HK1235425A1 - Method for purifying refined lipid phases - Google Patents

Abstract

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

Description

The present invention relates to a method for separating suspended solids from a lipid phase.

Background of the Invention

Lipid phases of biological origin contain, besides the neutral fats desired for further use, such as triglycerides, usually numerous organic accompanying substances that, within the biological context from which the lipids originate, help in solubilization. Therefore, these accompanying substances often exhibit a remarkably high lipophilicity despite their overall amphiphilic properties. This depends on the ratio of hydrophilic and hydrophobic molecular components. While compounds with a strong ability to bind water molecules, as is the case, for example, with hydratable phospholipids (phosphatidylcholine and phosphatidylethanolamine), can easily be washed out by water into a lipid phase, this is already difficult with structurally very similar phospholipids that are referred to as non-hydratable (phosphatidylinositol and phosphatidylserine),No longer present. Moreover, glycolipids and glycyglycerolipids are also found in most lipid phases, which often have very long-chain fatty acid residues and cannot be easily washed out from a lipid mixture using an aqueous medium despite the absence of polar groups. Furthermore, plant-derived lipid phases also contain sterol glycosides as well as hydrophobic pigments such as carotenoids and chlorophylls. These compounds are completely insoluble in water and therefore remain in the lipid phase during aqueous refining. Nevertheless, all the aforementioned compounds are capable of binding small amounts of water molecules via electrostatic interactions, for example, to OH-groups. Furthermore, the aforementioned compounds are usually found together in complex structures.Including ions from the group of alkaline earth metals and other metals. This further increases cohesion in the area of hydrophilic groups. This explains why it is necessary to clean such lipid mixtures with aqueous media containing strong bases and strong acids. Nevertheless, so far no process has been shown to enable a complete separation of compounds capable of binding water ions via OH-groups. Consequently, it is not possible to reduce the residual water content or the water absorption capacity of the refined oil to a level that meets product requirements both for food quality and for a lipid phase used as a technical product.such as for biofuels, is sufficient. To achieve drying of aqueous refined lipid mixtures according to the state of the art, the pretreated lipid phases are either heated or subjected to vacuum drying in order to remove water content, which can realistically reduce the residual moisture content to values between 0.05 and 0.15 weight percent. Such a drying process increases refining costs. Furthermore, the water-binding compounds remain in the lipid phase, so that upon renewed water ingress, water binding may occur again, resulting in cloudiness of the lipid phase. Therefore, these compounds are also partially referred to as cloudiness-causing substances, although the cloudiness caused by these substances is not visible in this context.not only do complex organic compounds become visible themselves, but the turbidity arises from water molecules bound by these organic compounds. In contrast to other complex organic substances, also referred to as turbidity-causing agents, which can be imaged using optical techniques and, because they are particulate in nature, can also be extracted and separated by filtration, the turbidity-causing agents mentioned here are characterized by their inability to be separated by a filtration technique based on size exclusion of particulate particles. The presence of such organic compounds can adversely affect the oxidation stability of the lipid phases in which they are located. Therefore, their removal from a lipid phase is desirable, as this leads to a significantly improved refining product.The refining steps following the aqueous refining of triglyceride mixtures according to the state of the art, such as treatment with bleaching earths and/or steam distillation (deodorization), are capable of significantly reducing the water-binding capacity of the aqueous pre-refined lipid phase. However, a disadvantage is that the subsequent process steps after the aqueous refining steps lead to a significant increase in production costs. Furthermore, treatment with bleaching earths also results in a relevant loss of triglycerides, which are removed along with these substances. A new aqueous refining process has now been established, which allows for a much more efficient separation of amphiphilic impurities from a lipid phase. In this process, both amphiphilic compounds, such as...B. The saccharides, such as glycolipids removed from lipid phases, as well as also fatty acids. Furthermore, a significant separation of colorants occurs, so that, for example, a quality of such refined oil is achieved that no further treatment with bleaching earth or deodorization is required. This makes an efficient and cost-effective aqueous refining of biogenic lipid phases possible, thus allowing process costs to be saved. However, it has been shown that especially when glycolipids, free fatty acids, phosphorus-containing compounds and alkaline earth metal ions are completely removed, the refined lipid phases obtained after centrifugal separation of these compounds together with the aqueous phases, ...Still show a distinct cloudiness. At that time, residual water contents of more than 1.5 weight percent were present, so that the oils did not meet the required product specifications, although the phosphorus content was reduced to values below 2 ppm, and the contents of calcium, magnesium, and iron to values below 0.05 ppm, as well as the free fatty acid content to below 0.15 weight percent. If such a refined cloudy oil phase was subjected to drying, for example by vacuum drying, the residual moisture content could be reduced to less than 0.1 weight percent. The dried oils were transparent. By mixing with water, significant amounts of water could be introduced into such oils, causing them to become cloudy again and making it impossible to clarify them by centrifugal processing techniques.A reduction of the residual moisture in a refined lipid phase is desired to obtain the clearest possible oil, but also the residual moisture is a crucial factor for improving the quality of the oil. Another aspect of residual moisture in a lipid phase concerns storage stability, which is adversely affected by a higher content of water molecules remaining in the lipid phase. This can also occur when compounds are present in the lipid phase that can bind water molecules, for example from the air. 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 particularly in oils and fats of plant or animal origin, chemical reactions occur to varying degrees, depending on storage conditions (exposure to air/light, temperature, container surfaces) as well as the presence of compounds that can cause oxidation of carbon double bonds (see detailed description of the p-anisidine value determination), and the presence of compounds that can enable radical binding or reduction, such as tocopherols, polyphenols or squalene. Through oxidative processes, aldehydes, ketones and free fatty acids can be formed, which further accelerate oxidative processes and are largely responsible for off-odors in vegetable oils. During a classical refining process, usually a reduction of these compounds occurs through de-gumming procedures,These oxidative processes are involved. When oils are treated with bleaching clays, acid-catalyzed oxidations may occur. Furthermore, compounds with antioxidant properties are partially depleted to varying degrees, so that the oxidation stability of an oil can significantly deteriorate through this process step. Basically, the same applies to the deodorization process, especially when higher steam temperatures (>220°C) and longer residence times (>15 minutes) of the oil are required. Therefore, the storage stability is influenced to varying extents by the conventional methods. Compared to cold-pressed oils, therefore, such refined oils often do not show any advantage regarding storage stability, since the antioxidants present in the native oils remain and no additional compounds have been introduced.They promote auto-oxidation. Substances that promote auto-oxidation usually have radical or radical-forming groups, or exhibit an ability to bind water molecules. A targeted depletion of these compounds is not possible according to the current state of the art.

It has been shown that water extraction methods, such as vacuum drying, lead to the desired removal of residual moisture. However, the application of these techniques makes the aqueous refining process uneconomical. Furthermore, it is still possible for water to re-enter a lipid phase that has already been aqueously refined and subsequently treated by vacuum drying. This significantly impairs the properties of the lipid phases. Since in these lipid phases, the content of associated substances has already been reduced to a level where further refining steps, such as bleaching or deodorization, are no longer required, it is necessary to economically and gently remove the remaining turbidity from the lipid phases. This serves two purposes: on one hand, reducing the residual moisture content to the required level, and on the other hand, minimizing the possibility of water re-entry.It was necessary to develop a new process. Surprisingly, a very simple and effective method has now been found, which allows the removal of residual water content from a lipid phase obtained after aqueous refining, even when the lipid phase is well-prepared but cloudy. At the same time, this method also removes the turbidity-causing substances. Furthermore, since the process can be carried out at ambient temperatures and without significant equipment requirements, using relatively inexpensive compounds, and with only minimal or completely negligible loss of neutral lipids, this process represents a considerable improvement over the previously described methods in the prior art and meets the desired conditions.It is therefore the object of the present invention to provide methods for drying lipid phases while simultaneously removing water-binding organic suspended solids.

Task of the invention

The object of the present invention is to provide a method for separating suspended solids from a lipid phase.

This task is solved by the technical teaching of the independent claims. Further advantageous embodiments of the invention emerge from the dependent claims, the description, the figures and the examples.

Detailed Description of the Invention

Lipid phases obtained under anhydrous conditions usually appear clear, provided that suspended particles, which are often misleadingly referred to as turbidity agents in the literature, have been filtered out. Often, it is difficult to introduce water into these lipid phases because the compounds capable of binding water molecules are complexed within the lipid phase in such a way that they are shielded by the surrounding neutral lipid phase. This complex association, which is particularly facilitated by non-hydratable phospholipids, as well as by alkaline earth metal ions and metal ions, must first be broken down in order for these compounds to interact with water molecules and thus be transferred into a water phase, which can then be removed together with the water phase.As a result, this leads to the breakdown of bound, more complex organic compounds, which can also bind water molecules, for example via OH groups. However, due to their strong lipophilicity, they cannot be transferred into the aqueous phase. This theory is supported by observations made during the refining of triglyceride mixtures. It was found that oils with a very high content of impurities showed an increase in turbidity of the triglyceride mixture after each aqueous refining step, following the centrifugal separation of the aqueous phase, despite a significant reduction in impurities. This is particularly true when glycolipids and glycoglycerolipids are present in the lipid phase.Provided that, in addition to an optional conventional aqueous degumming, which can be carried out with pure water and/or an acid (e.g., phosphoric acid), a subsequent treatment with at least two stages using slightly to strongly basic compounds is performed, an optimal reduction of impurities becomes possible. It has been shown that when at least one of the basic aqueous refining steps is carried out with a dissolved guanidine group- or amide group-carrying compound, lipid phases can be obtained which achieve a highly efficient depletion of impurities, with a phosphorus content of less than 5 ppm (or less than 5 mg/kg), a content of neutralizable acids of less than 0.15 weight-%, and practically complete extraction of alkaline earth metals and metal ions to values below 0.0.5 ppm (or <0.05 mg/kg) simultaneously with a significant reduction of plant pigments (such as chlorophylls) in the obtained lipid phases. On the other hand, the water content and cloudiness increased in the refined oil when particularly good refining results were achieved. This was especially evident when an intensive mixer addition was used, involving an aqueous solution containing guanidine or amide-containing compounds. The resulting emulsions were significantly cloudier than those obtained with a simple 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 using a DLS measurement. Furthermore, the tendency towards coalescence of the formed droplets was considerably lower after an intensive addition of the water phase.as a stirring entry. Moreover, the long-term stability of such emulsions was significantly higher. Nevertheless, phase separation could be achieved even with these very stable emulsions by centrifugation, although the obtained oils were cloudier than those after a stirring entry of the aqueous refining solution. A water removal could not be achieved in these cloudy oil phases either by varying the refining process, for example by different amounts of aqueous solutions introduced into the lipid phase using an intensive mixer, or by changing the conditions during the centrifugal phase separation (changing the centrifugation time or centrifugal acceleration). Thus, it could be shown that by introducing a water phase containing guanidino or amide-containing compounds more intensely, a more complete depletion of oil impurities can be achieved,Just as with a stirring entry, the turbidity of the obtained oil phase is stronger than that of an refining process using a stirring entry of the aqueous phase. The turbidity of the lipid phases, which were produced by hydrating water-binding organic impurities due to aqueous refining with at least one guanidine group or amide group containing compound, remained completely unchanged for months, and no spontaneous phase separation occurred.

Surprisingly, it was found that this hydration of water-binding lipophilic organic compounds can be used to adhere or complex these compounds, thereby allowing their extraction from their organic matrix and subsequent separation by physical methods. This is also surprising because, despite the reduction of known water-binding compounds from a lipid phase that can be removed during an aqueous refining process, especially with practically complete removal of alkaline earth metal ions and metal ions, water-binding organic compounds still remained in such biogenic lipid phases, which cannot be transferred into the aqueous phase. Therefore, these compounds exhibit a very high lipophilicity, with a low number or absence of ionizable groups. Indeed, such compounds are present in variable amounts in biogenic lipid phases, such as sterols, squalenes, phenols, waxes, wax acids, vitamins, glycolipids, or pigments.

Surprisingly, it has now been found that cellulose compounds allow a complete clarification of the hydrated cloudy oils, which resulted from an aqueous refining process as described herein, and which subsequently had oil quality values, such as those required for edible oils, e.g., a residual phosphorus content of less than 5 ppm (or less than 5 mg/kg) and a free fatty acid content of less than 0.15 weight-%. This is all the more surprising since the cellulose products according to the invention can only be dispersed in an oil phase and have only a limited ability to bind water. These results are also astonishing because the same cellulose compounds had no effect on the extractability of the water-binding organic impurities.If they were added either before the aqueous refining stages to a mixture of triglycerides, or after such an aqueous refining process, to a triglyceride mixture which had undergone vacuum drying and only contained a small residual water content. In both cases, following the separation of the cellulose preparations, there was again a possibility of water entering the lipid phase, whereas this was no longer the case after an aqueous extraction of the water-binding organic impurities according to the invention. Thus, a particularly advantageous effect of the inventive method is to refine an aqueously refined lipid phase, in which the water-binding organic impurities are present in a hydrated form, by achieving an interaction of the impurities with other compounds.so that the suspended solids can be extracted from their organic matrix. Thus, for the interaction of water-binding organic suspended solids, which allows the inventive separation of the suspended solids, their removal (extraction) from a mixture with other fat co-components is particularly possible when an aqueous refining has been carried out at least with a solution containing guanidino groups or amide group-bearing compounds, and through an optimal depletion of other water-soluble compounds and through the (simultaneous) presence of water, these suspended solids become hydratable. Hydratable means here the attachment of water molecules. The presence of water molecules on the suspended solids to be separated then represents the important determinant for the inventive interaction in the form of adsorption and/or complexation, leading to the extractability of the water-binding organic suspended solids.

A preferred embodiment is therefore the provision of a lipid phase in process step a), where organic particulates are present in a hydrated form.

The invention solves the problem by a method for adsorption and extraction or complexation and extraction of water-binding organic lipophilic impurities from aqueous refined lipid phases, characterized by: a) providing a lipid phase containing water-binding organic lipophilic impurities, wherein the lipid phase has been subjected to at least one aqueous refining with a neutral or basic solution, b) adding an adsorbent and/or a complexing agent to the lipid phase from step a), c) separating the adsorbed or complexed water-binding organic lipophilic impurities from step b) by phase separation, wherein the adsorbent is cellulose, a cellulose derivative, or a layered silicate, and wherein the complexing agent consists of aluminum ions or iron ions present in an aqueous solution.

Another inventive embodiment is a method for separating water-binding organic lipophilic impurities from an aqueous refined lipid phase, characterized by the steps of: a) providing a lipid phase containing water-binding organic lipophilic impurities, wherein the lipid phase has been subjected to at least one aqueous refining with a neutral or basic solution, b) adding an adsorbent and/or a complexing agent to the lipid phase obtained in step a), c) phase separation and removal of the adsorbed or complexed water-binding organic lipophilic impurities, wherein the adsorbent is cellulose, a cellulose derivative, or a layered silicate, and wherein the complexing agent consists of aluminum ions or iron ions present in an aqueous solution.

The supplied turbid lipid phase must undergo at least one aqueous refining process using a neutral or basic solution in order to ensure a sufficient reduction of impurities in the pretreated lipid phase. A neutral solution refers to water. A basic solution is defined as an aqueous solution with a pH value greater than 7.

For the production of an aqueous solution with a pH value greater than 7, salts are suitable which form carbonate (CO3²⁻), bicarbonate (HCO3⁻), metasilicate (SiO3²⁻), orthosilicate (SiO4⁴⁻), disilicate (Si2O5²⁻), trisilicate (Si3O7²⁻) or borate (BO3³⁻) upon dissociation in water. Furthermore, hydroxide compounds are preferred, especially those with monovalent cations of alkaline earth metals, such as sodium hydroxide, potassium hydroxide, but also other hydroxide compounds, such as ammonium hydroxide. In principle, any basic compound that dissociates in water and is known to experts can be used.

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

It is further preferred to provide a lipid phase in which, after an aqueous refining step with a compound carrying a guanidine or amide group, a largely complete reduction of phosphorus-containing compounds, alkaline earth metal and metal ions, and free acid groups has been achieved.

The water-binding organic impurities present in the pre-treated lipid phase are then brought into contact with an adsorbent and/or complexing agent in step b). In this process, the water-binding organic lipophilic impurities are adsorbed onto suitable adsorbents or can form complexes with certain ions, which are largely insoluble in water but can be separated into an aqueous phase due to their complexity. Thus, the process is completed in step c) by separating the adsorbed or complexed impurities from step b) through a phase separation, allowing the adhered or complexed water-binding organic impurities together with the extraction solvent to be separated, while maintaining an impurity-free and largely water-free lipid phase.

In one embodiment of the invention, in step a) of one of the methods described herein, at least one aqueous refining is carried out with an aqueous solution comprising at least one guanidino group- or amide group-containing compound having a log P value of less than 6.3.

The term KOW refers to the partition coefficient between n-octanol and water.

Technical teaching and examples show various embodiments of aqueous refining methods, which are understood as the invention's lipid phase in the sense of step a) of the method described herein.

Another essential procedural characteristic is the provision of adhesion and complexing agents.

The use of cellulose products is a preferred embodiment for the adsorption of hydrated water-binding organic suspended solids according to the invention. Preferably, cellulose and hemicellulose are used. These can be in their natural chemical structure or chemically modified by carrying substituents. As possible examples, only some are named here, such as carboxymethylcellulose, hydroxyethylcellulose, methylhydroxyethylcellulose, methylhydroxypropylcellulose, ethylhydroxyethylcellulose, hydroxypropylcellulose, and methylcellulose. Cellulose ester compounds are preferred. Further preferred compounds are cellulose ethers. These may be in a fibrous, crystalline, or amorphous form. The molecular weight is generally freely selectable, but it is preferably 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 also freely selectable, but preferred particle sizes are between 5 and 10,000 µm, more preferably between 20 and 5,000 µm, and most preferably between 50 and 500 µm.

Basically, other sugar-containing compounds can also be suitable as adsorbent materials according to the invention. These include, for example, β-1,4-glycosidically bound hexoses or pentoses, such as chitin, callose, or α-1,4-glycosidically bound hexoses or pentoses, such as starch, including amylose.

