WO2022118312A1 - Procédé et composition de traitement de l'eau - Google Patents

Procédé et composition de traitement de l'eau Download PDF

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Publication number
WO2022118312A1
WO2022118312A1 PCT/IL2021/051428 IL2021051428W WO2022118312A1 WO 2022118312 A1 WO2022118312 A1 WO 2022118312A1 IL 2021051428 W IL2021051428 W IL 2021051428W WO 2022118312 A1 WO2022118312 A1 WO 2022118312A1
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Prior art keywords
biocide
cis
bromine
acid
caa
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PCT/IL2021/051428
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English (en)
Inventor
Michal RODENSKY
Chen Zolkov
Jakob Oren
Nir GOLDSTEIN
Ari Ayalon
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Bromine Compounds Ltd.
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Publication of WO2022118312A1 publication Critical patent/WO2022118312A1/fr

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    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01P—BIOCIDAL, PEST REPELLANT, PEST ATTRACTANT OR PLANT GROWTH REGULATORY ACTIVITY OF CHEMICAL COMPOUNDS OR PREPARATIONS
    • A01P1/00—Disinfectants; Antimicrobial compounds or mixtures thereof
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N35/00—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom having two bonds to hetero atoms with at the most one bond to halogen, e.g. aldehyde radical
    • A01N35/08—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom having two bonds to hetero atoms with at the most one bond to halogen, e.g. aldehyde radical at least one of the bonds to hetero atoms is to nitrogen
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N37/00—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom having three bonds to hetero atoms with at the most two bonds to halogen, e.g. carboxylic acids
    • A01N37/06—Unsaturated carboxylic acids or thio analogues thereof; Derivatives thereof
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N37/00—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom having three bonds to hetero atoms with at the most two bonds to halogen, e.g. carboxylic acids
    • A01N37/34—Nitriles
    • 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
    • C02F1/68—Treatment of water, waste water, or sewage by addition of specified substances, e.g. trace elements, for ameliorating potable water
    • 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
    • C02F1/76—Treatment of water, waste water, or sewage by oxidation with halogens or compounds of halogens
    • C02F1/766—Treatment of water, waste water, or sewage by oxidation with halogens or compounds of halogens by means of halogens other than chlorine or of halogenated compounds containing halogen other than chlorine
    • 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
    • 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
    • C02F2103/26—Nature of the water, waste water, sewage or sludge to be treated from the processing of plants or parts thereof
    • C02F2103/28—Nature of the water, waste water, sewage or sludge to be treated from the processing of plants or parts thereof from the paper or cellulose industry
    • 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
    • C02F2103/32—Nature of the water, waste water, sewage or sludge to be treated from the food or foodstuff industry, e.g. brewery waste waters
    • 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
    • C02F2103/32—Nature of the water, waste water, sewage or sludge to be treated from the food or foodstuff industry, e.g. brewery waste waters
    • C02F2103/327—Nature of the water, waste water, sewage or sludge to be treated from the food or foodstuff industry, e.g. brewery waste waters from processes relating to the production of dairy products
    • 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
    • C02F2103/34—Nature of the water, waste water, sewage or sludge to be treated from industrial activities not provided for in groups C02F2103/12 - C02F2103/32
    • 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
    • C02F2103/42—Nature of the water, waste water, sewage or sludge to be treated from bathing facilities, e.g. swimming pools
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2303/00—Specific treatment goals
    • C02F2303/04—Disinfection
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2305/00—Use of specific compounds during water treatment
    • C02F2305/04—Surfactants, used as part of a formulation or alone

Definitions

  • the invention relates to microbial control of water, e . g . , eliminating planktonic and biofilm bacteria using a brominebased biocide in combination with an auxiliary agent which has been found to enhance the action of the biocide .
  • bromine in industrial water treatment is well established and a variety of bromine-based biocides are currently available in the market .
  • the working concentrations and frequency of supply of the biocide depend on the type of water, microbial load, organic load, the speci fic biocide under consideration, the dosing method, etc .
  • CDA cis- 2-decenoic acid
  • the present invention describes the use of cis-2-alkenoic acids (CAAs) of formula I or salts thereof, other than the aforementioned cis-2-decenoic acid, that is, where R in formula I is C3-6, 8-15 alkyl (e.g., 64-6,8-11 alkyl) or mixtures thereof (CDA can be included in a mixture alongside another CAA) , as an additive in bromine-based water treatment. Therefore, unless indicated otherwise, hereinafter the term cis-2-alkenoic acid and the abbreviation CAA do not include cis-2-decenoic acid (CDA) .
  • CAAs cis-2-alkenoic acids
  • CDA cis-2-decenoic acid
  • the invention is therefore primarily directed to a method of microbial control in water, comprising adding to the water one or more bromine-based biocide (s) and cis-2-alkenoic acid(s) (or a salt thereof) as defined above to achieve, for example, reduction of planktonic and/or biofilm bacteria, algae and fungi on a surface in contact with the water.
