EP0654527B1 - Process for degumming vegetable oils with enzymes - Google Patents

Process for degumming vegetable oils with enzymes Download PDF

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Publication number
EP0654527B1
EP0654527B1 EP94203211A EP94203211A EP0654527B1 EP 0654527 B1 EP0654527 B1 EP 0654527B1 EP 94203211 A EP94203211 A EP 94203211A EP 94203211 A EP94203211 A EP 94203211A EP 0654527 B1 EP0654527 B1 EP 0654527B1
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Prior art keywords
oil
enzymes
degumming
sludge
degummed
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German (de)
French (fr)
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EP0654527A1 (en
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Henning Dr. Buchold
Rudolf Dr. Boensch
Joerg Dr. Schroeppel
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GEA Group AG
Roehm GmbH Darmstadt
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Metallgesellschaft AG
Roehm GmbH Darmstadt
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    • 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
    • C11B3/003—Refining fats or fatty oils by enzymes or microorganisms, living or dead

Definitions

  • the invention relates to a method for degumming Vegetable oil, whereby the vegetable oil is adjusted to a pH of 3 to 6, an aqueous enzyme solution dispersed in the oil, which contains one of the enzymes phospholipase A1, A2 or B, which Enzymes in the oil with stirring at temperatures from 20 to 90 ° C in a degumming reactor can act and from the Degumming reactor withdrawn liquid degummed oil separates.
  • the invention is based, at the beginning mentioned processes the used enzymes in Degumming process at least partially to reuse. According to the invention, this is done in that the liquid withdrawn from the degumming reactor at temperatures of 20 to 90 ° C before or after the separation of the degummed oil a release agent or a Solubilizer admits and an aqueous, used enzyme containing, largely sludge-free solution that one at least partially leads back to the degumming reactor and dispersed in the oil to be degummed, the proportion used, recycled enzymes in total the enzyme dispersed in the oil is at least 10%. For cost reasons, it is advantageous if the share used, recycled enzymes in total of the enzymes dispersed in the oil at least 20% or more better, at least 50%.
  • a variant of the 2nd way is that of the Degumming reactor coming oily liquid admit a broker and then that separate degummed oil from the liquid, e.g. in a centrifuge. You get next to that degummed oil an aqueous, largely sludge-free Phase that contains the used enzymes. This The aqueous phase can be wholly or partly without further Treatment, before returning the degumming reactor, to mix them with the oil to be degummed.
  • solubilizer to be used or Release aids can vary widely, they is usually 0.1 to 100 g / l liquid. A Excess solubilizer or separation aid is not disturbing.
  • the vegetable oil to be completely degummed comes in accordance with Fig. 1 from the line (1), it is dosed from the Storage container (2) first an aqueous acidic solution, e.g. Citric acid, and one from the storage container (3) aqueous alkaline solution, e.g. Caustic soda, in such Amounts that the oil has a pH of 3 to 6 preferably about 5, through line (4) into one first disperser (5) occurs. In the disperser (5) an oil-water emulsion is created, which can be Line (6) in a retention tank (7) passes.
  • aqueous acidic solution e.g. Citric acid
  • aqueous alkaline solution e.g. Caustic soda
  • the reactor (13) shown has three levels (13a), (13b) and (13c), through which the oil to be treated with a certain dwell time on each floor from top to bottom flows.
  • Each floor can have different Treatment temperatures can be set, it is recommends on the top floor (13a) with the lowest temperature and on the lowest floor (13c) to work with the highest temperature.
  • the Treatment temperatures in the reactor (13) are in the range from 20 to 90 ° C with a total residence time in Reactor (13) of usually 3 to 5 hours.
  • the treated oil leaves the degumming reactor (13) through line (17) and becomes a centrifuge (18) given up.
  • the centrifuge is used as a product degummed oil obtained in the line (19) dissipates.
  • the enzyme-containing aqueous sludge phase in the Line (20) is given from the storage container (21) Separation aid and stir the whole thing in Disperser (22) intensive. Then you give the stirred phase in line (23) one Indwelling container (24), preferably with a Stirring device (25) is provided.
  • the temperatures are in the range from 30 to 85 ° C and preferably at about 60 ° C and man ensures dwell times in the range of 3 to 60 minutes.
  • 2 is correct between the Lines (1) and (17) with the previously together with Fig. 1st described method. 2 is also that coming from the degumming reactor (13) Water-phosphatide sludge-oil mixture through the Line (17) fed to the centrifuge (18), from which one withdraws degummed oil in line (19). Of the enzyme-containing water-sludge phase of the line (30) there one from the reservoir (31) solubilizer to and stir the whole thing in the retention tank (32). Here creates an aqueous, enzyme-containing solution, which one by the line (28) in the reservoir (10) to Reuse returns; an excess of the solution can be removed in line (29). In place the retention tank (32) can also be a Disperser (22), cf. Fig. 1.
  • rapeseed oil which with Water has been degummed in various ways Enzymes degummed.
  • Examples 1, 5 and 6 are Comparative examples in which the invention Procedure is not applied.
  • the degummed rapeseed oil in line (19) has one remaining phosphorus content of 6 ppm, the volume of Water-sludge phase is 370 ml.
  • the phosphorus content is a measure of the level of degumming, good degummed oil has a residual P content of less than 10 ppm.
  • Example 1 For the procedure according to the invention according to FIG. 2 Example 1 is repeated, with the Water-sludge phase of line (30) 3 g / l TWEEN 80 adds and the liquid 10 min in a disperser (Ultra-Turrax) stirs intensely. You get one sludge-free, enzyme-containing solution with no suspended Particles that one in the line (28) in the Returns storage container (10). On adding fresher Enzymes are avoided. The degummed oil of the Line (19) has a residual phosphorus content of 5 ppm per run.
  • a disperser Ultra-Turrax
  • Example 1 For the procedure according to the invention according to FIG. 2 Example 1 is repeated, the one from the Enzyme reactor exiting via line 17 Liquid mixture via line (33) 2.5 g Tween 80 per liter of mixture and the mixture in the Centrifuge 18 separates. You largely get one sludge-free, enzyme-containing solution that can be piped (34) and line (28) to the reservoir (10). Fresh enzymes are not added.
  • the degummed oil in line (19) has one Residual phosphorus content of 5 ppm.
  • Example 1 For the procedure according to the invention according to FIG. 1 Example 1 is repeated, with the Water-sludge phase of the line (20) per liter 2 g TWEEN 80 (manufacturer DuPont) adds and the Liquids in a disperser (22) (Ultra-Turrax) homogenized. After a dwell time of 10 minutes the phosphatide sludge by centrifuging the aqueous enzyme solution separated. The enzyme solution will via the line (28) into the storage container (10) traced back, adding fresher addition No enzyme solution whatsoever. The residual phosphorus content in the degummed oil of line (19) is 5 ppm.
  • Example 4 is modified so that instead of aqueous enzyme solution after centrifugation in the Line (27) occurring, pretreated with TWEEN 80 Phosphatide sludge via the dosing point (9) with the oil the line (8) is mixed. It turns out that this Phosphatide sludge to improve degumming is ineffective because it has no enzyme activity.
  • Example 1 For the procedure according to the invention Example 1 is repeated, taking the water-sludge phase the line (20) 2 liters of alginate protan per liter (Manufacturer: Pronova-Biopolymer, Norway) adds and the liquids in a disperser (22) (Ultra-Turrax) homogenized, cf. Fig. 1. After a The phosphatide sludge becomes a residence time of 10 minutes by centrifuging the aqueous enzyme solution severed. The enzyme solution is in the Storage container (10) returned. Without adding fresh enzymes the residual phosphorus content in degummed oil of line (19) 8 ppm.

