ES2392289B1 - CHEMICAL METHOD FOR THE DESTRUCTION OF CHLOROANISOLS IN AQUOUS AND CORK SOLUTION - Google Patents
CHEMICAL METHOD FOR THE DESTRUCTION OF CHLOROANISOLS IN AQUOUS AND CORK SOLUTION Download PDFInfo
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- ES2392289B1 ES2392289B1 ES201130848A ES201130848A ES2392289B1 ES 2392289 B1 ES2392289 B1 ES 2392289B1 ES 201130848 A ES201130848 A ES 201130848A ES 201130848 A ES201130848 A ES 201130848A ES 2392289 B1 ES2392289 B1 ES 2392289B1
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- 238000000034 method Methods 0.000 title claims abstract description 27
- 230000006378 damage Effects 0.000 title claims abstract description 26
- 239000000126 substance Substances 0.000 title claims description 15
- 239000007799 cork Substances 0.000 claims abstract description 72
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical class OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims abstract description 34
- QGRPVMLBTFGQDQ-UHFFFAOYSA-N 1-chloro-2-methoxybenzene Chemical class COC1=CC=CC=C1Cl QGRPVMLBTFGQDQ-UHFFFAOYSA-N 0.000 claims abstract description 27
- 239000007864 aqueous solution Substances 0.000 claims abstract description 20
- 238000006243 chemical reaction Methods 0.000 claims abstract description 16
- 229910052751 metal Chemical class 0.000 claims abstract description 15
- 239000002184 metal Chemical class 0.000 claims abstract description 15
- 150000003839 salts Chemical class 0.000 claims abstract description 14
- 239000008187 granular material Substances 0.000 claims abstract description 10
- 239000000463 material Substances 0.000 claims abstract description 10
- KMUONIBRACKNSN-UHFFFAOYSA-N potassium dichromate Chemical compound [K+].[K+].[O-][Cr](=O)(=O)O[Cr]([O-])(=O)=O KMUONIBRACKNSN-UHFFFAOYSA-N 0.000 claims abstract description 10
- 239000011684 sodium molybdate Substances 0.000 claims abstract description 8
- 235000015393 sodium molybdate Nutrition 0.000 claims abstract description 8
- TVXXNOYZHKPKGW-UHFFFAOYSA-N sodium molybdate (anhydrous) Chemical compound [Na+].[Na+].[O-][Mo]([O-])(=O)=O TVXXNOYZHKPKGW-UHFFFAOYSA-N 0.000 claims abstract description 8
- QLOKJRIVRGCVIM-UHFFFAOYSA-N 1-[(4-methylsulfanylphenyl)methyl]piperazine Chemical compound C1=CC(SC)=CC=C1CN1CCNCC1 QLOKJRIVRGCVIM-UHFFFAOYSA-N 0.000 claims abstract description 5
- 239000012286 potassium permanganate Substances 0.000 claims abstract description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 9
- 238000011282 treatment Methods 0.000 claims description 7
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 6
- 150000001875 compounds Chemical class 0.000 claims description 4
- 230000000694 effects Effects 0.000 claims description 4
- 239000000243 solution Substances 0.000 claims description 4
- 239000012153 distilled water Substances 0.000 claims description 3
- 230000008569 process Effects 0.000 claims description 3
- WCVOGSZTONGSQY-UHFFFAOYSA-N 2,4,6-trichloroanisole Chemical compound COC1=C(Cl)C=C(Cl)C=C1Cl WCVOGSZTONGSQY-UHFFFAOYSA-N 0.000 claims description 2
- 239000003054 catalyst Substances 0.000 claims description 2
- 230000035484 reaction time Effects 0.000 claims description 2
- 238000005406 washing Methods 0.000 claims description 2
- 230000002070 germicidal effect Effects 0.000 claims 2
- 239000004115 Sodium Silicate Substances 0.000 claims 1
- 239000003638 chemical reducing agent Substances 0.000 claims 1
- 238000000354 decomposition reaction Methods 0.000 claims 1
- 239000000645 desinfectant Substances 0.000 claims 1
- MEFBJEMVZONFCJ-UHFFFAOYSA-N molybdate Chemical compound [O-][Mo]([O-])(=O)=O MEFBJEMVZONFCJ-UHFFFAOYSA-N 0.000 claims 1
- 150000004045 organic chlorine compounds Chemical group 0.000 claims 1
- 150000002978 peroxides Chemical class 0.000 claims 1
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 claims 1
- 229910052911 sodium silicate Inorganic materials 0.000 claims 1
- 230000003330 sporicidal effect Effects 0.000 claims 1
- 230000003247 decreasing effect Effects 0.000 abstract 1
- 235000014101 wine Nutrition 0.000 description 16
- 238000005516 engineering process Methods 0.000 description 8
- 238000011109 contamination Methods 0.000 description 6
- 230000002538 fungal effect Effects 0.000 description 4
- 239000000575 pesticide Substances 0.000 description 4
- LINPIYWFGCPVIE-UHFFFAOYSA-N 2,4,6-trichlorophenol Chemical compound OC1=C(Cl)C=C(Cl)C=C1Cl LINPIYWFGCPVIE-UHFFFAOYSA-N 0.000 description 3
- 241000233866 Fungi Species 0.000 description 3
- 238000004140 cleaning Methods 0.000 description 3
- -1 clothes Substances 0.000 description 3
- 238000001784 detoxification Methods 0.000 description 3
