[go: up one dir, main page]

WO2017221249A1 - Solutions anti-encrassement contenant du brome et de l'urée et des additifs amplificateurs - Google Patents

Solutions anti-encrassement contenant du brome et de l'urée et des additifs amplificateurs Download PDF

Info

Publication number
WO2017221249A1
WO2017221249A1 PCT/IL2017/050691 IL2017050691W WO2017221249A1 WO 2017221249 A1 WO2017221249 A1 WO 2017221249A1 IL 2017050691 W IL2017050691 W IL 2017050691W WO 2017221249 A1 WO2017221249 A1 WO 2017221249A1
Authority
WO
WIPO (PCT)
Prior art keywords
hbr
urea
solution
naocl
bromourea
Prior art date
Application number
PCT/IL2017/050691
Other languages
English (en)
Inventor
Shlomo Antebi
Chen Zolkov
Original Assignee
Bromine Compounds Ltd.
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Bromine Compounds Ltd. filed Critical Bromine Compounds Ltd.
Publication of WO2017221249A1 publication Critical patent/WO2017221249A1/fr

Links

Classifications

    • 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
    • A01N47/00—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom not being member of a ring and having no bond to a carbon or hydrogen atom, e.g. derivatives of carbonic acid
    • A01N47/08—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom not being member of a ring and having no bond to a carbon or hydrogen atom, e.g. derivatives of carbonic acid the carbon atom having one or more single bonds to nitrogen atoms
    • A01N47/28—Ureas or thioureas containing the groups >N—CO—N< or >N—CS—N<
    • 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
    • A01N59/00—Biocides, pest repellants or attractants, or plant growth regulators containing elements or inorganic compounds
    • 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
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00—Treatment of water, waste water, or sewage
    • C02F1/50—Treatment of water, waste water, or sewage by addition or application of a germicide or by oligodynamic treatment
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2303/00—Specific treatment goals
    • C02F2303/04—Disinfection

