EP3152165A1

EP3152165A1 - Method and devices for de-emulsifying and complexing organic compounds in emulsions

Info

Publication number: EP3152165A1
Application number: EP15729368.9A
Authority: EP
Inventors: Max DIETZ
Original assignee: Drei Lilien Pvg Gmbh&co KG
Current assignee: Drei Lilien Pvg Gmbh&co KG
Priority date: 2014-06-03
Filing date: 2015-06-01
Publication date: 2017-04-12
Also published as: CN106794394A; US9994464B2; CA2949428A1; WO2015185516A1; US20170260072A1; AU2015270682A1; ZA201608220B

Abstract

The invention relates to a method for aggregating and separating an organic material mixture which is provided in a dissolved form in an aqueous emulsion. The method is characterized by the following steps: a) providing an aqueous emulsion with organic compounds which are provided in the emulsion in a dissolved form, said organic compounds being carboxylic acids, phospholipids, glycolipids, glyceroglycolipids, phenols, sterols, chlorophyll, and/or sinapines, b) mixing the emulsion from step a) with an aqueous solution containing copper(II) ions and/or calcium ions until an aggregate formation is achieved, and c) separating the aggregates from step b) by means of a sedimentation, filtration, or centrifugation process after achieving an aggregated phase of the organic compounds from step b).

Description

METHOD AND DEVICES FOR EMULSION CLASSIFICATION AND COMPLEXIZATION OF ORGANIC COMPOUNDS IN EMULSIONS

description

The present invention relates to the provision of a method for separating an organic substance mixture from an aqueous emulsion.

Background of the invention

Emulsions are water- or oil-based solutions in which dissolved compounds are present, which, due to their structural properties, can be described as amphiphilic, meaning that they allow hydrophilic and hydrophobic interactions. Therefore, such compounds are much better solved by a liquid system, which allows both an interaction with water molecules and organic compounds, when the emulsifying liquid molecules and compounds provides that allows the best possible interaction of the organic compound to be dissolved. Methods and methods are known from the prior art with which it is possible to prepare emulsions by mixing a water phase with an oil phase. If such a mixture contains no organic compounds which have amphiphilic properties, rapid separation of the two phases occurs. Organic compounds which cause stabilization of water-oil mixtures in the form of an emulsion, in which either water droplets in oil or oil droplets in water are present, are also called emulsifiers. Emulsions which are stabilized by emulsifiers are suitable for the absorption of further organic compounds, these being arranged and aligned at the phase boundaries according to thermodynamic basic principles. Therefore, emulsions are very well suited to replace organic compounds which interact in a non-covalent form with other organic or inorganic compounds, and to convert them into the liquid emulsion phase. An emulsifier-stabilized emulsion leads to an improvement in the solution properties. To achieve a further improvement of the solution properties, the phase boundary must be increased. In this respect, systems have been developed which enable the formation of microemulsions and nanoemulsions, which considerably increases the detachability and absorption capacity of such nanoemulsions for organic compounds which can be dissolved here, not least by the reduction of the surface tension of such emulsions caused thereby. On the other hand, the improved solubility of organic compounds has the consequence that these organic compounds stabilized by a solvation shell are only very soluble little or no aggregation with other such dissolved compounds can go into or received. As a result, such organic compounds may indeed exist in a dissolved form over a surprisingly long time even in a predominantly water or oil-based medium in which they would otherwise not or only badly dissolve, and it does not come, for. B. by gravity, to a settling or failure of these compounds. Therefore, a better emulsifying and dissolving power of an amphiphilic compound used for emulsion mediation hinders subsequent redetachability of the organic compounds dissolved therein.

The prior art WO 201 1/160857 A2 furthermore discloses methods and processes with which nanoemulsions can be prepared which are suitable for very stable dissolution of a multiplicity of organic compounds. One of these methods is obtained by aqueous solutions of guanidine- and / or amidino-containing compounds, which are very hydrophilic compounds with a K _ow of <6.3. _Kow is called the distribution coefficient, and indicates the distribution of a substance between n-octanol and water. In particular, carboxylic acids of guanidine or amidine groups are electrostatically adhered to an equimolar ratio, whereby the hydrophobic carboxylic acids receive a hydration shell which allows a solution in an aqueous medium. The electrostatic interaction can be reversed, for example, by protonation of the acid groups of the carboxylic acid. It has been found that it is possible to use dissolved guanidine or amidine group-bearing compounds for dissolving and separating carboxylic acids from a lipophilic medium with a very high separation efficiency. The interaction of the hydrophilic guanidine- and / or amidine-bearing compounds with carboxylic acids produces a hydration shell around such a dimer, which enables solubilization of this dimer into an aqueous medium to form a nanoemulsion. In addition, guanidine and / or amidine group bearing compounds cause the release of other organic and inorganic compounds that interact with the carboxylic acid. The hydrate shell of the guanidine- and / or amidine-bearing compounds on the one hand and the carbon radical, on the other hand, in addition to other hydrophobic groups of the carboxylic acids, allows electrostatic interaction with organic compounds, thereby partially hydrating them. The enormous penetrating power of nanoemulsions, even in densely packed and anhydrous organic mixtures, has already been proven in the scientific literature. Such applications are mostly for the purpose of separating the organic complexes to separate the compounds herein, to make them recoverable, and if necessary for commercial use. It has been shown that solutions containing guanidine- and / or amidine-group-containing compounds can be used to refine lipid phases in an extremely advantageous manner. This leads to a depletion of free carboxylic acids from the lipid phases to the industrially required minimum values. Furthermore, however, other organic compounds are dissolved from lipid phases and separated with the water phase in the form of an aqueous emulsion by a phase separation. These are in particular phospholipids, glycolipids but also dyes and flavorings. In addition, inorganic compounds such as sodium, potassium, calcium, magnesium, copper, iron and other compounds with the water phase are simultaneously removed. Other highly advantageous applications have also been documented for cleaning processes and decomplexing processes. This is especially true of materials (eg, vegetable kernel cakes, sewage sludge, fruit pods, or hulls) that have a significant proportion of organic and / or lipophilic compounds that are produced by the use of solutions containing guanidine and / or amidine group-bearing compounds or nanoemulsions with carboxylic acids and guanidine and / or amidino group bearing compounds, a tremendous separation performance of organic compounds, e.g. T. complexed with lipids or inorganic compounds are present in a sustainable aqueous emulsion is possible. The enormous emulsion performance of nanoemulsions, consisting of dissolved guanidine and / or Amidinruppentragenden compounds and carboxylic acids, causes an extremely stable solubilization of both lipophilic, hydrophilic and amphiphilic compounds, so that a separation of the present in the aqueous solutions / emulsions compounds very difficult (eg B. by ultracentrifugation) or under drastic conditions, such as a pH shift in a very strong acidic range (pH range of <3 [acidic workup]) is possible. Even after months, no visible change, in particular no settling of solid constituents, has been shown in most of the emulsions thus prepared, unless larger aggregates have been previously separated off. Thus, the particular stability of the emulsions thus prepared with an organic compound mixture is clear. A thermal treatment had no effect, extraction experiments with solvents such. As hexane, diethyl ether, dimethylformamide or chloroform, showed only a small separation efficiency for the dissolved organic compounds or the solvent remained in part or completely in the aqueous phase. Adsorptive methods, such as chromatography, had virtually no separation effects.

Strong protonation of the nanoemulsions consisting of a dissolved guanidine or amidine group bearing compound and a carboxylic acid results cause the carboxylic acids to be peeled off and, after phase separation, to be separated from the aqueous solution. However, for the reuse of the guanidine- or amidine-containing compound-containing solutions for the solubilization and separation of carboxylic acids in a lipid phase, a pH above 7.0 is required in order to provide sufficient solubility for carboxylic acids. Acid processing of said nanoemulsion would thus require subsequent adjustment of the pH of the guanidine or amidine group bearing compound-containing solution by means of a base for further recycling and thus render the recycling process of the aqueous solutions containing guanidine or amidine group bearing compounds uneconomical , In addition, under acidic conditions, chemical reactions occur which lead to an unwanted change in the dissolved organic compounds. Thus, an economic utility of the separated under acidic conditions organic compounds in most cases no longer exists.

Another known method is a displacement extraction of the carboxylic acids with an alcohol. It has been shown that a reduction of the pH is required here, too, in order to allow sufficient separation of the nano-emulsified fatty acids. The additional presence of an alcohol in an acidic reaction mixture leads to the chemical modification of many organic compounds. Such a method for the separation of nanoemulsified organic mixtures is also not suitable if the aqueous solution containing guanidine or amidino-containing compounds for re-separation of carboxylic acids from a lipid phase is to be reused since the separation efficiency of these compounds by an alcohol, which remains in the aqueous phase is reduced.

Thus, no methods or methods are available or are known in the art, with which nanoemulsions, consisting of guanidine and / or amidino-containing compounds and carboxylic acids, can be re-separated so that they under mild conditions, with simple measures and economic Purified methods, ie freed from dissolved therein organic compounds and can be brought to re-use. In order to be able to meet these conditions, it is necessary to have a suitable method and process technology and apparatus, in particular to allow the work-up of nanoemulsions consisting of guanidine- and / or amidine-group-containing compounds and carboxylic acids. Farther it would be particularly advantageous to use the separated chemical and structurally unchanged organic compounds economically.

Object of the invention

The object of the present invention is to provide a process for product-sparing and inexpensive separation of an organic substance mixture which is present dissolved in an aqueous emulsion.

This object is achieved by the technical teaching of the independent claims. Further advantageous embodiments of the invention will become apparent from the dependent claims, the description, the figures and the examples.

Detailed description of the invention

According to the invention, the object is achieved by means of water-soluble ionic copper compounds and calcium compounds which lead to an aggregation of the carboxylic acids and organic compounds other than the guanidine or amidine group-bearing compound present in the guanidine or amidine group-containing compounds-containing solution. The aggregates can subsequently be separated from the aqueous solution, which furthermore contains compounds containing guanidine and / or amidine groups.

According to the invention, the object is achieved by a process for the aggregation and separation of an organic substance mixture which is present dissolved in an aqueous emulsion, characterized by the steps:

a) providing an aqueous emulsion having dissolved therein organic compounds, wherein the organic compounds are carboxylic acids, phospholipids, glycolipids, glyceroglycolipids, phenols, sterols, chlorophylls, sinapines, peptides, proteins, carbohydrates, lipo-proteins, waxes and / or fatty alcohols These,

b) mixing the emulsion of step a) with an aqueous solution containing copper (II) ions and / or calcium ions until aggregate formation,

c) separating the aggregates from step b) by sedimentation, filtration or centrifugation after obtaining an aggregated phase of the organic compounds from step b).

In the context of studies of aqueous emulsions and nanoemulsions, by a refining process and or or a cleaning or Decomplexation process with solutions or nanoemulsions containing guanidine and / or amidino group-containing compounds, it was found that in addition to carboxylic acids and phospholipids, glycolipids, glyceroglycolipids, phenols, sterols, squalene, plant dyes such as chlorophylls and carotenes, sinapines, peptides, proteins , Carbohydrates, lipo-proteins, waxes and / or fatty alcohols are separated. The carboxylic acids, phospholipids, glycolipids, glyceroglycolipids, phenols, sterols, squalene, plant dyes such as chlorophylls and carotenes, sinapines, peptides, proteins, carbohydrates, lipoproteins, flavors, waxes and / or fatty alcohols can each be used individually or as a mixture in the aqueous emulsions available. For example, it may be a mixture of peptides, sterols and carbohydrates or a mixture of glycolipids and phospholipids. In the aqueous solution, which after use for purifying a lipid phase in addition to carboxylic acids and phospholipids, glycolipids, glyceroglycolipids, phenols, sterols, squalene, flavors, plant dyes such as chlorophylls and carotenes, and / or sinapine may contain, these substances are in an emulsion in front. This emulsion will hereinafter also be referred to as an aqueous extraction mixture or aqueous emulsion. In this case, the aqueous extraction mixture may be an aqueous extraction solution or extraction suspension.

Preference is given to an emulsion which contains carboxylic acids, phospholipids, glycolipids, glyceroglycolipids, phenols, sterols, chlorophylls, sinapine peptides, proteins, carbohydrates, lipo-proteins, waxes and / or fatty alcohols, either individually or as a mixture.

The invention also relates to processes for the aggregation and separation of an organic substance mixture which is dissolved in an aqueous emulsion, characterized by the steps:

a) providing an aqueous emulsion having organic compounds dissolved therein, wherein the organic compounds are carboxylic acids, phospholipids, glycolipids, glyceroglycolipids, phenols, sterols, chlorophylls and / or sinapines,

c) separating the aggregates from step b) by sedimentation, filtration or centrifugation after obtaining an aggregated phase of the organic compounds from step b). The invention further relates to processes for the aggregation and separation of an organic substance mixture which is dissolved in an aqueous emulsion, characterized by the steps:

b) mixing the emulsion from stage a) with calcium oxide, magnesium oxide and / or zinc oxide or with an aqueous solution containing copper (II) ions and / or calcium ions until aggregate formation,

The calcium oxide, magnesium oxide and / or zinc oxide is preferably added as a solid in powder form to the aqueous emulsion or added as an aqueous dispersion to the aqueous emulsion or added in suspended form to the aqueous emulsion.

The invention further relates to processes for the aggregation and separation of an organic substance mixture which is dissolved in an aqueous emulsion, characterized by the steps:

b) mixing the emulsion of step a) with calcium oxide, magnesium oxide and / or zinc oxide until aggregate formation,

The invention also relates to a process for the aggregation and separation of an organic substance mixture which is dissolved in an aqueous emulsion, characterized by the steps:

a) providing an aqueous emulsion having organic compounds dissolved therein, wherein the organic compounds are carboxylic acids, phospholipids, glycolipids, glyceroglycolipids, phenols, sterols, chlorophylls and / or sinapines, b) mixing the emulsion from step a) with an aqueous solution containing copper (II) ions and / or calcium ions and / or with an aqueous dispersion containing calcium oxide, magnesium oxide and / or zinc oxide and / or adding the emulsion from step a) with calcium oxide , Magnesium oxide and / or zinc oxide in solid form with mixing to achieve aggregate formation.

The emulsion of step a) in the processes disclosed herein (comprising the 14 processes immediately before the examples) can thus be treated with an aqueous solution containing copper (II) ions or with an aqueous solution containing calcium ions or with an aqueous solution containing copper (II). ion or calcium ions, or with calcium oxide in solid form or in powder form, or with magnesium oxide in solid form or in powder form, or with zinc oxide in solid form or in powder form, or with calcium oxide and magnesium oxide in solid form or in powder form, or with magnesium oxide and zinc oxide in solid form or in powder form, or with calcium oxide and zinc oxide in solid form or in powder form, or with calcium oxide and magnesium oxide and zinc oxide in solid form or in powder form, or with an aqueous dispersion of or containing calcium oxide , or with an aqueous dispersion of or containing magnesium oxide, or with an aqueous dispersion of or containing zinc oxide d, or with an aqueous dispersion of or containing calcium oxide and magnesium oxide, or with an aqueous dispersion of or containing calcium oxide and zinc oxide, or with an aqueous dispersion of or containing magnesium oxide and zinc oxide, or with an aqueous dispersion of or containing calcium oxide and magnesium oxide and Zinc oxide, or with a combination of two or three of the aforementioned solutions, dispersions or solids. The displacement was preferably carried out with mixing and / or preferably at a maximum of 75 ° C. and / or preferably with a laminar stirrer.

Aqueous extraction mixtures contain, in addition to the abovementioned carboxylic acids, phospholipids, glycolipids, glyceroglycolipids, phenols, sterols, squalene and plant dyes such as chlorophylls and carotenes, also relevant amounts of also with detached inorganic compounds such as sodium, potassium, magnesium, calcium, copper, iron and inorganic compounds that are typically found in plant extracts. Surprisingly, it has been found that despite the presence of copper ions in the aqueous emulsions containing dissolved guanidine or amidine group bearing compounds and other organic compounds, the addition of solutions with copper ions results in rapid and eventually complete aggregation of the dissolved organic compounds, the dissolved guanidine However, or amidino-containing compounds are not aggregated and remain in the aqueous solution.

The aggregate formation was already initiated by the addition of very small amounts of dissolved ionic copper compounds and led to a very rapid formation of aggregates, which continued without a further addition of copper ions until there is a complete separation of organic compounds by spontaneous sedimentation of the aggregates came.

Achieving an aggregate formation in stage b) thus means the beginning of the aggregation, which can be recognized by the eye.

The invention therefore relates to a method for aggregating organic compounds dissolved in an aqueous emulsion or nanoemulsion. In particular, the invention relates to a method for aggregating organic compounds dissolved in a neutral or basic aqueous emulsion or nanoemulsion.

In stage b) of the process according to the invention, the addition of an aqueous solution containing copper (II) ions and / or calcium (II) ions, to the aqueous emulsion of stage b) during the mixing of the emulsion.

Alternatively, in stage b) of the process according to the invention, the mixing can also take place only after the addition of an aqueous solution containing copper (II) ions and / or calcium ions to the emulsion. If no aggregate formation takes place, the process is repeated until the desired aggregate formation begins.

Amazingly enough, it was possible to achieve separations in which the final concentrations of copper ions in the obtained clarified water phases containing guanidine and / or amidine group-bearing compounds corresponded approximately to the concentrations of divalent cations which are also present in the aqueous extraction mixture, ie before such a separation. have been present. The aggregation proceeds independently, without requiring a pH shift. The pH of the clarified process water is almost identical to that of the initially used aqueous solution with the guanidine and / or amidine group-containing compounds, ie before the purification of the lipid phase. The clarified process water corresponds to the solution with compounds containing guanidine and / or amidine groups after removal of the carboxylic acid and other organic compounds.

It has also been found that the previously nano-emulsified carboxylic acids are also separated together with the other organic compounds present in an aqueous solution consisting of guanidine- or amidine-containing compounds in dissolved form. This is therefore particularly advantageous because the resulting aqueous solution with guanidine and / or Amidino-containing compounds now directly for reuse as extraction medium, eg. B. for a lipid phase is available. It could be shown that when an optimal dosage of the copper ion concentration required for the aggregation initiation according to the invention takes place, the resulting clarified solution contains virtually no other organic compounds besides the guanidine and / or amidine group bearing compounds and the concentration of copper ions contained therein re-use of the extraction medium in an extraction of lipid phases does not bother, or the extraction performance is not reduced. Thus, there is a very simple process with which the nano-emulsified carboxylic acids together with the dissolved organic compounds can be reduced to a required minimum in one step and the immediate reuse of the clarified water phase containing the guanidine- and / or amidine-containing compounds allowed. As a result, a complete separation of dissolved organic compounds from the process water can be achieved. In this case, the concentrations of dissolved organic compounds, apart from the guanidine- and / or amidine-group-containing compounds contained herein, in the clarified process water are less than 1.0 mmol / l.

The invention relates to methods by which a basic aqueous extraction medium of organic compounds dissolved therein can be purified and treated for reuse. The invention also relates to methods by which organic compounds which are dissolved in a neutral or basic extraction medium can be aggregated and separated. Furthermore, it has been found that dissolved calcium compounds as well as undissolved calcium oxide compounds are capable of initiating aggregate formation as found for the ionic copper compounds. Nevertheless, it was found that the amount of calcium ions or calcium oxide required for this purpose is considerably greater than with ionic copper compounds. The process management is difficult to make with calcium compounds. Ionic calcium is not detectable in the aqueous guanidine or amidine group bearing compounds as there is no haze or color change. Copper ions lead to a coloration of the aqueous medium, which has a blue to green color spectrum depending on the pH. This property is very well suited for process control, while the concrete analysis of the existing calcium ion concentration is more problematic.

Unexpectedly, aggregation initiation also occurred by the addition of powdered calcium oxide compounds, although these compounds have no solubility in water. Aggregate formation is significantly slower than that initiated by the addition of copper or calcium ions. Furthermore, it has been found that an addition of calcium oxide compounds leads to an increase in the pH of the clarified process water. To initiate aggregate formation of the organic substance mixture, the required amount of copper ions is considerably less than the amount of dissolved calcium ions. Oxides of magnesium and zinc also resulted in aggregate formation, while oxides of aluminum or copper were not suitable for this purpose.

A preferred embodiment of the aggregation initiation of process step b) is carried out with oxide compounds of calcium, magnesium or zinc.

Furthermore, the invention relates to a process wherein the aqueous emulsion according to step a) contains at least one guanidine or amidine group-carrying compound having a K _ow of <6.3.

The process according to the invention is particularly suitable for aqueous emulsions which originate from the refining of a lipid phase.

The invention relates to processes in which the aqueous emulsion according to step a) originates from a refining of a lipid phase.

Another particularly advantageous effect of using copper or calcium ions instead of calcium oxide compounds is that it results in less separation of guanidine or amidine groups Compounds from the extraction mixture comes. The loss of guanidine or amidine group bearing compounds upon initiation of aggregation with calcium oxide compounds is due to a greater inclusion of a water phase in the aggregate phase, consisting of separated organic compounds and calcium oxide. Furthermore, it has been shown that when using copper ion-containing solutions to initiate aggregation and clarify the aqueous emulsion, there is a loss of guanidine- or amidine-containing compounds of <10% by weight of the amount of these compounds present in the starting solution.

In addition, it was possible to show that the separation of the aggregates by means of filtration or sedimentation in the case of inorganic calcium oxide compounds, in comparison with copper ions, involves a far greater separation of water from the extraction mixture. Copper ion-containing solutions are therefore preferred for the present invention. As a result, a loss of guanidine and / or amidino-containing compounds from the process water can be reduced to a minimum. In accordance with the present invention, the recoverability of a process water phase containing guanidine and / or amidine group bearing compounds is at least 80 wt%, more preferably greater than 85 wt%, and most preferably greater than 90 wt% of the content of these compounds present prior to aggregation initiation of the invention ,

The invention therefore relates to processes with which a reprocessing and recyclability of a process water with guanidine and / or amidino-containing compounds can be achieved.

According to the invention, obtaining a reusable aqueous process solution includes guanidine and / or amidine group bearing compounds.

The copper ions remaining in the clarified process water can, if their whereabouts are not desired herein, also be removed to completeness with very simple methods. This is easy to realize because, if no desired shift of the pH z. B. was carried out by a buffer, the guanidine and / or amidino-containing compounds in the aqueous solution have an isoelectric charge and thus are not moved in an electrophoretic separation of the copper ions in the electric field, so that electrodes, for. B. from carbon, for elemental copper deposition can be placed either directly in the process water or electrophoretic separation with suitable membranes, such as these z. B. are common in electrodialysis, are made. This process step is possible with very little effort and easy in the process. Yet more advantageous is the separation of the copper ions by suitable cation-accepting compounds. From the prior art are suitable materials, such. For example, ion exchange resins known. This gives a purified aqueous solution ready for renewed use with the guanidine and / or amidine group-bearing compounds. Therefore, the process is in a particularly advantageous and unsurpassed ability to separate with minimal effort within a very short time a large amount of dissolved in a nanoemulsion organic compounds with minimal inclusion of water and at the same time recover a clarified process water, which is to be purified by simple means At the same time, the dissolved guanidine and / or Amidinruppentragenden compounds can be practically completely recovered.