- 238000011161 development Methods 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- VGVRPFIJEJYOFN-UHFFFAOYSA-N 2,3,4,6-tetrachlorophenol Chemical class OC1=C(Cl)C=C(Cl)C(Cl)=C1Cl VGVRPFIJEJYOFN-UHFFFAOYSA-N 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- 235000019568 aromas Nutrition 0.000 description 2
- 235000019993 champagne Nutrition 0.000 description 2
- 239000000796 flavoring agent Substances 0.000 description 2
- 235000019634 flavors Nutrition 0.000 description 2
- 235000013305 food Nutrition 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 230000005855 radiation Effects 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- 102000004190 Enzymes Human genes 0.000 description 1
- 108090000790 Enzymes Proteins 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- 240000008289 Quercus suber Species 0.000 description 1
- 235000016977 Quercus suber Nutrition 0.000 description 1
- 238000009825 accumulation Methods 0.000 description 1
- 239000012736 aqueous medium Substances 0.000 description 1
- 230000004888 barrier function Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- 239000011111 cardboard Substances 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 238000004587 chromatography analysis Methods 0.000 description 1
- 239000000356 contaminant Substances 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 239000000417 fungicide Substances 0.000 description 1
- ZZUFCTLCJUWOSV-UHFFFAOYSA-N furosemide Chemical compound C1=C(Cl)C(S(=O)(=O)N)=CC(C(O)=O)=C1NCC1=CC=CO1 ZZUFCTLCJUWOSV-UHFFFAOYSA-N 0.000 description 1
- 238000004128 high performance liquid chromatography Methods 0.000 description 1
- 235000000396 iron Nutrition 0.000 description 1
- 238000002803 maceration Methods 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 238000007069 methylation reaction Methods 0.000 description 1
- 230000000813 microbial effect Effects 0.000 description 1
- 230000005012 migration Effects 0.000 description 1
- 238000013508 migration Methods 0.000 description 1
- 230000009456 molecular mechanism Effects 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 239000011087 paperboard Substances 0.000 description 1
- 230000008447 perception Effects 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 230000003449 preventive effect Effects 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 239000002689 soil Substances 0.000 description 1
- 238000002470 solid-phase micro-extraction Methods 0.000 description 1
- 235000015040 sparkling wine Nutrition 0.000 description 1
- 241000894007 species Species 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 239000002351 wastewater Substances 0.000 description 1
- 239000003643 water by type Substances 0.000 description 1
- 239000002023 wood Substances 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B27—WORKING OR PRESERVING WOOD OR SIMILAR MATERIAL; NAILING OR STAPLING MACHINES IN GENERAL
- B27K—PROCESSES, APPARATUS OR SELECTION OF SUBSTANCES FOR IMPREGNATING, STAINING, DYEING, BLEACHING OF WOOD OR SIMILAR MATERIALS, OR TREATING OF WOOD OR SIMILAR MATERIALS WITH PERMEANT LIQUIDS, NOT OTHERWISE PROVIDED FOR; CHEMICAL OR PHYSICAL TREATMENT OF CORK, CANE, REED, STRAW OR SIMILAR MATERIALS
- B27K7/00—Chemical or physical treatment of cork
-
- 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
- C02F1/58—Treatment of water, waste water, or sewage by removing specified dissolved compounds
Landscapes
- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Hydrology & Water Resources (AREA)
- Environmental & Geological Engineering (AREA)
- Water Supply & Treatment (AREA)
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Wood Science & Technology (AREA)
- Forests & Forestry (AREA)
- Detergent Compositions (AREA)
Abstract
El método consiste en realizar una reacción química tanto de una solución acuosa como con material de corcho, conteniendo en ambos casos 2,4,6-TCA contaminados. El método químico de reacción ha demostrado una capacidad de destrucción de los cloroanisoles del 98% en solución acuosa y entre el 45% y 83% en tapones, descendiendo la destrucción hasta el 40%-55% para granulado de corcho.#En la reacción participa peróxido de hidrógeno y sal metálica, preferentemente molibdato de sodio y alternativamente cromato potásico, dicromato potásico o permanganato potásico.The method consists in carrying out a chemical reaction of both an aqueous solution and cork material, containing in both cases 2,4,6-TCA contaminated. The chemical reaction method has demonstrated a destruction capacity of 98% chloroanisoles in aqueous solution and between 45% and 83% in stoppers, the destruction decreasing to 40% -55% for cork granules. # In the reaction hydrogen peroxide and metal salt participate, preferably sodium molybdate and alternatively potassium chromate, potassium dichromate or potassium permanganate.
