Classifications

• • 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
  • C02F1/505—Treatment of water, waste water, or sewage by addition or application of a germicide or by oligodynamic treatment by oligodynamic treatment
• • 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
  • A01N59/16—Heavy metals; Compounds 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
  • A01N59/00—Biocides, pest repellants or attractants, or plant growth regulators containing elements or inorganic compounds
  • A01N59/16—Heavy metals; Compounds thereof
  • A01N59/20—Copper
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B82—NANOTECHNOLOGY
  • B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
  • B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites

Definitions

• the present invention relates to the use of an aqueous composition which contains an effective amount of a possibly organically coated nanometal powder of at least one element of group IB of the transition metals or an alloy of these elements with one another, optionally supplemented by hydrogen peroxide, as biocide.
• Copper (II) chloride and silver (II) chloride can be used against hospital germs such as Pseudomonas aeruginosa, Stenotrophomonas maltophilia and Acinetobacter baumannii (Hsin-I Huang et al., WATER RESEARCH 42 (2008) 73-80.
• water disinfection can be carried out by using UV disinfection or chemical disinfection systems (see DVGW_W290, drinking water disinfection - application and requirement criteria).
• DE102009056452A1 relates to a method for the treatment of fire-extinguishing water in a fire extinguishing system by means of a Bioziods in a non-harmful concentration.
• the only biocide is an isothiazolinone.
• This substance class is known for their allergies according to Googlerecherche. This applicant proposes in his catalog 2010, on page 84, a use exclusively in open systems, the biocide is not suitable as corrosion protection for steel and federal metals.
• DE102005046252A1 is intended to relate to a process for the antibacterial treatment of water in which silver pigments are metered into the water. What is understood by silver pigment, is not explained in the application, also an embodiment with the note which pigment source (manufacturer, trade name) in which purity, which particle size, concentration, etc. is used, as well as a credible made antibacterial effect.
• WO2009 / 088316A1 relates to a biocide for the protection of liquid media in hydrocarbon production, the biocide being derived from Group IB metals of the transition metals, which are in the form of ions or clusters to which stabilizers must be added (claim 1, page 6f). From technical water-contacting devices, especially in pipes, containers and on surfaces, the water can not be completely removed at a reasonable cost, so that a residual moisture and thus wetted with a water film surfaces remain.
• Biofilms can form under unfavorable conditions in pipes, containers and on surfaces. These biofilms are well protected against disinfectants, as this is a system property of biofilms to planktonically occurring microorganisms.
• the biofilm offers a protective cover, the biocide concentration can not or does not completely penetrate. Due to dead spaces and niches once established biofilms are extremely difficult or impossible to remove. This object is achieved by providing an aqueous composition containing a biocidally effective amount of a specific metal powder.
• the invention thus relates to the use of an aqueous composition
• an aqueous composition comprising an effective amount of an optionally organically coated metal powder of at least one element of group IB transition metals having a purity of at least 90%, preferably 99%, or an alloy of these elements, this element as contains its main component, wherein the particle size of the metal powder is less than 1250 nm, preferably less than 200 nm, as a biocide, optionally with conventional auxiliaries and additives. With a preferred particle size of less than 10 nm, even a sedimentation of the nanoparticles can be largely excluded.
• This composition is more stable and has a depot effect in technical devices, in particular in pipes, containers and on surfaces. Through this depot effect a recontamination / germination after filling or wetting with water by germs / spores is prevented. This precludes further germination / germination and / or biofilm formation in the tubes, containers and on surfaces during a stagnation or stagnation phase.
• This composition is durable even at high temperatures.
• the silver and copper concentrations are present in the fluid in such low concentrations that they pose no hazard.
• the water is removed from the pipes, containers and surfaces with disinfectant.
• the use of the bactericidal composition in the tubes, containers and on surfaces prevents the formation of biofilms and can cause germination in the water. During commissioning, residual / stagnant water is removed from the pipes, containers and surfaces.
• Advantages of this composition used as biocide are also no or a smaller amount of hydrogen peroxide. Due to the lower concentrations, oxidation-sensitive components (brass, bronze) are less stressed.
• the composition of the invention is more effective because it is more stable.
• the compositions have a high bactericidal activity against pathogens and other bacteria and a long-lasting effect (depot effect).
• the longer stability prevents biofilm formation in pipes, containers and on surfaces.
