EP2550389B1 - Machine, procédé et combinaison électrochimique de nettoyage de textiles ainsi qu'une balle de blanchissage electrolytique - Google Patents

Machine, procédé et combinaison électrochimique de nettoyage de textiles ainsi qu'une balle de blanchissage electrolytique Download PDF

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EP2550389B1
EP2550389B1 EP11709743.6A EP11709743A EP2550389B1 EP 2550389 B1 EP2550389 B1 EP 2550389B1 EP 11709743 A EP11709743 A EP 11709743A EP 2550389 B1 EP2550389 B1 EP 2550389B1
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electrode
wash
diamond
washing
electrolysis
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EP2550389A1 (fr
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Ulrich Griesbach
Steffen Maas
Florian Stecker
Andreas Fischer
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BASF SE
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BASF SE
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    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06F—LAUNDERING, DRYING, IRONING, PRESSING OR FOLDING TEXTILE ARTICLES
    • D06F35/00—Washing machines, apparatus, or methods not otherwise provided for
    • D06F35/003—Washing machines, apparatus, or methods not otherwise provided for using electrochemical cells

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  • the present invention relates to a washing machine with electrochemical cell, a method for the electrochemical cleaning of fibers, detergents for the electrochemical cleaning of fibers and the thus cleaned fibers, a corresponding method, a combination and an e-bleach ball.
  • the functionality of the washing machines can be increased.
  • the bleach-active compounds present a challenge.
  • Today's detergents contain bleach catalysts or bleach precursors and a source of peroxide, so that the bleaching is activated only during the washing process.
  • a challenge in formulating a detergent is to protect the delicate components of the detergent (e.g., enzymes, perfumes) from the bleaching components.
  • the diamond electrodes serve in this case, the electrochemical treatment of the wash water at the end of the wash cycle in terms of wastewater treatment (TOC degradation).
  • acid (anolyte) and basic (catholyte) water are formed by electrolysis to achieve a better washing result by sequential and repeated use of these wash solutions.
  • all systems are based on a split electrolysis cell.
  • a divided electrolysis cell requires not only a membrane but also additional containers and pumps in order to be able to operate the different circuits (anolyte and catholyte) separately from one another.
  • the membrane In places with a high flow velocity, the membrane can erode and even be destroyed by "hot spots" when locally increased current densities occur.
  • Direct contact of the (flexible) membranes with the electrodes, in particular the anode, is permanently detrimental and must be prevented by technical measures.
  • the membranes must not dry up, as, among other things, cracks can form. If sparingly soluble salts are present in the electrolyte (wash water, wash liquor), the free acids or bases in the membrane may crystallize under certain circumstances and thus lead to holes and cracks.
  • diamond electrodes in the context of a bleach activation, however, is described in WO 2009/06 7838.
  • Boron-doped diamond electrodes have traditionally been used in wastewater treatment (TOC degradation), where the aggressive OH radicals, which are formed at this electrode, attack organic material and oxidize to CO 2 . When used in textile washing machines thus significant color and fiber damage were expected.
  • electrochemical processes are used in a number of applications. The most common applications are those in which individual chemical substances are specifically converted into others. By electrochemical means z. B. bond cleavages, dimerizations, couplings, etc. are performed.
  • the subject of the present invention is a washing machine according to claim 1.
  • washing machine is preferred in which the current is applied during the filling and / or washing process.
  • the current can vary over time.
  • Inventive preferred embodiments have a constant current or a variable current intensity.
  • washing machine covers all types of washing machines, ie both washing machines for household and washing machines for industrial fiber and especially textile cleaning. Washing machines are often described, for.
  • EP 2 098 627 and EP 2 098 628 are often described, for.
  • electrode materials in particular as anode materials, in the electrochemical cell are preferably used materials with which one can achieve a high oxygen overvoltage, for example noble metals such as platinum or metal oxides such as ruthenium, chromium or lead oxide or mixed oxides of the type RuO x TiO x or per se known dimensionally stable anodes (DSA) or diamond electrodes.
  • noble metals such as platinum or metal oxides such as ruthenium, chromium or lead oxide or mixed oxides of the type RuO x TiO x or per se known dimensionally stable anodes (DSA) or diamond electrodes.
  • the electrode is selected from the group consisting of graphite electrode, diamond electrode, steel electrode, and platinum electrode.
  • Diamond electrodes are claimed. They are created by applying one or more diamond layers to a substrate. Possible support materials are niobium, silicon, tungsten, titanium, silicon carbide, tantalum, graphite or ceramic supports such as titanium suboxide. However, a support of niobium, titanium or silicon is preferred for the method according to the invention, very particular preference is given to a support of niobium, if a diamond electrode is used.
