EP0513709B2 - Enzymatisches Verfahren zur Verminderung des Gehaltes an phosphorhaltigen Bestandteilen in pflanzl. u. tierischen Olen - Google Patents

Enzymatisches Verfahren zur Verminderung des Gehaltes an phosphorhaltigen Bestandteilen in pflanzl. u. tierischen Olen Download PDF

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Publication number
EP0513709B2
EP0513709B2 EP92107888A EP92107888A EP0513709B2 EP 0513709 B2 EP0513709 B2 EP 0513709B2 EP 92107888 A EP92107888 A EP 92107888A EP 92107888 A EP92107888 A EP 92107888A EP 0513709 B2 EP0513709 B2 EP 0513709B2
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EP
European Patent Office
Prior art keywords
oil
ppm
phospholipase
vegetable
phosphorus
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Expired - Lifetime
Application number
EP92107888A
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German (de)
English (en)
French (fr)
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EP0513709A3 (en
EP0513709B1 (de
EP0513709A2 (de
Inventor
Erik Aalrust
Wolfgang Beyer
Hans Ottofrickenstein
Georg Penk
Hermann Dr. Plainer
Roland Dr. Reiner
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AB Enzymes GmbH
Roehm GmbH Darmstadt
Original Assignee
Metallgesellschaft AG
Roehm GmbH Darmstadt
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Application filed by Metallgesellschaft AG, Roehm GmbH Darmstadt filed Critical Metallgesellschaft AG
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Classifications

    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11B—PRODUCING, e.g. BY PRESSING RAW MATERIALS OR BY EXTRACTION FROM WASTE MATERIALS, REFINING OR PRESERVING FATS, FATTY SUBSTANCES, e.g. LANOLIN, FATTY OILS OR WAXES; ESSENTIAL OILS; PERFUMES
    • C11B3/00—Refining fats or fatty oils
    • C11B3/003—Refining fats or fatty oils by enzymes or microorganisms, living or dead

