EP3158036A1

EP3158036A1 - Method for degumming compositions containing triglyceride

Info

Publication number: EP3158036A1
Application number: EP15728894.5A
Authority: EP
Inventors: Ulrich Sohling; Kirstin Suck; Karin OBERPRIELER; Marion ROSSBAUER
Original assignee: Clariant Produkte Deutschland GmbH
Current assignee: Clariant Produkte Deutschland GmbH
Priority date: 2014-06-17
Filing date: 2015-06-17
Publication date: 2017-04-26
Also published as: RU2017101208A3; CN106459830A; CA2952291A1; BR112016029165A2; WO2015193367A1; RU2017101208A; AR100873A1; US20170158984A1; RU2680688C2

Abstract

The present invention relates to a method for degumming compositions containing triglyceride with addition of a solubilizer, and to a composition containing triglyceride which has been degummed by the method according to the invention.

Description

Process for degumming triglyceride-containing

compositions

The present invention relates to a method for

Degumming of triglyceride-containing compositions with the addition of a solubilizer and a triglyceride-containing composition which has been degummed by the process according to the invention.

Due to the worldwide increase in consumption of edible oil and the increasing use of vegetable oils as

Raw materials for the chemical industry and as fuel there is a constant need for degumming

Triglyceride-containing compositions, in particular of

Vegetable oils and / or vegetable oil slimes to improve. Triglycerides derived from vegetable raw materials, especially raw vegetable oils, contain phosphatides, proteins and carbohydrate-containing substances, phytochemicals and colloidal compounds, which greatly reduce the shelf life of the oil and reduce the yield of the purified oil. These substances must therefore be removed.

In the refining of vegetable oils these become

unwanted accompanying substances. There is a distinction between chemical and physical refining. Chemical refining consists of processes 1.

Degumming, in which phospholipids and metal ions are removed from the oil, 2. neutralization with lye, where the fatty acids are extracted, 3. bleaching to remove dyes, other metal ions and remaining

Mucilage, 4. deodorization, one

Steam distillation, in which further compounds are removed, the smell and the taste of the oil

affect. In physical refining, the Deacidification together with the deodorization at the end of the

Refining process performed.

The degumming of the oils can be achieved by extraction of the

Phospholipids with water or an aqueous solution of an acid that complexes Ca ²⁺ and Mg ²⁺ ions, such as citric acid or phosphoric acid. Frequently, an aqueous, so-called pre-degumming is first carried out by means of which the water-soluble phospholipids are removed. This is called hydratable phospholipids. The

Pre-degumming with water is generally used for

Production of the lecithin.

In US 2,544,725 a process for the aqueous

Desegermination described in the glyceride before the

Water addition up to 10% of certain oil-soluble fatty acid esters of polyhydroxy compounds are added to facilitate the subsequent separation of the water phase.

A disadvantage of the prior art oil degumming processes is that both aqueous pre-degumming and aqueous acid treatment result in oil losses caused by the phospholipids transferred to the water being emulsifiers which are part of the vegetable oil in the aqueous Emulsify phase, causing vegetable oil to be lost. As a rule of thumb, two molecules of phospholipid each contain about one molecule of triglyceride. This results in the application of the above methods on an industrial scale to considerable

financial losses.

Raw material for the chemical industry and as fuel there is a constant need for degumming Triglyceride-containing compositions, in particular of

Vegetable oils and / or vegetable oil slimes to improve.

The inventors of the present application have therefore set themselves the task of a method for degumming

Triglyceride-containing compositions, in particular raw or vorentschleimten vegetable oils, to provide, with which the phosphorus content of the triglyceride-containing

Composition further reduced, the oil yield can be increased and the reaction rate of degumming can be increased. At the same time, this method should enable economic implementation on an industrial scale.

It has now surprisingly been found that the

The object of the invention can be achieved by a process comprising the steps of (a) contacting a triglyceride-containing

Composition with at least one solubilizer;

(b) separating the slime phase from the triglyceride-containing composition.

The term "triglyceride" is used in the context of

The present invention is understood to mean every triple ester of glycerol with fatty acids, be it of vegetable or animal origin. For the purposes of the present invention, triglyceride-containing compositions include vegetable or animal fats and oils, and mixtures thereof both with each other and with synthetic or modified fats and oils. A triglyceride-containing composition according to the

present invention may be in addition to those in the context of

Triglycerides defined in the present application still contain a proportion of water and / or acid, preferably in the range of 0.001 to 50% by weight, more preferably in the range of 0.01 to 20% by weight, in particular in the range of 0.1 to 10% by weight and most preferably in the range of 0.5 to 5% by weight.

The term "vegetable oil" or "vegetable oil" in the context of the present invention means any vegetable oil

Origin understood. Both terms ("vegetable oil" and

"Vegetable oil") are used interchangeably in the context of the present invention. Preferred, particularly suitable vegetable oils are soybean oil, rapeseed oil, canola oil, sunflower oil, olive oil,

Palm oil, jatropha oil, camelina oil, cottonseed oil, peanut oil and their mixtures. Particularly suitable are "raw

The term "raw" refers to the fact that the oil still no degumming, neutralization, bleaching, deodorizing and / or

Preconditioning step has been subjected. The terms "crude vegetable oil", "crude vegetable oil" and "crude oil" are used interchangeably in the context of the present invention It is also possible within the scope of the process according to the invention that a mixture of several crude oils and / or pre-degummed

and / or preconditioned oils in a mixture as

Triglyceride-containing composition can be used.

In the context of the present invention, "slime phase", "mucilage" or "vegetable oil slime" is understood as meaning all substances which, after treatment with water and / or acid and / or lye, precipitate out of vegetable crude oils as a heavy phase. Schleimstoffe "," vegetable oil slime "are used synonymously in the context of the present invention. The use of this slime phase is advantageous, for example, as a starting material for the production of lecithin, since lecithin is an essential constituent of

Represents vegetable oil slime.

The term "degumming" refers to the separation of the aforementioned substances ("slime phase", "mucilage", "vegetable oil slime").

In the context of the present invention, the term "pre-degumming" or "wet degumming" is understood to mean the treatment of a crude oil with water and / or acid in order to obtain water-soluble To remove phospholipids from the oil. The terms "pre-degumming" and "wet degumming" are used synonymously in the context of the present invention. Also, in the context of a pre- or wet degumming with acid or an aqueous acid after the addition of acid, an addition of alkali or an aqueous liquor can be carried out to the acid

neutralize. Before further treatment of the

pre-degummed oil with a solubilizer and

optionally an enzyme, the separation of the

aqueous phase. By a pre-degumming is the

Phosphorus content in extracted crude oil of about 500-1500 ppm, e.g. for soy and rapeseed reduced to below 200 ppm in pre-degummed oil. From the resulting mucous phase, e.g.

Lecithin be won or the mucous phase as

Processed feed. The disadvantage of separating off the aqueous phase or lowering the phosphorus content, however, is a yield loss with respect to the oil. The phosphatides passing into the aqueous phase have an emulsifying effect and cause some of the oil to be emulsified in the aqueous phase and separated therewith.

The term "pre-degummed oil", "pre-degummed vegetable oil" or "pre-degummed vegetable oil" is understood in the context of the present invention to mean a crude oil which has been subjected to the previously defined "pre-degumming" process. All terms ("pre-degummed oil", "pre-degummed vegetable oil" and "pre-degummed vegetable oil") are used synonymously in the context of the present invention.

The term "preconditioning" of the triglyceride-containing composition is used in the context of the present invention

Invention understood the addition of water and / or acid and / or alkali to the triglyceride-containing composition. The amount of water and / or acid and / or lye is preferably in the range from 0.001 to 80% by weight, more preferably in the range from 0.01 to 65% by weight, in particular in the range from 0.1 to 50% by weight. and most preferably selected in the range of 5 to 40% by weight. Subsequently, however, no separation of the aqueous phase preconditioned On the contrary, triglyceride-containing compositions are directly followed by further steps, such as bringing them into contact with one another

Subject to solubilizers.

For the purposes of the present invention, the term "solubilizer" or "solubilizer" is understood to mean any substance which, by its presence, contributes to the solution of poorly soluble substances in a solvent. Both terms ("solubilizers" and "solubilizers") are used interchangeably in the context of the present invention. Solubilizers which are preferred in the context of the present invention are selected from the group of emulsifiers and coemulsifiers and have an HLB value of 5.5 to 13.5, preferably of 6 to 12 and particularly preferably of 7.5 to 10.5, on.

The HLB value (hydrophilic-JLipophilic balance) describes in chemistry the hydrophilic and lipophilic portion of

mainly nonionic surfactants. The term "HLB value" is understood in the context of the present invention to be the HLB value according to Griffin.

Preferred solubilizers are selected in the context of the present invention from the group consisting of

Polyhydroxy compounds, polyglycols, alcohols and mixtures thereof. Is it the at least one

Solubilizer to an alcohol, it is preferably selected from the group consisting of methanol, ethanol, butanol and mixtures thereof. It is further preferred in the context of the process according to the invention that the polyhydroxy compounds used as solubilizers are asymmetric

Have molecular structure. In the context of the present invention, particular preference is given to polyhydroxy compounds which are selected from the group consisting of 1,2-propanediol, 1,3-propanediol, 1,2-butanediol, methylglycol, methyl-1,3-propanediol, sucrose esters, mono- and diacetyl tartaric acid esters of monoglycerides, polyglycerol esters, sorbitan esters, polyoxyethylene sorbitan esters, polyethylene glycols, copolymers of ethylene oxide and propylene oxide units, and mixtures thereof. Also preferred are solubilizers which are selected from the group consisting of 1-octanol, 2,2-dimethyl-1,3 Propanediol, 2,3-butanediol, butanol, ethanol, isopropanol, ethylene oxide-propylene oxide monobutyl ether, 1-pentanol, 3-pentanol, 2-methyl-2, 4-pentanediol, 1-hexanol, 3-hexanol, 1,6- Hexanediol, 2, 5-hexanediol, 1-heptanol, 3-heptanol, 1.7

Heptanediol and mixtures thereof are selected. Among the polyethylene glycols and the copolymers of ethylene oxide and propylene oxide units, preferred are those bearing an alkyl group at one end. 1,2 Propanediol is particularly preferred in the context of the present invention, since it

inexpensive and suitable for use in triglyceride-containing compositions, the

Serve food production, such as vegetable oils of the aforementioned type.

Preferably, the at least one solubilizer in

Concentrations of 0.005 to 10% by weight, especially

preferably 0.01 to 5% by weight, very particularly preferably 0.025 to 2% by weight, particularly preferably less than 0.03 to 1% by weight and most preferably 0.075 to 3% by weight, based on the amount of oil used. A use of the at least one solubilizer with the properties given above leads to one

Comparison process without using the solubilizer

Surprisingly, in different variants of the aqueous degumming to a smaller amount of emulsified in the aqueous phase oil and thus to a higher oil yield and to a faster phase separation after the completion of the degumming process. Furthermore, compared to the comparison process without solubilizers, the contents of P, Ca ²⁺ , Mg ^{2+ are} significantly reduced. Of the

The process according to the invention has the advantage for the oil mill that, in particular when raw vegetable oil is used, a higher oil yield can be achieved compared to a comparison process and the resulting oil has a lower content

Contaminants. The addition of the at least one solubilizer further improves the economics of the overall oil degumming process by employing other additives in lower dosages can. Thus, for example, in an acid degumming the

Dosage of citric acid or phosphoric acid on

be reduced.

For this reason, propane-1,2-diol is particularly preferred because it is readily soluble in water, so that the greater part of it remains in the aqueous degumming solution.

The at least one enzyme which is added to the triglyceride-containing composition before separation of the slime phase according to step (b) of the process according to the invention is preferably a phospholipid-cleaving enzyme.

