EP3149133A1 - Procédé de clarification de phases lipidiques raffinées - Google Patents

Procédé de clarification de phases lipidiques raffinées

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Publication number
EP3149133A1
EP3149133A1 EP15730076.5A EP15730076A EP3149133A1 EP 3149133 A1 EP3149133 A1 EP 3149133A1 EP 15730076 A EP15730076 A EP 15730076A EP 3149133 A1 EP3149133 A1 EP 3149133A1
Authority
EP
European Patent Office
Prior art keywords
water
phase
oil
lipid
lipid phase
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.)
Granted
Application number
EP15730076.5A
Other languages
German (de)
English (en)
Other versions
EP3149133B1 (fr
Inventor
Max DIETZ
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Drei Lilien Pvg Gmbh&co KG
SE Tylose GmbH and Co KG
Original Assignee
Drei Lilien Pvg Gmbh&co KG
SE Tylose GmbH and Co KG
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Application filed by Drei Lilien Pvg Gmbh&co KG, SE Tylose GmbH and Co KG filed Critical Drei Lilien Pvg Gmbh&co KG
Priority to PL15730076T priority Critical patent/PL3149133T3/pl
Publication of EP3149133A1 publication Critical patent/EP3149133A1/fr
Application granted granted Critical
Publication of EP3149133B1 publication Critical patent/EP3149133B1/fr
Not-in-force legal-status Critical Current
Anticipated expiration legal-status Critical

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11B—PRODUCING, 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
    • C11B3/00—Refining fats or fatty oils
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11B—PRODUCING, 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
    • C11B3/00—Refining fats or fatty oils
    • C11B3/001—Refining fats or fatty oils by a combination of two or more of the means hereafter
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11B—PRODUCING, 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
    • C11B3/00—Refining fats or fatty oils
    • C11B3/10—Refining fats or fatty oils by adsorption
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11B—PRODUCING, 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
    • C11B1/00—Production of fats or fatty oils from raw materials
    • C11B1/10—Production of fats or fatty oils from raw materials by extracting
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11B—PRODUCING, 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
    • C11B3/00—Refining fats or fatty oils
    • C11B3/006—Refining fats or fatty oils by extraction
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11B—PRODUCING, 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
    • C11B3/00—Refining fats or fatty oils
    • C11B3/02—Refining fats or fatty oils by chemical reaction
    • C11B3/06—Refining fats or fatty oils by chemical reaction with bases
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11B—PRODUCING, 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
    • C11B3/00—Refining fats or fatty oils
    • C11B3/16—Refining fats or fatty oils by mechanical means

Definitions

  • the present invention relates to a process for the separation of suspensions from a lipid phase.
  • Lipid phases of biogenic origin contain in addition to the wished for further use neutral fats, such.
  • neutral fats such.
  • triglycerides usually numerous organic impurities, which provide in the biological context from which the lipids come, for a solubilization. Therefore, these concomitants, despite their overall amphiphilic properties, often have remarkably high lipophilicity. This depends on the ratio of hydrophilic and hydrophobic moieties.
  • sterol glycosides and hydrophobic dyes such as carotenes and chlorophylls are included.
  • Such compounds are completely water-insoluble and therefore remain in the lipid phase in an aqueous refining.
  • all of the above compounds are capable of small amounts of water molecules via electrostatic exchange forces z. B. to bind to OH groups.
  • the aforementioned compounds are furthermore usually present together in complex structures, including ions from the group of the alkaline earth metals and the metals. This further increases the cohesion in the area of hydrophilic groups. This explains why it is necessary to purify such lipid mixtures with aqueous media containing strong bases and strong acids.
  • turbidity In contrast to complex organic structures, also referred to as turbidity, which can be imaged by means of optical techniques and are therefore extractable and separable as a corpuscular structure by filtration, the turbidity herein is characterized by the fact that they do not rely on a filter technique based on a size exclusion based on particulate particles, can be separated.
  • the dried oils were transparent. In such oils could be added by mixing with water relevant amounts of water, so that these oils were cloudy again and could not be clarified by centrifugal processing techniques.
  • a reduction of the residual moisture of a refined lipid phase is desired in order to obtain as clear a oil as possible, but also for the improvement of the quality of the oil the residual moisture is a decisive determinant.
  • Another aspect of residual moisture of a lipid phase relates to storage stability, which is adversely affected by a higher content of water molecules remaining in a lipid phase. However, this also occurs when compounds are present in the lipid phase, the water molecules, eg. B. from the air, can bind.
  • Container surfaces and the presence of compounds that can cause oxidation of carbon double bonds (see p-Anisidinwertbetician), and the presence of compounds that allow a radical or reduction of radicals, such as tocopherols, polyphenols or squalene.
  • the oxidative processes include aldehydes, ketones and free fatty acids, which further accelerate oxidative processes and are largely responsible for off-flavors in vegetable oils.
  • the degumming process occurs usually a reduction of compounds that cause oxidative processes.
  • oils with bleaching earths can lead to acid-catalyzed oxidations and, to a variable extent, compounds which have antioxidative properties are depleted, so that the oxidation stability of an oil can be markedly worsened by this process step.
  • the same applies to the deodorization process especially when higher steam temperatures (> 220 ° C) and a longer residence time (> 15 minutes) of the oil are required. Therefore, the storage stability is influenced by the classical methods to varying degrees.
  • such refined oils often have no advantage in terms of storage stability, since in the native oils the antioxidants contained therein have been left and no compounds have been added which promote auto-oxidation.
  • Substances that promote auto-oxidation usually have free-radical or radical-forming groups, or have a binding capacity for water molecules. A targeted depletion of these compounds is not possible in the prior art.
  • Object of the present invention is to provide methods for the separation of turbidity from a lipid phase. This object is achieved by the technical teaching of the independent claims. Further advantageous embodiments of the invention will become apparent from the dependent claims, the description, the figures and the examples. Detailed description of the invention
  • Biogenic lipid phases which were obtained under anhydrous conditions, usually have a clear appearance, as far as suspended solids, which are confusingly often referred to in the literature as turbidity, were filtered off.
  • water entry into these lipid phases is difficult to achieve because the compounds capable of binding water molecules are so complexed in the lipid phase that they are shielded by the surrounding neutral lipid phase.
  • This complex cohesion which is made possible, in particular, by non-hydratable phospholipids, as well as by alkaline earth metal ions and metal ions, must first be disrupted so that these compounds can interact with water molecules and thereby be converted into a water phase in order to remove them with the water phase.
  • lipid phases in addition to an optional classical aqueous degumming, which can be done with pure water and / or an acid (eg phosphoric acid), a subsequent, at least 2-stage treatment with mild to strongly basic compounds, optimal reduction of accompanying substances is possible.
  • an optional classical aqueous degumming which can be done with pure water and / or an acid (eg phosphoric acid)
  • a subsequent, at least 2-stage treatment with mild to strongly basic compounds, optimal reduction of accompanying substances is possible.
  • the water content and the turbidity in the refined oil increased when particularly good refining results were achieved. This was particularly noticeable when refining was carried out with intensive mixing with an aqueous solution containing guanidine or amidine group-bearing compounds.
  • the resulting emulsions were significantly cloudier than after stirring addition of the aqueous refining solution. This is due to a much more homogeneous distribution of the water fraction in the oil phase, which could be demonstrated by measuring the droplet sizes herein by means of a DLS measurement. Further, the tendency for coalescence of the formed droplets was significantly lower after intensive application of the water phase than after stirring. The long-term stability of such an emulsion was also significantly higher.
  • cellulose compounds allow complete clarification of the hydrated cloudy oils resulting from an aqueous refining, which was carried out as described herein and in which subsequently values of the oil indices were such.
  • B. are to comply with edible oils, such as a residual phosphorus content of ⁇ 5 ppm (or ⁇ 5 mg / kg) and a content of free fatty acids of ⁇ 0.15% by weight. This is all the more surprising because the cellulose products according to the invention can be distributed only disperse in an oil phase and have only a limited binding capacity for water.
  • a particularly advantageous effect of the process according to the invention is to refine an aqueous refined lipid phase in which the water-binding organic turbid substances are present in a hydrated form, in that an interaction of the turbid substances with other compounds is achieved so that the turbid substances can be extracted from their organic matrix can be made.
  • a preferred embodiment is therefore to provide a lipid phase in process step a) in which organic turbid substances are present in a hydrated form.
  • the object is achieved by a method for the adsorption and extraction or complexing and extraction of hydrophilic organic lipophilic Trübstoffen aqueous refined lipid phases, which is characterized by a) providing a lipid phase containing water-binding organic lipophilic Trübstoffe, wherein the lipid phase of at least one aqueous refining with a b) contacting an adsorbent and / or a complexing agent with the lipid phase from step a),
  • the adsorbent is cellulose, a cellulose derivative or an inorganic alumina silicate with an aluminum content of> 0.1 mol%
  • the complexing agent is aluminum ions or iron ions present in an aqueous solution.
  • a further embodiment according to the invention is a process for the separation of water-binding organic lipophilic turbidity substances from an aqueous refined lipid phase, which is characterized by
  • lipid phase containing water-binding organic lipophilic turbidities, wherein the lipid phase has been subjected to at least one aqueous refining with a neutral or basic solution
  • lipid phase b) adding the lipid phase from step a) with an adsorbent and / or a complexing agent
  • the adsorbent is cellulose, a cellulose derivative or an inorganic alumina silicate having an aluminum content of> 0.1 mol%, and
  • the complexing agent is aluminum ions or iron ions present in an aqueous solution.
  • the provided contaminant-containing lipid phase must be subjected to at least one aqueous refining with a neutral to basic solution in order to ensure a sufficient reduction of accompanying substances of the prepurified lipid phase.
  • a neutral solution is understood to mean water.
  • a basic solution is an aqueous solution whose pH is greater than 7.
  • hydroxide compounds in particular with monovalent cations of the alkaline earth metals, such as sodium hydroxide, potassium hydroxide, but In principle, any basic compound which dissociates in water and is known to the person skilled in the art can be used.
  • a preferred embodiment of the process is the provision of a lipid phase in process step a) which has been subjected to at least one pre-purification step with a basic and / or acidic solution.
  • lipid phase in which, after an aqueous refining with a guanidine group or amidine group-bearing compound, a substantially complete reduction of phosphorus-containing compounds alkaline earth metal ions and metal free acid groups has been achieved.
  • the water-binding organic turbidities in the prepurified lipid phase are then brought into contact with an adsorption and / or complexing agent in step b).
  • the water-binding organic lipophilic turbidity is adsorbed on suitable adsorbents or can form complexes with certain ions that are largely insoluble in water, but can be separated by their complexity in a water phase.
  • the process is completed by in step c) the separation of the adsorbed or Complexed turbidity from step b) by a phase separation, the adhered or complexed water-binding organic Trübstoffe can be separated together with the extractant to obtain a low-turbidity and largely anhydrous lipid phase.
  • step a) the at least one aqueous extraction by means of an aqueous solution with at least one Guanidin phenomenon- or Amidin distributiontragende compound having a K ow of ⁇ 6.3 is performed.
  • K 0 w refers to the distribution coefficient between n-octanol and water.
  • Another important process feature is the provision of adhesion and complexing agents.
  • cellulose products is a preferred embodiment for the adsorption of hydrogenated water-binding organic turbidity according to the invention.
  • Cellulose and hemicellulose are preferred. These may be in their natural chemical structure or chemically modified by having substituents. Only a few examples may be mentioned here as examples, such as carboxymethylcellulose, hydroxyethylcellulose, methylhydroxyethylcellulose, methylhydroxypropylcellulose, ethylhydroxyethylcellulose, hydroxypropylcellulose, methylcellulose.
  • Cellulose ester compounds are preferred. Further preferred compounds are cellulose ethers. It may be a fibrous, crystalline or amorphous form.
  • the molecular weight is in principle arbitrary, but should preferably be in a range between 200 and 500,000 Da, more preferably between 1 .000 and 250,000 Da, and most preferably between 2,000 and 150,000 Da.
  • the particle size is likewise freely selectable, although preference is given to particle sizes between 5 and 10 ⁇ m, more preferably between 20 and 6 ⁇ m, and most preferably between 50 and 500 ⁇ m
  • sugar-containing compounds are also suitable as adsorption substances according to the invention, including, inter alia, ⁇ -1,4-glycosidically bound Hexoses or pentoses, such as. Chitin, callose, or a-1, 4-glycosidically linked hexoses or pentoses, starch such as amylose.
  • biopolymers are also advantageous because they can be very easily removed from the lipid phases by various processes from the prior art, such as sedimentation, centrifugation or filtration. It is also advantageous that after separation from the lipid phase hardly triglycerides are separated with. On the other hand, virtually no cellulose remains in the lipid phase.
  • Another advantage of such adsorptive separation of the hydrated water-binding turbidity is that they can be extracted and separated under mild process conditions and thus in principle be present in a chemically and structurally unchanged form and can be made available for further use.