  • CAA(s) can be easily incorporated into bromine delivery systems that are currently employed in the treatment of industrial water.
  • the bromine-based biocide (s) and CAA(s) can be delivered to an industrial water stream in contact with an infested surface using multiple feed solutions injected sequentially or simultaneously, either continuously or in batch mode to the water stream; the simultaneous injection may include the pre-mixing of the individual solutions to produce a single additive solution (i.e., the CAA(s) and biocide (s) solutions can be mixed before or just prior to addition to the water stream) .
  • the selected feeding method also depends on whether the biocide is supplied as a single component or not, as described below.
  • the method of microbial control in water as herein defined comprises sequentially adding to the water one or more bromine-based biocide (s) and at least one cis- 2-alkenoic acid (6AA) of formula I, for example where the at least one cis-2-alkenoic acid (6AA) of formula I is added to the water prior to the addition of one or more bromine-based biocide ( s ) .
  • liquid concentrates comprising suitably proportioned combinations of bromine-based biocide (s) and 6AA(s) can be prepared.
  • compositions e.g., a liquid concentrate
  • a composition comprising one or more brominebased biocide (s) and one or more cis-2-alkenoic acid(s) of formula I, where R is 63-6,8-15 alkyl (e.g., 64-6,8-11 alkyl) in a liquid carrier comprising water, water miscible solvent or mixture thereof, and optionally one or more additive (s) such as cosolvent ( s ) , antifreeze ( s ) and stabilizer ( s ) , e.g., antioxidants.
  • Solid compositions comprising the biocide (s) and CAA(s) , e.g., granules, flakes & tablets, are also contemplated by the present invention.
  • Bromine-based biocides suitable for use in the present invention are available in the marketplace in different forms, i.e., solids (such as powders and compacted forms e.g., granules and tablets) and liquids (e.g., aqueous concentrates or other flowable formulations that can be easily supplied to the aqueous system to be treated) .
  • solids such as powders and compacted forms e.g., granules and tablets
  • liquids e.g., aqueous concentrates or other flowable formulations that can be easily supplied to the aqueous system to be treated
  • the bromine-based biocidal agents for use in the present invention are commonly divided into two classes:
  • Non-oxidizing biocides may be selected from the groups of:
  • bronopol 2-bromo-2-nitro-l , 3-propanediol
  • the product is available (e.g., from ICL-IP) in a powder form or an aqueous solution and its normal dose level as active ingredient (when used alone) lies in the range from 1 to 1000 parts per million (ppm) , e.g., from 1 to 300 ppm.
  • DBNPA 2-dibromo-3-nitrilopropionamide
  • suitable non-oxidizing bromine-based biocides include 2-Bromo-4-hydroxyacetophenone (BHAP) , bis- bromo acetyl butene (BBAB) , p-bromo-p-nitro-styrene (BNS) , 2,2- dibromomalonamide and 1 , 2-Dibromo-2 , 4- dicyanobutane (DBDCB) , the preparation thereof is known in the art.
  • BHAP 2-Bromo-4-hydroxyacetophenone
  • BBAB bis- bromo acetyl butene
  • BNS p-bromo-p-nitro-styrene
  • DBDCB 4- dicyanobutane
  • Oxidizing bromine-based biocides are compounds which release active bromine species in water (e.g., hypobromous acid/hypobromite) , either by dissolution/ dissociation or through bromide oxidation that converts the Bn to elemental bromine/Br + (the oxidation is usually achieved with the aid of a chemical oxidant; however, supply of electrolytically-generated bromine to the water system to be treated is also included herein in conjunction with CAA(s) ) .
  • active bromine species in water e.g., hypobromous acid/hypobromite
  • the dosage of the oxidative biocides described herein is usually expressed as total CI2 that can be determined by iodometric titration using a titroprocessor : Titrino 848 plus or by DPD (Diethyl-p-PhenyleneDiamine) reagent method using a SQ-300 spectrophotometer: Merck SQ-300.
  • Oxidizing bromine-based biocides may be selected from the groups of:
  • Bl N-brominated amides and imides, such as 1 , 3-dihalo-5, 5- dialkylhydantoins , wherein at least one of the halogen atoms is bromine (the alkyl groups may be the same or different) ; commercially important biocides that belong to this class are 1- bromo-3-chloro-5, 5-dimethylhydantoin (BCDMH) , l-chloro-3-bromo-
  • DBDMH 1, 3-dibromo-5, 5-dimethylhydantoin
  • BCMEH 1- bromo-3-chloro-methylethylhydantoin
  • BCMEH 1- bromo-3-chloro-methylethylhydantoin
  • l-chloro-3-bromo- methylethylhydantoin or mixtures thereof.
