U.S. patent application number 10/588474 was filed with the patent office on 2009-07-23 for synergistic compositions.
Invention is credited to Christopher Jones, Robert Talbot.
Application Number | 20090186858 10/588474 |
Document ID | / |
Family ID | 31985590 |
Filed Date | 2009-07-23 |
United States Patent
Application |
20090186858 |
Kind Code |
A1 |
Talbot; Robert ; et
al. |
July 23, 2009 |
Synergistic compositions
Abstract
A synergistic composition comprising a THP salt and a
biopenetrant, in which the biopenetrant comprises a polymer of an
unsaturated carboxylic acid or a copolymer of an unsaturated
carboxylic acid with a sulphonic acid, said polymer or copolymer
being terminated by a mono- or diphosphonated unsaturated
carboxylic acid group or having such monomers incorporated into the
polymer backbone. This composition acts synergistically to enhance
the biocidal efficacy of the THP salt against both planktonic
(free-swimming) and sessile (attached) bacteria, and also acts
synergistically to enhance the efficacy of the THP salt in the
dissolution of iron sulphide scale.
Inventors: |
Talbot; Robert; (Cannock,
GB) ; Jones; Christopher; (Cheslyn Hay, GB) |
Correspondence
Address: |
BUCHANAN, INGERSOLL & ROONEY PC
POST OFFICE BOX 1404
ALEXANDRIA
VA
22313-1404
US
|
Family ID: |
31985590 |
Appl. No.: |
10/588474 |
Filed: |
February 3, 2005 |
PCT Filed: |
February 3, 2005 |
PCT NO: |
PCT/GB2005/000373 |
371 Date: |
November 14, 2008 |
Current U.S.
Class: |
514/129 |
Current CPC
Class: |
A01N 57/20 20130101;
B08B 17/00 20130101; C02F 2305/04 20130101; C23F 14/02 20130101;
A01N 57/34 20130101; C23F 11/1676 20130101; C11D 7/36 20130101;
C02F 1/50 20130101; C02F 5/14 20130101; A01N 2300/00 20130101; A01N
57/34 20130101; A01N 2300/00 20130101 |
Class at
Publication: |
514/129 |
International
Class: |
A01N 57/34 20060101
A01N057/34 |
Foreign Application Data
Date |
Code |
Application Number |
Feb 3, 2004 |
GB |
0402395.8 |
Claims
1-20. (canceled)
21. A synergistic composition comprising: (i) a THP salt and (ii) a
biopenetrant, wherein the biopenetrant comprises a polymer of an
unsaturated carboxylic acid or a copolymer of an unsaturated
carboxylic acid with a sulphonic acid, said polymer or copolymer
being terminated by a mono- or di-phosphonated unsaturated
carboxylic acid group or having such monomers incorporated into the
polymer backbone.
22. A composition according to claim 21, wherein the THP salt is
tetrakis(hydroxymethyl) phosphonium sulphate.
23. A composition according to claim 21, wherein the THP salt is
tetrakis (hydroxymethyl) phosphonium phosphite, bromide, fluoride,
chloride, phosphate, carbonate, acetate, formats, citrate, borate
or silicate.
24. A composition according to claim 21, wherein the biopenetrant
comprises a polymer of an unsaturated carboxylic acid or a
copolymer of an unsaturated carboxylic acid with a sulphonic acid,
said polymer or copolymer being either terminated by
vinylphosphonic acid (VPA) or vinylidene-1,1-diphosphonic acid
(VDPA) or having such monomers incorporated into the polymer
backbone.
25. A composition according to claim 21, wherein the polymer or
copolymer of the biopenetrant is a polyacrylate or an
acrylate/sulphonate copolymer.
26. A composition according to claim 25, wherein the biopenetrant
is a VPA end-capped polymer or a VDPA end-capped polymer or a
polyacrylate incorporating VPA and/or VDPA monomers.
27. A composition according to claim 25, wherein the biopenetrant
is a VDPA end-capped copolymer or a VPA end-capped copolymer (both
as hereinbefore defined) or an acrylate/sulphonate copolymer
incorporating VPA and/or VDPA monomers.
