EP3152165A1 - Procédé et dispositifs pour la séparation d'une émulsion et la complexification de composés organiques dans des émulsions - Google Patents

Procédé et dispositifs pour la séparation d'une émulsion et la complexification de composés organiques dans des émulsions

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Publication number
EP3152165A1
EP3152165A1 EP15729368.9A EP15729368A EP3152165A1 EP 3152165 A1 EP3152165 A1 EP 3152165A1 EP 15729368 A EP15729368 A EP 15729368A EP 3152165 A1 EP3152165 A1 EP 3152165A1
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EP
European Patent Office
Prior art keywords
compounds
phase
aqueous
organic compounds
acid
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
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Application number
EP15729368.9A
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German (de)
English (en)
Inventor
Max DIETZ
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Drei Lilien Pvg Gmbh&co KG
Drei Lilien Pvg Gmbh&co KG
Original Assignee
Drei Lilien Pvg Gmbh&co KG
Drei Lilien Pvg Gmbh&co KG
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Application filed by Drei Lilien Pvg Gmbh&co KG, Drei Lilien Pvg Gmbh&co KG filed Critical Drei Lilien Pvg Gmbh&co KG
Publication of EP3152165A1 publication Critical patent/EP3152165A1/fr
Withdrawn legal-status Critical Current

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    • CCHEMISTRY; METALLURGY
    • C02TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02FTREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00Treatment of water, waste water, or sewage
    • C02F1/52Treatment of water, waste water, or sewage by flocculation or precipitation of suspended impurities
    • C02F1/5236Treatment of water, waste water, or sewage by flocculation or precipitation of suspended impurities using inorganic agents
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01DSEPARATION
    • B01D17/00Separation of liquids, not provided for elsewhere, e.g. by thermal diffusion
    • B01D17/02Separation of non-miscible liquids
    • B01D17/0208Separation of non-miscible liquids by sedimentation
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01DSEPARATION
    • B01D17/00Separation of liquids, not provided for elsewhere, e.g. by thermal diffusion
    • B01D17/02Separation of non-miscible liquids
    • B01D17/0217Separation of non-miscible liquids by centrifugal force
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01DSEPARATION
    • B01D17/00Separation of liquids, not provided for elsewhere, e.g. by thermal diffusion
    • B01D17/02Separation of non-miscible liquids
    • B01D17/04Breaking emulsions
    • B01D17/047Breaking emulsions with separation aids
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01DSEPARATION
    • B01D17/00Separation of liquids, not provided for elsewhere, e.g. by thermal diffusion
    • B01D17/02Separation of non-miscible liquids
    • B01D17/04Breaking emulsions
    • B01D17/048Breaking emulsions by changing the state of aggregation
    • CCHEMISTRY; METALLURGY
    • C02TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02FTREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00Treatment of water, waste water, or sewage
    • C02F1/001Processes for the treatment of water whereby the filtration technique is of importance
    • CCHEMISTRY; METALLURGY
    • C02TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02FTREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00Treatment of water, waste water, or sewage
    • C02F1/38Treatment of water, waste water, or sewage by centrifugal separation
    • C02F1/385Treatment of water, waste water, or sewage by centrifugal separation by centrifuging suspensions
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    • C02TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02FTREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00Treatment of water, waste water, or sewage
    • C02F1/40Devices for separating or removing fatty or oily substances or similar floating material
    • CCHEMISTRY; METALLURGY
    • C02TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02FTREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00Treatment of water, waste water, or sewage
    • C02F1/52Treatment of water, waste water, or sewage by flocculation or precipitation of suspended impurities
    • C02F1/54Treatment of water, waste water, or sewage by flocculation or precipitation of suspended impurities using organic material
    • C02F1/56Macromolecular compounds
    • CCHEMISTRY; METALLURGY
    • C02TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02FTREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00Treatment of water, waste water, or sewage
    • C02F1/68Treatment of water, waste water, or sewage by addition of specified substances, e.g. trace elements, for ameliorating potable water
    • C02F1/681Treatment of water, waste water, or sewage by addition of specified substances, e.g. trace elements, for ameliorating potable water by addition of solid materials for removing an oily layer on water
    • CCHEMISTRY; METALLURGY
    • C07ORGANIC CHEMISTRY
    • C07BGENERAL METHODS OF ORGANIC CHEMISTRY; APPARATUS THEREFOR
    • C07B63/00Purification; Separation; Stabilisation; Use of additives