  • the anode is a diamond electrode, wherein the diamond electrode may also be doped with other elements. Boron and nitrogen are preferred as doping elements. Very particularly preferred is the claimed method with a boron-doped diamond electrode (BDD electrode) as the anode.
  • BDD electrode boron-doped diamond electrode
  • any known to the expert electrolysis cells can be used from the said electrodes - such as divided or undivided flow cell, Capillary gap cell or plate stack cell. Particularly preferred is the undivided flow cell. To achieve optimum space-time yields, a bipolar arrangement of several electrodes is advantageous.
  • diamond electrodes behave similar to heavy metal electrodes under the conditions of fiber and especially textile washing.
  • An advantage of the inventive method according to claim 3 is that no metal ions in the electrolyte (ie, the wash liquor) and thus reach the environment, since in the corrosion of the diamond layer of the BDD electrode heavy metal ions can not arise.
  • diamond electrodes which have been prepared by the CVD method (chemical vapor deposition).
  • Such electrodes are commercially available, for example from manufacturers: Condias, Itzehoe (Germany) and Adamant Technologies, La-Chaux-de-Fonds (Switzerland).
  • HTHP-BDD electrodes are commercially available from pro aqua, Niklasdorf (Austria), their properties are from A Cieciwa, R. Wüthrich and Ch. Comninellis in Electrochem. Commun. 8 (2006) 375-382 described.
  • the cathode materials unless the polarity of the electrode is to be reversed, for example iron, steel, stainless steel or nickel, otherwise also precious metals such as platinum and diamond electrodes come into consideration.
  • precious metals such as platinum and diamond electrodes come into consideration.
  • boron-doped diamond electrodes are used as the cathode.
  • the cathode is a diamond electrode.
  • This diamond electrode contains a diamond layer applied to a carrier material, wherein the carrier material is selected from the group of niobium, silicon, tungsten, titanium, silicon carbide, tantalum, graphite or ceramic carriers such as titanium suboxide. Particular preference is given to niobium or silicon as support material.
  • the diamond layer on the carrier may be doped with other elements. Boron- or nitrogen-doped diamond electrodes are preferred. Particularly preferred are boron-doped diamond electrodes.
  • boron-doped diamond electrode as an anode with steel as the cathode, wherein in particular the washing machine housing made of steel acts as a cathode.
  • the washing machine housing made of steel acts as a cathode.
  • stainless steel is used as steel.
  • the washing machine comprises two diamond electrodes, which are connected as anode and cathode.
  • the electrolysis can also be carried out at intervals and, if necessary, the polarity of the electrodes exchanged (short-term electrolysis, washing process, short-term electrolysis, washing process, etc.).
  • An advantage of this interval circuit is that sensitive components of the detergent would only briefly be exposed to possible degradation at the electrodes (primarily by OH radicals).
  • the method according to the invention is advantageous if the polarity in the diamond electrodes is reversed in the range from 0.1 to 200 minutes or from wash cycle to wash cycle to avoid electrode deposits (fouling).
  • the individual electrodes have a certain size, which has an influence on the effect.
  • a washing machine is preferred in which the individual electrode has an effective surface area of 0.5 to 1000 cm 2 , preferably 1 to 500 cm 2 and particularly preferably 2 to 100 cm 2 .
  • the electrode size refers to the surface of the single electrode, which is connected during the electrolysis as the anode and facing the cathode. If an anode is located between two cathodes, the electrode size of the anode results from the sum of the front and the back.
  • the effective electrode area of the single electrode is the electrode area of the anode, which comes in contact with the electrolyte during electrolysis and faces the cathode (s). If two electrodes are connected in such a way that they can alternately act as an anode or as a cathode, twice as large values for the total electrode area result.
  • the effective areas of the anode (s) and cathode (s) are preferably the same size, - this is particularly preferred when both anode (s) and cathode (s) are diamond electrodes.
  • the electrodes are arranged at a certain distance from each other. Preference is given to a distance of 0.1-20 mm, preferably 1-10 mm, more preferably 2-5 mm
  • An electrolytic cell in this case comprises a pair of electrodes, which are preferably not separated from each other by a membrane. To optimize the space-time yields, a bipolar arrangement of several electrodes is advantageous.
  • the cell is installed in the flooded area of the washing tub, preferably outside the washing drum.
  • the cell can also be installed in the supply line inside or outside the washing machine.
  • the cell can be a permanently installed component of the washing machine or a separate component (eg in the fresh water inlet between faucet and washing machine or as an e-bleach ball with its own energy supply in the drum).
  • a kit of parts comprising a washing machine and an electrolysis cell which can be connected to the water inlet constitutes a further subject matter of the present invention.
  • Another embodiment according to the invention consists in integrating the electrolysis cell into an additional water circulation within the machine.
