WO2010139816A1 - Composition and use of an adsorbent material for filtering toxic components during the process of incineration and/or distillation of glycerine generated from the production of biodiesel - Google Patents

Composition and use of an adsorbent material for filtering toxic components during the process of incineration and/or distillation of glycerine generated from the production of biodiesel Download PDF

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WO2010139816A1
WO2010139816A1 PCT/ES2009/070210 ES2009070210W WO2010139816A1 WO 2010139816 A1 WO2010139816 A1 WO 2010139816A1 ES 2009070210 W ES2009070210 W ES 2009070210W WO 2010139816 A1 WO2010139816 A1 WO 2010139816A1
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composition
incineration
glycerin
adsorbent material
biodiesel
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PCT/ES2009/070210
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Spanish (es)
French (fr)
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Pedro Romera Lorca
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Desarrollos Tecnicos Mc, S.L.
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Priority to PCT/ES2009/070210 priority Critical patent/WO2010139816A1/en
Publication of WO2010139816A1 publication Critical patent/WO2010139816A1/en

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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
    • B01D53/02—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols by adsorption, e.g. preparative gas chromatography
    • 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
    • B01J20/04—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising compounds of alkali metals, alkaline earth metals or magnesium
    • B01J20/043—Carbonates or bicarbonates, e.g. limestone, dolomite, aragonite
    • 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
    • B01J20/10—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising silica or silicate
    • B01J20/12—Naturally occurring clays or bleaching earth
    • 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
    • B01J20/20—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising free carbon; comprising carbon obtained by carbonising processes
    • 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
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2253/00—Adsorbents used in seperation treatment of gases and vapours
    • B01D2253/10—Inorganic adsorbents
    • B01D2253/102—Carbon
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2253/00—Adsorbents used in seperation treatment of gases and vapours
    • B01D2253/10—Inorganic adsorbents
    • B01D2253/106—Silica or silicates
    • B01D2253/11—Clays
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2257/00—Components to be removed
    • B01D2257/20—Halogens or halogen compounds
    • B01D2257/202—Single element halogens
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2257/00—Components to be removed
    • B01D2257/20—Halogens or halogen compounds
    • B01D2257/206—Organic halogen compounds
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2257/00—Components to be removed
    • B01D2257/30—Sulfur compounds
    • B01D2257/302—Sulfur oxides
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2257/00—Components to be removed
    • B01D2257/40—Nitrogen compounds
    • B01D2257/404—Nitrogen oxides other than dinitrogen oxide
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2257/00—Components to be removed
    • B01D2257/50—Carbon oxides
    • B01D2257/502—Carbon monoxide
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2257/00—Components to be removed
    • B01D2257/50—Carbon oxides
    • B01D2257/504—Carbon dioxide
    • 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
    • B01J2220/40—Aspects relating to the composition of sorbent or filter aid materials
    • B01J2220/46—Materials comprising a mixture of inorganic and organic materials
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02C—CAPTURE, STORAGE, SEQUESTRATION OR DISPOSAL OF GREENHOUSE GASES [GHG]
    • Y02C20/00—Capture or disposal of greenhouse gases
    • Y02C20/40—Capture or disposal of greenhouse gases of CO2