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

These biopolymers are also advantageous because they can be effectively removed from lipid phases using various methods known in the art, such as sedimentation, centrifugation, or filtration. Furthermore, it is advantageous that after separation from the lipid phase, only minimal amounts of triglycerides are separated. On the other hand, practically no cellulose remains in the lipid phase. Another advantage of this adsorptive separation of hydrated water-binding turbidity substances is that they can be extracted and separated under mild process conditions, thus remaining essentially in a chemically and structurally unchanged form and becoming available for further utilization.

Furthermore, very good refining results could be achieved using polyaluminum hydroxychloride sulfate. Thus, the present invention also relates to processes in which polyaluminum hydroxychloride salts are used.

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

In a preferred embodiment, the provision of lipid phases containing hydrated water-binding organic impurities occurs 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 occurs at a temperature below 40 °C. The amount of extractable hydratable organic impurities may vary depending on the application, as well as the adsorption capacity of the adsorbent used. Therefore, both the amount of adsorbent (cellulose, cellulose derivatives, and other saccharide-containing compounds as disclosed herein) required for refining a refined lipid phase, as well as the necessary duration for retaining the adsorbent in the pretreated lipid phase, must be determined for each application.Preferably, the dosage of the cellulose compounds to the lipid phase is less than 5 wt%, more preferably less than 3 wt%, and most preferably less than 1 wt%. Furthermore, a preferred adsorption time is from 1 minute to 12 hours, more preferably from 5 minutes to 8 hours, and most preferably from 10 minutes to 3 hours. The addition of the cellulose compounds is preferably carried out by stirring with a propeller mixer under mild agitation of the lipid phase until a completely homogeneous distribution in the lipid phase is achieved. Since the duration required for this naturally varies, the necessary duration must be determined. The duration of the stirring process is included in the adsorption time and should account for less than 20% of it.Cellulose compounds are preferably separated immediately after the required adsorption time. This can be done by sedimentation, centrifugal separation, or filtration. Filtration is preferred; the necessary equipment and filters are known to those skilled in the art. In a further embodiment, in order to achieve optimal hydration of the water-binding organic suspended solids, that is, the binding of water molecules to the organic suspended solids or the formation of a water shell, following one or more aqueous refining steps, an aqueous refining step is carried out using an aqueous solution containing a dissolved guanidinium group- or amide group-containing compound.

In a preferred embodiment, the hydration of water-binding organic colloidal substances is carried out by an aqueous refining step with a solution containing compounds having guanidine groups or amide groups. Preferably, the ratio of the lipid phase to the aqueous phase, which contains dissolved compounds having guanidine or amide groups, is 10:1, more preferably 10:0.5, and most preferably 10:0.1. An intensive mixing entry using a rotor-stator mixing system is preferred. The terms "homogenize," "disperse," "intensive addition," "intensively introduce," "intensive mixing," and "intensive mixing introduction" are used here essentially synonymously and denote the homogenization of oil with an aqueous solution. By the method of homogenizing lipid phases, which besides carboxylic acids also contain other organic compounds that do not correspond to a neutral fat or a non-polar solvent,Does it come to a very advantageous and effective co-emulsification of these compounds into the aqueous phase, when carbonic acids are present as a nanoemulsion? From the prior art, intensive mixing systems and methods are known, such as rotor-stator systems, colloid mills, high-pressure homogenizers or ultrasonic homogenizers. This preferred intensive mixing entry 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. A subsequent centrifugal phase separation is preferred,It occurs preferentially in less than 10 minutes, more preferentially in less than 7 minutes, and most preferentially in less than 5 minutes.

The inventive extraction of hydrated water-binding organic suspended solids from aqueous refined lipid phases can, depending on the application, be carried out using a powdered formulation of the adsorbent, preferably cellulose compounds or kaolin. In this case, the adsorbent can be added to the pre-treated lipid phase, or the lipid phase can be added to the adsorbent.

In one embodiment, also a solid and non-ionically soluble inorganic compound can be used as an adsorbent. For the adsorption of hydrated water-binding organic turbidity-causing substances according to the invention, layered silicates are used. In particular, clay minerals such as, for example, montmorillonite, chlorite, kaolin, and serpentine are preferred. Particularly preferred are aluminum-containing silicate compounds. They are especially advantageous because they are available on a large scale and, due to their physical structure, do not have toxic effects. In one embodiment, the use of layered silicates having an aluminum content of more than 25 wt.%, more preferably more than 30 wt.%, and most preferably more than 40 wt.% is favored. The preferred form of application is a microcrystalline powder.Kaolin is particularly preferred. More preferred is a microcrystalline powder form of kaolin. The amount of the inorganic compound powder depends on the specific adsorption capacity. A preferred weight ratio (g/g) of the powdered absorbent to the pre-treated lipid phase is less than 0.03:1, more preferably less than 0.01:1, and most preferably less than 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. It is preferred to carry out an immediate centrifugal phase separation, which preferably takes less than 10 minutes, more preferably less than 7 minutes, and most preferably less than 5 minutes.Furthermore, a separation by filtration is preferred.

In a preferred embodiment of the process step b), layer silicates containing more than 25 wt% aluminum are used for the adsorption of hydrated organic impurities. Preferably, the dosage of the silicates according to the invention is less than 5 wt%, more preferably less than 3 wt%, and most preferably less than 1 wt%. Furthermore, a preferred adsorption time is between 1 minute and 12 hours, more preferably between 5 minutes and 8 hours, and most preferably between 30 minutes and 3 hours. The addition of the silicate compounds is preferably carried out by stirring with a propeller mixer under mild agitation of the lipid phase until a completely homogeneous distribution is achieved. Since the duration required for this may naturally vary, the necessary duration must be determined. The duration of the stirring process is included in the adsorption time and should account for less than 20% of it. The silicate compounds are preferably separated immediately after the required adsorption time. This can be done by sedimentation, centrifugal separation, or filtration. Filtration is preferred, and the necessary equipment and filters are known to those skilled in the art.

In a further embodiment of the inventive method, the extraction of hydrated water-binding organic colloidal substances from the organic matrix is carried out by complexation thereof.

This task is accomplished by providing and entering ionically present compounds from the group of cations belonging to transition metals, metalloids, and metals.

In a preferred embodiment, the extraction of hydrated organic suspended solids is carried out by complexing with cations from the group of transition metals, metalloids, and metals.

In complexation, the formation of a complex or several complexes or coordination compounds is meant. Therefore, the complexation of a hydrated, water-binding organic turbidity substance refers to the binding of the said turbidity substance to a metal or transition metal, as disclosed herein, in the form of a coordination compound or complex. The intermolecular interactions leading to complexation may be caused by physicochemical bonding energy forms, such as hydrogen bonds and van der Waals interactions, or by a chemical interaction resulting in a covalent bond. The resulting complex can then be separated from the organic phase either as such or by aggregation with other complexes, using a physical separation method such as centrifugal or filtration separation.

In a particularly suitable manner, an aqueous solution containing aluminum chloride is appropriate here. This solution is introduced into the aqueous refined lipid phase containing hydrated water-binding colloidal substances through a mixing process, resulting in complexation or aggregation, which enables their separation easily by means of spontaneous phase separation, sedimentation, centrifugation, or filtration. 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 generally freely selectable; however, salts with sulfate, sulfide, nitrate, phosphate, hydroxide, fluoride, selenide, telluride, arsenide, bromide, borate, and so on are preferably used.Oxalate, citrate, ascorbate. Salts with chloride and sulfate are particularly preferred. However, the anions should be strongly hydrophilic in order to remain in the aqueous phase. The solutions should consist of otherwise ion-poor or ion-free water containing the preferably used cations at a molar concentration between 0.001 and 3, more preferably between 0.1 and 2, and most preferably between 0.5 and 1 molar. The volume of the aqueous solution used is in relation to the pre-prepared lipid phase less than 10 vol-%, more preferably less than 5 vol-%, and most preferably less than 1.5 vol-%. The addition is preferably carried out by rapid pouring.The mixing with the lipid phase is preferably carried out using a rapidly rotating propeller or foam mixer with a turbulent mixing entry. However, intensive mixing methods as described herein can also be applied. Since the required duration for this may naturally vary, the required duration must be determined. A mixing time of 1 to 60 minutes is preferred, more preferably between 5 and 45 minutes, and most preferably between 10 and 20 minutes. Furthermore, a complexing time of 1 minute to 5 hours is preferred, 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 preferred is an adjustment between 15 and 50 °C, and most preferred between 20 and 40 °C. It is preferred to perform a subsequent centrifugal phase separation, which preferably lasts less than 10 minutes, more preferably less than 7 minutes, and most preferably less than 5 minutes. However, phase separation can also be achieved by sedimentation or filtration. Furthermore, it is preferred to separate the phases using a separator.

Thus, the invention relates to a method in which in step c), a sedimentation, centrifugal, filtration or adsorption separation technique is carried out.

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

The complexed and separated suspended solids can be easily separated and quantified from the otherwise unchanged aqueous solutions containing alkaline earth metal ions or metal ions by means of a filter. In this embodiment, the extraction and separation of water-binding organic suspended substances is practically possible without any loss of triglycerides.

In a preferred embodiment, the extraction and separation of hydrated organic suspended solids is carried out without any loss of a triglyceride mixture.

Another aspect of the invention is that organic suspended solids, along with the water molecules bound to them, can be separated from the lipid phase through adsorption and complexation. This offers the enormous advantage that hydrated water-binding suspended solids and the bound water can be removed from a lipid phase in a single process step.

In a particular embodiment, the drying of a lipid phase containing hydrosoluble turbidity-causing substances is carried out by adsorption and separation and/or complexation and separation of the hydrosoluble turbidity-causing substances along with the bound water phase. It has been shown that lipid phases which had been treated according to a refining process described herein and subsequently exhibited turbidity and a water content of more than 1.0 wt% had a clear to brilliant appearance after the inventive processes of adsorption and separation or complexation and separation. This is due to a reduction of the residual moisture content contained in such refined lipid phases, which is reduced by at least > 75 wt%, more preferably by at least > 85 wt%, and most preferably by at least > 95 wt%.Compared to the initial value before the introduction of adsorption or complexing agents. Furthermore, the residual moisture is preferably reduced to less than 0.5 weight %, more preferably to less than 0.01 weight %, and most preferably to less than 0.008 weight %. This can be easily examined using methods known from the prior art, such as the Karl Fischer method. Since, in lipid phases treated with a one- or multi-stage aqueous refining process, in which compounds carrying guanidine groups or amide groups have been used in at least one of the process steps, an adequately sufficient depletion of fat-associated substances can already be achieved, the direct use of the lipid phases after removal of the water-binding impurities and the resulting drying is possible.B. as a cooking oil, as a cosmetic oil, as a lubricating or hydraulic oil, or as a fuel.

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

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

However, the removal of water-binding impurities provides additional advantages. It has been documented that the water-binding capacity of a lipid phase, which has been subjected to an aqueous refining process described herein, where in at least one of the process steps a refining with a solution containing compounds having guanidine groups or amide groups was carried out, is significantly reduced compared to other methods used for drying the lipid phases after such refining, by removing water-binding organic impurities using one of the methods disclosed herein.

The ability to reabsorb water, also referred to here as "water reabsorption capacity" or "water binding capacity." The term "water reabsorption capacity" refers to the ability to bind water into a lipid phase, which can be achieved by an emulsification process and leads to the retention of water in the lipid phase. The water reabsorption capacity can be determined by a water addition method. In these methods, deionized water at a temperature of 25 °C is mixed into the lipid phase to be examined. A water volume fraction of 5 vol.% relative to the refined lipid phase is provided and stirred with a stirrer at 500 rpm for 10 minutes. Subsequently, a centrifugal phase separation is carried out at 6000 rpm for 10 minutes, and the phases are separated from each other. The value of the water reabsorption capacity is the difference between the water content of the lipid phase after water addition and the water content of the lipid phase before water addition. According to the invention, a water reabsorption capacity of less than 40 wt.% is preferred, more preferably less than 15 wt.%, and most preferably less than 5 wt.%.

Furthermore, for the assessment of the inventive method for refining lipid phases, the water reabsorption capacity of the unrefined lipid phase was compared with that of the refined lipid phase. A difference between the two lipid phases of > 75% is preferred, more preferably > 85%, and most preferably > 90%.

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

Furthermore, the invention relates to the use of the methods described herein for reducing the water reabsorption capacity 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 water content and the re-addability of water, the transparency of the lipid phases is also improved in a particularly advantageous manner by the inventive adsorption and complexing process. Thus, refined lipid phases are obtained, containing hydratable organic compounds, whose hydrodynamic diameter is smaller than 100 nm in more than 90% and larger than 200 nm in less than 5%, determinable by analyzing light scattering at a phase boundary, such as the DLS method. Such lipid phases are optically brilliant.

Thus, the methods of adsorption and separation, as well as complexation and separation of water-binding organic suspended solids, also enable the preservation of an optically brilliant oil phase.

The removal of water-binding impurities, resulting in a reduced water-binding capacity of the obtained lipid phase, causes further highly advantageous effects. In one aspect of the invention, this relates to effects that can occur during storage of the obtained lipid phases. During such storage, lipid phases may come into contact with water molecules. For this purpose, merely contacting with air containing a certain amount of water is sufficient to allow the entry of water molecules through organic molecules having good water-binding properties. In addition to possible clouding of the lipid phase, other effects significant for storage stability may occur. Among these, the unfavorable effects on the oxidative stability of a lipid phase are primarily to be mentioned.In lipid phases, and particularly in oils of plant and animal origin, there are variable amounts of unsaturated organic compounds, the major part of which are unsaturated fatty acids. Exposure of these compounds to atmospheric oxygen, heating, energetic radiation (e.g., UV light), or contact with catalysts such as iron, nickel, free radicals, enzymes such as lipoxygenases, or a basic environment can cause oxidation at a double bond of an organic compound. In this process, oxygen radicals are also catalyzed by organic compounds present in a lipid phase, such as chlorophylls, riboflavin, or metal and heavy metal ions. As a result, hydroperoxides of the organic compounds are formed. These are chemically unstable and degrade into secondary oxidation products.Free alkoxy radicals are formed during decomposition. Since, as listed above, the primary oxidation products are usually not stable and are further degraded into secondary oxidation compounds, it is meaningful to determine these reaction products in order to assess the long-term stability of a lipid phase. A reaction with para-anisidine is suitable for this purpose, as para-anisidine reacts with secondary oxidation products such as aldehydes and ketones present in a lipid phase. The reaction product can be detected and quantified spectrometrically (absorbance at 350 nm). In particular, unsaturated aldehydes, which are often responsible for off-odors in oils, are detected by the para-anisidine reaction. The para-anisidine value is closely correlated with the peroxide value measured in a lipid phase, so the presence of peroxides can be estimated using the para-anisidine test method.The peroxide value indicates the number of primary oxidation products in a lipid phase and expresses the amount of milliequivalents of oxygen per kilogram of oil. Since secondary oxidation products increase more strongly over time, the determination of the p-anisidine value is more suitable for assessing storage stability.

Therefore, oils refined by the inventive method were tested for their storage stability under various conditions, with the anisidine value being determined sequentially to estimate oxidative stability. Surprisingly, lipid phases refined by the inventive methods showed a reduction in oxidation products compared to lipid phases that had been aqueous refined and subsequently either vacuum-dried or dried with other compounds. This suggests that oxidation products were extracted and separated by the inventive method. This becomes even more likely as, over the long term, the lipid phases refined according to the invention showed a significantly lower content of oxidation products.as with oils that had been treated with other substances or by vacuum drying. This assumption can also be made because during a refining process where the non-optimal removal of turbidity-causing substances occurred due to the compounds according to the invention, the storage stability was generally worse than in a refining process where optimal separation of turbidity-causing substances was achieved. In scientific literature it has been shown that there is a close relationship between the development of secondary oxidation products and the formation of off-odors and off-colors in a lipid phase. Consistent with these theoretical aspects resulting from the removal of water-binding organic turbidity-causing substances, it was found that the effects observed in the refining process also influence the storage stability in terms of reduced development of off-odors and off-colors.During storage of lipid phases, significantly fewer off-flavors were formed in refined lipid phases compared to lipid phases that otherwise underwent the same pretreatment and subsequently had their lipid phases dried by other methods, as determined in sensory tests on both unrefined and refined lipid phases that had been stored for at least 120 days. The formation of off-flavors correlated with the formation of secondary oxidation products, which were formed to a much lesser extent in lipid phases that had been refined, as shown in long-term studies. Therefore, the method for adsorption and separation or complexation and separation of water-binding organic turbidity substances is particularly suitable for improving the sensory storage stability of lipid phases.Therefore, the process is also aimed at maintaining sensorially stabilized lipid phases.

However, the oxidation of compounds located in the lipid phase can also promote corrosive processes in materials that come into contact with such a lipid phase (e.g., tank systems). Therefore, it is advisable to store the material under cooled conditions, excluding light exposure, and under an air-tight seal.

This makes the process preferable for obtaining a low-turbidity lipid phase, thereby reducing oxidation damage to tank systems and technical equipment.

Another aspect of the reduction of water retention capacity due to the removal of water-binding suspended solids concerns radical/oxidative changes that can lead to discoloration. In lipid phases that can be freed from water-binding suspended solids by the inventive method, these are lipid phases of biological origin that contain a variable amount of colorants. These are almost exclusively organic compounds that are completely nonpolar (e.g., carotenoids) or contain only a few polar groups, e.g., chlorophylls. Therefore, they pass very easily into the obtained lipid phase, or are extracted from their structures by it. The colorant classes differ significantly in their chemical properties. However, many of these compounds exhibit a distinct chemical reactivity or catalyze reactions.In particular, in the presence of a water fraction in the lipid phase or upon exposure to ionizing radiation (e.g., UV light). In particular, compounds can form through oxidative processes via the Maillard reaction, which can lead to off-colors and off-odors. This includes, for example, the formation of melanoidins, which are nitrogen-containing polymers from amino acids and carboxylic acids, and which cause a brown discoloration of the oil. Another example are tocopherols, which can be oxidized, for instance, during a bleaching process (especially in the presence of acid) and represent precursor stages for color pigments formed later. The discoloration of a refined oil is called "color reversal," which particularly occurs in corn oil. These colorants mainly include chlorophylls and their derivatives and degradation products such as:B. Pheophytin, but also flavonoids, curcumin, anthocyanins, indigo, kaempferol and xanthophylls, lignins, melanoidins. In accordance with the achieved improvement of storage stability regarding the development of off-odors, an improved color stability of the oils was also observed, where removal of water-binding turbidity substances had been performed. In this case, no or only minimal development of an off-color (color reversal) occurred during at least 120 days.

