WO1994026683A1 - Procede et dispositif permettant de produire un squalene a partir de residus d'huile d'olive - Google Patents

Procede et dispositif permettant de produire un squalene a partir de residus d'huile d'olive Download PDF

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Publication number
WO1994026683A1
WO1994026683A1 PCT/DE1994/000542 DE9400542W WO9426683A1 WO 1994026683 A1 WO1994026683 A1 WO 1994026683A1 DE 9400542 W DE9400542 W DE 9400542W WO 9426683 A1 WO9426683 A1 WO 9426683A1
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WO
WIPO (PCT)
Prior art keywords
squalene
supercritical
gas
extraction
mixture
Prior art date
Application number
PCT/DE1994/000542
Other languages
German (de)
English (en)
Inventor
Paolo Bondioli
Armando LANZANI
Enzo FEDELI
Andrea Mossa
Adam Müller
Original Assignee
Müller Extract Company 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 Müller Extract Company Gmbh filed Critical Müller Extract Company Gmbh
Publication of WO1994026683A1 publication Critical patent/WO1994026683A1/fr

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Classifications

    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D11/00—Solvent extraction
    • B01D11/04—Solvent extraction of solutions which are liquid
    • B01D11/0403—Solvent extraction of solutions which are liquid with a supercritical fluid
    • B01D11/0407—Solvent extraction of solutions which are liquid with a supercritical fluid the supercritical fluid acting as solvent for the solute
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C11/00—Aliphatic unsaturated hydrocarbons
    • C07C11/21—Alkatrienes; Alkatetraenes; Other alkapolyenes