  • the present invention also relates to processes using polyaluminum hydroxychloride salts.
  • the invention relates to the use of the methods described herein for the separation and recovery of water-binding organic lipophilic truncates.
  • the provision of the lipid phases containing hydrated hydrophilic organic suspending agents is at a temperature between 10 and 60 ° C, more preferably between 15 and 50 ° C and most preferably between 20 and 40 ° C.
  • the drying of a lipid phase takes place at a temperature of ⁇ 40 ° C.
  • the amount of extractable hydratable organic turbidity can vary depending on the application, as well as the adsorption capacity of the adsorbent used.
  • both the amount of adsorbent (cellulose, cellulose derivatives and other saccharide-containing compounds as disclosed herein) required to refine a refined lipid phase and the time required for the adsorbent to remain in the prepurified lipid phase for each application must be determined.
  • the dosage of the adsorbent to the lipid phase of ⁇ 5% by weight, more preferably ⁇ 3% by weight, and most preferably ⁇ 1% by weight.
  • an adsorption time of 1 minute to 12 hours, more preferably between 5 minutes and 8 hours, and most preferably between 10 minutes and 3 hours.
  • the introduction of the cellulose compounds is preferably carried out by stirring with a propeller stirrer with slight agitation of the lipid phase until a very homogeneous distribution in the lipid phase is achieved. Since the duration required for this can vary naturally, the required duration for this must be determined. The duration of the stirring process is included in the adsorption period and should account for a proportion thereof of ⁇ 20%.
  • the cellulose compounds are preferably separated immediately after the required adsorption time. This can be done by sedimentation, centrifugal separation, or filtration. Preference is given to filtration, the apparatus and filters required for this purpose are known to the person skilled in the art.
  • the hydration of water-binding organic turbidity is carried out by an aqueous refining step with a solution containing guanidine group- or amidino-containing compounds.
  • a quantitative ratio between the lipid phase and the water phase containing dissolved guanidine group or amidine group-bearing compounds of 10: 1, more preferably of 10: 0.5, and most preferably of 10: 0.1.
  • Preference is given to intensive mixed introduction with a rotor-stator mixing system.
  • the terms homogenizing, dispersing, intensive entry, intensive entry, intensive mixing and intensive mixing are used here essentially synonymously and refer to the homogenization of oil with an aqueous solution.
  • the temperature of the lipid phase is preferably between 10 and 60 ° C, more preferably between 15 and 50 ° C and most preferably between 20 and 40 ° C. Preference is given to an immediately subsequent centrifugal phase separation, which is preferably ⁇ 10 minutes, more preferably ⁇ 7 minutes and most preferably ⁇ 5 minutes.
  • the extraction according to the invention of hydrated water-binding organic turbidities of aqueous refined lipid phases can be carried out, depending on the application, with a powdery formulation of the adsorbents and preferably of cellulose compounds or of kaolin.
  • the adsorbent can be added to the prepurified lipid phase or the lipid phase to the adsorbent.
  • the adsorbent used may also be a solid and non-ionically soluble inorganic compound.
  • hydrated water-binding organic Trübstoffe are phyllosilicates suitable. In this case, particularly preferred clay minerals, such as. As montmorilonite, cholites, kaolins, serpentine.
  • aluminum-containing silicate compounds are already particularly advantageous because they are available on a large scale and have no toxic effects due to their physical structure.
  • the preferred form of application is a microcrystalline powder.
  • kaolin More preferred is a microcrystalline powder form of kaolin.
  • the amount of the powders of the inorganic compounds depends on the specific adsorption capacity. Preferred is an amount ratio (g / g) of the powdered absorbent to the prepurified lipid phase of ⁇ 0.03: 1, more preferably ⁇ 0.01: 1 and most preferably ⁇ 0.001: 1.
  • the temperature of the lipid phase is preferably between 10 and 60 ° C, more preferably between 15 and 50 ° C and most preferably between 20 and 40 ° C. Preference is given to an immediately subsequent centrifugal phase separation, which is preferably ⁇ 10 minutes, more preferably ⁇ 7 minutes and most preferably ⁇ 5 minutes. Further preferred is a separation by filtration.
  • phyllosilicates having an aluminum content of> 25% by weight are used for the adsorption of hydrated organic turbidity substances.
  • the dosage of the silicates according to the invention of ⁇ 5% by weight, more preferably of ⁇ 3% by weight and most preferably ⁇ 1% by weight.
  • an adsorption time of 1 minute to 12 hours, more preferably between 5 minutes and 8 hours, and most preferably between 30 minutes and 3 hours.
  • the entry of the silicate compounds is preferably carried out by stirring with a propeller stirrer with gentle agitation of the lipid phase until a very homogeneous distribution is achieved. Since the duration required for this can vary naturally, the required duration for this must be determined.
  • the duration of the stirring process is included in the adsorption period and should account for a proportion thereof of ⁇ 20%.
  • the silicate compounds are preferably separated immediately after the required adsorption time. This can be done by sedimentation, centrifugal separation, or filtration. Preference is given to filtration, the apparatus and filters required for this purpose are known to the person skilled in the art.
  • an extraction of hydrated water-binding organic turbidity substances from the organic matrix takes place by complexing them.
  • This object is achieved by the provision and introduction of ionic compounds from the group of cations from the group of transition metals, semimetals and metals.
  • an extraction of hydrated organic turbidity is carried out by complexation with cations from the group of transition metals, semimetals and metals.
  • Complexation refers to the formation of one or more complexes or coordination compounds.
  • it is meant to be a complexation of a hydrated water-binding organic vehicle, the binding of said turbid substance to a metal or transition metal as disclosed herein, in the form of a coordination compound.
  • the intermolecular interactions leading to complexation may be due to physicochemical bonding energy forms, such as hydrogen bonds, and van der Waals interactions, or to a chemical interaction leading to covalent bonding.
  • the resulting complex can be separated from the organic phase either by itself or by aggregation with other complexes by a physical separation technique, such as a centrifugal or a filtration separation process.
  • aqueous solution with aluminum chloride which is introduced into the aqueous refined lipid phase containing hydrated water-binding turbidity by a mixing process, which leads to a complexation or aggregate formation, their separation by both a spontaneous phase separation, a Sedimentation, centrifugation or filtration can be easily accomplished.
  • aqueous solution in which calcium, magnesium, iron, copper or nickel are present in ionized form.
  • calcium, magnesium, iron, copper or nickel are present in ionized form.
  • aluminum or iron (III) ions are present.
  • the counterions are in principle freely selectable, but salts with sulfate, sulfide, nitrate, phosphate, hydroxide, fluoride, selenide, telluride, arsenide, bromide, borate, oxalate, citrate, ascorbate are preferred. Very particular preference is given to salts with chloride and sulfates.
  • the anions should be highly hydrophilic so that they remain in the water phase.
  • the solutions should consist of otherwise ion-poor or ion-free water in which the preferably used cations are present in a molar concentration between 0.001 and 3, more preferably a molar concentration of 0.1 to 2, and most preferably between 0.5 and 1 molar.
  • the volume of the aqueous solution used is ⁇ 10% by volume, more preferably ⁇ 5% by volume and most preferably ⁇ 1.5% by volume in relation to the prepurified lipid phase.
  • the entry is preferably made by rapid pouring.
  • the mixture with the lipid phase is preferably carried out with a fast-rotating propeller or Schaumrrock réelle with a turbulent Mischeintrag.
  • intensive mixing methods as described herein may also be used. Since the duration required for this can vary naturally, the required duration for this must be determined.
  • Preferred is a blend of from 1 to 60 minutes, more preferably between 5 and 45 minutes, and most preferably between 10 and 20 minutes.
  • a complexation time 1 minute to 5 hours, more preferably between 5 minutes and 3 hours, and most preferably between 10 minutes and 1 hour.
  • the temperature of the lipid phase is preferably set to values between 10 and 60 ° C, more preferably between 15 and 50 ° C and most preferably between 20 and 40 ° C. Preference is given to an immediately subsequent centrifugal phase separation, which preferably takes place for a duration of ⁇ 10 minutes, more preferably ⁇ 7 minutes and most preferably ⁇ 5 minutes. Separation of the phases can also be achieved by sedimentative phase separation or filtration. Further preferred is a separation with a separator. Thus, the invention relates to a process in which in step c) a sedimentative centrifugal, filtration or adsorptive separation technique is carried out.
  • the separation according to step c) is carried out by a sedimentative centrifugal or filtration or adsorptive separation technique or by centrifugation or filtration.
  • the complexed and separated turbid substances can easily be separated and quantified from the otherwise unchanged aqueous solutions containing the alkaline earth metal ions or metal ions by means of a filter.
  • the extraction and separation of the water-binding organic turbidity is possible with virtually no loss of triglycerides.
  • the extraction and separation of hydrated organic turbidity occurs without product loss of a triglyceride mixture.
  • Another aspect of the invention is that the adsorption and complexation of organic turbid substances together with the water molecules bound to them can be separated from the lipid phase.
  • This has the enormous advantage that in one process step, the hydrated water-binding turbidity and the bound water can be removed from a lipid phase.
  • a drying of a lipid phase containing hydratable turbid substances takes place by adsorption and separation and / or complexing and separation of the hydratable turbidity together with the bound water phase.
  • lipid phases treated according to a refining process described herein and subsequently have turbidity and a water content of more than 1.0% by weight are subject to the adsorption and separation or complexing and separation processes of the present invention of turbids then had a clear to brilliant appearance. This is due to a reduction in the residual moisture content contained in the refined lipid phases, which is reduced by at least> 75% by weight, more preferably by at least> 85% by weight, and most preferably by at least> 95% by weight, compared to the starting value of prior to incorporation of the adsorptive or complexing agents.
  • the residual moisture is preferably less than 0.5% by weight, more preferably less than 0.01% by weight, and the most preferably lowered to less than 0.008% by weight.
  • This can easily be investigated by prior art methods, such as the Karl Fischer method. Since lipid phases which have been treated with a one-stage or multistage aqueous refining process in which at least one of the method steps with a solution containing Guanidin phenomenon- or Amidinruppentragende compounds, already a product-specific sufficient depletion of fat accompanying substances can be achieved by a Removal of water-binding turbidity and the achieved drying of the lipid phases whose immediate use z. B. as edible oil, as a cosmetic oil, as lubricating or hydraulic oil or as fuel possible.
  • the achievable with the method reduction of residual moisture causes further very beneficial effects:
  • the invention relates to methods for cost-effective and gentle product drying of refined lipid phases.
  • an invention relates to a method wherein after step c) a lipid phase is obtained with less than 0.5 wt.% Water content.
  • water-repellency or water-binding capacity
  • water absorption capacity is meant herein the ability to bind water into a lipid phase which can be effected by a blending process and result in the retention of water in the lipid phase.
  • the water recovery capability can be checked by a water entry procedure become.
  • ion-free water is stirred at a temperature of 25 ° C in the lipid phase to be examined.
  • An aqueous volume fraction of 5% by volume is provided relative to the refined lipid phase and stirred with a stirred mixer at a speed of 500 rpm for 10 minutes. This is followed by centrifugal phase separation at 6000 rpm for 10 minutes and the phases are separated from one another.
  • the value of water resorption capacity is the difference of the water content of a lipid phase after the water entry and the lipid phase before the water entry.
  • a water reuptake capacity of ⁇ 40% by weight is preferred, more preferably of ⁇ 15% by weight, and most preferably of ⁇ 5% by weight.
  • the water recoverability of the unrefined lipid phase was compared to the refined lipid phase.
  • a difference of the two lipid phases is> 75%, more preferably> 85% and most preferably> 90%.
  • the invention relates to the use of the methods described herein for reducing the resumption of water in a refined lipid phase and / or for improving the oil storage capacity or the oxidation stability of vegetable oil.
  • the transparency of the lipid phases is improved in a particularly advantageous manner by the adsorption and the complexing process according to the invention.
  • refined lipid phases are obtained in which hydratable organic compounds are present whose hydrodynamic diameter in> 90% is less than 100 nm and ⁇ 5% greater than 200 nm, determined by an analysis of the light scattering at a phase boundary, such.
  • the DLS method is obtained.
  • Such lipid phases are optically brilliant.
  • the methods for adsorption and separation as well as for the complexing and separation of water-binding organic turbidity also allow the obtaining of an optically brilliant oil phase.
  • the removal of water-binding turbidity with the resulting reduction of the water-binding capacity of the obtained lipid phase causes further very advantageous effects.
  • this relates to effects that can occur when storing the resulting lipid phases.
  • lipid phases may come into contact with water molecules.
  • contact with air in which there is a water content, sufficient to allow an entry of water molecules by organic molecules with a good water-binding capacity.
  • other effects that are significant for storage stability may occur.
  • the unfavorable effects on the oxidative stability of a lipid phase should be mentioned in the first place.