Description
Método químico para la destrucción de cloroanisoles en solución acuosa y en corcho. Chemical method for the destruction of chloroanisoles in aqueous solution and in cork.
La presente invención se refiere a un método químico para la destrucción de cloroanisoles en solución acuosa y en corcho, basándose en el empleo de peróxido de hidrógeno y una sal metálica. The present invention relates to a chemical method for the destruction of chloroanisoles in aqueous solution and in cork, based on the use of hydrogen peroxide and a metal salt.
El objeto de la invención es proporcionar una tecnología económica, de fácil aplicación, y que puede ser aplicada a la destrucción de cloroanisoles en ecosistemas acuáticos contaminados (preferentemente aguas residuales, ríos, lagos y lagunas), y también en la destrucción de 2,4,6-tricloroanisol presente superficialmente en el corcho (preferentemente planchas, tapones y granulado de corcho). The object of the invention is to provide an economical technology, easy to apply, and that can be applied to the destruction of chloroanisoles in contaminated aquatic ecosystems (preferably wastewater, rivers, lakes and lagoons), and also in the destruction of 2,4 , 6-trichloroanisole present superficially in the cork (preferably plates, caps and cork granules).
El método de la invención encuentra especial aplicación en la limpieza de ecosistemas acuáticos contaminados con cloroanisoles (sector medioambiental), así como en la limpieza del corcho (tapones, discos, granulado o plancha), en fábricas que manufacturan corcho (sector del corcho). The method of the invention finds special application in the cleaning of aquatic ecosystems contaminated with chloroanisoles (environmental sector), as well as in the cleaning of cork (corks, disks, granules or irons), in factories that manufacture cork (cork sector).
De acuerdo con el método, se ha comprobado una capacidad de destrucción de los cloroanisoles en solución acuosa de hasta al 98%, mientras que en el caso de corcho los niveles de destrucción oscilan entre el 45% y el 83% para tapones, y entre el 40% y 55% para granulado de corcho. According to the method, a destruction capacity of chloroanisoles in an aqueous solution of up to 98% has been proven, while in the case of cork the destruction levels range between 45% and 83% for stoppers, and between 40% and 55% for cork granules.
La principal aplicación del corcho es la elaboración de distintos tipos de tapones utilizados para cerrar botellas de vino. Aproximadamente cada año se fabrican en todo el mundo unos 20.000 millones de tapones de corcho. Los tapones de corcho pueden ser de distintos tipos, aunque los más normales son: (a) tapones naturales, los de mayor calidad extraídos directamente por medios mecánicos de tiras de corcho de alcornoque; (b) tapones de aglomerado de corcho, generalmente de menor valor y utilizados para vinos de menor calidad; (c) tapones para vinos espumosos, como cavas y champagnes, que constan de un cuerpo de aglomerado de corcho rematado en un extremo por dos discos de corcho natural; y (d) tapones técnicos ó 1+1 que constan de un cuerpo central de aglomerado de corcho rematado en ambos extremos por un disco de corcho natural. The main application of cork is the development of different types of caps used to close wine bottles. Approximately 20,000 million cork stoppers are manufactured worldwide every year. Cork stoppers can be of different types, although the most normal are: (a) natural plugs, the highest quality plugs directly extracted by mechanical means of cork cork strips; (b) cork agglomerate plugs, generally of lower value and used for lower quality wines; (c) sparkling wine stoppers, such as champagnes and champagnes, consisting of a cork agglomerate body topped at one end by two discs of natural cork; and (d) technical plugs or 1 + 1 consisting of a central body of cork agglomerate topped at both ends by a natural cork disk.
