Biocidal compositions, the compositions dissolving the iron sulfide, their application, methods of treatment of the water system

FIELD: organic chemistry; chemical industry; other industries; production of the biocidal compositions and their application.

SUBSTANCE: the invention is pertaining to the synergistic biocidal compositions and to the compositions dissolving sulfides of metals. The biocidal composition or the composition dissolving the iron sulfide includes (i) THP-salt and (ii) the biopenetrant. The biopenetrant represents the polymer of the non-saturated carboxylic acid or the interpolymer of the non-saturated carboxylic acid with the vinyl-sulfonic acid. At that the end groups of the indicated polymer or the interpolymer are the groups of the vinyl-sulfonic acid (VPA) or vinyliden-1,1 of the diphosphin acid (VDPA), either the indicated polymer or the interpolymer contains such monomers inserted into the main chain of the macromolecule. The present composition synergistically increases the biocidal effectiveness of the THP-salt concerning both the planktonic (free-floating) and the motionless (affixed) bacteria, and also synergistically increases the effectiveness of THP-salt in dissolution of the scale of iron sulfide. The invention also describes the application of the indicated composition in the capacity of the biocide or for dissolution of the metal sulfide and the method of treatment of the water system infected or inclined to be Infected by the micro-organisms such as bacteria, fungi, or algae with usage of the indicated composition, and the method of treatment of the water system containing the metal sulfide scale or being in contact with the metal sulfide scale, with usage of the indicated composition.

EFFECT: the invention ensures, that the biocidal compositions synergistically increase the biocidal effectiveness of the THP-salt concerning the free-floating and motionless bacteria and the increased effectiveness of THP-salt in dissolution of the iron sulfide scale.

18 cl, 5 ex, 3 tbl

 

This invention relates to a synergistic biocidal compositions or compositions, solvent sulfides of metals.

The present invention is a selective invention, associated with the published PCT patent application WO 99/33345, as claimed by the authors of the present invention.

In the specified WO 99/33345 disclosed synergistic biocidal compositions, including "TNR"compatible "TNR" bioinert that is not surface-active agent, and, optionally, surface-active substance.

The term "TPR" is defined in WO 99/33345 and means salt is tetrakis(hydroxyalkyl)or phosphonium Tris(hydroxyalkyl)phosphine. To avoid confusion later in the description they will be referred to as "TNR-salt" or "TNR", respectively.

Examples of non-surface-active substances of biphenylenes, described in the WO 99/33345 and include phosphonate derivatives of carboxylic acids, for example, posvyawennye telomeres, are described in published European application EP-A-0491391 and EP-A-0861846 authors of the present invention.

Examples of other non-surface-active, biphenylenes, described in the WO 99/33345 include a copolymer of N,N,N',N'-tetramethyl-1,2-diaminoethane and bis(2-chloroethyl)ether. This compound is commercially available under the trade name WSCP will continue upon natica under this name.

In those cases, when applied surfactants, examples described in the above-mentioned WO 99/33345 include sulfonated (anionic) surfactants, such as Quaternary ammonium derivatives, as well as nonionic and amphoteric semipolar surfactants.

The applicants of the present invention unexpectedly found that when bioinert is a polymer or copolymer with terminal groups of phosphinic acid, it shows synergy with TNR-salt, raising biocidal efficacy of TNR-salt against both planktonic (free-floating)and fixed (attached) bacteria.

Also unexpectedly found that when bioinert is a polymer or copolymer with terminal groups of phosphinic acid, it shows synergy with TNR-salt, thereby increasing the effectiveness of TNR-salt in relation to the scale dissolution of sulfides of metals, especially iron sulfide.

Accordingly, the present invention relates to a synergistic composition including:

(i) TNR-Sol (which is defined above), and

(ii) bioinert,

where bioinert includes a polymer of an unsaturated carboxylic acid or a copolymer of unsaturated carboxylic acid and sulfonic acid, and the specified polymer or with whom OLIMAR or contains end groups mono - or debastiani unsaturated carboxylic acid, or contains such monomers, is introduced into the main chain of the macromolecule polymer.

The synergistic composition may be a synergistic biocidal composition and/or synergistic composition, a solvent metal sulfide (e.g., iron sulfide).

Preferably, TNR-salt is a sulfate, tetrakis(hydroxymethyl)phosphonium (THPS). Other TNR-salt include postit, bromide, fluoride, chloride, phosphate, carbonate, acetate, formate, citrate, borate, and silicate.

