WO2005025825A1 - Method for the extraction of cork-containing material - Google Patents

Method for the extraction of cork-containing material Download PDF

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Publication number
WO2005025825A1
WO2005025825A1 PCT/EP2004/010133 EP2004010133W WO2005025825A1 WO 2005025825 A1 WO2005025825 A1 WO 2005025825A1 EP 2004010133 W EP2004010133 W EP 2004010133W WO 2005025825 A1 WO2005025825 A1 WO 2005025825A1
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Prior art keywords
cork
compressed gas
containing material
bed
extraction
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PCT/EP2004/010133
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German (de)
French (fr)
Inventor
Kurt Stork
Original Assignee
Degussa Ag
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Priority to AU2004272265A priority Critical patent/AU2004272265A1/en
Publication of WO2005025825A1 publication Critical patent/WO2005025825A1/en

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Classifications

    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01DSEPARATION
    • B01D11/00Solvent extraction
    • B01D11/02Solvent extraction of solids
    • B01D11/0203Solvent extraction of solids with a supercritical fluid
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01DSEPARATION
    • B01D11/00Solvent extraction
    • B01D11/02Solvent extraction of solids
    • B01D11/0292Treatment of the solvent
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B67OPENING, CLOSING OR CLEANING BOTTLES, JARS OR SIMILAR CONTAINERS; LIQUID HANDLING
    • B67BAPPLYING CLOSURE MEMBERS TO BOTTLES JARS, OR SIMILAR CONTAINERS; OPENING CLOSED CONTAINERS
    • B67B1/00Closing bottles, jars or similar containers by applying stoppers
    • B67B1/03Pretreatment of stoppers, e.g. cleaning, steaming, heating, impregnating or coating; Applying resilient rings to stoppers
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B27WORKING OR PRESERVING WOOD OR SIMILAR MATERIAL; NAILING OR STAPLING MACHINES IN GENERAL
    • B27KPROCESSES, APPARATUS OR SELECTION OF SUBSTANCES FOR IMPREGNATING, STAINING, DYEING, BLEACHING OF WOOD OR SIMILAR MATERIALS, OR TREATING OF WOOD OR SIMILAR MATERIALS WITH PERMEANT LIQUIDS, NOT OTHERWISE PROVIDED FOR; CHEMICAL OR PHYSICAL TREATMENT OF CORK, CANE, REED, STRAW OR SIMILAR MATERIALS
    • B27K2240/00Purpose of the treatment
    • B27K2240/10Extraction of components naturally occurring in wood, cork, straw, cane or reed
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B27WORKING OR PRESERVING WOOD OR SIMILAR MATERIAL; NAILING OR STAPLING MACHINES IN GENERAL
    • B27KPROCESSES, APPARATUS OR SELECTION OF SUBSTANCES FOR IMPREGNATING, STAINING, DYEING, BLEACHING OF WOOD OR SIMILAR MATERIALS, OR TREATING OF WOOD OR SIMILAR MATERIALS WITH PERMEANT LIQUIDS, NOT OTHERWISE PROVIDED FOR; CHEMICAL OR PHYSICAL TREATMENT OF CORK, CANE, REED, STRAW OR SIMILAR MATERIALS
    • B27K7/00Chemical or physical treatment of cork

