CA2129489C - 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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- CA2129489C CA2129489C CA002129489A CA2129489A CA2129489C CA 2129489 C CA2129489 C CA 2129489C CA 002129489 A CA002129489 A CA 002129489A CA 2129489 A CA2129489 A CA 2129489A CA 2129489 C CA2129489 C CA 2129489C
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- ppm
- paa
- peracetic acid
- oxidizing biocide
- microorganisms
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Classifications
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- 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
-
- 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
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10S210/00—Liquid purification or separation
- Y10S210/928—Paper mill waste, e.g. white water, black liquor treated
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 and a non-oxidizing biocide. The method of the present invention includes the step of adding sufficient amounts of the peracetic acid and the non-oxidizing biocide to industrial process waters.
Description
O8i0.~/94 lS:5f3 '$708 30S 29&5 ~022/U27 s p E C I F I C A T I O N
TITLE
"METgOD AI~TD CQl~dpGl6ITIOH ~'OR TNBIBITI1~'G GROWTB
OF MICROORCil~NISMS IHCLUDIlwG PERI~rCBTIC ACID
71ND A 344I~T-ORIDIZI~1G BIOCIDE"
$ACiCGFtQUND OF' ~'HE I_NVENTION
The pxesent invention relates generally to cvntrall.ing the growth of microorganisms. More specifically, the present invention relates to inhibiting to the growth of microorganisms in industrial waters.
The presence of microorganisms in waters, especially industrial waters, is a never-ending concern for industrial manufacturers. Examples of industrial waters where microorganisms can .interferes with industrial processes include: cooling tower water; mining process waters; food processing waters; sugar reprocessing waters; and the like.
In the paper indusctry, the growth of microorganisms in pulp and paper mill watQrs can adversely affect 2o finished paper products. Microbial lifQ depends an the nutrient sugply, the pH and the 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 vaxiety of microorganisms. These contaminating microorganisms are capable of causing spoilage of pulp, Tarnish, or chemical additives . The microorganist~s cause deposits that break loose and fall into the paper furnish, resulting in quality loss and/or end product 3D defects such as holez and spets. The end result is 08:04%94 15:58 'x'708 3U5 29!35 f~021~027 ~= X129489 _z_ unsalable paper or paper sold at a lo~rer value, Robertson, The use of v~~,~s~Q-contrast microscopy to assess and differentiate the m~obial nonulat'o of a saner mi 1, TAPPI Journal, pp. 83 (March 1993).
The presence of mioroorganisms within industrial water systems results in the formation of deposits of biological origin on industrial machines. These formation deposits give rise to: corrosion; breaks;
increased down time; loss of yield; high chemical Costs;
odors; and expensive deposit control programs. In the paper mill industry, slime depasit is reportedly responsible for nearly 7~~ of all breaks, blockages and pump failures. Safade, T~aklina the Slime Problem in a Paper-Mill, PTI, p. 280 (September 19s8).
13 Slime may be dofined ag an "accretion or accumulation caused by certain micro-organisms in the presence. of pulp fiber, filler, dirt and other materials, mixed in varied propartians, having variable physical charactex~isti.cs and accumulating at continuous changing 2o rates." ,~d. In most industrial process waters, especially pulp and paper mill systems, :pore forming bacteria and Pseudamoaas ~lerugiaos~a contribute to slime formation. The later is most ,prevalent in paper mill slimes. p~ungi is also a contributor toward slime 25 formation.
The conventional method of controlling microbial growth is through the use of biooides. aiocides are generally divided into two main groups: oxidizing; and non-oxidizing. These biocides act on the microorganisms 34 in one of three ways: either by attacking the cell wail;
the cytoplasmic membrane; or the cellular constituents.
,~ at 282.
08/O~i9.~ 15:55 $7U8 305 2P85 ~ p2Ui027 2iz~4s9 i~lhile biocides do inhibit miarabial growth, economic and environmental concerns ratguire improved methods. 1~ problem with the use of biocides is that high levels of expensive chemicals are needed to vantral microbial growth. To date, none of the oammercially available biocides have exhibited a prolonged biocidal effect. Their effectiveness is rapidly reduced as a result of exposure to physical conditions such as temperature or association with ingrediantc contained lay the system toward which they exhibit an affinity. This results in a restriction or elimination of their biocidal effectiveness.
Therefore, the use of such biocides involves continuous or frequent additions to paper mill systems.
Furthar, these additions must be made at a plurality of points or zon~as in the system. The costs of the biocides arid tha labor costs involved are considerable.
Moreover, such chQmicals are highly toxic in the quantities known to be required for effactive control of microbial populations. As a result, environmental regulations restrict the amount of biacides that can safely be discarded into the environment.
Therefore, a need exists far improved methods for controlling the growth of microorganisms in industrfa~l process waters.
'y~$Y OF THE 11 ENTZON
Fursuant to the present invention, the growth of microorganisms can be inhibited without the use of high levels of certain bfocides. The present invention provides compositions to be used !or inhibiting the growth of ~nicror~rganisms in industrial process waters.
The compositions include sugficient amounts of a ~94g 9 peracetic acid and a non-oxidizing biocide. The composition of the present invention possesses unexpected synergistic activity against microorganisms, including bacteria and fungi.
The present invention also provides a method for inhibiting the growth of the microorganisms in industrial process waters. The method includes the step of adding to the waters sufficient amounts of a peracetic acid (PAA) and a non-oxidizing biocide. Combining the peracetic acid with the non-oxidizing biocide has been found to enhance the effectiveness of the biocide.
In an embodiment, the biocide is chosen from the group consisting of: isothiazolin; glutaraldehyde; DBNPA; methylene biothiocyanate; carbamate; quaternary ammonium compounds;
bronopol, 4,5-dichloro-1, 2-dithiol-3-one; and 4,5-dichloro-2-N-octyl-4-isothiazolin-3-one.
In an embodiment, the peracetic acid is added prior to the biocide in the water system.
In other embodiments: the peracetic acid and the non-oxidizing biocide are added in a ratio from about 10:1 to 1:25;
and the amount of peracetic acid added ranges from approximately 5 to 250 ppm and the non-oxidizing biocide ranges from approximately 10 to 250 ppm.
An advantage of the present invention is that it provides improved compositions for use in inhibiting the growth of microorganisms.
Another advantage of the present invention is that it provides an improved method for inhibiting the growth of microorganisms.
Still further, an advantage of the present invention is that it lowers the level of expensive chemicals needed for inhibiting the growth 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.
The increased effectiveness removes the need for repetitive additions of the biocide at multiple points in the paper making system.
D
~2948'~
Moreover, an advantage of the present invention is that it provides a mcre cost effective and environmentally friendly method for treating microorganisms.
Additional features and advantages of the present invention are described in, and will be apparent from, the detailed description of the presently preferred embodiments.
BRIEF DESCRIPTT_ON OF THE DRAWING
The figure in the specification illustrates graphically colony forming units versus hours for microorganisms treated with a composition of the present invention compared to the treatment of peracetic acid or a biocide alone.
DETAILED DESCRIPTION
OF T'.riE PRESENTLY PREFERRED EMBODIMENT
The present invention provides, for inhibiting the growth of microorganisms, improved compositions and method of administering the same to a fluid system. The compositions include a sufficient amount of a peracetic acid 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 peracetis acid. E:~amples of suitable non-oxidizing biocides include: isothiazolin; methylene bisthiocyanate;
glutaraldehyde; DBNPA; carbamate; quaternary ammonium compounds; bronopol; 4,5-dichloro-1,2-dithiol-3-one; and 4,5-dichioro-2-N-octyi-4-isothiazolln-3-one. Natural'_y, mixtures of such biocides can also be used.
C
._ . ... .
