EP0654527A1 - Process for degumming vegetable oils with enzymes - Google Patents

Process for degumming vegetable oils with enzymes Download PDF

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Publication number
EP0654527A1
EP0654527A1 EP94203211A EP94203211A EP0654527A1 EP 0654527 A1 EP0654527 A1 EP 0654527A1 EP 94203211 A EP94203211 A EP 94203211A EP 94203211 A EP94203211 A EP 94203211A EP 0654527 A1 EP0654527 A1 EP 0654527A1
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EP
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Prior art keywords
oil
enzymes
degumming
degummed
sludge
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EP94203211A
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German (de)
French (fr)
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EP0654527B1 (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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Roehm GmbH Chemische Fabrik
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 process for degumming vegetable oil, adjusting the vegetable oil to a pH of 3 to 6, dispersing an aqueous enzyme solution in the oil which contains one of the enzymes phospholipase A1, A2 or B, the enzymes in the oil with stirring is allowed to act in a degumming reactor at temperatures of 20 to 90 ° C. and oil which has been degummed from the liquid drawn off from the degumming reactor is separated off.
  • the object of the invention is to at least partially reuse the enzymes used in the degumming process in the process mentioned at the beginning. According to the invention, this is done by adding a separating agent or a solubilizer to the liquid drawn off from the degumming reactor at temperatures of 20 to 90 ° C. before or after separating the degummed oil and obtaining an aqueous, used enzyme-containing, largely sludge-free solution which is obtained at least partially leads back to the degumming reactor and dispersed in the oil to be degummed, the proportion used, recycled enzymes in the total amount of the enzymes dispersed in the oil is at least 10%. For reasons of cost, it is advantageous if the proportion of used, recycled enzymes in the total amount of the enzymes dispersed in the oil is at least 20% or even better, at least 50%.
  • a variant of the second way is to add a solubilizer to the oily liquid coming out of the degumming reactor and then to separate the degummed oil from the liquid, e.g. in a centrifuge.
  • a solubilizer to the oily liquid coming out of the degumming reactor and then to separate the degummed oil from the liquid, e.g. in a centrifuge.
  • an aqueous, largely sludge-free phase is obtained which contains the used enzymes. All or part of this aqueous phase can be returned to the degumming reactor without further treatment in order to mix it with the oil to be degummed.
  • solubilizer or separation aid to be used can vary within a wide range; it is usually 0.1 to 100 g / l of liquid. An excess of solubilizers or release aids is not a problem.
  • lecithin To degum the edible oils with the help of enzymes, it is advisable to first degum the oil with water to obtain lecithin.
  • the phospholipases A1, A2 or B attack lecithin in the oil, so that it is expedient to lower the phosphorus content of the oil in the range from 50 to 500 ppm by pre-degumming, for example with water. This pretreatment is especially recommended for oils rich in lecithin, such as soybean oil.
  • the vegetable oil to be completely degummed comes from the line (1) according to Fig. 1, it is first metered from the storage container (2) into an aqueous acidic solution, e.g. Citric acid, and from the storage container (3) an aqueous alkaline solution, e.g. Sodium hydroxide solution in such amounts that the oil with a pH of 3 to 6, preferably about 5, enters the first disperser (5) through line (4).
  • An oil-water emulsion is produced in the disperser (5) and is passed through the line (6) into a retention tank (7).
  • the emulsion flows through line (8) to an addition point (9) for an aqueous enzyme solution which comes from the storage vessel (10). 10 to 100 mg of enzyme solution are added per liter of oil.
  • the enzymes dissolved in water are the phospholipase of type A1, A2 or B, for example with an activity of the solution of 10,000 lecitase units per milliliter.
  • the enzyme-containing oil is passed through a further disperser (11) and then passes through line (12) to a degumming reactor (13).
  • the reactor (13) consists of 1 to 5 floors, each floor having a stirring device (14) and a heater (15). There is a connecting line (16) between adjacent floors.
  • the reactor (13) shown has three levels (13a), (13b) and (13c) through which the oil to be treated flows from top to bottom with a certain dwell time in each level.
  • Different treatment temperatures can be set on each floor, it being recommended to work with the lowest temperature on the top floor (13a) and with the highest temperature on the bottom floor (13c).
  • the treatment temperatures in the reactor (13) are in the range from 20 to 90 ° C. with a total residence time in the reactor (13) of usually 3 to 5 hours.
  • the treated oil leaves the degumming reactor (13) through line (17) and is fed to a centrifuge (18).
  • degummed oil is obtained as a product and is discharged in line (19).
  • the enzyme-containing aqueous sludge phase in the line (20) is added from the storage container (21) separation aid and the whole thing is stirred intensively in the disperser (22).
