The presence of microorganisms in waters, especially industrial waters, is a never-ending concern for industrial manufacturers. Examples of industrial waters where microorganisms can interfere with industrial processes include: cooling tower waters; mining process waters: food processing waters; papermaking slurries; pulp and paper mill waters; sugar reprocessing waters;
and the like.
In the paper industry. the growth of microorganisms in pulp and paper mill waters can adversely affect finished paper products. Microbial life depends on nutrients, pH and temperature of a particular system. The warm temperatures and rich carbohydrate containing fluids of paper machines and process streams provide ideal growth conditions for a variety of microorganisms. These contaminating microorganisms are capable of causing spoilage of pulp, furnish, or chemical additives. The microorganisms cause deposits that break loose and fall into the paper furnish, resulting in quality loss and/or end product defects such as holes and spots. The end result is unsalable paper or paper sold at a lower value. Robertson, ~
Use of Phase-Contrast Microscopy to Assess and Differentiate the Microbial Population of a Paper Mill. TAPPI Journal. pp. 83 (March 199;).
The presence of microorganisms within industrial water systems results in the formation I s of deposits of biological origin on industrial machines. These deposits give rise to: corrosion;
breaks; increased dowm time: loss of yield: high chemical costs: odors; and expensive deposit control programs. In the paper mill industry. slime deposits are reportedly responsible for nearly 70% of all breaks, blockages and pump failures. Safade. Tackling the Slime Problem in a Papa Mill, PTI. p. 280 (September 1988).
Slime may be defined as an "accretion or accumulation caused by certain microorganisms in the presence of pulp fiber, filler, din and other materials, mixed in varied proportions, having variable physical characteristics and accumulating at continuously changing rates." Id. In most industrial process waters. especially pulp and paper mill systems, spore forming bacteria and Pseudomonas aeruginosa contribute to slime formation. The later is most prevalent in paper mill slimes. Fungi is also a contributor of slime formation.
The conventional method of controlling microbial growth is through the use of biocides.
Biocides are generally divided into two main groups: oxidizing; and non-oxidizing. These biocides act on the microorganisms in one of three ways: either by attacking the cell wall: the cyrtoplasmic membrane: or the cellular constituents. Id. at 282.
While biocides do inhibit microbial growth, economic and environmental concerns require improved methods. A problem with the use of biocides is that high levels of expensive chemicals are needed to control microbial growrth. To date. none of the commercially available biocides have exhibited a prolonged biocidal effect. Their effectiveness is rapidly reduced as a result of exposure to physical conditions such as temperature or association with ingredients contained by the system toward which they exhibit an affinity. This results in a restriction or elimination of their biocidal effectiveness.
1 ~ Therefore, the use of such biocides involves continuous or frequent additions to paper mill systems. Further, these additions must be made at a plurality of points or zones in the system. The costs of the biocides and the labor costs involved are considerable.
Moreover. such chemicals are highly toxic in the quantities known to be required for effective control of microbial populations. As a result. environmental regulations restrict the amount of biocides that can safely be discarded into the environment.
Therefore, a need exists for improved methods for controlling the growh of microorganisms in industrial process waters.
Peroxy-containing compositions are known for use in the production of microbicidal agents. One such composition is disclosed in Bowing et al., U.S. Patent No.
4,051,059 containing peracetic acid, acetic acid or mixtures of peracetic and acetic acid, hydrogen peroxide, anionic surface active compounds such as sulfonates and sulfates, and water.
Peracetic acid has been shown to be a good biocide, but only at fairly high concentrations (generally greater than 100 part per million (ppm)). Similarly, peroxyfatty acids have also been shown to be biocidal, but only at high concentrations (greater than 200 ppm), such as in the composition disclosed in European Patent Application No. 233,731.
Peracetic acids have been shown to exhibit synergy in combination with a number of biocides as shown in U.S.
Patent No. 5,494,588, U.S. Patent Nos. 5,200,189 and 5,314,687, issued to Oakes, et al., discuss the use of antimicrobial compositions comprising a diluted combination of a C1 to C4 peroxycarboxylic acid and a C6 to C18 peroxyacid.
Summary of the Invention Pursuant to the present invention, the growth of microorganisms can be inhibited without the use of high levels of certain organic peroxide biocides such as peracetic acid and other peracids. The present invention provides compositions to be used for controlling the growth of microorganisms in industrial process waters. The compositions may include sufficient amounts of a peracetic acid and a non-oxidizing biocide or a blend of peracetic acid and other peracids used in combination with a non-oxidizing biocide.
In particular, the invention provides a composition for inhibiting the growth of microorganisms in industrial process water comprising effective amounts of peracetic acid and a non-oxidizing biocide selected from the group consisting of 2-methyl-4,5-trimethylene-4-isothiazolin-3-one and 2-(thiocyanomethylthio)benzothiazole.
The present invention further provides a composition for inhibiting the growth of microorganisms in industrial process water comprising effective amounts of a peracetic acid/peracid blend and a non-oxidizing biocide selected from the group consisting of isothiazolin, glutaraldehyde, methylene bisthiocyanate, DBNPA, carbamate, quaternary ammonium compounds, 4,5-dichloro-1,2-dithio-3-one, 4,5-dichloro-2-N-octyl-4-isothiazolin-3-one, decylthioethylamine, orthophthaldehyde, 2-bromo-2-nitropropane-1,3-diol, 4,5-dichloro-1,2-dithiol-3-one, dodecylguanidine hydrochloride, 1-(3-chloroallyl)-3,5,7-triaza-1-azoniaadamantane chloride, dibromo dicyanobutane, bis(trichloromethyl)sulfone, 2-methyl-4,5-trimethylene-4-isothiazolin-3-one and 2-(thiocyanomethylthio)benzothiazole.
5a The present invention also provides a method for inhibiting the growth of the microorganisms in industrial process waters. Preferably, these process waters may be selected from the group ~~onsisting of pulp and paper mill process waters, industrial cooling waters and mining waters.
The method includes the step of adding to the 'waters sufficient amounts of a peracetic acid (PAA) or a peracetic acid/peracid blend and a non-oxidizing biocide. Combining the peracetic acid or peracetic acid/peracid blend with the non-oxidizing biocide has been found to enhance the effectiveness of the non-oxidizing biocide.
In particular, the present invention provides a method for controlling the growth of microorganisms in industrial process water comprising the step o:f administering a sufficient amount of a peracetic acid and a sufficient amount of a non-oxidizing biocide selected from the group consisting o.f 2-methyl-4,5-trimethylene-4-isothiazolin-3-one and 2-(thiocyanomethylthio)benzothiazole to the industrial process water to reduce the growth of the microorganisms.
The present invention also provides a method for controlling the growth of microorganisms in industrial process water including the step of administering a sufficient amount of a peracetic acid/perac:id blend and a sufficient amount of a non-oxidizing biocide to the industrial process water to reduce the growth of the microorganisms.
DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS
The present invention provides, under one embodiment for inhibiting the growth of microorganisms, irnproved organic peroxide compositions and method of administer_Lng the same to a fluid system. The compositions include a sufficient amount of a peracetic acid or other organic peroxide and a non-oxidizing biocide.
The biocide component of this invention includes biocides that exhibit a synergistic effect when added to a fluid stream with a peracetic acid. Examples of suitable non-oxidizing biocides include 2-methyl-4,5-trimethylene-4-isothiazolin-3-one and 2-(thiocyanomethylthio):benzothiazole.
Mixtures of such biocides are also contemplated within the claims of the invention.
The biocides of the invention can be obtained from a number of chemical suppliers such as American Cyanamid, Buckman, Betz, Dearborn Chemical, Economics Laboratory, Inc., Merck, Nalco Chemical Company, and Vineland Chemical.
6a Peracetic acid may also be obtained from a number of chemical suppliers. One such supplier is FMC Corporation of Philadelphia, Pennsylvania.
The combination of a peracetic acid along with such non-oxidizing biocides provides an unexpected synergistic relationship. The synergistic relationship is present in that the cooperative action of the combined peracetic acid with the non-oxidizing biocides yields a total effect which is greater than the sum of the effects of the biocide or the peracetic acid taken separately.
The optimal amounts of biocide and peracetic acid required for effectiveness in this invention depend on the type of industrial waters being treated. In addition, the concentration of the combined components varies greatly and can depend upon the conditions such as temperature and pH of the waters, and the microbial count. The concentrations may be as little as 1 part per million (ppm) by weight to as much as 250 ppm. With respect to the biocide, the lower and upper limits of the required concentration substantially depend upon the specific biocide or combination of biocides used.
In a preferred embodiment, the peracetic acid and the non-oxidizing biocide are added in a ratio from about 10:1 to 1:25.
Still further, since the suitable biocides that may be used in the present invention are often obtained at different usable concentrations (i. e. activity level), the ratios vary depending on the particular biocide combined with the peracetic acid. For example, the peracetic acid used in the examples below is 5~ active, the glutaraldehyde is 50~
active, and the DBNPA is 20~ active. Thus, a 1:1 ratio of PAA:Glut translates to 1:10 on an active basis, while a 1:1 ratio of PAA:DBNPA translates to a 1:4 based on actives.
By way of example, and not limitation, the following are biocides, including the percent active of each biocide, that may be used in the present invention: 2-methyl-4,5-trimethylene-4-7a isothiazolin-3-one (5 % a.i.) and 2-(thiocyanomethvlthio)benzothiazole (30 %
a.i.), wherein "a.i."
represents active ingredient.
Pursuant to the method of the present invention, the growth of microorganisms in industrial process waters can be inhibited. The method comprises the step of adding to the waters ~ the peracetic acid and the nonoxidizing biocide of the present invention. In one embodiment, the biocide and the peracetic acid are separate components that are added to the system.
In a preferred embodiment. the peracetic acid is added to the industrial water prior to the addition of the non-oxidizing biocide. The peracetic acid can be added pursuant to any known method that provides the desired concentration of the same in the waters.
After the controlled addition of the peracetic acid, the non-oxidizing biocide is then added to the water system. In an embodiment, the non-oxidizing biocide is added 30 minutes after the peracetic acid is added to the system. Similar to the peracetic acid addition.
the biocide can be added pursuant to any known method that provides the desired concentration of the biocide in the waters.
1 ~ In an embodiment, the method comprises adding approximately ~ to 2~0 ppm of the non-oxidizing biocide along with approximately 10 to ?50 ppm of the peracetic acid. In an embodiment. the biocide and the peracetic acid are present in a range from about 1 ppm to 1000 ppm of product.
Peracetic acid is a unique oxidant, utilizing a different mode of action than other ?0 oxidants. Given the structure of the molecule:
Hz(~OOOH
the hydrocarbon tail allows PAA to penetrate into the bacterial cell. This enables the molecule to disrupt S-S and S-H bonds both inside and outside of the organisms, killing more quickly and effectively than other oxidants. Other oxidants. such as HOCI, C102, H,O,.
etc. do not penetrate the cells in this manner because they do not have an organic portion to facilitate entrance into the bacterial cell.
Peracetic acid has always been applied by itself in high concentrations.
