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EP2627744A1 - Procédé d'élimination de composés contenant du phosphore de compositions contenant des triglycérides - Google Patents

Procédé d'élimination de composés contenant du phosphore de compositions contenant des triglycérides

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Publication number
EP2627744A1
EP2627744A1 EP11779117.8A EP11779117A EP2627744A1 EP 2627744 A1 EP2627744 A1 EP 2627744A1 EP 11779117 A EP11779117 A EP 11779117A EP 2627744 A1 EP2627744 A1 EP 2627744A1
Authority
EP
European Patent Office
Prior art keywords
oil
triglyceride
acid
ethanolamine
weight
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.)
Withdrawn
Application number
EP11779117.8A
Other languages
German (de)
English (en)
Inventor
Ulrich Sohling
Friedrich Ruf
Andrea Stege
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.)
Sued Chemie IP GmbH and Co KG
Original Assignee
Sued Chemie IP GmbH and Co KG
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 Sued Chemie IP GmbH and Co KG filed Critical Sued Chemie IP GmbH and Co KG
Publication of EP2627744A1 publication Critical patent/EP2627744A1/fr
Withdrawn legal-status Critical Current

Links

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
    • C11B3/10—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
    • 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

Definitions

  • the present invention relates to a method for
  • heterogeneous catalyst hydrogenated with hydrogen to paraffin is hydrogenated with hydrogen to paraffin.
  • One example of such a process is the so-called Nex BTL process from Neste in Finland. Since phosphorus-containing compounds can poison heterogeneous catalysts, a particularly low phosphorus content in the vegetable oil must be set for this process.
  • Catalysts require a particularly low phosphorus content in vegetable oil.
  • degummed soybean oil with a large amount of EDTA solution to remove calcium and phospholipids from the oil and to facilitate degumming (8 parts 10% EDTA solution to 1 part oil).
  • EDTA solution to remove calcium and phospholipids from the oil and to facilitate degumming (8 parts 10% EDTA solution to 1 part oil).
  • SU 1731793 Al is described as with a 0.1 to 0.5% aqueous solution of hydroxyethylenediphosphonic acid, nitrilotrimethylphosphonic acid or their K salts as
  • liquid adsorbent solutions for the further purification of already pre-degummed vegetable oils or fatty acid methyl esters.
  • liquid adsorbents are here successively or in mixtures aqueous solutions of citric acid, caustic soda and
  • Alfa-Laval AB describes, based on the RD 203006 a method in which shortly before the separation of the phospholipids after a
  • organic acids include maleic acid, acetic anhydride, lactic acid and oxalic acid in aqueous saturated solution.
  • Oilseeds Biorefinery Corporation George Town (EP 02053118 Al) describes the removal of phospholipids
  • Diethylenetriaminepentaacetic acid Diethylenetriaminepentaacetic acid, hydroxyethylethylenediaminetriacetic acid, iminodiacetate or an aqueous solution of an acid such as citric acid, lactic acid, fumaric acid, tartaric acid or phosphoric acid or both.
  • the oil is first treated with an organic acid from the group citric acid, malic acid,
  • Ethylenediaminetetraacetic acid treated tartaric acid, oxalic acid, maleic acid ⁇ or an inorganic acid such as phosphoric acid, salt ⁇ acid or sulfuric acid.
  • An aqueous solution of a carboxylic acid having at least 3 carboxyl groups in the acid form or as a salt with a monovalent ion as the electrolyte or complexing agent is added, in which case the sodium salt of EDTA is preferably used.
  • the non-hydratable phospholipids are thereby converted into a hydratable form and can be removed with the aqueous phase.
  • a surfactant Na lauryl sulfate
  • CA 2164840 an organic acid such as citric acid, phosphoric acid,
  • citric acid for degumming
  • Vegetable oils are treated in many other publications (eg DE 2609705 C3, DD 284043 A5, CA 2434499 C, CA 2351338 C, GB 01510056 A, Smiles et al.), wherein the acid in aqueous solution in different concentrations at different temperatures for different Long
  • Surfactants such as oxazoline, polymeric sulfonates or alkyl sulfates or with crude lecithin, which although to a
  • the inventors of the present application have therefore set themselves the task of developing such a method, which also has a reduction of the phosphorus content also of