Definitions

  • the present invention relates to reducing or preventing bio-contaminations and biofilm formation in aqueous liquids or on surfaces in contact with aqueous liquids, comprising applying a mixture of halogenated species, particularly bromourea in mixtures with enhancing agents, such as bromourea with other brominated and/or chlorinated biocidal agents.
  • Biofouling is an undesired accumulation of organisms, such as animals, plants, fungi, algae, protozoa, and bacteria, or their products or products of their decomposition in liquid volumes or on wet surfaces. Particularly, biofouling comprises microorganisms, such as prokaryotes, protozoa, algae, and fungi. Biofouling is found in almost all circumstances where water based liquids are in contact with other materials. Biofouling is controlled by a variety of methods, including coating the endangered surfaces, or applying biocides in their vicinity.
  • biocidal effects may be better exploited in fighting biofilms or suspended microbes. It is another object of this invention to provide a relatively simple method for producing different biocides simultaneously, using precursors in an aqueous solution to be treated with NaOCl to obtain a mixture of halogenated molecules - the biocide itself.
  • industrial waters including waters comprising pulp & paper industries, water transfer systems, effluent waters, and water with high level of TOC.
  • the invention provides a process of disinfecting, removing biofouling, or preventing biofouling in a volume of an aqueous liquid or on a surface in contact with an aqueous liquid, comprising contacting said volume or said surface with an acidic aqueous composition containing urea, bromourea, and an enhancing additive, wherein said additive is selected from amides and N- brominated forms thereof.
  • Said aqueous composition contains, in one preferred embodiment of said process, water, urea, bromourea, HBr, and an amide or N-brominated form thereof.
  • the process of the invention comprises an acidic composition, wherein said aqueous composition contains urea, bromourea, HBr, an amide or N-brominated form thereof, and an additional acid adjusting the pH of the mixture to 6 or less.
  • Said additional acid may comprise an inorganic acid, preferably HC1, or organic acid.
  • Sulfamic acid which can be used as said enhancing additive, may also adjust the pH to the desired value.
  • Said aqueous composition contains in other preferred embodiment water, urea, bromourea, HBr, HC1, and an amide or N- brominated form thereof.
  • Said amide may be, for example, selected from sulfamic acid, cyanoacetamide, and dimethylhydantoin.
  • Said enhancing additive is at least partially brominated by the active bromine and contributes to the biochemical effects of the brominated, and eventually chlorinated, species present in the mixture on the organisms causing said biofouling.
  • the process comprises steps of i) providing an aqueous solution A comprising urea and HBr, and at least one enhancing additive selected from amides, HC1, sulfonamides, and imides, wherein the molar ratio of urea to HBr is at least 1; ii) providing an aqueous solution B comprising NaOCl at a molar concentration higher than the HBr concentration and lower than the sum of the concentrations of acids, when NaOCl is expressed as C12; iii) combining said solutions A and B, and optionally diluting the combined solutions, thereby obtaining an antibiofouling composition comprising bromourea (BU) and other products formed in the mixture including brominated form of said enhancing additive; and iv
  • BU bro
  • the process of the invention comprises steps of i) providing an aqueous solution A comprising urea, HBr, HC1, and at least one enhancing additive selected from amides, sulfonamides, and imides, wherein the molar ratio of urea to HBr is at least 1; ii) providing an aqueous solution B comprising NaOCl in an amount corresponding to a molar concentration of NaOCl that is higher than the molar concentration of HBr and lower than the sum of molar concentrations of said HBr, HC1, and other acids, when NaOCl is expressed as C12; iii) combining said solutions A and B, and optionally diluting the combined solutions, thereby obtaining an antibiofouling composition comprising bromourea (BU) and chlorourea (CU), and other products formed in the mixture including brominated form of said enhancing additive; and iv) contacting said volume or said surface with said antibiofouling composition, wherein
  • the molar ration of urea to HBr is preferably from 2 to 10.
  • Said HBr in said solution A has usually a concentration of up to 20%.
  • Said antibiofouling composition in said step iii usually comprises a concentration of the active halogen as Cl 2 of about 0.5%.
  • Said antibiofouling composition in said step iv comprises an efficient concentration of the active halogen as Cl 2 of between 0.5 and 100 ppm, such as between 5 and 50 ppm.
  • said additive is sulfamic acid. In other embodiments it may be cyanoacetamide, or dimethylhydantoin,
  • Said solution A comprises in some preferred embodiments urea, HBr, and HC1.
  • Said solution A comprises, in other embodiments, urea, HBr, HC1, and sulfamic acid.
  • Said solution A preferably comprises urea, HBr, and HC1, wherein said HBr and said HC1 are in a molar ratio of one or less, such as about 1:1.