Definitions

  • the object of the present invention is a composition of adsorbent material that allows the elimination of toxic emissions in the incineration and / or distillation of glycerin in order to avoid the storage of large volumes of glycerin from the production of Large-scale biodiesel, which can be incinerated without contamination of the environment due to the carcinogenic products generated from the combustion of glycerin, in particular, acrolein.
  • Biodiesel is a product obtained by a process of transesterification (formation of methyl esters) of the fatty acids in vegetable oils (soy, sunflower, rape, ). Its characteristics are similar to that of diesel, although it should be noted that biodiesel has a flash point considerably higher than diesel, which makes it much less dangerous. The percentage of sulfur is also a factor to review, since it avoids the emission of this component to the atmosphere with its corresponding environmental improvement.
  • biodiesel is a mixture of fatty acid methyl esters.
  • the raw material, fats and oils, are fundamentally triglycerides of fatty acids.
  • the fundamental raw material is rapeseed, since it is the most economical oilseed existing, being able to use other vegetable oils such as sunflower, palm, soy, etc.
  • Other possibilities are to use animal fats of low cost or used oil that was used for fried foods.
  • the transesterification reaction is a reaction characteristic of the esters, and consequently of the lipids, in which the oil or fat reacts with fatty acids, alcohols or other esters with the exchange of acyl groups.
  • a catalyst mainly sodium methylate, soda or potash, as can be seen in the following reaction:
  • Glycerin is a product of the transesterification reaction and therefore its formation in the biodiesel production process cannot be avoided.
  • the amount of glycerin that is generated is very important, representing approximately 10% of the biodiesel produced.
  • crude glycerin will be obtained, with a percentage of glycerol around 80%, or pharmaceutical grade glycerin, with a percentage of glycerol of the 99.7%
  • the substances that accompany glycerin are, mainly, water, salts and organic matter (not glycerin), formed by soaps, free fatty acids and other impurities.
  • the crude glycerin obtained in the biodiesel industry has the great disadvantage of being composed of a series of miscible components and very different chemical properties (methanol, potassium, water, free fatty acids and glycerin). For this reason glycerin is still the big problem of biodiesel plants.
  • glycerin can be separated by spliting (acidification) to obtain a purity of around 80%, this method would entail new expenses associated with those of combustion technologies, the ideal would be to use raw glycerin directly, taking advantage of the calorific value of other components such as methanol, but with an efficient system of ash withdrawals generated by inorganic minerals originated and elimination of toxic gases.
  • An area that shows an appreciable potential to consume high amounts of glycerin is the use of glycerin for energy production. Glycerin burns well, but must be burned at high temperatures so that no toxic fumes of acrolein, which is formed mainly between 200 0 C and 300 0 C are produced, and other carcinogenic pollutants.
  • the presence of salts can cause corrosion problems in the burner nozzles and in the combustion facility itself.
  • the salts are flame inhibitors, which hinders the combustion of glicehna without using it in an auxiliary fuel.
  • the present invention satisfactorily solves the process of incineration and distillation of the glycerin, since it provides an adsorbent material that can be used in the filters at the exit of the chimneys or fluid discharge tubes and which is formed mainly of graphite in the state pure or combined with activated carbon from tires or any known element, both in combination with natural silicates such as enstatite or sepiolites, attapulgites, zeolites, or the like or their mixture and plasticizing and / or polymerizable agents or a mixture thereof ,
  • the resulting mixture is capable of adding carbonates of alkaline or alkaline earth metals in substitution of the plasticizing and / or polymerizable agents, which allow to reduce in its entirety the toxic emissions in the incineration of the glycerin obtained in the biodiesel production processes due to very high adsorbent potential.
  • the object of the invention is an adsorbent material that can be used in filters at the exit of chimneys or fluid discharge tubes in order to avoid toxic emissions of various pollutants such as: CO, Dioxins, Furans, PCBs. (Polychlorobiphenyls) , NO 2 , SO 2 , Halogens, Aldehydes, CO 2 ,
  • Acrolein, etc. in the process of incineration of non-pharmaceutical grade glycerin that is produced as a secondary product in the biodiesel production process, that is, a material that has an adsorption capacity superior to pure activated carbon and the same present time special mechanical qualities, also high surface performance, resistant to breakage and abrasion and easily conformable, by integrating the properties of natural silicates of clay or plasticizing and / or polymerizable agents or carbonates of alkali or alkaline earth metal carbonates to structures such as graphite and / or activated carbon.
  • the surface available for adsorption depends on the size of the adsorbate molecule and the pore diameter of the adsorbent material; if it is intended to adsorb large molecules it is of greater interest to have adsorbents with adequate pore diameter.
  • the intimate mixing of the aforementioned components produces several effects: a) it results in materials that have a significant increase in specific surface area and a greater volume of meso and macropores when compared with the values that would correspond to the starting products taking into account their percentages in the mixture; b) the graphite and / or activated carbon integrated in the mass limits the reduction in volume that normally occurs when a wet piece can be made of silicate, algae or carbonates is subjected to drying and subsequent heat treatment: c) the graphite also allows increase the adsorption capacity and avoid the attack of other chemical agents, since by means of the activation process of said graphite, it is possible to obtain a material formed by unions of elementary graffiti microcrystals, usually blocked by tars and carbonization residues that are the cause of the decrease in the adsorbent capacity of this graphite in its pure state.
  • any natural silicate from clays or other components can be used in the mixture, in particular bentonite, enstatite or ⁇ -sepiolite, attapulgite, zeolites, in the pure state or forming mixtures, the aggregate increases its mechanical capabilities.
  • the mixture adds one or more plasticizing and / or polymerizable agents independent of its origin or extraction procedure with a disaggregated particle size between 2 to 100 microns, the resulting porous texture of this material having an average surface area of 6 m 2 g "1 with a texture development with a tendency to macroporosity, so that they are treated at temperatures above 500 ° C in order to improve their mechanical and abrasion conditions, at that temperature carbon dioxide is released with formation of calcium and magnesium oxides whereby the specific surface of the material is reduced.
  • alkaline or alkaline earth metal carbonates may be added in substitution of the plasticizing and / or polymerizable agents which produce similar results.
  • the weight ratio between graphite, activated carbon, clay silicates and the agents plasticizers and / or polymerizable can vary between 1: 0: 2: 2 to 1: 1: 2: 1, in case of not using plasticizers and / or polymerizable agents, it is possible to use alkaline or alkaline earth metal carbonates as previously stated, but the results are significantly lower in their adsorption capacity, now an increase in the aggregate of graphite or activated carbon increases the adsorbent power but to the detriment of the mechanical qualities of the pieces obtained after drying and activation.
  • the adsorbent material graphite, activated carbon, clay fibrous silicates and the plasticizing and / or polymerizing agent in the range of the proportions specified above are mixed dry and homogeneously, preferably kneaded with water preferably deionized for approximately 5 hours ,
  • the resulting paste is molded or extruded, to obtain the desired shapes, which can be shaped as granules, pellets, spheres, hollow cylinders, plates or in parallel channel structures along the longitudinal axis
  • the composition has a structure of parallel channels along the longitudinal axis of between 5 and 100 channels per square centimeter of its cross section being preferably formed as hollow cylinders, of the smooth, striated, straight, curved "macaroni" type, of regular or irregular cut, in any shape and size in the form of hollow cylinders, spheres or the like, these may have an approximate length 0.4 cm to approximately 10 cm and the thickness of the wall can be between 0.03 to 0.5 cm in order to allow its application for large
  • the molded elements are dried at room temperature for at least 2 hours, then the product is heat treated in an inert atmosphere oven at a temperature ranging from 500 to 1000 0 C.
  • the resulting product has a unique composition and tested for use.
  • large-scale contaminant gas adsorption filters allowing the elimination of CO, Dioxins, Furans, PCBs (NO 2 , SO 2 , Halogens, Aldehydes, CO 2 , Acrolein, etc.) emissions in incineration processes , combustion and / or distillation of the glycerin, solving the problem of storage of said glycerin in the Biodiesel production plants, the filtering product can be used in the fixed bed and mobile bed filters

Abstract

The invention relates to an adsorbent material composition enabling the elimination of toxic emissions during the incineration and/or distillation of glycerine in order to avoid storing large volumes of glycerine generated from the large-scale production of biodiesel, the glycerine being incinerable without contaminating the environment with the carcinogenic products generated from the combustion of the glycerine, especially acrolein. For the preparation of the adsorbent material, graphite, activated carbon, fibrous clay silicates and polymerisable and/or plasticising agents are mixed in a dry and homogeneous manner.