Bioinert may include a polymer of an unsaturated carboxylic acid or a copolymer of unsaturated carboxylic acid and sulfonic acid, and the specified polymer or copolymer or contains end groups vinylphosphonic acid (VPA) or vinylidene-1,1-diphosphines acid (VDPA), or contains such monomers introduced into the main chain of the macromolecule polymer; accordingly, bioinert may be a random copolymer comprising the monomers VPA and/or VDPA.

The polymer or copolymer of bioinert may be a polyacrylate or a copolymer of acrylate and sulfonate.

In accordance with a preferred variant implementation of the present invention bioinert may be a polyacrylate with terminal groups vinylphosphonic acid (referred to hereinafter in the description of the "VPA-terminal polymer")or with the end groups of vinylidene-1,1-diphosphines acid (referred to hereinafter in the description "VDPA-terminal polymer") or polyacrylate, containing monomers VPA and/or VDPA.

In other preferred embodiments, the implementation of the present invention bioinert may be a copolymer of acrylate and sulfonate end groups vinylidene-1,1-diphosphines acid (hereinafter referred to as "VDPA-terminal copolymer") or vinylphosphonic acid (hereinafter in the description called "VPA-terminal copolymer"), or may be a copolymer of acrylate and sulfonate comprising monomers VPA and/or VDPA.

In the composition according to the present invention, the preferred ratio VPA or VDPA-end of the polymer or copolymer to TNR-salt is (percentage based on weight) from 0.5 to 50%, for example from 0.5 to 30%, preferably from 1 to 25%, for example from 1 to 20%, from 1% to 10% or from 2%to 8%, most preferably from 1 to 5%, for example, from 3 to 5% (based on active solids and from 1 to 75%, for example, 50%, the drug is active TNR-salt).

In one embodiment, the present invention bioinert is a VPA-terminal polymer or VDPA-terminal copolymer.

The preferred ratio of VPA-terminal polymer or VDPA-terminal copolymer to TNR-salt is (percentage based on weight) from 0.5 to 50%, for example from 0.5 to 30%, preferably from 1 to 25%, for example from 1 to 20%, from 1% to 10% or from 2%to 8%, most preferably from 1 to 5%, for example, from 3 to 5% (israsoma on active solids and from 1 to 74%, for example, 50% of the drug is active TNR-salt).

In accordance with one embodiment of the invention the composition is provided in the form of a solution, e.g. an aqueous solution.

Alternatively, the composition may be supplied in solid form, for example, a solid form obtained by coating components powder granular or porous acid bases, such as adipic acid, or by absorption of the components in powder granular or porous acid-based, such as adipic acid, or the introduction of a waxy base.

As noted above, the compositions according to the present invention can be used as biocides against planktonic (free-floating) and fixed (attached) bacteria.

The applicants of the present invention it was found that the compositions according to the present invention is effective to reduce the number of total heterotrophic bacteria and sulfate reducing bacteria in water systems.

Thus, the present invention also provides a method of processing water systems, infected or capable of infecting microorganisms, such as bacteria, fungi or algae, the method includes adding the specified system separately or together biocide active number TNR-salt and bi is the penetrant, where bioinert includes a polymer of an unsaturated carboxylic acid or a copolymer of unsaturated carboxylic acid and sulfonic acid, and the polymer or copolymer contains a terminal group mono - or debastiani unsaturated carboxylic acid or a random copolymer containing mono - or diphosphorous unsaturated carboxylic acid, whereby affected, at least some of these microorganisms.

The water system may be contaminated, for example, bacterial slime and/or planktonic bacteria. The invention can be applied to handle these aerobic systems, cooling tower systems, paper production and waste water, as well as for these anaerobic systems, such as oil wells, for example, in the secondary recovery process. The invention may also be suitable for use for the purpose of conservation of liquid clay and functional fluids such as drilling muds, fluids for drilling, fluid stimulation and fluid for hydraulic fracturing.

As mentioned above, the compositions according to the present invention can also be used for dissolution of sulfides of metals, preferably iron sulfide; in particular, they can be used for dissolving scale iron sulfide. However, the sulfide is atalla may be a sulfide of lead, or zinc sulfide, or a combination of sulfides of iron, or lead, and zinc.

The iron sulfide is usually can be a mackinawite (FeS) or pyrite (FeS2), but any other types of iron sulfide can be dissolved using the present invention.

Thus, the invention provides a method for processing aqueous system containing scale sulphides of metals, such as iron sulfide scale, or in contact with such scum, this method involves adding the specified system separately or together TNR-salt and bioinert where bioinert includes a polymer of an unsaturated carboxylic acid or a copolymer of unsaturated carboxylic acid and sulfonic acid, and the specified polymer or copolymer contains end groups mono - or debastiani unsaturated carboxylic acid, whereby at least a portion of a specified scale is dissolved.