Definitions

  • the present invention relates to a method for the extraction of cork-containing material with the aid of a compressed gas and under defined temperature and drain conditions.
  • Cork is a natural, impermeable, lightweight material made from the bark (“bark”) of certain oaks, such as the cork oak, which is typically found in the countries bordering the Mediterranean, in Europe and in North Africa.
  • Cork is a widely used material and is used in particular in the food sector as a closure for bottles but also in so-called crown corks as insert sheets, preferably in the beverage sector.
  • the natural product cork is a highly elastic, dimensionally stable, compressible and liquid-impermeable material with high gas permeability, it also contains numerous ingredients due to its original function as bark, which in their natural function as repellents, e.g. serve as feeding protection.
  • This typical cork of the wine or its musty smell and taste is not only due to the ingredients naturally present in the cork, they are also produced by mushroom cultures that grow on the peeled cork bark, which is usually stored in plate form.
  • Typical compounds that these fungal strains release to the cork are methyl isoborneol and its derivatives, which give off a musty and camphor-like odor, geosmin with a typically earthy odor and methylthio-ethyl-pyrazine with a musty and sulfur-like odor. Alcohols and unsaturated ketones produce mushroom-like scents.
  • chloranisols such as 2,4,6-TCA (trichloroanisole) and 2,3,4,6-TeCA (tetrachloroanisole) are particularly worth mentioning.
  • cork parts are first heated in a heat chamber at 120 ° C for 10 minutes and then exposed to a vacuum, whereupon an increased pressure is again applied. Then the mixture is finally heated to 130 ° C. for a further 10 minutes.
  • cork parts are exposed to a steam at 130 ° C under pressure conditions of 180 kPa for 18 to 20 minutes, after which the pressure is released to atmospheric pressure.
  • Both of these methods have the disadvantages that they are not very efficient in removing the organic compounds responsible for the undesirable taste and, moreover, they cannot kill microorganisms efficiently.
  • US Pat. No. 5,364,475 describes a process for the purification of wood and in particular for the extraction of pentachlorophenol (PCP) -like compounds, wherein the wood is first cut into small pieces and then subjected to a treatment with a supercritical liquid, such as CO 2 .
  • PCP pentachlorophenol
  • Methanol, ethanol and acetone can be used as co-solvents. Since this process is only suitable for the removal of PCP (including trichloroanisole and tetrachloroanisole) and, moreover, it is only able to extract these undesirable ingredients from cork to a limited extent, it is unsuitable for further treatment with regard to food-grade applications.
  • German published patent application DE 42 23 022 also teaches a process for extracting tar oils from old wood or wood waste, the starting material first being brought to a particle size between 10 and 40 mm and then with a supercritical extraction liquid such as CO 2 or an aliphatic C 3 . 5 -Carbohydrate is being treated. If the duration of treatment is sufficient, the tar oil content should reach a certain level Threshold can be reduced.
  • a co-solvent such as ethanol or isopropanol, can also be used in this process in proportions of 2 to 5% by volume, based on the moisture content of the wood.
  • European patent application 140061 describes a method for extracting ingredients from natural products using a pressurized fluid, the ingredients then being bound to an adsorbent material.
  • This method which is said to be primarily suitable for decaffeinating tea leaves with the aid of CO 2 , makes particular use of radial flow guidance through the bed of tea leaves, the compressed CO 2 being fed from the outside through the bed into an axial Horil cylinder.
  • This process with radial guidance of the extraction medium can only be carried out with homogeneous starting materials which, above all, should be very light, tend to stick or have an unstable structure which cannot withstand major pressure differences.
  • extraction materials such as cork, which due to its natural elasticity can also withstand higher pressure differences and neither tends to stick or has no unstable structures, this method with radial fluid guidance is therefore not very suitable.
  • the treatment of cork or cork-based materials should consequently succeed in that the cork material under pressure conditions of 10 to 600 bar and is brought into contact with a compressed liquid at temperatures between 10 and 120 ° C.
  • the extraction liquid should preferably be in the supercritical state, carbon dioxide, nitrogen oxide and C 5 -5 hydrocarbons being particularly suitable.
  • This method is intended to overcome the disadvantages of the prior art, which consist in the fact that none of the previously known methods for Treatment of cork uses compressed liquids - under pressure conditions and therefore does not take into account the specific properties of cork, such as elasticity and density.
  • the composition of cork in relation to suberin, lignin and cellulose, no suitable method is known from the prior art to remove secondary cork ingredients or decomposition products caused by fungi to a sufficient extent.
  • WO 01/23155 The method described last according to WO 01/23155 is also not suitable for economically removing trichloroanisole, tetrachloroanisole, pentachloxphenol as well as waxes and fats from cork-based material to such an extent that the material thus extracted is subsequently safe in the food sector and especially in Beverage sector can be used.
  • the object is therefore to provide a process for the extraction of cork-containing material with the aid of a compressed gas at temperatures between 10 and 120 ° C. and pressures between 10 and 600 bar, which, with a relatively simple procedure, produces organic contaminants from cork-containing Material removed to such an extent that it can subsequently be used in the food sector without negative effects.
  • This object was achieved with a method in which the extraction is carried out under isobaric conditions, in which the compressed gas flows radially or axially through the bed and in which the bed to be extracted is combined with an adsorption material.
  • this method has shown that, in contrast to the known methods for treating cork, not only the undesired organic compounds such as PCP, TCA and TeCA as well as waxes and fats can be removed below their detection limit, but also shaped cork products , such as bottle corks, can be extracted without losing their substance-specific properties, such as elasticity and density, Liquid impermeability and gas permeability, and in particular the dimensional stability, lose.
  • cork boards, cork granules, cork powder, bottle cork and / or pressed cork are used as cork-containing materials.
  • the starting material used may also have been subjected to a mechanical and / or chemical and / or physical pretreatment, such as that e.g. Comminution steps, acid-base treatment measures or a cooking process and how they are also taken into account by the present invention.
  • Temperatures which are between 40 and 100 ° C., more preferably between 60 and 80 ° C., are preferably used in the process according to the invention.
  • the process pressures used are preferably between 80 and 400 bar, more preferably between 100 and 150 bar, and particularly preferably between 120 and 140 bar.
  • the weight ratio between the compressed gas used and the cork-containing material is not limiting for the present method, but a corresponding weight ratio that has been found to be suitable is 1 to 100: 1.
  • Preferred weight ratios of 20 to 70: 1 and in particular 40: 1 are to be used in the context of the present invention for special applications.
  • the compressed gas is in the supercritical state.
  • the compressed gas flows radially or axially through the bed.
  • the compressed gas is first fed into a centrally arranged axial inner cylinder of the pressure vessel and then exits radially through openings into the bed, from where it flows outwards.
  • the invention provides as preferred representatives of at least one of the series activated carbon, aluminum oxide and / or silicon oxide, such as zeolites.
  • the bed can be combined with the adsorption material selected in each case by homogeneous or heterogeneous mixing, by introducing the adsorption material in layers into the bed or by adding the adsorption material. It is preferred of the present invention if the adsorption material is introduced into the bed in layers or if it is connected downstream of the bed to be extracted.
  • the compressed gas contains at least one entrainer or a co-solvent, such as water, C 1. 5 alcohols, for example methanol, ethanol, propanol, isopropanol, butanols and pentanols, and ether.
  • a co-solvent such as water, C 1. 5 alcohols, for example methanol, ethanol, propanol, isopropanol, butanols and pentanols, and ether.
  • this should particularly preferably take place in amounts which are between 0.1 and 10% by weight, preferably between 0.5 and 8% by weight, more preferably between 2 and 6% by weight, even more preferably between 3 and 5% by weight, based on the amount of gas used.
  • the present invention also provides that organic compounds and preferably (chlorinated) phenols from the cork-containing material and / or (chlorinated) anisoles and here in particular pentachlorophenol (PCP), trichloroanisole (TCA) and / or tetrachloroanisole (TeCA) as well as waxes and fats are removed.
  • PCP pentachlorophenol
  • TCA trichloroanisole
  • TeCA tetrachloroanisole
  • the arrangement of the individual device modules for carrying out the claimed method steps is not to be regarded as restrictive for the present method, but the present invention provides a variant in which the method is carried out in at least one autoclave, a module arrangement being particularly preferred, where two pressure vessels are connected at least in series or in parallel.
  • the process arrangement usually consists in that two autoclaves connected in parallel or in series with the cork-containing starting material are subjected to the extraction gas. Any adhering waxes and fats are then separated in a downstream cyclone at low temperatures and the cyclic organic compounds are separated from the extraction gas in a third autoclave, which is filled with the adsorption material in the form of activated carbon.
  • the present invention thus relates to a process for the extraction of cork-containing material with the aid of a compressed gas at temperatures between 10 and 120 ° C and pressures between 10 and 600 bar, the extraction being carried out under isobaric conditions, the compressed gas being the bed radially or flows axially and the bed to be extracted is combined with an adsorption material.
  • a compressed gas at temperatures between 10 and 120 ° C and pressures between 10 and 600 bar
  • the extraction being carried out under isobaric conditions
  • the compressed gas being the bed radially or flows axially and the bed to be extracted is combined with an adsorption material.
  • organic compounds such as, for example, pentachlorophenol, trichloroanisole, tetrachloroanisole and waxes and fats
  • two autoclaves connected in parallel were each filled with 270 kg of a powdered cork material and then flowed through with a flow rate of 18 m 3 / h of supercritical CO 2 isobar at a pressure of 120 bar and a process temperature of 60 ° C.
  • the ratio of compressed gas to cork-containing raw material was 66: 1.
  • the extraction gas loaded with the compounds to be extracted was transferred to a cyclone cooled to 0 ° C., which was also operated isobarically and in which waxes and fats were separated from the extraction gas.
  • the charged powdered cork material was freed quantitatively from the organic compounds PCP, TCA, TeCA as well as waxes and fats.

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  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Engineering & Computer Science (AREA)
  • Mechanical Engineering (AREA)
  • Extraction Or Liquid Replacement (AREA)
  • Chemical And Physical Treatments For Wood And The Like (AREA)

Abstract

The invention relates to a method for extracting cork-containing material with the aid of a compressed gas at temperatures ranging between 10 and 120 °C and pressures ranging between 10 and 600 bar. Extraction takes place in isobaric conditions while the compressed gas flows through the charge in a radial or axial direction and the charge that is to be extracted is combined with an adsorbing material. The inventive method allows cork plates, cork granules, bottle cork, or agglomerated cork, for example, to be quantitative removed from organic compounds such as pentachlorophenol, trichloroanisole, and tetrachloroanisole as well as waxes and fats such that the purified cork-containing materials can be used without reservation in the food sector and particularly in the beverage sector.

