EP3152283B1 - Verfahren und vorrichtung zur schrittweisen aufarbeitung eines organischen öls - Google Patents

Verfahren und vorrichtung zur schrittweisen aufarbeitung eines organischen öls Download PDF

Info

Publication number
EP3152283B1
EP3152283B1 EP15727638.7A EP15727638A EP3152283B1 EP 3152283 B1 EP3152283 B1 EP 3152283B1 EP 15727638 A EP15727638 A EP 15727638A EP 3152283 B1 EP3152283 B1 EP 3152283B1
Authority
EP
European Patent Office
Prior art keywords
oil
acid
phase
oil phase
addition
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.)
Active
Application number
EP15727638.7A
Other languages
German (de)
English (en)
French (fr)
Other versions
EP3152283A1 (de
Inventor
Steffen Hruschka
Wladislawa Boszulak
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.)
GEA Westfalia Separator Group GmbH
Original Assignee
GEA Westfalia Separator Group GmbH
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by GEA Westfalia Separator Group GmbH filed Critical GEA Westfalia Separator Group GmbH
Priority to PL15727638T priority Critical patent/PL3152283T3/pl
Publication of EP3152283A1 publication Critical patent/EP3152283A1/de
Application granted granted Critical
Publication of EP3152283B1 publication Critical patent/EP3152283B1/de
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Images

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
    • 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
    • C11B3/006—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
    • C11B3/04—Refining fats or fatty oils by chemical reaction with acids
    • 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
    • C11B3/10—Refining fats or fatty oils by adsorption