  • Waste oils and pomace oils in a simple manner, so that these without further processing for
  • Biodiesel production can be used. Furthermore, the inventors of the present application, the task of providing a method that is not only suitable for the preparation of crude vegetable oils, but can also be applied to other phosphorus-containing triglyceride compositions, in particular raw biodiesel.
  • compositions comprising the following steps: a) contacting the triglyceride-containing
  • Composition comprising at least one substance selected from organic acids, phosphoric acid, Ethanolamine and solid adsorbents based on clay minerals, bleaching earths, aluminosilicates or
  • step c) Contacting the triglyceride-containing composition of step c) with at least one substance selected from organic acids, phosphoric acid, ethanolamine and solid adsorbents based on clay minerals, bleaching earths, aluminosilicates or silicates; e) addition of H 2 O to the composition according to step d); f) separating the aqueous phase from the triglyceride-containing composition;
  • Phosphorus content in biodiesel these values can still be met.
  • phosphorus-containing compound is understood in the context of any compound which contains at least one phosphorus atom, in particular hydratable and non-hydratable phospholipids and phosphoglycosides.
  • triglyceride-containing composition means any composition which comprises at least one triglyceride (according to IUPAC:
  • triacylglycerol the terms "triglyceride” and
  • Triacylglycerol contains in particular biodiesel
  • Vegetable oil base and its precursors Vegetable oil base and its precursors.
  • biodiesel precursor as used in the context of
  • the present invention refers to any mixtures comprising mono and / or di-glycerides of fatty acids.
  • such mixtures can one
  • mixtures referred to as "biodiesel precursors” may optionally include fatty acid alkyl esters or fats.
  • fat in the context of the present invention may refer to any mixture comprising triglycerides. As a fat, both mixtures with solid
  • fats that are liquid at room temperature are often referred to as oils.
  • fats in the context of the present invention also includes any oils, such as the fats, which according to The general language traditions are referred to below as soybean oils, rapeseed oils, etc. The selection of a fat or a mixture of fats may be made in accordance with the general knowledge of one skilled in the art. Fats of different origin and composition are listed for example in the "textbook of food chemistry", Berlin, 2001, 5th edition, ISBN 3-540- 41096-1, by Belitz, Grosch, Schieberle.
  • the fat is a fat or oil having a lecithin content of less than 10% by weight, in particular less than 5% by weight, more preferably less than 10 ppm, in particular less than 5 ppm , According to one embodiment, degummed and / or deodorized fats or oils are also preferred
  • Biodiesel having the above lecithin contents.
  • the oils and / or fats are considered to be difficult to degummable due to their high content of non-hydratable phospholipids.
  • an oil is listed, which can still have a content of P up to 200 ppm after pre-degumming with water.
  • the process according to the present invention is based on triglyceride-containing compositions
  • soybean oil selected from the group consisting of soybean oil, rapeseed oil, sunflower oil, linseed oil, jatropha oil, canola oil,
  • Cottonseed oil pumpkin seed oil, coconut oil, rice germ oil,
  • Peanut oil corn oil, olive kernel oil, jojoba oil, almond oil,
  • Other oils used in the process can be used in the present invention are oils that can be obtained from algae.
  • triglyceride-containing compositions in particular oils, as above
  • pre-degumming for example using citric acid, phosphoric acid or water.
  • the process according to the invention is generally particularly suitable for triglyceride-containing compositions having a very high phosphorus content, in particular vegetable oils having a phosphorus content of more than 450 ppm, more than 550 ppm and more than 650 ppm. Even with these oils is achieved by application of the method according to the invention a reduction of the phosphorus content below the limit according to the EU standard EN 14214.
  • the term "bringing into contact” means any kind of contacting which is known to the person skilled in the art as suitable for the purpose according to the invention
