EP3149133A1

EP3149133A1 - Method for purifying refined lipid phases

Info

Publication number: EP3149133A1
Application number: EP15730076.5A
Authority: EP
Inventors: Max DIETZ
Original assignee: Drei Lilien Pvg Gmbh&co KG; SE Tylose GmbH and Co KG
Current assignee: Drei Lilien Pvg Gmbh&co KG; SE Tylose GmbH and Co KG
Priority date: 2014-05-30
Filing date: 2015-06-01
Publication date: 2017-04-05
Anticipated expiration: 2035-06-01
Also published as: PL3149133T3; HUE043439T2; CA2947462C; AU2015265839A1; AU2015265839B2; RU2689556C2; RU2016152218A3; US10053649B2; PT3149133T; CA2947462A1; CN106459827A; CN106459827B; US20170081611A1; ES2727082T3; EP3149133B1; WO2015181399A1; MY178981A; ZA201608251B; RU2016152218A

Abstract

The invention relates to a method for eliminating turbid matter from a lipid phase.

Description

Process for refining refined lipid phases

The present invention relates to a process for the separation of suspensions from a lipid phase.

Background of the invention

Lipid phases of biogenic origin contain in addition to the coveted for further use neutral fats, such. As triglycerides, usually numerous organic impurities, which provide in the biological context from which the lipids come, for a solubilization. Therefore, these concomitants, despite their overall amphiphilic properties, often have remarkably high lipophilicity. This depends on the ratio of hydrophilic and hydrophobic moieties. While compounds with a high binding capacity of water molecules, as is the case for example with the hydratable phospholipids (phosphatidylcholine and phosphatidyletolamine), can easily be washed out by a water entry into a lipid phase, this is already the case with structurally very similar phospholipids which are not hydratable (Phosphatidylinositols and phosphatidylserine), already no longer exist. Furthermore, glycolipids and glycoglycerolipids are also present in most lipid phases, which often have very long-chain fatty acid residues and, despite the absence of polar groups, can not simply be rinsed out by means of an aqueous medium from a lipid mixture. Furthermore, in most lipid phases of plant origin also sterol glycosides and hydrophobic dyes such as carotenes and chlorophylls are included. Such compounds are completely water-insoluble and therefore remain in the lipid phase in an aqueous refining. However, all of the above compounds are capable of small amounts of water molecules via electrostatic exchange forces z. B. to bind to OH groups. The aforementioned compounds are furthermore usually present together in complex structures, including ions from the group of the alkaline earth metals and the metals. This further increases the cohesion in the area of hydrophilic groups. This explains why it is necessary to purify such lipid mixtures with aqueous media containing strong bases and strong acids. However, it has not yet been possible to show for any process that complete separation of compounds which can bind water ions via OH groups is possible. Consequently, it is also not possible, by means of simple aqueous refining techniques, to lower the residual water content or the capacity of the refined oil for water to a level that meets the product requirements both to a food quality, as well as to a lipid phase, which is used as a technical product, such as. B. for biogenic fuels, is sufficient. In order to achieve drying of aqueous refined lipid mixtures according to the state of the art, the pretreated lipid phases are freed either by heating or by vacuum drying of water constituents therein, wherein a reduction of the residual water content to values between 0.05 and 0.15% by weight is realistically achievable is. Such a drying process increases the refining costs. Furthermore, the water-binding compounds remain in the lipid phase, so that it can come in a renewed water entry again to a water binding and thus clouding of the lipid phase. Therefore, these compounds are sometimes referred to as clouding agents, wherein turbidity by the turbidity herein understood is not visible in that complex organic compounds themselves are visible, but the turbidity by water molecules, which are bound by these organic compounds, arises. In contrast to complex organic structures, also referred to as turbidity, which can be imaged by means of optical techniques and are therefore extractable and separable as a corpuscular structure by filtration, the turbidity herein is characterized by the fact that they do not rely on a filter technique based on a size exclusion based on particulate particles, can be separated.

The presence of such organic compounds may also adversely affect the oxidation stability of the lipid phases in which they are located. Therefore, their removal from a lipid phase is desirable because it provides a much improved refining product. The refining steps downstream of the prior art of aqueous refining of triglyceride mixtures, such as treatment with bleaching earths and / or steaming (deodorization), are able to significantly reduce the water-binding capacity of aqueous pre-refined lipid phases. The disadvantage here is that the process steps following the aqueous refining steps result in a considerable increase in production costs. Furthermore, a treatment with bleaching earths also leads to a relevant loss of triglycerides, which are removed with them.

An aqueous refining process has now been established, which allows a much more efficient separation of amphiphilic concomitants from a lipid phase. This can very efficiently both amphiphilic compounds, z. As saccharides, such as glycolipids are removed from lipid phases, as well as carboxylic acids. Furthermore, there is also a relevant separation of dyes, so z. B. a quality of such a refined oil is achieved, which no longer requires further treatment with a bleaching earth or deodorization. As a result, an efficient and inexpensive aqueous refining of biogenic lipid phases is possible, whereby process costs can be saved. It has been found, however, that even with very complete removal of glycolipids, free fatty acids, phosphorus-containing compounds and alkaline earth metal ions, the refined lipid phases, which are obtained after centrifugal separation of these compounds together with the aqueous phases, still have a clear turbidity. Water was found to contain> 1, 5% by weight so that the oils did not meet the required product specifications, although a depletion of the phosphorus content to <2 ppm and the content of calcium, magnesium and iron was <0.05 ppm and the content of free fatty acids of <0.15% by weight had been achieved. When such a refined turbid oil phase was subjected to drying, for example by means of vacuum drying, the residual moisture content could be reduced to <0.1% by weight. The dried oils were transparent. In such oils could be added by mixing with water relevant amounts of water, so that these oils were cloudy again and could not be clarified by centrifugal processing techniques. A reduction of the residual moisture of a refined lipid phase is desired in order to obtain as clear a oil as possible, but also for the improvement of the quality of the oil the residual moisture is a decisive determinant. Another aspect of residual moisture of a lipid phase relates to storage stability, which is adversely affected by a higher content of water molecules remaining in a lipid phase. However, this also occurs when compounds are present in the lipid phase, the water molecules, eg. B. from the air, can bind. Therefore, it is necessary to reduce the residual water content to a product-specific minimum and it is desirable to eliminate organic compounds that promote water absorption into the lipid phase. In lipid phases and especially in oils and fats of plant or animal origin, chemical reactions occur to a variable extent, which depends on the storage conditions (air / light exposure, temperature conditions,

Container surfaces) and the presence of compounds that can cause oxidation of carbon double bonds (see p-Anisidinwertbestimmung), and the presence of compounds that allow a radical or reduction of radicals, such as tocopherols, polyphenols or squalene. The oxidative processes include aldehydes, ketones and free fatty acids, which further accelerate oxidative processes and are largely responsible for off-flavors in vegetable oils. During a classical refining process, the degumming process occurs usually a reduction of compounds that cause oxidative processes. The treatment of oils with bleaching earths can lead to acid-catalyzed oxidations and, to a variable extent, compounds which have antioxidative properties are depleted, so that the oxidation stability of an oil can be markedly worsened by this process step. In principle, the same applies to the deodorization process, especially when higher steam temperatures (> 220 ° C) and a longer residence time (> 15 minutes) of the oil are required. Therefore, the storage stability is influenced by the classical methods to varying degrees. Thus, compared to cold-pressed oils, such refined oils often have no advantage in terms of storage stability, since in the native oils the antioxidants contained therein have been left and no compounds have been added which promote auto-oxidation. Substances that promote auto-oxidation usually have free-radical or radical-forming groups, or have a binding capacity for water molecules. A targeted depletion of these compounds is not possible in the prior art.

It has been shown that water extraction processes, such as vacuum drying, result in the desired removal of residual water contents. However, the application of these techniques makes the aqueous refining process uneconomical. Furthermore, re-entry of water into a lipid phase that has been refined in water and then vacuum-dried is still possible. This significantly affects the product properties of the lipid phases. Since in these lipid phases already a depletion of impurities to a level was done, which makes further refining steps, such as bleaching or deodorization, no longer necessary and to free the thus obtained lipid phases economical and gentle on the product of the remaining turbidity and thus on the one hand A new procedure was needed to reduce the residual water content to the required level and to reduce the re-usability of water. Surprisingly, a very simple and effective method has now been found with which, in the case of such well prepurified but cloudy lipid phase, it is possible both to remove the residual content of water from a lipid phase which can be obtained following aqueous refining and at the same time to remove the responsible for this turbidity. Furthermore, since the process can be carried out at relatively low cost compounds at ambient temperatures as well as without significant expenditure on equipment, and at the same time only very little or even negligible loss of neutral lipids, this process represents a considerable improvement over the prior art described prior art process and meets the desired conditions. It is therefore the object of the present invention to provide processes for drying lipid phases with simultaneous removal of water-binding organic turbidity.

Object of the invention

Object of the present invention is to provide methods for the separation of turbidity from a lipid phase. This object is achieved by the technical teaching of the independent claims. Further advantageous embodiments of the invention will become apparent from the dependent claims, the description, the figures and the examples. Detailed description of the invention

Biogenic lipid phases, which were obtained under anhydrous conditions, usually have a clear appearance, as far as suspended solids, which are confusingly often referred to in the literature as turbidity, were filtered off. Often, water entry into these lipid phases is difficult to achieve because the compounds capable of binding water molecules are so complexed in the lipid phase that they are shielded by the surrounding neutral lipid phase. This complex cohesion, which is made possible, in particular, by non-hydratable phospholipids, as well as by alkaline earth metal ions and metal ions, must first be disrupted so that these compounds can interact with water molecules and thereby be converted into a water phase in order to remove them with the water phase. Inevitably, this leads to a breakup of tethered complexed organic compounds, which may also bind, for example via OH groups, water molecules, but can not be converted into the water phase due to their strong lipophilicity. This theory is supported by observations made in the refining of triglyceride mixtures. Here, it was found that for oils which have a very high content of accompanying substances, after each aqueous refining step an increase in the turbidity of the triglyceride mixture occurred after a centrifugal separation of the water phase, despite a significant depletion of accompanying substances. This is especially true when there are glycolipids and glycoglycerolipids in the lipid phase. Provided that in these lipid phases in addition to an optional classical aqueous degumming, which can be done with pure water and / or an acid (eg phosphoric acid), a subsequent, at least 2-stage treatment with mild to strongly basic compounds, optimal reduction of accompanying substances is possible. It has been found that, if at least one of the basic aqueous refining steps is carried out with a compound containing guanidine group or amidine group, it is possible to obtain lipid phases in which a highly efficient depletion of accompanying substances is achieved with a phosphorus content of <5 ppm ( or <5 mg / kg) of neutralizable acids of <0.15% by weight and a virtually complete extraction of alkaline earth metals and metal ions to values <0.05 ppm (or <0.05 mg / kg) with at the same time considerable reduction of plant dyes (such as chlorophylls) in the resulting lipid phases. On the other hand, the water content and the turbidity in the refined oil increased when particularly good refining results were achieved. This was particularly noticeable when refining was carried out with intensive mixing with an aqueous solution containing guanidine or amidine group-bearing compounds. The resulting emulsions were significantly cloudier than after stirring addition of the aqueous refining solution. This is due to a much more homogeneous distribution of the water fraction in the oil phase, which could be demonstrated by measuring the droplet sizes herein by means of a DLS measurement. Further, the tendency for coalescence of the formed droplets was significantly lower after intensive application of the water phase than after stirring. The long-term stability of such an emulsion was also significantly higher. Nonetheless, it was precisely in these very stable emulsions that it was possible to achieve phase separation by centrifugation, although the oils obtained were more turbid than was the case after stirring in the aqueous refining solution. A water discharge could not in these turbid oil phases by a variation of the refining process, eg. B. by varying amounts of introduced with an intensive mixer aqueous solutions in the lipid phase or by changing the conditions in the centrifugal phase separation (change in the centrifugation or centrifugal acceleration) can be achieved. Thus, it could be shown that by a more intensive entry of a water phase containing guanidine or amidine group-carrying compounds, although a complete depletion of Olbegleitstoffen can be achieved than in a Rühreintrag, at the same time the degree of turbidity of the resulting oil phase is stronger than that in a refining with a Rühreintrag the water phase.

The turbidity of the lipid phases, which was produced by hydration of the water-binding organic turbidity due to aqueous refining with at least one guanidine or amidine group-bearing compound, remained completely unchanged for months, spontaneous phase separation did not occur. Surprisingly, it has been found that this hydration of water-binding lipophilic organic compounds can be used to adhere or complex such compounds, whereby they can be extracted from their organic matrix and thus separated by physical methods.

This is also surprising because despite the achieved reduction of the known water-binding compounds from a lipid phase, which can be removed as part of an aqueous refining process and in particular virtually complete removal of alkaline earth metal ions and metal ions, in such biogenic lipid phases were still water-binding organic compound, the can not be converted into a water phase, so that therefore these compounds have a very high lipophilicity, with a small number or absence of ionizable groups. In fact, in biogenic lipid phases, such compounds are in variable amounts, such as. As sterols, squalene, phenols, waxes, wax acids, vitamins, glycolipids, or dyes.

Surprisingly, it has now been found that cellulose compounds allow complete clarification of the hydrated cloudy oils resulting from an aqueous refining, which was carried out as described herein and in which subsequently values of the oil indices were such. B. are to comply with edible oils, such as a residual phosphorus content of <5 ppm (or <5 mg / kg) and a content of free fatty acids of <0.15% by weight. This is all the more surprising because the cellulose products according to the invention can be distributed only disperse in an oil phase and have only a limited binding capacity for water.

These results are also astonishing because the same cellulose compounds had no effect on the extractability of the water-binding organic pulps either when added to a triglyceride mixture prior to the aqueous refining steps, or added to a triglyceride mixture following such aqueous refining Vacuum drying had been subjected and only had a low residual water content. In both cases, following the separation of the cellulose preparations, a renewed entry possibility of water into the lipid phase occurred, whereas this was no longer the case after extraction of the water-binding organic turbid substances according to the invention.

Thus, a particularly advantageous effect of the process according to the invention is to refine an aqueous refined lipid phase in which the water-binding organic turbid substances are present in a hydrated form, in that an interaction of the turbid substances with other compounds is achieved so that the turbid substances can be extracted from their organic matrix can be made. Thus, for the interaction of water-binding organic turbidity substances which permits the inventive separation of the turbid substances, their extraction (extraction) from a dressing with other fat accompanying substances just then very well possible if an aqueous refining with at least one solution containing Guanidingruppen- or Amidinruppentragende compounds and by an optimal Depletion of other water-soluble compounds and by the (simultaneous) presence of water, these turbidity become hydratable. Hydrated means in this context an attachment of water molecules. The presence of water molecules on the droplets to be separated then represents the important determinant for the interaction according to the invention in the form of adsorption and / or complexing for extractability of the water-binding organic turbidity substances.

A preferred embodiment is therefore to provide a lipid phase in process step a) in which organic turbid substances are present in a hydrated form.

According to the invention the object is achieved by a method for the adsorption and extraction or complexing and extraction of hydrophilic organic lipophilic Trübstoffen aqueous refined lipid phases, which is characterized by a) providing a lipid phase containing water-binding organic lipophilic Trübstoffe, wherein the lipid phase of at least one aqueous refining with a b) contacting an adsorbent and / or a complexing agent with the lipid phase from step a),

c) separation of the adsorbed or complexed water-binding organic lipophilic turbidity from stage b) by a phase separation,

wherein the adsorbent is cellulose, a cellulose derivative or an inorganic alumina silicate with an aluminum content of> 0.1 mol%, and

wherein the complexing agent is aluminum ions or iron ions present in an aqueous solution.

A further embodiment according to the invention is a process for the separation of water-binding organic lipophilic turbidity substances from an aqueous refined lipid phase, which is characterized by

a) providing a lipid phase containing water-binding organic lipophilic turbidities, wherein the lipid phase has been subjected to at least one aqueous refining with a neutral or basic solution, b) adding the lipid phase from step a) with an adsorbent and / or a complexing agent,

c) phase separation and separation of the adsorbed or complexed water-binding organic lipophilic turbidity,

wherein the adsorbent is cellulose, a cellulose derivative or an inorganic alumina silicate having an aluminum content of> 0.1 mol%, and

The provided contaminant-containing lipid phase must be subjected to at least one aqueous refining with a neutral to basic solution in order to ensure a sufficient reduction of accompanying substances of the prepurified lipid phase. A neutral solution is understood to mean water. A basic solution is an aqueous solution whose pH is greater than 7. To prepare an aqueous solution whose pH is greater than 7, are salts which upon dissociation in water, carbonate (CO32-), bicarbonate are (HCOs-) Metasilicat- (SiO ₃ ^{2 "),} Orthosilicat- (SiO ₄ ^{4 "} ), disilicate (Si ₂ O ₅ ^2" ), trisilicate (S 13 O 7 ^{2 "} or borate (BO ^{3 3"} ). Further preferred are hydroxide compounds, in particular with monovalent cations of the alkaline earth metals, such as sodium hydroxide, potassium hydroxide, but In principle, any basic compound which dissociates in water and is known to the person skilled in the art can be used.

A preferred embodiment of the process is the provision of a lipid phase in process step a) which has been subjected to at least one pre-purification step with a basic and / or acidic solution.

More preferably, the provision of a lipid phase in which, after an aqueous refining with a guanidine group or amidine group-bearing compound, a substantially complete reduction of phosphorus-containing compounds alkaline earth metal ions and metal free acid groups has been achieved.

The water-binding organic turbidities in the prepurified lipid phase are then brought into contact with an adsorption and / or complexing agent in step b). The water-binding organic lipophilic turbidity is adsorbed on suitable adsorbents or can form complexes with certain ions that are largely insoluble in water, but can be separated by their complexity in a water phase. Thus, the process is completed by in step c) the separation of the adsorbed or Complexed turbidity from step b) by a phase separation, the adhered or complexed water-binding organic Trübstoffe can be separated together with the extractant to obtain a low-turbidity and largely anhydrous lipid phase.

In one embodiment of the invention, the method described herein in any of step a), the at least one aqueous extraction by means of an aqueous solution with at least one Guanidingruppen- or Amidingruppentragende compound having a K _ow of <6.3 is performed.