Q8.04/94 15;54 '$'708 305 :985 ~017iU27 w.~ 212~~89 ThQ bi.ocides can be obtained from a number of chemical suppliers such as American Cyanamid, Buckman, Beta, Dearborn Chemical, Economi.as haboratory, Inc., Merck, Nalco Chemical Company, and Vinela~nd Chemical.
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 npn-oxidizing biocides yields a total effect which is greater than the sum of the effects of the biocxde ar the peracetic acid taken separately.
The optimal amounts of biocide and peracetic acid required for effectiveness in this invention depend or, 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 rind pH of thp waters, and the microbial count. The concentrations may be as little as 1 part pex million (ppm) by weight to as much as 25p ppm. with respect to the biocide, the Lower and upper limits of the required concentration substantially depend upon the specific biocide or combination of biocide.s used.
Still further, since the suitable biocides that may be used in the present invBx~tion are often obtainod at different usable concentrations (i.e. activity level), the ratios vary depending an the particular biocide 3o combined with the peracetia acid. For example, the peracetic acid used in the examples below is 5~ active, the gluta~raldehyde is 50; active, and the DBNPA is 20~
active. Thus, a 1:1 ratio of PAA:Glut translates to 1:10 '~294~9 _, _ on an actives basis, while a 1:1 ratio of PAA:pBNPA
translates to a 1:4 based on actives.
8y way o! example, and not limitation, the following ars biocide:, including the percs~nt active of each bivcide, that may be used in the present invention:
isothiazolin (1.5% a.i.) ; glutaraldehyde (50% a.i.);
methylene biothiocyanate (10~ a.i.); DBNPA (20% a.i.);
carbamate (30% a.i.); quaternary ammonium compounds (31~
a.i.); 4,5-dichloro-1,2- dithiol-3-one (5~ a.i.); and 4,5-dichloro-2-:~'octyl-4-isothiazolin-3-one (2~ 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 non-oxidizing biocide of the present invention. In an 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 providos the desired concentration of the same in the waters.
AftQr 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 Ghe waters.
In an embodiment, the method comprises adding approximately 5 to 250 ppm of the non-oxidizing biocide C
08/04/94 15:53 $'708 305 2985 ~ D1S~D27 _$_ along with approximately 10 to 250 ppm of the peraaetic acid. Ire an embodiment, the biocide and the peracetic acid are present in a range from about 1 ppm to looo ppm of product.
By wary of example, and not limitation, examples of the invention will now be given.
F~XAMPLEE
The following examples illustrate the synergistic relationship obtained with the compositions of the present invention.
Synergy is mathematically demonstrated by the industry accepted method described by s.C. Kull et al.
in Applied Microbial-oav, vol. 9, pages 538-54I (1961) .
As applied to this invention, it is as fol.lc~ws:
t1A ~ the ppm of active non-oxidizing biocide alone which produoes an endpoint.
the ppm of active peracetic acid alone which produces an endpoint.
- the ppm of active peracetic acid, in 2o combination with non-oxidizing biocide, which praduceg an endpoint.
Qb = the ppm of active non-oxidizing biocxde, in combination, which produces an endpoint.
+ fib" , z synergy index 2 5 Qa ~g tl, it indicate~ aytlergy if Synergy Index (SI) iBS -Z, it .indi~:at~a sdditivity ai, it indiaatea antagonism The following teat procedures were utilized during p the experimentation of the present invention.
Process watex from several papermills was obtained for test purposes. Aliquots of water from each mill were _- 0804!94 15: 53 '$?U8 3U5 2955 ~ a14: 02?
.g_ dosed with the indicated concentrations of peraaetic acid (5~ active obtained from FMG). After 30 minutes of contact time, the designated concentrations of non-oxidizing biocida were added to the aliquots previously dosed with PAA, mixed Well and incubated at 37°c in an orbital sha3cer. At the Qesignated contact times, each aliquot was sampled to determine the total number of viable organisms in colony forming units per mill.il.iter (CFUjrtlL} on Tryptone Glucose Extract (TGE) agar. An endpoint of 2,3,4 or 5 logla reduction in viable organisms was then selected ~or calculating synergy.
EXP~P~
Synergistic activity against microorganisms was demonstrated in mill furnish at pH 7Ø
8iocide (ppm 30 90 5 hr. 24 product) min min hr.
2 0 1. PAA-10 z.3 x 1064.0 x 106~.8 1066.4 106 x x 2, PAA-20 5.8 x 1059.3 x 1052.3 1056.5 105 x x 0 60 4.5 mire min hr 3. Glut-50 3.2 x 1063.2 x y04<101 <101 ~ 5 4. Glut-39 3.7 x 1062.5 x 105<lol <l0i s. Glut-20 4.2 x 1067.2 x lay2.6 1041.1 102 x x 6. Clut-10 4.4 x 1062.B x 1062,3 1069.5 102' x x 7. Glut--10/PAA-104.5 x 1053.2 x 1055.3 1041.9 102 x x 8. Glut-10/PAA-201.2 x 1055.3 x 1042.1 1043.1 10a x x 30 9. control-0 2.3 x 1061.0 x 1053,3 1055.C 106 x x 08!04194 15:52 'x'708 305 2985 I~ 013/027 ~~29489 ~' -10~
After 90 mi,nutQe of contact, s 2 Iot~lp drop is achiQVwd withs PAA y 20 ppm (40 ppm) Glutaraldmhyde = 50 Ppm FAA = 20 gpm/ Glut = 1o pgm s= ~ 10/ap t ao/40 = 0.~
After 5 hours of contact, a 2 1og10 drop is achiQVod withs PAA y 20 ppm (40 PPm) Glutaraldehyde = 2o ppm pAA - 10 ppm/ Giut = 10 ppm SI ~ 10/40 + 10/20 = 0.75 Aftar 24 hours of contact, a 4 logid dr4p is achitved with:
PAA > 20 ppm (4D ppm) Glutaraldehyde = 20 ppm PAA = 10 ppm/ Glut = 10 ppm 15 SI = 10/40 + 10/3D = G.75 20 Siocide (ppm 3o min 90 5 hr. .~.4 .
product) min hr 1. PAA-5 7.4 x 1058.5 105'7.8 105 a.8 106 x x x 2 5 p~-10 6.4 x 1055.7 1055.2 105 2.9 106 2. x x x 3. PAA-2D 4.D x 1055.4 1051.0 105 5.1 105 x x x O 60 4~
min min 4. bBNPA-100 3.9 x 10sc101 0101 X101 5. DBNPA-73 5.1 x 10~e101 x101 c101 30 6. DHNpA-50 6.b x 10$8.1 lOZc10'1 X101 x 7. DHNPA-25 6.0 x 1053.3 103<7.01 9.4 10a x x e. pBNPA-100/PAA-54.3 x .105<101 <101 <101 08!04/94 15:52 $7U8 105 2985 . ~IU12;02'r 2129-89 '~
9. DBNPA-T5/PP~A-S s.i x lv5 <lol ~lal «Q1 10. DBNpA-50/PAA-5 3.T x 105 1101 6101 c101 11. pBNPA~-25/PAA-5 g.g x 10~ 3.4 x 10~ 1.1 x lOZ 0141 12. Dt3NPA-100/FAA-105.5 x 105 <101 x101 c101 13. DHNPA-T5/pAA-10 1.4 x 1D5 <101 ci01 clD1 .4. DeNPA-50/P~-10 9.5 x I04 <141 X101 <ipl 15. bBNPA-25/PAA-10 3.6 x lOd <101 <1D1 <101 lE. DBNPA-100/PAA-20 2.0 x 105 X101 <101 <101 17. DgNPA-75/PAA-20 5.4 x 105 0101 <1D1 x101 18. DBNPA-50/PAA-20 4.5 X 105 <101 x101 <1p1 19. DBNPA~25/PA~1-20 3.7 x I05 c101 <101 <SO1 20. Co~~trol-0 3.7 x 105 9.D x 105 9.0 x 105 2.4 x 10~
After 90 minutes of Contact, a 5 1og10 was achirve~ with:
PAA > 20 ppm (40 ppn) DSNPA = '75 ppm PAA ~ 5 ppm/ DHNPA s 50 ppm sx ° 5/40 + 25/5D ~ 0.79 FAA ~ 10 ppm/ DBNPA = 25 ppm SS = 10/40 + 25/75 = 0.58 After 24 hours of aontaat, a 5 1og10 drop was achieved with:
pAA > 2D D1?m 140 ppm) bBNPA = 50 ppm PAA = 5 ppa/ DBNPA = 25 PFD
SI ~ 5/40 + 25/50 ~ 0.625 08/04/94 15:51 '$'708 305 2985 I~I011-027 ~I~~~8~
~~AMPLE 3 Synergistic activity againet microorganisms was demonstrated in mill furnish at pH '7.1.
siocide (ppm 30 2 5 24 hr.
product) min hr. hx.