Definitions

  • the invention relates to a method for reducing the content of phosphorus-containing components in edible oils by enzymatic degradation and separation of the degradation products.
  • edible oils includes vegetable and animal, preferably pre-degummed oils.
  • the NHP are created by the action of plant enzymes. These are used in the "Alcon process” inactivated by steam treatment of the soy flakes, so that the formation of the NHP is prevented and at the wet degumming of the crude oil the phosphatide content can be almost completely removed.
  • NHP NHP-degummed oil
  • aqueous surfactant solutions are extracted, however, one does not usually get below 30 ppm phosphorus. It is more successful Treatment with acids or alkalis, however, requires many steps.
  • Example 1 is a degummed oil at a temperature of 60 ° C for 48 hours treated with an enzyme solution with 3U phospholipase A activity.
  • the phosphorus content is reduced to 1300 ppm phospholipid. Only after treatment at 105 ° C and 30 Torr with the addition of clay, the phosphorus content can be reduced to 40 ppm phospholipid.
  • Example 3 degummed oil with a phosphorus content of 1638 ppm phospholipid 30 minutes, 1 hour, 2 hours or 4 hours at 50 ° C with a high enzyme concentration and with the addition of 100%, 500%, 1000% or 2000% water, based on the amount of oil treated.
  • the method for treating oil known from JP-A-2-153997 has the Disadvantage that it requires a very long reaction time (48 hours) and the phosphorus content is not sufficiently reduced becomes.
  • the variant in which a further reduction in the phosphorus content possible, in which clay is added to the reaction mixture, also has the disadvantage that the process must be carried out in two stages that the second stage takes place at a relatively high temperature and that a vacuum is applied must become. An additional filtration stage is also required.
  • the heating of the oil to a temperature above 80 ° C is disadvantageous. Oxidation reactions take place in the oil and it discolors what to use as an cooking oil is extremely disadvantageous.
  • the nutritional value of oils partially with a high content of polyunsaturated fatty acids when heated lost.
  • Example 3 The process described in Example 3 has the disadvantage that large enzyme and amounts of water are required, which are determined by the Oil must be separated again. Such conditions are technical and not economically sensible, since huge amounts of waste are generated and there is a risk that stable oil-in-water emulsions form. In addition, with a Except the phosphorus level is not sufficiently lowered, even at a very high one Phospholipase A activity, except for one example where 500% water, based on the oil is used.
  • JP-A 2-49593 describes a similar enzyme treatment of oils, which, however, does not the degumming of the oil, but aimed at the extraction of lysolecithin.
  • the process according to EP-A 328 789 is also about the conversion of soybean oil lecithin to lysolecithin by phospholipase A in the production of mayonnaise-like Products.
  • the aim of the invention is to further reduce the phosphorus and iron content Ingredients in pre-degummed animal or vegetable oils to a phosphorus content below 5 ppm due to enzymatic degradation.
  • the drastic reduction in the phosphorus content is surprising in that the phospholipases A 1 , A 2 and B have a pH optimum in the neutral to weakly alkaline range.
  • the process goal cannot be achieved with phospholipase C or D.
  • the invention therefore relates to a process for reducing the content of phosphorus-containing constituents in animal or vegetable oils by enzymatic degradation by means of a phospholipase.
  • a pre-degummed animal or vegetable oil with a phosphorus content of 50 to 250 ppm is stirred with an organic carboxylic acid and the pH of the mixture formed is adjusted to 4 to 6; an enzyme solution containing phospholipase A 1 , A 2 or B is added to the mixture in a mixing vessel with turbulent stirring and formation of fine droplets, an emulsion containing 0.5 to 5% by weight of water, based on the oil, is formed, which is passed through at least one subsequent reaction vessel with turbulent agitation for a reaction time of 0.1 to 10 hours at temperatures in the range from 20 to 80 ° C., and the treated oil, after separating off the aqueous solution, has a phosphorus content below 5 ppm having.
  • the starting material is therefore preferably pre-degummed oils, especially edible oils, which are generally characterized by a phosphorus content between 50 and 250 ppm. Oils with fluctuating quality can be processed on the same system. Pre-degummed oils, especially sunflower oil; Rapeseed oil and especially soybean oil are used. It is not necessary to dry the oil beforehand.
  • the phospholipase is advantageously used in an aqueous solution which is as fine as possible in the oil is emulsified.
  • the enzymatic reaction is expected to occur at the interface between the oil phase and the Water phase take place. It is mixed intensively, e.g. through turbulent stirring and additionally promoted by the addition of surfactants.
  • the degradation products of the NHP have a higher hydrophilicity and therefore go into the water phase. They are therefore, like the metal ions, simultaneously with the Water phase removed from the oil.
  • Phospholipase A 1 , A 2 and B are known enzymes; (See Pardun, loc.cit. Seiton 135-141). Phospholipase A 1 cleaves the fatty acid ester group on the G 1 atom of a phospholipid molecule. It is found, for example, in rat liver and in the pancreas. An enzyme with phospholipase A 1 activity could be isolated from mold cultures of Rhizopus arrhizus.
  • Phospholipase A 2 formerly also called lecithinase A, cleaves the fatty acid ester group on the C 2 atom of a phospholipid molecule. It occurs, mostly in association with other phospholipases, in almost all animal and plant cells. It is abundant in the snake venom of the rattlesnake and the cobra, as well as in the bee and scorpion venom. Technically, it can be obtained from pancreatic glands after activity-inhibiting accompanying proteins have been broken down with trypsin.