28. A composition according to claim 26, wherein the proportion of
VPA or VDPA polymer or copolymer is in the range of from 1 to 50%
by weight, based upon active solids and a 1 to 74% THP salt
formulation.
29. A composition according to claim 28, wherein the proportion is
in the range of from 1 to 25% by weight.
30. A composition according to claim 9, wherein the proportion is
in the range of from 1 to 5% by weight.
31. A method of treating a water system contaminated, or liable to
contamination, with microbes such as bacteria, fungi or algae,
comprising the steps of: a) adding to said system separately or
together, a biocidally active amount of a THP salt and a
biopenetrant, wherein the biopenetrant comprises a polymer of an
unsaturated carboxylic acid or a copolymer of an unsaturated
carboxylic acid with a sulphonic acid, said polymer or copolymer
being terminated by a mono- or di-phosphonated unsaturated
carboxylic acid group or being a random copolymer containing a mono
or di-phosphonated unsaturated carboxylic acid, thereby killing at
least some of said microbes.
32. A method of treating a water system containing or in contact
with an metal sulphide scale, comprising the step of: a) adding to
said system separately or together, a THP salt and a biopenetrant,
wherein the biopenetrant comprises a polymer of an unsaturated
carboxylic acid or a copolymer of an unsaturated carboxylic acid
with a sulphonic acid, said polymer or copolymer being terminated
by a mono- or di-phosphonated unsaturated carboxylic acid group or
being a random copolymer containing a mono or di-phosphonated
unsaturated carboxylic acid, and b) thereby dissolving at least
part of said scale.
33. The method of claim 32 wherein the scale is iron sulphide
scale.
Description
[0001] This invention relates to synergistic biocidal or metal
sulphide dissolving compositions.
[0002] The present invention is a selection invention relative to
our published P.C.T. application WO 99/33345.
[0003] The said WO 99/33345 discloses synergistic biocidal
compositions comprising "THP", a non-surfactant biopenetrant
compatible with "THP" and optionally a surfactant.
[0004] The term "THP" is defined in WO 99/33345 as meaning either a
tetrakis(hydroxyalkyl)phosphonium salt or a
tris(hydroxyalkyl)phosphine. To avoid confusion we shall
hereinafter refer to "THP salts" or "THP" respectively.
[0005] Examples of non-surfactant biopenetrants disclosed in the
said WO 99/33345 include phosphonated derivatives of carboxylic
acids, for example the phosphonated telomers disclosed in our
published European applications EP-A-0 491 391 and EP-A-0 861
846.
[0006] Other non-surfactant biopenetrants disclosed in the said WO
99/33345 include a copolymer of
N,N,N',N'-tetramethyl-1,2-diaminoethane with
bis(2-chloroethyl)ether. This is commercially available under the
trade name WSCP and will hereinafter be so referred to.
[0007] Where surfactants are used, examples disclosed in the said
WO 99/33345 include sulphonated (anionic) surfactants and cationic
surfactants such as those based on quaternary ammonium compounds,
as well as non-ionic, amphoteric and semi-polar surfactants.
[0008] We have now unexpectedly found that where the biopenetrant
is a phosphonic acid-tipped polymer or copolymer, it acts
synergistically with a THP salt to considerably enhance the
biocidal efficacy of the THP salt against both planktonic
(free-swimming) and sessile (attached) bacteria.
[0009] It has also unexpectedly been found that where the
biopenetrant is a phosphonic acid-tipped polymer or copolymer, it
acts synergistically with a THP salt to enhance the efficacy of the
THP salt in the dissolution of metal sulphide, especially iron
sulphide, scale.
[0010] Accordingly, the present invention provides a synergistic
composition comprising: [0011] (i) a THP salt (as hereinbefore
defined) and [0012] (ii) a biopenetrant in which the biopenetrant
comprises a polymer of an unsaturated carboxylic acid or a
copolymer of an unsaturated carboxylic acid with a sulphonic acid,
said polymer or copolymer being either terminated by a mono-or
di-phosphonated unsaturated carboxylic acid or having such monomers
incorporated into the polymer backbone.