Abstract

A process is disclosed for enzymatically degumming vegetable oil where the vegetable oil to be degummed is adjusted to a pH from 3 to 6 and is mixed with an aqueous enzyme solution, which contains one of the enzymes phospholipase A1, A2 or B. In a degumming reactor the enzymes are permitted to act on the oil at temperatures from 20 DEG to 90 DEG C. with stirring. Before or after a separation of the degummed oil a separation promoter or a solubilizer is added at temperatures from 20 DEG to 90 DEG C. to the liquid which has been withdrawn from the degumming reactor. A substantially sludgefree solution, which contains used enymes, is thus recovered and is recycled at least in part to a location preceding the degumming rector. The content of recycled used enzymes in the total amount of the enzymes dispersed in the oil is at least 10%.

Description

Die Erfindung betrifft ein Verfahren zum Entschleimen von Pflanzenöl, wobei man das Pflanzenöl auf einen pH-Wert von 3 bis 6 einstellt, eine wäßrige Enzymlösung im Öl dispergiert, die eines der Enzyme Phospholipase A1, A2 oder B enthält, die Enzyme im Öl unter Rühren bei Temperaturen von 20 bis 90°C in einem Entschleimungsreaktor einwirken läßt und aus der aus dem Entschleimungsreaktor abgezogenen Flüssigkeit entschleimtes Öl abtrennt.The invention relates to a method for degumming Vegetable oil, whereby the vegetable oil is adjusted to a pH of 3 to 6, an aqueous enzyme solution dispersed in the oil, which contains one of the enzymes phospholipase A1, A2 or B, which Enzymes in the oil with stirring at temperatures from 20 to 90 ° C in a degumming reactor can act and from the Degumming reactor withdrawn liquid degummed oil separates.

Ein solches Verfahren ist aus EP-A-0 513 709 bekannt. Beim beschriebenen Verfahren bleibt aber offen, wie man die gebrauchten Enzyme nach der Entschleimung des Öls zurückgewinnt, damit sie im Verfahren wiederverwendet werden können. Die Entschleimung von Speiseölen erfolgt beim Verfahren gemäß EP-B-0 122 727 mit hydrolysierten Phosphatiden. Die Phosphatide, z. B. Lecithin, können im Prozeß wiedergewonnen und zurückgeführt werden. In Database WPI Week 7738 (Derwent-Abstract zu JP-A-52 096 790) wird die Reinigung von Enzymen, darunter Phospholipase A, mittels vorbehandelter Träger beschrieben, auf denen die Enzyme adsorbiert werden.Such a method is known from EP-A-0 513 709. At the described method remains open, however, how to used enzymes after degumming the oil recovered so that they can be reused in the process can. The degumming of edible oils takes place at Process according to EP-B-0 122 727 with hydrolyzed Phosphatides. The phosphatides, e.g. As lecithin, can Process can be recovered and returned. In database WPI Week 7738 (Derwent abstract for JP-A-52 096 790) becomes the Purification of enzymes, including phospholipase A, using pretreated carrier described on which the enzymes be adsorbed.