1. 1PAA-25 2.2 10~'1.4 x10$ 2.9 x106 7.3x lUb x 2 PAA--50 2 . 104 7 x104 2 x1.041. x 106 , 9 . .1 S
x 5 3. PAA-100 6.8 102 6.1 x10a S.9 xlDa 2.4x 106 x 0 min .5 4.5 hr 24 hr hr 4. M9T-5 H.8 x106 7.1 x106 1.6x 106 5. M9T-10 3.6 X105 5.7 x106 3.8x 106 6. M8T-25 2.4 x106 8.0 x105 7.5x 106 7. MBT-50 2.2 106 2.1 x176 2.1 x105 3.4x 105 x 9. PAA-10/MBT-S 3.8 x106 7.7 x106 4.6x 106 9. PAA-10/MBT-10 4.3 x106 5.2 x106 4.5x 107 2 la. 1?AA-10/MBT-25 1.9 x106 2.5 x106 1.1x 207 n 11. PAA-10/MBT-503.8 10~'1.7 x106 3.4 x105 7.7x 104 x 12. PAA-20/1HHT-5 1.4 x106 2.1 x106 1.8x 107 13. PAA-20/MBTY10 1.9 x106 1.1 x106 1.6x 10T
14. PAA-20/MBT-25 1.1 x105 4_6 x105 3.3x 106 15. PAA-20/MBT-501.7 106 6.0 x105 G.3 x104 2.4x 103 x 16 PAA-40,~t3ar-5 8. x104 Z x104 1. x 107 . 2 . 2 B
17. p7~p-40/MBT-10 9.2 x104 2.5 x104 1.3x 107 18. pAA-40/M9T-25 6.3 x104 1.6 x104 4.0x 105 08/04194 15: 51 '$708 :fD' 2E~B3 C~ O10: D2 i v w 19. PAA-40/MBT-50 1.4 x 10'~ 4.9 x 104 a.2 x 104 1.8 x iD3 20. Control--0 1.1 x 1t17 1.5 x 10T 3.1 x 10T 7.5 x 103 After 24 hours of ~~ontdct, a 3 1o91p drop was achieved with:
PAA ~ l0U ppm (200 P1~) Glut a 50 ppm (100 ppm) PAA = 20 ppm/ f3lut = 50 ppm sI = 20/200 + ~o/loo = a.s After 5 Hours of contac~, a 3 1og10 drop was achieved with:
PAA = 50 ppm Glut > 54 ppm (100 ppm) PAA = 20 ppm/ Glut = 50 ppm SI = 20/SO f 50/100 = 0.9 EXAMFL~
.4 Synergist~.c ngainat microorga nisms was activity dr~monstrated mill furnish in at pH 7.28.
$ ioc j.de (ppm 30 min 2 hr. 5 24 product) hr. hr.
2 5 PAA-25 1.3 x 10$ 2.4 x 1.8 106 3.0 107 1. 105 x x 2. PAA-50 1.6 x 103 2.5 x 1.0 lOd 1.i 10T
103 x x 3. PAF,-100 1.3 x 103 1.5 x 1.5 103 8.1 106 103 x x 0 min 1 5._hr .4 24 5 hr hr 4. CARB-50 9.8 x 1.1 10T 2.5 lOg 10 x x 5. CARB-100 9.4 x 7.2 106 7.8 104 106 x x 6. CARH-150 1.1 X 1.D 106 3.8 104 106 X x 3. CARH-200 4.7 x 106 l.d x 1.0 106 3.0 104 10s x x 35 8. PAA-10/CARB-50 2.8 x 2.5 106 2.8 104 106 x x 08;04194 15:51 X708 305 2985 _ I~',009i027 ~-21294.89 ~14-9. PAA-10/CARB-100 3.2 x 106 5.0 104 4.0 x x 10. PAA-10/CRRB-150 3.0 x 106 2.5 104 4.8 104 x x 11. pAA-10/CAR$-200 2.2 x 106 105 5.9 104 2.6 103 1.4 x x x 12. pAA-20/C~'S0 1.1 x 1D5 2.o IOi 2.1 103 x x 13. PAA-20/CARB-100 3,9 x lD4 4.5 104 1.2 103 x x 1.4. PAA~20JCAR8-150 2.3 x 104 2.5 104 1.5 103 x x Z5. PAA-20/CARB-2o0 3.7 x 105 104 1.9 104 8.1 10Z
2.5 x x x 16. PAA-~fOJCARB-50 2.0 x 103 1.2 143 9.3 102 x x 17. PAA-40/CARB-I00 2.0 x 103 7.0 102 5.4 102 x x 1 18. pAA-40/CARH-150 1.4 x 103 6.6 1DZ 6.8 14Z
0 x x 19. fAA-40/CARB-200 1.0 x 104 103 5.6 lpa 6.0 lpZ
1.3 x x x 20. Control-0 1.2 x 107 3.0 1,06 3.0 106 9.2 107 x x x 1 After achieved 5 2 with:
hours of contact, a 1og10 drop ,apg PAA = 50 ppm CARB > 200 ppm (400 y~my PAA =.. 20 gpm/ C~ ~ 100 pprr, sI = 20/60 + 100/400 ~
.65 2 PAA = 4 0 ppttf / CARE
0 < 5 D ppm SI = 40/50 + 25/400 = 0.8fi25 After achieved 5 with:
hours of oontaat, a 1og10 drCp was pAA y 100 ppp~ ( 2 0 D
ppn, cARB > 2vo ppm (404 ppm) Z 8AA ~ 40 ppm/ CARS = 100 5 ppm SI = 4o/Z00 + 100/400 ~
.45 After op anhi~eved ith:
24 was w hours of corltaCt, a 1og10 dr PAA > 100 ppm (200 ppm) CARE > 200 ppm (44D ppm) 3 P~ = 10 ppn; jCi~tB = 200 b ppm 9I = 10/200 + 200/400 =
.55 08/04/94 15'50 "$708 305 2985 ~ OU8/027 pAl~ ~ 20 ppm/CARB = 50 ppm S2 = 20/200 + 50/400 = .215 PAA = 40 pgm/CAR~ = 50 ppao SI = 40/200 + 50/400 = .925 E X~ ~~E5 $l.PCi~E
(piun product 30 min 3 . S 2.4 ) hr hr. hr.