Therefore, the process is also directed toward improved color stability during storage of aqueous refined lipid phases in which removal of water-binding turbidity-causing substances has been carried out by adsorption and separation or complexation and separation. The invention is directed toward the obtaining of a lipid phase with high color stability during storage.

The present invention is therefore also directed to a largely complete removal of water-binding organic impurities from a lipid phase after an aqueous refining process. As the technical teaching and examples show, the ability of a lipid phase to reabsorb water after an inventive refining and purification of the lipid phase is so low that this also improves the storage stability.

In a particularly preferred embodiment, the addition of the adsorbents described herein or the contact of one or more adsorbents with the lipid phase is carried out by using the adsorbent(s) in a bound or complexed form, i.e., not as powder or microcrystalline. In step b), an adsorbent is used which is immobilized or bound to a fabric or texture or can form such a fabric or texture. The term "immobilized" refers to applying the adsorbent to the surface. A "fabric" refers to a one- or multi-dimensional arrangement of thread and/or strip material that is interconnected or connected together, thereby forming a planar or spatial structural composite (texture). Through a texture formed by the aforementioned materials, interstitial spaces are created which may be permeable to liquids and/or particulate substances. The texture-forming materials may be of natural origin (e.g., plant or animal origin, such as cotton or wool fibers) or synthetic origin (e.g., PP, PET, PU, etc.). The surfaces of the texture materials may need to be chemically modified in order to immobilize the adsorbents according to the invention on them. The immobilization can be physical, physicochemical, or chemical. Methods for this are known to those skilled in the art.

Another preferred embodiment involves providing bound or immobilized cellulose compounds. This can be, for example, in the form of a complex textured material, a plate or layered structure, such as a felt or filter plate or filter cartridge. In principle, an adsorptive separation using immobile silicates, as described herein, is also possible. In a preferred embodiment, the lipid phase is guided past or passed through the adsorption compounds together with the hydrated water-binding organic suspended solids. This can be achieved by introducing the texture/fabric into the lipid phase and bringing the lipid phase into contact with the texture/fabric or the fabric through agitation of the texture/fabric or the lipid phase, thereby allowing the suspended solids to be adsorbed. The adsorbed suspended solids can then be...By separating the lipid phase from the texture/tissue. In another embodiment, the lipid phase is guided through the texture/tissue, which is permeable to the lipid phase, and is passed through it. If the lipid phase, after passing through the texture/tissue, is obtained as a refined product, then the adsorption and separation of the suspended matter occur in one step. To increase the efficiency of such an application form, it may be expedient to guide the lipid phase sequentially through several layers of the texture/tissue. In another preferred embodiment, the texture consists of a packing of adsorbent materials through which the turbid lipid phase is passed. This is a preferred embodiment when using cellulose compounds.since they also allow the flow through a lipid phase, depending on the polymer size and geometry, even with a dense packing of the particles.

In a further preferred embodiment, complexing agents used in step b) are immobilized or bound to a fabric or texture. Here, "immobilized" means applying the complexing agent onto the surface. The materials used, as well as their texture and structural composition, can be identical to those described earlier for materials and fabrics used with adsorbents. This also applies to the application of these materials with immobilized complexing agents. Preferably, micro- or nanoparticles with a large internal surface area, such as zeolites or silica gels, which are loaded with complexing agents and provided in the form of a particle packing, are used. By passing the refined lipid phase containing hydrated particulate matter through these particles, the particulate matter is complexed with the immobilized complexing agents, thereby separating it from the lipid phase.

The invention relates to a method in which the adsorbent and/or the complexing agent of step b) is immobilized or bound in a fabric or a texture, wherein the fabric or texture is suitable for complexation and/or adsorption and/or filtration of the turbid lipid phase.

In a further preferred embodiment, the solutions already used for the inventive application, containing complexing agents, as well as the adsorbents used for the inventive application, can be reused. In practical application, it has been shown that in the aqueous phases containing the dissolved complexing agents, the complexed and separated suspended solids 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 2 µm). Microscopically, crystalline structures were visible. So far, no disintegration of the aggregates has been performed for the purpose of analyzing the compounds contained therein. It has been shown that when reusing the filtratively purified water phase, which still contains complexing agents, a reduction of the hydrated organic suspended solids occurs again upon subsequent application, as was the case during the first application.

Another aspect of the process concerns the minimal or nonexistent product loss of the purified lipid phase. The aqueous phases used according to the invention, containing complexing agents dissolved therein, were only slightly cloudy or brilliant after centrifugal separation from the lipid phase and contained no solids therein, except for the aforementioned aggregates, and in no case was there any emulsion formation. With respect to the oil phase, there was always a sharp phase boundary, so that separators are very suitable and preferred for separating the aqueous phase containing dissolved complexing agents. The separation of the complexed organic impurities could be achieved without any product loss. The adsorbents tested, which were mixed into the lipid phase, could be separated into compact masses by means of centrifuges and decanters after adsorbing the organic impurities. Analysis of triglyceride compounds present therein showed that these were only minimally carried over with the separated adsorbent mass. The product loss amounts to less than 0.2 weight percent based on the mass of the lipid phase.

It is preferred to have adsorption and separation and/or complexation and separation of hydrated organic suspended solids with little or no product loss, as well as a product-loss-minimized or product-loss-free drying of lipid phases.

Another aspect of the process is directed towards the recovery of separated organic suspended solids and the reusability of the adsorption and complexation agents used according to the invention. It has been shown that the organic suspended solids separated with the adsorption agents can be detached again from the adsorption agents. This can be achieved using polar and non-polar solvents known from the prior art. Since the organic suspended solids may consist of different compounds or compound classes, the selection of an appropriate solvent or mixture of solvents should be based on this. It may also be advantageous to perform a sequential elution of the adsorbed organic suspended solids. For example, it has been shown that when first removing neutral fats extracted with a non-polar solvent such as...B. n-Hexane is used in another washing step with a polar solvent, such as menthol, allowing compounds like phospholipids to be separated and fractionated. Other examples include extractions carried out with ethyl acetate, which yielded yellow colorants, or with chloroform, in which chlorophylls were found in the organic phase. Other fractions could be obtained using diethyl ether and alcohols, where organic compounds such as vitamin A, tocopherol, styryl glycosides, squalene, and glyceroglycolipids were identified. However, in some experiments, significant amounts of free fatty acids, waxy acids, and waxes were also extracted. This was particularly the case when the oil phase present after aqueous refining contained hydrated organic particulates.Another relatively high proportion of free fatty acids (> 0.2% by weight) was present. Adsorbents used according to the invention and separated, which are impregnated with at least one non-polar and at least one polar solvent in a solvent amount suitable for complete absorption of removable organic impurities or neutral fats, can subsequently be obtained as fractions using known methods, first by filtration, sedimentation, or a centrifugal separation process, and then again recovered in a powdered form by drying processes. It has been shown that when these, for example, impregnated with hydroxyethylcellulose and kaolin in lipid phases with hydrated organic impurities, are reused, they behave in the same way as during the first use of the adsorbents.The lipid phases from the suspended solids are removed. Thus, processes for separating and fractionating the isolated organic suspended solids and purification methods for the adsorbents used according to the invention are available, which allow for a renewed use of the adsorbents in accordance with the invention. On one hand, the separated organic compounds can be recovered and made available for further use, and on the other hand, the adsorbents can be reused. This makes the process particularly economically attractive and resource-saving.

A particularly preferred embodiment consists in the separation and recovery of adsorption-separated organic suspended solids. It is preferred to provide purified adsorbents and solutions containing complexing agents. Also preferred is the use of separated organic suspended solids.

Furthermore, the recovery of neutral fats that have been extracted using complexing and/or adsorption agents is preferred.

Methods Process for the preparation of an aqueous emulsion according to process step a):

In one embodiment of the present invention, a pre-purification of the lipid phase is carried out before refining the lipid phase with a solution containing guanidine and/or amide group-containing compounds, by mixing water or an aqueous solution having a preferred pH range between 7.0 and 14, more preferably between 9.5 and 13.5, and most preferably between 11.5 and 13.0, and after mixing with the lipid phase, a pre-purified lipid phase is obtained by a preferably centrifugal phase separation. In another embodiment, the aqueous solution used for pre-purification contains a base, which is preferably selected from sodium hydroxide, potassium hydroxide, ammonium hydroxide, sodium carbonate, sodium bicarbonate, sodium sesquicarbonate, potassium carbonate, and potassium bicarbonate, sodium metasilicate, and sodium borate.In a further embodiment, the pre-extraction of the lipid phase is carried out in an analogous manner to the basic pre-extraction, using an acid in concentrated form or by means of an aqueous solution of an acid. The pre-extraction is performed by mixing the undiluted acid or an aqueous solution containing acid with a pH value between 1.0 and 5, more preferably between 1.7 and 4, and most preferably between 3 and 3.5, with the lipid phase. After phase separation, the aqueous (heavy) phase is separated off. For adjusting the pH value, 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 used for pre-extraction with the oil phase are generally freely selectable and can be easily determined by a skilled person.Preferred concentrations of the basic solutions are between 0.1 and 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 aqueous phase and the oil phase should preferably be between 0.3 to 5 vol%, more preferably between 0.3 and 4 vol%, and most preferably between 1.5 and 3 vol%. Acids can be added undiluted or as an aqueous acid solution to the lipid phase. The undiluted acid is preferably added in a volume ratio between 0.1 and 2.0 vol%, more preferably between 0.2 and 1.0 vol%, and most preferably between 0.3 and 1.0 vol%.The aqueous acid solution is preferably added in a volume ratio between 0.5 and 5 vol-%, more preferably between 0.8 and 2.5 vol-%, and most preferably between 1.0 and 2.0 vol-%. The addition of the basic and acidic solutions for pre-cleaning can be carried out continuously or in a batch process, and the mixing of the two phases can be performed using stirring devices from the prior art or with an intensive mixer (e.g., a rotor-stator disperser), provided that this does not result in an emulsion that cannot be separated by physical methods. The objective of the pre-cleaning is to remove easily hydratable mucus substances from the lipid phase. The contact time during applications in a batch process is between 1 and 30 minutes.More preferably between 4 and 25 minutes, and most preferably between 5 and 10 minutes. When applying continuous mixing (so-called in-line process), the residence time in the mixer ranges from 0.5 seconds to 5 minutes, more preferably from 1 second to 1 minute, and most preferably from 1.5 seconds to 20 seconds. The preferred temperatures that the lipid phase as well as the mixed aqueous phase should have for intensive mixing lies between 15°C and 45°C, more preferably between 20°C and 35°C, and most preferably between 25°C and 30°C. The separation of the aqueous phase from the emulsion can preferably be carried out by centrifugal separation methods,Preferably, centrifuges, separators, and decanters are used. The duration of a centrifugal separation depends on product-specific parameters (water content, viscosity, etc.) and the separation method employed, and therefore must be determined individually. Centrifugation is preferably carried out for 2 to 15 minutes, more preferably for 8 to 12 minutes. The residence time in a separator or decanter is preferably between 2 and 60 seconds, more preferably between 10 and 30 seconds. The centrifugal acceleration should preferably be selected between 2,000 and 12,000·g, more preferably between 4,000 and 10,000 g. The temperature during phase separation should preferably be between 15 and 60°C.More preferred between 20 and 45°C, and most preferred between 25 and 35°C.

The effectiveness of pre-treatment can be determined by analyzing the phosphorus content and the amount of slime substances present in the lipid phase to be refined. Suitable lipid phases are those containing less than 100 ppm phosphorus and less than 0.5 wt% of non-saponifiable organic compounds. However, lipid phases exceeding these values can also be refined using solutions containing guanidine- and/or amide-group-containing compounds. If pre-treatment is necessary, the selection of an aqueous de-sliming process, i.e., a treatment with an acid (undiluted or as an aqueous solution) or a base, is generally freely selectable, thus allowing various possibilities for pre-treatment: I. acid treatment alone, II. base treatment alone,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 suitable and most cost-effective method can easily be carried out by a specialist. However, practical experience has shown that when a preliminary cleaning is required, the initial application of an aqueous acid treatment followed, if necessary, by an aqueous base treatment represents the most preferred embodiment. However, the technical teaching here also shows that the inventive separation process of water-binding organic suspended matter from the biogenic lipid phase largely depends on whether, initially, the lipid phase is freed from hydratable organic and inorganic as well as particulate components by means of aqueous extraction steps.thus enabling the hydratability of lipophilic water-binding organic suspended solids. It has been shown that the number and arrangement of refining steps are essentially irrelevant, as long as a neutral to basic compound is used at the final refining stage. In particular, it is advantageous if this basic compound contains one or more guanidine and/or amide groups. Therefore, an aqueous refining process using an aqueous solution containing compounds with a guanidine or amide group represents a significant feature for providing a hydrated form of water-binding suspended solids. In this hydrated form, the water-binding organic lipophilic suspended solids can be adhered to or complexed in an extremely advantageous manner, without causing a significant co-extraction of non-polar lipid components, and in particular without extracting triglycerides.

The lipid phases suitable for use in process stage a) have undergone at least one aqueous refining stage with a basic solution, followed by a final phase separation, which preferably takes place using a centrifugal separation technique. In principle, the time interval between refining and application of the inventive method is not relevant. It is preferred that this occurs immediately after the refining. The residual moisture present in the lipid phase is generally not significant; however, a better hydration of the water-binding organic impurities leads to a better extractability of such substances. Preferred residual water contents are 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 value 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 generally freely selectable; in viscous lipid phases, it may be necessary to heat them in order to make them more flowable and to improve the incorporability of complexing or adsorbing agents.

Procedure for Process Management and Monitoring:

The selection of an adhesion or complexing agent is generally freely selectable. Nevertheless, the most suitable complexing or adsorption agent must be individually determined. In some applications, it may be advantageous to use adsorption agents, as these, for example, may have approval for use as food additives. Moreover, the effectiveness of the adsorption and complexing agents according to the invention can vary depending on different lipid phases. If a gentle removal of hydrated particles is preferred, it may again be advantageous to use adsorption agents that are subsequently further purified. On the other hand, for the extensive exclusion of product loss, solutions with complexing agents are advantageous. The complexing agents are dissolved in a dissociated form in preferably low-ionic or otherwise ion-free water.Chelating agents are preferably used individually in a salt form. However, combinations of the compounds are also possible. The ratios of amounts and concentrations can be freely selected. The application of solutions containing these chelating agents can be continuous or performed as a single addition. Preferably, the application is automated. The process can be carried out as a batch process or as so-called in-line process. In an in-line process, a continuous mixing is preferably carried out, preferably with an intensive mixer. The reaction mixture can then be transported via a piping system or by feeding into a settling tank for the required reaction time. In a batch process, the reaction solution remains in the corresponding reactor vessel. The aforementioned concentrations,Volume ratios and temperatures should preferably be maintained. The mixture should be carried out as described for the batch reactor. The adsorbent is preferably added in a powdered form to the lipid phase. This can be done either as a single addition or as fractionated or continuous additions. Preferably, an automated dosing process is used. The mixing can be performed as described for the complexing agents; however, a stirring entry with a turbulent mixing entry is preferred. Furthermore, batch reaction processes are preferred.

The amount of volume addition at a certain concentration of complexing agents or adsorbents, as well as the minimum duration required to achieve sufficient complexation or adhesion of the hydrated components, can be easily determined by an experiment (e.g., experimental procedure according to Example 6). This can be modeled on a small volume of a refined lipid phase. The determined volume and concentration ratios as well as the measured duration can be easily transferred to large-scale approaches. The required product specification is checked by taking a sample (e.g., 100 ml), where phase separation is achieved using a centrifuge (4000 rpm, 5 minutes). The remaining oil fraction can then be analyzed for its water content.The required reduction of water-binding suspended solids is achieved when the residual moisture content contained in them is reduced by at least > 75 wt%, more preferably by at least > 85 wt%, and most preferably by at least > 95 wt%, compared to the initial value before the introduction of the adsorption or complexing agents. Furthermore, the residual moisture is preferably reduced to less than 0.5 wt%, more preferably to less than 0.01 wt%, and most preferably to less than 0.008 wt%. This can be easily examined using methods known from the state of the art, such as the Karl Fischer method. Another product specification is the water uptake capacity of the obtained oil fraction.This can be examined by incorporating deionized water at a temperature of 25°C. An aqueous volume fraction of 5 vol.% is provided relative to the refined lipid phase and stirred with a magnetic stirrer at a speed of 500 rpm for 10 minutes. Subsequently, a centrifugal separation is performed at 6000 rpm for 10 minutes. The product specification is met when the water reabsorption capacity of the modified lipid phase is reduced by more than 75% compared to the unmodified lipid phase.

Furthermore, a sufficient product specification is present when in the lipid phase only compounds are present whose hydrodynamic diameter is smaller than 100 nm in more than 90% of all particles contained therein and larger than 200 nm in less than 5%, determinable by analysis of light scattering at an interface, such as the DLS method. Such lipid phases are optically brilliant. A minimal requirement for carrying out the invention, i.e., complexation and separation or adsorption and separation of hydrated turbidity substances, is fulfilled if at least one of the aforementioned product specifications is present.

A special case and preferred embodiment of the invention's extraction and subsequent separation of turbidity-causing substances is a combination of extraction and separation of turbidity-causing substances as described herein. This special case occurs when one or more of the adsorption and/or complexing agents are immobilized on a support material. When such loaded support materials are added to a lipid phase containing hydrated turbidity-causing substances, or when such lipid phases are passed through the loaded support material, which should preferably have a porous or mesh-like structure, the extraction of the hydrated turbidity-causing substances can take place directly at the separation medium by adsorption or complexation, which can then be easily removed from/away from the lipid phase.