Description

Verfahren zur Extraktion von korkhaltigem Material Process for the extraction of cork-containing material
Beschreibungdescription
Gegenstand der vorliegenden Erfindung ist ein Verfahren zur Extraktion von korkhaltigem Material mit Hilfe eines komprimierten Gases und bei definierten Temperatur- und Drackbedingungen.The present invention relates to a method for the extraction of cork-containing material with the aid of a compressed gas and under defined temperature and drain conditions.
Bei Kork handelt es sich um ein natürliches, undurchlässiges Material von geringem Gewicht, das aus der Borke ("Rinde") bestimmter Eichen, wie z.B. der Korkeiche, gewonnen wird, wie sie typischerweise in den Anrainerländern des Mittelmeers, in Europa und Nordaf ika, anzutreffen sind.Cork is a natural, impermeable, lightweight material made from the bark ("bark") of certain oaks, such as the cork oak, which is typically found in the countries bordering the Mediterranean, in Europe and in North Africa.
Kork ist ein weit verbreitetes Gebrauchsmaterial und wird insbesondere im Lebensmittelbereich als Verschluss von Flaschen aber auch in sogenannten Kronkorken als Einlageblättchen, vorzugsweise im Getränkesektor, eingesetzt.Cork is a widely used material and is used in particular in the food sector as a closure for bottles but also in so-called crown corks as insert sheets, preferably in the beverage sector.
Speziell bei der Verwendung von Flaschenkorken liegt es in der Natur der Sache, dass die dem Flascheninhalt zugewandten Korkteile mit den in den Behältern enthaltenen Getränken (zumeist Wein, Schaumwein, Sekte und Champagner) in Berührung kommen.It is in the nature of things, especially when using bottle corks, that the cork parts facing the bottle contents come into contact with the drinks contained in the containers (mostly wine, sparkling wine, sparkling wine and champagne).
Zwar stellt das Naturprodukt Kork ein hochelastisches, formstabiles, komprimierbares und gegenüber Flüssigkeiten undurchlässiges Material bei gleichzeitig hoher Gasdurchlässigkeit dar, es enthält aber auch aufgrund seiner ursprünglichen Funktion als Borke zahlreiche Inhaltsstoffe, die in ihrer natürlichen Funktion als Abwehrstoffe, wie z.B. als Fraßschutz dienen.Although the natural product cork is a highly elastic, dimensionally stable, compressible and liquid-impermeable material with high gas permeability, it also contains numerous ingredients due to its original function as bark, which in their natural function as repellents, e.g. serve as feeding protection.
Bei der Berührung des unbehandelten Naturproduktes Kork mit lebensmittelgerechten Flüssigkeiten, bspw. Getränken, ist es unvermeidbar, dass in Abhängigkeit von der Lager- und damit Kontaktzeit lösliche Korkinhaltsstoffe in die flüssigen Medien übertreten. Dies äußert sich zumindest in einer geschmacksveränderten Weise, was landläufig als "Korken" des Getränkes bezeichnet wird. Diese aus Kork in die Getränke übertretenden Stoffe entwickeln eine zumeist unangenehme, modrige Geschmacksrxote und machen gemeinsam mit den ebenfalls sich im Getränk lösenden Korkfarbstoffe die betroffenen Getränke ungenießbar.When the untreated natural product cork comes into contact with food-grade liquids, e.g. drinks, it is inevitable that in Depending on the storage time and thus the contact time, soluble cork constituents pass into the liquid media. This manifests itself at least in a taste-changing manner, which is commonly referred to as the "cork" of the beverage. These substances that are corked into the drinks develop a mostly unpleasant, musty taste and, together with the cork dyes that also dissolve in the drink, make the affected drinks inedible.
Dieses typische Korken des Weines bzw. dessen muffiger Geruch und Geschmack gehen aber nicht nur auf die in natürlicher Weise im Kork vorhandenen Inhaltsstoffe zurück, sondern sie werden auch von Pilzkulturen erzeugt, die auf den geschälten Korkborken, die meist in Plattenform gelagert werden, wachsen.This typical cork of the wine or its musty smell and taste is not only due to the ingredients naturally present in the cork, they are also produced by mushroom cultures that grow on the peeled cork bark, which is usually stored in plate form.
Typische Verbindungen, die diese Pilzstämme an den Kork abgeben, sind Methylisoborneol und seine Derivate, die einen modrigen und Kampfer-artigen Geruch bedingen, Geosmin mit einem typischerweise erdigen Geruch sowie Methylthio-ethyl-pyrazin mit einem muffigen und Schwefel-artigen Geruch. Alkohole und ungesättigte Ketone rufen Champignon-artige Geruchsnoten hervor. Erwähnenswert in diesem Zusammenhang sind insbesondere Chloranisole, wie 2,4,6-TCA (Trichloranisol) und 2,3,4,6-TeCA (Tetrachloranisol).Typical compounds that these fungal strains release to the cork are methyl isoborneol and its derivatives, which give off a musty and camphor-like odor, geosmin with a typically earthy odor and methylthio-ethyl-pyrazine with a musty and sulfur-like odor. Alcohols and unsaturated ketones produce mushroom-like scents. In this connection, chloranisols such as 2,4,6-TCA (trichloroanisole) and 2,3,4,6-TeCA (tetrachloroanisole) are particularly worth mentioning.
Aus dem Stand der Technik sind zahlreiche Verfahren bekannt, um die genannten sekundären Inhaltsstoffe bzw. Stoffwechselprodukte aus Kork abzutrennen.Numerous methods are known from the prior art in order to separate the cork from the secondary ingredients or metabolic products mentioned.
Beim historischen Verfahren von F. Bordas aus dem Jahr 1904 werden Korkteile in einer Hitzekammer zunächst 10 Minuten lang auf 120 °C aufgeherzt und dann einem Vakuum ausgesetzt, worauf neuerlich ein erhöhter Druck angelegt wird. Dann wird abschließend für weitere 10 Minuten auf 130 °C aufgeheizt.In the historical process by F. Bordas from 1904, cork parts are first heated in a heat chamber at 120 ° C for 10 minutes and then exposed to a vacuum, whereupon an increased pressure is again applied. Then the mixture is finally heated to 130 ° C. for a further 10 minutes.