• the composition is a more stable product, which not only disinfects the water or the process solution, but because of the higher stability offers a depot effect and thus protects the tubes, containers and surfaces from biofilm formation.
• the use of disinfectants has been limited to the disinfection of water.
• the depot effect of the combination product ensures protection against re-contamination of the water in pipes, containers and on surfaces during prolonged periods of stagnation or downtime. It also prevents biofilms from forming that can not be removed.
• the advantage is that the biocidal composition is active even after prolonged stagnation or downtime and prevents recontamination and biofilm formation.
• the composition is characterized in that the element of group IB is the metal powder copper and / or silver or an alloy of these elements.
• a silver alloy for example, those with a silver content of 80% by weight or 92.5% by weight into consideration.
• the composition is characterized in that the organic coating is a water-swellable hydrocolloid.
• the effective amount of metal powder is 0.005 mg to 1 mg, preferably 0.01 mg to 0.5 mg, in 1 L of water.
• the composition further comprises hydrogen peroxide, wherein the weight ratio of hydrogen peroxide to metal powder is 10,000 to 1 to 500 to 1, preferably 5000 to 1 to 1000 to 1.
• the composition further contains 0.001 to 5 parts by weight, in particular 0.01 to 0.5 parts by weight, based on 100 parts by weight of the composition of a stabilizer selected from nonionic surfactants, citrates and / or synthetic water-soluble polymers and / or contains 0.00001 to 0.001 parts by weight, in particular 0.0001 to 0.005 parts by weight, based on 100 parts by weight of the composition of a corrosion inhibitor selected from orthophosphates, polyphosphates and / or silicates.
• a stabilizer selected from nonionic surfactants, citrates and / or synthetic water-soluble polymers
• a corrosion inhibitor selected from orthophosphates, polyphosphates and / or silicates.
• Suitable nonionic surfactants are, for example, those of the sulfonate and sulfates type.
• Sulphonate-type surfactants include alkylbenzenesulfonates (C6- C18 -
• Alkyl and olefinsulfonates ie mixtures of alkene and hydroxyalkanesulfonates and disulfonates, as obtained for example from C 12 -C 18 monoolefins with terminal or internal double bond by sulfonation with gaseous sulfur trioxide and subsequent alkaline or acidic hydrolysis of the sulfonation in consideration.
• alkanesulfonates from C 12 -C 18 alkanes by sulfochlorination or sulfoxidation and subsequent
• Suitable surfactants of the sulfate type are the sulfuric acid monoesters of primary Alcohols of natural and synthetic origin, ie from fatty alcohols such as coconut oil fatty alcohols, tallow fatty alcohols, oleyl alcohol, lauryl, myristyl, palmityl or Stearylalkoho ⁇ or the Cio-C2o-Oxoal-koholen, and those secondary
• the sulfuric acid monoesters of the long-chain primary and secondary alcohols ethoxylated with 1 to 6 mol of ethylene oxide (ether sulfates) are also suitable.
• sulfated fatty acid monoglycerides are also suitable.
• Particularly suitable are natural fatty acids, e.g. Coconut, palm kernel or tallow fatty acid derived soap mixtures. Preference is given to those which are composed of 50 to 100% of saturated C 10 -to fatty acid soaps and 0 to 50% of oleic acid soap.
• the anionic surfactants can be present in the form of their sodium, potassium and ammonium salts and as soluble salts of organic bases, such as mono-, di- or triethanolamine.
• the sodium salts are used.
• nonionic surfactants and alkyl glycosides of the general formula R-0- (G) x can be used in which R is a primary straight-chain or methyl-branched in the 2-position aliphatic radical having 8 to 22, preferably 12 to 18 carbon atoms, G a Is a symbol which stands for a glycose unit having 5 or 6 C atoms, and the degree of oligomerization x is between 1 and 10.
• an addition of 0.001 to 5 parts by weight, in particular 0.01 to 0.5 part by weight, based on 100 parts by weight of the composition is suitable.
• the water-soluble alkali metal salts may be used singly or in combination, with the sodium side rate and its hydrates being preferred, and trisodium citrate and its hydrates being particularly preferred.
• citrates an addition of 0.001 to 1 part by weight, especially 0.01 to 0.5 part by weight based on 100 parts by weight of the composition is suitable.
• water-soluble polymers is preferably polyvinylpyrrolidone (PVP) into consideration, with a concentration of 0.01 g / ml PVP is particularly suitable.
