WO2007110460A2 - Adsorbents for removing chlorides, bromides and iodides from water - Google Patents

Adsorbents for removing chlorides, bromides and iodides from water Download PDF

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Publication number
WO2007110460A2
WO2007110460A2 PCT/ES2007/000177 ES2007000177W WO2007110460A2 WO 2007110460 A2 WO2007110460 A2 WO 2007110460A2 ES 2007000177 W ES2007000177 W ES 2007000177W WO 2007110460 A2 WO2007110460 A2 WO 2007110460A2
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water
bromide
silver
chloride
elimination
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PCT/ES2007/000177
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Spanish (es)
French (fr)
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WO2007110460A3 (en
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José Oficina de Transferencia de Resultados de Investigación RIVERA UTRILLA
Manuel Oficina de Transferencia de Resultados de Investigación SÁNCHEZ POLO
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UNIVERSIDAD DE GRANADA Oficina de Transferencia de Resultados de Investigación
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Publication of WO2007110460A3 publication Critical patent/WO2007110460A3/en

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    • 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
    • C02F1/28—Treatment of water, waste water, or sewage by sorption
    • C02F1/288—Treatment of water, waste water, or sewage by sorption using composite sorbents, e.g. coated, impregnated, multi-layered
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
    • B01J20/0203—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising compounds of metals not provided for in B01J20/04
    • B01J20/0233—Compounds of Cu, Ag, Au
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/22—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising organic material
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/22—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising organic material
    • B01J20/26—Synthetic macromolecular compounds
    • B01J20/262—Synthetic macromolecular compounds obtained otherwise than by reactions only involving carbon to carbon unsaturated bonds, e.g. obtained by polycondensation
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/22—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising organic material
    • B01J20/26—Synthetic macromolecular compounds
    • B01J20/265—Synthetic macromolecular compounds modified or post-treated polymers
    • B01J20/267—Cross-linked polymers
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/28—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties
    • B01J20/28002—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties characterised by their physical properties
    • B01J20/28004—Sorbent size or size distribution, e.g. particle size
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/28—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties
    • B01J20/28014—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties characterised by their form
    • B01J20/28016—Particle form
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/28—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties
    • B01J20/28014—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties characterised by their form
    • B01J20/28033—Membrane, sheet, cloth, pad, lamellar or mat
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/28—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties
    • B01J20/28014—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties characterised by their form
    • B01J20/28047—Gels
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/28—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties
    • B01J20/28054—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties characterised by their surface properties or porosity
    • B01J20/28069—Pore volume, e.g. total pore volume, mesopore volume, micropore volume
    • B01J20/28071—Pore volume, e.g. total pore volume, mesopore volume, micropore volume being less than 0.5 ml/g
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/28—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties
    • B01J20/28054—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties characterised by their surface properties or porosity
    • B01J20/28069—Pore volume, e.g. total pore volume, mesopore volume, micropore volume
    • B01J20/28073—Pore volume, e.g. total pore volume, mesopore volume, micropore volume being in the range 0.5-1.0 ml/g
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/30—Processes for preparing, regenerating, or reactivating
    • B01J20/32—Impregnating or coating ; Solid sorbent compositions obtained from processes involving impregnating or coating
    • B01J20/3202—Impregnating or coating ; Solid sorbent compositions obtained from processes involving impregnating or coating characterised by the carrier, support or substrate used for impregnation or coating
    • B01J20/3206—Organic carriers, supports or substrates
    • B01J20/3208—Polymeric carriers, supports or substrates
    • B01J20/3212—Polymeric carriers, supports or substrates consisting of a polymer obtained by reactions otherwise than involving only carbon to carbon unsaturated bonds
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/30—Processes for preparing, regenerating, or reactivating
    • B01J20/32—Impregnating or coating ; Solid sorbent compositions obtained from processes involving impregnating or coating
    • B01J20/3231—Impregnating or coating ; Solid sorbent compositions obtained from processes involving impregnating or coating characterised by the coating or impregnating layer
    • B01J20/3234—Inorganic material layers
    • B01J20/3236—Inorganic material layers containing metal, other than zeolites, e.g. oxides, hydroxides, sulphides or salts
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/30—Processes for preparing, regenerating, or reactivating
    • B01J20/34—Regenerating or reactivating
    • B01J20/3425—Regenerating or reactivating of sorbents or filter aids comprising organic materials
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/30—Processes for preparing, regenerating, or reactivating
    • B01J20/34—Regenerating or reactivating
    • B01J20/3433—Regenerating or reactivating of sorbents or filter aids other than those covered by B01J20/3408 - B01J20/3425
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/30—Processes for preparing, regenerating, or reactivating
    • B01J20/34—Regenerating or reactivating
    • B01J20/345—Regenerating or reactivating using a particular desorbing compound or mixture
    • B01J20/3475—Regenerating or reactivating using a particular desorbing compound or mixture in the liquid phase
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2220/00—Aspects relating to sorbent materials
    • B01J2220/50—Aspects relating to the use of sorbent or filter aid materials
    • B01J2220/58—Use in a single column
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2303/00—Specific treatment goals
    • C02F2303/18—Removal of treatment agents after treatment
    • C02F2303/185—The treatment agent being halogen or a halogenated compound

Definitions

  • organic aerogels doped with silver cations as adsorbents for the removal of chloride, bromide and iodide anions from water.