  • Said enhancing additives have preferably a total molar concentration lower than said HBr, preferably lower than half of the HBr molar concentration.
  • Said solutions A and B may be provided in a batchwise manner or continuously, to be combined in situ. Said solutions A and B may be advantageously combined as two streams.
  • the invention provides an acidic biocidal antibiofouling composition
  • aqueous urea solution of up to 45 wt%, one other amide, HBr, HC1, and NaOCl, wherein the molar ratio of urea/HBr is at least 2, the molar ratio of the sum of HCl+HBr to NaOCl is greater than 1, and the molar ratio of said amide to said NaOCl is less than 0.5.
  • the invention provides an acidic biocidal antibiofouling composition preferably obtained by combining a mixture A consisting of water, urea at a concentration of up to 45 wt%, another amide, HBr, and HC1 with a mixture B consisting of water, NaOH, and NaOCl, wherein the molar ratio of urea/HBr is at least 2, the molar ratio of HC1 to HBr is greater than 1, the molar ratio of NaOCl to HBr is greater than 1, the molar ratio of NaOCl to the sum of HCl+HBr is less than 1, and the molar ratio of said amide to said HBr is less than 0.5.
  • the invention thus relates to disinfecting or removing biofouling, or preventing biofouling in a volume of an aqueous liquid or on a surface in contact with an aqueous liquid, comprising steps of providing an aqueous solution A comprising urea and HBr, and at least one component selected from HC1, other acids, amides, sulfonamides, and imides, wherein the molar ratio of urea to HBr is at least 2; providing an aqueous solution B comprising NaOCl in an amount corresponding to a molar concentration of NaOCl that is higher than the molar concentration of HBr and lower than the sum of molar concentrations of said HBr and other acids, when NaOCl is expressed as Cl 2 ; combining said solutions A and B, and optionally diluting the combined solutions, thereby obtaining an antibiofouling composition comprising bromourea (BU) and other products formed in the mixture, which combines a high stability of active halogen and
  • Said antibiofouling composition in said steps iii and iv has a concentration of active halogen as Cl 2 of up to 10%, such as between 0.5 and 5%, and after an eventual dilution for example between 0.0001 and 0.5%.
  • Said antibiofouling composition in said step iii comprises, in one embodiment of the invention, about 0.5% active halogen as Cl 2 .
  • Said antibiofouling composition in said step iv comprises, in one embodiment between 5 and 50 ppm, for example 15 ppm.
  • Solution A may comprise urea, HBr, HCl, and at least one component selected from other acids, amides, sulfonamides, and imides, wherein the molar ratio of urea to HBr is at least 2; said antibiofouling composition comprising bromourea (BU) and chlorourea (CU), which combines a high stability of active halogen and a high efficacy in removing biofilms.
  • Said other acid may be an inorganic acid or an organic acid supporting said HBr and HCl in neutralizing said solution B, which is strongly alkali.
  • Said amide may be, for example, cyanoacetamide.
  • Said amide or imide may be, for example, DMH.
  • Said acid is, in a preferred embodiment, sulfamic acid (which is also an amide and an acid).
  • solution A comprises urea, HBr, HCl, and sulfamic acid.
  • HBr and HCl have similar molar concentrations.
  • solutions A and B are provided in a batch process, and may be safely stored during prolonged time periods before use.
  • solutions A and B may be provided as two streams which are combined in situ, on the site of their use, possibly in a continuous manner.
  • the invention may also provide a biocidal composition
  • a biocidal composition comprising urea, HBr, HCl, optionally at least one component selected from other acids, amides, and imides, and NaOCl, wherein the molar ratio of urea to HBr is at least 1, and the molar ratio of NaOCl to the sum of said HBr, HCl, and other acids is less than 1, when NaOCl is expressed as Cl 2 .
  • urea is preferably present in a molar excess over the sum of all acids in the mixture.
  • the molar ratio of NaOCl to the sum of said HBr and HCl may be, for example 0.9.
  • the biocidal composition according to the invention usually comprises active halogen in a concentration of from 0.0001% to 10%.
  • compositions comprising at least two or three N-halohenated species are particularly efficacious in reducing bio-fouling, particularly compositions comprising bromourea and at least one or two other halogenated compound(s).
  • the compositions were prepared before the use by mixing an oxidizer with a non-active mixture comprising either i) urea, HBr and at least one enhancing additive, or ii) urea, HBr, HCl and at least one enhancing additive; wherein a preferred oxidizer is NaOCl and a preferred additive an amide.
  • compositions were prepared before the use by mixing chlorourea and/or bromourea with components selected from urea, HBr, HCl, and enhancing additives, such as amides.
  • enhancing additives such as amides.
  • Examples of efficient compositions contained bromourea and chlorourea in approximately equimolar amounts, together with enhancing additives.