  • the triglyceride-containing composition is mixed with the substance by stirring
  • the mixture is stirred for a period of 1 minute to 24 hours, more preferably 5 minutes to 12 hours, more preferably 15 minutes to 5 hours, and most preferably 30 minutes to 2 hours
  • H20 is added in an amount of from 0.1 to 15% by weight (based on the amount of the triglyceride-containing composition), preferably from 0.5 to 10% by weight. %, more preferably from 1 to 7 wt%, and most preferably from 2 to 5 wt%.
  • the composition is in a
  • the H20 added remains in the composition for a period of from 1 minute to 12 hours, preferably from 5 minutes to 5 hours, more preferably from 10 minutes to 2 hours, and most preferably from 30 minutes to 1 hour. In a particularly preferred
  • the composition is stirred continuously.
  • the separation of the aqueous phase from the composition according to steps c) and f) can be carried out in any manner known to those skilled in the art as suitable for the purpose according to the invention.
  • the separation of the aqueous phase by centrifugation is preferably carried out at 1000 to 5000 rpm, more preferably at 3000 to 4500 rpm and most preferably from 3500 to 4000 rpm, preferably for a period of 1 minute to 30 minutes preferably from 5 minutes to 15 minutes.
  • contacting according to steps a) and / or d) is carried out at a temperature of from 10 to 85 ° C., more preferably from 15 to 75 ° C., particularly preferably from 20 to 60 ° C, especially
  • the temperature is preferably carried out in a water bath.
  • the addition of H 2 O according to steps b) and e) is already at a temperature of 10 to 85 ° C, more preferably 15 to 75 ° C, particularly preferably 20 to 60 ° C, particularly preferably 25 to 50 ° C, and most preferably preheated from 35 to 45 ° C. Furthermore, it is possible in the context of the present invention that all steps a) to f) at different temperatures.
  • the organic acid is selected from the group consisting of malic acid, tartaric acid, citric acid,
  • Lactic acid formic acid, oxalic acid, malonic acid and mixtures thereof. Also preferred is the use of
  • Preferred concentrations of the organic and / or phosphoric acid are from 0.01 to 5% by weight (based on the weight of the triglyceride-containing composition), preferably from 0.05% to 5%, more preferably from 0.1% to 3%, and most preferably from 0.2% to 2%, by weight.
  • the solid adsorbent is selected from the group consisting of aluminosilicates, aluminum oxides,
  • Alumina hydrates, silica gels, clay minerals, bleaching earths and mixtures thereof are alumina hydrates, silica gels, clay minerals, bleaching earths and mixtures thereof.
  • Adsorbents are used on the basis of silica gels, as they are
  • Trisyl® are sold. These can be one
  • Clay minerals are used. It can be about
  • Attapulgites sepiolites or smectite clays, such as
  • Natural bleaching earth A special case of such natural bleaching earths are porous clays consisting of mixtures of smectite clays and silica gel. Such mixtures come
  • the preceding clays are commonly used for oil treatment in the form of so-called bleaching earth, d. H. These clays can be loaded with acids, which is then referred to as a so-called 'Surface Modified Bleaching Earth' (SMBE).
  • SMBE 'Surface Modified Bleaching Earth'
  • Bleaching earths are described, for example, in the following references: Practical Guide to Vegetable Oil Processing, M.K. Gupta, Chapter 5 Bleaching, pp 101, AOCS Press (2008);
  • Aluminum oxides such as. B., ß and ⁇ -alumina
  • composition comprises an aluminosilicate having a
  • the aluminosilicate preferably has, moreover, a S1O 2 - weight content of less than 0.8, preferably less than 0.7, more preferably less than 0, 65, based on the total weight percent of Si0 2 and A1 2 0 3.
  • the aluminosilicate has a specific surface area of more than 350 m 2 / g, preferably more than 400 m 2 / g, particularly preferably more than 450 m 2 / g.
  • aluminosilicates having a specific surface area of from 355 m 2 / g to 650 m 2 / g, more preferably from 365 m 2 / g to 600 m 2 / g, more preferably from 400 m 2 / g to 575 m 2 / g, more preferably from 455 m 2 / g to 550 m 2 / g.
  • the specific surface area is determined by the BET method.
