WO2011038903A1 - Utilisation d'adsorbants à base d'aluminosilicates pour la purification de triglycérides - Google Patents

Utilisation d'adsorbants à base d'aluminosilicates pour la purification de triglycérides Download PDF

Info

Publication number
WO2011038903A1
WO2011038903A1 PCT/EP2010/005946 EP2010005946W WO2011038903A1 WO 2011038903 A1 WO2011038903 A1 WO 2011038903A1 EP 2010005946 W EP2010005946 W EP 2010005946W WO 2011038903 A1 WO2011038903 A1 WO 2011038903A1
Authority
WO
WIPO (PCT)
Prior art keywords
aluminosilicate
oil
weight
composition
triglyceride
Prior art date
Application number
PCT/EP2010/005946
Other languages
German (de)
English (en)
Inventor
Ulrich Sohling
Friedrich Ruf
Andrea Stege
Original Assignee
Süd-Chemie AG
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 Süd-Chemie AG filed Critical Süd-Chemie AG
Priority to EP10763617A priority Critical patent/EP2483380A1/fr
Publication of WO2011038903A1 publication Critical patent/WO2011038903A1/fr

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
    • C11B7/00—Separation of mixtures of fats or fatty oils into their constituents, e.g. saturated oils from unsaturated oils
    • C11B7/0083—Separation of mixtures of fats or fatty oils into their constituents, e.g. saturated oils from unsaturated oils with addition of auxiliary substances, e.g. cristallisation promotors, filter aids, melting point depressors
    • 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