  • the proposed treatment system based on the use of silver-doped organic aerogels, as new adsorbent materials, is focused mainly on the elimination of bromide and iodide anions from drinking water, as well as on obtaining water High purity (MiIIi-Q water), very necessary in many chemical, pharmaceutical and different types of laboratories.
  • the object of the present invention is to take advantage of the presence of silver cations on the surface of the organic airgel, a solid material characterized by having a high surface area and porosity, to produce the chemical precipitation of the chloride, bromide and iodide anions of the water of a selective form on the surface of the material.
  • the present treatment system intends to use organic aerogels doped with silver as adsorbent materials for the removal of chloride, bromide and iodide anions from water. Due to the process of preparing these materials, it is possible to carry out the anchoring of the silver cations in their structure, avoiding their dissolution during their application in the water treatment. In addition, these materials are characterized by having a high surface area and porosity, which will allow adsorbing, at the same time, dissolved organic matter and organic microcontaminants present in the waters.
  • One of the great advantages of this material is that, due to the process of its preparation, it can be obtained in a wide variety of solid forms, which implies an increase in the technical possibilities of application.
  • the water treatment could be carried out i) by means of columns filled with this material in granular form, i) by filtration with developed membranes 77
  • the waters could be treated simply by adding powdered silver aerogels to them.
  • XPS X-ray spectrophotometry
  • the experimental system used for the treatment of waters contaminated with bromide and / or iodide ions consists of i) a peristaltic pump, ii) a column filled with silver doped airgel of the desired particle size, whereby filter the contaminated water and iii) a sample collector located at the exit of the column.
  • the columns used have the following dimensions: 8 cm high by 1 cm wide.
  • the granulometry of the material used is between 0.5-0.8 mm.
  • the flow used is 1.5 mL / min.
  • a system for the elimination of chloride, bromide and / or iodide anions from water characterized by using organic aerogeies doped with silver, both in granular form and in powder form, as adsorbents or using membranes prepared from doped aerogeies with silver
  • Organic aerogeies doped with silver can be subjected to a physical activation process with water vapor or carbon dioxide, or to a chemical activation process with alkaline hydroxides or with phosphoric acid, increasing their adsorptive properties.
  • This method has been used in a system comprising a peristaltic pump, a column filled with silver doped airgel of the desired particle size, whereby contaminated water is filtered and a sample collector located at the exit of the column.
  • EXAMPLE Elimination of bromide and iodide anions from water intended for human consumption through the use of silver aerogels as column adsorbents.
  • V0.0 2 Volume of treated water at the breaking point of column X0.
  • 02 Amount of halide adsorbed at the breaking point of the column.
  • H M ⁇ z Height of the mass transfer zone of the column.
  • X0.95 Percentage of halide adsorbed for the breakage value of
  • concentration of dissolved organic carbon was determined during the adsorption / regeneration process and X-ray phototransmission (XPS) spectrometry analysis of the airgel samples was carried out for the different cycles of adsorption / regeneration.
  • XPS X-ray phototransmission

Abstract

Adsorbents for removing chlorides, bromides and iodides from water, which are based on silver-cation-doped aerogels. The proposed system is geared principally to the removal of bromide and iodide anions from drinking water and also to obtaining water of high purity.

Description

ADSORBENTES PARA LA ELIMINACIÓN DE CLORUROS, BROMUROS Y YODUROS DE LAS AGUASADSORBENTS FOR THE ELIMINATION OF CHLORINE, BROMIDE AND IODURES FROM WATER
DESCRIPCIÓNDESCRIPTION
Uso de aerogeles orgánicos dopados con cationes plata como adsorbentes para Ia eliminación de aniones cloruro, bromuro y yoduro de las aguas.Use of organic aerogels doped with silver cations as adsorbents for the removal of chloride, bromide and iodide anions from water.
SECTOR DE LA TÉCNICA El sistema de tratamiento propuesto, basado en el uso de aerogeles orgánicos dopados con plata, como nuevos materiales adsorbentes, está enfocado, principalmente, a Ia eliminación de aniones bromuros y yoduros de aguas potables, así como a Ia obtención de aguas de gran pureza (agua MiIIi-Q), muy necesarias en numerosas industrias químicas, farmacéuticas y en diferentes tipos de laboratorios.SECTOR OF THE TECHNIQUE The proposed treatment system, based on the use of silver-doped organic aerogels, as new adsorbent materials, is focused mainly on the elimination of bromide and iodide anions from drinking water, as well as on obtaining water High purity (MiIIi-Q water), very necessary in many chemical, pharmaceutical and different types of laboratories.
OBJETO DE LA INVENCIÓNOBJECT OF THE INVENTION
El sistema de tratamiento basado en el uso de aerogeles orgánicos dopados con plata, como nuevos materiales adsorbentes, surge con el fin de reducir Ia concentración de iones cloruros, bromuros y yoduros de las aguas.The treatment system based on the use of organic aerogels doped with silver, as new adsorbent materials, arises in order to reduce the concentration of chloride ions, bromides and iodides of the waters.