1, pAp-a5 ~' 4.2 x 5.4 x 10 5.3 10~ .7 x 10~
10 x 1 2. PAA-50 4.4 x 1.1 x 10~'7.3 1D4 1.9 x 107 104 x 3. PAA-100 $.0 x 1.1 x 1031.1 103 1.3 x 107 l0a x min ,~ 4.5 24 5 hr hr _ht' 4. gUAT-25 2.7 x 1053.0 105 1.8 x 107 x 5. QUAT-50 1.0 x 1051.7 105 1.1 X 107 x 2 6. QUAT-100 7.9 x 1049.6 104 5.2 x 106 0 x 7. QUAT-200 7.5 x 6.4 x 10a7.2 l0a 1.6 x 102 104 x s. pAA-lol~2vAT-a~ 1.2 x 1052~a los 1.7 x l07 x 9. pAA-10/QUA1'-50 6.6 x 1041.3 1D5 7.3 x 104 x 10. PAA-10/QUAT'-100 1.3 x 1D33.1 103 :.6 x 107 x 2 11. 8AA-10/QUA2-2001.7 x 5.0 x 1026.d 102 2.9 x 106 5 105 x 12. PAA-20/QUAT-a5 l.B x 10$1.2 105 4.9 x 106 x 13. PAA-a0/QUAT-50 9.1 x 1041.2 105 6.5 x 106 x 14. PAA-20/QUAT-100 3.9 X 1036.8 103 5.0 a 106 X
15. PIaA-20/QUAT-2005.3 x 5.4 x 1026.6 102 2.4 x 102 :04 X
3 16. PAA-40/QUAx-25 3.4 x 1034.0 103 9.9 x 106 0 x 17. PR13~40/QUAx~50 1.9 x 1031.7 3.0 x 105 x 08/04!94 15:50 x'708 305 2985 - 0 007,,027 2124~8~
18. PAA-4D/Qvl~x-loo 2.0 x 1.7 x 4.D x 10'3 103 105 19. PAA-4D/QuA~-200 1.3 3.7 x 5.3 x 1.9 x x 103 lOZ 102 102 20. Control-0 1.1 x 10~ 1.4 x 1.3 x 2.1 x After 24 hours of conts,.~.. a 2 logib drop wtas achieved With:
pAA ~ 100 ppm (200 ppm) QUAT = 200 ppm PAA = 40 ppm,/ QUAT ~ 50 ppm SI = 40/200 + 50/200 = .45 1 0 After 3 hours & 5 hours of contact, a 4 1og10 drop was achiQVed with:
PAA = 100 ppm QUAT = 200 ppm PAA = 40 ppm/ OuAT = 2S ppm SI ---- 40/100 + 25J200 = .525 Synergistic activity against micraarganisms was demonstrated in mill furnish at px ~.5.
zo Biccide (ppm 30 min 94 5 24 hr.
product) min hr.
1. FA.A-10 4.9 x 10 5.0 x 2.5x i0 9.6x 10 id "t. PAA-25 2.9 x 105 4.8 x 4.2.x106 2.3x 106 3. pAA-50 6.3 x lOd 1.8 x 4.1x 109 2.5x 107 0 CO 4.5 24 min min hr hr 4. I5p-133 7.4 x 105 5,1 x 4.7x 105 1.6x 10q 5. ISO-lOD 7.3 x 105 5.6 x 4.2x 105 1.9x 104 b. I50-67 7.8 x 105 5.9 x 3.8x 10$ 9.6x 104 lOS
7. ISO-33 8.0 x 105 5.7 x 6.1x 1D5 2.2x 107 lOS
08/04194 15:5U 'x'708 3U5 2985 l~]OOB/027 _z;_ 8. FAA-10/IS4~1935.2 x 105 x105 2.1x105 1.1x104 1.6 g. PAA-10/ISO-1003.1 x 145 x105 3.4x105 2.1xl0a 1.4 10. PAA-1D/ISO-673.7 x 105 x105 4.8x105 4.9x104 2.1 11. PAA-lp/Ig0-332.6 x 10$ x105 b.4x105 5.3xlOb 2.2 12. pAA-25/ZSO-1331.4 x 105 x104 1.1x105 3.2x103 6.7 13. FAA-25/ISO-7.001.6 x 105 x104 1.2x105 4.2x103 B.7 I4. PAA-25/ISO-671.2 x 105 x104 1.4x105 4.9x103 B.0 15. FAA-25/ISO-1331.5 x 105 x10q 1.6x7.05 9.8x!05 9.4 36. PAA-50/IS0-13.31.8 x lo'~ xIo3 5.3x103 1_6xlOZ
5.5 17. PAi~-50/ISO-1001.4 x 3.04 x103 3.Sx104 3.2x102 6.8 18. PAA-50/ISa-673.3 x 104 x104 3.3x104 1.1x103 3.2 19. PAA-50/ISO-331.9 x 104 X104 5,1x1D4 5.4x103 2.3 20. Control-o 8.2 x fps xlOS 2.5x10d 4.3x106 7.1 After contact, lpdrop wasach~.ev~dwith:
90 a 1 log mcutes of PAA > 5p ppm (100 ppm' ISO > 133 (167 ppm) ppm PAA = Z5 Plan/ISO = 67 2 SI = 25/100 ppm 0 * 67/167 .55 After achiwad S with:
hours of Contact, a 1og10 drop was PAA > 50 ppm (100 ppm) Iso .~ 193 (1s7 ppm) ppm PAA = 50 ppm/ISO = 33 5I ~ 50/I00 ppm + 33/167 =
.70 After 24 hours drop of contact, was a 3 1og10 achieved with:
PAA > 50 ppm (lOG P1~>
ISO > 13's ppm (1B7 ppm) pAA = 25 Ppm/ISO = 67 30 SI = 25/100 pgm + 67/167 -.65 08r04!94 _, 15:.19 '708 30; 2985 f~]005:027 212949'.
_lg_ The figure of the speaifiGation illustrates comparative results df utilizing peraaetic acid or a biocide alone as compared with a combination of the two together. Graphing colony forming units ("CFU") versus hours demonstrat~e3 the effectiveness of the administered C3lemiGal~.
The present invention lowers the levels of expensive chemicals needed for inhibiting the growth of microorganisms. As illustrated in the figure, a l00 ppm 30 dosage of biocida. such as carbamate, in combination with 2o ppm dosage of peracetic acid is more effective than administering eithQr 25 ppm of paracetic acid or 200 ppm of the biocide alone. AccorBingly, the present invention provides a more cost effective and environmentally friendly method far treating microorganisms.
It should be understood that various changes and modifications to the presently preferred embodiments described herein will be apparent to thaw skil~.ed in ~Ghe 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 thQrefore intended that such change$
and modifications be covered by the appended claims.
TITLE
"METgOD AI~TD CQl~dpGl6ITIOH ~'OR TNBIBITI1~'G GROWTB
OF MICROORCil~NISMS IHCLUDIlwG PERI~rCBTIC ACID
71ND A 344I~T-ORIDIZI~1G BIOCIDE"
$ACiCGFtQUND OF' ~'HE I_NVENTION
The pxesent invention relates generally to cvntrall.ing the growth of microorganisms. More specifically, the present invention relates to inhibiting to the growth of microorganisms in industrial waters.
The presence of microorganisms in waters, especially industrial waters, is a never-ending concern for industrial manufacturers. Examples of industrial waters where microorganisms can .interferes with industrial processes include: cooling tower water; mining process waters; food processing waters; sugar reprocessing waters; and the like.
In the paper indusctry, the growth of microorganisms in pulp and paper mill watQrs can adversely affect 2o finished paper products. Microbial lifQ depends an the nutrient sugply, the pH and the 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 vaxiety of microorganisms. These contaminating microorganisms are capable of causing spoilage of pulp, Tarnish, or chemical additives . The microorganist~s cause deposits that break loose and fall into the paper furnish, resulting in quality loss and/or end product 3D defects such as holez and spets. The end result is 08:04%94 15:58 'x'708 3U5 29!35 f~021~027 ~= X129489 _z_ unsalable paper or paper sold at a lo~rer value, Robertson, The use of v~~,~s~Q-contrast microscopy to assess and differentiate the m~obial nonulat'o of a saner mi 1, TAPPI Journal, pp. 83 (March 1993).