A preferred embodiment of the method according to the invention is the clarification and purification of the aqueous emulsion according to one of the applications of the invention, to obtain an aqueous phase or a process water which is suitable for repeated use for the respective application.

Further preferred is the use of a purified process water phase containing guanidine or amidine group bearing compounds dissolved therein for an aqueous refining and / or purification or decomplexing process.

In addition to these surprising and advantageous effects, it was also possible to find a very simple and therefore preferred metering technique for the initiation of aggregation. Since the aggregation of the dissolved organic compounds occurs almost abruptly from a certain amount of added copper ions, in order to avoid unnecessary over-titration with copper ions, a modality for their control, which must be present especially in the control of a large-scale plant, had to be found. Surprisingly, the start of aggregation always takes place when a same color and color intensity is reached during a stirring process of a dissolved copper compound. The aggregation then proceeds completely spontaneously without the need for replenishment of copper ions.

After complete sedimentation of the aggregates or their separation by a phase separation then results in a pale green to turquoise transparent aqueous solution with a relation to the starting solution virtually unchanged pH. This allows a precise dosage of copper ions, so a subsequent Abtren nprozess the copper ions can be carried out very inexpensively.

For a complete precipitation of carboxylic acids from a guanidine- and / or amidine-containing compound-containing solution containing no organic constituents other than these, a larger amount of copper ions is required than is stoichiometrically required for salification with the contained carboxylic acid groups. In addition, it was possible to show that the aggregation initiation according to the invention in the case of dissolved organic mixtures was independent of the amount of nano-emulsified carboxylic acids herein. In an aqueous emulsion obtained from an aqueous refining process with an arginine solution in which initiation of aggregation with copper ions was initiated immediately or after admixture of oleic acid, the amount of copper ions required for complete separation of the organic compounds was the emulsion with the fatty acid addition slightly higher than was the case without an addition. The clarified process water was then subjected to another attempt to dissolve the same amount of oleic acid herein as in the previous experiment and re-aggregating with the copper compound. The amount of copper ions required to completely aggregate the dissolved oleic acid was almost twice the difference in the amount of added copper ions (with or without added oleic acid) in the previous experiment.

In summary, it must be assumed that in the case of the unexpectedly effective aggregation formation which can be achieved by the addition of copper ions, but also of calcium ions and powdery forms of calcium oxide which are added to one of the aqueous emulsions according to the invention, a complex formation between them dissolved organic constituents, preferably carboxylic acids, phospholipids, glycolipids, glyceroglycolipids, phenols, sterols, squalene, plant dyes such as chlorophylls and carotenes and / or sinapines, as well as flavors, which leads to a loss of the nanoemulgierenden effect of the guanidine or Amidinruppentragenden compounds due to the lack of solubilization, the self-aggregation of the organic compounds continues to progress so that they precipitate out of the aqueous solution. It must be assumed that intermolecular bonding forces additionally contribute to aggregate formation between the organic compounds and, as a result, better facilitate phase separation is as if an adsorption of the organic compounds would take place on a Adsorptionsm ittel.

In addition, for a complete aggregation of carboxylic acids, in an aqueous solution by guanidine contained herein and / or

Nano-emulsified amidino-containing compounds present, but at the same time contains more organic components than these, requires a smaller amount of copper ions for aggregation of all organic compounds, as is required if present in the solution only carboxylic acids and said guanidine and / or amidino-containing compounds. Therefore, by the method according to the invention an advantageous co-discharge of solubilized carboxylic acids, in the simultaneous presence of other organic compounds and thereby lower consumption of copper ions, whereby a complete separation of the organic compounds is achieved together with the carboxylic acids.

However, the copper ions remaining in the process water, but also the other ions listed herein, can also be separated with the devices described in the disclosure in order to obtain a purified water phase. This purification has the advantageous effect that the purified water phase, which in addition to the guanidine and / or amidine group-carrying compounds and for a further application contains non-solubilizing amount of ionic compounds still present here, is directly suitable for a renewed application, e.g. B. for an aqueous refining process is available. Suitable for this purification are ionophoretic methods, such as electrophoresis or electrodialysis. Furthermore, ion exchange resins can also be used. Therefore, a preferred method for removing copper ions remaining in the clarified process water is the use of adsorptive techniques or electrophoretic discharge by elemental deposition or deposition with an ion permeable membrane.

One embodiment of the process is the separation of copper (II) ions from the aqueous solution after step c). A further preferred embodiment is the purification of the clarified water phase to obtain a reusable process water phase.

A further particularly advantageous effect of the aggregation initiation of the dissolved organic compounds according to the invention is that these are also included Ambient temperature or even at temperatures of <15 ° C, or until the freezing point of the solution, runs in the same way. This is of particular interest when aggregating compounds which are readily hydrolyzed, degenerate or enzymatically altered in an aqueous or alkaline medium with enzymes or catalytically active substances dissolved out, and which undergo such alterations by aggregation or separation at reduced temperatures the dissolved organic compounds can be reduced or even prevented. It has thus been possible to show that phospholipids can be obtained substantially free of hydrolysis if they have been introduced into an aqueous emulsion from an vegetable oil under product-protecting conditions by means of an aqueous refining with a solution containing guanidine- and / or amidine-group-containing compounds Aggregation was initiated by copper ions. The phospholipids present in the cooled aggregate phase were separable as a low-hydrolysis fraction by a solvent-based extraction process, which was likewise carried out at reduced temperatures. Under increased temperatures and a longer residence time in the aqueous extraction phase phospholipids were obtained by the same method, which were partially hydrolyzed.

Therefore, the method of the invention is also directed to the aggregation of easily decomposable organic compounds in order to make them recoverable from the aggregate phase in a low-decomposition state. A preferred embodiment of process step b) is the aggregation of easily decomposable organic compounds with cooling of the reaction mixture during and after the initiation of aggregation.

Therefore, the method is also directed to the recovery or recovery of organic compounds in a substantially or completely free of decomposition state, which can then be used as food, pet food, technical, cosmetic or pharmaceutical product.

In this respect, the invention also relates to the use of separated organic compounds as food, pet food, technical, cosmetic or pharmaceutical product or as a flavoring.

Neutral lipids obtained in an emulsion or nanoemulsion consisting of guanidine and / or amidine group bearing compounds and carboxylic acids and others organic compounds, can not be separated from the nanoemulsion by physical means such as centrifugation or by raising the temperature. In contrast, separation of the neutral lipids can be achieved by means of the method according to the invention at elevated temperature and addition of copper ions.

The aggregation initiation according to the invention proceeds in this way, as is the case even at low temperatures. When the temperature of the reaction mixture is raised, the neutral lipids contained therein are not enclosed in the organic aggregate phase that forms and form their own phase, which settle on the clarified water phase due to the density difference. The neutral lipids thus detached can be readily separated from the clarified aqueous phase containing guanidine or amidine group-bearing compounds by suitable processes.

Therefore, a likewise particularly preferred variant of the method according to the invention, a heating of the emulsion or nanoemulsion with the claimed guanidine and / or Amidinruppentragenden compounds and carboxylic acids, and dissolved here present neutrals to make to separate the neutral lipids from the other zugeösten organic compounds, wherein the neutral lipids of the water phase float and are recoverable as a fraction.

As expected, it has been shown in the analysis of the lipid fractions obtained that these are predominantly neutral fats.

The separation of neutral lipids from an aqueous emulsion containing dissolved organic compounds by heating the emulsion before and / or during the aggregation initiation according to the invention is a further preferred embodiment of the process.

According to the invention, obtaining a phase of neutral fats from an aqueous solution of organic compounds. On the other hand, neutral fats could no longer be detected in the organic compounds obtained under these conditions. This can be very advantageous for further use of the resulting organic compounds. Thus, a substantially complete separation of neutral fats in the recovery of proteins but also of phospholipids or glycolipids but also in the recovery of carboxylic acid is very advantageous.

Therefore, the invention is also directed to the preservation and use of organic compounds having little or no residual neutral fat. Further advantageous effects arise in the separation and further utilization of the aggregated organic compounds. The already described effect of the very compact aggregation of the total organic compounds which were present in the aqueous emulsions with guanidine- and / or amidine-containing compounds, which causes a substantial displacement of the water phase and thus also the guanidine- or amidine-containing compounds, also has the consequence that the mass obtained with organic compounds is very compact and also has a low tackiness. Therefore, the separated complexed organic compounds can be separated in a particularly advantageous manner by means of a decanter and / or with shaking sieves and / or filtration processes, to a substantially anhydrous solid phase. In particular, a filtration technique for complete separation of the organic aggregates is suitable for small amounts of solids. This makes a very simple removal of the organic aggregates possible by means of established methods.

A preferred embodiment of process step c) is the use of decanters, separators or a filter technology for the separation of a low-residual organic aggregate phase.

In the case of organic aggregate phases in which the content of residual water and / or guanidine- or amidine-group-containing compounds still contained herein can be further reduced, it may be necessary to subject the aggregate phase to an aqueous purification step following process step c). This can be done by passing the aqueous cleaning phase through the aggregate phase or suspending the aggregate phase in the aqueous cleaning phase. Subsequently, for compacting one of the above-described methods for separating a compact organic aggregate phase is carried out. The aqueous cleaning phase can be pure (preferably ion-poor or ion-free) water or an acid or base added to the water.

A preferred process for reducing the residual water content and / or guanidine or amidine group-carrying compounds from the organic aggregate phase obtained according to process step c) is an aftertreatment of the organic aggregate phase with an aqueous purification step, followed by a renewed phase separation and a separation of the phases from one another. This also improves the shelf life and, in the event that the further process steps are to take place with a dry starting material, the energy costs for a dehydration. But also transport costs can be reduced.

Should it be necessary in certain applications to further reduce the residual water content, drying of the organic aggregation phase can be carried out. For this purpose, prior art processes are available, such as vacuum drying or the passage of an inert gas (e.g., nitrogen) or hot air.

A preferred embodiment is the drying of the organic aggregate phase following the process step c).

Drying results in many organic compounds included in the organic aggregate phase, such as. As proteins, glycolipids or lipoproteins to an almost unlimited shelf life of these organic compounds.

Preference is therefore given to the use of organic compounds obtained by one of the process steps according to the invention and preserved by drying the organic aggregate phase as food, pet food, technical, cosmetic or pharmaceutical product or as a flavoring.

Surprisingly, the aggregate phases, which were obtained by copper ions, but also by the other ions according to the invention and the oxide compounds according to the invention, exhibited astonishingly good storage stability even without drying. Also, more than 6 months after the recovery of aggregate phases obtained from refining of rapeseed oil and stored without further measures (e.g., heat application or irradiation) at room temperature in a closed vessel, there was no infestation by fungi or microorganisms. The fractionation by solvent digestion was still possible. In addition, it has been shown that organic compounds contained in the solid phases can be recovered in largely unchanged form.

A particularly preferred embodiment of the process according to the invention is directed to the preparation of a low-water storage-stable form of organic compounds which have been aggregated from an aqueous emulsion. Also preferred is the low-decomposition or decomposition-free storage of the organic compounds which have been obtained by aggregation according to the invention after process stage c). However, another decisive advantage is also that it has been possible to show that such aggregated organic compounds from the refining of a lipid phase are virtually unchanged chemically and can then be separated again into individual classes of compounds by the methods disclosed herein.

Therefore, the method according to the invention is also preferred for the gentle production and fractionation of organic compounds and preferably of carboxylic acids, but also of phospholipids, glycolipids, glyceroglycolipids, phenols, sterols, squalene, plant dyes, such as chlorophylls and carotenes, and / or sinapines from lipid phases and especially preferably of proteins, proteins, flavors, waxes, fatty alcohols, odors, flavors, carboxylic acids, but also of phospholipids, glycolipids, glyceroglycolipids, phenols, sterols, squalene, plant dyes, such as chlorophylls and carotenes, and / or sinapines used by lipid phases. Even if the aggregation according to the invention by copper ions and separation of all organic compounds, in an emulsion consisting of an aqueous solution containing guanidine and / amidino-containing compounds, to> 85 wt .-%, more preferably to> 90 wt .-% and am Most preferably to> 95 wt .-% and most of all to> 98 wt .-%, so these very beneficial effects of aggregation initiation can also be achieved for calcium ions or calcium oxide. Among the calcium ions, calcium dichloride (CaC) is considered preferable. Other possible ions which allow the initiation of aggregation according to the invention include magnesium (II), zinc (II) and iron (II), and iron (III) and aluminum. In principle, these can be brought to dissociation as salts with any counterion in an aqueous solution. Particularly advantageous and thus preferred are chloride salts. Further preferred are sulfate, or acetate. But are also conceivable z. Tartrates, oxalates, carbonates, borates. The combination of 2 or more of these salts or compounds is possible in principle and may be useful if the different organic compounds present in the aqueous emulsion can be aggregated to varying degrees by the aggregating agents that can be used. In such a case, by a combination of aggregating agents, the required total amount of cations or oxide compounds can be reduced. A combination may also be desired when one of the cations could chemically react with one of the organic compounds. The likelihood of such a reaction can be reduced by reducing the concentrations of the individual aggregating agents by a combination of aggregating agents that can be applied in process step b).

The salts are preferably used as aqueous solutions for initiating aggregation. These are dissolved in a preferably ion-poor or ion-free water. The compounds used for aggregation initiation are preferably in completely dissolved, d. H. dissociated form. The concentrations of the ionic copper and calcium and magnesium compounds used, which initiate the initiation of aggregation according to the invention, depends essentially on the process parameters. If it is undesirable to supply a larger volume of liquid in the course of the process, the ion concentration can be increased to the respective solubility limit. On the other hand, if only a minimum use of the cations used for aggregation initiation is emphasized, the concentration can be markedly reduced and the volume of liquid increased. Preferably, ion concentrations are between 0.001 and 3 molar, more preferably between 0.01 and 2 molar, and most preferably between 0.1 and 1 molar.

The salts for aggregation initiation are also referred to herein as aggregation initiators.

The temperature at which the compounds are dissolved for the application according to the invention is irrelevant, as long as the compound can be completely dissociated. For this purpose, it may be necessary in individual cases to increase the temperature of the aqueous solution. Both the aggregation initiator-containing aqueous solution and the guanidine- and / or amidine-containing compound-containing emulsion having the dissolved organic compounds of a lipid phase can be used at any temperature. Preferred are temperature ranges between 1 and 101 ° C, more preferably between 15 and 75 ° C, more preferably between 18 and 45 ° C and most preferably between 25 and 35 ° C.

In a further process according to the invention, step b) is carried out at a temperature of at most 75 ° C.

The addition of the aggregation initiator-containing aqueous solutions to the guanidine and / or amidine group bearing compound-containing emulsion with the dissolved organic compounds from the lipid phase can be continuous or discontinuously, e.g. B. by dripping done. Furthermore, combinations of both dosing methods are possible. Preference is given to a combination in which first the experiential amount of dissolved aggregation initiators is added and mixed, followed by a dropwise application until the recognition of the aggregation initiation has taken place. The amount of aggregation initiator to be added to the inventive aggregation initiation of the aqueous emulsion containing guanidine and / or amidine group bearing compounds varies with each application and must be determined individually.

The dosage determination can be very easily recognized by the fact that with the naked eye solid aggregates can be detected, while forming a clear aqueous phase. The onset of aggregate formation is best recognized by a quiescent, ie, non-agitated, emulsion. At a low agitation, however, this initiation is also recognized. Aggregation initiation also occurs upon strong agitation of the emulsion containing guanidine and / or amidine group bearing compounds as well as organic compounds. However, the just sufficient amount of aggregation initiator, which leads to a complete aggregation of the organic compounds, can be poorly estimated. Therefore, it is preferable to control the required amount of dissolved aggregation initiator needed for complete aggregation of the organic compounds by continuous process monitoring. This makes the process very attractive economically. Furthermore, it could be shown that the visual impression of the formation of a free water phase can be objectified by a change in the size distribution of the particles present in the emulsion. Aggregation causes the particles in the aqueous emulsion, which initially had more than 90% diameter between 10 and 1000 nm, to form aggregates with the appearance of a clear water phase, making the water phase particles> 90% Have a size of> 10μηη. In the water phase, there are practically no particles that are <than 1000 nm, which explains the optical effect of a clarification of the emulsion. This can be documented by the established process technology of light feedback control (DLS), which is available both as a remote method and also for an online measuring method.

In a preferred embodiment of the method according to the invention, a process control takes place by means of the detection of a free water phase and / or the formation of aggregates which are>90%> than 10μηη. A process control is also possible by other known techniques. The addition of ionic solutions leads to a change in the conductivity and the ion concentration of the aqueous emulsion, so that a process monitoring by means of a conductivity measurement or the determination of the ion concentration with suitable measuring probes is possible. In practical use, these parameters can be used to control especially in aqueous emulsions where there is little variability in the compounds dissolved therein. Their determination, the z. B. is carried out in an investigation to find the required minimum concentration, by the values of the measurement parameters are determined, which are present at the time of aggregation initiation, which leads to complete aggregation of the organic compounds. For a large-scale application, these parameter values can then be used for metering control. Other measuring methods represent the viscometry of the emulsions. It has been found that the viscosity of the aqueous emulsion increases with the addition of the aggregating agent. The increase is significantly greater with aggregating agents in oxide forms than with an ionic solution. In the formation of a free water phase, the viscosity of the aqueous reaction mixture decreases, so that this measurement parameter is also suitable for process control, the parameter determination can be carried out as described above. Furthermore, the specific gravity of the emulsion also changes.

In a very particularly preferred embodiment of the invention Aggregationinitialisierung the control and process monitoring by means of a determination of the entering in the aqueous reaction mixture during the addition of copper ions change in color and / or color intensity and / or transparency of the reaction mixture and / or the size and the Size distribution of particles in the forming water phase. It has been shown that it can be reliably predicted at the aggregation initiation with dissociated copper ions present at exactly the same color spectrum and / or color intensity and / or transparency of the reaction mixture, whether the amount of copper ions is already sufficient to the from now on self-continuing process the aggregation of the organic compounds, which is up to a complete removal of the organic compounds from the aqueous solution containing guanidine and / or Amidinruppentragenden compounds, run to run off. Unnecessary overdoses can be avoided hereby. However, if the process is not complete, copper ions can be further added until aggregation is complete. In addition, the determination of the color spectrum as well as the color intensity and the transparency with available analysis devices for both remote investigations and for an online process monitoring available. The determination of the parameter measurements to be achieved to predict complete aggregation with copper ions may be determined as part of finding a minimum required dosage, as set forth below and in the examples.

In a further preferred embodiment of the process, step b) is carried out under a discontinuous or continuous analysis of the color of the aqueous emulsion and / or its color intensity and / or its optical transparency and / or a determination of the particle size or particle size distribution contained herein, for controlling the Dosing of the aggregation initiation according to the invention.

It could also be shown that the copper ion initiated aggregates consisting of phospholipids, dyes (in particular chlorophylls), phenols and the like. m., could be brought into solution much easier in an organic solvent, as after precipitation of the organic compounds, which was achieved by an acid addition or an aggregation initiation by calcium salts or calcium oxide. As will be further disclosed below, it is possible to separate the aggregated organic substance mixtures into individual substance classes. It has surprisingly been found that, especially with the aggregates of organic compounds obtained by means of copper ions, a more effective separation into different solvent phases can be achieved than is the case with aggregates formed by aggregation initiation with calcium or other cations and with calcium oxide had been achieved. Fractionation of copper ion aggregated organic compounds was also much easier than with the coagulated mass obtained after precipitation with an acid. Further, by a solution of the organic compounds in organic solvents, the complexed and present copper ions can be converted into a water phase by an aqueous extraction step and thus recovered.

A preferred embodiment of the process is the recovery of aggregation initiators from a complexed organic aggregate phase by means of solvent removal and an aqueous washing step.

Therefore, the complexation of the in a emulsion or nanoemulsion, consisting of the claimed guanidine and / or Amidingruppentragenden compounds and carboxylic acids, dissolved organic compounds present with copper ions, a particularly advantageous embodiment of the separation process of dissolved organic compounds. In a further embodiment, the complexation of the dissolved organic components by alkaline earth metal oxides and metal oxides can be carried out by suspending them in the aqueous medium. This is particularly advantageous when it is desired to clarify the organic compounds present dissolved in a nanoemulsion consisting of guanidine- and / or amidine-substituted compounds and carboxylic acids. After a short time, aggregate formation occurs, which spontaneously sedimentes with simultaneous clarification of process water. The final separation can then take place, as described above, by means of decanters and / or screening techniques and / or filtering techniques. Preferred oxide compounds which are not known to be soluble in water, thereby calcium oxide, zinc oxide and magnesium oxide. Since these compounds decompose over time despite poor water solubility, it is advantageous to allow this separation step to proceed at room temperature or under refrigerated conditions. However, this can not prevent the decomposition, so that it can lead to formation of hydroxides, whereby the pH of the process water increases. If only a small amount of the oxides are suspended, only a slight increase in pH occurs, the aggregation reaction proceeds slowly. Although an excess of the amount of oxide required for aggregation results in a very rapid and complete aggregation, the pH value increases significantly to values> 13. This is not desirable and requires, as described above, a more intensive purification of the process water and thus unnecessary process costs. The actual amount of oxide can not be calculated and has to be determined by a test and therefore has to be determined individually for each separation. For this purpose, the examination described herein is applicable to the required minimum dose. In a preferred embodiment, these oxide compounds are applied under continuous pH control. An increase to a range to be determined for each application then represents the upper limit for the addition of the oxide compounds.

In a preferred embodiment, the process control is carried out by measuring the pH of the reaction mixture.

In this respect, the method according to the invention enables very advantageous processes in order to simply and cost-effectively purify a process water containing guanidine- and / or amidine-group-containing compounds dissolved therein, in which preferably> 95 wt .-% of all organic compounds, more preferably> 98 wt .-% of all organic compounds and most preferably> 99 wt .-% of all organic compounds, except the readily soluble and guanidine contained herein and / or or amidino-containing compounds, are removed from the process water. This includes in particular the separation of previously nano-emulsified carboxylic acids which belong to

> 98% by weight of all organic compounds and most preferred

> 99 wt .-% of an aqueous solution containing guanidine and / or amidino group-containing compounds can be removed by an aggregation of the invention.

However, it has been found that organic compounds remaining in a clarified or purified water phase do not interfere with the employability of a solution containing guanidine and / or amidine group bearing compounds when reapplied for nanoemulsive or emulsive purification or decomplexation these compounds have a very high hydrophilicity and thus are not distributed in or absorbed by a lipid phase to be refined.

Thus, the method is also directed to the substantially complete removal and recovery of carboxylic acids which have been separated from a lipid phase by means of an aqueous refining.