• PVP polyvinylpyrrolidone
• Suitable corrosion inhibitors are the ortho-phosphate monosodium dihydrogen phosphate, disodium monohydrogen phosphate,
• Trisodium phosphate monopotassium dihydrogen phosphate
• Suitable silicates are sodium silicate with a molar ratio of SiO 2 / Na 2 O of about 1.5 to 4.0. These substances can be used individually or as a mixture or mixtures of both phosphate salts.
• 0.00001 to 0.001 parts by weight is suitable.
• Preferred fürskonzentra tion is 1 mg / L orthophosphate, 1mg / L polyphosphate and 4 mg / l S1O2, so a total of 1 part of total phosphorus and 2 parts of silicate. If orthophosphates and / or polyphosphates are used, an additional use of stabilizers, such as surfactants, is not required.
• the hydrogen peroxide is present as 1 wt% to 35 wt% solution and the metal powder in separate containers.
• the biocide is used to prevent / minimize germs / germination and biofilm formation in / on water-related surfaces, pipes and containers.
• the surfaces, pipes and / or containers are those of devices, in particular pump test stands, pumps, pressure booster systems, drinking and fire extinguishing lines, air conditioning and cooling towers, air and water filters and other applications for drinking water or Process water in the food industry, in particular meat processing, the dairy industry, the beverage industry, the cosmetic, pharmaceutical and pharmaceutical industries medical technology industry, fish farming, aquaculture, agriculture, in the wellness area including swimming pools and sauna, in the area of hospitality and accommodation and care of persons.
• the biocide kills pathogenic microorganisms such as bacteria, fungi, viruses, protozoa and algae, in particular the bacteria E. coli, Pseudomonas aeruginosa, Enterococcus spec, coliforms, Legionella Spec, Salmonella spec, Shigella spec, Mycobacterium spec, Yersinia spec. Vibrio spec. from.
• pathogenic microorganisms such as bacteria, fungi, viruses, protozoa and algae
• pathogenic microorganisms such as bacteria, fungi, viruses, protozoa and algae, in particular the bacteria E. coli, Pseudomonas aeruginosa, Enterococcus spec, coliforms, Legionella Spec, Salmonella spec, Shigella spec, Mycobacterium spec, Yersinia spec. Vibrio spec. from.
• the water is a drinking water, a raw water or a process water.
• the biocide-treated water has no germs of E. coli, Pseudomonas aeruginosa, enterococci and coliform bacteria per 100 ml, preferably per 250 ml.
• the water treated in this way corresponds, for example, to the TrinkwV 2001 and comparable standards abroad.
• the present invention further relates to a method of using the aforementioned biocide.
• the metal powder is prepared by the standard citrate method of soluble metal salts of group IB in situ by means of trisodium citrate, in addition 0.001 to 5 parts by weight, in particular 0.01 to 0.5 parts by weight based on 100 parts by weight of the composition of a stabilizer selected from nonionic surfactants, citrates and / or synthetic water-soluble Polymers and / or 0.00001 to 0.001 parts by weight, in particular 0.0001 to 0.005 parts by weight, based on 100 parts by weight of the composition of a corrosion inhibitor selected from orthophosphates, polyphosphates and / or silicates added.
• a stabilizer selected from nonionic surfactants, citrates and / or synthetic water-soluble Polymers
• a corrosion inhibitor selected from orthophosphates, polyphosphates and / or silicates added.
• a commercially available solid nano-metal powder is used for the preparation of the aqueous composition according to the invention, dispersion prior to use must be carried out, for example by means of ultrasound, and stabilizers should be added, as explained below.
• the nano metal powder is prepared in situ from trisodium citrate by the standard citrate method of Group IB soluble metal salts, a dispersion stabilized by citrate is formed directly.
• the biocide is present in concentrated form as an application set in two separate, preferably reclosable containers, wherein both containers preferably each have a graduated scale, optionally together with application aids, such as e.g. Plastic gloves, goggles.
• application aids such as e.g. Plastic gloves, goggles.
• These containers are for example made of glass or plastic.
• MO denotes a biocide-free sample (blank sample)
• M1 to M3 relate to comparative examples with pure hydrogen peroxide of different concentration and origin and M4 to M8 biocidal compositions according to the invention.