Because it is also an equilibrium molecule. in that it dissociates back to its starting product after it is diluted, it was never expected to be active at low concentrations. However, its dissociation rate is much slower than expected. giving an unexpected synergy with other biocides when it is applied at low concentrations (as low as 10 ppm of a 5% product or 0.~ ppm active).
Peracetic acid has been used as a sterilant in the food industt~~ for many years. but is generally used at higher concentrations ( 1 O,OC10 to 100,000 ppm). Until recently it has not been used in the paper industry for the control of microorganisms in the papermachine process water.
1 s Peracetic acid is made up of a blend of hydrogen peroxide and acetic acid.
When longer chained carboxylic acids are used in place of acetic acid. other peracids are formed, some of which exhibit antimicrobial activity against bacteria and fungi. These alternate peracid blends demonstrate the same synergistic activity with non-oxidizing biocides as does peracetic acid since their mode of action is the same.
?0 A variety of C6-C,g peroxyacids may be employed in the composition of the invention, including peroxyfatty acids, monoperoxy- or diperoxydicarboxylic acids, and peroxyaromatic acids. The C~-C,g peroxyacids employed in the present invention may be structurally represented as follows: R,-C03H. wherein R, is a hydrocarbon moiety having from about ~ to 17 carbon atoms (a C,g peroxyacid is generally represented structurally as C--C03H). R, may have substituents in the chain, e.g., -OH. CO,H, or heteroatoms (e.g.. -O-as in alkvlether carboxylic acids). R, may be linear, branched, cyclic or aromatic. Preferred hydrocarbon moieties (i.e. preferred R,'s) include linear. saturated. hydrocarbon aliphatic moieties having from 7 to 1 1 carbon atoms.
Specific examples of suitable C6-C,H carboxylic fatty acids which can be reacted with hydrogen peroxide to form peroxyfatty acids include such saturated fatty acids as hexanoic (C6).
enanthic (heptanoic) (C~), caprylic (octanoic) (Cg), pelargonic (nonanoic) (C9), capric (decanoic) (C,~). undecvclic (undecanoic) (C"). lauric (dodecanoic) (C,z), trideclic (tridecanoic) (C1;).
myristic (tetradecanoic) (C,4), palmitic (hexadecanoic) (C,6), and stearic (octodecanoic) (C,8).
These acids can be derived from both natural and synthetic sources. Nastural sources include animal and vegetable fats or oils which should be fully hydrogenated.
Synthetic acids can be produced by the oxidation of petroleum wax. Particularly preferred peroxyfatv acids for use in I ~ the composition of the invention are linear monoperoxv aliphatic fatty acids such as peroxyoctanoic acid, peroxydecanoic acid. or mixtures thereof.
Other suitable C~--C,R peroxvacids are derived from the oxidation of dicarboxvlic acids and aromatic acids. Suitable dicarboxvlic acids include adipic acid (C~) and sebacic acid (C,0).
An example of a suitable aromatic acid is benzoic acid. 'These acids can be reacted with hydrogen peroxide to form the peracid form suitable for use in the composition of the invention.
Preferred peracids in this group include monoperoxv- or diperoxyadipic acid.
monoperoxy- or diperoxysebacic acid. and peroxvbenzoic acid.
The above peroxyacids provide antibacterial activity against a wide variey of microorganisms. such as gram positive (e.g.. .5~'taphylococcus aureus~ and gram negative (e.g..
Escherichia coli) microorganisms, yeast, molds. baterial spores, etc.
The antimicrobial composition of the present invention can comprise about 0.01 to I 0 w-t.
~ %, preferably about 0.05 to 5 w-t. %, and most preferably about 0.1 to 2 w~t. °ro of a C6-C, g peroxyacid. and about 0.1 to 2s w~t. %, preferably about 0.5 to 20 wt. %, and most preferably about I to 1 ~ wt. % of peracetic acid. The composition preferably has a weight ratio of peracetic acid to C~-C,g peroxyacid of about 1 ~:1 to 3:1. The composition of about ? to 8, preferably about 3 to 7.
The peracid components used in the composition of the invention can be produced in a simple manner by mixing a hydrogen peroxide~ (HBO,) solution with the desired amount of acid.
Vl%ith the higher molecular weight fatty acids, a hvdrotrope coupler may be required to help solubilize the fatty acid. The H,O, solution is then added to peracetic acid to produce the peracetic acidlperacid composition of the invention. The composition can contain about 1 to SO
1 ~ w~t. %. preferably abut ~ to 2s w. °~o of hydrogen peroxide.
The combination of a peracetic acid/peracid blend along with a non-oxidizing biocides provides an unexpected synergistic relationship. The synergistic relationship is demonstrated in that the cooperative action of the combined peracetic acid/peracid blend with the non-oxidizing biocides yields a total effect which is greater than the sum of the effects of the biocide or the peracetic acid/peracid blend taken separately.
The optimal amounts of biocide and peracetic acid required for effectiveness in the invention depend on the type of industrial waters being treated. In addition, the concentration of the combined components varies greatly and can depend upon the conditions such as temperature and pH of the waters. and the microbial count. The concentration of the peracetic acid/peracid blend may be as little as 1 part per million (ppm) by weight to as much as 250 ppm. With respect to the biocide, the lower and upper limits of the required concentration substantially depend upon the specific biocide or combination of biocides used.
Still further. since the suitable biocides that may be used in the present invention are often obtained at different usable concentrations (i.e. activity level). the ratios vary depending on the particular biocide combined with the peracetic acidlperacid blend.
The following are biocides, including the percent active of each biocide. may be used in the present invention in combination with the peracetic acid/peracid blend:
isothiazolin (1.5%
a.i.); glutaraldehyde (50% a.i.); methvlene bisthiocyanate (10% a.i.); DBNPA
(20% a.i.);
carbamate (30% a.i.); quaternary ammonium compounds (31% a.i.); 4,5-dichloro-1.2-dithio-3-one (5% a.i.): 4.5-dichloro-2-N-octvl-4-isothiazolin-3-one (2% a.i.);
decylthioethylamine (15%
a.i.); orthophthaldehvde (20% a.i.); 2-bromo-2-nitropropane-l,~-diol (10%
a.i.); 4,5-dichloro-1.2-dithiol-,-one (5°ro a.i.): dodecylguanidine hydrochloride (35%
a.i.); 1-(3-chloroallyl)-3.5,7-triaza-1-azoniaadamantane chloride (67.5% a.i.): dibromo dicyanobutane (25°io a.i.):
bis(trichloromethyl)sulfone (35°io a.i.); 2-methyl-4.5-trimethylene-4-isothiazolin-3-one (5% a.i.) and 2-(thiocyanomethylthio)benzothiazole (30% a.i.). wherein "a.i." represents active ingredient.
Pursuant to the method of the present invention, the growth of microorganisms in industrial process waters can be inhibited. The method comprises the step of adding to the waters the peracetic acid/peracid blend and the nonoxidizing biocide of the present invention. In an embodiment. the biocide and the peracetic acid/peracid blend are separate components that are added to the system.
In a preferred embodiment. the peracetic acidiperacid blend is added to the industrial water prior to the addition of the non-oxidizing biocide. The peracetic acid/peracid blend can be added pursuant to any know method that provides the desired concentration of the same in the waters.
After the controlled addition of the peracetic acid/peracid blend, the non-oxidizing biocide is then added to the water system. In an embodiment, the non-oxidizing biocide is added 30 minutes after the peracetic acid/peracid blend is added to the system.
Similar to the peracetic acid/peracid blend addition, the biocide can be added pursuant to any known method that provides the desired concentration of the biocide in the waters.
The composition of the invention can be made by combining by simple mixing an effective amount of a C~-C,g peroxvacid such as a peroxyfattv acid with peracetic acid. This composition would be formulated with preformed perfatty acid and preformed peracetic acid. A
I ~ preferred composition of the invention can be made by mixing peracetic acid. a C~-C, x carboxylic acid, a coupler and a stabilizer and reacting this mixture with hydrogen peroxide. A
stable equilibrium mixture is produced containing a peracetic acid and a C~-C,R peroxyacid by allowing the mixture to stand for from one to seven days at I S° C. to 25° C. As with any aqueous reaction of hydrogen peroxide with a free carboxylic acid, this gives a true equilibrium ?0 mixture. In this case, the equilibrium mixture will contain hydrogen peroxide, peracetic acid, a C~-C,g peroxyacid, water, and various couplers and stabilizers.
The present invention contemplates a peracetic acidlperacid composition which is diluted to a use solution prior to its utilization with the biocide of the invention.
The level of active components in the concentrate composition is dependent upon the intended dilution factor and desired acidity in the use solution. The C6~,g peroxvacid component is generally obtained by reacting a C6--C,g carboxylic acid with hydrogen peroxide in the presence of peracetic acid. The resulting concentrate is diluted with water to provide the use solution. Generally, a dilution of 1 fluid oz. to 4 gallons (i.e. dilution of 1 to X00 by volume) or to 8 gallons (i.e. dilution of 1 to 1,000 by volume) of water can be obtained with 2% to 20%
total peracids in the concentrate. Higher use dilution can be employed if elevated use temperature (greater than 20° C.) or extended exposure time (greater than 30 seconds) are also employed.
In one embodiment, the biocide and the peracetic acid/peracid blend are present in a range from about 1 ppm to 1000 ppm. respectively. In a preferred embodiment, the method comprises adding approximately ~ to 250 ppm of the non-oxidizing biocide along with 1 ~ approximately 10 to 2~0 ppm of the peracetic acid/peracid blend.
An advantage of the present invention is that it lowers the level of expensive chemicals needed for inhibiting the growh of microorganisms. With the addition of a peracetic acid in the water system, the non-oxidizing biocide is effective in low dosages, and as a result is long lasting as evidenced by reductions in microbial grow back. The increased effectiveness removes the need for repetitive additions of the biocide at multiple points in the paper making system.
A further advantage of the present invention is that it provides a more cost effective and environmentally friendly method for treating microorganisms.
Bv way of example, and not limitation. examples of the invention will now be given.
The following examples illustrate the synergistic relationship obtained with the compositions of the present invention.
Synergy is mathematically demonstrated by the industy accepted method described by S.C. Kull et al.in Allied Microbioloev, vol. 9, pages 538-541 (1961). As applied to this invention. it is as follows:
QA = the ppm of active peracetic acid alone which produces an endpoint.
QB = the ppm of active non-oxidizing biocide alone which produces an endpoint.
Q~ = the ppm of active peracetic acid. in combination with non-oxidizing biocide, which produces an endpoint.
Qh = the ppm of active non-oxidizing biocide, in combination. which produces an endpoint.
1 s Qa ; QA + Qh / QB = Synergy Index Synergy index is <:1. it indicates synergy =1, it indicates additivitv > 1. it indicates antagonism 'The following test procedures were utilized during the experimentation of the present mvennon.
Process water from several paper mills was obtained for test purposes.
Aliquots of water from each mill were dosed with the indicated concentrations of peracetic acid (~% active obtained from FMC) or peracetic acidlperacid blend (4.5% a.i. obtained from ECO lab). After 30 minutes of contact time, the designated concentrations of non-oxidising biocide were added to the aliquots previously dosed with PAA, mixed well and incubated at 37°C in an orbital shaker.