Definitions

  • the invention relates to a process for the production of squalene from olive oil residues according to claim 1, a device for extraction according to claim 13, an extract with a high squalene content according to claim 19 and a use of such an extract according to claim 21.
  • Squalene (2, 6,10,15,19,23-hexamethyl-2,6,10,14,18,22-tetra-cosahexaene) is an acyclic triterpene.
  • Squalene can be prepared synthetically from hexaphenyl-l, 4-butanediyldiphosphonium dibromide and 6,10-dimethyl-5,9-undecadien-2-one.
  • Squalene obtained by synthetic means, is very expensive because the required level of purity for commercial use can only be achieved, if at all, with unreasonable effort.
  • Squalene also occurs as a natural substance in large quantities in shark liver oil and in smaller quantities in many vegetable oils.
  • a product according to the invention is claimed in claim 19, a use according to the invention in claim 21.
  • An advantage of the squalene obtained according to the invention is that it is free of a strange smell or taste.
  • the process according to the invention of processing the olive oil residues can also be simplified under suitable conditions, in particular the choice of catalyst, in such a way that steps a) to c) can be carried out in one reaction.
  • steps a) to c) above a process is described which involves the conversion of a complex mixture, which is glycerides, squalene, methyl and ethyl esters contains free fatty acids and the free fatty acids themselves in a binary mixture which contains squalene and triglycerides in a manner which provides the optimum conditions for successful extraction by means of a supercritical and / or subcritical gas, in particular CO2.
  • a complex mixture which is glycerides, squalene, methyl and ethyl esters contains free fatty acids and the free fatty acids themselves in a binary mixture which contains squalene and triglycerides in a manner which provides the optimum conditions for successful extraction by means of a supercritical and / or subcritical gas, in particular CO2.
  • Step 1 Naturally present esters in the olive oil residues to be processed are saponified, the acid part then being present as a soap and the alcoholic part being released and being eliminated during a washing procedure.
  • Step 2 The fatty acids, which are present as soap, and the organic material, which is dissolved or dispersed in the saponification solution, are released and isolated as a water-insoluble layer which essentially contains squalene and free fatty acids.
  • the organic layer which forms is then washed and dried in order to remove alcohols and inorganic impurities.
  • esterification reaction between the free fatty acids and glycerin is then carried out.
  • the amount of glycerin added is added as a stoichiometric amount, calculated on the basis of the free fatty acids.
  • the esterification reaction takes place in the presence of a metallic catalyst.
  • the use of an metallic catalyst instead of the acid catalyst customary in the prior art means that the structure of the squalene is not changed. form rearrangements or isomerizations or the like.
  • tin-containing catalyst in particular tin (II ) - oxide, tin oxalate or tin-2-ethylhexilate or other tin salts or tin metal organic compounds, however, makes it possible to carry out the transesterification reaction between methyl or ethyl esters and glycerol simultaneously - and thus in one step.
  • esterification is carried out with the aid of an acid-containing catalyst and then an extraction with a supercritical and / or subcritical gas, in particular a CO2 extraction, in generally known devices, undesirably isomerized squalene products are reduced Get quality.
  • a supercritical and / or subcritical gas in particular a CO2 extraction
  • a high-quality squalene with a content of more than 90% is obtained in its natural composition without isomers if the esterification with a non-acidic catalyst, e.g. a metal-containing catalyst, in particular a zinc or tin-containing catalyst, for example zinc powder or tin oxide or the like.
  • a non-acidic catalyst e.g. a metal-containing catalyst, in particular a zinc or tin-containing catalyst, for example zinc powder or tin oxide or the like.
  • the quality of the squalene product can be increased further if a device according to claim 13 is used for the extraction with supercritical and / or subcritical gases.
  • the esterified material is e.g. B. introduced in the middle of a high-pressure extraction column, for example injected, which is specifically with different segments and is optionally equipped with a corresponding double jacket (see FIG. 1: segments A, B, C, D, E, F, G).
  • the undissolved constituents of the esterified product are obtained as a residue in the bottom zone G of the column.
  • the esterified product can be injected both at the top segment and in another segment of the column. It is important that the supercritical gas, e.g. CO2 is introduced at a point in the column, so that the CO2 can flow in countercurrent from the bottom to the top.
  • the supercritical gas e.g. CO2
  • the type of packing in the column is responsible for optimal contact between the product and supercritical and / or subcritical gas. According to this procedure, squalene is dissolved in CO2 and conveyed over the top of the column to the separator S.
  • the esterified material separated from squalene is collected as a residue in the bottom zone G of the column.
  • the column has at least two segments with temperature zones operating differently from one another.
  • Three or more segments are preferred which can be temperature-controlled independently of one another and which operate at different temperatures, wherein during operation they have an inwardly decreasing temperature gradient.
  • the temperature of the extraction gas can be subcritical, near the critical point, or supercritical.
  • the extraction pressure is usually supercritical, but can also be subcritical if necessary.
  • the extraction temperature can also be subcritical, close to the critical point, or supercritical.
  • the extraction pressure is usually supercritical here too.
  • the segments located further up e.g. B in the drawing
  • the extraction temperature and the extraction pressure have to be supercritical in order to separate any undissolved squalene residues.
  • the critical data for the supercritical gases used are known, e.g. the critical temperature for CO2 is + 31.1 ° C and the kitic pressure is 73.3 bar.
  • the present invention is not limited to extraction with CO2. Rather, one can also use a supercritical and / or subcritical gas as a - under normal conditions - gaseous solvent which is selected from the group consisting of: CO; Ethane; Propane; as well as their mixtures, in particular a mixture of CO2 and propane.