  • Phospholipase B is widespread in nature. It acts on the lysolecithin caused by the action of phospholipase A 1 by splitting off the second fatty acid ester residue. In some cases it is also regarded as a mixture of the phospholipases A 1 and A 2 . It occurs in rat liver and is also produced by some molds, such as Penicillium notatum.
  • Phospholipase A 2 and B are available as commercial products.
  • the use of purified enzymes is generally not necessary for technical applications.
  • a phospholipase preparation which is obtained from ground pancreatic pulp and which contains above all phospholipase A 2 is suitable for the process of the invention.
  • the enzyme is used in amounts of 0.001 to 1% by weight, based on oil.
  • a good distribution of the enzyme in the oil is ensured if it is dissolved in an amount of water of 0.5 to 5% by weight, based on oil, and emulsified in this form in the oil into droplets of less than 10 ⁇ m in diameter (weight average) becomes.
  • Turbulent stirring at radial speeds above 100 cm / s has proven itself. Instead, the oil can be circulated in the reactor using an external centrifugal pump. The enzymatic reaction can also be promoted by means of ultrasound.
  • the enzyme effect is achieved by adding an acid, preferably an organic carboxylic acid, increased, which is added before the enzyme treatment, Citric acid is preferred. It can be in the form of the free acid or in combination as a buffer system with their salt, such as an alkali salt (e.g. sodium citrate), an alkaline earth salt (e.g. calcium citrate) or a Ammonium salt can be used. Suitable amounts are 0.01-1% by weight, based on on oil, optimally 0.1% by weight.
  • the pH is adjusted to a value of 3 to 7, preferably 4 to 6, with the acid. The The optimum is around pH 5: Surprisingly, this pH is also optimal when the Phospholipase is used in the form of an enzyme complex from the pancreas.
  • the pancreatic enzyme complex otherwise has a pH optimum of 8 and is hardly effective at pH 5. Apparently it turns out to be Phase interface where the enzyme action occurs, a higher pH than within the aqueous phase a.
  • emulsifying additives are helpful.
  • Water-soluble emulsifiers in particular those with an HLB value above 9, such as sodium dodecyl sulfate, are suitable. It is effective in an amount of, for example, 0.001% by weight based on oil if it is added to the enzyme solution prior to emulsification in the oil.
  • Protein additives can be advantageous due to a certain surfactant effect.
  • the temperature in the enzyme treatment is not critical. Temperatures are between 20 and 80 ° C suitable. A temperature of 50 ° C is optimal, but it can also be briefly heated to 70 ° C. The duration of treatment depends on the temperature and can be shorter with increasing temperature being held. Times of 0.1 to 10, preferably 1 to 5 hours are usually sufficient.
  • a step program in which the first step at a temperature of 40 to 60 ° C and the second stage is carried out at a higher temperature in the range of 50 to 80 ° C. For example, the mixture is first stirred at 50 ° C. for 3 hours, then at 75 ° C. for one hour.
  • the enzyme solution together with the degradation products contained therein the NHP is separated from the oil phase, preferably by centrifugation. Because the enzymes get through a high stability and the amount of degradation products absorbed is low same enzyme solution can be reused several times.
  • the method is preferably carried out continuously.
  • the oil is emulsified in a first mixing vessel with the enzyme solution, in one or several subsequent reaction vessels, if necessary with increasing temperature, under turbulent Movement allowed to react, and then the aqueous enzyme solution separated in a centrifuge.
  • a part of it can be running replaced with fresh enzyme solution and the rest returned to the process.
  • the oil obtained has a phosphorus content below 5 ppm and is therefore for physical refining suitable for cooking oil. Thanks to the low iron content that has been achieved, it has good preconditions for Refining to achieve high resistance to oxidation.
  • 1 l wet degummed soybean oil with a residual phosphorus content of 110 ppm is heated to 75 ° C in a round bottom flask. With vigorous stirring with a 5 cm diameter paddle stirrer at 700 rpm, 10 ml of water containing 1 g of citric acid are added and stirring is continued for 1 hour. The mixture is then cooled to 40 ° C. and a solution of 0.1 g of phospholipase A 2 of the quality given in Example 1 and 50 mg of calcium chloride in 20 ml of 0.1 molar acetate buffer pH 5.5 are added. After a further 5 hours of intensive stirring, the water phase is centrifuged off. The oil obtained contains 2 ppm P and is suitable for physical refining.
  • Example 2 The procedure according to Example 1 is repeated with the difference that 1 g of a pancreatic preparation (pancreatin, 800 phospholipase units / g) is used instead of phospholipase A 2 .
  • the preparation contains phospholipase A 2 , proteinase, amylase, lipase.
  • the phosphorus content drops below 1 ppm. Due to the influence of lipase, there is only a slight increase in the acid number from 0.91 to 1.49.
  • 9 l wet-degummed rapeseed oil with a phosphorus content of 72 ppm is mixed with a solution of 8.6 g citric acid in 250 ml water and heated to 60 ° C.
  • the mixture is homogenized by circulating it once per minute using an external centrifugal pump.
  • the pH of the aqueous phase is adjusted to 5.0 with 30 g of 10% sodium hydroxide solution.
  • 9 g of phospholipase A 2 with an activity of 400 U / g are added together with a little calcium chloride and the mixture is circulated for 3 hours at 60 ° C. in the manner indicated. After centrifugation, a phosphorus content of 3 ppm is found.