The invention can be applied in the oil and gas industry for the processing of such systems, as oil wells, gas production wells, pipelines, storage tanks and production equipment, for example, in the secondary recovery process, and in other industrial water systems, for example, in systems for the paper industry.

Hereinafter the present invention will be illustrated using the reamers.

Various abbreviations used in the examples, have the following meanings:

VPA polymer:polyacrylate of molecular weight 4000 with integral groups vinylphosphonic acid
VDPA copolymer:a copolymer of acrylate and sulfonate molecular weight of 5,000-6,000 with terminal groups vinylidenefluoride acid
GHB:total heterotrophic bacteria
SRB:sulfate-reducing bacteria
WHO water:Water with hardness, corresponding to the standard world Health Organization (see table I below)
SMOW water:Water with average standard indicators of sea water (see table II below)
THPS:50% aqueous solution of sulfate tetrakis(hydroxymethyl)phosphonium

WSCP:Copolymer of N,N,N',N'-tetramethyl-1,2-diaminoethane and bis(2-chloroethyl)ether
Table I
Water of standard hardness according to who
1 liter contains:
CaCl2(anhydrous) 0,305 g
MgCl2·6H2O0,139 g
Table II
Sea water medium standard indices
5 liters contain:
NaCl122,65 g
MgCl2·6H2O55,52 g
Na2SO420,45 g
CaCl2·2H2O20,45 g
KClof 7.69 g
NaHCO33,48 g
NaHCO31,00 g
KBr0.50 g
The pH was adjusted to 8.2 with 0,1 N NaOH

Example 1

Quantitative analysis of bacterial suspension (planktonic bacteria) in the water WHO

The result of the analysisLog reduction in the number of total process bacteria (based on 50 ppm THPS)
The duration of the contact
1 hour3 hours
Control00
THPS, the e entered in the medication 15,8

THPS/VPA polymer*7,4Complete loss
THPS/VDPA polymer*7,4Complete loss
THPS/0.7 PERCENT WSCP3,77,4

Example 2

Quantitative analysis of bacterial suspension in drinking water

The result of the analysisLog reduction to 75 ppm A.I. THPS in contact for 3 hours
GHBSRB
Control00
THPS, is not entered in the medicationthe 3.83
THPS/VPA polymer*5.13

Example 3

Analysis of the biofilm (attached): freshwater (who)

The results of the analysisThe number of surviving bacteria (GHB) after 3-hour incubation at 75 ppm THPS
Control1×105
THPS, not typed in1×105
medication
THPS/VPA polymer*1×102
THPS/VDPA p is limer *<10
THPS/2% sulfonated1×103
Surfactant (a)

Example 4

Analysis of biofilms: sea water (SMOW)

The results of the analysisThe number of surviving bacteria after incubation for 3 hours at 75 ppm THPS
ControlGHBSRB
THPS, is not entered in the medication1×1041×106
THPS/VPA polymer*1×1021×104
THPS/VDPA polymer*<10<10
THPS/5% Quaternary1×1021×102
ammonium compound (b)
*In each case the ratio of THPS to a "polymer" is 50% A.I. THPS to 5% "polymer", "polymer" includes 25% solids in the form of sodium salt.

(a) Di-sodium salt of mixed mono - and dialkyldimethylammonium of diphenyloxide available as DOWFAX®A.

(b) Chloride, alkyldimethylbenzylammonium available as EMPIGEN®BAC 50.

Example 5

Tests of dissolution of sulfide same is ESA

Prepare the following solutions:

(a) THPS: - THPS (26,6 g) + deionized water (73,4 g)

(b) VPA polymer: - solution VPA polymer containing 20% active ingredient (20 g) + deionized water (80 g)

(c) VDPA polymer: - solution VDPA polymer containing 20% active ingredient (20 g) + deionized water (80 g)

(d) THPS/5% VPA polymer: - THPS (26,6 g) + VPA solution of polymer containing 20% active ingredient (5 g), + deionized water (68,4 g)

(e) THPS/5% VDPA polymer: - THPS (26,6 g)+solution VDPA polymer containing 20% active ingredient (5 g) + deionized water (68,4 g)

(f) THPS/20% VPA polymer: - THPS (26,6 g) + VPA solution of polymer containing 20% active ingredient (20 g) + deionized water (53,4 g)

(d) THPS/20% VDPA polymer: - THPS (26,6 g)+solution VDPA polymer containing 20% active ingredient (20 g) + deionized water (53,4 g)

To each of these solutions add 2 g (accurately weighed) iron sulfide scale of the oilfields (from the system of water injection into the reservoir). The solution is stirred in a heated water bath for 20 hours at 50°C, and then filtered through a weighed filter paper. Filter paper with solids dried before re-weighing; thus determine the mass remaining on her solids and calculate the % weight reduction.