Los tapones de corcho son la primera elección a la hora de cerrar botellas de vino. Sin embargo y desafortunadamente los tapones pueden contener diferentes sustancias, principalmente de origen microbiano, que al pasar al vino van a afectar negativamente sus cualidades organolépticas, al proporcionarles ciertos aromas y/o sabores desagradables. Cork stoppers are the first choice when closing bottles of wine. However, and unfortunately, the stoppers may contain different substances, mainly of microbial origin, which when they pass into the wine will negatively affect their organoleptic qualities, by providing certain unpleasant aromas and / or flavors.
Tradicionalmente se ha denominado a este fenómeno como contaminación del vino por corcho (cork taint). Traditionally this phenomenon has been termed as contamination of wine by cork (cork taint).
El compuesto químico más frecuentemente responsabilizado de este problema es el 2,4,6-TCA. Este compuesto confiere a los vinos un desagradable aroma a hongo o moho (aroma fúngico). Diversos estudios han tratado de cuantificar el porcentaje de vinos afectados por este problema. Así Butzke y col. [Detection of cork taint in wine using automated solid-phase microextraction in combination with GC/MS-SIM”. Chemistry of wine flavor. Waterhouse, AL and Ebeler, SE. Editores.ACS Symposium Series. American Chemical Society. Washington D.C.1999] estimaron que el porcentaje de vinos afectados por este problema oscilaría entre el 2-7% de los vinos que anualmente se ponen en el mercado. En otro estudio Soleas y colaboradores [J. Agric. Food Chem. 50: 1032-1039., 2002] establecieron que el nivel medio de contaminación de vinos con aromas fúngicos sería del 6.1%, aunque sorprendentemente sólo el 3.1% de los vinos analizados presentaron niveles de 2,4,6-TCA superiores a 2 ng/L (valor considerado como umbral de percepción). En cualquier caso las pérdidas económicas atribuibles a la contaminación de corcho por 2,4,6-TCA se han calculado en unos 1.000 millones de dólares anuales. The chemical compound most frequently responsible for this problem is 2,4,6-TCA. This compound gives the wines an unpleasant aroma of fungus or mold (fungal aroma). Several studies have tried to quantify the percentage of wines affected by this problem. Thus Butzke et al. [Detection of cork taint in wine using automated solid-phase microextraction in combination with GC / MS-SIM ”. Chemistry of wine flavor. Waterhouse, AL and Ebeler, SE. Editors.ACS Symposium Series. American Chemical Society Washington D.C. 1999] estimated that the percentage of wines affected by this problem would range between 2-7% of the wines that are placed annually in the market. In another study Soleas et al. [J. Agric Food Chem. 50: 1032-1039., 2002] established that the average level of contamination of wines with fungal aromas would be 6.1%, although surprisingly only 3.1% of the wines analyzed had higher levels of 2,4,6-TCA at 2 ng / L (value considered as perception threshold). In any case, the economic losses attributable to the contamination of cork by 2,4,6-TCA have been estimated at about 1 billion dollars annually.