  • the aluminosilicate preferably has a pore volume of from 0.5 ml / g to 1.4 ml / g, preferably a pore volume of from 0.55 ml / g to 1.3 ml / g, more preferably 0, 6 ml / g to 1.2 ml / g, more preferably from 0.6 ml / g to 0.99 ml / g, further more preferably from 0.6 ml / g to 0.95 ml / g, and most preferably from 0.6 ml / g to 0.90 ml / g.
  • the pore volume is calculated as the cumulative pore volume according to BJH (I.P. Barret, L.G.
  • the high specific surface area and the high pore volume make it possible to achieve a high adsorption capacity for the triglyceride-containing composition
  • the form comprises
  • Alumosilicate a proportion of other metals of less than 5 wt .-%, preferably less than 2 wt .-%, more preferably less than 1 wt .-%, particularly preferably less than 0.5 wt .-%. It is particularly preferred that the at least one aluminosilicate has a content of Fe 2 O 3 of at most 0.2% by weight, more preferably of at most 0.1% by weight, more preferably of at most 0.05% by weight and on most preferably of at most 0.02% by weight.
  • the at least one aluminosilicate has a content of Na 2 O of at most 0.05 wt .-%, more preferably of at most 0.01 wt .-%, more preferably of at most 0.008 wt .-% and most preferably of at most 0.005 wt .-% has.
  • the aluminosilicate has a content of C of at most 0.5% by weight, more preferably
  • Aluminosilicate a synthetic aluminosilicate.
  • Alumosilicates contained in this composition are of the same or different kind and are, for example, in their weight ratio of S1O 2 : Al 2 O 3 , the specific surface BET and / or the cumulative pore volume to BJH and / or other parameters differ as long as at least one of the aluminosilicates contained a weight fraction of S1O 2 of greater than 0.3 on the sum of
  • Particularly preferred aluminosilicate-containing compositions comprise at least one aluminosilicate having a weight fraction of SiO 2 of greater than 0.3 based on the sum of
  • aluminosilicate-containing compositions comprise at least one aluminosilicate having a weight fraction of SiO 2 of greater than 0.3 based on the sum of
  • Parts by weight of S1O 2 and Al 2 O 3 a water content of 5, 0 to 8.0 wt .-%, a BET surface area of 350 to 600 m 2 / g, a cumulative pore volume to BJH of 0.6 to 1, 0 cm 3 / g for pores having a diameter of 1.7 to 300 nm and an average pore diameter of 6.0 to 10.5 nm, and a C content of 0.1 to 0.3 wt .-%, a Fe20 3 content of 0.05 to 0.01 wt .-% and a Na 2 0 content of 0.01 to 0.001 wt .-%.
  • Particularly preferred are aluminosilicate-containing
  • compositions comprising at least one aluminosilicate having a weight fraction of S1O 2 of greater than 0.3 based on the sum of the proportions by weight of S1O 2 and Al 2 O 3 , a
  • the aluminosilicate according to the present invention can be prepared, for example, by using organic
  • Silica compounds are aged under hydrothermal conditions. Suitable aluminum compounds are
  • Aluminum alkyl chlorides or aluminum carboxylates A suitable method is described for example in DE 03839580 and US 6,245,310 Bl. This procedure is described for example in DE 03839580 and US 6,245,310 Bl. This procedure is described for example in DE 03839580 and US 6,245,310 Bl. This procedure is described for example in DE 03839580 and US 6,245,310 Bl. This procedure is described for example in DE 03839580 and US 6,245,310 Bl. This procedure is
  • hydrolyzable ones can also be used instead of silica
  • Organosilicon compounds are used, wherein the
  • hydrolyzable aluminum compounds is carried out together. Such a method is described for example in EP 0 931 017 Bl.
  • aluminosilicates which contain only S1O 2 and Al 2 O 3 as constituents.
  • those are preferred which have a weight ratio of Al 2 O 3 to S1O 2 of at least 0.3 and at most 0.7, preferably at least 0.35 and a maximum of 0.65.
  • the proportion of further metals, calculated as the most stable oxide is preferably less than 5% by weight, more preferably less than 3% by weight, more preferably less than 2% by weight and most preferably less than 1% by weight. selected.
  • Adsorbents are used.
  • the adsorbents used in the invention can be provided for example in the form of a powder.
  • a composition in the form of a powder is suitable, for example, when the adsorbent is stirred into the vegetable oil, that is in the form of a suspension.
  • the particle size of the powder is adjusted in the sense of the invention such that the adsorbent is purified from the purified material within a suitable period of time without difficulty by a suitable method, such as filtration