    • C07B63/02Purification; Separation; Stabilisation; Use of additives by treatment giving rise to a chemical modification
    • CCHEMISTRY; METALLURGY
    • C07ORGANIC CHEMISTRY
    • C07FACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F9/00Compounds containing elements of Groups 5 or 15 of the Periodic Table
    • C07F9/02Phosphorus compounds
    • C07F9/06Phosphorus compounds without P—C bonds
    • C07F9/08Esters of oxyacids of phosphorus
    • C07F9/09Esters of phosphoric acids
    • C07F9/10Phosphatides, e.g. lecithin
    • C07F9/103Extraction or purification by physical or chemical treatment of natural phosphatides; Preparation of compositions containing phosphatides of unknown structure
    • CCHEMISTRY; METALLURGY
    • C07ORGANIC CHEMISTRY
    • C07FACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F9/00Compounds containing elements of Groups 5 or 15 of the Periodic Table
    • C07F9/02Phosphorus compounds
    • C07F9/06Phosphorus compounds without P—C bonds
    • C07F9/08Esters of oxyacids of phosphorus
    • C07F9/09Esters of phosphoric acids
    • C07F9/117Esters of phosphoric acids with cycloaliphatic alcohols
    • CCHEMISTRY; METALLURGY
    • C11ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11BPRODUCING, e.g. BY PRESSING RAW MATERIALS OR BY EXTRACTION FROM WASTE MATERIALS, REFINING OR PRESERVING FATS, FATTY SUBSTANCES, e.g. LANOLIN, FATTY OILS OR WAXES; ESSENTIAL OILS; PERFUMES
    • C11B1/00Production of fats or fatty oils from raw materials
    • C11B1/10Production of fats or fatty oils from raw materials by extracting
    • C11B1/108Production of fats or fatty oils from raw materials by extracting after-treatment, e.g. of miscellae
    • CCHEMISTRY; METALLURGY
    • C11ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11BPRODUCING, e.g. BY PRESSING RAW MATERIALS OR BY EXTRACTION FROM WASTE MATERIALS, REFINING OR PRESERVING FATS, FATTY SUBSTANCES, e.g. LANOLIN, FATTY OILS OR WAXES; ESSENTIAL OILS; PERFUMES
    • C11B3/00Refining fats or fatty oils
    • C11B3/006Refining fats or fatty oils by extraction
    • CCHEMISTRY; METALLURGY
    • C11ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11BPRODUCING, e.g. BY PRESSING RAW MATERIALS OR BY EXTRACTION FROM WASTE MATERIALS, REFINING OR PRESERVING FATS, FATTY SUBSTANCES, e.g. LANOLIN, FATTY OILS OR WAXES; ESSENTIAL OILS; PERFUMES
    • C11B3/00Refining fats or fatty oils
    • C11B3/008Refining fats or fatty oils by filtration, e.g. including ultra filtration, dialysis
    • CCHEMISTRY; METALLURGY
    • C11ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11BPRODUCING, e.g. BY PRESSING RAW MATERIALS OR BY EXTRACTION FROM WASTE MATERIALS, REFINING OR PRESERVING FATS, FATTY SUBSTANCES, e.g. LANOLIN, FATTY OILS OR WAXES; ESSENTIAL OILS; PERFUMES
    • C11B3/00Refining fats or fatty oils
    • C11B3/02Refining fats or fatty oils by chemical reaction
    • CCHEMISTRY; METALLURGY
    • C11ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11BPRODUCING, e.g. BY PRESSING RAW MATERIALS OR BY EXTRACTION FROM WASTE MATERIALS, REFINING OR PRESERVING FATS, FATTY SUBSTANCES, e.g. LANOLIN, FATTY OILS OR WAXES; ESSENTIAL OILS; PERFUMES
    • C11B3/00Refining fats or fatty oils
    • C11B3/16Refining fats or fatty oils by mechanical means
    • CCHEMISTRY; METALLURGY
    • C02TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02FTREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00Treatment of water, waste water, or sewage
    • C02F2001/007Processes including a sedimentation step
    • CCHEMISTRY; METALLURGY
    • C02TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02FTREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2101/00Nature of the contaminant
    • C02F2101/30Organic compounds
    • CCHEMISTRY; METALLURGY
    • C02TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02FTREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2103/00Nature of the water, waste water, sewage or sludge to be treated
    • C02F2103/22Nature of the water, waste water, sewage or sludge to be treated from the processing of animals, e.g. poultry, fish, or parts thereof
    • CCHEMISTRY; METALLURGY
    • C02TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02FTREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2103/00Nature of the water, waste water, sewage or sludge to be treated
    • C02F2103/26Nature of the water, waste water, sewage or sludge to be treated from the processing of plants or parts thereof
    • CCHEMISTRY; METALLURGY
    • C02TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02FTREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2103/00Nature of the water, waste water, sewage or sludge to be treated
    • C02F2103/32Nature of the water, waste water, sewage or sludge to be treated from the food or foodstuff industry, e.g. brewery waste waters
    • CCHEMISTRY; METALLURGY
    • C02TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02FTREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2209/00Controlling or monitoring parameters in water treatment
    • C02F2209/09Viscosity

Definitions

  • the present invention relates to the provision of a method for separating an organic substance mixture from an aqueous emulsion.