Las concentraciones en las que se encuentran presentes los aniones bromuro y yoduro en las fuentes de agua destinadas a consumo humano suelen ser muy bajas (0- 1000 μg/L) (von Gunten U. Ozonation of drinking water: Parí II. Disinfection and by-product formation In presence of bromide, iodide or chloríde. Water Research, 37, 1469-1487 (2003)). Sin embargo, Ia presencia de estos aniones en las mismas puede ser muy perjudicial, ya que se pueden generar i) compuestos de elevada 007/000177The concentrations in which bromide and iodide anions are present in water sources intended for human consumption are usually very low (0-1000 μg / L) (von Gunten U. Ozonation of drinking water: Parí II. Disinfection and by -product formation In presence of bromide, iodide or chloride, Water Research, 37, 1469-1487 (2003)). However, the presence of these anions in them can be very harmful, since i) high compounds can be generated 007/000177
toxicidad para los seres humanos durante el proceso de su depuración, como es el caso de los aniones bromato, y ¡i) productos químicos que incrementen considerablemente las características organolépticas de las aguas (yodo-metanos) (Rock J. J., Formation of haloforms during chlorination of natural waters. Journal of Water Treatment and Examination, 23, 234-243, 1974). Por este motivo, es necesario llevar a cabo Ia eliminación de estos aniones (bromuros y yoduros) de las aguas antes de ser sometidas a los tratamientos clásicos de depuración. Por otro lado, si bien Ia presencia de iones cloruro en las aguas destinadas a consumo humano no es de gran preocupación, Ia búsqueda de nuevos sistemas que permitan una eliminación eficiente de los mismos es de especial interés para Ia obtención de aguas de gran pureza (agua MiIIi-Q), necesarias en numerosas industrias químicas y farmacéuticas.toxicity to humans during the purification process, as is the case with bromate anions, and i) chemicals that significantly increase the organoleptic characteristics of water (iodine-methanes) (Rock JJ, Formation of haloforms during chlorination of natural waters, Journal of Water Treatment and Examination, 23, 234-243, 1974). For this reason, it is necessary to carry out the elimination of these anions (bromides and iodides) from the water before being subjected to the classic treatment of purification. On the other hand, although the presence of chloride ions in the waters destined for human consumption is not of great concern, the search for new systems that allow an efficient elimination of them is of special interest for obtaining high purity waters ( MiIIi-Q water), necessary in numerous chemical and pharmaceutical industries.
El objeto de Ia presente invención consiste en aprovechar Ia presencia de cationes plata sobre Ia superficie del aerogel orgánico, material sólido caracterizado por presentar una elevada área superficial y porosidad, para producir Ia precipitación química de los aniones cloruro, bromuro y yoduro de las aguas de una forma selectiva sobre Ia superficie del material.The object of the present invention is to take advantage of the presence of silver cations on the surface of the organic airgel, a solid material characterized by having a high surface area and porosity, to produce the chemical precipitation of the chloride, bromide and iodide anions of the water of a selective form on the surface of the material.
ESTADO DE LA TÉCNICASTATE OF THE TECHNIQUE
Hasta ahora, los sistemas de tratamiento existentes para Ia eliminación de los aniones cloruro, bromuro y yoduro de las aguas se basan, principalmente, en el uso de diferentes tipos de resinas de intercambio iónico (Humbert H., Gallard H., Suty H., Croué J. P. Performance ofselected anión exchange resins for the treatment of a high DOC content suríace water. Wat. Res., 39, 1699-1708, 2005). Sin embargo, este tratamiento no es muy eficiente debido a su elevado coste y a Ia baja selectividad del proceso de intercambio. Actualmente, se están preparando carbones activados con iones plata depositados en su superficie con el fin de adsorber de forma selectiva los aniones cloruro, bromuro y yoduro presentes en aguas destinadas a consumo humano (Hoskins J.S., Karanfil T. Removal and sequestration of iodide using silver-impregnated activated carbón. Environmental Science and Technology, 36, 784-789, 2002). Los resultados obtenidos han mostrado que Ia eficiencia adsortiva de estos materiales no es muy elevada debido, principalmente, a Ia disolución de las especies de plata superficial durante el proceso de tratamiento. Estos nuevos carbones activados se encuentran aún en fase de desarrollo, por Io que aún no han sido aplicados a escala industrial.Until now, the existing treatment systems for the elimination of chloride, bromide and iodide anions from water are mainly based on the use of different types of ion exchange resins (Humbert H., Gallard H., Suty H. , Croué JP Performance of selected anion exchange resins for the treatment of a high DOC content suríace water. Wat. Res., 39, 1699-1708, 2005). But nevertheless, This treatment is not very efficient due to its high cost and the low selectivity of the exchange process. Currently, activated carbon with silver ions deposited on its surface are being prepared to selectively adsorb chloride, bromide and iodide anions present in waters intended for human consumption (Hoskins JS, Karanfil T. Removal and sequestration of iodide using silver -impregnated activated carbon, Environmental Science and Technology, 36, 784-789, 2002). The results obtained have shown that the adsorptive efficiency of these materials is not very high due, mainly, to the dissolution of the surface silver species during the treatment process. These new activated carbons are still under development, so they have not yet been applied on an industrial scale.