  • the stirred phase in line (23) is placed in a retention tank (24), which is preferably provided with a stirring device (25).
  • the temperatures are in the range from 30 to 85 ° C. and preferably around 60 ° C., and retention times in the range from 3 to 60 minutes are ensured.
  • the enzymes adsorbed on the phosphatide sludge are detached and transferred to the water phase.
  • the liquid is transferred from the retention tank (24) to a filtration device (26), which preferably works as microfiltration. Alternatively, centrifugation can also be carried out at this point. This separates the phosphatide sludge, which is removed in line (27).
  • the aqueous phase containing the used enzymes is in line (28) withdrawn and fed to the storage container (10) for reuse. If necessary, fresh enzyme solution comes from the line (29). In this way, it is possible to reuse the used enzymes for degumming the oil and thus significantly reduce the operating costs of the process.
  • the method according to FIG. 2 corresponds between lines (1) and (17) with the method previously described together with FIG. 1.
  • the water-phosphatide sludge-oil mixture coming from the degumming reactor (13) is fed through line (17) to the centrifuge (18), from which oil degummed in line (19) is drawn off.
  • the enzyme-containing water-sludge phase of the line (30) is added from the storage container (31) solubilizer and the whole thing is stirred in the retention tank (32). This creates an aqueous, enzyme-containing solution which is returned through the line (28) to the storage container (10) for reuse; an excess of the solution can be removed in line (29).
  • Rapeseed oil which has been degummed with water, is degummed in various ways with enzymes in a laboratory apparatus with a single-stage reactor (13) corresponding to the drawing.
  • Examples 1, 5 and 6 are comparative examples in which the method according to the invention is not used.
  • the degummed rapeseed oil in line (19) has a residual phosphorus content of 6 ppm, the volume of the water-sludge phase is 370 ml.
  • the phosphorus content is a measure of the degree of degumming, well degummed oil has one Residual P content of less than 10 ppm.
  • Example 1 is repeated for the procedure according to the invention according to FIG. 2, 3 g / l TWEEN 80 being added to the water-sludge phase of line (30) is added and the liquid is stirred intensively for 10 min in a disperser (Ultra-Turrax). This gives a sludge-free, enzyme-containing solution without suspended particles, which is returned via line (28) to the storage container (10). Fresh enzymes are not added.
  • the degummed oil from line (19) has a residual phosphorus content of 5 ppm per pass.
  • Example 1 is repeated for the procedure according to the invention according to FIG. 2, 2.5 g of Tween 80 per liter of mixture being added via line (33) to the liquid mixture emerging from the enzyme reactor via line 17 and the mixture being separated in the centrifuge 18 . A largely sludge-free, enzyme-containing solution is thus obtained, which is fed to the storage container (10) via line (34) and line (28). Fresh enzymes are not added.
  • the degummed oil from line (19) has a residual phosphorus content of 5 ppm.
  • example 1 is repeated, adding 2 g of TWEEN 80 (manufacturer DuPont) per liter to the water-sludge phase of the line (20) and the liquids in a disperser (22) (ultra Turrax) homogenized. After a dwell time of 10 minutes, the phosphatide sludge is separated from the aqueous enzyme solution by centrifugation. The enzyme solution is returned via line (28) to the storage container (10), with fresher addition No enzyme solution whatsoever. The residual phosphorus content in the degummed oil in line (19) is 5 ppm.
  • Example 4 is modified in such a way that, instead of the aqueous enzyme solution, the phosphatide sludge obtained after centrifugation in line (27) and pretreated with TWEEN 80 is mixed with the oil in line (8) via the metering point (9). It is shown that this phosphatide sludge is ineffective for improving degumming since it has no enzyme activity.
  • Example 4 The procedure is as in Example 4, but without recycling the aqueous enzyme solution in line (28).
  • the phosphatide sludge from line (27) is now resuspended in distilled water and homogenized for 10 minutes at 60 ° C. using a disperser (Ultra-Turrax).
  • the sludge phase is then separated off by centrifugation and the aqueous phase which is produced at the same time is returned to the metering point (9).
  • Fresh enzyme solution is no longer added.
  • a residual P content of 49 ppm is found in the rapeseed oil, which proves that no enzymes have been recovered from the phosphatide sludge from line (27).
  • Example 1 is repeated for the procedure according to the invention, with 2 g of alginate protan (manufacturer: Pronova biopolymer, Norway) being added to the water-sludge phase of the line (20) per liter and the liquids in a disperser (22) (Ultra -Turrax) homogenized, cf. Fig. 1. After a The phosphatide sludge is separated from the aqueous enzyme solution by centrifugation for 10 minutes. The enzyme solution is returned to the storage container (10). Without the addition of fresh enzymes, the residual phosphorus content in the degummed oil in line (19) is 8 ppm.
  • alginate protan manufactured by Pronova biopolymer, Norway

