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EP1171555A2 - Method for eliminating free fatty acids from fats and oils of biological origin or their vapor condensates - Google Patents

Method for eliminating free fatty acids from fats and oils of biological origin or their vapor condensates

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Publication number
EP1171555A2
EP1171555A2 EP00922646A EP00922646A EP1171555A2 EP 1171555 A2 EP1171555 A2 EP 1171555A2 EP 00922646 A EP00922646 A EP 00922646A EP 00922646 A EP00922646 A EP 00922646A EP 1171555 A2 EP1171555 A2 EP 1171555A2
Authority
EP
European Patent Office
Prior art keywords
fatty acids
weight
free fatty
water
organic nitrogen
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.)
Granted
Application number
EP00922646A
Other languages
German (de)
French (fr)
Other versions
EP1171555B1 (en
Inventor
Siegfried Peter
Eckhard Weidner
Martin Drescher
Wolfgang König
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.)
Peter Siegfried Prof Dr
Original Assignee
Peter Siegfried Prof Dr
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Filing date
Publication date
Application filed by Peter Siegfried Prof Dr filed Critical Peter Siegfried Prof Dr
Priority to DK00922646T priority Critical patent/DK1171555T3/en
Publication of EP1171555A2 publication Critical patent/EP1171555A2/en
Application granted granted Critical
Publication of EP1171555B1 publication Critical patent/EP1171555B1/en
Anticipated expiration legal-status Critical
Expired - Lifetime legal-status Critical Current

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11B—PRODUCING, e.g. BY PRESSING RAW MATERIALS OR BY EXTRACTION FROM WASTE MATERIALS, REFINING OR PRESERVING FATS, FATTY SUBSTANCES, e.g. LANOLIN, FATTY OILS OR WAXES; ESSENTIAL OILS; PERFUMES
    • C11B3/00—Refining fats or fatty oils
    • C11B3/02—Refining fats or fatty oils by chemical reaction
    • C11B3/06—Refining fats or fatty oils by chemical reaction with bases

Definitions

  • the present invention relates to a method for removing free fatty acids from fats and oils of biological origin or their damper condensates by extraction.
  • Oils and fats of biological origin play an important role in human nutrition and as raw materials for the chemical industry. For example, they serve as raw materials for the production of surfactants, plasticizers, waxes, lubricants, fatty alcohols, etc.
  • the essential components of fats and oils are the triesters of glycerides and fatty acids, the so-called triglycerides.
  • Fats and oils are determined a) by the chain length of the fatty acids, b) by the degree of saturation of the fatty acids and c) by the distribution of the various fatty acids over the three hydroxyl groups of the glycerol. Fats with a high proportion of saturated fatty acids are generally solid at ambient temperature. Fats or oils from predominantly unsaturated fatty acids are liquid at ambient temperature.
  • the fats and oils of biological origin contain a number of by-products that affect shelf life, smell, taste and appearance.
  • the most important by-products are: suspended matter, organic phosphorus compounds, free fatty acids, coloring and odorants.
  • Mucilage and other complex colloidal compounds can promote the hydrolytic breakdown of the fats and oils during their storage and are disruptive in the further refining. That is why they are removed by the process of so-called degumming.
  • the degumming is based on hydration with water or direct steam.
  • the organic phosphorus compounds (phosphatides) absorb water, swell and become insoluble. After phosphorus compounds and suspended matter have been removed by degumming and, if appropriate, filtration, the further task is to separate free fatty acids and colorants and odorants.
  • the fatty acid content of the refined fats and oils should generally be less than 0.1% by weight. While longer-chain free fatty acids usually do not affect the taste, the short-chain fatty acids have a soapy, rancid taste.
  • the deacidification to remove the free fatty acids is mainly carried out by treatment with aqueous alkali solutions or by steaming at temperatures of about 220 ° C. The removal of the free fatty acids by esterification with glycerol or with a monohydric alcohol, by selective solvent extraction or by adsorbents is of less importance. The previously known deacidification processes are explained in more detail below.
  • alkaline solutions Treatment with alkaline solutions as the most widely used method can be carried out batchwise or continuously.
  • Weakly alkaline solutions are generally sprayed onto the oil at 90 ° C and percolate downward through the heated oil. Stronger alkalis (4n to 7n), on the other hand, are usually stirred into the oil at 40 to 80 ° C.
  • the oil or fat After deacidification and removal of the soap stick, the oil or fat is washed with heavily diluted lye (approx. 0.5 n) and then with water to remove soap residues down to at least 0.05% by weight.
  • So-called steam deacidification has been developed as an alternative.
  • this process also known as physical refining or distillative deacidification
  • the free fatty acids are also continuously removed from the crude oils with hot steam under vacuum. It is not so important that the fatty acids are distilled off completely, because fatty acids remaining in small amounts can expediently be removed by post-refining with lye.
  • the crude fat Before deacidification by distillation, however, the crude fat must be freed as completely as possible of mucilage, phosphatides and traces of metal - usually by treatment with phosphoric acid - since the accompanying substances can lead to dark, unpleasant tasting substances during distillation, which can then hardly be removed.
  • Steam deacidification takes place at relatively high temperatures, for example palm oil is deacidified with direct steam at 220 ° C. The high temperature destroys a whole range of oil (or
  • Fat contained and desirable substances per se, for example antioxidants that increase the shelf life of the oil, or drives these substances into the so-called steam condensate, which is obtained after the condensation of the hot steam used for deacidification.
  • the neutralization of oils and fats by separating the free fatty acids from the crude fat by means of selectively acting solvents is another method that is particularly suitable for highly acidic oils and fats.
  • liquid extraction with ethanol enables the deacidification of olive oil with 22% by weight of free fatty acids down to about 3% by weight of free fatty acids.
  • Another extractant that only dissolves free fatty acids and very highly unsaturated triglycerides at suitable temperatures is furfural.
  • the Selexol process liquid propane is used as an extractant in countercurrent. The liquid Propane selectively dissolves saturated neutral oil, while fatty acids, oxidation products, unsaponifiable matter and the highly unsaturated glycerides are hardly dissolved and remain. This process is mainly used for the fractionation of fish oils and fish liver oils.
  • a decolorization step is generally switched on. It is usually decolorized with solid adsorbents, e.g. Bleaching earth and activated carbon. Air or chemical bleaching plays a minor role in edible fats.
  • odors and flavors are removed from the deacidified and bleached oils and fats.
  • Deodorization is essentially a steam distillation, in which the volatile compounds are separated from the non-volatile glycerides.
  • the aromas and flavors are predominantly aldehydes and ketones, which have formed through autoxidative or hydrolytic reactions during the processing and storage of fats and oils.
  • the low partial pressure of the connections to be removed requires that the damping be carried out in a vacuum. Steaming is usually carried out at 180 to 220 ° C and a pressure of 6 to 22 mbar. For reasons of environmental protection, the waste water from the alkaline deacidification must be carefully processed, which is associated with costs.
  • alkanolamine preferably ethanolamine
  • alkaline extraction agent which dissolves the free fatty acids as soaps in the aqueous phase. Residues of alkanolamines dissolved in the raffinate are washed out by washing with dilute sulfuric acid, acetic acid, lactic acid, citric acid or hydrochloric acid solutions.
  • the invention is therefore based on the object of specifying an improved process for the deacidification of oils and fats of biological origin which, on the one hand, can also handle high levels of free fatty acids without technical problems, and on the other hand enables the production of very high-quality fats and oils, such as those be desired by the food industry, for example.
  • the process according to the invention is based on the fact that, surprisingly, when deacidifying oils (or fats) with a high proportion of free fatty acids by means of aqueous solutions of organic bases, for example 2-dimethylaminoethanol, no viscous soapstock forms if the amine content in the aqueous Solution is at least about 20 wt .-% and at most about 60 wt .-% and preferably between about 30 wt .-% and about 40 wt .-%. Instead, both the oil phase and the extract phase are low viscosity liquids under such conditions. The phase separation runs quickly within a few minutes; the resulting phases are clear.
  • the concentration of the organic base, for example 2-dimethylaminoethanol, in the aqueous solution must be at least about 20% by weight, better still about 30 to 40% by weight, so that no viscous soap stick or cloudy
  • the aqueous solution used for deacidification must have a content of about 20% by weight to about 60% by weight of organic nitrogen compound.
  • Residues of the basic nitrogen compounds dissolved in the raffinate are preferably washed out with water or with dilute acetic acid, lactic acid, citric acid, sulfuric acid or hydrochloric acid solutions.
  • traces of the basic extractant in the raffinate are removed by stripping with carbon dioxide.
  • the carbon dioxide can be used as a dilute gas or as a dense, supercritical gas to remove traces of the basic nitrogen compounds used from the raffinate.
  • the extraction agent used according to the invention for example an aqueous solution of 2-dimethylaminoethanol
  • the vapor pressure of the water is approximately equal to or higher than the vapor pressure of the basic nitrogen compound (s) used.
  • the water and the basic organic compound are distilled off together, or the water is first preferably distilled off, the ratio of basic compound to water remaining constant or increasing and the formation of a viscous soap stick being avoided. If the vapor pressure of the basic compound were higher than the water vapor pressure, the ratio of the basic compound to water would decrease and finally the formation of a viscous soap stick would occur.
  • the boiling temperature of the basic nitrogen compound (s) must be on the one hand equal to or higher than the boiling temperature of the water and on the other hand lower than the boiling temperature of the fatty acids to be extracted.
  • Suitable basic, organic compounds for the process according to this invention should have the following properties: a) the compound should, if possible, not form any amides with the free fatty acids; b) the compound should be miscible with water in any ratio; c) the boiling temperature of the compound should be equal to or higher than that of water, d) the odor nuisance caused by the aqueous solutions should be as low as possible.
  • suitable organic nitrogen compounds are: N-methylmorpholine, 2-dimethylaminoethanol, 3- (diethylamino) -1-propanol, 2-diethylaminoethanol, 1- (dimethylamino) -2-propanol, dimethylformamide,
  • tertiary amines are preferred because of their higher basicity of binary and monosubstituted amines.
  • starting materials that can be deacidified well using the process according to the invention are beef tallow, lard, fish oil, corn oil, slaughter fat, palm oil, soybean oil, rapeseed oil, sunflower oil, rice germ oil, cottonseed oil, olive oil, peanut oil, safflower oil, coconut oil, pal kernel oil, grape germ oil, Wheat germ oil, etc.
  • the oils and fats to be deacidified should be degummed and filtered, especially if more than 100 pp of phosphatides are present.
  • the fat or oil prepared in this way still contains dissolved oxygen, which should also be removed before further processing.
  • the process according to the invention then deacidifies the starting material while protecting temperature-sensitive compounds such as carotenes, tocotrienols, tocopherols, etc. These compounds, which are also important in terms of nutritional physiology, become one in conventional physical refining, which is carried out by means of direct steam, due to the high temperatures Most of them destroyed or driven out.
  • the method according to the invention is also outstandingly suitable for removing the free fatty acids from the damper condensates of fats and oils, which can be obtained by means of the conventional physical refining just mentioned, i.e. by means of steam deacidification.
  • damper condensates generally contain free fatty acids in very high concentrations, mostly in the range from about 80 to 94% by weight. Due to the high content of free fatty acids, the extracting agent used according to the invention, ie the mixture of organic base and water, must be richer in the basic nitrogen compound than previously described in connection with the deacidification of fats and oils. The proportion of organic nitrogen compound in the extractant should be at least about 40% by weight. If such an aqueous solution rich in basic nitrogen compound, for example 60% by weight of 2-dimethylaminoethanol and 40% by weight of water, is used as the extractant for the liquid damper condensate added, you get a liquid, homogeneous mixture.
  • One to four parts, preferably two to four parts, of an alkane and / or an ester, in particular an ethyl acetate, are then added to one part of the liquid mixture to this liquid mixture.
  • the fats and oils present in the damper condensate are essentially dissolved in the alkane and / or ester phase.
  • the by-products such as tocopherols, tocotrienols and phytosterols, which are also dissolved in the steam condensate, also pass into the alkane phase with high selectivity.
  • the water-containing phase with the free fatty acids contained therein is of low viscosity, so that a phase separation took place approximately within 20 minutes after interruption of the mixing.