  • the inventors believe that the presence of several halogenated species in the mixture improves the antibiofouling effects of the biocide, wherein the oxidation species include for example bromourea with bromosulfamate, or bromourea with chlorourea, or bromourea, chlorourea and bromosulfamate.
  • compositions In a biofilm model comprising bacterial cells entrapped in alginate gels, these compositions combined higher stability of active chlorine with higher efficacy of active bromine, when the active halogens were stabilized with urea and their efficacy enhanced by enhancing additives selected from amides.
  • the compositions can be advantageously prepared by combining solution B comprising NaOCl and solution A, wherein said solution A for various applications may be prepared by combining urea and HBr with one or more enhancing additives selected from sulfamic acid, HC1, amides, and imides.
  • compositions can be advantageously prepared by combining components selected from the group consisting of bromourea, chlorourea, urea, HBr, and enhancing additives selected from sulfamic acid, HC1, amides, and imides.
  • the invention provides a broad palette of compositions with desired stability and efficacy for various uses and environments.
  • bromourea can be formed by the reaction of a solution comprising urea and HBr with a solution comprising NaOCl
  • chlorourea can be formed by the reaction of a solution comprising urea and HC1 with a solution comprising NaOCl. It has been found that the mentioned reactions may advantageously be employed in parallel, for example by combining a solution A comprising urea, HBr and HC1 with solution comprising NaOCl (solution B). The technique can provide a broad palette of biocide formulations by combining various solutions with solution B.
  • anti-antifouling composition denotes an aqueous solution comprising bromourea prepared according to the present invention.
  • two simple components may be combined at the time when the biocide is needed or on the site on which it is needed, for example solution A comprising urea, HBr, and HC1 may be combined with solution B comprising NaOCl; a composition comprising BU and CU is produced when the molar ratio NaOCl/HBr is greater than 1.
  • the molar ratio of NaOCl/(HBr+HCl) is less than 1, for example 0.9.
  • the technique of combining two components may be expanded by including additional components modifying the parameters of the system to the desired direction, in one embodiment, without changing the nature of solution B. Thus, in one aspect, only the amount of solution B will be changed to fit the modified component A.
  • solution A comprises urea, HBr, and one or two enhancing additives selected from the group consisting of amides and acids, preferably consisting of amides and HCl, such as a group comprising sulfamic acid, HCl, acetamide, cyanoacetamide, cyanuric acid, isocyanuric acid, hydantoin, and dimethylhydantoin.
  • the molar amounts of the acids in solution A is higher than the molar amount of the NaOCl in solution B.
  • the molar amount of each of the additives is preferably lower than the molar amount of the NaOCl.
  • This technology allows the preparation of new aqueous biocidal combinations, exhibiting unique properties in fighting biofouling and microbial contaminations.
  • the properties may include fast killing of the microbes in suspension, preventing the biofilm formation, destructing the biofilm, or sustaining activity during prolonged contact times.
  • the process of disinfecting, or removing biofouling, or preventing biofouling in a volume of an aqueous liquid or on a surface in contact with an aqueous liquid comprises steps of i) providing an aqueous solution A comprising urea, HCl and/or HBr, and optionally at least one component selected from other acids, amides, sulfonamides, and from imides, wherein the molar ratio of urea to HBr is at least 1, preferably at least 2; ii) providing an aqueous solution B comprising NaOCl in an amount corresponding to a molar concentration of NaOCl that is higher than the molar concentration of HBr and lower than the sum of molar concentrations of said HBr, HCl, and other acids, when NaOCl is expressed as Cl 2 ; iii) combining said solutions A and B, and optionally diluting the combined solutions, thereby obtaining an enhanced antibiofouling composition comprising chlorour
  • this technology provides biocidal mixtures comprising bromourea and chlorourea (for example when HBr and HC1 are employed in said solution A), biocidal mixtures comprising bomourea, chlorourea, and N-bromosulfamic acid (for example when HBr, HC1, and sulfamic acid are employed in said solution A), or biocidal mixtures comprising bomourea, chlorourea, and halogenated DMH (for example when HBr, HC1, and DMH are employed in said solution A).
  • the mixtures contain a relatively low amount of HBr or HC1, whereas the acidity is provided by sulfamic acid.
  • the mixtures comprising sulfamic acid contain N-chlorosulfamic acid or N-bromosulfamic acid derivatives.
  • the present invention relates to reducing or preventing bio-contaminations and biofilm formation in aqueous liquids or on surfaces in contact with aqueous liquids, comprising applying a) bromourea in mixtures with other brominated enhancing additives or b) bromourea and chlorourea in mixtures with other brominated and/or chlorinated enhancing additives.