The term K ₀ w refers to the distribution coefficient between n-octanol and water.

The technical teaching and the examples show various embodiments of the aqueous refining methods, which is to obtain a lipid phase according to the invention in the sense of step a) of the methods carried out herein.

Another important process feature is the provision of adhesion and complexing agents.

The use of cellulose products is a preferred embodiment for the adsorption of hydrogenated water-binding organic turbidity according to the invention. Cellulose and hemicellulose are preferred. These may be in their natural chemical structure or chemically modified by having substituents. Only a few examples may be mentioned here as examples, such as carboxymethylcellulose, hydroxyethylcellulose, methylhydroxyethylcellulose, methylhydroxypropylcellulose, ethylhydroxyethylcellulose, hydroxypropylcellulose, methylcellulose. Cellulose ester compounds are preferred. Further preferred compounds are cellulose ethers. It may be a fibrous, crystalline or amorphous form. The molecular weight is in principle arbitrary, but should preferably be in a range between 200 and 500,000 Da, more preferably between 1 .000 and 250,000 Da, and most preferably between 2,000 and 150,000 Da. The particle size is likewise freely selectable, although preference is given to particle sizes between 5 and 10 μm, more preferably between 20 and 6 μm, and most preferably between 50 and 500 μm

In principle, other sugar-containing compounds are also suitable as adsorption substances according to the invention, including, inter alia, β-1,4-glycosidically bound Hexoses or pentoses, such as. Chitin, callose, or a-1, 4-glycosidically linked hexoses or pentoses, starch such as amylose.

Furthermore, complex structures of the prescribed compounds are possible, as well as combinations thereof.

These biopolymers are also advantageous because they can be very easily removed from the lipid phases by various processes from the prior art, such as sedimentation, centrifugation or filtration. It is also advantageous that after separation from the lipid phase hardly triglycerides are separated with. On the other hand, virtually no cellulose remains in the lipid phase. Another advantage of such adsorptive separation of the hydrated water-binding turbidity is that they can be extracted and separated under mild process conditions and thus in principle be present in a chemically and structurally unchanged form and can be made available for further use.

Furthermore, very good finishing results could be achieved with Polyaluminiumhydroxychloridsulfat. Thus, the present invention also relates to processes using polyaluminum hydroxychloride salts.

Accordingly, the invention relates to the use of the methods described herein for the separation and recovery of water-binding organic lipophilic truncates.

In a preferred embodiment, the provision of the lipid phases containing hydrated hydrophilic organic suspending agents is at a temperature between 10 and 60 ° C, more preferably between 15 and 50 ° C and most preferably between 20 and 40 ° C.

In a preferred embodiment, the drying of a lipid phase takes place at a temperature of <40 ° C.

The amount of extractable hydratable organic turbidity can vary depending on the application, as well as the adsorption capacity of the adsorbent used. Thus, both the amount of adsorbent (cellulose, cellulose derivatives and other saccharide-containing compounds as disclosed herein) required to refine a refined lipid phase and the time required for the adsorbent to remain in the prepurified lipid phase for each application must be determined. Preferably, the dosage of the adsorbent to the lipid phase of <5% by weight, more preferably <3% by weight, and most preferably <1% by weight. Also preferred is an adsorption time of 1 minute to 12 hours, more preferably between 5 minutes and 8 hours, and most preferably between 10 minutes and 3 hours. The introduction of the cellulose compounds is preferably carried out by stirring with a propeller stirrer with slight agitation of the lipid phase until a very homogeneous distribution in the lipid phase is achieved. Since the duration required for this can vary naturally, the required duration for this must be determined. The duration of the stirring process is included in the adsorption period and should account for a proportion thereof of <20%. The cellulose compounds are preferably separated immediately after the required adsorption time. This can be done by sedimentation, centrifugal separation, or filtration. Preference is given to filtration, the apparatus and filters required for this purpose are known to the person skilled in the art.

In a further embodiment, to obtain an optimal hydration of the water-binding organic turbidity, d. H. Attachment of water molecules to the organic turbidity or formation of a water envelope, following one or more aqueous refining (s), an aqueous refining step with an aqueous solution containing a dissolved guanidine group or amidine group bearing compound.

In a preferred embodiment, the hydration of water-binding organic turbidity is carried out by an aqueous refining step with a solution containing guanidine group- or amidino-containing compounds. In this case, preference is given to a quantitative ratio between the lipid phase and the water phase containing dissolved guanidine group or amidine group-bearing compounds of 10: 1, more preferably of 10: 0.5, and most preferably of 10: 0.1. Preference is given to intensive mixed introduction with a rotor-stator mixing system. The terms homogenizing, dispersing, intensive entry, intensive entry, intensive mixing and intensive mixing are used here essentially synonymously and refer to the homogenization of oil with an aqueous solution. By the method of homogenization of lipid phases, in addition to carboxylic acids other organic compounds that do not correspond to a neutral or an apolar solvent, there is a very advantageous and effective co-discharge of these compounds in the water phase in the carboxylic acids dissolved nanoemulsively. Intensive mixing systems and methods are known from the prior art, such as. As rotor-stator systems, Kollidmühlen, high-pressure homogenizers or ultrasonic homogenizers. This preferred intensive mixer is preferably carried out over a period of 1 to 20 Minutes, more preferably between 2 and 10 minutes and most preferably between 3 and 5 minutes. The temperature of the lipid phase is preferably between 10 and 60 ° C, more preferably between 15 and 50 ° C and most preferably between 20 and 40 ° C. Preference is given to an immediately subsequent centrifugal phase separation, which is preferably <10 minutes, more preferably <7 minutes and most preferably <5 minutes.

The extraction according to the invention of hydrated water-binding organic turbidities of aqueous refined lipid phases can be carried out, depending on the application, with a powdery formulation of the adsorbents and preferably of cellulose compounds or of kaolin. In this case, the adsorbent can be added to the prepurified lipid phase or the lipid phase to the adsorbent. In one embodiment, the adsorbent used may also be a solid and non-ionically soluble inorganic compound. For the adsorption according to the invention hydrated water-binding organic Trübstoffe are phyllosilicates suitable. In this case, particularly preferred clay minerals, such as. As montmorilonite, cholites, kaolins, serpentine. Also particularly preferred are aluminum-containing silicate compounds. They are already particularly advantageous because they are available on a large scale and have no toxic effects due to their physical structure. In one embodiment, preference is given to the use of sheet silicates which have an aluminum content of> 25% by weight, more preferably> 30% by weight and most preferably> 40% by weight. The preferred form of application is a microcrystalline powder. Especially preferred is kaolin. More preferred is a microcrystalline powder form of kaolin. The amount of the powders of the inorganic compounds depends on the specific adsorption capacity. Preferred is an amount ratio (g / g) of the powdered absorbent to the prepurified lipid phase of <0.03: 1, more preferably <0.01: 1 and most preferably <0.001: 1. The temperature of the lipid phase is preferably between 10 and 60 ° C, more preferably between 15 and 50 ° C and most preferably between 20 and 40 ° C. Preference is given to an immediately subsequent centrifugal phase separation, which is preferably <10 minutes, more preferably <7 minutes and most preferably <5 minutes. Further preferred is a separation by filtration.

In a preferred embodiment of process step b), phyllosilicates having an aluminum content of> 25% by weight are used for the adsorption of hydrated organic turbidity substances. Preferably, the dosage of the silicates according to the invention of <5% by weight, more preferably of <3% by weight and most preferably <1% by weight. Also preferred is an adsorption time of 1 minute to 12 hours, more preferably between 5 minutes and 8 hours, and most preferably between 30 minutes and 3 hours. The entry of the silicate compounds is preferably carried out by stirring with a propeller stirrer with gentle agitation of the lipid phase until a very homogeneous distribution is achieved. Since the duration required for this can vary naturally, the required duration for this must be determined. The duration of the stirring process is included in the adsorption period and should account for a proportion thereof of <20%. The silicate compounds are preferably separated immediately after the required adsorption time. This can be done by sedimentation, centrifugal separation, or filtration. Preference is given to filtration, the apparatus and filters required for this purpose are known to the person skilled in the art. In a further embodiment of the process according to the invention, an extraction of hydrated water-binding organic turbidity substances from the organic matrix takes place by complexing them.

This object is achieved by the provision and introduction of ionic compounds from the group of cations from the group of transition metals, semimetals and metals.

In a preferred embodiment, an extraction of hydrated organic turbidity is carried out by complexation with cations from the group of transition metals, semimetals and metals.

Complexation refers to the formation of one or more complexes or coordination compounds. Thus, it is meant to be a complexation of a hydrated water-binding organic vehicle, the binding of said turbid substance to a metal or transition metal as disclosed herein, in the form of a coordination compound. The intermolecular interactions leading to complexation may be due to physicochemical bonding energy forms, such as hydrogen bonds, and van der Waals interactions, or to a chemical interaction leading to covalent bonding. The resulting complex can be separated from the organic phase either by itself or by aggregation with other complexes by a physical separation technique, such as a centrifugal or a filtration separation process. Particularly suitable for this purpose is an aqueous solution with aluminum chloride, which is introduced into the aqueous refined lipid phase containing hydrated water-binding turbidity by a mixing process, which leads to a complexation or aggregate formation, their separation by both a spontaneous phase separation, a Sedimentation, centrifugation or filtration can be easily accomplished.

However, it is also advantageous to provide an aqueous solution in which calcium, magnesium, iron, copper or nickel are present in ionized form. Preferably, aluminum or iron (III) ions are present.

The counterions are in principle freely selectable, but salts with sulfate, sulfide, nitrate, phosphate, hydroxide, fluoride, selenide, telluride, arsenide, bromide, borate, oxalate, citrate, ascorbate are preferred. Very particular preference is given to salts with chloride and sulfates. However, the anions should be highly hydrophilic so that they remain in the water phase. The solutions should consist of otherwise ion-poor or ion-free water in which the preferably used cations are present in a molar concentration between 0.001 and 3, more preferably a molar concentration of 0.1 to 2, and most preferably between 0.5 and 1 molar. The volume of the aqueous solution used is <10% by volume, more preferably <5% by volume and most preferably <1.5% by volume in relation to the prepurified lipid phase. The entry is preferably made by rapid pouring. The mixture with the lipid phase is preferably carried out with a fast-rotating propeller or Schaumrührgerät with a turbulent Mischeintrag. However, intensive mixing methods as described herein may also be used. Since the duration required for this can vary naturally, the required duration for this must be determined. Preferred is a blend of from 1 to 60 minutes, more preferably between 5 and 45 minutes, and most preferably between 10 and 20 minutes. Also preferred is a complexation time of 1 minute to 5 hours, more preferably between 5 minutes and 3 hours, and most preferably between 10 minutes and 1 hour.

The temperature of the lipid phase is preferably set to values between 10 and 60 ° C, more preferably between 15 and 50 ° C and most preferably between 20 and 40 ° C. Preference is given to an immediately subsequent centrifugal phase separation, which preferably takes place for a duration of <10 minutes, more preferably <7 minutes and most preferably <5 minutes. Separation of the phases can also be achieved by sedimentative phase separation or filtration. Further preferred is a separation with a separator. Thus, the invention relates to a process in which in step c) a sedimentative centrifugal, filtration or adsorptive separation technique is carried out.

In a further embodiment of the method according to the invention, the separation according to step c) is carried out by a sedimentative centrifugal or filtration or adsorptive separation technique or by centrifugation or filtration.

The complexed and separated turbid substances can easily be separated and quantified from the otherwise unchanged aqueous solutions containing the alkaline earth metal ions or metal ions by means of a filter. In this embodiment, the extraction and separation of the water-binding organic turbidity is possible with virtually no loss of triglycerides.

In a preferred embodiment, the extraction and separation of hydrated organic turbidity occurs without product loss of a triglyceride mixture.

Another aspect of the invention is that the adsorption and complexation of organic turbid substances together with the water molecules bound to them can be separated from the lipid phase. This has the enormous advantage that in one process step, the hydrated water-binding turbidity and the bound water can be removed from a lipid phase. In a particular embodiment, a drying of a lipid phase containing hydratable turbid substances takes place by adsorption and separation and / or complexing and separation of the hydratable turbidity together with the bound water phase.

It has been shown that lipid phases treated according to a refining process described herein and subsequently have turbidity and a water content of more than 1.0% by weight, are subject to the adsorption and separation or complexing and separation processes of the present invention of turbids then had a clear to brilliant appearance. This is due to a reduction in the residual moisture content contained in the refined lipid phases, which is reduced by at least> 75% by weight, more preferably by at least> 85% by weight, and most preferably by at least> 95% by weight, compared to the starting value of prior to incorporation of the adsorptive or complexing agents. Furthermore, the residual moisture is preferably less than 0.5% by weight, more preferably less than 0.01% by weight, and the most preferably lowered to less than 0.008% by weight. This can easily be investigated by prior art methods, such as the Karl Fischer method. Since lipid phases which have been treated with a one-stage or multistage aqueous refining process in which at least one of the method steps with a solution containing Guanidingruppen- or Amidinruppentragende compounds, already a product-specific sufficient depletion of fat accompanying substances can be achieved by a Removal of water-binding turbidity and the achieved drying of the lipid phases whose immediate use z. B. as edible oil, as a cosmetic oil, as lubricating or hydraulic oil or as fuel possible. The achievable with the method reduction of residual moisture causes further very beneficial effects:

- No heating or vacuum loading of the lipid phase

- Simple process technology with low production costs

- Short treatment time under product-gentle conditions

- Receipt of an immediately usable product

Thus, the invention relates to methods for cost-effective and gentle product drying of refined lipid phases.

Thus, an invention relates to a method wherein after step c) a lipid phase is obtained with less than 0.5 wt.% Water content.

From the removal of water-binding turbidity but there are other benefits. It has been documented that the water-binding capacity of a lipid phase, which was carried out by a refining process described in at least one of the process steps refining with a solution containing guanidine or amidino groups, by removal of water-binding organic Contaminants with any of the methods disclosed herein are significantly reduced over other methods used after such refining to dry the lipid phases.

The ability to absorb water, also referred to herein as "water-repellency" or "water-binding capacity".

By water absorption capacity is meant herein the ability to bind water into a lipid phase which can be effected by a blending process and result in the retention of water in the lipid phase. The water recovery capability can be checked by a water entry procedure become. In these methods, ion-free water is stirred at a temperature of 25 ° C in the lipid phase to be examined. An aqueous volume fraction of 5% by volume is provided relative to the refined lipid phase and stirred with a stirred mixer at a speed of 500 rpm for 10 minutes. This is followed by centrifugal phase separation at 6000 rpm for 10 minutes and the phases are separated from one another.

The value of water resorption capacity is the difference of the water content of a lipid phase after the water entry and the lipid phase before the water entry. According to the invention, a water reuptake capacity of <40% by weight is preferred, more preferably of <15% by weight, and most preferably of <5% by weight.

Further, in order to evaluate the lipid phase refining process of the present invention, the water recoverability of the unrefined lipid phase was compared to the refined lipid phase. Preferably, a difference of the two lipid phases is> 75%, more preferably> 85% and most preferably> 90%.

This result can be explained by an effective removal of water-binding suspensions from a lipid phase, which are then no longer available for a water binding in the purified lipid phase.

Furthermore, the invention relates to the use of the methods described herein for reducing the resumption of water in a refined lipid phase and / or for improving the oil storage capacity or the oxidation stability of vegetable oil.

In addition to the reduction of the water content and the re-enterability of water, the transparency of the lipid phases is improved in a particularly advantageous manner by the adsorption and the complexing process according to the invention. Thus, refined lipid phases are obtained in which hydratable organic compounds are present whose hydrodynamic diameter in> 90% is less than 100 nm and <5% greater than 200 nm, determined by an analysis of the light scattering at a phase boundary, such. B. the DLS method is obtained. Such lipid phases are optically brilliant.

Thus, the methods for adsorption and separation as well as for the complexing and separation of water-binding organic turbidity also allow the obtaining of an optically brilliant oil phase. The removal of water-binding turbidity with the resulting reduction of the water-binding capacity of the obtained lipid phase causes further very advantageous effects. In one aspect of the invention, this relates to effects that can occur when storing the resulting lipid phases. During such storage, lipid phases may come into contact with water molecules. For this alone contact with air, in which there is a water content, sufficient to allow an entry of water molecules by organic molecules with a good water-binding capacity. In addition to possible turbidity of the lipid phase, other effects that are significant for storage stability may occur. Here, the unfavorable effects on the oxidative stability of a lipid phase should be mentioned in the first place.

In lipid phases, and especially in oils of vegetable and animal origin, there are variable amounts of unsaturated organic compounds, the major part of which constitute unsaturated fatty acids. Exposure of these compounds to atmospheric oxygen, heating, high-energy radiation (eg, UV light), contacting with catalysts such as iron, nickel, free radicals, enzymes, such as lipoxygenases, or a basic medium may cause oxidation at one Double bond of an organic compound cause. Oxygen radicals are also catalyzed by organic compounds that are in a lipid phase, such as by chlorophylls, riboflavin or metal and heavy metal ions. This gives rise to hydroperoxides of the organic compounds. These are chemically unstable and degrade to secondary oxidation products. The decomposition leads to free Al koxy- radicals. Since, as stated above, the primary oxidation products are usually not stable and are further degraded to secondary oxide compounds, the determination of these reaction products is useful for detecting the long-term stability of a lipid phase. For this purpose, a reaction with para-anisidine, which reacts with secondary oxidation products such as aldehydes and ketones, which are present in a lipid phase is suitable. The reaction product can be detected and quantified spectrometrically (adsorption at 350 nm). In particular, unsaturated aldehydes, which are often responsible for malodors in oils, are detected by the p-anisidine reaction. The p-anisidine value is closely correlated with the peroxide value measured in a lipid phase, so the presence of peroxides can be estimated by the p-anisidine test method. The peroxide value indicates the number of primary oxidation products of a lipid phase and indicates the amount of milliequivalents of oxygen per kilogram of oil. Since there is a greater increase in the secondary oxidation products in the course, the p-anisidine value determination is more suitable for determining the storage stability. Therefore, oils refined with a method of the present invention were evaluated for their storage stability under various conditions, and the anisidine value was sequentially determined to estimate the oxidative stability. Surprisingly, in lipid phases which had been refined by the methods according to the invention, a reduction of oxidation products was obtained in comparison to lipid phases which were refined in water and in which either a vacuum drying was carried out or a drying of the lipid phase was carried out with other compounds. This suggests that oxidation products were extracted and separated by the method of the invention. This is all the more probable, as in the long-term course in the lipid phases refined according to the invention a significantly lower content of oxidation products was present than in the case of oils which had been treated with other substances or with vacuum drying. This can also be assumed because in a finishing treatment in which there was a non-optimal reduction of turbidity by the compounds of the invention, the storage stability tended to be worse than in a finishing in which optimal separation of the turbidity was achieved.