  • 5.5-dialkylhydantoins is 1 to 50 ppm as total CI2.
  • B2 inorganic bromide sources, namely bromide salts (e.g., alkali metal salts, ammonium bromide) and hydrobromic acid, which release bromine species in water upon oxidation (e.g., by chemical oxidation using, for example, hypochlorite, chlorine gas, hydrogen peroxide or ozone; and by electrochemical oxidation, namely, anodically-generated bromine) .
  • bromide salts e.g., alkali metal salts, ammonium bromide
  • hydrobromic acid which release bromine species in water upon oxidation (e.g., by chemical oxidation using, for example, hypochlorite, chlorine gas, hydrogen peroxide or ozone; and by electrochemical oxidation, namely, anodically-generated bromine) .
  • activated sodium bromide Consisting of an aqueous solution of sodium bromide and sodium hypochlorite prepared on-site and delivered immediately to the water system to be treated
  • activated ammonium bromide the biocide is prepared on-site by reacting ammonium bromide with an oxidizer
  • solution of HBr and urea which reacts with e.g., sodium hypochlorite on-site
  • Bactebrom® solution composed of HBr and urea, from ICL-IP; the resulting active form is sometimes named herein bromourea
  • dry mixtures of bromide/chlorine compound that are fed, for example, in a tablet form directly into the water system to be treated to react in-situ and produce the active bromine species.
  • bromide sources such as sodium bromide, hydrobromic acid, ammonium bromide and the solution of HBr (or NaBr) and urea may be oxidized on-site chemically (e.g., with hypochlorite, chlorine gas, hydrogen peroxide or ozone) or electrochemically.
  • oxidizing bromine-based biocides include sulfamate-stabilized bromine-based biocides for example as described in WO 99/06320 (stabilized aqueous alkali/alkaline earth metal hypobromite solution (e.g., NaBr as bromide source) ) , or WO 03/093171, available from ICL-IP as Bromosol®, and bromine chloride and stabilized forms thereof (see US 6,068,861) available in the market as aqueous concentrates.
  • WO 99/06320 stabilized aqueous alkali/alkaline earth metal hypobromite solution (e.g., NaBr as bromide source)
  • WO 03/093171 available from ICL-IP as Bromosol®, and bromine chloride and stabilized forms thereof (see US 6,068,861) available in the market as aqueous concentrates.
  • a sulfamate-stabilized bromine-based biocide is an aqueous solution of alkali hypobromite (e.g., NaOBr) stabilized by sulfamic acid or a salt thereof.
  • alkali hypobromite e.g., NaOBr
  • the alkali hypobromite is prepared, either by the reaction of a water- soluble bromide source, such as NaBr, with alkali hypochlorite, such as NaOCl; or by addition of elemental bromine to aqueous alkali hydroxide solution ( ⁇ 30 wt . % NaOH solution) .
  • sulfamic acid usually in the form of the in-situ prepared sodium sulfamate salt, is added to the hypobromite solution.
  • the pH of this sulfamate-stabilized hypobromite solution is strongly alkaline (>10, e.g., >11 or >12) , with Br2 levels in the range from e.g., 5 to 20%, 10 to 20%, 15 to 18% and 16 to 18% Br2.
  • Bromosol® a commercial product tested in the studies reported below, is the reaction product of Br2 and NaOH as described above, to which sodium sulfamate was added, with pH and bromine level indicated above.
  • sulfamate-stabilized hypobromite solution as described above, in combination with cis-2-heptenoic acid, cis- 2-undecenoic acid, cis-2-nonenoic acid or cis-2-octenoic acid, especially cis-2-heptenoic acid, is effective against biofilm and the use of these combinations form preferred embodiments of the invention.
  • Another major example of sulfamate-stabilized bromine-based biocides is an aqueous solution of bromine chloride, added to sodium sulfamate, usually concurrently with sodium hydroxide.
  • cis-2-alkenoic acid(s) it can be used as pure oil dissolved in a suitable solvent, such as ethanol.
  • the invention contemplates the use of pure cis-2- alkenoic acid(s) as well as their use in a crude form, e.g., 80- 95% (by gas chromatography (GC) , area %) .
  • the lower than 95% ( ⁇ 95%) pure CAA(s) is named herein "low purity CAA(s) grade".
  • pure CAA(s) refers to CAA(s) characterized in having a purity level of more than 95%, e.g., equal to or greater than 97% as detected by GC .