  • An e-bleach ball comprising a mains independent power supply, a diamond anode and a cathode arranged so that the electrodes can contact the electrolyte when the e-bleach ball is in the washing drum of a washing machine during the washing process is a further subject of the present invention.
  • an electrolyte is selected which is selected from the group consisting of water, methanol and ethanol. Particularly preferred is water.
  • the pH is in the range from 2 to 13, preferably from 3 to 12, particularly preferably in the range from 6 to 11.
  • the temperature for the inventive method is in the range of 10 to 95 ° C, preferably in the range of 15 to 90 ° C, more preferably in the range of 20 to 60 ° C and most preferably in the range of 25 to 40 ° C, such as eg 30 ° C.
  • the diamond electrode having an effective surface area of 0.5 to 1000 cm 2 , preferably from 1 to 500 cm 2 and more preferably from 2 to 100 cm 2 .
  • a process in which, in addition to the OH radicals (or its secondary products such as hydrogen peroxide and ozone) at least one compound selected from the group consisting of builder, surfactant, enzyme used for purification, represents a preferred variant.
  • a method is preferred which is carried out at a temperature up to 60 ° C, preferably up to 40 ° C, particularly preferably up to 30 ° C.
  • a method as described above having a soil removal rate for bleachable stains (e.g., tea) of at least 20% is another aspect of the present invention.
  • the degree of soil removal is determined as follows:
  • the determination is made by first soiling a white cotton test fabric and subjecting it to a reflection measurement at 460 nm before and after the method has been carried out, ie before and after the wash.
  • the reflectance measurements are carried out with a Spectrophotometer Gretag Macbeth, type Spectrolino under the following conditions: observer angle 10 °, illuminant D65, UV filter.
  • a detergent in particular a heavy-duty detergent, comprising bleach activator (s) and / or bleach catalyst (s) and less than 1% by mass of hydrogen peroxide or hydrogen peroxide-releasing compounds is a further constituent of the present invention.
  • a liquid detergent containing bleach activator (s) and / or bleach catalyst (s) is the subject of the present invention.
  • the liquid detergent contains the bleach activator in an amount of at least 0.01 to 10% by mass, preferably from 0.1 to 5% by mass, more preferably from 0.5 to 3% by mass.
  • the bleach activator is preferably selected from the below-mentioned suitable bleach activators. Particularly preferred is the bleach activator TAED.
  • Pre-washing agent (prespotter) containing bleach activator (s) and / or bleach catalyst (s) is a further subject of the present invention.
  • the prewash agent contains the bleach activator in an amount of at least 0.01 to 50% by mass, preferably from 0.1 to 30% by mass, particularly preferably from 0.5 to 10% by mass.
  • the bleach activator is preferably selected from the below-mentioned suitable bleach activators. Particularly preferred is the bleach activator TAED.
  • the detergent used may optionally contain bleach catalysts.
  • Suitable bleach catalysts are, for example, quaternized imines and sulfonimines, which are described, for example, in US Pat US-A 5,360,569 and EP-A 0 453 003 .
  • Particularly effective bleach catalysts are manganese complexes which are described, for example, in US Pat WO-A 94/21777 are described.
  • Such compounds are incorporated at most in amounts of up to 1.5% by weight, in particular up to 0.5% by weight.
  • Other suitable metal catalysts are, for example, in Angew. Chem. 2006, 118, 212-229 called.
  • conductive salts can be added during the process and most simply as a component of the detergent.
  • conductive salts z.
  • the conducting salts are particularly preferably selected from the group of the bis-N, N '- (tri C 1 - to C 8 -alkyl) -substituted tri-, tetra-, penta-, hexa etc. - methylenediammonium salts such as hexamethylenebis (dibutylethylammonium ) phosphate or hydroxide.
  • the electrolyte preferably by adding to the detergent according to the invention, also certain additives such as EDTA or triethanolamine to prevent the cathodic deposition of iron, which would have a detrimental effect on the desired high hydrogen overvoltage of the cathode.
  • EDTA EDTA
  • triethanolamine to prevent the cathodic deposition of iron, which would have a detrimental effect on the desired high hydrogen overvoltage of the cathode.
  • Borates such as disodium diborate or orthoboric acid may be added as anode corrosion inhibitors.
  • Suitable inorganic builders (A ') are, above all, crystalline or amorphous aluminosilicates having ion-exchanging properties, in particular zeolites.
  • zeolites Various types of zeolites are suitable, in particular zeolites A, X, B, P, MAP and HS in their Na form or in forms in which Na is partially exchanged with other cations such as Li, K, Ca, Mg or ammonium.
  • Suitable zeolites are described, for example, in EP-A 0 038 591 .
  • GB-A 2 013 259 EP-A 0 522 726 .