  • the raffinate (alkane phase or ester phase) which results after the aqueous phase has been separated off is, depending on the starting product, highly enriched in by-products, such as tocopherols, phytosterols, tocotrienols. Such valuable by-products can be obtained from such concentrates under economically attractive conditions.
  • alkanes examples include propane, butane, hexane, petroleum ether, heptane, heptane fractions, octane, etc.
  • propane propane
  • butane or propane as a solvent for the formation of two phases
  • the pressure in the mixing vessel must at least correspond to the respective vapor pressure so that the butane or propane is in liquid form.
  • esters are the ethyl acetate, for example ethyl acetate, propyl acetate, butyl acetate or a mixture thereof.
  • the concentration of free fatty acids in the starting material to be treated is more than about 50% by weight
  • the addition of alkanes is required so that the overall system (starting material and extractant) remains two-phase.
  • the addition of alkane or ester accordingly ensures the formation of two easy-to-handle liquid phases even at high concentrations of free fatty acids in the starting mixture, and extracts with high concentrations of free fatty acids can be obtained with the extractant used according to the invention by countercurrent extraction.
  • the solvent ratio can be small, which has an advantageous effect on the economy of the method according to the invention.
  • a starting product (oil, fat or steam condensate) is fed to a first extraction column 12 through a line 10.
  • the free fatty acids are extracted with high selectivity from the starting product using an extracting agent which consists of a mixture of a basic nitrogen compound and water.
  • the extractant used contains at least about 20% by weight and at most about 80% by weight of the organic nitrogen compound (organic base). Concentrations of the basic nitrogen compound of about 30 to 40% by weight have proven to be particularly favorable. However, the concentration of basic nitrogen compound can easily be selected to be even higher.
  • the oil or fat freed from the free fatty acids is fed through a line 14 to a washing column 16 (extraction column), in which residues of the basic nitrogen compound are washed out with water or with an aqueous solution which contains an acid, and leaves the washing column 16 as Raffinate R.
  • the washing solution emerging at the top of the washing column 16 through a line 18 is then worked up by distillation in a distillation column 20. In doing so
  • the extraction agent containing the free fatty acids, drawn off at the top of the extraction colon 12, is fed through a line 26 to a second distillation column 28.
  • Water and the basic nitrogen compound are obtained as the top product during distillation in the distillation column 28, while the extract containing the extracted free fatty acids and some neutral oil is withdrawn as a bottom product through a line 30 from the distillation column 28.
  • Distillation column 28 is fed as extraction medium through a line 32 to extraction column 12, in which the extraction of the free fatty acids takes place, whereby the extraction medium circuit is closed.
  • the energy required for distillation in the form of heating steam is fed through lines 34 and 36 to the distillation columns 20 and 28.
  • Example 1 250 g of an oil composed of 95.5% by weight of neutral oil, 4.2% by weight of free fatty acids and 1.7% by weight of tocopherol were mixed at 50 ° C. with 100 g of 2-dimethylaminoethanol and 70 g Water mixed by stirring. After the mixing process had been interrupted and the two liquid phases had been separated, samples were taken from both phases and analyzed.
  • the extractant-rich phase, minus the extractant contained 53.7% by weight of neutral oil, 45.0% by weight of free fatty acids and 0.3% by weight of tocopherol.
  • the oil-rich raffinate phase minus the extractant contained 98.2% by weight of neutral oil, 0.05% by weight of free fatty acids and 1.8% by weight of tocopherol.
  • Example 3 200 g of an oil with 5.1% by weight of free fatty acids and 0.3
  • tocopherol was mixed with an extractant composed of 100 g of water and 100 g of pyridine extractant at 60.degree. After the mixing process had been interrupted and the phases separated, a sample was taken from each of the two coexisting liquid phases and analyzed. The loading of the extractant was 2.1% by weight.
  • the extract, minus the extractant consisted of 20.8% by weight of free fatty acids, 0.3% by weight of tocopherols and 95.8% by weight of glycerides.
  • the raffinate minus the extractant contained 4.2% by weight of free fatty acids, 0.3% by weight of tocopherols and 95.1% by weight of glycerides.
  • the raffinate contained 0.05% by weight of free fatty acids, 1.4% by weight of tocopherol, 0.6% by weight of stigmasterol and 97.95% by weight of neutral oil. 0.46% by weight of the amount of neutral oil used remained in the extract.
  • the raffinate minus the extractant consisted of 0.3% by weight of free fatty acids, 0.4% by weight of tocopherols, 0.1% by weight of stigmasterol, and 99.4% by weight of neutral oil. 6% by weight of the amount of neutral oil used was in the extract. The solvent ratio had the low value of 0.14.
  • Example 6 100 g of palm oil containing 5.5% by weight of free fatty acids were mixed at 60 ° C. with 100 g of a mixture of 30 g of N, N- Dimethylamino-ethanol and 70 g water mixed together by stirring. After the mixing process had been interrupted, the phase separation, which had taken place after about 3 minutes, was waited for and samples were taken from both coexisting phases and analyzed.
  • the palm oil (raffinate) minus the extractant contained less than 0.1% by weight of free fatty acids.
  • the extract contained less extractant 77% by weight of fatty acids and 23% by weight of glycerides (mono-, di- and triglycerides; the latter the main component). About 1.2 g glycerides (approx. 1.2% of the weight) were extracted together with the free fatty acids.
  • the extract contained less extractant 67% by weight of fatty acids and 33% by weight of glycerides (mono-, di- and triglycerides).
  • the raffinate less extractant contained less than 0.1% free fatty acids.
  • the extract contained 2 g of glycerides (approx. 2% of the weight). 1.9% by weight of N, N-dimethylaminoethanol were dissolved in the raffinate and washed out with water.
  • 0.19% secondary components (tocopherols + tocotrienols + phytosterols) are dissolved in 400 g heptane fraction at 40 ° C.
  • the solution is extracted with 600 g of a solution of 40% N, N-dimethylaminoethanol in water at 40 ° C.
  • the extract (the one dissolved in the extractant) contains less extractant 96% fatty acids.
  • the raffinate minus the extractant consists of 13.4 g glycerides, 0.7 g free fatty acids, and 0.3 g secondary components (2% tocopherols + tocotrienols + phytosterols).
  • DMAE dimethylaminoethanol
  • the raffinate stream leaving the extraction column 12 comprised 24.424 kg / h neutral oil, 0.090 kg / h free fatty acids, 0.855 kg / h DMAE and 0.855 kg / h water.
  • the extract stream consisted of 14.145 kg / h DMAE, 14.145 kg / h water, 0.285 kg / h neutral oil and 1.20 kg / h free fatty acids.
  • the raffinate stream was fed to the washing column 16, in which it was countercurrented at 80 ° C. with 15.0 kg / h of water
  • DMAE was washed out.
  • the raffinate stream thus purified left the washing column 16 in the following composition: 28.424 kg / h neutral oil, 0.012 kg / h DMAE and less than 0.025 kg / h free fatty acids. This corresponds to a neutral oil with 0.00042% by weight DMAE and less than 0.00088% by weight free fatty acids.
  • the wash water left the wash column 16 with the following composition: 15.855 kg / h of water, 0.855 kg / h of DMAE and 0.064 kg / h free fatty acids.
  • the wash water was regenerated in the distillation column 20 at 100 ° C. As the top product, 15.0 kg / h of water were returned through line 24 to the washing column 16.
  • the bottom product with 0.855 kg / h of water and 0.855 kg / h of DMAE is combined with the extract stream from the extraction column 12 flowing through the line 26.
  • the extract stream from the extraction column 12 combined with the bottom product from the distillation column 20 was fed to the distillation column 28.
  • the top product of the distillation column 28 from 15.0 kg / h of water and 15.0 kg / h of DMAE was recycled as the extractant through line 32 into the extraction column 12.
  • the distillation column left 28 0.285 kg / h neutral oil and 1.264 kg / h free fatty acids. Accordingly, the extract consisted of 18.4% by weight of neutral oil and 81.6% by weight of free fatty acids.
  • the extraction agent cycle is thus closed and there are no waste disposal problems.

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Abstract

In order to eliminate fatty acids from fats and oils of biological origin or their vapor condensates, the free fatty acids are extracted with a mixture of basic organic nitrogen compounds and water as extracting agents at a temperature below boiling temperature of the organic nitrogen compounds. The proportion of basic organic nitrogen compounds in the extracting agent should amount at least to approximately 20 percent by weight and at most approximately 60 percent by weight, preferably between approximately 30 and approximately 40 percent by weight. This prevents the formation of a viscose soapstock that is difficult to eliminate. The boiling temperature of the basic organic nitrogen compound(s) used should be the same or higher than the boiling temperature of the water and lower than the boiling temperature of the fatty acids to be extracted in order to facilitate easy recovery of the extracting agent.

Description

Verfahren zur Entfernung freier Fettsäuren aus Fetten und Ölen biologischen Ursprungs oder deren Dämpferkondensaten Process for removing free fatty acids from fats and oils of biological origin or their damper condensates
Die vorliegende Erfindung betrifft ein Verfahren zur Entfernung freier Fettsäuren aus Fetten und Ölen biologischen Ursprungs oder deren Dämpferkondensaten durch Extraktion.The present invention relates to a method for removing free fatty acids from fats and oils of biological origin or their damper condensates by extraction.
In der menschlichen Ernährung und als Rohstoffe für die chemi- sehe Industrie spielen Öle und Fette biologischen Ursprungs eine wichtige Rolle. Sie dienen zum Beispiel als Rohstoffe für die Erzeugung von Tensiden, Weichmachern, Wachsen, Schmierstoffen, Fettalkoholen usw. Wesentliche Komponenten der Fette und Öle sind die Triester von Glyceriden und Fettsäuren, die soge- nannten Triglyceride. Die physikalischen Eigenschaften derOils and fats of biological origin play an important role in human nutrition and as raw materials for the chemical industry. For example, they serve as raw materials for the production of surfactants, plasticizers, waxes, lubricants, fatty alcohols, etc. The essential components of fats and oils are the triesters of glycerides and fatty acids, the so-called triglycerides. The physical properties of the
Fette und Öle werden a) durch die Kettenlänge der Fettsäuren, b) durch den Sättigungsgrad der Fettsäuren und c) durch die Verteilung der verschiedenen Fettsäuren auf die drei Hydroxylgruppen des Glycerins bestimmt. Fette mit einem hohen Anteil an gesättigten Fettsäuren sind im allgemeinen bei Umgebungstemperatur fest. Fette bzw. Öle aus vorwiegend ungesättigten Fettsäuren sind bei Umgebungstemperatur flüssig.Fats and oils are determined a) by the chain length of the fatty acids, b) by the degree of saturation of the fatty acids and c) by the distribution of the various fatty acids over the three hydroxyl groups of the glycerol. Fats with a high proportion of saturated fatty acids are generally solid at ambient temperature. Fats or oils from predominantly unsaturated fatty acids are liquid at ambient temperature.
