EP1624764A1 - Procede de separation selective de matieres - Google Patents

Procede de separation selective de matieres

Info

Publication number
EP1624764A1
EP1624764A1 EP04733797A EP04733797A EP1624764A1 EP 1624764 A1 EP1624764 A1 EP 1624764A1 EP 04733797 A EP04733797 A EP 04733797A EP 04733797 A EP04733797 A EP 04733797A EP 1624764 A1 EP1624764 A1 EP 1624764A1
Authority
EP
European Patent Office
Prior art keywords
substances
valuable
materials
aroma
production
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Withdrawn
Application number
EP04733797A
Other languages
German (de)
English (en)
Inventor
Johann Wiesmüller
Rudolf Zobel
Stephan Pilz
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Evonik Operations GmbH
Original Assignee
Degussa GmbH
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Degussa GmbH filed Critical Degussa GmbH
Publication of EP1624764A1 publication Critical patent/EP1624764A1/fr
Withdrawn legal-status Critical Current

Links

Classifications

    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01JCHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J20/00Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/02Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
    • B01J20/10Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising silica or silicate
    • B01J20/103Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising silica or silicate comprising silica
    • AHUMAN NECESSITIES
    • A23FOODS OR FOODSTUFFS; TREATMENT THEREOF, NOT COVERED BY OTHER CLASSES
    • A23LFOODS, FOODSTUFFS, OR NON-ALCOHOLIC BEVERAGES, NOT COVERED BY SUBCLASSES A21D OR A23B-A23J; THEIR PREPARATION OR TREATMENT, e.g. COOKING, MODIFICATION OF NUTRITIVE QUALITIES, PHYSICAL TREATMENT; PRESERVATION OF FOODS OR FOODSTUFFS, IN GENERAL
    • A23L27/00Spices; Flavouring agents or condiments; Artificial sweetening agents; Table salts; Dietetic salt substitutes; Preparation or treatment thereof
    • AHUMAN NECESSITIES
    • A23FOODS OR FOODSTUFFS; TREATMENT THEREOF, NOT COVERED BY OTHER CLASSES
    • A23LFOODS, FOODSTUFFS, OR NON-ALCOHOLIC BEVERAGES, NOT COVERED BY SUBCLASSES A21D OR A23B-A23J; THEIR PREPARATION OR TREATMENT, e.g. COOKING, MODIFICATION OF NUTRITIVE QUALITIES, PHYSICAL TREATMENT; PRESERVATION OF FOODS OR FOODSTUFFS, IN GENERAL
    • A23L27/00Spices; Flavouring agents or condiments; Artificial sweetening agents; Table salts; Dietetic salt substitutes; Preparation or treatment thereof
    • A23L27/10Natural spices, flavouring agents or condiments; Extracts thereof
    • A23L27/11Natural spices, flavouring agents or condiments; Extracts thereof obtained by solvent extraction
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01JCHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J20/00Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/02Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
    • B01J20/06Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising oxides or hydroxides of metals not provided for in group B01J20/04
    • B01J20/08Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising oxides or hydroxides of metals not provided for in group B01J20/04 comprising aluminium oxide or hydroxide; comprising bauxite
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01JCHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J20/00Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/02Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
    • B01J20/10Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising silica or silicate
    • B01J20/14Diatomaceous earth
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01JCHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J20/00Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/02Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
    • B01J20/10Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising silica or silicate
    • B01J20/16Alumino-silicates
    • B01J20/18Synthetic zeolitic molecular sieves
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01JCHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J20/00Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/02Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
    • B01J20/20Solid 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
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01JCHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J20/00Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/22Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising organic material
    • B01J20/24Naturally occurring macromolecular compounds, e.g. humic acids or their derivatives
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01JCHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J20/00Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/30Processes for preparing, regenerating, or reactivating
    • B01J20/34Regenerating or reactivating
    • B01J20/3408Regenerating or reactivating of aluminosilicate molecular sieves
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01JCHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J20/00Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/30Processes for preparing, regenerating, or reactivating
    • B01J20/34Regenerating or reactivating
    • B01J20/3416Regenerating or reactivating of sorbents or filter aids comprising free carbon, e.g. activated carbon
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01JCHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J20/00Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/30Processes for preparing, regenerating, or reactivating
    • B01J20/34Regenerating or reactivating
    • B01J20/3425Regenerating or reactivating of sorbents or filter aids comprising organic materials
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01JCHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J20/00Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/30Processes for preparing, regenerating, or reactivating
    • B01J20/34Regenerating or reactivating
    • B01J20/3433Regenerating or reactivating of sorbents or filter aids other than those covered by B01J20/3408 - B01J20/3425
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01JCHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J20/00Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/30Processes for preparing, regenerating, or reactivating
    • B01J20/34Regenerating or reactivating
    • B01J20/345Regenerating or reactivating using a particular desorbing compound or mixture
    • B01J20/3458Regenerating or reactivating using a particular desorbing compound or mixture in the gas phase
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01JCHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J38/00Regeneration or reactivation of catalysts, in general
    • B01J38/48Liquid treating or treating in liquid phase, e.g. dissolved or suspended
    • B01J38/50Liquid treating or treating in liquid phase, e.g. dissolved or suspended using organic liquids
    • B01J38/56Hydrocarbons