Description

COMPOSICIÓN Y USO DE UN MATERIAL ADSORBENTE PARA EL FILTRADO DE COMPONENTES TÓXICOS EN EL PROCESO DE COMPOSITION AND USE OF AN ADSORBENT MATERIAL FOR FILTERING TOXIC COMPONENTS IN THE PROCESS OF
INCINERACIÓN Y/O DESTILACIÓN DE LA GLICERINA PROCEDENTE DE LA PRODUCCIÓN DE BIODIESELINCINERATION AND / OR DISTILLATION OF GLYCERINE FROM BIODIESEL PRODUCTION
OBJETO DE LA INVENCIÓN El objeto de Ia presente invención es una composición de material adsorbente que permita Ia eliminación de emisiones tóxicas en Ia incineración y/o destilación de Ia glicerina con el fin de evitar el almacenamiento de grandes volúmenes de Glicerina provenientes de Ia producción de Biodiesel a gran escala, pudiendo esta ser incinerada sin Ia contaminación del medio debido a los productos cancerígenos generados de Ia combustión de Ia glicerina en particular Ia acroleína.OBJECT OF THE INVENTION The object of the present invention is a composition of adsorbent material that allows the elimination of toxic emissions in the incineration and / or distillation of glycerin in order to avoid the storage of large volumes of glycerin from the production of Large-scale biodiesel, which can be incinerated without contamination of the environment due to the carcinogenic products generated from the combustion of glycerin, in particular, acrolein.
ANTECEDENTES TÉCNICOSTECHNICAL BACKGROUND
El biodiesel es un producto obtenido por un proceso de transesterificación (formación de esteres metílicos) de los ácidos grasos existentes en los aceites vegetales (soja, girasol, colza,...). Sus características son similares a Ia del gasóleo aunque cabe destacar que el biodiesel posee un punto de inflamación considerablemente superior al del gasóleo, Io que Io hace mucho menos peligroso. El porcentaje de azufre es también un factor a reseñar, ya que evita Ia emisión de este componente a Ia atmósfera con su correspondiente mejora medioambiental.Biodiesel is a product obtained by a process of transesterification (formation of methyl esters) of the fatty acids in vegetable oils (soy, sunflower, rape, ...). Its characteristics are similar to that of diesel, although it should be noted that biodiesel has a flash point considerably higher than diesel, which makes it much less dangerous. The percentage of sulfur is also a factor to review, since it avoids the emission of this component to the atmosphere with its corresponding environmental improvement.
Desde el punto de vista químico el biodiesel es una mezcla de los esteres metílicos de los ácidos grasos. La materia prima, grasas y aceites, son fundamentalmente triglicéridos de los ácidos grasos. En Europa Ia materia prima fundamental es Ia colza, ya que es Ia oleaginosa existente más económica, pudiendo emplearse otros aceites vegetales como pueden ser: girasol, palma, soja, etc. Otras posibilidades son emplear grasas animales de bajo costo o el aceite usado que fuera empleado para frituras. La reacción de transesterificación es una reacción característica de los esteres, y consecuentemente de los lípidos, en Ia cual el aceite o Ia grasa reacciona con ácidos grasos, alcoholes u otros esteres con el intercambio de los grupos acilo. Para favorecer Ia reacción se utiliza un catalizador, principalmente metilato de sodio, sosa o potasa, tal y como puede verse en Ia siguiente reacción:From a chemical point of view, biodiesel is a mixture of fatty acid methyl esters. The raw material, fats and oils, are fundamentally triglycerides of fatty acids. In Europe the fundamental raw material is rapeseed, since it is the most economical oilseed existing, being able to use other vegetable oils such as sunflower, palm, soy, etc. Other possibilities are to use animal fats of low cost or used oil that was used for fried foods. The transesterification reaction is a reaction characteristic of the esters, and consequently of the lipids, in which the oil or fat reacts with fatty acids, alcohols or other esters with the exchange of acyl groups. To favor the reaction a catalyst is used, mainly sodium methylate, soda or potash, as can be seen in the following reaction:
Figure imgf000003_0001
Figure imgf000003_0001
La glicerina es un producto de Ia reacción de transesterificación y por Io tanto no puede evitarse su formación en el proceso de producción de biodiesel. La cantidad de glicerina que se genera es muy importante, representando aproximadamente el 10% del biodiesel producido. En función de los tratamientos a los que es sometida Ia corriente pesada que se origina en Ia reacción de transesterificación se obtendrá glicerina cruda, con un porcentaje de glicerol en torno al 80%, o bien glicerina de grado farmacéutico, con un porcentaje de glicerol del 99,7%. Las sustancias que acompañan a Ia glicerina son, principalmente, agua, sales y materia orgánica (no glicerina), formada por jabones, ácidos grasos libres y otras impurezas.Glycerin is a product of the transesterification reaction and therefore its formation in the biodiesel production process cannot be avoided. The amount of glycerin that is generated is very important, representing approximately 10% of the biodiesel produced. Depending on the treatments to which the heavy current that originates in the transesterification reaction is subjected, crude glycerin will be obtained, with a percentage of glycerol around 80%, or pharmaceutical grade glycerin, with a percentage of glycerol of the 99.7% The substances that accompany glycerin are, mainly, water, salts and organic matter (not glycerin), formed by soaps, free fatty acids and other impurities.
La glicerina cruda obtenida en Ia industria del biodiesel, posee el gran inconveniente de estar compuesta por una serie de componentes miscibles entre sí y de propiedades químicas muy diferentes (metanol, potasio, agua, ácidos grasos libres y glicerina). Por esta razón Ia glicerina sigue siendo el gran problema de las plantas de biodiesel.The crude glycerin obtained in the biodiesel industry has the great disadvantage of being composed of a series of miscible components and very different chemical properties (methanol, potassium, water, free fatty acids and glycerin). For this reason glycerin is still the big problem of biodiesel plants.