At the designated contact times, each aliquot was sampled to determine the total number of viable organisms in colony forming units per milliliter (CFU/mL) on T'ryptone Glucose Extract (TGE) agar. An endpoint of ?, 3, 4 or ~ log,° reduction in viable organisms was then selected for calculating synergy.
Example 1 Synergistic activity of peracetic acid and 2-methyl-4,5-trimethylene-4-isothiazolin-3-one (MTI).
also known as Promexal, against microorganisms in a papermill process water, pH 7.'_' is shown in the following data.
Biocide (ppm of product) 4 Hour Contact 24 Hour Contact PAA @ 12.5 ppm 1.5 x 107 CFU/mL 1.5 x 107 CFUImL
PAA ~ 25 ppm 1.5 x 106 CFU/mL 1.5 x 107 CFUImL
PAA ~~ 50 ppm < 103 CFU/mL 2.5 x 106 CFU/mL
PAA ~ 100 ppm < 103 CFU/mL < 103 CFU/mL
MTl ~ 12.5 ppm 1.6 x 107 CFU/mL 2.2 x 107 CFU/mL
MTI ~~ 25 ppm 1.4 x 107 CFUImL 1.2 x 107 CFUImL
MTI r' 50 ppm 8.0 x 106 CFUImL 8.6 x 106 CFUImL
MTI ~d~ 100 ppm 6.6 x 106 CFUImL 4.4 x 106 CFU/mL
PAA ~a~ 10 ppm plus MTI ~~ 12.5 ppm 7.2 x 106 CFUImL 1.3 x 107 CFU/mL
MTI ~~ 25 ppm 5.0 x 106 CFUimL 4.0 x 106 CFU/mL
MTI rci 50 ppm 6.6 x 106 CFU/mL 3.4 x 106 CFUImL
MTI r- 100 ppm 3,5 ~ 106 CFUimL 1.5 x 106 CFU/mL
PAA pct 20 ppm plus MTl ~' 12.5 ppm 1.6 x 106 CFU/mL 6.3 x 106 CFU/mL
MTI ~a~ 25 ppm g,5 ~ 10~ CFUImL 2.7 x 106 CFU/mL
MTI ia' S0 ppm 7:1 x 10~ CFU!mL 2.6 x 106 CFUImL
MTI ~~ 100 ppm 9.0 x 10~ CFU/mL 9.0 x 105 CFU/mL
PAA ~~ 40 ppm plus MTI ~ 12.5 ppm < 103 CFU~mL 1.5 x 104 CFUImL
MTI ~ 25 ppm < 103 CFU/mL 9.0 x 104 CFU/mL
MTl (a' 50 ppm < 103' CFUimL 3.0 x 103 CFU/mL
MTI ~ 100 ppm < 103 CFUimL < 103 CFU/mL
Control 2.1 x 10g CFUimL 1.1 x 107 CFUImL
Synergy Calculation:
After 24 hours of contact, a 3 log 1 p or greater reduction was achieved with:
PAA = 100 ppm MTI = > 100 ppm (200 ppm ) PAA = 40 ppm/MTI = 12.5 ppm SI = 40/100 + 12.5/200 = 0.4625 Example 2 Synergistic activiy of peracetic acid and 2-(thiocyanomethylthio)benzothiazole (TCMTB) against microorganisms in a papermill process water, pH 6.6 is shown in the following data.
Biocide (ppm of 4 Hour Contact 24 Hour Contact product) PAA ~ 50 ppm 1.6 x 108 CFtI/mL 9.2 x 107 CFU/mL
PAA ~ 100 ppm 1.1 x 107 CFU/mL 6.4 x 107 CFU/mL
PAA ~ 200 ppm 1.1 x 107 CFtI/mL 5.9 x 107 CFU/mL
J
TCMTB ~ 50 ppm 1.1 x 108 CFLJ/mL 7.8 x 107 CFU/mL
TCMTB ~~ 100 ppm 6.8 x 107 CFLJImL 6.4 x 107 CFUImL
TCMTB ~; 200 ppm 6.4 x 107 CFLJ/mL 9.7 x 106 CFU/mL
TCMTB ~~ 400 ppm 5.1 x 107 CFU/mL 3.8 x 106 CFU/mL
PAA ~; 80 ppm plus TCMTB ~a 50 ppm 1.6 x 107 CFLIimL 4.6 x 107 CFUImL
TCMTB ~; 100 ppm 9.7 x 106 CFLI/mL 3.9 x 106 CFU/mL
TCMTB ~ 200 ppm ~.; x 106 CFLI/mL 1.6 x 105 CFU/mL
TCMTB ~a~ 400 ;.6 4.3 x 104 CFU/mL
ppm 106 CFU/mL
a Control 2.1 x 108 CFL~/mL 2.5 x 108 CFU/mL
Synergy Calculation:
After 24 hours of contact. a 3 log 10 or greater reduction was achieved with:
PAA = >200 ppm (400 ppm) TCMTB = >400 ppm (800 ppm) PAA = 80 ppmITCMTB = 200 ppm SI = 80/400 + 200/800 = 0.45 Example 3 Another example of the synergy was expected m~hen peracetic acid was applied in combination with 1,2-Benzisothiazolone (Proxel) to a papermill process water, pH 7Ø
However.
~ unexpectedly, no synergy was seen, supporting the supposition that synergy is unique with peracetic acid and specific biocides.
Biocide (ppm of product) 5 Hour Contact 24 Hour Contact PAA ~:~ 1'.~ ppm 2.1 x 107 CFU/mL 1.0 x 107 CFU/mL
PAA rd' ?~ ppm 1.2 x 107 CFU/mL 1.1 x 107 CFU/mL
PAA ~; ~0 ppm ?,g x 106 CFU/mL 1.7 x 107 CFU/mL
PAA ~~ 100 ppm ~ < 103 CFU/mL 4.0 x 103 CFU/mL
Proxel r 2~ ppm ?.1 x 107 CFU/mL 9.6 x 106 CFU/mL
Proxel r' S0 ppm 1.3 x 107 CFU/mL 4.6 x 106 CFU/mL
Proxel ra 100 ppm 1.4 x 107 CFU/mL 3.2 x 106 CFUImL
PAA r 20 ppm plus Proxel r 2~ ppm 6.7 x 106 CFUi mL 8.8 x 106 CFU/mL
Proxel ~ 50 ppm 6,3 x 106 CFU/ mL 6.7 x 106 CFUImL
Proxel r 100 PPM ~,0 x 106 CFUImL 4.2 x 106 CFU/mL
PA.A r- 40 ppm plus Proxel r ?~ ppm 3,5 x 106 CFUimL 5.1 x 106 CFU/mL
Proxel r ~0 ppm 3.? x 106 CFUimL 4.3 x 106 CFU/mL
Proxel ra 100 ppm ?.6 x 10~ CFU/mL 2.1 x 106 CFU/mL
Control I .9 x 107 CFUImL ?.1 x 107 CFU/mL
Synergy Calculation:
After 24 hours of contact. a 1 log 10 or greater reduction was achieved with:
PAA = 100 ppm Proxel = 100 ppm 1 s PAA = 40 ppm/Proxel = 100 ppm SI = 40/100 + 100/100 = 1.4 Example 5 Along with showing synergistic activity against bacteria, the peroctanoic acid described in example #22 is also synergistic against fungi. When Aspergillus niger spores were seeded into papermill whitewater, pH 7Ø and treated with a combination of POAA and 5-chloro-2-methyl-4-isothiazolin-3-one and 2-methyl-4-isothiazolin-3-one (Iso), the following synergistic activity was seen.
Biocide (ppm of product) 24 Hour Contact 72 Hour Contact POAA r, 100 ppm 2.9 x 104 CFU/mL 3.1 x 104 CFU/mL
POAA ~ 2~0 ppm 3.1 x 103 CFU/mL 1.1 x 103 CFU/mL
POAA r' 500 ppm 1.2 x 101 CFU/mL 2.0 x 100 CFUImL
Iso ~ 23 ppm 2.0 x 104 CFLIimL 2.5 x 104 CFU/mL
Iso ~ ~0 ppm 2.3 x 1 ()4 CFL)ImL 2.4 x 104 CFUImL
Iso r' 100 ppm 1.0 x 104 CFLJimL 1.6 x 104 CFU/mL
Iso ~a 200 ppm 4.0 x 103 CFLJImL 6.0 x 103 CFU/mL
POAA r 250 ppm plus Iso r 2~ ppm 6.1 x I()2 CFLIImL l.~ x 102 CFU/mL
Iso ~. 50 ppm 5.0 x 102 CFLIimL I.5 x 102 CFU/mL
Iso 100 ppm 4.6 x 102 CFLIImL 1.0 x 102 CFU/mL
Iso ~ 200 ppm 3.6 x 102' CFLIimL 1.1 x 102 CFUimL
Control 3.8 x I (14 CFLI/mL 2.6 x 104 CFU/mL
Synergy Calculation After 24 hours of contact. a 2 log I 0 reduction in fungal spores was achieved with:
POAA = 500 ppm Iso = > 200 ppm (400 ppm) POAA = 250 ppm/Iso = 2~ ppm SI = 250/500 + 25/400 = 0.5625 1~
After 24 hours of contact. a 2 log I p or greater reduction was achieved with:
POAA = S00 ppm Iso = >200 ppm (400 ppm) POAA = 250 ppm/Iso = 25 ppm SI = 250/500 + 25/400 = 0.5625 Example 6 Another example of the synergy seen with the blend of peracetic acid and the peroctanoic acid is illustrated when POAA is applied to a papetmill process v'~ater, pH 7.0, that has also been dosed with 4,5-dichloro-2-N-octyl-4-isothiazolin-3-one (RH287).
Biocide (ppm of product)5 Hour Contact 24 Hour Contact POA.A ~ 2~ ppm 9.1 x 106 CFLIImL 1.9 x 107 CFU/mL
POAA ~' ~0 ppm 1.6 x 1 ()5 CFLT/mL2.3 x 107 CFU/mL
POAA ~ 100 ppm 1 x 103 CFUImL 6.1 x 10~ CFUImL
POAA ~d 200 ppm < 103 3.8 x 104 CFU/mL
C FU/mL
RH287 r- SO ppm 2.1 x 1 C16 CFU/mL7.1 x 106 CFU/mL
RH287 ~ 100 ppm 1.3 x 105 CFU/mL 2.8 x 106 CFUImL
RH287 ~ 200 ppm 1.6 x 104 CFU/mL 1.1 x 106 CFU/mL
POAA r. 20 ppm plus RH287 ~a ~0 ppm 1.1 x 10~ CFU/mL 5.6 x 106 CFU/mL
RH287 r, 100 ppm 3.6 x 104 CFU/mL 8.0 x 104 CFU/mL
RH287 r, 200 PPM g,0 x 103 CFU/mL 6.0 x 103 CFU/mL
PO.AA ~ 40 ppm plus RH287 r ~0 ppm 8.0 x 103 CFU/mL 2.7 x 104 CFU/mL
RH287 ~ 100 ppm 4.0 x 103 CFUImL < 103 CFU/mL
RH287 r 200 PPM 3.0 x 103 CFU/mL < 103 CFUImL
Control 3.0 x 107 CFUImL 4.9 x 107 CFUImL
Svnerev Calculation:
y .After ~ hours of contact, a 4 log 10 or greater reduction was achieved with:
POAA = 100 ppm RH287 = > 200 (400 ppm) POAA = 40 ppm/RH287 = ~0 ppm SI = 40/100 + 54/400 = 0.5?5 After 24 hours of contact, a 4 log. 10 or greater reduction was achieved with:
1 ~ POAA = > 200 ppm (400 ppm ) RH287 = > 200 ppm (400 ppm) POAA = 40 ppmlRH287 = 100 ppm SI = 40/400 + 100/400 = 0.35 It should be understood that various changes and modifications to the presently preferred embodiments described herein will be apparent to those skilled in the art.