Separation methods, method for carrying out step c):

The term "centrifugal phase separation," as used here, refers to the separation of phases by utilizing a centrifugal acceleration. It particularly includes methods known to specialists, such as the use of centrifuges and preferably separators. The separation processes are suitable both for phase separation in the aqueous refining stages disclosed herein, as well as for the separation of the adsorption or complexing agents claimed herein. Another centrifugal separation process is provided by decanters. Since the lipid mixtures that have been combined with an aqueous phase or with an adsorption or complexing agent essentially represent two phases with different densities, a phase separation is generally also possible by sedimentation.Practice shows that the organic compounds to be separated, which have been transferred into the aqueous phase or have aggregated or complexed as suspended solids, cannot largely separate spontaneously. Therefore, separation efficiency and speed must be increased by using pulling and pressure forces. According to the current state of the art, this is easily achievable by means of a simple centrifuge or a suitable separator. Also, pressurization or vacuum application is possible. Separators are systems in which either co-rotating or counter-rotating plates or discs are arranged to generate pulling forces alongside a simultaneous pressure buildup. The advantage of using separators is that they allow for continuous phase separation.Therefore, a particularly preferred embodiment for phase separation of lipid phases is to perform the phase separation using a separator. For the preferred phase separation by a separator, systems with a throughput volume of more than 3 m³/h are preferably used, more preferably more than 100 m³/h, and most preferably more than 400 m³/h. The separation of the aqueous refined lipid phase can, in principle, take place immediately after completion of a mixing or intensive mixing step. On the other hand, if the process flow requires it, 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 as well as on the process conditions. It is preferred that the phase separation takes place immediately following an intensive mixing step.The temperature of the lipid mixture to be separated can, in principle, correspond to that chosen for production. However, it may also be advantageous to vary the temperature and select a higher temperature, for example, if this enhances the effect of the separation tool, or a lower temperature, for example, if this increases the extraction efficiency. In general, a temperature range between 15°C and 50°C is preferred, more preferably between 18°C and 40°C, and most preferably between 25°C and 35°C. The residence time in a separator or centrifuge essentially depends on the device-specific properties. Generally, for economical operation, a as short as possible residence time in a separation device is preferred.A residence time as such is less than 10 minutes for a separator, more preferably less than 5 minutes, and most preferably less than 2 minutes. For centrifuges, a preferred residence time is less than 15 minutes, more preferably less than 10 minutes, and most preferably less than 8 minutes. The selection of the centrifugal acceleration depends on the density difference between the two phases to be separated and must be determined individually. Preferred 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 known as oil moisture) can be determined by various established methods. In addition to other methods, such as infrared spectroscopy, the Karl Fischer titration method according to DIN 51777 is used as a reference method. With this electrochemical method, in which the consumption of water present in the lipid phase required for the chemical reaction of iodine to iodide is determined by a color change, even a minimal water content of up to 10 µg/l (0.001 mg/kg) can be detected.

Water absorption capacity of a refined lipid phase and testing method

Herein, "water reabsorption capacity" refers to the ability to bind water into a lipid phase, which can be achieved through an emulsification process and leads to water remaining in the lipid phase. This can be tested by mixing deionized water at a temperature of 25°C, providing an aqueous volume fraction of 5 vol.% relative to the lipid phase, and stirring with a magnetic stirrer at a speed of 500 rpm for 10 minutes. Subsequently, a centrifugal separation is carried out at 3,000 g for 10 minutes. The value of the water reabsorption capacity is the difference between the water content of the lipid phase after adding water and the water content of the lipid phase before adding water. According to the invention, a water reabsorption capacity of less than 40 wt.% is preferred, more preferably less than 15 wt.%, and most preferably less than 5 wt.%. Furthermore, for the assessment of the inventive method for refining lipid phases, the water reabsorption capacity of the unrefined lipid phase was compared with that of the refined lipid phase. A difference of more than 75% between the two lipid phases is preferred, more preferably more than 85%, and most preferably more than 90%. The water content was determined using the same and herein disclosed measurement method.

Aqueous refining with compounds containing guanidino and/or amidino groups. The term "compounds containing guanidino and/or amidino groups" is used synonymously herein with the term "guanidino and/or amidino compounds." Suitable compounds are those having at least one guanidino group (also called guanidino compounds) and/or at least one amidino group (also called amidino compounds). A guanidino group refers to the chemical residue H2N-C(NH)-NH- as well as its cyclic forms, and an amidino group refers to the chemical residue H2N-C(NH)- as well as its cyclic forms (see examples below). Preferred are guanidino compounds which, in addition to the guanidino group, have at least one carboxylate group (-COOH). Moreover, it is preferred if the carboxylate group(s) are separated by at least one carbon atom from the guanidino group within the molecule. Also preferred are amidino compounds,which additionally have at least one carboxylate group (-COOH). Furthermore, it is preferred if the carboxylate group(s) are separated from the amidine group by at least one carbon atom within the molecule. These guanidino compounds and amidino compounds preferably have a partition coefficient KOW between n-octanol and water of less than 6.3 (KOW < 6.3). In particular, arginine is preferred, which can 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 the guanidino group and the carboxylate group or the amidino group and the carboxylate group are separated by at least one carbon atom, i.e., at least one of the following groups is located between the guanidino group or the amidino group and the carboxylate group: -CH2-.-CHR-, -CRR'-, where R and R' independently represent any chemical groups. Naturally, the distance between the guanidino group and the carboxylate group or between the amidino group and the carboxylate group can also be more than one carbon atom, for example in the following groups -(CH2)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 with more than one guanidino group and more than one carboxylate group are, for example, oligoarginine and polyarginine. Preferred arginine derivatives are compounds of the general formula (I) or (II) below, wherein R', R", R'" and R"" independently mean: -H, -OH, -CH=CH2,-CH2-CH=CH2, -C(CH3)=CH2, -CH=CH-CH3, -C2H4-CH=CH2, -CH3, -C2H5, -C3H7, -CH(CH3)2, -C4H9, -CH2-CH(CH3)2, -CH(CH3)-C2H5, -C(CH3)3, -C5H11, -CH(CH3)-C3H7, -CH2-CH(CH3)-C2H5, -CH(CH3)-CH(CH3)2, -C(CH3)2-C2H5, -CH2-C(CH3)3, -CH(C2H5)2, -C2H4-CH(CH3)2, -C6H13, -C7H15, cyclo-C3H5, cyclo-C4H7, cyclo-C5H9, cyclo-C6H11, -PO3H2, -PO3H-, -PO3^2-, -NO2, -C≡CH, -C≡C-CH3, -CH2-C≡CH, -C2H4-C≡CH, -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 stands for -NH-, -NR""-, -O-, -S-, -CH2-, -C2H4-, -C3H6-, -C4H8- or -C5H10- or for a C1 to C5 carbon chain which can be substituted with one or more of the following groups: -F, -Cl, -OH, -OCH3, -OC2H5, -NH2, -NHCH3, -NH(C2H5), -N(CH3)2, -N(C2H5)2, -SH, -NO2, -PO3H2, -PO3H-,-PO32-, -CH3, -C2H5, -CH=CH2, -C≡CH, -COOH, -COOCH3, -COOC2H5, -COCH3, -COC2H5, -O-COCH3, -O-COC2H5, -CN, -CF3, -C2F5, -OCF3, -OC2F5; L denotes a hydrophilic substituent selected from the group consisting of: -NH2, -OH, -PO3H2, -PO3H-, -PO32-, -OPO3H2, -OPO3H-, -OPO32-, -COOH, -COO-, -CO-NH2, -NH3+, -NH-CO-NH2, -N(CH3)3+, -N(C2H5)3+, -N(C3H7)3+, -NH(CH3)2+, -NH(C2H5)2+, -NH(C3H7)2+, -NHCH3, -NHC2H5, -NHC3H7, -NH2CH3+, -NH2C2H5+, -NH2C3H7+, -SO3H, -SO3-, -SO2NH2, -CO-COOH, -O-CO-NH2, -C(NH)-NH2, -NH-C(NH)-NH2, -NH-CS-NH2, -NH-COOH.

The preferentially used concentration of guanidine or amidine compounds, which must be dissolved in a preferably low- or free-ion water, is determined in one embodiment based on the acid number of the lipid phase to be refined, which can, for example, be determined by titration with KOH. The number of carboxyl groups derived from this serves to calculate the weight amount of the guanidine or amidine compounds. In this case, there must be at least an equal or higher number of guanidine or amidine groups present in free and ionizable form. The molar ratio determined in this way between the guanidine- or amidine-containing compounds and the total amount of compounds carrying free or releasable carboxyl groups, respectively, is as follows:The carboxylic acids must be present in a molar ratio greater than 1:1. Preferably, the molar ratio between the measurable carboxylic acids (here, particularly the acid number is decisive) and the guanidine or amide group-containing compounds should be 1:3, more preferably 1:2.2, and most preferably 1:1.3, and the solution is prepared in water free of ions. The molarity of the dissolved inventive solution containing guanidine or amide group-containing compounds is preferably 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 amide groups is ensured even at ambient temperatures, the preferred temperature for the inventive introduction of aqueous solutions containing dissolved guanidine or amide compounds ranges from 10°C to 50°C.More preferred between 28°C and 40°C, and most preferred between 25°C and 35°C. The introduction of aqueous solutions containing guanidine or amide group-containing compounds should preferably be carried out by an intensive mixing introduction. In principle, the volume ratio between the lipid phase and the water phase is not significant. However, a preferred embodiment is a volume ratio (v/v) of the aqueous solution to the lipid phase of 10 vol.% to 0.05 vol.%, preferably from 4.5 vol.% to 0.08 vol.%, more preferably from 3 vol.% to 0.1 vol.%.

The volume and concentration ratio can be affected by the fact that in some lipid phases, emulsifying compounds such as glycolipids can be extracted by an aqueous solution containing compounds with guanidino or amide groups, thereby making these compounds unavailable for the separation of carboxylic acids. Therefore, in one embodiment, it may be necessary to select a larger volume and/or concentration ratio of the aqueous solutions containing guanidino or amide group-containing compounds relative to the lipid phases to be refined.

Among suitable intensive mixers, those that operate according to the high-pressure or rotor-stator homogenization principle can be particularly mentioned.

In the intensive mixer, an intense mixing of the lipid phase and the aqueous phase then occurs. The intensive mixing takes place at atmospheric pressure and a temperature ranging from 10°C to 90°C, preferably from 15°C to 70°C, more preferably from 20°C to 60°C, and particularly preferably from 25°C to 50°C. Therefore, the mixing, and preferably the intensive mixing, takes place at low temperatures, preferably below 70°C, more preferably below 65°C, even more preferably below 60°C, even more preferably below 55°C, still more preferably below 50°C, and even more preferably below 45°C.

Therefore, it is particularly preferred if the entire aqueous refining process, preferably including the optional steps, is carried out 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 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 is between 7.0 and 14, more preferably between 9.5 and 13.5, and most preferably between 11.5 and 13. The basic washing solution is preferably added using intensive mixing, particularly preferred are rotor-stator mixers. The preferred contact time is between 1 and 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°C and 45°C, more preferably between 20°C and 35°C, and most preferably between 25°C and 30°C.

One embodiment of the pretreatment of lipid phases to be purified by aqueous refining consists of pretreating with an aqueous solution containing an acid and having a pH value between 1 and 7, more preferably between 2.5 and 4, and most preferably between 3 and 3.5. It is preferred to mix the acidic solution with an intensive mixing device as described herein, particularly preferred are rotor-stator mixing systems. The preferred duration of action is between 1 and 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°C and 45°C, more preferably between 20°C and 35°C, and most preferably between 25°C and 30°C.

In this respect, the inventive separation of particulate matter from a pre-treated lipid phase is also directed toward a particularly advantageous loss-reduced refining of neutral lipids, as well as toward the fact that therein less than 5 ppm, in particular less than 2 ppm, 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 sodium, potassium, magnesium, calcium, and/or iron ions are present.

In other words, the inventive separation of impurities from a pretreated lipid phase is also directed toward a particularly advantageous loss-reduced refining of neutral lipids, as well as to the fact that therein less than 5 ppm (or 5 mg/kg), in particular less than 2 ppm (mg/kg) phosphorus-containing compounds, less than 0.2 wt.% (or 0.2 g/100g), in particular less than 0.1 wt.% free fatty acids, and less than 3 ppm (or 3 mg/kg), in particular less than 0.02 ppm (or 0.02 mg/kg) sodium, potassium, magnesium, calcium and/or iron ions are present. Furthermore, the invention relates to refined and upgraded lipid phases obtainable by one of the methods described herein, having a content of less than 10% with respect to the initial amount of water-binding organic lipophilic impurities, wherein the lipid phase contains less than 5 ppm, less than 0.1 wt.%, free fatty acids, and less than 3 ppm of sodium, potassium, magnesium, calcium and/or iron ions.

Furthermore, the invention relates to refined and improved lipid phases obtainable according to one of the methods described herein, having a content of less than 10% with respect to the initial amount of water-binding organic lipophilic turbidity-causing substances, wherein the lipid phase contains less than 5 ppm (or 5 mg/kg), less than 0.1 wt.% (g/100g) free fatty acids, and less than 3 ppm (or 3 mg/kg) of Na, K, Mg, Ca, and/or Fe ions.

Furthermore, the inventive separation process is particularly advantageous because the solid adsorbents can be made usable again at low cost. Moreover, the inventive separation is aimed at making the separated organic suspended solids usable.

Definitions Lipid phase

In this context, the term "lipid phase" refers to all organic carbon compounds of biological origin. The term used here includes mixtures of substances of biological origin, which can be obtained from plants, algae, animals and/or microorganisms, and which have a water content of less than 10% and contain lipophilic substances, including monoacylglycerides, diacylglycerides and/or triacylglycerides, with a total content of more than 70 wt.-% or more than 75 wt.-% or more than 80 wt.-% or more than 85 wt.-% or more than 90 wt.-% or more than 95 wt.-%. Thus, lipid phases may, for example, include extracts of oil-containing plants and microorganisms, such as seeds of rapeseed, sunflower, soybean, flaxseed, jatropha, palm, castor, but also of algae and microalgae, as well as animal fats and oils. It is irrelevant whether the lipid phase is a suspension, emulsion or colloidal liquid. If the lipid phase consists of extracts or extraction phases of lipid substances from a previous separation or extraction process, the lipid phase can also consist to a degree of more than 50 vol.-% of organic solvents or hydrocarbon compounds.

Preferred lipid phases are vegetable oils, particularly pressing and extraction oils from oilseed kernels. However, animal fats are also preferred. Nonpolar aliphatic or cyclic hydrocarbon compounds are also included. These lipid phases are characterized by the fact that more than 95 wt.% of the compounds in them are nonpolar.

Among the lipid phases according to the definition used herein are, among others: Acai oil, Acrocomia oil, almond oil, babassu oil, blackcurrant seed oil, borage seed oil, canola oil, cashew oil, castor oil, coconut oil, coriander oil, corn oil, cottonseed oil, crambe oil, flaxseed oil, grape seed oil, hazelnut oil, other nut oils, hemp seed oil, jatropha oil, jojoba oil, macadamia nut oil, mango kernel oil, meadowfoam oil, mustard oil, neem oil, olive oil, palm oil, palm kernel oil, palm olein, peanut oil, pecan oil, pine nut oil, pistachio oil, poppy seed oil, rice bran oil, safflower oil, camellia oil, sesame oil, shea butter oil, soybean oil, sunflower oil, tall oil, tsubaki oil, walnut oil, types of "natural" oils with altered fatty acid compositions via genetically modified organisms (GMOs) or traditional breeding, 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 salina oil, Botryococcus braunii oil, Dunaliella tertiolecta oil, Nannochloris oil, Spirulina oil, Chlorophyceae oil, Bacillariophyta oil, a mixture of the aforementioned oils as well as animal oils (especially marine oils), algae oils, oils from by-products such as rice bran oil and biodiesel.

Refined lipid phase

Here, the term "modified lipid phase" refers to a lipid phase in which one of the invention's methods for adsorption and separation or complexation and separation of hydrated suspended solids has been carried out.

Refined lipid phase

The lipid phase obtained after an aqueous refining process is understood as the refined lipid phase, meaning the lipid phase obtained after the final process step of one of the inventive methods.

Purified lipid phase

Purified lipid phase refers to the lipid phase obtained after the final process step of one of the inventive methods. The terms "purified lipid phase" and "refined lipid phase" are used interchangeably.

Aqueous Refinement or Aqueously Refined Lipid Phase

In the present application, the term "aqueous refinement" refers to the aqueous cleaning step using a neutral or basic solution to provide the "aqueously refined lipid phase." Thus, "aqueously refined lipid phase" is synonymous with the "lipid phase" that is obtained after cleaning with a neutral or basic solution.

Pre-emulsified lipid phase

In the present application, the "pre-cleaned lipid phase" refers to the lipid phase that is obtained after cleaning with a neutral or basic solution. Thus, a pre-cleaned lipid phase also includes an aqueous refined lipid phase.

"Cleaning lipid phase"

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

Suspended solids

In this context, suspended solids refer to organic compounds that can be defined by the following characteristic properties: a) An organic compound naturally occurring in a biogenic lipid phase with lipophilic properties, characterized by a Kow value greater than 2, where the term Kow refers to the partition coefficient between n-octanol and water; b) an organic compound with a molecular weight of no more than 5000 Da; c) an organic compound that causes a hydrodynamic radius of more than 100 nm in a hydrated state; and d) an organic compound that allows the uptake of water molecules.

The organic suspended matter separable by adsorption or complexation according to the invention have at least two of the aforementioned characteristics, which can be examined by known and technically feasible methods for experts, such as molecular weight determination, calculation of the Kow partition coefficient, determination of the hydrodynamic radius using a dynamic light scattering method (DLS), as well as determination of the water content.

Among the organic water-binding compounds are organic dye compounds such as carotenoids and carotenes, chlorophylls and their degradation products, further phenols, phytosterols, especially β-sitosterol and campesterol as well as sigmasterol, steroids, sinapine, squalene. Phytoestrogens, such as isoflavones or lignans. Furthermore, steroids and their derivatives such as saponins, further glycolipids as well as glyceroglycolipids and glycerosphingolipids, further rhamnolipids, sophorolipids, trehalose lipids, mannosylerythritol lipids. Also polysaccharides, such as rhamnogalacturonans and polygalacturonic acid esters, arabinans (homoglycans), galactans and arabinogalactans, furthermore pectic acids and amidopectins. Further phospholipids, particularly phosphatidylinositol, phosphatides, such as phosphoinositols, further fatty acids and long-chain or cyclic carbon compounds, such as waxes, wax acids, further fatty alcohols, hydroxy- and epoxy-fatty acids. Also glycosides, liporoteins, lignins, phytate or phytic acid and gluconosides. Proteins, including albumins, globulins, oleosins, vitamins, such as retinol, (vitamin A) as well as derivatives, such as retinoic acid, riboflavin (vitamin B2), pantothenic acid (vitamin B5), biotin (vitamin B7), folic acid (vitamin B9), cobalamin (vitamin B12), calcitriol (vitamin D) as well as derivatives, tocopherols (vitamin E) and tocotrienols, phylloquinone (vitamin K) and menaquinone. Moreover, tannins, terpenoids, curcuminoids, xanthones, but also sugar compounds, amino acids, peptides, including polypeptides and also carbohydrates such as glycogen.

