CA1262084A

CA1262084A - Biocide

Info

Publication number: CA1262084A
Application number: CA000452590A
Authority: CA
Inventors: Richard Purdie Clifford; Gerard Anthony Birchall; Brian Greaves
Original assignee: Grace Dearborn Ltd
Current assignee: Suez WTS USA Inc
Priority date: 1983-04-25
Filing date: 1984-04-24
Publication date: 1989-10-03
Also published as: SG63088G; AU565431B2; ES531830A0; GB8331716D0; IT8420661A0; ES8603351A1; AU2724184A; IT1176114B; SE462888B; SE8402242D0; PH23046A; GB2138798A; DE3415295A1; FR2544709B1; FR2544709A1; IT8420661A1; DE3415295C2; SE8402242L

Abstract

ABSTRACT
"BIOCIDE"
A method for the treatment of an aqueous system is described which comprises adding to the water an ethoxylated phenol and, optionally, a biocide.

Description

~26~ 4 BIOCIDE

This invention relates to the -treatment of aqueous systems, especially cooling water systems and water systems used in paper pllping and manufacture.
In industrial cooling water systems, for instance 5 in industrial cooling towers, the water used is not, of co~1rse, sterile with the result that bacteria accumulate in the system and this quite commonly gives rise to a slimy deposit on the surfaces of the system ~hich come into direct contact with the cooling wa-ter. A similar situation applies 1~ in paper making, slime can dep~sit on any of the surfaces with which the water comes into contact including the paper pulping bath,on the p~per web and in the recirculating bac~
pipework. A large variety of different micro~iological control age~ts have been used fo~ the purpose of killin~
15 these bacteria and/o:- inhibiting slime formation or for d.ispersing and killing microbiological slime. Tnese chemicals are principally biostats such as lime or sulphlr dioxide or, more generally, biocides, for example isothia-zolones, methylene bis(thiocyanate), quaternary a~onium 20 co~ounds and chlorine release agents.
S~ch biocides ~re, howev2r, relatively expensive materials. It has now surprisingly been found, according to the present invention, that more effective biological control can be obtained if a variety of different biocides 25 are used in combination with certain ethoxylated phenols.
In effect, therefore, it has been found that it is possible to use less biocide by using the bio~ide in co~bination with ~e ~262~8a~

certain ethoxylated phenols. According to the present invention there is provided a method for the treatment of an a~ueo~ls system which comprises adding to the water either an ethoxylated phenol having the general formula:
R ~ OLc~2cH2o]m H

wllere m represents 2 to 40 and R represents Cn ~ n+l in which n is fro~ 0 to 18 without a microbiological control a~ent or a said ethoxylated phenol and a microbiological control agent which is a biocide as defined below.
Usually it will be necessary to add bioclde as well as the etho~ylated p~enol but sometimes the water will already contain sufficient biocide for thisto be unnecessary.
Although it will normally be more convenient to add the ethoxylate and biocide as a mixture it is, of course, 15 possible to add the~ to the water separately.
Typical ethoxylates which can be used in the present invention include those derived from phenol itself, nonyl phenol and dodscyl phenol. Typically, the number of etho~cylate groupings will vary from 4 to 15. In general, 20 with increasing chain leng-th of the alkyl phenol the nu~ber o~ ethoxylate groupings should also increase. A parti~ular etho~late which has been found to give good results is that sold under the trade mark Ethylan HB4. Tnis is believed to be a phenol ethoxylate having about 4 etho:~ylate units.
It has been fo-nd 'hat -the use of such ethoxylates is of general a,~licability and that beneficial results can be obtained with a variety of different types of bio_ide.
The biocides usable in the present invention fall into one ~26~ 34 of the following classes-(i) a substituted 5 or 6 membered ringheterocyclic compound in which the hetero atom or atoms are one or more of nitrogen, oxygen or sulphur and the 5 subs~ituent is an alkyl group, a keto group or a hydro~yl group or a halogen atom, such conpounds include isot'nia-zolones and in particular, those having the formula:
S ~ R
CH l ~

wherein R represents hyd~ogen o-- c~lorine. A ~lend of these 10 two iso'hiazolones is co~nercially available, the weight xatio of the chlorosubstituted compound to the unsubstituted coml~ound being about 2.65:1. Dilute a~ueous solutions of isothiazolones tend _o be unstable on s_orage. ~o counteract this, inorganis salts in general, more partic~larly 15 magnesium and co~er salts, specifically copper n.itrate, may be add3d;
(ii) a ~uaternary ammoniu~ comp~und typically an N-alkyl, dimethyl benzyl ammonium chloride, spacifically a product where ths alkyl part is 5~/0 ClL~, 4~/0 C12 and l~/o C