The presence of mioroorganisms within industrial water systems results in the formation of deposits of biological origin on industrial machines. These formation deposits give rise to: corrosion; breaks;
increased down time; loss of yield; high chemical Costs;
odors; and expensive deposit control programs. In the paper mill industry, slime depasit is reportedly responsible for nearly 7~~ of all breaks, blockages and pump failures. Safade, T~aklina the Slime Problem in a Paper-Mill, PTI, p. 280 (September 19s8).
13 Slime may be dofined ag an "accretion or accumulation caused by certain micro-organisms in the presence. of pulp fiber, filler, dirt and other materials, mixed in varied propartians, having variable physical charactex~isti.cs and accumulating at continuous changing 2o rates." ,~d. In most industrial process waters, especially pulp and paper mill systems, :pore forming bacteria and Pseudamoaas ~lerugiaos~a contribute to slime formation. The later is most ,prevalent in paper mill slimes. p~ungi is also a contributor toward slime 25 formation.
The conventional method of controlling microbial growth is through the use of biooides. aiocides are generally divided into two main groups: oxidizing; and non-oxidizing. These biocides act on the microorganisms 34 in one of three ways: either by attacking the cell wail;
the cytoplasmic membrane; or the cellular constituents.
,~ at 282.
08/O~i9.~ 15:55 $7U8 305 2P85 ~ p2Ui027 2iz~4s9 i~lhile biocides do inhibit miarabial growth, economic and environmental concerns ratguire improved methods. 1~ problem with the use of biocides is that high levels of expensive chemicals are needed to vantral microbial growth. To date, none of the oammercially available biocides have exhibited a prolonged biocidal effect. Their effectiveness is rapidly reduced as a result of exposure to physical conditions such as temperature or association with ingrediantc contained lay the system toward which they exhibit an affinity. This results in a restriction or elimination of their biocidal effectiveness.
Therefore, the use of such biocides involves continuous or frequent additions to paper mill systems.
Furthar, these additions must be made at a plurality of points or zon~as in the system. The costs of the biocides arid tha labor costs involved are considerable.
Moreover, such chQmicals are highly toxic in the quantities known to be required for effactive control of microbial populations. As a result, environmental regulations restrict the amount of biacides that can safely be discarded into the environment.
Therefore, a need exists far improved methods for controlling the growth of microorganisms in industrfa~l process waters.
'y~$Y OF THE 11 ENTZON
Fursuant to the present invention, the growth of microorganisms can be inhibited without the use of high levels of certain bfocides. The present invention provides compositions to be used !or inhibiting the growth of ~nicror~rganisms in industrial process waters.
The compositions include sugficient amounts of a ~94g 9 peracetic acid and a non-oxidizing biocide. The composition of the present invention possesses unexpected synergistic activity against microorganisms, including bacteria and fungi.
The present invention also provides a method for inhibiting the growth of the microorganisms in industrial process waters. The method includes the step of adding to the waters sufficient amounts of a peracetic acid (PAA) and a non-oxidizing biocide. Combining the peracetic acid with the non-oxidizing biocide has been found to enhance the effectiveness of the biocide.
In an embodiment, the biocide is chosen from the group consisting of: isothiazolin; glutaraldehyde; DBNPA; methylene biothiocyanate; carbamate; quaternary ammonium compounds;
bronopol, 4,5-dichloro-1, 2-dithiol-3-one; and 4,5-dichloro-2-N-octyl-4-isothiazolin-3-one.
In an embodiment, the peracetic acid is added prior to the biocide in the water system.
In other embodiments: the peracetic acid and the non-oxidizing biocide are added in a ratio from about 10:1 to 1:25;
and the amount of peracetic acid added ranges from approximately 5 to 250 ppm and the non-oxidizing biocide ranges from approximately 10 to 250 ppm.
An advantage of the present invention is that it provides improved compositions for use in inhibiting the growth of microorganisms.
Another advantage of the present invention is that it provides an improved method for inhibiting the growth of microorganisms.
Still further, an advantage of the present invention is that it lowers the level of expensive chemicals needed for inhibiting the growth 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.
The increased effectiveness removes the need for repetitive additions of the biocide at multiple points in the paper making system.
D
~2948'~
Moreover, an advantage of the present invention is that it provides a mcre cost effective and environmentally friendly method for treating microorganisms.
Additional features and advantages of the present invention are described in, and will be apparent from, the detailed description of the presently preferred embodiments.
BRIEF DESCRIPTT_ON OF THE DRAWING
The figure in the specification illustrates graphically colony forming units versus hours for microorganisms treated with a composition of the present invention compared to the treatment of peracetic acid or a biocide alone.
DETAILED DESCRIPTION
OF T'.riE PRESENTLY PREFERRED EMBODIMENT
The present invention provides, for inhibiting the growth of microorganisms, improved compositions and method of administering the same to a fluid system. The compositions include a sufficient amount of a peracetic acid 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 peracetis acid. E:~amples of suitable non-oxidizing biocides include: isothiazolin; methylene bisthiocyanate;
glutaraldehyde; DBNPA; carbamate; quaternary ammonium compounds; bronopol; 4,5-dichloro-1,2-dithiol-3-one; and 4,5-dichioro-2-N-octyi-4-isothiazolln-3-one. Natural'_y, mixtures of such biocides can also be used.
C
._ . ... .
Q8.04/94 15;54 '$'708 305 :985 ~017iU27 w.~ 212~~89 ThQ bi.ocides can be obtained from a number of chemical suppliers such as American Cyanamid, Buckman, Beta, Dearborn Chemical, Economi.as haboratory, Inc., Merck, Nalco Chemical Company, and Vinela~nd Chemical.
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 npn-oxidizing biocides yields a total effect which is greater than the sum of the effects of the biocxde ar the peracetic acid taken separately.
The optimal amounts of biocide and peracetic acid required for effectiveness in this invention depend or, 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 rind pH of thp waters, and the microbial count. The concentrations may be as little as 1 part pex million (ppm) by weight to as much as 25p ppm. with respect to the biocide, the Lower and upper limits of the required concentration substantially depend upon the specific biocide or combination of biocide.s used.
Still further, since the suitable biocides that may be used in the present invBx~tion are often obtainod at different usable concentrations (i.e. activity level), the ratios vary depending an the particular biocide 3o combined with the peracetia acid. For example, the peracetic acid used in the examples below is 5~ active, the gluta~raldehyde is 50; active, and the DBNPA is 20~
active. Thus, a 1:1 ratio of PAA:Glut translates to 1:10 '~294~9 _, _ on an actives basis, while a 1:1 ratio of PAA:pBNPA
translates to a 1:4 based on actives.
8y way o! example, and not limitation, the following ars biocide:, including the percs~nt active of each bivcide, that may be used in the present invention:
isothiazolin (1.5% a.i.) ; glutaraldehyde (50% a.i.);
methylene biothiocyanate (10~ a.i.); DBNPA (20% a.i.);
carbamate (30% a.i.); quaternary ammonium compounds (31~
a.i.); 4,5-dichloro-1,2- dithiol-3-one (5~ a.i.); and 4,5-dichloro-2-:~'octyl-4-isothiazolin-3-one (2~ 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 non-oxidizing biocide of the present invention. In an 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 providos the desired concentration of the same in the waters.
AftQr 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 Ghe waters.
In an embodiment, the method comprises adding approximately 5 to 250 ppm of the non-oxidizing biocide C
08/04/94 15:53 $'708 305 2985 ~ D1S~D27 _$_ along with approximately 10 to 250 ppm of the peraaetic acid. Ire an embodiment, the biocide and the peracetic acid are present in a range from about 1 ppm to looo ppm of product.
By wary of example, and not limitation, examples of the invention will now be given.
F~XAMPLEE
The following examples illustrate the synergistic relationship obtained with the compositions of the present invention.
Synergy is mathematically demonstrated by the industry accepted method described by s.C. Kull et al.
in Applied Microbial-oav, vol. 9, pages 538-54I (1961) .