The aggregates of organic compounds obtained after separation have a residual water content of preferably <30% by weight, more preferably of <20% by weight, more preferably of <15% by weight and most preferably of <10% by weight. % and can be used for fractionation immediately or after further dehydration. It has been shown that such fractionations by solvents, which are known in the art, can be achieved in a few steps. In this case, apolar solvents, such as. As octane, hexane, heptane, petroleum ether, dimethyl ether, and low polarity solvents, such as. B. CHCl 3 or CHCl 2 or polar solvents such as ethyl acetate and alcohols such. As isopropyl alcohol, methanol, ethanol, 1-butanol, as well as small amounts of water may be used, optionally with the addition of an acid or a base. Furthermore, combinations of the aforementioned classes of compounds are possible. In this case, fractions of organic compound classes are obtained, for example, a> 90% solubility in a methanol phase and those having a minimum of 80% solubility in a petroleum ether phase and compounds having> 75% solubility in an alcohol. This can be in the organic Mixture containing organic compound classes having a purity of preferably> 70%, more preferably of> 80% and most preferably> 85% by a sequential separation with one or more solvents in one of the above groups fractionate.

Therefore, the invention relates to carboxylic acids, phospholipids, glycolipids, glyceroglycolipids, glycerol phospholipids, chlorophylls, carotenoids, squalene, phenols, sinapines, peptides, proteins, carbohydrates, lipoproteins, waxes and / or fatty alcohols, obtainable by any of the processes described herein, wherein the carboxylic acids , Phospholipids, glycolipids, glyceroglycolipids, glycerolphingolipids, chlorophylls, carotenoids, squalene, phenols, sinapines, peptides, proteins, carbohydrates, lipoproteins, waxes and / or fatty alcohols obtained with a purity of the respective class of compounds of> 75%.

The invention further relates to the fractionability of carboxylic acids, phospholipids, glycolipids, glyceroglycolipids, glycerolphingolipids, chlorophylls, carotenoids, squalene, phenols, sinapines, peptides, proteins, carbohydrates, lipoproteins, waxes and / or fatty alcohols, obtainable by one of the processes described herein, the carboxylic acids, phospholipids, glycolipids, glyceroglycolipids, glycerolphingolipids, chlorophylls, carotenoids, squalene, phenols, sinapines, peptides, proteins, carbohydrates, lipoproteins, waxes and / or fatty alcohols obtained with a purity of the respective class of compounds of> 75% ,

The sequence of solvent fractionation with which the separation of the organic compounds can best take place must be determined for each mixture of substances which differs in the nature and number of organic compounds present therein. The same applies to the required proportions of the solvents in relation to the mass of the organic compounds to be fractionated and the solvents with one another. The separation of the solvent phases can be carried out by phase separation, if necessary, a centrifugal separation is required to increase the efficiency. For acidification, it is possible in principle to use any acids which are known to the person skilled in the art, but preference is given to HCl, sulfuric acid and oxalic acid. Bases forming substances are also known in the art, such as. For example, sodium hydroxide. The fractionated in the solvent phases organic compounds can now be obtained as a solid by the solvents are evaporated, for example by means of vacuum evaporation. The resulting solids can then be used in suitable Solvents or solvent mixtures are resuspended and further purified or such purification is carried out from the organic solvent phases in which they have been obtained. By these prior art techniques, fractions of organic compounds can then be obtained in which a purity of> 90%, more preferably of> 95%, and most preferably of> 98% is achieved for compounds from the classes of carboxylic acids, phospholipids , Glycolipids, glyceroglycolipids, glycerolphingolipids, chlorophylls, carotenoids, squalene, phenols, sinapines, peptides, proteins, carbohydrates, lipoproteins, waxes and / or fatty alcohols, obtainable by any of the methods described herein, wherein the carboxylic acids, phospholipids, glycolipids, glyceroglycolipids, Glycerolphingolipids, chlorophylls, carotenoids, squalene, phenols, sinapines, peptides, proteins, carbohydrates, lipoproteins, waxes, fatty alcohols and other organic compounds which have been complexed with the aggregation according to the invention. Furthermore, a> 90%, more preferably> 95% and most preferably> 98% recovery of the copper ions used for aggregation formation is possible. These separation processes may be carried out under usual temperature conditions, preferably between 0 and 120 ° C, more preferably between 10 and 50 ° C and most preferably between 15 and 35 ° C. The exposure times are subject to the process conditions. The extractions are carried out according to the permissible work protection conditions, preferably in closed systems.

Thus, an embodiment of the invention relates to a process for the production of carboxylic acids, phospholipids, glycolipids, glyceroglycolipids, glycerolphingolipids, chlorophylls, carotenoids, squalene, phenols, sinapines, peptides, proteins, carbohydrates, Liporoteinen, flavors, waxes and / or fatty alcohols. Thus, the process of the invention is also directed to the recovery and use of high purity organic compounds which are preferably> 90%, more preferably> 95% and most preferably> 98%, chemically and structurally unaltered from their presence in the lipid phase from which they were extracted by means of an aqueous extraction containing guanidine and / or amidino group-containing compounds, and to the substance classes of carboxylic acids, phospholipids, glycolipids, glyceroglycolipids, glycerolphingolipids, chlorophylls, carotenoids, squalene, phenols, sinapines, peptides, proteins, carbohydrates , Liporoteine flavors, waxes and / or fatty alcohols, as well as other organic compounds are attributable. It has also been found that the inventive method for aggregation initiation is not or significantly worse, when an aqueous emulsion containing the same organic compounds, but by a refining process with a base-forming compound such. B. with sodium, has been prepared. It should be noted that a solution of the organic compounds, such as is obtained in aqueous emulsions containing guanidine- and / or Amidinruppentragenden compounds, predominantly does not occur. While in the present invention related aqueous extraction solutions used in the refining of z. As rapeseed and Camelinaöl be obtained when there was virtually no support in a filtration with a 20μηη filter, the water phases could not be practically filtered after refining with NaOH or Na carbonate, since the filters were added after a short time. In this respect, it may be assumed that there are already larger aggregates, the addition of cations disclosed herein, on the other hand, gave no or insufficient results in aggregation initiation.

Aqueous nanoemulsions, consisting of guanidine- or amidine-containing compounds and carboxylic acids, are also suitable for breaking up complexed organic mixtures and dissolving them in the aqueous medium, and then emulsions or suspensions are present. The dissolved organic compounds have predominantly amphiphilic properties, but may also be largely apolar. Such emulsions or suspensions can be produced in a wide variety of industrial sectors. For example, it has been shown that biomass of various origins can be completely dissolved by the aforementioned nanoemulsions by treatment with the abovementioned nanoemulsions by organic compounds which are complexed in the biomass and can not be dissolved out by other aqueous extraction methods and are separated from solids with the water phase can be. Thus, for example, it has been shown that large amounts of the organic compounds present in this process can be separated off from the press residues of plants and especially of plant seeds into the water phase and thus separated from the fiber fractions. The same is true for intermediates or residues in the processing of food or animal use. As a separation of organic compounds or fruit pulp, which remain on the cores or peels of plant fruits, very easily possible with such nanoemulsions. It is also possible to convert and separate usable organic compounds from fermentative processes or bioreactors into the water phase of these nanoemulsions. The low surface tension of such nanoemulsions also causes the penetration of the water phase into hydrophobic, highly complexed aggregates. Thus, it could be shown that dried sludge granules were able to dissolve and separate most of the organic compounds included therein. These nanoemulsions also penetrate into porous rocks and are able to dissolve complexes of organic compounds and virtually pure lipids and transport them in total with the water phase.

Surprisingly, the aggregation method according to the invention is also suitable for aggregating and separating organic compounds which have been dissolved out of their organic or inorganic matrix by a nanoemulsive treatment of complex and complexed substance mixtures. The methods described herein may equally be applied to such aqueous emulsions and suspensions.

A particularly preferred embodiment of the aggregation method according to the invention is the aggregation and separation of organic compounds contained in aqueous emulsions which originate from a nanoemulsive purification and / or refining process.

Again, the addition of copper or calcium ions and calcium oxide is aggregation-initiating, so that it comes after the addition of a small amount of the substances of the invention, which must be determined for the particular application, to an aggregation initiation, which causes a complete aggregation of the dissolved organic compounds and obtaining a clear water phase which further contains the guanidine or amidine group bearing compounds dissolved therein. The aggregates contain very different proportions of organic compound classes according to the different origin or the range of application of the aqueous nanoemulsions. For example, a high proportion of proteins was found in emulsions obtained in the aqueous extraction of press residues from plant seeds, as well as lipoproteins, glycolipids, carbohydrates, lignins and phenols. On the other hand, in the nanoemulsive purification of sewage sludge residues by the aggregation initiation according to the invention organic compounds were separated, such. As phospholipids and proteins and amino acids.

Therefore, the method is also directed to the recovery of organic compounds obtained by a nanoemulsive purification or decomplexing or a nanoemulsive refining process with an aqueous solution containing a guanidine and / or amidino group-bearing compound or a Nanoemulsion, consist of an aqueous solution containing a guanidine and / or Amidinruppentragenden compound and one or more carboxylic acids are dissolved. Preference is given to the recovery and use of carboxylic acids, phospholipids, glycolipids, glyceroglycolipids, glycerolphingolipids, chlorophylls, carotenoids, squalene, phenols, sinapines, peptides, proteins, carbohydrates, liporoteins, flavorings, waxes and / or fatty alcohols obtained from a nanoemulsive cleaning and / or or refining process.

A particularly preferred embodiment of the aggregation initiation according to the invention is directed to the aggregation and separation of organic compounds obtained from a digestion and / or purification process by means of nanoemulsions consisting of an aqueous solution containing dissolved guanidine or amidine group-bearing compounds and one or more carboxylic acids and in an aqueous emulsion.

methods

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

In one embodiment of the present invention, prior to refining a lipid phase with a solution containing guanidine and / or amidine group bearing compounds, pre-cleaning the lipid phase is performed by admixing 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 1 1, 5 and 13.0, and after mixing with the lipid phase, a pre-purified lipid phase is obtained by preferably centrifugal phase separation. In another embodiment, the pre-purification aqueous solution contains a base which is preferably selected from sodium hydroxide, potassium hydroxide, ammonium hydroxide, sodium carbonate, sodium hydrogencarbonate, sodium bicarbonate, potassium carbonate and potassium bicarbonate, sodium metasilicate, sodium borate.

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

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

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

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

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

Aqueous emulsions for the initiation of aggregation according to the invention according to process step a)

For the aggregation of organic compounds according to the invention, the preparation of an aqueous phase containing one or more guanidine- and / or amidine-containing compounds (also referred to herein as amidine compounds) constitutes an essential component. The aqueous phases according to the invention with organic compounds contained herein can in principle be used in all Purification or refining of lipid phases are obtained. The volume and quantity ratios between the organic compounds dissolved therein and the water phase or the guanidine- and / or amidine-group-containing compounds dissolved therein naturally vary by application Application. The same applies to the concentrations of the guanidine and / or Amidinruppentragenden compounds. However, the following ranges may be taken as preferred embodiments, particularly in the refining of oils and fats.

The preferably used concentration of guanidine- or amidine-containing compounds (also referred to herein as amindine and guanidine compounds) dissolved in a preferably ion-poor or ion-free water is, in one embodiment, determined by the detectable acid number of a lipid phase to be refined, e.g. B. determined by a methanolic titration with KOH determined. The derivable from this number of carboxylic acid groups is used to calculate the amount by weight of the guanidine or amidine-carrying compounds. In this case, an at least equal or higher number of guanidine or amidine groups, which are present in free and ionizable form, must preferably be present. The molar ratio that can be determined between the guanidine or amidine groups and the total of the free or releasable carboxyl groups of organic compounds or carboxylic acids must be> 1: 1. Preferably, a molar ratio between the determinable carboxylic acids (in particular the acid number) and the guanidine group-containing compounds (also called guanidine compounds herein) or amidino-containing compounds (also referred to herein as amidinedin compounds) should be 1: 3, more preferably 1: 2.2 and most preferably 1: 1, 3 in an ion-free water. The molarity of the solution according to the invention with the guanidine- or amidine-group-containing compounds dissolved therein may preferably be between 0.001 and 0.8 molar, more preferably between 0.05 and 0.7 molar, more preferably between 0.1 and 0.65 molar and on most preferably between 0.4 and 0.6 molar. Since the interaction of the guanidine or amidine groups is ensured even at ambient temperatures, the preferred temperature at which the inventive entry of the aqueous solutions (containing dissolved guanidine or amidine group-bearing compounds) can take place is between 10 and 50 ° C., more preferably between 28 and 40 ° C, and most preferably between 25 and 35 ° C. In this case, the volume ratio between the lipid phase and the aqueous phase according to the invention is in principle irrelevant due to the intensive introduction of the aqueous solutions according to the invention with guanidine- or amidine-group-containing compounds. However, in order to obtain the particularly advantageous resource-saving effects of the process, the volume of the water phase should be reduced to the required minimum. In one embodiment, therefore, the quantity ratio (v / v) of the aqueous solution is too the lipid phase from 10% to 0.055%, preferably, from 5% to 0.08%, more preferably from 3% to 0.1%.

The volume and concentration ratio may need to be adjusted, especially if there are also emulsion-forming compounds in lipid phases, such as. As glycolipids, which can be liberated by an aqueous solution with guanidine or amidino-containing compounds and thus the guanidine or amidino-containing compounds are not available for the separation of carboxylic acids available. Therefore, in one embodiment, it may be necessary to choose a greater volume and / or concentration ratio of aqueous solutions containing guanidine or amidine group-bearing compounds to that of the lipid phases to be refined.

In a further advantageous embodiment, the mixture of the lipid phase is carried out with the aqueous solution containing guanidine and / or amidino-containing compounds, with an intensive mixing entry. This causes a nanoemulsive MiscI cleaning process. Suitable for this are those mixing systems that allow a high interaction rate of the two phases. Preference is given here to systems which are also used for the homogenization of liquids. The intensive mixing takes place at atmospheric pressure and a temperature in the range of 10 ° C to 90 ° C, preferably 15 ° C to 70 ° C, more preferably 20 ° C to 60 ° C and most preferably 25 ° C to 50 ° C instead. Therefore, the thorough mixing and preferably intensive mixing at low temperatures of preferably below 70 ° C, more preferably below 65 ° C, more preferably below 60 ° C, more preferably below 55 ° C, even more preferably below 50 ° C. , even more preferably below 45 ° C. The low temperatures during mixing as well as in the subsequent separation, for example by centrifugation and the subsequent work-up ensure that no hydrolysis of organic compounds takes place.

Thus, the present invention is also directed to a process for the hydrolysis-free or at least low-hydrolysis separation of phospholipids, glycolipids, glyceroglycolipids, vitamins and other readily hydrolyzable organic compounds from lipoid phases. The phase separation to obtain the aqueous emulsion of process step a) is preferably carried out by a centrifugal separation technique from the prior art. Preference is given to a phase separation through a separator, further preferred throughput volumes of more than 3m ³ / h, more preferably> 100m ³ / h and most preferably> 400m ³ / h. The separation of the lipid phases can in principle immediately after completion of a mixture or an intensive mixing entry. On the other hand, if required by the process, the emulsified or nanoemulsified reaction 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 nanoemulsive reaction solution and the process conditions. Preferably, the phase separation is immediately following a mixture or intensive mixture. The temperature of the emulsified or nano-emulsified reaction mixture to be separated may in principle correspond to that chosen for the preparation thereof. However, it may also be advantageous to vary the temperature and to choose a higher temperature when z. B. thereby the effect of the separation tool is increased, or a lower, z. B. if this increases the extraction efficiency, especially in a nanoemulsion. In general, a temperature range between 15 and 50 ° C is preferred, more preferably from 18 to 40 ° C, and most preferably between 25 and 35 ° C. The residence time in a separating separator or a centrifuge depends essentially on the apparatus-specific properties. In general, the lowest possible residence time in a separation apparatus is preferred for economic implementation, such a preferred residence time is <10 minutes, more preferably <5 minutes and most preferably <2 minutes for a separation separator. For centrifuges, a preferred residence time is <15 minutes, more preferably <10 minutes, and most preferably <8 minutes. The selection of the centrifugal acceleration depends on the density difference of the two phases to be separated and is to be determined individually. Preferably, acceleration forces are between 1,000 and 15,000 grams, more preferably between 2,000 and 12,000 grams, and most preferably between 3,000 and 10,000 grams.

Preferred is a separation into an oil and a water phase in which an oil and a water phase are obtained, which is> 90% by volume, more preferably> 97% by volume and most preferably> 99% by volume, as pure oil - or water phase is present.

A process for obtaining an aqueous emulsion according to process step a) thus comprises, on the one hand, the immediate refining of lipid phases with a solution containing guanidine and / or amidino group-containing compounds and, on the other hand, the refining of lipid phases which have been precleaned with an acid or alkali-based step and Combinations thereof are made.

Preparation of nanoemulsions and dosages for nanoemulsive cleaning / refining Nanoemulsions which enable nanoemulsive refining of lipid phases or purification or decomplexation of organic substance complexes consist of a guanidine or amidine group bearing compound completely dissolved in a preferably ion-poor or ion-free water as described herein. Nanoemulsification is with a liquid or liquified form of a carboxylic acid as disclosed herein. In this case, the molar ratio between the solubilizing guanidine or amidine group-bearing compound and one or the entirety of carboxylic acids to be solubilized can be between 1: 1 and 1: 0.0001. Preferably, a molar ratio is between 1: 0.9 and 1: 0.001, more preferably between 1: 0.85 and 1: 0.01, and most preferably between 1: 0.7 and 1: 0.1. The decisive factor is the solubility of the two compounds. Because of the variety of possible combinations, it may therefore be necessary to choose a lower concentration of the carboxylic acid to ensure the preservation of a nanoemulsion as defined herein. A nanoemulsion exists when a clear liquid is obtained which remains thermodynamically stable for months. Physically, such a nanoemulsion is characterized by droplet sizes or particle sizes which are less than 100 nm, preferably less than 50 nm, particularly preferably less than 10 nm and in particular less than 3 nm. This can be documented by means of a dynamic laser steel spectroscopy (dynamic light scattering). The hydrodynamic diameters of the particles are measured. These also refer to the above information on the sizes.

Nanoemulsions can be prepared with carboxylic acids by being stirred into an aqueous solution containing therein already completely dissolved guanidine or amidine group-bearing compounds. The initially resulting increase in viscosity, and any solid formation that may occur, can be completely reversed by heating the solution, continuing the addition of the stirring for up to 24 hours.

The concentration of the guanidine- or amidine-containing compounds and the aqueous nanoemulsion can be chosen freely depending on the application, as long as the solubility product is not exceeded. For arginine z. B. this is at about 0.6 molar concentration.

The concentration of the carboxylic acid (s) or a carboxylic acid mixture to be dissolved then depends on the solubility of the guanidine- or amidine-group-containing compounds used for the solution. Even if the concentration is determined essentially by the process conditions, as well as by the individual solubility of guanidine or amidino groups Compounds is determined, preferably a concentration range between 0.001 to 0.8 molar, more preferably selected between 0.01 and 0.6 molar, and most preferably between 0.1 and 0.5 molar. The application of the nanoemulsions according to the invention can be carried out manually or automatically. This takes place in the form of the aqueous form described dropwise or in the form of a jet or in the form of an agitating or turbulent directly in the form of an entry with a homogenizer. Depending on the application, the nanoemulsions can be added in any desired ratio to the lipid phase to be refined or to an organic substance mixture to be purified or decompressed. Thus, an amount ratio of a nanoemulsion to the lipid phase or an organic substance mixture of 0.5: 1 to 100: 1 can be used in principle. More preferred, however, is a ratio between 0.6: 1 and 10: 1 and more preferably a ratio between 0.8: 1 and 5: 1. However, for economical use, low dosages are preferred ranging from 0.49: 1 to 0.0001: 1, more preferably between 0.2: 1 and 0.001: 1, and most preferably between 0.1: 1 and 0.01: 1.

However, the carboxylic acids present in the lipid phase can just as well be used to prepare the nanoemulsions according to the invention. Complete nanoemulsification of all carboxylic acids present in dissolved or soluble form in the lipid phase is a particularly preferred embodiment for the preparation of a nanoemulsive refining process. The aforementioned concentrations, volume and volume ratios are applicable in an identical manner. It is preferred to first determine the concentration of the present in the lipid phase and quantifiable carboxylic acids in order to adjust the parameters for the desired nanoemulsion can. Such a determination can be determined by established methods such as acid number determination or gas chromatography. If the concentration is not known, the aqueous solution containing the guanidine- or amidine-group-containing compound dissolved therein may be added to the lipid phase by the techniques described above until a liquid lipid phase is formed. By liquid lipid phase herein is meant, when the viscosity of the resulting reaction mixture is preferably 1 to 2x10 ⁴ mPa s, more preferably between 1.2 to 1 x 10 ⁴ mPa s, and most preferably between 1.3 to 5 x 10 ³ mPa s is. For the production it may be necessary to increase the temperature of the water phase with the guanidine or amidine group-carrying compound therein and / or the temperature of the dissolved or dissolved carboxylic acid. As a result, the production of nanoemulsion can be significantly accelerated, in addition, the viscosity of the resulting nanoemulsion decreases. If the nanoemulsion is prepared only by the intensive entry into the lipid phase, it may be necessary to heat the lipid phase as well. For the preparation of such nanoemulsions, a temperature range of 15 to 60 ° C is preferred, more preferred is a range between 20 and 50 ° C, and most preferably between 25 and 40 ° C.

Another important adjustment parameter is the viscosity of separately prepared nanoemulsions, ie, an aqueous solution containing guanidine or amidine group bearing compounds as disclosed herein with nano-emulsified carboxylic acids added to this solution for nanoemulsification, or nanoemulsion prepared by the intensive input of the nanoemulsions aqueous solution containing guanidine or amidine group-bearing compounds, in a lipid phase. In principle, it can be stated that, when an equimolar ratio between the number of acid groups and guanidine and / or amidine groups is reached, depending on the absolute concentration, an increase in viscosity increasingly occurs. The resulting viscosity is to be determined specifically for the particular components used. For nanoemulsive refining, it is advantageous if the resulting nanoemulsion or emulsion is liquid, that is, slightly flowing. This property can be determined by suitable methods, such as a ball viscometer. The preferred viscosity values are between 1 and 5 × 10 ³ mPa s, more preferably between 1 and 1 × 10 ³ mPa s, and most preferably between 1 and 10 × 10 ² mPa s.

If the lipid phase already has a higher viscosity, the viscosity of the nanoemulsive reaction mixture to be generated can be adjusted by an aqueous solution containing a larger volume of the solubilizing guanidine or amidine group-containing compounds or a lower concentration of the guanidine or amidine group-containing compounds contained herein.

Preferred compounds for preparing the nanoemulsions of the invention are arginine and arginine derivatives in the guanidine or amidine group-bearing compounds, as described herein. For the carboxylic acids, oleic acid and stearic acid are the preferred nano-emulsifiable carboxylic acids in the lipid phase. In artificially prepared nanoemulsions, preferred carboxylic acids are those for a nanoemulsive refining, phytic acid and sinapinic acid.