The scientific literature has shown that there is a close correlation between the development of secondary oxidation products and the formation of off-flavors and off-color in a lipid phase. Consistent with these theoretical aspects resulting from the removal of water-binding organic contaminants, it has been found that the effects found in the finishing process also affect storage stability in terms of reduced development of off-flavors and off-color. In the course of storage of lipid phases, significantly fewer off-flavor lipoproteins have developed over lipid phases which otherwise had undergone the same pretreatment and subsequently lipid phases were dried by other methods, such as in sensory tests on non-refined and refined lipid phases, over at least 120 had been stored, could be found. The formation of off-flavors correlated with the generation of secondary oxidation products, which were significantly less developed in the long-term studies of lipid phases that had been refined

Therefore, the method of adsorbing and separating or complexing and separating water-binding organic suspensions is particularly suited to improve the sensory storage stability of lipid phases.

The method is therefore also directed to obtaining sensory-stabilized lipid phases. However, oxidation of compounds in the lipid phase also promotes corrosive processes on materials that come into contact with such a lipid phase (eg tank system), therefore, it is endeavored to store under cooled conditions, excluding exposure to light and exclusion of air.

Thus, the method is preferred for obtaining a low-sulfide lipid phase for the reduction of oxidation damage to tank systems and technical equipment. Another aspect of reducing water-repellency by removing water-binding suspensions relates to radical / oxidative changes that can lead to a false color.

In lipid phases which can be freed of water-binding suspensions with the method according to the invention are lipid phases of biogenic origin, which have a variable proportion of dyes. These are almost exclusively organic compounds which are completely apolar (eg carotenes) or contain only a few polar groups, eg. B. chloroplyles. Therefore, they go very easily into the obtained lipid phase, or are removed by these from their structures. The classes of dyes differ considerably in their chemical properties. However, many of these compounds exhibit significant chemical reactivity or catalyze reactions, especially in the presence of a water fraction in the lipid phase or upon exposure to ionizing radiation (eg, UV light). In particular, oxidative processes can produce compounds via a Maillard reaction which lead to a false color and a false flavor. This concerns z. As the emergence of melanoidins, which are nitrogen polymers of amino acids and carboxylic acids, and lead to a brown color appearance of the oil. Another example is tocopherols, which, for example, can be oxidized during a bleaching process (especially in the presence of an acid) and are precursors for color pigments formed in the course. The discoloration of a refined oil is called "color reversion" and is particularly noticeable in corn oil, which are chlorophylls and their derivatives and degradation products such as pheophytin, as well as flavonoids, curcumins, anthrocyans, indigo, kaempferol and xantophylls, lignins, melanoidineins

Consistent with the achieved improvement in storage stability with respect to the development of off-flavors, there was also improved color stability of the oils which have been removed from water-binding suspending agents. There was no or only a very slight development of a color defect (color reversion) over a period of at least 120 days. Therefore, the method is also directed to the improved color stability upon storage of aqueous refined lipid phases where removal of water-binding suspensions has been by adsorption and separation or complexation and separation.

The invention is directed to obtaining a lipid phase having a high color stability during storage.

The present invention is therefore also directed to a substantially complete removal of water-binding organic suspensions from a lipid phase after an aqueous refining. As shown in the technical teaching and the examples herein, the water reuptake capacity of a lipid phase after a refining and refinement of the lipid phase carried out according to the invention is so low that it also increases the storage stability.

In a particularly preferred embodiment, the addition of the adsorbents described herein or the contacting of one or more adsorbents with the lipid phase is accomplished by having the adsorbent (s) in a bound or complexed form rather than a powder or microcrystalline. In this case, an adsorbent is used in step b), which is immobilized on a tissue or a texture or bound or can form such / such. In this context, "immobilized" means the application of the adsorbent to the surface. "Tissue" is understood to mean a one-dimensional or multidimensional arrangement of thread and / or strip material which is linked or connected to one another, so that a planar or spatial structure composite (texture ) will be produced. A texture of the aforementioned materials creates gaps which may be permeable to liquids and / or particulate matter. The texture-forming materials may be of natural origin (eg of vegetable or animal origin, such as cotton or sheep's wool fibers) or of synthetic origin (eg PP, PET PU, etc.). If necessary, the surfaces of the texture materials must be chemically modified in order to immobilize the adsorbents according to the invention. The immobilization can be physical, physico-chemical or chemical. Processes for this are known to the person skilled in the art.

Another preferred embodiment is the provision of bound or immobilized cellulose compounds. This can be z. B. in the form of a complex texture material, a plate or layer structure, for. B. as a tile or filter plate or filter cartridge done. In principle, an adsorptive separation by immobile silicates as described herein is possible.

In a preferred embodiment, the lipid phase is conducted past or through the adsorption compounds with the hydrated water-binding organic turbidity substances. This can be done by adding the texture / tissue into the lipid phase and agitating the texture / tissue or lipid phase to contact the lipid phase with the texture / tissue to adsorb the turbidities. The adsorbed turbid matter can then be separated from the lipid phase by removal of the texture / tissue. In another embodiment, the lipid phase is passed through and through the texture / tissue which is permeable to the lipid phase. If the lipid phase is obtained after flowing through the texture / the tissue as a refined product, the adsorption and separation of the turbid matter takes place in one operation. To increase the efficiency of such an application, it may be desirable to serially direct the lipid phase through multiple layers of the texture / tissue.

In another preferred embodiment, the texture consists of a packing of adsorbent materials through which the opacifier-containing lipid phase is passed. This is a preferred embodiment in the use of cellulose compounds, since this allows, depending on the polymer size and geometry, even with a dense packing of the particles, a flow through a lipid phase.

In a further preferred embodiment, in method step b) complexing agents are used which are immobilized or bound to a tissue or texture. The term "immobilized" refers to the application of the complexing agent to the surface, and the materials that can be used, as well as their texture and structure, can be made with the same materials and fabrics as the materials and fabrics described above for adsorbent application for the use of these materials with immobilized complexing agents, preferred are micro- or nanoparticles with a large internal surface, such as zeolites or silica gels, which are loaded with the complexing agents and provided in the form of a packing of the particles With hydrated turbidity lipid phase, they are complexed with the immobilized complexing agent, thereby separating them from the lipid phase.

The invention relates to a process wherein the adsorbent and / or the complexing agent of stage b) in a fabric or in a texture immobilized or bound, wherein the tissue or texture is suitable for complexation and / or adsorption and / or filtration of the opacifier-containing lipid phase. In a further preferred embodiment, the solutions already brought to the application according to the invention may contain

Complexing agents and the used for inventive adsorbents are reused. In practical application, it has been found that in the aqueous phases containing the dissolved complexing agents, the complexed and separated turbid substances are present in the form of particles.

These macroscopically visible aggregates floated on the water phase and could be completely separated from the otherwise clear water phase by filtration (sieve size 2μηη). Microscopically, crystal-like structures were recognizable. A digestion of the aggregates for the purpose of analyzing the compounds contained herein has not been done. It has been found that reuse of the filtratively purified water phase, which further contains complexing agents, when used again results in a reduction of the hydrated organic turbidity, as was the case in the first application.

Another aspect of the method concerns the minimal or non-existent product loss of the purified lipid phase.

The water phases used according to the invention with complexing agents dissolved therein were only slightly turbid to brilliant after centrifugal separation from the lipid phase and, apart from the above-described aggregates, had no solids, and in no case did they form an emulsion. The oil phase has always had a sharp phase boundary, so separators are very suitable and preferred for separating the aqueous phase containing dissolved complexing agent. The separation of the complexed organic turbidity could be achieved without product loss.

The investigated adsorbents, which were mixed into the lipid phases, could be separated after the adsorption of organic turbidity by means of centrifuges and decanters to compact masses. The analysis on triglyceride compounds herein shows that they are only carried out to a very small extent with the separated adsorbent mass. The product loss amounts to <0.2% by weight based on the mass of the lipid phase. Preference is given to adsorption and separation and / or complexing and separation of hydrated organic turbidity with little or no loss of product, as well as product loss-free or loss-free drying of lipid phases.

Another aspect of the process is directed to the recovery of separated organic turbidity and the reusability of the adsorbents and complexing agents used in the invention. It could be shown that the separated with the adsorbents organic Trübstoffe can be separated again from the adsorbents. This can be done with polar and nonpolar solvents known in the art. Since the organic turbidity substances can be different compounds or classes of compounds, the selection of a suitable solvent or solvent mixture should be based thereon. It may also be appropriate to carry out sequential detachment of the adsorbed organic turbidity. So it has been shown that when initially a distance of discharged neutral fats by an apolar solvent such. B. n-hexane is carried out in a further washing step with a polar solvent, for. As menthol, compounds such as phospholipids can be separated and fractionated. Other examples are extractions carried out with ethyl acetate, in which yellow dyes were obtained or with chloroform, in this organic phase were u. a. Chlorophylls found. Again, other fractions could be recovered with diethyl ether and alcohols to find organic compounds such as vitamin A, tocopherol, styrene glycosides, squalene and glyceroglycolipids. In some experiments, however, relevant amounts of free fatty acids as well as wax acids and waxes were extracted. This was particularly the case when in the present after an aqueous refining oil phase with hydrated organic turbidity, still a relatively high proportion of free fatty acids (> 0.2Gew%) was present.

According to the invention used and separated adsorbent, which is suitable with at least one nonpolar and at least one polar solvent in an amount of solvent which is suitable for complete absorption of removable organic Trübstoffen or with discharged neutral fats, then using known methods first filtration, sedimentation or by a centrifugal separation process obtained as a fraction and then be returned by a drying process in a powdery form. It could be shown that in a renewed use of z. B. with hydroxyethyl cellulose and kaolin in lipid phases with hydrated organic turbidity, these in the same way as in the first use of the adsorbents, the lipid phases are cleared of the turbidity. Thus, there are methods for the separation and fractionation of separated organic turbidity and purification processes for the adsorbents used in the invention, which allow a renewed use of the adsorbent according to the invention. Thus, on the one hand, the separated organic compounds can be recovered and fed to a further use and, on the other hand, the adsorbents can be reused. This makes the process particularly economically attractive, and saves resources.

A particularly preferred embodiment consists in the separation and recovery of adsorptively separated organic turbidity.

It is preferred to provide purified adsorbents and solutions containing complexing agents.

Preference is also the use of separated organic turbidity.

It is also preferred to recover neutral fats discharged by complexing and / or adsorbing agents.

methods

Process for the preparation of an aqueous emulsion according to process step a): In one embodiment of the present invention, prior to refining a lipid phase with a solution containing guanidine and / or amidine group-bearing compounds, a pre-purification of the lipid phase is carried out by admixing water or an aqueous solution which has a preferred pH range of between 7.0 and 14, more preferably between 9.5 and 13.5, and most preferably between 1.1, 5 and 13.0, and, after mixing with the lipid phase, a pre-purified lipid phase a preferably centrifugal phase separation is obtained. In another embodiment, the pre-purification aqueous solution contains a base which is preferably selected from sodium hydroxide, potassium hydroxide, ammonium hydroxide, sodium carbonate, sodium hydrogencarbonate, sodium bicarbonate, potassium carbonate and potassium bicarbonate, sodium metasilicate, sodium borate.

In a further embodiment, the pre-purification of the lipid phase takes place in analogous form as the basic pre-cleaning with an acid in concentrated form or by means of an aqueous solution of an acid. The pre-purification is carried out by the undiluted acid or an acid-containing aqueous solution having a pH between 1, 0 and 5, more preferably between 1, 7 and 4 and am most preferably between 3 and 3.5 of the lipid phase is added and after phase separation, the aqueous (heavy) phase is separated. To adjust the pH, acids are preferred, and particularly preferred is an acid selected from phosphoric acid, sulfuric acid, citric acid and oxalic acid. The suitable concentrations and the mixing ratio of the aqueous phases which can be used for the pre-purification with the oil phase are, in principle, freely selectable and easy to find out by a person skilled in the art. Preferably, concentrations of the basic solutions are between 0.1 to 3 molar, more preferably between 0.5 and 2 molar, and most preferably between 0.8 and 1.5 molar. The volume ratio between the basic water phase and the oil phase should preferably be between 0.3 to 5% by volume, more preferably between 0.3 and 4% by volume and most preferably between 1, 5 and 3% by volume.

Acids can be added neat or as an aqueous acid solution to the lipid phase. The undiluted acid is preferably added in a volume ratio of 0.1 to 2.0% by volume, more preferably between 0.2 and 1.0% by volume, and most preferably between 0.3 and 1.0% by volume. The aqueous acid solution is preferably added in a volume ratio of between 0.5 and 5% by volume, more preferably between 0.8 and 2.5% by volume, and most preferably between 1.0% and 2.0% by volume

The entry of the basic and acidic solutions for pre-cleaning can be carried out continuously or in a batch process and the mixture of the two phases with prior art stirrers or with an intensive mixer (eg rotor-stator dispersing equipment), provided this does not lead to an emulsion which is no longer separable by physical processes. The aim of the pre-cleaning is to remove easily hydratable mucilage from the lipid phase.

The exposure time in batch process applications is between 1 to 30 minutes, more preferably between 4 and 25 minutes, and most preferably between 5 and 10 minutes. When using continuous mixing (so-called in-line process), the residence time in the mixer is between 0.5 seconds to 5 minutes, more preferably between 1 second and 1 minute, and most preferably between 1.5 seconds to 20 seconds. The preferred temperatures which the lipid phase as well as the admixed aqueous phase should have for an intensive mixture is between 15 ° and 45 ° C, more preferably between 20 ° and 35 ° C and most preferably between 25 ° and 30 ° C. The separation of the aqueous phase from the emulsion can preferably be carried out by centrifugal separation processes; preference is given to the use of centrifuges, separators and decanters. The duration of a centrifugal separation depends on the product-specific parameters (water content, Viscosity, etc.) and the separation process used and must therefore be determined individually. Preferably, centrifugation is to be carried out for 2 to 15 minutes, more preferably for 8 to 12 minutes. The fate in a separator or decanter is preferably 2 to 60 seconds, more preferably 10 to 30 seconds. The centrifugal acceleration is preferably selected between 2,000 and 12,000 g, more preferably a centrifugal acceleration between 4,000 and 10,000 g. The temperature during phase separation should preferably be between 15 and 60 ° C, more preferably between 20 and 45 ° C, and most preferably between 25 and 35 ° C.

The effectiveness of the pre-purification can be determined by determining the phosphorus content and the amount of mucilage present in the lipid phase to be refined. Suitable are lipid phases containing less than 100 ppm phosphorus and less than 0.5% by weight unsaponifiable organic compounds. However, it is also possible to refine lipid phases which are above these indices with solutions containing guanidine- and / or amidine-group-containing compounds. If there is a need for a pre-cleaning, the choice of an aqueous degumming process, ie a treatment with an acid (neat or as an aqueous solution) or a lye, in principle freely selectable, so that different possibilities of pre-cleaning arise: I. sole acid treatment, II. sole base treatment, III. first acid treatment, then base treatment, IV. first base treatment, then acid treatment, V. repeated acid treatment, VI. repeated base treatment. The selection of the most suitable and cost-effective method can easily be carried out by a person skilled in the art. However, practical experience has shown that, if pre-purification is required, the initial application of an aqueous acid treatment followed, if necessary, by an aqueous base treatment, is the most preferred embodiment.

However, the technical teaching herein also shows that the separation process according to the invention of water-binding organic suspensions from biogenic lipid phase depends to a great extent on whether the lipid phase is first freed from hydratable organic and inorganic and corpuscular fractions by means of aqueous extraction steps, in order thereby to provide hydration of lipophilic water-binding to allow organic turbidity. It has been found that the number and arrangement of the refining steps is in principle irrelevant, as long as a neutral to basic compound is used in the last refining step. It is particularly advantageous if this basic compound one or more Guanidine and / or amidine groups. Therefore, an aqueous refining process with an aqueous solution containing compounds containing a guanidine or amidine group is an essential feature for providing a hydrated form of water-binding suspensions. In this hydrated form, the water-binding organic lipophilic cloudy substances can be adhered or complexed in a highly advantageous manner. without relevant co-removal of apolar lipid components and especially not of triglycerides.

The lipid phases suitable for use in process step a) have undergone at least one aqueous refining step with a basic solution with a final phase separation, which is preferably carried out by a centrifugal separation technique. Is. In principle, the time interval between the refining and the application of the method according to the invention plays no role. It is preferred that this takes place immediately after the refining. The residual moisture present in the lipid phase is in principle insignificant, but a better hydration of the water-binding organic turbidity causes better extractability of the like. Preferably, residual water contents between 10.0 and 0.001 wt%, more preferably between 5.0 and 1.0 wt%, and most preferably between 2.0 and 1.2 wt%. The pH present in the lipid phase should preferably be between 6 and 14, more preferably between 8 and 13, and most preferably between 8.5 and 12.5. The temperature of the lipid phase is in principle freely selectable, in the case of viscous lipid phases it may be necessary to heat the latter in order to make it more free-flowing and to improve the ability of the complexing agents or adsorbents to be incorporated.