  • lipid phases and especially in oils of vegetable and animal origin, there are variable amounts of unsaturated organic compounds, the major part of which constitute unsaturated fatty acids. Exposure of these compounds to atmospheric oxygen, heating, high-energy radiation (eg, UV light), contacting with catalysts such as iron, nickel, free radicals, enzymes, such as lipoxygenases, or a basic medium may cause oxidation at one Double bond of an organic compound cause. Oxygen radicals are also catalyzed by organic compounds that are in a lipid phase, such as by chlorophylls, riboflavin or metal and heavy metal ions. This gives rise to hydroperoxides of the organic compounds. These are chemically unstable and degrade to secondary oxidation products.
  • catalysts such as iron, nickel, free radicals, enzymes, such as lipoxygenases, or a basic medium
  • Oxygen radicals are also catalyzed by organic compounds that are in a lipid phase, such as by chlorophylls, riboflavin or metal and heavy
  • the decomposition leads to free Al koxy- radicals. Since, as stated above, the primary oxidation products are usually not stable and are further degraded to secondary oxide compounds, the determination of these reaction products is useful for detecting the long-term stability of a lipid phase. For this purpose, a reaction with para-anisidine, which reacts with secondary oxidation products such as aldehydes and ketones, which are present in a lipid phase is suitable. The reaction product can be detected and quantified spectrometrically (adsorption at 350 nm). In particular, unsaturated aldehydes, which are often responsible for malodors in oils, are detected by the p-anisidine reaction.
  • the p-anisidine value is closely correlated with the peroxide value measured in a lipid phase, so the presence of peroxides can be estimated by the p-anisidine test method.
  • the peroxide value indicates the number of primary oxidation products of a lipid phase and indicates the amount of milliequivalents of oxygen per kilogram of oil. Since there is a greater increase in the secondary oxidation products in the course, the p-anisidine value determination is more suitable for determining the storage stability. Therefore, oils refined with a method of the present invention were evaluated for their storage stability under various conditions, and the anisidine value was sequentially determined to estimate the oxidative stability.
  • the method of adsorbing and separating or complexing and separating water-binding organic suspensions is particularly suited to improve the sensory storage stability of lipid phases.
  • the method is therefore also directed to obtaining sensory-stabilized lipid phases.
  • oxidation of compounds in the lipid phase also promotes corrosive processes on materials that come into contact with such a lipid phase (eg tank system), therefore, it is endeavored to store under cooled conditions, excluding exposure to light and exclusion of air.
  • the method is preferred for obtaining a low-sulfide lipid phase for the reduction of oxidation damage to tank systems and technical equipment.
  • Another aspect of reducing water-repellency by removing water-binding suspensions relates to radical / oxidative changes that can lead to a false color.
  • lipid phases which can be freed of water-binding suspensions with the method according to the invention are lipid phases of biogenic origin, which have a variable proportion of dyes. These are almost exclusively organic compounds which are completely apolar (eg carotenes) or contain only a few polar groups, eg. B. chloroplyles. Therefore, they go very easily into the obtained lipid phase, or are removed by these from their structures.
  • the classes of dyes differ considerably in their chemical properties. However, many of these compounds exhibit significant chemical reactivity or catalyze reactions, especially in the presence of a water fraction in the lipid phase or upon exposure to ionizing radiation (eg, UV light).
  • oxidative processes can produce compounds via a Maillard reaction which lead to a false color and a false flavor.
  • melanoidins which are nitrogen polymers of amino acids and carboxylic acids, and lead to a brown color appearance of the oil.
  • tocopherols which, for example, can be oxidized during a bleaching process (especially in the presence of an acid) and are precursors for color pigments formed in the course.
  • color reversion The discoloration of a refined oil is called "color reversion" and is particularly noticeable in corn oil, which are chlorophylls and their derivatives and degradation products such as pheophytin, as well as flavonoids, curcumins, anthrocyans, indigo, kaempferol and xantophylls, lignins, melanoidineins
  • the method is also directed to the improved color stability upon storage of aqueous refined lipid phases where removal of water-binding suspensions has been by adsorption and separation or complexation and separation.
  • the invention is directed to obtaining a lipid phase having a high color stability during storage.
  • the present invention is therefore also directed to a substantially complete removal of water-binding organic suspensions from a lipid phase after an aqueous refining.
  • the water reuptake capacity of a lipid phase after a refining and refinement of the lipid phase carried out according to the invention is so low that it also increases the storage stability.
  • the addition of the adsorbents described herein or the contacting of one or more adsorbents with the lipid phase is accomplished by having the adsorbent (s) in a bound or complexed form rather than a powder or microcrystalline.
  • an adsorbent is used in step b), which is immobilized on a tissue or a texture or bound or can form such / such.
  • immobilized means the application of the adsorbent to the surface.
  • tissue is understood to mean a one-dimensional or multidimensional arrangement of thread and / or strip material which is linked or connected to one another, so that a planar or spatial structure composite (texture ) will be produced.
  • a texture of the aforementioned materials creates gaps which may be permeable to liquids and / or particulate matter.
  • the texture-forming materials may be of natural origin (eg of vegetable or animal origin, such as cotton or sheep's wool fibers) or of synthetic origin (eg PP, PET PU, etc.). If necessary, the surfaces of the texture materials must be chemically modified in order to immobilize the adsorbents according to the invention.
  • the immobilization can be physical, physico-chemical or chemical. Processes for this are known to the person skilled in the art.
  • Another preferred embodiment is the provision of bound or immobilized cellulose compounds.
  • This can be z. B. in the form of a complex texture material, a plate or layer structure, for. B. as a tile or filter plate or filter cartridge done.
  • an adsorptive separation by immobile silicates as described herein is possible.
  • the lipid phase is conducted past or through the adsorption compounds with the hydrated water-binding organic turbidity substances. This can be done by adding the texture / tissue into the lipid phase and agitating the texture / tissue or lipid phase to contact the lipid phase with the texture / tissue to adsorb the turbidities. The adsorbed turbid matter can then be separated from the lipid phase by removal of the texture / tissue.
  • the lipid phase is passed through and through the texture / tissue which is permeable to the lipid phase. If the lipid phase is obtained after flowing through the texture / the tissue as a refined product, the adsorption and separation of the turbid matter takes place in one operation. To increase the efficiency of such an application, it may be desirable to serially direct the lipid phase through multiple layers of the texture / tissue.
  • the texture consists of a packing of adsorbent materials through which the opacifier-containing lipid phase is passed.
  • cellulose compounds This is a preferred embodiment in the use of cellulose compounds, since this allows, depending on the polymer size and geometry, even with a dense packing of the particles, a flow through a lipid phase.
  • complexing agents are used which are immobilized or bound to a tissue or texture.
  • immobilized refers to the application of the complexing agent to the surface, and the materials that can be used, as well as their texture and structure, can be made with the same materials and fabrics as the materials and fabrics described above for adsorbent application for the use of these materials with immobilized complexing agents, preferred are micro- or nanoparticles with a large internal surface, such as zeolites or silica gels, which are loaded with the complexing agents and provided in the form of a packing of the particles With hydrated turbidity lipid phase, they are complexed with the immobilized complexing agent, thereby separating them from the lipid phase.
  • the invention relates to a process wherein the adsorbent and / or the complexing agent of stage b) in a fabric or in a texture immobilized or bound, wherein the tissue or texture is suitable for complexation and / or adsorption and / or filtration of the opacifier-containing lipid phase.
  • the solutions already brought to the application according to the invention may contain
  • Another aspect of the method concerns the minimal or non-existent product loss of the purified lipid phase.
  • the water phases used according to the invention with complexing agents dissolved therein were only slightly turbid to brilliant after centrifugal separation from the lipid phase and, apart from the above-described aggregates, had no solids, and in no case did they form an emulsion.
  • the oil phase has always had a sharp phase boundary, so separators are very suitable and preferred for separating the aqueous phase containing dissolved complexing agent. The separation of the complexed organic turbidity could be achieved without product loss.
  • the investigated adsorbents which were mixed into the lipid phases, could be separated after the adsorption of organic turbidity by means of centrifuges and decanters to compact masses.
  • the analysis on triglyceride compounds herein shows that they are only carried out to a very small extent with the separated adsorbent mass.
  • the product loss amounts to ⁇ 0.2% by weight based on the mass of the lipid phase. Preference is given to adsorption and separation and / or complexing and separation of hydrated organic turbidity with little or no loss of product, as well as product loss-free or loss-free drying of lipid phases.
  • Another aspect of the process is directed to the recovery of separated organic turbidity and the reusability of the adsorbents and complexing agents used in the invention. It could be shown that the separated with the adsorbents organic Trübstoffe can be separated again from the adsorbents. This can be done with polar and nonpolar solvents known in the art. Since the organic turbidity substances can be different compounds or classes of compounds, the selection of a suitable solvent or solvent mixture should be based thereon. It may also be appropriate to carry out sequential detachment of the adsorbed organic turbidity. So it has been shown that when initially a distance of discharged neutral fats by an apolar solvent such. B.
  • n-hexane is carried out in a further washing step with a polar solvent, for.
  • a polar solvent for.
  • compounds such as phospholipids can be separated and fractionated.
  • Other examples are extractions carried out with ethyl acetate, in which yellow dyes were obtained or with chloroform, in this organic phase were u. a. Chlorophylls found.
  • other fractions could be recovered with diethyl ether and alcohols to find organic compounds such as vitamin A, tocopherol, styrene glycosides, squalene and glyceroglycolipids.
  • relevant amounts of free fatty acids as well as wax acids and waxes were extracted. This was particularly the case when in the present after an aqueous refining oil phase with hydrated organic turbidity, still a relatively high proportion of free fatty acids (> 0.2Gew%) was present.
  • adsorbent which is suitable with at least one nonpolar and at least one polar solvent in an amount of solvent which is suitable for complete absorption of removable organic Trübstoffen or with discharged neutral fats, then using known methods first filtration, sedimentation or by a centrifugal separation process obtained as a fraction and then be returned by a drying process in a powdery form. It could be shown that in a renewed use of z. B. with hydroxyethyl cellulose and kaolin in lipid phases with hydrated organic turbidity, these in the same way as in the first use of the adsorbents, the lipid phases are cleared of the turbidity.
  • a particularly preferred embodiment consists in the separation and recovery of adsorptively separated organic turbidity.
  • Preference is also the use of separated organic turbidity.
  • a pre-purification of the lipid phase is carried out by admixing water or an aqueous solution which has a preferred pH range of between 7.0 and 14, more preferably between 9.5 and 13.5, and most preferably between 1.1, 5 and 13.0, and, after mixing with the lipid phase, a pre-purified lipid phase a preferably centrifugal phase separation is obtained.
  • 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 the undiluted acid or an acid-containing aqueous solution having a pH between 1, 0 and 5, more preferably between 1, 7 and 4 and am most preferably between 3 and 3.5 of the lipid phase is added and after phase separation, the aqueous (heavy) phase is separated.
  • acids are preferred, 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-specific parameters (water content, Viscosity, etc.) and the separation process used and must therefore be determined individually.
  • centrifugation is to be carried out for 2 to 15 minutes, more preferably for 8 to 12 minutes.
  • the fate in a separator or decanter is preferably 2 to 60 seconds, more preferably 10 to 30 seconds.
  • the centrifugal acceleration is preferably selected between 2,000 and 12,000 g, more preferably a centrifugal acceleration between 4,000 and 10,000 g.
  • the temperature during phase separation should preferably be between 15 and 60 ° C, more preferably between 20 and 45 ° C, and most preferably between 25 and 35 ° C.
  • the effectiveness of the pre-purification can be determined by determining the phosphorus content and the amount of mucilage present in the lipid phase to be refined. Suitable are lipid phases containing less than 100 ppm phosphorus and less than 0.5% by weight unsaponifiable organic compounds. However, it is also possible to refine lipid phases which are above these indices with solutions containing guanidine- and / or amidine-group-containing compounds. If there is a need for a pre-cleaning, the choice of an aqueous degumming process, ie a treatment with an acid (neat or as an aqueous solution) or a lye, in principle freely selectable, so that different possibilities of pre-cleaning arise: I. sole acid treatment, II.
  • the technical teaching herein also shows that the separation process according to the invention of water-binding organic suspensions from biogenic lipid phase depends to a great extent on whether the lipid phase is first freed from hydratable organic and inorganic and corpuscular fractions by means of aqueous extraction steps, in order thereby to provide hydration of lipophilic water-binding to allow organic turbidity. It has been found that the number and arrangement of the refining steps is in principle irrelevant, as long as a neutral to basic compound is used in the last refining step. It is particularly advantageous if this basic compound one or more Guanidine and / or amidine groups.
  • an aqueous refining process with an aqueous solution containing compounds containing a guanidine or amidine group is an essential feature for providing a hydrated form of water-binding suspensions.
  • the water-binding organic lipophilic cloudy substances can be adhered or complexed in a highly advantageous manner. without relevant co-removal of apolar lipid components and especially not of triglycerides.