  • 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.
  • 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.
  • 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.
  • 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.
  • 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.
  • 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 .
  • chemical reactions occur which lead to an unwanted change in the dissolved organic compounds.
  • 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.
  • 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.
  • 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.
  • 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:
  • organic compounds are carboxylic acids, phospholipids, glycolipids, glyceroglycolipids, phenols, sterols, chlorophylls, sinapines, peptides, proteins, carbohydrates, lipo-proteins, waxes and / or fatty alcohols
  • step b) mixing the emulsion of step a) with an aqueous solution containing copper (II) ions and / or calcium ions until aggregate formation,
  • step b) separating the aggregates from step b) by sedimentation, filtration or centrifugation after obtaining an aggregated phase of the organic compounds from step b).
  • 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.
  • 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.
  • the aqueous extraction mixture may be an aqueous extraction solution or extraction suspension.
  • 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:
  • aqueous emulsion having organic compounds dissolved therein, wherein the organic compounds are carboxylic acids, phospholipids, glycolipids, glyceroglycolipids, phenols, sterols, chlorophylls and / or sinapines,
  • step b) mixing the emulsion of step a) with an aqueous solution containing copper (II) ions and / or calcium ions until aggregate formation,
  • 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:
  • aqueous emulsion having organic compounds dissolved therein, wherein the organic compounds are carboxylic acids, phospholipids, glycolipids, glyceroglycolipids, phenols, sterols, chlorophylls and / or sinapines,
  • stage 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,
  • step b) separating the aggregates from step b) by sedimentation, filtration or centrifugation after obtaining an aggregated phase of the organic compounds from step b).
  • 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:
  • aqueous emulsion having organic compounds dissolved therein, wherein the organic compounds are carboxylic acids, phospholipids, glycolipids, glyceroglycolipids, phenols, sterols, chlorophylls and / or sinapines,
  • step b) mixing the emulsion of step a) with calcium oxide, magnesium oxide and / or zinc oxide until aggregate formation,
  • step b) 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 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:
  • the organic compounds are carboxylic acids, phospholipids, glycolipids, glyceroglycolipids, phenols, sterols, chlorophylls and / or sinapines
  • step b) separating the aggregates from step b) by sedimentation, filtration or centrifugation after obtaining an aggregated phase of the organic compounds from step b).
  • step a) in the processes disclosed herein 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
  • 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.
  • 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.
  • the invention relates to a method for aggregating organic compounds dissolved in a neutral or basic aqueous emulsion or nanoemulsion.
  • 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.
  • 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.
  • 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.
  • 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.
  • 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.
  • dissolved calcium compounds as well as undissolved calcium oxide compounds are capable of initiating aggregate formation as found for the ionic copper compounds.
  • 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.
  • 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.
  • 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.
  • a loss of guanidine and / or amidino-containing compounds from the process water can be reduced to a minimum.
  • 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.
  • 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.
  • 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.
  • 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.
  • the copper ions remaining in the process water 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.
  • 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.
  • 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.
  • 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.
  • 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.
  • 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.
  • 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.
  • 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.
  • 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.
  • 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.
  • 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.
  • 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.
  • 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.
  • drying of the organic aggregation phase can be carried out.
  • 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.
  • 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).
  • 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.
  • 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.
  • ions which allow the initiation of aggregation according to the invention include magnesium (II), zinc (II) and iron (II), and iron (III) and aluminum.
  • 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.
  • 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.
  • 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.
  • 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.
  • 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.
  • 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.
  • 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.
  • 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> 10 ⁇ .
  • 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.
  • DLS light feedback control
  • 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 10 ⁇ .
  • 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.
  • 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.
  • 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.
  • 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.
  • 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.
  • 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.