2~ (iii) a phenol or chlo1:inated p~enol such as pentachlorophQnol, (iv) an amine or am~ide including 2,2-dibromo-3~
nil:rilopropionamide, (v) a halogen release agent i.e. materials whlch 2~ liberate haLogen (bro~ine, chlor.ine or iodine) when diss~lved in water, including halogenated isocyanmates, ' ~L2~

halogena-ted hydantoins and alkyl derivatives of alkyl oxazolidinones, such as trichloroisocyanuric acid as well as chlorine i-tself and sodium and calcium hypochlorite (vi) an organic cyanide or thiocyanate, 5 particularly methylene bis(thiocyanates), (vii) a sulphone including halosulphones, particularly hexachlorodimethylsulphone, (viii) a tin compound, particularly tributyltin oxide and chloride, (ix) a straight chain aliphatic aldehyde, particularly ylutaraldehyde;
(x) a triazine, particularly thio and/or amino-substituted alkyl triazines, ' (xi~ an alkyl phosphorium compound, (xii) bis bromo acetoxy butene; and (xiii) a dithiocarbamate, especially the monomethyl, dimethyl, monoethyl and diethyl derivatives, typically in the form of sodium salts.
It will, of course, be appreciated that some of 20 these materials are not normally used by themselves but only in conjunction with other biocides.
A particular ad~antage of the use of -the specified ethoxylates is that the ethoxylate can, in addition to improving the biocidal activity, act as a solvent for 25 relatively insoluble biocides. This accordingly facilitates the introduction of the biocide to the system.
If the ethoxylate and biocide are added as a composition, the concentration of ethoxylate will, in general, be from 0.1 to 99.9% by weight If the ethoxylate 30 is to be used as a solvent it will generally be present at a concentration from 75 to 98% by weight. On the other hand, when the ethoxylate is not used as a solvent it will normally represent from 2 to 2~/o, especially 2 to 5% by weight of the composition. Clearly, if the ingredients 35 are added to the water separately the same relative concentrations apply.

i20~4 The amount of ethoxylate added to the system will normally be from 0.1 to lO00 ppm but, in general, it is sufficient to use 2 to lO ppm and preferably 2 to 5 ppm. However, if the ethoxylate is being used as a solvent typical concentrations will be from 10 to 300 ppm. The concentrations of biocide will, of course, vary depending on the nature of the biocide and on the nature andamount of the bacteria present but, clearly, an amount effective to control the bacteria present should be 10 used. As a rough guide, however, it can be said that the concentration of biocide (active ingredient basis) should vary from 0.5 to 250 ppm.
The biodispersant properties of the ethoxylate are such that, in some instances, it is , 15 possible to use a high concentration of the ethoxylate ; with a low concentration of biocide, especially to ; clean systems which have already become heavily bio-fouled as a result of past bacterial activity.
Indeed, in some instances it is possible to dispense 20 with the biocide altogether and merely disperse the fouled material with the aid of the ethoxylate and thus keep the heat exchange or other surfaces clean.

.

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A preferred composition which can be used either for cooling water systems or paper making water systems has the formula by weight:

Water 82.25%
5-chloro-2-methyl-4-isothiazolin-3-one 1.36~
2-methyl-4-isothiazoline-3-one 0.51%
Magnesium Chloride 1.20~
Magnesium Nitrate 2.00%
Glutaraldehyde 7.50%
10 Copper Nitrate 0.18 Ethylan HB4 5.00%

Other preferred compositions which can be used especially in cooling water systems include (i) a mixture of Ethylan HB4 (97% by weight) and methylene bis thiocyanate (3% by weight), (ii) a 10% aqueous solution of Ethylan HB4, (iii) an aqueous solution containing 5 by weight of Ethylan HB4 and 6.25% by weight of an N-alkyl, dimethyl benzyl ammonium chloride and (iv) a mixture of:
20 Ethylan HB 4 93.75% (by weight) Methylene bis thiocyanate 1.00%
Hexachlorodimethylsulphone 4.00 tributyl tin chloride 1.25%