Der Erfindung liegt die Aufgabe zugrunde, beim eingangs genannten Verfahren die gebrauchten Enzyme im Entschleimungsverfahren mindestens teilweise wiederzuverwenden. Erfindungsgemäß geschieht dies dadurch, daß man der aus dem Entschleimungsreaktor abgezogenen Flüssigkeit bei Temperaturen von 20 bis 90°C vor oder nach dem Abtrennen des entschleimten Öls ein Trennhilfsmittel oder einen Lösungsvermittler zugibt und eine wäßrige, gebrauchte Enzyme enthaltende, weitgehend schlammfreie Lösung gewinnt, die man mindestens teilweise vor den Entschleimungsreaktor zurückführt und im zu entschleimenden Öl dispergiert, wobei der Anteil gebrauchter, zurückgeführter Enzyme in der Gesamtmenge der im Öl dispergierten Enzyme mindestens 10 % beträgt. Aus Kostengründen ist es vorteilhaft, wenn der Anteil gebrauchter, zurückgeführter Enzyme in der Gesamtmenge der im Öl dispergierten Enzyme mindestens 20 % oder noch besser, mindestens 50 % beträgt.The invention is based, at the beginning mentioned processes the used enzymes in Degumming process at least partially to reuse. According to the invention, this is done in that the liquid withdrawn from the degumming reactor at temperatures of 20 to 90 ° C before or after the separation of the degummed oil a release agent or a Solubilizer admits and an aqueous, used enzyme containing, largely sludge-free solution that one at least partially leads back to the degumming reactor and dispersed in the oil to be degummed, the proportion used, recycled enzymes in total the enzyme dispersed in the oil is at least 10%. For cost reasons, it is advantageous if the share used, recycled enzymes in total of the enzymes dispersed in the oil at least 20% or more better, at least 50%.

Die aus dem Entschleimungsreaktor abgezogene Flüssigkeit enthält entschleimtes Öl. Wenn man aus dieser Flüssigkeit das entschleimte Öl abtrennt, z.B. in einer Zentrifuge, fällt gleichzeitig eine Wasser-Schlamm-Phase an, die die gebrauchten Enzyme enthält. Um diese Enzyme wiederverwendbar zu machen, kann man zwei verschiedene Wege beschreiten:

  • 1. Weg: Bei einer Temperatur im Bereich von 20 bis 90°C dispergiert man in der Wasser-Schlamm-Phase ein Trennhilfsmittel, rührt das Ganze in einem Verweilbehälter und trennt aus der schlammhaltigen Flüssigkeit, z.B. durch Filtration, eine wäßrige, weitgehend schlammfreie Phase ab, welche die gebrauchten Enzyme enthält. Diese wäßrige Phase wird ganz oder teilweise vor den Entschleimungsreaktor zurückgeführt und in dem zu entschleimenden Öl dispergiert.
  • 2. Weg: Bei einer Temperatur im Bereich von 20 bis 90°C gibt man der Wasser-Schlamm-Phase einen Lösungsvermittler zu und erhält unter Rühren eine wäßrige, weitgehend schlammfreie Lösung, welche die gebrauchten Enzyme enthält. Diese Lösung wird ganz oder teilweise vor den Entschleimungsreaktor zurückgeführt und mit dem zu entschleimenden Öl gemischt. Der Lösungsvermittler sorgt dafür, daß ein Ausfallen von phosphatidhaltigem Schlamm mit adsorbierten Enzymen unterbleibt.
    • The liquid withdrawn from the degumming reactor contains degummed oil. If you remove the degummed oil from this liquid, for example in a centrifuge, a water-sludge phase is formed which contains the used enzymes. There are two ways to make these enzymes reusable:
  • 1st way: At a temperature in the range from 20 to 90 ° C, a separating aid is dispersed in the water-sludge phase, the whole is stirred in a retention tank and an aqueous, largely sludge-free phase is separated from the sludge-containing liquid, for example by filtration which contains the used enzymes. All or part of this aqueous phase is returned to the degumming reactor and dispersed in the oil to be degummed.
  • 2nd route: At a temperature in the range from 20 to 90 ° C., a water solubilizer is added to the water-sludge phase and an aqueous, largely sludge-free solution is obtained which contains the used enzymes. All or part of this solution is returned to the degumming reactor and mixed with the oil to be degummed. The solubilizer ensures that phosphatide-containing sludge with adsorbed enzymes does not precipitate.

    • Eine Variante des 2. Wegs besteht darin, der aus dem Entschleimungsreaktor kommenden ölhaltigen Flüssigkeit einen Lösungsvermittler zuzugeben und dann das entschleimte Öl aus der Flüssigkeit abzutrennen, z.B. in einer Zentrifuge. Man erhält hierbei neben dem entschleimten Öl eine wäßrige, weitgehend schlammfreie Phase, welche die gebrauchten Enzyme enthält. Diese wäßrige Phase kann man ganz oder teilweise, ohne weitere Behandlung, vor den Entschleimungsreaktor zurückführen, um sie mit dem zu entschleimenden Öl zu mischen.A variant of the 2nd way is that of the Degumming reactor coming oily liquid admit a broker and then that separate degummed oil from the liquid, e.g. in a centrifuge. You get next to that degummed oil an aqueous, largely sludge-free Phase that contains the used enzymes. This The aqueous phase can be wholly or partly without further Treatment, before returning the degumming reactor, to mix them with the oil to be degummed.

    Sowohl als Trennhilfsmittel als auch als Lösungsvermittler können folgende Substanzen oder Substanzgemische dienen:

  • a) Polyethylen-Zucker-Fettsäureester, insbesondere TWEEN 20 bis TWEEN 85 (Hersteller: DuPont),
  • b) Rizinusethoxylat,
  • c) ethoxyliertes Palmitat,
  • d) ethoxylierter synthetischer primärer Alkohol, wobei der Alkohol vorzugsweise ein C9- bis C11-Alkohol ist, der z.B. 12 Ethoxylgruppen aufweist,
  • e) ethoxylierter Laurylalkohol, z.B. mit 11 Ethoxylgruppen,
  • f) ethoxylierter Talgfettalkohol, z.B. mit 25 Ethoxylgruppen, oder
  • g) hydrophobes Tensid, z.B. SPAN 40 oder SPAN 80 (Hersteller: ICI).
    • The following substances or mixtures of substances can serve both as separation aids and as solubilizers:
  • a) polyethylene sugar fatty acid esters, in particular TWEEN 20 to TWEEN 85 (manufacturer: DuPont),
  • b) castor ethoxylate,
  • c) ethoxylated palmitate,
  • d) ethoxylated synthetic primary alcohol, the alcohol preferably being a C 9 to C 11 alcohol which has, for example, 12 ethoxyl groups,
  • e) ethoxylated lauryl alcohol, for example with 11 ethoxyl groups,
  • f) ethoxylated tallow fatty alcohol, for example with 25 ethoxyl groups, or
  • g) hydrophobic surfactant, for example SPAN 40 or SPAN 80 (manufacturer: ICI).