A "phospholipid-cleaving enzyme" may be a phospholipase capable of cleaving either a fatty acid residue or a phosphatidyl residue or a head group from a phospholipid

Phospholipase AI, phospholipase A2, phospholipase C,

Phospholipase B, phospholipase D or mixtures of

Phospholipases. Furthermore, it can also be a

so-called acyltransferase, in which the cleavage of the fatty acid residue is associated with a transfer of this residue, followed by an ester formation, with a free sterol in the oil phase. "Phospholipid-cleaving" in the context of the present invention, any enzyme called

Phospholipase activity and / or acyltransferase activity as major or minor activity. Phospholipases are enzymes belonging to the group of hydrolases and the ester linkage of phospholipids

hydrolyze. Phospholipases are after their

Regioselectivity in phospholipids divided into 5 groups:

Phospholipases AI (PLA1), which cleave the fatty acid in the snI position to form the 2-lysophospholipid

Phospholipases A2 (PLA2), which cleave the fatty acid in the sn2 position to form the 1-lysophospholipid. Phospholipases C (PLC) which cleave a phosphoric acid monoester.

Phospholipases D (PLD), which split or exchange the head group.

Phospholipases B (PLB), which cleave the fatty acid at both the snl and sn2 positions to form a 1,2-lysophospholipid.

An acyltransferase is understood in the context of

present invention, an enzyme containing acyl groups, for. B.

Fatty acids, from a phospholipid to a suitable one

Acceptor, z. A sterol, to form an ester.

In a further preferred embodiment, the at least one enzyme corresponding to the composition before separation of the gum phase according to step (b) of the

is added to an enzyme selected from the group of glycoside-cleaving enzymes. The enzyme from the group of glycoside-cleaving enzymes can be used either alone or in combination with one or more of the abovementioned phospholipid-cleaving enzymes. The glycoside-cleaving enzyme is preferably selected from the group consisting of amylase, amyloglucosidase,

Laminaranase, glucoamylase, glucosidase, galactosidase,

Glucanase, mannanase, pectinase, cellulase, xylanase,

Pullulanase, arabinase, dextranase or mixtures thereof.

The at least one enzyme can be isolated from any organism (for example also isolated from a thermophilic

Organism) or a synthetic source. The at least one enzyme may be of animal origin, for example from the pancreas, of plant origin or microbial Origin, z. B. from yeast, fungi, algae or bacteria. It is also possible in the context of the present invention that enzymes of the same kind are used, but which originate from different sources or species. Also included are recombinantly produced chimeric fusion proteins from two or more different species having enzymatic activity.

In the context of the present invention are phospholipase AI, phospholipase A2, phospholipase C, phospholipase B,

Phospholipase D, acyltransferase, glycoside-cleaving enzymes and mixtures thereof preferably from the following species

used: porcine pancreas, bovine pancreas, snake venom, bee venom, Aspergillus, Bacillus, Citrobacter, Clostridium, Dictyostelium, Edwardsieila, Enterobacter, Escherichia,

Erwinia, Fusarium, Klebsiella, Listeria, Mucor, Well,

Neurospora, Pichia, Proteus, Pseudomonas, Providencia,

Rhizomucor, Rhizopus, Salmonella, Sclerotinia, Serratia,

Shigella, Streptomyces, Thermomyces, Trichoderma,

Trichophyton, Whetzelinia, Yersinia.

Particularly preferred are phospholipase AI, phospholipase A2, phospholipase C, phospholipase B, phospholipase D,

Acyltransferase and its mixtures of Aspergillus awamori, Aspergillus foetidus, Aspergillus fumigatus, Aspergillus japonicus, Aspergillus niger, Aspergillus oryzae, Bacillus alvei, Bacillus amyloliquefaciens, Bacillus anthracis,

Bacillus atrophaeus, Bacillus cereus, Bacillus circulans, Bacillus coagulans, Bacillus larvae, Bacillus laterosporus, Bacillus megaterium, Bacillus natto, Bacillus pasteurii,

Bacillus pumilus, Bacillus sphaericus, Bacillus

sporothermodurans, Bacillus subtilis, Bacillus thuringiensis, Bacillus pseudoanthracis, Citrobacter amalonaticus,

Citrobacter braakii, Citrobacter farmeri, Citrobacter

freundii, Citrobacter gillenii, Citrobacter koseri, Citrobacter murliniae, Citrobacter rodentium, Citrobacter sedlakii, Citrobacter werkmanii, Citrobacter youngae,

Clostridium perfringens, Dictyostelium discoideum,

Dictyostelium mucoroides, Dictyostelium polycephalum,

Edwardsieila hoshinae, Edwardsieila ictaluri, Edwardsieila tarda, Enterobacter amnigenus, Enterobacter aerogenes,

Enterobacter cloacae, Enterobacter gergoviae, Enterobacter intermedius, Enterobacter pyrinus, Escherichia albertii,

Escherichia blattae, Escherichia coli, Escherichia fergusonii, Escherichia hermannii, Escherichia senegalensis, Escherichia vulneris, Erwinia amylovora, Erwinia aphidicola, Erwinia billingiae, Erwinia carotovora, Erwinia herbicola, Erwinia oleae, Erwinia mallotivora, Erwinia papayae, Erwinia

persicina, Erwinia piriflorinigrans, Erwinia psidii, Erwinia pyrifoliae, Erwinia rhapontici, Erwinia tasmaniensis, Erwinia toletana, Erwinia tracheiphila, Fusarium avenaceum, Fusarium avenaceum, Fusarium chlamydosporum, Fusarium coeruleum,

Fusarium culmorum, Fusarium dimerum, Fusarium incarnatum, Fusarium heterosporum, Fusarium moniliforme, Fusarium

napiforme, Fusarium oxysporum, Fusarium poae, Fusarium

sporotrichiella, Fusarium tricinctum, Fusarium proliferatum, Fusarium sacchari, Fusarium solani, Fusarium sporotrichioides, Fusarium subglutinans, Fusarium tabacinum, Fusarium

verticillioides, Klebsiella oxytoca, Klebsiella mobilis,

Klebsiella singaporensis, Klebsiella granulomatis, Klebsiella pneumoniae, Klebsiella variicola, Listeria monocytogenes, Mucor amphibiorum, Mucor circinelloides, Mucor hiemalis, Mucor indicus, Mucor javanicus, Mucor mucedo, Mucor paronychius, Mucor piriformis, Mucor subtilissimus, Mucor racemosus, Naja mossambica, Neurospora Africana , Neurospora crassa, Neurospora discrete, Neurospora dodgei, Neurospora galapagosensis,

Neurospora intermedia, Neurospora lineolata, Neurospora pannonica, Neurospora sitophila, Neurospora sublineolata, Neurospora terricola, Neurospora tetrasperma, Pichia barkeri, Pichia cactophila, Pichia cecembensis, Pichia cephalocereana, Pichia deserticola, Pichia eremophilia, Pichia exigua, Pichia fermentans, Pichia heedii, Pichia kluyveri, Pichia

kudriavzevii, Pichia manshurica, Pichia membranifaciens,

Pichia nakasei, Pichia norvegensis, Pichia orientalis, Pichia pastoris (Komagataella pastoris), Pichia pseudocactophila, Pichia scutulata, Pichia sporocuriosa, Pichia terricola,

Proteus hauseri, Proteus mirabilis, Proteus myxofaciens,

Proteus penneri, Proteus vulgaris, Pseudomonas aeruginosa, Pseudomonas fluorescens, Pseudomonas putida, Pseudomonas syringae, Providencia rettgeri, Providencia stuartii,

Rhizomucor endophyticus, Rhizomucor miehei, Rhizomucor

pakistanicus, Rhizomucor pusillus, Rhizomucor tauricus,

Rhizomucor variabilis, Rhizopus arrhizus, Rhizopus

azygosporus, Rhizopus circinans, Rhizopus japonicus, Rhizopus microsporus, Rhizopus nigricans, Rhizopus oligosporus,

Rhizopus oryzae, Rhizopus schipperae, Rhizopus sexualis,

Rhizopus stolonifer, Rhizopus artocarpi, Salmonella bongori, Salmonella enterica, Salmonella typhimurium, Sclerotinia borealis, Sclerotinia homoeocarpa, Sclerotinia libertiana, Sclerotinia minor, Sclerotinia ricini, Sclerotinia

sclerotiorum, Sclerotinia spermophila, Sclerotinia

trifoliorum, Serratia entomophila, Serratia ficaria, Serratia fonticola, Serratia grimesii, Serratia liquefaciens, Serratia marcescens, Serratia odorifera, Serratia plymuthica, Serratia proteamaculans, Serratia quinivorans, Serratia rubidaea,

Serratia symbiotica, Shigella dysenteriae, Shigella flexneri, Shigella boydii, Shigella sonnei, Streptomyces achromogenes, Streptomyces ambofaciens, Streptomyces aureofaciens,

Streptomyces avermitilis, Streptomyces carcinostaticus,

Streptomyces cervinus, Streptomyces clavuligerus, Streptomyces coelicolor, Streptomyces coeruleorubidus, Streptomyces

Davavensis, Streptomyces fradiae, Streptomyces griseus,

Streptomyces hygroscopicus, Streptomyces lavendulae,

Streptomyces lincolnensis, Streptomyces natalensis,

Streptomyces nodosus, Streptomyces noursei, Streptomyces peuceticus, Streptomyces platensis, Streptomyces rimosus, Streptomyces spectabilis, Streptomyces toxytricini,

Streptomyces venezuelae, Streptomyces violaceoniger,

Streptomyces violaceoruber, Thermomyces lanuginosa,

Trichoderma harzianum, Trichoderma koningii, Trichoderma longibrachiatum, Trichoderma pseudokoningii, Trichoderma reesei, Trichoderma viride, Trichophyton concentricum,

Trichophyton eboreum, Trichophyton equinum, Trichophyton gourvilii, Trichophyton kanei, Trichophyton megninii,

Trichophyton mentagrophytes, Trichophyton phaseoliforme,

Trichophyton raubitschekii, Trichophyton rubrum, Trichophyton schoenleinii, Trichophyton simii, Trichophyton soudanense, Trichophyton terrestre, Trichophyton tonsurans, Trichophyton vanbreuseghemii, Trichophyton verrucosum, Trichophyton

Violaceum, Trichophyton yaoundei, Whetzelinia sclerotiorum, Yersinia aldovae, Yersinia aleksiciae, Yersinia bercovieri, Yersinia enterocolitica, Yersinia frederiksenii, Yersinia intermedia, Yersinia kristensenii, Yersinia massiliensis, Yersinia molletii, Yersinia pestis, Yersinia

pseudotuberculosis, Yersinia rohdei, Yersinia ruckeri,

Yersinia similis used.

In a particularly preferred embodiment

Phospholipase A _lr Phospholipase A ₂ , Phospholipase B,

Phospholipase C and / or phospholipase D, which consist of Aspergillus niger, Aspergillus oryzae, Bacillus cereus,

Bacillus megaterium, Bacillus subtilis, Citrobacter freudii, Enterobacter aerogenes, Enterobacter cloacae, Edwardsieila tarda, Erwinia herbicola, Escherichia coli Clostridium

perfringens, Dictyostelium discoideum, Fusarium oxysporium, Klebsiella pneumoniae, Listeria monocytogenes, Mucor

javanicus, Mucor mucedo, Mucor subtilissimus, Naja mossambica, Neurospora crassa, Pichia pastoris (Komagataella pastoris), Pseudomonas species, Proteus vulgaris, Providencia stuartii, Rhizomucor pusillus, Rhizopus arrhizus, Rhizopus japonicus, Rhizopus stolonifer Salmonella typhimurium, Serratia marcescens, Serratia liquefaciens, Sclerotinia libertiana, Shigella flexneri, Streptomyces violaceoruber, Trichophyton rubrum, Thermomyces lanuginosus, Trichoderma reesei,

Whetzelinia sclerotiorum, Yersinia enterocolitica,

Pig pancreas, bovine pancreas, snake venom or

Bee venom.