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In paper making, the ethoxylated phenol and, optionally, biocide may be added directly to the paper pulping bath or to the recirculating backwater, or indirectly, for example to a holding tank containing, generally moist, pulp or along with one or more chemical additives used in paper making. Such additives include starch, for example potato or corn starch, titanium dioxide, a defoamer such as a fatty acid alcohol, a size for example a rosin size based on abietic acid, a neutral 10 size based on alkyl ketene dimer or a succinic acid anhydride based size, a wet strength resin such as, if neutral, an epichlorohydrin polyamide or, if acid, a melamine- or urea-formaldehyde resin, various polymers used as dispersants or retention aids such as 15 polyacrylates, polymethacrylates, polyamides and polyacrylamides, clay, chalk, fillers such as carboxymethyl cellulose, polyvinyl alcohol and optical brightening agents.
In cooling water systems, the ethoxylated phenol and, optio~ally, biocide may be introduced at any location where it will be quickly and efficiently mixed with the water of the syste~ although it will generally be most convenient to add it to the make-up or feed water lines through which the water enters the system. Typically, an injector calibrated to deliver a pre-determined amount periodically or continuously to the make-up water is employed. Of course, conventional water treatment additives such as dispersants, corrosion inhibitors, and li~nin derivatives can also be included.

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T'ne following E~amples further illustrate the present invention.

A mixture of water and slime from an 5 industrial cooling tower was split into four parts.
One part was used as a control, the second part was treated with 135 ppm of a mixture of isothiazolones (5-chloro-2-methyl~4-isothiazolin-3-one and 2-methyl-4-isothiazolin-3-one in a ratio of 2.66:1), 10 the third part was treated with 135 ppm of the mixture of isothiazolones and 600 ppm of aromatic ethoxylate (Ethylan HB4), and the fourth part was treated with 600 ppm of aromatic ethoxylate. Total bacterial counts were measured initially, and after 1 15 and 2 hours. Subsequently the second, third, and fourth parts of the mixture were re-treated as above, and total counts measured after 3 and 4 hours.
Afterwards, the second, third and fourth parts of the mixture were again treated as above, and total counts 20 measured after 5 and 6 hours. The results obtained are shown in the following Table.

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TIME TOTAL BACTERIAL COI~NT/ML ON EACH PART OF THE SA~PLE
( HOURS ) PART 1 PART 2 PART 3 PART 4 039 . 7 x 10639 . 7 x 106 39 . 7 x 106 39 . 7 x 106 65 . 2 x 106 18 . 2 x 106 15 . 4 x 106 268 . 9 x 10615 . 5 x 106 14 . ~ x 106 520 x 106

3 74.4 x 10611.1 x 106 10.8 x 106

4 106~9 X 10615.0 X 106 12.3 X 106 699 x 106

5 102.8 x 10611.9 x 106 9.1 x 106 699 . 3 X 1067 . 4 X 106 6 . 13 X 106 643 x 106 These results illustrate that the presence of the aromatic ethoxylate in combination with the biocide results in more effective microbiological control, as measured by reduced counts, than the presence of the biocide alone. In addition they show that the aromatic ethoxylate did not, on its own, have any biocidal action, but, in practice, led to increased counts, owing to its ability to disperse slime aggregates.

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. EXAMPLE 2 9 x 1 g samples of a microbiological slime from an industrial cooling system were each dispersed in 10 ml of water. One of these was used as a control and to the others were added the biocide and, in some cases, the aromatic ethoxylate used in Example 1, and the bacterial counts on each sample measured after

6 hours.
SAMPLE ADDTTION

1 (Control) 0 0 1.2 x 106 2 0.56 ppm 0 2.9 x 102 3 1.13 ppm 0 2 x 102 4 2.25 ppm 0 9 4.50 ppm 0 Nil 6 0.56 ppm 2.5 ppm 2.8 x 102

7 1.13 ppm 5.0 ppm 5

8 2.25 ppm 10.0 pprn 2

9 4.50 ppm 20.0 ppm Nil This Example shows increased effectiveness of the combination of the isothiazolones with the aromatic ethoxylate.