Procedures for process control and monitoring:

The choice of an adhesion or complexing agent is in principle freely selectable. However, the most suitable complexing or adsorbent to be determined individually. In some applications, it may be advantageous to use adsorbents, as these, for example, have an approval for use as food. Also, the effectiveness of the adsorption and complexing agents according to the invention may vary at different lipid phases. If the most gentle possible discharge of hydrated turbidity is preferred, it may again be advantageous to use adsorbents, which are then further purified. By contrast, to largely exclude a product discharge, solutions with complexing agents are advantageous. The complexing agents are dissolved in dissociated form in a preferably ion-poor or otherwise ion-free water. The complexing agents are preferably used singly in a salt form. But there are also combinations of compounds possible. The quantitative and concentration ratios are freely selectable. The application of the solutions with complexing agents contained herein can be carried out continuously or in the form of a single addition. Preferred is an automated application. The process can be carried out as a batch or so-called in-line process. In an in-line method, it is preferable to carry out a continuous mixing, preferably with an intensive mixer. The reaction mixture can then be conveyed through a piping system or through inlet into a reservoir for the required reaction time. In a batch process, the reaction solution and the corresponding reactor vessel remain. The aforementioned concentrations, volume ratios, temperatures are preferably to be observed. The mixture in a batch reactor should be as described above. The adsorbents are preferably added in powdered form to the lipid phase. This can be done in the form of a one-time addition or in the form of fractionated or continuous additions. Preferred is an automated dosing process. The mixture can be carried out as described for the complexing agent, but preference is given to stirring with a turbulent mixture. Further, batch reaction procedures are preferred.

The amount of volume addition at a particular concentration of complexing agent or adsorbent, as well as the minimum time required to achieve sufficient complexation or adhesion of the hydrated one, can be readily determined by experiment (e.g., experimentation as in Example 6) The required volume and concentration ratios as well as the determined duration can easily be transferred to large-scale commercial applications.The required product specification is checked by taking a sample (eg 100ml) which contains a centrifuge (4000 rpm, 5 minutes) The supernatant oil fraction can then be tested for water content The required reduction of water-binding turbidity is when the residual moisture content contained therein is at least> 75% by weight, more preferred is reduced by at least> 85% by weight, and most preferably by at least> 95% by weight, in comparison to the starting value which existed before the incorporation of the adsorption or complexing agents. Further, the residual moisture is preferably lowered to less than 0.5% by weight, more preferably to less than 0.01% by weight, and most preferably to less than 0.008% by weight. This can easily be investigated with prior art methods such as the Karl Fischer method. A further product specification represents the water absorption capacity of the oil fraction obtained. This can be investigated by stirring in ion-free water at a temperature of 25 ° C. An aqueous volume fraction of 5% by volume is provided relative to the refined lipid phase and stirred with a stirred mixer at a speed of 500 rpm for 10 minutes. This is followed by centrifugal separation at 6000 rpm for 10 minutes. The product specification is achieved when the water resorption capacity of the grafted lipid phase is reduced by> 75% compared to the non-grafted lipid phase.

Furthermore, a sufficient product specification is present if in the lipid phase only compounds are present whose hydrodynamic diameter in> 90% of all particles contained herein is less than 100nm and <5% greater than 200nm, determined by an analysis of light scattering at a phase boundary, such , B. the DLS method is obtained. Such lipid phases are optically brilliant.

A minimum requirement for carrying out a complexation according to the invention and separation or adsorption and separation of hydrated turbidity is given if at least one of the abovementioned product specifications is present.

A special case and preferred embodiment of the extraction according to the invention and subsequent separation of turbidity, represents a combination of an extraction and a separation of turbidity, as described herein. This special case is given when one or more of the adsorbing and / or complexing agents / immobilized on a carrier material is / are. If such loaded carrier materials are added to a lipid phase which contains hydrated turbid substances and / or such lipid phases are passed through the loaded carrier material, which should preferably have a porous or mesh-like structure, extraction of the hydrated turbid substances by adsorption or complexing can take place directly take place the separation medium, which can then be easily removed from / from the lipid phase.

Separation method, method for performing the method step c):

The term "centrifugal phase separation" as used herein refers to a separation of phases utilizing centrifugal acceleration. In particular, it comprises processes known to the person skilled in the art, such as the use of centrifuges and, preferably, separators. The separation methods are suitable for both the phase separation of the aqueous disclosed herein Raffinationsstufen, as well as a separation of claimed herein adsorption or complexing agents. Another centrifugal separation process is provided by decanters.

Since the lipid mixtures which have been mixed with an aqueous phase or with an adsorption agent or a complexing agent are in principle two phases of different density, in principle a phase separation is also possible by sedimentation. Practice shows that the organic compounds to be separated, which have been converted into a water phase or aggregated or complexed as turbidity, for the most part can not spontaneously separate, so that by means of tensile and compressive forces, the separation efficiency and speed must be increased. This is easily possible according to the prior art by means of a simple centrifuge or a separator suitable for this purpose. A pressurization or negative pressure is possible. Separators are systems in which equal or non-uniform plates or plates appropriate tensile forces are set up in addition to a simultaneous pressure build-up. The advantage of using separators is that a continuous phase separation can be carried out with them. Therefore, a particularly preferred embodiment for the phase separation of the lipid phases is to carry out the phase separation with a separating separator.

For the preferred phase separation by a separator, systems having a throughput volume of more than 3m ³ / h, more preferably> 100m ³ / h, and most preferably> 400m ³ / h, are preferred

The separation of the aqueous refined lipid phases can in principle be carried out immediately after completion of a mixed or intensive mixing input. On the other hand, if required by the process, the aqueous refined lipid mixture to be separated can first be collected in a storage tank. The duration of storage depends solely on the chemical stability of the compounds present in the lipid phase and the process conditions. Preferably, the phase separation is immediately following an intensive mixing entry.

The temperature of the lipid mixture to be separated can in principle correspond to that which has been chosen for the preparation. However, it may also be advantageous to vary the temperature and to choose a higher temperature when z. B. thereby the effect of the separation tool is increased, or a lower, z. B. if this increases the extraction efficiency. In general, a temperature range between 15 ° C and 50 ° C is preferred, more preferably from 18 ° C to 40 ° C, and most preferably between 25 ° C and 35 ° C.

The residence time in a separation separator or a centrifuge depends essentially on the apparatus-specific properties. In general, the lowest possible residence time in economic terms Separator preferably, such a preferred residence time is <10 minutes, more preferably <5 minutes, and most preferably <2 minutes for a separation separator. For centrifuges, a preferred residence time is <15 minutes, more preferably <10 minutes, and most preferably <8 minutes. The selection of the centrifugal acceleration depends on the density difference of the two phases to be separated and is to be determined individually. Preferably, acceleration forces are between 1. 000 g and 15,000 g, more preferably between 2,000 g and 12,000 g, and most preferably between 3,000 g and 10,000 g. The water content of a lipid phase (also called oil moisture) can be determined by various established methods. In addition to other methods, such. As the IR spectroscopy, the Karl Fischer titration method according to DIN 51777 is performed as a reference method. With this electrochemical process, in which the required for the chemical conversion of iodine to iodide consumption of existing in the lipid phase water is determined by a color change, a minimum water content of up to 10 g / l (0.001 mg / kg) can be determined.

Water absorbency of a refined lipid phase and testing method

By water absorption capacity is meant herein the ability to bind water into a lipid phase which can be effected by a blending process and result in the retention of water in the lipid phase. This can be checked by stirring ion-free water at a temperature of 25 ° C by providing an aqueous volume fraction of 5% by volume to the lipid phase and stirring with a stirrer at a speed of 500 rpm for 10 minutes. This is followed by centrifugal separation at 3,000 g for 10 minutes.

The value of water resorption capacity is the difference of the water content of a lipid phase after the water entry and the lipid phase before the water entry. According to the invention, a water reuptake capacity of <40% by weight is preferred, more preferably of <15% by weight, and most preferably of <5% by weight. Further, in order to evaluate the lipid phase refining process of the present invention, the water recoverability of the unrefined lipid phase was compared to the refined lipid phase. Preferably, a difference of the two lipid phases is> 75%, more preferably> 85% and most preferably> 90%.

The water content was determined by the same method of measurement disclosed herein. Aqueous refining with guanidine and / or amidine group bearing compounds. The term guanidine and / or amidine group bearing compounds is used synonymously herein with the term guanidine and or amidine linkages.

Suitable compounds are those having at least one guanidino group (also called guanidino compounds) and / or having at least one amidino group (also called amidino compounds). The guanidino group is the chemical radical H ₂ NC (NH) -NH- and its cyclic forms, and the amidino group is the chemical radical H ₂ NC (NH) - and its cyclic forms (see examples below). Preference is given to guanidino compounds which, in addition to the guanidino group, have at least one carboxylate group (-COOH). It is further preferred if the carboxylate group (s) are separated from the guanidino group in the molecule by at least one carbon atom. Also preferred are amidino compounds which, in addition to the amidino group, have at least one carboxylate group (-COOH). It is further preferred if the carboxylate group (s) are separated from the amidino group in the molecule by at least one carbon atom.

These guanidino compounds and amidino compounds preferably have a distribution coefficient K ₀ w between n-octanol and water of no 6.3 (Kow <6.3).

Particularly preferred is arginine, which may be present in D or L configuration or as a racemate. More preferred are arginine derivatives. Arginine derivatives are defined as compounds having a guanidino group and a carboxylate group or an amidino group and a carboxylate group, wherein guanidino group and carboxylate group or amidino group and carboxylate group are separated by at least one carbon atom, ie at least one of the following groups between the guanidino group or the amidino group and the carboxylate group is: -CH ₂ -, -CHR-, -CRR'-, wherein R and R 'independently represent any chemical radicals. Of course, the distance between the guanidino group and the carboxylate group or the amidino group and the carboxylate group may also be more than one carbon atom, for example in the following groups - (CH ₂ ) _n -, - (CHR) n -, - (CRR ') n-, with n = 2, 3, 4, 5, 6, 7, 8 or 9 as is the case, for example, with amidinopropionic acid, amidinobutyric acid, guanidinopropionic acid or guanidinobutyric acid. Compounds having more than one guanidino group and more than one carboxylate group are, for example, oligoarginine and polyarginine.

Preferred arginine derivatives are compounds of the following general formula (I) or (II)

wherein

R ', R ", R'" and R "" independently of one another are: -H, -OH, -CH = CH ₂ , -CH ₂ -CH = CH ₂ , -C (CH 3) = CH ₂ , -CH = CH-CH 3 - C2H ₄ - CH = CH2, - CH3, - C2H5, -C3H _7, -CH (CH3) 2, C ₄ Hg, -CH2-CH (CH3) 2, -CH (CH3) _-C2 H5, -C (CH3) 3, -C5H11, -CH (CH ₃₎ -C ₃ H7, -CH ₂ -CH (CH 3) -C ₂ H 5, -CH (CH ₃₎ -CH (CH ₃₎ _2, - C (CH 3) 2 -C 2 H 5, - CH 2 -C (CH 3) 3, - CH (C 2 H 5) 2, - C 2 H ₄ - CH (CH 3) 2, - C ₆ H 13, -C ₇ H 15, CVCl 10-C ₃ H 5, cyclo-C ₄ H ₇ , cyclo-C ₅ H ₉ , cyclo-C 6 H 1 1, -PO ₃ H ₂ , -PO ₃ H ^" ,

-CH2-C ^ C-CH3, or R 'and R "together form one of the following groups: -CH2-CH2-, -CO-CH2-, -CH2-CO-, -CH = CH-, -CO-CH = CH-, -CH = CH-CO-, -CO-CH2-CH2-, -CH2-CH2-CO-, -CH2-CO-CH2- or -CH2-CH2-CH2-;

X is -NH-, -NR "" -, -O-, -S-, -CH ₂ -, -C ₂ H ₄ -, -C ₃ H ₆ -, -C ₄ H ₈ - or -C ₅ H ₁₀ - or represents a _C1-C5 carbon chain which may be substituted with one or more of the following radicals: -F, -Cl, -OH, _-OCH3, -OC2H5, -NH _2, -NHCH 3, -NH (C ₂ H ₅ ), -N (CH ₃ ) ₂ , -N (C ₂ H ₅ ) ₂ , -SH, -NO ₂ , -PO ₃ H ₂ , -PO 3 H-, -PO 3 ^{2 "} , -CH ₃ , -C ₂ H ₅ , - CH = CH _2, -C CH, -COOH, -COOCH3, -COOC2H5, -COCH3, -COC2H5, -O-COCH3, -O-COC2H5, -CN, _-CF3, -C2F5, -OCF3, -OC2F5 ;

L is a hydrophilic substituent selected from the group consisting of:

-NH ₂ , -OH, -PO 3 H ² , -PO 3 H, -PO 3 ^{2 "} , -OPO 3 H ² , -OPO 3 H-, -OPO 3 ^2" ,

-COOH, -COO ^", -CO-NH2, -NH ₃ ^+, -NH-CO-NH2, -N (CH3) 3+, -N (C2H5) ₃ ^+, -N (C3H7) ₃ ^+, -NH (CH ₃ ) ₂ ⁺ , -NH (C ₂ H ₅ ) ₂ ⁺ , -NH (C ₃ H ₇ ) ₂ ⁺ , -NHCH ₃ , -NHC ₂ H ₅ , -NHC ₃ H ₇ , -NH ₂ CH ₃ ⁺ , - NH ₂ C ₂ H ₅ ⁺ , -NH ₂ C ₃ H ₇ ⁺ , -SO ₃ H, -SO ₃ ^" , -SO ₂ NH ₂ , -CO-COOH, -O-CO-NH ₂ , -C (NH) -NH ₂ , -NH-C (NH) -NH ₂ , -NH-CS-NH ₂ , -NH-COOH.

The preferably used concentration of guanidine or amidine compounds, which must be present dissolved in a preferably ion-poor or ion-free water, is in one embodiment based on the detectable acid number of the lipid phase to be refined, the z. B. determined by a titration with KOH determined. The derivable number of carboxyl groups serves to calculate the amount by weight of the guanidine or amidine compounds. In this case, an at least equal or higher number of guanidine or amidine groups, in free and ionizable form be present, be present. The thus determined molar ratio between the Guanidingruppen- or amidino-containing compounds and the total of the free or releasable carboxyl-bearing compounds or carboxylic acids must be> 1: 1. Preferably, a molar ratio between the determinable carboxylic acids (here in particular the acid number) and the guanidine group- or amidino-containing compounds should be 1: 3, more preferably 1: 2.2, and most preferably 1: 1, 3 in an ion-free Water are produced. In this case, the molarity of the dissolved solution according to the invention with guanidine group- or amidine-group-containing compounds may preferably be between 0.001 and 0.8 molar, more preferably between 0.01 and 0.7 molar and most preferably between 0.1 and 0.6 molar. Since the interaction of the guanidine or amidine groups is also ensured at ambient temperatures, the preferred temperature at which the inventive entry of the aqueous solutions containing dissolved guanidine or amidine compounds can be between 10 ° C and 50 ° C, more preferably between 28 ° C. and 40 ° C, and most preferably between 25 ° C and 35 ° C. The registration of the aqueous solutions containing guanidine group- or amidino-containing compounds should preferably be carried out by intensive mixing. The volume ratio between the lipid phase and the water phase is irrelevant in principle. However, as an embodiment, a ratio by volume (v / v) of the aqueous solution to the lipid phase of from 10% by volume to 0.05% by volume, preferably from 4.5% by volume to 0.08% by volume, is more preferred from 3% by volume to 0.1% by volume.

The volume and concentration ratio can be influenced by the fact that in some lipid phases and emulsion-forming compounds such. B.

Glycolipids, by an aqueous solution with Guanidingruppen- or

Dissolve Amidino-containing compounds and thereby this

Compounds are not available for the separation of carboxylic acids.

Thus, in one embodiment, it may be necessary to include a greater volume and / or concentration ratio of the aqueous solutions

Guanidine group or amidino group-bearing compounds to be refined to the lipid phases to be refined.

Particularly suitable intensive mixers are those intensive mixers which operate on the high-pressure or rotor-stator homogenization principle.

In the intensive mixer, intensive mixing of the lipoid phase and the aqueous phase takes place. The intensive mixing takes place at atmospheric pressure and a temperature in the range of 10 ° C to 90 ° C, preferably 15 ° C to 70 ° C, more preferably 20 ° C to 60 ° C and most preferably 25 ° C to 50 ° C instead. Therefore, the thorough mixing and preferably intensive mixing at low temperature of preferably below 70 ° C, more preferably below 65 ° C, more preferably below 60 ° C, more preferably below 55 ° C, even more preferably below 50 ° C. , even more preferably below 45 ° C.

Therefore, it is particularly preferred if the entire aqueous refining process preferably including the optional steps at temperatures in the range of 10 ° C to 90 ° C, preferably 13 ° C to 80 ° C, preferably 15 ° C to 70 ° C, more preferably 18 ° C is carried out to 65 ° C, more preferably 20 ° C to 60 ° C, more preferably 22 ° C to 55 ° C and particularly preferably 25 ° C to 50 ° C or 25 ° C to 45 ° C.

For the optional washing step with an aqueous solution having a basic pH, the preferred pH range for this is between 7.0 and 14, more preferably between 9.5 and 13.5, and most preferably between 1.1 and 5 and 13. The entry of the basic wash solution is preferably carried out with an intensive mixing, particularly preferred in this case rotor-stator mixer. The preferred exposure time is between 1 to 30 minutes, more preferably between 4 and 25 minutes, and most preferably between 5 and 15 minutes. The preferred temperatures of the lipid phase are between 15 ° and 45 ° C, more preferably between 20 ° and 35 ° C and most preferably between 25 ° and 30 ° C.

One embodiment of pretreating the lipid phases to be purified with the aqueous refining is pretreatment with an aqueous solution containing an acid and having a pH of between 1 and 7, more preferably between 2.5 and 4, and most preferably between 3 and 3.5. Preference is given to an interference of the acidic solution with an intensive entry as described herein, particularly preferred are rotor-stator mixing systems. The preferred exposure time is between 1 to 30 minutes, more preferably between 4 and 25 minutes, and most preferably between 5 and 10 minutes. The preferred temperatures of the lipid phase are between 15 ° and 45 ° C, more preferably between 20 ° and 35 ° C and most preferably between 25 ° and 30 ° C.