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  • Chemical & Material Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Microbiology (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Biochemistry (AREA)
  • Wood Science & Technology (AREA)
  • Organic Chemistry (AREA)
  • Fats And Perfumes (AREA)
  • Edible Oils And Fats (AREA)
  • Preparation Of Compounds By Using Micro-Organisms (AREA)
  • Enzymes And Modification Thereof (AREA)
  • Treatment Of Sludge (AREA)

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 process for degumming vegetable oil, adjusting the vegetable oil to a pH of 3 to 6, dispersing an aqueous enzyme solution in the oil which contains one of the enzymes phospholipase A1, A2 or B, the enzymes in the oil with stirring is allowed to act in a degumming reactor at temperatures of 20 to 90 ° C. and oil which has been degummed from the liquid drawn off from the degumming reactor is separated off.

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. In etwas anderer Weise erfolgt die Entschleimung von Speiseölen beim Verfahren gemäß EP-B-0 122 727, wobei man mit hydrolysierten Phosphatiden arbeitet. Die in diesem Patent genannten Phosphatide, z.B. Lecithin, können im Prozeß wiedergewonnen und zurückgeführt werden.Such a method is known from EP-A-0 513 709. In the process described, however, it remains open how to recover the used enzymes after degumming the oil so that they can be reused in the process. The degumming of edible oils takes place in a somewhat different way in the process according to EP-B-0 122 727, one working with hydrolyzed phosphatides. The phosphatides mentioned in this patent, e.g. Lecithin can be recovered and recycled in the process.

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 object of the invention is to at least partially reuse the enzymes used in the degumming process in the process mentioned at the beginning. According to the invention, this is done by adding a separating agent or a solubilizer to the liquid drawn off from the degumming reactor at temperatures of 20 to 90 ° C. before or after separating the degummed oil and obtaining an aqueous, used enzyme-containing, largely sludge-free solution which is obtained at least partially leads back to the degumming reactor and dispersed in the oil to be degummed, the proportion used, recycled enzymes in the total amount of the enzymes dispersed in the oil is at least 10%. For reasons of cost, it is advantageous if the proportion of used, recycled enzymes in the total amount of the enzymes dispersed in the oil is at least 20% or even 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 separation 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 way: At a temperature in the range from 20 to 90 ° C., a water-sludge phase is added to a solubilizer 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 second way is to add a solubilizer to the oily liquid coming out of the degumming reactor and then to separate the degummed oil from the liquid, e.g. in a centrifuge. In addition to the degummed oil, an aqueous, largely sludge-free phase is obtained which contains the used enzymes. All or part of this aqueous phase can be returned to the degumming reactor without further treatment in order to mix it 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 C₉ to C₁₁ 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 or separation aid to be used can vary within a wide range; it is usually 0.1 to 100 g / l of liquid. An excess of solubilizers or release aids is not a problem.