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A mixture of water and slime from an industrial cooling system was split into 7 parts, each part was treated for two hours with the biocide and, in some cases, the aromatic ethoxylate, used in Example 1 as well as glutaraldehyde, and the total bacterial count on each part measured.

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~62~:)84 7 x 1 g samples of a microbiological slime from an industrial cooling system were each dispersed in 10 ml of water. One of these was used as a control and to the others were added the biocide and, in some cases, the aromatic ethoxylate, used in Example 1, as well as glut~raldehyde, and the total bacterial counts on each sample measured after 2 hours.

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EXAMPLE
A mixture of water and slime from an industrial cooling system was split into three parts, the first part was used as a control and the other two parts treated for two hours with the following biocide and, in the third part,the aromatic ethoxylate used in Example 1 also, and the total bacterial counts measured.
SAMPLE ADDITION
MET AROMATIC TOTAL
BISTHIOCYANATE ETHOXYLATE COUNT~ML
1 (Control) O 0 23.9 x 106 2 5.7 ppm 0 17.9 x 106 3 5.7 ppm 10 ppm 11.9 x 106 15 The Example shows the increased effectiveness of the methylene bis thiocyanate aromatic ethoxylate combination.

~L~V(3 EX~MPLE 6 A mixture of water and slime from an industrial cooling system was split into three paxts, the first part was used as a control and the other two treated for 2 hours with the following biocide and~ in the third part, the aromatic ethoxylate used in Example 1 also, and the total count on each measured.

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~2~2Q84 3 x 1 g samples of a microbiological slime from an industrial cooling system were each dispersed in 10 ml of water. One of these was used as a control, and the other two treated for 6 hours with biocide and, with the thixd part, the aromatic ethoxylate used in Example 1 also, and the total counts on the samples measured.
SAMPLE ADDITION

METHYLENE AROMATIC TOTAL
BIS THIOCYA~D.TE ETHOXYLATE COUNT~ML
1 (Control) 0 0 >1 x 106 2 3 ppm 0 1 x 106 3 3 ppm 97 ppm 7 x 103 This Example shows the increased effectiveness of the methylene bis thiocyanate -; aromatic ethoxylate combination.

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Fi~MPLE 8 3 x 1 g samples of a microbiological slime from an industrial cooling system were each dispersed in 10 ml of water. One of these was used as a control, and the other two treated for 6 hours with biocide and, in the case of the third part, with aromatic ethoxylate as used in Example 1 also, and the total counts on the samples measured.

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~26 _ 21 --Algae was allowed to develop and grow in tap water contained in a circular glass tank. The contents of the tank were stirred to give constant turbidity as measured by light transmission of a sample withdrawn from the tank. The aromatic etho~ylate used in Example 1 was introduced to give a concentration of 2 ppm. Within 20 minutes the turbidity of the dispersion as measured by light transmission had increased by 12.5%. For the next 15 minutes the turbidity remained constant, whereupon a further 3 ppm of the aromatic ethoxylate was added which led to a further 1.5% increase in turbidity.
; This Example demonstrates the ability of the aromatic ethoxylate to disperse aggregates of algae.

' . .

12~i2 Algae was allowed to develop and grow in tap water in a circular glass tank. The contents of the tank were stirred to yive a constant turbidity as measured by light transmission of a sample withdrawn from the tank. 10 ppm of various different aromatic ethoxylates with the m and n values of the general formula given above was introduced into the tank, and the turbidity of the dispersion measured at various times by light transmission. The dispersants and penetrants studied, and the results obtained were:-m n Transmission (%) Measured at Various Times 015 mins 30 mins 45 mins 156 9 100 %10~ % 99.5 % 97 %
9 9 100 %100 % 98 %96.5 %
9 100 %9~.5 % 98 %95 %
9 100 %97.5 % 97 %95 %
9 100 %100 % 100 %100 %
20~ 0 100 %100 % 92 %89~5 %
11 12 100 %98 % 93 %85 %
12 100 %92 % 8g.5 % 89.5 %
The results demonstrate the ability of thevarious ethoxylates listed to disperse algae.
The only exception is the ethoxylated nonyl phenol containing 30 moles of ethylene oxide.