Debido al incremento exponencial de Ia producción de biodiesel, Ia glicerina bruta generada en Ia reacción de transesterificación de los aceites vegetales está alcanzando grandes cantidades. Independientemente del amplio abanico de aplicaciones del glicerol puro en alimentación, el sector farmacéutico, cosmético y otras muchas industrias, resulta muy costoso refinar Ia glicerina cruda hasta una elevada pureza, especialmente por los pequeños y medianos productores de biodiesel. Por cada 9 kg. de biodiesel producido, se genera 1 kg. de glicerina cruda, así se están investigando y analizando diferentes formas de utilizar Ia glicerina cruda generada por los productores de biodiesel. Debido a esta gran cantidad generada, se esta investigando Ia conversión de Ia glicerina cruda en productos específicos que ayudarían a disminuir los costes de producción del biodiesel. Si bien se puede separar Ia glicerina mediante spliting (acidificación) para obtener una pureza en torno al 80%, este método conllevaría nuevos gastos asociados a los de las tecnologías de combustión, Io ideal sería utilizar Ia glicerina cruda directamente, aprovechando el poder calorífico de otros componentes como el metanol, pero con un sistema eficiente de retiradas de cenizas generadas por los minerales inorgánicos originados y eliminación de gases tóxicos. Un área que muestra un apreciable potencial para consumir elevadas cantidades de glicerina es Ia utilización de Ia glicerina para Ia producción energética. La glicerina arde bien, pero tiene que ser quemada a elevadas temperaturas para que no se produzcan humos tóxicos de acroleína, que se forma principalmente entre los 2000C y los 3000C, además de otros contaminantes cancerígenos. La utilización directa de Ia glicerina cruda como un combustible líquido asimilable a los aceites residuales tiene algunos inconvenientes: Tiene un bajo poder calorífico (entre 2.800 y 3.500 kcal/kg), Io que hace que sea incapaz de mantener Ia llama en un quemador convencional. Esto se agrava por Ia presencia de agua en Ia mezcla. Su elevada viscosidad hace que sea difícil Ia pulverización.Due to the exponential increase in biodiesel production, the crude glycerin generated in the transesterification reaction of vegetable oils is reaching large quantities. Regardless of the wide range of applications of pure glycerol in Food, pharmaceutical, cosmetic and many other industries, it is very expensive to refine the raw glycerin to high purity, especially for small and medium producers of biodiesel. For every 9 kg. of biodiesel produced, 1 kg is generated. of crude glycerin, so they are investigating and analyzing different ways of using the raw glycerin generated by biodiesel producers. Due to this large amount generated, the conversion of raw glycerin into specific products that would help reduce the production costs of biodiesel is being investigated. Although glycerin can be separated by spliting (acidification) to obtain a purity of around 80%, this method would entail new expenses associated with those of combustion technologies, the ideal would be to use raw glycerin directly, taking advantage of the calorific value of other components such as methanol, but with an efficient system of ash withdrawals generated by inorganic minerals originated and elimination of toxic gases. An area that shows an appreciable potential to consume high amounts of glycerin is the use of glycerin for energy production. Glycerin burns well, but must be burned at high temperatures so that no toxic fumes of acrolein, which is formed mainly between 200 0 C and 300 0 C are produced, and other carcinogenic pollutants. The direct use of crude glycerin as a liquid fuel assimilable to residual oils has some drawbacks: It has a low calorific value (between 2,800 and 3,500 kcal / kg), which makes it unable to keep the flame in a conventional burner. This is aggravated by the presence of water in the mixture. Its high viscosity makes spraying difficult.
La presencia de sales puede causar problemas de corrosión en las boquillas de los quemadores y en Ia propia instalación de combustión. Las sales son inhibidores de llama, Io que dificulta Ia combustión de Ia glicehna sin utilizar en un combustible auxiliar.The presence of salts can cause corrosion problems in the burner nozzles and in the combustion facility itself. The salts are flame inhibitors, which hinders the combustion of glicehna without using it in an auxiliary fuel.
Otros procesos como Ia biogasificación, gasificación, procesos Fisher- Tropsch..., se están desarrollando en Ia actualidad pero únicamente a nivel de investigación y no están dando resultados satisfactorios. La purificación de Ia glicehna hasta grado farmacéutico no es rentable con las tecnologías actuales, por eso nadie ha intentado atreverse a utilizar esta vía. La glicehna cruda sigue siendo un problema real que limita Ia ya muy mermada capacidad de las plantas de biodiesel, que se mantienen con vida todavía. La presente invención resuelve satisfactoriamente el proceso de incineración y destilación de Ia glicerina, ya que aporta un material adsorbente que puede ser utilizado en los filtros a Ia salida de las chimeneas o tubos de descarga de fluido y que se encuentra formado fundamentalmente de grafito en estado puro o combinado con carbón activado proveniente de neumáticos o de cualquier elemento conocido, ambos en combinación con silicatos naturales como pueden ser enstatita o sepiolitas, atapulgitas, zeolitas, o similares o bien su mezcla y agentes plastificantes y/o polimerizables o una mezcla de ellos , Ia mezcla resultante es susceptible de adicionar carbonatos de metales alcalinos o alcalinotérreos en sustitución de los agentes plastificantes y/o polimerizables, que permitan reducir en su totalidad las emisiones tóxicas en Ia incineración de Ia glicerina obtenida en los procesos de producción de biodiesel debido altísimo potencial adsorbente. Other processes such as biogasification, gasification, Fisher-Tropsch processes ..., are currently being developed but only at the research level and are not giving satisfactory results. The purification of glicehna to pharmaceutical grade is not profitable with current technologies, so nobody has tried to dare to use this route. Crude glicehna remains a real problem that limits the