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.To degum the edible oils with the help of enzymes, it is advisable to first degum the oil with water to obtain lecithin. The phospholipases A1, A2 or B attack lecithin in the oil, so that it is expedient to lower the phosphorus content of the oil in the range from 50 to 500 ppm by pre-degumming, for example with water. This pretreatment is especially recommended for oils rich in lecithin, such as soybean oil.

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 Losung, 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 from the line (1) according to Fig. 1, it is first metered from the storage container (2) into an aqueous acidic solution, e.g. Citric acid, and from the storage container (3) an aqueous alkaline solution, e.g. Sodium hydroxide solution in such amounts that the oil with a pH of 3 to 6, preferably about 5, enters the first disperser (5) through line (4). An oil-water emulsion is produced in the disperser (5) and is passed through the line (6) into a retention tank (7).

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 residence time in the range from 1 to 30 minutes, the emulsion flows through line (8) to an addition point (9) for an aqueous enzyme solution which comes from the storage vessel (10). 10 to 100 mg of enzyme solution are added per liter of oil. The enzymes dissolved in water are the phospholipase of type A1, A2 or B, for example with an activity of the solution of 10,000 lecitase units per milliliter. The enzyme-containing oil is passed through a further disperser (11) and then passes through line (12) to a degumming reactor (13). The reactor (13) consists of 1 to 5 floors, each floor having a stirring device (14) and a heater (15). There is a connecting line (16) between adjacent floors. The one in the drawing The reactor (13) shown has three levels (13a), (13b) and (13c) through which the oil to be treated flows from top to bottom with a certain dwell time in each level. Different treatment temperatures can be set on each floor, it being recommended to work with the lowest temperature on the top floor (13a) and with the highest temperature on the bottom floor (13c). The treatment temperatures in the reactor (13) are in the range from 20 to 90 ° C. with a total residence time in the 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 is fed to a centrifuge (18). In the centrifuge, degummed oil is obtained as a product and is discharged in line (19). The enzyme-containing aqueous sludge phase in the line (20) is added from the storage container (21) separation aid and the whole thing is stirred intensively in the disperser (22). Subsequently, the stirred phase in line (23) is placed in a retention tank (24), which is preferably provided with a stirring device (25). In the retention tank (24), the temperatures are in the range from 30 to 85 ° C. and preferably around 60 ° C., and retention times in the range from 3 to 60 minutes are ensured. Under the action of the separation aid, the enzymes adsorbed on the phosphatide sludge are detached and transferred to the water phase. To separate the water phase containing the enzyme, the liquid is transferred from the retention tank (24) to a filtration device (26), which preferably works as microfiltration. Alternatively, centrifugation can also be carried out at this point. This separates the phosphatide sludge, which is removed in line (27). The aqueous phase containing the used enzymes is in line (28) withdrawn and fed to the storage container (10) for reuse. If necessary, fresh enzyme solution comes from the line (29). In this way, it is possible to reuse the used enzymes for degumming the oil and thus significantly reduce the operating costs of the process.