Los mecanismos moleculares por los cuales se produce el 2,4,6-TCA en corcho son bien conocidos. Su formación es el resultado de una reacción de O-metilación del pesticida 2,4,6-TCP o 2,4,6-triclorofenol [Coque y col., 2003. Appl. Environ. Microbiol. 69: 5089-5095]. Se trata de una reacción de detoxificación que llevan a cabo fundamentalmente especies fúngicas que se desarrollan sobre materiales de corcho en la fábrica o sobre la corteza del alcornoque [Álvarez-Rodrígues y col., 2002. Appl. Environ. Microbiol. 68: 5860-5869]. El 2,4,6-triclorofenol en particular, y los clorofenoles en general, son pesticidas ampliamente utilizados como fungicidas en diversos materiales como madera, ropas, papel y cartón, etc. La contaminación del corcho con estos pesticidas resulta en su detoxificación por los hongos que se desarrollan sobre el corcho y la consecuente producción de 2,4,6-TCA, que de esta manera llega a contaminar los tapones de corcho. Por otro lado la detoxificación fúngica de clorofenoles presentes en aguas y suelos resulta en la acumulación de cloroanisoles en esos ambientes, ya que por su mayor estabilidad son más difícilmente degradables que los pesticidas clorofenólicos de los que derivan. The molecular mechanisms by which 2,4,6-TCA is produced in cork are well known. Its formation is the result of an O-methylation reaction of the 2,4,6-TCP or 2,4,6-trichlorophenol pesticide [Coque et al., 2003. Appl. Environ. Microbiol 69: 5089-5095]. It is a detoxification reaction that is mainly carried out by fungal species that develop on cork materials in the factory or on the cork oak bark [Álvarez-Rodrígues et al., 2002. Appl. Environ. Microbiol 68: 5860-5869]. 2,4,6-Trichlorophenol in particular, and chlorophenols in general, are pesticides widely used as fungicides in various materials such as wood, clothes, paper and cardboard, etc. The contamination of the cork with these pesticides results in its detoxification by the fungi that develop on the cork and the consequent production of 2,4,6-TCA, which thus contaminates the cork stoppers. On the other hand, the fungal detoxification of chlorophenols present in water and soil results in the accumulation of chloroanisoles in these environments, since due to their greater stability they are more difficult to degrade than the chlorophenolic pesticides from which they derive.
Debido a su impacto económico en los últimos años se han desarrollado diferentes tecnologías para Due to its economic impact in recent years, different technologies have been developed to
ES 2 392 289 Al ES 2 392 289 Al
disminuir el nivel medio de contaminación de corcho por 2,4,6-TCA, o alternativamente prevenir su transferencia desde los tapones de corcho al vino. Estas tecnologías, revisadas por Coque y col. [2006. Wine contamination by haloanisoles: toward the development of biotechnological strategies to remove chloroanisoles from cork stoppers”. Editores: J.J.R. Coque y J.F. Martín. (INBIOTEC, León)] tienen una efectividad variable, pero nunca definitiva se basan en: (a) técnicas basadas en el empleo de solventes orgánicos; (b) técnicas que utilizan vapor de agua como agente para extraer 2,4,6-TCA de corcho; (c) tecnologías basadas en el empleo de diversas radiaciones (microondas, ionizantes, radiación gamma); (d) tecnologías basadas en la extracción de 2,4,6-TCA mediante el empleo de dióxido de carbono en estado supercrítico; (e) tecnologías preventivas basadas en el empleo de métodos para impedir el desarrollo de hongos sobre el corcho; (f) tecnologías basadas el lavado/tratamiento de tapones con diferentes sustancias incluyendo ozono, suspensiones de carbón activo o enzimas tipo lacasa; (f) tecnologías basadas en el empleo de sustancias con un efecto barrera para impedir la migración del 2,4,6-TCA desde el corcho al vino. decrease the average level of cork contamination by 2,4,6-TCA, or alternatively prevent its transfer from cork stoppers to wine. These technologies, reviewed by Coque et al. [2006. Wine contamination by haloanisoles: towards the development of biotechnological strategies to remove chloroanisoles from cork stoppers ”. Publishers: J.J.R. Coque and J.F. Martin. (INBIOTEC, León)] have a variable effectiveness, but never definitive are based on: (a) techniques based on the use of organic solvents; (b) techniques that use water vapor as an agent to extract 2,4,6-TCA from cork; (c) technologies based on the use of various radiations (microwaves, ionizers, gamma radiation); (d) technologies based on the extraction of 2,4,6-TCA through the use of carbon dioxide in the supercritical state; (e) preventive technologies based on the use of methods to prevent the development of fungi on cork; (f) technologies based on the washing / treatment of plugs with different substances including ozone, activated carbon suspensions or lacasa-type enzymes; (f) technologies based on the use of substances with a barrier effect to prevent the migration of 2,4,6-TCA from cork to wine.
El método químico que se preconiza está concebido para resolver la problemática anteriormente expuesta, es decir para conseguir una óptima o máxima destrucción de cloroanisoles, tanto en solución acuosa como en corcho, basándose en una combinación de peróxido de hidrógeno y una sal metálica, pudiendo ser ésta molibdato de sodio y alternativamente cromato potásico, dicromato potásico o permanganato potásico. The chemical method that is recommended is designed to solve the problem described above, that is, to achieve optimal or maximum destruction of chloroanisoles, both in aqueous solution and in cork, based on a combination of hydrogen peroxide and a metal salt, which can be this sodium molybdate and alternatively potassium chromate, potassium dichromate or potassium permanganate.