  • the lipid phases suitable for use in process step a) have undergone at least one aqueous refining step with a basic solution with a final phase separation, which is preferably carried out by a centrifugal separation technique.
  • the time interval between the refining and the application of the method according to the invention plays no role. It is preferred that this takes place immediately after the refining.
  • the residual moisture present in the lipid phase is in principle insignificant, but a better hydration of the water-binding organic turbidity causes better extractability of the like.
  • residual water contents between 10.0 and 0.001 wt%, more preferably between 5.0 and 1.0 wt%, and most preferably between 2.0 and 1.2 wt%.
  • the pH present in the lipid phase should preferably be between 6 and 14, more preferably between 8 and 13, and most preferably between 8.5 and 12.5.
  • the temperature of the lipid phase is in principle freely selectable, in the case of viscous lipid phases it may be necessary to heat the latter in order to make it more free-flowing and to improve the ability of the complexing agents or adsorbents to be incorporated.
  • an adhesion or complexing agent is in principle freely selectable. However, the most suitable complexing or adsorbent to be determined individually. In some applications, it may be advantageous to use adsorbents, as these, for example, have an approval for use as food. Also, the effectiveness of the adsorption and complexing agents according to the invention may vary at different lipid phases. If the most gentle possible discharge of hydrated turbidity is preferred, it may again be advantageous to use adsorbents, which are then further purified. By contrast, to largely exclude a product discharge, solutions with complexing agents are advantageous. The complexing agents are dissolved in dissociated form in a preferably ion-poor or otherwise ion-free water.
  • the complexing agents are preferably used singly in a salt form. But there are also combinations of compounds possible.
  • the quantitative and concentration ratios are freely selectable.
  • the application of the solutions with complexing agents contained herein can be carried out continuously or in the form of a single addition. Preferred is an automated application.
  • the process can be carried out as a batch or so-called in-line process. In an in-line method, it is preferable to carry out a continuous mixing, preferably with an intensive mixer.
  • the reaction mixture can then be conveyed through a piping system or through inlet into a reservoir for the required reaction time. In a batch process, the reaction solution and the corresponding reactor vessel remain.
  • the aforementioned concentrations, volume ratios, temperatures are preferably to be observed.
  • the mixture in a batch reactor should be as described above.
  • the adsorbents are preferably added in powdered form to the lipid phase. This can be done in the form of a one-time addition or in the form of fractionated or continuous additions. Preferred is an automated dosing process.
  • the mixture can be carried out as described for the complexing agent, but preference is given to stirring with a turbulent mixture. Further, batch reaction procedures are preferred.
  • the amount of volume addition at a particular concentration of complexing agent or adsorbent, as well as the minimum time required to achieve sufficient complexation or adhesion of the hydrated one, can be readily determined by experiment (e.g., experimentation as in Example 6)
  • the required volume and concentration ratios as well as the determined duration can easily be transferred to large-scale commercial applications.
  • the required product specification is checked by taking a sample (eg 100ml) which contains a centrifuge (4000 rpm, 5 minutes) The supernatant oil fraction can then be tested for water content
  • the required reduction of water-binding turbidity is when the residual moisture content contained therein is at least> 75% by weight, more preferred is reduced by at least> 85% by weight, and most preferably by at least> 95% by weight, in comparison to the starting value which existed before the incorporation of the adsorption or complexing agents.
  • the residual moisture is preferably lowered to less than 0.5% by weight, more preferably to less than 0.01% by weight, and most preferably to less than 0.008% by weight.
  • a further product specification represents the water absorption capacity of the oil fraction obtained. This can be investigated by stirring in ion-free water at a temperature of 25 ° C. An aqueous volume fraction of 5% by volume is provided relative to the refined lipid phase and stirred with a stirred mixer at a speed of 500 rpm for 10 minutes. This is followed by centrifugal separation at 6000 rpm for 10 minutes.
  • the product specification is achieved when the water resorption capacity of the grafted lipid phase is reduced by> 75% compared to the non-grafted lipid phase.
  • lipid phase only compounds are present whose hydrodynamic diameter in> 90% of all particles contained herein is less than 100nm and ⁇ 5% greater than 200nm, determined by an analysis of light scattering at a phase boundary, such , B. the DLS method is obtained.
  • Such lipid phases are optically brilliant.
  • a minimum requirement for carrying out a complexation according to the invention and separation or adsorption and separation of hydrated turbidity is given if at least one of the abovementioned product specifications is present.
  • a special case and preferred embodiment of the extraction according to the invention and subsequent separation of turbidity represents a combination of an extraction and a separation of turbidity, as described herein.
  • This special case is given when one or more of the adsorbing and / or complexing agents / immobilized on a carrier material is / are. If such loaded carrier materials are added to a lipid phase which contains hydrated turbid substances and / or such lipid phases are passed through the loaded carrier material, which should preferably have a porous or mesh-like structure, extraction of the hydrated turbid substances by adsorption or complexing can take place directly take place the separation medium, which can then be easily removed from / from the lipid phase.
  • centrifugal phase separation refers to a separation of phases utilizing centrifugal acceleration.
  • it comprises processes known to the person skilled in the art, such as the use of centrifuges and, preferably, separators.
  • the separation methods are suitable for both the phase separation of the aqueous disclosed herein Raffinationsmatn, as well as a separation of claimed herein adsorption or complexing agents.
  • Another centrifugal separation process is provided by decanters.
  • lipid mixtures which have been mixed with an aqueous phase or with an adsorption agent or a complexing agent are in principle two phases of different density, in principle a phase separation is also possible by sedimentation.
  • Practice shows that the organic compounds to be separated, which have been converted into a water phase or aggregated or complexed as turbidity, for the most part can not spontaneously separate, so that by means of tensile and compressive forces, the separation efficiency and speed must be increased. This is easily possible according to the prior art by means of a simple centrifuge or a separator suitable for this purpose. A pressurization or negative pressure is possible.
  • Separators are systems in which equal or non-uniform plates or plates appropriate tensile forces are set up in addition to a simultaneous pressure build-up.
  • the advantage of using separators is that a continuous phase separation can be carried out with them. Therefore, a particularly preferred embodiment for the phase separation of the lipid phases is to carry out the phase separation with a separating separator.
  • phase separation by a separator systems having a throughput volume of more than 3m 3 / h, more preferably> 100m 3 / h, and most preferably> 400m 3 / h, are preferred
  • the separation of the aqueous refined lipid phases can in principle be carried out immediately after completion of a mixed or intensive mixing input.
  • the aqueous refined lipid mixture to be separated can first be collected in a storage tank.
  • the duration of storage depends solely on the chemical stability of the compounds present in the lipid phase and the process conditions.
  • the phase separation is immediately following an intensive mixing entry.
  • the temperature of the lipid mixture to be separated can in principle correspond to that which has been chosen for the preparation. However, it may also be advantageous to vary the temperature and to choose a higher temperature when z. B. thereby the effect of the separation tool is increased, or a lower, z. B. if this increases the extraction efficiency. In general, a temperature range between 15 ° C and 50 ° C is preferred, more preferably from 18 ° C to 40 ° C, and most preferably between 25 ° C and 35 ° C.
  • the residence time in a separation separator or a centrifuge depends essentially on the apparatus-specific properties. In general, the lowest possible residence time in economic terms Separator preferably, such a preferred residence time is ⁇ 10 minutes, more preferably ⁇ 5 minutes, and most preferably ⁇ 2 minutes for a separation separator. For centrifuges, a preferred residence time is ⁇ 15 minutes, more preferably ⁇ 10 minutes, and most preferably ⁇ 8 minutes.
  • the selection of the centrifugal acceleration depends on the density difference of the two phases to be separated and is to be determined individually. Preferably, acceleration forces are between 1. 000 g and 15,000 g, more preferably between 2,000 g and 12,000 g, and most preferably between 3,000 g and 10,000 g.
  • the water content of a lipid phase (also called oil moisture) can be determined by various established methods. In addition to other methods, such. As the IR spectroscopy, the Karl Fischer titration method according to DIN 51777 is performed as a reference method. With this electrochemical process, in which the required for the chemical conversion of iodine to iodide consumption of existing in the lipid phase water is determined by a color change, a minimum water content of up to 10 g / l (0.001 mg / kg) can be determined.
  • water absorption capacity is meant herein the ability to bind water into a lipid phase which can be effected by a blending process and result in the retention of water in the lipid phase. This can be checked by stirring ion-free water at a temperature of 25 ° C by providing an aqueous volume fraction of 5% by volume to the lipid phase and stirring with a stirrer at a speed of 500 rpm for 10 minutes. This is followed by centrifugal separation at 3,000 g for 10 minutes.
  • the value of water resorption capacity is the difference of the water content of a lipid phase after the water entry and the lipid phase before the water entry.
  • a water reuptake capacity of ⁇ 40% by weight is preferred, more preferably of ⁇ 15% by weight, and most preferably of ⁇ 5% by weight.
  • the water recoverability of the unrefined lipid phase was compared to the refined lipid phase.
  • a difference of the two lipid phases is> 75%, more preferably> 85% and most preferably> 90%.
  • the water content was determined by the same method of measurement disclosed herein.
  • Aqueous refining with guanidine and / or amidine group bearing compounds The term guanidine and / or amidine group bearing compounds is used synonymously herein with the term guanidine and or amidine linkages.
  • Suitable compounds are those having at least one guanidino group (also called guanidino compounds) and / or having at least one amidino group (also called amidino compounds).
  • the guanidino group is the chemical radical H 2 NC (NH) -NH- and its cyclic forms
  • the amidino group is the chemical radical H 2 NC (NH) - and its cyclic forms (see examples below).
  • amidino compounds which, in addition to the amidino group, have at least one carboxylate group (-COOH). It is further preferred if the carboxylate group (s) are separated from the amidino group in the molecule by at least one carbon atom.
  • guanidino compounds and amidino compounds preferably have a distribution coefficient K 0 w between n-octanol and water of no 6.3 (Kow ⁇ 6.3).
  • arginine which may be present in D or L configuration or as a racemate. More preferred are arginine derivatives.
  • Arginine derivatives are defined as compounds having a guanidino group and a carboxylate group or an amidino group and a carboxylate group, wherein guanidino group and carboxylate group or amidino group and carboxylate group are separated by at least one carbon atom, ie at least one of the following groups between the guanidino group or the amidino group and the carboxylate group is: -CH 2 -, -CHR-, -CRR'-, wherein R and R 'independently represent any chemical radicals.
  • 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)
  • L is a hydrophilic substituent selected from the group consisting of:
  • the preferably used concentration of guanidine or amidine compounds, which must be present dissolved in a preferably ion-poor or ion-free water, is in one embodiment based on the detectable acid number of the lipid phase to be refined, the z. B. determined by a titration with KOH determined.
  • the derivable number of carboxyl groups serves to calculate the amount by weight of the guanidine or amidine compounds. In this case, an at least equal or higher number of guanidine or amidine groups, in free and ionizable form be present, be present.
  • the thus determined molar ratio between the Guanidin phenomenon- or amidino-containing compounds and the total of the free or releasable carboxyl-bearing compounds or carboxylic acids must be> 1: 1.
  • a molar ratio between the determinable carboxylic acids (here in particular the acid number) and the guanidine group- or amidino-containing compounds should be 1: 3, more preferably 1: 2.2, and most preferably 1: 1, 3 in an ion-free Water are produced.
  • the molarity of the dissolved solution according to the invention with guanidine group- or amidine-group-containing compounds may preferably be between 0.001 and 0.8 molar, more preferably between 0.01 and 0.7 molar and most preferably between 0.1 and 0.6 molar. Since the interaction of the guanidine or amidine groups is also ensured at ambient temperatures, the preferred temperature at which the inventive entry of the aqueous solutions containing dissolved guanidine or amidine compounds can be between 10 ° C and 50 ° C, more preferably between 28 ° C. and 40 ° C, and most preferably between 25 ° C and 35 ° C.
  • the registration of the aqueous solutions containing guanidine group- or amidino-containing compounds should preferably be carried out by intensive mixing.
  • the volume ratio between the lipid phase and the water phase is irrelevant in principle.
  • a ratio by volume (v / v) of the aqueous solution to the lipid phase of from 10% by volume to 0.05% by volume, preferably from 4.5% by volume to 0.08% by volume, is more preferred from 3% by volume to 0.1% by volume.
  • the volume and concentration ratio can be influenced by the fact that in some lipid phases and emulsion-forming compounds such.
  • Glycolipids by an aqueous solution with Guanidin phenomenon- or
  • Guanidine group or amidino group-bearing compounds to be refined to the lipid phases to be refined.
  • Particularly suitable intensive mixers are those intensive mixers which operate on the high-pressure or rotor-stator homogenization principle.
  • the intensive mixer intensive mixing of the lipoid phase and the aqueous phase takes place.