Beim sogenannten "Champcork- Verfahren" werden Korkteile einem 130 °C heißem Dampf unter Druckbedingungen von 180 kPa für 18 bis 20 Minuten ausgesetzt, worauf auf Atmosphärendruck entspannt wird. Diese beiden Verfahren weisen allerdings die Nachteile auf, dass sie wenig effizient sind, um die organischen Verbindungen zu entfernen, die für den unerwünschten Geschmack verantwortlich sind, und zudem können sie nicht effizient Mikroorganismen abtöten.In the so-called "Champcork process", cork parts are exposed to a steam at 130 ° C under pressure conditions of 180 kPa for 18 to 20 minutes, after which the pressure is released to atmospheric pressure. Both of these methods, however, have the disadvantages that they are not very efficient in removing the organic compounds responsible for the undesirable taste and, moreover, they cannot kill microorganisms efficiently.
Ein technisch aufwendigeres Verfahren beschreiben Ana M. Miianda et al ("High Pressure Extraction of Cork with CO2 and 1.4-dioxane", Process. Techno 1. Proc. (1996), 12 "High Pressure Chemical Engineering", p. 417 bis 422). Demnach wird Kork unter hohen Druckbedingungen von 170 bar bei Temperaturen von 160 bis 180 °C mit CO2 und Dioxan behandelt, wodurch die Entfernung von Suberin, einem Bestandteil der Zellwände von Kork in Form von modifiziertem Lignin, gelingt. Dieses Verfahren ist allerdings nicht dafür geeignet, Kork zu behandeln, der anschließend als Flaschenkork verwendet werden soll.Ana M. Miianda et al ("High Pressure Extraction of Cork with CO 2 and 1.4-dioxane", Process. Techno 1. Proc. (1996), 12 "High Pressure Chemical Engineering", p. 417 bis 422). Accordingly, cork is treated with CO 2 and dioxane under high pressure conditions of 170 bar at temperatures of 160 to 180 ° C, whereby suberin, a component of the cell walls of cork in the form of modified lignin, is removed. However, this method is not suitable for treating cork, which is then to be used as bottle cork.
Das US-Patent 5,364,475 beschreibt ein Verfahren zur Aufreinigung von Holz und insbesondere zur Extraktion von Pentachlorphenol (PCP) ähnlichen Verbindungen, wobei das Holz zuerst in kleine Stückchen geschnitten wird und dann einer Behandlung mit einer überkritischen Flüssigkeit, wie z.B. CO2, unterzogen wird. Dabei können als Co-Lösemittel Methanol, Ethanol und Aceton eingesetzt werden. Da sich dieses Verfahren ausschließlich zur Entfernung von PCP (einschließlich von Trichloranisol und Tetrachloranisol) eignet und darüber hinaus diese unerwünschten Inhaltsstoffe aus Kork auch nur im beschränkten Umfang zu extrahieren vermag, ist es für eine weitergehende Behandlung im Hinblick auf Lebensmittel- geeignete Anwendungsfälle ungeeignet.US Pat. No. 5,364,475 describes a process for the purification of wood and in particular for the extraction of pentachlorophenol (PCP) -like compounds, wherein the wood is first cut into small pieces and then subjected to a treatment with a supercritical liquid, such as CO 2 . Methanol, ethanol and acetone can be used as co-solvents. Since this process is only suitable for the removal of PCP (including trichloroanisole and tetrachloroanisole) and, moreover, it is only able to extract these undesirable ingredients from cork to a limited extent, it is unsuitable for further treatment with regard to food-grade applications.
Auch die deutsche Offenlegungsschrift DE 42 23 022 lehrt ein Verfahren zur Extraktion von Teerölen aus altem Holz oder Holzabfall, wobei das Ausgangsmaterial zunächst auf eine Teilchengröße zwischen 10 und 40 mm gebracht und anschließend mit einer überkritischen Extraktionsflüssigkeit, wie CO2 oder einem aliphatischen C3.5 -Kohlenwasserstoff behandelt -wird. Bei einer ausreichenden Behandlungsdauer soll so der Gehalt an Teerölen auf einen gewissen Schwellenwert reduzierbar sein. Bei diesem Verfahren kann ebenfalls ein Co- Lösemittel, wie Ethanol oder Isopropanol, in Anteilen von 2 bis 5 Vol-%, bezogen auf den Feuchtigkeitsgehalt des Holzes, eingesetzt werden.German published patent application DE 42 23 022 also teaches a process for extracting tar oils from old wood or wood waste, the starting material first being brought to a particle size between 10 and 40 mm and then with a supercritical extraction liquid such as CO 2 or an aliphatic C 3 . 5 -Carbohydrate is being treated. If the duration of treatment is sufficient, the tar oil content should reach a certain level Threshold can be reduced. A co-solvent, such as ethanol or isopropanol, can also be used in this process in proportions of 2 to 5% by volume, based on the moisture content of the wood.
Die Europäische Patentanmeldung 140061 beschreibt ein Verfahren zur Extraktion von Inhaltsstoffen aus Naturprodukten mittels eines unter Druck stehenden Fluids, wobei anschließend die Inhaltsstoffe an ein Adsorptionsmaterial gebunden werden. Dieses Verfahren, das hauptsächlich zur Entkoffeinierung von Teeblättern mit Hilfe von CO2 geeignet sein soll, bedient sich insbesondere der radialen Strömungsfiihrung durch die Teeblätterschüttung, wobei das komprimierte CO2 von außen durch die Schüttung nach innen in einen axialen Horilzylinder geführt wird. Dieses Verfahren mit radialer Führung des Extraktionsmediums kann ausschheßlich mit homogenen Ausgangsmaterialien durchgeführt werden, die vor allem sehr leicht sein sollen, zum Verkleben neigen oder instabile Strukturell aufweisen, die keinen größeren Druckdifferenzen widerstehen können. Für Extraktionsmateriahen, wie bspw. Kork, der aufgrund seiner natürlichen Elastizität auch höheren Druckdifferenzen widerstehen kann und weder zum Verkleben neigt bzw. keine instabilen Strukturen aufweist, ist dieses Verfahren mit radialer Fluid ührung somit wenig geeignet.European patent application 140061 describes a method for extracting ingredients from natural products using a pressurized fluid, the ingredients then being bound to an adsorbent material. This method, which is said to be primarily suitable for decaffeinating tea leaves with the aid of CO 2 , makes particular use of radial flow guidance through the bed of tea leaves, the compressed CO 2 being fed from the outside through the bed into an axial Horil cylinder. This process with radial guidance of the extraction medium can only be carried out with homogeneous starting materials which, above all, should be very light, tend to stick or have an unstable structure which cannot withstand major pressure differences. For extraction materials such as cork, which due to its natural elasticity can also withstand higher pressure differences and neither tends to stick or has no unstable structures, this method with radial fluid guidance is therefore not very suitable.