[0013] The synergistic composition may be a synergistic biocidal
composition and/or a synergistic metal sulphide (e.g. iron
sulphide) dissolving composition.
[0014] Preferably, the THP salt is
tetrakis(hydroxymethyl)phosphonium sulphate (THPS). Other THP salts
include the phosphite, bromide, fluoride, chloride, phosphate,
carbonate, acetate, formate, citrate, borate, and silicate.
[0015] The biopenetrant may comprise a polymer of an unsaturated
carboxylic acid or a copolymer of an unsaturated carboxylic acid
with a sulphonic acid, said polymer or copolymer being either
terminated by vinylphosphonic acid (VPA) or
vinylidene-1,1-diphosphonic acid (VDPA) or having such monomers
incorporated into the polymer backbone; accordingly the
biopenetrant may be a random copolymer incorporating VPA and/or
VDPA monomers.
[0016] The polymer or copolymer of the biopenetrant may suitably be
a polyacrylate or an acrylate/sulphonate copolymer.
[0017] In accordance with preferred embodiments of the present
invention, the biopenetrant may be a polyacrylate terminated with
vinylphosphonic acid, (hereinafter "VPA end-capped polymer") or
with vinylidene-1,1-diphosphonic acid (hereinafter "VDPA end-capped
polymer"), or may be a polyacrylate incorporating VPA and/or VDPA
monomers.
[0018] In other preferred embodiments, the biopenetrant may be an
acrylate/sulphonate copolymer terminated with
vinylidene-1,1-diphosphonic acid (hereinafter "VDPA end-capped
copolymer") or with vinylphosphonic acid (hereinafter "VPA
end-capped co-polymer"), or may be an acrylate/sulphonate copolymer
incorporating VPA and/or VDPA monomers.
[0019] In the composition of the present invention, the preferred
ratio of VPA or VDPA end-capped polymer or copolymer to THP salt,
is, when expressed as a percentage by weight, in the range of from
0.5 to 50%, such as from 0.5 to 30%; preferably from 1 to 25%, such
as from 1 to 20%, for example from 1 to 10% or from 2 to 8%; most
preferably from 1 to 5%, for example from 3 to 5% (based upon
active solids and upon a 1 to 74%, for example a 50%, active THP
salt formulation).
[0020] In one embodiment, the biopenetrant is a VPA end-capped
polymer or VDPA end-capped copolymer.
[0021] The preferred ratio of VPA end-capped polymer or VDPA
end-capped copolymer to THP salt is, when expressed as a percentage
by weight, in the range of from 0.5 to 50%, such as from 0.5 to
30%; preferably from 1 to 25%, such as from 1 to 20%, for example
from 1 to 10% or from 2 to 8%; most preferably from 1 to 5%, for
example from 3 to 5% (based upon active solids and upon a 1 to 74%,
for example a 50%, active THP salt formulation).
[0022] The composition may, in one embodiment, be provided in the
form of a solution, for example an aqueous solution.
[0023] Alternatively the composition may be supplied as a solid,
for example a solid formed by coating the components onto, or
absorbing the components into, a powdery granular or porous acid
substrate such as adipic acid or by incorporation into a waxy
substrate.
[0024] As noted above, the compositions according to the present
invention may be used as biocides against both planktonic
(free-swimming) and sessile (attached) bacteria.
[0025] We have found that the compositions according to the present
invention are equally effective in reducing the level of general
heterotrophic bacteria and of sulphate reducing bacteria in
waters.
[0026] The invention therefore also provides a method of treating a
water system contaminated, or liable to contamination, with
microbes such as bacteria, fungi or algae, which method comprises
adding to said system separately or together, a biocidally active
amount of a THP salt and a biopenetrant, in which the biopenetrant
comprises a polymer of an unsaturated carboxylic acid or a
copolymer of an unsaturated carboxylic acid with a sulphonic acid,
said polymer or copolymer being terminated by a mono- or
di-phosphonated unsaturated carboxylic acid group or being a random
copolymer containing a mono or di-phosphonated unsaturated
carboxylic acid, thereby killing at least some of said
microbes.