    • Darüber hinaus können als Trennhilfsmittel auch verwendet werden:

  • h) anionaktive Verbindungen, insbesondere
  • h1) heißwasserlösliche Methylcellulosen oder
  • h2) heißwasserlösliche Carboxymethylcellulosen,
  • i) nichtionogene Verbindungen, insbesondere
  • i1) Polysaccharide, z.B. wasserlösliche Stärke,
  • i2) Xerogele, z.B. Agar-Agar oder hydrolysierte Gelatine,
  • i3) Biopolymere, insbesondere Alginate oder Chitosane.
    • In addition, the following can also be used as separation aids:
  • h) anionic compounds, in particular
  • h1) hot water soluble methyl celluloses or
  • h2) hot water-soluble carboxymethyl celluloses,
  • i) non-ionic compounds, in particular
  • i1) polysaccharides, for example water-soluble starch,
  • i2) xerogels, for example agar agar or hydrolyzed gelatin,
  • i3) biopolymers, in particular alginates or chitosans.

    • Die Menge des anzuwendenden Lösungsvermittlers oder Trennhilfsmittels kann im breiten Bereich variieren, sie liegt zumeist bei 0,1 bis 100 g/l Flüssigkeit. Ein Überschuß an Lösungsvermittler oder Trennhilfsmittel ist nicht störend.The amount of solubilizer to be used or Release aids can vary widely, they is usually 0.1 to 100 g / l liquid. A Excess solubilizer or separation aid is not disturbing.

    Für die Entschleimung der Speiseöle unter Mitwirkung von Enzymen ist es zweckmäßig, das Öl zunächst mit Wasser für die Gewinnung von Lecithin vorzuentschleimen. Die Phospholipasen A1, A2 oder B greifen nämlich Lecithin im Öl an, so daß es zweckmäßig ist, den Phosphorgehalt des Öls durch eine Vorentschleimung, z.B. mit Wasser, in den Bereich von 50 bis 500 ppm abzusenken. Diese Vorbehandlung ist vor allem für lecithinreiche Öle, wie z.B. Sojaöl, zu empfehlen. For degumming the edible oils with the participation of It is advisable for enzymes to first use water for the oil to degum the extraction of lecithin. The Phospholipases A1, A2 or B attack lecithin in Oil on, so that it is appropriate to the phosphorus content of Oil by pre-degumming, e.g. with water in the Lower range from 50 to 500 ppm. This Pretreatment is especially for oils rich in lecithin, such as e.g. Soybean oil, recommended.

    Ausgestaltungsmöglichkeiten des Verfahrens werden mit Hilfe der Zeichnung erläutert.

    Fig. 1
    zeigt das Fließschema einer Verfahrensvariante mit Zugabe eines Trennhilfsmittels und
    Fig. 2
    zeigt Verfahrensvarianten mit Zugabe eines Lösungsvermittlers.
    Design options of the method are explained with the aid of the drawing.
    Fig. 1
    shows the flow diagram of a process variant with the addition of a separation aid and
    Fig. 2
    shows process variants with the addition of a solubilizer.

    Das vollständig zu entschleimende Pflanzenöl kommt gemäß Fig. 1 aus der Leitung (1), man dosiert ihm aus dem Vorratsbehälter (2) zunächst eine wäßrige saure Lösung, z.B. Zitronensäure, und aus dem Vorratsbehälter (3) eine wäßrige alkalische Lösung, z.B. Natronlauge, in solchen Mengen zu, daß das Öl mit einem pH-Wert von 3 bis 6, vorzugsweise etwa 5, durch die Leitung (4) in einen ersten Dispergierer (5) eintritt. Im Dispergierer (5) wird eine Öl-Wasser-Emulsion erzeugt, die man durch die Leitung (6) in einen Verweilbehälter (7) leitet.The vegetable oil to be completely degummed comes in accordance with Fig. 1 from the line (1), it is dosed from the Storage container (2) first an aqueous acidic solution, e.g. Citric acid, and one from the storage container (3) aqueous alkaline solution, e.g. Caustic soda, in such Amounts that the oil has a pH of 3 to 6 preferably about 5, through line (4) into one first disperser (5) occurs. In the disperser (5) an oil-water emulsion is created, which can be Line (6) in a retention tank (7) passes.