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Two water samples taken from a paper machine system were divided into three parts. One part was used as a control the second part was treated with 13.5ppm of a mixture of isothiozolones (5-chloro-2-methyl-4-isothiazolin-3-one and 2-mehtyl-4-isothiazolin-3-one in the ratio 2.66:lJ commercially available as Kathon WT, and tne third part was treated with 13.5ppm of the mixture of isothiazolones and 10ppm or aromatic ethoxylate (Ethylan HB4). Total bacterial counts were measured initially and after 2 hours and 24 hours the results obtained are shown in the following table:-Time Total bacterial count/ml. on each part of the sample Sample (hours) Part 1 Part 2 Part 3 1 ~ 1.8 x 10 1.8 x 105 1.8 x 10 2 2.0 x 105 3.3 x 10' 2.3 x 10~

24 2.7 x 105 3.9 x 10 8.3 x 103 2 0 2.3 x 10 2.~ x 10 2.3 x 10 2 2.3 x 105 7.1 x 104 3.6 x lOq ~4 2.3 x 10 2.8 x 10 1.9 x 10 *Trade Mark ;

'

Claims

THE EMBODIMENTS OF THE INVENTION IN WHICH AN EXCLUSIVE
PROPERTY OR PRIVILEGE IS CLAIMED ARE DEFINED AS FOLLOWS:

1. A method for the treatment of an aqueous system which comprises adding to the water an effective amount of an additive selected from (i) an ethoxylated phenol having the general formula:
where m represents 2 to 40 and R represents Cn H2n+1 in which n is from 0 to 18 without a microbiological control agent and (ii) a said ethoxylated phenol and a microbiological control agent which is a biocide selected from one of the following formulae:
(i) a substituted 5 or 6 membered ring heterocyclic compound in which the hetero atom or atoms are one or more of nitrogen, oxygen or sulphur and the substituents are selected from the group consisting of alkyl groups, keto groups, hydroxyl groups and halogen atoms (ii) a quaternary ammonium compound (iii) a phenol or chlorinated phenol (iv) an amine or amide (v) a halogen release agent (vi) an organic cyanide or thiocyanate (vii) a sulphone (viii) a tin compound (ix) a straight chain aliphatic aldehyde (x) a triazine (xi) an alkyl phosphonium compound (xii) bis bromo acetoxy butene; and (xiii) a dithiocarbamate.

2. A method according to Claim 1 wherein R
represents hydrogen, or a nonyl or dodecyl radical.

3. A method according to Claim 1 wherein the ethoxylated phenol is added without a microbiological control agent.

4. A method according to Claim 1 wherein the ethoxylated phenol is added with a biocide selected from the formulai (i), (ii), (iii), (v), (vi), (vii), (ix), (x), (xi), (xii), and (xiii).

5. A method according to Claim 1 wherein the biocide is selected from a quaternary ammonium compound, an amine, a phenol, a halogen release agent, a thiocyanate, a straight chain aliphatic aldehyde, a sulphone, and a tin compound

6. A method according to Claim 5 wherein the biocide is selected from an N-alkyl, dimethyl benzyl ammonium chloride, glutaraldehyde, methylene-bis thiocyanate, hexachlorodimethylsulphone, and tributyl tin oxide and tributyl tin chloride.

7. A method according to Claim 1 wherein the biocide is an isothiazolone having the formula:
wherein R' represents hydrogen or chlorine.

8. A method according to Claim 3, 5, or 7 wherein R
represents hydrogen, or a nonyl or dodecyl radical.

9. A method according to Claim 4 wherein R
represents hydrogen.

10. A method according to Claim 1, 2, or 4 wherein m represents from 4 to 15.

11. A method according to Claim 1, 2, or 4 wherein the ethoxylated phenol is a phenol ethoxylate having about 4 ethoxylate units.

12. A method according to Claim 1, 2, or 4 which comprises adding to the water from 0.1 to 1,000 ppm of ethoxylate and from 0.5 to 250 ppm of biocide.

13. A method according to Claim 1, 4, or 9 which comprises adding to the water 2 to 10 ppm of the ethoxylate and from 0.5 to 250 ppm of biocide.

14. A method according to Claim 1, 2, or 4 which comprises adding to the water 2 to 5 ppm of ethoxylate and from 0.5 to 250 ppm of biocide.