Such changes and modifications can be made without departing from the spirit and scope of the present invention and without diminishing its attendant advantages. It is therefore intended that such changes and modifications be covered by the appended claims:
Background of the Invention The presence of microorganisms in waters, especially industrial waters, is a never-ending concern for industrial manufacturers. Examples of industrial waters where microorganisms can interfere with industrial processes include: cooling tower waters; mining process waters: food processing waters; papermaking slurries; pulp and paper mill waters; sugar reprocessing waters;
and the like.
In the paper industry. the growth of microorganisms in pulp and paper mill waters can adversely affect finished paper products. Microbial life depends on nutrients, pH and temperature of a particular system. The warm temperatures and rich carbohydrate containing fluids of paper machines and process streams provide ideal growth conditions for a variety of microorganisms. These contaminating microorganisms are capable of causing spoilage of pulp, furnish, or chemical additives. The microorganisms cause deposits that break loose and fall into the paper furnish, resulting in quality loss and/or end product defects such as holes and spots. The end result is unsalable paper or paper sold at a lower value. Robertson, ~
Use of Phase-Contrast Microscopy to Assess and Differentiate the Microbial Population of a Paper Mill. TAPPI Journal. pp. 83 (March 199;).
The presence of microorganisms within industrial water systems results in the formation I s of deposits of biological origin on industrial machines. These deposits give rise to: corrosion;
breaks; increased dowm time: loss of yield: high chemical costs: odors; and expensive deposit control programs. In the paper mill industry. slime deposits are reportedly responsible for nearly 70% of all breaks, blockages and pump failures. Safade. Tackling the Slime Problem in a Papa Mill, PTI. p. 280 (September 1988).
Slime may be defined as an "accretion or accumulation caused by certain microorganisms in the presence of pulp fiber, filler, din and other materials, mixed in varied proportions, having variable physical characteristics and accumulating at continuously changing rates." Id. In most industrial process waters. especially pulp and paper mill systems, spore forming bacteria and Pseudomonas aeruginosa contribute to slime formation. The later is most prevalent in paper mill slimes. Fungi is also a contributor of slime formation.
The conventional method of controlling microbial growth is through the use of biocides.
Biocides are generally divided into two main groups: oxidizing; and non-oxidizing. These biocides act on the microorganisms in one of three ways: either by attacking the cell wall: the cyrtoplasmic membrane: or the cellular constituents. Id. at 282.
While biocides do inhibit microbial growth, economic and environmental concerns require improved methods. A problem with the use of biocides is that high levels of expensive chemicals are needed to control microbial growrth. To date. none of the commercially available biocides have exhibited a prolonged biocidal effect. Their effectiveness is rapidly reduced as a result of exposure to physical conditions such as temperature or association with ingredients contained by the system toward which they exhibit an affinity. This results in a restriction or elimination of their biocidal effectiveness.
1 ~ Therefore, the use of such biocides involves continuous or frequent additions to paper mill systems. Further, these additions must be made at a plurality of points or zones in the system. The costs of the biocides and the labor costs involved are considerable.
Moreover. such chemicals are highly toxic in the quantities known to be required for effective control of microbial populations. As a result. environmental regulations restrict the amount of biocides that can safely be discarded into the environment.
Therefore, a need exists for improved methods for controlling the growh of microorganisms in industrial process waters.
Peroxy-containing compositions are known for use in the production of microbicidal agents. One such composition is disclosed in Bowing et al., U.S. Patent No.
4,051,059 containing peracetic acid, acetic acid or mixtures of peracetic and acetic acid, hydrogen peroxide, anionic surface active compounds such as sulfonates and sulfates, and water.
Peracetic acid has been shown to be a good biocide, but only at fairly high concentrations (generally greater than 100 part per million (ppm)). Similarly, peroxyfatty acids have also been shown to be biocidal, but only at high concentrations (greater than 200 ppm), such as in the composition disclosed in European Patent Application No. 233,731.
Peracetic acids have been shown to exhibit synergy in combination with a number of biocides as shown in U.S.
Patent No. 5,494,588, U.S. Patent Nos. 5,200,189 and 5,314,687, issued to Oakes, et al., discuss the use of antimicrobial compositions comprising a diluted combination of a C1 to C4 peroxycarboxylic acid and a C6 to C18 peroxyacid.
Summary of the Invention Pursuant to the present invention, the growth of microorganisms can be inhibited without the use of high levels of certain organic peroxide biocides such as peracetic acid and other peracids. The present invention provides compositions to be used for controlling the growth of microorganisms in industrial process waters. The compositions may include sufficient amounts of a peracetic acid and a non-oxidizing biocide or a blend of peracetic acid and other peracids used in combination with a non-oxidizing biocide.
In particular, the invention provides a composition for inhibiting the growth of microorganisms in industrial process water comprising effective amounts of peracetic acid and a non-oxidizing biocide selected from the group consisting of 2-methyl-4,5-trimethylene-4-isothiazolin-3-one and 2-(thiocyanomethylthio)benzothiazole.
The present invention further provides a composition for inhibiting the growth of microorganisms in industrial process water comprising effective amounts of a peracetic acid/peracid blend and a non-oxidizing biocide selected from the group consisting of isothiazolin, glutaraldehyde, methylene bisthiocyanate, DBNPA, carbamate, quaternary ammonium compounds, 4,5-dichloro-1,2-dithio-3-one, 4,5-dichloro-2-N-octyl-4-isothiazolin-3-one, decylthioethylamine, orthophthaldehyde, 2-bromo-2-nitropropane-1,3-diol, 4,5-dichloro-1,2-dithiol-3-one, dodecylguanidine hydrochloride, 1-(3-chloroallyl)-3,5,7-triaza-1-azoniaadamantane chloride, dibromo dicyanobutane, bis(trichloromethyl)sulfone, 2-methyl-4,5-trimethylene-4-isothiazolin-3-one and 2-(thiocyanomethylthio)benzothiazole.
5a The present invention also provides a method for inhibiting the growth of the microorganisms in industrial process waters. Preferably, these process waters may be selected from the group ~~onsisting of pulp and paper mill process waters, industrial cooling waters and mining waters.
The method includes the step of adding to the 'waters sufficient amounts of a peracetic acid (PAA) or a peracetic acid/peracid blend and a non-oxidizing biocide. Combining the peracetic acid or peracetic acid/peracid blend with the non-oxidizing biocide has been found to enhance the effectiveness of the non-oxidizing biocide.
In particular, the present invention provides a method for controlling the growth of microorganisms in industrial process water comprising the step o:f administering a sufficient amount of a peracetic acid and a sufficient amount of a non-oxidizing biocide selected from the group consisting o.f 2-methyl-4,5-trimethylene-4-isothiazolin-3-one and 2-(thiocyanomethylthio)benzothiazole to the industrial process water to reduce the growth of the microorganisms.
The present invention also provides a method for controlling the growth of microorganisms in industrial process water including the step of administering a sufficient amount of a peracetic acid/perac:id blend and a sufficient amount of a non-oxidizing biocide to the industrial process water to reduce the growth of the microorganisms.
DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS
The present invention provides, under one embodiment for inhibiting the growth of microorganisms, irnproved organic peroxide compositions and method of administer_Lng the same to a fluid system. The compositions include a sufficient amount of a peracetic acid or other organic peroxide and a non-oxidizing biocide.
The biocide component of this invention includes biocides that exhibit a synergistic effect when added to a fluid stream with a peracetic acid. Examples of suitable non-oxidizing biocides include 2-methyl-4,5-trimethylene-4-isothiazolin-3-one and 2-(thiocyanomethylthio):benzothiazole.
Mixtures of such biocides are also contemplated within the claims of the invention.
The biocides of the invention can be obtained from a number of chemical suppliers such as American Cyanamid, Buckman, Betz, Dearborn Chemical, Economics Laboratory, Inc., Merck, Nalco Chemical Company, and Vineland Chemical.
6a Peracetic acid may also be obtained from a number of chemical suppliers. One such supplier is FMC Corporation of Philadelphia, Pennsylvania.
The combination of a peracetic acid along with such non-oxidizing biocides provides an unexpected synergistic relationship. The synergistic relationship is present in that the cooperative action of the combined peracetic acid with the non-oxidizing biocides yields a total effect which is greater than the sum of the effects of the biocide or the peracetic acid taken separately.
The optimal amounts of biocide and peracetic acid required for effectiveness in this invention depend on the type of industrial waters being treated. In addition, the concentration of the combined components varies greatly and can depend upon the conditions such as temperature and pH of the waters, and the microbial count. The concentrations may be as little as 1 part per million (ppm) by weight to as much as 250 ppm. With respect to the biocide, the lower and upper limits of the required concentration substantially depend upon the specific biocide or combination of biocides used.
In a preferred embodiment, the peracetic acid and the non-oxidizing biocide are added in a ratio from about 10:1 to 1:25.
Still further, since the suitable biocides that may be used in the present invention are often obtained at different usable concentrations (i. e. activity level), the ratios vary depending on the particular biocide combined with the peracetic acid. For example, the peracetic acid used in the examples below is 5~ active, the glutaraldehyde is 50~
active, and the DBNPA is 20~ active. Thus, a 1:1 ratio of PAA:Glut translates to 1:10 on an active basis, while a 1:1 ratio of PAA:DBNPA translates to a 1:4 based on actives.
By way of example, and not limitation, the following are biocides, including the percent active of each biocide, that may be used in the present invention: 2-methyl-4,5-trimethylene-4-7a isothiazolin-3-one (5 % a.i.) and 2-(thiocyanomethvlthio)benzothiazole (30 %
a.i.), wherein "a.i."
represents active ingredient.
Pursuant to the method of the present invention, the growth of microorganisms in industrial process waters can be inhibited. The method comprises the step of adding to the waters ~ the peracetic acid and the nonoxidizing biocide of the present invention. In one embodiment, the biocide and the peracetic acid are separate components that are added to the system.
In a preferred embodiment. the peracetic acid is added to the industrial water prior to the addition of the non-oxidizing biocide. The peracetic acid can be added pursuant to any known method that provides the desired concentration of the same in the waters.
After the controlled addition of the peracetic acid, the non-oxidizing biocide is then added to the water system. In an embodiment, the non-oxidizing biocide is added 30 minutes after the peracetic acid is added to the system. Similar to the peracetic acid addition.
the biocide can be added pursuant to any known method that provides the desired concentration of the biocide in the waters.