  • a) bromourea in mixtures with other brominated enhancing additives or b) bromourea and chlorourea in mixtures with other brominated and/or chlorinated enhancing additives.
  • Any of said brominated and chlorinated materials and additives are biocidal, but their combinations exhibit synergist increased or synergist actions.
  • Said step of applying may comprise mixing at least three components selected from bromourea, chloroures, urea, HBr, HC1, and enhancing additives such as amides; preferably, at least bromourea, urea, and enhancing additives are mixed, optionally with HC1.
  • Said step of applying may comprise mixing at least solution A and solution B, wherein said A comprises urea, HBr, and enhancing additives such as amides, and optionally HC1, and said B comprises NaOCl.
  • Said enhancing additive is preferably a compound comprising a moiety -ONR 1 - or having a formula NH2 _ R 2 , wherein R 1 is H or C, and R 2 is acyl (a moiety derived by the removal of hydroxyl groups from an oxoacid acid).
  • Bromourea and chlorourea are formed in the composition according to the invention from urea and HBr, or from urea and HC1, by oxidation with NaOCl; alternatively, bromourea and/or chlorourea may be prepared from urea and elemental bromine or chlorine, and then mixed with other components selected from urea, HBr, and enhancing additives.
  • a biocidal composition is formed on the site where biofouling is to be eliminated or prevented by combining two or more solutions, while avoiding the use of elemental halogens.
  • solutions A and B are combined before the use, wherein B comprises an oxidizer, preferably NaOCl, and B comprises urea, HBr, and enhancing additives.
  • B comprises an oxidizer, preferably NaOCl
  • B comprises urea, HBr, and enhancing additives.
  • at least two components are mixed before the use, one of which comprises bromourea, either solid or in solution.
  • liquid and solid components are mixed or diluted according to the desired final concentrations.
  • the biocidal composition is preferably formed before the use, either near the site of the antibiofouling action or by mixing liquid streams directly in situ.
  • a stable solution A and a stable solution B are combined before the use, wherein said solution B comprises at least urea, HBr, and an enhancing additive! in other embodiment, said solution B comprises urea, HBr, HCl, and an enhancing additive.
  • the biocidal composition being prepared before the use comprises at least urea, bromourea, and an enhancing additive, optionally with HCl.
  • the enhancing additive preferably comprises an amide. The sum of the acids is in a molar excess over the oxidizer. Each of the additives is in a lower molar amount than the oxidizer.
  • the invention provides a number of new biocide formulations, each having a unique efficacy and chemical composition; each component in the composition contributing to the overall effect to fight microbes.
  • the aim is fast microbes killing in suspension, destruction of the existing biofilm and continued biocidal activity during a longer contact time, and prevention of the biofilm formation.
  • the method of the invention provides mixtures of brominated moieties, such as N-brominated moieties, and mixtures of brominated moieties and chlorinated moieties; for example, the mixtures may comprise bromourea and chlorourea, or bromourea and N-bromosulfamic acid, or bromourea with chlorourea and N-bromosulfamic acid.
  • the method provides a mixture of bromourea, chlorourea, and N-bromosulfamic acid after combining solution A containing HBr, HCl, and sulfamic acid with solution B comprising NaOCl.
  • solution A may be prepared from solutions of components or from solids by mixing of urea, HBr, and additives selected from amides and HC1, and solution B consists of alkali aqueous NaOCl.
  • Solution A may comprise, in one preferred embodiment, beside urea and HBr, sulfamic acid, DMH, cyanuric acid, cyanoacetamide, or other amide.
  • Solution A may comprise, in other preferred embodiment, beside urea and HBr, also HC1 and further an amide selected from sulfamic acid, DMH, cyanuric acid, or cyanoacetamide.
  • the amount of NaOCl will change in accordance with the composition of the final required composition.
  • the simplicity of the method and the diversity of the biocide combinations complies with the need of new combinations for fighting the biofouling problem.
  • the mixture of brominated amides, as well as the mixture of brominated and chlorinated amides, comprising synergist effects provides a rich supply for the high demand.
  • the mixture comprises bromourea and chlorourea in a molar ratio of about 1:1.
  • the biocidal effects were verified, among others, on alginate beads with entrapped bacteria, for example at values of TOC about 50 ppm.
  • the tests for the above combinations showed that they the method is extremely powerful, and exhibits combined effects both toward microbes in solution and toward biofilms, enabling both preventing and eliminating the biofouling phenomenon.
  • Various demands may be easily satisfied, for example, by simply combining the recited basic chemicals in solution A with solution B in various amounts to produce the requested biocides.