The at least one enzyme may be derived from the same or different sources, preferably from one or more of the aforementioned organisms, more preferably from Aspergillus niger, Aspergillus oryzae, Fusarium oxysporium, Naja mossambica, Pichia pastoris (Komagataella pastoris), Streptomyces violaceous, Thermomyces

lanuginosus, Trichoderma reesei, porcine pancreas or

Bovine pancreas.

With respect to the glycoside-cleaving enzymes are those

preferably, the CC (1-4) glycosidic, CC (1-2) glycosidic,

(1-6) cleave glycosidic, ß (1-3) glycosidic, ß (1-4) glycosidic and / or ß (1-6) glycosidic bonds.

Furthermore, amylases, in particular CC-amylases, β-amylases, γ-amylases and isoamylases, and also mannanases are preferred.

With respect to the amylases are those from Bacillus or

Pseudomonas or fungal species or from pancreas, in particular those from Bacillus sp. such as Bacillus subtilis, Bacillus licheniformis, Bacillus megaterium, Bacillus

amyloliquefaciens, Bacillus stearothermophilus, Pseudomonas aeroginus, Pseudomonas fluorescens, Aspergillus oryzae, Aspergillus niger or Trichoderma reesei.

Furthermore, any mixtures of the aforementioned enzymes are preferred. To make the process cost effective, it is preferably, the enzyme activity of the at least one enzyme in the range of 0.01 to 5 units / g triglyceride-containing

Composition, more preferably in the range of 0.1 to 3 units / g triglyceride-containing composition, more preferably in the range of 0.2 to 2.5 units / g triglyceride-containing composition, and most preferably in the range of 0.3 to 1 units / g triglyceride-containing composition. (Unit: International unit for enzyme activity, 1 unit corresponds to substrate turnover of 1 pmol / min).

In other words, the amount of enzyme relative to the triglyceride-containing composition is used in a range of 10 to 500 ppm, more preferably 15 to 200 ppm, most preferably 20 to 100 ppm.

It is likewise preferred within the scope of the present invention

Invention, for example, when using two

different enzymes, the ratio of the enzyme activity of the at least one first enzyme (preferably phospholipid-cleaving) to the enzyme activity of the second enzyme (preferably glycoside-cleaving) in the range of 0.01: 6 units / g

Triglyceride-containing composition up to 6: 0.01 units / g

Triglyceride-containing composition is preferably in

Range of 0.1: 3 units / g triglyceride-containing

Composition up to 3: 0.1 units / g triglyceride-containing

Composition. It is also preferred if the proportion of both enzymes is the same size, for example, both proportions in the range of 0.1 to 0.5 units / g triglyceride-containing

Composition can be chosen.

The at least one enzyme may be, for example

freeze-dried and in appropriate enzyme buffer

(Standard buffers for each enzyme are in the literature

described) can be used dissolved, eg citrate buffer 0.1 M, pH 5 or acetate buffer 0.1 M, pH 5. In a preferred

Embodiment, the at least one enzyme is taken up in enzyme buffer and added to the triglyceride-containing composition. In order to achieve a better solubility of the at least one enzyme, is also the addition of organic

Solvents possible. Preferably used are nonpolar organic solvents such as e.g. Hexane or acetone or

Mixtures, preferably in an amount of 1 to 30 wt .-%.

Other preferred ingredients are selected from the group consisting of citrate buffer and acetate buffer.

In a further preferred embodiment, the

at least one enzyme used in supported form. in the

Support materials which are preferred in the context of the present invention are inorganic support materials, such as e.g. Silica gels, precipitated silicas, silicates or aluminosilicates, and

organic carrier materials, such as e.g. Methacrylates or

Ion exchange resins. The carrier materials facilitate the recyclability of the enzyme from the triglyceride-containing composition.

The "bringing into contact" of the triglyceride-containing

Composition with the at least one solubilizer according to step a) of the process according to the invention can be carried out in the context of the process according to the invention in any manner which is known to the person skilled in the art as suitable for the purpose according to the invention. A preferred mode of contacting in accordance with step a) of the method according to the invention is mixing the triglyceride-containing composition and the at least one solubilizer.

After contacting the triglyceride-containing

Composition with the at least one solubilizer according to step a) of the method according to the invention, the mixture of the triglyceride-containing composition and the at least one solubilizer preferably stirred, more preferably with a paddle at 200 to 800 U / min, preferably 250 to 600 U / min and most preferably at 300 to 500 U / min.

The temperature of the mixture during contacting in step a) of the process according to the invention is preferably in the range from 15 to 99.degree. C., more preferably in the range from 20 to 95.degree. C., more preferably from 22 to 90.degree. C., likewise preferred from 35 to 85 ° C, more preferably from 40 to 85 ° C.

The duration of the contacting according to step a) of the

The process according to the invention is preferably in the range from 1 minute to 12 hours, more preferably from 5 minutes to 10 hours, also preferably from 10 minutes to 6 hours, more preferably from 10 minutes to 3 hours.

The pH of the mixture during the contacting according to step a) of the method according to the invention is preferably in the range of pH 3 to pH 7.5, more preferably in the range of pH 4 to pH 6 and particularly preferably in the range of pH 4, 0 to pH 5.5.

In a preferred embodiment of the method according to the invention, prior to separation of the slime phase from the triglyceride-containing composition according to step (b)

at least one enzyme to the triglyceride-containing

Given composition. The addition of the at least one enzyme can thereby

at the same time, before or even after bringing into contact with the at least one solubilizer. It is preferred in the context of the present invention, when the triglyceride-containing composition first with the at least one

Solver is brought into contact before the at least an enzyme is added. In the case that the triglyceride-containing composition first with the at least one

Solubilizer is brought into contact, it is particularly preferred if before addition of the at least one enzyme for 1 to 300 minutes, preferably 2 to 100 minutes, also preferably from 3 to 30 minutes, and most preferably stirred for 5 to 15 minutes.

The "separation" of the gums in step b) of the process according to the invention can be carried out in any manner which is known to the person skilled in the art as suitable for the purpose according to the invention, however, the separation preferably takes place via separators of any type, such as centrifuges or

Filtration units. Preferred separators for the

inventive methods are nozzle separators,

PreßSchneckenSeparatoren, KammerSeparatoren,

Plate separators, solid plate separators, two-phase decanters, three-phase decanters, three-column centrifuges,

Single-buffer centrifuges, sliding vibrating centrifuges,

Vibrating centrifuges, solid bowl centrifuges, solid bowl centrifuges, tube centrifuges, drum centrifugal centrifuges, pusher centrifuges, screw centrifuges, chip centrifuges, inverting filter centrifuges and

Centrifuges. Centrifugation involves phase separation of the triglyceride-containing composition such that, for example, in the preferred embodiment utilizing crude vegetable oil as the triglyceride-containing composition, the treated vegetable oil, mucilage and, if present, the enzyme component, are in separate phases. which can be easily separated from each other.

In another aspect, the present invention relates to a degummed triglyceride-containing composition according to the inventive method as defined above and described in more detail.

In a further aspect, the present invention relates to the use of one or more solubilizers for

Degumming of a triglyceride-containing composition. The above definition and preferred embodiments claim accordingly.

In the following, particularly preferred embodiments of the present invention are described which, however, in no way limit the scope of the present invention but merely serve to further illustrate:

Preferred Embodiment A) Method comprising the steps

(a) contacting a triglyceride-containing

Composition with at least one solubilizer; (b) separating the slime phase from the triglyceride-containing composition; wherein the triglyceride-containing composition is a crude oil, preferably a crude vegetable oil, and the solubilizer is selected from the group consisting of emulsifiers and coemulsifiers and mixtures thereof, which are preferably 1,2-propanediol and 1,3 Propandiol acts. Preferably, the at least one solubilizer is used in a concentration of 0.005 to 10% by weight, more preferably 0.01 to 5% by weight and most preferably 0.075 to 3% by weight.

Preferred Embodiment B) Method comprising the steps

(a) contacting a triglyceride-containing

Composition with at least one solubilizer; (a (i)) addition of at least one enzyme;

(b) separating the slime phase from the triglyceride-containing composition; wherein the triglyceride-containing composition is a crude oil, preferably a crude vegetable oil, and the solubilizer is selected from the group consisting of emulsifiers and coemulsifiers and mixtures thereof, which are preferably 1,2-propanediol and 1,3 propanediol

is. Preferably, the at least one solubilizer is used in a concentration of 0.005 to 10% by weight, more preferably 0.01 to 5% by weight and most preferably 0.075 to 3% by weight. The at least one enzyme is selected from the group consisting of phospholipases and glucosidases and mixtures thereof, which is preferably phospholipase AI, A2 and / or C and / or alpha and / or beta-glucosidase. The at least one enzyme is preferably added after or together with the at least one solubilizer.

Preferred embodiment C)

Process according to embodiment A) or B) wherein the triglyceride-containing composition is preconditioned vegetable oil.

Preferred embodiment D)

A method according to embodiment A) or B) wherein the triglyceride-containing composition is degummed vegetable oil.

Preferred embodiment E)

A method according to any of embodiments A) to D), wherein prior to contacting in step (a) the crude

Vegetable oil is added to water and / or acid and / or alkali without a separation step is carried out prior to the separation of the gum phase according to step (b). Preferred embodiment F

A process as described in embodiment A wherein the solubilizer is selected from the group consisting of 1-octanol, 2,2-dimethyl-1,3-propanediol, 2,3-butanediol, butanol, ethanol, isopropanol, ethylene oxide-propylene oxide monobutyl ether, Pentanol, 3-pentanol, 2-methyl-2, 4-pentanediol, 1-hexanol, 3-hexanol, 1, 6-hexanediol, 2, 5-hexanediol, 1-heptanol, 3-heptanol and 1,7-heptanediol , Preferred embodiment G

A process as described in embodiment B, wherein the solubilizer is selected from the group consisting of 1-octanol, 2,2-dimethyl-1,3-propanediol, 2,3-butanediol, butanol, ethanol, isopropanol, ethylene oxide-propylene oxide monobutyl ether, Pentanol, 3-pentanol, 2-methyl-2, 4-pentanediol, 1-hexanol, 3-hexanol, 1, 6-hexanediol, 2, 5-hexanediol, 1-heptanol, 3-heptanol and 1,7-heptanediol ,

Preferred embodiment H

A process as described in embodiment C, wherein the solubilizer is selected from the group consisting of 1-octanol, 2,2-dimethyl-1,3-propanediol, 2,3-butanediol, butanol, ethanol, isopropanol, ethylene oxide-propylene oxide monobutyl ether, Pentanol, 3-pentanol, 2-methyl-2, 4-pentanediol, 1-hexanol, 3-hexanol, 1, 6-hexanediol, 2, 5-hexanediol, 1-heptanol, 3-heptanol and 1,7-heptanediol ,

Preferred embodiment I

A process as described in embodiment D, wherein the solubilizer is selected from the group consisting of 1-octanol, 2,2-dimethyl-1,3-propanediol, 2,3-butanediol, butanol, ethanol, isopropanol, ethylene oxide-propylene oxide monobutyl ether,

Pentanol, 3-pentanol, 2-methyl-2, 4-pentanediol, 1-hexanol, 3-hexanol, 1, 6-hexanediol, 2, 5-hexanediol, 1-heptanol, 3-heptanol and 1,7-heptanediol , Preferred embodiment J

A process as described in embodiment E, wherein the solubilizer is selected from the group consisting of 1-octanol, 2,2-dimethyl-1,3-propanediol, 2,3-butanediol, butanol, ethanol, isopropanol, ethylene oxide-propylene oxide monobutyl ether,

Pentanol, 3-pentanol, 2-methyl-2, 4-pentanediol, 1-hexanol, 3-hexanol, 1, 6-hexanediol, 2, 5-hexanediol, 1-heptanol, 3-heptanol and 1,7-heptanediol ,

methods

The following analysis methods were used:

Determination of Phosphorus Content in Vegetable Oils Phosphorus was determined by ICP according to DEV E-22.