1 ~ In an embodiment, the method comprises adding approximately ~ to 2~0 ppm of the non-oxidizing biocide along with approximately 10 to ?50 ppm of the peracetic acid. In an embodiment. the biocide and the peracetic acid are present in a range from about 1 ppm to 1000 ppm of product.
Peracetic acid is a unique oxidant, utilizing a different mode of action than other ?0 oxidants. Given the structure of the molecule:
Hz(~OOOH
the hydrocarbon tail allows PAA to penetrate into the bacterial cell. This enables the molecule to disrupt S-S and S-H bonds both inside and outside of the organisms, killing more quickly and effectively than other oxidants. Other oxidants. such as HOCI, C102, H,O,.
etc. do not penetrate the cells in this manner because they do not have an organic portion to facilitate entrance into the bacterial cell.
Peracetic acid has always been applied by itself in high concentrations.
Because it is also an equilibrium molecule. in that it dissociates back to its starting product after it is diluted, it was never expected to be active at low concentrations. However, its dissociation rate is much slower than expected. giving an unexpected synergy with other biocides when it is applied at low concentrations (as low as 10 ppm of a 5% product or 0.~ ppm active).
Peracetic acid has been used as a sterilant in the food industt~~ for many years. but is generally used at higher concentrations ( 1 O,OC10 to 100,000 ppm). Until recently it has not been used in the paper industry for the control of microorganisms in the papermachine process water.
1 s Peracetic acid is made up of a blend of hydrogen peroxide and acetic acid.
When longer chained carboxylic acids are used in place of acetic acid. other peracids are formed, some of which exhibit antimicrobial activity against bacteria and fungi. These alternate peracid blends demonstrate the same synergistic activity with non-oxidizing biocides as does peracetic acid since their mode of action is the same.
?0 A variety of C6-C,g peroxyacids may be employed in the composition of the invention, including peroxyfatty acids, monoperoxy- or diperoxydicarboxylic acids, and peroxyaromatic acids. The C~-C,g peroxyacids employed in the present invention may be structurally represented as follows: R,-C03H. wherein R, is a hydrocarbon moiety having from about ~ to 17 carbon atoms (a C,g peroxyacid is generally represented structurally as C--C03H). R, may have substituents in the chain, e.g., -OH. CO,H, or heteroatoms (e.g.. -O-as in alkvlether carboxylic acids). R, may be linear, branched, cyclic or aromatic. Preferred hydrocarbon moieties (i.e. preferred R,'s) include linear. saturated. hydrocarbon aliphatic moieties having from 7 to 1 1 carbon atoms.
Specific examples of suitable C6-C,H carboxylic fatty acids which can be reacted with hydrogen peroxide to form peroxyfatty acids include such saturated fatty acids as hexanoic (C6).
enanthic (heptanoic) (C~), caprylic (octanoic) (Cg), pelargonic (nonanoic) (C9), capric (decanoic) (C,~). undecvclic (undecanoic) (C"). lauric (dodecanoic) (C,z), trideclic (tridecanoic) (C1;).
myristic (tetradecanoic) (C,4), palmitic (hexadecanoic) (C,6), and stearic (octodecanoic) (C,8).
These acids can be derived from both natural and synthetic sources. Nastural sources include animal and vegetable fats or oils which should be fully hydrogenated.
Synthetic acids can be produced by the oxidation of petroleum wax. Particularly preferred peroxyfatv acids for use in I ~ the composition of the invention are linear monoperoxv aliphatic fatty acids such as peroxyoctanoic acid, peroxydecanoic acid. or mixtures thereof.
Other suitable C~--C,R peroxvacids are derived from the oxidation of dicarboxvlic acids and aromatic acids. Suitable dicarboxvlic acids include adipic acid (C~) and sebacic acid (C,0).
An example of a suitable aromatic acid is benzoic acid. 'These acids can be reacted with hydrogen peroxide to form the peracid form suitable for use in the composition of the invention.
Preferred peracids in this group include monoperoxv- or diperoxyadipic acid.
monoperoxy- or diperoxysebacic acid. and peroxvbenzoic acid.
The above peroxyacids provide antibacterial activity against a wide variey of microorganisms. such as gram positive (e.g.. .5~'taphylococcus aureus~ and gram negative (e.g..
Escherichia coli) microorganisms, yeast, molds. baterial spores, etc.
The antimicrobial composition of the present invention can comprise about 0.01 to I 0 w-t.
~ %, preferably about 0.05 to 5 w-t. %, and most preferably about 0.1 to 2 w~t. °ro of a C6-C, g peroxyacid. and about 0.1 to 2s w~t. %, preferably about 0.5 to 20 wt. %, and most preferably about I to 1 ~ wt. % of peracetic acid. The composition preferably has a weight ratio of peracetic acid to C~-C,g peroxyacid of about 1 ~:1 to 3:1. The composition of about ? to 8, preferably about 3 to 7.
The peracid components used in the composition of the invention can be produced in a simple manner by mixing a hydrogen peroxide~ (HBO,) solution with the desired amount of acid.
Vl%ith the higher molecular weight fatty acids, a hvdrotrope coupler may be required to help solubilize the fatty acid. The H,O, solution is then added to peracetic acid to produce the peracetic acidlperacid composition of the invention. The composition can contain about 1 to SO
1 ~ w~t. %. preferably abut ~ to 2s w. °~o of hydrogen peroxide.
The combination of a peracetic acid/peracid blend along with a non-oxidizing biocides provides an unexpected synergistic relationship. The synergistic relationship is demonstrated in that the cooperative action of the combined peracetic acid/peracid blend with the non-oxidizing biocides yields a total effect which is greater than the sum of the effects of the biocide or the peracetic acid/peracid blend taken separately.
The optimal amounts of biocide and peracetic acid required for effectiveness in the invention depend on the type of industrial waters being treated. In addition, the concentration of the combined components varies greatly and can depend upon the conditions such as temperature and pH of the waters. and the microbial count. The concentration of the peracetic acid/peracid blend may be as little as 1 part per million (ppm) by weight to as much as 250 ppm. With respect to the biocide, the lower and upper limits of the required concentration substantially depend upon the specific biocide or combination of biocides used.
Still further. since the suitable biocides that may be used in the present invention are often obtained at different usable concentrations (i.e. activity level). the ratios vary depending on the particular biocide combined with the peracetic acidlperacid blend.
The following are biocides, including the percent active of each biocide. may be used in the present invention in combination with the peracetic acid/peracid blend:
isothiazolin (1.5%
a.i.); glutaraldehyde (50% a.i.); methvlene bisthiocyanate (10% a.i.); DBNPA
(20% a.i.);
carbamate (30% a.i.); quaternary ammonium compounds (31% a.i.); 4,5-dichloro-1.2-dithio-3-one (5% a.i.): 4.5-dichloro-2-N-octvl-4-isothiazolin-3-one (2% a.i.);
decylthioethylamine (15%
a.i.); orthophthaldehvde (20% a.i.); 2-bromo-2-nitropropane-l,~-diol (10%
a.i.); 4,5-dichloro-1.2-dithiol-,-one (5°ro a.i.): dodecylguanidine hydrochloride (35%
a.i.); 1-(3-chloroallyl)-3.5,7-triaza-1-azoniaadamantane chloride (67.5% a.i.): dibromo dicyanobutane (25°io a.i.):
bis(trichloromethyl)sulfone (35°io a.i.); 2-methyl-4.5-trimethylene-4-isothiazolin-3-one (5% a.i.) and 2-(thiocyanomethylthio)benzothiazole (30% a.i.). wherein "a.i." represents active ingredient.
Pursuant to the method of the present invention, the growth of microorganisms in industrial process waters can be inhibited. The method comprises the step of adding to the waters the peracetic acid/peracid blend and the nonoxidizing biocide of the present invention. In an embodiment. the biocide and the peracetic acid/peracid blend are separate components that are added to the system.
In a preferred embodiment. the peracetic acidiperacid blend is added to the industrial water prior to the addition of the non-oxidizing biocide. The peracetic acid/peracid blend can be added pursuant to any know method that provides the desired concentration of the same in the waters.
After the controlled addition of the peracetic acid/peracid blend, the non-oxidizing biocide is then added to the water system. In an embodiment, the non-oxidizing biocide is added 30 minutes after the peracetic acid/peracid blend is added to the system.
Similar to the peracetic acid/peracid blend addition, the biocide can be added pursuant to any known method that provides the desired concentration of the biocide in the waters.
The composition of the invention can be made by combining by simple mixing an effective amount of a C~-C,g peroxvacid such as a peroxyfattv acid with peracetic acid. This composition would be formulated with preformed perfatty acid and preformed peracetic acid. A
I ~ preferred composition of the invention can be made by mixing peracetic acid. a C~-C, x carboxylic acid, a coupler and a stabilizer and reacting this mixture with hydrogen peroxide. A
stable equilibrium mixture is produced containing a peracetic acid and a C~-C,R peroxyacid by allowing the mixture to stand for from one to seven days at I S° C. to 25° C. As with any aqueous reaction of hydrogen peroxide with a free carboxylic acid, this gives a true equilibrium ?0 mixture. In this case, the equilibrium mixture will contain hydrogen peroxide, peracetic acid, a C~-C,g peroxyacid, water, and various couplers and stabilizers.
The present invention contemplates a peracetic acidlperacid composition which is diluted to a use solution prior to its utilization with the biocide of the invention.
The level of active components in the concentrate composition is dependent upon the intended dilution factor and desired acidity in the use solution. The C6~,g peroxvacid component is generally obtained by reacting a C6--C,g carboxylic acid with hydrogen peroxide in the presence of peracetic acid. The resulting concentrate is diluted with water to provide the use solution. Generally, a dilution of 1 fluid oz. to 4 gallons (i.e. dilution of 1 to X00 by volume) or to 8 gallons (i.e. dilution of 1 to 1,000 by volume) of water can be obtained with 2% to 20%
total peracids in the concentrate. Higher use dilution can be employed if elevated use temperature (greater than 20° C.) or extended exposure time (greater than 30 seconds) are also employed.
In one embodiment, the biocide and the peracetic acid/peracid blend are present in a range from about 1 ppm to 1000 ppm. respectively. In a preferred embodiment, the method comprises adding approximately ~ to 250 ppm of the non-oxidizing biocide along with 1 ~ approximately 10 to 2~0 ppm of the peracetic acid/peracid blend.
An advantage of the present invention is that it lowers the level of expensive chemicals needed for inhibiting the growh of microorganisms. With the addition of a peracetic acid in the water system, the non-oxidizing biocide is effective in low dosages, and as a result is long lasting as evidenced by reductions in microbial grow back. The increased effectiveness removes the need for repetitive additions of the biocide at multiple points in the paper making system.
A further advantage of the present invention is that it provides a more cost effective and environmentally friendly method for treating microorganisms.
Bv way of example, and not limitation. examples of the invention will now be given.
The following examples illustrate the synergistic relationship obtained with the compositions of the present invention.