Since lipid phases of different origins can be purified from turbidity substances by the inventive method, the selection of turbidity substances is not limited to those specifically mentioned herein. Preferably, water-binding organic lipophilic turbidity substances, such as carotenoids, chlorophylls, phenols, sterols, squalenes, waxes, wax acids, wax alcohols, glycolipids, glyceroglycolipids and/or glycosphingolipids, are separated by means of one of the methods described herein. Furthermore, aldehydes, ketones, peroxide compounds and carboxylic acids.

Acids and Bases

Here, acids are referred to as compounds that are capable of donating protons to a reaction partner, particularly water.

Accordingly, the term "bases" refers to compounds that are able to accept protons, especially in aqueous solutions.

Carboxylic acids

Carboxylic acids, also known as carbonic acids here, are organic compounds that contain one or more carboxyl groups. They can be divided into 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 with a carboxyl group. The carbon atoms can be connected by single bonds (saturated fatty acids) or by double bonds (unsaturated fatty acids); these double bonds can be in a cis- or trans-configuration. According to this definition, compounds containing more than four consecutive carbon atoms besides the carboxyl group are referred to as fatty acids. Examples of linear saturated fatty acids include nonanoic acid (caprylic acid), dodecanoic acid (lauric acid), tetradecanoic acid (myristic acid), hexadecanoic acid (palmitic acid), octadecanoic acid (stearic acid), n-eicosanoic acid (arachidic acid), and n-docosanoic acid (behenic acid).

Separation

In the field of expertise, separation refers to the process of separating a mixture of substances. Depending on the type of separation method applied, which each require an energy input to achieve a certain degree of separation, substances of different purities are obtained. Separation is a synonym for separation, and both terms are used synonymously in this present application. Therefore, separation means the removal of substances from a mixture. The separation methods applied here include phase separation of liquid mixtures, which can be achieved by sedimentation and/or centrifugation and/or filtration. Centrifugal separation can be carried out continuously using a separator or decanter technology or discontinuously using a centrifuge. A filtration-based separation can be performed by passing the lipid phase, in which the compounds/aggregates to be separated are already present, through a filter having a specific mesh size, thereby retaining the compounds/aggregates, which are preferably larger than the minimum mesh size, and preventing them from passing through the filter. Other phase separation techniques known to those skilled in the art may also be used.

Extraction

"Extraction" is a term used by experts for a separation process in which specific components are separated from solid or liquid substance mixtures by using suitable solvents (extraction agents). There are two types: solid-liquid extraction and liquid-liquid extraction. In the case of liquid-liquid extraction, the phases are mixed together and followed by a phase separation, during which the phases are separated from each other. The term "extraction," as used here, refers to the removal of suspended matter from its material (organic) matrix by an extraction agent, which may consist of an adsorbent or a complexing agent for the suspended matter to be separated. In other words, the extractability of hydrated suspended matter is achieved through an adsorptive attachment to an adsorbent, as described herein, or through ionic or covalent bonding with a cation described herein, which is defined here as complexation.

Adsorption

Adsorption is the adhesion of substances to the surface of solids, according to experts. Such adhesions are mainly caused by physico-chemical interactions, although chemical compounds can also be involved.

Adsorbent

Under the term "adsorbent," which is synonymous with the term "adsorbent," here it refers to a material composed of inorganic and/or organic components in a solid state. The adsorbent has surface properties that enable the adsorption of elements or compounds. In particular, the suspended solids described herein can be adsorbed and/or incorporated by means of the adsorbents understood in this context, and thus bound.

Aggregation

In general, aggregation refers to the accumulation or gathering of atoms or molecules. In the field of separation processes, a specialist understands by aggregation the accumulation of atoms or molecules in a liquid until the aggregate is no longer soluble and precipitates out.

Complexation

Under this term is understood a physical and/or physico-chemical and/or chemical bond between two or more elements and/or compounds. The elements may be present in their elemental or ionized form, while compounds may exist as molecules consisting of two or more atoms, regardless of whether they are organic or inorganic compounds. Furthermore, the term includes complexation, which refers to a physical and/or physico-chemical and/or chemical bond with or between complexes that have already formed through complexation with a complexing agent, as described herein, thereby also allowing the formation of aggregates.

Chelating agents

Under the term complexing agents, as used herein, elements are understood to be those that are ionizable in water or release ions, thereby enabling complexation with turbidity-causing substances, as described herein.

Cellulose and Cellulose Derivatives

Cellulose is a polysaccharide with the molecular formula (C6H10O5), more precisely: an isotactic beta-1,4-polyacetal of cellobiose (4-O-beta-D-glucopyranosyl-D-glucose). Cellobiose in turn consists of two glucose molecules. Approximately 500 to 5000 glucose units are linearly and non-branched connected, resulting in average molecular weights of 50,000 to 500,000. In cellulose derivatives, the hydrogen atoms at the free hydroxyl groups of the glucose units can be replaced by -CH3, -C2H5, -C3H7, -C4H9, -C5H11, -CH2CH2OH, -CH2CH2CH2OH, -CH2CH2CH2CH2OH, -CH2CH2CH2CH2CH2OH, -CH2CH(OH)CH3, -CH2CH(OH)CH2OH, -CH2CO2H, -CH2CH2SO3H, -CH2CH2SO3-, -C(=O)CH3, -C(=O)CH2CH3, -C(=O)CH2CH2CH3, -C(=O)CH2CH2CH2CH3, -C(=O)CH(OH)CH3, hydrophobic long-chain branched and unbranched alkyl groups, hydrophobic long-chain branched and unbranched alkylaryl groups or arylalkyl groups, cationic groups, -NO2, -SO3H, -SO3-.

Examples of cellulose derivatives are Hydroxyethylcellulose (HEC), Hydroxypropylcellulose (HPC), Ethylhydroxyethylcellulose (EHEC), Carboxymethylhydroxyethylcellulose (CMHEC), Hydroxypropylhydroxyethylcellulose (HPHEC), Methylcellulose (MC), Methylhydroxypropylcellulose (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), hydrophobically modified Methylhydroxyethylcellulose (hmMHEC), hydrophobically modified Carboxymethylmethylcellulose (hmCMMC), Sulfoethylcellulose (SEC), Hydroxyethylsulfoethylcellulose (HESEC), Hydroxypropylsulfoethylcellulose (HPSEC), Methylhydroxyethylsulfoethylcellulose (MHESEC), Methylhydroxypropylsulfoethylcellulose (MHPSEC), Hydroxyethylhydroxypropylsulfoethylcellulose (HEHPSEC), Carboxymethylsulfoethylcellulose (CMSEC), hydrophobically modified Sulfoethylcellulose (hmSEC), hydrophobically modified Hydroxyethylsulfoethylcellulose (hmHESEC), hydrophobically modified Hydroxypropylsulfoethylcellulose (hmHPSEC), as well as hydrophobically modified Hydroxyethylhydroxypropylsulfoethylcellulose (hmHEHPSEC).

Plant Dyes - Coloring Substances

Under the term "coloring agents," organic compounds are grouped together that typically occur in oils and fats of biological origin in different quantities and compositions side by side.

Under the term "plant pigments" mentioned here, all color-producing compounds occurring in lipid phases are summarized. The most dominant and by far the most abundant pigment found in vegetable oils forms the group of chlorophylls and their degradation products, such as pheophytins. In addition, other compounds belonging to the group of carotenoids or carotenes are also present. Furthermore, other compound classes such as flavonoids, curcumin, anthocyanes, betaines, xanthophylls (which also include carotenes and lutein), indigo, kaempferol, and xanthophylls such as neoxanthin or zeaxanthin are present. These pigments can be present in different proportions within the lipid phase. These pigments exhibit different solubility in water or an organic solvent. With the aqueous refining processes described here, it is possible to separate lipophilic compounds into an aqueous nanoemulsion, thereby enabling otherwise insoluble compounds in water to be transferred into an aqueous phase and separated from it.

The most common plant pigments are chlorophylls. Chlorophylls are typically found in vegetable oils in quantities ranging from 10 ppm (or 10 mg/kg) to 100 ppm (or 100 mg/kg). Oils with a high content of chlorophylls include particularly canola and rapeseed oils.

Chlorophyll

Under the term "chlorophylls" here, compounds are grouped together that consist of a derivatized porphyrin ring and are further divided into subgroups a, b, c1, c2, and d according to their organic residues. Furthermore, they differ in the number of double bonds between carbon atoms 17 and 18.

Chlorophylls are the most common colorants found in plant oils. Due to their hydrophobicity or lipophilicity, they distribute very well in lipid phases, especially in mixtures of triglycerides. They cause a green color of the lipid phase, and they also reduce the oxidation stability of the lipid phase through the binding/insertion of magnesium or copper ions. Therefore, their removal from such a lipid phase is desired, particularly when it involves a cooking oil. The absolute amounts found in lipid phases, and especially in plant oils, vary greatly, ranging from 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 unsuitable for extracting these pigments from a lipid phase. Since the determination of absolute concentrations can be obtained through a high analytical effort, it is more practical to determine the pigment content by spectrometrically measuring the color intensity of a lipid phase. The established method for this is the determination of various color spectra in an oil using the Lovibond method, in which the intensity levels of red, yellow, and green color tones are determined and compared with a reference value. Thus, it is possible to assess the oil's color in general as well as changes in its coloration.

Application Areas

The inventive refining process for raffinates is applicable to all lipid phases, as described herein, which are of biological origin and contain water-binding, strongly lipophilic compounds that appear as cloudiness during or after a refining process due to water introduction. Since the cloudiness substances, for the inventive refining process, must first be released or decomplexed from an organic matrix, the inventive use of the refining process is limited to a refining stage following an aqueous refining step, as described herein. This relates to the purification/refining of oils, particularly plant oils, but also animal fats, where the removal of cloudiness substances is desired. This especially concerns edible oils, fragrance oils, massage oils, skin oils, up to lamp oils. Furthermore, other organic mixtures, such as plant extracts or their distillation products, can be refined. Additionally, natural or synthetic mixtures of hydrocarbons or esterified fatty acids. Moreover, lipid phases suitable for technical applications, such as oil-based lubricants or hydraulic oils.

Furthermore, the invention relates to a process for adsorption and extraction or complexation and extraction of carotenoids, chlorophylls, phenols, sterols, squalenes, glycolipids, glyceroglycolipids and/or glycerosphingolipids and/or waxes or fatty acids from aqueous refined lipid phases, characterized by: a) providing a lipid phase containing carotenoids, chlorophylls, phenols, sterols, squalenes, glycolipids, glyceroglycolipids and/or glycerosphingolipids and/or waxes or fatty acids, wherein the lipid phase has undergone at least one aqueous refining step with a neutral or basic solution, b) adding an adsorbent and/or a complexing agent to the lipid phase from step a), c) separating the adsorbed or complexed carotenoids, chlorophylls, phenols, sterols, squalenes, glycolipids, glyceroglycolipids, glycerosphingolipids and/or waxes or fatty acids from step b) by means of phase separation, wherein the adsorbent is cellulose, a cellulose derivative or a layered silicate, and wherein the complexing agent consists of aluminum ions or iron ions present in an aqueous solution.

Furthermore, the invention relates to a method for adsorption and extraction or complexation and extraction of water-binding organic lipophilic impurities from aqueous refined lipid phases, characterized by: a) Providing a lipid phase containing water-binding organic lipophilic impurities, wherein the lipid phase has been subjected to at least one aqueous refining with an aqueous solution containing at least one guanidine group- or amide group-containing compound having a log P value of less than 6.3. b) Adding an adsorbent and/or a complexing agent to the lipid phase from step a). c) Separating the adsorbed or complexed water-binding organic lipophilic impurities from step b) by phase separation, wherein the adsorbent is cellulose, a cellulose derivative, or a layered silicate, and wherein the complexing agent consists of aluminum ions or iron ions present in an aqueous solution.

The invention relates to a method for the adsorption and extraction of water-binding organic lipophilic turbidity substances from aqueous refined lipid phases, characterized by: a) providing a lipid phase containing water-binding organic lipophilic turbidity substances, wherein the lipid phase has been subjected to at least one aqueous refining with a neutral or basic solution, b) adding cellulose or a cellulose derivative to the lipid phase from step a), c) separating the adsorbed organic lipophilic turbidity substances from step b) by means of a phase separation.

The invention relates to a method for the adsorption and extraction of water-binding organic lipophilic impurities from aqueous refined lipid phases, characterized by: a) providing a lipid phase containing water-binding organic lipophilic impurities, wherein the lipid phase has been subjected to at least one aqueous refining with a neutral or basic solution, b) adding an adsorbent to the lipid phase from step a), c) separating the adsorbed organic lipophilic impurities from step b) by means of phase separation, wherein the adsorbent is cellulose, a cellulose derivative or a layered silicate.

Furthermore, the invention relates to a process for the adsorption and extraction or complexation and extraction of carotenoids, chlorophylls, phenols, sterols, squalenes, glycolipids, glyceroglycolipids and/or glycosphingolipids and/or waxes or fatty acids from aqueous refined lipid phases, characterized by: a) providing a lipid phase containing carotenoids, chlorophylls, phenols, sterols, squalenes, glycolipids, glyceroglycolipids and/or glycosphingolipids and/or waxes or fatty acids, wherein the lipid phase has been subjected to at least one aqueous refining step with an aqueous solution containing at least one guanidino group- or amide group-containing compound having a log P value of less than 6.3. b) adding an adsorbent and/or a complexing agent to the lipid phase from step a), c) separating the adsorbed or complexed carotenoids, chlorophylls, phenols, sterols, squalenes, glycolipids, glyceroglycolipids and/or glycosphingolipids and/or waxes or fatty acids from step b) by phase separation, wherein the adsorbent is cellulose, a cellulose derivative or a layered silicate, and wherein the complexing agent consists of aluminum ions or iron ions present in an aqueous solution.

The invention relates to a process for the adsorption and extraction of carotenoids, chlorophylls, phenols, sterols, squalenes, glycolipids, glyceroglycolipids and/or glycosphingolipids and/or waxes or fatty acids from aqueous refined lipid phases, characterized by: a) providing a lipid phase containing carotenoids, chlorophylls, phenols, sterols, squalenes, glycolipids, glyceroglycolipids, glycosphingolipids and/or waxes or fatty acids, wherein the lipid phase has been subjected to at least one aqueous refining with a neutral or basic solution, b) adding cellulose or a cellulose derivative to the lipid phase from step a), c) separating the adsorbed carotenoids, chlorophylls, phenols, sterols, squalenes, glycolipids, glyceroglycolipids and/or glycosphingolipids and/or waxes or fatty acids from step b) by means of a phase separation.

The invention relates to a process for the adsorption and extraction of carotenoids, chlorophylls, phenols, sterols, squalenes, glycolipids, glyceroglycolipids and/or glycerosphingolipids and/or waxes or fatty acids from aqueous refined lipid phases, characterized by: a) providing a lipid phase containing carotenoids, chlorophylls, phenols, sterols, squalenes, glycolipids, glyceroglycolipids, glycerosphingolipids and/or waxes or fatty acids, wherein the lipid phase has been subjected to at least one aqueous refining with a neutral or basic solution, b) adding an adsorbent to the lipid phase from step a), c) separating the adsorbed carotenoids, chlorophylls, phenols, sterols, squalenes, glycolipids, glyceroglycolipids and/or glycerosphingolipids and/or waxes or fatty acids from step b) by means of phase separation, wherein the adsorbent is cellulose, a cellulose derivative or a layered silicate.

The invention relates to a method for the adsorption and extraction of carotenoids, chlorophylls, phenols, sterols, squalenes, glycolipids, glyceroglycolipids and/or glycosphingolipids and/or waxes or fatty acids from aqueous refined lipid phases, characterized by: a) providing a lipid phase containing carotenoids, chlorophylls, phenols, sterols, squalenes, glycolipids, glyceroglycolipids, glycosphingolipids and/or waxes or fatty acids, wherein the lipid phase has been subjected to at least one aqueous refining with a neutral or basic solution, b) adding cellulose or a cellulose derivative to the lipid phase from step a), c) separating the adsorbed carotenoids, chlorophylls, phenols, sterols, squalenes, glycolipids, glyceroglycolipids and/or glycosphingolipids and/or waxes or fatty acids from step b) by means of phase separation.

The invention relates to a method for the adsorption and extraction of carotenoids, chlorophylls, phenols, sterols, squalenes, glycolipids, glyceroglycolipids and/or glycerosphingolipids and/or waxes or fatty acids from aqueous refined lipid phases, characterized by: a) providing a lipid phase containing carotenoids, chlorophylls, phenols, sterols, squalenes, glycolipids, glyceroglycolipids, glycerosphingolipids and/or waxes or fatty acids, wherein the lipid phase has been subjected to at least one aqueous refining with an aqueous solution containing at least one guanidine group- or amide group-containing compound having a log P value of less than 6.3, b) adding an adsorbent to the lipid phase from step a), c) separating the adsorbed carotenoids, chlorophylls, phenols, sterols, squalenes, glycolipids, glyceroglycolipids and/or glycerosphingolipids and/or waxes or fatty acids from step b) by means of a phase separation, wherein the adsorbent is cellulose, a cellulose derivative or a layered silicate.

Furthermore, the invention relates to a method for complexing and extracting water-binding organic lipophilic turbidity-causing substances from aqueous refined lipid phases, characterized by: a) Providing a lipid phase containing water-binding organic lipophilic turbidity-causing substances, wherein the lipid phase has been subjected to at least one aqueous refining with an aqueous solution containing at least one guanidino group- or amide group-containing compound having a log P value of less than 6.3, b) Adding a complexing agent to the lipid phase from step a), c) Separating the complexed water-binding organic lipophilic turbidity-causing substances from step b) by phase separation, wherein the complexing agent is aluminum ions or iron ions present in an aqueous solution.