  • Cis-2-alkenoic acid(s) for use by the present invention are commercially available, or can be prepared for example by a two-step synthesis consisting of brominating the corresponding 2-alkanone to give crude 1 , 3-dibromo-2-alkanone as a main product alongside other isomers, followed by rearrangement of the 1 , 3-dibromo-2-alkanone to the unsaturated acid, depicted by the scheme below:
  • R' is alkyl, e.g., C2H5, C3H7, C4H9, C 6 HI 3 , C7H15, C 8 HI 7 and C9H19, etc.
  • Rappe et al. Acta Chemica Scandinavica (1965) , Vol. 19 p. 383-389) .
  • the rearrangement took place in an alkaline environment, using alkali carbonate or alkali bicarbonates as a base.
  • a similar approach was reported by the same research group in Organic Syntheses (1973) , Vol. 53, p.123-127.
  • US 8,748,486 the same synthetic pathway is described, but with alkali hydroxide in place of carbonates/bicarbonates .
  • a beneficial synthetic pathway arriving at cis-2-alkenoic acid is further illustrated by the scheme shown below, where 1 , 3-dibromo-2-alkanone is rearranged in an alkaline solution of potassium carbonate to the corresponding acid (in the form of potassium salt) , in the presence of a catalytically effective amount of the potassium salt of the cis-2-alkenoic acid.
  • Cis-2-alkenoic acid in the form o f the free acid, is obtained by acidi fication ( e . g . , with concentrated hydrochloric acid) of the aqueous phase of the reaction mixture , i . e . , after phase separation .
  • the 1 , 3-dibromo-2-alkanones are accessible by brominating the corresponding 2-alkenone in concentrated hydrobromic acid by slow addition of bromine , as illustrated below for the preparation of 1 , 3-dibromo-2-nonanone (1,3-DBN) and 1,3-dibromo-
  • another aspect of the invention is a method of microbial control in water, which comprises combatting planktonic bacteria and/or biofilm bacteria on a surface in contact with the water and/or inhibiting biofilm formation on a surface prone to such formation, by adding to the water an effective microbiocidal amount of the bromine-based biocide (s) and an enhancement-inducing amount of the cis-2-alkenoic acid(s) to achieve biofilm reduction which is at least 1 log unit, e.g., at least 2, 3 or more log units higher than the reduction achieved with the same dosage of the biocide acting alone, for example, down to ⁇ 10 5 CFU/cm 2 , e.g., ⁇ 10 3 CFU/cm 2 and preferably ⁇ 10 2 CFU/cm 2 or even substantial biofilm eradication, i.e. ⁇ 10 2 CFU/cm 2 .
  • the effective microbiocidal amount of the bromine-based biocide(s) is from 0.1 to 1000 ppm, e.g., 0.1 to 300 ppm as active biocide, for example, 0.2 to 100 ppm; 0.5 to 100 ppm, and the enhancement-inducing amount of CAA(s) is from 1 nM to 30 mM. It should be borne in mind that dosage levels may vary broadly depending on factors such as the identity of biocide and intended use. But in general, effective dosing ratios biocide : CAA(s) as w/w in the water stream may vary in the range from 20:1 to 5000:1 preferably from 100:1 to 3000:1.
  • the enhancement-inducing amount of CAA(s) can be determined by trial and error in the site of use to achieve targeted biofilm reduction.
  • an enhancement-inducing amount of CAA(s) could be from 0.001 to 15 ppm, e.g., from 0.005 to 10 ppm, for example, from 0.01 to 10 ppm, e.g., across the range of 0.005 to 0.5 ppm.
  • the present invention is particularly directed to provide microbial control over Pseudomonas aeruginosa, Staphylococcus aureus, Bacillus mycoides , Candida albicans , Aspergillus niger, and combinations of microorganisms growing in mixed-species communities derived from an industrial or an environmental water source .
  • FIG. 1 schematically illustrates one convenient method to feed a bromine-based biocide and CAA into an industrial water system.
  • the water stream that comes in contact with a biofilm surface or a surface prone to biofilm formation is indicated by numeral (1) .
  • the term "industrial water” is used to indicate any aquatic industrial water treatable by a bromine-based biocide according to the methods of the present invention, for example, recirculating and once-through cooling systems, cooling towers, pulp and paper mill systems, membranes, oil & gas applications, including biodiesel and diesel, floating production storage and offloading (FPSO) systems, sulphate reduction units (SRU) , steel mills, sugar & ethanol production, dairy production, swimming pools and spas, water distribution systems, irrigation systems, air washers, evaporative condensers, scrubbing systems, brewery pasteurizers, decorative fountains and oil recovery injection water .
  • FPSO floating production storage and offloading
  • SRU sulphate reduction units
  • Biocides which fit well into the method shown in Figure 1 are biocides which are applied as a single pumpable formulation, for example, non-oxidizing biocides available in the marketplace as storage stable liquid formulations, e.g., concentrated bronopol and DBNPA solutions (e.g., 5 to 50 wt% concentrates) , and stabilized solutions of bromine or hypobromite (e.g., sulfamate- stabilized bromine-based biocide) .