Definitions

  • the invention relates to the use of aluminosilicate-containing compositions for the purification of triglyceride-containing
  • compositions as well as a method for the purification of
  • Triglyceride-containing compositions using the aluminosilicate-containing compositions of the invention Triglyceride-containing compositions using the aluminosilicate-containing compositions of the invention.
  • the purification of crude oil should ideally include the removal of all undesirable substances. These are in particular the color carriers chlorophyll A, carotenoids and other dyes, phospholipids, free fatty acids and metal ions.
  • Degumtning This refers to the removal of the phospholipids.
  • Phospholipid content must be followed by one or usually a number of other AdsorbensANen. In one case, one goes directly to a treatment with a so-called bleaching earth. If the phosphorus contents of the prepurified vegetable oil are still too high after the aqueous treatment or after the treatment with aqueous acid, it may be necessary to add one more
  • Adsorbent treatment be interposed, with the
  • Phospholipids are associated. These metal ions themselves also have a detrimental effect on the purified oil. Thus, calcium and magnesium ions can form precipitates,
  • Biodiesel end product according to the specifications of the EU and the US standard limited (see EU standard for the specification of Biodiesel EN 14214).
  • adsorbents are already available on the market, such as. B. a silica-based adsorbent from the company. Grace, which is sold under the trade name Trisyl. Furthermore, Süd-Chemie AG, Moosburg, offers bleaching earth-based adsorbents on the market.
  • Impurities are in particular phospholipids and associated metal ions. It can be assumed that this patent describes the production process of the product trisyl. Reference is made in particular to applications in soybean oil and it should be noted that the pre-degummed oil can contain up to 200 ppm of phosphorus. Typically, a reduction to below 15 ppm phosphorus is achieved. The process of purification is contacting with the adsorbent and subsequent separation of the adsorbent, which is then loaded with the contaminants. In a series of other patents Trisyl is now combined with other adsorbents or the amorphous silicon combined with other patents or even surface-modified. So
  • Patent EP 340717 A2 to Grace describes a
  • Vegetable oil wherein the oil in the first stage is contacted with an amorphous silica gel to remove the phospholipids and soaps. In a second stage, it is passed through a packed bed of bleaching earth to remove the pigments (dyes).
  • the patent EP 0295418 Bl of Grace describes a process for the removal of dyes from glyceridols by
  • Silicon dioxide adsorbent for obtaining glyceridols with economically acceptable amounts of chlorophyll and / or red and yellow color bodies.
  • the patent EP 507217 AI of the company Grace describes the use of a base treated, inorganic, porous adsorbent for the removal of impurities from vegetable oils.
  • the selection of adsorbents in this case also includes alumina,
  • the adsorbent is before the oil treatment applied with a base.
  • the basic material is in particular soda,
  • Adsorbent be bound on the basis of amorphous silica gel. This is a special case of using amorphous silica to clean the oil.
  • EP 0558173 A1 (Grace) describes a process for purifying vegetable oils with the aid of silica gel containing alumina. The content of aluminum oxide in the adsorbent is limited to 10% by weight. In particular, it is argued that the adsorbents are particularly well suited to remove chlorophyll, yellow and red dyes from the oil.
  • Patent WO 9421765 A to PQ Corporation describes
  • Nock investigated silica hydrogel as a suitable adsorbent in edible oil to remove phospholipids, metals, and soaps.
  • the moisture content of the materials was examined in connection with the addition of acid or alkali for degumming in order to improve the adsorption capacity.
  • Silicon dioxide are removed, although the silicon dioxide was not yet saturated. As a possible reason, micelle formation, Ca salt formation with the phospholipids as well as a
  • Silica gel rises when the temperature is raised from 20 to 60 ° C and when the moisture on the surface of the silica gel is increased.
  • the optimum pore size of the silica gel is given as 60-80 ⁇ . (Maslozhirovaya Promyshlennost (1977), (7), 21-3).
  • Adsorbents involving the removal of phospholipids and Metal ions from triglyceride-containing compositions in a simple manner, ie without the need for treatment by a number of different materials and in a single step allow. Furthermore, there is a need for such a method, even on a large scale in a simple way, little time-consuming and cost-effective
  • phospholipids and / or metal ions can be removed particularly effectively from triglyceride-containing compositions if one or more aluminosilicates are used as adsorbents which have a weight fraction of Si0 2 of greater than 0.3 based on the sum of the weight fractions of Si0 2 and Al 2 0 3 have.