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.The method according to FIG. 2 corresponds between lines (1) and (17) with the method previously described together with FIG. 1. 2, the water-phosphatide sludge-oil mixture coming from the degumming reactor (13) is fed through line (17) to the centrifuge (18), from which oil degummed in line (19) is drawn off. The enzyme-containing water-sludge phase of the line (30) is added from the storage container (31) solubilizer and the whole thing is stirred in the retention tank (32). This creates an aqueous, enzyme-containing solution which is returned through the line (28) to the storage container (10) for reuse; an excess of the solution can be removed in line (29). In place of the retention tank (32), 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 to add the solubilizer through the dashed line (33) to the water-sludge-oil mixture of line (17) before the centrifuge (18) in the process of FIG. 2, the centrifuge also being used as a mixing device serves. In addition to the degummed oil from line (19), an aqueous, enzyme-containing solution comes out of the centrifuge (18), which is wholly or partly passed through lines (30), (34) and (28) into the storage container (10) for reuse. returns. The reservoir (31) and the retention tank (32) can be 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.Rapeseed oil, which has been degummed with water, is degummed in various ways with enzymes in a laboratory apparatus with a single-stage reactor (13) corresponding to the drawing. Examples 1, 5 and 6 are comparative examples in which the method according to the invention is not used.

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 of pre-degummed rapeseed oil are mixed with 60 ml of an aqueous 10% citric acid solution at 60 ° C; 48 ml of an aqueous 5% NaOH solution are added to adjust the pH to 5.0. After a residence time of 30 minutes, 205 ml of an aqueous phospholipase A2 solution with 3800 lecitase units are added to the reaction mixture. After a treatment period of 5 hours at 60 ° C. with thorough mixing, the water-oil emulsion is separated into an oil and a water-sludge phase by means of a centrifuge (18). The degummed rapeseed oil in line (19) has a residual phosphorus content of 6 ppm, the volume of the water-sludge phase is 370 ml. The phosphorus content is a measure of the degree of degumming, well degummed oil has one 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.Example 1 is repeated for the procedure according to the invention according to FIG. 2, 3 g / l TWEEN 80 being added to the water-sludge phase of line (30) is added and the liquid is stirred intensively for 10 min in a disperser (Ultra-Turrax). This gives a sludge-free, enzyme-containing solution without suspended particles, which is returned via line (28) to the storage container (10). Fresh enzymes are not added. The degummed oil from line (19) has a residual phosphorus content of 5 ppm per pass.

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.Example 1 is repeated for the procedure according to the invention according to FIG. 2, 2.5 g of Tween 80 per liter of mixture being added via line (33) to the liquid mixture emerging from the enzyme reactor via line 17 and the mixture being separated in the centrifuge 18 . A largely sludge-free, enzyme-containing solution is thus obtained, which is fed to the storage container (10) via line (34) and line (28). Fresh enzymes are not added. The degummed oil from line (19) has a 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.1, example 1 is repeated, adding 2 g of TWEEN 80 (manufacturer DuPont) per liter to the water-sludge phase of the line (20) and the liquids in a disperser (22) (ultra Turrax) homogenized. After a dwell time of 10 minutes, the phosphatide sludge is separated from the aqueous enzyme solution by centrifugation. The enzyme solution is returned via line (28) to the storage container (10), with fresher addition No enzyme solution whatsoever. The residual phosphorus content in the degummed oil in 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 in such a way that, instead of the aqueous enzyme solution, the phosphatide sludge obtained after centrifugation in line (27) and pretreated with TWEEN 80 is mixed with the oil in line (8) via the metering point (9). It is shown that this phosphatide sludge is ineffective for improving degumming since 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 recycling the aqueous enzyme solution in line (28). The phosphatide sludge from line (27) is now resuspended in distilled water and homogenized for 10 minutes at 60 ° C. using a disperser (Ultra-Turrax). The sludge phase is then separated off by centrifugation and the aqueous phase which is produced at the same time is returned to the metering point (9). Fresh enzyme solution is no longer added. After a treatment period of 5 hours, a residual P content of 49 ppm is found in the rapeseed oil, which proves that no enzymes have been recovered from the phosphatide sludge from line (27).