Concretamente, el método químico se basa en establecer una reacción entre una solución acuosa a tratar y la sal metálica con peróxido de hidrógeno, o bien el material de corcho a tratar también con peróxido de hidrógeno y sal metálica, de manera que en cualquier caso se produce una destrucción de cloroanisoles presentes como contaminantes en aguas contaminadas y/o presentes en la superficie de material de corcho. Specifically, the chemical method is based on establishing a reaction between an aqueous solution to be treated and the metal salt with hydrogen peroxide, or the cork material to be treated also with hydrogen peroxide and metal salt, so that in any case It produces a destruction of chloroanisoles present as contaminants in contaminated waters and / or present on the surface of cork material.
En la solución acuosa las condiciones óptimas de la reacción corresponden a un pH comprendido entre 9 y 11, a una temperatura comprendida entre 30º y 40º C, y a un tiempo de reacción óptimo de aproximadamente 30 minutos, participando la sal metálica entre 1 y 2 mM, en tanto que el peróxido de hidrógeno participa entre 25 y 30 mM, en un volumen total de solución de 50 ml. In the aqueous solution, the optimal reaction conditions correspond to a pH between 9 and 11, at a temperature between 30º and 40º C, and at an optimal reaction time of approximately 30 minutes, with the metal salt participating between 1 and 2 mM , while hydrogen peroxide participates between 25 and 30 mM, in a total solution volume of 50 ml.
En el caso de ser aplicable la reacción a un material de corcho, éste puede concretarse en tapones, ya sean de corcho natural, como de corcho aglomerado o incluso discos y granulado, realizándose la reacción mediante un tratamiento rotatorio en recipiente cerrado, conteniendo agua destilada, tapones, peróxido de hidrógeno y molibdato de sodio como sal metálica, a un pH comprendido entre 9 y 11, una temperatura comprendida entre 50º y 60º C, y durante un tiempo comprendido entre 30 y 60 minutos, en donde el diámetro de los tapones de corcho está comprendido entre 3 y 5 mm. If the reaction to a cork material is applicable, it can be specified in stoppers, whether of natural cork, such as agglomerated cork or even discs and granules, the reaction being carried out by means of a rotary treatment in a closed container, containing distilled water , plugs, hydrogen peroxide and sodium molybdate as metal salt, at a pH between 9 and 11, a temperature between 50º and 60º C, and for a time between 30 and 60 minutes, where the diameter of the plugs Cork is between 3 and 5 mm.
Preferentemente el agua destilada participa con un contenido de 20 litros, con un pH de 11, participando el corcho con una cantidad de 200 tapones, 1.500 discos o 100 gr de granulado de corcho, en tanto que el peróxido de hidrógeno participa en una cantidad de 50 mM, y la sal metálica participa como molibdato de sodio-2 hidro, en una cantidad de 2 mM. Preferably the distilled water participates with a content of 20 liters, with a pH of 11, the cork with an amount of 200 caps, 1,500 discs or 100 gr of cork granules participating, while hydrogen peroxide participates in a quantity of 50 mM, and the metal salt participates as sodium molybdate-2 hydro, in an amount of 2 mM.
La destrucción de cloroanisoles en la solución acuosa de acuerdo con la reacción química de la invención, alcanza valores superiores al 83%, mientras en el corcho puede variar, dependiendo del tipo de tapón que sea, entre el 50% y el 80%. The destruction of chloroanisoles in the aqueous solution according to the chemical reaction of the invention, reaches values greater than 83%, while in the cork it can vary, depending on the type of plug that is, between 50% and 80%.