already very depleted capacity of biodiesel plants, which are still alive. The present invention satisfactorily solves the process of incineration and distillation of the glycerin, since it provides an adsorbent material that can be used in the filters at the exit of the chimneys or fluid discharge tubes and which is formed mainly of graphite in the state pure or combined with activated carbon from tires or any known element, both in combination with natural silicates such as enstatite or sepiolites, attapulgites, zeolites, or the like or their mixture and plasticizing and / or polymerizable agents or a mixture thereof , The resulting mixture is capable of adding carbonates of alkaline or alkaline earth metals in substitution of the plasticizing and / or polymerizable agents, which allow to reduce in its entirety the toxic emissions in the incineration of the glycerin obtained in the biodiesel production processes due to very high adsorbent potential.
DESCRIPCIÓN DE LA INVENCIÓNDESCRIPTION OF THE INVENTION
El objeto de Ia invención es un material adsorbente que puede ser utilizado en filtros a Ia salida de chimeneas o tubos de descargas de fluidos con el fin de evitar las emisiones tóxicas de diversos contaminantes como: CO, Dioxinas, Furanos, PCB's.(Policlorobifenilos), NO2, SO2, Halógenos, Aldehidos, CO2,The object of the invention is an adsorbent material that can be used in filters at the exit of chimneys or fluid discharge tubes in order to avoid toxic emissions of various pollutants such as: CO, Dioxins, Furans, PCBs. (Polychlorobiphenyls) , NO 2 , SO 2 , Halogens, Aldehydes, CO 2 ,
Acroleína, etc., en el proceso de incineración de Ia glicerina de grado no farmacéutica que es producida como producto secundario en el proceso de producción de biodiesel, esto es, un material que tenga una capacidad de adsorción superior al carbón activado puro y al mismo tiempo presente cualidades mecánicas especiales, así mismo altas prestaciones superficiales, resistente a Ia rotura y Ia abrasión y fácilmente conformables, mediante Ia integración de las propiedades de los silicatos naturales de arcilla o agentes plastificantes y/o polimerizables o carbonatos de metales alcalinos o alcalino térreos a estructuras como grafito y/o carbón activado. La superficie disponible para Ia adsorción depende del tamaño de Ia molécula del adsorbato y del diámetro de poro del material adsorbente; si se pretende adsorber moléculas de gran tamaño es de mayor interés disponer de adsorbentes con diámetro de poro adecuado. La mezcla intima de los componentes citados produce varios efectos : a) da como resultado unos materiales que presentan un aumento significativo de superficie especifica y un mayor volumen de meso y macroporos cuando se compara con los valores que corresponderían a los productos de partida teniendo en cuenta sus porcentajes en Ia mezcla; b) el grafito y/o el carbón activado integrado en Ia masa limita Ia reducción de volumen que normalmente se produce cuando una pieza húmeda pudiendo ser de silicato, algas o carbonatos se somete a secado y posterior tratamiento térmico: c) el grafito también permite aumentar Ia capacidad de adsorción y evitar el ataque de otros agentes químicos, ya que mediante el proceso de activación de dicho grafito, se consigue obtener un material formado por uniones de microcristales grafiticos elementales, usualmente taponados por alquitranes y residuos de carbonización que son los causantes de Ia disminución de Ia capacidad adsorbente de este grafito en su estado puro.Acrolein, etc., in the process of incineration of non-pharmaceutical grade glycerin that is produced as a secondary product in the biodiesel production process, that is, a material that has an adsorption capacity superior to pure activated carbon and the same present time special mechanical qualities, also high surface performance, resistant to breakage and abrasion and easily conformable, by integrating the properties of natural silicates of clay or plasticizing and / or polymerizable agents or carbonates of alkali or alkaline earth metal carbonates to structures such as graphite and / or activated carbon. The surface available for adsorption depends on the size of the adsorbate molecule and the pore diameter of the adsorbent material; if it is intended to adsorb large molecules it is of greater interest to have adsorbents with adequate pore diameter. The intimate mixing of the aforementioned components produces several effects: a) it results in materials that have a significant increase in specific surface area and a greater volume of meso and macropores when compared with the values that would correspond to the starting products taking into account their percentages in the mixture; b) the graphite and / or activated carbon integrated in the mass limits the reduction in volume that normally occurs when a wet piece can be made of silicate, algae or carbonates is subjected to drying and subsequent heat treatment: c) the graphite also allows increase the adsorption capacity and avoid the attack of other chemical agents, since by means of the activation process of said graphite, it is possible to obtain a material formed by unions of elementary graffiti microcrystals, usually blocked by tars and carbonization residues that are the cause of the decrease in the adsorbent capacity of this graphite in its pure state.
Se puede utilizar en Ia mezcla cualquier silicato natural proveniente de las arcillas o de otros componentes, en particular bentonita, enstatita o ά- sepiolita, atapulgita, zeolitas, en estado puro o formando mezclas, el agregado aumenta sus capacidades mecánicas.Any natural silicate from clays or other components can be used in the mixture, in particular bentonite, enstatite or ά-sepiolite, attapulgite, zeolites, in the pure state or forming mixtures, the aggregate increases its mechanical capabilities.