Synergy is mathematically demonstrated by the industy accepted method described by S.C. Kull et al.in Allied Microbioloev, vol. 9, pages 538-541 (1961). As applied to this invention. it is as follows:
QA = the ppm of active peracetic acid alone which produces an endpoint.
QB = the ppm of active non-oxidizing biocide alone which produces an endpoint.
Q~ = the ppm of active peracetic acid. in combination with non-oxidizing biocide, which produces an endpoint.
Qh = the ppm of active non-oxidizing biocide, in combination. which produces an endpoint.
1 s Qa ; QA + Qh / QB = Synergy Index Synergy index is <:1. it indicates synergy =1, it indicates additivitv > 1. it indicates antagonism 'The following test procedures were utilized during the experimentation of the present mvennon.
Process water from several paper mills was obtained for test purposes.
Aliquots of water from each mill were dosed with the indicated concentrations of peracetic acid (~% active obtained from FMC) or peracetic acidlperacid blend (4.5% a.i. obtained from ECO lab). After 30 minutes of contact time, the designated concentrations of non-oxidising biocide were added to the aliquots previously dosed with PAA, mixed well and incubated at 37°C in an orbital shaker.
At the designated contact times, each aliquot was sampled to determine the total number of viable organisms in colony forming units per milliliter (CFU/mL) on T'ryptone Glucose Extract (TGE) agar. An endpoint of ?, 3, 4 or ~ log,° reduction in viable organisms was then selected for calculating synergy.
Example 1 Synergistic activity of peracetic acid and 2-methyl-4,5-trimethylene-4-isothiazolin-3-one (MTI).
also known as Promexal, against microorganisms in a papermill process water, pH 7.'_' is shown in the following data.
Biocide (ppm of product) 4 Hour Contact 24 Hour Contact PAA @ 12.5 ppm 1.5 x 107 CFU/mL 1.5 x 107 CFUImL
PAA ~ 25 ppm 1.5 x 106 CFU/mL 1.5 x 107 CFUImL
PAA ~~ 50 ppm < 103 CFU/mL 2.5 x 106 CFU/mL
PAA ~ 100 ppm < 103 CFU/mL < 103 CFU/mL
MTl ~ 12.5 ppm 1.6 x 107 CFU/mL 2.2 x 107 CFU/mL
MTI ~~ 25 ppm 1.4 x 107 CFUImL 1.2 x 107 CFUImL
MTI r' 50 ppm 8.0 x 106 CFUImL 8.6 x 106 CFUImL
MTI ~d~ 100 ppm 6.6 x 106 CFUImL 4.4 x 106 CFU/mL
PAA ~a~ 10 ppm plus MTI ~~ 12.5 ppm 7.2 x 106 CFUImL 1.3 x 107 CFU/mL
MTI ~~ 25 ppm 5.0 x 106 CFUimL 4.0 x 106 CFU/mL
MTI rci 50 ppm 6.6 x 106 CFU/mL 3.4 x 106 CFUImL
MTI r- 100 ppm 3,5 ~ 106 CFUimL 1.5 x 106 CFU/mL
PAA pct 20 ppm plus MTl ~' 12.5 ppm 1.6 x 106 CFU/mL 6.3 x 106 CFU/mL
MTI ~a~ 25 ppm g,5 ~ 10~ CFUImL 2.7 x 106 CFU/mL
MTI ia' S0 ppm 7:1 x 10~ CFU!mL 2.6 x 106 CFUImL
MTI ~~ 100 ppm 9.0 x 10~ CFU/mL 9.0 x 105 CFU/mL
PAA ~~ 40 ppm plus MTI ~ 12.5 ppm < 103 CFU~mL 1.5 x 104 CFUImL
MTI ~ 25 ppm < 103 CFU/mL 9.0 x 104 CFU/mL
MTl (a' 50 ppm < 103' CFUimL 3.0 x 103 CFU/mL
MTI ~ 100 ppm < 103 CFUimL < 103 CFU/mL
Control 2.1 x 10g CFUimL 1.1 x 107 CFUImL
Synergy Calculation:
After 24 hours of contact, a 3 log 1 p or greater reduction was achieved with:
PAA = 100 ppm MTI = > 100 ppm (200 ppm ) PAA = 40 ppm/MTI = 12.5 ppm SI = 40/100 + 12.5/200 = 0.4625 Example 2 Synergistic activiy of peracetic acid and 2-(thiocyanomethylthio)benzothiazole (TCMTB) against microorganisms in a papermill process water, pH 6.6 is shown in the following data.
Biocide (ppm of 4 Hour Contact 24 Hour Contact product) PAA ~ 50 ppm 1.6 x 108 CFtI/mL 9.2 x 107 CFU/mL
PAA ~ 100 ppm 1.1 x 107 CFU/mL 6.4 x 107 CFU/mL
PAA ~ 200 ppm 1.1 x 107 CFtI/mL 5.9 x 107 CFU/mL
J
TCMTB ~ 50 ppm 1.1 x 108 CFLJ/mL 7.8 x 107 CFU/mL
TCMTB ~~ 100 ppm 6.8 x 107 CFLJImL 6.4 x 107 CFUImL
TCMTB ~; 200 ppm 6.4 x 107 CFLJ/mL 9.7 x 106 CFU/mL
TCMTB ~~ 400 ppm 5.1 x 107 CFU/mL 3.8 x 106 CFU/mL
PAA ~; 80 ppm plus TCMTB ~a 50 ppm 1.6 x 107 CFLIimL 4.6 x 107 CFUImL
TCMTB ~; 100 ppm 9.7 x 106 CFLI/mL 3.9 x 106 CFU/mL
TCMTB ~ 200 ppm ~.; x 106 CFLI/mL 1.6 x 105 CFU/mL
TCMTB ~a~ 400 ;.6 4.3 x 104 CFU/mL
ppm 106 CFU/mL
a Control 2.1 x 108 CFL~/mL 2.5 x 108 CFU/mL
Synergy Calculation:
After 24 hours of contact. a 3 log 10 or greater reduction was achieved with:
PAA = >200 ppm (400 ppm) TCMTB = >400 ppm (800 ppm) PAA = 80 ppmITCMTB = 200 ppm SI = 80/400 + 200/800 = 0.45 Example 3 Another example of the synergy was expected m~hen peracetic acid was applied in combination with 1,2-Benzisothiazolone (Proxel) to a papermill process water, pH 7Ø
However.
~ unexpectedly, no synergy was seen, supporting the supposition that synergy is unique with peracetic acid and specific biocides.
Biocide (ppm of product) 5 Hour Contact 24 Hour Contact PAA ~:~ 1'.~ ppm 2.1 x 107 CFU/mL 1.0 x 107 CFU/mL
PAA rd' ?~ ppm 1.2 x 107 CFU/mL 1.1 x 107 CFU/mL
PAA ~; ~0 ppm ?,g x 106 CFU/mL 1.7 x 107 CFU/mL
PAA ~~ 100 ppm ~ < 103 CFU/mL 4.0 x 103 CFU/mL
Proxel r 2~ ppm ?.1 x 107 CFU/mL 9.6 x 106 CFU/mL
Proxel r' S0 ppm 1.3 x 107 CFU/mL 4.6 x 106 CFU/mL
Proxel ra 100 ppm 1.4 x 107 CFU/mL 3.2 x 106 CFUImL
PAA r 20 ppm plus Proxel r 2~ ppm 6.7 x 106 CFUi mL 8.8 x 106 CFU/mL
Proxel ~ 50 ppm 6,3 x 106 CFU/ mL 6.7 x 106 CFUImL
Proxel r 100 PPM ~,0 x 106 CFUImL 4.2 x 106 CFU/mL
PA.A r- 40 ppm plus Proxel r ?~ ppm 3,5 x 106 CFUimL 5.1 x 106 CFU/mL
Proxel r ~0 ppm 3.? x 106 CFUimL 4.3 x 106 CFU/mL
Proxel ra 100 ppm ?.6 x 10~ CFU/mL 2.1 x 106 CFU/mL
Control I .9 x 107 CFUImL ?.1 x 107 CFU/mL
Synergy Calculation:
After 24 hours of contact. a 1 log 10 or greater reduction was achieved with:
PAA = 100 ppm Proxel = 100 ppm 1 s PAA = 40 ppm/Proxel = 100 ppm SI = 40/100 + 100/100 = 1.4 Example 5 Along with showing synergistic activity against bacteria, the peroctanoic acid described in example #22 is also synergistic against fungi. When Aspergillus niger spores were seeded into papermill whitewater, pH 7Ø and treated with a combination of POAA and 5-chloro-2-methyl-4-isothiazolin-3-one and 2-methyl-4-isothiazolin-3-one (Iso), the following synergistic activity was seen.
Biocide (ppm of product) 24 Hour Contact 72 Hour Contact POAA r, 100 ppm 2.9 x 104 CFU/mL 3.1 x 104 CFU/mL
POAA ~ 2~0 ppm 3.1 x 103 CFU/mL 1.1 x 103 CFU/mL
POAA r' 500 ppm 1.2 x 101 CFU/mL 2.0 x 100 CFUImL
Iso ~ 23 ppm 2.0 x 104 CFLIimL 2.5 x 104 CFU/mL
Iso ~ ~0 ppm 2.3 x 1 ()4 CFL)ImL 2.4 x 104 CFUImL
Iso r' 100 ppm 1.0 x 104 CFLJimL 1.6 x 104 CFU/mL
Iso ~a 200 ppm 4.0 x 103 CFLJImL 6.0 x 103 CFU/mL
POAA r 250 ppm plus Iso r 2~ ppm 6.1 x I()2 CFLIImL l.~ x 102 CFU/mL
Iso ~. 50 ppm 5.0 x 102 CFLIimL I.5 x 102 CFU/mL
Iso 100 ppm 4.6 x 102 CFLIImL 1.0 x 102 CFU/mL
Iso ~ 200 ppm 3.6 x 102' CFLIimL 1.1 x 102 CFUimL
Control 3.8 x I (14 CFLI/mL 2.6 x 104 CFU/mL
Synergy Calculation After 24 hours of contact. a 2 log I 0 reduction in fungal spores was achieved with:
POAA = 500 ppm Iso = > 200 ppm (400 ppm) POAA = 250 ppm/Iso = 2~ ppm SI = 250/500 + 25/400 = 0.5625 1~
After 24 hours of contact. a 2 log I p or greater reduction was achieved with:
POAA = S00 ppm Iso = >200 ppm (400 ppm) POAA = 250 ppm/Iso = 25 ppm SI = 250/500 + 25/400 = 0.5625 Example 6 Another example of the synergy seen with the blend of peracetic acid and the peroctanoic acid is illustrated when POAA is applied to a papetmill process v'~ater, pH 7.0, that has also been dosed with 4,5-dichloro-2-N-octyl-4-isothiazolin-3-one (RH287).