15. A method according to Claim 1, 2, or 4 for the treatment of an industrial cooling water system.

16. A method according to Claim 1, 2, or 4 which comprises adding the ethoxylate and, if desired, the biocide to a recirculating backwater used for the paper pulping bath used in papermaking.

17. A method according to Claim 1/ 2, or 4 which comprises adding the ethoxylate and, if desired, the biocide directly to the paper pulping bath used in papermaking.

18. A method according to Claim 1, 2, or 4 which comprises adding the ethoxylate and, if desired, the biocide to a holding tank containing moist pulp used in papermaking.

19. A method according to Claim 1, 2, or 4 which comprises adding the ethoxylate and, if desired, the biocide in combination with a chemical additive which is added to the paper pulping bath used in papermaking.

20. A method according to Claim 1, 2, or 4 which comprises adding the ethoxylate and, if desired, the biocide in combination with a chemical additive used in papermaking selected from starch, titanium dioxide, a defoamer, a size, a wet strength resin, a dispersant or retention aid, a filler, and an optical brightening agent.

21. A method according to Claim 1 of an industrial cooling water system which comprises adding to the system 0.1 to 1,000 ppm of ethoxylate where m is about 4 and R is hydrogen and 0.5 to 250 ppm of an isothiazolone having the formula:
wherein R' represents hydrogen or chlorine, glutaraldehyde, methylene bis thiocyanate or N-alkyl, dimethyl benzyl ammonium chloride.

22. A composition suitable for addition to an aqueous system which comprises a biocide selected from one of the following formulae:
(i) a substituted 5 or 6 membered ring heterocyclic compound in which the hetro atom or atoms are one or more of nitrogen, oxygen or sulphur and the constituents are selected from the group consisting of alkyl groups, keto groups, hydroxyl groups and halogen atoms (ii) a quaternary ammonium compound (iii) a phenol or chlorinated phenol (iv) an amino or amide (v) a halogen release agent (vi) an organic cyanide or thiocyanate (vii) a sulphone (viii) a tin compound (ix) a straight chain aliphatic aldehyde (x) a triazine (xi) an alkyl phosphonium compound (xii) bis bromo acetoxy butene; and (xiii) a dithiocarbamate and an ethoxylated phenol having the general formula:
where m and R are as defined in Claim 1 except that when the biocide is an alkyl dimethyl benzyl ammonium chloride, the ethoxylated phenol is not a nonylphenol ethoxylate containing 9 ethylene oxide units; and when the biocide is a bromine release agent, it is selected from a bromonated isocyanate, a bromonated hydantoin, and a brominated alkyl oxazolidinone.

23. A composition according to Claim 22 which comprises from 0.1 to 99.9 percent by weight of the ethoxylate.

24. A composition according to Claim 22 which comprises from 2 to 10 percent by weight of the ethoxylate.

25. A composition according to Claim 22 comprising the ethoxylated phenol is added with a biocide selected from the formulai (i), (ii), (iii), (v), (vi), (vii), (ix), (x), (xi), (xii), and (xiii).

26. A composition according to Claim 25 wherein R
represents hydrogen, or a nonyl or dodecyl radical.

27. A composition according to Claim 22, 23, or 25 wherein R represents hydrogen.

28. A composition according to Claim 22, 25, or 26 which comprises 25 to 99 percent by weight of the ethoxylate.

29 A composition according to Claim 22, 24, or 25 which also contains another chemical additive used in a paper pulping bath.

30. A composition according to Claim 22, 24, or 25 which also contains a chemical additive used in papermaking selected from starch, titanium dioxide, a defoamer, a size, a wet strength resin, a dispersant or retention aid, a filler, and an optical brightening agent.

31. A composition according to Claim 22, 24, or 26 which also contains paper pulp.

32. A composition according to Claim 22, 23, or 24 in which the biocide is an isothiazolone having the formula:
wherein R' represents hydrogen or chlorine, N-alkyl, dimethyl benzyl ammonium chloride or glutaraldehyde.

33. A composition according to Claim 22 in which the biocide is methylene bis isocyanate or hexachlorodimethyl-sulphone.

34. A composition according to Claim 33 which comprises 25 to 99 percent by weight of the ethoxylate.