  • EP-A 0 384 070 and WO-A 94/24251 are, above all, crystalline or amorphous aluminosilicates having ion-exchanging properties.
  • Suitable crystalline silicates (A ') are, for example, disilicates or layered silicates, for. B. SKS-6 (manufacturer: Hoechst).
  • the silicates may be used in the form of their alkali metal, alkaline earth metal or ammonium salts, preferably as Na, Li and Mg silicates.
  • Amorphous silicates such as sodium metasilicate, which comprises a polymeric structure, or Britesil ® H20 (manufactured by Akzo) are also useful.
  • Suitable inorganic builders based on carbonate are carbonates and bicarbonates. These can be used in the form of their alkali metal, alkaline earth metal or ammonium salts. Preference is given to using Na, Li and Mg carbonates or bicarbonates, in particular sodium carbonate and / or sodium bicarbonate.
  • Usual phosphates as inorganic builders are polyphosphates such.
  • the stated components (A ') can be used individually or in mixtures with one another.
  • inorganic builder component is a mixture of aluminosilicates and carbonates, in particular of zeolites, especially zeolite A, and alkali metal carbonates, especially sodium carbonate, in a weight ratio of 98: 2 to 20: 80, in particular from 85: 15 to 40:60.
  • other components (A ') may be present.
  • the detergent contains 0.1 to 20 wt .-%. in particular from 1 to 12% by weight of organic cobuilders (B ') in the form of low molecular weight, oligomeric or polymeric carboxylic acids, in particular polycarboxylic acids, or phosphonic acids or their salts, in particular sodium or potassium salts.
  • organic cobuilders (B ') in the form of low molecular weight, oligomeric or polymeric carboxylic acids, in particular polycarboxylic acids, or phosphonic acids or their salts, in particular sodium or potassium salts.
  • the group (i) comprises monoethylenically unsaturated C 3 -C 8 monocarboxylic acids such as acrylic acid, methacrylic acid, crotonic acid and vinylacetic acid.
  • acrylic acid and methacrylic acid are used.
  • Group (ii) comprises monoethylenically unsaturated C 2 -C 22 -olefins, vinylalkyl ethers having C 1 -C 8 -alkyl groups, styrene, vinyl esters of C 1 -C 8 -carboxylic acids, (meth) acrylamide and vinylpyrrolidone.
  • C 2 -C 6 -olefins, vinylalkyl ethers having C 1 -C 4 -alkyl groups, vinyl acetate and vinyl propionate are preferably used from group (ii).
  • Group (iii) comprises (meth) acrylic esters of C 1 -C 8 -alcohols, (meth) acrylonitrile, (meth) acrylamides of C 1 -C 8 -amines, N-vinylformamide and vinylimidazole.
  • polymers of group (ii) contain copolymerized vinyl esters, these may also be partially or completely hydrolyzed to vinyl alcohol structural units.
  • Suitable copolymers and terpolymers are for example US-A 3,887,806 such as DE-A 43 13 909 known.
  • Suitable unsaturated carboxylic acids are maleic acid, fumaric acid, itaconic acid, citraconic acid, acrylic acid, methacrylic acid, crotonic acid and vinylacetic acid and also mixtures of acrylic acid and maleic acid which are grafted in amounts of from 40 to 95% by weight, based on the component to be grafted.
  • Suitable modifying monomers are the above-mentioned monomers of groups (ii) and (iii).
  • Grafted degraded or degraded reduced starches and grafted polyethylene oxides are preferably used from this group, with from 20 to 80% by weight of monomers, based on the grafting component, being used in the graft polymerization.
  • a mixture of maleic acid and acrylic acid in a weight ratio of 90:10 to 10:90 is preferably used.
  • suitable polyamidocarboxylic acids and modified polyamidocarboxylic acids are known, for example from EP-A 454 126 .
  • WO-A 94/01486 and EP-A 581 452 are known, for example from EP-A 454 126 .
  • polyaspartic acids or cocondensates of aspartic acid with further amino acids C 4 -C 25 -mono- or -dicarboxylic acids and / or C 4 -C 25 -mono- or -diamines are also used as (B ').
  • Particular preference is given to using polyaspartic acids prepared in phosphorus-containing acids and modified with C 6 -C 22 -mono- or dicarboxylic acids or with C 6 -C 22 -mono- or -diamines.
  • Suitable (B ') condensation products of citric acid with hydroxycarboxylic acids or polyhydroxy compounds are known, for example WO-A 93/22362 and WO-A 92/16493 , Such condensates containing carboxyl groups usually have molecular weights of up to 10,000, preferably up to 5,000.
  • (B ') are ethylenediamine disuccinic acid, oxydisuccinic acid, aminopolycarboxylates, aminopolyalkylene phosphonates and polyglutamates.