    Nach einer Verweilzeit im Bereich von 1 bis 30 Minuten fließt die Emulsion durch die Leitung (8) zu einer Zugabestelle (9) für eine wäßrige Enzymlösung, die aus dem Vorratsgefäß (10) kommt. Pro Liter Öl werden hierbei 10 bis 100 mg an Enzymlösung zudosiert. Bei den in Wasser gelösten Enzymen handelt es sich um die Phospholipase vom Typ A1, A2 oder B, z.B. mit einer Aktivität der Lösung von 10 000 Lecitaseeinheiten pro Milliliter. Das enzymhaltige Öl wird durch einen weiteren Dispergierer (11) geführt und gelangt dann in der Leitung (12) zu einem Entschleimungsreaktor (13). Der Reaktor (13) besteht aus 1 bis 5 Etagen, wobei jede Etage eine Rühreinrichtung (14) und eine Beheizung (15) aufweist. Zwischen benachbarten Etagen gibt es eine Verbindungsleitung (16). Der in der Zeichnung dargestellte Reaktor (13) weist drei Etagen (13a), (13b) und (13c) auf, durch die das zu behandelnde Öl mit einer gewissen Verweilzeit in jeder Etage von oben nach unten fließt. In jeder Etage können unterschiedliche Behandlungstemperaturen eingestellt werden, wobei es sich empfiehlt, in der obersten Etage (13a) mit der niedrigsten Temperatur und in der untersten Etage (13c) mit der höchsten Temperatur zu arbeiten. Die Behandlungstemperaturen im Reaktor (13) liegen im Bereich von 20 bis 90°C bei einer gesamten Verweilzeit im Reaktor (13) von üblicherweise 3 bis 5 Stunden.After a dwell time in the range of 1 to 30 minutes the emulsion flows through line (8) to one Addition point (9) for an aqueous enzyme solution consisting of the storage vessel (10) comes. Here, per liter of oil 10 to 100 mg of enzyme solution were added. With those in water dissolved enzymes is the phospholipase from Type A1, A2 or B, e.g. with an activity of the solution of 10,000 units of lecitase per milliliter. The enzyme-containing oil is replaced by another Disperser (11) guided and then arrives in the Line (12) to a degumming reactor (13). Of the Reactor (13) consists of 1 to 5 floors, each floor a stirring device (14) and a heater (15) having. There is one between adjacent floors Connection line (16). The one in the drawing The reactor (13) shown has three levels (13a), (13b) and (13c), through which the oil to be treated with a certain dwell time on each floor from top to bottom flows. Each floor can have different Treatment temperatures can be set, it is recommends on the top floor (13a) with the lowest temperature and on the lowest floor (13c) to work with the highest temperature. The Treatment temperatures in the reactor (13) are in the range from 20 to 90 ° C with a total residence time in Reactor (13) of usually 3 to 5 hours.

    Das behandelte Öl verläßt den Entschleimungsreaktor (13) durch die Leitung (17) und wird einer Zentrifuge (18) aufgegeben. In der Zentrifuge wird als Produkt entschleimtes Öl gewonnen, das man in der Leitung (19) abführt. Der enzymhaltigen wäßrigen Schlammphase in der Leitung (20) gibt man aus dem Vorratsbehälter (21) Trennhilfsmittel zu und rührt das Ganze im Dispergierer (22) intensiv. Anschließend gibt man die gerührte Phase in der Leitung (23) einem Verweilbehälter (24) auf, der vorzugsweise mit einer Rühreinrichtung (25) versehen ist. Im Verweilbehälter (24) liegen die Temperaturen im Bereich von 30 bis 85°C und vorzugsweise bei etwa 60°C und man sorgt für Verweilzeiten im Bereich von 3 bis 60 Minuten. Unter der Wirkung des Trennhilfsmittels werden die am Phosphatidschlamm adsorbierten Enzyme abgelöst und in die Wasserphase überführt. Zum Abtrennen der enzymhaltigen Wasserphase gibt man die Flüssigkeit aus dem Verweilbehälter (24) in eine Filtrationseinrichtung (26), die bevorzugt als Mikrofiltration arbeitet. Alternativ kann an dieser Stelle auch zentrifugiert werden. Man trennt so den Phosphatidschlamm ab, den man in der Leitung (27) entfernt. Die die gebrauchten Enzyme enthaltende wäßrige Phase wird in der Leitung (28) abgezogen und zur Wiederverwendung dem Vorratsbehälter (10) zugeführt. Frische Enzymlösung kommt, soweit notwendig, aus der Leitung (29). Auf diese Weise ist es möglich, die gebrauchten Enzyme für die Entschleimung des Öls wiederzuverwenden und damit die Betriebskosten des Verfahrens ganz erheblich zu senken.The treated oil leaves the degumming reactor (13) through line (17) and becomes a centrifuge (18) given up. In the centrifuge is used as a product degummed oil obtained in the line (19) dissipates. The enzyme-containing aqueous sludge phase in the Line (20) is given from the storage container (21) Separation aid and stir the whole thing in Disperser (22) intensive. Then you give the stirred phase in line (23) one Indwelling container (24), preferably with a Stirring device (25) is provided. in the Dwell containers (24), the temperatures are in the range from 30 to 85 ° C and preferably at about 60 ° C and man ensures dwell times in the range of 3 to 60 minutes. Under the effect of the release agent, the am Phosphatid sludge adsorbed enzymes detached and into the Water phase transferred. To separate the enzyme-containing Water phase gives the liquid out of the Indwelling container (24) into a filtration device (26), which preferably works as microfiltration. Alternatively can also be centrifuged at this point. Man separates the phosphatide sludge, which is in the Line (27) removed. The used enzymes containing aqueous phase is in line (28) deducted and reused for Storage container (10) supplied. Fresh enzyme solution comes from line (29) if necessary. To this It is possible to find the used enzymes for the Degreasing of the oil and thus the reuse Lower the operating costs of the process considerably.