  • the invention utilizes the antifouling action of chlorourea and bromourea with enhancing additives, providing better results in comparison to the separate use of components.
  • the method of the invention allows the preparation of biocide solutions for various tasks, including fast-killing in a microbe suspension, preventing a biofilm formation, eliminating biofilms, or providing a prolonged protective activity.
  • the solutions comprise a mixture of bromourea and chlorourea, when HBr and HC1 are used in solution A, or a mixture of bromourea, chlorourea and N-bromosulfamic acid, when HBr, HC1 and sulfamic acid were included in solution A.
  • the biocidal efficacy of the tested materials was examined at an organic load solution of 50 ppm TOC (comprised of Tryptone), at different biocide concentrations (0, 5, 10 and 15 ppm, expressed as total active chlorine) at pH 7.
  • the inoculum of the tested bacteria was taken from an activated sludge (from Domestic Waste Water treatment Plant - Naharia). After contact times of 3, 24 and 48 hours of shaking (100 rpm) at 30°C, the biocide was neutralized and the solution was diluted and inoculated on a R2A agar (pour plate method). After the plates were incubated at 25°C for 5-7 days, the bacteria count was recorded. Table 1-2 describe the surviving colony forming units (CFU) of the bacteria after different biocides treatment at different contact times.
  • CFU colony forming units
  • the 1 st mixture contained urea, HBr, and NaOCl in the molar ratios of 2 : 1.1 : V, as the hypochlorite oxidizes the bromide to hypobromite, the active halogen is mainly comprised in bromourea (abbreviated as BU).
  • BU bromourea
  • the 2 nd mixture contained urea, HBr, HC1, sulfamic acid, and NaOCl in the molar ratios of 4 : 1 : 1 : 0.4 : 1.9; the active halogen is comprised in bromourea and chlorourea (abbreviated CU) in a molar ratio of about 1 1, and also in N- bromosulfamate.
  • the 3 rd mixture contained urea, HBr, HC1, and NaOCl in the molar ratios of 4 : 0.5 : 3 : 1, ' bromourea and chlorourea being in a molar ratio of about 1 ⁇ 1.
  • the 4 th mixture contained urea, HC1, and NaOCl in the molar ratios of 2 1.1 1, ' the active halogen is comprised in chlorourea.
  • the 5 th mixture contained a hypobromite stabilized with sulfamic acid sodium salt (resulting in N-bromo-sulfamic acid sodium salt, abbreviated Br- sulfamate) prepared according to WO03/093171. Each mixture was diluted to provide the same active halogen concentration.
  • the results for the contact times between the bacteria and the biocide of 3 hrs., 24 hrs., and 48 hrs. are presented in Tab. 1, Tab. 2, and Tab. 3, respectively.
  • Table 3 Biocidal efficacy of active halogen solutions against inoculum taken from activated sludge (TOC 50 ppm) after 48 hrs. contact time; the effect of five biocidal solutions, providing the same active halogen concentration of between 0 and 15 ppm (expressed as active chlorine), on the bacterial count (in colony forming units per ml) in the aqueous mixture is examined.
  • a biofilm simulation system alginate beads, developed by the Biofilm Bozeman Institute Montana (Grobe, K.J, Zahller, J and Stewart P.S., 2002 in "Role of dose concentration in biocide efficacy against Pseudomonas Aaeruginosa Biofilms", J. Industrial Microbiology & Biotechnology, vol. 29, pp 10-15), was used in order to evaluate the efficacy of biocidal solutions against biofilm.
  • the biofilm simulation system comprised entrapping bacteria in alginate gel beads.
  • a plate of R2A agar was streaked with Pseudomonas aeruginosa (ATCC 15442) and incubated at 35°C overnight.
  • Buffer phosphate, pH 7.2 was used to scrap off the bacteria from the agar plate and to create a suspension.
  • the bacterial suspension was mixed with an equal volume of an aqueous 4% sodium alginate solution, to make a final 2% alginate solution.
  • the alginate and bacterial slurry were placed in a 50 ml syringe attached to a gauge needle (22), connected to a compressed air tank, allowing the syringe to be pressurized.
  • the supernatant of the beads buffer suspension containing 5mM CaC was decanted and replaced by the 100 ml biocide solution with the required concentration.
  • 10 beads were removed and placed in a 5 g/1 sodium thiosulfate solution containing 50mM sodium citrate.
  • the sodium citrate was used to dissolve the alginate gel and release the bacteria into the solution.
  • the neutralizer-citrate solution was placed in the refrigerator for 2 hours, than diluted and placed on R2A agar plates using pour plate technique. The plates were incubated at 35°C for 24-48 hours and counted. The efficacy and toxicity of the neutralizer were checked as well as a control experiment without biocide addition.
  • Various biocide concentrations and various contact times were tested. The following table shows the biocidal effects of active halogen concentration of 0.75 ppm for contact times up to 48 hours.
  • the 1 st mixture contained urea, HBr, HCl, and NaOCl in the molar ratios of 2 : 1.1 : 0 : V, as the hypochlorite oxidizes HBr to HOBr, the active halogen is mainly comprised in bromourea (abbreviated as BU).