Die Fette und Öle biologischen Ursprungs enthalten eine Reihe von Beiprodukten, die Haltbarkeit, Geruch, Geschmack und Aussehen beeinträchtigen. Die wichtigsten Beiprodukte sind: Schwebstoffe, organische Phosphorverbindungen, freie Fettsäuren, Färb- und Geruchsstoffe. Schleimstoffe und andere komplexe kolloide' Verbindungen können den hydrolytischen Abbau der Fette und Öle bei deren Lagerung fördern und sind bei der weiteren Raffination störend. Deshalb werden sie durch den Prozeß der sogenannten Entschleimung entfernt. Die Entschleimung beruht auf einer Hydratation mit Wasser oder direktem Dampf. Die organischen Phosphorverbindungen (Phosphatide) nehmen dabei Wasser auf, quellen und werden unlöslich. Nachdem durch Entschleimung und gegebenenfalls Filtration Phosphorverbindungen und Schwebstoffe entfernt sind, besteht die weitere Aufgabe darin, freie Fettsäuren sowie Färb- und Geruchsstoffe abzutrennen. Handelsübliche Rohfette und Rohöle enthalten im Durchschnitt 1 bis 3 Gew.-% freie Fettsäuren, gute Sorten 0,5 Gew.-% und weniger, manche Palm-, Oliven- und Fischöle 20 Gew.-% und mehr. Der Fettsäuregehalt der raffinierten Fette und Öle soll demgegenüber in der Regel unter 0,1 Gew.-% liegen. Während längerkettige freie Fettsäuren meist keine geschmackliche Beeinträchtigung verursachen, besitzen die kurzkettigen Fettsäuren einen seifigen, ranzigen Geschmack. In der Praxis wird die zur Enfernung der freien Fettsäuren erfolgende Entsäuerung überwiegend durch Behandlung mit wäßrigen Alkalilösungen oder durch Dämpfung bei Temperaturen von ca. 220 °C ausgeführt. Die Entfernung der freien Fettsäuren durch Veresterung mit Glycerin oder mit einem einwertigen Alkohol, durch selektive Lösungsmittelextraktion oder durch Adsorbentien hat hingegen eine geringere Bedeutung. Im folgenden werden die bisher bekannten Entsäuerungsverfahren näher erläutert.The fats and oils of biological origin contain a number of by-products that affect shelf life, smell, taste and appearance. The most important by-products are: suspended matter, organic phosphorus compounds, free fatty acids, coloring and odorants. Mucilage and other complex colloidal compounds can promote the hydrolytic breakdown of the fats and oils during their storage and are disruptive in the further refining. That is why they are removed by the process of so-called degumming. The degumming is based on hydration with water or direct steam. The organic phosphorus compounds (phosphatides) absorb water, swell and become insoluble. After phosphorus compounds and suspended matter have been removed by degumming and, if appropriate, filtration, the further task is to separate free fatty acids and colorants and odorants. Commercial crude fats and crude oils contain on average 1 to 3% by weight of free fatty acids, good types 0.5% by weight and less, some palm, olive and fish oils 20% by weight and more. In contrast, the fatty acid content of the refined fats and oils should generally be less than 0.1% by weight. While longer-chain free fatty acids usually do not affect the taste, the short-chain fatty acids have a soapy, rancid taste. In practice, the deacidification to remove the free fatty acids is mainly carried out by treatment with aqueous alkali solutions or by steaming at temperatures of about 220 ° C. The removal of the free fatty acids by esterification with glycerol or with a monohydric alcohol, by selective solvent extraction or by adsorbents is of less importance. The previously known deacidification processes are explained in more detail below.
Die Behandlung mit alkalischen Lösungen als die am meisten angewandte Methode kann chargenweise oder kontinuierlich durchgeführt werden. Je höher die Laugenkonzentration, desto leichter werden unerwünschte Begleitstoffe in die entstehende Seife, den sog. Soapstock, aufgenommen. Schwach alkalische Lösungen werden im allgemeinen bei 90°C auf das Öl aufgesprüht und perkolieren durch das erwärmte Öl nach unten. Stärkere Laugen (4n bis 7n) hingegen werden normalerweise bei 40 bis 80 °C in das Öl hinein gerührt. Nach der Entsäuerung und dem Abziehen des Soapstocks wird das Öl oder Fett mit stark verdünnter Lauge (ca. 0.5 n) und danach mit Wasser nachgewaschen, um Seifenreste bis auf mindestens 0,05 Gew.-% zu entfernen. Unter Verwendung von Zentrifugen läßt sich eine vollkontinuierliche Anlage zur Neutralisierung der Fette und Öle nach dieser Methode aufbauen. Wenn die zu entsäuernden Fette und Öle einen hohen Gehalt an freien Fettsäuren aufweisen, führt die Entsäuerung mittels alkalischer Lösungen zu einem relativ harten Soapstock, der sich aus der Anlage nur schwer entfernen läßt.Treatment with alkaline solutions as the most widely used method can be carried out batchwise or continuously. The higher the alkali concentration, the easier it is to absorb unwanted accompanying substances in the soap that is formed, the so-called soap stick. Weakly alkaline solutions are generally sprayed onto the oil at 90 ° C and percolate downward through the heated oil. Stronger alkalis (4n to 7n), on the other hand, are usually stirred into the oil at 40 to 80 ° C. After deacidification and removal of the soap stick, the oil or fat is washed with heavily diluted lye (approx. 0.5 n) and then with water to remove soap residues down to at least 0.05% by weight. Using centrifuges, a fully continuous system for neutralizing fats and oils can be built using this method. If the fats and oils to be deacidified have a high content of free fatty acids, deacidification leads to alkaline solutions to a relatively hard soap stick that is difficult to remove from the system.
Als Alternative ist deshalb die sogenannte Dampfentsäuerung entwickelt worden. Bei diesem auch als physikalische Raffination oder destillative Entsäuerung bezeichneten Verfahren werden die freien Fettsäuren mit heißem Wasserdampf unter Vakuum ebenfalls kontinuierlich aus den Rohölen entfernt. Dabei kommt es nicht so darauf an, daß die Fettsäuren restlos abdestilliert werden, denn in geringer Menge verbleibende Fettsäuren können zweckmäßigerweise durch eine Laugen-Nachraffination entfernt werden. Vor der destillativen Entsäuerung muß das Rohfett jedoch möglichst vollständig von Schleimstoffen, Phosphatiden und Metallspuren befreit werden - üblicherweise durch die Behandlung mit Phosphorsäure - da die Begleitstoffe während der Destillation zu dunklen, unangenehm schmeckenden Stoffen führen können, die dann kaum mehr zu entfernen sind. Die Dampfentsäue- rung findet bei relativ hohen Temperaturen statt, Palmöl beispielsweise wird mit 220°C heißem, direktem Dampf entsäuert. Die hohe Temperatur zerstört eine ganze Reihe von im Öl (oderSo-called steam deacidification has been developed as an alternative. In this process, also known as physical refining or distillative deacidification, the free fatty acids are also continuously removed from the crude oils with hot steam under vacuum. It is not so important that the fatty acids are distilled off completely, because fatty acids remaining in small amounts can expediently be removed by post-refining with lye. Before deacidification by distillation, however, the crude fat must be freed as completely as possible of mucilage, phosphatides and traces of metal - usually by treatment with phosphoric acid - since the accompanying substances can lead to dark, unpleasant tasting substances during distillation, which can then hardly be removed. Steam deacidification takes place at relatively high temperatures, for example palm oil is deacidified with direct steam at 220 ° C. The high temperature destroys a whole range of oil (or
Fett) enthaltener und an sich erwünschter Stoffe, beispielsweise die Lagerfähigkeit des Öls erhöhende Antioxidantien, oder treibt diese Stoffe in das sogenannte Dämpferkondensat, das nach der Kondensation des zur Entsäuerung verwendeten, heißen Dampfes anfällt.Fat) contained and desirable substances per se, for example antioxidants that increase the shelf life of the oil, or drives these substances into the so-called steam condensate, which is obtained after the condensation of the hot steam used for deacidification.
Die Neutralisation von Ölen und Fetten durch Abtrennung der freien Fettsäuren aus dem Rohfett mittels selektiv wirkender Lösungsmittel ist eine weitere Methode, die vor allem für hochsaure Öle und Fette in Frage kommt. Beispielsweise ermöglicht die Flüssigextraktion mit Ethanol die Entsäuerung von Olivenöl mit 22 Gew.-% freien Fettsäuren bis auf etwa 3 Gew.-% freie Fettsäuren. Ein anderes Extraktionsmittel, welches bei geeigneten Temperaturen nur freie Fettsäuren und sehr stark ungesättigte Triglyceride löst, ist Furfurol. Bei einem noch anderen Verfahren, dem Selexol-Verfahren, wird flüssiges Propan als Extraktionsmittel im Gegenstrom eingesetzt. Das flüssige Propan löst selektiv gesättigtes Neutralöl, während Fettsäuren, Oxidationsprodukte, Unverseifbares und die stark ungesättigten Glyceride kaum gelöst werden und zurückbleiben. Dieses Verfahren wird hauptsächlich zur Fraktionierung von Fischölen und Fischleberölen angewandt.The neutralization of oils and fats by separating the free fatty acids from the crude fat by means of selectively acting solvents is another method that is particularly suitable for highly acidic oils and fats. For example, liquid extraction with ethanol enables the deacidification of olive oil with 22% by weight of free fatty acids down to about 3% by weight of free fatty acids. Another extractant that only dissolves free fatty acids and very highly unsaturated triglycerides at suitable temperatures is furfural. In yet another process, the Selexol process, liquid propane is used as an extractant in countercurrent. The liquid Propane selectively dissolves saturated neutral oil, while fatty acids, oxidation products, unsaponifiable matter and the highly unsaturated glycerides are hardly dissolved and remain. This process is mainly used for the fractionation of fish oils and fish liver oils.
Der Prozeß der selektiven Extraktion wird großtechnisch fast ausschließlich für Fette mit sehr hohem Anteil an freien Fettsäuren eingesetzt. Beispiele sind: Kakaofett aus Schalen, Olivenöl aus dem Preßkuchen, schlechte Qualitäten von Reis- und Baumwollsaatöl. Als Alkohol wird dabei Isopropylalkohol eingesetzt. Für die Entsäuerung einer Tonne Öl gibt Bernardini (E. Bernardini, Oilseeds, Oils and fats, Publishing House Rom, 1985) folgende Verbrauchsmengen an: Energie und Hilfsstoffe, Dampf 800 kg, elektrische Energie 14 kWh, Hexan 15 kg, Isopro- panol 18 kg. Solchermaßen gewonnenes Öl wird nicht als Speiseöl verwandt.The process of selective extraction is used almost exclusively on an industrial scale for fats with a very high proportion of free fatty acids. Examples are: cocoa fat from shells, olive oil from the press cake, poor qualities of rice and cottonseed oil. Isopropyl alcohol is used as the alcohol. For the deacidification of one ton of oil, Bernardini (E. Bernardini, Oilseeds, Oils and fats, Publishing House Rome, 1985) gives the following consumption quantities: energy and auxiliary materials, steam 800 kg, electrical energy 14 kWh, hexane 15 kg, isopropanol 18 kg. Oil obtained in this way is not used as cooking oil.
Obwohl die Entschleimung und Alkaliraffination bereits zu einer gewissen Aufhellung führt, wird im allgemeinen noch eine Entfärbungsstufe eingeschaltet. Man entfärbt üblicherweise mit festen Adsorptionsmitteln, wie z.B. Bleicherde und Aktivkohle. Das Bleichen mit Luft oder Chemikalien spielt für Speisefette eine untergeordnete Rolle.Although degumming and alkali refining already lead to a certain lightening, a decolorization step is generally switched on. It is usually decolorized with solid adsorbents, e.g. Bleaching earth and activated carbon. Air or chemical bleaching plays a minor role in edible fats.
In der letzten Phase des Raffinationsprozesses werden Geruchsund Geschmackstoffe aus den entsäuerten und gebleichten Ölen und Fetten entfernt. Die Desodorisierung ist im wesentlichen eine Wasserdampfdestillation, bei der die flüchtigen Verbindun- gen von den nichtflüchtigen Glyceriden abgetrennt werden. Die Geruchs- und Geschmacksstoffe sind überwiegend Aldehyde und Ketone, die sich durch autoxidative oder hydrolytische Reaktionen während der Verarbeitung und Lagerung der Fette und Öle gebildet haben. Der niedrige Partialdruck der zu entfernenden Verbindungen erfordert, daß die Dämpfung im Vakuum durchgeführt wird. Gedämpft wird meistens bei 180 bis 220°C und einem Druck von 6 bis 22 mbar. Aus Gründen des Umweltschutzes müssen die Abwässer aus der alkalischen Entsäuerung sorgfältig aufgearbeitet werden, was mit Kosten verbunden ist. Deshalb ist in jüngster Zeit das Interesse an physikalischen Verfahren zur Raffination von Ölen und Fetten wieder erwacht. Bereits in den zwanziger Jahren des zwanzigsten Jahrhunderts wurden die Möglichkeiten der Entsäuerung mit Hilfe der Flüssig-Flüssig-Extraktion mit wasserhaltigen niederen Alkoholen untersucht (Bailey, 5. Auflage 1996, Band 5) . Als bestes Extraktionsmittel wurde wäßriger Ethylalko- hol gefunden. In seiner Selektivität in bezug auf freie Fettsäuren und Triglyceride ist reines Methanol zwar günstiger, jedoch wurde es - vermutlich wegen seiner Giftigkeit - auf seine Eignung als Extraktionsmittel für die Entsäuerung von Fetten und Ölen nicht näher untersucht.In the last phase of the refining process, odors and flavors are removed from the deacidified and bleached oils and fats. Deodorization is essentially a steam distillation, in which the volatile compounds are separated from the non-volatile glycerides. The aromas and flavors are predominantly aldehydes and ketones, which have formed through autoxidative or hydrolytic reactions during the processing and storage of fats and oils. The low partial pressure of the connections to be removed requires that the damping be carried out in a vacuum. Steaming is usually carried out at 180 to 220 ° C and a pressure of 6 to 22 mbar. For reasons of environmental protection, the waste water from the alkaline deacidification must be carefully processed, which is associated with costs. For this reason, interest in physical processes for refining oils and fats has recently reawakened. Already in the twenties of the twentieth century, the possibilities of deacidification using liquid-liquid extraction with water-containing lower alcohols were investigated (Bailey, 5th edition 1996, volume 5). Aqueous ethyl alcohol was found as the best extractant. Pure methanol is cheaper in its selectivity with regard to free fatty acids and triglycerides, but its suitability as an extracting agent for the deacidification of fats and oils has not been examined in detail - presumably because of its toxicity.