Así mismo, Ia mezcla adiciona uno o varios agentes plastificantes y/o polimerizables independiente de su procedencia o procedimiento de extracción con un tamaño de partícula desagregada comprendido entre 2 a 100 mieras, teniendo Ia textura resultante porosa de este material una superficie media de 6 m2g"1 con un desarrollo de su textura con tendencia a Ia macroporosidad, por Io que se tratan a temperaturas superiores a los 500° C con el fin de mejorar sus condiciones mecánicas y de abrasión, a dicha temperatura se desprende dióxido de carbono con formación de óxidos de calcio y magnesio por Io que se reduce Ia superficie específica del material.Likewise, the mixture adds one or more plasticizing and / or polymerizable agents independent of its origin or extraction procedure with a disaggregated particle size between 2 to 100 microns, the resulting porous texture of this material having an average surface area of 6 m 2 g "1 with a texture development with a tendency to macroporosity, so that they are treated at temperatures above 500 ° C in order to improve their mechanical and abrasion conditions, at that temperature carbon dioxide is released with formation of calcium and magnesium oxides whereby the specific surface of the material is reduced.
También a Ia mezcla se puede adicionar otros carbonatos de metales alcalino o alcalino térreos en sustitución de los agentes plastificantes y/o polimerizables los cuales producen resultados similares, En Ia mezcla resultante Ia relación ponderal entre grafito, carbón activado, silicatos de arcilla y los agentes plastificantes y/o polimerizables puede variar entre 1 :0:2:2 a 1 :1 :2:1 , en caso de no utilizar agentes plastificantes y/o polimerizables se pueden como se dijo anteriormente usar carbonatos de metales alcalino o alcalino térreos, pero los resultados son significativamente inferiores en su capacidad de adsorción, ahora bien un aumento del agregado de grafito o carbón activado aumenta el poder adsorbente pero en detrimento de las cualidades mecánicas de las piezas obtenidas después del secado y activación. Para la preparación del material adsorbente se mezclan en seco y en forma homogénea el grafito, carbón activado, silicatos fibrosos de arcilla y el agente plastificante y/o polimerizante en rango de las proporciones especificadas anteriormente, se amasa con agua preferentemente desionizada durante aproximadamente 5 horas, Ia pasta resultante se moldea o se extruye , para obtener las formas deseadas, que pueden ser conformadas como granulos, pastillas, esferas, cilindros huecos, placas o en estructuras de canales paralelos a Io largo del eje longitudinal, Ia composición presenta una estructura de canales paralelos a Io largo del eje longitudinal de entre 5 y 100 canales por centímetro cuadrado de su sección trasversal siendo conformada preferentemente como cilindros huecos, del tipo "macarrón" liso, estriado, recto, curvo, de corte regular o irregular, en cualquier forma y tamaño en forma de cilindros huecos, esferas o similares, estos pueden tener una longitud de aproximadamente 0,4 cm a aproximadamente 10 cm y el espesor de Ia pared puede tener entre 0,03 a 0,5 cm con el fin de permitir su aplicación para grandes volúmenes de gases con mínimas pérdidas de carga mediante el empleo de unidades de lecho fluidizado.Also to the mixture other alkaline or alkaline earth metal carbonates may be added in substitution of the plasticizing and / or polymerizable agents which produce similar results. In the resulting mixture the weight ratio between graphite, activated carbon, clay silicates and the agents plasticizers and / or polymerizable can vary between 1: 0: 2: 2 to 1: 1: 2: 1, in case of not using plasticizers and / or polymerizable agents, it is possible to use alkaline or alkaline earth metal carbonates as previously stated, but the results are significantly lower in their adsorption capacity, now an increase in the aggregate of graphite or activated carbon increases the adsorbent power but to the detriment of the mechanical qualities of the pieces obtained after drying and activation. For the preparation of the adsorbent material, graphite, activated carbon, clay fibrous silicates and the plasticizing and / or polymerizing agent in the range of the proportions specified above are mixed dry and homogeneously, preferably kneaded with water preferably deionized for approximately 5 hours , The resulting paste is molded or extruded, to obtain the desired shapes, which can be shaped as granules, pellets, spheres, hollow cylinders, plates or in parallel channel structures along the longitudinal axis, the composition has a structure of parallel channels along the longitudinal axis of between 5 and 100 channels per square centimeter of its cross section being preferably formed as hollow cylinders, of the smooth, striated, straight, curved "macaroni" type, of regular or irregular cut, in any shape and size in the form of hollow cylinders, spheres or the like, these may have an approximate length 0.4 cm to approximately 10 cm and the thickness of the wall can be between 0.03 to 0.5 cm in order to allow its application for large volumes of gases with minimal head losses through the use of bed units fluidized
Los elementos moldeados se secan a temperatura ambiente como mínimo 2 horas, luego el producto se trata térmicamente en un horno de atmósfera inerte a una temperatura que oscila entre los 500 a 10000C. El producto resultante presenta una composición única y probada para ser utilizada en filtros de adsorción de gases contaminantes a gran escala permitiendo eliminar las emisiones de CO, Dioxinas, Furanos, PCB's.(Policlorobifenilos), NO2, SO2, Halógenos, Aldehidos, CO2, Acroleína, etc., en los procesos de incineración, combustión y/o destilación de Ia glicerina, resolviendo el problema de almacenaje de dicha glicerina en las plantas de producción de Biodiesel, el producto filtrante puede ser utilizado en los filtros de lecho fijo como de lecho móvil The molded elements are dried at room temperature for at least 2 hours, then the product is heat treated in an inert atmosphere oven at a temperature ranging from 500 to 1000 0 C. The resulting product has a unique composition and tested for use. in large-scale contaminant gas adsorption filters allowing the elimination of CO, Dioxins, Furans, PCBs (NO 2 , SO 2 , Halogens, Aldehydes, CO 2 , Acrolein, etc.) emissions in incineration processes , combustion and / or distillation of the glycerin, solving the problem of storage of said glycerin in the Biodiesel production plants, the filtering product can be used in the fixed bed and mobile bed filters