  • the present invention therefore relates in a first aspect to the use of a composition comprising at least one aluminosilicate for the removal of phospholipids and metal ions from triglyceride-containing compositions, wherein the
  • Aluminosilicates weight proportions of Si0 2 of greater than 0.3 based on the sum of the weight fractions of Si0 2 and Al 2 0 3 have.
  • the fatty acids preferably comprise more than 10 carbon atoms and preferably comprise 15 to 40
  • the alkyl chain of the fatty acids is preferably straight-chain. It may be fully hydrogenated or may comprise one or more double bonds.
  • Starting materials are, for example, vegetable fats and oils, such as rapeseed oil, sunflower oil, thistle oil, nut oil, peanut oil, olive oil, soybean oil or palm oil, but also animal Fats and oils such as fish oil.
  • Non-edible fats and oils can also be used as starting materials, such as jatropha oil, jojoba oil, tall oil or oils obtained from algae, waxes, mineral oils or even tallow. These oils / fats are not suitable for human consumption. In principle, any conceivable mixture of oils or fats can be used in the context of the present invention.
  • compositions used in the context of the use according to the invention and the process according to the invention comprise, in addition to one or more
  • triglycerides also phospholipids and / or
  • compositions contain other substances, for example, naturally contained in crude contaminants such as dyes and oxidized components of glyceride oils, waxy
  • the composition comprising at least one aluminosilicate has at least one aluminosilicate having a weight fraction Si0 2 of greater than 0.3, preferably greater than 0.35, particularly preferably greater than 0.4, based on the sum of the weight fractions of SiO 2 and Al 2 0 3 on.
  • the at least one aluminosilicate moreover preferably has an SiO 2 weight fraction of less than 0.8, preferably less than 0.7, particularly preferably less than 0.65, based on the sum of
  • the composition comprising at least one aluminosilicate has at least one aluminosilicate with a specific surface area of more than 350 m 2 / g, preferably more than 400 m / 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 / g preferably from 455 m 2 / g to 550 m 2 / g.
  • the specific surface is determined by the BET method
  • Composition comprising at least one aluminosilicate in the context of the present invention, at least one aluminosilicate with a high pore volume.
  • the alumina-containing component 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 from 0.6 ml / g to 1 , 2 ml / g, more preferably from 0.6 ml / g to 0.99 ml / g, even 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 determined as the cumulative pore volume according to BJH (I.P. Barret, L. G. Joiner, P. P. Haienda, J. Am. Chem. Soc., 73, 1991, 373) for pores with a diameter of 1.7 to 300 nm.
  • Impurities such as phospholipids and metal ions and a rapid kinetics of adsorption, so that the method is particularly suitable for industrial application.
  • the at least one aluminosilicate comprises 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. -% and is. It is particularly preferred that the at least an aluminosilicate has an Fe 2 O 3 content of at most 0.2% by weight, more preferably at most 0.1% by weight, more preferably at most 0.05% by weight, and most preferably at most 0.02 Wt .-% possesses.
  • 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.
  • Alumosilikat a proportion of C of at most 0.5 wt .-%
  • composition comprising at least one aluminosilicate may further comprise one or more further constituents, which are preferably selected from the group consisting of
  • At least one aluminosilicate is a synthetic aluminosilicate.
  • Particularly preferred aluminosilicate-containing compositions comprise at least one alumino-silicate with a content by weight of Si0 2 of greater than 0.3 based on the total weight percent of Si0 2 and A1 2 0 3, a BET specific surface area of more than 350 m 2 / g and a cumulative pore volume after BJH of more than 0.7 ml / g for pores between 1.7 and 300 nm, preferably greater than 0.8 ml / g, particularly preferably greater than 0.9 ml / g.
  • Particularly preferred aluminosilicate-containing compositions comprise at least one alumino-silicate with a content by weight of Si0 2 of greater than 0.3 based on the total weight percent of Si0 2 and A1 2 0 3, a water content from 5.0 to 8.0 wt .-% , one
  • BET surface area 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 Fe 2 0 3 content of 0.05 to 0.01 wt -.% And a Na 2 0 content of 0.01 to 0.001% by weight.
  • Aluminosilicate-containing compositions comprising at least one aluminosilicate having a weight fraction of Si0 2 of greater than 0.3 based on the sum of the weight proportions of Si0 2 and Al 2 0 3 , a water content of 6.0 to 8.0 wt .-%, a BET surface area of 450 to 570 m 2 / g, a cumulative pore volume to BJH of 0.75 to 0.95 cm 3 / g for pores having a diameter of 1.7 to 300 nm and an average pore diameter of 7.2 to 7.9 nm, and a C content of 0.1 to 0.3 wt .-%, a Fe 2 0 3 content of 0.05 to 0.01 wt -.% And a Na 2 0 content of 0.01 to 0, 001 weight -.