Definitions

  • the present invention relates to a method and an apparatus for the gradual workup of an organic oil.
  • An organic oil contains lipid components and various other accompanying substances, the latter reducing the quality of valuable products obtained from the oil and possibly limiting their use.
  • the CN 103 396 884 A discloses treating raw rapeseed oil, then adding vinegar, adding deionized water, and finally adding sodium carbonate. All substances are combined in a single step in a mixture.
  • the US 4,808,426 A discloses an extraction process when adding foreign oil. A degumming is described in this publication. This is followed by the addition of a binding agent in the form of sodium acetate. The oil is then further treated by adding various other agents, such as soy protein or sodium soap.
  • Example I discloses the treatment of degummed oil with sodium carbonate (not sodium hydrogen carbonate).
  • Example VI an electrolyte with sodium acetate is used.
  • oils are usually subjected to a so-called degumming process for the purpose of technical refining in order to convert hydratable compounds into a water phase, as a result of which the dissolved or aggregated compounds can be separated off using processes for phase separation.
  • degumming process for the purpose of technical refining in order to convert hydratable compounds into a water phase, as a result of which the dissolved or aggregated compounds can be separated off using processes for phase separation.
  • the majority of hydratable and some non-hydratable phospholipids are separated by these processes.
  • This can include, for example, saponification of the free fatty acids.
  • Magnesium and / or calcium salts and / or chelates such as chlorophyll, such as chlorophyll, can usually be present in the vegetable oil. However, these are difficult to separate from the free fatty acids and therefore, after the free fatty acids have been separated off, dissolved or undissolved alkaline earth metal salts can be present as accompanying substances in the free fatty acid fraction.
  • a method according to the invention relates to the gradual workup of an oil according to claim 1.
  • This step-by-step refurbishment can preferably be integrated into an established refining process for producing an edible oil or a fuel for internal combustion engines as a sequence of steps.
  • the step-by-step process includes the following steps: A Provision of a crude oil
  • the crude oil can be obtained, for example, from plants by pressing or extraction processes. However, a variety of other provision variants are also possible.
  • the crude oil does not necessarily have to be obtained directly from living beings, but, as with deep-frying oil, can also have been used as intended once or several times.
  • B Deguming the crude oil by adding water and / or acid to the crude oil and forming at least two phases, an aqueous phase and an oil phase, and separating the aqueous phase enriched with phospholipid from the oil phase
  • Degumming is a known process step in itself. One differentiates between water degumming and the less frequently used acid degumming. The latter is preferred in the method according to the invention.
  • the acid addition can be the addition of a dilute acid or, likewise preferably, the addition of a concentrated acid in connection with a subsequent addition of water.
  • Mainly hydratable mucilages such as hydratable phosphoglycerides such as phosphatidylinositols and phosphatidylcholines, are separated from the oil phase and transferred to the aqueous phase. These can be separated centrifugally.
  • the addition of sodium hydrogen carbonate has a separation of alkaline earth compounds and / or iron compounds, e.g. also chlorophyll, other magnesium complexes or also calcium complexes or iron complexes.
  • iron ions or iron compounds results in a lower susceptibility to oxidation of the oil phase.
  • Some of the alkaline earth compounds can be present as phospholipids.
  • the addition of sodium hydrogen bicarbonate also removes non-hydratable phospholipids, preferably non-hydratable phosphoglycerides, such as e.g. Phosphatidylethanolaminen and even of phosphatidic acid and its salts, especially their alkali and alkaline earth salts, takes place.
  • the separation can preferably be carried out by phase separation of an aqueous and an oil phase in a centrifugal field.
  • an organic oil is obtained which, compared to the degummed oil fraction in step B, has a lower proportion of one or more accompanying oils (sterylglycosides, alkaline earth compounds and / or phospholipids), which is usually difficult to obtain from an organic oil separately from the free fatty acids can be.
  • the free fatty acid content compared to the oil fraction from step B is surprisingly almost unchanged after step C.
  • step D free fatty acids are saponified in step D with the addition of an alkaline agent to the oil phase from step C, whereby these saponified fatty acids can be separated from the oil phase.
  • the saponified fatty acids can pass as a relatively pure fraction from the oil phase into a water phase, which is formed by adding water before, during or after the addition of the alkaline agent.
  • the saponified fatty acid has less than 3% by weight of organic contaminants. These soaps can then be broken down again under pressure or with the addition of acid to free fatty acids. This reaction is commonly known as soap splitting. Due to the relatively high purity of the soap fraction, there is only a less contaminated water phase during soap splitting. Contaminated soap fractions, on the other hand, would make soap splitting difficult.
  • the separation can preferably be carried out by phase separation of an aqueous and an oil phase in the centrifugal field.
  • step C or D further refining of the oil phase can also take place in step C or D. This is done through the optional step E Bleaching and / or deodorising the oil phase
  • bleaching process can be carried out much more effectively. Bleaching can be carried out particularly effectively, for example, by bleaching earth.
  • Deodorization can also be designed effectively. As is known, deodorization can be done mechanically by e.g. by steam distillation in a so-called deodoriser.
  • degumming is carried out by adding an acid which is selected from one or more of the following acids: citric acid, acetic acid, formic acid, oxalic acid, hydrochloric acid, sulfuric acid, nitric acid and / or phosphoric acid.
  • Organic acids have proven to be particularly suitable for the separation of mucilage from the aforementioned acids.
  • step C The addition of sodium hydrogen carbonate after step C can be repeated until the turbidity of the water phase and / or a determined content of alkaline earth metal ions in the oil phase and / or a determined phosphorous content in the oil phase falls below a predetermined target value. Due to the addition as a powder or suspension and comparatively little water, there is no extensive water phase to be worked up. In this way, step C can be carried out several times without the workup becoming uneconomical due to the resulting solvents. At the same time, the quantitatively improved separation of accompanying substances is achieved by the multiple addition.
  • an aqueous phase can be separated off which contains a proportion of free fatty acids which corresponds to a separation of less than 0.2 percentage points of free fatty acids from the oil phase.
  • step C can preferably be used to separate an aqueous phase in which organic constituents are dissolved or are present in suspension, which contain more than 30% by weight, preferably more than 50% by weight, of steryl glycosides.
  • the saponified fatty acid can preferably have less than 1% by weight of organic contaminants.
  • the alkaline agent added in step D is an inorganic alkali liquor, preferably a sodium hydroxide solution.
  • the addition of this comparatively inexpensive agent is sufficient after separation of sterylglycosides and / or phospholipids and / or alkaline earth metal compounds in order to obtain an oil phase which is predominantly free of accompanying substances.
  • Fig. 2 shows a device which has a receptacle 1 for receiving the aqueous phase or the salt solution or a suspension of the salts described herein.
  • a line 2 into which a pump 14 is connected
  • a container 3 is preferably designed as a constant pressure buffer container.