Claims

REIVINDICACIONES
1 -Composición de un material adsorbente para el filtrado de gases tóxicos en el proceso de incineración de Ia glicerina en plantas de biodiesel, Ia cual es empleada en filtros de lecho fijo o móvil a Ia salida de las unidades de descarga de fluidos y que se caracteriza por contener los siguientes componentes: -grafito puro y/o carbón activado1 -Composition of an adsorbent material for the filtering of toxic gases in the process of incineration of glycerin in biodiesel plants, which is used in fixed or mobile bed filters at the exit of the fluid discharge units and which characterized by containing the following components: - pure graph and / or activated carbon
-silicatos naturales de arcilla-natural clay silicates
-un agente plastificante y/o polimerizable o una mezcla de ellos o carbonatas de metales alcalino o alcalino térreos.-a plasticizing and / or polymerizable agent or a mixture thereof or alkaline or alkaline earth metal carbonates.
2-Composición de un material adsorbente para el filtrado de gases tóxicos en el proceso de incineración de Ia glicerina en plantas de biodiesel, según Ia reivindicación 1 que se caracteriza por que Ia relación ponderada de Ia mezcla de grafito, carbón activado, silicatos y agentes plastificantes y/o polimerizables varía entre 1 :0:2:2 a 1 :1 :2:1.2-Composition of an adsorbent material for the filtering of toxic gases in the process of incineration of glycerin in biodiesel plants, according to claim 1, characterized in that the weighted ratio of the mixture of graphite, activated carbon, silicates and agents Plasticizers and / or polymerizable ranges from 1: 0: 2: 2 to 1: 1: 2: 1.
3- Composición de un material adsorbente para el filtrado de gases tóxicos en el proceso de incineración de Ia glicerina en plantas de biodiesel según Ia reivindicación 1 que se caracteriza por que Ia composición es susceptible de sustituir los agentes plastificantes y/o polimerizables por carbonatas de metales alcalino y alcalino térreos.3- Composition of an adsorbent material for the filtering of toxic gases in the process of incineration of the glycerin in biodiesel plants according to claim 1, characterized in that the composition is capable of replacing the plasticizing and / or polymerizable agents with carbonates of alkaline and alkaline earth metals.
4-Composición de un material adsorbente para el filtrado de gases tóxicos en el proceso de incineración de Ia glicerina en plantas de biodiesel según Ia reivindicación 1 por que Ia composición está conformada por granulos, pastillas, esferas, cilindros macizos, cilindros huecos o placas.4-Composition of an adsorbent material for the filtering of toxic gases in the process of incineration of glycerin in biodiesel plants according to claim 1, in which the composition is made up of granules, pellets, spheres, solid cylinders, hollow cylinders or plates.
5- Composición de un material adsorbente para el filtrado de gases tóxicos en el proceso de incineración de Ia glicerina en plantas de biodiesel según Ia reivindicación 4 por que cilindros huecos se encuentran seleccionados del grupo que comprenden: cilindros lisos de corte regular o irregular, cilindros estriados de corte regular o irregular, cilindros rectos de corte regular o irregular, cilindros curvos de corte regular o irregular.5- Composition of an adsorbent material for the filtration of toxic gases in the process of incineration of glycerin in biodiesel plants according to Ia claim 4 by which hollow cylinders are selected from the group comprising: smooth cylinders of regular or irregular cut, fluted cylinders of regular or irregular cut, straight cylinders of regular or irregular cut, curved cylinders of regular or irregular cut.
6- Composición de un material adsorbente para el filtrado de gases tóxicos en el proceso de incineración de Ia glicerina en plantas de biodiesel según Ia reivindicación 5 por que los cilindros huecos tiene una longitud de aproximadamente 0,4 cm a aproximadamente 10 cm y el espesor de Ia pared puede tener entre 0,03 a 0,5 cm.6- Composition of an adsorbent material for the filtering of toxic gases in the process of incineration of glycerin in biodiesel plants according to claim 5, because the hollow cylinders have a length of about 0.4 cm to about 10 cm and the thickness of the wall can be between 0.03 to 0.5 cm.
7-Composición de un material adsorbente para el filtrado de gases tóxicos en el proceso de incineración de Ia glicerina en plantas de biodiesel según Ia reivindicación 4, caracterizada por que dicha composición presenta una estructura de canales paralelos a Io largo del eje longitudinal de entre 5 y 100 canales por centímetro cuadrado de su sección trasversal.7-Composition of an adsorbent material for the filtering of toxic gases in the process of incineration of glycerin in biodiesel plants according to claim 4, characterized in that said composition has a structure of parallel channels along the longitudinal axis of between 5 and 100 channels per square centimeter of its cross section.
8-Composición de un material adsorbente para el filtrado de gases tóxicos en el proceso de incineración de Ia glicerina en plantas de biodiesel según Ia reivindicación 1 , caracterizada por que los silicatos naturales de arcilla preferentemente se seleccionan del grupo que comprende enstatita, ά- sepiolita, atapulgita, zeolitas o una mezcla de ellas.8-Composition of an adsorbent material for the filtering of toxic gases in the process of incineration of the glycerin in biodiesel plants according to claim 1, characterized in that the natural clay silicates are preferably selected from the group comprising enstatite, ά-sepiolite , attapulgite, zeolites or a mixture of them.
9-EI uso de una composición adsorbente para ser utilizada en filtros de lecho fijo o móvil de descarga de gases emitidos en el proceso de incineración de glicerina, que se caracteriza por contener en el filtro los siguientes componentes :9-The use of an adsorbent composition to be used in fixed or mobile bed filters for the discharge of gases emitted in the glycerin incineration process, which is characterized by containing the following components in the filter:
-grafito puro y/o carbón activado -silicatos naturales de arcilla -un agente plastificante y/o polimerizable o una mezcla de ellos o carbonatas de metales alcalino o alcalino térreos.- pure graph and / or activated carbon - natural clay silicates -a plasticizing and / or polymerizable agent or a mixture thereof or alkaline or alkaline earth metal carbonates.
10- El uso de una composición adsorbente para ser utilizada en filtros de lecho fijo o móvil de descarga de gases emitidos en el proceso de incineración de glicerina según Ia reivindicación 8, que se caracteriza por que Ia relación ponderada de Ia mezcla de grafito, carbón activado, silicatos y agentes plastificantes y/o polimerizables en el filtro varía entre 1 :0:2:2 a 1 :1 :2:1.10- The use of an adsorbent composition to be used in fixed or mobile bed filters for the discharge of gases emitted in the glycerin incineration process according to claim 8, characterized in that the weighted ratio of the mixture of graphite, carbon activated, silicates and plasticizers and / or polymerizable agents in the filter ranges from 1: 0: 2: 2 to 1: 1: 2: 1.
11 - El uso de una composición adsorbente para ser utilizada en filtros de lecho fijo o móvil de descarga de gases emitidos en el proceso de incineración de glicerina según Ia reivindicación 8, por que Ia composición está conformada por granulos, pastillas, esferas, cilindros macizos, cilindros huecos o placas.11 - The use of an adsorbent composition to be used in fixed or mobile bed filters for the discharge of gases emitted in the glycerin incineration process according to claim 8, because the composition is formed by granules, pellets, spheres, solid cylinders , hollow cylinders or plates.
12- El uso de una composición adsorbente para ser utilizada en filtros de lecho fijo o móvil de descarga de gases emitidos en el proceso de incineración de glicerina según Ia reivindicación 8 que se caracteriza por eliminar emisiones tóxicas de gases como: CO, Dioxinas, Furanos, PCB's (Policlorobifenilos)., NO2, SO2, Halógenos, Aldehidos, CO2, Acroleína. 12- The use of an adsorbent composition to be used in fixed or mobile bed filters for the discharge of gases emitted in the glycerine incineration process according to claim 8, characterized by eliminating toxic emissions of gases such as: CO, Dioxins, Furans , PCB's (Polychlorobiphenyls)., NO2, SO2, Halogens, Aldehydes, CO2, Acrolein.
PCT/ES2009/070210 2009-06-05 2009-06-05 Composition and use of an adsorbent material for filtering toxic components during the process of incineration and/or distillation of glycerine generated from the production of biodiesel WO2010139816A1 (en)