  • the at least one aluminosilicate according to the present invention can be prepared, for example, by adding organic
  • Aluminum compounds are hydrolyzed under acidic conditions and then aged together with silicic acid or silicic acid compounds under hydrothermal conditions.
  • Aluminum compounds are, for example, aluminum alcoholates, aluminum hydroxyalcoholates, aluminum acetylacetonates,
  • Aluminum alkyl chlorides or aluminum carboxylates are described for example in DE 03839580 and US 6,245,310 Bl. This method is particularly advantageous because it can achieve very high specific surface areas and porosities.
  • hydrolyzable organosilicon compounds may be used instead of silica, the hydrolysis of the
  • Aluminum compounds is carried out together. Such a method is described for example in EP 0 931 017 Bl.
  • aluminosilicates which contain only Si0 2 and A1 2 0 3 as the components.
  • 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.
  • the composition comprising at least one aluminosilicate may in the context of the present invention comprise further constituents which are preferably selected from the group consisting of bleaching earths,
  • aluminosilicate-containing composition may comprise any further constituent known to those skilled in the art.
  • the composition comprising at least one aluminosilicate may be provided, for example, in the form of a powder.
  • a composition in the form of a powder is, for example
  • 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 so that the adsorbent can be easily separated from the purified vegetable oil within a suitable period of time by a suitable method such as filtration.
  • a powder which is suspended in the crude vegetable oil
  • the dry sieve residue of the adsorbent on a sieve having a mesh of 63 ⁇ m is preferably more than 25% by weight and is preferably in a range of 30 to 50% by weight.
  • the dry sieve residue 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 sieve residue on a sieve with a mesh size of 45 ⁇ m is preferably more than 35% by weight, particularly preferably more than 45% by weight.
  • adsorbent is preferably used in the form of granules.
  • column packings is preferred
  • Granules used which has a grain 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 the finely ground adsorbent with a
  • Granulating for example, water, applied and then in a conventional granulation in a mechanically generated Fluidized bed is granulated.
  • other methods can be used to prepare the granules.
  • the powdered adsorbent for example, by
  • composition comprising at least one aluminosilicate can also be provided as shaped articles, which can be obtained, for example, by extrusion of a plastic mass.
  • alumina-containing component and, if necessary. other components, such as a binder, by adding a liquid, preferably water, a paste
  • This paste is then extruded and the extrudate is comminuted, for example by cutting the extruded strand into short cylindrical pieces, and then drying the resulting shaped articles.
  • massive cylinders in this way e.g. also hollow cylinder can be produced.
  • the granules or the shaped bodies After shaping, the granules or the shaped bodies can still be heat-treated and sintered, for example, by heating. As a result, the stability of the granules or the shaped bodies can still be heat-treated and sintered, for example, by heating. As a result, the stability of the granules or the shaped bodies can still be heat-treated and sintered, for example, by heating. As a result, the stability of the granules or the
  • the shaped bodies or the granules are preferably heated to a temperature of more than 300 ° C., according to a further embodiment to a temperature of more than 400 ° C. According to one
  • the temperature is less than 1000 ° C, selected according to another temperature less than 800 ° C, most preferably less than 550 ° C.
  • the heat treatment is preferably selected for a duration of at least 30 minutes, according to a further embodiment for a duration of at least 60 minutes. According to one embodiment, the duration of treatment is chosen to be less than 5 hours.
  • the composition comprising at least one aluminosilicate is provided in the form of a column packing, it is provided in the form of larger granules to prevent excessive pressure drop across the column packing.
  • the composition comprising at least one aluminosilicate is preferably used in the form of a granule having a particle diameter of more than 0.1 mm, more preferably a particle diameter in the range of 0.2 to 5 mm.
  • the triglyceride-containing composition is preferably heated to a temperature above room temperature before being added to the column.
  • composition according to the invention in the form of a column comprising at least one aluminosilicate also enables regeneration of the column, e.g. with solvents, whereby the column packing can be used several times.