    Das Verfahren gemäß Fig. 2 stimmt zwischen den Leitungen (1) und (17) mit dem zuvor zusammen mit Fig. 1 beschriebenen Verfahren überein. Auch gemäß Fig. 2 wird das aus dem Entschleimungsreaktor (13) kommende Wasser-Phosphatidschlamm-Öl-Gemisch durch die Leitung (17) der Zentrifuge (18) zugeführt, aus der man in der Leitung (19) entschleimtes Öl abzieht. Der enzymhaltigen Wasser-Schlamm-Phase der Leitung (30) gibt man aus dem Vorratsbehälter (31) Lösungsvermittler zu und verrührt das Ganze im Verweilbehälter (32). Dabei entsteht eine wäßrige, enzymhaltige Lösung, die man durch die Leitung (28) in den Vorratsbehälter (10) zum Wiederverwenden zurückführt; ein Überschuß der Lösung kann in der Leitung (29) entfernt werden. An die Stelle des Verweilbehälters (32) kann auch ein Dispergierer (22), vgl. Fig. 1, treten.2 is correct between the Lines (1) and (17) with the previously together with Fig. 1st described method. 2 is also that coming from the degumming reactor (13) Water-phosphatide sludge-oil mixture through the Line (17) fed to the centrifuge (18), from which one withdraws degummed oil in line (19). Of the enzyme-containing water-sludge phase of the line (30) there one from the reservoir (31) solubilizer to and stir the whole thing in the retention tank (32). Here creates an aqueous, enzyme-containing solution, which one by the line (28) in the reservoir (10) to Reuse returns; an excess of the solution can be removed in line (29). In place the retention tank (32) can also be a Disperser (22), cf. Fig. 1.

    Eine Alternative besteht darin, daß man im Verfahren der Fig. 2 den Lösungsvermittler durch die gestrichelte Leitung (33) bereits vor der Zentrifuge (18) dem Wasser-Schlamm-Öl-Gemisch der Leitung (17) zugibt, wobei die Zentrifuge auch als Mischeinrichtung dient. Neben dem entschleimten Öl der Leitung (19) kommt hierbei eine wäßrige, enzymhaltige Lösung aus der Zentrufige (18), die man durch die Leitungen (30), (34) und (28) zum Wiederverwenden ganz oder teilweise in den Vorratsbehälter (10) zurückleitet. Der Vorratsbehälter (31) und der Verweilbehälter (32) können bei dieser Verfahrensvariante entfallen. An alternative is that in the process of Fig. 2 the solubilizer by the dashed Line (33) before the centrifuge (18) Add water-sludge-oil mixture to line (17), whereby the centrifuge also serves as a mixing device. Next to the degummed oil of line (19) comes here aqueous, enzyme-containing solution from the centrifuge (18), the one through lines (30), (34) and (28) to Reuse in whole or in part in the Returns storage container (10). Of the Storage container (31) and the retention container (32) can omitted in this process variant.

    BeispieleExamples

    In einer der Zeichnung entsprechenden Laborapparatur mit einem einstufigen Reaktor (13) wird Rapsöl, das mit Wasser vorentschleimt ist, auf verschiedene Weise mit Enzymen entschleimt. Die Beispiele 1, 5 und 6 sind Vergleichsbeispiele, bei denen das erfindungsgemäße Verfahren nicht angewandt wird.In a laboratory apparatus corresponding to the drawing a one-stage reactor (13) is rapeseed oil, which with Water has been degummed in various ways Enzymes degummed. Examples 1, 5 and 6 are Comparative examples in which the invention Procedure is not applied.

    Beispiel 1example 1

    6 l vorentschleimtes Rapsöl werden bei 60°C mit 54 ml einer wäßrigen, 10 %igen Zitronensäurelösung versetzt; zur Einstellung des pH-Werts auf 5,0 gibt man 48 ml einer wäßrigen, 5 %igen NaOH-Lösung zu. Nach einer Verweilzeit von 30 Minuten werden 205 ml einer wäßrigen Phospholipase-A2-Lösung mit 3800 Lecitaseeinheiten dem Reaktionsgemisch zugesetzt. Nach einer Behandlungsdauer von 5 Stunden bei 60°C unter intensiver Durchmischung wird die Wasser-Öl-Emulsion mittels einer Zentrifuge (18) in eine Öl- und eine Wasser-Schlamm-Phase separiert. Das entschleimte Rapsöl in der Leitung (19) weist einen restlichen Phosphor-Gehalt von 6 ppm auf, das Volumen der Wasser-Schlamm-Phase beträgt 370 ml. Der Phosphor-Gehalt ist ein Maß für den Grad der Entschleimung, gut entschleimtes Öl weist einen Rest-P-Gehalt von weniger als 10 ppm auf.6 l pre-degummed rapeseed oil are mixed with 54 ml at 60 ° C an aqueous 10% citric acid solution; 48 ml of one is added to adjust the pH to 5.0 aqueous, 5% NaOH solution. After a dwell of 30 minutes, 205 ml of an aqueous Phospholipase A2 solution with 3800 lecitase units Reaction mixture added. After a treatment period 5 hours at 60 ° C with thorough mixing the water-oil emulsion is centrifuged (18) separated into an oil and a water-sludge phase. The degummed rapeseed oil in line (19) has one remaining phosphorus content of 6 ppm, the volume of Water-sludge phase is 370 ml. The phosphorus content is a measure of the level of degumming, good degummed oil has a residual P content of less than 10 ppm.

    Beispiel 2Example 2

    Für die erfindungsgemäße Verfahrensweise gemäß Fig. 2 wird das Beispiel 1 wiederholt, wobei man der Wasser-Schlamm-Phase der Leitung (30) 3 g/l TWEEN 80 zusetzt und die Flüssigkeit 10 min in einem Dispergierer (Ultra-Turrax) intensiv rührt. Man erhält so eine schlammfreie, enzymhaltige Lösung ohne suspendierte Partikel, die man über die Leitung (28) in den Vorratsbehälter (10) zurückführt. Auf die Zugabe frischer Enzyme wird verzichtet. Das entschleimte Öl der Leitung (19) weist einen Rest-Phosphor-Gehalt von 5 ppm pro Durchgang auf.For the procedure according to the invention according to FIG. 2 Example 1 is repeated, with the Water-sludge phase of line (30) 3 g / l TWEEN 80 adds and the liquid 10 min in a disperser (Ultra-Turrax) stirs intensely. You get one sludge-free, enzyme-containing solution with no suspended Particles that one in the line (28) in the Returns storage container (10). On adding fresher Enzymes are avoided. The degummed oil of the Line (19) has a residual phosphorus content of 5 ppm per run.