The solutions or nanoemulsions which can be used for refining or decomplexation may contain, in addition to guanidine- or amidine-group-bearing compounds, also further compounds which bring about an improvement in the refining or decomplexing properties of the solutions or nanoemulsions. These are preferably non-ionic but also ionic surfactants or, to a certain extent, alcohols or solvents which can be mixed with the cleaning-decomplexing solutions.

The emulsion to be provided for process step a) thus represents a water-based phase in which one or a plurality of organic compounds in any composition or concentration are present in dissolved or suspended form, the solution for solubilizing the organic compounds containing a base image Preferably, the base image is a guanidine and / or amidine group bearing compound in a dissolved form. The aqueous solution may be in the form of a nanoemulsion, microemulsion and / or macroemulsion. It can come from a refining process of lipid phases or purification or decomplexing processes. The aqueous phase should still be flowable or a flowability to produce.

Process for process control and monitoring

The inventive aggregation of organic compounds in aqueous emulsions and nanoemulsions containing guanidine and / or amidine group-bearing compounds and carboxylic acids can be monitored and controlled by various methods.

As a preferred embodiment, for process control and process control, the color reaction and color intensity can be used with addition of copper-containing compounds.

In this case, a specific value of an absorption spectrum of a light beam can be used to detect a concentration of the copper ions in the reaction mixture, whereby the dosage of the copper ion-containing solution can be controlled by a control technique until a predefined color scale value is reached. Since the color spectrum of a solution with copper compound is also pH-dependent, it is necessary to codetermine this value and if necessary to include it as a correction factor in the control technology. Since the temperature can also influence the color spectrum, a temperature measurement should be carried out at the same time possibly also used to correct the regulation. In this case, both the wavelength of a transmitted or emitted light, as well as its intensity or attenuation can be used as a control. The applicability of the modalities depends on the respective applications. For complex mixtures with a high concentration of organic compounds often a transmission of a light beam is not possible, so here, if necessary, a dilution must be made, including a sample taken from the reaction mixture and separately (externally) to the present concentration of copper ion concentration, the degree of turbidity or the color spectrum can be examined. At low concentrations and less complex mixtures of organic compounds, a transmission of a light beam is possible with a small layer thickness of the liquid volume, so that a device for continuous spectral analysis can be used to determine the color spectrum. At higher turbidity, it is advantageous to perform a spectral analysis of the adsorption in the wavelength range of visible light and in the infrared range. This makes it possible to correct a reduced or altered color intensity caused by a corpuscular haze (turbidity complex station). Both techniques can be done in continuous operation under real-time conditions. For this purpose, a corresponding measuring unit can be introduced into the mixing reactor, which is immersed in the reaction liquid with a measuring cell. On the other hand, it is conceivable to set up a measuring window in a region of the mixing reactor which is filled with the reaction mixture, which makes possible the possibility of light beam transmission or emission. pH-metry

The color reaction also depends on the pH present. In that regard, the continuous monitoring of the pH also serves to control the metering device for the addition of a copper ion-containing aqueous medium. On the other hand, pH monitoring is an important tool for optimized addition of calcium oxide compounds as well as

Alkaline earth metal oxides and metal oxides.

viscometry

The aggregation leads to characteristic progressions of the viscosity of the reaction liquids. After a certain latency, there is a sudden increase in the viscosity to the maximum, after which the viscosity drops abruptly. Reaction fluids which were centrifuged after onset of the drop in viscosity had a clear supernatant. In these cases had one further addition of copper ion or calcium oxide has no effect on the further course of aggregation. Therefore, methods for determining the viscosity, which preferably takes place in the reaction mixture, are suitable for optimizing the process control or for determining the required minimum amount of copper ions or calcium oxide compounds and other cations according to the invention for initiating aggregation. However, the measurement is also applicable to aggregation initiation by oxide compounds.

The determination can be made with suitable viscometers from the prior art. Particularly suitable are so-called process viscometers, which can also be used for continuous process monitoring and control. Rotational, vibratory or quartz viscometers are suitable here.

Determination of calcium ion concentrations

The addition of calcium to an aqueous emulsion initially leads only to a slow increase in the calcium ion concentration. When aggregation initiation is achieved, the ion concentration increases rapidly. The calcium ion concentration can be determined continuously with ion-selective single-rod measuring sensors (for example: CA60, Sl-Analytics, Germany). The method is therefore suitable for process monitoring and control.

The aforementioned measuring methods are suitable for controlling the metering of aggregating agents. Individual readings or a plurality of readings that allow prediction of sufficient dosage of the aggregating agents can be determined in a study to the minimum dose required. The parameter measurements found can be used for prior art control techniques for automatic metering of aggregating agents.

A preferred embodiment is to carry out a study to find a minimum dose of aggregating agents for optimally adjusting an automated dosing technique of the aggregation method of the invention

Preference is given to the use of an automated control and metering technique for aggregating agents for process economization.

Mix

The ionic copper compounds are metered in dissolved form in an otherwise preferably ion-poor or ion-free aqueous medium. This is preferably done in the form of a small volume addition, continuous or discontinuously (eg in drop form). The discontinuous addition in small portions is preferred, since it can be determined only after successful mixing entry on the basis of the measurement results, whether the amount added sufficient and thus overdose can be avoided.

In a further process according to the invention, in step b), a discontinuous addition of the aqueous solution containing copper (II) ions and / or calcium ions to the aqueous emulsion takes place. The entry is preferably made by a stirring mixer, which does not exert high shear forces on the liquid, since an initiated aggregation promotes further aggregation and comminution of the already formed aggregates unnecessarily increases the consumption of copper and other cations and oxide compounds. Therefore, a preferred embodiment is the use of a laminar stirrer. Examples of this are spiral or fork mixers in an application with a low rotational speed.

The invention relates to a method wherein a laminar stirrer is used for mixing in step b).

The mixture can be continuous or discontinuous and depends on the process conditions.

Aggregierungssubstanzen

The terms aggregation substances, aggregating agents or aggregation-initiating compounds are used synonymously herein. Preferred compounds for carrying out the aggregation of organic compounds according to the invention, which are dissolved in aqueous emulsions or nanoemulsions with the guanidine- and / or amidine-containing compounds and carboxylic acids, are water-soluble compounds of copper. Further preferred are magnesium, iron, zinc and aluminum ions. Preferred are chloride salts, but also salts with carboxylic acids, such as carbonates, acetates, tartar, oxalates. The latter are preferred if the smallest possible amount of the counterions should remain in the process water, since the carboxylic acids remain with increasing carbon chain length in the organic aggregation phase and are thus removed from the process water. But as counterions are also suitable: sulfate, sulfide, nitrate, phosphate, hydroxide, fluoride, selenide, telluride, arsenide, bromide, borate, oxalate, citrate, ascorbate. The use of sulfate or citrate is a preferred embodiment. The application is preferably carried out in completely dissociated form of the compounds in one preferably ion-poor or ion-free water. The concentration is to be adapted to the substance amount of the organic compounds to be aggregated as well as the viscosity of the nanoemulsion. In principle, very dilute or highly concentrated solutions can be used. Preferably, the use of a concentration is between 0.001 and 3 molar, more preferably between 0.01 and 2 molar, and most preferably between 0.1 and 1 molar. In the case of highly concentrated solutions of copper salts, but also of the other salts according to the invention, the pH of the solution may be between 3 and 8, preferably solutions having a pH of between 5 and 7 and more preferably between 6 and 7. In one In another embodiment, a suitable buffer can be added to achieve a pH of the cation-containing solution, as well as the other solutions according to the invention.

The required amount of cations must be determined for each reaction mixture, preferably this is done with the assay described herein to the required minimum dose. Preferably, the amount or mass of cations required to initiate aggregation is <5% by weight, more preferably <3% by weight, and most preferably <1% by weight, based on the weight of the organic compounds to be separated. The volume of the aqueous solution containing the aggregation-initiating cations is arbitrary. Preferably, a volume ratio of the aqueous solution to the aqueous emulsion of <8% by volume, more preferably <5% by volume, and most preferably <2% by volume. It is also possible to use combinations of the salts.

In addition, undissolved oxide compounds are suitable for initiating aggregation. Oxides of calcium, magnesium and zinc are preferred for this purpose. Preferred of these is calcium oxide. The oxides are stirred in powdered or microcrystalline form into the emulsion having the claimed guanidine and / or amidine group bearing compounds and carboxylic acids and dissolved organic compounds. But according to the invention is also the use of an aqueous suspension of oxide compounds. This can be advantageous in the case of large volume entries since the already dispersed oxides can be better mixed into the emulsions or nanoemulsions. Also in the case of the oxide compounds, there is a progressing aggregation process in which a continuous or discontinuous addition is possible. The progress of the aggregation can be monitored by changing the turbidity, or the formation of larger aggregates with the formation of a free water phase, as well as a pH change and thus control the further dosage. It is very advantageous initially stir the oxide powder quickly and then only to provide intermittently for a slight circulation of the reaction mixture. The required amount of oxide compounds must be determined for each reaction mixture become. Addition amounts of <15% by weight, more preferably <10% by weight, and most preferably <8% by weight, based on the weight of the organic compounds to be separated, are preferred. It is also possible to use combinations of the oxide compounds

According to the invention, the combination of aggregating agents is also selected from one or more of the cationic compounds which are in dissolved form and / or one or more oxide compounds which are in powdered or suspended form and which are added to the reaction mixture in any order, combination and proportions.

Separation of aggregated organic compounds in process step c) The aggregation initiation, which is caused by the substances and processes according to the invention, ends after their complete completion in large sedimenting aggregates and a clear water phase. For the purpose of condensing the aggregates can be easily separated with a decanter, the free water phase. Alternatively, the entire contents of the reaction vessel can also be completely separated into a solid and a water phase by a sieve from the aggregates and possibly still existing suspended matter. In the aggregation initiation by calcium oxide compounds or other oxide compounds usually a little more water remains in the solid phase, so it may be useful to rinse the solid phase with a sufficient amount of preferably ion-poor or ion-free water phase to wash out included guanidine and / or amidino-containing compounds herein. If no damage to the aggregated organic compounds thereby occurs, the rinsing liquid may also be mixed with an acid or a weak liquor. Subsequently, the solid phases could be further freed by pressing or by centrifugal separation of water fractions. If necessary, a drying by a moderate increase in temperature, a warm air flow or a vacuum drying can be carried out under normal temperatures. Since the storage stability is significantly improved by the removal of the water in most applications and also a subsequent fractionation of the organic compounds can be made easier, the drying of the solid phase to a residual water content of <5% is a preferred embodiment of the process technology. If decomposition-hazardous organic compounds are to be separated from an aqueous emulsion, it is advantageous to carry out a separation of the organic aggregate phase under cooled conditions. Cooled means a temperature of 1 - 18 ° C. In a preferred embodiment, the aggregation initiation and separation of the aggregate phase occurred at a temperature of 1-18 ° C.

If neutral fats are to be separated from an aqueous emulsion, it is advantageous to carry out a heating of the reaction mixture and to maintain the temperature increase during the separation process. Temperature increase means a temperature between 45 and 101 ° C. The neutral fats separate from the aggregating organic compounds and become visible on the water phase. As a result, they can also be separated on a large scale using known techniques.

In a further preferred embodiment, the aggregation initiation and separation of the aggregate phase took place at a temperature between 45 and 101 ° C. If an aggregation according to the invention is successfully completed, the water phase of the former aqueous emulsion is optically clear and contains virtually no suspended matter. It could be shown that the visual impression of a clear water phase, can be objectified by a turbidimetric measurement and no corpuscular compounds are present in the clarified water phase, which lead to a light scattering (FTU values <10). It has been found that by lowering the pH to <1, 0 virtually all organic compounds are coagulated. Therefore, an acid addition (acid sample) to reach a pH <1, 0 is a very simple method for testing an effective depletion of organic compounds from the aqueous emulsion. A negative acid sample means that no or only minimal amounts ( <0.5% by weight of the water phase) on organic solids. It could be shown that, after a successful aggregation of the organic compounds, by addition of acid into the clarified water phase can no longer be separated solids. Practically, in large process runs, a small sample (e.g., 10 ml) can be removed from the mixed reaction mixture and centrifuged (e.g., 3000 g for 10 minutes). If, on the one hand, a clear water phase and, on the other hand, a compact solid phase (if organic compounds have been present in the reaction solution) are obtained, the acid sample is subjected to the separated water phase.

The phase separation that occurs after sufficient aggregation formation (acid sample negative) can be carried out using the prior art separation methods listed herein.

Preference is given to testing for sufficient or complete aggregation of the organic compounds present in the reaction solution through an acid sample before carrying out process step c). Process for the decomplexation, digestion and fractionation of aggregated organic compounds

Since the composition of the aggregated organic compounds may vary from application to application, the selection of the organic and / or aqueous (basic or acidic) solvents to be used for digestion or decomplexation and the order of application for each organic compound mixture must be determined individually. The use of chloroform has been found to be the preferred solvent of the aggregate phase of organic compounds, which can dissolve or suspend most of the organic compounds present in this phase. By the addition of a polar solvent, such as. As methanol, can be polar compounds such. As phospholipids, then easily extract and separate by phase separation. The addition of a small amount of acid, such as. As HCl, and / or water can increase the separation efficiency. Alternatively, the aggregated mass may also be first suspended in a highly nonpolar solvent such as hexane or dimethyl ether and then a separation of dyes, e.g. with a medium-chain alcohol, i. Monools or diols having 2 to 6 carbon atoms, such as. B. 1 -propanol, 1-Buatol, 1, 2-butanediol, 1, 3-butanediol, 1, 4-butanediol, 1-pentanol, 1, 2-pentanediol, 1, 3-pentanediol, 1, 4-pentanediol, 1, 5-pentanediol done. The fractionation of the solvent phases is carried out by means of continuous or discontinuous processes, such as centrifugation, perseveration or distillation. The organic compounds present in the individual solvent phases can be separated off by conventional techniques, such as chromatographic adsorption or evaporation of the solvent, as solid for direct use or for further purification.

separation processes

The term "centrifugal phase separation" as used herein refers to a separation of phases utilizing centrifugal acceleration. In particular, it comprises processes such as centrifugation and preferably apparatuses suitable for this purpose, such as decanters and separators, which are known to the person skilled in the art.

Emulsions resulting from lipid phases in the refining process with aqueous solutions containing guanidine and / or amidine group-bearing compounds must be separated into a lipid phase and an aqueous emulsion phase by the described centrifugal phase separation methods. Preference is given to separators which allow a continuous separation. Separators are systems in which by the same or non-uniform plates or plates corresponding tensile forces are set up next to a simultaneously occurring pressure build-up. Therefore, a particularly preferred embodiment for the phase separation of the aqueous emulsions (containing guanidine and / or amidino-containing compounds) from the lipid phases is to carry out the phase separation with a separating separator. Under certain circumstances, it may be necessary to remove any remaining suspended matter in the clarified water phase by passing the clarified water phase through a sieve or a filter.

The aggregated organic compounds can by sedimentation or by a filtration z. B. by sieves or filters or centrifugal accelerators such as separators or decanters are separated from the prior art. In the filters, the sieve size depends on the size of the aggregates to be separated, generally nominal pore sizes of <100 μιτι more preferably <50μηη and most preferably <20μηη suitable for complete separation of the solids and suspended solids of the organic compounds. For centrifugal phase separation, 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 preferably between 20 and 45 ° C, and most preferably between 25 and 35 ° C.

Purification of the clarified water phases

The clarified water phases obtained after separation of the aggregated organic compounds further do not contain complexation-spent cations and anions added for aggregation initiation. Also, a solution of cations and the formation of hydroxide ions in uses of the oxide compounds of the invention are possible. The presence as well as the concentration of the corresponding ions or oxides can be determined by methods from the prior art (eg ICP). Oxides can be separated by use of suitable filter materials (eg membrane filters with a pore size of 0.04μηη). This is not the case with the ions. However, a separation can be carried out using established methods. For this electrophoresis or electrodialysis are suitable in which a deposition of the cations takes place at a cathode in elemental form, or the ions are passed through preferably ion-selective membranes in the electric field voltage and separated. Another possibility is adsorption of the ions by adsorbents, suitable for this purpose are, for. B. ion exchange resins. Another possibility is chemical binding of the ions. In particular, calcium and magnesium ions can be obtained by the addition of phosphoric acid aggregate into an insoluble complex that can be easily separated from the water phase using conventional filters. If this is done under pH control, removal of the cations can be accomplished without protonation of the contained guanidine and / or amidine group bearing compounds. Therefore, it is preferred to carry out the complexation of ions in the clarified water phase while continuously controlling the pH.

Definitions reaction mixture

By "reaction mixture" herein is meant an aqueous emulsion or nanoemulsion consisting of a guanidine and / or amidine group bearing compound as well as dissolved organic compounds together with cations and / or oxide compounds which are suitable for initiating aggregation according to the invention.

lipid phase

As the lipid phase herein all lipophilic organic carbon compounds of biological origin are summarized. The term as used herein includes in particular mixtures of biological origin, which can therefore be obtained from plants, algae, animals and / or microorganisms and which have a water content of <10% and a content of lipophilic substances comprising monoacylglycerides, diacylglycerides and / or triacylglycerides of in total> 70% by weight or> 75% by weight or> 80% by weight or> 85% by weight or> 90% by weight or> 95% by weight. For example, the lipid phases may be extracts of oleaginous plants and microorganisms, such as seeds or germs of oilseed rape, sunflower, soy, camelina, jatropha, palms, 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 phases are extracts or extraction phases of lipoid substances from a previous separation or extraction, the lipid phase may also consist of a proportion of> 50% of organic solvents or hydrocarbon compounds.

Preferred lipid phases are vegetable oils, in particular pressing and extraction oils of oil plant seeds. However, animal fats are also preferred. But also included are non-polar aliphatic or cyclic hydrocarbon compounds. These lipid phases are characterized in that> 95% of the compounds are apolar. Acid oil, Acrocomia oil, almond oil, Babassu oil, currant seed oil, borage seed oil, rapeseed oil, cashew oil, castor oil, coconut oil, coriander oil, corn oil, cottonseed oil, Kramben oil, linseed oil, grapeseed oil, among others, include the lipid phases as used herein , Hazelnut oil, other nut oils, hemp seed oil, jatropha oil, jojoba oil, macadamia nut oil, mango seed oil, meadowfoam seed oil, mustard oil, footworm oil, olive oil, palm oil, palm kernel oil, palnnolein oil, peanut oil, pecan oil, pine nut oil, pistachio oil, poppy seed oil, rice germ oil, Thistle oil, camellia oil, sesame oil, shea butter oil, soybean oil, sunflower oil, tall oil, tsubaki oil, walnut oil, varieties of "natural" oils with altered fatty acid compositions via genetically modified organisms (GMO) or traditional varieties, Neochloroisoleoabundans oil, Scenedesmusdimorphus oil, Euglenagracilis oil, Phaeodactylumtricornutum oil, Pleurochrysiscarterae oil, Prymnesiumparvum oil, Tetraselmischui oil, Te traselmissuecica oil, Isochrysisgalbana oil, Nannochloropsissalina oil, Botryococcus brown oil, Dunaliellatertiolecta oil, Nannochloris oil, Spirulina oil, Chlorophyceae oil, Bacilliarophyta oil, a mixture of the foregoing oils and animal oils (especially marine oils), algae oils, oils from bran production e.g. Rice bran oil and biodiesel. Cleaning-decomplexing method with aqueous solutions or nanoemulsions

Solutions containing dissolved guanidine and / or amidine group bearing compounds as well as nanoemulsions as described herein can be used for the purification and decomplexation of organic and inorganic materials to dissolve, dissolve, hydrate or mobilize the organic compounds present or therein and into the water phase of a forming one To convert emulsion. This method is, among the many applications that arise from this inevitably, in particular as a cleaning method used for. B. in grease traps or filters, food production, plant and cell extracts or decomplexing used as z. B. in the digestion of plant products, such as press cake and residues, cell lysates, sewage sludge, sands and rocks. Refining a lipid phase

Refining of a lipid phase in the present invention means the purification of a lipid phase by means of aqueous extraction methods. This also includes the process described herein, wherein an aqueous solution containing guanidine and / or amidine group bearing compounds having a lipid phase is mixed and then carried out a phase separation. In particular, this also includes nanoemulsive refining of lipid phases.

Aqueous emulsion of process step a)

The term "aqueous emulsion" as used herein refers to water-based nanomicro or macroemulsions as described herein, but also includes suspensions of organic compounds These emulsions contain, in addition to the dissolved guanidine and / or amidine group-bearing compounds defined herein The concentrations of the guanidine- and / or amidine-group-bearing compounds and of one or more organic compounds can be up to exceeding the solubility limit in the aqueous emulsion The aqueous emulsions can be optically transparent or be in the form of a cloudy solution Viscosity may range from 0.5 mPas to 3000 mPas, the pH may be between 5 and 14. The aqueous emulsions may contain a buffer system, solvent or one or more co-surfactants Connections art be generated or a refining, cleaning or Dekomplexierungsprozess come from. Contained therein may be the organic compounds listed herein in dissolved or partially complexed form.

aggregation

In general, aggregation means an accumulation or accumulation of atoms or molecules and / or ions into a larger dressing, the aggregate. The accumulation or accumulation is effected by van der Waals forces, hydrogen bonding, and / or other chemical or physicochemical bonding modes.

Aggregated phase

The precipitate resulting from an aggregation, or the sediment which results from spontaneous phase separation or centrifugal separation, is referred to as the aggregated phase.

nanoemulsion

A nanoemulsion exists when a water-based solution containing a water-soluble surfactant and an amphiphilic or lipophilic compound acts as a clear liquid that remains thermodynamically stable for months. Physically, such a nanoemulsion is particularly preferred by droplet sizes or particle sizes less than 100 nm, preferably less than 50 nm less than 10 nm and especially less than 3 nm are characterized. This can be documented by means of a dynamic laser steel spectroscopy (dynamic light scattering). The hydrodynamic diameters of the particles are measured. These also refer to the above information on the sizes.

emulsion

The term "emulsion" as used herein refers to all forms of liquid mixtures which have a water phase and an oil or fat phase, the proportion of liquid phases being variable, a special case being nanoemulsions In order to make it clear that an emulsion is not a transparent nanoemulsion, for oil-in-water or water-in-oil emulsions, which have a clear to strong haze, the term "macroemulsion "synonymously related to the term emulsion. However, emulsions may also be formed by hydrophobic organic compounds that do not correspond to a lipid as defined herein which are in an aqueous solution containing guanidine and / or amidine group-bearing compounds in a dissolved state. There are transitions to suspensions in which organic compounds in the form of aggregates can also be present.

Free water phase

By free water phase it is meant herein an optically transparent volume of water, besides corpuscular suspended matter or aggregates to be recognized herein with sharp contours. The free water phases understood herein develop from an aqueous emulsion or suspension which has a cloudy appearance and is opaque at a layer thickness of 3 mm. The free water phase as understood herein is optically transparent to this distance. Objectively, the presence of a free water phase according to the invention z. Example by means of a determination of corpuscular portions in the water phase, for. B. by a laser beam reflection analysis (DLS). It can be seen here that the formation of a free water phase results in the removal of particles which are smaller than 1 μm. On the other hand, there are aggregates which are> 10 μιτι.