Die Entsäuerung von Ölen und Fetten mit Hilfe von Aminen wurde bereits 1937 im US-Patent 2,164,012 vorgeschlagen. Es wird ein Alkanolamin, vorzugsweise Ethanolamin, als alkalisches Extraktionsmittel vorgeschlagen, welches die freien Fettsäuren als Seifen in der wäßrigen Phase auflöst. Im Raffinat gelöste Reste an Alkanolaminen werden durch Waschen mit verdünnter Schwefelsäure-, Essigsäure-, Milchsäure-, Zitronensäure- oder Salzsäure-Lösungen ausgewaschen.The deacidification of oils and fats with the help of amines was proposed as early as 1937 in US Pat. No. 2,164,012. An alkanolamine, preferably ethanolamine, is proposed as an alkaline extraction agent, which dissolves the free fatty acids as soaps in the aqueous phase. Residues of alkanolamines dissolved in the raffinate are washed out by washing with dilute sulfuric acid, acetic acid, lactic acid, citric acid or hydrochloric acid solutions.
Im US Patent 2,157,882 wird ebenfalls anstelle der Extraktion der freien Fettsäuren mit Natronlauge die Extraktion mit einem Alkanolamin vorgeschlagen, um den größten Teil der freien Fettsäuren und einen Teil der Farbstoffe zu entfernen. Das so behandelte Öl ist jedoch trübe und neigt zur Zersetzung bei der Lagerung. Deswegen wird vorgeschlagen, auf die Wäsche mitIn US Pat. No. 2,157,882, extraction with an alkanolamine is also proposed instead of extraction of the free fatty acids with sodium hydroxide solution in order to remove most of the free fatty acids and some of the dyes. However, the oil treated in this way is cloudy and tends to decompose during storage. That is why it is suggested to use the laundry
Ethanolamin eine Wäsche mit einer verdünnten Natronlauge folgen zu lassen. Danach wird das entsäuerte Öl mit Wasser gewaschen, um letzte Alkalispuren zu beseitigen.Ethanolamine to follow a wash with a dilute sodium hydroxide solution. The deacidified oil is then washed with water to remove the last traces of alkali.
In einem Aufsatz, der 1955 im Journal of the American OilIn an essay published in the 1955 Journal of the American Oil
Chemist's Society (JAOCS, Vol. 32, 1955 pp. 561-564) erschien, wird über Untersuchungen zur Raffination von Reisöl mit Monoethanolamin, Triethanolamin, Tetraethanolammoniumhydrid, Ethylendiamin, Ethylamin, Triethylamin berichtet. Reisöle enthalten etwa 5 bis 7 Gew.-% freie Fettsäuren. Der hohe Fettsäuregehalt führt bei der alkalischen Raffination normalerweise zu hohen Fettverlusten. Diese Verluste können durch Zusatz der genannten Amine vor der regulären Raffination auf Werte von 3 bis 5 Gew.-% vermindert werden.Chemist's Society (JAOCS, Vol. 32, 1955 pp. 561-564) appeared, is about investigations into the refining of rice oil with Monoethanolamine, triethanolamine, tetraethanolammonium hydride, ethylenediamine, ethylamine, triethylamine are reported. Rice oils contain about 5 to 7% by weight of free fatty acids. The high fatty acid content usually leads to high fat losses in alkaline refining. These losses can be reduced to values of 3 to 5% by weight by adding the amines mentioned before the regular refining.
Wie sich aus der vorhergehenden Schilderung der unterschiedli- chen Entsäuerungsverfahren ergibt, sind diese Verfahren entweder mit anlagentechnischen Problemen behaftet und/oder sie sind aufgrund ihres Verbrauchs an Hilfsmitteln und Energie sowie einer gegebenenfalls erforderlichen, nachgeschalteten Aufarbeitung relativ kostenintensiv. Zudem werden in manchen Verfahren an sich erwünschte Bestandteile der Fette und Öle zerstört.As can be seen from the previous description of the different deacidification processes, these processes are either associated with technical system problems and / or they are relatively cost-intensive due to their consumption of auxiliaries and energy and any subsequent processing that may be required. In addition, in some processes desirable components of the fats and oils are destroyed.
Der Erfindung liegt daher die Aufgabe zugrunde, ein verbessertes Verfahren zur Entsäuerung von Ölen und Fetten biologischen Ursprungs anzugeben, das einerseits auch hohe Gehalte an freien Fettsäuren ohne anlagentechnische Probleme bewältigen kann, und das andererseits die Erzeugung qualitativ sehr hochwertiger Fette und Öle ermöglicht, wie sie beispielsweise von der Nahrungsmittelindustrie gewünscht werden.The invention is therefore based on the object of specifying an improved process for the deacidification of oils and fats of biological origin which, on the one hand, can also handle high levels of free fatty acids without technical problems, and on the other hand enables the production of very high-quality fats and oils, such as those be desired by the food industry, for example.
Diese Aufgabe ist erfindungsgemäß mit dem im Patentanspruch 1 angegebenen Verfahren gelöst. Das er indungsgemäße Verfahren beruht darauf, daß sich überraschenderweise beim Entsäuern von Ölen (oder Fetten) mit einem hohen Anteil an freien Fettsäuren mittels wäßriger Lösungen organischer Basen, beispielsweise 2-Dimethylamino-ethanol, dann kein viskoser Soapstock bildet, wenn der Amingehalt in der wäßrigen Lösung mindestens etwa 20 Gew.-% und höchstens etwa 60 Gew.-% und vorzugweise zwischen etwa 30 Gew.-% und etwa 40 Gew.-% beträgt. Statt dessen sind unter solchen Bedingungen sowohl die Ölphase als auch die Extraktphase Flüssigkeiten mit niedriger Viskosität. Die Phasentrennung verläuft dabei zügig innerhalb weniger Minuten; die entstehenden Phasen sind klar. Dagegen bildete sich bei Amingehalten der wäßrigen Lösungen, die den Konzentrationen der Natronlaugen bei der chemischen Entsäuerung entsprechen, ein hochviskoser Soapstock aus. Die nähere Prüfung ergab, daß die basische Stickstoffverbindung mindestens etwa 40 Gew.-% Wasser enthalten muß, damit imThis object is achieved with the method specified in claim 1. The process according to the invention is based on the fact that, surprisingly, when deacidifying oils (or fats) with a high proportion of free fatty acids by means of aqueous solutions of organic bases, for example 2-dimethylaminoethanol, no viscous soapstock forms if the amine content in the aqueous Solution is at least about 20 wt .-% and at most about 60 wt .-% and preferably between about 30 wt .-% and about 40 wt .-%. Instead, both the oil phase and the extract phase are low viscosity liquids under such conditions. The phase separation runs quickly within a few minutes; the resulting phases are clear. On the other hand, a highly viscous soap stick was formed with the amine contents of the aqueous solutions, which correspond to the concentrations of the sodium hydroxide solutions during chemical deacidification. A closer examination showed that the basic nitrogen compound must contain at least about 40% by weight of water so that the
Gleichgewicht mit dem zu entsäuernden Öl zwei Phasen gebildet werden. Umgekehrt muß die Konzentration der organischen Base, beispielsweise des 2-Dimethylamino-ethanols, in der wäßrigen Lösung wenigstens etwa 20 Gew.-%, besser noch etwa 30 bis 40 Gew.-% betragen, damit kein viskoser Soapstock oder trübeEquilibrium with the oil to be deacidified two phases are formed. Conversely, the concentration of the organic base, for example 2-dimethylaminoethanol, in the aqueous solution must be at least about 20% by weight, better still about 30 to 40% by weight, so that no viscous soap stick or cloudy
Phasen entstehen. Das bedeutet, daß die zum Entsäuern verwendete wäßrige Lösung erfindungsgemäß einen Gehalt von etwa 20 Gew.-% bis etwa 60 Gew.-% an organischer Stickstoffverbindung aufweisen muß.Phases arise. This means that, according to the invention, the aqueous solution used for deacidification must have a content of about 20% by weight to about 60% by weight of organic nitrogen compound.
Wird beispielsweise Palmöl mit einem Gehalt von 4,5 Gew.-% freien Fettsäuren bei 50°c mit einer Lösung von 55 Gew.-% 2-Dimethylamino-ethanol in Wasser im Verhältnis 1:1 vermischt, so wird nach Trennung der Phasen ein Öl erhalten, welches abzüglich Extraktionsmittel nur noch 0,03 Gew.-% freie Fettsäuren bei einem Ölverlust von lediglich 0,8 Gew.-% enthält. Mit dem erfindungsgemäßen Extraktionsverfahren ist somit eine temperaturschonende und effiziente Entsäuerung bei geringen Ölverlusten in wenigen Stufen im Gegenstrom möglich.If, for example, palm oil with a content of 4.5% by weight of free fatty acids is mixed at 50 ° C with a solution of 55% by weight of 2-dimethylaminoethanol in water in a ratio of 1: 1, the phases are separated after Obtain oil which, minus the extractant, contains only 0.03% by weight of free fatty acids with an oil loss of only 0.8% by weight. With the extraction method according to the invention, temperature-friendly and efficient deacidification with low oil losses is possible in a few steps in countercurrent.
Im Raffinat gelöste Reste der basischen Stickstoffverbindungen werden vorzugsweise mit Wasser oder mit verdünnter Essigsäure-, Milchsäure, Zitronensäure-, Schwefelsäure- oder Salzsäure- Lösungen ausgewaschen. Alternativ werden Spuren der basischen Extraktionsmittel im Raffinat durch Strippen mit Kohlendioxid entfernt. Bei der Strippung mit Kohlendioxid erfolgt gleichzeitig eine Trocknung des Öles. Das Kohlendioxid kann als verdünntes Gas oder als dichtes, überkritisches Gas zur Beseitigung von Spuren der verwendeten basischen Stickstoffverbindungen aus dem Raffinat verwendet werden. Die Abtrennung des erfindungsgemäß verwendeten Extraktionsmittels (zum Beispiel eine wäßrige Lösung von 2-Dimethylamino- ethanol) aus dem Extrakt kann auf einfachem Wege durch Destillation erfolgen. Voraussetzung ist dabei, daß der Dampfdruck des Wassers etwa gleich oder höher ist als der Dampfdruck der verwendeten basischen StickstoffVerbindung (en) . Das Wasser und die basische organische Verbindung werden gemeinsam abdestilliert oder das Wasser wird zunächst bevorzugt abdestilliert, wobei das Verhältnis von basischer Verbindung zu Wasser kon- stant bleibt oder sich erhöht und die Bildung eines viskosen Soapstocks vermieden wird. Wäre der Dampfdruck der basischen Verbindung höher als der Wasserdampfdruck, würde das Verhältnis von basischer Verbindung zu Wasser abnehmen und schließlich die Bildung eines viskosen Soapstocks eintreten. Anders ausgedrückt muß die Siedetemperatur der basischen StickstoffVerbindung (en) einerseits gleich oder höher als die Siedetemperatur des Wassers und andererseits geringer als die Siedetemperatur der zu extrahierenden Fettsäuren sein.Residues of the basic nitrogen compounds dissolved in the raffinate are preferably washed out with water or with dilute acetic acid, lactic acid, citric acid, sulfuric acid or hydrochloric acid solutions. Alternatively, traces of the basic extractant in the raffinate are removed by stripping with carbon dioxide. When stripping with carbon dioxide, the oil is dried at the same time. The carbon dioxide can be used as a dilute gas or as a dense, supercritical gas to remove traces of the basic nitrogen compounds used from the raffinate. The extraction agent used according to the invention (for example an aqueous solution of 2-dimethylaminoethanol) can be separated off from the extract in a simple manner by distillation. The prerequisite for this is that the vapor pressure of the water is approximately equal to or higher than the vapor pressure of the basic nitrogen compound (s) used. The water and the basic organic compound are distilled off together, or the water is first preferably distilled off, the ratio of basic compound to water remaining constant or increasing and the formation of a viscous soap stick being avoided. If the vapor pressure of the basic compound were higher than the water vapor pressure, the ratio of the basic compound to water would decrease and finally the formation of a viscous soap stick would occur. In other words, the boiling temperature of the basic nitrogen compound (s) must be on the one hand equal to or higher than the boiling temperature of the water and on the other hand lower than the boiling temperature of the fatty acids to be extracted.