  • oxidized starches may be used as organic co-builders in addition to (B ').
  • Suitable anionic surfactants (C) are, for example, fatty alcohol sulfates of fatty alcohols having 8 to 22, preferably 10 to 18 carbon atoms, for. C 9 -C 11 alcohol sulfates, C 12 -C 14 alcohol sulfates, cetyl sulfate, myristyl sulfate, palmityl sulfate, stearyl sulfate and tallow fatty alcohol sulfate.
  • alkanesulfonates such as C 8 -C 24 -, preferably C 10 -C 18 -Alkansulfonate and soaps such as the Na and K salts of C 8 -C 24 carboxylic acids.
  • anionic surfactants are C 9 -C 20 linear alkyl benzene sulphonates (LAS) and alkyl toluenesulphonates.
  • anionic surfactants (C) are C 8 -C 24 -olefinsulfonates and -disulfonates, which may also be mixtures of alkene and hydroxyalkanesulfonates or disulfonates, alkyl ester sulfonates, sulfonated polycarboxylic acids, alkyl glycerol sulfonates, fatty acid glycerol ester sulfonates, alkylphenol polyglycol ether sulfates, paraffin sulfonates with ca From about 20 to about 50 carbon atoms (based on paraffin or paraffin mixtures obtained from natural sources), alkyl phosphates, acyl isethionates, acyltaurates, acylmethyltaurates, alkylsuccinic acids, alkenylsuccinic acids or their half-esters or hemiamides, alkylsulfosuccinic acids or their amide
  • the anionic surfactants are preferably added to the fiber and textile treatment agent in the form of salts.
  • Suitable cations in these salts are alkali metal ions such as sodium, potassium and lithium and ammonium salts such as hydroxyethylammonium, di (hydroxyethyl) ammonium and tri (hydroxyethyl) ammonium salts.
  • the component (C) is preferably present in the fiber and textile treatment agent in an amount of 3 to 30 wt .-%, in particular 5 to 20 wt .-% before. If C 9 -C 20 linear alkylbenzenesulfonates (LAS) are also used, they are usually used in an amount of up to 25% by weight, in particular up to 20% by weight.
  • LAS linear alkylbenzenesulfonates
  • anionic surfactants can be used alone, for example only fatty alcohol sulfates or only alkylbenzenesulfonates, but it is also possible to use mixtures of different classes, eg. B. a mixture of fatty alcohol sulfates and alkylbenzenesulfonates. Within the individual classes of anionic surfactants it is also possible to use mixtures of different species.
  • nonionic surfactants D are nonionic surfactants D, in particular alkylphenol alkoxylates such as alkylphenol ethoxylates with C 6 -C 14 -alkyl chains and 5 to 30 mol of alkylene oxide units.
  • nonionic surfactants are alkyl polyglucosides or hydroxyalkyl polyglucosides having from 8 to 22, preferably 10 to 18, carbon atoms in the alkyl chain. These compounds usually contain 1 to 20, preferably 1.1 to 5, glucoside units.
  • Another class of nonionic surfactants are N-alkylglucamides with C 6 -C 22 alkyl chains. Such compounds are obtained, for example, by acylation of reducing aminated sugars with corresponding long-chain carboxylic acid derivatives.
  • nonionic surfactants are block copolymers of ethylene oxide, propylene oxide and / or butylene oxide (Pluronic®) and Tetronic®) brands from BASF), polyhydroxy or polyalkoxy fatty acid derivatives such as polyhydroxy fatty acid amides, N-alkoxy or N-aryloxy polyhydroxy fatty acid amides, fatty acid amide ethoxylates, in particular end-capped, and fatty acid alkanolamide alkoxylates.
  • Pluronic® propylene oxide and / or butylene oxide
  • Tetronic® Tetronic®
  • the component (D) is present in the fiber and textile treatment agent according to the invention preferably in an amount of 1 to 20 wt .-%, in particular 3 to 12 wt .-% before.
  • Only one class of nonionic surfactants can be used alone, in particular only alkoxylated C 8 -C 22 -alcohols, but it is also possible to use mixtures of different classes. Within the individual classes of nonionic surfactants, mixtures of different species can also be used.
  • anionic surfactants (C) and nonionic surfactants (D) are preferably in a weight ratio of 95: 5 to 20:80, especially 80 : 20 to 50: 50.
  • the surfactant constituents of the surfactant mixture according to the invention are to be considered.
  • cationic surfactants (E) can also be present in the fiber and textile treatment agents according to the invention.