  • the container 3 can have an overflow return 4, which serves to return liquid from the container 2 into the receptacle 1 when an overflow level is exceeded.
  • the container 3 also has a drain line 5 (preferably at its lower end), in which a valve 6 is connected here.
  • the volume flow in the drain line 5 can be controlled with the valve 6.
  • the drain line opens into a mixer 7.
  • a further phase, preferably the lipoid-containing (lipid) phase, can be passed through the feed line 8 into the mixer 7.
  • the mixer 7 also has an outlet line 9 which opens into an inlet of a centrifuge 10. The two supplied phases are mixed in the mixer 7.
  • the mixer 7 can be designed in various ways. So a static mixer or a dynamic mixer can be used. Special shapes such as a high-shear mixer or a nanoreactor are also suitable. It is also conceivable to use the centrifuge itself as a mixer. In this case, the lipoid phase and the salt solution (aqueous solution) passed through separate feed lines into the centrifuge, where - for example in a distributor 15 of the centrifuge drum - these two phases are mixed. Such distributors are known per se and are used to transfer the incoming product into the rotating drum.
  • a separator with a vertical axis of rotation which is designed to separate two liquid phases of different densities, is preferably used as the centrifuge.
  • the device can also be designed to operate under pressure p which is higher than atmospheric pressure.
  • the preferred rule is: 1 bar ⁇ p ⁇ 10 bar.
  • the outlet pressure in the outlets 11 and 12 should be higher than the inlet pressure in the inlet to the centrifuge.
  • An air inlet in the inlet should preferably be avoided in order to prevent an emulsion from forming to a disruptive extent in the mixer and / or in the centrifuge drum.
  • this device prevents the formation of emulsions, which means that on the one hand it is easier to separate fractions containing phospholipids, alkaline earth-containing compounds and / or sterylglycosides, because there is better phase separation and, on the other hand, the depletion of the oil phase is more complete than with a mixing and separation system that does not prevent the exclusion of air / gas entry according to the invention.
  • a first step A crude oil, ie the organic oil to be worked up, is made available.
  • Main products obtained from the oil can be used, for example, but not exclusively, as fuels or as edible oils. If necessary the obtained valuable products can also be esterified in one processing step to produce biodiesel.
  • Preparatory steps can be taken to extract crude oil.
  • Starting from plant seeds these can be prepared, e.g. peeled, and then oiled.
  • the de-oiling can take place, for example, by means of a pressing process.
  • Hot pressing and cold pressing processes are known for the extraction of vegetable oil.
  • Extraction processes e.g. hexane extraction can be used.
  • crude oil organic oil
  • organic oil encompasses mixtures of substances of biological origin which can therefore be obtained from plants, algae, animals and / or microorganisms and which have a water content of ⁇ 10% and a content of lipophilic substances comprising monoacylglycerides , Diacylglycerides and / or triacylglycerides totaling> 70% by weight or> 75% by weight or> 80% by weight or> 85% by weight or> 90% by weight or> 95% by weight .
  • the lipoid phases can be extracts of oil-containing plants and microorganisms such as kernels from rapeseed, soybeans, camelina, jatropha, palm trees, but also from algae and microalgae as well as animal fats and oils.
  • oil-containing plants and microorganisms such as kernels from rapeseed, soybeans, camelina, jatropha, palm trees, but also from algae and microalgae as well as animal fats and oils.
  • An organic oil or a crude oil can be a vegetable oil, for example.
  • the crude oil can also be an oil of animal origin.
  • the crude oil can also be an already used oil, e.g. Frying fat, act which has already been used and which it is for further use, e.g. as fuel to be processed.
  • Many other refined oils are conceivable, which have to be worked up within the scope of the present invention.
  • the crude oil may also consist of> 50% organic solvents or hydrocarbon compounds.
  • fats and oils are classified in the class of lipids, while the group of lipoids includes all other compounds of the Class waxes, carotenoids, glycolipids, phosphatides, prostaglandins, etc. includes. (Definition after Beyer, Walter, "Textbook of Organic Chemistry” 21st edition S.Hirzel Verlag, 1988 - p.248 )
  • oils or fats such as, for example, vegetable oils
  • Table 1 summarizes some substance classes found in oils and / or fats that were obtained from various useful plants. It can already be seen here that the neutral lipids usually make up the majority of the oils or fats, but the proportion of phospholipids and glycolipids / glycoglycerolipids / glycosphingolipids is extremely variable.
  • the percentage of glycolipids, glycoglycerolipids and glycosphingolipids ranges from 0.2% in coconut oil, over approx. 2% in borage oil and 6.3 - 7% in rice bran oil to 19.4% in oil from avocado seeds.
  • Tab. 1 Content of lipids without ionic groups (NL), phospholipids (PL) and glycolipids together with glycoglycerolipids and glycosphingolipids (GL) in the seeds (S) or the oils obtained from selected plants.
  • the PL and GL content is given as a percentage of the total oil. In the case of seeds, it is also sometimes stated how high the percentage of oil (total) is compared to the seed mass.
  • Crude oils as defined herein include 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, crab oil, linseed oil, grape seed oil, hazelnut oil, other nut oil oils, hemp seed oil, hemp seed oil , Jojoba oil, macadamia nut oil, mango kernel oil, cuckoo oil, mustard oil, claw oil, olive oil, palm oil, palm kernel oil, palm olein oil, peanut oil, pecan oil, pine nut oil, pistachio oil, poppy seed oil, rice germ oil, thistle oil, camellia oil, sesame oil, sheab oil , Soybean oil, sunflower oil, tall oil, tsubaki oil, walnut oil, varieties of "natural” oils with modified fatty acid compositions via genetically modified organisms (GMOs) or traditional breeds, Neoch
  • a crude oil phase and a solid phase are obtained.
  • the solids of the solid phase can be processed further, for example to isolate or enrich feed, fiber, proteins, polyphenols or other valuable substances.
  • Glycerin sterylglycosides
  • the free fatty acids phospholipids, tocopherol and other substances.
  • These are preferably present in the crude oil at a content of less than 400 ppm, preferably less than 100 ppm.
  • Phospholipids are separated. These are phosphorus-containing organic substances that have the properties of a fat. A distinction is made between phospholipids in non-hydratable phospholipids (NHP) and hydratable phospholipids (HP). Hydratable phospholipids are, for example, phosphatidylinositol or its salts, phosphatidylcholine. Non-hydratable phospholipids are, for example, phosphatidylethanolamine and phosphatidic acid or salts thereof. Typical cations of the phospholipids are e.g. Sodium, potassium, calcium, etc.
  • hydratable phospholipids and / or non-hydratable phospholipids which can easily be converted into a hydratable form, are first separated off.
  • water is added to the crude oil and phospholipids, if they can be hydrated, are hydrated. These phospholipids accumulate as sludge and can be centrifugally separated from the oil.
  • Non-hydratable phospholipids can be destroyed by heating, by adding certain adsorbents, by filtration and / or by adding an acid as a complex and thereby converted into a hydratable form.
  • the addition of acid is called acid degumming, while the exclusive addition of water is known as water degumming.
  • water degumming After degumming, a degummed oil fraction is obtained, which however still has a residual proportion of phospholipids, in particular non-hydratable phospholipids (see section 3.1).
  • An acidic aqueous phase which contains, for example, citric acid, acetic acid, formic acid and / or oxalic acid can advantageously be used for acid degumming.
  • hydrochloric acid, sulfuric acid, nitric acid and / or phosphoric acid can be used less preferably.
  • Fig. 6 shows clearly and exemplarily the classification of the phospholipids in non-hydratable and hydratable phospholipids. (NHP's and HP's). In acidic processes, PE can easily be converted into a hydratable form by protonating the amino group as shown in the figure.