Furthermore, the invention relates to a method for complexation and extraction of carotenoids, chlorophylls, phenols, sterols, squalenes, glycolipids, glyceroglycolipids and glycerosphingolipids and/or waxes or fatty acids from aqueous refined lipid phases, characterized by: a) Providing a lipid phase containing carotenoids, chlorophylls, phenols, sterols, squalenes, glycolipids, glyceroglycolipids and/or glycerosphingolipids, and/or waxes or fatty acids, wherein the lipid phase has been subjected to at least one aqueous refining with an aqueous solution containing at least one guanidine group- or amide group-containing compound with a log P value of less than 6.3, b) Adding a complexing agent to the lipid phase from step a), c) Separating the complexed carotenoids, chlorophylls, phenols, sterols, squalenes, glycolipids, glyceroglycolipids, glycerosphingolipids and/or ...

Growing or carboxylic acids from step b) by means of a phase separation, wherein the complexing agent consists of aluminum ions or iron ions present in an aqueous solution.

Another inventive embodiment is a method for separating water-binding organic lipophilic impurities from an aqueous refined lipid phase, characterized by the steps of: a) providing a lipid phase containing water-binding organic lipophilic impurities, wherein the lipid phase has been subjected to at least one aqueous refining with a neutral or basic solution, b) contacting the lipid phase from step a) with an adsorbent and/or a complexing agent, c) phase separation and removal of the adsorbed or complexed water-binding organic lipophilic impurities, wherein the adsorbent is cellulose, a cellulose derivative, or a layered silicate, and wherein the complexing agent consists of aluminum ions or iron ions present in an aqueous solution.

Another inventive embodiment is a method for separating carotenoids, chlorophylls, phenols, sterols, squalenes, glycolipids, glyceroglycolipids, glycerosphingolipids and/or waxes or fatty acids from an aqueous refined lipid phase, characterized by: a) providing a lipid phase containing carotenoids, chlorophylls, phenols, sterols, squalenes, glycolipids, glyceroglycolipids, glycerosphingolipids and/or waxes or fatty acids, wherein the lipid phase has been subjected to at least one aqueous refining with a neutral or basic solution, b) adding an adsorbent and/or a complexing agent to the lipid phase from step a), c) phase separation and separation of the adsorbed or complexed carotenoids, chlorophylls, phenols, sterols, squalenes, glycolipids, glyceroglycolipids, glycerosphingolipids and/or waxes or fatty acids, wherein the adsorbent is cellulose, a cellulose derivative or a layered silicate, and wherein the complexing agent consists of aluminum ions or iron ions present in an aqueous solution.

Another inventive embodiment is a method for separating water-binding organic lipophilic impurities from an aqueous refined lipid phase, characterized by the steps of: a) providing a lipid phase containing water-binding organic lipophilic impurities, wherein the lipid phase has been subjected to at least one aqueous refining with an aqueous solution comprising at least one guanidine group- or amide group-containing compound having a log P value of less than 6.3, b) contacting the lipid phase from step a) with an adsorbent and/or a complexing agent, c) phase separation and removal of the adsorbed or complexed water-binding organic lipophilic impurities, wherein the adsorbent is cellulose, a cellulose derivative, or a layered silicate, and wherein the complexing agent comprises aluminum ions or iron ions present in an aqueous solution.

Another inventive embodiment is a method for separating carotenoids, chlorophylls, phenols, sterols, squalenes, glycolipids, glyceroglycolipids, glycerosphingolipids and/or waxes or fatty acids from an aqueous refined lipid phase, characterized by: a) providing a lipid phase containing carotenoids, chlorophylls, phenols, sterols, squalenes, glycolipids, glyceroglycolipids, glycerosphingolipids and/or waxes or fatty acids, wherein the lipid phase has been subjected to at least one aqueous refining with an aqueous solution containing at least one guanidine group- or amide group-containing compound having a log P value of less than 6.3, b) adding an adsorbent to the lipid phase obtained in step a), c) phase separation and separation of the adsorbed carotenoids, chlorophylls, phenols, sterols, squalenes, glycolipids, glyceroglycolipids, glycerosphingolipids and/or waxes or fatty acids from the lipid phase, wherein the adsorbent is cellulose, a cellulose derivative or a layered silicate.

Another inventive embodiment is a method for separating water-binding organic lipophilic impurities from an aqueous refined lipid phase, characterized by the steps of: a) providing a lipid phase containing water-binding organic lipophilic impurities, wherein the lipid phase has been subjected to at least one aqueous refining with an aqueous solution comprising at least one guanidine group- or amide group-containing compound having a log P value of less than 6.3, b) contacting the lipid phase from step a) with an adsorbent, c) phase separation and removal of the adsorbed water-binding organic lipophilic impurities, wherein the adsorbent is cellulose, a cellulose derivative, or a layered silicate.

Another inventive embodiment is a method for separating water-binding organic lipophilic impurities from an aqueous refined lipid phase, characterized by the steps of: a) providing a lipid phase containing water-binding organic lipophilic impurities, wherein the lipid phase has been subjected to at least one aqueous refining step with an aqueous solution containing at least one guanidino group- or amide group-containing compound having a log P value of less than 6.3, b) adding a complexing agent to the lipid phase obtained in step a), c) phase separation and separation of the complexed water-binding organic lipophilic impurities, wherein the complexing agent comprises aluminum ions or iron ions present in an aqueous solution.

Another inventive embodiment is a method for separating carotenoids, chlorophylls, phenols, sterols, squalenes, glycolipids, glyceroglycolipids and/or glycosphingolipids and/or waxes or fatty acids from an aqueous refined lipid phase, characterized by: a) providing a lipid phase containing carotenoids, chlorophylls, phenols, sterols, squalenes, glycolipids, glyceroglycolipids and/or glycosphingolipids, and/or waxes or fatty acids, wherein the lipid phase has been subjected to at least one aqueous refining step with an aqueous solution containing at least one guanidino group- or amide group-containing compound having a log P value of less than 6.3, b) adding a complexing agent to the lipid phase obtained in step a), c) phase separation and separation of the complexed carotenoids, chlorophylls, phenols, sterols, squalenes, glycolipids, glyceroglycolipids and/or glycosphingolipids, and/or waxes or fatty acids, wherein the complexing agent comprises aluminum ions or iron ions present in an aqueous solution.

Character Description

Figure 1: shows Table 1.3 for Example 1. Figure 2: shows Table 2.2 for Example 2. Figure 3: shows Table 5.2 for Example 5. Figure 4: shows Table 6.1 for Example 6. Figure 5: shows Table 7 for Example 7.

Examples Measurement Methods

The following measurement methods were used within the scope 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 are given in ppm (or in mg/kg).

The content of free fatty acids in the lipid phase was determined by means of a methanolic KOH titration using a Titroline 7000 titrator (SI-Analytics, Germany). Values are given in weight percent (g/100g).

The water content in the lipid phase, also referred to as oil moisture, was determined by automatic titration according to the Karl Fischer method (Titroline 7500 KF trace SI-Analytics, Germany), with values given in weight percent (wt%).

The turbidity of a lipid phase was determined by visual inspection, in which a cuvette with a diameter of 3 cm was filled with the oil to be tested, and two observers assessed the visibility of image lines when viewed through the cuvette under standardized lighting conditions. Additionally, the brilliance of the sample was evaluated under daylight. If image lines were clearly visible and there was optical clarity, the oil sample was rated as transparent. If there was a noticeable distortion of line contours, making it difficult to recognize the image lines, and the transparency was no longer clear, the sample was rated as slightly turbid. If the image lines were still visible but could no longer be differentiated, and the optical appearance was cloudy,Thus, the classification was "moderately cloudy." When no lines were visible anymore and the oil sample could no longer be viewed through, the classification was "strongly cloudy." A classification as "milky" was applied when the appearance resembled that of milk. In comparison to parallel measurements performed using turbidimetry (see below), it became evident that oils classified as transparent (turbidity (TR) = 1) had values below 15 FTU; for oils with a slight turbidity (TR = 2), FTU values ranged from 16 to 50; and for oils with moderate turbidity (TR = 3), FTU values ranged between 51 and 200.At a strong turbidity (TR = 4), FTU values between 201 and 1000 were measured, and at milky emulsions (TR = 5), FTU values above 1000 were found.

A quantification of the turbidity (turbidimetry) of oil phases was also performed using a light scattering detection method, where the re-entry of a scattered light beam at 90° was measured by a sensor immersed in a sample volume of 10 ml (InPro 8200 measuring sensor, M800-1 transmitter, Mettler Toledo, Germany).

The measurement range is 5 to 4000 FTU. Duplicate measurements were always performed for each sample. Drop or particle size determinations were carried out using a non-invasive laser light backscatter analysis (DLS) (Zetasizer Nano S, Malvern, UK). For this purpose, 2 ml of the liquid to be analyzed were filled into a measuring cuvette and inserted into the measuring cell. The analysis of particles or droplets forming phase boundaries is automatic. A measurement range from 0.3 nm to 10 µm is covered.

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

All tests were conducted under normal pressure conditions (101.3 Pa) and at room temperature (25 °C), unless otherwise specified.

Example 1

300 kg of rapeseed oil with the characteristics specified in Table 1.3 (Figure 1) were subjected to a multi-stage refining process. For this purpose, the rapeseed oil was filled into a pre-tank (pre-tank 1). Subsequently, the oil in pre-tank 1 was heated to 50°C and then supplemented with 0.1 wt.% citric acid (25 wt.%, at room temperature) and homogenized for 30 minutes using a rotor-stator homogenizer (Fluco MS 4, Fluid Kotthoff, Germany) at a rotation frequency of 1000 rpm. After that, 0.4 wt.% water was added and stirred for 15 minutes at 100 rpm. Then, phase separation was performed using a separator (OSD 1000, MKR, Germany) at a throughput of 100 l/h and a rotation frequency of 10,000 rpm. The obtained clear oily phase A was transferred to another pre-tank (pre-tank 2). 125 ml of oily phase A were used for chemical analysis.

The oily phase A obtained in this way is brought to a process temperature of 40°C, and then 4 to 10 vol.% of a potassium carbonate solution is added. Subsequently, intensive mixing is carried out using the aforementioned homogenizer at a rotation frequency of 1000 rpm for 15 minutes. The resulting emulsion is pumped into the separation separator, and a phase separation is performed with the same adjustment parameters. The obtained slightly turbid oily phase B is transferred to the pre-storage tank 3. 125 ml of the oily phase B were used for chemical analysis.

The oily phase B is heated to a process temperature of 35°C and 3 vol-% of a 0.5 molar arginine solution is added. Subsequently, an intensive mixing is carried out for 10 minutes using the aforementioned mixing device with the same settings. The resulting emulsion is pumped into the separator, and phase separation is achieved at a flow rate of 200 l/h. The obtained clearly turbid oily phase C is transferred to the pre-tank 4. 125 ml of the oily phase C were used for chemical analysis (determination of oil indices according to measurement methods).

After that, in independent experiments, 10 kg of pre-treated rapeseed oil were mixed with the adsorbents listed in the following table, as powdered solids, in one portion added to the aqueous refined oil, stirred over a period of 20 minutes at a constant temperature of 30 °C using a propeller mixer (200 rpm): Tabelle 1.1

Versuchs Nr.	Adsorptionsmittel	PS (µm)	MW (Da)	Menge
1.1	Hydroxyethylcellulose (H 200000 YP2)	<180	400	50 g
1.2	Celite (VWR)	n.a.	n.a.	100 g
1.3	Tiisyl (Grace)	n.a.	n.a.	100 g
1.4	Kaolin (VWR)	n.a.	n.a.	80 g
1.5	Tonsil Optimum 210 FF	n.a.	n.a.	250 g
1.6	Tonsil Supreme 118 FF	n.a.	n.a.	250 g
1.7	Hydroxyethylcellulose (H 60000 YP2)	< 180	300	25 g
1.8	Hydroxyethylcellulose (H 60000 YP2)	< 180	300	100 g
1.9	Methylhydroxypropyl-cellulose(90SH-100000)	<150	150	25 g
1.10	Methylhydroxypropyl-cellulose(90SH-100000)	< 150	150	100 g
1.11	Methylhydroxyethyl-cellulose(MHS 300000 P4)	< 120	500	25 g
1.12	Methylhydroxyethyl-cellulose(MHS 300000 P4)	<120	500	100 g

Tabelle 1.1

PS: Partikelgröße; MW: Molekulargewicht; n. a.: nicht angegeben

Furthermore, in additional experiments, single additions of 100 ml of the solutions listed in the following table 1.2 were carried out, which were incorporated into the pre-prepared oil phase C of 10 kg each as described previously: Tabelle 1.2

Versuchs Nr.	Komplexierungsmittel
2.1	wässrige Lösung einer 1,5 molaren Aluminiumchlorid-Lösung
2.2	2 molaren Aluminiumsulfat-Lösung
2.3	3,5 molaren Eisen(III)chlorid-Lösung
2.4	3 molare Calciumchlorid-Lösung
2.5	3 molare Magnesium-Sulfat-Lösung
2.6	3 molare Kupferchlorid-Lösung
2.7
2.8	3 molare Aluminiumsulfat-Lösung
2.9	0,5 molare Aluminiumchlorid-Lösung
2.10	9 Gew% Poly-Aluminium-Chlorid-Lösung

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

As a reference (reference experiment [RE]), 1 kg of the pre-treated lipid phase was dried using a vacuum dryer (VC-130SC, Cik, Germany) at a temperature of 85°C for a duration of 120 minutes and under a pressure of 0.01 Pa.

Following the adsorptive treatment according to experiments 1.1 to 1.12 and the complexing treatment according to experiments 2.1 to 2.10, 1 liter of each treated oil phase was taken and mixed with 50 ml of demineralized water using a stirrer at a speed of 500 rpm for 10 minutes at a temperature of 25°C. Subsequently, a centrifugal separation was performed at 3,000·g for 10 minutes. After that, the water content of these oil phases was determined again, as well as the turbidity (see measurement methods for details). Furthermore, 10 ml samples were taken from each treated oil phase, one of which was immediately frozen (D 0), while the other was stored in an open container under daylight for 120 days (D120). Subsequently, the anisidine value was determined (procedure according to the description under measurement methods), where the D0 samples were thawed again and analyzed in a sample run together with the stored samples (D120).

Results (Numerical results are summarized in Table 1.3 (Figure 1)): A very good clarification of the aqueous refined oils could be achieved using the cellulose ethers according to the invention (Experiment 1.1) as well as the kaolin used according to the invention (Experiment 1.4). The other adsorbents used in experiments 1.2, 1.3, 1.5 and 1.6 did not allow a satisfactory clarification. Further investigations on the cellulose ethers according to the invention, as described in experiments V 1.7 to V 1.12, confirm the removal of turbidity from the purified oil phase when 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, V 2.8 to V 2.10 also showed a complete clarification of the pre-purified oil phases, and to a lesser extent in solutions with dissolved iron(III) ions (V 2.3), whereas other metal ions (experiment V 2.4 to V 2.7), which were present in dissociated form in an aqueous solution, did not allow this.

After repeated agitation with water and subsequent centrifugal phase separation, it was found that after an inventive treatment with an adsorption or complexing agent, only a very small amount of water re-entered the refined lipid phases, thereby keeping these oil phases clear. This was not the case for the alternatively used substances. A renewed water ingress was also possible when the pre-treated oil had undergone only vacuum drying. In the crude oil, secondary oxidation products were present, which could be largely removed by means of the aqueous refining process. By treating the pre-treated lipid phase with the inventive adsorbents or complexing agents, the content of secondary oxidation products was reduced to a level (due to methodological limitations) no longer measurable. The secondary oxidation products were only slightly reduced or even increased by the comparative substances. Secondary oxidation products were formed in all oils due to exposure to atmospheric oxygen and light irradiation. The differences between the oil phases treated with the inventive compounds and those that had not been treated or had been treated with comparative compounds remained significantly greater after 90 days than they had been immediately after the initial treatment.

Example 2

Through a fermentative conversion of organic waste materials followed by esterification of the resulting lipid mixture, 50 liters of organic phase (approximately 98% fatty acid methyl esters) were obtained. The aqueous refining was carried out under basically identical mixing and separation conditions as described in Example 1. In the first stage, 2 vol-% of a 15 wt-% solution of metasilicate was used, with the reaction temperature being different at 50°C. The separated oily phase A was slightly cloudy. The second refining step was performed using a 2 vol-% solution of 0.6 molar arginine. The reaction temperature was 28°C in this case. The obtained oil phase B was strongly cloudy. Samples were taken for analysis (determination of oil characteristics according to measurement methods). 30 kg of the pretreated biodiesel were further refined using the adsorbents listed below. In independently conducted experiments, each consisting of 1.5 kg, the adsorbents listed below were added. One sample was dried by vacuum drying as described in Example 1. Tabelle 2.1

V.-Nr.	Adsorptionsmittel	Menge
1.1	Hydroxyethylcellulose (H 200000 YP2)	1,0 g
1.2	Hydroxyethylcellulose (H 60000 YP2)	1,0 g
1.3	Methylhydroxyethyl-cellulose (MHS 300000 P4)	1,5 g
1.4	Methylhydroxypropyl-cellulose (90SH-100000)	1,5 g
1.5	Hypromellose 2910	3,0 g
1.6	Methylhydroxyethyl-cellulose (MCE 100TS)	3,0 g
1.7	Hydroxyethylcellulose (HX 6000 YG4)	3,0 g
1.8	Kaolin	3,0 g

Furthermore, aluminum chloride was added, which was dissolved in low-ionic water at concentrations of 0.01, 0.05 and 0.1 molar (Experiment numbers 2.1 to 2.3), as well as polyaluminum chloride (Al2(OH)2.1Cl3.9 x 2–3 H2O), which was present in the same concentrations in an aqueous solution (Experiment numbers V 2.4 to V 2.6). Each of these solutions received 10 ml addition to the solution mixtures. The substances were mixed with a hand mixer for a period of 5 minutes. After that, the samples were left to stand for 30 minutes. Subsequently, they were centrifuged at 3000 rpm for 7 minutes. The oil phases were decanted from the adsorbents, while in the aqueous extractions, the oil phases were removed. For one sample of the pre-treated oil phase (V1.9), a vacuum drying was performed as described in Example 1. Then, deionized water was added in the same way as described in Example 1 to all the obtained oil phases. The analysis of the water content and the turbidity of the organic phases was carried out as described in Example 1 or according to the measurement methods.

Results: The use of cellulose ethers as adsorbents, the aluminum-containing layered silicate, and the aluminum ion-containing solutions used for complexation all led to complete clarification of the lipid phases (Table 2.2 (Figure 2)), resulting in all refined oil phases eventually becoming transparent. Consequently, the residual moisture in all samples to which adsorbents had been added was within a range of 0.01 to 0.09% by weight, while in oils treated with complexing agents it ranged from 0.01 to 0.14% by weight.