  • a supercritical and / or subcritical gas as a - under normal conditions - gaseous solvent which is selected from the group consisting of: CO; Ethane; Propane; as well as their mixtures, in particular a mixture of CO2 and propane.
  • a gaseous solvent can also be used which contains an entrainer, for example an alcohol, preferably ethanol.
  • Preferred extraction conditions are, for example, those according to claims 10 and / or 11.
  • the device according to the drawing described below is used. It should be noted here that the number of segments can be more, but also less than three.
  • the column consists of the segments B D F and the intermediate segments A C E G, which are connected to one another by flanges.
  • the column is filled with packs, e.g. Sulzer packs. If necessary, the segments can only be partially filled with packing material. In addition, it is also possible to use different packing materials per segment and / or in different segments.
  • the segments B D F each have a double jacket, which can be tempered independently and individually by flowing through them using a temperature-controlled medium.
  • the pump P- ⁇ draws liquid CO2 from the condenser L and brings it to the desired supercritical pressure.
  • the CO2 which is supercritical in terms of pressure flows from segment G to the top of column A.
  • the CO2 which is subcritical or supercritical in terms of temperature is essentially purified. applies and controlled by the double jacket systems that are specific to the individual BDF segments.
  • the esterified material is introduced at the upper part of the segment D or the intermediate segment C of the drawing using the metering pump P2 and the valve Vj.
  • the starting material flows continuously from P2 to C.
  • the invention is not limited to this point of introduction of the starting material. According to the invention it is possible to choose a different entry point on the column, either lower or higher than point C.
  • the remaining solution of the squalene parts not yet dissolved in CO2 takes place in segment B.
  • a top product dissolved in CO2 is obtained, which flows from the top of column A to the proportionally controlled valve V2, where the extraction pressure is reduced.
  • the extraction temperature is also reduced in the subsequent heat exchanger H ⁇ . Under these conditions, the extract reaches the separator S, where the separation from the CO2 takes place.
  • the extract obtained contains almost all of the squalene and can be continuously removed from the separating tank through valve V3.
  • a particular advantage lies in the fact that the squalene obtained is virtually free of pesticide residues.
  • the bottom product is collected in segment G and can be continuously discharged through valve 4. will wear.
  • the evaporating CO2 in the separator S is free of extract, is liquefied in the heat exchanger H2 and flows into the so-called liquefier L, which essentially represents a collecting container for liquefied CO2.
  • the carbon dioxide can be used again by the pump Pj for a new extraction cycle.
  • 500 g of liquid residues from olive oil production are treated under reflux with 500 ml of methanol, 500 ml of water and with an excess of NaOH or KOH, calculated on the basis of the saponification number.
  • the duration of treatment is approximately three hours.
  • the alkaline solution is then mixed with 85% phosphoric acid.
  • the fatty acid splitting is carried out at a reaction temperature of 70 ° C. The completeness of the fatty acid splitting is achieved when two immiscible liquid layers can be observed.
  • the organic layer of the treated product - as described above - is transferred to a 1,000 ml glass cylinder, which is connected to a magnetic stirrer and vacuum pump.
  • the temperature is raised to 180 ° C. and glycerol and zinc powder 1% are added as a catalyst.
  • the glycerol content is calculated on the basis of the free fatty acid component.
  • the vacuum must be maintained during the esterification.
  • 300 ml of the present esterified product with a content of 28% squalene as starting material are injected into the described extraction column, which works with CO2 as the supercritical gas.
  • the extraction pressure is 150 bar, the extraction temperature in the middle segment (D) 40 ° C, in the upper segment (B) 50 ° C, in the lower segment (F) 30 ° C.
  • the flow rate of CO2 in the example is approximately 100 kg / h.
  • a starting material which is produced as a waste product in olive oil production and which is known, for example, by the term "skam" is used.
  • This starting material is analyzed before processing for its free fatty acid content and its saponification number.
  • the mixture is then heated under a reduced pressure of 100 mm Hg until a temperature of 150 ° C. is reached.
  • the use of a reduced pressure at least during the esterification reaction has the meaning of removing the water formed during the reaction and the water which is present anyway, together with the low-boiling alcohols, such as, for example, methanol and / or ethanol.
  • the removal of water and the low-boiling alcohols from the reaction mixture therefore also has the purpose of shifting the reaction equilibrium in the direction of the end products.
  • the calculated amount of glycerin is added dropwise under reduced pressure during the esterification reaction.
  • the progress of the reaction is periodically checked by analyzing the free fatty acid content and thin-layer chromatography (with hexane: diethyl ether in a ratio of 9: 1.
  • the thin-layer plate is sprayed with sulfuric acid and in an oven at 100 ° C. for 15 minutes
  • a new amount of glycerin, calculated on the residual content of free fatty acids is added generally preferred because a significant part of the previously added glycerol can distill off together with water and alcohol under the pressure and temperature conditions described.
  • the amount of this new addition depends primarily on the design of the device as long as HRT until the residual free fatty acid content lower than 0.3%, which are present as oleic acid, is.
  • the mixture will then cooled to 80 ° C and filtered to remove the catalyst.
  • This reaction mixture obtained is then extracted with CO2 under supercritical and / or subcritical conditions in the device according to the invention, an extract being obtained which has a squalene content of from about 85% by weight to in particular about 97% by weight. , 96% by weight in the example.
  • An extract with a high squalene content obtained with the method according to the invention can be used immediately without further purification as an ointment base for pharmaceutical and / or cosmetic purposes, without having the odor nuisance which inevitably occurs due to extracts from fish liver.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Fats And Perfumes (AREA)