Determination of calcium and magnesium content in the

vegetable oils

The determination of calcium and magnesium was carried out by ICP according to DEV E-22. Determination of the water content according to Karl Fischer

The determination of the water content of oil was according to Karl

Fischer, DIN51777.

Determination of the content of free fatty acids (FFA)

To determine the free fatty acids, a Foodlab device from the company cdR (Italy) is used, which is a self-contained, compact analyzer with a built-in

Represents spectrophotometer; it consists of one

temperature-controlled incubation block with 12 cells for cuvettes and 3 independent measuring cells, each with 2 light beams of different wavelengths.

After switching on the Foodlab device for the photometric determination of the proportion of free fatty acids (FFA), the ready-to-use measuring cuvettes from the company CDR are at 37 ° C

preheated, then the selection of the method for FFA determination in the menu and the determination of the blank value of the

Cuvette. Subsequently, the required volume

Vegetable oil in the solution of the cuvette, consisting of a Mix of various alcohols, KOH and phenolphthalein derivatives, pipetted. Depending on the FFA content are for soybean oil

usually 2.5 pL and for rapeseed oil 1 pL sample used. The volume taken from the vegetable oil sample is discarded one time to rinse the pipette, then re-sampled and pipetted into the final assay solution. The pipette is then rinsed with the measuring solution exactly ten times to minimize the volume of the oil sample

distort. The cuvette is then pivoted ten times by hand. The fatty acids in the sample (at pH <7.0)

react with a chromogenic moiety and form one

Color complex whose intensity is then determined at 630 nm in the measuring cell of the device. He gets in from the device

Percent of oleic acid is displayed and is proportional to

Total acid concentration in the sample.

Determination of mucus volume

By means of this provision, the oil contained in the oil

Slime phase of enzymatically untreated and enzymatically treated mucus measured. A 10 mL sling glass is heated to the working temperature of the reaction mixture, the

Samples (2X 2 mL) are filled in and tempered for at least 4 minutes at 3000 rpm to separate the slime phase from the oil. From the upper oil phases samples are taken for analysis. For documentation purposes, the result of the phase formation is additionally photographed.

Determination of the oil yield

The oil yield is determined by mass weighing of the oil, before and after the reaction.

Determination of HLB value according to Griffin The HLB value for nonionic surfactants was calculated as follows: where Μχ denotes the molecular weight of the lipophilic portion of a molecule and M denotes the molecular weight of the entire molecule. The factor 20 is one of Griffin's free choice

Scaling factor. This results in a scale of 0 to 20.

An HLB value of 1 indicates a lipophilic compound, and a chemical compound with an HLB value of 20 has a high hydrophilic content. A value between 3 and 8 is assigned to water / oil (W / O) emulsifiers, between 8-18 it is assigned to O / W emulsifiers.

Examples and figures

The invention will be explained in more detail below with reference to examples and figures. It is to be understood that the examples and figures are merely illustrative and illustrate particularly preferred embodiments of the present invention and are not intended to limit the scope of the present invention in any way.

Show it:

Olausbeute after the degumming of crude soybean oil with various concentrations of 1, 2-propanediol compared to standard degumming without 1,2-propanediol

Oil yield after degumming of crude soybean oil with various concentrations of 1,2-propanediol and 0.5 U / g of oil PLA1 compared to standard PLA1 degumming (0.5 U / g of oil) without 1,2-propanediol

Separation of soybean oil on pilot plant scale after aqueous degumming

Separation of the soybean oil on a technical scale after the aqueous degumming with the addition of 2.2% by weight of 1, 2 propanediol

The examples were carried out using the following reaction variants to which they refer: Table 1: Solvents used:

Additive HLB

value

formula

1,2-propanediol 8,70

1-octanol 2, 65

2, 2-dimethyl-1,3,5,6-propanediol

2,3-butanediol 7.57

Butanol 4, 62

H ₃ C OH

Ethanol 7,42

Isopropanol 5, 69

Polyglycol Bll / 50 Ethylene oxide propylene oxide 9, 58 monobutyl ether, middle

Molecular weight: 1300 g / mol

Reaction variant 1: degumming of crude oil with

Citric acid, complete neutralization

The amount of crude to be treated, 400 to 600 g, is poured into a Duran reactor DN120 1000 mL and samples for analysis are taken. The oil in the Duran reactor is heated with the aid of a hot plate to a temperature of 40 to 85 ° C, preferably 45 to 80 ° C. Once the desired temperature is reached, preconditioning is started. For a defined, of the amount of oil

dependent amount, citric acid (eg 1000 ppm) is metered to the oil. Subsequently, the mixture is dispersed using an Ultraturrax ^® for 5 seconds to 1 minute and the reaction mixture mixed for an additional 15 minutes at 150 rpm, the

To await reaction of the acid. As an alternative, the

Reaction mixture are incubated with vigorous stirring at about 600 rpm. Subsequently, a defined amount of sodium hydroxide solution (1 mol / L, residual amount of 1.5 to 2.5% by volume minus water from acid addition and enzyme addition) is added. The goal of caustic soda addition is one

Complete neutralization of the acid including the free

Fatty acids in the oil. For this purpose, a lye excess of 10-30% is needed, preferably 20%. The amount of sodium hydroxide solution required is calculated by the amounts of the acids and their molar mass. Alternatively, a pH of 7 to 8 can be set with an excess of sodium hydroxide solution. After cooling to 48 ° C or holding the temperature at 45 ° C or 80 ° C, the caustic soda solution for 5 seconds with an Ultraturrax®

be dispersed. The reaction mixture is mixed for a further 10 minutes. It will then be the remaining amount

Water (between 0.5 to 5%) minus the already supplied amount of water supplied by addition of acid and alkali. The Temperature remains at 45 to 48 ° C or at 80 ° C throughout the reaction.

The addition of one or more solubilizers (0.05 to

0.3 weight% solubilizer / oil) can be made at different times during the overall reaction, see Table 2 below. For this purpose, the stirrer speed can be briefly increased (1 minute to 900 rpm), then at

lower speed (150rpm) further stirred.

Sampling takes place at defined time intervals. The sample is taken off with the aid of a pipette, filled into a tempered glass spin (temperature of the reaction mixture) and tempered and at least 4 minutes at 3000 rpm

centrifuged to separate the slime phase from the oil. To

For documentation purposes, the result of the phase formation is photographed, from the supernatant samples are taken to determine the phosphorus, calcium and magnesium content.

The separation of the slime phase from the oil is carried out according to the following steps:

1. Switch off the stirrer 2. Transfer the oil into a centrifuge cup

3. Tempering the filled centrifuge cup in

Drying cabinet at 80 ° C for 15 minutes

4. Separation of oil and heavy phase in the

Laboratory centrifuge Eppendorf 5810 R at 4000 rpm for 10 minutes Dosage variants of the solubilizers:

The solubilizers listed above can be added at different times to reaction variant 1. The Dosage times are examples and can be done at any time during the reaction.

Table 2: Varied dosage times of the solubilizers in acid degumming with full neutralization:

Reaction variant 2: crude oil, aqueous pre-degumming

(Lecithinhersteilung)

In a further reaction variant, 0.05 to 5% by volume of water is added to the crude oil. The emulsion is mixed. Ideally, the reaction is carried out at 30 to 80 ° C, preferably at 40 to 78 ° C. Subsequently, the Phase separation waited, the solids settle or can be prepared by a standard method known in the art, for. B. be removed by centrifugation or filtration.

1. Switch off the stirrer

2. Transfer the oil to a centrifuge cup

3. Tempering the filled centrifuge cup in

Drying oven at 80 ° C for 15 minutes 4. Separation of oil and heavy phase in the

Laboratory centrifuge Eppendorf 5810 R at 4000 rpm for 10 minutes

The addition of one or more solubilizers (0.05 to 0.3% by weight of solubilizer / oil) at different times, eg. B. before the addition of water or after the

Water addition, during the overall reaction, see Table 3 below. For this, the stirrer speed can be briefly increased (1 minute to 900 rpm), then stirring is continued at a lower speed (150 rpm). Dosage variants of the solubilizers:

The solubilizers listed above can be added at different times to reaction variant 2. Dosage times are examples and may occur at any time during the reaction. Table 3: Varied dosage times of the solubilizers in the water degumming:

Reaction variant 3: Crude oil, partial neutralization The quantity of crude oil to be treated, 400 to 600 g, is poured into a Duran reactor DN120 1000 mL and samples for the analysis are taken. The oil in the Duran reactor is heated by means of a hot plate to a temperature of 40 to 85 ° C, preferably 48 to 80 ° C. Once the temperature is reached, the preconditioning is started. This is a defined, dependent on the amount of oil

Citric acid, (eg 1000 ppm), added to the oil. Then the mixture with an Ultraturrax ^® is for 1 minute

mixed. As an alternative, stirring at about

600 rpm for 15 minutes incubated to await the reaction of the acid. Subsequently, a defined amount

Sodium hydroxide solution (4 mol / L, residual amount to 1.5 to 2.5% by volume minus water from acid addition) is added until a pH of about 4 to 5 is reached and it is incubated for a further 10 minutes with stirring. It is then the remaining amount of water (between 0.5 to 5% by volume) minus the already supplied amount of water by acid and alkali addition

fed. The temperature remains at 45 to 80 ° C throughout the reaction. The addition of one or more solubilizers (0.05 to

0.3% by weight of solubilizer / oil) can be carried out at different times during the overall reaction, see Table 4. For this purpose, the stirrer speed can be briefly increased (1 minute to 900 rpm), then stirring is continued at a lower rpm (150 rpm).

Sampling takes place at defined time intervals. The sample is removed with the aid of a pipette, filled into a temperature-controlled spin-on glass (temperature of the reaction mixture) and heated for at least 4 minutes at 3000 rpm to separate the slime phase from the oil. To

For documentation purposes, the result of the phase formation is photographed, from the supernatant samples are taken to determine the phosphorus, calcium and magnesium content. The separation of the slime phase from the oil is carried out according to the following steps:

1. Switch off the stirrer

2. Transfer the oil to a centrifuge cup

3. Tempering the filled centrifuge cup in

Drying cabinet at 80 ° C for 15 minutes

4. Separation of oil and heavy phase in the

Laboratory centrifuge Eppendorf 5810 R at 4000 rpm for 10 minutes

Dosage variants of the solubilizers:

The solubilizers listed above can be added at different times to reaction variant 3. The

Dosage times are examples and can be done at any time during the reaction. Table 4: Varied dosage times of the solubilizers in acid degumming with partial neutralization:

Reaction variant 4: Crude oil, partial neutralization with enzyme The amount of crude oil to be treated, 400 to 600 g, is charged into a Duran reactor DN120 1000 mL and samples for the analysis are taken. The oil in the Duran reactor is heated by means of a hot plate to a temperature of 40 to 85 ° C, preferably 48 to 80 ° C. Once the temperature is reached, the preconditioning is started. This is a defined, dependent on the amount of oil

Citric acid, (eg 1000 ppm), added to the oil. Subsequently The mixture is mixed with an Ultraturrax ^® for 1 minute. As an alternative, stirring at about

Sodium hydroxide solution (4 mol / L, residual amount to 1.5 to 2.5% by volume minus water from acid addition and enzyme addition) is added until a pH of about 4 to 5 is reached and it is incubated for a further 10 minutes with stirring , After cooling to 48 ° C, the addition of an enzyme, an enzyme mixture or an immobilizate, for which the stirrer speed can be increased briefly (1 minute to 900 rpm), then stirring is continued at a lower speed. It is then the remaining amount of water (between 0.5 to 5% by volume) minus the already supplied amount of water by acid and

Laugenzugabe supplied. The temperature remains at 45 to 80 ° C throughout the reaction. The choice of temperature is dependent on the thermal stability of each case

used enzyme or the enzyme mixture used.