  • a third step III of the oil processing sodium hydrogen carbonate is added. It has surprisingly been found that when sodium hydrogen carbonate is added, additional separation of remaining phospholipids, in particular non-hydratable phospholipids, in particular phosphatidic acid compounds, such as e.g. dissolved salts.
  • a separation of a proportion of sterylglycosides also takes place when sodium bicarbonate is added, which are separated from the degummed oil fraction.
  • the proportion of calcium, magnesium and possibly also iron ions is greatly reduced, since these are displaced by the addition of sodium ions in the form of sodium hydrogen carbonate.
  • the free fatty acids remain almost completely in the oil phase.
  • fatty acids is used synonymously with the term “free fatty acids”.
  • free is intended to clarify that the fatty acids are not bound because the majority of the constituents in the nonpolar oil phase contain bound fatty acids, e.g. as triacylglycerides, diacylglycerides or monoacylglycerides.
  • Aliphatic monocarboxylic acids with at least 8 carbon atoms are referred to as fatty acids.
  • fatty acids refers to free fatty acids (also abbreviated to FFAs), i.e. fatty acids which are free and are not glyceridically (i.e. to glycerol) or glycosidically (i.e. to sugar residues) bound.
  • fatty acids preferably includes the following compounds: hexanoic acid, octanoic acid, decanoic acid, dodecanoic acid, tetradecanoic acid, hexadecanoic acid, heptadecanoic acid, octadecanoic acid, eicosanoic acid, docosanoic acid, tetracosanoic acid, cis-9-tetradecenoic acid, cis-9-hexadecenoic acid, cis-9-cenadecenoic acid , cis-9-octadecenoic acid, cis-11-octadecenoic acid, cis-9-eicosenoic acid, cis-11-eicosenoic acid, cis-13-docosenoic acid, cis-15-tetracosenoic acid, t9-octadecenoic acid, t11-
  • free fatty acids can easily form oxidative compounds. To ensure the durability of refined oil and oil derivatives, these free fatty acids should therefore be removed from the processed oil phase. This takes place in a fourth step D in which the worked-up oil phase is mixed with an alkaline agent.
  • an alkaline agent It is an inorganic alkali lye, i.e. a sodium hydroxide or a potassium hydroxide solution, the use of sodium hydroxide solution having proven to be particularly efficient and inexpensive.
  • This lye separates the free fatty acids as accompanying substances from the oil phase.
  • the free fatty acids are saponified and can be recovered in a very high degree of purity by separating both phospholipids and unwanted cations (alkaline earth metal ions and iron ions).
  • soap splitting e.g. by adding acid
  • the free fatty acids can be extracted from the soaps.
  • the fourth step by adding an alkaline agent, separates a fraction of a comparatively pure fatty acid as soap.
  • the phosphorus content in the worked-up oil phase can be reduced to a content of less than 3 ppm, preferably even less than 1 ppm, since portions of NHPs are removed more easily after step 3 with the soap.
  • the main product ie the oils and fats, is refined further by bleaching and / or deodorising.
  • Bleaching earth can predominantly be used as an agent in bleaching, which can be used more efficiently in the present process. It is also possible to add the bleaching earth at the same time as the sodium hydrogen carbonate or sodium acetate. Deodorization can be carried out, for example, by steam distillation in a so-called deodoriser. In this way, for example, undesirable odorous substances can be removed from the oil
  • Further steps in the refining process of the oil and / or fat can optionally also take place before or after the bleaching and / or deodorization. These include, for example, oil polishing and / or drying under vacuum to remove water components.
  • sodium acetate can also be added instead of the sodium bicarbonate. It has surprisingly been found that when sodium acetate is added there is an additional enrichment of sterylglycosides in the aqueous phase which are separated from the degummed oil fraction. At the same time residual phospholipids, free fatty acids and alkaline earth compounds, e.g. Chlorophyll remains predominantly or almost completely in the oil phase.
  • the steryl glycosides are sterols which are glycosidically linked to at least one saccharide residue via a hydroxyl group.
  • Sterylglycosides are found in plants, animals, fungi and also in some bacteria. In animals, for example, there is cholesterol glucoronide, in which a cholesterol residue is linked to a glucuronic acid residue.
  • the sterol residue is preferably campesterol, stigmasterol, sitosterol, brassicasterol or dihydrositosterol and the saccharide residue is preferably glucose, galactose, Mannose, glucuronic acid, xylose, rhamnose or arabinose.
  • the saccharide residue in plant steryl glycosides is linked to the sterol via the hydroxy group on the C3 of the A ring of the sterol. Further saccharide residues can be linked to this first saccharide residue via a ⁇ -1,4-glycosidic bond or a ⁇ -1,6-glycosidic bond.
  • acylated sterylglycosides (ASGs) in which a saccharide residue at its hydroxyl group at position 6 is esterified with a fatty acid. In many plants, acylated sterylglycosides were found in practically all parts of the plant in up to 0.125% by weight.
  • the proportion of non-acylated and acylated steryl glycosides in palm and soybean oil is particularly high.
  • a high proportion of steryl glycosides is discussed in connection with poorer filterability.
  • An oil phase remains in which the sterylglycoside content has already been significantly reduced, which facilitates further processing.
  • a phase can be separated by adding an alkaline agent.
  • the proportion of sterylglycoside in the water phase is relatively high, ie at least over 60% by weight, preferably over 80% by weight, compared to the proportion of sterylglycoside in the oil phase.
  • the sterylglycosides obtained can be used in cosmetic and / or pharmaceutical products.
  • a fourth step D in which the worked-up oil phase is mixed with an alkaline agent, the separation into non-polar oil phase and polar aqueous soap phase takes place.
  • This is preferably an alkali liquor, that is to say a sodium hydroxide or a potassium hydroxide solution, the use of sodium hydroxide solution also having proven particularly preferred in this case.
  • This lye separates the free fatty acids, as well as the remaining phospholipids and alkaline earth species, including chlorophyll, as accompanying substances in an aqueous phase from the oil phase.
  • the free fatty acids are saponified and can optionally be recovered by subsequent soap splitting.
  • Crude oil (FFA content 0.48% by weight, H 2 O content 0.05% by weight, iron content 1.13 ppm, phosphorus content 80.42 ppm, magnesium content 8.47 ppm, calcium content 45 , 10 ppm) is filled into the storage tank (storage tank 1) as press oil from a rapeseed.
  • the crude oil in the storage tank 1 is then heated to 85 ° C. and then 0.1% by weight of dilute citric acid (33% by weight, to room temperature) is added and the mixture is stirred vigorously for 30 seconds and then at about 10 minutes Stirred 100 to 150 rpm. Then 0.6% by weight of water is added.
  • the mixture of oil and dilute citric acid is then pumped into the separation separator and then the aqueous phase B is separated from the oily phase A at a rate of 200 l / h.
  • the aqueous phase A is collected and stored until further use.
  • the oily phase A is transferred to a further storage tank (storage tank 2) for further processing.
  • the oily phase A is then analyzed (FFA content 0.48% by weight, H 2 O content 0.23% by weight, iron content 0.34 ppm, phosphorus content 26.1 ppm, magnesium content 2 , 32 ppm, calcium content 9.04 ppm).
  • the oily phase A obtained in this way is brought to a process temperature of 45 ° C. and a sufficient volume of 8% by weight sodium hydrogen carbonate solution is added so that a theoretical degree of neutralization of the free fatty acids of 90% is achieved.
  • a sufficient volume of sodium hydrogen carbonate can be chosen such that more than 0.1% by weight NaHCO 3 , based on the weight of the oil phase used, for example 0.3% by weight NaHCO 3, is added.
  • the addition need not necessarily be made as a solution, but can also be done as a powder. Water can then be added separately.
  • the mixture is stirred intensively for 30 seconds but without the entry of air, ie without the introduction of gas, and then for 10 minutes normally but still without the entry of air, ie without the introduction of gas.