Clarified water phase

A clarified water phase or clarified process water phase is understood herein to mean the water phase which is obtained after an aggregation of organic compounds according to the invention and their separation into Process step c), which is carried out in an aqueous emulsion consisting of a dissolved guanidine and / or amidino-containing compound, with organic compounds dissolved therein. The term clarified stands for an optically clear solution in which there are no or only occasionally suspended matter. This can be quantified eg by a turbidity measurement, whereby a value of 10 FTU is not exceeded. The term clarified also includes a removal of dissolved organic compounds. This can be checked by an acid test by bringing the pH of the clarified water phase to <1.0, by adding an acid (eg HCL). Organic compounds are thereby coagulated and can be separated and quantified by centrifugal separation techniques or filtration. Another method of quantifying any organic compounds still present herein is HPLC and / or MS. Purified water phase

By a purified water phase is meant herein a clarified water phase or clarified process water phase as defined herein in which a depletion of the ions or oxides added for aggregation initiation has been achieved by> 95% by weight. This can be verified by elemental analysis (eg ICP) or atomic absorption spectroscopy.

Organic compounds

The term organic compounds includes all organic compounds of biogenic origin which can be dissolved by a refining, extraction or decomplexing process or a purification process with one of the processes described herein from biogenic or fossil materials and in an aqueous emulsion according to the invention containing dissolved guanidine and / or amidino-containing compounds. This includes nanoemulsions containing dissolved guanidine and / or amidine group bearing compounds. According to the different origins of these emulsions organic compounds of various groups of substances are found, which are present individually, but usually in different combinations and in a different ratio. In the following, therefore, only the essential groups of substances to which the organic compounds can be assigned, without being restricted to them, are listed: waxes, wax acids, lingins, hydroxy-, and mycolic acids, fatty acids with cyclic hydrocarbon structures, such as the shikimic acid or 2- hydroxy-1 1 -cycloheptylic acid, mannosteryl erythritol lipid, dyes such as carotenes and carotenoids, chlorophylls, and their degradation products Phenols, phytosterols, especially β-sitosterol and campesterol, as well as Sigmasterol, Sterols, Sinapine, Squalene. Phytoestrogens, such as isoflavones or lignans. Furthermore, steroids and their derivatives, such as saponins, furthermore glycolipids as well as glyceroglycolipids and glycerosphingolipids, furthermore rhamnolipids, sophrolipids, trehalose lipids, mannosterylerythritol lipids. Also polysaccharides, including pectins such as rhamnogalacturonans and polygalacturonic acid esters, arabinans (homoglycans), galactans and arabinogalactans, as well as pectic acids and amidopectins. Furthermore, phospholipids, in particular phosphotidylinositol, phosphatides, such as phosphoinositol, furthermore long-chain or cyclic carbon compounds, furthermore fatty alcohols, hydroxy and epoxy fatty acids. Likewise glycosides, lipo-proteins, lignins, phytate or phytic acid as well as glucoinosilates. Proteins, including albumins, globulins, oleosins, vitamins such as retinol, (vitamin A) and derivatives such. B. retinoic acid, riboflavin (vitamin B2), pantothenic acid vitamin B5), biotin (vitamin B7), folic acid (vitamin B9), cobalamins (vitamin B12), calcite ol (vitamin D) and derivatives, tocopherols (Vitanmin E) and tocotrienols, Phylloquinone (vitamin K) and menaquinone. Tannins, terpenoids, curcumanoids, xanthones. But also sugar compounds, amino acids, peptides, including polypeptides, but also carbohydrates, such as glucogen. The likewise associated carboxylic acids, flavorings, or odorants and flavorings, dyes, phospholipids and glycolipids, waxes or wax acids and fatty alcohols are further defined below.

carboxylic acids

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

In general, fatty acids are aliphatic carbon chains having a carboxylic acid group. The carbon atoms may be linked with single bonds (saturated fatty acids) or with double bond bridges (unsaturated fatty acids), these double bonds may be in an ice or trans configuration. As defined herein, as fatty acids, such compounds having more than 4 consecutive carbon atoms besides the carboxyl group are referred to as fatty acids. Examples of linear saturated fatty acids are nonanecarboxylic acid (capric acid), dodecanoic acid (lauric acid), tetradecanoic acid (myristic acid), hexadecanoic acid (palmitic acid), octadecanoic acid (Stearic acid), n-eicosanoic acid (arachidic acid) and n-docosanoic acid (behenic acid). Examples of monoolefin fatty acids are myristoleic acid, palmetoleic acid, petroselinic acid, oleic acid, elaidic acid, dicelic acid and the euruca acid. Examples of polyolefins fatty acids are linoleic acid, linolenic acid, punicic acid, arachidonic acid and nervonic acid.

Fatty acids may also carry functional groups such as. As the vernolic acid, ricinoleic acid and lactobacillic acid. The functional groups herein also include terminal carbon cyclic radicals.

Examples of the term "fatty acids" used herein are, for example, the following compounds: hexanoic, octanoic, decanoic, dodecanoic, Tetrad ecan acid, hexadecanoic, heptadecanoic, octadecanoic, eicosanoic, docosanic, tetracosanic, cis-9-tetradecenoic, cis-9 Hexadecenoic acid, cis-6-octadecenoic acid, cis-9-octadecenoic acid, cis-1-octadecenoic acid, cis-9-eicosenoic acid, cis-1-eicosenoic acid, cis-13-docosenoic acid, cis-15-tetracenoic acid, t9-octadecenoic acid , t1 1-octadecenoic acid, t3-hexadecenoic acid, 9,12-octadecadienoic acid, 6,9,12-octadecatrienoic acid, 8,1 1, 14-eicosatrienoic acid, 5,8,1,1,14-eicosatetraenoic acid, 7,10,13, 16-docosatetraenoic acid, 4,7,10,13,16-docosapentaenoic acid, 9,12,15-octadecatrienoic acid, 6,9,12,15-octadecatetraenoic acid, 8,1 1, 14,17-eicosatetraenoic acid, 5,8,1 1, 14,17-eicosapentaenoic acid, 7,10,13,16,19-

Docosapentaenoic acid, 4,7,10,13,16,19-docosahexaenoic acid, 5,8,1 1 -

Eicosatrienoic acid, 9c1 1t13t-eleostearic acid, 8t10t12c-calendulic acid, 9c1 1 t13c-catalpinic acid, 4,7,9,1,1,13,16,19-docosaheptadecanoic acid, taxoleinic acid, pinolenic acid, sciadonic acid, 6-octadecynoic acid, tl-octadecene-9 acid, 9-octadecanoic acid, 6-octadecene-9-enoic acid, t10-heptadecene-8-amino acid, 9-octadecene-12-acetic acid, t7, t1 1-octadecadiene-9-amino acid, t8, t10-octadecadiene-12- acid, 5,8,1 1, 14-eicosatetraic acid, retinoic acid, isopalmitic acid, pristanoic acid, phytanic acid, 1 1, 12-methylene-octadecanoic acid, 9,10-methylene-hexadecanoic acid, coronaric acid, (R, S) -lipoic acid, (S. ) -Liponic acid, (R) -lipoic acid, 6,8 (methylsulfanyl) -octanoic acid, 4,6-bis (methylsulfanyl) -hexanoic acid, 2,4-bis (methylsulfanyl) -butanoic acid, 1, 2-dithiolane-carboxylic acid, ( R, S) -6,8-dithiane-octanoic acid, (S) -6,8-dithiane-octanoic acid, tariric acid, santalbic acid, stearolic acid, 6,9-octadecenoic acid, pyrulic acid, crepeninic acid, heisteric acid, t8, t10-octadecadiene-12 acid, ETYA, cerebronic acid and hydroxynvonic acid, ricinoleic acid, lesquerolic acid, brassylic acid, and thapsic acid, phytic acid, sinapinic acid, cinnamic acid, trihydroxybenzoic acid, phosphatidic acid.

fatty alcohols In general, fatty alcohols are aliphatic carbon chains having a primary hydroxy group. The carbon atoms may be linked with single bonds (saturated fatty acids) or with double bond bridges (unsaturated fatty acids), these double bonds may be in an ice or trans configuration. As defined herein, as fatty acids, such compounds having more than 5 consecutive carbon atoms besides the hydroxy group are referred to as fatty alcohols. Examples of linear saturated fatty alcohols are 1-hexanol, 1-heptanol, 1-octanol, 1-nonanol, 1-decanol, 1-undecanol, 1-dodecanol, 1-tridecaol, tetradecanol, 1-pentadecaol, 1-hexadecanol, 1 - Heptadecanol, 1-octadecanol, 1-nonadecanol, 1-eicosanol, 1 -heicosanol, 1-docoanol, 1-tetracosanol, 1-octacosanol, 1-triaciaconaol, 1-triacontanol.

Examples of monoolefin fatty alcohols are cis-9-hexdecene-1-ol, cis-9-octadecene-1-ol, trans-9-octadecene-1-ol and cis-1 1-octadecene-1-ol. Examples of polyunsaturated fatty alcohols are all-cis-9,12-octadecenedien-1-ol, 5,8,1 1, 14-eicosatetraen-1-ol.

waxes

Waxes here are understood as meaning the monoesters (fatty acid esters) from a fatty acid or wax acid and a primary fatty alcohol or wax alcohol. Long chain carboxylic acids starting with 22 carbon atoms are also called wax acids. The transitions between the fatty acids and wax acids are fluid. The long-chain primary alcohols consisting of 22 carbon atoms and more are also called wax alcohols. Again, the transitions between the fatty alcohols and wax alcohols are fluid. The naturally occurring waxes often consist of mixtures. Naturally occurring wax is present as a mixture of fatty acids or wax acids, fatty alcohols or wax alcohols and a fatty acid ester.

Examples of vegetable waxes are candellia wax, carnauba wax, Japan wax, esparto wax, cork wax, guaruma wax,

Rice germ wax, sugarcane wax, ouricury wax and montan wax. Examples of animal waxes are beeswax, shellac wax, spermaceti, lanolin (wool wax) and raffia fat. Examples of petrochemical waxes are petrolatum, paraffin waxes and microwaxes.

Odors and flavors

The term olfactory and flavor is also synonymously used herein with flavoring. In almost all organic mixtures of biogenic origin organic compounds are present which lead to a sensory perception in the Meaning of a taste or an odor. There is an extremely large heterogeneity of the possible organic compounds. Only with the highly hydrophobic compounds found in the various lipid phases is the structural composition of these carbon-based compounds uneven. Some typical classes of compounds are alkaloids, alcohols, aldehydes, amino acids, aromatic hydrocarbons, esters, lactones, cyclic ethers, furans, furanoids, free fatty acids, flavonols, glycosides, ketones, saturated and unsaturated hydrocarbons, enamine ketones, ketopiperazines, isoprenoids, mono- Terpenes, terpenes, cyclic terpenes, triterpenes, triterpenoids, tetraterpenes, sesquiterpenes, sequiterpenoids, sterols, phytosterols, purine derivatives, phenylpropanoids, phenols and / or hydroxycinnamic acid derivatives. These classes of compounds can occur both individually and in any composition in a crude lipid phase derived from a biogenic raw material. These are, in particular, 1,5-octadien-3-ol, butanal, hexanal, octanal, nonenal, nonadineal, decanal, dodecanal, piperonal, cysteine, cystine, methionine, phenanthrene, anthracene, pyrene, benzpyrene, 4-hydroxybutyric acid, Ethylhexanoate, coumarin, maltol, diacetylfuran, pentylfuran, perillene, rosefuran, caprylic acid, capric acid, hydroxyfatty acids, amygdalin, progoitrin, 2-heptanone, 2-nonanone, decatrienal, 1-octen-3-one, vinylamyl ketone, 4- (4-hydroxyphenyl ) -butan-2-one), mycosporine, diketopiperazine, humulones and lupulones (bitters acids), mono-terpenes: myrcene, ocimene and cosme, linalool, myrcenol, ipsdienol, neral; Citronellol and geranial, citronellal, mycres, limonene, linalool, nerol, geraniol, terpinolene, terpinene and p-cymene, carvone and carvenone, thymol, dihydroxycarveol, 2-pinene, α- and β-pinene, limonene, phellandrene, menthan, camphor ; Fenchone, xanthophylline, bisabolane, germacrane, elemane and humulane, farnesene, rotundone, sterols, phytosterols p-cresol, guaiacol, ferulic acid, lignin, sinapine, catechins, eugenol, vanillin, 3-butenylisothiocyanate, 4-petenylisothocyanate, 4-pentenenitrile, 5 Hexenitrile, camphene, dodecane, cinnamyl alcohol, fenchyl alcohol, 1 R, 2S, 5R-isopulegol, 2-ethylfenchol, menthol, 4-hydroxy-3,5-dimethoxybenzyl alcohol, (R) - (-) - lavandulol,

Piperonyl alcohol, thujyl alcohol, 1,8-cineole, 4-ethyl guaiacol, N - [[(1R, 2S, 5R) -5-methyl-2- (1-methylethyl) cyclohexyl] carbonyl] -glycine ethyl ester, (1R, 2S , 5R) -N-cyclopropyl-5-methyl-2-isopropylcyclohexanecarboxamide, L-alanine, aspartic acid, 2,4-dimethylthiazole, lenthionine, (+) - cedrol, 3-methylphenol, anisole, 1-methoxy-4-propylbenzene, 4-allyl-2,6-dimethoxyphenol, 2,6-dimethoxy-4-vinylphenol, ethyl 4-hydroxy-3-methoxybenzyl ether, vetiverol, 2-butyl ethyl ether, ethylgeranyl ether, carvacrol, 2-methylpropanal, cinnamaldehyde, p-tolualdehyde, 2-methylbutyraldehyde, salicylaldehyde, acetic acid, lactic acid, 3-methylbutyric acid, hexanoic acid, malic acid and / or anethole. These compounds can be used individually as well as in one another any composition in a crude lipid phase derived from a biogenic raw material.

Guanidino and / or amidine bearing compounds

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

Amidino compounds which have at least one carboxylate group (-COOH) in addition to the amidino group. It is further preferred if the carboxylate group (s) are separated from the amidino group in the molecule by at least one carbon atom.

These guanidino compounds and amidino compounds preferably have a distribution coefficient K ₀ w between n-octanol and water of less than 6.3 (K ₀ w <6.3). Preferably, the K _{o is} w <1, 8 (log K ₀ w <0.26), more preferably <0.63 (log K ₀ w <-0.2), and most preferably <0.4 (log K ₀ w <-0.4).

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

The following are examples of preferred compounds having a guanidino group or an amidino group and a carboxylate group.

Guanidinoacetic acid creatine glycocyannin

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

wherein

R ', R ", R'" and R "" independently of one another are: -H, -OH, -CH = CH ₂ , -CH ₂ -CH = CH ₂ , -C (CH ₃ ) = CH ₂ , -CH = CH-CH ₃ , -C ₂ H ₄ -CH = CH ₂ , -CH ₃ , -C ₂ H ₅ , -C ₃ H ₇ , -CH (CH ₃ ) ₂ , -C ₄ H ₉ , -CH ₂ -CH (CH ₃ ) ₂ , -CH (CH ₃ ) -C ₂ H ₅ -C (CH ₃ ) ₃ , -C ₅ Hn, -CH (CH ₃ ) -C ₃ H ₇ , -CH ₂ -CH ( CH ₃ ) -C ₂ H ₅ , -CH (CH ₃ ) -CH (CH ₃ ) ₂ , -C (CH ₃ ) ₂ -C ₂ H ₅ , -CH ₂ -C (CH ₃ ) ₃ , -CH ( C ₂ H ₅ ) ₂ , -C ₂ H ₄ -CH (CH ₃ ) ₂ , -C ₆ Hi ₃ , -C ₇ Hi _5> cyclo-C ₃ H ₅ , cyclo-C ₄ H ₇ , cyclo-C ₅ H ₉ , cyclo-C ₆ Hn, -PO ₃ H ₂ , -PO ₃ H ^" , -PO ₃ ^2" , -NO ₂ , -C ^ CH, -C-CH ₃ , -CH ₂ -C ^ CH , -C ₂ H ₄ -C ^ CH, -ΟΗ ₂ -ΟΞΟ-ΟΗ ₃ , or R 'and R "together form one of the following groups: -CH ₂ -CH ₂ -, -CO-CH ₂ -, -CH ₂ -CO-, -CH = CH-, -CO-CH = CH-, -CH = CH-CO-, -CO-CH2-CH2-, -CH2-CH2-CO-, -CH2-CO-CH2- or -CH2-CH2-CH2-;

X is -NH-, -NR "" -, -O-, -S-, -CH ₂ -, -C ₂ H ₄ -, -C ₃ H ₆ -, -C ₄ H ₈ - or -C ₅ H ₁₀ - or represents a C1-C5 carbon chain which may be substituted with one or more of the following radicals: (-F, -Cl, -OH, _-OCH3, -OC2H5, -NH _2, -NHCH _3, -NH C ₂ H ₅ ), -N (CH ₃ ) ₂ , -N (C ₂ H ₅ ) ₂ , -SH, -NO ₂ , -PO ₃ H ₂ , -ΡΟ 3ΗΓ, -PO 3 ^{2 "} , -CH ₃ , -C ₂ H ₅ , -CH CHCH ₂ , -C 1 CH, -COOH, -COOCH 3, -COOC 2 H 5, -COCH 3, -COC 2 H 5, -O-COCH 3, -O-COCl 2 H 5, -CN, -CF ₃ , -C 2 F 5,

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

-NH _2, -OH, -PO3H2, -PO3H-, -PO3 ^{2 ",} -OPO3H2, ^-OPOsH", -OPO3 ^{2 ",} -COOH, ^-COO", -CO-NH2, -NH ₃ ^+, -NH -CO-NH ₂ , -N (CH ₃ ) ₃ ⁺ , -N (C ₂ H ₅ ) 3 ⁺ , -N (C ₃ H ₇ ) ₃ \ -NH (CH ₃ ) ₂ ⁺ , -NH (C ₂ H ₅ ) ²⁺ , -NH (C ₃ H ₇ ) ₂ ⁺ , -NHCH ₃ , -NHC ₂ H ₅ , -NHC ₃ H ₇ , -NH ₂ CH ₃ ⁺ , -NH ₂ C ₂ H ₅ ⁺ , -NH ₂ C ₃ H ₇ ⁺ , -SO ₃ H, -SO ₃ ^" , -SO ₂ NH ₂ , -CO-COOH, -,

Plant color pigments and dyes

The term "dyes" summarizes organic compounds which occur in oils and fats of biogenic origin, typically in different quantities and compositions side by side. The term "plant dyes" herein includes all coloring compounds present in lipid phases The most dominant and by far the largest quantity in vegetable oils is the group of chlorophylls and their degradation products such as pheophylline, chlorophyllide, pheophorbide, phyropheophytine, chlorin In addition, however, other compounds such as flavonoids, curcumins, anthrocyans, betaines, xanthophylls, which include carotenes and lutein, are also included , Indigo, kaempferol and xanthophylline, such as neoxanthine or zeaxanthin These dyes may be present in different proportions in the lipid phases These dyes have a different solubility in water or an organic solvent. The most common representatives of plant dyes are chlorophylls. In vegetable oils, chlorophylls are typically found in quantities ranging from 10 to 100 ppm (or 100 mg / kg). Representatives with a high content of chlorophylls are especially canola and rapeseed oils.

chlorophylls

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

phospholipids

By the term "phospholipids" as used herein are amphiphilic lipids containing a phosphate group and belonging to either the phosphoglycerides or the phosphosphingolipids. Furthermore, acid glycoglycerolipids such. B. sulfoquinovosyldiacylglycerol or sulfoquinovosyldiacylglycerol.

"Phosphoglycerides" (also referred to as glycerophospholipids or phosphoglycerolipids) consist of a diacylglyceride whose remaining terminal hydroxy group is attached to a phosphate radical which is either not further modified (phosphatidic acid) or esterified with an alcohol. The most common representatives of the latter group are phosphatidylcholines (also called lecithins as), phosphatidylethanolamines and phosphatidylserines.

"Glycophosphatidylinositols" are compounds in which saccharideglycosidically bound to the inositol group of phosphatidylinositols

Glvcolipide

By the term "glycolipid" as used herein is meant compounds in which one or more monosaccharide residues are linked via a glycosidic bond to a hydrophobic acyl residue.

Glvcoclvcerolipide

The term glycoglycerolipids herein includes both phosphoglycosphingolipids and phosphonoglycosphingolipids as well as glycosphingolipids, further sulfoglycosphingolipids also sialoglycosphingolipids, as well as mono-, oligo-, and polyglycosylsphingoide and mono-, oligo-, and polyglycosylceramides. Further examples are rhamnolipids, sophor lipids, trehalose lipids and lipopolysaccharides. application areas

With guanidine- and / or amidine-group-containing compounds dissolved in water, carboxylic acids can be effectively dissolved from organic mixtures and removed with the aqueous phase, whereby aqueous nanoemulsions according to process step a) can be provided. The aggregation method according to the invention is particularly suitable for carrying out an aggregation and separation of carboxylic acids which are present in such aqueous nanoemulsions consisting of carboxylic acids and guanidine- and / or amidine-group-containing compounds. Such applications can be carried out in the purification of lipid mixtures, especially oils and fats, in which, z. By hydrolysis, an unacceptable amount of carboxylic acids is present. This applies, in addition to oil phases of biogenic origin, also to fossil lipid phases. If the carboxylic acids are present in complex form with other organic compounds, dissolution is likewise possible, it then being possible to obtain a solution of the other organic compounds by introducing water molecules. This phenomenon can be used to effect solubilization in a wide variety of biogenic materials and mixtures. If no carboxylic acids are present in the aggregates which can be nano-emulsified with the claimed guanidine- and / or amidine-containing compounds, dissolution / decomplexation of organic aggregates may also be effected by the one aqueous nanoemulsion consisting of carboxylic acids in a solution containing guanidine. and / or amidino-containing compounds. As a result, the refining process is suitable for virtually all lipid phases, as described herein, as well as for organic substance complexes. The fields of application from which the aqueous emulsions or nanoemulsions originate are therefore particularly in the field of agricultural, biotechnological or industrial processes / processes in which the Reinigungsbzw. Refining process with an aqueous solution containing guanidine and / or Amidinruppentragenden compounds, can be used to thereby convert carboxylic acids and other organic compounds in an aqueous nanoemulsion or (macro-) emulsion can. With the aggregation method of the invention, the separated carboxylic acids can be fractionated at a purity of> 85%, more preferably> 95% and most preferably> 98% for their class of material. These include processes in the refining of vegetable oils or animal fats, process fluids in wood processing or bio-technological production of carboxylic acids. Also preferred are applications in processes in which aqueous emulsions and suspensions arise as a result of a decomplexation process, a purification process or an extraction process in which the aqueous solution containing guanidine and / or amidino group-containing compounds, with or without nano-emulsified carboxylic acids herein. Such applications relate, for example, to the digestion of biomass or processes in food processing or processing, as well as wastes containing organic compounds or extractions of lipid phases or organic compounds of porous inorganic materials. It has been found that for the provision of an aqueous emulsion according to process step a) it is irrelevant whether carboxylic acids are present in the organic compound mixture so that process step b) according to the invention can take place.