  • the design shown in Figure 1 can be modified to enable the use of hypobromite-based biocidal solutions prepared on-site by oxidizing the bromide source just prior to use (these solutions must be applied immediately due to the instability of the hypobromite) , by installing a third feed system into the process (i.e., one dosing pump is dedicated for supplying the CAA and two dosing pumps are used for the individual components of the biocide, i.e., the bromide source and the oxidant) .
  • a third feed system i.e., one dosing pump is dedicated for supplying the CAA and two dosing pumps are used for the individual components of the biocide, i.e., the bromide source and the oxidant
  • Incorporation of CAA(s) into water treatments where the bromine based-biocide is applied in solid forms such as granules or tablets (fed to the inflow water line through erosion feeders) could be achieved by injecting the CAA(s) solution with the aid of a dosing pump to the water line or to a subsidiary water stream diverted from the main stream into the feeder to dissolve the added solids.
  • the biocide (s) and CAA(s) solutions are dosed with metering pumps (2p and 3p, respectively) controlled by timers set up according to the treatment program.
  • the biocide (s) and CAA(s) feed solutions may be injected directly to the water stream (1) but premixing of the two individual solutions in a mixing chamber (not shown) and delivery of the combined solution to the water stream is also possible to enable a treatment program based on simultaneous application of the two components of the treatment.
  • monitoring and upstream mixing (4) devices are included, namely, halogen monitoring, oxidation reduction potential (ORB) , pH sensors and online static mixers.
  • the separately supplied CAA(s) can be applied neat or dissolved in a water miscible solvent or mixture of solvents such as aliphatic alcohols up to 4 carbons, tert-butyl methyl ether (MTBE) , tetrahydrofuran (THE) , dimethyl sulfoxide (DMSO) , glycols and polyethylene glycols, acetonitrile, optionally in the presence of surfactants and stabilizers.
  • a water miscible solvent or mixture of solvents such as aliphatic alcohols up to 4 carbons, tert-butyl methyl ether (MTBE) , tetrahydrofuran (THE) , dimethyl sulfoxide (DMSO) , glycols and polyethylene glycols, acetonitrile, optionally in the presence of surfactants and stabilizers.
  • solvents such as aliphatic alcohols up to 4 carbons, tert-butyl methyl ether (MTBE)
  • the invention provides a method wherein the bromine-based biocide (s) and CAA(s) are supplied to an industrial water stream in contact with an infested surface using multiple feed solutions, whereby the biocide (s) and CAA(s) are added sequentially or simultaneously to the water.
  • sequential treatment with cis-2-alkenoic acid(s) can be performed by injecting the cis-2-alkenoic acid(s) from 20 minutes to 24 hours or more, prior to the biocide application.
  • Cis-2-alkenoic acid(s) may also be added following the biocide application to enhance the activity of the residual biocide in a water sample any time over the period of time that the active biocide is present in a system.
  • the method of the invention does not necessarily require multiple feeds as shown in Figure 1.
  • CAA(s) and either the precursor of oxidative biocide (inorganic bromide sources) , sulfamate-stabilized bromine-based biocides or non-oxidizing biocides can be co-formulated in a liquid concentrate, e.g., with the aid of suitable stabilizers (antioxidant such as butylated hydroxytoluene (BHT) ) .
  • BHT butylated hydroxytoluene
  • the invention also provides a method wherein the bromine-based biocide (s) and CAA(s) are supplied to an industrial water stream in contact with an infested surface using a single feed solution, whereby the biocide and CAA are added simultaneously to the water.
  • the invention relates to a composition comprising one or more bromine-based biocide (s) and cis-2-alkenoic acid(s) or a salt(s) thereof (e.g.
  • a nonoxidizing bromine-based biocide (s) and CAA(s) are formulated in a liquid concentrate, which is supplied to the industrial water stream using a single feed solution.
  • the liquid concentrates of the present invention comprise: a suitably proportioned mixture of (one or more) nonoxidizing bromine-based biocide (s) and cis-2-alkenoic acid(s) (or a salt(s) thereof) , e.g., at a weight ratio from 1000:1 to 20:1, preferably from 500:1 to 20:1, e.g., from 250:1 to 20:1, such that on dilution in an industrial water stream the two active components are applied at an effective ratio; for example, in the liquid concentrate, the concentration of the biocide is from 2 to 50%, preferably from 10 to 50% and the concentration of cis-2-alkenoic acid(s) is from 0.05 to 2%, preferably from 0.1 to 1.0% (by weight based on the total weight of the liquid concentrate) ; and a carrier comprising water, water miscible solvent or a mixture thereof (i.e., water alone, organic solvent alone or aqueous/organic solvent system) ; and optionally one or more
  • Figure 1 is a schematic illustration of an exemplary feeding of a bromine-based biocide and CAA into an industrial water system.