DESCRIPCIÓN DE LA INVENCIÓNDESCRIPTION OF THE INVENTION
El presente sistema de tratamiento pretende utilizar aerogeles orgánicos dopados con plata como materiales adsorbentes para Ia eliminación de aniones cloruro, bromuro y yoduro de las aguas. Debido al proceso de preparación de estos materiales, es posible llevar a cabo el anclaje de los cationes plata en su estructura, evitando Ia disolución de los mismos durante su aplicación en el tratamiento de aguas. Además, estos materiales se caracterizan por presentar una elevada área superficial y porosidad, por Io que permitirán adsorber, al mismo tiempo, materia orgánica disuelta y microcontaminantes orgánicos presentes en las aguas. Una de las grandes ventajas de este material reside en que, debido al procedimiento de su preparación, se puede obtener en una gran variedad de formas sólidas, Io que implica un incremento de las posibilidades técnicas de aplicación. Así, el tratamiento de las aguas se podría llevar a cabo i) mediante columnas rellenas de este material en forma granular, ¡i) mediante filtración con membranas desarrolladas 77The present treatment system intends to use organic aerogels doped with silver as adsorbent materials for the removal of chloride, bromide and iodide anions from water. Due to the process of preparing these materials, it is possible to carry out the anchoring of the silver cations in their structure, avoiding their dissolution during their application in the water treatment. In addition, these materials are characterized by having a high surface area and porosity, which will allow adsorbing, at the same time, dissolved organic matter and organic microcontaminants present in the waters. One of the great advantages of this material is that, due to the process of its preparation, it can be obtained in a wide variety of solid forms, which implies an increase in the technical possibilities of application. Thus, the water treatment could be carried out i) by means of columns filled with this material in granular form, i) by filtration with developed membranes 77
4 a partir del mismo, e incluso, iii) incluyendo un sistema de separación de fases apropiado al final del proceso de tratamiento, las aguas se podrían tratar simplemente añadiendo los aerogeles de plata en forma de polvo a las mismas.4 from it, and even, iii) including an appropriate phase separation system at the end of the treatment process, the waters could be treated simply by adding powdered silver aerogels to them.
El aerogel utilizado para llevar a cabo estas experiencias, se obtuvo mezclando las proporciones adecuadas de acetato de plata, resorcinol, formaldehído y agua. Posteriormente esta mezcla fue introducida en tubos de vidrio de 25 cm de longitud y 0.5 cm de diámetro y sometida a un proceso de curación. Finalmente, el sólido obtenido fue cortado en forma de pequeñas pastillas y sometido a un proceso de secado supercrítico con dióxido de carbono (muestra A). Este material se caracteriza por presentar un valor de área superficial de 428 m2/g, un volumen de mesoporos V2 = 0.35 cm3/g, un volumen de macroporos V3 = 0.84 cm3/g, un valor del pH del punto cero de carga pHPZc = 4.5 y un contenido en átomos de plata superficial, determinado mediante espectrofotometría de Rayos X (XPS) del 10%.The airgel used to carry out these experiences was obtained by mixing the appropriate proportions of silver acetate, resorcinol, formaldehyde and water. Subsequently, this mixture was introduced into glass tubes 25 cm long and 0.5 cm in diameter and subjected to a healing process. Finally, the solid obtained was cut in the form of small tablets and subjected to a supercritical drying process with carbon dioxide (sample A). This material is characterized by presenting a surface area value of 428 m 2 / g, a volume of mesopores V 2 = 0.35 cm 3 / g, a volume of macropores V 3 = 0.84 cm 3 / g, a pH value of the point zero charge pH PZ c = 4.5 and a content of surface silver atoms, determined by X-ray spectrophotometry (XPS) of 10%.
A partir del aerogel de plata (A) se obtuvo una muestra de aerogel activado de Ag, muestra que denominaremos A-A. Este material fue obtenido sometiendo el aerogel original (A) a un proceso de carbonización, en una atmósfera de N2 a elevada temperatura y, posteriormente, a un proceso de activación física con dióxido de carbono. El tratamiento aplicado desarrolló considerablemente el valor del área superficial (845 m2/g) del aerogel original (A).From the silver airgel (A) a sample of activated airgel of Ag was obtained, a sample that we will call AA. This material was obtained by subjecting the original airgel (A) to a carbonization process, in a high temperature N 2 atmosphere and, subsequently, to a physical activation process with carbon dioxide. The applied treatment considerably developed the surface area value (845 m 2 / g) of the original airgel (A).
El sistema experimental utilizado para el tratamiento de las aguas contaminadas con iones bromuro y/o yoduro consta de i) una bomba peristáltica, ii) una columna rellena del aerogel dopado con plata del tamaño de partícula deseado, por Ia que se filtra el agua contaminada y iii) un colector de muestras situado a Ia salida de Ia columna.The experimental system used for the treatment of waters contaminated with bromide and / or iodide ions consists of i) a peristaltic pump, ii) a column filled with silver doped airgel of the desired particle size, whereby filter the contaminated water and iii) a sample collector located at the exit of the column.