The addition of one or more solubilizers (0.05 to 0.3% by weight of solubilizer / oil) may be different

During the entire reaction, see Table 5. For this, the stirrer speed can be briefly increased (1 minute to 900 rpm), then stirring is continued at a lower speed (150 rpm). Sampling takes place at defined time intervals. The sample is removed with the aid of a pipette, filled into a temperature-controlled spin-on glass (temperature of the reaction mixture) and heated for at least 4 minutes at 3000 rpm to separate the slime phase from the oil. To

1. Switch off the stirrer

2. Transfer the oil into a centrifuge beaker. 3. Temper the filled centrifuge beaker in the centrifuge bowl

Drying cabinet at 80 ° C for 15 minutes

4. Separation of oil and heavy phase in the

Laboratory centrifuge Eppendorf 5810 R at 4000 rpm for 10 minutes

Dosage variants of the solubilizers: The solubilizers listed above can be added to reaction variant 4 at various times. Dosage times are examples and may occur at any time during the reaction.

Table 5: Varied dosage times of the solubilizers in acid degumming with partial neutralization and enzyme addition:

A

Before acid addition

B

Simultaneously with acid addition

C

After the acid addition before the addition of alkali

D

Simultaneously with lye addition After the lye addition, before the

E water addition

after the addition of water

F

G Before the end of the reaction

Reaction variant 5: crude oil

The amount of crude to be treated, 400 to 600 g, is poured into a Duran reactor DN120 1000 mL and samples for analysis are taken. The oil in the Duran reactor is heated by means of a hot plate to a temperature of 40 to 85 ° C, preferably 48 to 80 ° C. Once the desired temperature is reached, preconditioning is started. For a defined, of the amount of oil

dependent amount, citric acid (eg 1000 ppm), metered to the oil. The mixture is then mixed with an Ultraturrax ^® for 1 minute. Alternatively, it is incubated with stirring at about 600 rpm for 15 minutes to await the reaction of the acid. Subsequently, a defined amount of sodium hydroxide solution (1 mol / L, residual amount to 1.5 to 2.5% by volume less water from acid addition and enzyme addition) is added until a pH of about 4 to 5 is reached and there are more Incubated for 10 minutes with stirring. Alternatively, a pH of 7 to 8 can be set with an excess of sodium hydroxide solution and incubated for a further 10 minutes with stirring. After cooling to 48 ° C or after holding the

Temperature at 80 ° C, the addition of 1,2-propanediol as a solubilizer (0.05 to 0.3% by weight of 1, 2-propanediol oil), for which the stirrer speed can be increased briefly (1 minute to 900 rpm), then continue stirring at lower speed.

centrifuged to separate the slime phase from the oil. To

Reaction variant 6: crude oil

The amount of crude to be treated, 400 to 600 g, is poured into a Duran reactor DN120 1000 mL and samples for analysis are taken. The oil in the Duran reactor is heated by means of a hot plate to a temperature of 40 to 85 ° C, preferably 48 to 80 ° C. Once the temperature is reached, the preconditioning is started. This is a defined, dependent on the amount of oil

mixed. As an alternative, stirring at about

Sodium hydroxide solution (1 mol / L, residual amount to 1.5 to 2.5% by volume minus water from acid addition and enzyme addition) is added until a pH of about 4 to 5 is reached and it is incubated for a further 10 minutes with stirring , After cooling to 48 ° C, the addition of 1,2-propanediol as a solubilizer and an enzyme, an enzyme mixture or an immobilizate, for which the stirrer speed can be increased briefly

(1 minute to 900 rpm), then continue stirring at lower speed. Sampling takes place at defined time intervals. The sample is removed with the aid of a pipette, filled into a temperature-controlled spin-on glass (temperature of the reaction mixture) and heated for at least 4 minutes at 3000 rpm to separate the slime phase from the oil. To

Examples Example 1:

According to reaction variant 5, a crude soybean oil with the following starting contents was used: phosphorus 860 ppm, calcium 63 ppm, magnesium 60 ppm and a content of free fatty acids of 0.45%. The crude oil was heated to 80 ° C and subjected to preconditioning at this temperature using aqueous citric acid (1000 ppm) and then neutralized with aqueous sodium hydroxide solution (1 mol / L) to pH 7-8. Subsequently, various concentrations of 1,2-propanediol (0.05-0.2% by weight of propanediol) were added and further stirred. In comparison, a sample was stirred without 1,2-propanediol (standard degumming). The

Oil / water ratio (weight) was 98.5: 1.5. Samples were taken regularly (see Table 6). At the end of the reaction, the slime phase was centrifuged off and the

Oil yield determined by mass weighing.

The results are summarized in Table 6. It can be clearly seen that an increasing concentration of 1,2-propanediol leads to a reduction of the ions calcium (Ca), magnesium (Mg) and phosphorus (P). In the

Standard degumming of the soybean oil, the following ion values were reached after one hour of reaction time: Ca: 4.7 ppm; mg:

3.7ppm and P: 42ppm. After one hour of reaction time, with 0.2% by weight of 1,2-propanediol, ion values of: Ca: 1, lppm, Mg: 0.69 ppm and P: 10 ppm were achieved. In addition, the oil yield with 1,2-propanediol increased from 95.5 to 95.8% by weight. The values were confirmed in duplicate. It was thus shown that the addition of 1,2-propanediol makes the oil degumming more effective and a higher oil yield is achieved. Table 6: Degumming with different concentrations of 1,2-propanediol compared to standard degumming

Example 2

According to reaction variant 6, a crude soybean oil with the following starting contents was used: phosphorus 860 ppm, calcium 63 ppm, magnesium 60 ppm and a free fatty acid content of 0.45%. The crude oil was preconditioned using aqueous citric acid (1000 ppm) and then neutralized to pH 4-5 with aqueous sodium hydroxide solution (1 mol / L). Subsequently, according to reaction variant 6 a

Thermolyses lanuginosus phospholipase AI (PLA1) and various concentrations of 1, 2-propanediol (0.05 to 0.2% by weight) were added and further stirred. In comparison, a sample without 1,2-propanediol (PLA1) was

Standard degumming). The oil / water ratio

(Weight) was 98.5: 1.5. Samples were taken regularly. At the end of the reaction, the mucus phase became

centrifuged and the oil yield determined by mass weighing. The reaction temperature was over the whole

Reaction time kept at 48 ° C. With regard to the separation, the procedure was as described in reaction variant 6. Before separation, the samples were each preheated to 80 ° C.

The results are summarized in Table 7. It can be clearly seen that an increasing concentration

1, 2-Propanediol leads to an increased oil yield and that the use of e.g. 0.2% by weight 1,2 propanediol + PLA1 a further increase of about 1% degummed soybean oil

allows. The values were confirmed in duplicate. It was thus shown that the addition of 1,2-propanediol makes the oil degumming more effective and a higher oil yield is achieved.

Table 7: Degumming with different concentrations of 1,2-propanediol and PLA1 compared to PLA1 standard degumming

Example 3: Water degumming or lecithin production in crude soybean oil and crude rapeseed oil (reaction variant 2) In the context of this example, the influence of the

inventive additives to the aqueous degumming of crude soybean oil and crude rapeseed oil examined. The solubilizers were used for this purpose in a concentration of 0.2 wt .-% based on the amount of oil. The raw used for this purpose

Vegetable oils are identified by the following analysis data:

Table 8: Characterization data of Example 3

used oils

530 g of crude vegetable oil (crude soybean oil and rapeseed oil) were added after weighing the reactor pot in a Duran reactor, heated to 60 ° C and stirred at a stirrer speed of 150 rpm. Thereafter, the water and, where appropriate, solubilizer dosage were used: 2.5% total water was used for soybean oil and 3% total water for rapeseed oil.

In the batches according to the invention, the additive was first mixed with the water in a beaker and then introduced via a funnel into the Duran reactor. The mixture was further stirred at 60 ° C for 60 minutes. Thereafter, the reaction mixture was sampled for analysis of the contents of P, Ca, Mg and the free fatty acids. Finally, the reaction mixture was heated to 80 ° C in preparation for separation, the stirrer was switched off, and the reaction mixture was allowed to stand for 5 minutes. Thereafter, the oil (the reaction mixture) was transferred to a centrifuge cup and heated again in the oven at 80 ° C for 15 minutes, then centrifuged in a laboratory centrifuge for 10 minutes at 4000 rpm. Finally, the oil phase was emptied and determined by the weight of the centrifuge cup, the mass of heavy phase. Finally, the oil yield was determined by weighing the residual oil after degumming using the mass of oil used.

Table 9: Results for aqueous degumming of crude soybean oil with and without inventive additives

Heptanol Mg [ppm] 69

P [ppm] 290

0.3

FFA [%]

1

Mucus [%] 5.7

, 20% Ca [ppm] 145

-Heptanol Mg [ppm] 66

P [ppm] 275

95, 0

0.2

FFA [%]

9

Mucus [%] 5.7, 20% Ca [ppm] 145

Hexanol Mg [ppm] 62

P [ppm] 310 94, 9

FFA [%] -

Slime [%] 5, 1, 20% Ca [ppm] 136 -hexanol Mg [ppm] 63

94, 9

P [ppm] 250

FFA [%] 0.3

Slime [%] 5.5, 20% Ca [ppm] 145 -Pentanol Mg [ppm] 66

P [ppm] 275 95, 0

0.2

FFA [%]

9

Mucus [%] 5.5, 20% Ca [ppm] 150

95, 0-pentanol Mg [ppm] 68

P [ppm] 295 FFA [%] -

Mucus [%] 5.5

0.20% Ca [ppm] 116

1,7-heptanediol Mg [ppm] 57

95, 7

P [ppm] 210

FFA [%] -

Mucus [%] 3, 8

0.20% Ca [ppm] 128

2-methyl-2, 4-

Mg [ppm] 61

pentanediol

P [ppm] 235 95.2

0.3

FFA [%]

1

Mucus [%] 4,5

0.20% Ca [ppm] 155

1,6-hexanediol Mg [ppm] 76

P [ppm] 260 95, 6

FFA [%] -

Mucus [%] 3.2

0.20% Ca [ppm] 145

1, 2-hexanediol Mg [ppm] 62

95.2

P [ppm] 300

FFA [%] -

Mucus [%] 4, 6

0.20% Ca [ppm] 153

2,5-hexanediol Mg [ppm] 75 95, 6

P [ppm] 250

FFA [%] - Mucus [%] 3.7

142

0.20% Ca [ppm]

62

2, 2-dimethyl-1,3

Mg [ppm] 3

propanediol

95.5

P [ppm] 250

0.3

FFA [%]

0

4.0

Mucus [%]

0.20% Ca [ppm] 140

2,3-butanediol Mg [ppm] 65

P [ppm] 260

95, 1

0.2

FFA [%]

9

Mucus [%] 4.4

0.20% Ca [ppm] 140

1, 2-propanediol Mg [ppm] 70

95, 1

P [ppm] 255

FFA [%] -

Mucus [%] 4, 6

The investigations with different solubilizers at a dosage of 0.2% by weight show for some of the solubilizers a significant increase in the oil yield. The best results show 1,7-heptanediol, 2,6-hexanediol, 2,5-hexanediol and 2, 2-dimethyl-1,3-propanediol. With these additives, an increase of the oil yield by 1% and more is achieved under the specified conditions.

Table 10 to Example 3: Results for the aqueous

Degumming of raw rapeseed oil with and without according to the invention

additives 0.20% Ca [ppm] 48

1,2-propanediol Mg [ppm] 7.4

93, 8

P [ppm] 63

FFA [%] 0.92

Mucus [%] 5.5

The results in the preceding table show that it is also possible with individual additives according to the invention to increase the oil yield in the aqueous degumming of rapeseed oils.

Both in the aqueous degumming of soybean oil and in the aqueous degumming of rapeseed oil, the P values are not greatly reduced with the additives according to the invention. This effect is desirable because in the case of lecithin production from the aqueous mucus, the non-hydratable phospholipids, which in this case remain in oil, should not change into the aqueous mucus. In the work-up of the lecithin, these would only dilute the hydratable phospholipids, in particular the phosphatidylcholine, and would have to be removed in a complicated manner.