  • Thensiebrückstand on a sieve with a mesh size of 25 ⁇ is preferably more than 80 wt .-% and is preferably in a range of 85 to 88 wt .-%.
  • the dry residue on a sieve with a mesh size of 45 ⁇ preferably more than 35 wt .-%, more preferably more than 45 wt .-%.
  • the adsorbent in the form of a column packing but also larger particle sizes are suitable.
  • the adsorbent is preferably used in the form of granules.
  • a granulate is preferably used which has a particle size of more than 0.1 mm.
  • the granules have a particle size in the range of 0.2 to 5 mm, particularly preferably 0.3 to 2 mm.
  • the grain size can be adjusted, for example, by sieving.
  • the granules can be prepared by conventional methods, for example, by applying a finely ground adsorbent with a granulating agent, for example water, and then granulated in a conventional granulating in a mechanically generated fluidized bed.
  • a finely ground adsorbent with a granulating agent, for example water
  • granulating agent for example water
  • other methods can be used to control the granules
  • Preferred concentrations of the adsorbent are from 0.05 to 6 wt .-% (based on the weight of the triglyceride-containing
  • Composition preferably 0.1 to 5 wt .-%, more preferably from 0.15 to 3 wt .-% and most preferably from 0.2 to 2 wt. -%.
  • ethanolamine is selected from the group consisting of monoethanolamine, diethanolamine, triethanolamine and mixtures thereof, with monoethanolamine being particularly preferred.
  • concentrations of the ethanolamine are from 0.001 to 5% by weight (based on the weight of the triglycerides-containing Composition), preferably 0.005 to 5 wt .-%, further
  • step a) and / or d) is carried out at atmospheric pressure or under vacuum.
  • Atmospheric pressure or under vacuum is performed.
  • Composition comprising at least one substance selected from organic acids, phosphoric acid, ethanolamine and solid adsorbents based on clay minerals, bleaching earths, aluminosilicates or silicates or mixtures thereof
  • organic acid preferably citric acid
  • the process is carried out at a temperature of 35 to 45 ° C, preferably at 40 ° C.
  • the organic acid is used in a concentration of 0.1 to 0.5 wt .-%, preferably 0.2 wt .-%, and it is particularly preferably a 20% citric acid.
  • the ethanolamine is added in the form of monoethanolamine, preferably in a concentration of 0.1 to 1 wt .-%, particularly preferably 0.5 wt .-%.
  • composition with at least one ethanolamine, preferably monoethanolamine; e) addition of H 2 O to the composition according to step d); f) separating the aqueous phase from the triglyceride-containing composition.
  • the process is carried out at a temperature of 35 to 45 ° C, preferably at 40 ° C.
  • the organic acid in an absolute concentration of 0.1 to 2 wt .-%, preferably 1 wt .-% is used and especially here
  • a 50% strength citric acid solution is used.
  • the ethanolamine is added in the form of monoethanolamine, preferably in one Concentration of 0.1 to 1 wt .-%, particularly preferably 0.5 wt. -%.
  • composition with at least one ethanolamine, preferably monoethanolamine b) adding H20 to the composition according to step a); c) separating the aqueous phase from the triglyceride-containing composition; d) contacting the triglyceride-containing
  • adsorbent preferably an aluminosilicate
  • the process is carried out at a temperature of 35 to 45 ° C, preferably at 40 ° C.
  • the ethanolamine is added in the form of monoethanolamine, preferably in a concentration of 0.1 to 1 wt .-%, particularly preferably 0.5 Wt .-%.
  • the adsorbent in a concentration of 0.1 to 2 wt .-%, preferably 1 wt .-%
  • composition according to step c) with at least one ethanolamine, preferably monoethanolamine; e) addition of H 2 O to the composition according to step d); f) separating the aqueous phase from the triglyceride-containing composition.
  • the process is carried out at a temperature of from 35 to 45 ° C, preferably at 40 ° C. In addition, it is preferable if the
  • Ethanolamine in the form of monoethanolamine is added, preferably in a concentration of 0.1 to 1 wt .-%, more preferably 0.5% by weight. It is likewise preferred if the adsorbent is added in a concentration of 0.1 to 2% by weight, preferably 1% by weight.
  • the crude oil is heated to 40 ° C. with stirring. Under
  • the crude oil is heated to 40 ° C. with stirring. Under