  • the complexation of the in a emulsion or nanoemulsion consisting of the claimed guanidine and / or Amidin recognitiontragenden compounds and carboxylic acids, dissolved organic compounds present with copper ions, a particularly advantageous embodiment of the separation process of dissolved organic compounds.
  • 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.
  • 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.
  • 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.
  • the process control is carried out by measuring the pH of the reaction mixture.
  • 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.
  • an aqueous solution containing guanidine and / or amidino group-containing compounds can be removed by an aggregation of the invention.
  • 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.
  • 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.
  • methanol, ethanol, 1-butanol, as well as small amounts of water may be used, optionally with the addition of an acid or a base.
  • combinations of the aforementioned classes of compounds are possible.
  • 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.
  • 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.
  • 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.
  • 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.
  • 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.
  • 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.
  • 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.
  • 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.
  • 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
  • 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.
  • 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.
  • 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.
  • 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.
  • 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.
  • 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.
  • 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.
  • 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.
  • 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.
  • 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.
  • 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.
  • 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.
  • 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.
  • 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.
  • 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 phase containing one or more guanidine- and / or amidine-containing 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.
  • 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.
  • 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.
  • the volume of the water phase should be reduced to the required minimum.
  • 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.
  • lipid phases such 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.
  • 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.
  • 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.
  • 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.
  • 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.
  • 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.
  • 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.
  • 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.
  • 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.
  • 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.
  • 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.
  • 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.
  • 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.
  • 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.
  • 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.
  • 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.
  • 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.
  • 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.
  • 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.
  • the production of nanoemulsion can be significantly accelerated, in addition, the viscosity of the resulting nanoemulsion decreases.
  • the nanoemulsion is prepared only by the intensive entry into the lipid phase, it may be necessary to heat the lipid phase as well.
  • 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.
  • nanoemulsion prepared by the intensive input of the nanoemulsions aqueous solution containing guanidine or amidine group-bearing compounds, in a lipid phase.
  • 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.
  • 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.
  • carboxylic acids oleic acid and stearic acid are the preferred nano-emulsifiable carboxylic acids in the lipid phase.
  • preferred carboxylic acids are those for a nanoemulsive refining, phytic acid and sinapinic acid.
  • 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
  • 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.
  • 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.
  • the color reaction and color intensity can be used with addition of copper-containing compounds.
  • 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.
  • the color reaction also depends on the pH present.
  • the continuous monitoring of the pH also serves to control the metering device for the addition of a copper ion-containing aqueous medium.
  • pH monitoring is an important tool for optimized addition of calcium oxide compounds as well as
  • Alkaline earth metal oxides and metal oxides Alkaline earth metal oxides and metal oxides.
  • 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.
  • the addition of calcium to an aqueous emulsion initially leads only to a slow increase in the calcium ion concentration.
  • 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.
  • 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.
  • 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.
  • 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.
  • 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.
  • very dilute or highly concentrated solutions can be used.
  • 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.
  • 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.
  • 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.
  • 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.
  • 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.
  • 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.
  • 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.
  • 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
  • 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.
  • 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.
  • the aggregates can be easily separated with a decanter, the free water phase.
  • 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.
  • 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.
  • 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.
  • 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.
  • 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.
  • phase separation that occurs after sufficient aggregation formation can be carried out using the prior art separation methods listed herein.
  • 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.
  • 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.
  • 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.
  • a highly nonpolar solvent such as hexane or dimethyl ether
  • 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.
  • centrifugal phase separation refers to a separation of phases utilizing centrifugal acceleration.
  • 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.
  • 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.
  • the sieve size depends on the size of the aggregates to be separated, generally nominal pore sizes of ⁇ 100 ⁇ more preferably ⁇ 50 ⁇ and most preferably ⁇ 20 ⁇ suitable for complete separation of the solids and suspended solids of the organic compounds.
  • 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.
  • 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.
  • 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 0.04 ⁇ ). This is not the case with the ions. However, a separation can be carried out using established methods.
  • 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.
  • adsorption of the ions by adsorbents suitable for this purpose are, for. B. ion exchange resins.
  • Another possibility is chemical binding of the ions.
  • 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.
  • 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.
  • 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.
  • 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)
  • 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.
  • 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 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
  • 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 Dekomplex michsvon come from. Contained therein may be the organic compounds listed herein in dissolved or partially complexed form.
  • 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.
  • 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.
  • 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.
  • 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 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
  • 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 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.
  • the presence of a free water phase according to the invention z.