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.Example 1 is repeated for the procedure according to the invention, with 2 g of alginate protan (manufacturer: Pronova biopolymer, Norway) being added to the water-sludge phase of the line (20) per liter and the liquids in a disperser (22) (Ultra -Turrax) homogenized, cf. Fig. 1. After a The phosphatide sludge is separated from the aqueous enzyme solution by centrifugation for 10 minutes. The enzyme solution is returned to the storage container (10). Without the addition of fresh enzymes, the residual phosphorus content in the degummed oil in line (19) is 8 ppm. The same result is achieved with 2 g / l hydrolyzed gelatin (manufacturer: Gibco, Scotland) instead of alginate protane. If 2 g / l of water-soluble starch (manufacturer: Merck, Darmstadt) is used as a separating aid, a residual phosphorus content of 2 ppm is achieved in the degummed oil.

Claims (8)

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, dadurch gekennzeichnet, 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.Process for degumming vegetable oil, adjusting the vegetable oil to a pH of 3 to 6, dispersing an aqueous enzyme solution in the oil containing one of the enzymes phospholipase A1, A2 or B, the enzymes in the oil with stirring at temperatures of 20 up to 90 ° C in a degumming reactor and oil removed from the degummed liquid removed from the degumming reactor, characterized in that the liquid drawn off from the degumming reactor at temperatures of 20 to 90 ° C before or after the degummed oil has been separated off is a separating aid or adds a solubilizer and obtains a largely sludge-free solution containing used enzymes, which is at least partially returned to the degumming reactor and dispersed in the oil to be degummed, the proportion of used, recycled enzymes in the total amount of enzymes dispersed in the oil being at least 10% is . Verfahren nach Anspruch 1, dadurch gekennzeichnet, daß man aus der aus dem Entschleimungsreaktor abgezogenen Flüssigkeit entschleimtes Öl abtrennt und dabei eine Wasser-Schlamm-Phase gewinnt, in welcher man bei Temperaturen im Bereich von 20 bis 90°C Trennhilfsmittel dispergiert, wobei man die Wasser-Schlamm-Phase in einem Verweilbehälter rührt, aus der gerührten Wasser-Schlamm-Phase eine wäßrige, weitgehend schlammfreie, gebrauchte Enzyme enthaltende Phase abtrennt und mindestens teilweise vor den Entschleimungsreaktor zurückführt.A method according to claim 1, characterized in that degummed oil is removed from the liquid drawn off from the degumming reactor and thereby a water-sludge phase is obtained in which dispersing aids are dispersed at temperatures in the range from 20 to 90 ° C, the water -Sludge phase stirred in a retention tank, an aqueous, largely sludge-free, used enzyme-containing phase is separated from the stirred water-sludge phase and at least partially returned to the degumming reactor. Verfahren nach Anspruch 1, dadurch gekennzeichnet, daß man aus der aus dem Entschleimungsreaktor abgezogenen Flüssigkeit entschleimtes Öl abtrennt und dabei eine Wasser-Schlamm-Phase gewinnt, welcher man bei Temperaturen im Bereich von 20 bis 90°C Lösungsvermittler zugibt und unter Rühren eine wäßrige, gebrauchte Enzyme enthaltende, weitgehend schlammfreie Lösung erzeugt, die man mindestens teilweise vor den Entschleimungsreaktor zurückführt.A process as claimed in claim 1, characterized in that degummed oil is removed from the liquid drawn off from the degumming reactor and a water-sludge phase is obtained, which is added to solubilizers at temperatures in the range from 20 to 90 ° C and an aqueous, Generates used, largely sludge-free solution containing enzymes, which is at least partially returned to the degumming reactor. Verfahren nach Anspruch 1, dadurch gekennzeichnet, daß man der aus dem Entschleimungsreaktor abgezogenen Flüssigkeit