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Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103506082A (en) * 2012-06-29 2014-01-15 中原工学院 Preparation method of flax fiber/expanded graphite composite fiber adsorbing material
CN103506085A (en) * 2012-06-29 2014-01-15 中原工学院 Preparation method of cotton fiber/expanded graphite composite fiber ultrafiltration water-adsorbing material
CN103506095A (en) * 2012-06-29 2014-01-15 中原工学院 Preparation method of kendir fiber/expanded graphite composite fiber adsorbing material
CN105327673A (en) * 2015-11-03 2016-02-17 李明顺 Preparation of composite adsorbent for removing residual ammonia nitrogen after sewage treatment and application of composite adsorbent

Citations (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0776696A2 (en) * 1995-12-01 1997-06-04 Kawata Mfg Co., Ltd. Honeycomb-shaped ceramic and method for producing it
WO1998039093A1 (en) * 1997-03-05 1998-09-11 Blanco Alvarez Jesus Natural silicates with fibrous structure
CN1486940A (en) * 2003-08-13 2004-04-07 涉 张 Composite stuffing for sewage treating biofilm process
JP2005177576A (en) * 2003-12-17 2005-07-07 Yahashi Kogyo Kk Agent for detoxifying halogen-based gas and acidic gas
CN1872401A (en) * 2006-04-28 2006-12-06 夏先明 Micro-filtration membrane for purifying Chinese traditional medicine
WO2007085672A1 (en) * 2006-01-27 2007-08-02 Bionatur Biotechnologies S.L. Adsorbent composition containing enstatite, method for obtaining same and use thereof
CN101310854A (en) * 2008-02-22 2008-11-26 周奇迪 Filter media and preparation method, filter element, purifier and drinking machine using the filter media
CN101417193A (en) * 2008-11-07 2009-04-29 江苏正本净化节水科技实业有限公司 Nano crystallite composite filter material and supplement of manufacture method thereof
WO2009103831A1 (en) * 2008-02-19 2009-08-27 Bionatur Biotechnologies S.L. Composition of a material having a porous structure, preparation methods and corresponding uses

Patent Citations (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0776696A2 (en) * 1995-12-01 1997-06-04 Kawata Mfg Co., Ltd. Honeycomb-shaped ceramic and method for producing it
WO1998039093A1 (en) * 1997-03-05 1998-09-11 Blanco Alvarez Jesus Natural silicates with fibrous structure
CN1486940A (en) * 2003-08-13 2004-04-07 涉 张 Composite stuffing for sewage treating biofilm process
JP2005177576A (en) * 2003-12-17 2005-07-07 Yahashi Kogyo Kk Agent for detoxifying halogen-based gas and acidic gas
WO2007085672A1 (en) * 2006-01-27 2007-08-02 Bionatur Biotechnologies S.L. Adsorbent composition containing enstatite, method for obtaining same and use thereof
CN1872401A (en) * 2006-04-28 2006-12-06 夏先明 Micro-filtration membrane for purifying Chinese traditional medicine
WO2009103831A1 (en) * 2008-02-19 2009-08-27 Bionatur Biotechnologies S.L. Composition of a material having a porous structure, preparation methods and corresponding uses
CN101310854A (en) * 2008-02-22 2008-11-26 周奇迪 Filter media and preparation method, filter element, purifier and drinking machine using the filter media
CN101417193A (en) * 2008-11-07 2009-04-29 江苏正本净化节水科技实业有限公司 Nano crystallite composite filter material and supplement of manufacture method thereof

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
MOLINA-SABIO, M. ET AL.: "Adsorption of NH3 and H2S on activated carbon and activated carbon- sepiolite pellets", CARBON, vol. 42, 2004, pages 423 - 460 *

Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103506082A (en) * 2012-06-29 2014-01-15 中原工学院 Preparation method of flax fiber/expanded graphite composite fiber adsorbing material
CN103506085A (en) * 2012-06-29 2014-01-15 中原工学院 Preparation method of cotton fiber/expanded graphite composite fiber ultrafiltration water-adsorbing material
CN103506095A (en) * 2012-06-29 2014-01-15 中原工学院 Preparation method of kendir fiber/expanded graphite composite fiber adsorbing material
CN103506085B (en) * 2012-06-29 2015-04-29 中原工学院 Preparation method of cotton fiber/expanded graphite composite fiber ultrafiltration water-adsorbing material
CN105327673A (en) * 2015-11-03 2016-02-17 李明顺 Preparation of composite adsorbent for removing residual ammonia nitrogen after sewage treatment and application of composite adsorbent

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