  • the intensive mixing takes place at atmospheric pressure and a temperature in the range of 10 ° C to 90 ° C, preferably 15 ° C to 70 ° C, more preferably 20 ° C to 60 ° C and most preferably 25 ° C to 50 ° C instead. Therefore, the thorough mixing and preferably intensive mixing at low temperature of preferably below 70 ° C, more preferably below 65 ° C, more preferably below 60 ° C, more preferably below 55 ° C, even more preferably below 50 ° C. , even more preferably below 45 ° C.
  • the entire aqueous refining process preferably including the optional steps at temperatures in the range of 10 ° C to 90 ° C, preferably 13 ° C to 80 ° C, preferably 15 ° C to 70 ° C, more preferably 18 ° C is carried out to 65 ° C, more preferably 20 ° C to 60 ° C, more preferably 22 ° C to 55 ° C and particularly preferably 25 ° C to 50 ° C or 25 ° C to 45 ° C.
  • the preferred pH range for this is between 7.0 and 14, more preferably between 9.5 and 13.5, and most preferably between 1.1 and 5 and 13.
  • the entry of the basic wash solution is preferably carried out with an intensive mixing, particularly preferred in this case rotor-stator mixer.
  • the preferred exposure time is between 1 to 30 minutes, more preferably between 4 and 25 minutes, and most preferably between 5 and 15 minutes.
  • the preferred temperatures of the lipid phase are between 15 ° and 45 ° C, more preferably between 20 ° and 35 ° C and most preferably between 25 ° and 30 ° C.
  • pretreating the lipid phases to be purified with the aqueous refining is pretreatment with an aqueous solution containing an acid and having a pH of between 1 and 7, more preferably between 2.5 and 4, and most preferably between 3 and 3.5. Preference is given to an interference of the acidic solution with an intensive entry as described herein, particularly preferred are rotor-stator mixing systems.
  • the preferred exposure time is between 1 to 30 minutes, more preferably between 4 and 25 minutes, and most preferably between 5 and 10 minutes.
  • the preferred temperatures of the lipid phase are between 15 ° and 45 ° C, more preferably between 20 ° and 35 ° C and most preferably between 25 ° and 30 ° C.
  • the inventive separation of turbidity from a prepurified lipid phase is also directed to a particularly advantageous low-loss refining of neutral lipids, as well as that herein less than 5 ppm, in particular less than 2 ppm of phosphorus-containing compounds, less than 0.2%, in particular less than 0 , 1% free fatty acids, and less than 3 ppm, in particular less than 0.02 ppm of Na, K, Mg, Ca and / or Fe ions.
  • the separation of suspensions from a prepurified lipid phase according to the invention is also directed to a particularly advantageous low-loss refining of neutral lipids, and that herein less than 5 ppm (or 5 mg / kg), in particular less than 2 ppm (mg / kg) phosphorus-containing Compounds, less than 0.2% by weight (or 0.2 g / 100 g), in particular less than 0.1% by weight of free fatty acids, and less than 3 ppm (or 3 mg / kg), in particular less than 0, 02 ppm (or 0.02 mg / kg) of Na, K, Mg, Ca and / or Fe ions are contained.
  • the invention relates to refined and refined lipid phases obtainable by one of the processes described herein with a content of less than 10% relative to the starting amount of water-binding organic lipophilic suspensions, the lipid phase being less than 5 ppm, less than 0.1% by weight. free fatty acids, and containing less than 3 ppm of Na, K, Mg, Ca and / or Fe ions.
  • the invention relates to refined and refined lipid phases obtainable by one of the methods described herein at a level of less than 10% relative to the starting amount of hydrophilic organic lipophilic truncates, the lipid phase being less than 5 ppm (or 5 mg / kg), less 0.1 wt.% (g / 100 g) of free fatty acids, and less than 3 ppm (or 3 mg / kg) of Na, K, Mg, Ca and / or Fe ions.
  • the separation process according to the invention is therefore also particularly advantageous use, since the solid adsorbent are inexpensive to make it operational again. Furthermore, the separation according to the invention is aimed at making available the separated organic turbid substances.
  • the term as used herein includes mixtures of biological origin, which can thus be obtained from plants, algae, animals and / or microorganisms and having a water content of ⁇ 10% and a content of lipophilic substances comprising monoacylglycerides, diacylglycerides and / or triacylglycerides of total > 70 wt .-% or> 75 wt .-% or> 80 wt .-% or> 85 wt .-% or> 90 wt .-% or> 95 wt .-%.
  • the lipid phases may be extracts of oleaginous plants and microorganisms, such as rape seed, sunflower, soya, camelina, jatropha, palm, castor, but also algae and Microalgae and animal fats and oils. It is irrelevant whether the lipid phase is a suspension, emulsion or colloidal liquid. If the lipid phases are extracts or extraction phases of lipoid substances from a previous separation or extraction, the lipid phase may also consist of a proportion of> 50% by volume of organic solvents or hydrocarbon compounds.
  • Preferred lipid phases are vegetable oils, in particular pressing and extraction oils of oil plant seeds. However, animal fats are also preferred. But also included are non-polar aliphatic or cyclic hydrocarbon compounds. These lipid phases are characterized in that> 95% by weight of the compounds are apolar.
  • the lipid phases include, but are not limited to: Acai Oil, Acrocomia Oil, Almond Oil, Babassu Oil, Currant Seed Oil, Borage Seed Oil, Rapeseed Oil, Cashew Oil, Castor Oil, coconut Oil, Coriander Oil, Corn Oil, Cottonseed Oil, Kramben Oil, Linseed Oil, Grapeseed Oil, Hazelnut Oil, Other Nut Oils, Hemp Seed Oil, Jatropha Oil , Jojoba oil, macadamia nut oil, mango seed oil, meadowfoam seed oil, mustard oil, foot oil, olive oil, palm oil, palm kernel oil, palm oil, peanut oil, pecan oil, pine nut oil, pistachio oil, poppy seed oil, rice germ oil, thistle oil, camellia oil, sesame oil, shea butter oil , Soybean oil, sunflower oil, tall oil, tsubaki oil, walnut oil, varieties of "natural” oils with altered fatty acid compositions via genetically modified organisms
  • Refined lipid phase herein is understood to mean a lipid phase in which one of the methods according to the invention for the adsorption and separation or complexing and separation of hydrated turbidity has occurred.
  • the lipid phase obtained after an aqueous refining is understood as a refined lipid phase, this means the lipid phase which is obtained after the last method step of one of the methods according to the invention.
  • Purified lipid phase means the lipid phase obtained after the last step of one of the methods of the invention. "Purified lipid phase” and “Refined lipid phase” are used interchangeably. Aqueous refining or aqueous refined lipid phase
  • aqueous refining refers to the aqueous purification step with a neutral or basic solution to provide the "aqueous refined lipid phase”.
  • aqueous refined lipid phase is synonymous with “lipid phase” which is present after purification with a neutral or basic solution.
  • pre-purified lipid phase is the lipid phase present after purification with a neutral or basic solution
  • a pre-purified lipid phase is also understood to mean an aqueous-refined lipid phase.
  • the lipid phase to be purified is the crude lipid phase before it has been subjected to at least one aqueous refining with a neutral or basic solution.
  • Turbidity herein summarizes organic compounds that can be defined by the following characteristics: a) Organic, in a biogenic lipid phase naturally occurring compound with lipophilic properties, characterized by a K ow of> 2, where name K ow refers to the distribution coefficient between n-octanol and water, and b) an organic compound having a molecular weight of not more than 5,000 Da, and also c) an organic compound which has a hydrodynamic radius of more than 100 nm in a hydrated state and d) an organic compound allowed by water molecules.
  • the inventively adsorptive or complexed separable organic Trübstoffe have at least two of the above features, which by known and practicable methods, such.
  • B. a molecular weight determination, a calculation of Kow distribution coefficient, a determination of the hydrodynamic radius by means of a dynamic laser light scattering method (DLS) and the determination of the water content can be examined.
  • the organic water-binding compounds include organic dye compounds such as carotenes and carotenoids, chlorophylls, and their degradation products, phenols, phytosterols, in particular ß-sitosterol and campesterol and Sigmasterol, sterols, sinapines, squalene.
  • Phytoestrogens such as isoflavones or lignans.
  • steroids and their derivatives such as saponins, furthermore glycolipids as well as glyceroglycolipids and glycerosphingolipids, furthermore rhamnolipids, sophrolipids, trehalose lipids, mannosterylerythritol lipids.
  • polysaccharides 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 carboxylic acids and long-chain or cyclic carbon compounds, such as waxes, wax acids, also fatty alcohols, hydroxy and epoxy fatty acids.
  • carboxylic acids such as waxes, wax acids, also fatty alcohols, hydroxy and epoxy fatty acids.
  • carboxylic acids such as waxes, wax acids, also fatty alcohols, hydroxy and epoxy fatty acids.
  • glycosides such as glycosides, lipo-proteins, lignins, phytate or phytic acid as well as glucoinosilates.
  • Proteins including albumins, globulins, oleosins, vitamins, e.g. Retinol, (vitamin A) and derivatives such.
  • vitamin B2 As retinoic acid, riboflavin (vitamin B2), pantothenic acid (vitamin B5), biotin (vitamin B7), folic acid (vitamin B9), cobalamins (vitamin B12), calcite ol (vitamin D) and derivatives, tocopherols (vitamin E) and tocotrienols , Phylloquinone (vitamin K) and menaquinone.
  • vitamin B2 As retinoic acid, riboflavin (vitamin B2), pantothenic acid (vitamin B5), biotin (vitamin B7), folic acid (vitamin B9), cobalamins (vitamin B12), calcite ol (vitamin D) and derivatives, tocopherols (vitamin E) and tocotrienols , Phylloquinone (vitamin K) and menaquinone.
  • tannins, terpenoids, curcumanoids, xanthones but also sugar
  • lipid phases of different origin can be freed of turbidity by the method according to the invention, the choice of turbidity is not limited to those mentioned herein by name.
  • Water-binding organic lipophilic clouding agents such as carotenes, chlorophylls, phenols, sterols, squalene, waxes, wax acids, wax alcohols, glycolipids, glyceroglycolipids and / or glycerosphingolipids are preferably separated by one of the methods described herein.
  • aldehydes, ketones, peroxide compounds and carboxylic acids are preferably separated by one of the methods described herein.
  • Acids referred to herein are compounds which are capable of giving off protons to a reactant, in particular water.
  • the term refers to bases, compounds capable of absorbing protons, especially in aqueous solutions.
  • Carboxylic acids also referred to herein as carboxylic acids, are organic compounds which carry one or more carboxyl groups. A distinction is made between aliphatic, aromatic and heterocyclic carboxylic acids. Aliphatic forms of carboxylic acids, also called alkanoic acids, are fatty acids and are further listed in the following paragraph.
  • fatty acids are aliphatic carbon chains having a carboxyl group.
  • the carbon atoms may be linked with single bonds (saturated fatty acids) or with double bond bridges (unsaturated fatty acids), these double bonds may be in an ice or trans configuration.
  • 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 (arachic acid) and n-docosanoic acid (behenic acid).
  • capric acid nonanecarboxylic acid
  • dodecanoic acid lauric acid
  • tetradecanoic acid myristic acid
  • hexadecanoic acid palmitic acid
  • octadecanoic acid stearic acid
  • n-eicosanoic acid arachic acid
  • n-docosanoic acid behenic acid
  • Separation By separation, the skilled person understands the separation of a substance mixture. Depending on the type of separation process used, each of which requires an energy expenditure under which one achieves a certain degree of separation, substances of different purity are obtained. Separation is synonymous with separation and both terms are also used synonymously in this application. Separation thus means the separation of substances from a mixture of substances. Separation methods, as used herein, include phase separation of liquid mixtures which may be accomplished by sedimentation and / or centrifugation and / or filtration. The centrifugal separation can be carried out continuously by a separator or decanter technology or discontinuously by means of a centrifuge.
  • a filtration separation can be carried out by passing or passing the lipid phase, in which the compounds / aggregates already to be separated, through a filter having a certain screen size, wherein the compounds / aggregates are preferably 100% larger than the minimum Sieve size, be retained and do not pass the filter.
  • Other techniques for separating phases known to those skilled in the art may also be used. extraction
  • extraction is for a person skilled in a designation for a separation process by leaching of certain constituents from solid or liquid substance mixtures with the aid of suitable solvents (extractant).)
  • extraction is meant the extraction of turbidity from their material (organic) matrix by an extractant which may consist of an adsorbent or complexing agent for the suspended matter to be separated, in other words, extractability of the hydrogenated turbidity by adsorptive attachment to an adsorbent as described herein or by an ionic or covalent bond with a herein n described cation, which is defined herein as complexation achieved.
  • Adsorption is for a person skilled in the deposition of substances on the surface of solids. Such deposits are mainly due to physicochemical interactions, but chemical compounds are also possible.
  • adsorbent which is used synonymously for the terms adsorbent, is understood herein to mean a material compound of inorganic and / or organic constituents, with a solid state of matter.
  • the adsorbent has surface properties that allow for adsorption of elements or compounds.
  • the suspending agents described herein may be incorporated and / or incorporated and bonded therewith.