As applied to this invention, it is as fol.lc~ws:
t1A ~ the ppm of active non-oxidizing biocide alone which produoes an endpoint.
the ppm of active peracetic acid alone which produces an endpoint.
- the ppm of active peracetic acid, in 2o combination with non-oxidizing biocide, which praduceg an endpoint.
Qb = the ppm of active non-oxidizing biocxde, in combination, which produces an endpoint.
+ fib" , z synergy index 2 5 Qa ~g tl, it indicate~ aytlergy if Synergy Index (SI) iBS -Z, it .indi~:at~a sdditivity ai, it indiaatea antagonism The following teat procedures were utilized during p the experimentation of the present invention.
Process watex from several papermills was obtained for test purposes. Aliquots of water from each mill were _- 0804!94 15: 53 '$?U8 3U5 2955 ~ a14: 02?
.g_ dosed with the indicated concentrations of peraaetic acid (5~ active obtained from FMG). After 30 minutes of contact time, the designated concentrations of non-oxidizing biocida were added to the aliquots previously dosed with PAA, mixed Well and incubated at 37°c in an orbital sha3cer. At the Qesignated contact times, each aliquot was sampled to determine the total number of viable organisms in colony forming units per mill.il.iter (CFUjrtlL} on Tryptone Glucose Extract (TGE) agar. An endpoint of 2,3,4 or 5 logla reduction in viable organisms was then selected ~or calculating synergy.
EXP~P~
Synergistic activity against microorganisms was demonstrated in mill furnish at pH 7Ø
8iocide (ppm 30 90 5 hr. 24 product) min min hr.
2 0 1. PAA-10 z.3 x 1064.0 x 106~.8 1066.4 106 x x 2, PAA-20 5.8 x 1059.3 x 1052.3 1056.5 105 x x 0 60 4.5 mire min hr 3. Glut-50 3.2 x 1063.2 x y04<101 <101 ~ 5 4. Glut-39 3.7 x 1062.5 x 105<lol <l0i s. Glut-20 4.2 x 1067.2 x lay2.6 1041.1 102 x x 6. Clut-10 4.4 x 1062.B x 1062,3 1069.5 102' x x 7. Glut--10/PAA-104.5 x 1053.2 x 1055.3 1041.9 102 x x 8. Glut-10/PAA-201.2 x 1055.3 x 1042.1 1043.1 10a x x 30 9. control-0 2.3 x 1061.0 x 1053,3 1055.C 106 x x 08!04194 15:52 'x'708 305 2985 I~ 013/027 ~~29489 ~' -10~
After 90 mi,nutQe of contact, s 2 Iot~lp drop is achiQVwd withs PAA y 20 ppm (40 ppm) Glutaraldmhyde = 50 Ppm FAA = 20 gpm/ Glut = 1o pgm s= ~ 10/ap t ao/40 = 0.~
After 5 hours of contact, a 2 1og10 drop is achiQVod withs PAA y 20 ppm (40 PPm) Glutaraldehyde = 2o ppm pAA - 10 ppm/ Giut = 10 ppm SI ~ 10/40 + 10/20 = 0.75 Aftar 24 hours of contact, a 4 logid dr4p is achitved with:
PAA > 20 ppm (4D ppm) Glutaraldehyde = 20 ppm PAA = 10 ppm/ Glut = 10 ppm 15 SI = 10/40 + 10/3D = G.75 20 Siocide (ppm 3o min 90 5 hr. .~.4 .
product) min hr 1. PAA-5 7.4 x 1058.5 105'7.8 105 a.8 106 x x x 2 5 p~-10 6.4 x 1055.7 1055.2 105 2.9 106 2. x x x 3. PAA-2D 4.D x 1055.4 1051.0 105 5.1 105 x x x O 60 4~
min min 4. bBNPA-100 3.9 x 10sc101 0101 X101 5. DBNPA-73 5.1 x 10~e101 x101 c101 30 6. DHNpA-50 6.b x 10$8.1 lOZc10'1 X101 x 7. DHNPA-25 6.0 x 1053.3 103<7.01 9.4 10a x x e. pBNPA-100/PAA-54.3 x .105<101 <101 <101 08!04/94 15:52 $7U8 105 2985 . ~IU12;02'r 2129-89 '~
9. DBNPA-T5/PP~A-S s.i x lv5 <lol ~lal «Q1 10. DBNpA-50/PAA-5 3.T x 105 1101 6101 c101 11. pBNPA~-25/PAA-5 g.g x 10~ 3.4 x 10~ 1.1 x lOZ 0141 12. Dt3NPA-100/FAA-105.5 x 105 <101 x101 c101 13. DHNPA-T5/pAA-10 1.4 x 1D5 <101 ci01 clD1 .4. DeNPA-50/P~-10 9.5 x I04 <141 X101 <ipl 15. bBNPA-25/PAA-10 3.6 x lOd <101 <1D1 <101 lE. DBNPA-100/PAA-20 2.0 x 105 X101 <101 <101 17. DgNPA-75/PAA-20 5.4 x 105 0101 <1D1 x101 18. DBNPA-50/PAA-20 4.5 X 105 <101 x101 <1p1 19. DBNPA~25/PA~1-20 3.7 x I05 c101 <101 <SO1 20. Co~~trol-0 3.7 x 105 9.D x 105 9.0 x 105 2.4 x 10~
After 90 minutes of Contact, a 5 1og10 was achirve~ with:
PAA > 20 ppm (40 ppn) DSNPA = '75 ppm PAA ~ 5 ppm/ DHNPA s 50 ppm sx ° 5/40 + 25/5D ~ 0.79 FAA ~ 10 ppm/ DBNPA = 25 ppm SS = 10/40 + 25/75 = 0.58 After 24 hours of aontaat, a 5 1og10 drop was achieved with:
pAA > 2D D1?m 140 ppm) bBNPA = 50 ppm PAA = 5 ppa/ DBNPA = 25 PFD
SI ~ 5/40 + 25/50 ~ 0.625 08/04/94 15:51 '$'708 305 2985 I~I011-027 ~I~~~8~
~~AMPLE 3 Synergistic activity againet microorganisms was demonstrated in mill furnish at pH '7.1.
siocide (ppm 30 2 5 24 hr.
product) min hr. hx.
1. 1PAA-25 2.2 10~'1.4 x10$ 2.9 x106 7.3x lUb x 2 PAA--50 2 . 104 7 x104 2 x1.041. x 106 , 9 . .1 S
x 5 3. PAA-100 6.8 102 6.1 x10a S.9 xlDa 2.4x 106 x 0 min .5 4.5 hr 24 hr hr 4. M9T-5 H.8 x106 7.1 x106 1.6x 106 5. M9T-10 3.6 X105 5.7 x106 3.8x 106 6. M8T-25 2.4 x106 8.0 x105 7.5x 106 7. MBT-50 2.2 106 2.1 x176 2.1 x105 3.4x 105 x 9. PAA-10/MBT-S 3.8 x106 7.7 x106 4.6x 106 9. PAA-10/MBT-10 4.3 x106 5.2 x106 4.5x 107 2 la. 1?AA-10/MBT-25 1.9 x106 2.5 x106 1.1x 207 n 11. PAA-10/MBT-503.8 10~'1.7 x106 3.4 x105 7.7x 104 x 12. PAA-20/1HHT-5 1.4 x106 2.1 x106 1.8x 107 13. PAA-20/MBTY10 1.9 x106 1.1 x106 1.6x 10T
14. PAA-20/MBT-25 1.1 x105 4_6 x105 3.3x 106 15. PAA-20/MBT-501.7 106 6.0 x105 G.3 x104 2.4x 103 x 16 PAA-40,~t3ar-5 8. x104 Z x104 1. x 107 . 2 . 2 B
17. p7~p-40/MBT-10 9.2 x104 2.5 x104 1.3x 107 18. pAA-40/M9T-25 6.3 x104 1.6 x104 4.0x 105 08/04194 15: 51 '$708 :fD' 2E~B3 C~ O10: D2 i v w 19. PAA-40/MBT-50 1.4 x 10'~ 4.9 x 104 a.2 x 104 1.8 x iD3 20. Control--0 1.1 x 1t17 1.5 x 10T 3.1 x 10T 7.5 x 103 After 24 hours of ~~ontdct, a 3 1o91p drop was achieved with:
PAA ~ l0U ppm (200 P1~) Glut a 50 ppm (100 ppm) PAA = 20 ppm/ f3lut = 50 ppm sI = 20/200 + ~o/loo = a.s After 5 Hours of contac~, a 3 1og10 drop was achieved with:
PAA = 50 ppm Glut > 54 ppm (100 ppm) PAA = 20 ppm/ Glut = 50 ppm SI = 20/SO f 50/100 = 0.9 EXAMFL~
.4 Synergist~.c ngainat microorga nisms was activity dr~monstrated mill furnish in at pH 7.28.