  • the supernatant oil is the citric acid pre-degummed oil for subsequent tests. Degumming with organic acids, phosphoric acid, solid adsorbent or ethanolamine
  • pre-degummed oil pre-degumming a or b
  • pre-degumming a or b 20 g of the pre-degummed oil
  • the mixture is stirred in a 40 ° C tempered water bath. After 60 minutes, this mixture 2% dist.
  • Water (based on the amount pre-degummed oils) is added dropwise and stirred for a further 30 min in a water bath at 40 ° C. Subsequently, the oil is separated from the precipitate and the water phase by centrifuging at 4000 rpm for a period of 15 minutes.
  • the thus purified oil is fed to the metal and P-analysis or can be subjected to a second degumming stage.
  • the oil obtained from the 1st degumming stage is reused and carried out analogously to the 1st stage
  • the physical properties of the adsorbents were determined by the following methods:
  • Micromeritics type ASAP 2010 determined.
  • the sample is cooled in a high vacuum to the temperature of liquid nitrogen. Subsequently, it becomes continuous
  • Nitrogen dosed into the sample chambers By detecting the adsorbed amount of gas as a function of pressure, an adsorption isotherm is determined at a constant temperature. In a pressure equalization, the analysis gas is gradually
  • the pore volume is also determined from the measurement data using the BJH method (I.P. Barret, L.G. Joiner, P.P.
  • Pore volumes of certain volume size ranges are determined by summing up incremental pore volumes obtained from the evaluation of the BJH adsorption isotherm.
  • the total pore volume by BJH method refers to pores with a diameter of 1.7 to 300 nm.
  • the water content of the products at 105 ° C is determined using the method DIN / ISO-787/2.
  • the strainer is covered with a plastic lid and the vacuum cleaner is switched on. After 5 minutes, the vacuum cleaner is switched off and the amount of remaining on the screen, coarser portions by differential weighing
  • Measuring cylinder forms a Schüttkegel.
  • the pouring cone is made with the help of a ruler, which over the opening of the
  • Measuring cylinder is guided, stripped and ge filled
  • Adsorbents listed which are used in the following examples. Trisyl® 300 is a commercially available silica gel from Grace in Worms. Table la: Chemical composition of the adsorbents Adsorbent aluminosilicate 1
  • Fig. 1 The concentrations of Ca, Mg and P after
  • Fig. 2 The concentrations of Ca, Mg and P after
  • This pre-degummed oil (SO 1.1a) is treated with 0.5% ethanolamine (SO 1.1b) with 0.5% ethanolamine in the 1st stage (corresponds to step a) of the process according to the invention) and treated with 2% aqueous citric acid (50%) in the 2nd stage (corresponding to step b) of the process according to the invention) (SO 1.1 c). treated with 2% aqueous citric acid (50%) in the 1st stage and treated with 0.5% ethanolamine in the 2nd stage SO 1. ld). treated with 2% aqueous citric acid (50%) (SOI.le).
  • SO 1.1a is treated with 0.5% ethanolamine (SO 1.1b) with 0.5% ethanolamine in the 1st stage (corresponds to step a) of the process according to the invention) and treated with 2% aqueous citric acid (50%) in the 2nd stage (corresponding to step b) of the process according to the invention)
  • SO 1.1 c treated with 2%
  • the raw soybean oil from Example 1.1a is pre-degummed with citric acid (SO 1.2a). This pre-degummed oil is treated with 0.5% ethanolamine (SO 1.2b) or with 2% 50% citric acid (SO 1.2c)
  • Dosage can be used. A sole degumming with citric acid or ethanolamine is not enough.
  • a raw soybean oil is pre-degummed with water. This pre-degummed oil is treated with 0.5% ethanolamine as the first step. The oil obtained from this is further treated in a second stage with 1% adsorbent.
  • the adsorbents used are a bleaching earth, an aluminosilicate and a silica gel (see description of the adsorbents).
  • the silica gel is the product Trisyl® 300 from Grace, Worms.
  • a combination of aluminosilicate 1 with ethanolamine removes Ca, Mg and P almost completely, whereas the
  • Adsorbent eg bleaching earth 1, Trisyl® 300 supplied and treated at 110 ° C for 30 min and 30 mbar. Even with a 2% Adsorbensdosage used here was still a P content of 38 ppm, Ca content of 18 ppm and Mg content of 12 ppm for Trisyl ® 300 and 66 ppm (P), 34 ppm (Ca), 23 ppm (Mg) for bleaching earth 1 was obtained. The necessary specification of below 4 ppm P and below 10 ppm Ca and Mg could not be achieved in this way.