Las columnas utilizadas presentan las siguientes dimensiones: 8 cm de alto por 1 cm de ancho. La granulometría del material utilizado está comprendida entre 0.5- 0.8 mm. El flujo utilizado es de 1.5 mL/min.The columns used have the following dimensions: 8 cm high by 1 cm wide. The granulometry of the material used is between 0.5-0.8 mm. The flow used is 1.5 mL / min.
En resumen, se propone un sistema para Ia eliminación de aniones cloruros, bromuros y/o yoduros de aguas caracterizado por utilizar aerogeies orgánicos dopados con plata, tanto en forma granular como en polvo, como adsorbentes o bien utilizando membranas preparadas a partir de aerogeies dopados con plata.In summary, a system is proposed for the elimination of chloride, bromide and / or iodide anions from water characterized by using organic aerogeies doped with silver, both in granular form and in powder form, as adsorbents or using membranes prepared from doped aerogeies with silver
Los aerogeies orgánicos dopados con plata pueden ser sometidos a un proceso de activación física con vapor de agua o con dióxido de carbono, o bien a un proceso de activación química con hidróxidos alcalinos o con ácido fosfórico, incrementándose las propiedades adsortivas de los mismos.Organic aerogeies doped with silver can be subjected to a physical activation process with water vapor or carbon dioxide, or to a chemical activation process with alkaline hydroxides or with phosphoric acid, increasing their adsorptive properties.
Este método ha sido utilizado en un sistema que comprende una bomba peristáltica, una columna rellena del aerogel dopado con plata del tamaño de partícula deseado, por Ia que se filtra el agua contaminada y un colector de muestras situado a Ia salida de Ia columna.This method has been used in a system comprising a peristaltic pump, a column filled with silver doped airgel of the desired particle size, whereby contaminated water is filtered and a sample collector located at the exit of the column.
MODO DE REALIZACIÓN PREFERIDOPREFERRED EMBODIMENT
A continuación se indica, a modo de ejemplo ilustrativo pero no limitativo, una realización práctica del procedimiento objeto de Ia presente patente: EJEMPLO: Eliminación de aniones bromuro y yoduro de aguas destinadas a consumo humano mediante el uso de aerogeles de plata como adsorbentes en columna.Next, by way of illustrative but not limiting example, a practical embodiment of the process object of the present patent is indicated: EXAMPLE: Elimination of bromide and iodide anions from water intended for human consumption through the use of silver aerogels as column adsorbents.
Se ha utilizado el sistema descrito anteriormente para comparar Ia capacidad de los aerogeles de Ag con el carbón activado Sorbo® en Ia eliminación de bromuros de aguas del Lago de Zurich.The system described above has been used to compare the capacity of Ag aerogels with Sorbo® activated carbon in the removal of water bromides from Lake Zurich.
Con el fin de determinar Ia máxima capacidad de adsorción de los aerogeles de plata, se llevó a cabo Ia determinación de las isotermas de adsorción de los aniones cloruro, bromuro y yoduro sobre este nuevo material a una temperatura de 250C.To determine Ia maximum adsorption capacity of the aerogels silver, it was carried out the determination of adsorption isotherms of the anions chloride, bromide and iodide on this new material at a temperature of 25 0 C.
Los resultados se presentan en Ia Figura 1. La elevada capacidad de adsorción observada es debida a Ia presencia de Ag en su superficie, Ia cual puede dar lugar a Ia formación de los correspondientes haluros de Ag caracterizados por presentar muy baja solubilidad. Así, los valores de las constantes de los productos de solubilidad (KPS) para estos compuestos oscilan entre 10"13 para el caso del AgBr y 10~17 para el caso del AgI. Esto hace que los correspondientes aniones haluro disueltos en agua queden retenidos en la superficie del carbón mediante un proceso de quimisorción.The results are presented in Figure 1. The high adsorption capacity observed is due to the presence of Ag on its surface, which can lead to the formation of the corresponding Ag halides characterized by having very low solubility. Thus, the values of the constants of the solubility products (K PS ) for these compounds range between 10 "13 for the case of AgBr and 10 ~ 17 for the case of AgI. This makes the corresponding halide anions dissolved in water remain retained on the surface of the coal through a chemisorption process.