$ ioc j.de (ppm 30 min 2 hr. 5 24 product) hr. hr.
2 5 PAA-25 1.3 x 10$ 2.4 x 1.8 106 3.0 107 1. 105 x x 2. PAA-50 1.6 x 103 2.5 x 1.0 lOd 1.i 10T
103 x x 3. PAF,-100 1.3 x 103 1.5 x 1.5 103 8.1 106 103 x x 0 min 1 5._hr .4 24 5 hr hr 4. CARB-50 9.8 x 1.1 10T 2.5 lOg 10 x x 5. CARB-100 9.4 x 7.2 106 7.8 104 106 x x 6. CARH-150 1.1 X 1.D 106 3.8 104 106 X x 3. CARH-200 4.7 x 106 l.d x 1.0 106 3.0 104 10s x x 35 8. PAA-10/CARB-50 2.8 x 2.5 106 2.8 104 106 x x 08;04194 15:51 X708 305 2985 _ I~',009i027 ~-21294.89 ~14-9. PAA-10/CARB-100 3.2 x 106 5.0 104 4.0 x x 10. PAA-10/CRRB-150 3.0 x 106 2.5 104 4.8 104 x x 11. pAA-10/CAR$-200 2.2 x 106 105 5.9 104 2.6 103 1.4 x x x 12. pAA-20/C~'S0 1.1 x 1D5 2.o IOi 2.1 103 x x 13. PAA-20/CARB-100 3,9 x lD4 4.5 104 1.2 103 x x 1.4. PAA~20JCAR8-150 2.3 x 104 2.5 104 1.5 103 x x Z5. PAA-20/CARB-2o0 3.7 x 105 104 1.9 104 8.1 10Z
2.5 x x x 16. PAA-~fOJCARB-50 2.0 x 103 1.2 143 9.3 102 x x 17. PAA-40/CARB-I00 2.0 x 103 7.0 102 5.4 102 x x 1 18. pAA-40/CARH-150 1.4 x 103 6.6 1DZ 6.8 14Z
0 x x 19. fAA-40/CARB-200 1.0 x 104 103 5.6 lpa 6.0 lpZ
1.3 x x x 20. Control-0 1.2 x 107 3.0 1,06 3.0 106 9.2 107 x x x 1 After achieved 5 2 with:
hours of contact, a 1og10 drop ,apg PAA = 50 ppm CARB > 200 ppm (400 y~my PAA =.. 20 gpm/ C~ ~ 100 pprr, sI = 20/60 + 100/400 ~
.65 2 PAA = 4 0 ppttf / CARE
0 < 5 D ppm SI = 40/50 + 25/400 = 0.8fi25 After achieved 5 with:
hours of oontaat, a 1og10 drCp was pAA y 100 ppp~ ( 2 0 D
ppn, cARB > 2vo ppm (404 ppm) Z 8AA ~ 40 ppm/ CARS = 100 5 ppm SI = 4o/Z00 + 100/400 ~
.45 After op anhi~eved ith:
24 was w hours of corltaCt, a 1og10 dr PAA > 100 ppm (200 ppm) CARE > 200 ppm (44D ppm) 3 P~ = 10 ppn; jCi~tB = 200 b ppm 9I = 10/200 + 200/400 =
.55 08/04/94 15'50 "$708 305 2985 ~ OU8/027 pAl~ ~ 20 ppm/CARB = 50 ppm S2 = 20/200 + 50/400 = .215 PAA = 40 pgm/CAR~ = 50 ppao SI = 40/200 + 50/400 = .925 E X~ ~~E5 $l.PCi~E
(piun product 30 min 3 . S 2.4 ) hr hr. hr.
1, pAp-a5 ~' 4.2 x 5.4 x 10 5.3 10~ .7 x 10~
10 x 1 2. PAA-50 4.4 x 1.1 x 10~'7.3 1D4 1.9 x 107 104 x 3. PAA-100 $.0 x 1.1 x 1031.1 103 1.3 x 107 l0a x min ,~ 4.5 24 5 hr hr _ht' 4. gUAT-25 2.7 x 1053.0 105 1.8 x 107 x 5. QUAT-50 1.0 x 1051.7 105 1.1 X 107 x 2 6. QUAT-100 7.9 x 1049.6 104 5.2 x 106 0 x 7. QUAT-200 7.5 x 6.4 x 10a7.2 l0a 1.6 x 102 104 x s. pAA-lol~2vAT-a~ 1.2 x 1052~a los 1.7 x l07 x 9. pAA-10/QUA1'-50 6.6 x 1041.3 1D5 7.3 x 104 x 10. PAA-10/QUAT'-100 1.3 x 1D33.1 103 :.6 x 107 x 2 11. 8AA-10/QUA2-2001.7 x 5.0 x 1026.d 102 2.9 x 106 5 105 x 12. PAA-20/QUAT-a5 l.B x 10$1.2 105 4.9 x 106 x 13. PAA-a0/QUAT-50 9.1 x 1041.2 105 6.5 x 106 x 14. PAA-20/QUAT-100 3.9 X 1036.8 103 5.0 a 106 X
15. PIaA-20/QUAT-2005.3 x 5.4 x 1026.6 102 2.4 x 102 :04 X
3 16. PAA-40/QUAx-25 3.4 x 1034.0 103 9.9 x 106 0 x 17. PR13~40/QUAx~50 1.9 x 1031.7 3.0 x 105 x 08/04!94 15:50 x'708 305 2985 - 0 007,,027 2124~8~
18. PAA-4D/Qvl~x-loo 2.0 x 1.7 x 4.D x 10'3 103 105 19. PAA-4D/QuA~-200 1.3 3.7 x 5.3 x 1.9 x x 103 lOZ 102 102 20. Control-0 1.1 x 10~ 1.4 x 1.3 x 2.1 x After 24 hours of conts,.~.. a 2 logib drop wtas achieved With:
pAA ~ 100 ppm (200 ppm) QUAT = 200 ppm PAA = 40 ppm,/ QUAT ~ 50 ppm SI = 40/200 + 50/200 = .45 1 0 After 3 hours & 5 hours of contact, a 4 1og10 drop was achiQVed with:
PAA = 100 ppm QUAT = 200 ppm PAA = 40 ppm/ OuAT = 2S ppm SI ---- 40/100 + 25J200 = .525 Synergistic activity against micraarganisms was demonstrated in mill furnish at px ~.5.
zo Biccide (ppm 30 min 94 5 24 hr.
product) min hr.