La eficacia de la reacción en la solución acuosa se determina midiendo el nivel de disolución de cloroanisoles por HPLC y valorando la liberación de cloro al medio acuoso producida al romperse la estructura molecular, de manera que para realizar estos ensayos se probaron un total de 26 posibles catalizadores metálicos (sales de distintos metales), de los cuales solo cuatro dieron resultados satisfactorios (niveles de destrucción de 2,4,6-TCA), superiores al 70%. Las cuatro sales metálicas seleccionadas fueron cromato potásico, dicromato potásico, permanganato potásico y molibdato de sodio (2-hidrato), siendo este último compuesto el que rindió los mejores resultados, permitiendo obtener de manera rutinaria niveles de destrucción de cloroanisoles superiores al 83%. The efficiency of the reaction in the aqueous solution is determined by measuring the level of chloroanisoles dissolution by HPLC and assessing the release of chlorine to the aqueous medium produced when the molecular structure is broken, so that in order to perform these tests a total of 26 possible metal catalysts (salts of different metals), of which only four gave satisfactory results (destruction levels of 2,4,6-TCA), above 70%. The four metal salts selected were potassium chromate, potassium dichromate, potassium permanganate and sodium molybdate (2-hydrate), the latter compound being the one that yielded the best results, allowing routinely to obtain levels of destruction of chloroanisoles greater than 83%.
Por su parte, el método aplicado en la destrucción de cloroanisoles presentes en corcho, tras la finalización de la correspondiente reacción, se sometió el corcho a una maceración con solución hidroalcohólica (etanol al 12%) a fin de extraer y cuantificar la cantidad de 2,4,6-TCA presente en los materiales de corcho tras su tratamiento. El 2,4,6-TCA se cuantificó por cromatografía de gases-masas, de acuerdo a la metodología descrita por Álvarez-Rodríguez y colaboradores [Eur Food Res Tecnol. 230: 135-143, 2009]. On the other hand, the method applied in the destruction of chloroanisoles present in cork, after the completion of the corresponding reaction, the cork was subjected to a maceration with hydroalcoholic solution (12% ethanol) in order to extract and quantify the amount of 2 , 4,6-TCA present in cork materials after their treatment. 2,4,6-TCA was quantified by gas-mass chromatography, according to the methodology described by Álvarez-Rodríguez and collaborators [Eur Food Res Tecnol. 230: 135-143, 2009].
Los resultados obtenidos indicaron que el método aplicado permitía destruir entre el 53% y el 81% de 2,4,6-TCA presente en tapones; entre el 45% y el 77% del 2,4,6-TCA presente en discos de corcho; y entre el 45% y 68% en el caso de granulado de corcho. The results obtained indicated that the method applied allowed destroying between 53% and 81% of 2,4,6-TCA present in caps; between 45% and 77% of 2,4,6-TCA present in cork discs; and between 45% and 68% in the case of cork granules.
ES 2 392 289 Al ES 2 392 289 Al
EJEMPLOS DE REALIZACIÓN Y APLICACIÓN INDUSTRIAL EXAMPLES OF REALIZATION AND INDUSTRIAL APPLICATION
En el caso de limpieza de aguas (preferentemente industriales) contaminadas con cloroanisoles, el proceso se realizaría en balsas, estanques o depósitos cerrados, incluyendo un sistema de agitación, de manera que primero se In the case of cleaning water (preferably industrial) contaminated with chloroanisoles, the process would be carried out in rafts, ponds or closed tanks, including a stirring system, so that first
5 debe modificar el pH por adición de una base (preferentemente NaOH) hasta alcanzar un valor de 10-11. una vez ajustado el pH se adiciona peroxido de hidrógeno (al menos a una concentración de 25 mN), y molibdato de sodio (2-hidrato) a una concentración de 2 mM. La mezcla debe homogeneizarse mediante agitación para conseguir una mezcla perfecta de los componentes. La reacción transcurrirá por un periodo mínimo de 30 minutos, antes de continuar con otros posibles tratamientos posteriores. 5 you must change the pH by adding a base (preferably NaOH) to a value of 10-11. Once the pH is adjusted, hydrogen peroxide (at least at a concentration of 25 mN), and sodium molybdate (2-hydrate) are added at a concentration of 2 mM. The mixture must be homogenized by stirring to achieve a perfect mixture of the components. The reaction will run for a minimum period of 30 minutes, before continuing with other possible subsequent treatments.