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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)
  • Edible Oils And Fats (AREA)
  • Fats And Perfumes (AREA)
  • Preparation Of Compounds By Using Micro-Organisms (AREA)
  • Enzymes And Modification Thereof (AREA)
EP92107888A 1991-05-16 1992-05-11 Enzymatisches Verfahren zur Verminderung des Gehaltes an phosphorhaltigen Bestandteilen in pflanzl. u. tierischen Olen Expired - Lifetime EP0513709B2 (de)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE4115938A DE4115938A1 (de) 1991-05-16 1991-05-16 Enzymatisches verfahren zur verminderung des gehaltes an phosphorhaltigen bestandteilen in pflanzlichen und tierischen oelen
DE4115938 1991-05-16

Publications (4)

Publication Number Publication Date
EP0513709A2 EP0513709A2 (de) 1992-11-19
EP0513709A3 EP0513709A3 (en) 1992-12-30
EP0513709B1 EP0513709B1 (de) 1995-03-29
EP0513709B2 true EP0513709B2 (de) 1999-10-06

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Country Status (15)

Country Link
US (1) US5264367A (da)
EP (1) EP0513709B2 (da)
CN (1) CN1034587C (da)
AR (1) AR245193A1 (da)
AT (1) ATE120482T1 (da)
BR (1) BR9201859A (da)
CA (1) CA2068933C (da)
DE (2) DE4115938A1 (da)
DK (1) DK0513709T4 (da)
ES (1) ES2072043T5 (da)
GR (2) GR3015920T3 (da)
HU (1) HU213754B (da)
PL (1) PL170548B1 (da)
RU (1) RU2033422C1 (da)
TW (1) TW203625B (da)

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US7807398B2 (en) 2003-01-17 2010-10-05 Danisco A/S Method of using lipid acyltransferase
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JP2794574B2 (ja) * 1988-08-11 1998-09-10 昭和産業株式会社 リゾレシチンの製造方法
JP2709736B2 (ja) * 1988-08-11 1998-02-04 昭和産業株式会社 油脂の精製方法
JP2701387B2 (ja) * 1988-12-06 1998-01-21 三菱化学株式会社 記録液
JPH0738771B2 (ja) * 1989-01-17 1995-05-01 花王株式会社 液状食用油組成物