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  • Chemical & Material Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
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  • 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)

Abstract

La présente invention concerne un procédé d'élimination de composés contenant du phosphore de compositions contenant des triglycérides.
EP11779117.8A 2010-10-13 2011-10-13 Procédé d'élimination de composés contenant du phosphore de compositions contenant des triglycérides Withdrawn EP2627744A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE102010048367A DE102010048367A1 (de) 2010-10-13 2010-10-13 Verfahren zur Entfernung von Phosphor-haltigen Verbindungen aus Triglycerid-haltigen Zusammensetzungen
PCT/EP2011/067852 WO2012049232A1 (fr) 2010-10-13 2011-10-13 Procédé d'élimination de composés contenant du phosphore de compositions contenant des triglycérides

Publications (1)

Publication Number Publication Date
EP2627744A1 true EP2627744A1 (fr) 2013-08-21

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CN109628210A (zh) * 2018-12-07 2019-04-16 四川德阳市年丰食品有限公司 一种菜籽油精炼方法
CN110643424A (zh) * 2018-12-19 2020-01-03 宁夏福煦农业科技发展有限公司 一种亚麻籽油精炼工艺
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US8987487B2 (en) 2015-03-24
US20140012025A1 (en) 2014-01-09
DE102010048367A1 (de) 2012-04-19
WO2012049232A1 (fr) 2012-04-19

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