After the second water addition, samples treated with the lowest concentrations of complexing agents showed slightly higher reentry values for water compared to samples treated with higher concentrations of the substances. Removal of residual water from the pre-treated oil could also be achieved by vacuum drying; however, in this oil phase, a further water ingress in a significant amount was possible. In the aqueous phase of the separated complexing agents, aggregated particles were visible, and their quantity did not differ between the selected concentrations.

Example 3

500 kg of Jatropha press oil was subjected to multi-stage aqueous refining, the process technology being essentially the same as in Example 1. The aqueous refining was carried out under fundamentally identical mixing and separation conditions, as listed in Example 1. In contrast, in the first stage, 4 vol-% of an 8 wt-% sodium borate solution was used, which was introduced at 25 °C with a propeller mixer. The separated oily phase A was slightly cloudy. The second refining step was performed by adding 3 vol-% of a 5 wt-% sodium bicarbonate solution at 50 °C. Again, the addition was carried out with a propeller mixer over 30 minutes. The obtained oil B was slightly cloudy. The third aqueous refining stage was conducted using 2 vol-% of a 12 wt-% orthosilicate solution.The obtained oil phase C was slightly cloudy. In the 4th refining step, 2 vol% of a 0.3 molar arginine solution, as described in Example 1, was added by intensive mixing. The reaction temperature was 32°C. The resulting pre-treated oil phase D was strongly cloudy. Samples were taken for analysis. Furthermore, a reference sample (VR) was taken, where vacuum drying was performed as described in Example 1. For the dried oil, an experiment was conducted to test the re-addition of water according to Example 1. (Determination of oil indices according to measurement methods). The oil samples showed the values listed in the following Table 3. Tabelle 3.1

Phosphorgehalt [ppm]	252	87	18	6	0,8
Magnesium [ppm]	56	39	1,2	0,5	0,01
Freie Fettsäuren [Gew-%]	1,4	1,2	0,7	0,15	0,04
Wassergehalt [Gew-%]	1,2	1,5	2,4	3,2	4,6
Öltrübung	1	1	1 -2	3	3

Tabelle 3.1

Wdh. = Wiederholter Wassereintrag; Öltrübung: 1 = transparent, 2 = leicht trüb, 3 = mäßig trüb, 4 = stark trüb, 5 = milchartig; n. d. = nicht durchgeführt.

The following methylcelluloses were investigated: V 1. Hydroxyethylcellulose (H 200000 YP2), V 2. Methylhydroxypropyl-cellulose (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 test V 4, kaolin powder was mixed with the purified oil in a mass ratio (adsorbent/oil (m/m)) of a) 1:499 and b) 1:999. Moreover, various volume ratios of an aluminum chloride (test 5) and a polyaluminum chloride (test 6) solution, each with a concentration of 1.5 mol/L, were examined. The addition was performed in the ratio a) 1:99, b) 1:999, and c) 1:9999. The mixing of the oil phase with the cellulose preparations as well as with kaolin was carried out using a propeller mixer, while the introduction of the aqueous solutions was done with an Ultra-Turrax at 9000 rpm.

The determination of oil moisture and oil clarity (see measurement methods) was carried out according to the individual refining stages as well as according to the inventive refining processes, as well as after a renewed water addition and subsequent centrifugal separation of the water phase, as described in Example 1. Tabelle 3.2

V 1 a)	0,01	1	0,03	1
V 1 b)	0,02	1	0,06	1
V 1 c)	0,09	1	0,14	1
V 2 a)	0,01	1	0,09	1
V 2 b)	0,02	1	0,06	1
V 2 c)	0,12	1	0,16	1
V 3 a)	0,05	1	0,09	1
V 3 b)	0,08	1	0,12	1
V 3 c)	0,12	1	0,15	1
V 4 a)	0,03	1	0,06	1
V 4 b)	0,10	1	0,13	1
V 5 a)	0,01	1	0,02	1
V 5 b)	0,03	1	0,04	1
V 5 c)	0,07	1	0,12	1
V 6 a)	0,02	1	0,02	1
V 6 b)	0,03	1	0,04	1
V 6 c)	0,04	1	0,07	1
VR	0,01	1	0,95	1-2

Tabelle 3.2

Öltrübung: 1 = transparent, 2 = leicht trüb, 3 = mäßig trüb, 4 = stark trüb, 5 = milchartig

Results:

The cellulose preparations investigated showed removal of hydrated impurities in the cloudy oil phase obtained through aqueous refining, at all selected volume ratios, resulting in water contents of the refined oils all being ≤ 0.12 wt%. Consequently, the treated oil phases were all transparent. After a renewed addition of water followed by another centrifugal phase separation, a slight increase in water content occurred in the oils treated with the smallest amount of cellulose esters (maximum 0.16 wt%). Also with the inventive complexing processes using dissolved aluminum ions, a complete reduction of cloudiness was achieved at all tested concentration ratios, with a similarly good reduction of oil moisture. Even after a renewed water addition, the oil moisture was below 0.13 wt% for all concentrations, and accordingly, the oil phases were transparent. A similar result was observed with kaolin. Through vacuum drying, the oil moisture could also be reduced, and in this case, a significant water addition was possible.

Example 4:

For the investigations, the following cold-pressed oils were used: rapeseed oil (RÖ), sunflower seed oil (SBÖ), and grape seed oil (TKÖ), with the following characteristics: 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 crude oils were clear. 60 ml of a 0,5 molar arginine solution was added. The mixture was carried out with an Ultra-Turrax T18 at 24 TDS rpm for 5 minutes. Subsequently, the water-in-oil emulsion was centrifuged in a beaker centrifuge at 5000 rpm for 10 minutes. The obtained pre-treated oil phases showed the following characteristics for RÖ: 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 wt.%, 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 wt.%, and for TKÖ: phosphorus content 0.5 ppm (or 0.5 mg/kg), calcium 0.02 ppm (or 0.02 mg/kg), ...02 mg/kg), iron < 0.002 ppm (or < 0.002 mg/kg), free fatty acids 0.011 weight-%. All obtained oils are slightly to clearly cloudy. (Determination of oil indicators according to measurement methods).

To 200 ml of the pretreated oils, hydroxyethylcellulose (H 200000 YP2) (V 1) and methylhydroxypropylcellulose (90SH-100000) (V 2) are added in a weight ratio of adsorbent to oil of 1:499. Furthermore, kaolin powder (V 3) is added in a weight ratio of adsorbent to oil of 1:199. Moreover, a 0.5 molar solution of aluminum dichloride (V 4), aluminum sulfate (V 5), and polyaluminum hydroxide chloride sulfate (V 6) is added in a weight ratio of complexing agent solution to oil of 1:99. The adsorbents and complexing agents are continuously mixed with a propeller mixer at an rotation frequency of 500 rpm after initial complete addition. After a) 7 minutes, b) after 15 minutes,c) After 30 minutes and d) after 60 minutes, 10 ml of the stirred oil phase were withdrawn and separated from the solid and/or water phase using a centrifuge (3800 rpm / 5 minutes). Subsequently, the optical transparency and water content were determined (see measurement methods). A reference sample of the pre-treated oil, in which deionized water was added to the oil in a weight ratio of 1:99, was also agitated with a stirrer. From this sample, a portion for vacuum drying was taken at the end of the testing period, as described in Example 1 (V 7), and then examined for transparency, water content, and the re-dispersibility of water.

In all experiments, at the end of each trial, two samples (20 ml) were taken (20 ml) (in experiment V7 after drying the oil) and filled into sealable containers. Each sample was frozen (D0), while the second one was kept for 90 days at room temperature in daylight under an air-free condition (D90). After 90 days, the anisidine value was determined for all stored samples as well as for the thawed D0 samples (see measurement methods). Tabelle 4.1

Vorgereinigtes Öl	2,3	2-3	n. d.	n. d.	n. d.	n. d.
V 1 a)	0,98	1-2	1,00	1-2	n. d.	n. d.
V 1 b)	0,65	1	0,92	1-2	n. d.	n. d.
V 1 c)	0,05	1	0,10	1	n. d.	n. d.
V 1 d)	0,01	1	0,02	1	0,5	6,3
V 2 a)	0,82	1	0,95	1	n. d.	n. d.
V 2 b)	0,07	1	0,15	1	n. d.	n. d.
V 2 c)	0,05	1	0,16	1	n. d.	n. d.
V 2 d)	0,02	1	0,04	1	0,5	6,1
V 3 a)	1,84	2	2,32	2	n. d.	n. d.
V 3 b)	1,25	1-2	1,65	1-2	n. d.	n. d.
V3 c)	0,95	1	1,15	1-2	n. d.	n. d.
V 3 d)	0,04	1	0,10	1	0,5	5,9
V 4 a)	1,23	1-2	1,48	1-2	n. d.	n. d.
V 4 b)	0,52	1	0,76	1	n. d.	n. d.
V4 c)	0,06	1	0,08	1	n. d.	n. d.
V 4 d)	0,02	1	0,04	1	0,9	7,3
V 5 a)	1,34	1-2	1,67	1-2	n. d.	n. d.
V 5 b)	0,32	1	0,45	1	n. d.	n. d.
V 5 c)	0,07	1	0,12	1	n. d.	n. d.
V5 d)	0,04	1	0,07	1	0,5	5,5
V 6 a)	0,65	1	0,82	1	n. d.	n. d.
V 6 b)	0,12	1	0,25	1	n. d.	n. d.
V 6 c)	0,06	1	0,07	1	n. d.	n. d.
V 6 d)	0,01	1	0,04	1	0,5	6,5
V 7	0,03	1	2,86	2	0,8	16

Tabelle 4.1

Wdh. = Wiederholter Wassereintrag; Öltrübung: 1 = transparent, 2 = leicht trüb, 3 = mäßig trüb, 4 = stark trüb, 5 = milchartig; n. d. = nicht durchgeführt.

Tabelle 4.2

	Sonnenblumen kern-Öl
Vorgereinigtes Öl	3,4	3	n. d.	n. d.	n. d.	n. d.
V 1 a)	1,62	1-2	1,73	2	n. d.	n. d.
V 1 b)	0,83	1	1,22	1-2	n. d.	n. d.
V 1 c)	0,12	1	0,19	1	n. d.	n. d.
V 1 d)	0,05	1	0,09	1	0,5	5,1
V 2 a)	1,82	2	2,11	2	n. d.	n. d.
V 2 b)	0,93	1	1,12	1-2	n. d.	n. d.
V 2 c)	0,13	1	0,19	1	n. d.	n. d.
V 2 d)	0,05	1	0,08	1	0,5	4,9
V 3 a)	1,98	2	2,31	2	n. d.	n. d.
V 3 b)	1,34	1-2	1,68	1-2	n. d.	n. d.
V3 c)	0,12	1	0,23	1	n. d.	n. d.
V 3 d)	0,09	1	0,12	1	0,5	5,1
V 4 a)	2,13	2	2,75	2	n. d.	n. d.
V 4 b)	1,88	2	2,13	2	n. d.	n. d.
V4 c)	1,00	1	1,65	2	n. d.	n. d.
V 4 d)	0,11	1	0,18	1	0,5	6,9
V 5 a)	1,1	1-2	1,34	1-2	n. d.	n. d.
V 5 b)	0,45	1	0,66	1	n. d.	n. d.
V 5 c)	0,08	1	0,14	1	n. d.	n. d.
V5 d)	0,06	1	0,08	1	0,5	5,4
V 6 a)	0,92	1	1,12	1-2	n. d.	n. d.
V 6 b)	0,19	1	0,29	1	n. d.	n. d.
V 6 c)	0,08	1	0,12	1	n. d.	n. d.
V 6 d)	0,05	1	0,06	1	0,5	4,3
V 7	0,07	1	3,75	3	1,1	18

Tabelle 4.2

Wdh. = Wiederholter Wassereintrag; Öltrübung: 1 = transparent, 2 = leicht trüb, 3 = mäßig trüb, 4 = stark trüb, 5 = milchartig; n. d. = nicht durchgeführt.

Tabelle 4.3

	Traubenkern-Öl
Vorgereinigtes Öl	3,64	3	n. d.	n. d.	n. d.	n. d.
V 1 a)	1,52	1-2	1,98	2	n. d.	n. d.
V 1 b)	0,92	1	1,34	1-2	n. d.	n. d.
V 1 c)	0,21	1	0,34	1	n. d.	n. d.
V 1 d)	0,02	1	0,09	1	0,5	6,2
V 2 a)	1,65	1-2	1,95	2	n. d.	n. d.
V 2 b)	1,12	1-2	1,34	1-2	n. d.	n. d.
V 2 c)	0,36	1	0,68	1	n. d.	n. d.
V 2 d)	0,03	1	0,10	1	0,5	5,8
V 3 a)	1,61	2	2,21	2	n. d.	n. d.
V 3 b)	1,34	1-2	1,85	1-2	n. d.	n. d.
V3 c)	0,43	1	0,82	1	n. d.	n. d.
V 3 d)	0,09	1	0,16	1	0,5	6,1
V 4 a)	2,55	2	3,10	3	n. d.	n. d.
V 4 b)	1,91	2	2,70	3	n. d.	n. d.
V4 c)	1,23	1-2	1,45	1-2	n. d.	n. d.
V 4 d)	0,02	1	0,04	1	0,8	7,2
V 5 a)	1,62	1-2	1,78	1-2	n. d.	n. d.
V 5 b)	0,42	1	0,65	1	n. d.	n. d.
V 5 c)	0,13	1	0,21	1	n. d.	n. d.
V5 d)	0,02	1	0,08	1	0,5	5,2
V 6 a)	0,91	1	1,02	1	n. d.	n. d.
V 6 b)	0,22	1	0,27	1	n. d.	n. d.
V 6 c)	0,09	1	0,17	1	n. d.	n. d.
V 6 d)	0,04		0,07	1	0,5	6,1
V 7	0,09	1	3,84	3	1,2	22

Tabelle 4.3

Wdh. = Wiederholter Wassereintrag; Öltrübung: 1 = transparent, 2 = leicht trüb, 3 = mäßig trüb, 4 = stark trüb, 5 = milchartig; n. d. = nicht durchgeführt.

Summary: A very good reduction of residual moisture is achieved by vacuum drying of pretreated oil phases, but there is a clear re-entry possibility of water. The adsorption and complexation agents tested led to a rapid reduction of cloudiness in purified oil phases. This was associated with a significant reduction in the re-entry of water into the oil phase. While the pretreated and dried oils still contained secondary oxidation products, the refined and treated oil phases no longer contained any secondary oxidation products that could be determined by the p-anisidine method. Over the course of 90 days, significantly more secondary oxidation products formed in the pretreated and dried oils compared to the oil phases treated with adsorption or complexation agents.

Example 5:

Study on the Influence of Pre-treatment of a Lipid Phase on the Extractability of Turbidity Substances.

Linseed oil, with the numbers (determination of oil numbers according to measurement methods) as per Table 5.1, was aqueously refined according to the following procedures: V 1: Phosphoric acid (85% by weight, addition amount 0.4% by weight, contact time 30 minutes), followed by an aqueous solution of sodium carbonate (20% by weight, addition amount 3 volume %, contact time 5 minutes) V 2: Phosphoric acid (85% by weight, addition amount 0.4% by weight, contact time 30 minutes), followed by an aqueous solution of sodium carbonate (20% by weight, addition amount 3 volume %, contact time 5 minutes), then an aqueous solution of arginine (0.3 molar, addition amount 2 volume %, contact time 5 minutes) V 3: Phosphoric acid (85% by weight, addition amount 0.4% by weight, contact time 30 minutes), followed by an aqueous solution of sodium bicarbonate (20% by weight, addition amount 3 volume %, contact time 5 minutes),After that, aqueous solution of sodium hydroxide (1N, addition amount 3%, contact time 5 minutes). V 4: Aqueous solution of sodium bicarbonate (20 wt.%, addition amount 3 vol.%, contact time 30 minutes), followed by phosphoric acid (85 wt.%, addition amount 0.4 wt.%, contact time 30 minutes). V 5: Aqueous solution of sodium bicarbonate (20 wt.%, addition amount 3 vol.%, contact time 30 minutes), followed by phosphoric acid (85 wt.%, addition amount 0.4 wt.%, contact time 30 minutes), followed by aqueous solution of arginine (0.3 molar, addition amount 2 vol.%, contact time 5 minutes). V 6: Aqueous solution of sodium carbonate (20 wt.%, addition amount 3 vol.%, contact time 30 minutes), followed by phosphoric acid (85 wt.%, addition amount 0.4 wt.%, contact time 30 minutes), followed by aqueous solution of sodium hydroxide (1N, addition amount 3%,Contact time 5 minutes)V 7: Aqueous solution of sodium bicarbonate (20 wt.%, addition amount 3 vol.%, contact time 30 minutes), followed by an aqueous solution of sodium metasilicate (20 wt.%, addition amount 2%, contact time 5 minutes)V 8: Aqueous solution of sodium bicarbonate (20 wt.%, addition amount 3 vol.%, contact time 30 minutes), followed by an aqueous solution of sodium metasilicate (20 wt.%, addition amount 2%, contact time 5 minutes), followed by an aqueous solution of arginine (0.3 molar, addition amount 2 vol.%, contact time 5 minutes)V 9: Aqueous solution of sodium bicarbonate (20 wt.%, addition amount 3 vol.%, contact time 30 minutes), followed by an aqueous solution of sodium metasilicate (20 wt.%, addition amount 2%, contact time 5 minutes), followed by phosphoric acid (85 wt.%, addition amount 0.4 wt.%, contact time 30 minutes)V 10: Aqueous solution of sodium hydrogen carbonate (20 wt.,Additive amount 3 vol.%, contact time 30 minutes), then aqueous solution of sodium metasilicate (20 wt.%, additive amount 2%, contact time 5 minutes), then aqueous solution with sodium hydroxide (1N, additive amount 3%,

The aqueous solutions as well as the undiluted phosphoric acid were added to 10 liters of crude oil at the specified concentrations and dosages, and then homogenized using an intensive mixer (Ultra-Turrax, T50, 10,000 rpm for 5 minutes). Subsequently, phase separation was carried out using a separator (OTC 350, MKR, Germany) (capacity 30 L/h, drum frequency 10,000 rpm). After that, a sample was taken for the determination of the key parameters (Table 5.1). Tabelle 5.1

Phosphorgehalt [ppm]	16,2	3,3	0,92	2,9	6,5	1,4	4,6	5,12	1,1	6,3	4,92
Calzium (mg/kg)	29,2	0,93	0,06	0,82	4,23	0,05	1,45	4,34	0,23	0,73	4,01
Eisen (mg/kg)	2,2	0,05	0,02	0,05	1,12	0,04	0,23	1,32	0,05	0,08	1,12
Carbonsäuren (Gew%)	1,2	0,48	0,02	0,32	0,92	0,11	0,33	0,45	0,12	0,85	0,4
Wassergehalt [Gew-%]	1,18	1,82	3,61	2,22	0,21	2,55	1,92	2,32	3,83	0,32	2,45
Öltrübung	1	1-2	2-3	2	1	2	2	2	3	1	2

Tabelle 5.1

Öltrübung: 1 = transparent, 2 = leicht trüb, 3 = mäßig trüb, 4 = stark trüb, 5 = milchartig

1000 g of the pre-treated oil fractions were treated with the following adsorption and complexing agents: a) Hydroxyethylcellulose (H 200000 YP2) 0.5 wt% b) Methylhydroxypropyl-cellulose (90SH-100000) 0.5 wt% c) Kaolin (1.5 wt%) d) Aluminum chloride solution (3 molar, addition amount 1 vol%) e) Polyaluminum chloride solution (9 wt%, addition amount 1 vol%)

The mixing of the oils treated with adsorption or complexing agents was carried out using a propeller mixer at 300 rpm for 30 minutes. Subsequently, phase separation was performed using a beaker centrifuge (4000 rpm, 5 minutes). After that, samples were taken for determining the characteristic values (Table 5.2 (Figure 3)).