  • Solvents are used, which are particularly preferably used consecutively. Particular preference is given to using acetone and / or n-hexane in a first step in order to remove the adhering oil / fat. Subsequently, the
  • Adsorbent with at least one polar solvent such as methanol, ethanol and / or i-propanol
  • the at least one aluminosilicate of the aluminosilicate-containing composition of the present invention is a regenerable aluminosilicate.
  • the triglyceride-containing composition according to the invention can be brought into contact with a regeneration agent, so that the components adsorbed to the at least one aluminosilicate, which are preferably phospholipids and / or metals, of the at least one
  • Alumosilicate be solved. Especially preferred
  • Regenerants are solvents that are preferred
  • Solvents such as acetone, n-hexane and polar solvents such as methanol, ethanol or i-propanol.
  • the present invention relates
  • the invention relates to processes for the purification of triglyceride-containing compositions, comprising the steps of a) providing a triglyceride-containing
  • composition b) contacting the triglyceride-containing composition with a composition comprising at least one aluminosilicate as defined in any one of claims 1 to 8;
  • the contacting is preferably carried out at a temperature of 95-120 ° C., preferably 100-110 ° C.
  • the contacting is more preferably carried out at 110 ° C. Is it correct? the triglyceride-containing composition to sunflower or olive oil, the contacting is particularly preferably carried out at 100 ° C. Is it the triglyceride-containing
  • composition around palm oil is particularly preferably carried out at 95 ° C.
  • the contacting is preferably carried out for a period of 10 to 50 minutes, more preferably 15 to 40 minutes and most preferably 20 to 30 minutes.
  • the triglyceride-containing composition is rapeseed oil, soybean oil, sunflower oil or olive oil, the
  • the contacting is preferably carried out for a period of 50 minutes. More preferably, the contacting is preferably under
  • Vacuum conditions preferably carried out under 30 - 50 mbar. If the triglyceride-containing composition is rapeseed oil, soybean oil, sunflower oil or olive oil, the triglyceride-containing composition is rapeseed oil, soybean oil, sunflower oil or olive oil, the triglyceride-containing composition is rapeseed oil, soybean oil, sunflower oil or olive oil, the triglyceride-containing composition is rapeseed oil, soybean oil, sunflower oil or olive oil, the
  • composition around palm oil the contacting is preferably carried out for a period of 20 minutes under atmospheric conditions and subsequently for a period of 30 minutes under a pressure of 100 mbar. While contacting the triglyceride-containing
  • compositions comprising a composition comprising at least one aluminosilicate as defined in any one of claims 1 to 8 are those in the triglyceride-containing compositions
  • at least one phospholipid and / or metal adsorbed to the at least one aluminosilicate.
  • Composition contained phospholipids and / or metals, preferably at least 85 wt .-%, more preferably at least 90%, more preferably at least 95 wt .-%, more preferably at least 99% and most preferably 100 wt .-% of the triglyceride containing composition
  • Phospholipids and / or metals to the at least one
  • the method according to the invention further comprises the step: c) separating the at least one aluminosilicate from the
  • Triglyceride-containing composition Triglyceride-containing composition
  • Triglyceride-containing composition can be carried out in any way that is known to those skilled than suitable for the purpose of the invention.
  • a triglyceride-containing composition is obtained, which is preferably less than 20 wt .-%, more preferably less than 15 wt .-%, also preferably less than 10 wt .-%, particularly preferably less than 5 wt .-% of the original
  • a triglyceride-containing composition is obtained which is free from the original
  • Contaminants such as dyes and oxidized components of
  • Glyceride oils waxy ingredients or free fatty acids. These ingredients are also preferably at least 85 wt%, more preferably at least 90 wt%, more preferably at least 95 wt%, even more preferably at least 99 wt%, and most preferably 100 wt% the triglyceride-containing composition removed.
  • regenerable aluminosilicate Composition around a regenerable aluminosilicate.
  • regenerable aluminosilicate is used in the context of
  • the present invention is understood to mean any aluminosilicate which, after contacting the triglyceride-containing composition with the aluminosilicate-containing composition, can be contacted with a solvent whereby the phospholipids and / or metals adsorbed to the at least one aluminosilicate are removed from the at least one aluminosilicate.
  • Process according to the invention therefore further comprises the step of: d) contacting the composition comprising at least one aluminosilicate with a solvent selected from the group consisting of apolar solvents such as acetone, n-hexane and polar solvents such as methanol, ethanol or i-propanol.