  • Suitable cationic surfactants are, for example, ammonium-containing surface-active compounds such as, for example, alkyldimethylammonium halides and compounds of the general formula RR'R "R"'N + X- in which the radicals R to R "'are alkyl, aryl radicals, alkylalkoxy, arylalkoxy, hydroxyalkyl (alkoxy), hydroxyaryl (alkoxy) groups and X is a suitable anion.
  • ammonium-containing surface-active compounds such as, for example, alkyldimethylammonium halides and compounds of the general formula RR'R "R"'N + X- in which the radicals R to R "'are alkyl, aryl radicals, alkylalkoxy, arylalkoxy, hydroxyalkyl (alkoxy), hydroxyaryl (alkoxy) groups and X is a suitable anion.
  • the fiber and textile treatment agents may also contain ampholytic surfactants (F), such as aliphatic derivatives of secondary or tertiary amines containing an anionic group in one of the side chains, alkyldimethylamine oxides or alkyl or alkoxymethylamine oxides.
  • F ampholytic surfactants
  • Components (E) and (F) may contain up to 25%, preferably 3-15% in the fiber and textile treatment agents.
  • the fiber and textile treatment agent additionally contains 0.05 to 4% by weight of enzymes (J).
  • enzymes are proteases, amylases, lipases and cellulases.
  • the enzymes preferably amounts of 0.1 to 1.5 wt .-%, particularly preferably 0.2 to 1.0 wt .-%, of the formulated enzyme is added.
  • Suitable proteases are, for. Savinase and Esperase (manufacturer: Novo Nordisk).
  • a suitable lipase is e.g. Lipolase (manufacturer: Novo Nordisk).
  • a suitable cellulase is for example Celluzym (manufacturer: Novo Nordisk).
  • the use of peroxidases to activate the bleaching system is also possible. You can use individual enzymes or a combination of different enzymes.
  • the textile detergent formulation according to the invention can still enzyme stabilizers, z. As calcium propionate, sodium formate or boric acids or their salts, and / or oxidation inhibitors.
  • a fiber treated according to the claimed method or in contact with a detergent constitutes a further subject of the present invention.
  • the fibers may be both natural and synthetic fibers.
  • Non-inclusive examples of natural fibers are: cotton, wool, linen and viscose.
  • Fibers, non-exhaustive examples of synthetic fibers are: polypropene, polyamide, polyester, nylon, perlon, Teflon®, Lycra®, fibers.
  • the fibers are preferably woven, knitted, spun, knitted, knotted, laceed.
  • Fig. 1 Schematic representation of the experimental apparatus
  • exemplary detergents were dosed in deionized water as follows: 4.8 g / L detergent, 0.67 g / L sodium percarbonate, 0.15 g / L TAED.
  • the total volume of the wash solution is 300 mL, unless stated otherwise.
  • Dirt removal was determined by subjecting the test fabric to a reflectance measurement at 460 nm before and after the wash.
  • Reference Example R 1 describes the soil removal achieved solely by the wash solution (700 g deionized water, 10 g NaHCO 3 ). This test is a reference for determining the achieved dirt removal.
  • Example 1 describes the bleaching effect achieved by electrolysis of the wash solution (700 g deionized water, 10 g NaHCO 3 ) on boron-doped diamond electrodes without the addition of a bleach activator or bleach precursor such as TAED. Compared to the reference experiment R 1, a significant increase in soil removal can be observed. Table 1: Dirt removal using the example of test fabric EMPA 167 (tea on cotton).
  • Examples 2 to 6 show the soil removal (test fabric EMPA 167, tea on cotton), which is achieved as a function of the current strength using the method according to the invention in the presence of the bleach activator TAED.
  • Table 2 Influence of the current on the removal of dirt (tea on cotton, EMPA 167). Dirt removal in% at 40 ° C a (remission measurement at 460 nm) example amperage
  • Electrolysis time 30 min 2 0.06 A 29 3 0.12 A 47 4 0.6A 49 5 1.2 A 59 6 6.0A 67 a The electrolyte used (washing liquid) typically has the following composition: 700 g of deionized water, 10 g of NaHCO 3 , 0.16 g of TAED
  • Reference examples R 2 to R 4 represent the results of bleaching with a system of H 2 O 2 and TAED in different compositions.
  • Table 3 Influence of the composition of H ⁇ sub> 2 ⁇ / sub> O ⁇ sub> 2 ⁇ / sub> / TAED on soil removal on the example of test fabric EMPA 167 (tea on cotton). Dirt removal in% at 40 ° C (remission measurement at 460 nm) example H 2 O 2 / TAED [mmol / L] Test duration 30 min R2 8.1 72 R3 4.1 64 R4 4 / 0.5 59
  • Examples 7 and 8 describe the difference between sequential splitting of the two steps (example 7) and parallelization of electrolysis and cleaning process (example 8) on the result of dirt removal.