Geeignete basische, organische Verbindungen für das Verfahren nach dieser Erfindung sollten folgende Eigenschaften aufweisen: a) die Verbindung soll nach Möglichkeit keine Amide mit den freien Fettsäuren bilden; b) die Verbindung soll mit Wasser in jedem Verhältnis mischbar sein; c) die Siedetemperatur der Verbindung soll gleich oder höher sein als die des Wassers, d) die Geruchsbelästigung durch die wäßrigen Lösungen soll möglichst gering sein. Beispiele von geeigneten, organischen StickstoffVerbindungen sind: N-methylmorpholin, 2-Dimethyl- amino-ethanol, 3- (Diethylamino) -1-propanol, 2-Diethylamino- ethanol, 1- (Dimethylamino) -2-propanol , Dimethylformamid,Suitable basic, organic compounds for the process according to this invention should have the following properties: a) the compound should, if possible, not form any amides with the free fatty acids; b) the compound should be miscible with water in any ratio; c) the boiling temperature of the compound should be equal to or higher than that of water, d) the odor nuisance caused by the aqueous solutions should be as low as possible. Examples of suitable organic nitrogen compounds are: N-methylmorpholine, 2-dimethylaminoethanol, 3- (diethylamino) -1-propanol, 2-diethylaminoethanol, 1- (dimethylamino) -2-propanol, dimethylformamide,
N-Methylmorpholin, 2-Methylethylamino-ethanol, 2-Dibutylamino- ethanol, Dimethylformamid, Morpholin, 2-Diisopropylamino- ethanol, usw. Allgemein werden tertiäre Amine wegen ihrer höheren Basizität binären und einfach substituierten Aminen vorgezogen. Beispiele für Ausgangsmaterialien, die mit dem erfindungsgemäßen Verfahren gut entsäuert werden können, sind Rindertalg, Schmalz, Fischöl, Maisöl, Schlachtfette, Palmöl, Sojaöl, Rapsöl, Sonnenblumenöl, Reiskeimöl, Baumwollsaatöl, Olivenöl, Erdnußöl, Safloröl, Kokosöl, Pal kernöl, Traubenkeimöl, Weizen- keimöl usw. Vor der Anwendung des erfindungsgemäßen Verfahrens sollten die zu entsäuernden Öle und Fette entschleimt und filtriert werden, insbesondere wenn mehr als 100 pp Phosphatide vorhanden sind. Das so aufbereitete Fett oder Öl enthält noch Sauerstoff gelöst, der ebenfalls vor der weiteren Aufbereitung entfernt werden sollte. Mittels des erfindungsgemäßen Verfahrens erfolgt dann die Entsäuerung des Ausgangsmaterials unter Schonung temperaturempfindlicher Verbindungen wie z.B. Carotine, Tocotrienole, Tocopherole usw. Diese unter anderem auch ernährungsphysiologisch wichtigen Verbindungen werden bei der herkömmlichen physikalischen Raffination, die mittels direktem Dampf durchgeführt wird, aufgrund der hohen Temperaturen zu einem Großteil zerstört oder ausgetrieben.N-methylmorpholine, 2-methylethylaminoethanol, 2-dibutylaminoethanol, dimethylformamide, morpholine, 2-diisopropylaminoethanol, etc. Generally, tertiary amines are preferred because of their higher basicity of binary and monosubstituted amines. Examples of starting materials that can be deacidified well using the process according to the invention are beef tallow, lard, fish oil, corn oil, slaughter fat, palm oil, soybean oil, rapeseed oil, sunflower oil, rice germ oil, cottonseed oil, olive oil, peanut oil, safflower oil, coconut oil, pal kernel oil, grape germ oil, Wheat germ oil, etc. Before the process according to the invention is used, the oils and fats to be deacidified should be degummed and filtered, especially if more than 100 pp of phosphatides are present. The fat or oil prepared in this way still contains dissolved oxygen, which should also be removed before further processing. The process according to the invention then deacidifies the starting material while protecting temperature-sensitive compounds such as carotenes, tocotrienols, tocopherols, etc. These compounds, which are also important in terms of nutritional physiology, become one in conventional physical refining, which is carried out by means of direct steam, due to the high temperatures Most of them destroyed or driven out.
In einer etwas abgewandelten Form eignet sich das erfindungsgemäße Verfahren auch hervorragend zur Entfernung der freien Fettsäuren aus den Dämpferkondensaten von Fetten und Ölen, die mittels der soeben erwähnten herkömmlichen physikalischen Raffination, d.h. mittels Dampfentsäuerung, entsäuert wurden.In a somewhat modified form, the method according to the invention is also outstandingly suitable for removing the free fatty acids from the damper condensates of fats and oils, which can be obtained by means of the conventional physical refining just mentioned, i.e. by means of steam deacidification.
Diese Dämpferkondensate enthalten im allgemeinen freie Fettsäuren in sehr hohen Konzentrationen, meist im Bereich von etwa 80 bis 94 Gew.-%. Aufgrund des hohen Gehaltes an freien Fettsäuren muß das erfindungsgemäß verwendete Extraktionsmittel, d.h. das Gemisch aus organischer Base und Wasser, allerdings reicher an der basischen StickstoffVerbindung sein, als zuvor im Zusammenhang mit der Entsäuerung von Fetten und Ölen beschrieben. Der Anteil der organischen Stickstoffverbindung am Extraktionsmittel sollte zumindest etwa 40 Gew.-% betragen. Wird eine solche, an basischer StickstoffVerbindung reiche wäßrige Lösung, beispielsweise 60 Gew.-% 2-Dimethylamino-ethanol und 40 Gew.-% Wasser, als Extraktionsmittel dem flüssigen Dämpferkondensat zugesetzt, erhält man eine flüssige, homogene Mischung. Dieser flüssigen Mischung werden dann ein bis vier Teile, vorzugsweise zwei bis vier Teile, eines Alkans und/oder eines Esters, insbesondere eines Essigesters, auf ein Teil der flüssigen Mischung zugesetzt. Aus der zuvor homogenen Mischung entstehen dadurch zwei koexistierende, flüssige Phasen, von denen die wasserhaltige Phase mit hoher Selektivität die freien Fettsäuren enthält.These damper condensates generally contain free fatty acids in very high concentrations, mostly in the range from about 80 to 94% by weight. Due to the high content of free fatty acids, the extracting agent used according to the invention, ie the mixture of organic base and water, must be richer in the basic nitrogen compound than previously described in connection with the deacidification of fats and oils. The proportion of organic nitrogen compound in the extractant should be at least about 40% by weight. If such an aqueous solution rich in basic nitrogen compound, for example 60% by weight of 2-dimethylaminoethanol and 40% by weight of water, is used as the extractant for the liquid damper condensate added, you get a liquid, homogeneous mixture. One to four parts, preferably two to four parts, of an alkane and / or an ester, in particular an ethyl acetate, are then added to one part of the liquid mixture to this liquid mixture. This creates two coexisting, liquid phases from the previously homogeneous mixture, of which the water-containing phase contains the free fatty acids with high selectivity.
In der Alkan- und/oder Esterphase sind im wesentlichen die im Dämpferkondensat vorhandenen Fette und Öle gelöst. Die im Dämpferkondensat auch gelösten Nebenprodukte, wie Tocopherole, Tocotrienole und Phytosterole, gehen ebenfalls mit hoher Selektivität in die Alkanphase über. Die wasserhaltige Phase mit den darin enthaltenen freien Fettsäuren ist niedrigviskos, so daß eine Phasentrennung etwa innerhalb von 20 Minuten nach Unterbrechung der Durchmischung erfolgt ist.The fats and oils present in the damper condensate are essentially dissolved in the alkane and / or ester phase. The by-products, such as tocopherols, tocotrienols and phytosterols, which are also dissolved in the steam condensate, also pass into the alkane phase with high selectivity. The water-containing phase with the free fatty acids contained therein is of low viscosity, so that a phase separation took place approximately within 20 minutes after interruption of the mixing.
Das sich nach Abtrennung der wäßrigen Phase ergebende Raffinat (Alkanphase oder Esterphase) ist je nach Ausgangsprodukt stark an Nebenprodukten, wie Tocopherolen, Phytosterolen, Tocotrieno- len angereichert. Aus solchen Konzentraten ist die Gewinnung dieser wertvollen Nebenprodukte unter wirtschaftlich attraktiven Bedingungen möglich.The raffinate (alkane phase or ester phase) which results after the aqueous phase has been separated off is, depending on the starting product, highly enriched in by-products, such as tocopherols, phytosterols, tocotrienols. Such valuable by-products can be obtained from such concentrates under economically attractive conditions.
Als Alkane sind beispielsweise Propan, Butan, Hexan, Petrol- ether, Heptan, Heptan-Fraktionen, Oktan usw. geeignet. Bei Verwendung von Butan oder Propan als Lösemittel für die Bildung zweier Phasen muß der Druck im Mischgefäß dem jeweiligen Dampf- druck zumindest entsprechen, damit das Butan oder Propan in flüssiger Form vorliegt. Als Ester eignen sich insbesondere die Essigester, beispielsweise Ethylacetat, Propylacetat, Butyl- acetat oder eine Mischung daraus.Examples of suitable alkanes are propane, butane, hexane, petroleum ether, heptane, heptane fractions, octane, etc. When using butane or propane as a solvent for the formation of two phases, the pressure in the mixing vessel must at least correspond to the respective vapor pressure so that the butane or propane is in liquid form. Particularly suitable as esters are the ethyl acetate, for example ethyl acetate, propyl acetate, butyl acetate or a mixture thereof.
Bei dem erfindungsgemäßen Verfahren wird allgemein dann, wenn die Konzentration der freien Fettsäuren im zu behandelnden Ausgangsmaterial (Öl, Fett oder Dämpferkondensat) mehr als etwa 50 Gew.-% beträgt, der Zusatz von Alkanen erforderlich, damit das Gesamtsystem (Ausgangsmaterial und Extraktionsmittel) zweiphasig bleibt. Durch den Alkan- oder Esterzusatz ist demnach auch bei hohen Konzentrationen an freien Fettsäuren im Ausgangsgemisch die Bildung zweier leicht zu handhabender flüssiger Phasen gesichert, und es können mit dem erfindungsgemäß verwendeten Extraktionsmittel durch eine Extraktion im Gegenstrom Extrakte mit hohen Konzentrationen an freien Fettsäuren erhalten werden. Das Lösemittelverhältnis kann infolge- dessen klein sein, was sich auf die Wirtschaftlichkeit des erfindungsgemäßen Verfahrens vorteilhaft auswirkt.In the method according to the invention, in general, when the concentration of free fatty acids in the starting material to be treated (oil, fat or steam condensate) is more than about 50% by weight, the addition of alkanes is required so that the overall system (starting material and extractant) remains two-phase. The addition of alkane or ester accordingly ensures the formation of two easy-to-handle liquid phases even at high concentrations of free fatty acids in the starting mixture, and extracts with high concentrations of free fatty acids can be obtained with the extractant used according to the invention by countercurrent extraction. As a result, the solvent ratio can be small, which has an advantageous effect on the economy of the method according to the invention.