  • aggregation means the accumulation or accumulation of atoms or molecules.
  • the person skilled in the art understands this to mean the accumulation of atoms or molecules in liquid up to the point where the aggregate is no longer soluble and precipitates.
  • a physical and / or physicochemical and / or chemical compound between two or more elements and / or compounds.
  • the elements may be present in their elemental or ionized form, compounds as molecules having 2 or more atoms, it is irrelevant whether they are organic or inorganic compounds.
  • complexation encompasses a physical and / or physicochemical and / or chemical compound with or between complexes which has already been formed by complexation with a complexing agent as described herein with a compound, which may also form aggregates.
  • complexing agent as used herein is meant elements which are ionizable in water / or donate ions, thereby allowing complexation with clouding agents as described herein.
  • Cellulose is a polysaccharide of the formal Bruttozusmmen authority (C6H10O 5), more precisely an isotactic beta-1, 4-polyacetal of cellobiose (4-O-beta-D-glucopyranosyl-D-glucose).
  • Cellobiose in turn consists of two molecules of glucose. Approximately 500 to 5000 glucose units are linked to one another unbranched in the form of a chain, resulting in average molar masses of 50,000 to 500,000.
  • the hydrogen atoms on the free hydroxyl groups of the glucose units may be replaced -CH 3 , -C 2 H 5 , -C 3 H 7,
  • cellulose derivatives are hydroxyethyl cellulose (HEC), hydroxypropyl cellulose (HPC), ethyl hydroxyethyl cellulose (EHEC), carboxymethyl hydroxyethyl cellulose (CMHEC), hydroxypropyl hydroxyethyl cellulose (HPHEC), methyl cellulose (MC), methyl hydroxypropyl cellulose (MHPC),
  • HEC hydroxyethyl cellulose
  • HPC hydroxypropyl cellulose
  • EHEC ethyl hydroxyethyl cellulose
  • CHEC carboxymethyl hydroxyethyl cellulose
  • HPHEC hydroxypropyl hydroxyethyl cellulose
  • MC methyl cellulose
  • MHPC methyl hydroxypropyl cellulose
  • Methylhydroxypropylhydroxyethylcellulose MHPHEC
  • methylhydroxyethylcellulose MHEC
  • carboxymethylcellulose CMC
  • hydrophobically modified Hydroxyethylcellulose hmHEC
  • hydrophobically modified hydroxypropylcellulose hmHPC
  • hydrophobically modified ethylhydroxyethylcellulose hmEHEC
  • hydrophobically modified carboxymethylhydroxyethylcellulose hydrophobically modified hydroxypropylhydroxyethylcellulose (hmHPHEC)
  • hydrophobically modified methylcellulose hmMC
  • hydrophobically modified methylhydroxypropylcellulose hmMHPC
  • hydrophobic modified methylhydroxyethylcellulose hmMHEC
  • hydrophobically modified carboxymethyl methylcellulose sulfoethylcellulose (SEC), hydroxyethylsulfoethylcellulose (HESEC)
  • HPSEC Hydroxypropylsulfoethylcellulose
  • MHESEC methylhydroxyethylsulfoethylcellulose
  • MHPSEC methylhydroxypropylsulfoethylcellulose
  • HEHPSEC hydroxyethyl-hydroxypropylsulfoethylcellulose
  • CMSEC carboxymethylsulfoethylcellulose
  • HmSEC hydrophobically modified sulfoethylcellulose
  • hmHESEC hydrophobically modified hydroxyethylsulfoethylcellulose
  • hmHPSEC hydrophobically modified hydroxypropylsulfoethylcellulose
  • HmHEHPSEC hydrophobic modified hydroxyethylhydroxypropylsulfoethylcellulose
  • dye summarizes organic compounds which occur in oils and fats of biogenic origin, typically in different quantities and compositions side by side.
  • plant colorants herein includes all coloring compounds present in lipid phases, the most dominant and by far the largest quantity in vegetable oils is the group of chlorophylls and their degradation products, such as pheophyline.
  • other classes of compounds such as flavonoids, curcumins, anthrocyans, betaines, xanthophylls, which include carotenes and lutein, indigo, kaempferol and xantphylls, such as neoxanthine or zeaxanthin, are also included.
  • chlorophylls are typically found in quantities between 10 ppm (or 10 mg / kg) and 100 ppm (or 100 mg / kg) or between 10 ppm (or 10 mg / kg) and 100 ppm (or 100 mg / kg). be.
  • Representatives with a high content of chlorophylls are especially canola and rapeseed oils.
  • 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.
  • Chlorophylls are the most common dyes found in vegetable oils. Due to their hydrophobicity or lipophilicity, they are very well distributed in lipid phases, in particular triglyceride mixtures. They cause a green color of the lipid phase, furthermore they cause a lower oxidation stability of the lipid phase due to the compound / entry of magnesium or copper ions. Therefore, their removal from such a lipid phase is desired, especially if it is an edible oil.
  • Non-degraded chlorophylls are practically insoluble in water. Therefore, aqueous refining processes are also not suitable for extracting these dyes from a lipid phase. Since the determination of the absolute concentrations can be obtained by a high analytical effort, it is more practicable to determine the content of dyes by a spectrometric determination of the color contents of a lipid phase. For this purpose, the determination of different color spectra in an oil is established by the Lovibond method in which intensity levels red yellow and green shades are determined and compared with a reference value. Thus, an evaluation of the oil color in general, as well as a change in color, can be judged. application areas
  • the refining process of raffinates according to the invention is applicable to all lipid phases, as described herein, which are of biogenic origin and contain water-binding, highly lipophilic compounds which are turbidity-causing substances in the context of refining or subsequently thereto by water introduction. Because the Turbidity, for the inventive finishing process, first must be dissolved or decomplexed out of an organic matrix, the inventive use of the refining process is limited to a refining step after an aqueous refining, as described herein. This concerns the purification / refining of oils, especially of vegetable oils, but also animal fats, where the removal of turbidity is desired. This applies in particular to edible oils, fragrance oils, massage oils, skin oils and lamp oils.
  • organic mixtures such as plant extracts, or their distillation products can be refined.
  • natural or synthetically produced mixtures of hydrocarbon compounds or esterified fatty acids can be refined.
  • lipid phases which are suitable for industrial applications, such as oil-based fuels or lubricants or hydraulic oils
  • the invention relates to a process for the adsorption and extraction or complexing and extraction of carotenes, chlorophylls, phenols, sterols, squalene, glycolipids, glyceroglycolipids and / or glycerosphingolipids and / or waxes or aqueous refined lipid phases, which is characterized by
  • lipid phase comprising carotenes, chlorophylls, phenols, sterols, squalene, glycolipids, glyceroglycolipids and / or glycerosphingolipids and / or waxes or carboxylic acids, the lipid phase being subjected to at least one aqueous refining with a neutral or basic solution,
  • the complexing agent is aluminum ions or iron ions present in an aqueous solution.
  • the invention further relates to a process for the adsorption and extraction or complexing and extraction of water-binding organic lipophilic suspensions of aqueous refined lipid phases, which is characterized by
  • lipid phase containing water-binding organic lipophilic turbidities, wherein the lipid phase has undergone at least one aqueous refining with an aqueous solution having at least one guanidine group or amidine group-bearing compound having a Kow of ⁇ 6.3.
  • Adsorptionsmittei to Ceiiuiose, a Ceiiuiosederivat or an inorganic Aiuminiumoxid Siiikat with a Aiuminiumanteii of> 0.1 moi% is and
  • the complexing agent is ammonium ions or iron ions present in an aqueous solution.
  • the invention relates to a process for the adsorption and extraction of water-binding organic lipophilic suspensions of aqueous refined lipid phases, which is characterized by
  • lipid phase containing water-binding organic lipophilic turbidity, wherein the lipid phase of at least one aqueous
  • the invention relates to a process for the adsorption and extraction of water-binding organic lipophilic suspensions of aqueous refined lipid phases, which is characterized by
  • the invention further relates to a process for the adsorption and extraction or complexing and extraction of carotenes, chiorophyllene, phenols, sterols, squaienen, glycoipids, glycerolipids and / or glycerosphingolipids and / or waxes or carboxylic acids of aqueous refined lipid phases, which is characterized by
  • lipid phase containing carotenes, chlorophylls, phenols, sterols, squaienen, glycoipids, glyceryl glycolipids and / or glycerosphingolipids and / or waxes or carboxylic acids, wherein the lipid phase of at least one aqueous refining with an aqueous solution having at least one guanidine group or amidino group-bearing compound was subjected to a kow of ⁇ 6.3.
  • the adsorbent is cellulose, a cellulose derivative or an inorganic alumina silicate with an aluminum content of> 0.1 mol%
  • the complexing agent is aluminum ions or iron ions present in an aqueous solution.
  • the invention relates to a process for the adsorption and extraction of carotenes, chlorophylls, phenols, sterols, squaienen, glycoipids, glycerylglycolipids and / or glycerosphingolipids and / or waxes or carboxylic acids of aqueous refined lipid phases, which is characterized by
  • the invention relates to a process for the adsorption and extraction of carotene, chiorophyly, phenols, steroids, squaienen, Giycolipiden, Glycerogiycoiipiden and / or Glycerosphingolipiden and / or waxes or carboxylic acids aqueous refined lipid phases, which is characterized by,
  • lipid phase containing carotenes, chlorophylls, phenols, sterols, squaienes, glycoipids, glyceroglycolipids, glycerolgipolipids and / or waxes or carboxylic acids, the lipid phase being subjected to at least one aqueous refining with a neutral or basic solution,
  • the adsorbent is Ceiiuiose, a Ceiiulosederivat or an inorganic Aiuminiumoxid silicate with a Aluminiumanteii of> 0.1 mol%.
  • the invention relates to a process for the adsorption and extraction of carotenes, chiorophylys, phenols, steroids, squaienen, Giycolipids, Glycerogiycoiipiden and / or glycerosphingolipids and / or waxes or carboxylic acids aqueous refined lipid phases, which is characterized by,
  • lipid phase containing carotenes, chlorophylls, phenols, sterols, squaienes, glycoipids, glyceroglycolipids, glycerolgipolipids and / or waxes or carboxylic acids, the lipid phase having been subjected to at least one aqueous refining with a neutral or basic solution,
  • the invention relates to a method for the adsorption and extraction of carotenes, Chiorophyiien, phenols, steroids, Squaienen, Giycolipids, Glycerogiycoiipiden and / or glycerosphingolipids and / or waxes or carboxylic acids of aqueous refined lipid phases, which is characterized by
  • lipid phase containing carotenes, chlorophylls, phenols, sterols, squalene, glycolipids, glyceroglycolipids, glycerosphingolipids and / or waxes or carboxylic acids, wherein the lipid phase of at least one aqueous refining with an aqueous solution having at least one guanidine group or amidino group-bearing compound with a Kow was subjected to ⁇ 6.3
  • the adsorbent is cellulose, a cellulose derivative or an inorganic alumina silicate with an aluminum content of> 0.1 mol%.
  • the invention further relates to a process of complexing and extraction of water-binding organic lipophilic suspensions of aqueous refined lipid phases, which is characterized by
  • lipid phase containing water-binding organic lipophilic turbidity, wherein the lipid phase has undergone at least one aqueous refining with an aqueous solution having at least one guanidine group- or amidino-containing compound having a Kow of ⁇ 6.3,
  • the complexing agent is aluminum ions or iron ions present in an aqueous solution.
  • the invention relates to a process complexing and extraction of carotenes, chlorophylls, phenols, sterols, squalene, glycolipids, glyceroglycolipids and glycerosphingolipids and / or waxes or carboxylic acids of aqueous refined lipid phases, which is characterized by
  • lipid phase containing carotenes, chlorophylls, Phenols, sterols, squalene, glycolipids, glyceroglycolipids and / or glycerosphingolipids, and / or waxes or carboxylic acids, the lipid phase being subjected to at least one aqueous refining with an aqueous solution having at least one guanidine group or amidine group-bearing compound having a Kow of ⁇ 6.3 has been,
  • a further embodiment according to the invention is a process for the separation of water-binding organic lipophilic suspensions from an aqueous refined lipid phase, which is characterized by
  • lipid phase containing water-binding organic lipophilic turbidities, wherein the lipid phase has been subjected to at least one aqueous refining with a neutral or basic solution, b) adding the adsorption agent and / or a complexing agent to the lipid phase from stage a),
  • the adsorbent is cellulose, a cellulose derivative or an inorganic alumina silicate having an aluminum content of> 0.1 mol%, and
  • the complexing agent is ammonium ions or iron ions present in an aqueous solution.
  • a further embodiment according to the invention is a process for the separation of carotenes, chlorophyls, phenols, sterols, squalene, glycolipids, glyceroglycolipids, glycerosphingolipids and / or waxes or carboxylic acids from an aqueous refined lipid phase, which is characterized by
  • Adsorptionsmittei to cellulose, a Ceiiuiosederivat or an inorganic alumina silicate with a Aluminiumanteii of> 0.1 mol% is and
  • the complexing agent is ammonium ions or iron ions present in an aqueous solution.