Abstract

L'invention concerne un procédé et un dispositif permettant de produire un squalène à partir de résidus d'huile d'olive. Le procédé comporte quatre étapes qui peuvent être ramenées à deux en cas de nécessité. Ces quatre étapes sont les suivantes: saponification, craquage et estérification des acides gras, et extraction par gaz surcritiques et/ou sous-critiques. Pour procéder à l'extraction par gaz surcritiques ou sous-critiques, on utilise un produit estérifié au préalable avec un catalyseur contenant du métal, qui est injecté dans une colonne d'extraction sous haute pression comportant des zones de colonne pouvant être mises à la température désirée indépendamment les unes des autres. Ce procédé et ce dispositif permettent d'obtenir un squalène commercialisable, d'une pureté supérieure à 90 %.
PCT/DE1994/000542 1993-05-18 1994-05-11 Procede et dispositif permettant de produire un squalene a partir de residus d'huile d'olive WO1994026683A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE19934316620 DE4316620A1 (de) 1993-05-18 1993-05-18 Verfahren und Vorrichtung zur Herstellung von Squalen aus Olivenölrückständen
DEP4316620.2 1993-05-18

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Publication Number Publication Date
WO1994026683A1 true WO1994026683A1 (fr) 1994-11-24

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Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2010023551A2 (fr) 2008-08-28 2010-03-04 Michael Broeker Production de squalène à partir de levures hyperproductrices
WO2013156720A2 (fr) 2012-04-16 2013-10-24 Roquette Freres Procédé de raffinage du squalène produit par microalgues
WO2016044374A1 (fr) * 2014-09-18 2016-03-24 Glaxosmithkline Consumer Healthcare Holdings (Us) Llc Nouvelles formulations
CN108676610A (zh) * 2018-05-16 2018-10-19 浙江海润达科技有限公司 一种从鱿鱼副产物中获取活性物质的方法
EP3511020A1 (fr) 2014-12-02 2019-07-17 Novartis AG Fabrication de compositions contenant des tensioactifs

Families Citing this family (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE4447116A1 (de) * 1994-12-29 1996-07-04 Sueddeutsche Kalkstickstoff Verfahren zur Fraktionierung bzw. Raffination von lipiden Naturstoffen
DE19830171C1 (de) * 1998-07-06 1999-09-16 Henkel Kgaa Verfahren zur Herstellung von Phytosqualan
DE10051427C1 (de) * 2000-10-17 2002-06-13 Adam Mueller Verfahren zur Herstellung eines Tetrahydrocannabinol- und Cannabidiol-haltigen Extraktes aus Cannabis-Pflanzenmaterial sowie Cannabis-Extrakte
WO2013065051A1 (fr) 2011-11-01 2013-05-10 Naveh Pharma (1996) Ltd. Formulation et dispositif utilisés dans le traitement de la céruminose

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
FR2576303A1 (fr) * 1985-01-21 1986-07-25 Derivan Sa Procede d'obtention de squalene et de squalane a partir de sous-produits du raffinage des huiles vegetales
GB2217729A (en) * 1987-03-25 1989-11-01 Tadeval S A Preparation of Squalane
EP0541999A1 (fr) * 1991-11-15 1993-05-19 MÜLLER-EXTRACT-COMPANY GmbH Procédé et dispositif pour la préparation de squalène à partir de résidu d'huile d'olive

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
FR2576303A1 (fr) * 1985-01-21 1986-07-25 Derivan Sa Procede d'obtention de squalene et de squalane a partir de sous-produits du raffinage des huiles vegetales
GB2217729A (en) * 1987-03-25 1989-11-01 Tadeval S A Preparation of Squalane
EP0541999A1 (fr) * 1991-11-15 1993-05-19 MÜLLER-EXTRACT-COMPANY GmbH Procédé et dispositif pour la préparation de squalène à partir de résidu d'huile d'olive

Non-Patent Citations (2)

* Cited by examiner, † Cited by third party
Title
CHEMICAL ABSTRACTS, vol. 109, no. 26, 26 December 1988, Columbus, Ohio, US; abstract no. 236988y, page 389; *
E. STAHL ET AL: "Extraction mit überkritischen Gasen in direkter Kopplung mit der Dünnschicht-Chromatographie", CHEMIE. INGENIEUR. TECHNIK, vol. 48, no. 9, September 1976 (1976-09-01), WEINHEIM DE, pages 773 - 778 *

Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2010023551A2 (fr) 2008-08-28 2010-03-04 Michael Broeker Production de squalène à partir de levures hyperproductrices
EP2369003A1 (fr) 2008-08-28 2011-09-28 Novartis AG Production de squalène à partir de levures hyperproductrices
WO2013156720A2 (fr) 2012-04-16 2013-10-24 Roquette Freres Procédé de raffinage du squalène produit par microalgues
WO2016044374A1 (fr) * 2014-09-18 2016-03-24 Glaxosmithkline Consumer Healthcare Holdings (Us) Llc Nouvelles formulations
EP3511020A1 (fr) 2014-12-02 2019-07-17 Novartis AG Fabrication de compositions contenant des tensioactifs
CN108676610A (zh) * 2018-05-16 2018-10-19 浙江海润达科技有限公司 一种从鱿鱼副产物中获取活性物质的方法

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Publication number Publication date
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