Anhand der ein Verfahrensfließbild zeigenden, einzigen Figur wird ein Ausführungsbeispiel des erfindungsgemäßen Verfahrens näher erläutert. Durch eine Leitung 10 wird ein Ausgangsprodukt (Öl, Fett oder Dämpferkondensat) einer ersten Extraktionskolonne 12 zugeführt. In der Extraktionskolonne 12 werden aus dem Ausgangsprodukt die freien Fettsäuren mit einem Extraktionsmittel, das aus einem Gemisch einer basischen StickstoffVerbindung und Wasser besteht, mit hoher Selektivität extrahiert. Das verwendete Extraktionsmittel enthält zumindest etwa 20 Gew.-% und höchstens etwa 80 Gew.-% der organischen StickstoffVerbindung (organische Base) . Als besonders günstig haben sich Konzentrationen der basischen StickstoffVerbindung von etwa 30 bis 40 Gew.-% erwiesen. Die Konzentration an basischer Stickstoffverbindung kann jedoch ohne weiteres noch höher gewählt werden.An embodiment of the method according to the invention is explained in more detail with reference to the single figure showing a process flow diagram. A starting product (oil, fat or steam condensate) is fed to a first extraction column 12 through a line 10. In the extraction column 12, the free fatty acids are extracted with high selectivity from the starting product using an extracting agent which consists of a mixture of a basic nitrogen compound and water. The extractant used contains at least about 20% by weight and at most about 80% by weight of the organic nitrogen compound (organic base). Concentrations of the basic nitrogen compound of about 30 to 40% by weight have proven to be particularly favorable. However, the concentration of basic nitrogen compound can easily be selected to be even higher.
Das von den freien Fettsäuren befreite Öl oder Fett wird durch eine Leitung 14 einer Waschkolonne 16 (Extraktionskolonne) zugeführt, in der Reste der basischen StickstoffVerbindung mit Wasser oder mit einer wäßrigen Lösung, die eine Säure enthält, ausgewaschen werden, und verläßt die Waschkolonne 16 als Raffinat R. Die am Kopf der Waschkolonne 16 durch eine Leitung 18 austretende Waschlösung wird anschließend durch Destillation in einer Destillationskolonne 20 aufgearbeitet. Dabei werdenThe oil or fat freed from the free fatty acids is fed through a line 14 to a washing column 16 (extraction column), in which residues of the basic nitrogen compound are washed out with water or with an aqueous solution which contains an acid, and leaves the washing column 16 as Raffinate R. The washing solution emerging at the top of the washing column 16 through a line 18 is then worked up by distillation in a distillation column 20. In doing so
Wasser und gegebenenfalls die im Wasser gelöste leichtflüchtige Säure (wie z. B. Essigsäure) soweit abdestilliert, bis das Sumpfprodukt der Destillationskolonne 20 die Zusammensetzung des Extraktionsmittels erreicht hat. Dieses Sumpfprodukt wird dann durch eine Leitung 22 dem nachfolgend beschriebenen Extraktionsmittelkreislauf zugeleitet, während das Destillat der Destillationskolonne 20 als Waschflüssigkeit über eine Leitung 24 der bereits erwähnten Waschkolonne 16 zugeführt wird.Water and optionally the volatile acid (such as acetic acid) dissolved in the water are distilled off until the Bottom product of the distillation column 20 has reached the composition of the extractant. This bottom product is then fed through a line 22 to the extractant circuit described below, while the distillate is fed to the distillation column 20 as washing liquid via a line 24 to the washing column 16 already mentioned.
Das die freien Fettsäuren enthaltende, am Kopf der Extraktions- kolone 12 abgezogene Extraktionsmittel wird durch eine Leitung 26 einer zweiten Destillationskolonne 28 zugeführt. Wasser und die basische Stickstoffverbindung fallen bei der Destillation in der Destillationskolonne 28 als Kopfprodukt an, während der die extrahierten freien Fettsäuren und etwas Neutralöl enthaltende Extrakt als Sumpfprodukt durch eine Leitung 30 aus der Destillationskolonne 28 abgezogen wird. Das Kopfprodukt derThe extraction agent containing the free fatty acids, drawn off at the top of the extraction colon 12, is fed through a line 26 to a second distillation column 28. Water and the basic nitrogen compound are obtained as the top product during distillation in the distillation column 28, while the extract containing the extracted free fatty acids and some neutral oil is withdrawn as a bottom product through a line 30 from the distillation column 28. The top product of
Destillationskolonne 28 wird als Extraktionsmittel durch eine Leitung 32 der Extraktionskolonne 12 zugeführt, in der die Extraktion der freien Fettsäuren stattfindet, womit der Extraktionsmittelkreislauf geschlossen ist. Durch Leitungen 34 und 36 wird den Destillationskolonnen 20 und 28 die zur Destillation erforderliche Energie in Form von Heizdampf zugeführt.Distillation column 28 is fed as extraction medium through a line 32 to extraction column 12, in which the extraction of the free fatty acids takes place, whereby the extraction medium circuit is closed. The energy required for distillation in the form of heating steam is fed through lines 34 and 36 to the distillation columns 20 and 28.
Auf diese Weise werden durch Extraktion ein säurefreies Öl oder Fett als Raffinat und die extrahierten freien Fettsäuren, die noch kleine Mengen an Neutralöl enthalten, bei geschlossenem Kreislauf aller Hilfsstoffe erzeugt. Abfallströme entstehen nicht. Im Ausgangsprodukt enthaltende Nebenprodukte, wie beispielsweise Tocopherole, Tocotrienole, Carotine, Phytosterole, Cholesterole usw. , verbleiben im Raffinat R.In this way, extraction produces an acid-free oil or fat as raffinate and the extracted free fatty acids, which still contain small amounts of neutral oil, in a closed cycle of all auxiliary substances. Waste flows do not arise. By-products contained in the starting product, such as tocopherols, tocotrienols, carotenes, phytosterols, cholesterols etc., remain in the raffinate R.
Mit dem erfindungsgemäßen Verfahren wurden eine Reihe von Versuchen durchgeführt, die im folgenden erläutert sind.With the method according to the invention, a number of tests were carried out, which are explained below.
Beispiel 1 250 g eines Öles aus 95,5 Gew.-% Neutralöl, 4,2 Gew.-% freien Fettsäuren und 1,7 Gew.-% Tocopherol wurden bei 50°C mit 100 g 2-Dimethylamino-ethanol und 70 g Wasser durch Rühren vermischt. Nach Unterbrechung des Mischvorgangs und Trennung der beiden flüssigen Phasen wurden aus beiden Phasen Proben entnommen und analysiert. Die an Extraktionsmittel reiche Phase enthielt abzüglich Extraktionsmittel 53,7 Gew.-% Neutralöl, 45,0 Gew.-% freie Fettsäuren und 0,3 Gew.-% Tocopherol. Die ölreiche Raffinatphase enthielt abzüglich Extraktionsmittel 98,2 Gew.-% Neutralöl, 0,05 Gew.-% freie Fettsäuren und 1,8 Gew.-% Tocopherol.Example 1 250 g of an oil composed of 95.5% by weight of neutral oil, 4.2% by weight of free fatty acids and 1.7% by weight of tocopherol were mixed at 50 ° C. with 100 g of 2-dimethylaminoethanol and 70 g Water mixed by stirring. After the mixing process had been interrupted and the two liquid phases had been separated, samples were taken from both phases and analyzed. The extractant-rich phase, minus the extractant, contained 53.7% by weight of neutral oil, 45.0% by weight of free fatty acids and 0.3% by weight of tocopherol. The oil-rich raffinate phase minus the extractant contained 98.2% by weight of neutral oil, 0.05% by weight of free fatty acids and 1.8% by weight of tocopherol.
Beispiel 2Example 2
200 g eines Öles mit 5,5 Gew.-% freien Fettsäuren, 1,8 Gew.-% Tocopherolen wurde bei 50°C mit 150 g eines Extraktionsmittels, das 40 Gew.-% Wasser und 60 Gew.-% 2-Dimethylamino-ethanol enthielt, vermischt. Nach Unterbrechung des Mischvorgangs und Phasentrennung wurde aus jeder der beiden koexistierenden, flüssigen Phasen eine Probe entnommen und analysiert. Die Extraktphase hatte eine Beladung von 8,9 Gew.-%. Abzüglich des Extraktionsmittels bestand der Extrakt aus 92 Gew.-% freien Fettsäuren, 0,3 Gew.-% Tocopherolen, und 7,7 Gew.-% Glyceriden. Die Raffinatphase enthielt abzüglich des Extraktionsmittels200 g of an oil with 5.5 wt .-% free fatty acids, 1.8 wt .-% tocopherols was at 50 ° C with 150 g of an extracting agent, the 40 wt .-% water and 60 wt .-% 2-dimethylamino -ethanol contained, mixed. After interruption of the mixing process and phase separation, a sample was taken from each of the two coexisting liquid phases and analyzed. The extract phase had a loading of 8.9% by weight. Less the extractant, the extract consisted of 92% by weight of free fatty acids, 0.3% by weight of tocopherols, and 7.7% by weight of glycerides. The raffinate phase contained minus the extractant
0,05 Gew.-% freie Fettsäuren, 1,8 Gew.-% Tocopherol, und 98,2 Gew.-% Glyceride.0.05% by weight of free fatty acids, 1.8% by weight of tocopherol, and 98.2% by weight of glycerides.
Beispiel 3 200 g eines Öles mit 5,1 Gew.-% freien Fettsäuren und 0,3Example 3 200 g of an oil with 5.1% by weight of free fatty acids and 0.3
Gew.-% Tocopherol wurden mit einem Extraktionsmittel aus 100 g Wasser und 100 g Pyridin bestehendem Extraktionsmittel bei 60°C vermischt. Nach Unterbrechung des Mischvorgangs und Trennung der Phasen wurden aus jeder der beiden koexistierenden, flüssi- gen Phasen eine Probe entnommen und analysiert. Die Beladung des Extraktionsmittels betrug 2,1 Gew.-%. Der Extrakt bestand abzüglich Extraktionsmittel aus 20,8 Gew.-% freien Fettsäuren, 0,3 Gew.-% Tocopherolen und 95,8 Gew.-% Glyceriden. Das Raffinat enthielt abzüglich Extraktionsmittel 4,2 Gew.-% freie Fettsäuren, 0,3 Gew.-% Tocopherole und 95,1 Gew.-% Glyceride. Beispiel 4% By weight of tocopherol was mixed with an extractant composed of 100 g of water and 100 g of pyridine extractant at 60.degree. After the mixing process had been interrupted and the phases separated, a sample was taken from each of the two coexisting liquid phases and analyzed. The loading of the extractant was 2.1% by weight. The extract, minus the extractant, consisted of 20.8% by weight of free fatty acids, 0.3% by weight of tocopherols and 95.8% by weight of glycerides. The raffinate minus the extractant contained 4.2% by weight of free fatty acids, 0.3% by weight of tocopherols and 95.1% by weight of glycerides. Example 4
151 g eines Öles einer Zusammensetzung aus 4,3 Gew.-% freien Fettsäuren, 1,4 Gew.-% Tocopherol, 0,6 Gew.-% Stigmasterin und 93,7 Gew.-% Neutralöl wurden bei 50°C mit 150 g eines Extrakti- onsmittels aus 60 Gew.-% 2- (Dimethylamino) -ethanol und 40 Gew.- % Wasser vermischt. Nach Beendigung des Mischvorgangs entstanden im Verlauf von etwa 10 Minuten zwei Phasen. Nach Beseitigung einer schwachen Trübung durch Zentrifugieren wurden aus beiden Phasen Proben entnommen und analysiert. Die Extraktphase hatte abzüglich des Extraktionsmittels folgende Zusammensetzung: 84 Gew.-% freie Fettsäuren, 0,5 Gew.-% Tocopherol, 0,5 Gew.-% Stigmasterin und 15 Gew.-% Neutralöl. Das Raffinat enthielt 0,05 Gew.-% freie Fettsäuren, 1,4 Gew.-% Tocopherol, 0,6 Gew.-% Stigmasterol und 97,95 Gew.-% Neutralöl. Im Extrakt verblieben 0,46 Gew.-% der eingesetzten Menge an Neutralöl.151 g of an oil with a composition of 4.3% by weight of free fatty acids, 1.4% by weight of tocopherol, 0.6% by weight of stigmasterol and 93.7% by weight of neutral oil were mixed at 150 with 50 g of an extractant of 60% by weight of 2- (dimethylamino) ethanol and 40% by weight of water. After the mixing process was completed, two phases developed over a period of about 10 minutes. After removing a slight turbidity by centrifugation, samples were taken from both phases and analyzed. The extract phase, minus the extractant, had the following composition: 84% by weight of free fatty acids, 0.5% by weight of tocopherol, 0.5% by weight of stigmasterol and 15% by weight of neutral oil. The raffinate contained 0.05% by weight of free fatty acids, 1.4% by weight of tocopherol, 0.6% by weight of stigmasterol and 97.95% by weight of neutral oil. 0.46% by weight of the amount of neutral oil used remained in the extract.