Lösungsvermittler zugibt, die Flüssigkeit durch eine Trenneinrichtung führt und entschleimtes Öl und getrennt davon eine wäßrige, gebrauchte Enzyme enthaltende, weitgehend schlammfreie Lösung erhält, wobei man die Lösung mindestens teilweise vor den Entschleimungsreaktor zurückführt.Process according to Claim 1, characterized in that solubilizers are added to the liquid drawn off from the degumming reactor, the liquid is passed through a separating device and degummed oil and, separately therefrom, an aqueous, used enzyme-containing, largely sludge-free solution is obtained, the solution being at least partially pre- returns the degumming reactor. Verfahren nach Anspruch 1 oder einem der folgenden, dadurch gekennzeichnet, daß man als Trennhilfsmittel und Lösungsvermittler a) Polyethylen-Zucker-Fettsäureester, b) Rizinusethoxylat, c) ethoxyliertes Palmitat, d) ethoxylierter synthetischer primärer Alkohol, e) ethoxylierter Laurylalkohol, f) ethoxylierter Talgfettalkohol oder g) hydrophobes Tensid verwendet.Process according to Claim 1 or one of the following, characterized in that the separation aids and solubilizers are used a) polyethylene sugar fatty acid esters, b) castor ethoxylate, c) ethoxylated palmitate, d) ethoxylated synthetic primary alcohol, e) ethoxylated lauryl alcohol, f) ethoxylated tallow fatty alcohol or g) hydrophobic surfactant used. Verfahren nach einem der Ansprüche 1 bis 5, dadurch gekennzeichnet, daß man als Trennhilfsmittel mindestens h) eine anionaktive Verbindung oder i) eine nichtionogene Verbindung verwendet.Method according to one of claims 1 to 5, characterized in that at least one as a separation aid h) an anionic compound or i) a non-ionic compound used. Verfahren nach Anspruch 1 oder einem der folgenden, dadurch gekennzeichnet, daß man das Trennhilfsmittel oder den Lösungsvermittler pro Liter Flüssigkeit in einer Menge von 0,1 bis 100 g zugibt.Process according to Claim 1 or one of the following, characterized in that the separating aid or the solubilizer is added per liter of liquid in an amount of 0.1 to 100 g. Verfahren nach einem der Ansprüche 1 bis 4, dadurch gekennzeichnet, daß der Anteil gebrauchter Enzyme in der Gesamtmenge der im zu entschleimenden Öl dispergierten Enzyme mindestens 20 % beträgt.Method according to one of claims 1 to 4, characterized in that the proportion of used enzymes in the total amount of the enzymes dispersed in the oil to be degummed is at least 20%.
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US6103505A (en) * 1996-12-09 2000-08-15 Novo Nordisk A/S Method for reducing phosphorus content of edible oils
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US7588925B2 (en) 2002-05-21 2009-09-15 Dsm Ip Assets B.V. Phospholipases and uses thereof
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US7588925B2 (en) 2002-05-21 2009-09-15 Dsm Ip Assets B.V. Phospholipases and uses thereof
US7838274B2 (en) 2002-05-21 2010-11-23 Dsm Ip Assets B.V. Phospholipases and uses thereof
US8956853B2 (en) 2007-01-30 2015-02-17 Bunge Oils, Inc. Enzymatic degumming utilizing a mixture of PLA and PLC phospholipases
US8460905B2 (en) 2007-09-11 2013-06-11 Bunge Oils, Inc. Enzymatic degumming utilizing a mixture of PLA and PLC phospholipases with reduced reaction time
US8241876B2 (en) 2008-01-07 2012-08-14 Bunge Oils, Inc. Generation of triacylglycerols from gums
US8541211B2 (en) 2008-01-07 2013-09-24 Bunge Oils, Inc. Generation of triacylglycerols
US11142492B2 (en) 2019-08-26 2021-10-12 Wisconsin Alumni Research Foundation Methods of isolating phenols from phenol-containing media
US11548845B2 (en) 2019-08-26 2023-01-10 Wisconsin Alumni Research Foundation Methods of isolating phenols from phenol-containing media

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DK0654527T3 (en) 1998-03-16
GR3026501T3 (en) 1998-07-31

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