  • a further embodiment according to the invention is a process for the separation of water-binding organic lipophilic turbidity substances from an aqueous refined lipid phase, which is characterized by
  • lipid phase containing water-binding organic lipophilic turbidities, wherein the lipid phase has undergone at least one aqueous refining with an aqueous solution having at least one guanidine group or amidine group-bearing compound having a Kow of ⁇ 6.3,
  • step b) adding the lipid phase from step a) to an adsorption agent and / or a competing agent,
  • Adsorptionsmittei to cellulose, a Ceiiuiosederivat or an inorganic Aiuminiumoxid Siiikat having an aluminum content of> 0.1 mol% is and
  • the complexing agent is ammonium ions or iron ions present in an aqueous solution.
  • a further embodiment of the invention is a process for the separation of carotenes, chlorophylls, phenols, steroids, squaienen, Giycolipiden, Glyceroglycolipiden, Glycerosphingoiipiden and / or waxes or carboxylic acids from an aqueous refined lipid phase, which is characterized by,
  • step b) adding the phase of the lipid from step a) with an adsorption agent c) phase separation and separation of the adsorbed carotenes, chiorophyly, phenols, sterols, squalene, glycolipids, glycerolipolides,
  • Adsorptionsmittei to Ceiiuiose, a Ceiiuiosedenvat or an inorganic aluminum oxide Siiikat with a Aluminiumanteii of> 0.1 mol% is.
  • a further embodiment according to the invention is a process for the separation of water-binding organic lipophilic turbidity substances from an aqueous refined lipid phase, which is characterized by
  • lipid phase comprising water-binding organic iipophilic turbidities, wherein the lipid phase has undergone at least one aqueous refining with an aqueous solution having at least one guanidine group- or amidine-group-bearing compound having a Kow of ⁇ 6.3,
  • step b) adding to the lipid phase from step a) an adsorption agent c) phase separation and separation of the adsorbed water-binding organic lipophilic turbid substances,
  • Adsorptionsmittei to Ceiiuiose, a Celluiosederivat or an inorganic alumina silicate with a Aluminiumanteii of> 0.1 mol% is.
  • a further embodiment according to the invention is a process for the separation of water-binding organic lipophilic turbidity substances from an aqueous refined lipid phase, which is characterized by
  • Iipophilic turbidities wherein the lipid phase has undergone at least one aqueous refining with an aqueous solution having at least one guanidine group or amidine group-bearing compound having a Kow of ⁇ 6.3,
  • step b) adding the lipid phase from step a) to a complexing agent, c) phase separation and separation of the complexed water-binding organic lipophilic turbid substances,
  • a further embodiment according to the invention is a process for separating carotenes, chlorophylls, phenols, sterols, squalene, glycolipids, glyceroglycoipids and / or glycerosphingolipids and / or waxes or carboxylic acids from an aqueous refined lipid phase, which is characterized by
  • lipid phase containing carotenes, chlorophylls, phenols, sterols, squalene, glycolipids, glyceroglycolipids and / or glycerosphingolipids, and / or waxes or carboxylic acids wherein the lipid phase of at least one aqueous refining with an aqueous solution having at least one guanidine group or amidino group-bearing compound was subjected to a Kow of ⁇ 6.3,
  • FIG. 1 shows Table 1 .3 for Example 1.
  • FIG. 2 shows Table 2.2 for Example 2.
  • FIG. 3 shows Table 5.2 for Example 5.
  • FIG. 4 shows Table 6.1 for Example 6.
  • FIG. 5 shows Table 7 for Example 7. Examples of measurement methods
  • the content of phosphorus, calcium, magnesium and iron in the lipid phase was determined by ICP OES (Optima 7300, PerkinElmer, Germany). Values in ppm (or in mg / kg).
  • the proportion of free fatty acids in the lipid phase was determined by means of a methanolic KOH titration with a Titroline 7000 titrator (Sl-Analytics, Germany) values in% by weight (g / 100 g).
  • the water content in the lipid phase which is also referred to herein as oil moisture, was determined by means of an automatic titration according to the Karl Fischer method (Titroline 7500 KF trace Sl-Analytics, Germany), values in% by weight.
  • the determination of haze of a lipid phase was made by visual inspection by filling a 3 cm diameter cuvette with the oil to be tested and by 2 investigators, the visibility of image lines as viewed through the cuvette, under standardized light conditions.
  • the brilliance of the sample was assessed by looking through the daylight. With distortion-free image lilies and optical brilliance, the oil sample was rated as transparent. With significant distortion of the line contours with difficult recognition of the image lines as well as a no longer clear view, the assessment was carried out as slightly cloudy. If image lines were still recognizable, but could no longer be differentiated, and the visual appearance was dim, classification was as moderately murky.
  • Quantification of the turbidity (turbidimetry) of oil phases was also carried out by means of a scattered light detector in which reentry of a scattered beam at 90 ° with a measuring probe immersed in a sample volume of 10 ml (InPro 8200 measuring sensor, M800-1 transmitter, Mettler Toledo, Germany).
  • the measuring range is 5 to 4000 FTU.
  • Droplet or particle size determinations were made by non-invasive laser light backscatter analysis (DLS) (Zetasizer Nano S, Malvern, UK).
  • DLS non-invasive laser light backscatter analysis
  • 2 ml of a liquid to be analyzed were filled into a measuring cuvette and inserted into the measuring cell. The analysis on particles or phase boundary forming droplets proceeds automatically. It is covered a measuring range of 0.3 nm to 10 ⁇ .
  • the determination of secondary oxidation products in a lipid phase was carried out with a p-anisidine reaction, which was quantified photometrically.
  • 20 ⁇ of an oil sample were filled into a test cuvette already containing the test reagent and immediately placed in the measuring cell of an automatic analyzer (FoodLab, Italy). The measuring range is between 0.5 and 100. Each sample was analyzed twice.
  • rapeseed oil with the characteristic numbers given in Table 1 .3 (FIG. 1) were subjected to a multi-stage refining process.
  • the rapeseed oil was filled into a storage tank (storage tank 1).
  • the oil in the storage tank 1 is heated to 50 ° C. and then treated with 0.1% by weight of citric acid (25% by weight, to room temperature) and stirred for 10 minutes with a rotor-stator homogenizer (Fluco MS 4, Fluid Kotthoff, Germany) at a rotational frequency of 1000 rpm for 30 minutes homogenized and. Thereafter, 0.4 wt .-% of water are added and stirred for 15 min at 100 rpm.
  • a rotor-stator homogenizer Fluco MS 4, Fluid Kotthoff, Germany
  • phase separation with a separation separator (OSD 1000, MKR, Germany) at a throughput of 1001 / h and a rotational frequency of 10,000 rpm.
  • the resulting clear oily phase A is transferred to a further storage tank (storage tank 2). 125 ml of oily phase A was used for chemical analysis.
  • oily phase A is brought to a process temperature of 40 ° C and added to a 4 vol% of 10 wt% potassium carbonate solution.
  • the mixture is then carried out by means of the above-mentioned homogenizer at a rotational frequency of 1000 rpm for 15 minutes with intensive mixing.
  • the resulting emulsion is pumped into the separation separator and phase separation performed with the same adjustment parameters.
  • the resulting slightly cloudy oily phase B is transferred to the storage tank 3. 125 ml of oily phase B was used for chemical analysis.
  • the oily phase B is brought to a process temperature of 35 ° C and added 3 vol% of 0.5 molar arginine solution.
  • each 1 liter of the treated oil phases were withdrawn and provided with 50 ml of demineralized water and with a stirrer at a speed of 500rpm for 10 minutes at a temperature of 25 ° C. touched. This is followed by centrifugal separation at 3,000 g for 10 minutes. Afterwards a new determination of the water content of these oil phases as well as an evaluation of the turbidity took place (execution see measuring methods). Of the treated oil phases, 10 ml samples were also taken, one immediately frozen (D 0) and the second stored in an open vessel in daylight for 120 days (D120).
  • Example 1 500 kg of Jatropha press oil were refined in a multistage aqueous state, with the process technology essentially corresponding to that of Example 1.
  • the aqueous refining was carried out under basically the same mixing and separation conditions as listed in Example 1.
  • 4% by volume of an 8% by weight sodium borate solution introduced at 25 ° C with a propeller stirrer was used.
  • the separated oily phase A was discretely cloudy.
  • the second refining step was carried out with an addition of 3% by volume of a 5% strength by weight sodium bicarbonate solution at 50 ° C. Again, the entry was made with a propeller stirrer over 30 minutes.
  • the resulting oil B was slightly cloudy.
  • the 3rd aqueous refining step was carried out with 2% by volume of a 12% by weight orthometasilicate solution.
  • the resulting oil phase C was moderately cloudy.
  • 2% by volume of a 0.3 molar arginine solution, as described in Example 1 are introduced through an intensive mixture.
  • the reaction temperature was 32 ° C.
  • the prepurified oil phase D obtained was very turbid.
  • For the dried oil an attempt was made to reenterability of water according to Example 1. (Determination of the oil indices according to measuring methods)
  • the following cold press oils were used: from rapeseed (R ⁇ ), sunflower seeds (SB ⁇ ) and grape seeds (TK ⁇ ) with the key figures: for R ⁇ : phosphorus content 4.2 ppm (or 4.2 mg / kg), calcium 25 ppm (or 25 mg / kg), iron 2.1 ppm (or 2.1 mg / kg), free fatty acids 1, 0 wt .-%, and for SB ⁇ : phosphorus content 7.2 ppm (or 7.2 mg / kg), calcium 28 ppm (or 28 mg / kg), iron 2.3 ppm (or 2.3 mg / kg), free fatty acids 1, 2 wt .-% and for TK ⁇ : phosphorus content 3.8 ppm (or 3 , 8 mg / kg), calcium 12 ppm (or 12 mg / kg), iron 1, 1 ppm (or 1, 1 mg / kg), free fatty acids 0.8 wt .-%.
  • the prepurified oil phases obtained have the following ratios for RO: Phosphorus content 1, 2 ppm (or 1.2 mg / kg), Calcium 0.9 ppm (or 0.9 mg / kg), Iron 0.08 ppm (or 0 , 08 mg / kg), free fatty acids 0.2% by weight, for SB ⁇ : phosphorus content 0.8 ppm (or 0.8 mg / kg), calcium 0.2 ppm (or 0.2 mg / kg), iron 0.05 ppm (or 0.05 mg / kg), free fatty acids 0.13% by weight and for TK ⁇ : phosphorus content 0.5 ppm (or 0.5 mg / kg), calcium 0.02 ppm (or 0, 02 mg / kg), iron ⁇ 0.002 ppm (or ⁇ 0.002 mg / kg), free fatty acids 0.01 1% by weight. All oils obtained are moderately to significantly cloudy. (Determination of oil indices according to measuring methods).
  • hydroxyethylcellulose H 200000 YP2
  • methylhydroxypropylcellulose 90SH-100000
  • V 2 methylhydroxypropylcellulose
  • V3 kaolin powder
  • V6 polyaluminum hydroxide chloride sulfate
  • the adsorption and the complexing agent are mixed continuously with a propeller stirrer at a rotation frequency of 500 rpm after initial complete addition. After 10 minutes, b) after 15 minutes, c) after 30 minutes and d) after 60 minutes each 10 ml of the agitated oil phases are removed and centrifuged (3800 rpm / 5 minutes) from the solid or water phase separated. Subsequently, a determination of the optical transparency and the water content (see measuring methods).
  • a comparative sample of the prepurified oil added to the oil in a weight ratio of 1: 99 ion-free water was also agitated with the stirrer and sampled at the end of the study period Vacuum drying, as described in Example 1, removed (V 7) and then examined for transparency and water content and on the re-enterability of water.