Concrete application examples derived from these areas are u. a aqueous extractions of seed press cakes, fermentation residues of biogas plants, condensates of fatty deposits, eg in slaughterhouses or in the fish industry, further purification of fruit kernels or fruit pods, separation of organic components of sewage sludge, decomplexation and release of lipid phases from rocks. As a result, the separated organic compounds are made recoverable and can be made available by a fractionation and purification for the food, animal feed, cosmetic, pharmaceutical or chemical industry. Further preferred is the recovery of flavorings, which together with other organic compounds in aqueous emulsion containing guanidine and / or amidino group-bearing compounds, especially in plant extraction processes, herein and can be fractionated by the separation methods. A variety of flavors can thus be obtained in a purity for the substance group of at least 50%, more preferably> 75% and most preferably> 90%. Examples of flavors are limonene, phellandrene, menthan, camphor; Fenchon, xanthophylline, bisabolane, germacrane, elemane and humulane, farnesene, rotundone, sterols, phytosterols, p-cresol, guaiacol, ferulic acid, lignin, sinapine, catechins, eugenol, vanillin and anethole.

Among the preferred organic compounds which can be obtained by the process of the invention are organic dye compounds. Therefore, a preferred field of use are plant extracts obtained by aqueous extraction by any of the methods described herein, e.g. As a nanoemulsiven aqueous extraction, were obtained and can be aggregated and separated by the method according to the invention. Preference is given to the recovery of the plant dyes from the group of chlorophylls and carotenes. These can be done by suitable Techniques can be obtained in a purity of at least 50%, more preferably of at least 75%, and most preferably of> 90% for their group of substances.

Furthermore, a preferred field of application is the extraction and recovery of fat-soluble vitamins, phytosterols, fragrances, dyes and flavors. These can be obtained by the above-described methods from the organic mixtures by suitable techniques in a purity for their group of substances of at least 50%, more preferably of at least 75% and most preferably of> 90%.

Further preferred fields of application are the extraction and recovery of polyphenols, squalene, lignins, limonene, phellandrene, menthan, camphor; Fenchon, xanthophylline, bisabolane, germacrane, elemane and humulane, farnesene, rotundone, sterols, phytosterols, p-cresol, guaiacol, ferulic acid, lignin, sinapine, catechins, eugenol, vanillin and anethole. These can be obtained by the above-described methods from the organic mixtures by suitable techniques in a purity for their group of substances of at least 50%, more preferably of at least 75% and most preferably of> 90%.

Also preferred is the separation and recovery of peptides, and proteins such as albumins and globulins. These can be obtained by suitable techniques in a purity of at least 50%, more preferably at least 75%, and most preferably> 90% for their group of substances.

Particularly preferred is the separation and recovery of so-called mucilage, among these particularly preferred is the recovery of phospholipids, especially Phosphotidylcholine and phosphoinositols and glycolipids and Glycerglycolipide. These can be obtained by suitable techniques in a purity of at least 50%, more preferably at least 75%, and most preferably> 90%, for their group of substances.

The method of aggregating organic compounds according to the invention is particularly suitable for allowing reusability of solutions containing therein guanidine and / or amiodine group-bearing compounds in the form of a clarified or purified purification or process water phase.

Use of organic aggregates

The possible uses of the separated organic compounds depends both on the starting material and the classes of compounds which are to be obtained and processed in as pure a form as possible. In principle, all classes of compounds such as carboxylic acids, phospholipids, glycolipids, glyceroglycolipids, dyes, phenols, sinapines, squalene, vitamins, phytosterols, Fractionate amino acids, peptides, proteins, carbohydrates, lipoproteins, waxes, fatty alcohols and aromatics by selecting suitable solvents.

It is particularly advantageous that the separated fraction of chlorophylls following a separation with copper ions has a particularly intense green color, which virtually did not discolored even when the separated fraction was allowed to stand. Therefore, a particularly advantageous recovery of chemically and structurally unchanged chlorophylls from a separation of an organic material mixture, which is obtained by the aggregation according to the invention with copper ions, possible. Furthermore, it is particularly preferable to obtain a very pure phospholipid fraction, since these can be easily separated from the complexed carboxylic acids. These phospholipids are largely hydrolysis-free in a fractionation that takes place under appropriate conditions (rapid sample processing / cooling / drying). Therefore, it is preferred to recover and use a pure and low-hydrolysis phospholipid fraction having a purity of preferably> 90%, more preferably> 95%, and most preferably> 98%. Also particularly preferred is the possible recovery of chemically unmodified carboxylic acids by the process according to the invention. These can be recovered in a suitable solvent phase having a purity for the class of compounds of preferably> 90%, more preferably> 95%, and most preferably> 98%. Furthermore, it is preferred to obtain proteins and amino acids which can be fractionated by fractionation with a purity of preferably greater than 70%, more preferably greater than 85%, and most preferably greater than 90%, for this group of substances. Preference is furthermore given to obtaining sterol compounds, such as glycerosterols, calciferol (vitamin D ₂ ), cholecalciferol (vitamin D ₃ ),

Of particular interest are fat-soluble vitamins as well as phenols, which can be separated from the purifications of plant extracts. With a fractionation as described herein, a purity for this substance group of preferably> 70%, more preferably> 85% and most preferably> 90% can be achieved.

Further preferred is the recovery of flavors contained in the complexed organic compounds. With a fractionation as described herein, a purity for this substance group of preferably> 70%, more preferably> 85% and most preferably> 90% can be achieved. The obtainable organic compounds may find use in the food or feed industry, in hygiene or cosmetic articles, flavor preparations, such as seasonings, food additives, essential oils, in pharmacological or pharmaceutical preparations or in the chemical industry, incl. for the production of biopolymers.

Furthermore, the invention relates to a process for the aggregation and separation of an organic substance mixture which is present dissolved in an aqueous emulsion, characterized by the steps:

a) providing an aqueous emulsion or nanoemulsion having dissolved therein organic compounds, wherein the organic compounds are carboxylic acids, phospholipids, glycolipids, glyceroglycolipids, phenols, sterols, chlorophylls and / or sinapines, and wherein the aqueous emulsion according to step a ) contains at least one guanidine or amidine group bearing compound having a Kow of <6.3. b) mixing the emulsion from step a) with an aqueous solution containing copper (II) ions and / or calcium ions until an aggregate formation,

c) separating the aggregates from step b) by sedimentation, filtration or centrifugation after obtaining an aggregated phase of the organic compounds from step b). Step b) in the aforementioned method may alternatively also be as follows:

b) mixing the emulsion from step a) with an aqueous solution containing copper (II) ions and / or calcium ions and / or with an aqueous dispersion containing calcium oxide, magnesium oxide and / or zinc oxide and / or adding the emulsion from step a) with calcium oxide , Magnesium oxide and / or zinc oxide in solid form with mixing until

Achieving aggregate formation.

In addition, the invention relates to a process for the aggregation and separation of an organic substance mixture dissolved in an aqueous emulsion, characterized by the steps:

a) providing an aqueous emulsion having dissolved therein organic compounds, wherein the organic compounds are carboxylic acids, phospholipids, glycolipids, glyceroglycolipids, phenols, sterols, chlorophylls and / or sinapines, and wherein the aqueous emulsion of a refining of the lipid phase comes.

c) separating the aggregates from stage b) by sedimentation, filtration or Centrifugation after obtaining an aggregated phase of the organic compounds from step b).

Step b) in the aforementioned method may alternatively also be as follows:

b) mixing the emulsion from step a) with an aqueous solution containing copper (II) ions and / or calcium ions and / or with an aqueous dispersion containing calcium oxide, magnesium oxide and / or zinc oxide and / or adding the emulsion from step a) with calcium oxide , Magnesium oxide and / or zinc oxide in solid form with mixing to achieve aggregate formation.

Thus, the invention also relates to a process for the aggregation and separation of an organic substance mixture dissolved in an aqueous emulsion, characterized by the steps:

a) providing an aqueous emulsion having dissolved therein organic compounds, wherein the organic compounds are carboxylic acids, phospholipids, glycolipids, glyceroglycolipids, phenols, sterols, chlorophylls and / or sinapines, and wherein the aqueous emulsion according to step a) at least contains a guanidine or amidine group-bearing compound with a Kow of <6.3, and is derived from refining a lipid phase.

Step b) in the aforementioned method may alternatively also be as follows:

Furthermore, the invention relates to a process for the aggregation and separation of an organic substance mixture which is present dissolved in an aqueous emulsion, characterized by the steps: Providing an aqueous emulsion having organic compounds dissolved therein, the organic compounds being carboxylic acids, phospholipids, glycolipids, glyceroglycolipids, phenols, sterols, chlorophylls and / or sinapines, and wherein the aqueous emulsion according to step a) comprises at least one guanidine or amidino-containing compound having a Kow of <6.3.

Mixing the emulsion from step a) with an aqueous solution containing copper (II) ions and / or calcium ions at a maximum of 75 ° C until aggregate formation,

Separating the aggregates from step b) by sedimentation, filtration or centrifugation after obtaining an aggregated phase of the organic compounds from step b).

Step b) in the aforementioned method may alternatively also be as follows:

b) mixing the emulsion from step a) with an aqueous solution containing copper (II) ions and / or calcium ions and / or with an aqueous dispersion containing calcium oxide, magnesium oxide and / or zinc oxide and / or adding the emulsion from step a) with calcium oxide , Magnesium oxide and / or zinc oxide in solid form with mixing at a maximum of 75 ° C until aggregate formation.

a) providing an aqueous emulsion having dissolved therein organic compounds, wherein the organic compounds are carboxylic acids, phospholipids, glycolipids, Glyceroglycoiipide, phenols, sterols, chlorophylls and / or sinapines, and wherein the aqueous emulsion of a refining of the lipid phase comes.

b) mixing the emulsion from step a) with an aqueous solution containing copper (II) ions and / or calcium ions at a maximum of 75 ° C. until aggregate formation,

Step b) in the aforementioned method may alternatively also be as follows:

b) mixing the emulsion from step a) with an aqueous solution containing copper (II) ions and / or calcium ions and / or with an aqueous solution Dispersion comprising calcium oxide, magnesium oxide and / or zinc oxide and / or adding the emulsion from stage a) with calcium oxide, magnesium oxide and / or zinc oxide in solid form with mixing at a maximum of 75 ° C until aggregate formation.

b) mixing the emulsion from stage a) with an aqueous solution containing copper (II) ions and / or calcium ions at a maximum of 75 ° C. until aggregate formation,

c) separating the aggregates from step b) by sedimentation, filtration or centrifugation after obtaining an aggregated phase of the organic

Compounds from stage b).

Step b) in the aforementioned method may alternatively also be as follows:

b) mixing the emulsion of step a) with an aqueous solution containing copper (II) ions and / or Caiciumionen and / or with an aqueous

Dispersion comprising calcium oxide, magnesium oxide and / or zinc oxide and / or adding the emulsion from stage a) with calcium oxide, magnesium oxide and / or zinc oxide in solid form with mixing at a maximum of 75 ° C until aggregate formation.

a) providing an aqueous emulsion having dissolved therein organic compounds, wherein the organic compounds are carboxylic acids, phospholipids, glycolipids, glyceroglycolipids, phenols, sterols, chlorophylls and / or sinapines, and wherein the aqueous emulsion according to step a) at least contains a guanidine or amidine group bearing compound having a Kow of <6.3. b) mixing the emulsion from step a) with an aqueous solution comprising copper (II) ions and / or calcium ions with a laminar agitator until aggregate formation is achieved,

Compounds from stage b).

Step b) in the aforementioned method may alternatively also be as follows:

b) mixing the emulsion of step a) with an aqueous solution containing copper (I) ions and / or calcium ions and / or with an aqueous solution

Dispersion comprising calcium oxide, magnesium oxide and / or zinc oxide and / or adding the emulsion from stage a) with calcium oxide, magnesium oxide and / or zinc oxide in solid form while mixing with a laminar agitator until aggregate formation is achieved.

b) mixing the emulsion of step a) with an aqueous solution containing copper (II) ions and / or calcium ions with a laminar stirrer until

Achieving aggregate formation,

Step b) in the aforementioned method may alternatively also be as follows:

b) mixing the emulsion from step a) with an aqueous solution containing copper (II) ions and / or calcium ions and / or with an aqueous dispersion containing calcium oxide, magnesium oxide and / or zinc oxide and / or adding the emulsion from step a) with calcium oxide .

Magnesium oxide and / or zinc oxide in solid form with mixing with a Laminarrührwerk until aggregation.

Thus, the invention also relates to a process for aggregation and separation an organic substance mixture dissolved in an aqueous emulsion, characterized by the steps of:

b) mixing the emulsion from step a) with an aqueous solution comprising copper (II) ions and / or calcium ions with a laminar agitator until aggregate formation is achieved,

Step b) in the aforementioned method may alternatively also be as follows:

b) mixing the emulsion from step a) with an aqueous solution containing copper (II) ions and / or calcium ions and / or with an aqueous dispersion containing calcium oxide, magnesium oxide and / or zinc oxide and / or adding the emulsion from step a) with calcium oxide , Magnesium oxide and / or zinc oxide in solid form with mixing with a Laminarrührwerk until aggregation.

a) providing an aqueous emulsion having dissolved therein organic compounds, wherein the organic compounds are carboxylic acids, phospholipids, glycolipids, glyceroglycolipids, phenols, sterols, chlorophylls and / or sinapines, and wherein the aqueous emulsion according to step a) at least contains a guanidine or amidine group bearing compound having a Kow of <6.3.

b) mixing the emulsion of step a) with an aqueous solution containing copper (I!) ions and / or calcium ions with a laminar agitator at a maximum of 75 ° C until aggregate formation,

c) separating the aggregates from step b) by sedimentation, filtration or centrifugation after obtaining an aggregated phase of the organic compounds from step b). Step b) in the aforementioned process may alternatively also be as follows: b) mixing the emulsion from step a) with an aqueous solution containing copper (II) ions and / or calcium ions and / or with an aqueous dispersion containing calcium oxide, magnesium oxide and / or Zinc oxide and / or addition of the emulsion from step a) with calcium oxide, magnesium oxide and / or zinc oxide in solid form with mixing with a laminar at maximum 75 ° C until aggregate formation.

b) mixing the emulsion of step a) with an aqueous solution containing copper (II) ions and / or calcium ions with a laminar agitator at a maximum of 75 ° C until aggregate formation,

Step b) in the aforementioned method may alternatively also be as follows:

b) mixing the emulsion from step a) with an aqueous solution containing copper (II) ions and / or calcium ions and / or with an aqueous dispersion containing calcium oxide, magnesium oxide and / or zinc oxide and / or adding the emulsion from step a) with calcium oxide , Magnesium oxide and / or zinc oxide in solid form with mixing with a laminar agitator at a maximum of 75 ° C until aggregate formation.

a) providing an aqueous emulsion having dissolved therein organic compounds, wherein it is the organic compounds are carboxylic acids, phospholipids, glycolipids, glyceroglycolipids, phenols, sterols, chlorophylls and / or sinapines, and wherein the aqueous emulsion according to step a) contains at least one guanidine or amidine group-carrying compound having a Kow of <6.3 and from a refining of a Lipid phase originates.

Mixing the emulsion from step a) with an aqueous solution containing copper (II) ions and / or calcium ions with a laminar agitator at a maximum of 75 ° C until aggregate formation,

Step b) in the aforementioned method may alternatively also be as follows:

b) mixing the emulsion from step a) with an aqueous solution containing copper (II) ions and / or calcium ions and / or with an aqueous solution

Dispersion containing calcium oxide, magnesium oxide and / or zinc oxide and / or adding the emulsion from step a) with calcium oxide, magnesium oxide and / or zinc oxide in solid form with mixing with a laminar at maximum 75 ° C until aggregate formation.

a) providing an aqueous emulsion with dissolved therein organic compounds, wherein the organic compounds are carboxylic acids, phospholipids, glycolipids, glyceroglycolipids, phenols, sterols, chlorophylls and / or sinapines.

b) mixing the emulsion of step a) with an aqueous solution containing copper (II) ions until aggregate formation,

d) separating the copper (II) ions from the aqueous solution.

Step b) in the aforementioned method may alternatively also be as follows:

b) mixing the emulsion from step a) with an aqueous solution containing copper (II) ions and / or with an aqueous dispersion containing magnesium oxide and / or zinc oxide and / or adding the emulsion from step a) with magnesium oxide and / or zinc oxide in solid form with mixing until it reaches an aggregate formation.

b) mixing the emulsion from step a) with discontinuous addition with an aqueous solution containing copper (II) ions and / or calcium ions until aggregate formation,

Compounds from stage b).

Step b) in the aforementioned method may alternatively also be as follows:

b) mixing the emulsion of step a) with discontinuous addition with an aqueous solution containing copper (II) ions and / or calcium ions and / or with discontinuous addition with an aqueous dispersion containing calcium oxide, magnesium oxide and / or zinc oxide and / or adding the emulsion from step a) with discontinuous addition with calcium oxide, magnesium oxide and / or zinc oxide in solid form with mixing until the formation of an aggregate.

Examples of measurement methods

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

The oil content of phosphorus, sodium, potassium, calcium and iron was determined by means of ICP-OES (iCAP 7400, Thermo-Fisher, Scientific, Germany).

Chlorophyll concentrations were determined, unless otherwise indicated, by analyzing oil samples in 10mm cuvettes without further dilution with a UV-Vis Spectrometer (UV-1601, Shimadzu, Japan) at 630, 670 and 710nm. The Chroropyhlpigmentgehalt.es was calculated according to the formula of the AOCS method Cc 13e-92.

The proportion of free fatty acids in the lipid phase was determined by methanolic KOH titration. Values in% by weight (g / 100g).

The pH was determined with a glass capillary electrode (Blue-Line, ProLab 2000, Sl-Analytics, Germany).

The concentration of benzo-a-pyrene was carried out according to the DGF method III 17a.

Droplet or particle size determinations were made by non-invasive laser light backscatter analysis (DLS) (Zetasizer Nano S, Malvern, UK). For this purpose, 2 ml of a liquid to be analyzed were filled into a measuring cuvette and inserted into the measuring cell. The analysis on particles or phase boundaries forming droplets is automatic. It is covered a measuring range of 0.3 nm to 10 μιτι.

The determination of turbidity of the water phases was made by visual inspection by filling a cuvette, 3 mm in diameter, with the liquid to be tested and assessed by 2 investigators, the visibility of image lines when viewed through the cuvette, under standardized light conditions. In a distortion-free recognition of the image lilies, the water phase was evaluated as transparent. With significant distortion of the line contours with difficult recognition of the image lines as well as a no longer clear view, the assessment was carried out as slightly cloudy. If image lines were still recognizable, but could no longer be differentiated, and the visual appearance was dim, classification was as moderately murky. If no lines were recognizable and a review was no longer possible, the classification was considered very cloudy. A classification as "milk-like" was made with an appearance that equals that of a milk. A quantification of the turbidity (turbidimeth) of the water phases (aqueous emulsions) was also carried out by means of a scattered light detection, in which the re-entry of a scattered beam at 90 ° is determined with a probe immersed in a sample volume of 10 ml (InPro 8200 measuring sensor, M800 -1 transmitter, Mettler Toledo, Germany). The measuring range is 5 to 4000 FTU. There were always duplicate determinations per sample.

Compared to parallel measurements by turbidimetry (see below) it was found that water phases, which were assessed as transparent (turbidity (TR) = 1), measured in the range <10 FTU, with a slight turbidity (TR = 2) Oils had FTU values from 1 1 to 75, and at moderate turbidity (TR = 3) FTU values ranged from 76 to 300, and at high turbidity (TR = 4), FTU values between 301 and 2000 were measured and recorded Milky emulsions (TR = 5) had FTU values of> 2000.

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

All solutions contain the compounds according to the invention or guanidine or amidine group-bearing compounds have been dissolved in an ion-poor or ion-free water phase.

All the ionizable compounds according to the invention were completely dissolved in an ion-poor water.

example 1

Rice bran oil (ricebran) was subjected to an aqueous extraction process (gassing with phosphoric acid (85% strength, volume addition 0.4%, temperature 38 ° C., duration of action 30 minutes, sodium carbonate (15% by weight, volume addition 3% by volume, temperature 38 ° C. The phase separations were carried out by means of a separator (OSD 1000, MKR, Germany, with a throughput of 100 l / h and a centrifugal acceleration of 10,000 g.) The moderately turbid oil obtained after the preliminary purification was tested for oil indices: phosphorus content 14.1 ppm (or 14.1 mg / kg), calcium 28 ppm (or 28 mg / kg), iron 3.5 ppm (or 3.5 mg / kg), free fatty acids 1, 2% by weight 200 liters of the oil with an arginine solution (0.5 molar, volume addition 3%) which was introduced with a propeller mixer at 35 ° C. for 20 minutes to give a milky oily emulsion, followed by phase separation as described above with the separator The oil phase was almost clear and rejected that Phosphorus content 2.1 ppm (or 2.1 mg / kg), calcium 0.05 ppm (or 0.05 mg / kg), iron 0.02 ppm (or 0.5 mg / kg), free fatty acids 0.15% by weight. The water phase was very turbid and had a whitish-yellow color, the pH value was 12.5. The aqueous emulsion had one unpleasant stinging plant odor. A 50 ml sample of the aqueous emulsion was filtered with a membrane filter having a nominal exclusion size of 0.45 μm. The filtrate did not differ from the starting solution, the microscopic analysis of the filter paper showed no visible residues. To 100 ml of the aqueous emulsion were added dropwise while stirring the solution by means of a magnetic stirrer (200 rpm) aqueous solutions of the following compounds (concentration 3 molar or as indicated): HCl (25%), iron (III) chloride (2 , 4 molar), copper (II) chloride (3.1 molar), copper (II) acetate, copper (II) sulfate, copper (II) citrate, calcuim chloride, magnesium chloride, aluminum trichloride (2.8 molar), potassium chloride (3 , 8 molar) and sodium chloride (2 molar). Stirring was stopped every 30 seconds for 10 seconds. As soon as well-identifiable solid particles formed in the quiescent emulsion and a free water phase present between the particles forming was recognizable, the experiment was terminated. The end of the experiment was reached even when a volumetric addition of 10% by volume was achieved. The suspensions were then allowed to stand for 10 minutes. Thereafter, the phase separation was carried out with a beaker centrifuge (3800 rpm for 5 minutes). Thereafter, the water phase and a solid phase (if present) were separated by stripping off the water phase. The water phase was examined for haze (visual inspection and turbidimetry (see Measurement Methods)), the presence of suspended matter (visual inspection) and the pH (pH-measurement, see measuring methods) of the solution. Furthermore, the volume of the solid phase was determined after pouring still existing liquid.