Aus der internationalen Patentanmeldung WO 01/23155 ist ein Verfahren zur Behandlung und Extraktion von Kork-typischen organischen Verbindungen mit Hilfe von verdichteten Flüssigkeiten bekannt: Die Behandlung von Kork oder Korkbasierten Materialien soll demzufolge dadurch gelingen, dass das Korkmaterial unter Druckbedingungen von 10 bis 600 bar und bei Temperaturen zwischen 10 und 120 ° C mit einer verdichteten Flüssigkeit in Kontakt gebracht wird. Die Extraktionsflüssigkeit soll sich vorzugsweise im überkritischen Zustand befinden, wobei Kohlendioxid, Stickstoffoxid und Cι-5-Kohlenwasserstoffe besonders geeignet sind.From the international patent application WO 01/23155, a process for the treatment and extraction of cork-typical organic compounds with the aid of compressed liquids is known: The treatment of cork or cork-based materials should consequently succeed in that the cork material under pressure conditions of 10 to 600 bar and is brought into contact with a compressed liquid at temperatures between 10 and 120 ° C. The extraction liquid should preferably be in the supercritical state, carbon dioxide, nitrogen oxide and C 5 -5 hydrocarbons being particularly suitable.
Mit diesem Verfahren sollen die Nachteile des Standes der Technik überwunden werden, die darin bestehen, dass keines der bislang bekannten Verfahren zur Behandlung von Kork auf verdichtete Flüssigkeiten -unter Druckbedingungen zurückgreift und das demzufolge auch nicht den spezifischen Eigenschaften von Kork, wie Elastizität und Dichte, Rechnung trägt. Insbesondere im Hinblick auf die Zusammensetzung von Kork, betreffend Suberin, Lignin und Cellulose, ist aus dem Stand der Technik bislang kein geeignetes Verfahren bekannt, um sekundäre Korkinhaltsstoffe oder durch Pilze verursachte Abbauprodukte in ausreichendem Maß zu entfernen.This method is intended to overcome the disadvantages of the prior art, which consist in the fact that none of the previously known methods for Treatment of cork uses compressed liquids - under pressure conditions and therefore does not take into account the specific properties of cork, such as elasticity and density. In particular with regard to the composition of cork, in relation to suberin, lignin and cellulose, no suitable method is known from the prior art to remove secondary cork ingredients or decomposition products caused by fungi to a sufficient extent.
Auch das zuletzt beschriebene Verfahren gemäß WO 01/23155 ist nicht dazu geeignet, Trichloranisol, Tetrachloranisol, Pentachloxphenol sowie Wachse und Fette aus Kork-basierten Material auf wirtschaftliche Weise in einem Ausmaß zu entfernen, dass das so extrahierte Material anschließend unbedenklich im Lebensmittelbereich und insbesondere im Getränkesektor eingesetzt werden kann.The method described last according to WO 01/23155 is also not suitable for economically removing trichloroanisole, tetrachloroanisole, pentachloxphenol as well as waxes and fats from cork-based material to such an extent that the material thus extracted is subsequently safe in the food sector and especially in Beverage sector can be used.
Für die vorhegende Erfindung hat sich deshalb die Aufgabe gestellt, ein Verfahren zur Extraktion von korkhaltigem Material mit Hilfe eines komprimierten Gases bei Temperaturen zwischen 10 und 120 °C und Drücken zwischen 10 und 600 bar bereitzustellen, das bei relativ einfacher Verfahrensf hrung organische Störstoffe aus korkhaltigem Material in einem Ausmaß entfernt, dass dieses anschließend ohne negative Auswirkungen im Lebensmittelbereich verwendet werden kann.For the present invention, the object is therefore to provide a process for the extraction of cork-containing material with the aid of a compressed gas at temperatures between 10 and 120 ° C. and pressures between 10 and 600 bar, which, with a relatively simple procedure, produces organic contaminants from cork-containing Material removed to such an extent that it can subsequently be used in the food sector without negative effects.
Gelöst wurde diese Aufgabe mit einem Verfahren, bei dem die Extraktion bei isobaren Bedingungen durchgeführt wird, bei dem das komprimierte Gas die Schüttung radial oder axial durchströmt und bei dem die zu extrahierende Schüttung mit einem Adsorptionsmaterial kombiniert ist.This object was achieved with a method in which the extraction is carried out under isobaric conditions, in which the compressed gas flows radially or axially through the bed and in which the bed to be extracted is combined with an adsorption material.
Überraschend hat sich mit diesem Verfahren herausgestellt, dass im Gegensatz zu den bekannten Verfahren zur Behandlung von Kork nicht nur die unerwünschten organischen Verbindungen, wie PCP, TCAund TeCA sowie Wachse und Fette, bis unter ihre Nachweisgrenze entfernt werden können, sondern dass damit auch geformte Korkprodukte, wie bspw. Flaschenkorke, extrahiert werden können, ohne dass sie dabei ihre stoffspezifischen Eigenschaften, wie Elastizität und Dichte, Flüssigkeitundurchlässigkeit und Gasdurchlässigkeit, sowie insbesondere die Formstabilität, verlieren.Surprisingly, this method has shown that, in contrast to the known methods for treating cork, not only the undesired organic compounds such as PCP, TCA and TeCA as well as waxes and fats can be removed below their detection limit, but also shaped cork products , such as bottle corks, can be extracted without losing their substance-specific properties, such as elasticity and density, Liquid impermeability and gas permeability, and in particular the dimensional stability, lose.
Die Vorteile dieses Verfahrens waren in diesem Ausmaß nicht zu erwarten.The advantages of this process were not to be expected to this extent.
Das erfindungsgemäße Verfahren ist zwar auf kein bestimmtes korkhaltiges Material beschränkt, es hat sich allerdings als sehr vorteilhaft erwiesen, wenn als korkhaltige Materiaüen Korkplatten, Korkgranulate, Korkpulver, Flaschenkork und/oder Presskork eingesetzt werden. Dabei kann das verwendete Ausgangsmaterial auch einer mechanischen und/oder chemischen und/oder physikalischen Vorbehandlung unterworfen worden sein, wie sie z.B. Zerkleinerungsschritte, Säure-Base- Behandlungsmaßnahmen oder ein Kochvorgang darstellen und wie sie von der vorliegenden Erfindung ebenfalls berücksichtigt werden.Although the method according to the invention is not restricted to any specific cork-containing material, it has proven to be very advantageous if cork boards, cork granules, cork powder, bottle cork and / or pressed cork are used as cork-containing materials. The starting material used may also have been subjected to a mechanical and / or chemical and / or physical pretreatment, such as that e.g. Comminution steps, acid-base treatment measures or a cooking process and how they are also taken into account by the present invention.