Biocide (ppm of product)5 Hour Contact 24 Hour Contact POA.A ~ 2~ ppm 9.1 x 106 CFLIImL 1.9 x 107 CFU/mL
POAA ~' ~0 ppm 1.6 x 1 ()5 CFLT/mL2.3 x 107 CFU/mL
POAA ~ 100 ppm 1 x 103 CFUImL 6.1 x 10~ CFUImL
POAA ~d 200 ppm < 103 3.8 x 104 CFU/mL
C FU/mL
RH287 r- SO ppm 2.1 x 1 C16 CFU/mL7.1 x 106 CFU/mL
RH287 ~ 100 ppm 1.3 x 105 CFU/mL 2.8 x 106 CFUImL
RH287 ~ 200 ppm 1.6 x 104 CFU/mL 1.1 x 106 CFU/mL
POAA r. 20 ppm plus RH287 ~a ~0 ppm 1.1 x 10~ CFU/mL 5.6 x 106 CFU/mL
RH287 r, 100 ppm 3.6 x 104 CFU/mL 8.0 x 104 CFU/mL
RH287 r, 200 PPM g,0 x 103 CFU/mL 6.0 x 103 CFU/mL
PO.AA ~ 40 ppm plus RH287 r ~0 ppm 8.0 x 103 CFU/mL 2.7 x 104 CFU/mL
RH287 ~ 100 ppm 4.0 x 103 CFUImL < 103 CFU/mL
RH287 r 200 PPM 3.0 x 103 CFU/mL < 103 CFUImL
Control 3.0 x 107 CFUImL 4.9 x 107 CFUImL
Svnerev Calculation:
y .After ~ hours of contact, a 4 log 10 or greater reduction was achieved with:
POAA = 100 ppm RH287 = > 200 (400 ppm) POAA = 40 ppm/RH287 = ~0 ppm SI = 40/100 + 54/400 = 0.5?5 After 24 hours of contact, a 4 log. 10 or greater reduction was achieved with:
1 ~ POAA = > 200 ppm (400 ppm ) RH287 = > 200 ppm (400 ppm) POAA = 40 ppmlRH287 = 100 ppm SI = 40/400 + 100/400 = 0.35 It should be understood that various changes and modifications to the presently preferred embodiments described herein will be apparent to those skilled in the art.
Such changes and modifications can be made without departing from the spirit and scope of the present invention and without diminishing its attendant advantages. It is therefore intended that such changes and modifications be covered by the appended claims:
Claims (18)
1. A composition for inhibiting the growth of microorganisms in industrial process water comprising effective amounts of peracetic acid and a non-oxidizing biocide selected from the group consisting of 2-methyl-4,5-trimethylene-4-isothiazolin-3-one and 2-(thiocyanomethylthio)benzothiazole.
2. The composition of claim 1 wherein the amount of peracetic acid ranges from approximately 5 to 250 ppm and the amount of non-oxidizing biocide ranges from approximately 10 to 250 ppm.
3. A method for controlling the growth of microorganisms in industrial process water comprising the step of administering a sufficient amount of a peracetic acid and a sufficient amount of a non-oxidizing biocide selected from the group consisting of 2-methyl-4,5-trimethylene-4-isothiazolin-3-one and 2-(thiocyanomethylthio)benzothiazole to the industrial process water to reduce the growth of the microorganisms.
4. The method of claim 3, wherein the industrial process water is selected from the group consisting of water of a pulp and paper mill system, cooling water and mining.
5. The method of claim 3 or 4, wherein the peracetic acid and the non-oxidizing biocide are added in a ratio from about 10:1 to 1:25.
6. The method of claim 3, 4 or 5, wherein the amount of peracetic acid added ranges from approximately 5 to 250 ppm and the non-oxidizing biocide ranges from approximately 1.0 to 250 ppm .
7. The method of any one of claims 3 to 6, wherein the microorganisms contain bacteria.
8. The method of any one of claims 3 to 6, wherein the microorganisms contain fungi.
9. The method of any one of claims 3 to 8, wherein the peracetic acid is added to the industrial water prior to the addition of the non-oxidizing biocide.
10. A composition for inhibiting the growth of microorganisms in industrial process water comprising effective amounts of a peracetic acid/peracid blend and a non-oxidizing biocide selected from the group consisting of isothiazolin, glutaraldehyde, methylene bisthiocyanate, DBNPA, carbamate, quaternary ammonium compounds, 4,5-dichloro-1,2-dithio-3-one, 4,5-dichloro-2-N-octyl-4-isothiazolin-3-one, decylthioethylamine, orthophthaldehyde, 2-bromo-2-nitropropane-1,3-diol, 4,5-dichloro-1,2-dithiol-3-one, dodecylguanidine hydrochloride, 1-(3-chloroallyl)-3,5,7-triaza-1-azoniaadamantane chloride, dibromo dicyanobutane, bis(trichloromethyl)sulfone, 2-methyl-4,5-trimethylene-4-isothiazolin-3-one and 2-(thiocyanomethylthio)henzothiazole.
11. The composition of claim 10 wherein the amount of peracetic acid/peracid blend ranges from about 5 to about 250 parts per million and the amount of non-oxidizing biocide ranges from about 10 to about 250 parts per million.
12. A method for controlling the growth of microorganisms in industrial process water including the step of administering a sufficient amount of a peracetic acid/peracid blend and a sufficient amount of a non-oxidizing biocide to the industrial process water to reduce the growth of the microorganisms.
13. The method of claim 12 wherein the industrial process water is selected from the group consisting of water of a pulp and paper mill system, cooling water and mining water.
14. The method of claim 12 or 13, wherein the peracetic acid and the non-oxidizing biocide are added in a ratio from about 10:1 to about 1:25.
15. The method of claim 12, 13 or 14, wherein the amount of peracetic acid added ranges from about 5 to about 250 parts per million and the amount of non-oxidizing biocide added ranges from about 10 to about 250 parts per million.
16. The method of any one of claims 12 to 15, wherein the microorganisms contain bacteria.
17. The method of any one of claims 12 to 15, wherein the microorganisms contain fungi.
18. The method of any one of claims 12 to 17, wherein the peracetic acid/peracid blend is added to the industrial water prior to the addition of the non-oxidizing biocide.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US08/848,326 US5785867A (en) | 1993-08-05 | 1997-04-30 | Method and composition for inhibiting growth of microorganisms including peracetic acid and a non-oxidizing biocide |
| US08/848,326 | 1997-04-30 |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CA2236160A1 CA2236160A1 (en) | 1998-10-30 |
| CA2236160C true CA2236160C (en) | 2003-01-21 |
Family
ID=25302976
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA002236160A Expired - Fee Related CA2236160C (en) | 1997-04-30 | 1998-04-29 | Method and composition for inhibiting growth of microorganisms including peracetic acid and a non-oxidizing biocide |
Country Status (14)
| Country | Link |
|---|---|
| US (1) | US5785867A (en) |
| EP (1) | EP0875145A3 (en) |
| JP (1) | JP4523081B2 (en) |
| KR (1) | KR19980081830A (en) |
| AR (1) | AR012846A1 (en) |
| AU (1) | AU735264B2 (en) |
| BR (2) | BR9801495A (en) |
| CA (1) | CA2236160C (en) |
| ID (1) | ID20248A (en) |
| MY (1) | MY120038A (en) |
| NO (1) | NO323851B1 (en) |
| NZ (1) | NZ330265A (en) |
| TW (1) | TW520272B (en) |
| ZA (1) | ZA983525B (en) |
Families Citing this family (73)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5785867A (en) * | 1993-08-05 | 1998-07-28 | Nalco Chemical Company | Method and composition for inhibiting growth of microorganisms including peracetic acid and a non-oxidizing biocide |
| US5965617A (en) * | 1998-02-03 | 1999-10-12 | Angus Chemical Company | Method and composition for controlling microbial growth using bromontrostyene and peracetic acid |
| US6010729A (en) | 1998-08-20 | 2000-01-04 | Ecolab Inc. | Treatment of animal carcasses |
| US6409926B1 (en) | 1999-03-02 | 2002-06-25 | United States Filter Corporation | Air and water purification using continuous breakpoint halogenation and peroxygenation |
| US6143184A (en) | 1999-03-02 | 2000-11-07 | United States Filter Corporation | Air and water purification using continuous breakpoint halogenation |
| DE60000804T2 (en) * | 1999-04-16 | 2003-09-11 | Rohm & Haas | Stable microbicidal formulation |
| US6342528B1 (en) * | 2000-01-18 | 2002-01-29 | Lynntech, Inc. | Control of microbial populations in the gastrointestinal tract of animals |
| AU2001253777B2 (en) | 2000-04-28 | 2005-05-19 | Ecolab Inc. | Antimicrobial composition |
| US6419817B1 (en) | 2000-06-22 | 2002-07-16 | United States Filter Corporation | Dynamic optimization of chemical additives in a water treatment system |
| CA2413888A1 (en) | 2000-06-22 | 2001-12-27 | United States Filter Corporation | Corrosion control utilizing a hydrogen peroxide donor |
| US7150884B1 (en) * | 2000-07-12 | 2006-12-19 | Ecolab Inc. | Composition for inhibition of microbial growth |
| US6716359B1 (en) | 2000-08-29 | 2004-04-06 | United States Filter Corporation | Enhanced time-based proportional control |
| US6479454B1 (en) | 2000-10-05 | 2002-11-12 | Ecolab Inc. | Antimicrobial compositions and methods containing hydrogen peroxide and octyl amine oxide |
| US7316824B2 (en) * | 2000-12-15 | 2008-01-08 | Ecolab Inc. | Method and composition for washing poultry during processing |
| US6514556B2 (en) * | 2000-12-15 | 2003-02-04 | Ecolab Inc. | Method and composition for washing poultry during processing |
| US6964787B2 (en) * | 2001-02-01 | 2005-11-15 | Ecolab Inc. | Method and system for reducing microbial burden on a food product |
| US6620315B2 (en) | 2001-02-09 | 2003-09-16 | United States Filter Corporation | System for optimized control of multiple oxidizer feedstreams |
| AU2002250386A1 (en) * | 2001-03-22 | 2002-10-08 | Pioneer Hi-Bred International, Inc. | Expansin protein and polynucleotides and methods of use |
| US6635286B2 (en) * | 2001-06-29 | 2003-10-21 | Ecolab Inc. | Peroxy acid treatment to control pathogenic organisms on growing plants |
| US6627593B2 (en) | 2001-07-13 | 2003-09-30 | Ecolab Inc. | High concentration monoester peroxy dicarboxylic acid compositions, use solutions, and methods employing them |
| US7060301B2 (en) | 2001-07-13 | 2006-06-13 | Ecolab Inc. | In situ mono-or diester dicarboxylate compositions |
| US6776926B2 (en) * | 2001-08-09 | 2004-08-17 | United States Filter Corporation | Calcium hypochlorite of reduced reactivity |
| US6991735B2 (en) * | 2002-02-26 | 2006-01-31 | Usfilter Corporation | Free radical generator and method |