  • the resulting mixture is then in the separation separator pumped and thus separated the aqueous phase B from the oily phase A at a rate of 200 l / h.
  • the aqueous phase B is collected. In this, sterylglycosides were detected by TLC.
  • the oily phase A is transferred back to the storage tank 1 for further processing.
  • the oily phase is then analyzed (FFA content 0.32% by weight, H 2 O content 0.23% by weight, iron content 0.15 ppm, phosphorus content 5.75 ppm, magnesium content 0. 69 ppm, calcium content 3.46 ppm).
  • Crude oil (FFA content 0.43% by weight, H 2 O content 0.05% by weight, iron content 0.60 ppm, phosphorus content 52.52 ppm, magnesium content 5.43 ppm, calcium content 31 , 33 ppm) is filled into the storage tank (storage tank 1) as press oil from a rapeseed.
  • the crude oil in the storage tank 1 is then heated to 85 ° C. and then 0.1% by weight of citric acid (33%, to room temperature) is added and the mixture is stirred vigorously for 30 seconds and then stirred at about 100 to 150 rpm for 10 minutes. Then 0.6% by weight of water is added.
  • the mixture of crude oil and dilute citric acid is then pumped into the separation separator and then the aqueous phase B is separated from the oily phase A at a rate of 200 l / h.
  • the aqueous phase A is collected and stored until further use.
  • the oily phase A is transferred to a further storage tank (storage tank 2) for further processing.
  • the oily phase A is then analyzed (FFA content 0.43% by weight, H 2 O content 0.26% by weight, iron content 0.17 ppm, phosphorus content 12.49 ppm, magnesium content 0 , 40 ppm, calcium content 1.85 ppm).
  • the oily phase A obtained in this way is brought to a process temperature of 45 ° C. and a sufficient volume of 8% sodium acetate solution is added so that a degree of neutralization of the free fatty acids of 90% is achieved.
  • the mixture is then stirred intensively and preferably free of gas for 30 seconds using a Ystral mixer and then stirred normally and preferably for 10 minutes without gas.
  • the resulting mixture is then pumped into the separation separator and thus the aqueous phase B is separated from the oily phase A at a rate of 200 l / h.
  • aqueous phase B sterylglycosides were detected using TLC.
  • the oily phase A is transferred back to the storage tank 1 for further processing.
  • the oily phase A is analyzed (FFA content 0.43% by weight, H 2 O content 0.24% by weight, iron content 0.09 ppm, phosphorus content 5.79 ppm, magnesium content 0.25 ppm, calcium content 0.89 ppm).
  • Crude oil (FFA content 0.54%, H 2 O content 0.05%, iron content 0.53 ppm, phosphorus content 78.32 ppm, magnesium content 5.70 ppm, calcium content 33.04 ppm) is filled into the storage tank (storage tank 1) as press oil from a rapeseed.
  • the crude oil in the storage tank 1 is then heated to approx. 85 ° C. and then 0.1% by weight of citric acid (33%, at room temperature) is added and the mixture is stirred intensively for 30 seconds and then at about 100 to 150 rpm for 10 minutes touched. Then 0.6% by weight of water is added.
  • the mixture of crude oil and dilute citric acid is then pumped into the separation separator and then the aqueous phase B is separated from the oily phase A at a rate of 200 l / h.
  • the aqueous phase A is collected and stored until further use.
  • the oily phase B is transferred to another storage tank (storage tank 2) for further processing.
  • the oily phase A is then analyzed (FFA content 0.48% by weight, H 2 O content 0.53% by weight, iron content 0.15 ppm, phosphorus content 16.57 ppm, magnesium content 0 , 28 ppm, calcium content 1.78 ppm).
  • the oily phase A obtained in this way is brought to a process temperature of 40-45 ° C. and a sufficient volume of 8% sodium carbonate solution is added so that a theoretical degree of neutralization of the free fatty acids of 90% is achieved.
  • the mixture is then stirred intensively and preferably free of gas for 30 seconds using a Ystral mixer and then stirred normally for 10 minutes, preferably free of gas.
  • the resulting mixture is then pumped into the separation separator and thus the aqueous phase B is separated from the oily phase A at a rate of 200 l / h.
  • aqueous phase B sterylglycosides were detected using TLC.
  • the oily phase A is transferred back to the storage tank 1 for further processing.
  • the oily phase A is analyzed (FFA content 0.25% by weight, H 2 O content 0.49% by weight, iron content 0.15 ppm, phosphorus content 2.21 ppm, magnesium content 0, 07 ppm, calcium content 0.32 ppm).
  • Examples 1 and 2 are subsequently produced by adding a sufficient amount of 12% NaOH solution in a so-called oil polishing process worked up.
  • the oil phase is separated from saponified free fatty acids. It can then be bleached and deodorized.
  • Fig. 3 shows on the basis of experimentally determined data that the addition of a sodium hydrogen carbonate solution in step C reduces the phosphorus content in the oil phase. This reduced phosphorus content goes hand in hand with the reduction of phospholipids in the oil phase.
  • Fig. 4 also shows that the proportion of free fatty acids is not reduced when sodium hydrogen carbonate is added. In comparison, you can see in Fig. 4 that there is a reduction in fatty acids in the oil phase when sodium carbonate is added.
  • Crude oil A1 was treated with aqueous citric acid solution (33%, addition: 1000 ppm) at 85 ° C. and mixed with a shaving head mixer for 30 seconds. After a reaction time of 10 minutes, a sample was taken and the oil phase A2 was measured.
  • Fig. 5a shows an exemplary sequence of process steps B and C, as well as the optional process step D.
  • citric acid is first added as an aqueous solution. This reduces the phosphorus content and thus the proportion of phospholipids in the oil phase.
  • the aqueous phase r 1 is separated from the oil phase.
  • a portion of sodium bicarbonate is added to the oil phase as a solution, suspension or as a powder - preferably in the case of powder addition with subsequent water addition. This leads to a further reduction in phospholipids in the oil phase.
  • the aqueous phase r 2 is separated from the oil phase. Further phospholipids can then be separated off in optional step D.
  • the concentration of phospholipids in the oil phase can, however, be very low, so that they can hardly be taken into account in relation to the fatty acids.
  • the limit Z between the two steps can thus be chosen variably. And depends, among other things, on the desired targets for the purity of the FFA phase.
  • the molar masses of KOH and oleic acid can be used to directly calculate the free fatty acid content in mass percent in the fat / oil.
  • the direct and quantitative determination of the elements phosphorus, calcium, magnesium and iron in the oil samples is carried out by means of Inductively Coupled Plasma - Emission Spectral Analysis (ICP).
  • ICP Inductively Coupled Plasma - Emission Spectral Analysis
  • the sample material atomized into an aerosol is injected into the hot core of an argon plasma. At a temperature of more than 8000K, the sample material is atomized and simultaneously excited. It can be analyzed qualitatively and quantitatively for trace elements in the emission spectrum.
  • the HLB value was determined in the aqueous phases and in the oil phases of the respective process steps.
  • the analysis is carried out with an Asahipak GF-310 HQ multiple solvent GPC column. This enables ionic and non-ionic surfactants to be differentiated and classified according to their HLB value.
  • a DC method thin layer chromatography was used to detect the respective accompanying substances, for example sterylglycosides.
  • the thin layer chromatography was carried out with silica gel G plates. The separation takes place with a mixture of chloroform / acetone / water (30/60/2).
  • the development was carried out with a naphthyl ethylenediamine reagent, which allows sugar residues of the oil accompanying substances to be displayed in color.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Microbiology (AREA)
  • Engineering & Computer Science (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Wood Science & Technology (AREA)
  • Organic Chemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Fats And Perfumes (AREA)
  • Edible Oils And Fats (AREA)
EP15727638.7A 2014-06-05 2015-06-03 Verfahren und vorrichtung zur schrittweisen aufarbeitung eines organischen öls Active EP3152283B1 (de)