  • the 2 nd mixture contained urea, HBr, HCl, and NaOCl in the molar ratios of 5 : 1 : 2 : 1.25; the active halogen is comprised in chlorourea and bromourea (abbreviated CU) in a molar ratio of CU : BU of about 0.25 : 1.
  • the 3 rd mixture contained urea, HBr, HCl, and NaOCl in the molar ratios of 3 : 1 : 2 : 1.5; the active halogen is comprised in chlorourea and bromourea in a molar ratio of about 0.5 : 1.
  • the 4 th mixture contained urea, HBr, HCl, and NaOCl in the molar ratios of 4 : 0.5 : 3 : V, the active halogen is comprised in chlorourea and bromourea in a molar ratio of CU : BU about 1 : 1.
  • Table 4 clearly demonstrates the advantage of a roughly equimolar ratio of CU and BU in the biocidal mixture.
  • bromourea alone reduces the bacterial load within the beads by more than two orders (from 10 6 to 10 4 ); when admixing to BU 1 ⁇ 4 or 1 ⁇ 2 moles of CU, relatively to BU, the bacterial load within the beads decreased by two more orders (to 10 2 instead of to 10 4 ); however, when admixing BU to CU to an equimolar ratio, the residual amount of bacteria within the beads decreased nearly to zero.
  • Various biocidal mixtures comprising urea, HBr, HCl, NaOCl, and eventually sulfamic acid or DMH, were prepared as described in the following examples.
  • Solution B 9.9 % aq. NaOCl (5.06g; 0.5 g as 100%, Mw 71, 7.06 mmol) was diluted with 45.1 g distilled water to a total of 50.15 g (as 1% NaOCl).
  • Solution A was added drop wise to a flask containing 47.7 g distilled- water, then solution B was added drop wise during 20 min.
  • 100 g of bromourea solution (orange) was obtained containing 0.45% as Cl 2 (90.4% from theoretical 0.5%).
  • pH 3.42 UV spectrum 268-267 nm. After 85 min 0.38% as Cl 2 was detected (76.2% from theoretical); after 4 hrs. and 11 min. 0.33% as Cl 2 (65.6% from theoretical), and after 22 hrs. 0.25% as Cl 2 (49.6% from theoretical); pH 2.38.
  • composition of solution 26.54% urea, 8.94% HBr, 4.03% HCl, 4.3 % sulfamic acid.
  • Solution B 11.2 % aq. NaOCl (8.54; 0.95g as 100%, Mw 71, 13.44 mmol) was diluted to 1% NaOCl with 86.7 g distilled water to a total of 95.26 g.
  • Solution A was added drop wise to a flask containing 88.6 g distilled-water, then solution B was added drop wise during 20 min.
  • composition of solution 35.8% urea, 6.08% HBr, 16.34% HC1.
  • Solution B 9.91% aq. NaOCl (5.06g; 0.5 g as 100%, Mw 71, 7.06 mmol) was diluted to 1% NaOCl with 45. lg distilled water to a total of 50.15 g.
  • Solution A was added drop wise to a flask containing 45.1 g distilled- water, then solution B was added drop wise during 20 min.
  • 100 g of a biocide solution comprising bromourea and chlorourea solution (orange) was obtained containing 0.5% as Cl 2 (98.4% from theoretical 0.5%). pH 0.97, UV broad peak 240-260 nm.
  • composition of solution 42.76 % urea, 11.52 %, HBr, 10.44% HC1.
  • Solution B 9.9% aq. NaOCl (6.325g; 0.63 g as 100%, Mw 71, 8.83mmol) was diluted to 1% NaOCl with 56 g distilled water to a total of 62.33 g.
  • Solution A was added drop wise to a flask containing 57.74 distilled-water, then solution B was added drop wise during 20 min. 125 g of solution
  • composition of solution 31.04% urea, 13.94% HBr, 12.63% HC1.
  • Solution B 9.9% aq. NaOCl (7.6 g; 0.75 g as 100%, Mw 71, 10.59mmol) was diluted to 1% NaOCl with 67 g distilled water to a total of 74.6 g.
  • Solution A was added drop wise to a flask containing 71.3 distilled-water, then solution B was added drop wise during 20 min. 150 g of solution
  • Solution B 11.2 % aq. NaOCl (8.54; 0.95 g as 100%, Mw 71, 13.44 mmol) was diluted to 1% NaOCl with 86.72 g distilled water to a total of 95.26 g.
  • Solution A was added drop wise to a flask containing 91 g distilled- water, then solution B was added drop wise during 20 min. 190.4 g of solution (orange) comprising bromourea, chlorourea and possibly brominated DMH, was obtained containing 0.48% as Cl 2 (96% from theoretical 0.5%). pH 4.29, UV- not distinct.
  • Solution B 10.5% aq. NaOCl (9.1; 0.95 g as 100%, Mw 71, 13.44 mmol) was diluted to 1% NaOCl with 86 g distilled water to a total of 95.1 g.
  • Solution A was added drop wise to a flask containing 91.7 g distilled- water, then solution B was added drop wise during 20 min. 190.3 of solution (orange) comprising bromourea chlorourea and possibly Bromo-DMH was obtained, containing 0.50% as Cl 2 (100% from theoretical 0.5%). pH 4.44. After 54 min 0.48% as Cl 2 (81% from theoretical) was detected. pH 2.64. After 226 min 0.40% as Cl 2 (91% from theoretical 0.5%); after 22 hrs. 0.23% as Cl 2 (46% from theoretical), pH 1.9;
  • composition in solution 24.82% urea, 29.33% HBr, 13.31% DMH.
  • Solution B 10.5% aq. NaOCl (6.72; 0.71g as 100%, Mw 71, 9.94 mmol) was diluted to 1% NaOCl with 63.5 g distilled water to a total of 70.2 g.
  • Solution A was added drop wise to a flask containing 64.7g distilled-water, then solution B was added drop wise during 20 min. 137.6 g of solution (orange) comprising bromourea and possibly bromo-DMH was obtained containing 0.52% as Cl 2 (117% from theoretical 0.5%). pH 6.28.
  • Solution A was added drop wise to a flask containing 91.6 g distilled-water, then solution B was added drop wise during 20 min. 190.83 g of solution (orange) comprising bromourea, chlorourea and possibly bromo-DMH was obtained containing 0.48% as Cl 2 (95% from theoretical 0.5%). pH 5.92;