    Beispiel 3Example 3

    Für die erfindungsgemäße Verfahrensweise gemäß Fig. 2 wird das Beispiel 1 wiederholt, wobei man dem aus dem Enzymreaktor über die Leitung 17 austretenden Flüssigkeitsgemisch über die Leitung (33) 2,5 g Tween 80 pro Liter Gemisch zusetzt und das Gemisch in der Zentrifuge 18 auftrennt. Man erhält so eine weitgehend schlammfreie, enzymhaltige Lösung, die man über Leitung (34) und Leitung (28) dem Vorratsbehälter (10) zuführt. Auf die Zugabe frischer Enzyme wird verzichtet. Das entschleimte Öl der Leitung (19) weist einen Rest-Phosphor-Gehalt von 5 ppm auf.For the procedure according to the invention according to FIG. 2 Example 1 is repeated, the one from the Enzyme reactor exiting via line 17 Liquid mixture via line (33) 2.5 g Tween 80 per liter of mixture and the mixture in the Centrifuge 18 separates. You largely get one sludge-free, enzyme-containing solution that can be piped (34) and line (28) to the reservoir (10). Fresh enzymes are not added. The degummed oil in line (19) has one Residual phosphorus content of 5 ppm.

    Beispiel 4Example 4

    Für die erfindungsgemäße Verfahrensweise gemäß Fig. 1 wird das Beispiel 1 wiederholt, wobei man der Wasser-Schlamm-Phase der Leitung (20) pro Liter 2 g TWEEN 80 (Hersteller DuPont) zusetzt und die Flüssigkeiten in einem Dispergierer (22) (Ultra-Turrax) homogenisiert. Nach einer Verweilzeit von 10 Minuten wird der Phosphatidschlamm durch Zentrifugieren von der wäßrigen Enzymlösung abgetrennt. Die Enzymlösung wird über die Leitung (28) in den Vorratsbehälter (10) zurückgeführt, wobei man auf die Zugabe frischer Enzymlösung ganz verzichtet. Der Rest-Phosphor-Gehalt im entschleimten Öl der Leitung (19) beträgt 5 ppm.For the procedure according to the invention according to FIG. 1 Example 1 is repeated, with the Water-sludge phase of the line (20) per liter 2 g TWEEN 80 (manufacturer DuPont) adds and the Liquids in a disperser (22) (Ultra-Turrax) homogenized. After a dwell time of 10 minutes the phosphatide sludge by centrifuging the aqueous enzyme solution separated. The enzyme solution will via the line (28) into the storage container (10) traced back, adding fresher addition No enzyme solution whatsoever. The residual phosphorus content in the degummed oil of line (19) is 5 ppm.

    Beispiel 5Example 5

    Das Beispiel 4 wird so abgewandelt, daß anstelle der wäßrigen Enzymlösung der nach Zentrifugieren in der Leitung (27) anfallende, mit TWEEN 80 vorbehandelte Phosphatidschlamm über die Dosierstelle (9) mit dem Öl der Leitung (8) vermischt wird. Es zeigt sich, daß dieser Phosphatidschlamm zum Verbessern der Entschleimung wirkungslos ist, da er keine Enzymaktivität aufweist.Example 4 is modified so that instead of aqueous enzyme solution after centrifugation in the Line (27) occurring, pretreated with TWEEN 80 Phosphatide sludge via the dosing point (9) with the oil the line (8) is mixed. It turns out that this Phosphatide sludge to improve degumming is ineffective because it has no enzyme activity.

    Beispiel 6Example 6

    Man arbeitet gemäß Beispiel 4, doch ohne die Rückführung der wäßrigen Enzymlösung in der Leitung (28). Es wird nun der Phosphatidschlamm der Leitung (27) in destilliertem Wasser resuspendiert und 10 Minuten lang bei 60°C mit einem Dispergierer (Ultra-Turrax) homogenisiert. Dann trennt man die Schlammphase durch Zentrifugieren ab und führt die gleichzeitig angefallene wäßrige Phase zur Dosierstelle (9) zurück. Frische Enzymlösung wird nicht mehr zugegeben. Nach einer Behandlungsdauer von 5 Stunden wird im Rapsöl ein restlicher P-Gehalt von 49 ppm gefunden, der beweist, daß aus dem Phosphatidschlamm der Leitung (27) keine Enzyme zurückgewonnen wurden.The procedure is as in Example 4, but without recirculation the aqueous enzyme solution in line (28). It will now the phosphatide sludge of line (27) in distilled Resuspended water and with at 60 ° C for 10 minutes homogenized using a disperser (Ultra-Turrax). Then one separates the sludge phase by centrifugation and leads the aqueous phase obtained at the same time Dosing point (9) back. Fresh enzyme solution will not admitted more. After 5 hours of treatment is a residual P content of 49 ppm in rapeseed oil found, which proves that from the phosphatide sludge the Line (27) no enzymes were recovered.