| US7108781B2 (en) * | 2002-02-26 | 2006-09-19 | Usfilter Corporation | Enhanced air and water purification using continuous breakpoint halogenation with free oxygen radicals |
| US7622606B2 (en) * | 2003-01-17 | 2009-11-24 | Ecolab Inc. | Peroxycarboxylic acid compositions with reduced odor |
| JP2007520479A (en) * | 2004-01-09 | 2007-07-26 | イーコラブ インコーポレイティド | Medium chain peroxycarboxylic acid composition |
| US7887641B2 (en) * | 2004-01-09 | 2011-02-15 | Ecolab Usa Inc. | Neutral or alkaline medium chain peroxycarboxylic acid compositions and methods employing them |
| US7507429B2 (en) * | 2004-01-09 | 2009-03-24 | Ecolab Inc. | Methods for washing carcasses, meat, or meat products with medium chain peroxycarboxylic acid compositions |
| 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 |
| 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 |
| US7771737B2 (en) | 2004-01-09 | 2010-08-10 | Ecolab Inc. | Medium chain peroxycarboxylic acid compositions |
| US20100112543A1 (en) * | 2005-03-16 | 2010-05-06 | Manh-Dan Ngo | Processing soft tissue, methods and compositions related thereto |
| US7754670B2 (en) | 2005-07-06 | 2010-07-13 | Ecolab Inc. | Surfactant peroxycarboxylic acid compositions |
| US20090074881A1 (en) * | 2006-05-02 | 2009-03-19 | Bioneutral Laboratories Corporation Usa | Antimicrobial cidality formulations with residual efficacy, uses thereof, and the preparation thereof |
| US8652336B2 (en) | 2006-06-06 | 2014-02-18 | Siemens Water Technologies Llc | Ultraviolet light activated oxidation process for the reduction of organic carbon in semiconductor process water |
| US10343939B2 (en) | 2006-06-06 | 2019-07-09 | Evoqua Water Technologies Llc | Ultraviolet light activated oxidation process for the reduction of organic carbon in semiconductor process water |
| 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 |
| US9725343B2 (en) | 2007-04-03 | 2017-08-08 | Evoqua Water Technologies Llc | System and method for measuring and treating a liquid stream |
| US9365435B2 (en) | 2007-04-03 | 2016-06-14 | Evoqua Water Technologies Llc | Actinic radiation reactor |
| US9365436B2 (en) | 2007-04-03 | 2016-06-14 | Evoqua Water Technologies Llc | Method of irradiating a liquid |
| US20080245737A1 (en) * | 2007-04-03 | 2008-10-09 | Siemens Water Technologies Corp. | Method and system for providing ultrapure water |
| US8961798B2 (en) | 2007-04-03 | 2015-02-24 | Evoqua Water Technologies Llc | Method for measuring a concentration of a compound in a liquid stream |
| US8741155B2 (en) | 2007-04-03 | 2014-06-03 | Evoqua Water Technologies Llc | Method and system for providing ultrapure water |
| US8753522B2 (en) | 2007-04-03 | 2014-06-17 | Evoqua Water Technologies Llc | System for controlling introduction of a reducing agent to a liquid stream |
| US8591730B2 (en) | 2009-07-30 | 2013-11-26 | Siemens Pte. Ltd. | Baffle plates for an ultraviolet reactor |
| US9242880B2 (en) * | 2010-12-28 | 2016-01-26 | Nalco Company | Strategy for on-site in situ generation of oxidizing compounds and application of the oxidizing compound for microbial control |
| WO2012090124A2 (en) | 2010-12-29 | 2012-07-05 | Ecolab Usa Inc. | IN SITU GENERATION OF PEROXYCARBOXYLIC ACIDS AT ALKALINE pH, AND METHODS OF USE THEREOF |
| PL2687094T3 (en) | 2010-12-29 | 2018-09-28 | Ecolab Usa Inc. | Generation of peroxcarboxylic acids at alkaline pH, and their use as textile bleaching and antimicrobial agents |
| EP2527301B1 (en) | 2011-05-26 | 2016-04-27 | Evoqua Water Technologies GmbH | Method and arrangement for a water treatment |
| CA2849348C (en) | 2011-09-30 | 2019-08-27 | Kemira Oyj | Prevention of starch degradation in pulp, paper or board making processes |
| US9321664B2 (en) | 2011-12-20 | 2016-04-26 | Ecolab Usa Inc. | Stable percarboxylic acid compositions and uses thereof |
| BR112014020748B1 (en) | 2012-03-30 | 2021-02-23 | Ecolab Usa Inc. | water treatment method, water source treatment method and aqueous water treatment composition with antimicrobial activity |
| WO2014035953A1 (en) * | 2012-08-27 | 2014-03-06 | Nalco Company | The use of a buffer with a biocide precursor |
| 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 |
| US10165774B2 (en) | 2013-03-05 | 2019-01-01 | Ecolab Usa Inc. | Defoamer useful in a peracid composition with anionic surfactants |
| US8822719B1 (en) | 2013-03-05 | 2014-09-02 | Ecolab Usa Inc. | Peroxycarboxylic acid compositions suitable for inline optical or conductivity monitoring |
| US20140256811A1 (en) | 2013-03-05 | 2014-09-11 | Ecolab Usa Inc. | Efficient stabilizer in controlling self accelerated decomposition temperature of peroxycarboxylic acid compositions with mineral acids |
| CN103734184A (en) * | 2013-12-09 | 2014-04-23 | 乌鲁木齐德安东升环保设备有限公司 | Multiple-effect sterilizing agent and preparation method thereof |
| JP6078170B2 (en) * | 2013-12-20 | 2017-02-08 | 日本曹達株式会社 | Disinfectant composition |
| US11161762B2 (en) | 2015-01-21 | 2021-11-02 | Evoqua Water Technologies Llc | Advanced oxidation process for ex-situ groundwater remediation |
| US10494281B2 (en) | 2015-01-21 | 2019-12-03 | Evoqua Water Technologies Llc | Advanced oxidation process for ex-situ groundwater remediation |
| US10136642B2 (en) * | 2015-02-19 | 2018-11-27 | Agri-Neo, Inc. | Composition of peracetic acid and at least one organic fungicide for the control and/or the treatment of diseases associated with the presence of pathogens, and method, use and kit involving said composition |
| MX2018002171A (en) | 2015-08-21 | 2018-06-15 | Ecolab Usa Inc | Complexation and removal of mercury from flue gas desulfurization systems. |
| US10569221B2 (en) | 2015-08-21 | 2020-02-25 | Ecolab Usa Inc. | Complexation and removal of mercury from flue gas desulfurization systems |
| WO2017034999A1 (en) | 2015-08-21 | 2017-03-02 | Ecolab Usa Inc. | Complexation and removal of mercury from flue gas desulfurization systems |
| US11110393B2 (en) | 2017-07-06 | 2021-09-07 | Ecolab Usa Inc. | Enhanced injection of mercury oxidants |
| EP3450623B1 (en) | 2017-08-29 | 2023-06-28 | Kemira Oyj | Method for controlling growth of microorganisms and/or biofilms in an industrial process |
| EP3450626B1 (en) | 2017-08-29 | 2020-05-06 | Kemira Oyj | Method for controlling growth of microorganisms and/or biofilms in an industrial process |
| EP4008689A1 (en) * | 2017-09-25 | 2022-06-08 | Ecolab USA Inc. | Use of medium chain peracids for biofilm inhibition in industrial recirculating water systems |
| AU2019222696B2 (en) | 2018-02-14 | 2024-02-29 | Ecolab Usa Inc. | Compositions and methods for the reduction of biofilm and spores from membranes |
Family Cites Families (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4966775A (en) * | 1988-09-12 | 1990-10-30 | Betz Laboratories | Biocidal compositions and use thereof |
| US5200189A (en) * | 1991-07-23 | 1993-04-06 | Ecolab Inc. | Peroxyacid antimicrobial composition |
| CA2129489C (en) * | 1993-08-05 | 2000-10-10 | Judy G. Lazonby | Method and composition for inhibiting growth of microorganisms including peracetic acid and a non-oxidizing biocide |
| US5785867A (en) * | 1993-08-05 | 1998-07-28 | Nalco Chemical Company | Method and composition for inhibiting growth of microorganisms including peracetic acid and a non-oxidizing biocide |
| US5658467A (en) * | 1993-08-05 | 1997-08-19 | Nalco Chemical Company | Method and composition for inhibiting growth of microorganisms including peracetic acid and a non-oxidizing biocide |
| US5494904A (en) * | 1993-09-24 | 1996-02-27 | Buckman Laboratories International, Inc. | Synergistic antimicrobial compositions containing 2-(thiocyanomethylthio)benzothiazole and an organic acid |
| US5368749A (en) * | 1994-05-16 | 1994-11-29 | Nalco Chemical Company | Synergistic activity of glutaraldehyde in the presence of oxidants |
| CA2204279A1 (en) * | 1994-11-04 | 1996-05-17 | Robert M. Gerhold | Synergistic biocidal combinations |
-
1997
- 1997-04-30 US US08/848,326 patent/US5785867A/en not_active Expired - Lifetime
-
1998
- 1998-04-23 NZ NZ330265A patent/NZ330265A/en not_active IP Right Cessation
- 1998-04-24 AU AU63607/98A patent/AU735264B2/en not_active Ceased
- 1998-04-27 NO NO19981904A patent/NO323851B1/en not_active IP Right Cessation
- 1998-04-27 EP EP98303225A patent/EP0875145A3/en not_active Withdrawn
- 1998-04-27 MY MYPI98001898A patent/MY120038A/en unknown
- 1998-04-28 ZA ZA983525A patent/ZA983525B/en unknown
- 1998-04-28 JP JP11868998A patent/JP4523081B2/en not_active Expired - Lifetime
- 1998-04-28 BR BR9801495A patent/BR9801495A/en active IP Right Grant
- 1998-04-28 BR BRPI9801495A patent/BRPI9801495B1/en unknown
- 1998-04-29 TW TW087106618A patent/TW520272B/en not_active IP Right Cessation
- 1998-04-29 ID IDP980638A patent/ID20248A/en unknown
- 1998-04-29 KR KR1019980015332A patent/KR19980081830A/en not_active Application Discontinuation
- 1998-04-29 CA CA002236160A patent/CA2236160C/en not_active Expired - Fee Related
- 1998-04-29 AR ARP980101998A patent/AR012846A1/en not_active Application Discontinuation
Also Published As
| Publication number | Publication date |
|---|---|
| NO981904L (en) | 1998-11-02 |
| AR012846A1 (en) | 2000-11-22 |
| KR19980081830A (en) | 1998-11-25 |
| ID20248A (en) | 1998-11-05 |
| BRPI9801495B1 (en) | 2018-09-04 |
| BR9801495A (en) | 1999-07-20 |
| CA2236160A1 (en) | 1998-10-30 |
| JP4523081B2 (en) | 2010-08-11 |
| ZA983525B (en) | 1999-06-09 |
| AU735264B2 (en) | 2001-07-05 |
| TW520272B (en) | 2003-02-11 |
| NO981904D0 (en) | 1998-04-27 |
| MY120038A (en) | 2005-08-30 |
| NO323851B1 (en) | 2007-07-16 |
| JPH1135410A (en) | 1999-02-09 |
| US5785867A (en) | 1998-07-28 |
| EP0875145A3 (en) | 1999-06-23 |
| EP0875145A2 (en) | 1998-11-04 |
| NZ330265A (en) | 1999-02-25 |
| AU6360798A (en) | 1998-11-05 |
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Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| EEER | Examination request | ||
| MKLA | Lapsed |
Effective date: 20140429 |