Landscapes

  • Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Dentistry (AREA)
  • General Health & Medical Sciences (AREA)
  • Pest Control & Pesticides (AREA)
  • Plant Pathology (AREA)
  • Health & Medical Sciences (AREA)
  • Agronomy & Crop Science (AREA)
  • Chemical & Material Sciences (AREA)
  • Environmental Sciences (AREA)
  • Wood Science & Technology (AREA)
  • Zoology (AREA)
  • Inorganic Chemistry (AREA)
  • Hydrology & Water Resources (AREA)
  • Environmental & Geological Engineering (AREA)
  • Water Supply & Treatment (AREA)
  • Organic Chemistry (AREA)
  • Agricultural Chemicals And Associated Chemicals (AREA)

Abstract

L'invention concerne une composition désinfectante et anti-encrassement, ainsi qu'un procédé de lutte contre l'encrassement utilisant une composition aqueuse acide stable contenant du brome et de l'urée et des composants biocides bromés supplémentaires.
PCT/IL2017/050691 2016-06-22 2017-06-21 Solutions anti-encrassement contenant du brome et de l'urée et des additifs amplificateurs WO2017221249A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
US201662353201P 2016-06-22 2016-06-22
US62/353,201 2016-06-22

Publications (1)

Publication Number Publication Date
WO2017221249A1 true WO2017221249A1 (fr) 2017-12-28

Family

ID=60784390

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/IL2017/050691 WO2017221249A1 (fr) 2016-06-22 2017-06-21 Solutions anti-encrassement contenant du brome et de l'urée et des additifs amplificateurs

Country Status (1)

Country Link
WO (1) WO2017221249A1 (fr)

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2013059074A1 (fr) * 2011-10-21 2013-04-25 Nalco Company Biorégulation améliorée par l'intermédiaire de l'utilisation de mélanges chlore-agent stabilisateur
WO2013132492A1 (fr) * 2012-03-08 2013-09-12 Bromine Compounds Ltd. Procédé de préparation de compositions aqueuses biocides et antisalissures comprenant de l'acide bromhydrique, de l'urée et de l'hypochlorite de sodium

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2013059074A1 (fr) * 2011-10-21 2013-04-25 Nalco Company Biorégulation améliorée par l'intermédiaire de l'utilisation de mélanges chlore-agent stabilisateur
WO2013132492A1 (fr) * 2012-03-08 2013-09-12 Bromine Compounds Ltd. Procédé de préparation de compositions aqueuses biocides et antisalissures comprenant de l'acide bromhydrique, de l'urée et de l'hypochlorite de sodium

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
AMJAD ET AL., THE SCIENCE AND TECHNOLOGY OF INDUSTRIAL WATER TREATMENT, 31 December 2010 (2010-12-31), pages 121 *

Similar Documents

Publication Publication Date Title
CA2763586C (fr) Solutions de brome stabilisees et activees en tant que biocide et agent anti-encrassement
US4966716A (en) Method for the control of biofouling in recirculating water systems
CA2642113C (fr) Formulations contenant un biocide non oxydant et une source d&#39;halogene actif et son utilisation pour le traitement de l&#39;eau
EP0378659B1 (fr) Procede de regulation de biosalissures dans des systemes d&#39;eau a recirculation
US9420797B2 (en) Method for preparing biocidal aqueous compositions
CA2351619C (fr) Composition biocide et methode de sterilisation l&#39;utilisant
US20150208661A1 (en) Method for preparing bromine based biocidal aqueous compositions
JP2014100650A (ja) 微生物の増殖抑制方法
WO2017221249A1 (fr) Solutions anti-encrassement contenant du brome et de l&#39;urée et des additifs amplificateurs
JP2014176801A (ja) 微生物の増殖抑制方法
AU2015202057B2 (en) Stabilized and activated bromine solutions as a biocide and as an antifouling agent
US20150099014A1 (en) Method for preparing biocidal and antifouling aqueous compositions comprising hydrobromic acid, urea and sodium hypochlorite
Worley et al. Disinfecting water with a mixture of free chlorine and an organic N‐halamine
US20160366886A1 (en) Biocidal composition, preparation and methods of use thereof
JP6814917B2 (ja) 水系のスライム抑制方法
US20160192659A1 (en) Method for preparing biocidal and antifouling aqueous compositions comprising hydrobromic acid, urea and sodium hypochlorite

Legal Events

Date Code Title Description
121 Ep: the epo has been informed by wipo that ep was designated in this application

Ref document number: 17814896

Country of ref document: EP

Kind code of ref document: A1

NENP Non-entry into the national phase

Ref country code: DE

122 Ep: pct application non-entry in european phase

Ref document number: 17814896

Country of ref document: EP

Kind code of ref document: A1