Priority Applications (1)

Application Number Priority Date Filing Date Title
PL15727638T PL3152283T3 (pl) 2014-06-05 2015-06-03 Sposób i urządzenie do stopniowego przetwarzania oleju organicznego

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE102014107976 2014-06-05
PCT/EP2015/062434 WO2015185657A1 (de) 2014-06-05 2015-06-03 Verfahren und vorrichtung zur schrittweisen aufarbeitung eines organischen öls

Publications (2)

Publication Number Publication Date
EP3152283A1 EP3152283A1 (de) 2017-04-12
EP3152283B1 true EP3152283B1 (de) 2020-08-05

Family

ID=53366022

Family Applications (1)

Application Number Title Priority Date Filing Date
EP15727638.7A Active EP3152283B1 (de) 2014-06-05 2015-06-03 Verfahren und vorrichtung zur schrittweisen aufarbeitung eines organischen öls

Country Status (12)

Country Link
US (1) US10214705B2 (da)
EP (1) EP3152283B1 (da)
JP (1) JP6574837B2 (da)
CN (1) CN106459828A (da)
BR (1) BR112016027964B1 (da)
CA (1) CA2950806C (da)
DK (1) DK3152283T3 (da)
ES (1) ES2829643T3 (da)
MY (1) MY177293A (da)
PL (1) PL3152283T3 (da)
RU (1) RU2016150076A (da)
WO (1) WO2015185657A1 (da)

Families Citing this family (17)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP3098293A1 (en) 2015-05-27 2016-11-30 Evonik Degussa GmbH A process for removing metal from a metal-containing glyceride oil comprising a basic quaternary ammonium salt treatment
EP3098292A1 (en) 2015-05-27 2016-11-30 Evonik Degussa GmbH A process for refining glyceride oil comprising a basic quaternary ammonium salt treatment
GB2538758A (en) 2015-05-27 2016-11-30 Green Lizard Tech Ltd Process for removing chloropropanols and/or glycidol
DE102015212749A1 (de) 2015-07-08 2017-01-12 Evonik Degussa Gmbh Verfahren zur Entfeuchtung von feuchten Gasgemischen
DE102016210484A1 (de) 2016-06-14 2017-12-14 Evonik Degussa Gmbh Verfahren zur Entfeuchtung von feuchten Gasgemischen
EP3257568B1 (de) 2016-06-14 2019-09-18 Evonik Degussa GmbH Verfahren zur entfeuchtung von feuchten gasgemischen mit ionischen flüssigkeiten
DE102016210478A1 (de) 2016-06-14 2017-12-14 Evonik Degussa Gmbh Verfahren zur Entfeuchtung von feuchten Gasgemischen
BR112019024641B1 (pt) 2017-05-24 2023-01-10 Poet Research, Inc Método para alterar uma ou mais propriedades do asfalto, composição de mistura de asfalto e composição de mistura de aglutinante de asfalto
WO2019092013A1 (de) 2017-11-10 2019-05-16 Evonik Degussa Gmbh Verfahren zur extraktion von fettsäuren aus triglyceridölen
EP3483237A1 (de) 2017-11-10 2019-05-15 Evonik Degussa GmbH Verfahren zur extraktion von fettsäuren aus triglyceridölen
WO2019092017A1 (de) 2017-11-10 2019-05-16 Evonik Degussa Gmbh Verfahren zur extraktion von fettsäuren aus triglyceridölen
US10711221B2 (en) 2018-02-09 2020-07-14 Poet Research, Inc. Method of refining a grain oil composition to make one or more grain oil products, and related systems
CA3103242C (en) 2018-06-11 2023-08-29 Poet Research, Inc. Methods of refining a grain oil composition feedstock, and related systems, compositions and uses
FI128504B (en) 2018-12-14 2020-06-30 Upm Kymmene Corp A process for purifying a renewable feed comprising triglycerides
KR102395099B1 (ko) * 2019-08-02 2022-05-13 주식회사 청담 탈산 장치 및 이를 이용하는 탈산유 제조 방법
WO2022032011A1 (en) 2020-08-06 2022-02-10 Poet Research, Inc. Endogenous lipase for metal reduction in distillers corn oil
KR102639682B1 (ko) * 2021-04-07 2024-02-22 농업회사법인 크레이지피넛 주식회사 땅콩오일 정제방법