Example 4: Water degumming or lecithin production with varied times for solubilizer dosage for

So yesöl (reaction variant 2)

In order to investigate the influence of the dose time of the solubilizers on the oil yield, the solubilizer 1,7-heptanediol and 1,2-propanediol was selected. The investigations were carried out with soybean oil according to Example 3. The procedure was generally analogous to Example 3, but the Dosage time for the two solubilizers used was varied:

Table 11: Example 4: Water degumming or lecithin production with varied times of solubilizer dosage for soybean oil (using 1.7 heptanediol and 1,2-propanediol as solubilizer)

P [ppm] 300

5 minutes before FFA [%] 0, 32

mucus

End of reaction 4

[%]

Soybean oil solubilizer 1,2

propanediol

0.20% Ca [ppm] 140

1, 2-propanediol Mg [ppm] 70

as standard P [ppm] 255 95, 1

FFA [%] -

mucus

with water addition 4, 6

[%]

0.20% Ca [ppm] 140

1, 2-propanediol Mg [ppm] 68

P [ppm] 270 95.2

5 minutes before FFA [%] 0.3

mucus

Water addition 4

[%]

0.20% Ca [ppm] 108

1, 2-propanediol Mg [ppm] 53

P [ppm] 210 95.2

30 minutes after FFA [%] 0.3

mucus

Water addition 4,5

[%]

0.20% Ca [ppm] 145

1, 2-propanediol Mg [ppm] 69

P [ppm] 290 95, 4

5 minutes before FFA [%] 0.35

mucus

End of the reaction 4,5

[%]

For the solubilizer 1.7 heptanediol it is shown that this is best used with the water together with the water directly at the beginning of the lecithin extraction in order to achieve the highest possible oil yield. For 1,2-propanediol, the dosage of the additive is most favorable shortly before completion of the reaction. The results indicate that the most favorable dosage time point is dependent on the chemical structure of the solubilizer.

Example 5

Partial neutralization in crude oil at 48 ° C without enzyme, separation at 80 ° C - Experiments with soybean oil and rapeseed oil

(Reaction variant 3)

In this reaction variant conditions were set, as they are typically set in the enzymatic oil degumming, but no enzyme was added. These measurements serve as a reference to the case ^¬ play examined in later reaction mixtures for the enzymatic Ölentschleimung. The influence of the additives on the initial situation for enzymatic oil degumming can be investigated. In addition, the results document the positive influence of the additives of the invention in a partial neutralization of citric acid. The following table shows the characterization data of the oils used:

Table 12: Characterization data of Example 5

used oils

530 g of crude vegetable oil (crude soybean oil and rapeseed oil) were placed in a Duran reactor after weighing the reactor pot, heated to 48 ° C and stirred at a stirrer speed of 150 rpm. Thereafter, 1000 ppm of 50% citric acid (depending on the calcium and magnesium values and the phosphorus value) were metered in and stirred for a further 15 minutes. Thereafter, the partial neutralization with 4 molar (16%) sodium hydroxide solution to pH 4. The amount of alkali required for this purpose had previously been determined in a titration curve with citric acid. After an additional reaction time of 10 minutes, the water (comparative experiments) or the water added with the solubilizer (feedthrough according to the invention) were metered in. In the case of degumming of soybean oil 2.5% total water was used, in the case of rapeseed oil with 3% total water. The amount of water added at this stage corresponded to the total water, minus the amount of water supplied with acid and caustic, and 0.2% solubilizer.

When the additives according to the invention were used, they were mixed (in each case 0.2% by weight of additive based on the total amount of oil) with the water in a beaker and then added to the reaction mixture via a funnel. The reaction time was 60 minutes. For analyzes, samples were taken from the reaction mixture after 10, 30 and 60 minutes.

Finally, the reaction mixture was heated to 80 ° C in preparation for separation, the stirrer was switched off, and the reaction mixture was allowed to stand for 5 minutes. Thereafter, the oil (the reaction mixture) was transferred to a centrifuge cup and heated again in the oven at 80 ° C for 15 minutes, then centrifuged in a laboratory centrifuge for 10 minutes at 4000 rpm. Finally, the oil phase was emptied and determined by the weight of the centrifuge cup, the mass of heavy phase.

Table 13 to Example 5: Partial neutralization of soybean oil after citric acid treatment: FFA [%] - - -

Mucus [%] 3.5 4.5 4.3

0.20% Ca [ppm] 34 32 33 3-hexanol Mg [ppm] 9.5 6, 8 6.5

P [ppm] 56 40 37 95.3

FFA [%] - - -

Mucus [%] 4.5 4 4

0.20% Ca [ppm] 32 22 24

1-pentanol Mg [ppm] 22 12 13

95, 6

P [ppm] 152 83 83

FFA [%] 0.86-0.92

Mucus [%] 3, 9 4.5 3.7

0.20% Ca [ppm] 33 27 30

3-pentanol Mg [ppm] 21 13 14

95, 7

P [ppm] 148 83 83

FFA [%] 0.84-0.9

Mucus [%] 4 4,5 4

0.20% Ca [ppm] 20 18 18 1.7 -

Mg [ppm] 8.2 6.5 6.2

heptane

96, 4

P [ppm] 53 44 40

FFA [%] - - -

Mucus [%] 4 4 4.3

0.20% Ca [ppm] 24 23 23

2-methyl-96, 0 2.4-Mg [ppm] 12 9.8 8.4

pentanediol P [ppm] 82 65 51

FFA [%] - - -

Mucus [%] 4.7 4.2 4.3

0.20% Ca [ppm] 68 40 51

1, 6

Mg [ppm] 29 9.8 14

hexanediol

95, 6

P [ppm] 190 45 74

FFA [%] - - -

Mucus [%] 4.5 4.5 4.2

0.20% Ca [ppm] 29 21 21 1,2-

Mg [ppm] 11 6.4 6.3

hexanediol

96, 4

P [ppm] 64 42 41

FFA [%] - - -

Mucus [%] 4.5 4.5 4.5

0.20% Ca [ppm] 40 30 30 2.5-

Mg [ppm] 18 11 9.8

hexanediol

96, 8

P [ppm] 110 59 56

FFA [%] - - -

Mucus [%] 4 4 4

0.20% Ca [ppm] 18 16 16

2,2-

dimethyl

Mg [ppm] 9.3 7.3 6.3

1,23-propanediol 96, 1

P [ppm] 63 46 39

FFA [%] 0, 94 - 0, 92

Mucus [%] 4 4 4

0.20% Ca [ppm] 37 28 29

96, 1 2,3-

Mg [ppm] 19 13 12

butanediol P [ppm] 125 78 69

FFA [%]

Mucus [%] 4.5 4.4 4.3

0.20% Ca [ppm] 38 33 36

1,2-

Mg [ppm] 21 14 14

propanediol

P [ppm] 135 79 75 95, 8

FFA [%] 0.88-0.91

Mucus [%] 4 4.3 4.3

The measurement results for soybean oil in the preceding table show that the solubilizers according to the invention under these reaction conditions lead to an increase in the oil yield. At the concentration of 0.2% by weight used, oil yield increases of up to 1.5% can be achieved. However, the additives also contribute to a reduction of the P content in the oil and to a reduction of the divalent ions Mg ²⁺ and Ca ²⁺ in the oil.

Example 5: Partial neutralization of rapeseed oil after citric acid treatment:

P [ppm] 25 21 17

FFA [%] 0, 98 - 1, 01

mucus

5, 5 5 5, 2

[%]

Ca

0.20% 13 8.8 5, 2

[Ppm]

2-methyl-2, 4-Mg

2.2 1.5 1, 1

Pentanediol [ppm]

93, 9

P [ppm] 23 19 15

FFA [%] 0, 97 - 1.00

mucus

6 5,7 5, 2

[%]

Ca

0.20% 12 7, 9 4.4

[Ppm]

mg

1, 2-propanediol 2.2 1.7 1.3

[Ppm]

93, 8

P [ppm] 20 17 16

FFA [%] 0, 94-0, 96

mucus

6 5.5 5, 5

[%]

The table shows that it is possible with individual additives according to the invention to increase the olive yield according to the invention even in the degumming of rapeseed oil under these conditions. For this particular 1, 7-heptanediol is suitable.

Example 6: Partial neutralization in crude oil at 48 ° C without enzyme, separation at 80 ° C with varied times to

Solubilizer addition (reaction variant 3)

In the context of this example, the influence of the dosage time on the oil degumming at partial neutralization in crude oil is examined, as shown in Example 5. Around To ensure the comparability of the results, the same soybean oil used as for Example 5:

Table 15: Characterization data of Example 6

used soybean oil

To carry out the degumming of soybean oil was exactly as described in Example 5, proceeded. There were

only different Dosagezeitpunkte for the

additives according to the invention chosen:

Variant 4a: 0.2% solubilizer addition 5 minutes before

addition of acid

Variant 4b: 0.2% addition of solubilizer together with the acid addition

Variant 4c: 0.2% solubilizer addition 7 minutes after the acid addition

Variant 4d: 0.2% addition of solubilizer together with the alkali addition

Variant 4e: 0.2% addition of solubilizer 5 minutes after addition of the alkali

Variant 4f: 0.2% solubilizer addition 30 minutes after the addition of water

Variant 4g: 0.2% solubilizer addition 5 minutes before the end of the reaction Table 16: to Example 6 partial neutralization of soybean oil and 1.7 heptanediol and 1, 2-propanediol as an additive

mg

1,7-heptanediol 17 15 14

[Ppm]

P [ppm] 92 80 74

with FFA [%] 0, 99 1, 02

Addition of acid mucus

4, 1 4,4 4,8

(Variant b) [%]

Ca

0.20% 46 46 43

[Ppm]

mg

1,7-heptanediol 18 17 14

[Ppm]

P [ppm] 92 83 75 96, 4

7 minutes after FFA [%] 0, 96 1, 05

Addition of acid mucus

4.2 4, 6 4.4

(Variant c) [%]

Ca

0.20% 30 25 25

[Ppm]

mg

1,7-heptanediol 15 10 9,3

[Ppm]

95, 9

P [ppm] 98 60 52

with FFA [%] 1, 01 1, 01

Alkaline added mucus

3, 9 4 4

(Variant d) [%]

Ca

0.20% 42 31 30

[Ppm]

mg

1,7-heptanediol 26 14 11

[Ppm]

P [ppm] 165 80 60 96, 0

5 minutes after FFA [%] 1, 01 0, 95

Alkaline added mucus

3 4 4

(Variant e) [%]

Ca

0.20% 57 28 33 96, 1

[Ppm] mg

1,7-heptanediol 41 16 17

[Ppm]

P [ppm] 280 103 105

30 minutes after FFA [%] 1, 01 0, 97

Water added mucus

3, 5 4 4

(Variant f) [%]

Ca

0.20% 46 23 19

[Ppm]

mg

1,7-heptanediol 33 14 13

[Ppm]

P [ppm] 230 95 89

96, 0

5 minutes before FFA [%] 0, 94 1

End of the reaction mucus

3, 5 / | / |

(Variant g) [%]

Ca

0.20% 38 33 36

[Ppm]

mg

1, 2-propanediol 21 14 14

[Ppm]

95, 8 as standard P [ppm] 135 79 75 with FFA [%] 0, 88-0, 91

mucus

Water addition 4 4.3 4.3

[%]

Ca

0.20% 36 21 19

[Ppm]

Mg 96, 0

1, 2-propanediol 27 14 8, 9

[Ppm]

P [ppm] 200 100 56 5 minutes before FFA [%] 0, 92 0.89

Addition of acid mucus

3, 5 4.4 4.4

(Option A) [%]

Ca

0.20% 35 24 23

[Ppm]

mg

1, 2-propanediol 26 16 11

[Ppm]

95, 7

P [ppm] 185 110 60

with FFA [%] 0, 99 0, 91

Addition of acid mucus

3, 5 4.5 4.5

(Variant b) [%]

Ca

0.20% 34 36 26

[Ppm]

mg

1, 2-propanediol 24 18 11

[Ppm]

P [ppm] 165 110 65 95, 9

7 minutes after FFA [%] 0, 93 0.89

Addition of acid mucus

3 4.5 4.5

(Variant c) [%]

Ca

0.20% 47 25 35

[Ppm]

mg

1, 2-propanediol 29 15 14

[Ppm]

95, 9

P [ppm] 200 103 78

with FFA [%] 0.96 0.88

Alkaline added mucus

3, 5 4,3 4,2

(Variant d) [%]

Ca

0.20% 26 25 27

[Ppm]

Mg 95, 9

1, 2-propanediol 18 12 12

[Ppm]

P [ppm] 130 78 70 5 minutes after FFA [%] 0, 97 0, 96 0, 95

Alkaline added mucus

4 4.5 4

(Variant e) [%]

Ca

0.20% 33 23 28

[Ppm]

mg

1, 2-propanediol 24 13 13

[Ppm]

P [ppm] 168 83 82 96.2

30 minutes after FFA [%] 0, 9 0, 93 0, 95

Water added mucus

4 4,8 4

(Variant f) [%]

Ca

0.20% 36 25 28

[Ppm]

mg

1, 2-propanediol 26 14 13

[Ppm]

P [ppm] 200 88 77

96, 1

5 minutes before FFA [%] 1 0, 94 1, 02

End of the reaction mucus

3, 5 4 4,3

(Variant g) [%]

In 1, 7-heptanediol as an additive shows both in terms of oil yield and with respect to the lowering of P and

Ion values that a dosage with the water or the acid is most favorable.