In further experiments, powdered calcium oxide, magnesium oxide, zinc oxide, copper oxide and titanium oxide were added in increments of 3 g every 10 minutes to 100 ml of the aqueous emulsion. The solution was continuously mixed by means of a magnetic stirrer (200 rpm). As soon as particles became visible in the solution and a free water phase formed, the stirring and metering were stopped. The suspensions were allowed to stand for 60 minutes, followed by phase separation and separation as described above. The individual tests were repeated three times in each case and the average amount added was calculated. The volumes of the resulting solid phases were determined and the relative ratio to the total volume of the starting solution was calculated. The solid phases were vacuum dried at 60 ° C for 12 hours and weighed. In one batch each, the separated from the solid phase clarified water phases or the emulsion phases were mixed with 5 ml of a 25% HCl solution and mixed (acid sample). Then phase separation by centrifugation, such as described above and pH-metry of the free water phases. The aqueous supernatants were poured off and the solid phases were subjected to vacuum drying as described above. Subsequently, the solid phases were weighed (values in Table 1 [amount of solids2], acid sample negative if no amount of solid is quantifiable). The resulting solid phases after aggregation with copper and calcium chloride solutions were examined in decomplexation studies for their ingredients. In this case, sequential extractions with mixtures or extraction sequences, inter alia, with chloroform / methanol-KOH, chlorofrom-HCl / butanol, chloroform / ethyl acetate. From a fractionated chloroform phase, a gas chromatographic analysis is carried out after methylation.

Results (Numerical values are summarized in Table 1):

Acid treatment resulted in a rapid clarification of the water phase, which subsequently had a yellowish color, when the pH dropped below 3.0 and after further addition of acid. The precipitated solid had a strong yellow color and a tough-pasty and sticky consistency. The pH at the time of complete clarification was 2.5. By a sodium or potassium salt solution, there was no aggregation of organic compounds up to the maximum volume ratio used of 10% by volume. With the addition of copper (II) chloride, clearly visible aggregates were formed after just a few drops. The addition was stopped at a consumption of 0.007 mol of copper (II) chloride. The aggregation of the previously dissolved organic compounds then proceeded completely. A light blue clear water phase was obtained. The solid, which had a green-blue color, was separated by centrifugation as a compact, somewhat friable mass.

Other solutions containing copper (II) ions also led to the initiation of aggregation, which led to complete aggregation of the organic compounds even after completion of the addition of copper ions. The addition of calcium ions resulted in a comparable aggregation initiation but a larger amount of calcium ions was required leaving a slight haze and suspended solids in the water phase. Furthermore, the volume of the aggregate phase was larger compared to the experiments with copper ions. The same was achieved by the addition of iron (III) ions. In contrast, iron (II) ions as well as magnesium or aluminum ions had a significantly lower effect on aggregation initiation and caused only a moderate separation result in the case of Mg ²⁺ and Al ³⁺ or no complete separation when using Fe ^{3+ of} the organic compounds , Aggregation initiation also occurred by the addition of powdered calcium oxide, magnesium oxide and Zinc oxide. However, the initiation of aggregation was significantly slower than the addition of ionic copper (II) or calcium (II), and the recognition of aggregation initiation by clouding caused by the oxide compounds was much more difficult. In the aforementioned oxides, there was a complete separation of the organic compounds, the solid phases were, however, voluminous than in an aggregation initiation with copper ions. Other oxides such as iron (II) and iron (III) oxide, CuO and titanium oxide had no aggregation-initiating effect.

One sample (5 g) of the aggregate phases obtained after aggregation initiation with copper chloride and with copper sulfate were weighed and then subjected to vacuum drying at 60 ° C for 12 hours and weighed again. From the weight difference to the mass after vacuum drying resulted in a removable water content of 5 wt .-%. The viscous but not adhesive masses obtained after drying were completely dissolved in 50 ml of chloroform. To the solutions was added 15 ml of a solution consisting of methanol and water (95: 5 v: v) and shaken vigorously. This was followed by phase separation by centrifugation (4000 rpm / 10 minutes). The methanol phases were withdrawn. In a

Thin-layer chromatography, which was carried out in each case with a sample of the methanol phase, showed, by comparison with a phospholipid standard which was applied, intensive and well-limited band formation, which could be attributed to phophotidylcholine and phosphodidylinositols. There were virtually no other Adsorptionsbanden recognizable. The chloroform phases were washed twice with an ethanol / water mixture (1: 1 v: v), then separation by centrifugal phase separation. 0.2 mmol of HCl was added to the chloroform phases and mixed with it. Subsequently, 5 ml H ₂ O were added. After centrifugation, the water phases were separated. After a further washing step with water, one sample each was taken for gas chromatographic analysis. In this the fatty acids octanoic acid, dodecanoic acid hexadecanoic acid, octadecanoic acid, oleic acid and linoleic acid were detected. Also detectable were ferulic acid and phytic acid. From a fractionation, a high concentration of tocopherol was found in a Losoctanfraktion by RP-HPLC. In a further fractionation ß-sitosterol was present in an ethanol phase, the detection was carried out by LC-GC.

The free water phase (10 ml) which had been obtained by aggregation with CuC and CuSO _4, the cation exchange resins CHELITE P and Dowex 50WX4 (Serva, Germany) were added in an amount to ion exchange a cation of> 1 eq / l had. Under slight agitation the changed Color of the solutions from light blue to a light shade of yellow. The replacement resins then had an intense blue color. The supernatant (purified water phase) was poured off, the pH determined herein was identical to the pH of the starting solution. The purified solutions were virtually odorless. The solutions were brought to pH 1 by addition of HCl, no precipitate. Even in other clarified water phases, which were obtained after successful aggregation of organic compounds, could be separated by lowering the pH <1, 0 no measurable amounts of organic compounds. On the other hand, in the water phases, which were still cloudy or the water phase still consisted of an emulsion, there was precipitation of organic compounds by addition of an acid. This result had a close relationship with the visual appearance and the degree of turbidity present in the water phase.

Table 1

Aggregation Consumption Turbidity Sw pH Solid Solids Solid

- (% by Vol.) (FTU) Materials Value Volume Quantity 1 quantity 2

Substance (% by volume) (g) (g)

CuCl ₂ 2,1 3 0 12,1 21 18,2 0

Cu (0 ₂ CCH ₃ ) ₂ 2.8 5 0 1 1, 3 23 18.4 0

CuSO ₄ 2.6 4 0 1 1, 9 21 18.3 0

Cu citrate 3.1 7 0 1 1, 5 25 17.9 0

CaCl ₂ 3.6 26 1 12.1 36 17.1 0.5

MgCl ₂ 6.5 152 2 12.3 46 8.4 9.6

FelllCl ₂ 5.2 97 1 13.1 29 9.4 8.6

FellCIs> 10 3122 n. B. 12.6 12 2.1 17.3

AICIs 7.2 2544 2 1 1, 8 42 12.5 7.4

NaCl> 10 3623 n. B. 12.3 n. B. n. b. 18.3

KCl> 10 3177 n. B. 12.5 n. B. n. b. 17.9

HCl (25% by volume) 2.5 5 0 1, 8 15 18.1 0

CaO 4.5% by weight 814 1 13.2 45 22.4 0.4

MgO 5.8% by weight 18 1 12.9 38 23.1 1, 2

ZnO 7.6% by weight 22 1 13 31 23.8 1, 8

CuO> 10Gew% 3256 nb 12.1 nb ^* ) 18.3

TiO> 10Gew% 3644 nb 12nb ^* ) 18.0

AIOO> 10Gew% 04122 nb 1 1, 7 n. B ^* ) 17,8 Suspended solids: 0 = none, 1 = isolated, 2 = many; nb = not assessable, because nonexistent, or not evaluable due to turbidity intensity. Solid amount 1: solid in g, obtained after aggregation of the aqueous emulsion, centrifugation and drying; Solids quantity 2: solid in g, obtained from the water / emulsion phase after initial aggregation test and after HCl addition, phase separation and drying; *) = the separated solid phase contained no recognizable organic compounds and corresponded to the oxide used.

Example 2

Wet and oily sewage sludge (400g) was mixed with 1000ml of a solution mixture consisting of a nanoemulsion produced by an aqueous solution containing arginine (50mmol / l) and caproic acid (10mmol / l) and a glycoglycerolipid mixture (100mg / l). , which were stirred intensively with each other. In order to prepare a liquid suspension of the sewage sludge, a 2-fold volume excess of the solution mixture was required. The suspension was further stirred for 60 minutes at 40 ° C. This was followed by a sedimentation phase over 2 hours. The supernatant (mixed solution) was poured off. The sediment was rinsed in a sieve and air dried. The resulting weight was determined. The mixed solution containing the organic compounds contained therein had a deep black-brown color and a very high haze. The pH was 1 1, 6. 0.5 ml of cupric chloride, copper (II) sulfate, copper (II) acetate, calcium chloride, iron (III) chloride, sodium hydroxide (in each case 2 molar concentrations) and hydrochloric acid were added to 100 ml portions of the mixed solution every 10 seconds (10% by weight) and grams of powdered oxides of calcium and magnesium added during a continuous stirring with a Laminarmischer (helical stirrer, 100 rpm). Changes in the emulsion were detected by observation. Upon recognizable aggregate formation with simultaneous formation of a clear liquid phase in addition to easily recognizable aggregates, the experiment was terminated. The samples to which ionic compounds had been added were centrifuged after 5 minutes (4000rpm / 10 minutes). A centrifugation of the samples to which oxide compounds had been added took place with a standing time of 60 minutes. The liquid supernatants were decanted and the turbidity was determined optically and by turbidimetry. The volume of the separated solids was determined and the residual water content was examined as in Example 1, by vacuum drying, the dried solid masses were then weighed. The subsequently determined dry weight is listed in Table 2. Crushed particles of the original sewage sludge, as well as particles of the cleaned and dried sediment after treatment with the mixed solution, were analyzed with respect to the composition and with a reflected-light microscope Surface texture of the particles examined. For all clarified water phases, an acid sample was carried out (experimental procedure according to Example 1).

Table 2

Haze level (visual assessment): 0 = transparent, 1 = light, 2 = moderate, 3 = clear; Turbidity = FTU value of turbidimetry; Suspended solids (visual assessment): 0 = none, 1 = isolated, 2 = many; Volume FP = volume of the solid phases after centrifugation and decanting of the aqueous phase in relation to the sample volume; Quantity FP = weight of the solid phase after vacuum drying; Water content FP = Calculated relative amount of water removed by vacuum drying based on the dry weight.

Results:

As a result of the solution mixture used, larger amounts of soluble constituents were dissolved out of the sewage sludge investigated, giving rise to a dark-colored emulsion. Initially, the sewage sludge particles had a microscopic fibrous appearance, only occasionally were surfaces visible, which were sandy or quartz-like. After being detached by the solution mixture, the sediment had essentially sand- and quartz-like structures; organic constituents were not recognizable by the microscope and thus transferred to the mixed solution. The dry weight of the purified sediment was 128g.

With the ionic copper (II) -, calcium (II) - and iron (III) compounds as well as with oxides of the calcuim, and the magnesium an aggregation of the aqueous emulsion could be initiated, which led to a complete separation and clarification of the water phase. The acid sample was negative for all clarified water phases. All organic aggregate phases had a solid consistency. Roof drying of the aggregate phase corresponded to the amount by weight, in the case of the aggregate phases produced with ionic compounds, about the amount of organic Compounds that had been removed from the sewage sludge. The dry weight of aggregates induced by aggregation initiation with oxides was greater than that after aggregation with ionic compounds by the oxide compounds included herein. The calculated amount of trapped and discharged water was below 5% by weight for solid phases obtained by copper ion addition. For calcium- and magnesium-induced aggregations, the water content of the solid phase was slightly larger. With sodium hydroxide, no aggregation of organic compounds could be achieved.

The dried solid phases were dissolved in a mixture of dichloromethane and methanol, followed by phase separation by centrifugation 4000rpm / 10 minutes). The methanol phase was separated. Thin layer chromatographic detection (experiment as in Example 1) of phospholipids.

Example 3

In the extraction of fruit kernel ingredients, it may be necessary to first rid the kernels of pulp residues. This is especially true for avocado fruits. Residues that have already dried are virtually impossible to dissolve with water at room temperature because they have a high content of lipophilic compounds. Furthermore, on shells of plant germs and seeds that have been separated from the cores located therein, lipids and proteins that are currently not sufficiently economically exploitable.

After a mechanical removal of the pulp mass of avocado seeds, 6 kg of the kernels, which had dried-on or dried-on residues of fruit pulp, were placed in 2.5 liters of a nanoemulsion consisting of aqueous solution of 150 mmol of arginine and 50 mmol of caprylic acid 30 ° C with continuous rotation of the kettle contents for 30 minutes left. The resulting aqueous emulsion 1 (WE 1) had a milk-like character with a slightly green-yellowish color.

Sunflower seed shells (800 g) were placed in 2 liters of 2.0 molar arginine solution and agitated at 40 ° C for 3 hours with a hook stirrer. Subsequently, the shells were separated from the now dark brown water phase (WE 2) by means of a sieve. The trays were then filled into a screw press to separate the liquid phase still bound therein, which was then added to the already separated aqueous emulsion (WE 2). To each 100 ml of the two aqueous emulsion solutions obtained were added dropwise aqueous solutions (in each case 3 molar) of the following compounds: copper chloride, copper carbonate, copper sulfate, copper acetate until a clearly visible aggregation with formation of a free water phase began. A further test batch was carried out with powdered calcium oxide and magnesium oxide, the metered addition was carried out as described in Example 2. Furthermore, experiments were carried out with potassium hydroxide (3 molar) and HCl (10 vol%). The aqueous emulsion phases were mixed with a helical stirrer (100 rpm), and the mixing was stopped every 30 seconds for 15 seconds, during which time addition of aggregation-initiating compounds was also avoided. During the lifetime of the formation of a free water phase was examined by inspection. In addition, a viscosity measurement of the emulsion was made. To do this, attach a vibration viscometer (Viscolite d15, PCE-Instruments, Germany) to a tripod so that the viscometer is immersed in the upper layer of the process fluid. Measurements are made during the service life.

In preliminary investigations it could be shown that in the aqueous emulsions relevant amounts of neutral fats (eg triglyceride fraction between 1 and 5% by weight) exist, which have been removed from the organic compound complexes. As a result, the aggregation according to the invention can be influenced and the detection of a separation of the forming units. There is therefore a heating of the emulsion phases at 90 ° C for 5 minutes. Then, the aqueous compounds were introduced into the heated emulsion under continued heating, which was set at 60 ° C. Very rapidly, all ionic compounds showed the formation of oil droplets on the liquid surfaces with simultaneously visible aggregates, in a free water phase forming. The addition of the compounds was stopped at this moment and the reaction solutions after the end of the entry of ionic compounds after 10 minutes and after the end of the entry of the oxidic compounds after 60 minutes at a temperature of 50 ° C centrifuged (3800rpm, 10 minutes). In all experiments, which were carried out with the ionic compounds according to the invention, there was a separation of a compact amount of solids, which survived a clarified water phase. On this turn, there was a slimy-oily phase, which was easy to skim off. The oil phases were subjected to vacuum drying and then weighed. The relative weight fraction to that of the dried solid phases was determined and reported in Tables 3.1 and 3.2. The dried oil phases were dissolved in n-hexane and shaken out with a 3% citric acid solution. Thereafter, phase separation by centrifugation and removal of the organic phase, which is concentrated in a rotary evaporator and then weighed. The determined weight of the thus obtained Neutral fat fractions are given in relation to the weight of the oil phases in Tables 3.1 and 3.2. For all clarified water phases an acid sample was made. The residual water content of the aggregate phases was determined according to Example 1. The dried aggregate phases were digested with organic solvents. For this purpose, inter alia, an aggregate phase (CaC) from the cleaning of the avocado seeds in an octanol / water mixture (95/5, v / v) was suspended and agitated at 40 ° C for 10 minutes. Centrifugation (3800 rpm, 5 min) to give a yellowish clear alcohol phase which was analyzed by HPLC-MS (VTM1). In another approach after aggregation with CuC, the aggregate phase was suspended in an ethyl acetate / water mixture (80/20, v / v) and agitated at 40 ° C for 10 minutes. Centrifugation at 3800 rpm (5 min), followed by a transparent organic phase and a clear blue water phase, at the phase boundary was a yellowish-white mass. This was further processed according to the Kjeldahl method for nitrogen determination (VTM2). The transparent solvent phase was subjected to thin layer chromatography to determine lipid fractions (VTM3).

Table 3.1

Table 3.2

CuCl ₂ Cu (0 ₂ CCH ₃ ) ₂ CuS0 ₄ CaCl ₂ HCl KOH

WE 2

Consumption (Vol%) 2.3 3.2 2.5 5.9 5.2> 10

Turbidity 0 0 0 0 0 3

Suspended matter 0 0 0 1 0 nb pH value 1 1, 4 1 1, 2 1 1, 4 1 1, 7 2.4 14

lphase (% by weight)

Turbidity: 0 = transparent, 1 = light, 2 = moderate, 3 = distinct; Suspended matter: 0 = none, 1 = isolated, 2 = many. Nb = not determinable The aggregate phase of sunflower husk purification (aggregation with CuSO ₄ ) was suspended in a petroleum ether / isopropyl alcohol / acetic acid (85/12/3, v / v / v) mixture and mixed as prescribed and phase separated. The petroleum ether phase was removed and, after methylation, a sample was analyzed by gas chromatography (VTM 4). In another approach (VTM 5) (aggregation with CaC), the dry mass was suspended in a mixture of chloroform and admixed with 5% by volume of water and mixed as described above and a phase separation was carried out. The liquid phases were clear, at the phase boundary was a solid mass, which was further digested as in the experiment VTM 2.

Results:

The viscosity measurements made in the course of the initiation of aggregation during the stance phases showed characteristic courses, as long as there was an inventive and complete aggregation of the organic compounds. The viscosity of the aqueous emulsions (WE 1: 12.1 mPa ^■ s; WE 2: 4.2 mPa s ^■) increased in the course of the aggregation initiation slowly at first, then steeply up to a maximum value of 646.6 mPa s at ^■ WE1 and 85.9 mPa s at ^■ WE 2nd, then rapid drop to values of 1, 5, and 1, 3 mPa s ^■ the clarified WE 1 and WE 2 corresponded to the clarified reaching the respective maximum value of the observed formation of large and easily visible aggregates in a clear or clarifying water phase. The criterion for the completion of the metered addition of an aggregating agent corresponded in each case to the time at which a maximum value of the viscosity was exceeded. The acid sample was negative at the clarified water phases. These water phases had only a minimal smell.

The aqueous emulsions from the decomplexing or solution investigations in vegetable products in which a high proportion of lipophilic organic compounds is present, showed that the process also liberate or decomplex strongly lipophilic or apolar compounds. In the aqueous emulsions obtained by a nanoemulsion or by a sole solution containing guanidine and / or Amidino group, a separation of apolar organic compounds took place at the moment, in which an aggregation of the other organic compounds by the complexing agents according to the invention took place, wherein the aqueous Medium was heated. The investigation of the presence of neutral skins in the oil phases floating in the clarified water phases shows that these are predominantly triglycerides. In contrast, under the same conditions but with the use of oxidic compounds, there was no or minimal separation of neutral fats from the free water phase. Accordingly, in the aggregates obtained by means of the ionic compounds according to the invention, virtually no neutral fats could be found, whereas neutral fats were present in the aggregates obtained with the oxidic compounds. Separation of neutral fats also did not occur when aggregation of the dissolved organic compounds was induced by acidification of the aqueous emulsions. All solid phases after drying had a pasty consistency and a non-sticky or oily character. With the exception of the solids mass obtained by acidification, the remaining WE 1 solids had a yellow-greenish color (in the case of copper compounds this was turquoise) and an intense avocado smell. The WE2 solid phases were brown to blackish and had a moldy odor. The residual water content of these solid phases was <15% by weight in all the ionic copper compounds investigated. For the solid phases obtained by aggregation with the oxide compounds, the water content was between 18 and 36% by weight.

By fractionation of the dried solid phases with organic solvents fractions were obtained in which squalene (VTM1), protein compounds (VTM2, VTM5), triglycerides (VTM3), and phenolic acids, such as chlorogenic acid and caffeic acid (VTM4) could be detected.

Example 4

Investigation to find a minimum dose for the initiation of aggregation and purification of the clarified water phase

A distillate of microbially produced biodiesel, which was obtained from biogenic wastes, with a content of methyl esters of> 95% and a content of carboxylic acids of 1, 2Gew%, was cleaned twice with an aqueous 0.5 molar arginine solution. Thereafter, the two aqueous emulsions obtained were combined, which then had a milk-like character with a yellowish color. to Establishment of a process technology for the separation of the emulsified organic ingredients, a continuous analysis of the color spectrum during a dropwise continuous addition of a copper acetate solution (0.5 and 2 molar) was investigated with simultaneous slow mixing of the reaction liquid. To validate a spectroscopic monitoring and control technique, the minimum concentration of copper ion addition required to initiate complete aggregation initiation was determined. For this purpose, the metering and the mixing process was interrupted every 30 seconds or after an application amount of 0.2% by volume for 15 seconds in order to be able to carry out a visual analysis of the aggregation progress during this time. In each case, a sample (2 ml) was taken for particle size determination (method and procedure, see Methods of measurement). When the formation of a free water phase and well-defined aggregates could be seen there was no further addition of the ion solution and the samples were centrifuged after 15 minutes (4000rpm / 10 min). If in the centrifuged sample the water phase was not transparent or the acid sample (test procedure according to Example 1) was positive, the experiment was repeated, then the total amount of the solution was continuously added dropwise with copper ions, with a relative to the aqueous emulsion phase by 0, 2 vol% larger volume than in the previous experiment. The amount of volume which was found to be 3 times as the amount that allowed aggregation initiation with complete separation of the organic compounds was defined as a minimum amount and used to validate spectroscopic color spectral and color intensity measurements. A photometric measurement was carried out during these experiments with a rod probe immersed in the reaction liquid. In addition, experiments were carried out in which the determined minimum dose amounts of copper ion solution were exceeded by 20 vol%. The minimum volume for the initiation of aggregation determined as described above was added to the aqueous emulsions in three modalities: a) continuous dropwise addition with continuous stirring, b) discontinuous addition and mixing, as described above, and c) initially complete metering of the total volume to the aqueous emulsion and subsequent mixing over the same period as that required under modality a). All samples were, as described above, centrifuged after 15 minutes and investigated for completeness of aggregation (including acid sample). The measurements were repeated 5 times. The during the Einrührbzw. Stance phase obtained values of the spectroscopic measurement were averaged and analyzed for characteristic values which were used for the detection of a Aggregation initiation are suitable. Then, with each of the metering schemes a), b) and c), which were carried out with both concentrations of the copper acetate, a metered addition into the aqueous emulsion with continuous measurement of the Farbspetrums and the color intensity. Upon reaching the previously defined value for the color spectrum and the color intensity, the metered addition was terminated. The samples were centrifuged as described above and examined for completeness of separation of organic compounds as in Example 1. Furthermore, the clarified process water was tested for carboxylic acids contained herein. For this purpose, samples were acidified with HCl and any carboxylic acids present herein extracted into a hexane phase. After methylation, a gas chromatographic determination was carried out.