  • Table 4 Influence of the duration of the electrolysis on the removal of dirt (test fabric EM-PA 167). Dirt removal in% at 40 ° C (remission measurement at 460 nm) example Pre-electrolysis [min] / electrolysis [min] 30 minutes after TAED 7 10/0 46 8th 10/30 61
  • Examples 9 to 12 and the reference examples R 5 and R 6 describe the treatment of various types of stains with the method according to the invention for electrochemical bleach activation. The results show that the dirt removal achieved is as expected different degrees of severity with respect to various soils. Comparative Examples R 5 and R 6 each describe the pure washing action in the absence of TAED and without electrolysis. Accordingly, both with respect to red wine (Ex 9 and 10) and to blueberry juice (Ex 11 and 12), good soil removal is achieved by the method according to the invention. Table 5: Dirt removal on the example of test fabric EMPA 114 (red wine on cotton).
  • Examples 13-26 and reference examples R 7-R 20 describe the treatment of various textile dyes with the method according to the invention for electrochemical bleach activation.
  • 0.25 g of TAED and the color monitors were added and pumped without current for 45 minutes.
  • the color monitors were rinsed briefly with deionized water and after every 5 wash cycles a remission measurement at 460 nm to determine the degree of color removal. In total, 15 wash cycles (3 x 5) were performed per color monitor.
  • Table 8 Color damage analysis by a reference system using selected color monitors after 15 washing cycles. Color removal in% example color monitor 5 wash cycles 10 wash cycles 15 washing cycles R7 AISE 1 9% 21% 32% R8 AISE 3 -4% -4% -4% R9 AISE 5 -4% -5% -6% R10 AISE 8 -1% -1% -1 % R11 AISE 16 -1% -1% -1 % R12 AISE 20 3% 5% 8th% R13 AISE 21 1% 2% 3% R14 AISE-22 3% 7% 11% R15 AISE 24 -26% -23% -22% R16 AISE 26 4% 6% 8th% R17 AISE 27 -1% 0% 0% 0% R18 AISE 29 0% 1% 1% R19 AISE 33 0% 0% 0% 0% 0% R20 AISE 39 0% 0% 0% 0% 0% 0% 0% 0% 0% 0% 0% 0% 0% 0% 0% R20 AISE 39 0% 0% 0% 0%
  • Reference Examples 21 to 24 show the soil removal (test fabric EMPA 167, tea on cotton) achieved by the detergent formulations in the presence and absence of sodium percarbonate and TAED at 40 ° C within 30 min.
  • the protective distance in the absence of sodium percarbonate and TAED thus shows the pure washing effect, which is not due to chemical bleaching operations (Reference Examples 21 and 23).
  • Table 9 Effect of detergent composition on soil removal (tea on cotton, EMPA 167, 40 ° C).
  • Examples 27 to 30 describe the result of the sequential splitting of the two steps (electrolysis and cleaning process) on the result of dirt removal.
  • the solution of the respective detergent was subjected to pre-electrolysis for 10 minutes prior to the addition of the textile samples. It turns out that the dirt removal of the pure detergent solutions is not significantly influenced by the pre-electrolysis (see also reference examples R21 and R23).
  • Examples 28 and 30 after a 10 minute pre-electrolysis of the respective wash solution, both the fabric samples and TAED were added. Accordingly, a significant increase in soil removal is already found after 10 minutes pre-electrolysis (at 1.2 A). The inventive method is thus compatible with complex detergent formulations.
  • Table 10 Dirt removal by pre-electrolysis of detergent formulations (test fabric EMPA 167). Dirt removal in% at 40 ° C (remission measurement at 460 nm) example Pre-electrolysis [min] / current [A] Duration of test after addition of TAED or test tissue: 30 min 27 10 min / 1.2 A 28 a 28 10 min / 1.2 A 38 b 29 10 min / 1.2 A 27 c 30 10 min / 1.2 A 35 d a : ECE98 in deionized water, pre-electrolysis for 10 min, then test tissue addition b : ECE98 in deionized water, pre-electrolysis for 10 min, then TAED and test tissue addition c : AATCC1993 in deionized water, 10 min pre-electrolysis, then test tissue addition d : AATCC1993 in deionized water, pre-electrolysis for 10 min, then TAED and test tissue addition
  • Examples 31 to 34 describe the result of the parallel execution of the two steps (electrolysis and cleaning process) on the result of dirt removal.
  • the detergent solution was subjected to electrolysis for 30 minutes after the textile samples had been added. It turns out that the dirt removal of the pure detergent solutions is only slightly influenced by the continuous electrolysis (see Reference Examples R21 and R23 and Examples 27 and 29).
  • both textile samples and TAED were added to the detergent solution.