  • Figure 2 is a bar diagram showing the average bacterial load per area (in colony forming units (CFU) per cm 2 , in logarithmic scale) in a biofilm based on Pseudomonas aeruginosa that was treated with phosphate buffer (control) , cis-2-heptenoic acid, Bromosol® and a combination of Bromosol® and cis-2-heptenoic acid at the indicated concentrations.
  • CFU colony forming units
  • Figure 3 is a bar diagram showing the average bacterial load per area (in colony forming units (CFU) per cm 2 , in logarithmic scale) in a biofilm based on Pseudomonas aeruginosa that was treated with phosphate buffer (control) , cis-2-undecenoic acid, Bromosol® and a combination of Bromosol® and cis-2-undecenoic acid at the indicated concentrations .
  • CFU colony forming units
  • Figure 4 is a bar diagram showing the average bacterial load per area (in colony forming units (CFU) per cm 2 , in logarithmic scale) in a biofilm based on Pseudomonas aeruginosa that was treated with phosphate buffer (control) , cis-2-nonenoic acid, Bromosol® and a combination of Bromosol® and cis-2-noneoic acid at the indicated concentrations.
  • CFU colony forming units
  • Figure 5 is a bar diagram showing the average bacterial load per area (in colony forming units (CFU) per cm 2 , in logarithmic scale) in a biofilm based on Pseudomonas aeruginosa that was treated with phosphate buffer (control) , cis-2-octenoic acid, Bromosol® and a combination of Bromosol® and cis-2-octenoic acid at the indicated concentrations .
  • CFU colony forming units
  • Stock solution 2 - NaOCl ⁇ 1% prepared by 23.58g of NaOCl 10.6% w/w diluted with 226.42 g of distilled-water .
  • Stock solution 2 (250.00 g of NaOCl 1.0%) was added gradually while stirring to the above diluted Bactebrom® solution (stock solution 1) , to get the active biocide (orange solution) - total weight 500.00g.
  • the concentration of the product was based on the concentration of the Na- Hypochlorite ( ⁇ 1000 ppm as CI2) .
  • Step 2 (rearranging 1 , 3-dibromo-2-nonanone (1,3-DBN) ) :
  • the end of the reaction was determined by the pH (drop in the pH from 13.3 to 9.1) and by GC analysis of the reaction mixture (disappearance of 1,3-DBN to ⁇ 1% , area %) .
  • the phases were separated.
  • the organic phase (42.6g) was organic waste.
  • the aqueous phase (948 g) was washed three times with dichloromethane (DCM, 3 x 250 g) .
  • an aqueous phase was obtained containing cis-2-nonenoic acid potassium salt (CNA-K) , organic by-products, KBr and KHCO3.
  • CNA-K cis-2-nonenoic acid potassium salt
  • the aqueous phase was acidified by the dropwise addition of aq. 32% HC1 (227 g) over 1 h. During the acidification, CO2 was emitted.
  • Step 1 (brominating 2-undecanone ) :
  • Step 2 (rearranging 1 , 3-dibromo-2-undecanone (1,3-DBUD) ) :
  • DBUD is rearranged to cis-2-undecenoic acid (CUDA) by the following reaction:
  • Step 1
  • the end of the reaction was determined by the pH (drop in the pH from 13.5 to 9.3) and by GC analysis of the reaction mixture (disappearance of 1,3-DBH to ⁇ 1% , areal) .
  • After completion of the reaction cooling to RT and stopping the stirring, an organic phase appeared above the aqueous phase which contained unreacted 3-BH and 3,3-DBH, and by-products formed by a condensation reaction of crude DBH.
  • the phases were separated.
  • the organic phase (24 g) is organic waste.
  • an aqueous phase was obtained containing cis-2-heptenoic acid potassium salt (CHA-K) , organic by-products, KBr and KHCO3.
  • cis-2-heptenoic acid potassium salt cis-2-heptenoic acid potassium salt
  • the aqueous phase was acidified by the dropwise addition of aq. 32% HC1 (193 g) over 1 h. During the acidification, CO2 was emitted.
  • the purity of the CHA obtained was 95.6% (by GC, area%) .
  • Step 1
  • Step 2
  • the end of the reaction was determined by the pH (drop in the pH from 13.7 to 9.3) and by GC analysis of the reaction mixture (disappearance of 1,3-DBO to ⁇ 1% , area%) .
  • an aqueous phase was obtained containing cis-2-octenoic acid potassium salt (COA-K) , organic by-products, KBr and KHCO3.
  • COA cis-2-octenoic acid potassium salt
  • the aqueous phase was acidified by the dropwise addition of aq. 32% HC1 (178 g) over 1 h. During the acidification, CO2 was emitted.