Los resultados observados (Figura 2) muestran que el aerogel presenta una capacidad de adsorción muy superior a Ia observada para el carbón activado Sorbo®. El carbón activado Sorbo® es un carbón ampliamente utilizado en las plantas de tratamiento de agua potable, y que, como se puede observar en Ia Figura 2 no es capaz de adsorber aniones bromuros y yoduros de las aguas. En Ia Figura 3 se representan, a modo de ejemplo, los resultados obtenidos para el proceso de adsorción de bromuros sobre Ia muestra de aerogel activado. Así, se puede concluir que el proceso de activación (muestra A-A) incrementa Ia capacidad de adsorción de iones bromuro y yoduro de los aerogeles considerablemente. Este hecho sería debido principalmente a i) un incremento en Ia microporosidad de Ia muestra, Io que provocaría que existiesen un mayor número de sitios de plata superficiales accesibles a los aniones bromuro y yoduro y, además ii) a un aumento en Ia hidrofobicidad de Ia misma, produciendo un incremento en las interacciones electrostáticas atractivas entre Ia superficie de Ia muestra, cargada positivamente al pH de trabajo y el anión correspondiente.The results observed (Figure 2) show that the airgel has an adsorption capacity much higher than that observed for Sorbo® activated carbon. Sorbo® activated carbon is a carbon widely used in drinking water treatment plants, and which, as can be seen in Figure 2, is not capable of adsorbing bromide and iodide anions from water. Figure 3 shows, by way of example, the results obtained for the bromide adsorption process on the activated airgel sample. Thus, it can be concluded that the activation process (sample AA) increases the adsorption capacity of bromide and iodide ions of the aerogels considerably. This fact would be mainly due to i) an increase in the microporosity of the sample, which would cause a greater number of surface silver sites accessible to the bromide and iodide anions and, in addition ii) to an increase in the hydrophobicity of the same , producing an increase in attractive electrostatic interactions between the surface of the sample, positively charged to the working pH and the corresponding anion.
Con el fin de determinar Ia aplicabilidad de los aerogeles de plata en el proceso de eliminación de aniones haluros de las aguas destinadas a consumo humano, se llevaron a cabo estudios de adsorción de los aniones bromuro y yoduro en régimen dinámico mediante el uso de las columnas indicadas anteriormente.In order to determine the applicability of silver aerogels in the process of removing halide anions from water intended for human consumption, studies of adsorption of bromide and iodide anions in dynamic regime were carried out through the use of columns indicated above.
En Ia Figura 4, se representa, a modo de ejemplo, las curvas de rotura de Ia columna para el anión bromuro durante dos ciclos de adsorción/regeneración, así como Ia evolución de Ia concentración de bromuros durante el proceso de regeneración aplicado. El proceso de regeneración de las columnas saturadas se llevó a cabo haciendo pasar durante 12 horas una disolución de amoniaco de concentración 0.02 M a través de Ia columna a un flujo de 1.5 mL/min. Posteriormente, y con el fin de eliminar el NH3 adsorbido sobre Ia superficie del aerogel, se llevó a cabo el lavado de Ia columna haciendo pasar agua MiIIi-Q durante 24 horas a través de Ia misma a un flujo de 1.5 mL/min. A partir de las curvas de rotura de las columnas correspondientes a los procesos de adsorción de los aniones bromuro y yoduro se han determinado los valores de las características de las columnas que se exponen en Ia Tabla 1. En ella se observa que Ia cantidad adsorbida en el punto de rotura de Ia columna (X0.02) es más elevada para el anión bromuro que para el anión yoduro. Además, de los resultados presentados en Ia Tabla 1 , es interesante destacar que, independientemente del anión considerado, Ia altura de Ia zona de transferencia de masa de las columnas es muy baja (HMτz)> mientras que Ia capacidad fraccional (φ) en esta zona es próxima a uno. Estos resultados indican una gran efectividad de las columnas en el proceso de eliminación de yoduros y bromuros de las aguas, como pone de manifiesto el grado de utilidad de las mismas, con valores comprendidos entre 60 % y 72 %.In Figure 4, the rupture curves of the column for the bromide anion during two adsorption / regeneration cycles, as well as the evolution of the bromide concentration during the applied regeneration process, is represented by way of example. The regeneration process of the saturated columns was carried out by passing for 12 hours a solution of 0.02 M concentration of ammonia through the column at a flow of 1.5 mL / min. Subsequently, and in order to remove the NH 3 adsorbed on the surface of the airgel, the washing of the column was carried out by passing MiIIi-Q water for 24 hours through it at a flow of 1.5 mL / min. From the breakage curves of the columns corresponding to the adsorption processes of the bromide and iodide anions, the values of the characteristics of the columns set forth in Table 1 have been determined. It shows that the amount adsorbed in The breaking point of the column (X 0 .0 2 ) is higher for the bromide anion than for the iodide anion. In addition, from the results presented in Table 1, it is interesting to note that, regardless of the anion considered, the height of the mass transfer zone of the columns is very low (H M τz) > while the fractional capacity (φ) In this area it is close to one. These results indicate a great effectiveness of the columns in the process of eliminating iodides and bromides from the waters, as evidenced by their degree of utility, with values between 60% and 72%.
Los resultados obtenidos después de aplicar el proceso de regeneración del aerogel descrito anteriormente indican una gran efectividad del mismo (Tabla 1), recuperándose, de acuerdo con el balance de masas realizado (Figura 4) el 100 % de Ia capacidad adsortiva del aerogel. De hecho, las características de Ia columna se mantienen prácticamente constantes después de tres ciclos de adsorción/regeneración (Tabla 1), tanto para el caso del anión bromuro como para el anión yoduro. Tabla 1. Características de las columnas de adsorción estudiadas.The results obtained after applying the regeneration process of the airgel described above indicate its great effectiveness (Table 1), recovering, according to the mass balance performed (Figure 4), 100% of the adsorptive capacity of the airgel. In fact, the characteristics of the column remain practically constant after three cycles of adsorption / regeneration (Table 1), both for the bromide anion and for the iodide anion. Table 1. Characteristics of the adsorption columns studied.