Example 7 Enzymatic degumming with phospholipase AI partial neutralization in crude oil at 48 ° C. with enzyme, separation at 80 ° C. (reaction variant 6) In this Example, the effect of the solubilizers Invention ^¬ according to the enzymatic Ölentschleimung with phospholipase AI is examined. In order to be able to separate the effects of enzyme and additives, the measured data are to be compared with the results in Example 5 (identical experimental conditions but without enzyme addition).

The following table shows the characterization data of the oils used:

Table 17: Characterization data of Example 7

used oils (identical oil to Examples 5 and 6)

For these investigations the procedure was analogous to the partial neutralization (without enzyme) described for example 5; i.e. the same conditions were used as in Example 5, but only one enzyme was added. As the enzyme, PLA1 was used in an amount of 0.5 U / g of oil.

The solubilizers were used in a concentration of 0.2% by weight based on the oil. The enzyme dosage was carried out after the partial neutralization with the addition of water (and solubilizer in the inventive approaches.) It was as in Example 5 with 2.5% total water in soybean oil and 3% total water in rapeseed oil, minus the amount of acid and alkali, and 0.2% solubilizer based on the amount of oil worked. The solubilizer and the enzyme are first mixed with the water in a beaker and then added via a funnel to the reaction mixture. The procedure was then as described in Example 5, proceed. -

Table 18 to Example 7: Enzymatic degumming of soybean oil

Ca

, 20% 27 22 22

[Ppm]

mg

Heptanol 12 8, 6 8.1

[Ppm]

96.3 + 0.5 U / g PLAl P [ppm] 58 39 37

FFA [%] 0, 92 1.09

mucus

5, 6, 4.5, 3, 5

[%]

Ca

, 20% 20 20 16

[Ppm]

mg

-Hexanol 7, 9 7.5 5.7

[Ppm]

96.3 + 0.5 U / g PLAl P [ppm] 48 42 28

FFA [%] 0, 8 - 1.03

mucus

4,2 4,5 4

[%]

Ca 28 48 34

, 20%

[Ppm]

Mg 7, 9 14 6, 3

hexanol

[Ppm]

96, 1 + 0.5 U / g PLAl P [ppm] 41 85 29

FFA [%] 0, 95 - 0, 9

Mucus 4 4,5 3, 5

[%]

Ca

, 20% 20 16 12

[Ppm]

mg

-Pentanol 9, 4 8,3 5,4

[Ppm]

96.2 + 0.5 U / g PLAl P [ppm] 56 42 25

FFA [%] 0, 87 - 1, 01

mucus

5, 3, 4,5 3, 8

[%]

Ca

, 20% 21 18 15

[Ppm]

mg

-Pentanol 11 8.8 6, 6 96.2

[ppm] +0.5 U / g PLAIp [ppm] 61 46 33

FFA [%] 0, 85-1.06 mucus

5 4 3.7

[%]

Ca

, 20% 12 15 14

[Ppm]

mg

, 7-heptanediol 5,7 5, 9 5, 8

[Ppm]

96.4 + 0.5 U / g PLAl P [ppm] 36 39 36

FFA [%] 0, 97 - 1.09

mucus

4 3,7 3, 5

[%]

Ca

, 20% 21 11 17

[Ppm]

mg

-Methyl 2, 4-pentanediol 7, 9 4 5.4

[Ppm]

96.5 + 0.5 U / g PLAl P [ppm] 45 21 27

FFA [%] 0, 9 - 1,1

mucus

4,7 4 3, 5

[%]

Ca

, 20% 44 43 33

[Ppm]

mg

, 6-hexanediol 11 9, 4 7.3

[Ppm]

96.2 + 0.5 U / g PLAl P [ppm] 52 43 28

FFA [%] 0, 85 - 1, 01

mucus

5.7 3.7 3.7

[%]

Ca

, 20% 16 14 11

[Ppm]

mg

, 2-hexanediol 6, 3, 5, 3, 9

[Ppm]

96.5 + 0.5 U / g PLAl P [ppm] 38 34 24

FFA [%] 0, 97-1, 15

mucus

4 3, 9 3

[%]

Ca

, 20% 12 24 22 96.2

[Ppm] mg

2, 5-hexanediol 6, 8 8.2 7.5

[Ppm]

+0.5 U / g PLA1 P [ppm] 33 43 40

FFA [%] 0, 99 - 1.09

mucus

4 3.5 3, 2

[%]

Ca

0.20% 4, 9 11 11

[Ppm]

2, 2-dimethyl-1, 3-Mg

2, 6 5, 1 4, 9

propanediol [ppm]

96.2

+0.5 U / g PLA1 P [ppm] 15 29 27

FFA [%] 0, 96 - 0, 91

mucus

4,3 4 3, 5

[%]

Ca

0.20% 8.7 5, 1 10

[Ppm]

mg

2, 3-butanediol 5, 1 2.5 4.3

[Ppm]

96.3

+0.5 U / g PLA1 P [ppm] 28 14 26

FFA [%]

mucus

4 4 3.7

[%]

Ca

0.20% 16 7.7 13

[Ppm]

mg

1, 2-propanediol 6, 9 3.4 5, 6

[Ppm]

96.3

+0.5 U / g PLA1 P [ppm] 39 18 31

FFA [%] - 1.08

mucus

4,3 4 3, 5

[%]

The results show that oil yield can be increased by enzymatic soot degumming with Phopholipase 1 through a series of additives selected dosage of 0.2%, the largest increase in the oleaginous yield of 0.5% when using 2-methyl-2, 4-pentanediol and 1,2-hexanediol results. Some additives, in particular 1-octanol, 3-heptanol, 2,3-dimethyl-1,3-propanediol, 2,3-butanediol and 1,2-propanediol also lead to an acceleration of the reaction with respect to enzymatic desliming without additive, the especially recognizable by the P-values of the oil after 10 minutes. An example of this is the additive 2, 2-dimethyl-l, 3-propanediol, the use of which the P value is lowered to 15 ppm after 10 minutes, compared to 57 ppm P in the enzymatic desulphurization without additive. Table 19 to Example 7: Enzymatic desulphurization of rapeseed oil without and with the addition of solubilizers

Mucus 5, 5 5 4,7

[%]

Ca 13 10 8,2

, 20%

[Ppm]

2.1 1, 6 1.2

mg

- heptanol

[Ppm]

94.5 + 0.5 U / g PLAl P [ppm] 18 14 10

FFA [%] 1, 18 - 1.53

Mucus 5, 5 5,3 5, 0

[%]

Ca

, 20% 6, 8 4, 9 4.4

[Ppm]

mg

, 7-heptanediol 1.3 1.3 1

[Ppm]

94.5 + 0.5 U / g PLAl P [ppm] 9.7 12 7.5

FFA [%] 1.34 - 1.53

mucus

5 5,4 5

[%]

Ca 6, 3 4, 9 4,2

, 20%

[Ppm]

1.2 1 0, 9

mg

-Methyl 2, 4-pentanediol

[Ppm]

94, 6 +0.5 U / g PLAl P [ppm] 7.7 7.2 7

FFA [%] 1.45 - 1.68

Mucus 5,4 5,4 5, 3

[%]

Ca

, 20% 5, 6 4.5 4, 1

[Ppm]

mg

, 2-propanediol 1.2 0, 9

[ppm] 1, 1

94.4 + 0.5 U / g PLAl P [ppm] 9.1 6.3 7.2

FFA [%] 1, 32 - 1, 69

mucus

5, 5, 5, 5, 1

[%] It turns out that the additives have an effect on enzymatic degumming of rapeseed oil with PLA1 in a different way than on soybean oil. It is also possible to identify additives according to the invention which show positive effects with regard to the reduction of the P values and ion values. This is particularly the case with the use of 2-methyl-2, 4-pentanediol and 1, 2-propanediol the case.

Example 8 Partial neutralization and enzymatic degumming with the addition of polyglycols

Using the reaction conditions in Example 7, the influence of a polyglycol on the partial neutralization of citric acid and the enzymatic degumming were examined (reaction variants 3 and 4). For this purpose, a polyglycol Bll / 50 was used. It is an ethylene oxide-propylene oxide monobutyl ether, wherein the ethylene oxide and propylene oxide groups are randomly distributed (average molecular weight: 1300 g / mol and HLB value: 9.58). The compound was obtained from Clariant Products (Germany) GmbH in Gendorf.

For this purpose, a soybean oil with the following characterization data was used:

Table 20: Characterization data of the soybean oils used

Raw soybean oil

Ca content [ppm] 172

Mg content [ppm] 129

P content [ppm] 800

FFA content [%] 0, 99 For the experiments with the partial neutralization, the procedure was as described in Example 5 (reaction variant 3), for the experiments on enzymatic degumming, the procedure was as described in Example 7 (reaction variant 4). Only the addition of water was reduced from 2.5 to 2%. In the batches with additive in each case 0.2% by weight of additive based on the oil was used.

The results of the investigations are shown in the following table:

Table 21: Results of degumming with ethylene propylene oxide mono-butyl ether as a solubilizer in part ^¬ neutralization of crude soybean oil and in enzymat een degumming of crude soybean oil

mucus

3.6 3.9 3.8

[%]

Ca

14 13 8.8

[Ppm]

mg

Partial neutralization 8 7.9 4.6

[Ppm]

96

+0.5 U / g PLA1 P [ppm] 48 45 21

FFA [%] 0.85 0.93

mucus

4.8 4.0 3.5

[%]

Ca

Partial neutralization 11 5.9 4.6

[Ppm]

mg

+0.5 U / g PLA1 4.5 2.9 2.3

[Ppm]

With the addition of 96, 4

ethylene oxide

P [ppm] 27 19 15

Propylene oxide monobutyl ether

FFA [%] 0.98 - 1.12

mucus

4.1 3.2 2.9

[%]

The results show the effect of the polyglycol according to the invention on the oil degumming. In the partial neutralization without subsequent use of phospholipase, although the oil yield is not increased, however, the values of P, Ca and Mg both after 10 min and after 30 min and 60 minutes reaction time compared to the comparative measurement significantly reduced.