  • DLS laser beam reflection analysis
  • 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
  • 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 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.
  • organic compounds of various groups of substances are found, which are present individually, but usually in different combinations and in a different ratio.
  • waxes such as 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 ⁇ -sitosterol and campesterol, as well as Sigmasterol, Sterols, Sinapine, Squalene. Phytoestrogens, such as isoflavones or lignans.
  • steroids and their derivatives such as saponins, furthermore glycolipids as well as glyceroglycolipids and glycerosphingolipids, furthermore rhamnolipids, sophrolipids, trehalose lipids, mannosterylerythritol lipids.
  • polysaccharides including pectins such as rhamnogalacturonans and polygalacturonic acid esters, arabinans (homoglycans), galactans and arabinogalactans, as well as pectic acids and amidopectins.
  • phospholipids in particular phosphotidylinositol, phosphatides, such as phosphoinositol, furthermore long-chain or cyclic carbon compounds, furthermore fatty alcohols, hydroxy and epoxy fatty acids.
  • phospholipids in particular phosphotidylinositol, phosphatides, such as phosphoinositol, furthermore long-chain or cyclic carbon compounds, furthermore fatty alcohols, hydroxy and epoxy fatty acids.
  • 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.
  • 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 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
  • 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.
  • saturated fatty acids saturated fatty acids
  • double bond bridges unsaturated fatty acids
  • fatty acids such compounds having more than 4 consecutive carbon atoms besides the carboxyl group are referred to as fatty acids.
  • 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).
  • monoolefin fatty acids are myristoleic acid, palmetoleic acid, petroselinic acid, oleic acid, elaidic acid, dicelic acid and the euruca acid.
  • polyolefins fatty acids are linoleic acid, linolenic acid, punicic acid, arachidonic acid and nervonic acid.
  • Fatty acids may also carry functional groups such as.
  • the functional groups herein also include terminal carbon cyclic radicals.
  • fatty acids 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
  • 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,
  • 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.
  • saturated fatty acids saturated fatty acids
  • double bond bridges unsaturated fatty acids
  • 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 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 Rice germ wax, sugarcane wax, ouricury wax and montan wax.
  • animal waxes are beeswax, shellac wax, spermaceti, lanolin (wool wax) and raffia fat.
  • petrochemical waxes are petrolatum, paraffin waxes and microwaxes.
  • olfactory and flavor is also synonymously used herein with flavoring.
  • organic compounds are present which lead to a sensory perception in the Meaning of a taste or an odor.
  • 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, d
  • 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).
  • 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.
  • 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).
  • 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).
  • 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.
  • Compounds having more than one guanidino group and more than one carboxylate group are, for example, oligoarginine and polyarginine.
  • Preferred arginine derivatives are compounds of the following general formula (I) or (II)
  • 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 , - ⁇ 3 ⁇ , -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-
  • L is a hydrophilic substituent selected from the group consisting of:
  • dyes summarizes organic compounds which occur in oils and fats of biogenic origin, typically in different quantities and compositions side by side.
  • 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
  • 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.
  • 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.
  • chlororophylls 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 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
  • glycerophospholipids 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.
  • phosphatidylcholines also called lecithins as
  • phosphatidylethanolamines phosphatidylserines.
  • Glycophosphatidylinositols are compounds in which saccharideglycosidically bound to the inositol group of phosphatidylinositols
  • 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.
  • 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
  • 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.
  • 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 markets pointed. 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.
  • the separated carboxylic acids can be fractionated at a purity of> 85%, more preferably> 95% and most preferably> 98% for their class of material.
  • processes in the refining of vegetable oils or animal fats process fluids in wood processing or bio-technological production of carboxylic acids.
  • 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.
  • 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%.
  • 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.
  • organic dye 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.
  • 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%.
  • peptides and proteins such as albumins and globulins.
  • proteins such as albumins and globulins.
  • mucilage 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.
  • phospholipids especially Phosphotidylcholine and phosphoinositols and glycolipids and Glycerglycolipide.
  • 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.
  • 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.
  • 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.
  • 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).
  • a pure and low-hydrolysis phospholipid fraction having a purity of preferably> 90%, more preferably> 95%, and most preferably> 98%.
  • 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%.
  • 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 ),
  • 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.
  • 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.
  • 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:
  • 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.
  • Step b) in the aforementioned method may alternatively also be as follows:
  • step 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
  • 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:
  • step b) mixing the emulsion of step a) with an aqueous solution containing copper (II) ions and / or calcium ions until aggregate formation,
  • Step b) in the aforementioned method may alternatively also be as follows:
  • step 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 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:
  • 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.