• the subsamples were stored refrigerated between preparation of the preparations and use. Two sub-samples of the preparations and the reference sample (tap water without any additives) were taken (each 2x30 ml in sterile 50 ml Falcon tubes with lid) and treated with two germs, which were to serve as microbial water load model microorganisms. The following germs were used:
• DSM 1128 water u. soil bacterium Before loading, the living cell count of the inoculum was determined by plating:
• test parameters or test methods were used:
• MO The number of bacteria in E. coli and P. aeruginosa decreases continuously until the time of collection t3. From t4 no test germs are detectable. The dying off of test germs in tap water can be explained, for example, by chlorine in the water used.
• E. coli showed increased growth of other germs in the range> 10,000 CFU / ml in the test series.
• foreign germs in the range of> 100,000 CFU / ml were found after 28 days.
• E. coli was no longer detectable at t1 in this approach.
• the concentration of P. aeruginosa initially decreased and was initially no longer detectable at time t2. With the withdrawals from t3 (after 24 h, 15 d, 28 d), however, P. aeruginosa could be detected again.
• E. coli was no longer detectable at t1 in this approach.
• the concentration of P. aeruginosa initially decreased and was initially no longer detectable at time t1.
• the number of germs increased again and stabilized at removal t4 at approx. 103 CFU / ml.
• P. aeruginosa used no adequate preservative effect could be detected.
• Fig. 1 a cone of pump housing made of gray cast iron GJL 250 after 4 months of storage in an aqueous composition of 2 wt .-% H 2 O 2 and 0.1 ppm nano-Ag.
• Fig. 2 a cone of pump housing made of cast iron GJL 250 after 4 months of storage in an aqueous composition of 150 ppm H2O2 and 0.1 ppm nano-Ag.
• Fig. 3 a cone of pump housing made of gray cast iron GJL 250 (magnification) after 4 months of storage in an aqueous composition of 2 wt .-% H 2 0 2 and 0.1 ppm nano-Ag.
• Fig. 4 a cone of pump housing made of gray cast iron GJL 250 (magnification) after 4 months of storage in an aqueous composition of 150 ppm H 2 0 2 and 0.1 ppm nano-Ag.
• Fig. 5 is a brass component (uncoated) after 4 months of storage in an aqueous composition of 150 ppm H2O2 and 0.1 ppm nano-Ag.
• Fig. 6 shows a brass component (uncoated) after 4 months storage in an aqueous composition of 150 ppm H2O2 and 0.1 ppm nano-AgCu2.5.
• K2 with 150 ppm H2O2 (Evonik) and 0.1 ppm nano-Ag corresponds to the sample M5
• K3 with 150 ppm H2O2 (Evonik) and 0.1 ppm nano-AgCu2.5 corresponds to the sample M7.
• Lamellar gray cast iron GJL 250 (steel with up to 1% molybdenum, up to 1% chromium and up to 6% nickel) as shown in Figs. 1-4 and brass components (uncoated), i. Brass CuZn39Pb3-CW 614N, e.g. according to DIN EN 1982 according to FIGS. 5-6.
• Castings painted with black KTL were outsourced with the above-mentioned hydrogen peroxide and silver-containing compositions.
• the H 2 O 2 concentration is rapidly reduced.
• the cone of pump housing made of cast iron GJL 250 after 4 months of storage in an aqueous composition of 2 wt .-% H2O2 and 0.1 ppm nano-Ag shows a noticeable corrosion (Fig. 1)
• the cone of pump housing made of gray cast iron GJL 250 after 4 months storage in an aqueous composition of 150 ppm H2O2 and 0.1 ppm nano-Ag shows a significantly lower corrosion (Fig. 2).
• Fig. 3 shows a cone of pump housing made of gray cast iron GJL 250 in magnification after 4 months of storage in an aqueous composition of 2 wt .-% H2O2 and 0.1 ppm nano-Ag. The cone shows clear signs of corrosion (hatching at top and bottom center).
• Fig. 4 shows a cone of pump housing made of cast iron GJL 250 in magnification after 4 months of storage in an aqueous composition of 150 ppm H2O2 and 0.1 ppm nano-Ag. The cone is significantly less corroded here. Results Outsourcing of solutions containing nanometal with brass components

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Citations (10)

• 2012
  • 2012-01-16 DE DE201210000707 patent/DE102012000707A1/de active Pending
  • 2012-11-22 WO PCT/EP2012/004829 patent/WO2013107475A1/de active Application Filing

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