In the case of enzymatic oil degumming, the addition of the additive leads both to an increase in the oil yield and to a significant reduction in the values for P, Ca and Mg in the oil compared with the comparison measurements without additive at 20 min, 30 min and 60 min. The increase of the FFA value with the additive documents the higher conversion of the phospholipase after 10 min and 60 min. Example 9 Aqueous degumming with citric acid according to

Reaction variant 5 According to reaction variant 5, a crude soybean oil with the following starting contents was used: phosphorus 860 ppm, calcium 63 ppm, magnesium 60 ppm and a free fatty acid content of 0.45%.

The crude oil was preconditioned using aqueous citric acid (1000 ppm) and then neutralized to pH 7-8 with aqueous sodium hydroxide solution (1 mol / L). Subsequently, various were

Concentrations of 1,2-propanediol (0.05-0.2% by weight of propanediol) were added and stirring continued. In comparison, a sample was stirred without 1,2-propanediol (standard degumming). The oil / water ratio (weight) was 98.5: 1.5. Samples were taken regularly (see Table 22). At the end of the reaction, the slime phase was centrifuged off and the oil yield was determined by mass weighing. The results are summarized in Table 22. It can be clearly seen that an increasing concentration of 1,2-propanediol leads to a reduction of the ions calcium (Ca), magnesium (Mg) and phosphorus (P). In the standard degumming of soybean oil, the following ion values were reached after one hour of reaction time: Ca: 4.7 ppm; Mg: 3.7 ppm and P: 42ppm. After one hour of reaction time, with 0.2% by weight of 1,2-propanediol, ionic values of: Ca: 1.1 ppm, Mg: 0.69 ppm and P: 10 ppm were reached. In addition, the oil yield with 1,2-propanediol increased from 95.5 to 95.8% by weight. The values were confirmed in duplicate. It was thus shown that the addition of 1,2-propanediol makes the oil degumming more effective and a higher oil yield is achieved. Table 22: Degumming with different concentrations of 1,2-propanediol compared to standard degumming

Example 10: Enzymatic degumming according to

Reaction variant 6

According to reaction variant 6, a crude soybean oil with the following starting contents was used: phosphorus 860 ppm, calcium 63 ppm, magnesium 60 ppm and a free fatty acid content of 0.45%. The crude oil was preconditioned using aqueous citric acid (1000 ppm) and then neutralized to pH 4-5 with aqueous sodium hydroxide solution (1 mol / L). Subsequently, according to reaction variant 6, a phospholipase AI (PLA1) from Thermomyces lanuginosus and various concentrations of 1,2-propanediol (0.05 to 0.2% by weight) were added and stirring was continued. In comparison, a sample without 1,2-propanediol (PLA1) was

Standard degumming). The oil / water ratio (Weight) was 98.5: 1.5. Samples were taken regularly (see Table 23). At the end of the reaction, the slime phase was centrifuged off and the oil yield was determined by means of a mass weighing.

The results are summarized in Table 23. It can be clearly seen that an increasing concentration of 1, 2-propanediol leads to an increased oil yield and that the use of e.g. 0.2% by weight 1,2 propanediol + PLAl a further increase by about 1% degummed soybean oil allows. The values were confirmed in duplicate. It was thus shown that the addition of 1,2-propanediol makes the oil degumming more effective and a higher oil yield is achieved.

Table 23: Degumming with different concentrations of 1,2-propanediol and PLAl compared to PLA1 standard degumming

Example 11: Aqueous degumming of soybean oil on a pilot scale

As part of the degumming processes in oil refining on an industrial scale, the separation of the oil phase and the water phase is usually carried out in a continuous process, wherein in the prior art plate separators are used. To simulate this process, a pilot plant experiment was carried out using a plate separator, which is typically used for industrial degumming processes ("pilot scale").

For mixing the crude oil with the aqueous phase, a plant for Ölentschleimung in the scale of 100 to 120 kg of vegetable oil with a stirrer, temperature-jacketed ^¬ jacketed reactor and with an industry comparable pumping system of the company IST, type 060-TRA-10 1, was used. For the separation, a separating separator OSC 4 from GEA-Westfalia (Oelde) was used. Such a separator is characterized labeled in ^¬ characterized in that the filling with oil and emptying of the gerei ^¬-adjusted oil is carried out continuously, while the heavy phase (water with plant oil mucus or lecithin) is discontinuous, namely, whenever the separator is filled with mucus is.

For the experiments, a crude soybean oil was used whose characterization ^data are summarized in the following table: Table 24: Characterization data for the

Technikumsversuche used raw soybean oil

In each case 100-120 kg of the crude soybean oil were first stirred at 60 ° C for 60 minutes in a jacketed reactor with 2 wt .-% water and then subjected to a phase separation with the plate separator. This attempt served as

Comparative Example for a Standard Separation. Analogously, in a second variant, 0.2% by weight (based on the mass of the oil used) of the invention

Solubilizer 1,2 Propandiol added to the water used for degumming.

With regard to the separation, the following procedure was used in both cases: The volumetric flow rate was set at 100 l / h for all experiments, the back pressure of the light phase was set at 3.5 bar.

The time interval between the partial emptying was defined as a variable size. After stirring for 60 minutes with the aqueous phase, the mixture was heated to 80 ° C for 10 minutes. The separator was then preheated with the reaction mixture until the first partial emptying, then adjusted to the predetermined parameters until the second partial emptying (volume flow and counter-pressure). Meanwhile, the separated oil was run in a separate container and weighed. The mass of the heavy phase was also determined separately. Then, after the second partial emptying, the conversion to the actual separation vessel took place.

Until the third partial emptying the separator was again set to a constant separation. This includes heating the separator and checking the clarity of the light phase in the sight glass. Exactly in the interval after the third partial emptying to the fourth partial emptying, two samples were taken each time at the tap of the sight glass window of the clear water. The first sample for the determination of the ions, the second sample was a spin glass sample to determine the proportion of heavy phase in the separated oil. For this, these were centrifuged four minutes at 4000rpm in a Laborzen ^¬ trifuge after the sampling.

Sampling and sample analysis was performed always after the third partial emptying to prevent influences of the start of the Se ^¬ paration for the results. One minute was chosen as sampling interval.

From a good separation is spoken according to the device ^¬ manufacturer, if the proportion of heavy phase in the clear (separated oil) is 0.1% to 0.2% or better. Both processes were repeated, with no signi ^¬ fikanten differences in the measured data. The results in a purely aqueous degumming and with the addition of 0.2% by weight of 1,2 propanediol to the oil are shown in the following two tables and figures which show the analysis data relating to the separated oil as a function of the separation time.

Table 25: Separation of soybean oil on pilot plant scale after aqueous degumming

FIG. 3 shows the separation of the soybean oil on a pilot plant scale after aqueous degumming (according to the data according to Table 25). Table 26: Separation of the soybean oil on pilot plant scale after aqueous degumming with the addition of 2.2% by weight of 1,2-propanediol

FIG. 4 shows the separation of the soybean oil on a pilot plant scale after the aqueous degumming with the addition of 2.2% by weight of 1,2-propanediol (according to the data according to Table 26).

From the comparison of the content of the heavy phase of the separated oil (determined by the P content) as a function of the separation time, the following statements can be made:

In the purely aqueous degumming occur from the beginning of strong fluctuations in the content of heavy phase, the can not be attributed to the running of the separator. The upper limit, defined on an industrial scale according to the specifications of the separator manufacturer, with respect to the P content in the oil after separation is almost always exceeded and there are strong fluctuations.

The addition of 1,2-propanediol greatly improves the separation under the chosen experimental conditions. In a period of up to 6 minutes, the content of the heavy phase in the separated oil is very low and well below the upper limit of 0.2 wt. Then, a steep increase is caused by the running of the container for the slime in the separator. On an industrial scale, an automatic emptying of the separator would take place here.

Indirectly, the slower content of the slime in the oil as a function of time can be deduced from the course of the heavy phase content in the oil, and thus a higher oil yield can be derived by using 1,2-propanediol as an additive, with precise quantification using these experimental data alone not possible. Considering the first peak in the aqueous degumming as process fluctuation caused, since then the content of heavier phase again below 0.2% by weight reduced, so remains from 4 minutes, the content of heavy phase above the limit of 0.2%, i. the separator is already filled with heavy phase. This case occurs when using 1, 2-propanediol only from 7 min on.

Claims

claims

Process for degumming of triglyceride-containing

Compositions comprising the steps

(a) contacting a triglyceride-containing

Composition with at least one solubilizer;

(b) separating the slime phase from the triglyceride-containing composition.

The method of claim 1, wherein the at least one

Solubilizer has an HLB value of 5.5 to 13.5.

The method of claim 1 or 2, wherein the at least one solubilizer is selected from the group consisting of polyhydroxy compounds, polyglycols, alcohols and mixtures thereof.

A method according to claim 3, wherein the

Polyhydroxy compounds have an asymmetric molecular structure.

A process according to any one of the preceding claims wherein the at least one solubilizer is selected from the group consisting of 1,2-propanediol, 1,3-propanediol, 1,2-butanediol, methyl glycol, methyl 1,3-propanediol, 1-octanol, 2, 2-dimethyl-1,3-propanediol, 2,3-butanediol, butanol, ethanol, isopropanol, ethylene oxide-propylene oxide monobutyl ether, 1-pentanol, 3-pentanol, 2-methyl-2, 4-pentanediol, 1-hexanol, 3 Hexanol, 1,6-hexanediol, 2,5-hexanediol, 1-heptanol, 3-heptanol, 1,7-heptanediol,

Sucrose esters, mono- and diacetyl tartaric acid esters of monoglycerides, polyglycerol esters, sorbitan esters,

Polyoxyethylene sorbitan esters, polyethylene glycols, Copolymers of ethylene oxide and propylene oxide units and mixtures thereof.

A method according to any one of the preceding claims wherein, prior to separating the slime phase from the triglyceride-containing composition according to step (b), at least one enzyme is added to the triglyceride-containing composition.

The method of claim 6, wherein the at least one

Solubilizer before the at least one enzyme is added.

A method according to any one of claims 6 or 7, wherein the at least one enzyme is selected from the group consisting of phospholipid-cleaving enzymes, glycosolating enzymes and mixtures thereof.

The method of any one of claims 6 to 8, wherein the at least one enzyme has alpha or beta glucosidase activity.

Method according to one of claims 6 to 9, wherein the at least one enzyme is selected from the group consisting of phospholipase AI, phospholipase A2,

Phospholipase C, acyltransferase, alpha-glucosidase, beta-glucosidase and mixtures thereof.

11. The method according to any one of claims 6 to 10, wherein the

at least one enzyme comprises an amylase.

12. The method according to any one of the preceding claims, wherein as a triglyceride-containing composition crude vegetable oil or pre-degummed vegetable oil is used.

13. The method according to claim 1, wherein the triglyceride-containing composition is crude vegetable oil and, prior to contacting with step (a), water and / or acid and / or lye are added to the crude vegetable oil without before the

Separating the slime phase according to step (b)

Separation step is performed.

14. Use of at least one solubilizer for

Degumming of a triglyceride-containing composition.

15. Use according to claim 14, wherein the at least one

Solubilizer is selected from the group consisting of 1,2-propanediol, 1,3-propanediol, 1,2-butanediol, methyl glycol, methyl 1,3-propanediol, 1-octanol, 2,2-dimethyl-1,3

Propanediol, 2,3-butanediol, butanol, ethanol, isopropanol, ethylene oxide-propylene oxide monobutyl ether, 1-pentanol, 3-pentanol, 2-methyl-2, 4-pentanediol, 1-hexanol, 3-hexanol,

1, 6-hexanediol, 2, 5-hexanediol, 1-heptanol, 3-heptanol, 1.7 heptanediol, sucrose ester, mono- and diacetyl

Tartaric acid esters of monoglycerides, polyglycerol esters,

Sorbitan esters, polyoxyethylene sorbitan esters,

Polyethylene glycols, copolymers of ethylene oxide and

Propylene oxide units and mixtures thereof.