In this respect, the inventive separation of turbidity from a prepurified lipid phase is also directed to a particularly advantageous low-loss refining of neutral lipids, as well as that herein less than 5 ppm, in particular less than 2 ppm of phosphorus-containing compounds, less than 0.2%, in particular less than 0 , 1% free fatty acids, and less than 3 ppm, in particular less than 0.02 ppm of Na, K, Mg, Ca and / or Fe ions. In other words, the separation of suspensions from a prepurified lipid phase according to the invention is also directed to a particularly advantageous low-loss refining of neutral lipids, and that herein less than 5 ppm (or 5 mg / kg), in particular less than 2 ppm (mg / kg) phosphorus-containing Compounds, less than 0.2% by weight (or 0.2 g / 100 g), in particular less than 0.1% by weight of free fatty acids, and less than 3 ppm (or 3 mg / kg), in particular less than 0, 02 ppm (or 0.02 mg / kg) of Na, K, Mg, Ca and / or Fe ions are contained.

Furthermore, the invention relates to refined and refined lipid phases obtainable by one of the processes described herein with a content of less than 10% relative to the starting amount of water-binding organic lipophilic suspensions, the lipid phase being less than 5 ppm, less than 0.1% by weight. free fatty acids, and containing less than 3 ppm of Na, K, Mg, Ca and / or Fe ions.

Furthermore, the invention relates to refined and refined lipid phases obtainable by one of the methods described herein at a level of less than 10% relative to the starting amount of hydrophilic organic lipophilic truncates, the lipid phase being less than 5 ppm (or 5 mg / kg), less 0.1 wt.% (g / 100 g) of free fatty acids, and less than 3 ppm (or 3 mg / kg) of Na, K, Mg, Ca and / or Fe ions.

Furthermore, the separation process according to the invention is therefore also particularly advantageous use, since the solid adsorbent are inexpensive to make it operational again. Furthermore, the separation according to the invention is aimed at making available the separated organic turbid substances.

definitions

lipid phase

As the lipid phase, all organic carbon compounds of biological origin are summarized herein. The term as used herein includes mixtures of biological origin, which can thus be obtained from plants, algae, animals and / or microorganisms and having a water content of <10% and a content of lipophilic substances comprising monoacylglycerides, diacylglycerides and / or triacylglycerides of total > 70 wt .-% or> 75 wt .-% or> 80 wt .-% or> 85 wt .-% or> 90 wt .-% or> 95 wt .-%. For example, the lipid phases may be extracts of oleaginous plants and microorganisms, such as rape seed, sunflower, soya, camelina, jatropha, palm, castor, but also algae and Microalgae and animal fats and oils. It is irrelevant whether the lipid phase is a suspension, emulsion or colloidal liquid. If the lipid phases are extracts or extraction phases of lipoid substances from a previous separation or extraction, the lipid phase may also consist of a proportion of> 50% by volume of organic solvents or hydrocarbon compounds.

Preferred lipid phases are vegetable oils, in particular pressing and extraction oils of oil plant seeds. However, animal fats are also preferred. But also included are non-polar aliphatic or cyclic hydrocarbon compounds. These lipid phases are characterized in that> 95% by weight of the compounds are apolar.

The lipid phases, as defined herein, include, but are not limited to: Acai Oil, Acrocomia Oil, Almond Oil, Babassu Oil, Currant Seed Oil, Borage Seed Oil, Rapeseed Oil, Cashew Oil, Castor Oil, Coconut Oil, Coriander Oil, Corn Oil, Cottonseed Oil, Kramben Oil, Linseed Oil, Grapeseed Oil, Hazelnut Oil, Other Nut Oils, Hemp Seed Oil, Jatropha Oil , Jojoba oil, macadamia nut oil, mango seed oil, meadowfoam seed oil, mustard oil, foot oil, olive oil, palm oil, palm kernel oil, palm oil, peanut oil, pecan oil, pine nut oil, pistachio oil, poppy seed oil, rice germ oil, thistle oil, camellia oil, sesame oil, shea butter oil , Soybean oil, sunflower oil, tall oil, tsubaki oil, walnut oil, varieties of "natural" oils with altered fatty acid compositions via genetically modified organisms (GMO) or traditional breeds, Neochloris oleoabundans oil, Scenedesmus dimorphus oil, Euglena gracilis oil, Phaeodactylum tricornutum oil, Pleurochrysis carterae oil, Prymnesium parvum oil, Tetraselmis chui oil, Tetraselmis suecica oil, Isochrysis galbana oil, Nannochloropsis sali na Oil, Botryococcus braunii oil, Dunaliella tertiolecta oil, Nannochloris oil, Spirulina oil, Chlorophyceae oil, Bacilliarophyta oil, a mixture of the foregoing oils and animal oils (especially marine oils), algae oils, oils from bran production eg. Rice bran oil and biodiesel. Refined lipid phase

Refined lipid phase herein is understood to mean a lipid phase in which one of the methods according to the invention for the adsorption and separation or complexing and separation of hydrated turbidity has occurred. Refined lipid phase

The lipid phase obtained after an aqueous refining is understood as a refined lipid phase, this means the lipid phase which is obtained after the last method step of one of the methods according to the invention.

Purified lipid phase Purified lipid phase means the lipid phase obtained after the last step of one of the methods of the invention. "Purified lipid phase" and "Refined lipid phase" are used interchangeably. Aqueous refining or aqueous refined lipid phase

In the present application, "aqueous refining" refers to the aqueous purification step with a neutral or basic solution to provide the "aqueous refined lipid phase". Thus, "aqueous refined lipid phase" is synonymous with "lipid phase" which is present after purification with a neutral or basic solution.

Pre-purified lipid phase

In the present application, the "pre-purified lipid phase" is the lipid phase present after purification with a neutral or basic solution Thus, a pre-purified lipid phase is also understood to mean an aqueous-refined lipid phase.

"Lipid phase to be cleaned"

The lipid phase to be purified is the crude lipid phase before it has been subjected to at least one aqueous refining with a neutral or basic solution.

turbidity

Turbidity herein summarizes organic compounds that can be defined by the following characteristics: a) Organic, in a biogenic lipid phase naturally occurring compound with lipophilic properties, characterized by a K _ow of> 2, where name K _ow refers to the distribution coefficient between n-octanol and water, and b) an organic compound having a molecular weight of not more than 5,000 Da, and also c) an organic compound which has a hydrodynamic radius of more than 100 nm in a hydrated state and d) an organic compound allowed by water molecules.

The inventively adsorptive or complexed separable organic Trübstoffe have at least two of the above features, which by known and practicable methods, such. B. a molecular weight determination, a calculation of _Kow distribution coefficient, a determination of the hydrodynamic radius by means of a dynamic laser light scattering method (DLS) and the determination of the water content can be examined. The organic water-binding compounds include organic dye compounds such as carotenes and carotenoids, chlorophylls, and their degradation products, phenols, phytosterols, in particular ß-sitosterol and campesterol and Sigmasterol, sterols, sinapines, squalene. Phytoestrogens, such as isoflavones or lignans. Furthermore, steroids and their derivatives such as saponins, furthermore glycolipids as well as glyceroglycolipids and glycerosphingolipids, furthermore rhamnolipids, sophrolipids, trehalose lipids, mannosterylerythritol lipids. Likewise polysaccharides such as rhamnogalacturonans and polygalacturonic acid esters, arabinans (homoglycans), galactans and arabinogalactans, as well as pectic acids and amidopectins.

Furthermore, phospholipids, in particular phosphotidylinositol, phosphatides, such as phosphoinositol, furthermore carboxylic acids and long-chain or cyclic carbon compounds, such as waxes, wax acids, also fatty alcohols, hydroxy and epoxy fatty acids. Likewise glycosides, lipo-proteins, lignins, phytate or phytic acid as well as glucoinosilates. Proteins, including albumins, globulins, oleosins, vitamins, e.g. Retinol, (vitamin A) and derivatives such. As retinoic acid, riboflavin (vitamin B2), pantothenic acid (vitamin B5), biotin (vitamin B7), folic acid (vitamin B9), cobalamins (vitamin B12), calcite ol (vitamin D) and derivatives, tocopherols (vitamin E) and tocotrienols , Phylloquinone (vitamin K) and menaquinone. Furthermore, tannins, terpenoids, curcumanoids, xanthones, but also sugar compounds, amino acids, peptides, including polypeptides and carbohydrates such as glucogen. Since lipid phases of different origin can be freed of turbidity by the method according to the invention, the choice of turbidity is not limited to those mentioned herein by name. Water-binding organic lipophilic clouding agents such as carotenes, chlorophylls, phenols, sterols, squalene, waxes, wax acids, wax alcohols, glycolipids, glyceroglycolipids and / or glycerosphingolipids are preferably separated by one of the methods described herein. Furthermore, aldehydes, ketones, peroxide compounds and carboxylic acids

acids and bases

Acids referred to herein are compounds which are capable of giving off protons to a reactant, in particular water.

Accordingly, the term refers to bases, compounds capable of absorbing protons, especially in aqueous solutions. carboxylic acids

Carboxylic acids, also referred to herein as carboxylic acids, are organic compounds which carry one or more carboxyl groups. A distinction is made between aliphatic, aromatic and heterocyclic carboxylic acids. Aliphatic forms of carboxylic acids, also called alkanoic acids, are fatty acids and are further listed in the following paragraph.

fatty acids

In general, fatty acids are aliphatic carbon chains having a carboxyl group. The carbon atoms may be linked with single bonds (saturated fatty acids) or with double bond bridges (unsaturated fatty acids), these double bonds may be in an ice or trans configuration. As defined herein, as fatty acids, such compounds having more than 4 consecutive carbon atoms besides the carboxyl group are referred to as fatty acids. Examples of linear saturated fatty acids are nonanecarboxylic acid (capric acid), dodecanoic acid (lauric acid), tetradecanoic acid (myristic acid), hexadecanoic acid (palmitic acid), octadecanoic acid (stearic acid), n-eicosanoic acid (arachic acid) and n-docosanoic acid (behenic acid). separation

By separation, the skilled person understands the separation of a substance mixture. Depending on the type of separation process used, each of which requires an energy expenditure under which one achieves a certain degree of separation, substances of different purity are obtained. Separation is synonymous with separation and both terms are also used synonymously in this application. Separation thus means the separation of substances from a mixture of substances. Separation methods, as used herein, include phase separation of liquid mixtures which may be accomplished by sedimentation and / or centrifugation and / or filtration. The centrifugal separation can be carried out continuously by a separator or decanter technology or discontinuously by means of a centrifuge. A filtration separation can be carried out by passing or passing the lipid phase, in which the compounds / aggregates already to be separated, through a filter having a certain screen size, wherein the compounds / aggregates are preferably 100% larger than the minimum Sieve size, be retained and do not pass the filter. Other techniques for separating phases known to those skilled in the art may also be used. extraction

The "extraction" is for a person skilled in a designation for a separation process by leaching of certain constituents from solid or liquid substance mixtures with the aid of suitable solvents (extractant).) A distinction between solid-liquid extraction and liquid-liquid extraction Liquid Extraction, the phases are mixed together and the extraction phase separation, in which the phases are separated from each other.The term extraction, as used herein, is meant the extraction of turbidity from their material (organic) matrix by an extractant which may consist of an adsorbent or complexing agent for the suspended matter to be separated, in other words, extractability of the hydrogenated turbidity by adsorptive attachment to an adsorbent as described herein or by an ionic or covalent bond with a herein n described cation, which is defined herein as complexation achieved.

adsorption

Adsorption is for a person skilled in the deposition of substances on the surface of solids. Such deposits are mainly due to physicochemical interactions, but chemical compounds are also possible.

adsorbent

The term adsorbent, which is used synonymously for the terms adsorbent, is understood herein to mean a material compound of inorganic and / or organic constituents, with a solid state of matter. The adsorbent has surface properties that allow for adsorption of elements or compounds. In particular, with the adsorbents as herein understood, the suspending agents described herein may be incorporated and / or incorporated and bonded therewith.

aggregation

In general, aggregation means the accumulation or accumulation of atoms or molecules. In the field of separation processes, the person skilled in the art understands this to mean the accumulation of atoms or molecules in liquid up to the point where the aggregate is no longer soluble and precipitates. complexation

By the term is meant herein a physical and / or physicochemical and / or chemical compound between two or more elements and / or compounds. The elements may be present in their elemental or ionized form, compounds as molecules having 2 or more atoms, it is irrelevant whether they are organic or inorganic compounds. Further, the term complexation encompasses a physical and / or physicochemical and / or chemical compound with or between complexes which has already been formed by complexation with a complexing agent as described herein with a compound, which may also form aggregates.

complexing

By the term complexing agent as used herein is meant elements which are ionizable in water / or donate ions, thereby allowing complexation with clouding agents as described herein.

Cellulose and cellulose derivatives

Cellulose is a polysaccharide of the formal Bruttozusmmensetzung (C6H10O _5), more precisely an isotactic beta-1, 4-polyacetal of cellobiose (4-O-beta-D-glucopyranosyl-D-glucose). Cellobiose in turn consists of two molecules of glucose. Approximately 500 to 5000 glucose units are linked to one another unbranched in the form of a chain, resulting in average molar masses of 50,000 to 500,000. In cellulose derivatives, the hydrogen atoms on the free hydroxyl groups of the glucose units may be replaced -CH ₃ , -C 2 H ₅ , -C ₃ H _7,

- C ₄ Hg, - C 5 H 11, - CH 2 CH 2 OH, - CH 2 CH 2 CH 2 OH, - CH 2 CH 2 CH 2 CH 2 OH,

-CH ₂ CH ₂ CH ₂ CH ₂ CH ₂ OH, -CH ₂ CH (OH) CH ₃ , -CH ₂ CH (OH) CH ₂ OH, -CH ₂ CO ₂ H, -CH ₂ CH ₂ SO ₃ H, -CH ₂ CH ₂ SO 3 ^" , -C (= O) CH ₃ , -C ( = O) CH ₂ CH ₃ ,

-C (= O) CH ₂ CH ₂ CH _3, -C (= O) CH 2 CH ₂ CH ₂ CH 3, -C (= O) CH (OH) CH _3, hydrophobic long-chain branched and unbranched alkyl radicals, hydrophobic long-chain branched and non-branched alkylaryl radicals or arylalkyl radicals, cationic radicals, -NO 2, -SO 3 H, -SO 3 ^" .

Examples of cellulose derivatives are hydroxyethyl cellulose (HEC), hydroxypropyl cellulose (HPC), ethyl hydroxyethyl cellulose (EHEC), carboxymethyl hydroxyethyl cellulose (CMHEC), hydroxypropyl hydroxyethyl cellulose (HPHEC), methyl cellulose (MC), methyl hydroxypropyl cellulose (MHPC),

Methylhydroxypropylhydroxyethylcellulose (MHPHEC), methylhydroxyethylcellulose (MHEC), carboxymethylcellulose (CMC), hydrophobically modified Hydroxyethylcellulose (hmHEC), hydrophobically modified hydroxypropylcellulose (hmHPC), hydrophobically modified ethylhydroxyethylcellulose (hmEHEC), hydrophobically modified carboxymethylhydroxyethylcellulose (hmCMHEC), hydrophobically modified hydroxypropylhydroxyethylcellulose (hmHPHEC), hydrophobically modified methylcellulose (hmMC), hydrophobically modified methylhydroxypropylcellulose (hmMHPC), hydrophobic modified methylhydroxyethylcellulose (hmMHEC), hydrophobically modified carboxymethyl methylcellulose (hmCMMC), sulfoethylcellulose (SEC), hydroxyethylsulfoethylcellulose (HESEC),

Hydroxypropylsulfoethylcellulose (HPSEC), methylhydroxyethylsulfoethylcellulose (MHESEC), methylhydroxypropylsulfoethylcellulose (MHPSEC), hydroxyethyl-hydroxypropylsulfoethylcellulose (HEHPSEC), carboxymethylsulfoethylcellulose (CMSEC), hydrophobically modified sulfoethylcellulose (hmSEC), hydrophobically modified hydroxyethylsulfoethylcellulose (hmHESEC), hydrophobically modified hydroxypropylsulfoethylcellulose (hmHPSEC), and hydrophobic modified hydroxyethylhydroxypropylsulfoethylcellulose (hmHEHPSEC).

Plant color pigments dyes

The term "dyes" summarizes organic compounds which occur in oils and fats of biogenic origin, typically in different quantities and compositions side by side.

The term "plant colorants" herein includes all coloring compounds present in lipid phases, the most dominant and by far the largest quantity in vegetable oils is the group of chlorophylls and their degradation products, such as pheophyline. In addition, however, other classes of compounds, such as flavonoids, curcumins, anthrocyans, betaines, xanthophylls, which include carotenes and lutein, indigo, kaempferol and xantphylls, such as neoxanthine or zeaxanthin, are also included. These dyes may be present in different proportions in the lipid phases These dyes have a different solubility in water or an organic solvent With the aqueous refining processes described herein, the separation of lipophilic compounds into a w Aqueous nanoemulsion allows, which otherwise can not be converted into water-soluble compounds in an aqueous phase and separated with this. The most common representatives of plant dyes are chlorophylls. In vegetable oils, chlorophylls are typically found in quantities between 10 ppm (or 10 mg / kg) and 100 ppm (or 100 mg / kg) or between 10 ppm (or 10 mg / kg) and 100 ppm (or 100 mg / kg). be. Representatives with a high content of chlorophylls are especially canola and rapeseed oils.

chlorophylls

The term "chlorophylls" herein comprises compounds consisting of a derivatized porphyrin ring which are subdivided into the subgroups a, b, c1, c2 and d by the organic radicals and differ in the number of double bonds between the carbon atoms. Atom 17 and 18.