The clarified process water had a bright blue color after aggregation with the determined minimum amount. 100 ml of the clarified water phases were combined in a beaker. Here, 2 carbon electrodes were placed and the electrodes were connected to a DC power source. A DC current of 12 V was applied at a current of 5 mA over the duration of 24 hours. Following this, the water phase was colorless. The cathode-related carbon electrode had a slightly shiny coating that could be scratched off. This solid proved to be copper-containing. The purified water phase thus obtained was examined for the concentration of arginine contained therein. The determination of the arginine concentration was carried out photometrically after a color reaction with the chromia reagent reagent. The ratio between the starting and final concentrations of arginine was calculated. At 3 of the resulting solid phases after aggregation with copper ions, digestion was performed by suspending the mass in hexane, followed by the addition of isopopyl alcohol and HCl (25 wt%), so that a ratio of 90/9/1 (v / v / v) was present. As a result, rapid and complete release of the aggregates. After phase separation transparent colorless hexane phase and pale light-green alcohol-water phase. Samples of the hexane phases were prepared for fatty acid analysis (see Experimental Methods).

Results:

The minimum amount of copper ion required to effect complete aggregation of organic compounds present in an arginine solution can be determined by visual inspection for solutions containing copper ions, at different concentrations and using different dosing schemes. The copper ion dose required at the time of the attainable complete aggregation can be reproducibly reproduced by process monitoring by means of a determination of the color spectrum or the color intensity be determined. Further, continuous spectroscopic analysis of the reaction solution is apt to determine a predefined color spectrum and associated color intensity to determine the timing of sufficient dosing of copper ions for complete aggregation initiation. The exceeding of a color scale value as well as a color intensity turned out to be a reliable and reproducible criterion for the detection of the end time for the dosing of the ionic compounds. Thus, a characteristic color spectrum can be identified for the prediction of a final clarification of the reaction liquid. It could also be shown that if this criterion was used for a faster entry of the copper-containing solution for dose control, the required consumption of the copper ion-containing solution can be reproduced to +/- 5%. Between the measurements at a slow rate of addition or discontinuous addition, the volume of entry varied only by 2.5%. At all doses controlled by the photometric analysis result, the reaction solution was completely clarified (acid samples negative). The clarified process water had a slightly turquoise color. Electrophoretic separation of the copper ions present in the clarified water phase is possible in the process liquid, with elemental copper being deposited. The process can be monitored by a complete disappearance of a blue coloration. Particles were present in the aqueous emulsion which had> 95% mean size of 150 nm (peak 1) and 490 nm (peak 2). During the addition of copper ions, larger aggregates (4000 to 6000 nm) were formed and the frequency of smaller particles decreased. Upon reaching the optical criterion of the formation of a free water phase, were for the first time no particles in the aqueous phase, which were smaller than 10μηη in the measuring range.

In the clarified process water, virtually no carboxylic acids were detectable by gas chromatography. The arginine concentration of the clarified and purified from copper ions process water was only minimally lower than in the starting solution (minus 3 +/- 1, 5Gew-%). By a loss of process water in the aggregated organic compound, a mean total loss of arginine of 4.8% by weight was determined. In the hexane phase, the extraction of the aggregate phase, a high concentration of the fatty acids, especially for oleic acid, linoleic acid is determined.

Example 5

Presscake (1.5 kg) of a screw press of rapeseed, which was largely freed by means of a hexane extraction of oil fractions and was present as an agglomerated solid, was immersed in an aqueous arginine solution (10 liters / 1 OOmmolar) dissolved with continuous stirring. After 3 hours, a mixture of an emulsion and aggregates suspended therein was formed. Centrifugation was performed with a beaker centrifuge (3800 rpm / 10 minutes). Thereby separating a dark brown coarse and fibrous mass from a cloudy aqueous beige-yellow emulsion, which was easily separated by decantation. Per 100 ml of the aqueous emulsion phase, the following compounds were added: aqueous solutions with (2 molar) of a) copper chloride, b) copper sulfate, c) calcium chloride, d) calcium acetate, and powdery forms of e) calcium oxide or f) zinc oxide. The addition was carried out for the aqueous or solid forms of administration according to Example 1. The addition of all compounds resulted in initiation of aggregation and required dose levels were: 8.6 ml for a), 9.8 ml for b), 10.7 ml for c), 14.5 ml for d), 21.5 g e), 22.1 g at f). Further, 2 samples (Reference 1 and 2) were each provided with 20 ml of NaCl solution (3 molar) and stirred for 20 minutes. Phase separation occurs under the same conditions as in Example I. The clarified water phases were decanted. These were colorless except for the phases that came from the aggregation with copper ions. All samples were virtually odorless. The resulting solid phases had a pungent mustard-like odor. The reference sample 1 was (20 minutes Optima XPN-90 Beckman / Coulter, Germany, 960,000 ^■ / g) subjected to ultracentrifugation reference sample 2 was stored at 10 ° C for 3 months. The water content of the solid phase was determined according to Example 1. Samples of the dried aggregate fractions were digested to analyze their contents. For this, the solid phases which had been aggregated with copper ions (light green) (VK) and those with calcium ions (beige) (VC) were suspended in ethyl acetate and water and isopropanol (final volume ratio 60/25/15%) were added and the mixture was allowed to stand for 10 minutes 40 ° C agitated. Then phase separation (3800rpm / 5min). The upper clear yellowish phases as well as the lower phases, greenish in Experiment VC, were decanted, leaving semisolid masses in the centrifuge glass. These were suspended in chloroform, followed by addition of water and methanol (final volume ratio 70/20/10%). Mixture and phase separation as before. After separation of the liquid phases by decantation, a pale yellow (VK) or a cream-colored (VC) semi-solid mass were obtained. A digestion was carried out according to the Kjeldahl method for determining nitrogen, from which the protein content of the resulting mass was determined in relation to the dry weight (experiment). The transparent water / methanol phase was fed to a thin film chromatograph for determination of phospholipids (Run 2). Results:

An aqueous emulsion of a nanoemulsive extraction of plant extracts could be completely clarified with the studied ionic solutions and the oxide compounds to obtain a transparent water phase and a compact solid phase. By means of an ultracentrifugation (reference experiment 1) only a small amount of solids could be sedimented. Even after a longer service life (reference experiment 2), there was still a turbid emulsion, with a character that was identical in comparison to the original emulsion. After careful pouring, only a small amount of sediment was found.

The determined residual moisture of the aggregation phase was between 5 and 12% by weight. Purification and fractionation in solvent or solvent mixtures was possible, while in the experiment a mass was obtained which consisted of 87% by weight of proteins. In another solvent phase (Experiment 2), there was a high concentration of phospholipids, especially phosphotidylcholine and phosphoinositol.

Example 6

Cold-pressed plum kernel oil is subjected to a 3-stage refining process for the purpose of deodorization. The crude oil was clear and had an intense plum smell and taste. The refining was carried out by 1) an aqueous refining with a 5 wt% citric acid solution (addition volume 3% by volume) was (stirring for 30 minutes, then phase separation by means of a centrifuge), 2) an aqueous refining with a 10% sodium bicarbonate solution (volume addition 2% by volume) (homogenization of the emulsion with an intensive mixer for 2 minutes, then phase separation with a centrifuge) and 3) with a nanoemulsive aqueous refining with a 0.4 molar arginine solution (addition volume 1, 5 vol%) was completed (homogenizing the emulsion with homogenised an intensive mixer for 5 minutes, then phase separation with a centrifuge (6000 ^■ g for 10 minutes). the oil phase was then almost clear and had almost no odor, plum taste was much lower than in the crude oil. the aqueous emulsion was significantly cloudy and had an intense plum odor. To 100 ml aqueous emulsions of the third purification stage, a copper tartrate (2 molar) or a copper sulfate (3 molar) solution during mixing with a magnetic stirrer (100rpm) were added dropwise until the formation of a free water phase was visible. After completion of the addition and mixing. After 15 minutes of centrifugation (3800 rpm / 5 minutes) clarified water phases are obtained, which were virtually odorless. After pouring the water phases, the resulting solid phases are in each case in Dissolved ethanol and suspended with stirring at 40 ° C for 10 minutes. Then centrifugation as previously described. There are obtained 2 clear liquid phases with a phase boundary. The light phase is subtracted. The heavy phase has an oily character and a very intense plum odor.

Example 7

Investigation of the storage stability of aggregated organic compounds

A lipid phase derived from a fish separation process was refined into a fish oil by a 3-stage aqueous refining method (1st stage citric acid treatment, 2nd stage sodium hydrogencarbonate treatment, 3rd stage treatment with an arginine solution (0.2mlor, volume ratio of 4% by volume) The aqueous emulsion phase obtained in the 3rd refining step had a milky character and an intense fishy odor, and the aqueous emulsion became an aqueous solution in which copper acetate (0.5 molar) and calcium chloride (1.5 molar) were dissolved Centrifugal phase separation (3800 rpm / 5 minutes) took place after 30 minutes The clarified water phase was transparent and almost odorless, the acid samples (test procedure according to Example 1) were negative compact mass, based on a sample was a water content of 7.3 G ew% determined (experimental procedure according to Example 1). A sample was taken which was stored at -40 ° C until the end of the experiment. The solid phase was placed in a vessel which was hermetically sealed and stored at about 22 ° C for 6 months in a darkened room. Subsequently, the stored and thawed Sample 1 were examined for color, odor, mycotic or microbial colonization, protein detection and fatty acid characterization.

Furthermore, an aggregate phase of an aqueous refining of thistle oil was investigated. This was obtained after a refining step with a 0.6 molar arginine solution (volume addition 3 vol%). The aqueous emulsion obtained after centrifugal phase separation showed a strong turbidity. An aggregation initiation was carried out with a copper (II) chloride solution (2 molar). After phase separation (3800 rpm / 5 minutes), transparent clarified water phase and a yellow pasty solid phase are obtained. Analogous to the previous experiment, samples of the water phase and the solid phase were taken and the storage of the solid phase was carried out as described. At the end of the trial at 6 months, the cryopreserved and stored samples were analyzed for mycotic or microbial colonization, stigmasterol, camesterol and tocopherol levels and qualitative detection of glycolipids and phospholipids by thin layer chromatography. Results:

The aggregate phase originating from fish waste refining had a protein content of 35% by weight, polyunsaturated fatty acids were present at 4.6% by weight, and phospholipids, at 12.4% by weight, which contained specimens preserved by freezing no difference in the composition or proportions by weight of the particular ingredients compared to the stored sample. In particular, there was no shift in the levels of polyunsaturated fatty acids. Mycotic or microbial colonization was absent in both samples.

In the aggregate phase of a vegetable oil refining, there was a content of β-sitosterols of 3.2% by weight and of alpha tocoperol with a weight fraction of 1.8% by weight. There was no difference in the content of the measured β-sitosterols or the alpha tocopherol content compared to the preserved solid sample. The chromatographically obtained bands, which i.a. Phosphotidylcholine and phosphoinosiols were in both samples sharply limited in the expression comparable, so there was no evidence of hydrolysis of the compounds.

Example 8

Large-scale application of the aggregation method.

2000kg of a Leindotter Press Oil with the Olkennzahlen: Phosphorus 33 ppm (or 33 mg / kg), Calcium 4.2 ppm (or 4.2 mg / kg), Magnesium 1, 7 ppm (or 1, 7 mg / kg), Iron 1, 1 ppm (or 1, 1 mg / kg), acid value 0.75% by weight, chlorophyll 6.2 ppm (or 6.2 mg / kg), in the first refining step with a citric acid solution (25% by weight) Volumetric addition 3% by volume) by conveying the phases by means of two metering pumps through a respective pipeline, which united in front of the dispersing tool, and into an in-line rotor-stator-shear mixer (Fluco DMS 2.2 / 26-10, Fluid Kotthoff , Germany) (rotor frequency 2500 rpm, throughput volume 3m ³ / h) were pumped where they were homogenized. The resulting water-in-oil emulsion was introduced into the original tank A. From this, the emulsion was pumped by means of a feed pump (delivery rate of 3 m ³ / h) into a plate separator (AC 1500-430 FO, Flottweg, Germany), which was at a drum speed of 6600 rpm (maximum centrifugal acceleration 10,000 g). was set. The oil had heated to a temperature of 32 ° to 35 ° C after exiting the separator and was pumped via a pipeline in the storage tank B. This was followed by a second aqueous refining step with sodium bicarbonate solution (10% by weight, volume addition 3% by volume) with the above-described test arrangement and in the same sequence, an inline homogenization (hereinafter introduced into the storage tank C) and a subsequent phase separation with the separator, with the same settings for the dispersion, the volume flow rates and temperature conditions. The oil phase was pumped into the storage tank D after the phase separation (temperature 33 ° C.). The refined oil had the following oil indices: phosphorus 8.2 ppm (or 8.2 mg / kg), calcium 0.21 ppm (or 0.21 mg / kg), magnesium 0.12 ppm (or 0.12 mg / kg), iron 0.09 ppm (or 0.09 mg / kg), acid value 0.35 wt% (g / 100g), chlorophyll 3.2 ppm (or 3.2 mg / kg). In the storage tank E, 5.4 kg of arginine were brought to complete dissolution in 50 L of ion-poor water. From this tank, the metered addition (volume addition 2% by volume) by means of the above-described metering through the pipe system to the flow of the oil phase from storage tank D. The phase mixture was continuously homogenized with the in-line intensive mixer described above (oil intake in storage tank F) and with the Separation unit carried out a phase separation, with the same settings as before. The resulting refined oil was pumped into the feed tank G and had a temperature of 37 ° C. From this, sampling for the analysis of oil indices. The separated aqueous emulsion was fed to the feed tank H. Here are the end of refining 49 I of a yellowish-green, highly cloudy emulsion included. The emulsion has an intense and pungent odor. 200 ml of the aqueous emulsion were taken from the storage tank H and, as described in Example 4, tested for the required minimum dose of copper II ions for aggregation initiation, with simultaneous spectroscopic analysis of the emulsion. The values of the temperature and the pH of the reaction solution were recorded. For a 2 molar copper II chloride solution, a minimum addition volume of 0.36 vol% is determined. The spectroscopic values were recorded. In the storage tank H a fork agitator was embedded, also took place via a hose the removal of the process water from the middle of the reactor, by means of a roller pump continuously through a spectroscopy measuring cell (AF26, Optitek, Germany) with a flow rate of 50mf / min The measuring cell was connected to a converter (Control 8000, Optitek, Germany). Hereby, the color spectrum in the visible light range and the NIR adsorption were determined continuously. Also, the temperature and pH of the reaction solution were continuously measured by pH and temperature probes immersed therein. Care was taken to insure that the same temperature and pH conditions exist as when testing for the minimum required dosage of the ion solution. The aqueous emulsion in feed tank H was agitated with the fork mixer at a speed of 300 rpm. Over a Roller pump, the 2 molar copper (II) chloride solution was first admitted into the storage tank H at a rate of 50 ml / minute for 5 minutes. Thereafter, the speed of the agitator were reduced to 80 / minute and the inlet flow rate to 10 ml / minute. The dosing was stopped at the time when the previously determined color spectrum (with turbidity compensation) in which aggregation initiation had been sufficiently initiated in the preliminary study was stopped. This was the case with an applied total volume of 210ml. The mixing process was then stopped. The values of the pH and the temperature of the reaction solution corresponded to those which were present in the preliminary test. After a standing time of 15 minutes via a bottom outlet of the feed tank H, promote solid / liquid phase through a pipeline into a Labordekanter (MD80, Lemitec, Germany,), hereby carried out a centrifugal separation of the solid phase (centrifugal 4,000 ^■ g, throughput volume 80 liters /Hour). The solid phase was conveyed to the container 1. The resulting water phase was passed to the template tank I. From this samples were taken for analysis. A turbidimetric measurement and investigation for the presence of organic compounds was made by adding concentrated hydrochloric acid to a sample until a pH of 1.0 was obtained. The water phase of the template tank I was passed through a 60 cm-long column filled with 800 g of Dowex 50 WX4 ion exchange resin by means of a roller pump at a flow rate of 0.5 liter / hour and introduced into the reservoir tank E1. From this, taking samples for the analysis of the arginine concentration (determination according to Example 4).

Another refining trial was carried out with the same crude oil and following the same procedure as described above. Subsequent to the refining stage 2, the addition of the purified water phase from feed tank E1 to the oil from feed tank D1, which was fed via the above-described pipe system to the in-line dispersion unit (hereinafter inlet into feed tank F1), followed by a phase separation, such as before and introduction of the oil phase in storage tank G1. The water phase is passed into storage tank H1. The volume obtained here was 45 liters. Taking samples from the storage tanks G1 and H1 for analysis, as described above. The aqueous emulsion was metered into a cupric chloride solution under the same feed conditions as described above. The control was carried out as before by means of a continuous spectroscopic analysis of the reaction mixture. The volume of the copper (II) chloride solution required to reach the spectroscopic target parameters was 201 ml. Phase separation took place after a standing time of 15 minutes, as described above. Introducing the clarified water phase in storage tank 11 and the solids phase in container 2. The weight of the container in container 1 and 2 solid phases is determined. From this, samples are taken for the determination of the water content, determined according to Example 1. Per 100g of the solid phases were submitted investigations for Lösungslauflaufschluss. For this purpose, inter alia, a solution in chloroform (300ml). Then add 30 ml of methanol and 10 ml of water. After stirring for 60 minutes in a water bath (40 ° C) phase separation. 100 ml of the chloroform phase were concentrated to dryness in a rotary evaporator. This was followed by suspension in n-hexane, and after the addition of the mass, the addition of a 10% ethanol solution, which had a pH of 2 by addition of HCl. Afterwards phase separation and removal of the clear hexane phase. This was prepared by gas chromatography for determination of the free fatty acids contained herein and measured. Carrying out a thin-layer chromatographic detection method (test procedure as in Example 1) of phospholipids of a sample of the methanol phase.

Results: The aqueous emulsion obtained after refining with an arginine solution could be clarified with a solution containing copper ions by aggregation initiation. It was possible to successfully control the aggregation initiation by large-scale spectroscopic parameters after dose determination on an experimental scale. The aggregation was complete, allowing for phase separation with a decanter. The water phase was optically and trubidimetrisch (5 FTU) transparent and without suspended matter and had a light blue color. Acidification did not result in solid precipitation. After passage of the clarified water phase through an ion exchange resin, this was slightly pale-yellowish, the ion exchange resin partially blue. The thus clarified and copper ion-purified solution was used for the 2nd time for the 3rd aqueous refining step, which was carried out under the same conditions as before. From this aqueous refining, an aqueous emulsion was obtained, which did not differ from the previously obtained. Aggregation initiation was possible by adjusting the addition of the copper Il ion solution over the previously determined spectroscopic parameters. The solids mass obtained therefrom after decantation was comparable to that obtained in the first separation (6.8 kg vs. 6.5 kg). The residual water content in the solid phase was determined to be 5.6 and 5.9% by weight. The clarification of the water phase was again complete, organic compounds could no longer be separated, the depletion of copper ions was again possible. The arginine concentration of the recycled arginine solution was 1 1, 2 wt% lower than that of the starting solution.

The oil refined with the arginine solution used for the first time did not differ in the oil performance figures obtained from the oil used with the recycled arginine solution Phosphorus: 0.8 / 0.9, calcium: <0.02 / <0.02, magnesium: <0.02 / <0.02, iron: <0.02 / <0.02, acid number : 0.03 / 0.04 chlorophyll 0.02 / 0.01.

In the schlesschichchromatographischen analysis of a methanolic digestion phase of the separated solid phase, the phospholipids phosphotidylcholine and phosphoinositol were detected.

Gas chromatographically, high concentrations of oleic, linoleic and linolenic acids as well as other fatty acids could be detected from a solvent digestion phase. In further digestion procedures fractions of squalene tocoperols, chloropyll and benzo [a] pyrene were detected.

Claims

claims

Process for the aggregation and separation of an organic substance mixture dissolved in an aqueous emulsion, characterized by the steps:

Process according to claim 1 for the aggregation and separation of an organic substance mixture dissolved in an aqueous emulsion, characterized by the steps:

a) providing an aqueous emulsion having organic compounds dissolved therein, the organic compounds being proteins, proteins, flavorings, waxes, fatty alcohols, perfumes, flavorings, carboxylic acids, phospholipids, glycolipids, glyceroglycolipids, phenols, sterols, chlorophylls and / or or Sinapine acts,

A process according to claim 1 or 2, wherein the aqueous emulsion according to step a) contains at least one guanidine or amidine group-carrying compound having a Kow of <6.3.

A method according to any one of claims 1-3, wherein the aqueous emulsion according to step a) from a refining of a lipid phase.

5. The method according to any one of claims 1-3, wherein the aqueous emulsion according to step a) originates from a nanoemulsive cleaning or decompexation process of organic compounds.

6. The method according to any one of claims 1-5, wherein the aqueous emulsion is an aqueous nanoemulsion.

7. The method according to any one of claims 1-6, wherein the step b) is carried out at a temperature of at most 75 ° C.

8. The method according to any one of claims 1-7, wherein copper (II) ions are separated from the aqueous solution after step c).

9. The method according to any one of claims 1-8, wherein together with or instead of the aqueous solution containing the copper (II) ions and / or calcium ions in step b) calcium oxide, magnesium oxide and / or zinc oxide in solid form or dispersed form of the aqueous emulsion be added with mixing until reaching an aggregate formation.

10. The method according to any one of claims 1-9 for the recovery of carboxylic acids, phospholipids, glycolipids, glyceroglycolipids, phenols, sterols, chlorophylls and / or sinapines.

1 1. A method according to any one of claims 1-9 for the production of proteins, proteins, flavorings, waxes, fatty alcohols, perfumes, flavorings, carboxylic acids, phospholipids, glycolipids, glyceroglycolipids, phenols, sterols, chlorophylls and / or sinapines.

12. Carboxylic acids, phospholipids, glycolipids, glyceroglycolipids, phenols, sterols, chlorophylls and / or sinapines obtainable by a process according to any one of claims 1-9, wherein the carboxylic acids, phospholipids, glycolipids, glyceroglycolipids, phenols, sterols, chlorophylls and / or sinapines having a purity of the respective class of compounds of> 75%.

13. Proteins, Proteins, Flavorings, Waxes, Fatty alcohols, Odorants, Flavorings, Carboxylic acids, Phospholipids, Glycolipids, Glyceroglycolipids, phenols, sterols, chlorophylls and / or sinapines obtainable by a process according to any one of claims 2-9, wherein the proteins, proteins, flavors, waxes, fatty alcohols, perfumes, flavorings, carboxylic acids, phospholipids, glycolipids, glyceroglycolipids, phenols, sterols , Chlorophylls and / or Sinapine with a purity of the respective class of compounds of> 75%.

Clarified aqueous phase containing dissolved guanidine and / or amidine group-bearing compounds according to step c) according to a method according to any one of claims 1-9.

A process according to any one of claims 1-9, wherein a clarified and / or purified water phase obtained after step c) is used for aqueous refining.

Obtaining neutral fats by a process according to any one of claims 1-9.