  • apolar solvents such as acetone, n-hexane
  • polar solvents such as methanol, ethanol or i-propanol.
  • the physical properties of the adsorbents were determined by the following methods: BET surface area / pore volume after BJH and BET:
  • 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. Wassergehal:
  • the water content of the products at 105 ° C is determined using the method DIN / ISO-787/2.
  • Ignition loss In a heat-treated, weighed porcelain crucible with lid approx. 1 g of dried sample is weighed to the nearest 0.1 mg and annealed for 2 hours at 1000 ° C in a muffle furnace. Thereafter, the crucible is cooled in a desiccator and weighed.
  • the pour cone is using a
  • the ruler which is passed over the opening of the measuring cylinder, stripped and weighed the filled measuring cylinder again.
  • the difference corresponds to the bulk density.
  • a) Water degumming For the removal of phospholipids, the oil is weighed accurately, covered with inert gas and, while stirring gently at room temperature, 10% by weight of deionized water are added. Subsequently, the oil / water mixture is heated with stirring (180 U / min) to 80 ° C. After reaching the temperature of 80 ° C, this is maintained for 20 min under atmospheric conditions and with stirring. The separation of the oil phase is carried out by subsequent centrifugation at 3000 U / min for 20 minutes. The oil phase is decanted and optionally filtered. b) degumming with citric acid The crude oil or the decanted / filtered oil phase from a) is weighed again, coated with inert gas and at
  • the oil / citric acid mixture is immediately after the expiry of the 20 min at 80 ° C while maintaining the temperature and
  • the crude oil or the water-degummed oil is weighed in, coated with inert gas and mixed with room temperature at room temperature
  • Color measurement and P- and metal and Phospholipidbeées be made.
  • the color numbers are determined using a Lovibond PFX995 in the AF 960-m (r, y) scale and, unless otherwise stated, in a 1-inch cuvette.
  • Adsorbents Used Various commercially available aluminosilicates were used for the purification of crude vegetable oil, the
  • Bleaching b) Degumming with citric acid is further degummed The bleaching process is carried out as described under c) "bleaching process” c) l
  • Adsorbents 3 and trisyl 300 used in each 2.0% dosage (wt .-%) were used in each 2.0% dosage (wt .-%). Table 1 and Figure 1 show the results of the metal, P and phospholipid contents. The data show that the aluminosilicates according to the invention having an SiO 2 content of 40% by weight are particularly suitable for removing the impurities mentioned below.
  • the crude rapeseed oil I contains 128 ppm P.
  • the adsorbent 3 reduces this P content to ⁇ 10 ppm, it also removes the chlorophyll A and also has a significant bleaching effect compared to the others
  • Table 1 (for example 1, 2, 0 wt .-% adsorbent in the degummed
  • Table 3a and 3b list the remaining Ca, Mg, P and phospholipid levels. It is clear that the degumming of rapeseed oil I does not achieve a significant reduction in the resulting Ca, Mg and P contents. The subsequent treatment with the adsorbent 3 of the invention, however, removes the metals and phosphorus in
  • Phospholipids and metals can be removed with the adsorbent 3 according to the invention even without vorschleeschaltetem degumming with the same dosage.
  • Table 3a (for example 3):
  • Crude rapeseed oil 1 128 0,001 0,009 ⁇ 0,001 0,004 with 2,0 Gew. -%
  • Adsorbent 3 6.5 ⁇ 0.001 0.001 0.001 0.002 degummed rapeseed oil 1 122 0.001 0.009 ⁇ 0.001 0.003 with 2.0% by weight
  • Adsorbent 3 9.6 ⁇ 0.001 0.001 ⁇ 0.001 0.003
  • PC phosphatidylcholine
  • PE phosphatidylethanolamine
  • PI phosphatidylinositol
  • PA phosphatidic acid
  • Figure 4 show the results.
  • the inventive adsorbent 3 with 40 wt .-% Si0 2 shows the lowest residual contents of Ca, Mg and P. In addition, it shows a clear lightening effect compared to the other adsorbents used and it completely removes the chlorophyll A. Even the inventive
  • Table 4 (for example 4, 2.0 wt% adsorbent in crude rapeseed oil
  • Example 5 80,000 g of crude rapeseed oil I are weighed in and processed analogously to Example 4. The dosage of the adsorbent amounts to 1.0 wt .-%. The results are shown in Table 5 and FIG.
  • Example 6 80,000 g of rapeseed oil I is weighed out analogously to Example 1 and with 3.0 wt .-% adsorbent 3 or Trisyl 0 300 treated.
  • 80,000 g of crude soybean oil I is treated analogously to Example 1.
  • adsorbent 2.0 wt .-% adsorbent 3 or Trisyl 41,300 are used.
  • Example 1 80,000 g of crude soybean oil I is treated analogously to Example 1. 2.0% by weight of adsorbent are used.
  • the adsorbents of the invention are shown with increasing Si0 2 content in Table 8 and Figure 8.
  • the adsorbent 3 shows the best here
  • Table 8 (for example 8; 2.0 wt% adsorbent in degummed