Beispiel 5Example 5
300 g Palmöl mit einem Gehalt von 4,5 Gew.-% freien Fettsäuren, 0,4 Gew.-% Tocolen, 0,15 Gew.-% Stigmasterin, 94,95 Gew.-% Neutralöl wurden mit 42 g eines Extraktionsmittels vermischt, welches zu 60 Gew.-% aus 2- (Dimethylamino) -ethanol und zu 40 Gew.-% aus Wasser bestand, bei 50°C vermischt. Nach Unterbrechung des Mischvorgangs und Phasentrennung, die etwa 35 Minuten dauerte, wurden aus beiden Phasen Proben entnommen und analy- siert. Der Extrakt enthielt abzüglich des Extraktionsmittels 40,0 Gew.-% freie Fettsäuren, 0,4 Gew.-% Tocopherole, 0,25 Gew.-% Stigmasterin und 59,35 Gew.-% Neutralöl. Das Raffinat bestand abzüglich Extraktionsmittels aus 0,3 Gew.-% freien Fettsäuren, 0,4 Gew.-% Tocopherolen, 0,1 Gew.-% Stigmasterin, und 99,4 Gew.-% Neutralöl. 6 Gew.-% der eingesetzten Menge an Neutralöl befanden sich im Extrakt. Das Lösemittelverhältnis hatte den geringen Wert von 0,14.300 g of palm oil containing 4.5% by weight of free fatty acids, 0.4% by weight of tocols, 0.15% by weight of stigmasterol, 94.95% by weight of neutral oil were mixed with 42 g of an extractant , which consisted of 60 wt .-% of 2- (dimethylamino) ethanol and 40 wt .-% of water, mixed at 50 ° C. After the mixing process had been interrupted and the phases separated, which took about 35 minutes, samples were taken from both phases and analyzed. The extract contained, minus the extracting agent, 40.0% by weight of free fatty acids, 0.4% by weight of tocopherols, 0.25% by weight of stigmasterol and 59.35% by weight of neutral oil. The raffinate minus the extractant consisted of 0.3% by weight of free fatty acids, 0.4% by weight of tocopherols, 0.1% by weight of stigmasterol, and 99.4% by weight of neutral oil. 6% by weight of the amount of neutral oil used was in the extract. The solvent ratio had the low value of 0.14.
Beispiel 6 100 g Palmöl mit einem Gehalt von 5,5 Gew.% freien Fettsäuren wurden bei 60°C mit 100 g eines Gemisches aus 30 g N,N- Dimethylamino-ethanol und 70 g Wasser durch Rühren miteinander vermischt. Nach Unterbrechung des Mischvorgangs wurde die Phasentrennung, die nach etwa 3 Minuten erfolgt war, abgewartet und aus beiden koexistierenden Phasen Proben entnommen und analysiert. Das Palmöl (Raffinat) enthielt abzüglich des Extraktionsmittels weniger als 0,1 Gew.% freie Fettsäuren. Der Extrakt enthielt abzüglich Extraktionsmittel 77 Gew.% Fettsäuren und 23 Gew.% Glyceride (Mono-, Di, und Triglyceride; letztere die Hauptkomponente). Etwa 1,2 g Glyceride (ca. 1,2 % der Einwaage) wurden mit den freien Fettsäuren gemeinsam extrahiert.Example 6 100 g of palm oil containing 5.5% by weight of free fatty acids were mixed at 60 ° C. with 100 g of a mixture of 30 g of N, N- Dimethylamino-ethanol and 70 g water mixed together by stirring. After the mixing process had been interrupted, the phase separation, which had taken place after about 3 minutes, was waited for and samples were taken from both coexisting phases and analyzed. The palm oil (raffinate) minus the extractant contained less than 0.1% by weight of free fatty acids. The extract contained less extractant 77% by weight of fatty acids and 23% by weight of glycerides (mono-, di- and triglycerides; the latter the main component). About 1.2 g glycerides (approx. 1.2% of the weight) were extracted together with the free fatty acids.
Beispiel 7Example 7
100 g Palmöl mit 4,3 Gew.% freien Fettsäuren wurden bei 80°C mit einer Lösung aus 40 Gew.% N,N-Dimethylamino-ethanol in100 g of palm oil with 4.3% by weight of free fatty acids were mixed in at 80 ° C. with a solution of 40% by weight of N, N-dimethylaminoethanol
Wasser durch Rühren miteinander vermischt. Nach Trennung der koexistierenden Phasen wurden aus jeder der Phasen Proben entnommen und analysiert. Der Extrakt enthielt abzüglich Extraktionsmittel 67 Gew.% Fettsäuren und 33 Gew.% Glyceride (Mono-, Di-, und Triglyceride) . Das Raffinat enthielt abzüglich Extraktionsmittel weniger als 0,1 % freie Fettsäuren. Im Extrakt befanden sich 2 g an Glyceriden (ca. 2 % der Einwaage). Im Raffinat waren 1,9 Gew.% N,N-Dimethylamino-ethanol gelöst, die mit Wasser ausgewaschen wurden.Water mixed together by stirring. After the coexisting phases had been separated, samples were taken from each of the phases and analyzed. The extract contained less extractant 67% by weight of fatty acids and 33% by weight of glycerides (mono-, di- and triglycerides). The raffinate less extractant contained less than 0.1% free fatty acids. The extract contained 2 g of glycerides (approx. 2% of the weight). 1.9% by weight of N, N-dimethylaminoethanol were dissolved in the raffinate and washed out with water.
Beispiel 8Example 8
100 g Palmöl mit 4,2 Gew.% freien Fettsäuren wurden bei 50°C mit 100 g einer Lösung von 40 Gew.% N,N-Dimethylamino-ethanol in Wasser extrahiert. Der Extrakt bestand abzüglich Extrakti- onsmittel zu 75 Gew.% aus Fettsäuren und zu 25 Gew.% aus Glyceriden. Außer 3,1 g Fettsäuren enthält der Extrakt noch 1 g Glyceride (einem Verlust an Fett von 1 % entsprechend) . Das Raffinat enthielt 0,1 Gew.% freie Fettsäuren. Beispiel 9100 g of palm oil with 4.2% by weight of free fatty acids were extracted at 50 ° C. with 100 g of a solution of 40% by weight of N, N-dimethylaminoethanol in water. Less extractant, the extract consisted of 75% by weight of fatty acids and 25% by weight of glycerides. In addition to 3.1 g of fatty acids, the extract also contains 1 g of glycerides (corresponding to a loss of fat of 1%). The raffinate contained 0.1% by weight of free fatty acids. Example 9
200 g Dämpferkondensat mit 92 Gew.% freien Fettsäuren und200 g steam condensate with 92% by weight of free fatty acids and
0,19 % Nebenkomponenten (Tocopherole + Tocotrienole + Phytoste- rine) werden in 400 g Heptan-Fraktion bei 40°C gelöst. Die Lösung wird mit 600 g einer Lösung von 40 % N,N-Dimethylamino- ethanol in Wasser bei 40°C extrahiert. Es entstehen zwei klare koexistierende Phasen, die sich in wenigen Minuten ausbilden. Der Extrakt (das im Extraktionsmittel Gelöste) enthält abzüglich Extraktionsmittel 96 % Fettsäuren. Das Raffinat besteht abzüglich Extratsionsmittel aus 13,4 g Glyceriden, 0,7 g freien Fettsäuren, und 0,3 g Nebenkomponenten (2 % Tocopherole + Tocotrienole + Phytosterine) .0.19% secondary components (tocopherols + tocotrienols + phytosterols) are dissolved in 400 g heptane fraction at 40 ° C. The solution is extracted with 600 g of a solution of 40% N, N-dimethylaminoethanol in water at 40 ° C. There are two clear coexisting phases that develop in a few minutes. The extract (the one dissolved in the extractant) contains less extractant 96% fatty acids. The raffinate minus the extractant consists of 13.4 g glycerides, 0.7 g free fatty acids, and 0.3 g secondary components (2% tocopherols + tocotrienols + phytosterols).
Beispiel 10 Palmöl wurde in einer Anlage gemäß der beigefügten Figur in die erste Extraktionskolonne 12 mit einer Menge von 30,0 kg/h zugeführt. Da das Palmöl 4,3 Gew.-% freie Fettsäuren enthielt, bestand der Zulauf durch die Leitung 10 aus 28,71 kg/h Neutralöl und 1,29 kg/h freien Fettsäuren. In der Extraktionskolonne 12 wurde das Palmöl bei 80°C mit 30,0 kg/h Extraktionsmittel im Gegenstrom in Kontakt gebracht. Das Extraktionsmittel war aus Dimethylamino-ethanol (DMAE) und Wasser im Verhältnis 1:1 zusammengesetzt. Der die Extraktionskolonne 12 verlassende Raffinatstrom umfaßte 24,424 kg/h Neutralöl, 0,090 kg/h freie Fettsäuren, 0,855 kg/h DMAE und 0,855 kg/h Wasser. Der Extraktstrom setzte sich aus 14,145 kg/h DMAE, 14,145 kg/h Wasser, 0,285 kg/h Neutralöl und 1,20 kg/h freien Fettsäuren zusammen.Example 10 Palm oil was fed into the first extraction column 12 at a rate of 30.0 kg / h in a system according to the attached figure. Since the palm oil contained 4.3% by weight of free fatty acids, the feed through line 10 consisted of 28.71 kg / h of neutral oil and 1.29 kg / h of free fatty acids. In the extraction column 12, the palm oil was brought into contact at 80 ° C. with 30.0 kg / h of extractant in countercurrent. The extractant was composed of 1: 1 dimethylaminoethanol (DMAE) and water. The raffinate stream leaving the extraction column 12 comprised 24.424 kg / h neutral oil, 0.090 kg / h free fatty acids, 0.855 kg / h DMAE and 0.855 kg / h water. The extract stream consisted of 14.145 kg / h DMAE, 14.145 kg / h water, 0.285 kg / h neutral oil and 1.20 kg / h free fatty acids.