Bei dem erfindungsgemäßen Verfahren werden bevorzugt Temperaturen angewandt, die zwischen 40 und 100 °C, mehr bevorzugt zwischen 60 und 80 °C, liegen. Die angewandten Verfahrensdrücke hegen vorzugsweise zwischen 80 und 400 bar, mehr bevorzugt zwischen 100 und 150 bar, und besonders bevorzugt zwischen 120 und 140 bar.Temperatures which are between 40 and 100 ° C., more preferably between 60 and 80 ° C., are preferably used in the process according to the invention. The process pressures used are preferably between 80 and 400 bar, more preferably between 100 and 150 bar, and particularly preferably between 120 and 140 bar.
Das Gewichtsverhältnis zwischen eingesetztem komprimiertem Gas und dem korkhaltigen Material ist für das vorliegende Verfahren zwar nicht limitierend, doch hat sich ein entsprechendes Gewichtsverhältnis als geeignet herausgestellt, das 1 bis 100 : 1 beträgt. Bevorzugte Gewichtsverhältnisse von 20 bis 70 : 1 sowie insbesondere 40 : 1 sind im Rahmen der vorhegenden Erfindung für besondere Anwendungsfälle heranzuziehen.The weight ratio between the compressed gas used and the cork-containing material is not limiting for the present method, but a corresponding weight ratio that has been found to be suitable is 1 to 100: 1. Preferred weight ratios of 20 to 70: 1 and in particular 40: 1 are to be used in the context of the present invention for special applications.
Als ebenfalls bevorzugt wird es erfindungsgerriäß angesehen, wenn sich das komprimierte Gas im überkritischen Zustand befindet.It is also preferred according to the invention if the compressed gas is in the supercritical state.
Als u.a. erfindungswesenthch ist angegeben, dass das komprimierte Gas die Schüttung radial oder axial durchströmt. Insbesondere bzgl. der radialen Fahrweise hat es sich als günstig erwiesen, wenn die Strömungsrichtung von innen nach außen führt. Das komprimierte Gas wird dabei zunächst in einen zentral angeordneten axialen Innenzylinder des Druckgefäßes eingespeist und tritt dann durch Öffnungen radial in die Schüttung aus, von wo es nach außen strömt.It is stated, among other things, that the compressed gas flows radially or axially through the bed. Especially with regard to the radial driving style it has proven to be advantageous if the flow direction leads from the inside to the outside. The compressed gas is first fed into a centrally arranged axial inner cylinder of the pressure vessel and then exits radially through openings into the bed, from where it flows outwards.
Bezüghch des weiteren erfindungswesentlichen Merkmals, dass die zu extrahierende Schüttung mit einem Adsorptionsmaterial kombiniert ist, sieht die Erfindung als bevorzugte Vertreter mindestens einen der Reihe Aktivkohle, Aluminiumoxid und/oder Siliciumoxid, wie bspw. Zeolithe, vor. Die Kombination der Schüttung mit dem jeweils gewählten Adsorptionsmaterial kann dabei durch homogenes oder heterogenes Durchmischen, durch schichtweises Einbringen des Adsorptionsmaterials in die Schüttung oder durch Nachschalten des Adsorptionsmaterials erfolgen. Bevorzugt wird von der vorhegenden Erfindung, wenn das Adso tionsmaterial schichtweise in die Schüttung eingebracht wird oder aber wenn es der zu extrahierenden Schüttung nachgeschaltet wird.With regard to the further feature essential to the invention that the bed to be extracted is combined with an adsorption material, the invention provides as preferred representatives of at least one of the series activated carbon, aluminum oxide and / or silicon oxide, such as zeolites. The bed can be combined with the adsorption material selected in each case by homogeneous or heterogeneous mixing, by introducing the adsorption material in layers into the bed or by adding the adsorption material. It is preferred of the present invention if the adsorption material is introduced into the bed in layers or if it is connected downstream of the bed to be extracted.
In Abhängigkeit vom zu extrahierenden korkhaltigen Material bzw. dessen Inhaltsstoffen kann es vorteilhaft sein, wenn dem komprimierten Gas mindestens ein Schleppmittel oder ein Co-Solvens, wie z.B. Wasser, Cι.5-Alkohole, bspw. Methanol, Ethanol, Propanol, Isopropanol, Butanole und Pentanole, und Ether, zugemischt werden. Besonders bevorzugt sollte dies erfindungsgemäß in Mengen erfolgen, die zwischen 0,1 und 10 Gew.-%, bevorzugt zwischen 0,5 und 8 Gew.-%, mehr bevorzugt zwischen 2 und 6 Gew.-%, noch mehr bevorzugt zwischen 3 und 5 Gew.-%, bezogen auf den eingesetzten Gasanteil, Hegen.Depending on the cork-containing material to be extracted or its ingredients, it may be advantageous if the compressed gas contains at least one entrainer or a co-solvent, such as water, C 1. 5 alcohols, for example methanol, ethanol, propanol, isopropanol, butanols and pentanols, and ether. According to the invention, this should particularly preferably take place in amounts which are between 0.1 and 10% by weight, preferably between 0.5 and 8% by weight, more preferably between 2 and 6% by weight, even more preferably between 3 and 5% by weight, based on the amount of gas used.