Definitions

  • the present invention relates to a process for the selective separation of valuable substances with the aid of compressed C 2 - to C 4 ⁇ hydrocarbons.
  • liquid or solid process streams occur in large quantities either as waste or as secondary raw materials, for example as animal feed, or else processed, such as through appropriate clarification and purification measures.
  • loaded adsorbents are obtained, which are usually disposed of, since purification of the loaded adsorbents is uneconomical.
  • adsorbents such as activated carbon or diatomaceous earth
  • a disadvantage of all established processes that use adsorbents is that the adsorbents used do not separate them selectively, but that, depending on the specific surfaces of the adsorbents, valuable substances, such as aromas and odors, contained in the process streams are also bound to the adsorbents , which is why they usually contain significant amounts of these valuable substances.
  • no economic processes are known which, for example, make it possible to selectively separate valuable substances bound to adsorbents in the form of aromatic and odorous substances and to add further value.
  • lipophilic organic solvents are also used to obtain aroma and odor substances in the context of corresponding extraction processes.
  • the aroma and fragrance concentrates obtained in this way mostly contain a certain amount of residues of the organic solvents used, which leads to an easily understandable impairment of the product qualities.
  • adsorption materials are therefore also used, which are intended to remove the organic solvent residues from the products, but due to the physical properties of the adsorbents used, this does not take place to an adequate degree and why the flavor and odor concentrates are depleted in a disadvantageous manner by the adsorbents with regard to the sensory active ingredients.
  • fractional extraction is available, in which the different ingredients are extracted sequentially from the natural product using different process parameters such as pressure, temperature or entrainer feed and collected separately.
  • fractional separation is possible, in which the various ingredients are initially extracted together, but are then separated from the gas under different conditions.
  • the present invention therefore has the general task of providing a process for the selective separation of valuable substances with the aid of compressed C 2 to C 4 hydrocarbons, with which the desired products can be obtained in a relatively simple manner good quality.
  • “absorption” means the binding of valuable substances by liquids or solid substances.
  • “Adsorption” means the corresponding accumulation of valuable substances in the dissolved state on solid bodies, the adsorption being directly proportional to the surface of the solid adsorbent body used.
  • the present method is particularly suitable for valuable substances which are aromatic and / or odorous substances.
  • the valuable materials can also be in the form of organic intermediates or end products, as obtained in particular with the help of biotechnological processes. This primarily includes fermentation processes.
  • the valuable materials can also be bound to catalysts, in which case not only the actual valuable materials are obtained, but also the cleaned carrier materials.
  • the process according to the invention is preferably carried out at temperatures of 1 120 ° C. and pressures of ⁇ 50 MPa, the temperature being particularly preferably between 20 and 40 ° C. and the pressure between 0.5 and 10 MPa.
  • Compressed ethane, propane, butane or mixtures thereof have proven to be particularly suitable C 2 - to C 8 hydrocarbons, the present invention providing in certain applications the compressed hydrocarbon (mixture) entrainer, such as dimethyl ether or alcohols, preferably in proportions of 0.5 to 50% by weight, more preferably 5 to 20% by weight.
  • the compressed hydrocarbon (mixture) entrainer such as dimethyl ether or alcohols, preferably in proportions of 0.5 to 50% by weight, more preferably 5 to 20% by weight.
  • the method according to the invention is particularly suitable for a batchwise procedure. Depending on the area of application, the claimed method can also be carried out continuously or semi-continuously.
  • solid substances with large inner and / or outer surfaces have been shown to be suitable, and preferably those with surfaces> 0.1 m 2 / g, preferably> 10 m 2 / g, more preferably> 100 m 2 / g and more preferably> 500 m 2 / g (according to BET DIN 66131) and / or fluid substances.
  • Activated carbons, clays, silicas, diatomaceous earth, aluminosilicates, zeolites and / or polysaccharides, such as cyclodextrins, are particularly suitable solid substances.
  • the present method takes into account in particular starting materials that come from food production and / or production or from aroma production, but also from juice, wine and spirits production and processing and / or meat, fruit and vegetable processing ,
  • the method according to the invention has proven to be particularly advantageous in the production of natural, nature-identical and / or synthetic aroma and fragrance substances, which the present invention also takes into account.
  • the invention also encompasses processes in which aroma and fragrance substances are obtained in liquid or pasty form or else as a powder.
  • the aromas and fragrances can be finally dissolved in the process according to the invention, which should preferably be done in alcohol.
  • the claimed process develops its advantageous properties in particular when it is carried out in a separation column or in another suitable pressure vessel, it having proven particularly advantageous with regard to the separation column used if the process is carried out according to the countercurrent principle.
  • the present invention also provides that the pressure vessel can be coupled to a separator and that the extracted valuable substances can be separated, for example in the form of aroma and odorous substances, preferably by lowering the pressure and / or increasing the temperature.
  • the process according to the invention also enables the hydrocarbons used as extractants to be recycled, which also contributes to its economy.
  • the invention also provides a special process variant in which the actual process is preceded by an adsorption step: first, solid substances with large inner and / or outer surfaces> 0.1 m 2 / g, preferably> 10 m 2 / g, more preferably> 100 m 2 / g and even more preferably> 500 m 2 / g (BET DIN 66131) loaded with valuable substances; this loaded complex is then treated with compressed C 2-4 hydrocarbons as described.
  • the present method with its preferred variants is not only suitable for the selective separation of adsorbed or absorbed aroma and odor substances from carrier materials which contain these valuable substances only because of the insufficient selectivity of the adsorbents. Rather, this method can also be used to produce high-quality aroma or odorant concentrates, for example by adding an adsorbent to commercially available concentrates obtained with the aid of organic solvents or with compressed CO 2 . As a result, sensory lead compounds are selected from the concentrate and subsequently the adsorbents loaded in this way, such as treated to be claimed. In this way, typical lead compounds of the aromas and fragrances are selectively concentrated, which leads to high-quality end products.
  • the present invention also takes into account the removal of less valuable compounds which are bound to adsorption or absorption materials.
  • the main focus is on the extraction or purification of the carrier materials and less on the substances adsorbed or absorbed on them.
  • linalool linalyl alcohol
  • a linalool content determination by means of gas chromatography of a tea aroma from activated carbon according to the invention (a) gave the following values in comparison to a conventional black tea aroma (b) obtained by ethanol extraction:

Landscapes

  • Chemical & Material Sciences (AREA)
  • Analytical Chemistry (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Inorganic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Nutrition Science (AREA)
  • Health & Medical Sciences (AREA)
  • Food Science & Technology (AREA)
  • Polymers & Plastics (AREA)
  • Materials Engineering (AREA)
  • Geochemistry & Mineralogy (AREA)
  • Fats And Perfumes (AREA)
  • Extraction Or Liquid Replacement (AREA)
  • Solid-Sorbent Or Filter-Aiding Compositions (AREA)
  • Seasonings (AREA)

Abstract

L'invention concerne un procédé de séparation sélective de matières à l'aide d'hydrocarbures C2-C4 comprimés, tels que l'éthane, le propane et/ou le butane. Selon ledit procédé on utilise un matériau de départ qui contient lesdites matières à l'état absorbé et/ou adsorbé. Pour ce procédé, qui est mis en oeuvre à des températures = 120 DEG C et à des pressions < 50 Mpa, de préférence en continu, on utilise, comme matériaux de départ, des charbons actifs, des argiles, des acides siliciques, des zéolites ou des polysaccharides chargés avec lesdites matières. Le procédé présenté permet en particulier d'obtenir des substances aromatiques et odorantes à partir de matériaux de départ qui proviennent de la production et/ou de l'extraction de produits alimentaires et, de préférence, de l'extraction d'arômes, de la production et du traitement de jus, de vins et de spiritueux ou du traitement de la viande, des fruits et des légumes.
EP04733797A 2003-05-20 2004-05-19 Procede de separation selective de matieres Withdrawn EP1624764A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE10322564A DE10322564A1 (de) 2003-05-20 2003-05-20 Verfahren zur selektiven Abtrennung von Wertstoffen
PCT/EP2004/005436 WO2004103093A1 (fr) 2003-05-20 2004-05-19 Procede de separation selective de matieres