Anión Ciclos Vo.02 Xθ.02 Xθ.95 H MTZ Φ Gu adsorción/regeneración (L) (μmol/g) (μmol/g) (cm)Anion Cycles Vo.02 Xθ.02 Xθ.95 H MTZ Φ Gu adsorption / regeneration (L) (μmol / g) (μmol / g) (cm)
Bf 1 0.30 0.18 0.30 4.77 0.95 60Bf 1 0.30 0.18 0.30 4.77 0.95 60
Bf 2 0.37 0.23 0.32 2.94 0.96 72Bf 2 0.37 0.23 0.32 2.94 0.96 72
Bf 3 0.35 0.22 0.34 3.25 0.96 65 r 1 0.32 0.14 0.21 5.11 0.97 66 r 2 0.33 0.15 0.22 4.71 0.97 68 r 3 0.30 0.14 0.21 6.76 0.93 66Bf 3 0.35 0.22 0.34 3.25 0.96 65 r 1 0.32 0.14 0.21 5.11 0.97 66 r 2 0.33 0.15 0.22 4.71 0.97 68 r 3 0.30 0.14 0.21 6.76 0.93 66
V0.02 : Volumen de agua tratada en el punto de rotura de Ia columna X0.02: Cantidad de haluro adsorbido en el punto de rotura de Ia columna.V0.0 2 : Volume of treated water at the breaking point of column X0. 02 : Amount of halide adsorbed at the breaking point of the column.
HMτz : Altura de Ia zona de transferencia de masa de Ia columna. X0.95 : Porcentaje de haluro adsorbido para el valor de rotura deH M τz: Height of the mass transfer zone of the column. X0.95: Percentage of halide adsorbed for the breakage value of
0.95. φ : Capacidad fraccional de Ia zona de transferencia de masa.0.95. φ: Fractional capacity of the mass transfer zone.
Gu: Grado de utilidad (Xo.O2/Xo.95)x100.G u : Degree of utility (X o . O 2 / Xo.95) x100.
Un aspecto muy importante, desde el punto de vista de Ia aplicabilidad de este material en los tratamientos de aguas, es Ia posible disolución de los diferentes precursores del polímero orgánico creado, así como Ia posible reducción en Ia concentración de plata superficial después de varios ciclos de adsorción/regeneración. Con el fin de dilucidar estos aspectos se determinó Ia concentración de carbono orgánico disuelto durante el proceso de adsorción/regeneración y se llevaron a cabo análisis de espectrometría de fototoemisión de rayos X (XPS) de Ia muestras de aerogel para los distintos ciclos de adsorción/regeneración. Los resultados obtenidos mostraron que Ia concentración de carbono orgánico a Ia salida de Ia columna era igual a cero, mientras que Ia concentración de plata superficial fue de 8% y un 10% para Ia muestra sometida a 3 ciclos de adsorción/regeneración y Ia muestra original, respectivamente. Estos resultados indicarían que no se produce Ia disolución de los precursores orgánicos de los aerogeles y que Ia concentración de plata superficial no está modificada significativamente después de 3 ciclos de adsorción/regeneración. A very important aspect, from the point of view of the applicability of this material in water treatments, is the possible dissolution of the different precursors of the organic polymer created, as well as the possible reduction in the concentration of surface silver after several cycles of adsorption / regeneration. In order to elucidate these aspects, the concentration of dissolved organic carbon was determined during the adsorption / regeneration process and X-ray phototransmission (XPS) spectrometry analysis of the airgel samples was carried out for the different cycles of adsorption / regeneration. The results obtained showed that the concentration of organic carbon at the exit of the column was equal to zero, while the concentration of surface silver was 8% and 10% for the sample subjected to 3 adsorption / regeneration cycles and the sample original, respectively. These results would indicate that the dissolution of the organic precursors of the aerogels does not occur and that the concentration of surface silver is not significantly modified after 3 adsorption / regeneration cycles.
DESCRIPCIÓN DE LAS FIGURASDESCRIPTION OF THE FIGURES
Figura 1. Isotermas de adsorción en agua MiIIi-Q de los haluros sobre el aerogelFigure 1. MiIIi-Q water adsorption isotherms of halides on the airgel
orgánico de plata (muestra A). (o) indica cloruros; (0) indica bromuros y (Δ) indicaOrganic silver (sample A). (o) indicates chlorides; (0) indicates bromides and (Δ) indicates
yoduros.iodides
Figura 2. Comparación de Ia capacidad de los aerogeles de Ag con el carbón activado comercial en Ia eliminación de bromuros de aguas del Lago de Zurich. (D)Figure 2. Comparison of the capacity of Ag aerogels with commercial activated carbon in the removal of bromides from waters of Lake Zurich. (D)
indica aerogel A y (o) indica carbón activado Sorbo®.indicates airgel A and (o) indicates activated carbon Sorbo®.