Da im Vordergrund der vorliegenden Erfindung die Aufgabe stand, korkhaltiges Material so zu extrahieren, dass die Reduzierung der unerwünschten Inhalts- und Begleitstoffe zu lebensmittelgerechten Produkten führen, sieht die vorhegende Erfindung auch vor, dass aus dem korkhaltigen Material organische Verbindungen und bevorzugt (chlorierte) Phenole und/oder (chlorierte) Anisole und hier insbesondere Pentachlorphenol (PCP), Trichloranisol (TCA) und/oder Tetrachloranisol (TeCA) sowie Wachse und Fette entfernt werden. Die Anordnung der einzelnen Vorrichtungs-Module zur Ausführung der beanspruchten Verfahrensschritte ist zwar für das vorliegende Verfahren nicht als einschränkend anzusehen, jedoch sieht die vorhegende Erfindung eine Variante vor, bei dem das Verfahren in mindestens einem Autoklaven durchgeführt wird, wobei eine Modulanordnung besonders bevorzugt wird, bei der zwei Druckbehälter mindestens in Reihe oder parallel geschaltet werden.Since the object of the present invention was to extract cork-containing material in such a way that the reduction of the undesirable contents and accompanying substances lead to food-grade products, the present invention also provides that organic compounds and preferably (chlorinated) phenols from the cork-containing material and / or (chlorinated) anisoles and here in particular pentachlorophenol (PCP), trichloroanisole (TCA) and / or tetrachloroanisole (TeCA) as well as waxes and fats are removed. The arrangement of the individual device modules for carrying out the claimed method steps is not to be regarded as restrictive for the present method, but the present invention provides a variant in which the method is carried out in at least one autoclave, a module arrangement being particularly preferred, where two pressure vessels are connected at least in series or in parallel.
Üblicherweise besteht die Verfahrensanordnung darin, dass zwei mit dem korkhaltigen Ausgangsmaterial parallel oder in Reihe geschaltete Autoklaven mit dem Extraktionsgas beaufschlagt werden. Die Abscheidung evtl. anhaftender Wachse und Fette erfolgt anschließend in einem nachgeschalteten Zyklon bei tiefen Temperaturen und die Abtrennung der zyklischen organischen Verbindungen aus dem Extraktionsgas in einem dritten Autoklaven, der mit dem Adsorptionsmaterial in Form von Aktivkohle gefüllt ist.The process arrangement usually consists in that two autoclaves connected in parallel or in series with the cork-containing starting material are subjected to the extraction gas. Any adhering waxes and fats are then separated in a downstream cyclone at low temperatures and the cyclic organic compounds are separated from the extraction gas in a third autoclave, which is filled with the adsorption material in the form of activated carbon.
Mit dem vorgeschlagenen Verfahren erfolgt insbesondere aufgrund der isobaren Bedingungen und der radialen oder axialen Strömungs hrung des komprimierten Extraktionsgases eine nahezu quantitative Entfernung der unerwünschten organischen Korkinhaltsstoffe, so dass die erhaltenen aufgereinigten Korkmaterialien unbedenklich ihrer Verwendung im Lebensmittelbereich zugeführt werden können.With the proposed method, in particular due to the isobaric conditions and the radial or axial flow of the compressed extraction gas, an almost quantitative removal of the undesired organic cork ingredients takes place, so that the purified cork materials obtained can be safely used in the food industry.
Gegenstand der vorliegenden Erfindung ist somit ein Verfahren zur Extraktion von korkhaltigem Material mit Hilfe eines komprimierten Gases bei Temperaturen zwischen 10 und 120 °C und Drücken zwischen 10 und 600 bar, wobei die Extraktion bei isobaren Bedingungen durchgeführt wird, das komprimierte Gas die Schüttung radial oder axial durchströmt und die zu extrahierende Schüttung mit einem Adsorptionsmaterial kombiniert ist. Auf diese Weise gelingt es bspw. Korkplatten, Korkgranulate, Flaschenkork oder Presskork von organischen Verbindungen, wie bspw. Pentachlorphenol, Trichloranisol, Tetrachloranisol sowie Wachsen und Fetten, quantitativ zu entfernen, so dass die aufgereinigten korkhaltigen Materialien ohne Bedenken Verwendungszwecken im Lebensmittelbereich und insbesondere im Getränkesektor zugeführt werden können.The present invention thus relates to a process for the extraction of cork-containing material with the aid of a compressed gas at temperatures between 10 and 120 ° C and pressures between 10 and 600 bar, the extraction being carried out under isobaric conditions, the compressed gas being the bed radially or flows axially and the bed to be extracted is combined with an adsorption material. In this way it is possible, for example, to remove cork plates, cork granules, bottle cork or pressed cork from organic compounds, such as, for example, pentachlorophenol, trichloroanisole, tetrachloroanisole and waxes and fats, so that the cleaned ones cork-containing materials can be used without hesitation in the food sector and in particular in the beverage sector.
Das nachfolgende Beispiel veranschaulicht die Vorteile dieses Verfahrens zur Extraktion von korkhaltigem Material mit Hilfe eines komprimierten Gases.The following example illustrates the advantages of this method for the extraction of cork-containing material with the help of a compressed gas.
Beispielexample
In diesem Beispiel wurden zwei parallel geschaltete Autoklaven mit jeweils 270 kg eines pulverformigen Korkmaterials gefüllt und anschließend mit einer Durchflussmenge von 18 m3/h an superkritischem CO2 isobar bei einem Druck von 120 bar und einer Verfahrenstemperatur von 60 °C durchströmt. Das Verhältnis von komprimiertem Gas zum korkhaltigem Ausgangsmaterial betrug 66 : 1.In this example, two autoclaves connected in parallel were each filled with 270 kg of a powdered cork material and then flowed through with a flow rate of 18 m 3 / h of supercritical CO 2 isobar at a pressure of 120 bar and a process temperature of 60 ° C. The ratio of compressed gas to cork-containing raw material was 66: 1.
Im Anschluss wurde das mit den zu extrahierenden Verbindungen beladene Extraktionsgas in einen auf 0 °C gekühlten Zyklon übergeführt, der ebenfalls isobar betrieben wurde αnd in dem aus dem Extraktionsgas Wachse und Fette abgeschieden wurden.Subsequently, the extraction gas loaded with the compounds to be extracted was transferred to a cyclone cooled to 0 ° C., which was also operated isobarically and in which waxes and fats were separated from the extraction gas.
Abschließend gelangte das nun nur noch mit den organischen zyklischen Verbindungen beaufschlagte Extraktionsgas in einen nachgeschalteten dritten Autoklaven, der mit 2 to Aktivkohle befüllt war.Finally, the extraction gas, which was now only loaded with the organic cyclic compounds, was passed into a downstream third autoclave, which was filled with 2 tons of activated carbon.
Nach einer Stunde absoluter Extraktionszeit war das beaufschlagte pulverformige Korkmaterial quantitativ von den organischen Verbindungen PCP, TCA, TeCA sowie Wachsen und Fetten befreit. After one hour of absolute extraction time, the charged powdered cork material was freed quantitatively from the organic compounds PCP, TCA, TeCA as well as waxes and fats.