  • the dirt removal achieved by the continuous electrolysis is expected to be slightly higher (see Example 28) or comparable (see Example 30) to the dirt removal achieved by short-term (but energy-saving) pre-electrolysis.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Textile Engineering (AREA)
  • Detergent Compositions (AREA)
  • Detail Structures Of Washing Machines And Dryers (AREA)
  • Electrodes For Compound Or Non-Metal Manufacture (AREA)
  • Electrolytic Production Of Non-Metals, Compounds, Apparatuses Therefor (AREA)
  • Accessory Of Washing/Drying Machine, Commercial Washing/Drying Machine, Other Washing/Drying Machine (AREA)
  • Water Treatment By Electricity Or Magnetism (AREA)

Claims (10)

  1. Machine à laver comprenant une électrode et une unité de réglage, dans laquelle un courant de 0,02 à 30 A peut être appliqué à l'électrode pendant le processus de lavage et dans laquelle l'électrode est une électrode en diamant et la polarité de l'électrode en diamant est inversée après une durée dans la plage allant de 0,1 à 200 min ou de processus de lavage en processus de lavage pour éviter les dépôts sur l'électrode.
  2. Machine à laver selon la revendication 1, dans laquelle l'électrode présente une surface active de 0,5 à 1 000 cm2.
  3. Procédé de nettoyage de fibres, dans lequel des radicaux OH et/ou de l'H2O2 sont générés dans une solution aqueuse par application d'un courant de 0,02 à 30 A à une électrode, l'électrode étant une électrode en diamant et la polarité de l'électrode en diamant étant inversée après une durée dans la plage allant de 0,1 à 200 min ou de processus de lavage en processus de lavage pour éviter les dépôts sur l'électrode.
  4. Procédé selon la revendication 3, dans lequel l'électrode présente une surface active de 0,5 à 1 000 cm2.
  5. Procédé selon la revendication 3 ou 4, dans lequel au moins un composé choisi dans le groupe constitué par un adjuvant, un tensioactif et une enzyme est utilisé pour le nettoyage en plus des radicaux OH (ou leurs produits dérivés).
  6. Procédé selon l'une quelconque des revendications 3 à 5, qui est réalisé à une température de jusqu'à 60 °C.
  7. Procédé selon l'une quelconque des revendications 3 à 6, présentant un degré d'élimination des salissures pour les salissures blanchissables d'au moins 20 %.
  8. Procédé, dans lequel une machine à laver selon la revendication 1 ou 2 et un agent de lavage contenant un ou plusieurs activateurs de blanchissage et/ou un ou plusieurs catalyseurs de blanchissage et moins de 1 % en masse de peroxyde d'hydrogène ou de composés libérant du peroxyde d'hydrogène, ou
    un agent de lavage choisi dans le groupe constitué par les agents de lavage universels, liquides, pour les couleurs et pour la laine, sont utilisés.
  9. Combinaison comprenant une machine à laver et une cellule d'électrolyse pouvant être placée au niveau de l'alimentation d'eau, dans laquelle l'électrode est une électrode en diamant et la polarité de l'électrode en diamant est inversée après une durée dans la plage allant de 0,1 à 200 min ou de processus de lavage en processus de lavage pour éviter les dépôts sur l'électrode.
  10. Balle de blanchissage électrolytique, comprenant une alimentation en courant indépendante du réseau électrique, une anode en diamant et une cathode, qui sont agencées de manière à ce que les électrodes puissent rentrer en contact avec l'électrolyte lorsque la balle de blanchissage électrolytique se trouve dans le tambour de lavage d'une machine à laver pendant le processus de lavage.
EP11709743.6A 2010-03-25 2011-03-24 Machine, procédé et combinaison électrochimique de nettoyage de textiles ainsi qu'une balle de blanchissage electrolytique Active EP2550389B1 (fr)

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EP10157748 2010-03-25
PCT/EP2011/054542 WO2011117350A1 (fr) 2010-03-25 2011-03-24 Procédé électrochimique de nettoyage de textiles
EP11709743.6A EP2550389B1 (fr) 2010-03-25 2011-03-24 Machine, procédé et combinaison électrochimique de nettoyage de textiles ainsi qu'une balle de blanchissage electrolytique

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DE102021132611A1 (de) 2021-12-10 2023-06-15 Miele & Cie. Kg Reinigungsgerät, Steuervorrichtung und Verfahren zum Behandeln von Reinigungsgut

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CN102906325A (zh) 2013-01-30
JP2013524868A (ja) 2013-06-20
WO2011117350A1 (fr) 2011-09-29
BR112012023991A2 (pt) 2016-08-02
EP2550389A1 (fr) 2013-01-30
MX2012010906A (es) 2012-10-09
JP2015077411A (ja) 2015-04-23

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