    Beispiel 7Example 7

    Für die erfindungsgemäße Verfahrensweise wird das Beispiel 1 wiederholt, wobei man der Wasser-Schlamm-Phase der Leitung (20) pro Liter 2 g Alginat Protan (Hersteller: Pronova-Biopolymer, Norwegen) zusetzt und die Flüssigkeiten in einem Dispergierer (22) (Ultra-Turrax) homogenisiert, vgl. Fig. 1. Nach einer Verweilzeit von 10 Minuten wird der Phosphatidschlamm durch Zentrifugieren von der wäßrigen Enzymlösung abgetrennt. Die Enzymlösung wird in den Vorratsbehälter (10) zurückgeführt. Ohne Zusatz von frischen Enzymen beträgt der Rest-Phosphor-Gehalt im entschleimten Öl der Leitung (19) 8 ppm. Das gleiche Ergebnis wird mit 2 g/l hydrolysierter Gelatine (Hersteller: Gibco, Schottland) anstelle von Alginat Protan erreicht. Wenn man als Trennhilfsmittel 2 g/l wasserlösliche Stärke (Hersteller: Merck, Darmstadt) verwendet, erreicht man im entschleimten Öl einen Rest-Phosphor-Gehalt von 2 ppm.For the procedure according to the invention Example 1 is repeated, taking the water-sludge phase the line (20) 2 liters of alginate protan per liter (Manufacturer: Pronova-Biopolymer, Norway) adds and the liquids in a disperser (22) (Ultra-Turrax) homogenized, cf. Fig. 1. After a The phosphatide sludge becomes a residence time of 10 minutes by centrifuging the aqueous enzyme solution severed. The enzyme solution is in the Storage container (10) returned. Without adding fresh enzymes the residual phosphorus content in degummed oil of line (19) 8 ppm. The same The result is with 2 g / l hydrolyzed gelatin (Manufacturer: Gibco, Scotland) instead of alginate Protan reached. If you as a separation aid 2 g / l water-soluble starch (manufacturer: Merck, Darmstadt) used, you get one in the degummed oil Residual phosphorus content of 2 ppm.

    Claims (8)

    1. A method for degumming vegetable oil, in which the vegetable oil is adjusted to a pH value of 3 to 6, an aqueous enzyme solution which contains one of the enzymes phospholipase A1, A2 or B is dispersed in the oil, the enzymes are allowed to act in the oil, with stirring, at temperatures of 20 to 90°C in a degumming reactor and degummed oil is separated off from the liquid withdrawn from the degumming reactor,
      characterised in that a separation promoter or a solubiliser is added to the liquid withdrawn from the degumming reactor at temperatures of 20 to 90°C before or after the degummed oil has been separated off, and an aqueous, largely sludge-free solution containing spent enzymes is obtained which is recycled at least in part to a location before the degumming reactor and is dispersed in the oil to be degummed, the proportion of spent, recycled enzymes in the total quantity of enzymes dispersed in the oil being at least 10%.
    2. A method according to Claim 1, characterised in that degummed oil is separated off from the liquid withdrawn from the degumming reactor and in so doing a water/sludge phase is obtained in which separation promoter is dispersed at temperatures in the range from 20 to 90°C, the water/sludge phase being stirred in a detention tank, an aqueous, largely sludge-free phase containing spent enzymes is separated off from the stirred water/sludge phase and recycled at least in part to a location before the degumming reactor.
    3. A method according to Claim 1, characterised in that degummed oil is separated off from the liquid withdrawn from the degumming reactor and in so doing a water/sludge phase is obtained to which solubiliser is added at temperatures in the range from 20 to 90°C, and, with stirring, an aqueous, largely sludge-free phase containing spent enzymes is produced which is recycled at least in part to a location before the degumming reactor.
    4. A method according to Claim 1, characterised in that solubiliser is added to the liquid withdrawn from the degumming reactor, the liquid is passed through a separating means and degummed oil and, separately therefrom, an aqueous, largely sludge-free solution containing spent enzymes is obtained, the solution being recycled at least in part to a location before the degumming reactor.
    5. A method according to Claim 1 or one of the following claims, characterised in that
      a) polyethylene-sugar-fatty acid ester,
      b) ricinus ethoxylate,
      c) ethoxylated palmitate,
      d) ethoxylated synthetic primary alcohol,
      e) ethoxylated lauryl alcohol,
      f) ethoxylated tallow fatty alcohol or
      g) hydrophobic surfactant
      are used as separation promoter and solubiliser.
    6. A method according to one of Claims 1 to 5, characterised in that at least
      h) one anion-active compound or
      i) one non-ionogenic compound
      is used as separation promoter.
    7. A method according to Claim 1 or one of the following claims, characterised in that the separation promoter or the solubiliser is added in a quantity of 0.1 to 100 g per litre of liquid.
    8. A method according to one of Claims 1 to 4, characterised in that the proportion of spent enzymes in the total quantity of enzymes dispersed in the oil to be degummed is at least 20%.
    EP94203211A 1993-11-19 1994-11-04 Process for degumming vegetable oils with enzymes Expired - Lifetime EP0654527B1 (en)

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    DE4339556A DE4339556C1 (en) 1993-11-19 1993-11-19 Process for degumming vegetable oil by means of enzymes
    DE4339556 1993-11-19

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    EP0654527B1 true EP0654527B1 (en) 1998-01-14

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    JPH07188691A (en) 1995-07-25
    BR9404496A (en) 1995-07-11
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    TW279900B (en) 1996-07-01
    CN1112156A (en) 1995-11-22
    EP0654527A1 (en) 1995-05-24
    ES2111841T3 (en) 1998-03-16
    CN1046760C (en) 1999-11-24
    DE59405028D1 (en) 1998-02-19
    GR3026501T3 (en) 1998-07-31
    CA2136050A1 (en) 1995-05-20
    DE4339556C1 (en) 1995-02-02
    ATE162210T1 (en) 1998-01-15

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