Family Cites Families (14)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2752378A (en) * 1952-10-25 1956-06-26 Glidden Co Hydration method of refining glyceride oils
US4160774A (en) * 1978-01-25 1979-07-10 Cadbury India Limited Process of degumming fatty glycerides using sodium acetate and acetic acid buffer
JPS54120609A (en) * 1978-03-14 1979-09-19 Hohnen Oil Co Ltd Preparation of oil for cooking on hot plate
JPS60248798A (ja) * 1984-05-23 1985-12-09 ミヨシ油脂株式会社 油脂の脱酸脱色方法
US4808426A (en) * 1986-04-23 1989-02-28 Epe Incorporated Vegetable oil extraction process
US5315021A (en) * 1992-07-01 1994-05-24 The Procter & Gamble Company Process for removing chlorophyll color impurities from vegetable oils
US6197357B1 (en) 1998-05-28 2001-03-06 University Of Massachusetts Refined vegetable oils and extracts thereof
CN102191127B (zh) * 2011-04-20 2012-11-21 陕西省动物研究所 一种简便的水貂油精制方法
CN102504946B (zh) * 2011-11-04 2013-09-04 福建春辉生物工程有限公司 一种对三高人群有益的油茶籽毛油精炼方法
CN103396880A (zh) * 2013-07-23 2013-11-20 怀宁县小市植物油厂 一种炒籽菜籽油及其制备方法
CN103396884A (zh) * 2013-07-23 2013-11-20 怀宁县小市植物油厂 一种菜籽油及其制备方法
CN103382411B (zh) * 2013-07-26 2015-06-24 怀宁县小市植物油厂 一种低温压榨复配菜籽油的生产工艺
CN103509648A (zh) * 2013-07-31 2014-01-15 安徽省霍山县聚一科技有限公司 一种山茶油的精制脱脂方法
DE102014210662A1 (de) 2014-06-04 2015-12-17 Gea Westfalia Separator Group Gmbh Vorrichtung und Verfahren zur Gewinnung von Glycoglycerolipiden und Glycosphingolipiden aus lipoiden Phasen

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
None *

Also Published As

Publication number Publication date
ES2829643T3 (es) 2021-06-01
BR112016027964A2 (pt) 2017-08-22
CN106459828A (zh) 2017-02-22
RU2016150076A (ru) 2018-07-09
DK3152283T3 (da) 2020-11-02
JP6574837B2 (ja) 2019-09-11
PL3152283T3 (pl) 2021-02-08
JP2017519892A (ja) 2017-07-20
EP3152283A1 (de) 2017-04-12
US10214705B2 (en) 2019-02-26
BR112016027964B1 (pt) 2021-11-30
CA2950806C (en) 2021-12-28
MY177293A (en) 2020-09-11
CA2950806A1 (en) 2015-12-10
US20170107449A1 (en) 2017-04-20
RU2016150076A3 (da) 2018-09-21
WO2015185657A1 (de) 2015-12-10

Similar Documents

Publication Publication Date Title
EP3152283B1 (de) Verfahren und vorrichtung zur schrittweisen aufarbeitung eines organischen öls
DE69711374T3 (de) Verfahren zum extrahieren von sterol mit einem polaren lösungsmittel zur herstellung eines mikrobiellen öles mit niedrigem sterolgehalt
EP1828361B1 (de) Verfahren zur herstellung eines rohöls aus gemischen von mikroorganismen und pflanzen, das so hergestellte öl sowie die spezifischen verwendungen des so hergestellten und gegebenenfalls zusätzlich raffinierten öls
EP1838171B1 (de) Herstellung und anwendung eines antioxidativ wirksamen extraktes aus crypthecodinium sp
DE69403958T2 (de) Unverseifbare materialien pflanzlichen ursprungs und diese enthaltende kosmetische präparate
WO2015185516A1 (de) Verfahren und vorrichtungen zur emulsionsspaltung und zur komplexierung von organischen verbindungen in emulsionen
EP2334773A1 (de) Verfahren zur isolierung von ölen aus zellen und biomasse
EP3148345A1 (de) Verfahren zum raffinieren von lipidphasen und verwendung
EP3152219B1 (de) Verfahren zur gewinnung von glycoglycerolipiden und glycosphingolipiden aus lipoiden phasen
DE69111048T2 (de) Verfahren zum extrahieren von nebenfettverbindungen aus einer substanz biologischer herkunft.
WO2015181399A1 (de) Verfahren zur veredelung raffinierter lipidphasen
EP2311929A1 (de) Verfahren zur Aufarbeitung von leicht verseifbarem Rohöl pflanzlicher oder tierischer Herkunft, für die Weiterverarbeitung zu Biodiesel
DE2147327A1 (de) Verfahren zur Trennung von Phos phatiden aus Phosphaüdmischungen
WO2009003710A1 (de) Verfahren zur schonenden raffination von pflanzenölen mit naturbleicherde
EP1500695B1 (de) Verwendung eines Verfahrens zur Aufbereitung von glycosidhaltigen Pflanzenölen, um genießbare und lagerfähige Pflanzenöle zu bereiten.
DE2551342B2 (de) Verfahren zur gewinnung von lipiden aus kartoffeln
DE68916630T2 (de) Lipidzusammensetzung mit genügender sicherheit und starker oberflächenwirkung.
WO2014096024A1 (de) Verfahren zur herstellung einer lipid-reichen zusammensetzung aus mikroorganismen
WO2015185676A1 (de) Vorrichtung und verfahren zur gewinnung von glycoglycerolipiden und glycosphingolipiden aus lipoiden phasen
DE102017220041A1 (de) Verfahren zur Extraktion von Chlorid aus Triglyceridölen
DE102017220045A1 (de) Verfahren zur Extraktion von 3-Chlor-1,2-Propandiol aus Triglyceridölen
DE2921499A1 (de) Verfahren zur herstellung mehrerer nahrungsmittelfraktionen aus natuerlichen fetten, wie z.b. oelen oder fetten und insbesondere palmoel
DE1042363B (de) Verfahren zur Stabilisierung von Fetten und OElen