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

In related aqueous refining processes, oils retained significant amounts of water in different forms. Upon re-introducing water and separating the aqueous phase by centrifugation, all pre-treated oil phases retained a similar amount of water. The inventive use of adsorption or complexing agents led to an optimal reduction of residual moisture in refined oils having an increased water content. At the same time, the re-enterability of water into all oils was reduced, with the effect being significantly stronger in refined oils that had been pre-treated with an arginine solution, especially when the last aqueous refining step had been carried out using an arginine solution. A clearly worse removal of turbidity, along with a significantly higher re-enterability of water into the refined oil phase, was observed when an acidic washing step had been performed prior to applying the inventive substances.

Example 6:

Investigations on product loss due to adsorption and complexing agents.

Mustard oil (20 liters) with the following characteristics (determination of oil parameters according to measurement 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 weight %, was treated with an aqueous refining process consisting of a citric acid solution (25 weight %, addition amount 0.5 weight %, contact time 20 minutes) as well as an aqueous arginine solution (0.4 molar, addition amount 3%), by adding the aqueous solutions using an intensive mixer (Ultra-Turrax T50, 10 TSD rpm) for 5 minutes. Subsequently, phase separation was performed using a beaker centrifuge (4000 rpm, 5 minutes). The purified oil had the following characteristics: phosphorus content 0.7 ppm (or 0.7 mg/kg), calcium <0.02 ppm (or <0.02 mg/kg), ...0.02 mg/kg), iron <0.02 ppm (or <0.02 mg/kg), free fatty acids 0.05 weight%. The oil was slightly cloudy and had a water content of 2.43 weight%. To determine the dose (minimum dose) that allows a reduction of the residual water content to a value of <0.15 weight% and a reduction of reabsorbability (test performed according to Example 1) of a water content to a value of <0.25 weight%, adsorbents a) hydroxyethylcellulose (H 200000 YP2), b) hydroxyethylcellulose (H 60000 YP2), c) methylhydroxypropyl-cellulose (90SH-100000) and d) kaolin were each added in steps of 0.2 weight% every 10 minutes, under continuous mixing with a propeller mixer (400 rpm).Added. Before each subsequent addition, a sample was taken for the analysis of the residual water content and the reusability of water, then centrifuged after 60 minutes and subsequently analyzed or processed accordingly. In a similar manner, the minimum dose for the complexing agents e) aluminum chloride, f) aluminum sulfate, as well as g) polyaluminum chloride (9% by weight) were also determined, where in each case 0.2% by weight of a 0.5 molar solution of compounds e) and f) was mixed with a purified oil phase, as described previously. The sample preparation and analysis were carried out as described earlier. After determining the minimum dose (see Table 6.1 (Figure 4)), another test was performed with the adhesion or complexing agents, by adding these in the respective determined minimum dose over 30 minutes into 500 ml of the pre-treated oil,As previously described, the adhesion agents were mixed in. Subsequently, phase separation was carried out as before. The adhesion agents then appeared as a solid, crumbly mass at the bottom of the centrifuge tube. The oil phase was decanted, and the centrifuge tubes were stored in an oven at 50°C for 12 hours in such a way that any remaining oil could drain completely. Afterwards, the adsorbent material was completely removed and suspended in 150 ml n-hexane at 50°C for 20 minutes. Thereafter, the suspensions were filtered through a membrane filter (mesh size 20 µm), and the solvent phase was collected, which was then concentrated in a vacuum evaporator. The aqueous phases of the complexing agents were carefully and completely removed after centrifugation. The slightly turbid aqueous phases were vigorously shaken with 150 ml n-hexane each, and the phases were separated by centrifugation.The solvent phase is removed and compressed as before. The remaining solvent is weighed, and the obtained mass is related to the mass of the original oil phase, in order to determine the product loss. The oily residues obtained from the hexane phase are assumed to be the extracted triglyceride fraction. The results are listed in Table 6.1 (Figure 4). The cellulose compounds extracted with hexane were further washed with other solvents. A washing was carried out with methanol. The phase was concentrated and a thin-layer chromatography was performed for the analysis of phospholipids. In another washing with chloroform, with the addition of HCl, a sample preparation (methylation) for fatty acid analysis was performed, followed by a gas chromatographic investigation.

Summary (numerical results in Table 6.1 as Figure 4)

With the determined minimum dosages of the adsorption and complexing agents, it is possible to separate suspended solids without product loss by using the complexing agents, while the adsorption agents remove the suspended solids with minimal product loss. It was demonstrated that with the adsorption agents, fatty acids, waxy acids, phospholipids, and chlorophylls can be removed from the oil.

Example 7:

Evening primrose oil (5000 ml) with the following parameters (determination of oil parameters according to measurement 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 weight percent (or 0.82 g/100g), was subjected to ultrafiltration using a membrane filter with a nominal pore size of 5 µm and further with a pore size of 0.45 µm. A sample of the transparent oil was analyzed; the parameters remained practically unchanged compared to the original material. A determination of particulate components in the oil phase was carried out by means of DLS (see measurement methods). Only minimal amounts of particles were present in the filtered oil, these had a diameter of less than 20 nm for more than 90% of all particles. The filtered crude oil was optically transparent; a water content of 0.41 weight percent was determined. According to the procedure described in Example 1, water was added, resulting in a water content of the oil of 2.62 weight percent.

The filtered oil was divided into the following experimental groups: A) aqueous refining using an arginine solution (0.6 molar, addition volume 3 vol%), which was carried out by adding the aqueous solution using an intensive mixer (Ultraturrax T18, 24 TSD rpm) over 10 minutes; B) aqueous refining as described in A), but with a mixture added via a propeller mixer (500 rpm for 10 minutes); C) direct addition of the adsorption or complexation agents to the oil and mixing as described in B).

Following the aqueous refining of test arms A) and B), a phase separation was carried out as in Example 5, resulting in the retention of oil phases A1) and B1). The following characteristics were determined for the pre-treated oils: 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 wt.%, 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 wt.%. Both oils were slightly cloudy. A vacuum drying was performed on half of the pre-treated oil phases from A1) and B1).so that equal volume portions of the pre-treated oil phases A1) and B1), as well as the pre-treated and dehydrated oil phases A2) and B2) were obtained. The obtained oil phase A2) was divided in half, and one half was reserved for a further experiment designated as A4). To the oil phases A1), A2), B1), and B2), the adsorbents hydroxyethylcellulose (H 60000 YP2) (a) and methylhydroxypropyl-cellulose (90SH-100000) (b) (each added in an amount of 0.5 weight %) as well as the complexing agents aluminum chloride (1.0 molar, added in an amount of 1 weight %) (c) and polyaluminum chloride (9 weight %, added in an amount of 0.5 weight %) (d) were added. The mixture was stirred with a propeller mixer (500 rpm for 20 minutes), followed by phase separation using a beaker centrifuge (3800 rpm/10 minutes).The obtained oil residues A1"), A2"), B1") and B2") were removed, and samples for analysis as well as for a test on the water solubility, according to the procedure of Example 1, were taken. The obtained oil phases A2") and B2") were treated with an arginine solution (0.1 molar, addition amount 2 weight-%) and the phases were homogenized using an intensive mixer (24,000 rpm, 2 minutes). Subsequently, phase separation was carried out as described above, resulting in the retention of the oil phases A3) and B3). Both oil phases were cloudy, and samples for analysis were taken. Thereafter, the adsorption or complexing agents (a), (b), (c) and (d) were again added to the pre-treated oil phases A3) and B3) obtained, in the same volume and concentration ratios as before, and mixed as previously described.Subsequently, phase separation by centrifugation. Samples for analysis and investigation of water solubility were taken from the obtained refined and purified oils A3") and B3"). The oil phase A4) obtained after aqueous refining was filtered using the filter unit described at the beginning. The resulting filtered oil phase A4f) showed a lower turbidity visually. Samples for analysis and an experiment on the re-solubility of water were taken.

The oil from test arm C), which was obtained after treatment with the adsorption or complexing agents added in the same volume ratios and concentrations and under the same process parameters as in test arms A) and B), and after appropriate phase separation as oil phase C", was examined regarding its water content and water solubility, as described above. The oil phase C" was then pre-treated using an aqueous refining process with an arginine solution according to the procedure and process parameters applied in test arm A). After phase separation, which was carried out analogously as previously, the pre-treated cloudy oil phase C1 was obtained, from which samples were taken for analysis and for testing water solubility. The pre-treated oil C1 was then again treated with the adsorption or complexing agents (a), (b), (c), and (d) in the same volume and concentration ratios as before, under the same process conditions. Subsequently, phase separation was performed, resulting in the refined and improved oil phase C1", and samples were taken for analysis and for testing water solubility, as previously described.

In all pre-treated and refined oil phases, a parallel evaluation was conducted of the turbidity determined optically as well as the determination of a turbidity value using a turbidimeter system (see measurement methods). Additionally, measurements of particles or droplets contained in the refined oil phases were carried out using DLS.

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

The adsorbents according to the invention, which were added in an anhydrous form to an ultrafiltered crude oil, resulted in a slight reduction of the water content present therein. The introduction of aqueous solutions containing the complexing agents according to the invention into an ultrafiltered but not aqueously refined oil phase led to an increase in the water content of the oil phase. After centrifugal separation of the adsorbents and complexing agents, in both cases there was a clear possibility for water to be introduced into the oil phase. The pre-treated oil phases then showed, after subsequent aqueous refining, similar values for bound water or for further incorporable water into the pre-treated oil phase as when the crude oil had been directly treated with a similar aqueous refining process.Thus, no significant removal of suspended matter occurred by introducing the inventive adsorbents or complexing agents into a crude oil. Oil that had undergone an inventive aqueous refining and in which the remaining suspended matter was present in a hydrated form could be freed from suspended matter by means of the adsorbents or complexing agents, thereby achieving a low residual moisture content and a low reentry tendency of water. If the pre-treated oil phases, after vacuum drying, no longer contained significant amounts of water, then a significant removal of suspended matter by the applied adsorbents or complexing agents was not possible, as evidenced by a clear reentry of water into the treated oil phases.Provided that during such an oil phase, another aqueous refining step had occurred and the turbidity-causing substances were again present in a hydrated form, it was possible to reduce the turbidity substances using the same adsorption or complexing agents, while maintaining a low residual oil moisture and a low re-entry of water into the oil phase. A determination of the particles or droplets contained in the refined oils showed that for all samples judged as transparent and having a turbidity value of 5 FTU, less than 5% of all measured particles/droplets were larger than 20 nm. In transparent refined oil phases, where turbidity measurements yielded values up to 16 FTU, particles/droplets were also present with a peak at 60 nm or higher.with a ratio of less than 5% to particles/droplets smaller than 10 nm. Thus, it can be largely excluded that aggregates or complexes formed by the used compounds or the used dispersing agents remain in the refined oil phase.

Example 8: Large-scale Application

5000 liters of rapeseed oil is subjected to aqueous refining according to the following scheme: 1. Phosphoric acid (85% concentration, addition amount 0.4%), 2. Aqueous solution with sodium carbonate (20 wt%, addition amount 3 wt%), 3. Aqueous solution with arginine (0.3 molar, addition amount 2 wt%). The acid and aqueous solutions are homogenized using an inline intensive mixer (DMS2.2/26-10, Fluko, Fluid Kotthoff, Germany) with a throughput volume of 3 m³/h, at a rotation frequency of the dispersing tool of 2700 rpm. After each mixing step, phase separation is carried out using a separator (AC1500-430 FO, Flottweg, Germany) at a throughput capacity of 3 m³/h and a drum speed of 6500 rpm (maximum centrifugal acceleration 10,000·g). The refined oil fractions are stored in a holding tank until the next refining stage is carried out. After the third purification step, the oil has the following properties: 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 wt%, water content 2.9 wt%. (See experimental methods for details). The oil is visibly cloudy. The purified oil from the third step.

The refined product is filled into storage tanks 1 and 3 in two fractions of 2450 liters each. To the pre-tank 1, 6.6 kg of hydroxyethylcellulose (H 200000 YP2), which is available as a fine powder, is added under continuous stirring with a propeller mixer (400 rpm) within 3 minutes and then stirred for an additional 15 minutes. Thereafter, the oil phase is pumped via a pump into a candle filter unit (mesh size 2 µm). The outlet of the filter unit is connected to pre-tank 2 for storing the filtered oil phase.

The purified oil in the feed tank 3 is mixed with 46 liters of a 3 molar aluminum chloride solution. The oil/water mixture is pumped via a bottom outlet of the feed tank, connected to a pipeline, into the aforementioned inline rotor-stator mixer and mixed here at an rotational frequency of 1000 rpm with a product throughput of 6 m³/h. The mixed oil/water phase is returned back to the feed tank 3. The mixing process is carried out for 15 minutes, during which theoretically the entire volume of the oil mixture passes through the mixer three times. Subsequently, a phase separation is performed using the aforementioned separator, as described previously. The oil phase is then introduced into the feed tank 4 via a pipeline. Samples are taken from the feed tanks 2 and 4 for analysis. Both refined oil phases are transparent; the oil from feed tank 2 contains a residual moisture content of 0.02 wt%, and that from feed tank 4 contains 0.03 wt%. The reusability of water is examined as described in Example 1. The results show a water content of 0.09 wt% in the oil from feed tank 2 and 0.08 wt% in the oil from feed tank 4.

Claims (10)

1. A method for adsorbing and extracting or complexing and extracting water-binding organic lipophilic turbidity-inducing agents of aqueously refined lipid phases, characterized by

   a) providing a lipid phase containing water-binding organic lipophilic turbidity-inducing agents, the lipid phase having been subjected to at least one aqueous refining with a neutral or basic solution,

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

   c) separating the adsorbed or complexed water-binding organic lipophilic turbidity-inducing agents from step b) by means of a phase separation,

   wherein the adsorption agent is cellulose, a cellulose derivative or a phyllosilicate and the complexing agent is aluminum ions or iron ions which are present in an aqueous solution.
2. The method according to claim 1, characterized in that the at least one aqueous refining is carried out in step a) with an aqueous solution containing at least one guanidine-group- or amidine-group-bearing compound having a K_OW of < 6.3.
3. The method according to claim 1 or 2, wherein a sedimentation-based, centrifugal, filtration-based or adsorptive separation technique is carried out in step c).
4. The method according to any one of claims 1 - 3, wherein the adsorption agent and/or the complexing agent of step b) has been immobilized or bound in a fabric or in a texture, wherein the fabric or the texture is suitable for complexing and/or adsorption and/or filtration of the turbidity-inducing agents.
5. The method according to any one of claims 1 - 4, characterized in that a lipid phase containing less than 0.5 % by weight of water is obtained after step c).
6. The method according to any one of claims 1 - 5, wherein the aqueous refined lipid phase is acai oil, acrocomia oil, almond oil, babassu oil, blackcurrant seed oil, borage seed oil, rapeseed oil, cashew oil, castor oil, coconut oil, coriander oil, corn oil, cotton seed oil, crambe oil, linseed oil, grape seed oil, hazelnut oil, other nut oils, hempseed oil, jatropha oil, jojoba oil, macadamia nut oil, mango seed oil, cuckoo flower oil, mustard oil, hoof oil, olive oil, palm oil, palm kernel oil, palm olein oil, peanut oil, pecan oil, pine nut oil, pistachio oil, poppy seed oil, rice germ oil, safflower oil, camellia oil, sesame oil, shea butter oil, soy oil, sunflower oil, tall oil, tsubaki oil, walnut oil, varieties of "natural" oils with altered fatty acid compositions via genetically modified organisms (GMOs) or traditional breeds, Neochloris oleoabundans oil, Scenedesmus dimorphus oil, Euglena gracilis oil, Phaeodactylum tricornutum oil, Pleurochrysis carterae oil, Prymnesium parvum oil, Tetraselmis chuii oil, Tetraselmis suecica oil, Isochrysis galbana oil, Nannochloropsis salina oil, Botryococcus braunii oil, Dunaliella tertiolecta oil, nannochloris oil, spirulina oil, chlorophyceae oil, bacilliariophyta oil, a mixture of the preceding oils and animal oils (especially marine animal oils), algae oils or oils from bran recoveries such as rice bran oil and biodiesel.
7. The method according to any one of claims 1 - 5, wherein the aqueous refined lipid phase is rapeseed oil, grape seed oil or sunflower oil.
8. Use of the method according to any one of claims 1 - 7 for removing and for obtaining water-binding organic lipophilic turbidity-inducing agents.
9. The use of the method according to any one of claims 1 - 8 for reducing the water reuptake capacity in a lipid phase and/or for improving the oil shelf life or the oxidation stability of plant oil.
10. Lipidphase obtainable according to claim 6 or 7.