Publications (1)

Publication Number Publication Date
EP1624764A1 true EP1624764A1 (fr) 2006-02-15

Family

ID=33440984

Family Applications (1)

Application Number Title Priority Date Filing Date
EP04733797A Withdrawn EP1624764A1 (fr) 2003-05-20 2004-05-19 Procede de separation selective de matieres

Country Status (5)

Country Link
US (1) US20070275144A1 (fr)
EP (1) EP1624764A1 (fr)
JP (1) JP2007533427A (fr)
DE (1) DE10322564A1 (fr)
WO (1) WO2004103093A1 (fr)

Families Citing this family (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE102007033907A1 (de) * 2007-07-20 2009-01-22 Uhde High Pressure Technologies Gmbh Naturstoffextraktion
CN105021748A (zh) * 2014-04-29 2015-11-04 中国科学院大连化学物理研究所 一种茶叶挥发性香气成分分析方法
EP3002327A1 (fr) * 2014-10-02 2016-04-06 Sensient Flavors Limited Procédé de modification de la composition d'huiles essentielles
EP3175897B1 (fr) 2015-12-04 2018-04-04 Evonik Degussa GmbH Procede ameliore d'extraction de matieres aromatiques a partir de phases liquides aqueuses et/ou contenant des graisses
US11471859B2 (en) 2016-07-20 2022-10-18 Abs Materials, Inc. Treatment and regeneration system and method for extracting organic solutes from-water
JP2018153134A (ja) * 2017-03-17 2018-10-04 株式会社エルビー 紅茶飲料

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US2566613A (en) * 1948-07-20 1951-09-04 Phillips Petroleum Co Aromatic recovery process
US3071474A (en) * 1961-05-24 1963-01-01 Fred L Rahal Food flavor recovery
JPS5072874A (fr) * 1973-10-31 1975-06-16
GB2089639B (en) * 1980-12-19 1984-07-18 Gen Foods Corp Process for recovery of aroma volatiles
US4442210A (en) * 1981-09-02 1984-04-10 Mobil Oil Corporation Process for the production of fermentation ethanol
DE3145673A1 (de) * 1981-11-19 1983-05-26 Merck Patent Gmbh, 6100 Darmstadt "verfahren zur gewinnung oder anreicherung von aromastoffen"
DE3229041A1 (de) * 1982-08-04 1984-02-09 Fried. Krupp Gmbh, 4300 Essen Verfahren zur gewinnung von lecithin
US4900575A (en) * 1989-04-17 1990-02-13 General Foods Corporation Aroma recovery from the thermal hydrolysis of spent grounds
AU7468291A (en) * 1990-11-13 1992-06-11 Portwall Pty Limited Lipid fractionation and products so obtained
US5759549A (en) * 1994-11-25 1998-06-02 Helsinki University Licensing, Ltd. Processes for the separatin of lipids
DE19820032A1 (de) * 1998-05-05 1999-11-11 Aev Altmark Eiveredlung Gmbh Eiprodukte mit stark reduziertem Cholesteringehalt und Verfahren zu deren Herstellung
AU2002212501A1 (en) * 2000-11-06 2002-05-15 Ineos Fluor Holdings Limited Solvent extraction process
GB0027047D0 (en) * 2000-11-06 2000-12-20 Ici Plc Process for reducing the concentration of undesired compounds in a composition
DE10252168B4 (de) * 2002-11-09 2007-01-11 Degussa Ag Verwendung eines Verfahrens zur selektiven Abtrennung von flüchtigen Aromastoffen aus einphasigen, flüssigen Ausgangsmaterialien mit einem Fett- und/oder Öl-Gehalt ≦20 Gew.-%

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
See references of WO2004103093A1 *

Also Published As

Publication number Publication date
JP2007533427A (ja) 2007-11-22
WO2004103093A1 (fr) 2004-12-02
DE10322564A1 (de) 2004-12-09
US20070275144A1 (en) 2007-11-29

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