Der Raffinatstrom wurde der Waschkolonne 16 zugeführt, in welcher ihm bei 80°C mit 15,0 kg/h Wasser im Gegenstrom dasThe raffinate stream was fed to the washing column 16, in which it was countercurrented at 80 ° C. with 15.0 kg / h of water
DMAE ausgewaschen wurde. Der so gereinigte Raffinatstrom verließ die Waschkolonne 16 in folgender Zusammensetzung: 28,424 kg/h Neutralöl, 0,012 kg/h DMAE und weniger als 0,025 kg/h freie Fettsäuren. Das entspricht einem Neutralöl mit 0,00042 Gew.-% DMAE und weniger als 0,00088 Gew.-% freiem Fettsäuren. Das Waschwasser verließ die Waschkolonne 16 mit folgender Zusammensetzung: 15,855 kg/h Wasser, 0,855 kg/h DMAE und 0,064 kg/h freien Fettsäuren. Das Waschwasser wurde in der Destillationskolonne 20 bei 100°C regeneriert. Als Kopfprodukt wurden 15,0 kg/h Wasser durch die Leitung 24 in die Waschkolonne 16 zurückgeführt. Das Sumpfprodukt mit 0,855 kg/h Wasser und 0,855 kg/h DMAE wird mit dem durch die Leitung 26 strömenden Extraktstrom aus der Extraktionskolonne 12 vereinigt.DMAE was washed out. The raffinate stream thus purified left the washing column 16 in the following composition: 28.424 kg / h neutral oil, 0.012 kg / h DMAE and less than 0.025 kg / h free fatty acids. This corresponds to a neutral oil with 0.00042% by weight DMAE and less than 0.00088% by weight free fatty acids. The wash water left the wash column 16 with the following composition: 15.855 kg / h of water, 0.855 kg / h of DMAE and 0.064 kg / h free fatty acids. The wash water was regenerated in the distillation column 20 at 100 ° C. As the top product, 15.0 kg / h of water were returned through line 24 to the washing column 16. The bottom product with 0.855 kg / h of water and 0.855 kg / h of DMAE is combined with the extract stream from the extraction column 12 flowing through the line 26.
Der mit dem Sumpfprodukt aus der Destillationskolonne 20 vereinigte Extraktstrom aus der Extraktionskolonne 12 wurde der Destillationskolonne 28 zugeführt. Das Kopfprodukt der Destillationskolonne 28 aus 15,0 kg/h Wasser und 15,0 kg/h DMAE wurde als Extraktionsmittel durch die Leitung 32 in die Extraktionskolonne 12 zurückgeführt. Als Sumpfprodukt verließ die Destillationskolonne 28 0,285 kg/h Neutralöl und 1,264 kg/h freie Fettsäuren. Der Extrakt bestand demnach zu 18,4 Gew.-% aus Neutralöl und zu 81,6 Gew.-% aus freien Fettsäuren.The extract stream from the extraction column 12 combined with the bottom product from the distillation column 20 was fed to the distillation column 28. The top product of the distillation column 28 from 15.0 kg / h of water and 15.0 kg / h of DMAE was recycled as the extractant through line 32 into the extraction column 12. As the bottom product, the distillation column left 28 0.285 kg / h neutral oil and 1.264 kg / h free fatty acids. Accordingly, the extract consisted of 18.4% by weight of neutral oil and 81.6% by weight of free fatty acids.
Der Kreislauf des Extraktionsmittels ist somit geschlossen, Abfallbeseitigungsprobleme bestehen nicht. The extraction agent cycle is thus closed and there are no waste disposal problems.

Claims

Patentansprüche claims
1. Verfahren zur Entfernung freier Fettsäuren aus Fetten oder Ölen biologischen Ursprungs durch Extrahieren der freien Fettsäuren mit einem Gemisch aus basischen, organischen Stickstoff- Verbindungen und Wasser als Extraktionsmittel bei einer Temperatur unterhalb der Siedetemperatur der organischen Stick- stoffVerbindungen, wobei der Anteil der basischen, organischen StickstoffVerbindungen am Extraktionsmittel mindestens etwa 20 Gew.-% und höchstens etwa 60 Gew.-%, vorzugsweise zwischen etwa 30 Gew.-% und etwa 40 Gew.-%, beträgt und die Siedetemperatur der verwendeten basischen, organischen StickstoffVerbindung (en) gleich oder größer der Siedetemperatur des Wassers und kleiner als die Siedetemperatur der zu extrahierenden Fettsäuren ist.1. Process for removing free fatty acids from fats or oils of biological origin by extracting the free fatty acids with a mixture of basic, organic nitrogen compounds and water as an extractant at a temperature below the boiling point of the organic nitrogen compounds, the proportion of the basic, organic nitrogen compounds on the extractant is at least about 20% by weight and at most about 60% by weight, preferably between about 30% by weight and about 40% by weight, and the boiling temperature of the basic organic nitrogen compound (s) used is the same or greater than the boiling point of the water and less than the boiling point of the fatty acids to be extracted.
2. Verfahren nach Anspruch 1, dadurch gekennzeichnet, daß die basischen Stickstoffverbin- dung(en) in dem durch die Extraktion erhaltenen, raffinierten Fett oder Öl mittels Wasser oder wäßriger Lösungen flüchtiger Säuren ausgewaschen werden.2. The method according to claim 1, characterized in that the basic nitrogen compound (s) in the refined fat or oil obtained by the extraction are washed out by means of water or aqueous solutions of volatile acids.
3. Verfahren nach Anspruch 1 oder 2 , dadurch gekennzeichnet, daß bei der Entsäuerung von Fetten und Ölen mit einem Gehalt an freien Fettsäuren von etwa 50 Gew.-% und mehr den zu entsäuernden Ausgangsstoffen Alkane und/oder ein Ester, insbesondere ein Essigsäureester, in einer Konzentration zugesetzt werden, die dazu ausreicht, daß das System aus Extraktionsmittel, Alkan und Ausgangsstoff in zwei Phasen zerfällt.3. The method according to claim 1 or 2, characterized in that in the deacidification of fats and oils with a free fatty acid content of about 50 wt .-% and more, the starting materials to be deacidified alkanes and / or an ester, especially an acetic acid ester, are added in a concentration sufficient to cause the extractant, alkane and starting material system to disintegrate into two phases.
4. Verfahren zur Entfernung freier Fettsäuren aus Dämpferkondensaten von Fetten oder Ölen biologischen Ursprungs, mit den Schritten:4. A method for removing free fatty acids from steamer condensates from fats or oils of biological origin, comprising the steps:
- Extrahieren der freien Fettsäuren mit einem Gemisch aus basischen, organischen StickstoffVerbindungen und Wasser als Extraktionsmittel bei einer Temperatur unterhalb der Siedetemperatur der organischen StickstoffVerbindungen, wobei der Anteil der basischen, organischen Stickstoffverbindungen am Extraktionsmittel mindestens etwa 40 Gew.-% und höchstens etwa 60 Gew.-%, vorzugsweise etwa 50 Gew.-% und mehr, beträgt und die Siedetemperatur der verwendeten basischen, organischen StickstoffVerbindung (en) gleich oder größer der Siedetemperatur des Wassers und kleiner als die Siedetemperatur der zu extrahierenden Fettsäuren ist, und - Zugeben von 1 bis 4 Teilen, vorzugsweise 2 bis 4 Teilen Alkan und/oder eines Esters, insbesondere eines Essigsäureester, auf 1 Teil der im vorhergehenden Extrak ionsschritt erhaltenen flüssigen, homogenen Mischung.- Extract the free fatty acids with a mixture of basic, organic nitrogen compounds and water as Extractant at a temperature below the boiling point of the organic nitrogen compounds, the proportion of basic, organic nitrogen compounds in the extractant being at least about 40% by weight and at most about 60% by weight, preferably about 50% by weight and more, and the The boiling point of the basic organic nitrogen compound (s) used is equal to or greater than the boiling point of the water and less than the boiling point of the fatty acids to be extracted, and - addition of 1 to 4 parts, preferably 2 to 4 parts, of alkane and / or an ester, in particular of an acetic acid ester, to 1 part of the liquid, homogeneous mixture obtained in the previous extraction step.
5. Verfahren nach Anspruch 3 oder 4, dadurch gekennzeichnet, daß die basischen StickstoffVerbindung (en) in der Alkan- und/oder Esterphase mittels Wasser oder wäßriger Lösungen flüchtiger Säuren ausgewaschen werden.5. The method according to claim 3 or 4, characterized in that the basic nitrogen compound (s) in the alkane and / or ester phase are washed out by means of water or aqueous solutions of volatile acids.
6. Verfahren nach einem der Ansprüche 2 oder 5, dadurch gekennzeichnet, daß die nach dem Auswaschschritt im Wasser oder der wäßrigen Lösung flüchtiger Säuren gelöste (n) organische (n) StickstoffVerbindung (en) durch Destillieren abgetrennt werden.6. The method according to any one of claims 2 or 5, characterized in that the organic nitrogen compound (s) dissolved in the water or the aqueous solution of volatile acids after the washing step are separated off by distillation.
7. Verfahren nach einem der Ansprüche 3 bis 6, dadurch gekennzeichnet, daß als Alkan Propan, Butan, Pentan, Hexan, Heptan, Heptan-Fraktion, Oktan oder eine Mischung daraus verwendet wird.7. The method according to any one of claims 3 to 6, characterized in that the alkane used is propane, butane, pentane, hexane, heptane, heptane fraction, octane or a mixture thereof.
8. Verfahren nach einem der Ansprüche 3 bis 7 , dadurch gekennzeichnet, daß als Ester Ethylacetat, Propylace- tat, Butylacetat oder eine Mischung daraus verendet wird.8. The method according to any one of claims 3 to 7, characterized in that the ester used is ethyl acetate, propyl acetate, butyl acetate or a mixture thereof.
9. Verfahren nach einem der vorhergehenden Ansprüche, dadurch gekennzeichnet, daß die extrahierten Fettsäuren vom Extraktionsmittel durch Destillieren des die Fettsäuren enthal- tenden Extraktionsmittels bei Atmosphärendruck oder Unterdr ck abgetrennt werden.9. The method according to any one of the preceding claims, characterized in that the extracted fatty acids from the extractant by distilling the fatty acids contained be extracted extractant at atmospheric pressure or negative pressure.
10. Verfahren nach einem der vorhergehenden Ansprüche, dadurch gekennzeichnet, daß als basische, organische StickstoffVerbindung tertiäre Amine verwendet werden.10. The method according to any one of the preceding claims, characterized in that tertiary amines are used as the basic, organic nitrogen compound.
11. Verfahren nach einem der vorhergehenden Ansprüche, dadurch gekennzeichnet, daß als basische, organische Stick- stoffVerbindung 2-Dimethylamino-ethanol , 2-Methylamino- diethanol, 4-Methylmorpholin, 2-Diisopropylamino-ethanol, 2-Dibutylamino-ethanol , 3-Dimethylamino-propanol , l-Dimethylamino-2-propanol , 2-Dimethylamino-ethanol , 2-Dimethylamino-l-butanol, 2- (Methylethylamino) -ethanol, Dimethylformamid, Morpholin, Pyridin, 2-Dimethylamino-2-methyl- 1-propanol, 4-Methyl-pyridin, 1-Methyl-pyrrol, 2-Dibutylamino- ethanol, 2-Dimethylamino-ethylamin, Monoethanolamin, 3-Dimethylamino-l-propanol , Dimethylamino-2-propanon, 1-Dimethylamino-l-propylenamin, oder eine Mischung dieser Verbindungen verwendet wird. 11. The method according to any one of the preceding claims, characterized in that 2-dimethylaminoethanol, 2-methylamino-diethanol, 4-methylmorpholine, 2-diisopropylaminoethanol, 2-dibutylaminoethanol, 3- as basic organic nitrogen compound Dimethylamino-propanol, l-dimethylamino-2-propanol, 2-dimethylamino-ethanol, 2-dimethylamino-l-butanol, 2- (methylethylamino) -ethanol, dimethylformamide, morpholine, pyridine, 2-dimethylamino-2-methyl-1- propanol, 4-methyl-pyridine, 1-methyl-pyrrole, 2-dibutylaminoethanol, 2-dimethylamino-ethylamine, monoethanolamine, 3-dimethylamino-l-propanol, dimethylamino-2-propanone, 1-dimethylamino-l-propyleneamine, or a mixture of these compounds is used.
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WO2000063327A2 (en) 2000-10-26
EP1171555B1 (en) 2004-06-16
ES2218150T3 (en) 2004-11-16
US6579996B2 (en) 2003-06-17
MXPA01010698A (en) 2002-06-04
TR200103038T2 (en) 2002-03-21
IL145977A (en) 2004-12-15
DK1171555T3 (en) 2004-11-01
RU2242505C2 (en) 2004-12-20
AU756898B2 (en) 2003-01-23
PL350431A1 (en) 2002-12-16
AU4296400A (en) 2000-11-02
CN1347445A (en) 2002-05-01
WO2000063327A3 (en) 2001-04-05
BR0009895A (en) 2002-01-15
JP3711023B2 (en) 2005-10-26
AR023552A1 (en) 2002-09-04

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