The concentration of iron in the filtered R the sites also determined using the method for determination of iron on the spectrophotometer Hach DR2000 (see table III)

Table III
Dissolving substancepH% weight lossThe concentration of Fe2+in solution (ppm)
(a) THPS3,23632120
(b) VPA polymer4,54601310
(C) VDPA polymer3,28471430
(d) THPS + 5% VPA polymerof 3.77743320
(e) THPS + 5% VDPA polymer3,13783560
(f) THPS + 20% VPA polymer3,94763480
(g) THPS + 20% VDPA polymer2,99835260

1. Synergistic biocidal composition comprising

(i) THP-salt and

(ii) bioinert,

where bioinert includes a polymer of an unsaturated carboxylic acid or a copolymer of unsaturated carboxylic acids with vinyl sulfonic acid, and the terminal groups of the specified polymer or copolymer are groups vinylphosphonic acid (VPA) or vinylidene-1,1-diphosphines acid (VDPA) or the polymer or copolymer contains the monomer introduced into the main chain mA is romolecules.

2. The composition according to claim 1, where TNR-salt is a sulfate, tetrakis(hydroxymethyl)phosphonium.

3. The composition according to claim 1, where TNR-Sol is postit, bromide, fluoride, chloride, phosphate, carbonate, acetate, formate, citrate, borate or silicate tetrakis(hydroxymethyl)phosphonium.

4. Composition according to any one of claims 1 to 3, where the polymer or copolymer of bioinert is a polyacrylate or a copolymer of acrylate and vinyl sulfonate.

5. The composition according to claim 4, where bioinert is a polymer with VDPA-terminal group or VPA-terminal group or polyacrylate containing monomers VPA and/or VDPA.

6. The composition according to claim 4, where bioinert is a copolymer with VDPA-terminal group or VPA-terminal group or a copolymer of acrylate and vinyl sulfonate, including VPA and/or VDPA monomers.

7. The composition according to claim 5 or 6, in which the content of VPA or VDPA-polymer or copolymer is in the range from 1 to 50% based on the weight (in terms of solid active substance and a drug containing from 1 to 74% TNR-salt).

8. The composition according to claim 7, in which the specified content is in the range from 1 to 25% based on the weight.

9. The composition according to claim 8, in which the specified content is in the range from 1 to 5% based on the weight.

10. The synergistic composition, dissolving the iron sulfide, including TNR-salt and bioinert, the de bioinert includes a polymer of an unsaturated carboxylic acid or a copolymer of unsaturated carboxylic acids with vinyl-sulfonic acid, moreover, the terminal groups of the specified polymer or copolymer are groups vinylphosphonic acid (VPA) or vinylidene-1,1-diphosphines acid (VDPA) or the polymer or copolymer contains the monomer introduced into the main chain of the macromolecule.

11. The use of a composition according to any one of claims 1 to 9 as a biocide.

12. The application of item 11 to protect against planktonic (free-floating) and/or fixed (attached) bacteria.

13. The application of item 11 or 12, to reduce the content of the General process of bacteria and/or sulfate-reducing bacteria in the water.

14. The method of processing water systems infected or capable of infecting microorganisms, such as bacteria, fungi or algae, the method includes adding the specified system separately or together biocide active number TNR-salt and bioinert where bioinert includes a polymer of an unsaturated carboxylic acid or a copolymer of unsaturated carboxylic acids with vinyl-sulfonic acid and the polymer or copolymer contains a terminal group vinylphosphonic acid (VPA) or vinylidene-1,1-diphosphines acid (VDPA) or contains such monomers in the main chain of the macromolecule, whereby affected, at least some of these microorganisms.

15. The use of synergistic companies who stand according to any one of claims 1 to 9 and 10 for the dissolution of metal sulfide.

16. The application indicated in paragraph 15, where the sulfide of the metal is an iron sulfide scale.

17. The method of processing the aqueous system containing scale sulfide or metal in contact with the scum of the metal sulfide, the method includes adding the specified system separately or together TNR-salt and bioinert where bioinert includes a polymer of an unsaturated carboxylic acid or a copolymer of unsaturated carboxylic acids with vinyl-sulfonic acid and the polymer or copolymer contains a terminal group vinylphosphonic acid (VPA) or vinylidene-1,1-diphosphines acid (VDPA) or contains such monomers in the main chain of the macromolecule, whereby dissolves at least a portion of a specified scale.

18. The method according to 17, where scale is a scale iron sulfide.



 

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