[0027] The water system may, for instance, be contaminated with
bacterial slime and/or planktonic bacteria. The invention may be of
use for treating aerobic systems such as cooling towers, paper
processing systems and waste water systems, and also for anaerobic
systems, such as oil wells, e.g. during secondary recovery. The
invention may also be suitable for use in the preservation of
slurries and functional fluids, such as drilling muds, completion
fluids, stimulation fluids and fracturing fluids.
[0028] As mentioned above, the compositions according to the
present invention may also be used to dissolve metal sulphides,
preferably iron sulphide; in particular they may be used to
dissolve iron sulphide scale. However, the metal sulphide may be
lead sulphide or zinc sulphide or a combination of iron or lead and
zinc sulphides.
[0029] The iron sulphide may typically be troilite (FeS) or pyrite
(FeS.sub.2), but any iron sulphide species can be dissolved using
the invention.
[0030] The invention therefore also provides a method of treating a
water system containing or in contact with a metal sulphide scale,
for example an iron sulphide scale, which method comprises adding
to said system separately or together, a THP salt and a
biopenetrant, in which the biopenetrant comprises a polymer of an
unsaturated carboxylic acid or a copolymer of an unsaturated
carboxylic acid with a sulphonic acid, said polymer or copolymer
being terminated by a mono- or di-phosphonated unsaturated
carboxylic acid group or being a random copolymer containing a mono
or di-phosphonated unsaturated carboxylic acid, thereby dissolving
at least part of said scale.
[0031] The invention may be of use in the oil and gas industry, for
treating systems such as oil wells, gas wells, pipelines, storage
vessels and production equipment, e.g. during secondary recovery,
and in other industrial water systems,. for instance in paper
industry systems.
[0032] The present invention will be illustrated by way of the
following examples.
[0033] In the examples, the various abbreviations have the
following meaning: [0034] VPA polymer: a vinylphosphonic
acid-terminated polyacrylate of molecular weight about 4000 [0035]
VDPA copolymer: a vinylidene-diphosphonic acid-terminated
acrylate/sulphonate copolymer of molecular weight 5000-6000 [0036]
GHB: general heterotrophic bacteria [0037] SRB: sulphate reducing
bacteria [0038] WHO water: World Health Organisation Standard
Hardness Water (see TABLE I below) [0039] SMOW water: Standard Mean
Ocean Water. (see TABLE II below) [0040] THPS: a 50% aqueous
solution of tetrakis (hydroxymethyl) phosphonium sulphate [0041]
WSCP: copolymer of N,N,N',N'-tetramethyl-1,2-diamino ethane and
bis(2-chloroethyl)ether.
TABLE-US-00001 [0041] TABLE I WHO Standard Hardness Water 1 litre
contains: CaCl.sub.2 (anhydrous) 0.305 g MgCl.sub.2.cndot.6H.sub.2O
0.139 g
TABLE-US-00002 TABLE II Standard Mean Ocean Water 5 litres contain:
NaCl 122.65 g MgCl.sub.2.cndot.6H.sub.2O 55.52 g Na.sub.2SO.sub.4
20.45 g CaCl.sub.2.cndot.2H.sub.2O 7.69 g KCl 3.48 g NaHCO.sub.3
1.00 g KBr 0.50 g pH adjusted to 8.2 by means of 0.1N NaOH
EXAMPLE 1
Quantitative Suspension Test (Planktonic Bacteria) in WHO Water
TABLE-US-00003 [0042] Log Reduction of General Heterotrophic
Bacteria (based upon 50 ppm ai THPS) Contact period Test Product 1
hour contact 3 hour contact Control 0 0 Unformulated THPS 1 5.8
THPS/VPA polymer* 7.4 Total kill THPS/VDPA polymer* 7.4 Total kill
THPS/0.7% WSCP 3.7 7.4
EXAMPLE 2
Quantitative Suspension Test in De Inking Water
TABLE-US-00004 [0043] Log reduction values for 75 ppm ai THPS/3
hour contact Test Product GHB SRB Control 0 0 Unformulated THPS 3.8
3 THPS/VPA polymer* 5.1 3
EXAMPLE 3
Biofilm (Sessile) Tests: Freshwater (WHO)
TABLE-US-00005 [0044] Viable bacteria (GHB) after 75 ppm ai THPS
dosed for 3 hours Test Product Control 1 .times. 10.sup.5
Unformulated THPS 1 .times. 10.sup.5 THPS/VPA polymer* 1 .times.