  • organic compounds are carboxylic acids, phospholipids, glycolipids, glyceroglycolipids, phenols, sterols, chlorophylls and / or sinapines
  • step b) mixing the emulsion of step a) with an aqueous solution containing copper (II) ions and / or calcium ions until aggregate formation,
  • step b) 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:
  • step 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 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.
  • Step b) in the aforementioned method may alternatively also be as follows:
  • step 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.
  • 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:
  • step 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) 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:
  • step 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.
  • 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.
  • 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:
  • 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.
  • organic compounds are carboxylic acids, phospholipids, glycolipids, glyceroglycolipids, phenols, sterols, chlorophylls and / or sinapines
  • step b) separating the aggregates from step b) by sedimentation, filtration or centrifugation after obtaining an aggregated phase of the organic
  • Step b) in the aforementioned method may alternatively also be as follows:
  • step 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.
  • 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:
  • 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.
  • step 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) separating the aggregates from step b) by sedimentation, filtration or centrifugation after obtaining an aggregated phase of the organic
  • Step b) in the aforementioned method may alternatively also be as follows:
  • step 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.
  • 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:
  • step b) mixing the emulsion of step a) with an aqueous solution containing copper (II) ions and / or calcium ions with a laminar stirrer until
  • step b) 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:
  • step 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 .
  • 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:
  • 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.
  • organic compounds are carboxylic acids, phospholipids, glycolipids, glyceroglycolipids, phenols, sterols, chlorophylls and / or sinapines
  • step 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) 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:
  • step 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 Laminarrrockwerk until aggregation.
  • 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:
  • 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.
  • step 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,
  • 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.
  • 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:
  • step 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) 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:
  • step 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.
  • 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:
  • 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.
  • Step b) in the aforementioned method may alternatively also be as follows:
  • step 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
  • 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:
  • organic compounds are carboxylic acids, phospholipids, glycolipids, glyceroglycolipids, phenols, sterols, chlorophylls and / or sinapines.
  • step b) mixing the emulsion of step a) with an aqueous solution containing copper (II) ions until aggregate formation
  • step b) 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:
  • step 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.
  • 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:
  • aqueous emulsion having organic compounds dissolved therein, wherein the organic compounds are carboxylic acids, phospholipids, glycolipids, glyceroglycolipids, phenols, sterols, chlorophylls and / or sinapines,
  • step 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,
  • step b) separating the aggregates from step b) by sedimentation, filtration or centrifugation after obtaining an aggregated phase of the organic
  • Step b) in the aforementioned method may alternatively also be as follows:
  • step 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.
  • 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 ⁇ .
  • DLS non-invasive laser light backscatter analysis
  • 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.
  • 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.
  • 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.
  • 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.
  • 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.
  • 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.
  • a sodium or potassium salt solution there was no aggregation of organic compounds up to the maximum volume ratio used of 10% by volume.
  • 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.
  • 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.
  • the calculated amount of trapped and discharged water was below 5% by weight for solid phases obtained by copper ion addition.
  • 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.
  • 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).
  • aqueous solutions in each case 3 molar
  • 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.
  • 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.
  • 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.
  • 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).
  • the aggregate phase was suspended in an ethyl acetate / water mixture (80/20, v / v) and agitated at 40 ° C for 10 minutes.
  • 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).
  • 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.
  • 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.
  • 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.
  • 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.
  • 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.
  • the water content was between 18 and 36% by weight.
  • VTM1 squalene
  • VTM2, VTM5 protein compounds
  • VTM3 triglycerides
  • phenolic acids such as chlorogenic acid and caffeic acid (VTM4) could be detected.
  • 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.
  • 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.
  • the minimum concentration of copper ion addition required to initiate complete aggregation initiation was determined.
  • 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.
  • a sample (2 ml) was taken for particle size determination (method and procedure, see Methods of measurement).
  • 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 Einrhak,. 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.
  • 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.
  • 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.
  • 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.
  • 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.
  • isopopyl alcohol and HCl 25 wt%
  • 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.
  • 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).
  • larger aggregates (4000 to 6000 nm) were formed and the frequency of smaller particles decreased.
  • no particles in the aqueous phase were smaller than 10 ⁇ in the measuring range.
  • 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).
  • 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.
  • 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.
  • 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.
  • 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.
  • 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).
  • 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.
  • 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.
  • the resulting water-in-oil emulsion was introduced into the original tank A. Fr