  • Bacteria are cultured in EPRI medium supplemented with Hutners mineral solution and glucose (0.2%) . Microorganisms are incubated at room temperature (22°C) , under aerobic conditions with shaking.
  • a biofilm culture system includes polystyrene 24- well plates that are treated with protein to enhance attachment and growth of biofilm bacteria according to the method described in Davies DG, Marques CN, 2009, J Bacteriol 191:1393-1403.
  • a treatment consists of 100 pL of 310 nM CAA and brominecontaining biocide (or bromine-containing biocide alone in the comparative treatment) , at concentrations used in commercial water treatment (e.g., from 5 to 15 ppm) , water can be used as a carrier, for a contact time determined by activity of each biocide and ranging from 1 hour to 24 hours.
  • the medium from each well is removed by pipet and 1 mL of DE neutralization broth is added in order to stop the treatment. Bacteria from each well are then removed by scraping the biofilm formed in the well with a sterile cellscraper, and 1.0 mL of culture is transferred to chilled (4°C) 9.0 mL DE neutralizing broth and homogenized for 15 seconds at 40,000 rpm on ice. Further dilutions are performed prior to enumeration (further neutralizing biocide activity) . Recovery of bacteria is tested at different dilutions of biocide in water, in LB medium with thioglycolate and in DE neutralizing broth to ensure the active agent has been properly neutralized. Viable bacteria are enumerated via the drop plate method.
  • Each bromine-containing biocide is evaluated using 24-well plates, equally divided to control cultures (Ctl) inoculated with P. aeruginosa but not treated, a CAA minus test (-CAA) treated with bromine-containing biocide only, and a CAA plus test treated with bromine-containing biocide and CAA (+CAA) .
  • the ef ficacy test on the coupons is performed according to the single tube method (E2871- 13 ) .
  • This test method is used for growing a reproducible P. aeruginosa biofilm in a CDC Biofilm Reactor .
  • the biofilm is established by operating the reactor in a batch mode (no flow of the nutrients ) for 4 hours . A steady state population is reached after the reactor operated for an additional 3 days with continuous flow of the nutrients . During the entire 3-day period, the bio film is exposed to continuous fluid shear from the rotation of a baf fertil stir bar . At the end of the 3 days , the biofilm from the coupons is sampled as follows : a . The coupons are rinsed to remove planktonic cells . The rods are oriented in a vertical position directly over a 50 mL conical centri fuge tube which contains 30 mL sterile buf fered water .
  • the rods are immersed with a continuous motion into the buf fered water with minimal to no splashing, then immediately removed .
  • a new 50 mL conical tube containing 30 mL sterile buf fered water is used for each rod .
  • the rods are held with one of the randomly selected coupons centered over an empty, sterile 50 mL conical tube .
  • the set screws are loosened, allowing the coupons to drop directly to the bottom of the tube .
  • Sequential addition of CAA and bromine-containing biocide a.
  • the combined treatment is carried out as a sequential treatment in which CAA is introduced first, and after 1 hour contact time with CAA, the coupons are transferred to another tube containing the biocide and incubated at 20 °C, under shaking of 200 rpm for another 1 hour contact time. After the one-hour contact time, 36 ml of a neutralizer are added to each tube.
  • Biofilms were grown using the CDC Biofilm Reactor, as detailed above , utili zing the Pseudomonas aeruginosa strain ATCC 700888 .
  • the Single Tube Method described above was used to evaluate the ef ficacy of the agents used against the Pseudomonas aeruginosa biofilm, alone or in combination, according to the sequential application protocol described above . Briefly, the single tube experiment was carried out by first adding the fatty acids solution to the tube , at a concentration of 310 nM, for one hour . After one hour , the treated coupon was moved to a second tube , containing a biocide solution in the desired concentration .
  • the bromine-based biocide tested in this study was Bromosol® ( stabili zed bromine ) .
  • the biocide Bromosol® ( at 5 mg/L or 5 ppm) when applied alone , reduced the total count of bacteria in the biofilm by about three log units .
  • the total count reduction improved by additional ⁇ 3 log units with respect to the ef fect of the biocide acting alone .
  • a total count reduction of about 6 . 5 log units as compared to the control was obtained .
  • Example 2 Enhancing the effect of a bromine-based biocide on massive biofilm with the aid of cis-2-undecenoic acid
  • the inventors have next examined the ef fect of cis-2-undecenioc acid (CUDA) in improving the ef ficacy of various biocides on biofilm removal and prevention, as detailed below .
  • CUDA cis-2-undecenioc acid
  • Biofilms were grown using the CDC Biofilm Reactor, as detailed above , utili zing the Pseudomonas aeruginosa strain ATCC 700888 .