10.sup.2 THPS/VDPA polymer* <10 THPS/2% sulphonated 1 .times.
10.sup.3 surfactant (a)
EXAMPLE 4
Biofilm Tests: Seawater (SMOW)
TABLE-US-00006 [0045] Viable bacteria after 75 ppm ai THPS dosed
for 3 hours Test Product GHB SRB Control 1 .times. 10.sup.4 1
.times. 10.sup.6 Unformulated THPS 1 .times. 10.sup.2 1 .times.
10.sup.4 THPS/VPA polymer* <10 <10 THPS/VDPA polymer* 1
.times. 10.sup.2 1 .times. 10.sup.2 THPS/5% quaternary 1 .times.
10.sup.2 1 .times. 10.sup.3 ammonium compound(b) *In each case, the
ratio of THPS to "polymer" was 50% a.i. THPS to 5% "polymer", the
"polymer" comprising 25% solids as the sodium salt.
[0046] (a) A di-sodium salt of a mixed mono- and di-alkyl
disulphonated diphenyl oxide, available as DOWFAX.RTM. 2A1.
[0047] (b) An alkyl dimethyl benzyl ammonium chloride, available as
EMPIGEN.RTM.BAC 50.
EXAMPLE 5
Iron Sulphide Dissolution Tests
[0048] The following solutions were made:
[0049] (a) THPS: -THPS (26.6 g)+de-ionised water (73.4 g)
[0050] (b) VPA polymer: -VPA polymer solution having 20% active
ingredient (20 g)+de-ionised water (80 g)
[0051] (c) VDPA polymer: -VDPA polymer solution having 20% active
ingredient (20 g)+de-ionised water (80 g)
[0052] (d) THPS/5% VPA polymer: -THPS (26.6 g)+VPA polymer solution
having 20% active ingredient (5 g)+de-ionised water (68.4 g).
[0053] (e) THPS/5% VDPA polymer: -THPS (26.6 g)+VDPA polymer
solution having 20% active ingredient (5 g)+de-ionised water (68.4
g)
[0054] (f) THPS/20% VPA polymer: -THPS (26.6 g)+VPA polymer
solution having 20% active ingredient (20 g)+de-ionised water (53.4
g)
[0055] (g) THPS/20% VDPA polymer: -THPS (26.6 g)+VDPA polymer
solution having 20% active ingredient (20 g)+de-ionised water (53.4
g)
[0056] To each of these solutions was added 2 g (accurately
weighed) of an iron sulphide field scale (from a water injection
system). The solutions were then stirred in a heated water bath for
20 hrs at 50.degree. C., after this time they were filtered through
a weighed filter paper. The filter paper and solids were then
allowed to dry before re-weighing; the weight of solids remaining
was therefore determined, and the % weight loss calculated.
[0057] The iron concentrations in the filtered solutions were also
measured using the iron method on the Hach DR2000
spectrophotometer.
TABLE-US-00007 Fe.sup.2+ concentration Dissolver pH % wt loss in
solution ppm (a)THPS 3.23 63 3120 (b)VPA polymer 4.54 60 1310
(c)VDPA polymer 3.28 47 1430 (d)THPS + 5% VPA 3.77 74 3320 polymer
(e)THPS + 5% VDPA 3.13 78 3560 polymer (f)THPS + 20% VPA 3.94 76
3480 polymer (g)THPS + 20% VDPA 2.99 83 5260 polymer
* * * * *