Figura 3. Isotermas de adsorción de los aniones bromuro enagua MiIIi-Q sobre lasFigure 3. Adsorption isotherms of the bromide anions in MiIIi-Q water on the
muestras de aerogel de Ag estudiadas, (Δ) indica muestra A; (α) indica muestra A-Ag airgel samples studied, (Δ) indicates sample A; (α) indicates sample A-
A.TO.
Figura 4. Curvas de rotura del aerogel orgánico dopado con Ag en Ia adsorción delFigure 4. Breaking curves of the organic airgel doped with Ag in the adsorption of the
anión bromuro en agua MiIIi-Q. T 220C1 pH 7, [Br']¡nιc¡ai = 150 μg/L. (o) representa elwater bromide anion MiIIi-Q. T 22 0 C 1 pH 7, [Br ' ] ¡ n ι c ¡ a i = 150 μg / L. (o) represents the
primer ciclo adsorción/regeneración, (Δ) el segundo ciclo adsorción/regeneración yfirst adsorption / regeneration cycle, (Δ) the second adsorption / regeneration cycle and
(β) indica Ia regeneración con NH3 (0.02 M). (β) indicates the regeneration with NH 3 (0.02 M).

Claims

REIVINDICACIONES
1. Sistema para Ia eliminación de aniones cloruros, bromuros y/o yoduros de aguas caracterizado por utilizar aerogeles orgánicos dopados con plata como adsorbentes.1. System for the elimination of chloride anions, bromides and / or water iodides characterized by using organic aerogels doped with silver as adsorbents.
2. Sistema para Ia eliminación de aniones cloruros, bromuros y yoduros en aguas según Ia reivindicación anterior, caracterizado porque los aerogeles orgánicos utilizados como adsorbente se encuentran en forma granular. 2. System for the elimination of chloride, bromide and iodide anions in water according to the previous claim, characterized in that the organic aerogels used as adsorbent are in granular form.
3. Sistema para Ia eliminación de aniones cloruros, bromuros y/o yoduros en aguas, según Ia reivindicación 1 , caracterizado porque los aerogeles orgánicos utilizados como adsorbente se encuentran en forma de polvo.3. System for the elimination of chloride, bromide and / or iodide anions in water, according to claim 1, characterized in that the organic aerogels used as adsorbent are in powder form.
4. Sistema para Ia eliminación de aniones cloruros, bromuros y/o yoduros en aguas, caracterizado por usar membranas preparadas a partir de aerogeles dopados con plata.4. System for the elimination of chloride, bromide and / or iodide anions in water, characterized by using membranes prepared from aerogels doped with silver.
5. Sistema para Ia eliminación de aniones cloruros, bromuros y/o yoduros en aguas, según cualquiera de las reivindicaciones anteriores, caracterizado por usar aerogeles orgánicos dopados con plata sometidos a un proceso de activación física con vapor de agua. 5. System for the elimination of chloride, bromide and / or iodide anions in water, according to any of the preceding claims, characterized by using organic aerogels doped with silver subjected to a physical activation process with water vapor.
6. Sistema para Ia eliminación de aniones cloruros, bromuros y/o yoduros en aguas, según cualquiera de las reivindicaciones 1 a 4, caracterizado por usar aerogeles orgánicos dopados con plata sometidos a un proceso de activación física con dióxido de carbono.6. System for the elimination of chloride, bromide and / or iodide anions in water, according to any one of claims 1 to 4, characterized by using organic aerogels doped with silver subjected to a physical activation process with carbon dioxide.
7. Sistema para Ia eliminación de aniones cloruros, bromuros y/o yoduros en aguas, según cualquiera de las reivindicaciones 1 a 4, caracterizado por usar aerogeles orgánicos dopados con plata sometidos a un proceso de activación química con hidróxidos alcalinos.7. System for the elimination of chloride, bromide and / or iodide anions in water, according to any of claims 1 to 4, characterized for using organic aerogels doped with silver undergoing a chemical activation process with alkaline hydroxides.
8. Sistema para Ia eliminación de aniones cloruros, bromuros y/o yoduros en aguas, según cualquiera de las reivindicaciones 1 a 4, sometidos caracterizado por usar aerogeles orgánicos dopados con plata sometidos a un proceso de activación química con ácido fosfórico.8. System for the elimination of chloride, bromide and / or iodide anions in water, according to any one of claims 1 to 4, subject to using organic aerogels doped with silver subjected to a chemical activation process with phosphoric acid.
9. Sistema integrado para el tratamiento de aguas según cualquiera de las reivindicaciones anteriores que comprende: a. Una bomba peristáltica b. Una columna rellena del aerogel dopado con plata del tamaño de partícula deseado, por Ia que se filtra el agua contaminada. c. Un sistema de separación de fases. d. Un colector de muestras situado a Ia salida de Ia columna. 9. Integrated water treatment system according to any of the preceding claims comprising: a. A peristaltic pump b. A column filled with silver doped airgel of the desired particle size, whereby the contaminated water is filtered. C. A phase separation system. d. A sample collector located at the exit of the column.
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US6843919B2 (en) * 2002-10-04 2005-01-18 Kansas State University Research Foundation Carbon-coated metal oxide nanoparticles

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