Legal Events

Date Code Title Description
STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: THE INTERNATIONAL PUBLICATION HAS BEEN MADE

PUAI Public reference made under article 153(3) epc to a published international application that has entered the european phase

Free format text: ORIGINAL CODE: 0009012

STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: REQUEST FOR EXAMINATION WAS MADE

17P Request for examination filed

Effective date: 20161207

AK Designated contracting states

Kind code of ref document: A1

Designated state(s): AL AT BE BG CH CY CZ DE DK EE ES FI FR GB GR HR HU IE IS IT LI LT LU LV MC MK MT NL NO PL PT RO RS SE SI SK SM TR

AX Request for extension of the european patent

Extension state: BA ME

DAV Request for validation of the european patent (deleted)
DAX Request for extension of the european patent (deleted)
TPAC Observations filed by third parties

Free format text: ORIGINAL CODE: EPIDOSNTIPA

STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: EXAMINATION IS IN PROGRESS

17Q First examination report despatched

Effective date: 20180507

GRAP Despatch of communication of intention to grant a patent

Free format text: ORIGINAL CODE: EPIDOSNIGR1

STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: GRANT OF PATENT IS INTENDED

INTG Intention to grant announced

Effective date: 20200310

GRAS Grant fee paid

Free format text: ORIGINAL CODE: EPIDOSNIGR3

GRAA (expected) grant

Free format text: ORIGINAL CODE: 0009210

STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: THE PATENT HAS BEEN GRANTED

AK Designated contracting states

Kind code of ref document: B1

Designated state(s): AL AT BE BG CH CY CZ DE DK EE ES FI FR GB GR HR HU IE IS IT LI LT LU LV MC MK MT NL NO PL PT RO RS SE SI SK SM TR

REG Reference to a national code

Ref country code: GB

Ref legal event code: FG4D

Free format text: NOT ENGLISH

REG Reference to a national code

Ref country code: CH

Ref legal event code: EP

REG Reference to a national code

Ref country code: AT

Ref legal event code: REF

Ref document number: 1298726

Country of ref document: AT

Kind code of ref document: T

Effective date: 20200815

REG Reference to a national code

Ref country code: DE

Ref legal event code: R096

Ref document number: 502015013174

Country of ref document: DE

REG Reference to a national code

Ref country code: IE

Ref legal event code: FG4D

Free format text: LANGUAGE OF EP DOCUMENT: GERMAN

REG Reference to a national code

Ref country code: DK

Ref legal event code: T3

Effective date: 20201030

REG Reference to a national code

Ref country code: FI

Ref legal event code: FGE

REG Reference to a national code

Ref country code: NL

Ref legal event code: FP

REG Reference to a national code

Ref country code: SE

Ref legal event code: TRGR

REG Reference to a national code

Ref country code: LT

Ref legal event code: MG4D

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: PT

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20201207

Ref country code: BG

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20201105

Ref country code: LT

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20200805

Ref country code: HR

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20200805

Ref country code: NO

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20201105

Ref country code: GR

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20201106

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: RS

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20200805

Ref country code: LV

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20200805

Ref country code: IS

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20201205

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: RO

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20200805

Ref country code: SM

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20200805

Ref country code: EE

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20200805

Ref country code: CZ

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20200805

REG Reference to a national code

Ref country code: DE

Ref legal event code: R097

Ref document number: 502015013174

Country of ref document: DE

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: AL

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20200805

REG Reference to a national code

Ref country code: ES

Ref legal event code: FG2A

Ref document number: 2829643

Country of ref document: ES

Kind code of ref document: T3

Effective date: 20210601

PLBE No opposition filed within time limit

Free format text: ORIGINAL CODE: 0009261

STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: NO OPPOSITION FILED WITHIN TIME LIMIT

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: SK

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20200805

26N No opposition filed

Effective date: 20210507

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: SI

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20200805

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: MC

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20200805

REG Reference to a national code

Ref country code: CH

Ref legal event code: PL

GBPC Gb: european patent ceased through non-payment of renewal fee

Effective date: 20210603

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: LU

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20210603

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: LI

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20210630

Ref country code: IE

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20210603

Ref country code: GB

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20210603

Ref country code: CH

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20210630

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: HU

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT; INVALID AB INITIO

Effective date: 20150603

P01 Opt-out of the competence of the unified patent court (upc) registered

Effective date: 20230413

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: CY

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20200805

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: DE

Payment date: 20230627

Year of fee payment: 9

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: ES

Payment date: 20230703

Year of fee payment: 9

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: MK

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20200805

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: DK

Payment date: 20240625

Year of fee payment: 10

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: NL

Payment date: 20240627

Year of fee payment: 10

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: AT

Payment date: 20240626

Year of fee payment: 10

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: FR

Payment date: 20240626

Year of fee payment: 10

Ref country code: FI

Payment date: 20240626

Year of fee payment: 10

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: PL

Payment date: 20240529

Year of fee payment: 10

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: SE

Payment date: 20240626

Year of fee payment: 10

Ref country code: BE

Payment date: 20240625

Year of fee payment: 10

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: MT

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20200805

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: IT

Payment date: 20240627

Year of fee payment: 10