  • the Single Tube Method detailed above was used to evaluate the ef ficacy of the agents used against the Pseudomonas aeruginosa biofilm alone or in combination, according to the sequential application protocol described above .
  • the single tube experiments were performed by first adding the fatty acids solution to the tube in the desired concentration for one hour . After one hour the coupon was moved to a second tube containing a biocide solution in the desired concentration, for an additional incubation of 1 hour .
  • the bromine-based biocide tested in this study was Bromosol® ( stabili zed Bromine , at 5 mg/L or 5 ppm) .
  • Figure 3 is a bar graph showing that Bromosol® at 5 mg/L ( 5 ppm) reduced the total count of bacteria in the biofilm by about 3 log units .
  • Cis-2-undecenioc acid was shown to improve the ef ficacy of Bromosol® for biofilm removal , as demonstrated in Figure 3 .
  • the total count reduction improved by additional 2 . 5 log units .
  • a total count reduction of about 5 log units as compared to the control was obtained in the presence of the combination of the biocide and cis-2-undecenioc acid.
  • Example 3 Enhancing the effect of a bromine-based biocide on massive biofilm with the aid of cis-2-nonenoic acid
  • the inventors have next examined the ef fect of cis-2-nonenoic acid ( CNA) in improving the ef ficacy of various biocides on biofilm removal and prevention, as detailed below .
  • CNA cis-2-nonenoic acid
  • Biofilms were grown using the CDC Biofilm Reactor, as detailed above , utili zing the Pseudomonas aeruginosa strain ATCC 700888 .
  • the Single Tube Method detailed above was used to evaluate the ef ficacy of the agents used against the Pseudomonas aeruginosa biofilm alone or in combination, according to the sequential application protocol described above .
  • the single tube experiments were performed by first adding the fatty acids solution to the tube in the desired concentration for one hour . After one hour the coupon was moved to a second tube containing a biocide solution in the desired concentration, for an additional incubation of 1 hour .
  • the bromine-based biocide tested in this study was Bromosol® ( stabili zed Bromine , at 5 mg/L or 5 ppm) .
  • Figure 4 is a bar graph showing that Bromosol® at 5 mg/L ( 5 ppm) reduced the total count of bacteria in the biofilm by about 3 log units .
  • Cis-2-nonenoic acid was shown to improve the ef ficacy of Bromosol® for biofilm removal , as shown in Figure 4 .
  • the total count reduction improved by additional ⁇ 2 log units .
  • a total count reduction of about 4 . 5 log units as compared to the control was obtained in the presence of the combination of the biocide and cis-2-nonenoic acid.
  • Example 4 Enhancing the effect of a bromine-based biocide on massive biofilm with the aid of cis-2-octenoic acid
  • the inventors have next examined the ef fect of cis-2-octenoic acid ( COA) on improving the ef ficacy of various biocides in biofilm removal and prevention, as detailed below .
  • COA cis-2-octenoic acid
  • Biofilms were grown using the CDC Biofilm Reactor, as detailed above , utili zing the Pseudomonas aeruginosa strain ATCC 700888 .
  • the Single Tube Method detailed above was used to evaluate the ef ficacy of the agents used against the Pseudomonas aeruginosa biofilm alone or in combination, according to the sequential application protocol described above .
  • the single tube experiments were performed by first adding the fatty acids solution to the tube in the desired concentration for one hour . After one hour the coupon was moved to a second tube containing a biocide solution in the desired concentration, for an additional incubation of 1 hour .
  • the bromine-based biocide tested in this study was Bromosol® ( stabili zed Bromine , at 5 mg/L or 5 ppm) .
  • Figure 5 is a bar graph showing that Bromosol® at 5 mg/L ( 5 ppm) reduced the total count of bacteria in the biofilm by about 3 log units .
  • Cis-2-octenoic acid was shown to improve the ef ficacy of Bromosol® for biofilm removal , as demonstrated in Figure 5 .
  • the total count reduction improved by additional one and a hal f ( 1 . 5 ) log units .
  • a total count reduction of about 4 log units as compared to the control was obtained in the presence of the combination of the biocide and cis-2-octenoic acid.

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Abstract

L'invention concerne des procédés et des compositions pour la lutte antimicrobienne de l'eau, en particulier pour éliminer les bactéries planctoniques et biofilm de celles-ci, à l'aide d'un biocide à base de brome en combinaison avec un acide cis-2-alcénoïque en tant qu'agent auxiliaire qui a été trouvé pour améliorer l'action du biocide.
PCT/IL2021/051428 2020-12-02 2021-12-01 Procédé et composition de traitement de l'eau WO2022118312A1 (fr)

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WO2023238135A1 (fr) * 2022-06-08 2023-12-14 Bromine Compounds Ltd. Préparation et purification d'acides cis-2-alcénoïques

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