  • Leverwort oil with the key figures (determination of the oil indices according to measurement methods) according to Table 5.1, was refined by the following methods:
  • V 1 phosphoric acid (85% strength by weight, addition amount 0.4% by weight, exposure time 30 minutes), then aqueous solution with sodium carbonate (20% strength by weight, addition amount 3% by volume, exposure time 5 minutes)
  • V 2 phosphoric acid (85% strength by weight, addition amount 0.4% by weight, duration of action 30 minutes), then aqueous solution with sodium carbonate (20% strength by weight, addition amount 3% by volume, exposure time 5 minutes), then aqueous solution with arginine (0.3 molar, addition amount 2% by volume, exposure time 5 minutes)
  • V 3 phosphoric acid (85% strength by weight, addition amount 0.4% by weight, duration of action 30 minutes), then aqueous solution with sodium hydrogen carbonate (20% strength by weight, addition amount 3% by volume, exposure time 5 minutes), then aqueous solution with sodium hydroxide (1 N, added amount 3%, exposure time 5 minutes)
  • V 4 Aqueous solution of sodium bicarbonate (20% by weight, added amount 3% by volume, exposure time 30 minutes), then phosphoric acid (85% by weight, added amount 0.4% by weight, exposure time 30 minutes)
  • V 5 Aqueous solution of sodium bicarbonate (20% by weight, added amount 3% by volume, exposure time 30 minutes), then phosphoric acid (85% by weight,
  • V 6 Aqueous solution of sodium carbonate (20% by weight, added amount 3% by volume, exposure time 30 minutes), then phosphoric acid (85% by weight, added amount 0.4 % By weight, exposure time 30 minutes), then aqueous solution with sodium hydroxide (1 N, addition amount 3%, exposure time 5 minutes)
  • V 7 Aqueous solution of sodium bicarbonate (20% by weight, added amount 3% by volume, exposure time 30 minutes), then aqueous solution of sodium metasilicate (20% by weight, added amount 2%, exposure time 5 minutes)
  • V 8 Aqueous solution of sodium bicarbonate (20% by weight, added amount 3% by volume, exposure time 30 minutes), then aqueous solution of sodium metasilicate (20% by weight, addition amount 2%, exposure time 5 minutes), then aqueous solution with arginine ( 0.3 molar, addition amount 2% by volume, exposure time 5 minutes)
  • V 9 Aqueous solution of sodium bicarbonate (20% by weight, added amount 3% by volume, exposure time 30 minutes), then aqueous solution of sodium metasilicate (20% by weight, addition amount 2%, exposure time 5 minutes), then phosphoric acid (85% by weight). %, addition amount 0.4% by weight, exposure time 30 minutes)
  • V 10 Aqueous solution of sodium bicarbonate (20% by weight, added amount 3% by volume, exposure time 30 minutes), then aqueous solution of sodium metasilicate
  • aqueous solutions and the undiluted phosphoric acid were added in the indicated concentrations and addition amounts to 10 liters of crude oil and homogenized with an intensive mixer (Ultrathurrax, T50, 10 TSD rpm for 5 minutes). Subsequently, phase separation with a separator (OTC 350, MKR, Germany) (flow rate 30 L / h, drum frequency l O.OOOrpm) then separated taking a sample for the determination of the ratios (Table 5.1).
  • intensive mixer Ultrathurrax, T50, 10 TSD rpm for 5 minutes.
  • phase separation with a separator (OTC 350, MKR, Germany) (flow rate 30 L / h, drum frequency l O.OOOrpm) then separated taking a sample for the determination of the ratios (Table 5.1).
  • the purified oil had the characteristics: Phosphorus content 0.7 ppm (or 0.7 mg / kg), calcium ⁇ 0.02 ppm (or ⁇ 0.02 mg / kg), iron ⁇ 0.02 ppm (or ⁇ 0.02 mg / kg), free fatty acids 0.05% by weight.
  • the oil was moderately cloudy and had a water content of 2.43% by weight.
  • the adsorbent a) hydroxyethyl cellulose (H 200000 YP2), b) hydroxyethyl cellulose (H 60000 YP2), c) methyl hydroxypropyl cellulose (90SH-100000) and d) kaolin, in increments of 0.2 wt % every 10 minutes, with continuous mixing with a propeller stirrer (400rpm).
  • primrose oil (5000ml) with the key figures (determination of the oil indices according to measuring methods): Phosphorus content 6.2 ppm (or 6.2 mg / kg), Calcium 1, 2 ppm (or 1, 2 mg / kg), Iron 0.31 ppm (or 0.31 mg / kg), free fatty acids 0.82% by weight (or 0.82 g / 100g) was subjected to ultrafiltration with a membrane filter having a nominal sieve size of 5 ⁇ and further with a sieve size of 0.45 ⁇ subjected. A sample of the transparent oil was analyzed and the numbers were virtually unchanged from the starting material. There was a determination of corpuscular components in the oil phase by means of DLS (for description, see Methods of measurement).
  • the filtered crude oil was optically transparent, it was determined a water content of 0.41% by weight, by means of the example 1 described experiment carried out a water entry, with a resulting water content of the oil of 2.62 wt%.
  • the filtered oil was subdivided for the following experimental arms: A) aqueous shirring by means of an arginine solution (0.6 molar, 3 vol% addition amount), which was carried out by passing the aqueous solution through an intensive mixer (Ultrathurrax T18, 24 TSD rpm) 10 minutes was entered; B) aqueous refining, as under A), but with a mixed addition by a propeller stirrer (500 rpm over 10 minutes; C) immediate addition of the adsorption or complexing agent to the oil and stirring as in B).
  • A aqueous shirring by means of an arginine solution (0.6 molar, 3 vol% addition amount), which was carried out by passing the aqueous solution through an intensive mixer (Ultrathurrax T18, 24 TSD rpm) 10 minutes was entered; B) aqueous refining, as under A), but with a mixed addition by a propeller stirrer (500 rpm over 10 minutes; C) immediate
  • Example 5 Following the aqueous refining of the experimental arms A) and B), a phase separation was carried out as in Example 5 to obtain the oil phases A1) and B1).
  • the following parameters were determined for the pre-cleaned oil, for A1): Phosphorus content 0.7 ppm (or 0.7 mg / kg), Calcium 0.02 ppm (or 0.02 mg / kg), Iron ⁇ 0.02 ppm (or ⁇ 0.02 mg / kg), free fatty acids 0.08% by weight and for B1): phosphorus content 1.2 ppm (or 1.2 mg / kg), calcium 0.09 ppm (or 0.09 mg / kg), iron 0.03 ppm (or 0.03 mg / kg), free fatty acids 0.10% by weight. Both oils were moderately cloudy.
  • the oil phases A1), A2), B1) and B2) were the adsorbents hydroxyethyl cellulose (H 60000 YP2) (a) and methylhydroxypropyl cellulose (90SH 100000) (b) (each 0.5 wt% added) and the complexing agent aluminum trichloride (1.0 molar, 1 wt% addition amount) (c) and polyaluminum chloride (9 wt%, 0.5 wt% addition amount) (d) are added. It was mixed with a propeller stirrer (500 rpm for 20 minutes) and then phase separated with a beaker centrifuge (3800 rpm / 10 minutes).
  • the resulting oil supernatants A1 "), A2"), B1 ") and B2" were withdrawn and samples were taken for the analysis and for an attempt to registrability of water, according to the experimental procedure of Example 1.
  • the resulting oil phases A2 ") and B2") were mixed with an arginine solution (0.1 molar, added amount 2% by weight) and the phases were homogenized with the intensive mixer (24 tsd rpm, 2 minutes). Subsequently, phase separation as described above, to obtain the oil phases A3) and B3). Both oil phases were cloudy, samples were taken for analysis.
  • the adsorbents according to the invention which were added in anhydrous form to an ultrafiltered crude oil, led to a slight reduction in the water content present therein.
  • the incorporation of aqueous solutions containing the complexing agents of the present invention into an ultrafiltered but non-aqueous refined oil phase resulted in an increase in the water content of the oil phase. After centrifugal separation of the adsorption and complexing agents. In both cases, there was a distinct registrability of water into the oil phase.
  • a determination of the particles or droplets contained in the refined oils showed that for all samples that were judged to be transparent and had a haze value of 5 FTU, less than 5% of all measured particles / droplets were> 20 nm.
  • the turbidity measurement yielded values up to 16 FTU, there were also particles / droplets with a peak at 60 nm, with a ratio of less than 5% to particles / droplets ⁇ 10 nm.
  • aqueous refining 5000 liters of rapeseed press oil is subjected to aqueous refining according to the following scheme: 1. Phosphoric acid (85%, addition amount 0.4%), 2. Aqueous solution with sodium carbonate (20% by weight, addition amount 3% by weight), 3. Aqueous solution with arginine (0.3 molar, addition amount 2% by weight).
  • the acid and the aqueous solutions are homogenized by means of an in-line intensive mixer (DMS2.2 / 26-10, Fluko, Fluid Kotthoff, Germany) with a throughput volume of 3 m 3 / h, at a rotational frequency of the dispersing tool of 2700rpm.
  • DMS2.2 / 26-10 Fluko, Fluid Kotthoff, Germany
  • a phase separation is carried out with a separator (AC1500-430 FO, Flottweg, Germany) at a throughput of 3 m 3 / h and a drum speed of 6500 rpm (maximum centrifugal acceleration 10,000 g).
  • the refined oil fractions are stored in each case in a storage container until the next refining step.
  • the oil has the following characteristics: Phosphorus content 0.9 ppm (or 0.9 mg / kg), Calcium ⁇ 0.02 ppm (or ⁇ 0.02 mg / kg), Iron ⁇ 0.02 ppm (or ⁇ 0.02 mg / kg), free fatty acids 0.07% by weight, water content 2.9% by weight.
  • the oil is clearly cloudy.
  • the purified oil from the 3. Refining stage is filled in 2 fractions of 2450 liters each in the storage tanks 1 and 3.
  • To the template tank 1 6.6 kg of hydroxyethyl cellulose (H 200000 YP2), which is in the form of a fine powder, is added with continuous stirring with a propeller stirrer (400 rpm) over 3 minutes and then further stirred for 15 minutes.
  • the oil phase is pumped into a candle filter unit (screen size 2 ⁇ ) via a pump.
  • the outlet of the filter unit is connected to the storage tank 2 for storage of the refined oil phase.
  • the purified oil in storage tank 3 is added 46 liters of a 3 molar aluminum trichloride solution. Via a bottom outlet of the reservoir tank, which is connected to a pipeline, the oil / water mixture is pumped into the above-mentioned inline rotor-stator mixing unit and mixed therein at a rotational frequency of 1000 rpm at a product throughput of 6 m 3 / h.
  • the mixed oil / water phase is returned to the storage tank 3 again.
  • the mixing process is carried out for 15 minutes, theoretically a 3-times throughput of the total oil mixture volume through the mixing unit. This is followed by a phase separation with the abovementioned separator, as described above.
  • the oil phase is then introduced into the storage tank 4 via a pipeline.

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Abstract

La présente invention concerne un procédé de séparation de composés générateurs de turbidité d'une phase lipidique.
EP15730076.5A 2014-05-30 2015-06-01 Procédé de clarification de phases lipidiques raffinées Not-in-force EP3149133B1 (fr)

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CN107874258A (zh) * 2017-11-21 2018-04-06 荣成海锐芯生物科技有限公司 一种利用粗鱼肝油提取物制备鱼肝油胶囊的方法
CN109294727A (zh) * 2018-11-16 2019-02-01 苏州市贝克生物科技有限公司 一种橄榄油的精炼方法

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JP2685145B2 (ja) * 1988-01-25 1997-12-03 王子製紙株式会社 酵素電極
CA2040677A1 (fr) * 1991-04-03 1992-10-04 Gabriella J. Toeneboehn Produits chimiques a chaine grasse et esters paraffiniques
ES2117648T3 (es) 1992-02-19 1998-08-16 Nestle Sa Procedimiento de decoloracion de un ester de acido graso y composicion alimenticia o cosmetica que lo contiene.
JPH0815705A (ja) * 1994-06-28 1996-01-19 Hoechst Japan Ltd 液晶表示素子
CN1267174C (zh) * 2001-12-12 2006-08-02 马泰克生物科学博尔德公司 从含油种子和微生物来源提取和冬化脂类的方法
DE102006061604A1 (de) 2006-12-27 2008-07-03 Alois Dotzer Verfahren zur Herstellung eines Kraftstoffs aus Pflanzenöl
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WO2009148919A1 (fr) * 2008-06-06 2009-12-10 Cargill, Incorporated Procédés de raffinage d’huile
US20110269849A1 (en) * 2010-05-03 2011-11-03 Yuan Yao Emulsions and Methods for the Preparation Thereof, and Methods for Improving Oxidative Stability of Lipids
EP2399885A1 (fr) * 2010-06-22 2011-12-28 Ulrich Dietz Dispositif et procédé pour solubiliser, séparer, supprimer et faire réagir les acides carboxyliques dans des solutions aqueuses ou organiques au moyen d'une micro ou nano-émulsification
EP2616531B1 (fr) 2010-09-13 2017-01-11 Palsgaard A/S Huile végétale raffinée et procédé pour la produire
CN103756782B (zh) * 2014-02-12 2015-05-20 中国农业科学院油料作物研究所 一种制取植物油的方法

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CN106459827B (zh) 2020-12-08
CA2947462C (fr) 2019-02-26
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PL3149133T3 (pl) 2019-08-30
ES2727082T3 (es) 2019-10-14
RU2016152218A3 (fr) 2018-12-05
RU2689556C2 (ru) 2019-05-28
EP3149133B1 (fr) 2019-02-27
ZA201608251B (en) 2018-05-30
WO2015181399A1 (fr) 2015-12-03
US20170081611A1 (en) 2017-03-23
HUE043439T2 (hu) 2019-08-28
AU2015265839B2 (en) 2019-04-11
PT3149133T (pt) 2019-05-17

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