Claims

Patentansprüche claims
1. Verfahren zur Extraktion von korkhaltigem Material mit Hilfe eines komprimierten Gases bei Temperaturen zwischen 10 und 120 °C und Drücken zwischen 10 und 600 bar, dadurch gekennzeichnet, dass die Extraktion bei isobaren Bedingungen durchgeführt wird, dass das komprimierte Gas die Schüttung radial oder axial durchströmt und dass die zu extrahierende Schüttung mit einem Adsorptionsmaterial kombiniert ist.1. Process for the extraction of cork-containing material with the aid of a compressed gas at temperatures between 10 and 120 ° C and pressures between 10 and 600 bar, characterized in that the extraction is carried out under isobaric conditions, that the compressed gas is the fill radial or axial flows through and that the bed to be extracted is combined with an adsorption material.
2. Verfahren nach Anspruch 1, dadurch gekennzeichnet, dass es sich beim korkhaltigen Material um Korkplatten, Korkgranulat, Korkpulver, Flaschenkork und/oder Presskork handelt.2. The method according to claim 1, characterized in that the cork-containing material is cork boards, cork granules, cork powder, bottle cork and / or pressed cork.
3. Verfahren nach Anspruch 2, dadurch gekennzeichnet, dass ein korkhaltiges Material eingesetzt wird, das einer mechanischen und/oder chemischen und/oder physikalischen Vorbehandlung, wie z.B. einem Zerkleinerungsschritt, einer Säure-Base-Behandlung oder einem Kochvorgang, unterworfen worden ist.3. The method according to claim 2, characterized in that a cork-containing material is used, the mechanical and / or chemical and / or physical pretreatment, such as. a crushing step, an acid-base treatment or a cooking process.
4. Verfahren nach einem der Ansprüche 1 bis 3, dadurch gekennzeichnet, dass es bei Temperaturen zwischen 40 und 100 °C und Drücken zwischen 100 und 150 bar durchgeführt wird.4. The method according to any one of claims 1 to 3, characterized in that it is carried out at temperatures between 40 and 100 ° C and pressures between 100 and 150 bar.
5. Verfahren nach einem der Ansprüche 1 bis 4, dadurch gekennzeichnet, dass es bei einem Gewichts-Verhältnis komprimiertes Gas : korkhaltigem Material von 1 bis 100 : 1 durchgeführt wird.5. The method according to any one of claims 1 to 4, characterized in that it is carried out at a weight ratio of compressed gas: cork-containing material from 1 to 100: 1.
6. Verfahren nach Anspruch 5, dadurch gekennzeichnet, dass es bei einem Gewichts- Verhältnis komprimiertes Gas : korkhaltigem Material von 20 bis 70 : 1, insbesondere 40 : 1, durchgeführt wird.6. The method according to claim 5, characterized in that it is carried out at a weight ratio of compressed gas: cork-containing material from 20 to 70: 1, in particular 40: 1.
7. Verfahren nach einem der Ansprüche 1 bis 6, dadurch gekennzeichnet, dass das komprimierte Gas im überkritischen Zustand eingesetzt wird. 7. The method according to any one of claims 1 to 6, characterized in that the compressed gas is used in the supercritical state.
8. Verfahren nach einem der Ansprüche 1 bis 7, dadurch gekennzeichnet, dass die Schüttung vom komprimierten Gas radial von innen nach außen durchströmt wird.8. The method according to any one of claims 1 to 7, characterized in that the bed is flowed through by the compressed gas radially from the inside to the outside.
9. Verfahren nach einem der Ansprüche 1 bis 8, dadurch gekennzeichnet, dass die zu extrahierende Schüttung mit mindestens einem Adsorptionsmaterial, ausgewählt aus der Gruppe bestehend aus Aktivkohle, Aluminiumoxid und Siliciumoxid, wie bspw. Zeolithe, kombiniert ist.9. The method according to any one of claims 1 to 8, characterized in that the bed to be extracted is combined with at least one adsorption material selected from the group consisting of activated carbon, aluminum oxide and silicon oxide, such as. Zeolites.
10. Verfahren nach einem der Ansprüche 1 bis 9, dadurch gekennzeichnet, dass das Adsorptionsmaterial in der Schüttung schichtweise oder der zu extrahierenden Schüttung nachgeschaltet eingesetzt wird.10. The method according to any one of claims 1 to 9, characterized in that the adsorption material is used in layers in the bed or downstream of the bed to be extracted.
11. Verfahren nach einem der Ansprüche 1 bis 10, dadurch gekennzeichnet, dass dem komprimierten Gas mindestens ein Schleppmittel oder ein Co-Solvens, wie z.B. Wasser, Cι-5-Alkohole und Ether, zugemischt wird.11. The method according to any one of claims 1 to 10, characterized in that at least one entrainer or a co-solvent, such as water, Cι -5 alcohols and ethers, is added to the compressed gas.
12. Verfahren nach Anspruch 11, dadurch gekennzeichnet, dass das Schleppmittel oder Co-Solvens in Mengen zwischen 0,1 und 10 Gew.-% bezogen auf den Gasanteil zugemischt wird.12. The method according to claim 11, characterized in that the entrainer or co-solvent is mixed in amounts between 0.1 and 10 wt .-% based on the gas content.
13. Verfahren nach einem der Ansprüche 1 bis 12, dadurch gekennzeichnet, dass aus dem korkhaltigen Material organische Verbindungen und bevorzugt (chlorierte) Phenole und/oder (chlorierte) Anisole und besonders bevorzugt Pentachlorphenol (PCP), Trichloranisol (TCA) und/oder Tetrachloranisol (TeCA) sowie Wachse und Fette entfernt werden.13. The method according to any one of claims 1 to 12, characterized in that from the cork-containing material organic compounds and preferably (chlorinated) phenols and / or (chlorinated) anisoles and particularly preferably pentachlorophenol (PCP), trichloroanisole (TCA) and / or tetrachloroanisole (TeCA) as well as waxes and fats are removed.
14. Verfahren nach einem der Ansprüche 1 bis 13, dadurch gekennzeichnet, dass es in mindestens einem Autoklaven durchgeführt wird und bevorzugt in mindestens zwei in Reihe oder parallel geschalteten Druckbehältern. 14. The method according to any one of claims 1 to 13, characterized in that it is carried out in at least one autoclave and preferably in at least two pressure vessels connected in series or in parallel.
PCT/EP2004/010133 2003-09-10 2004-09-10 Method for the extraction of cork-containing material WO2005025825A1 (en)

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US7332042B2 (en) 1999-09-27 2008-02-19 Commissariat A L'energie Atomique Process for treatment and extraction of organic cork compounds by a dense fluid under pressure
FR2936730A1 (en) * 2008-10-08 2010-04-09 Univ La Rochelle PROCESS FOR EXTRACTING AROMATIC LIGHT-INDUCED ARTIFICIAL MOLECULES THERMO-HYDRO-MECHANICAL INSTANTALLY CONTROLLED INSTANT LIFT (DIC) TREATMENT IN SUCCESSIVE FORM (EDS)
WO2010040949A1 (en) * 2008-10-08 2010-04-15 Universite De La Rochelle Process for the extraction of undesirable aromatic molecules from cork via a thermo-hydro-mechanical treatment of instantaneous controlled pressure drop (dic) optionally in successive form (eds)
EP2404647A1 (en) 2010-07-08 2012-01-11 Dartes Krup, S.L. Method for extracting organic compounds from granulated cork
WO2013098440A1 (en) * 2011-12-30 2013-07-04 Asociación De Investigación De La Industria Agroalimentaria Method for removing various undesirable compounds from cork
EP2799199A4 (en) * 2011-12-30 2015-09-16 Invest De La Ind Agroalimentaria Asoc De Method for removing various undesirable compounds from cork
ES2423255A1 (en) * 2012-03-13 2013-09-18 Universidad De Salamanca Process for the elimination of the haloanisoles and halophenols present in cork and installation to carry out said elimination
EP3906981A1 (en) 2020-05-07 2021-11-10 Feyecon Development & Implementation B.V. Method for extraction using carbon dioxide
WO2021224093A1 (en) 2020-05-07 2021-11-11 Amorim Cork, S.A. Process and system for decontaminating cork material
WO2021224502A1 (en) 2020-05-07 2021-11-11 Feyecon Development & Implementation B.V. Method and apparatus for extraction using carbon dioxide

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