En este caso las pruebas se realizan en un tambor giratorio y herméticamente cerrado, preferentemente de un material inerte como puede ser plástico o polietileno, introduciéndose en el tambor 20 litros de agua con un pH ajustado a 11 y preferentemente a una temperatura de 60ºC. A continuación y dependiendo del material que se quiera limpiar, se introduce en el depósito 200 tapones de dimensiones estándar, 1.500 discos de corcho natural o 100 gr de granulado de In this case the tests are carried out in a rotating and hermetically sealed drum, preferably of an inert material such as plastic or polyethylene, with 20 liters of water being introduced into the drum with a pH set at 11 and preferably at a temperature of 60 ° C. Then, depending on the material to be cleaned, 200 caps of standard dimensions, 1,500 discs of natural cork or 100 gr of granulate are introduced into the tank
15 corcho (contenido dentro de una malla que impida su salida). Seguidamente se añade peróxido de hidrógeno hasta alcanzar una concentración final de 50 mM y molibdato de sodio a una concentración final de 2 mM. La mezcla se incuba a continuación con agitación por un periodo mínimo de 30 minutos para eliminar los cloroanisoles presentes en la superficie del corcho. 15 cork (contained within a mesh that prevents its exit). Then hydrogen peroxide is added until a final concentration of 50 mM and sodium molybdate are reached at a final concentration of 2 mM. The mixture is then incubated with stirring for a minimum period of 30 minutes to remove the chloroanisoles present on the surface of the cork.
ES 2 392 289 Al ES 2 392 289 Al
Claims (3)
- Categoría Category
- 56 Documentos citados Reivindicaciones afectadas 56 Documents cited Claims Affected
- A A A A A A
- ES 2076185 T3 (HENKEL) 01/11/1995, páginas 2 y 3 ES 8700128 A (SABATE Y MASSE) 01/01/1987, página 2, lin14-16; ejemplos 1 y 2 US 6483006 B1 (HITACHI ZOSEN CO.) 19/11/1992, resumen; ejemplos 1 a 4 1-5 1-5 1-5 ES 2076185 T3 (HENKEL) 01/11/1995, pages 2 and 3 EN 8700128 A (SABATE AND MASSE) 01/01/1987, page 2, lin14-16; Examples 1 and 2 US 6483006 B1 (HITACHI ZOSEN CO.) 11/19/1992, summary; examples 1 to 4 1-5 1-5 1-5
- Categoría de los documentos citados X: de particular relevancia Y: de particular relevancia combinado con otro/s de la misma categoría A: refleja el estado de la técnica O: referido a divulgación no escrita P: publicado entre la fecha de prioridad y la de presentación de la solicitud E: documento anterior, pero publicado después de la fecha de presentación de la solicitud Category of the documents cited X: of particular relevance Y: of particular relevance combined with other / s of the same category A: reflects the state of the art O: refers to unwritten disclosure P: published between the priority date and the date of priority submission of the application E: previous document, but published after the date of submission of the application
- El presente informe ha sido realizado • para todas las reivindicaciones • para las reivindicaciones nº: This report has been prepared • for all claims • for claims no:
- Fecha de realización del informe 24.07.2012 Date of realization of the report 24.07.2012
- Examinador M. Ojanguren Fernández Página 1/4 Examiner M. Ojanguren Fernández Page 1/4
- Novedad (Art. 6.1 LP 11/1986) Novelty (Art. 6.1 LP 11/1986)
- Reivindicaciones Reivindicaciones 1-5 SI NO Claims Claims 1-5 IF NOT
- Actividad inventiva (Art. 8.1 LP11/1986) Inventive activity (Art. 8.1 LP11 / 1986)
- Reivindicaciones Reivindicaciones 1-5 SI NO Claims Claims 1-5 IF NOT
- Documento Document
- Número Publicación o Identificación Fecha Publicación Publication or Identification Number publication date
- D01 D01
- ES 2076185 T3 (HENKEL) 01.11.1995 ES 2076185 T3 (HENKEL) 01.11.1995
- D02 D02
- ES 8700128 A (SABATE Y MASSE) 01.01.1987 ES 8700128 A (SATURDAY AND MASSE) 01.01.1987
- D03 D03
- US 6483006 B1 (HITACHI ZOSEN CO.) 19.11.1992 US 6483006 B1 (HITACHI ZOSEN CO.) 19.11.1992
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| FR2574696B1 (en) * | 1984-12-19 | 1987-06-05 | Champagne M Sabate Sa Bouchons | SPECIAL TREATMENT PROCESS FOR CORK PRODUCTS |
| FR2635292B1 (en) * | 1988-08-12 | 1990-11-16 | Henkel France | PROCESS FOR TREATING CORK STOPPERS |
| JP2000301170A (en) * | 1999-02-16 | 2000-10-31 | Hitachi Zosen Corp | Method for decomposition treatment of organochlorine compound |
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