1. FA.A-10 4.9 x 10 5.0 x 2.5x i0 9.6x 10 id "t. PAA-25 2.9 x 105 4.8 x 4.2.x106 2.3x 106 3. pAA-50 6.3 x lOd 1.8 x 4.1x 109 2.5x 107 0 CO 4.5 24 min min hr hr 4. I5p-133 7.4 x 105 5,1 x 4.7x 105 1.6x 10q 5. ISO-lOD 7.3 x 105 5.6 x 4.2x 105 1.9x 104 b. I50-67 7.8 x 105 5.9 x 3.8x 10$ 9.6x 104 lOS
7. ISO-33 8.0 x 105 5.7 x 6.1x 1D5 2.2x 107 lOS
08/04194 15:5U 'x'708 3U5 2985 l~]OOB/027 _z;_ 8. FAA-10/IS4~1935.2 x 105 x105 2.1x105 1.1x104 1.6 g. PAA-10/ISO-1003.1 x 145 x105 3.4x105 2.1xl0a 1.4 10. PAA-1D/ISO-673.7 x 105 x105 4.8x105 4.9x104 2.1 11. PAA-lp/Ig0-332.6 x 10$ x105 b.4x105 5.3xlOb 2.2 12. pAA-25/ZSO-1331.4 x 105 x104 1.1x105 3.2x103 6.7 13. FAA-25/ISO-7.001.6 x 105 x104 1.2x105 4.2x103 B.7 I4. PAA-25/ISO-671.2 x 105 x104 1.4x105 4.9x103 B.0 15. FAA-25/ISO-1331.5 x 105 x10q 1.6x7.05 9.8x!05 9.4 36. PAA-50/IS0-13.31.8 x lo'~ xIo3 5.3x103 1_6xlOZ
5.5 17. PAi~-50/ISO-1001.4 x 3.04 x103 3.Sx104 3.2x102 6.8 18. PAA-50/ISa-673.3 x 104 x104 3.3x104 1.1x103 3.2 19. PAA-50/ISO-331.9 x 104 X104 5,1x1D4 5.4x103 2.3 20. Control-o 8.2 x fps xlOS 2.5x10d 4.3x106 7.1 After contact, lpdrop wasach~.ev~dwith:
90 a 1 log mcutes of PAA > 5p ppm (100 ppm' ISO > 133 (167 ppm) ppm PAA = Z5 Plan/ISO = 67 2 SI = 25/100 ppm 0 * 67/167 .55 After achiwad S with:
hours of Contact, a 1og10 drop was PAA > 50 ppm (100 ppm) Iso .~ 193 (1s7 ppm) ppm PAA = 50 ppm/ISO = 33 5I ~ 50/I00 ppm + 33/167 =
.70 After 24 hours drop of contact, was a 3 1og10 achieved with:
PAA > 50 ppm (lOG P1~>
ISO > 13's ppm (1B7 ppm) pAA = 25 Ppm/ISO = 67 30 SI = 25/100 pgm + 67/167 -.65 08r04!94 _, 15:.19 '708 30; 2985 f~]005:027 212949'.
_lg_ The figure of the speaifiGation illustrates comparative results df utilizing peraaetic acid or a biocide alone as compared with a combination of the two together. Graphing colony forming units ("CFU") versus hours demonstrat~e3 the effectiveness of the administered C3lemiGal~.
The present invention lowers the levels of expensive chemicals needed for inhibiting the growth of microorganisms. As illustrated in the figure, a l00 ppm 30 dosage of biocida. such as carbamate, in combination with 2o ppm dosage of peracetic acid is more effective than administering eithQr 25 ppm of paracetic acid or 200 ppm of the biocide alone. AccorBingly, the present invention provides a more cost effective and environmentally friendly method far treating microorganisms.
It should be understood that various changes and modifications to the presently preferred embodiments described herein will be apparent to thaw skil~.ed in ~Ghe 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 thQrefore intended that such change$
and modifications be covered by the appended claims.
Claims (16)
1. A composition for inhibiting the growth of microorganisms comprising effective amounts of peracetic acid and a non-oxidizing biocide.
2. The composition of Claim 1 wherein the non-oxidizing biocide is selected from the group consisting of: isothiazolin;
glutaraldehyde; methylene biothiocyanate; DBNPA; carbamate;
quaternary ammonium compounds; bronopol; 4,5-dichloro-1,2-dithiol-3-one; and 4,5-dichloro-2-N-octyl-4-isothiazolin-3-one.
glutaraldehyde; methylene biothiocyanate; DBNPA; carbamate;
quaternary ammonium compounds; bronopol; 4,5-dichloro-1,2-dithiol-3-one; and 4,5-dichloro-2-N-octyl-4-isothiazolin-3-one.
3. 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.
4. A method for controlling the growth of microorganisms in industrial process water including the step of administering a sufficient amount of a peracetic acid and a sufficient amount of a non-oxidizing biocide to the industrial process water to at least reduce the growth of the microorganisms.
5. The method of Claim 4 wherein the industrial process water is the water of a pulp and paper mill system.
6. The method of Claim 4 wherein the peracetic acid and the non-oxidizing biocide are added in a ratio from about 10:1 to 1:25.
7. The method of Claim 4 wherein the amount of peracetic acid added ranges from approximately 5 to 250 ppm and the non-oxidizing biocide ranges from approximately 10 to 250 ppm.
8. The method of Claim 4 wherein the microorganisms contain bacteria.
9. The method of Claim 4 wherein the microorganisms contain fungi.
10. The method of Claim 4 wherein the peracetic acid is added to the industrial water prior to the addition of the non-oxidizing biocide.
11. The method of Claim 4 wherein the non-oxidizing biocide is selected from the group consisting of: isothiazolin;
glutaraldehyde; methylene biothiocyanate; DBNPA; carbamate;
quaternary ammonium compounds; bronopol; 4,5-dichloro-1,2-dithiol-3-one; and 4,5-dichloro-2-N-octyl-4-isothiazolin-3-one.
glutaraldehyde; methylene biothiocyanate; DBNPA; carbamate;
quaternary ammonium compounds; bronopol; 4,5-dichloro-1,2-dithiol-3-one; and 4,5-dichloro-2-N-octyl-4-isothiazolin-3-one.
12. A method for controlling the growth of microorganisms in industrial process water including the step of adding to the industrial water peracetic acid and a non-oxidizing biocide selected from the group consisting of isothiazolin;
glutaraldehyde; methylene biothiocyanate; DBNPA; carbamate;
quaternary ammonium compounds; bronopol; 4,5-dichloro-1,2-dithiol-3-one; and 4,5-dichloro-2-N-octyl-4-isothiazolin-3-one.
glutaraldehyde; methylene biothiocyanate; DBNPA; carbamate;
quaternary ammonium compounds; bronopol; 4,5-dichloro-1,2-dithiol-3-one; and 4,5-dichloro-2-N-octyl-4-isothiazolin-3-one.
13. The method of Claim 12 wherein the industrial process water is the water of a pulp and paper mill system.
14. The method of Claim 12 wherein the peracetic acid and the non-oxidizing biocide are added in a ratio from about 10:1 to 1:25.
15. The method of Claim 12 wherein the amount of peracetic acid added ranges from approximately 5 to 250 ppm and the non-oxidizing biocide ranges from approximately to to 250 ppm.
16. The method of Claim 12 wherein the peracetic acid 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 |
|---|---|---|---|
| US10228693A | 1993-08-05 | 1993-08-05 | |
| US08/102,286 | 1993-08-05 |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CA2129489A1 CA2129489A1 (en) | 1995-02-06 |
| CA2129489C true CA2129489C (en) | 2000-10-10 |
Family
ID=22289087
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA002129489A Expired - Fee Related CA2129489C (en) | 1993-08-05 | 1994-08-04 | Method and composition for inhibiting growth of microorganisms including peracetic acid and a non-oxidizing biocide |
Country Status (2)
| Country | Link |
|---|---|
| US (1) | US5494588A (en) |
| CA (1) | CA2129489C (en) |
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-
1994
- 1994-08-04 CA CA002129489A patent/CA2129489C/en not_active Expired - Fee Related
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| CA2129489A1 (en) | 1995-02-06 |
| US5494588A (en) | 1996-02-27 |
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