Chlorophylls are the most common dyes found in vegetable oils. Due to their hydrophobicity or lipophilicity, they are very well distributed in lipid phases, in particular triglyceride mixtures. They cause a green color of the lipid phase, furthermore they cause a lower oxidation stability of the lipid phase due to the compound / entry of magnesium or copper ions. Therefore, their removal from such a lipid phase is desired, especially if it is an edible oil. The absolute levels found in lipid phases, and particularly vegetable oils, vary considerably, ranging from 0.001 ppm (or 0.001 mg / kg) to 1000 ppm (or 1000 mg / kg) or 0.001 ppm (or 0.001 mg / kg) to 1000 ppm (or 1000 mg / kg)

Non-degraded chlorophylls are practically insoluble in water. Therefore, aqueous refining processes are also not suitable for extracting these dyes from a lipid phase. Since the determination of the absolute concentrations can be obtained by a high analytical effort, it is more practicable to determine the content of dyes by a spectrometric determination of the color contents of a lipid phase. For this purpose, the determination of different color spectra in an oil is established by the Lovibond method in which intensity levels red yellow and green shades are determined and compared with a reference value. Thus, an evaluation of the oil color in general, as well as a change in color, can be judged. application areas

The refining process of raffinates according to the invention is applicable to all lipid phases, as described herein, which are of biogenic origin and contain water-binding, highly lipophilic compounds which are turbidity-causing substances in the context of refining or subsequently thereto by water introduction. Because the Turbidity, for the inventive finishing process, first must be dissolved or decomplexed out of an organic matrix, the inventive use of the refining process is limited to a refining step after an aqueous refining, as described herein. This concerns the purification / refining of oils, especially of vegetable oils, but also animal fats, where the removal of turbidity is desired. This applies in particular to edible oils, fragrance oils, massage oils, skin oils and lamp oils. Furthermore, other organic mixtures, such as plant extracts, or their distillation products can be refined. Furthermore, natural or synthetically produced mixtures of hydrocarbon compounds or esterified fatty acids. Furthermore, lipid phases which are suitable for industrial applications, such as oil-based fuels or lubricants or hydraulic oils

Furthermore, the invention relates to a process for the adsorption and extraction or complexing and extraction of carotenes, chlorophylls, phenols, sterols, squalene, glycolipids, glyceroglycolipids and / or glycerosphingolipids and / or waxes or aqueous refined lipid phases, which is characterized by

a) providing a lipid phase comprising carotenes, chlorophylls, phenols, sterols, squalene, glycolipids, glyceroglycolipids and / or glycerosphingolipids and / or waxes or carboxylic acids, the lipid phase being subjected to at least one aqueous refining with a neutral or basic solution,

b) contacting an adsorbent and / or a complexing agent with the lipid phase from step a),

c) separation of the adsorbed or complexed carotenes, chlorophylls, phenols, sterols, squalene, glycolipids, glyceroglycolipids, glycerosphingolipids and / or waxes or carboxylic acids from stage b) by a phase separation,

wherein it is the Adsorptionsmittei to cellulose, a cellulose derivative or an inorganic alumina silicate with an aluminum content of> 0.1 mol%, and

The invention further relates to a process for the adsorption and extraction or complexing and extraction of water-binding organic lipophilic suspensions of aqueous refined lipid phases, which is characterized by

a) providing a lipid phase containing water-binding organic lipophilic turbidities, wherein the lipid phase has undergone at least one aqueous refining with an aqueous solution having at least one guanidine group or amidine group-bearing compound having a Kow of <6.3.

b) bringing into contact a Adsorptionsmitteis and / or a

Complexing agent with the lipid phase from stage a),

c) separation of the adsorbed or complexed water-binding organic hydrophilic turbidity from stage b) by a phase separation,

wherein the Adsorptionsmittei to Ceiiuiose, a Ceiiuiosederivat or an inorganic Aiuminiumoxid Siiikat with a Aiuminiumanteii of> 0.1 moi% is and

wherein the complexing agent is ammonium ions or iron ions present in an aqueous solution.

The invention relates to a process for the adsorption and extraction of water-binding organic lipophilic suspensions of aqueous refined lipid phases, which is characterized by

a) providing a lipid phase containing water-binding organic lipophilic turbidity, wherein the lipid phase of at least one aqueous

B) contacting glutinous acid or a cellulose derivative with the lipid phase from step a),

c) Separation of the adsorbed organic lipophilic turbidity from stage b) by a phase separation.

a) Provision of a lipid phase containing water-binding organic lipophilic turbidities, wherein the lipid phase has been subjected to at least one aqueous refining with a neutral or basic solution, b) contacting an adsorption agent with the lipid phase from stage a),

c) Separation of the adsorbed organic lipophilic turbidity

Stage b) by a phase separation,

wherein the Adsorptionsmittei to Ceiiuiose, a Ceiiuiosederivat or an inorganic Aiuminiumoxid Siiikat with an aluminum content of> 0.1 mol% is. The invention further relates to a process for the adsorption and extraction or complexing and extraction of carotenes, chiorophyllene, phenols, sterols, squaienen, glycoipids, glycerolipids and / or glycerosphingolipids and / or waxes or carboxylic acids of aqueous refined lipid phases, which is characterized by

a) providing a lipid phase containing carotenes, chlorophylls, phenols, sterols, squaienen, glycoipids, glyceryl glycolipids and / or glycerosphingolipids and / or waxes or carboxylic acids, wherein the lipid phase of at least one aqueous refining with an aqueous solution having at least one guanidine group or amidino group-bearing compound was subjected to a kow of <6.3.

c) separation of the adsorbed or complexed carotenes, chlorophylls, phenols, sterols, squaienes, glycolipids, glyceroglycolipids and / or glycerosphingolipids and / or waxes or carboxylic acids from stage b) by a phase separation,

The invention relates to a process for the adsorption and extraction of carotenes, chlorophylls, phenols, sterols, squaienen, glycoipids, glycerylglycolipids and / or glycerosphingolipids and / or waxes or carboxylic acids of aqueous refined lipid phases, which is characterized by

a) providing a lipid phase containing carotenes, chlorophylls,

Phenols, sterols, squaienes, glycolipids, glyceroglycolipids, glycerosphingolipids and / or waxes or carboxylic acids, the lipid phase being subjected to at least one aqueous refining with a neutral or basic solution,

b) bringing into contact cellulose or a cellulose derivative with the

Lipid phase from stage a),

c) Separation of the adsorbed carotenes, chlorophylls, phenols, sterols, squaienes, glycolipids, glyceroglycolipids and / or glycerosphingolipids and / or waxes or carboxylic acids from stage b) by a Phase separation.

The invention relates to a process for the adsorption and extraction of carotene, chiorophyly, phenols, steroids, squaienen, Giycolipiden, Glycerogiycoiipiden and / or Glycerosphingolipiden and / or waxes or carboxylic acids aqueous refined lipid phases, which is characterized by,

a) providing a lipid phase containing carotenes, chlorophylls, phenols, sterols, squaienes, glycoipids, glyceroglycolipids, glycerolgipolipids and / or waxes or carboxylic acids, the lipid phase being subjected to at least one aqueous refining with a neutral or basic solution,

b) contacting an adsorbent with the lipid phase from step a),

c) separation of the adsorbed carotenes, chlorophylls, phenols, sterols, squaienes, glycoipids, glyceroglycolipids and / or glycerolgipolipids and / or waxes or carboxylic acids from stage b) by a phase separation,

wherein the adsorbent is Ceiiuiose, a Ceiiulosederivat or an inorganic Aiuminiumoxid silicate with a Aluminiumanteii of> 0.1 mol%.

The invention relates to a process for the adsorption and extraction of carotenes, chiorophylys, phenols, steroids, squaienen, Giycolipids, Glycerogiycoiipiden and / or glycerosphingolipids and / or waxes or carboxylic acids aqueous refined lipid phases, which is characterized by,

a) providing a lipid phase containing carotenes, chlorophylls, phenols, sterols, squaienes, glycoipids, glyceroglycolipids, glycerolgipolipids and / or waxes or carboxylic acids, the lipid phase having been subjected to at least one aqueous refining with a neutral or basic solution,

b) contacting glutathione or a cellulose derivative with the lipid phase from step a),

c) Separation of the adsorbed carotenes, chlorophylls, phenols, sterols, squaienes, glycoipids, glyceroglycolipids and / or glycerolgipolipids and / or waxes or carboxylic acids from stage b) by a

Phase separation.

The invention relates to a method for the adsorption and extraction of carotenes, Chiorophyiien, phenols, steroids, Squaienen, Giycolipids, Glycerogiycoiipiden and / or glycerosphingolipids and / or waxes or carboxylic acids of aqueous refined lipid phases, which is characterized by

a) providing a lipid phase containing carotenes, chlorophylls, phenols, sterols, squalene, glycolipids, glyceroglycolipids, glycerosphingolipids and / or waxes or carboxylic acids, wherein the lipid phase of at least one aqueous refining with an aqueous solution having at least one guanidine group or amidino group-bearing compound with a Kow was subjected to <6.3

b) contacting an adsorbent with the lipid phase from step a),

c) separation of the adsorbed carotenes, chlorophylls, phenols, sterols, squalene, glycolipids, glyceroglycolipids and / or glycerosphingolipids and / or waxes or carboxylic acids from stage b) by a phase separation,

wherein the adsorbent is cellulose, a cellulose derivative or an inorganic alumina silicate with an aluminum content of> 0.1 mol%.

The invention further relates to a process of complexing and extraction of water-binding organic lipophilic suspensions of aqueous refined lipid phases, which is characterized by

a) providing a lipid phase containing water-binding organic lipophilic turbidity, wherein the lipid phase has undergone at least one aqueous refining with an aqueous solution having at least one guanidine group- or amidino-containing compound having a Kow of <6.3,

b) contacting a complexing agent with the lipid phase from step a),

c) separation of the complexed water-binding organic lipophilic turbidity from stage b) by a phase separation,

Furthermore, the invention relates to a process complexing and extraction of carotenes, chlorophylls, phenols, sterols, squalene, glycolipids, glyceroglycolipids and glycerosphingolipids and / or waxes or carboxylic acids of aqueous refined lipid phases, which is characterized by

a) providing a lipid phase containing carotenes, chlorophylls, Phenols, sterols, squalene, glycolipids, glyceroglycolipids and / or glycerosphingolipids, and / or waxes or carboxylic acids, the lipid phase being subjected to at least one aqueous refining with an aqueous solution having at least one guanidine group or amidine group-bearing compound having a Kow of <6.3 has been,

b) contacting a complexing agent with the lipid phase from step a),

c) Separation of the complexed carotenes, chiorophyly, phenols, sterols, squalene, glycolipids, glyceroglycolipids, glycerosphingolipids and / or

Waxing or carboxylic acids from step b) by a phase separation, wherein the Kompiexierungsmittei is Aiuminiumionen or iron ions, which are present in an aqueous solution. A further embodiment according to the invention is a process for the separation of water-binding organic lipophilic suspensions from an aqueous refined lipid phase, which is characterized by

a) providing a lipid phase containing water-binding organic lipophilic turbidities, wherein the lipid phase has been subjected to at least one aqueous refining with a neutral or basic solution, b) adding the adsorption agent and / or a complexing agent to the lipid phase from stage a),

c) phase separation and separation of the adsorbed or complexed water-binding organic lipophilic turbid substances,

A further embodiment according to the invention is a process for the separation of carotenes, chlorophyls, phenols, sterols, squalene, glycolipids, glyceroglycolipids, glycerosphingolipids and / or waxes or carboxylic acids from an aqueous refined lipid phase, which is characterized by

a) providing a lipid phase containing carotenes, chiorophyi,

Phenols, sterols, squalene, glycolipids, glyceroglycolipids, glycerosphingolipids and / or waxes or carboxylic acids, the lipid phase being subjected to at least one aqueous refining with a neutral or basic solution, b) adding the lipid phase from step a) with an adsorbent and / or a complexing agent,

c) phase separation and separation of the adsorbed or complexed carotenes, chiorophyly, phenols, sterols, squalene, glycolipids, glyceroglycolipids, glycerosphingolipids and / or waxes or

carboxylic acids

wherein the Adsorptionsmittei to cellulose, a Ceiiuiosederivat or an inorganic alumina silicate with a Aluminiumanteii of> 0.1 mol% is and

a) providing a lipid phase containing water-binding organic lipophilic turbidities, wherein the lipid phase has undergone at least one aqueous refining with an aqueous solution having at least one guanidine group or amidine group-bearing compound having a Kow of <6.3,

b) adding the lipid phase from step a) to an adsorption agent and / or a competing agent,

wherein the Adsorptionsmittei to cellulose, a Ceiiuiosederivat or an inorganic Aiuminiumoxid Siiikat having an aluminum content of> 0.1 mol% is and

A further embodiment of the invention is a process for the separation of carotenes, chlorophylls, phenols, steroids, squaienen, Giycolipiden, Glyceroglycolipiden, Glycerosphingoiipiden and / or waxes or carboxylic acids from an aqueous refined lipid phase, which is characterized by,

a) providing a lipid phase containing carotenes, chiorophyi,

Phenols, sterols, squalene, glycolipids, Glycerogiycolipide, glycerosphingolipids and / or waxes or carboxylic acids, wherein the lipid phase of at least one aqueous refining with an aqueous solution having at least one guanidine group or Amidino-containing compound having a Kow of <6.3 has been subjected,

b) adding the phase of the lipid from step a) with an adsorption agent c) phase separation and separation of the adsorbed carotenes, chiorophyly, phenols, sterols, squalene, glycolipids, glycerolipolides,

Glycerosphingoiipideund / or waxes or carboxylic acids lipophilic turbidity,

wherein the Adsorptionsmittei to Ceiiuiose, a Ceiiuiosedenvat or an inorganic aluminum oxide Siiikat with a Aluminiumanteii of> 0.1 mol% is.

a) providing a lipid phase comprising water-binding organic iipophilic turbidities, wherein the lipid phase has undergone at least one aqueous refining with an aqueous solution having at least one guanidine group- or amidine-group-bearing compound having a Kow of <6.3,

b) adding to the lipid phase from step a) an adsorption agent c) phase separation and separation of the adsorbed water-binding organic lipophilic turbid substances,

wherein the Adsorptionsmittei to Ceiiuiose, a Celluiosederivat or an inorganic alumina silicate with a Aluminiumanteii of> 0.1 mol% is.

a) providing a lipid phase containing water-binding organic

Iipophilic turbidities, wherein the lipid phase has undergone at least one aqueous refining with an aqueous solution having at least one guanidine group or amidine group-bearing compound having a Kow of <6.3,

b) adding the lipid phase from step a) to a complexing agent, c) phase separation and separation of the complexed water-binding organic lipophilic turbid substances,

wherein the complexing agent is aluminum ions or iron ions present in an aqueous solution. A further embodiment according to the invention is a process for separating carotenes, chlorophylls, phenols, sterols, squalene, glycolipids, glyceroglycoipids and / or glycerosphingolipids and / or waxes or carboxylic acids from an aqueous refined lipid phase, which is characterized by

a) providing a lipid phase containing carotenes, chlorophylls, phenols, sterols, squalene, glycolipids, glyceroglycolipids and / or glycerosphingolipids, and / or waxes or carboxylic acids wherein the lipid phase of at least one aqueous refining with an aqueous solution having at least one guanidine group or amidino group-bearing compound was subjected to a Kow of <6.3,

c) phase separation and separation of the complexed carotenes, chlorophylls, phenols, sterols, squalene, glycolipids, glyceroglycolipids and / or glycerosphingolipids, and / or waxes or carboxylic acids, wherein the Kompiexierungsmittei to aluminum ions or iron ions, which are present in an aqueous solution.

figure description

FIG. 1: shows Table 1 .3 for Example 1. FIG. 2: shows Table 2.2 for Example 2.

FIG. 3: shows Table 5.2 for Example 5. FIG. 4 shows Table 6.1 for Example 6. FIG. 5 shows Table 7 for Example 7. Examples of measurement methods

The following measuring methods were used in the context of the exemplary embodiments described below:

The content of phosphorus, calcium, magnesium and iron in the lipid phase was determined by ICP OES (Optima 7300, PerkinElmer, Germany). Values in ppm (or in mg / kg).

The proportion of free fatty acids in the lipid phase was determined by means of a methanolic KOH titration with a Titroline 7000 titrator (Sl-Analytics, Germany) values in% by weight (g / 100 g).

The water content in the lipid phase, which is also referred to herein as oil moisture, was determined by means of an automatic titration according to the Karl Fischer method (Titroline 7500 KF trace Sl-Analytics, Germany), values in% by weight.

The determination of haze of a lipid phase was made by visual inspection by filling a 3 cm diameter cuvette with the oil to be tested and by 2 investigators, the visibility of image lines as viewed through the cuvette, under standardized light conditions. In addition, the brilliance of the sample was assessed by looking through the daylight. With distortion-free image lilies and optical brilliance, the oil sample was rated as transparent. With significant distortion of the line contours with difficult recognition of the image lines as well as a no longer clear view, the assessment was carried out as slightly cloudy. If image lines were still recognizable, but could no longer be differentiated, and the visual appearance was dim, classification was as moderately murky. If no lines were recognizable and a review by the oil sample was no longer possible, the classification was considered very cloudy. A classification as "milk-like" was made in a similar appearance to a milk compared to parallel measurements by turbidimetry (see below), that oils, which were assessed as transparent (turbidity (TR) = 1) in the FTU values of 16 to 50 were present for a slight turbidity (TR = 2) of the oils and FTU values between 51 and 200 for a moderate turbidity (TR = 3); TR = 4), FTU values were measured between 201 and 1000, and milky emulsions (TR = 5) had FTU values of> 1000. Quantification of the turbidity (turbidimetry) of oil phases was also carried out by means of a scattered light detector in which reentry of a scattered beam at 90 ° with a measuring probe immersed in a sample volume of 10 ml (InPro 8200 measuring sensor, M800-1 transmitter, Mettler Toledo, Germany). The measuring range is 5 to 4000 FTU. There were always duplicate determinations per sample. Droplet or particle size determinations were made by non-invasive laser light backscatter analysis (DLS) (Zetasizer Nano S, Malvern, UK). For this purpose, 2 ml of a liquid to be analyzed were filled into a measuring cuvette and inserted into the measuring cell. The analysis on particles or phase boundary forming droplets proceeds automatically. It is covered a measuring range of 0.3 nm to 10 μιτι.

The determination of secondary oxidation products in a lipid phase was carried out with a p-anisidine reaction, which was quantified photometrically. For this purpose, 20μΙΙ of an oil sample were filled into a test cuvette already containing the test reagent and immediately placed in the measuring cell of an automatic analyzer (FoodLab, Italy). The measuring range is between 0.5 and 100. Each sample was analyzed twice.