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US7781001B2 (en) 1998-07-21 2010-08-24 Danisco A/S Foodstuff
US8163315B2 (en) 1998-07-21 2012-04-24 Danisco A/S Foodstuff
US7718204B2 (en) 1998-07-21 2010-05-18 Danisco A/S Foodstuff
US7972638B2 (en) 1998-07-21 2011-07-05 Danisco A/S Foodstuff
US8278062B2 (en) 2003-01-14 2012-10-02 Dupont Nutrition Biosciences Aps Method of using lipid acyltransferase
US7807398B2 (en) 2003-01-17 2010-10-05 Danisco A/S Method of using lipid acyltransferase
US8003095B2 (en) 2003-01-17 2011-08-23 Danisco A/S Method of using lipid acyltransferase
US7955813B2 (en) 2003-01-17 2011-06-07 Danisco, A/S Method of using lipid acyltransferase
US7955814B2 (en) 2003-01-17 2011-06-07 Danisco A/S Method
US7713727B2 (en) 2003-12-19 2010-05-11 Bunge Oils, Inc. Process for improving enzymatic degumming of vegetable oils and reducing fouling of downstream processing equipment
US7906307B2 (en) 2003-12-24 2011-03-15 Danisco A/S Variant lipid acyltransferases and methods of making
US7718408B2 (en) 2003-12-24 2010-05-18 Danisco A/S Method
US8030044B2 (en) 2003-12-24 2011-10-04 Danisco A/S Lipid acyltransferases
EP3190182A1 (en) 2004-03-08 2017-07-12 DSM IP Assets B.V. Phospholipases, nucleic acids encoding them and methods for making and using them
US8012732B2 (en) 2004-03-12 2011-09-06 Danisco A/S Fungal lypolytic and amylase enzyme composition and methods using the same
US8535900B2 (en) 2004-07-16 2013-09-17 Dupont Nutrition Biosciences Aps Lipolytic enzyme uses thereof in the food industry
US7666618B2 (en) 2004-07-16 2010-02-23 Danisco A/S Lipolytic enzyme: uses thereof in the food industry
US8192782B2 (en) 2004-07-16 2012-06-05 Danisco A/S Enzymatic oil-degumming method
US8889371B2 (en) 2004-07-16 2014-11-18 Dupont Nutrition Biosciences Aps Lipolytic enzyme: uses thereof in the food industry
US7993876B2 (en) 2006-10-02 2011-08-09 Ab Enzymes Gmbh DNA encoding phospholipases and methods of using same
US7960150B2 (en) 2007-01-25 2011-06-14 Danisco A/S Production of a lipid acyltransferase from transformed Bacillus licheniformis cells
US8652809B2 (en) 2007-08-17 2014-02-18 Dupont Nutrition Biosciences Aps Method for producing ultra-heat treatment milk
US8313918B2 (en) 2008-08-29 2012-11-20 Bunge Oils, Inc. Hydrolases, nucleic acids encoding them and methods to produce triglycerides
US8349578B2 (en) 2008-08-29 2013-01-08 Bunge Oils, Inc. Hydrolases, nucleic acids encoding them and methods for biocatalytic synthesis of structured lipids
US8541191B2 (en) 2008-08-29 2013-09-24 Bunge Oils, Inc. Hydrolases, nucleic acids encoding them and methods for biocatalytic synthesis of structured lipids
DE102009006920A1 (de) 2009-02-02 2010-08-05 Lurgi Gmbh Verfahren, Anlage und Mittel zur Vermeidung von Sterolglycoside enthaltenden Ausfällungen bei der Herstellung von Fettsäurealkylestern
DE102009006921A1 (de) 2009-02-02 2010-08-05 Lurgi Gmbh Verfahren, Anlage und Mittel zur Vermeidung von Sterolglycoside enthaltenden Ausfällungen bei der Herstellung von Fettsäurealkylestern
WO2011046812A1 (en) 2009-10-16 2011-04-21 Verenium Corporation Phospholipases, nucleic acids encoding them and methods for making and using them
US9512382B2 (en) 2009-10-16 2016-12-06 Bunge Global Innovation, Llc Oil degumming methods
DE102010055159A1 (de) 2010-12-18 2012-06-21 Lurgi Gmbh Verfahren zur enzymatischen Reinigung von Ölen pflanzlicher oder tierischer Herkunft

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EP0513709A3 (en) 1992-12-30
CA2068933A1 (en) 1992-11-17
CA2068933C (en) 1995-12-19
ES2072043T3 (es) 1995-07-01
HU213754B (en) 1997-09-29
CN1034587C (zh) 1997-04-16
TW203625B (da) 1993-04-11
RU2033422C1 (ru) 1995-04-20
ATE120482T1 (de) 1995-04-15
HUT64578A (en) 1994-01-28
PL294543A1 (en) 1993-01-25
US5264367A (en) 1993-11-23
EP0513709B1 (de) 1995-03-29
EP0513709A2 (de) 1992-11-19
DE59201753D1 (de) 1995-05-04
GR3015920T3 (en) 1995-07-31
ES2072043T5 (es) 2000-02-01
HU9201630D0 (en) 1992-08-28
BR9201859A (pt) 1993-01-05
GR3031804T3 (en) 2000-02-29
PL170548B1 (pl) 1996-12-31
DK0513709T4 (da) 1999-12-27
CN1066679A (zh) 1992-12-02
AR245193A1 (es) 1993-12-30
DK0513709T3 (da) 1995-07-24
DE4115938A1 (de) 1992-11-19

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