All investigations were carried out under normal pressure conditions (101, 3 Pa) and at room temperature (25 ° C), unless stated otherwise.

example 1

300 kg rapeseed oil with the characteristic numbers given in Table 1 .3 (FIG. 1) were subjected to a multi-stage refining process. For this purpose, the rapeseed oil was filled into a storage tank (storage tank 1). Subsequently, the oil in the storage tank 1 is heated to 50 ° C. and then treated with 0.1% by weight of citric acid (25% by weight, to room temperature) and stirred for 10 minutes with a rotor-stator homogenizer (Fluco MS 4, Fluid Kotthoff, Germany) at a rotational frequency of 1000 rpm for 30 minutes homogenized and. Thereafter, 0.4 wt .-% of water are added and stirred for 15 min at 100 rpm. Subsequently, phase separation with a separation separator (OSD 1000, MKR, Germany) at a throughput of 1001 / h and a rotational frequency of 10,000 rpm. The resulting clear oily phase A is transferred to a further storage tank (storage tank 2). 125 ml of oily phase A was used for chemical analysis.

The thus obtained oily phase A is brought to a process temperature of 40 ° C and added to a 4 vol% of 10 wt% potassium carbonate solution. The mixture is then carried out by means of the above-mentioned homogenizer at a rotational frequency of 1000 rpm for 15 minutes with intensive mixing. The resulting emulsion is pumped into the separation separator and phase separation performed with the same adjustment parameters. The resulting slightly cloudy oily phase B is transferred to the storage tank 3. 125 ml of oily phase B was used for chemical analysis. The oily phase B is brought to a process temperature of 35 ° C and added 3 vol% of 0.5 molar arginine solution. Subsequently, an intensive mixing is carried out by means of the above-mentioned mixing tool with the identical setting for 10 minutes. The resulting emulsion is pumped into the separation separator and the phase separation is effected at a rate of 200 l / h. The resulting cloudy oily phase C is transferred to the storage tank 4. 125 ml of oily phase C was used for chemical analysis. (Determination of Olkennzahlen according to measurement methods).

Thereafter, to each 10 kg of the pre-purified rapeseed oil in mutually independent experiments, with a propeller mixer (200rpm), the adsorbents listed in the table below were added as powdered solids in one portion of the aqueous refined oil over a 20 minute period stirred at a constant temperature of 30 ° C:

Table 1 .1

PS: particle size; MW: molecular weight; na: not specified Furthermore, in further experiments, the one-time addition of 100 ml of the solutions listed in the following Table 1 .2, which was stirred as described above in each case 10 kg pre-purified oil phase C: Table 1 .2

After 60 minutes, a phase separation of the individual oil phases was carried out with a separator (as described above).

As reference (reference experiment [RV]), 1 kg of the prepurified lipid phase was treated with a vacuum dryer (VC-130SC, Cik, Germany) at a temperature of 85 ° C over a period of 120 minutes and under a pressure of 0.01 Pa dried.

Following the adsorptive treatment according to Experiments 1 .1 to 1 .12 and the complexing treatment according to Experiments 2.1 to 2.10 each 1 liter of the treated oil phases were withdrawn and provided with 50 ml of demineralized water and with a stirrer at a speed of 500rpm for 10 minutes at a temperature of 25 ° C. touched. This is followed by centrifugal separation at 3,000 g for 10 minutes. Afterwards a new determination of the water content of these oil phases as well as an evaluation of the turbidity took place (execution see measuring methods). Of the treated oil phases, 10 ml samples were also taken, one immediately frozen (D 0) and the second stored in an open vessel in daylight for 120 days (D120). Then determination of the anisidine value (procedure as described under Measuring Methods), for which the samples DO were thawed again and analyzed in a sample run with the stored samples (D120). Results (Numerical results are summarized in Table 1 .3 (FIG. 1)): The cellulose ethers used according to the invention (Experiment 1 .1) and the kaolin used according to the invention (Experiment 1 .4) achieved a very good clarification of the aqueous-refined oils become. The other adsorbents used in the experiments 1 .2, 1 .3, 1 .5 and 1 .6 did not allow satisfactory clarification. Further investigations on the cellulose ethers according to the invention according to Experiments V 1 .7 to V 1 .12 confirm the removal of turbidity from the purified oil phase using different molar ratios. In the aqueous refining step according to the invention, the dissolved aluminum compounds of Experiments V 2.1, V 2.2, V2.8 to V 2.10 also show a complete clarification of the prepurified oil phases, and to a lesser extent solutions of dissolved iron III ions (V2.3), while other metal ions (experiment V 2.4 to V 2.7) dissociate in an aqueous solution templates did not allow this.

After renewed agitation with water and subsequent centrifugal phase separation, it was found that after a treatment according to the invention with an adsorption or complexing agent only a very small re-introduction of water into the refined lipid phases occurs, as a result of which these oil phases also remained clear. This was not the case with the alternative substances used. A re-entry of water was also possible if the pre-cleaned oil had only been subjected to vacuum drying. Crude oil contained secondary oxidation products, which were largely removed by the aqueous refining process. By treating the prepurified lipid phase with the adsorption or complexing agents according to the invention, the content of secondary oxidation products was reduced to a (by method-related) no longer measurable range. By the comparison substances, the secondary oxidation products were only slightly reduced or even increased. Exposure to atmospheric oxygen and light radiation produced secondary oxidation products in all oils. The differences between the oil phases treated with the compounds according to the invention and those which had not been treated or compared with comparison compounds were still significantly greater after 90 days than was the case after the initial treatment. Example 2

From a fermentative conversion of organic waste materials with subsequent transesterification of the obtained lipid mixture, 50 liters of organic phase (about 98% fatty acid methyl ester) were obtained. The aqueous refining was carried out under basically the same mixing and separation conditions as listed in Example 1. In the first stage, 2% by volume of a 15% strength by weight metasilicate solution are used, the reaction temperature being deviating to 50 ° C. The separated oily phase A was moderately cloudy. The 2nd refining step was carried out with a 2% by vol. 0.6 molar arginine solution. The reaction temperature was 28 ° C. The obtained oil phase B was very cloudy. In each case acceptance of samples for analysis. (Determination of the oil indices according to measuring methods)

30 kg of the thus pre-cleaned biodiesel were further refined with the adsorbents listed below. In this case, the following adsorbents were added in independent experiments to each 1, 5 kg. A sample was dried by vacuum drying as listed in Example 1.

Table 2.1

Furthermore, aluminum trichloride was added which was dissolved in an ion-poor water in the concentrations of 0.01, 0.05 and 0.1 molar (test numbers 2.1 to 2.3) and with polyaluminum chloride (Al ₂ (OH) ₂ .iCl 3 .9 x 2-3 H ₂ O), which was present in the same concentrations in an aqueous solution (test numbers V 2.4 to V 2.6), by adding in each case 10 ml to the solutions. The substances were mixed with a hand mixer over a period of 5 minutes. Thereafter, the samples were allowed to stand for 30 minutes. It was then centrifuged with a centrifuge at 3000 rpm for a period of 7 min. The oil phases were poured off at the adsorbents, in the aqueous extractions, the oil phases were withdrawn. For a sample of the prepurified oil phase (V1.9), vacuum drying was performed as indicated in Example 1. Subsequently, in all samples, an entry of demineralized water into the oil phases obtained took place in the same way as described in Example 1. The analysis of the water content and the turbidity of the organic phases were carried out as described in Example 1 or under measuring methods. Results: Both the adsorbent-related cellulose ethers and the aluminum-containing phyllosilicate as well as the complexation-related aluminum ion-containing solutions resulted in a complete clarification of the lipid phases (Table 2.2 (Figure 2)), so that all refined oil phases were ultimately transparent. Accordingly, the residual moisture in all samples to which adsorbents had been added was in a range between 0.01 and 0.09 wt%. and between 0.01 and 0.14% by weight of the oils treated with the complexing agents.

After the re-entry of water, the samples with the lowest concentrations were present. Complexing agents had slightly higher reuse values for water than the samples treated with higher concentrations of the substances. A removal of residual water from the pre-cleaned oil, could also be carried out with a vacuum drying, in this oil phase, however, a re-entry of water was to a relevant extent possible. In the aqueous phase of the separated complexing agents, aggregated particles were recognizable whose amount did not differ between the selected concentrations. Example 3

500 kg of Jatropha press oil were refined in a multistage aqueous state, with the process technology essentially corresponding to that of Example 1. The aqueous refining was carried out under basically the same mixing and separation conditions as listed in Example 1. In contrast, in the first stage, 4% by volume of an 8% by weight sodium borate solution introduced at 25 ° C with a propeller stirrer was used. The separated oily phase A was discretely cloudy. The second refining step was carried out with an addition of 3% by volume of a 5% strength by weight sodium bicarbonate solution at 50 ° C. Again, the entry was made with a propeller stirrer over 30 minutes. The resulting oil B was slightly cloudy. The 3rd aqueous refining step was carried out with 2% by volume of a 12% by weight orthometasilicate solution. The resulting oil phase C was moderately cloudy. In the 4th refining step, 2% by volume of a 0.3 molar arginine solution, as described in Example 1, are introduced through an intensive mixture. The reaction temperature was 32 ° C. The prepurified oil phase D obtained was very turbid. In each case acceptance of samples for analysis. Further decrease of a reference sample (VR) at which a vacuum drying, as described in Example 1, took place. For the dried oil, an attempt was made to reenterability of water according to Example 1. (Determination of the oil indices according to measuring methods)

The oil samples had the analysis results shown in Table 3.1 below Table 3.1

Wdh. = Repeated water entry; Oil cloudiness: 1 = transparent, 2 = slightly cloudy, 3 = moderately cloudy, 4 = very cloudy, 5 = milky; n. d. = not performed.

The following methylcelluloses were investigated: V 1. Hydroxyethylcellulose (H 200000 YP2), V 2. Methylhydroxypropylcellulose (90SH-100000) V 3. Hydroxyethylcellulose (H 60000 YP2) with different dosages (weight ratio of cellulose ether / oil (m / m)) Cellulose: lipid phase: a) 1: 99 , b) 1: 499 and c) 1: 999. Furthermore, in Experiment V 4, kaolin powder in an amount ratio (adsorbent / oil (m / m)) of a) 1: 499 and b) 1: 999 was added to the purified oil. Further, various volume ratios of an aluminum trichloride (Run 5) and a poly (aluminum chloride) (Run 6) solution, each at a 1.5 molar concentration, were examined. The metered addition in the ratio a) 1: 99, b) 1: 999 and c) 1: 9999. The mixture of the oil phase with the cellulose preparations and the kaolin was carried out with a propeller stirrer, the entry of the aqueous solutions with an Ultrathurrax at 9000 rpm ,

The determination of oil moisture and oil clouding (see measuring methods) was carried out after the individual refining stages and after the refining according to the invention and after a renewed introduction of water and subsequent centrifugal separation of the water phase, as described in Example 1.

Table 3.2

Water content Turbidity Wdh. Wdh Turbidity

(Wt%) water content

(Wt%)

Oil cloudiness: 1 = transparent, 2 = slightly cloudy, 3 = moderately cloudy, 4 = very cloudy, 5 = milky

Results:

The investigated cellulose preparations showed, in the case of the cloudy oil phase obtained by the aqueous refining, at all chosen volume ratios, a removal of the hydrated turbidity, so that the obtained water contents of the refined oils all amounted to </ = 0.12% by weight. Accordingly, the thus treated oil phases were all transparent. After re-introduction of water followed by renewed centrifugal phase separation, the oils treated with the least amount of cellulose esters showed a slight increase in water content (at most 0.16% by weight). Even in the case of the complexing processes according to the invention with dissolved aluminum ions, a complete reduction of the turbidity with a similarly good reduction of the oil moisture occurred in all proportions investigated. Even after renewed entry of water, the oil moisture content at all concentrations was <0.13% by weight, correspondingly the oil phases were transparent. A similar result was found for kaolin. By vacuum drying, the oil moisture could also be reduced, with this oil, a relevant water entry was possible. Example 4:

For the investigations, the following cold press oils were used: from rapeseed (RÖ), sunflower seeds (SBÖ) and grape seeds (TKÖ) with the key figures: for RÖ: phosphorus content 4.2 ppm (or 4.2 mg / kg), calcium 25 ppm (or 25 mg / kg), iron 2.1 ppm (or 2.1 mg / kg), free fatty acids 1, 0 wt .-%, and for SBÖ: phosphorus content 7.2 ppm (or 7.2 mg / kg), calcium 28 ppm (or 28 mg / kg), iron 2.3 ppm (or 2.3 mg / kg), free fatty acids 1, 2 wt .-% and for TKÖ: phosphorus content 3.8 ppm (or 3 , 8 mg / kg), calcium 12 ppm (or 12 mg / kg), iron 1, 1 ppm (or 1, 1 mg / kg), free fatty acids 0.8 wt .-%. All raw oils were clear. For each 2000 ml of the oils, 60 ml of a 0.5 molar arginine solution was added. Mix with an Ultrathurrax T18 at 24 TDS rpm for 5 minutes. Then, centrifuge the water-in-oil emulsion in a cup spinner at 5000rpm for 10 minutes. The prepurified oil phases obtained have the following ratios for RO: Phosphorus content 1, 2 ppm (or 1.2 mg / kg), Calcium 0.9 ppm (or 0.9 mg / kg), Iron 0.08 ppm (or 0 , 08 mg / kg), free fatty acids 0.2% by weight, for SBÖ: phosphorus content 0.8 ppm (or 0.8 mg / kg), calcium 0.2 ppm (or 0.2 mg / kg), iron 0.05 ppm (or 0.05 mg / kg), free fatty acids 0.13% by weight and for TKÖ: phosphorus content 0.5 ppm (or 0.5 mg / kg), calcium 0.02 ppm (or 0, 02 mg / kg), iron <0.002 ppm (or <0.002 mg / kg), free fatty acids 0.01 1% by weight. All oils obtained are moderately to significantly cloudy. (Determination of oil indices according to measuring methods).

To each 200 ml of the prepurified oils are added the hydroxyethylcellulose (H 200000 YP2) (V 1) and methylhydroxypropylcellulose (90SH-100000) (V 2) in a weight ratio of the adsorbent to the oil of 1: 499. Further, kaolin powder (V3) is added in a weight ratio of adsorbent to oil of 1: 199. Further, a 0.5 molar solution of aluminum dicholride (V4), aluminum sulfate (V5) and polyaluminum hydroxide chloride sulfate (V6), a weight ratio of the complexing agent solution to the oil of 1:99 is added. The adsorption and the complexing agent are mixed continuously with a propeller stirrer at a rotation frequency of 500 rpm after initial complete addition. After 10 minutes, b) after 15 minutes, c) after 30 minutes and d) after 60 minutes each 10 ml of the agitated oil phases are removed and centrifuged (3800 rpm / 5 minutes) from the solid or water phase separated. Subsequently, a determination of the optical transparency and the water content (see measuring methods). A comparative sample of the prepurified oil added to the oil in a weight ratio of 1: 99 ion-free water was also agitated with the stirrer and sampled at the end of the study period Vacuum drying, as described in Example 1, removed (V 7) and then examined for transparency and water content and on the re-enterability of water.

In all experiments, 2 samples (20 ml) were taken at the end time (in experiment V7 after drying the oil) and filled into closable containers. One sample was frozen (DO), the second was allowed to stand in the light of daylight for 90 days at room temperature (D90). After 90 days, the anisidine value was determined for all stored and thawed samples from time DO (see Methods of measurement).

Table 4.1

Table 4.2

V 7 0.07 1 3.75 3 1, 1 18

Table 4.3

Wdh. = Repeated water entry; Oil cloudiness: 1 = transparent, 2 = slightly cloudy, 3 = moderately cloudy, 4 = very cloudy, 5 = milky; nd = not performed. Summary: By a vacuum drying of pre-cleaned oil phases, a very good reduction of the residual moisture is achieved, but there is a clear re-introduction of water. The investigated adsorption and complexing agents lead to a rapid reduction in the turbidity of purified oil phases. This was associated with a significant reduction in the re-applicability of water in the oil phase. While the prepurified and dried oils still contained secondary oxidation products, the refined and refined oil phases contained no secondary oxidation products that could be determined by the p-anisidine method. Over the course of 90 days, the prepurified and dried oils formed much more secondary oxidation products than the oil phases that had been upgraded with the adsorptive or complexing agents.

Example 5:

Investigation on the influence of the pre-purification of a lipid phase on the extractability of turbidity.

Leverwort oil, with the key figures (determination of the oil indices according to measurement methods) according to Table 5.1, was refined by the following methods:

V 1: phosphoric acid (85% strength by weight, addition amount 0.4% by weight, exposure time 30 minutes), then aqueous solution with sodium carbonate (20% strength by weight, addition amount 3% by volume, exposure time 5 minutes)

V 2: phosphoric acid (85% strength by weight, addition amount 0.4% by weight, duration of action 30 minutes), then aqueous solution with sodium carbonate (20% strength by weight, addition amount 3% by volume, exposure time 5 minutes), then aqueous solution with arginine (0.3 molar, addition amount 2% by volume, exposure time 5 minutes)

V 3: phosphoric acid (85% strength by weight, addition amount 0.4% by weight, duration of action 30 minutes), then aqueous solution with sodium hydrogen carbonate (20% strength by weight, addition amount 3% by volume, exposure time 5 minutes), then aqueous solution with sodium hydroxide (1 N, added amount 3%, exposure time 5 minutes)

V 4: Aqueous solution of sodium bicarbonate (20% by weight, added amount 3% by volume, exposure time 30 minutes), then phosphoric acid (85% by weight, added amount 0.4% by weight, exposure time 30 minutes)

V 5: Aqueous solution of sodium bicarbonate (20% by weight, added amount 3% by volume, exposure time 30 minutes), then phosphoric acid (85% by weight,

Addition amount 0.4% by weight, exposure time 30 minutes), then aqueous solution with arginine (0.3 molar, addition amount 2% by volume, exposure time 5 minutes)

V 6: Aqueous solution of sodium carbonate (20% by weight, added amount 3% by volume, exposure time 30 minutes), then phosphoric acid (85% by weight, added amount 0.4 % By weight, exposure time 30 minutes), then aqueous solution with sodium hydroxide (1 N, addition amount 3%, exposure time 5 minutes)

V 7: Aqueous solution of sodium bicarbonate (20% by weight, added amount 3% by volume, exposure time 30 minutes), then aqueous solution of sodium metasilicate (20% by weight, added amount 2%, exposure time 5 minutes)

V 8: Aqueous solution of sodium bicarbonate (20% by weight, added amount 3% by volume, exposure time 30 minutes), then aqueous solution of sodium metasilicate (20% by weight, addition amount 2%, exposure time 5 minutes), then aqueous solution with arginine ( 0.3 molar, addition amount 2% by volume, exposure time 5 minutes)

V 9: Aqueous solution of sodium bicarbonate (20% by weight, added amount 3% by volume, exposure time 30 minutes), then aqueous solution of sodium metasilicate (20% by weight, addition amount 2%, exposure time 5 minutes), then phosphoric acid (85% by weight). %, addition amount 0.4% by weight, exposure time 30 minutes)

V 10: Aqueous solution of sodium bicarbonate (20% by weight, added amount 3% by volume, exposure time 30 minutes), then aqueous solution of sodium metasilicate

(20% by weight, addition amount 2%, exposure time 5 minutes), then aqueous solution with sodium hydroxide (1 N, addition amount 3%, exposure time 5 minutes)

The aqueous solutions and the undiluted phosphoric acid were added in the indicated concentrations and addition amounts to 10 liters of crude oil and homogenized with an intensive mixer (Ultrathurrax, T50, 10 TSD rpm for 5 minutes). Subsequently, phase separation with a separator (OTC 350, MKR, Germany) (flow rate 30 L / h, drum frequency l O.OOOrpm) then separated taking a sample for the determination of the ratios (Table 5.1).

Table 5.1

Per 1000 g of the pre-purified oil fractions were mixed with the following adsorption and complexing agents:

a) Hydroxyethyl cellulose (H 200000 YP2) 0.5% by weight

b) Methylhydroxypropylcellulose (90SH-100000) 0.5% by weight

c) kaolin (1, 5 wt%)

d) aluminum chloride solution (3 molar, added 1 vol%)

e) polyaluminium chloride solution (9% by weight, added amount 1% by volume)

The mixture of the oils added with adsorption or complexing agents was carried out with a propeller stirrer at 300 rpm for 30 minutes. This was followed by a phase separation with beaker centrifuge (4000 rpm, 5 minutes). Subsequently, taking samples to determine the ratios (Table 5.2 (Figure 3)).

Summary (numerical summary in Table 5.2 as Figure 3):

In the related aqueous refining processes remained in the oils significant amounts of water in varying degrees. With a renewed entry of water and centrifugal separation of the water phase remained at all pre-cleaned oil phases, a somewhat equal amount of water in the oil. The use according to the invention of adsorption or complexing agents has led, in the case of refined oils which have an increased water content, to an optimum reduction of the residual water content. At the same time, the re-enterability of water in all oils was reduced, the effect being significantly greater for refined oils pre-cleaned with arginine solution, and especially when the last aqueous refining step was with an arginine solution. A significantly poorer depletion of turbidity, with a much higher Wiederertragbarkeit of water in the refined oil phase, turned out to be when an acidic washing step was carried out prior to the application of the substances according to the invention.

Example 6:

Product loss studies by adsorption and complexing agents. Mustard oil (20 liters) with the key figures (determination of the oil indices according to measuring methods): Phosphorus content 16.2 ppm (or 16.2 mg / kg), calcium 8.4 ppm (or 8.4 mg / kg), iron 0.56 ppm (or 0.56 mg / kg), free fatty acids 0.9 wt.% Was, with an aqueous shirring consisting of a citric acid solution (25% by weight, added 0.5 wt%, exposure time 20 minutes) and a aqueous arginine solution (0.4 molar, 3% addition) treated by the aqueous Solutions by means of an intensive mixer (Ultrathurrax T50, 10 TSD rpm) over 5 minutes were entered. In each case phase separation with a beaker centrifuge (4000 rpm, 5 minutes) .. The purified oil had the characteristics: Phosphorus content 0.7 ppm (or 0.7 mg / kg), calcium <0.02 ppm (or <0.02 mg / kg), iron <0.02 ppm (or <0.02 mg / kg), free fatty acids 0.05% by weight. The oil was moderately cloudy and had a water content of 2.43% by weight. To find the dose (minimum dose), which allows for a reduction of the residual water content to a value of <0.15% by weight and a reduction of re-enterability (experimental procedure according to Example 1) of a water content to a value of <0.25% by weight , In each 1500g of the purified oil, the adsorbent a) hydroxyethyl cellulose (H 200000 YP2), b) hydroxyethyl cellulose (H 60000 YP2), c) methyl hydroxypropyl cellulose (90SH-100000) and d) kaolin, in increments of 0.2 wt % every 10 minutes, with continuous mixing with a propeller stirrer (400rpm). Before each additional dosing, a sample was taken for the analysis of the residual water content and the re-enterability of water, centrifuged after 60 minutes and then analyzed and processed accordingly. In an analogous manner, the minimum dose for the complexing agents e) aluminum trichloride f) aluminum sulfate and g) polyaluminum chloride (9% by weight) were determined, in each case 0.2% by weight of a 0.5 molar solution of the compounds e) and f) a purified oil phase, as described above, was added. Sample preparation and analysis were as previously described. After determining the minimum dose (see Table 6.1 (FIGURE 4), a further attempt was made with the adhesives or complexing agents by stirring them in the respectively determined minimum dose over 30 minutes in 500 ml of the prepurified oil as described above The adhesives then lay as a solid friable mass on the centrifuge glass bottom, the oil phase was poured off, and the centrifuge tubes were stored in an oven at 50 ° C for 12 hours so that residual oil could drain off completely, followed by complete removal of the adsorbent mass and suspension in 150 ml of n-hexane at 50 ° C. for 20 minutes, after which the suspensions are filtered through a membrane filter (sieve size 20 μm) and the solvent phase is collected, which is then concentrated in a vacuum evaporator

Complexing agents are carefully completely removed after centrifugation. The slightly turbid water phases are shaken vigorously with 150 ml of n-hexane and the phases separated by centrifugation, the solvent phase is removed and concentrated as before. The solvent residues are weighed and set the resulting mass in relation to the mass of the oil phase used, to determine the product loss. The resulting oily residues from the Hexane phase are assumed to be discharged triglyceride fraction. The results are listed in Table 6.1 (Figure 4). The extracted with hexane cellulose compounds were washed out with other solvents. A washout was carried out with methanol. The phase was concentrated by means of which thin-layer chromatography was carried out for the analysis of phospholipids. In another wash with chloroform, with an addition of HCL, a sample preparation (methylation) was carried out for fatty acid analysis and a gas chromatographic analysis performed. In another washout with a mixture of acetone and 1-pentanol, a sample preparation for the determination of chlorophyll was carried out (determination method see measurement methods)

Summary (numerical results in Table 6.1 as Figure 4)

With the determined minimum dosages of the adsorption and complexing agent, a product loss-free separation of turbidity by the complexing agents used is possible by the adsorbents used, the turbid substances are removed with minimal loss of product. It could be shown that with the adsorbent fatty acids, wax acids, phospholipids and chlorophylls are discharged from the oil.

Example 7:

Evening primrose oil (5000ml) with the key figures (determination of the oil indices according to measuring methods): Phosphorus content 6.2 ppm (or 6.2 mg / kg), Calcium 1, 2 ppm (or 1, 2 mg / kg), Iron 0.31 ppm (or 0.31 mg / kg), free fatty acids 0.82% by weight (or 0.82 g / 100g) was subjected to ultrafiltration with a membrane filter having a nominal sieve size of 5μηη and further with a sieve size of 0.45μηη subjected. A sample of the transparent oil was analyzed and the numbers were virtually unchanged from the starting material. There was a determination of corpuscular components in the oil phase by means of DLS (for description, see Methods of measurement). In the filtered oil only minimal amounts of particles were present, these had> 90% of all particles a diameter of <20 nm. The filtered crude oil was optically transparent, it was determined a water content of 0.41% by weight, by means of the example 1 described experiment carried out a water entry, with a resulting water content of the oil of 2.62 wt%. The filtered oil was subdivided for the following experimental arms: A) aqueous shirring by means of an arginine solution (0.6 molar, 3 vol% addition amount), which was carried out by passing the aqueous solution through an intensive mixer (Ultrathurrax T18, 24 TSD rpm) 10 minutes was entered; B) aqueous refining, as under A), but with a mixed addition by a propeller stirrer (500 rpm over 10 minutes; C) immediate addition of the adsorption or complexing agent to the oil and stirring as in B).

Following the aqueous refining of the experimental arms A) and B), a phase separation was carried out as in Example 5 to obtain the oil phases A1) and B1). The following parameters were determined for the pre-cleaned oil, for A1): Phosphorus content 0.7 ppm (or 0.7 mg / kg), Calcium 0.02 ppm (or 0.02 mg / kg), Iron <0.02 ppm (or <0.02 mg / kg), free fatty acids 0.08% by weight and for B1): phosphorus content 1.2 ppm (or 1.2 mg / kg), calcium 0.09 ppm (or 0.09 mg / kg), iron 0.03 ppm (or 0.03 mg / kg), free fatty acids 0.10% by weight. Both oils were moderately cloudy. In each case half of the prepurified oil phases from A1) and B1), a vacuum drying was carried out, so that the same volume fractions, the pre-cleaned oil passages A1) and B1) and the prepurified and dehumidified oil phases A2) and B2) were obtained. The resulting oil phase A2) was halved and one half returned for a further experiment called A4). The oil phases A1), A2), B1) and B2) were the adsorbents hydroxyethyl cellulose (H 60000 YP2) (a) and methylhydroxypropyl cellulose (90SH 100000) (b) (each 0.5 wt% added) and the complexing agent aluminum trichloride (1.0 molar, 1 wt% addition amount) (c) and polyaluminum chloride (9 wt%, 0.5 wt% addition amount) (d) are added. It was mixed with a propeller stirrer (500 rpm for 20 minutes) and then phase separated with a beaker centrifuge (3800 rpm / 10 minutes). The resulting oil supernatants A1 "), A2"), B1 ") and B2") were withdrawn and samples were taken for the analysis and for an attempt to registrability of water, according to the experimental procedure of Example 1. The resulting oil phases A2 ") and B2") were mixed with an arginine solution (0.1 molar, added amount 2% by weight) and the phases were homogenized with the intensive mixer (24 tsd rpm, 2 minutes). Subsequently, phase separation as described above, to obtain the oil phases A3) and B3). Both oil phases were cloudy, samples were taken for analysis. Thereafter, the adsorptive or complexing agents (a), (b), (c) and (d) were again added to the obtained prepurified oil phases A3) and B3) in the same volume and concentration ratios as before and mixed as described above. Then phase separation by centrifugation. From the obtained refined and refined oils A3 ") and B3"), samples were taken for analysis and investigation of water penetration. The obtained after aqueous refining oil phase A4) was filtered with the filter unit described above. The resulting filtered oil phase A4f) had optically a lower turbidity. Samples for the analysis and an attempt to re-introduce water are made. The oil of the experimental arm C), which after treatment with the Adsorptionsbzw. Complexing agents added in the same volume ratios and concentrations and with the same process parameters as in the experimental arms A) and B) and, after appropriate phase separation, as oil phase C "were tested for water content and water registrability as described above The oil phase C "was then prepurified by means of an aqueous refining with an arginine solution according to the procedure and the process parameters in the experimental arm A). After phase separation, which was carried out analogously to the abovementioned, the prepurified cloudy oil phase C1 was obtained, taking samples for analysis and water penetration. The pre-purified oil C1) were again Adsorptionsbzw. Complexing agent (a), (b), (c) and (d) stirred in the same volume and concentration ratios as before and under the same process conditions. Subsequently, phase separation to obtain the refined and refined oil phase C1 ") and sampling for analysis and water introduction, as described above.

In all pre-cleaned and refined oil phases, an evaluation of the optically determined turbidity as well as the determination of a turbidity value by a turbidimetric measuring system was carried out in parallel (see measuring methods). Additionally, in the refined oil phases, determinations of particles or droplets contained herein were made by DLS.

Results (the numerical results are shown in Table 7 (Figure 5)):

The adsorbents according to the invention, which were added in anhydrous form to an ultrafiltered crude oil, led to a slight reduction in the water content present therein. The incorporation of aqueous solutions containing the complexing agents of the present invention into an ultrafiltered but non-aqueous refined oil phase resulted in an increase in the water content of the oil phase. After centrifugal separation of the adsorption and complexing agents. In both cases, there was a distinct registrability of water into the oil phase. The oil phases pretreated in this way, after a subsequent aqueous refining, had similarly high values for water bound here or for a further introduction of water into the pre-purified oil phase, as was the case when the crude oil had been treated directly with a similar aqueous refining. Thus, no relevant discharge of turbidity by the incorporation of the adsorption or complexing agent according to the invention is carried out in a crude oil. Oil which had been subjected to an aqueous refining according to the invention and in which the turbid substances remaining in hydrated form were present, could be freed from the turbidity by the adsorption or complexing agents whereby a low residual moisture content and a low re-enterability of water could be achieved. If the prepurified oil phases no longer contained any relevant amounts of water due to vacuum drying, a relevant discharge of turbidity by the adsorptive or complexing agents used was not possible, as was evident by a clear recovery of water into the treated oil phases. If, in such an oil phase, a further aqueous refining step had taken place and the turbid substances were present again in hydrated form, it was possible to deplete the turbid substances with the same adsorption or complexing agents, while retaining a low residual oil moisture content and a low re-injectability of water into the oil phase. A determination of the particles or droplets contained in the refined oils showed that for all samples that were judged to be transparent and had a haze value of 5 FTU, less than 5% of all measured particles / droplets were> 20 nm. In transparent, refined oil phases, where the turbidity measurement yielded values up to 16 FTU, there were also particles / droplets with a peak at 60 nm, with a ratio of less than 5% to particles / droplets <10 nm. Thus, it can largely be ruled out that aggregates or complexes formed by the compounds used or the aggregating agents themselves used remain in the refined oil phase.

Example 8:

Large-scale application

5000 liters of rapeseed press oil is subjected to aqueous refining according to the following scheme: 1. Phosphoric acid (85%, addition amount 0.4%), 2. Aqueous solution with sodium carbonate (20% by weight, addition amount 3% by weight), 3. Aqueous solution with arginine (0.3 molar, addition amount 2% by weight). The acid and the aqueous solutions are homogenized by means of an in-line intensive mixer (DMS2.2 / 26-10, Fluko, Fluid Kotthoff, Germany) with a throughput volume of 3 m ³ / h, at a rotational frequency of the dispersing tool of 2700rpm. After each mixing step, a phase separation is carried out with a separator (AC1500-430 FO, Flottweg, Germany) at a throughput of 3 m ³ / h and a drum speed of 6500 rpm (maximum centrifugal acceleration 10,000 g). The refined oil fractions are stored in each case in a storage container until the next refining step. After the third purification step, the oil has the following characteristics: Phosphorus content 0.9 ppm (or 0.9 mg / kg), Calcium <0.02 ppm (or <0.02 mg / kg), Iron <0.02 ppm (or <0.02 mg / kg), free fatty acids 0.07% by weight, water content 2.9% by weight. (Execution see experimental methods) The oil is clearly cloudy. The purified oil from the 3. Refining stage is filled in 2 fractions of 2450 liters each in the storage tanks 1 and 3. To the template tank 1, 6.6 kg of hydroxyethyl cellulose (H 200000 YP2), which is in the form of a fine powder, is added with continuous stirring with a propeller stirrer (400 rpm) over 3 minutes and then further stirred for 15 minutes. Thereafter, the oil phase is pumped into a candle filter unit (screen size 2μηη) via a pump. The outlet of the filter unit is connected to the storage tank 2 for storage of the refined oil phase.

The purified oil in storage tank 3 is added 46 liters of a 3 molar aluminum trichloride solution. Via a bottom outlet of the reservoir tank, which is connected to a pipeline, the oil / water mixture is pumped into the above-mentioned inline rotor-stator mixing unit and mixed therein at a rotational frequency of 1000 rpm at a product throughput of 6 m ³ / h. The mixed oil / water phase is returned to the storage tank 3 again. The mixing process is carried out for 15 minutes, theoretically a 3-times throughput of the total oil mixture volume through the mixing unit. This is followed by a phase separation with the abovementioned separator, as described above. The oil phase is then introduced into the storage tank 4 via a pipeline. Samples are taken from the storage tanks 2 and 4 for analysis. Both refined oil phases are transparent, the oil from storage tank 2 contains a residual moisture content of 0.02% by weight, that of storage tank 4 0.03% by weight. It is, as described in Example 1, the re-entry of water examined. This results in a water content of the oil from storage tank 2 of 0.09% by weight and in the case of the oil from storage tank 4 of 0.08% by weight.

Claims

claims

Process for the adsorption and extraction or complexing and extraction of water-binding organic lipophilic suspensions of aqueous refined lipid phases, characterized by

a) providing a lipid phase containing water-binding organic lipophilic turbidity, wherein the lipid phase has been subjected to at least one aqueous refining with a neutral or basic solution, b) contacting an adsorbent and / or a complexing agent with the lipid phase from step a),

A method according to claim 1, characterized in that in step a) the at least one aqueous refining is carried out with an aqueous solution of at least one guanidine group- or amidine-containing compound having a Kow of <6.3.

A process according to claim 1 or 2, wherein in step c) a sedimentation centrifugal, filtration or adsorptive separation technique takes place.

A method according to any one of claims 1-3, wherein the adsorbent and / or complexing agent of step b) is immobilized or bound in a tissue or texture, the tissue or texture for complexation and / or adsorption and / or filtration the turbid matter is suitable.

Method according to one of claims 1 - 4, characterized in that after step c) a lipid phase with less than 0.5 wt.% Water is obtained. Use of the method according to any one of claims 1-5 for the separation and recovery of water-binding organic lipophilic Trübstoffen.

Use of the method according to any one of claims 1-6 for reducing the resumption of water into a lipid phase and / or for improving the oil storage capacity or the oxidation stability of vegetable oil.

A lipid phase obtainable according to any one of claims 1-7, having a content of less than 10% by weight relative to the initial amount of hydrophilic organic lipophilic suspensions, said lipid phase being characterized as having therein less than 5 ppm of phosphorus containing compounds, less than 0.2 Wt .-% of free fatty acids, and less than 3 ppm of Na, K, Mg, Ca and / or Fe ions are included.