Landscapes

  • Chemical & Material Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Wood Science & Technology (AREA)
  • Organic Chemistry (AREA)
  • Microbiology (AREA)
  • Fats And Perfumes (AREA)

Abstract

L'invention concerne l'utilisation de compositions contenant des aluminosilicates pour la purification de compositions contenant des triglycérides, ainsi qu'un procédé pour la purification de compositions contenant des triglycérides à l'aide de compositions contenant des aluminosilicates selon l'invention.
PCT/EP2010/005946 2009-09-29 2010-09-29 Utilisation d'adsorbants à base d'aluminosilicates pour la purification de triglycérides WO2011038903A1 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
EP10763617A EP2483380A1 (fr) 2009-09-29 2010-09-29 Utilisation d'adsorbants à base d'aluminosilicates pour la purification de triglycérides

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE102009043418.6 2009-09-29
DE102009043418A DE102009043418A1 (de) 2009-09-29 2009-09-29 Alumosilikat-basierte Adsorbentien zur Aufreinigung von Triglyceriden

Publications (1)

Publication Number Publication Date
WO2011038903A1 true WO2011038903A1 (fr) 2011-04-07

Family

ID=43430619

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/EP2010/005946 WO2011038903A1 (fr) 2009-09-29 2010-09-29 Utilisation d'adsorbants à base d'aluminosilicates pour la purification de triglycérides

Country Status (3)

Country Link
EP (1) EP2483380A1 (fr)
DE (1) DE102009043418A1 (fr)
WO (1) WO2011038903A1 (fr)

Citations (18)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB1224367A (en) * 1968-08-26 1971-03-10 Bitterfeld Chemie Process for the purification of edible natural and synthetic fats, esters and ester mixtures
DE1767849A1 (de) * 1968-06-24 1972-04-13 Bitterfeld Chemie Verfahren zur Reinigung von natuerlichen oder synthetischen Fetten,Estern oder Estergemischen
US3955004A (en) 1973-08-24 1976-05-04 Lever Brothers Company Glyceride oil treatment with oxide and bleaching earth
US4443379A (en) * 1982-03-17 1984-04-17 Harshaw/Filtrol Partnership Solid bleaching composition for edible oils
US4499196A (en) * 1982-05-04 1985-02-12 Etsuji Yuki Adsorbing deacidifier for oily substances
US4629588A (en) 1984-12-07 1986-12-16 W. R. Grace & Co. Method for refining glyceride oils using amorphous silica
EP0340717A2 (fr) 1988-05-06 1989-11-08 W.R. Grace & Co.-Conn. Adsorption et traitement biphases d'huiles de glyceride
EP0376406A1 (fr) * 1988-12-30 1990-07-04 Unilever N.V. Composition Amorphe, synthétique, macroporeuse de silice alumine et procédé pour raffiner de l'huile glycéridique
DE3839580C1 (fr) 1988-11-24 1990-07-05 Condea Chemie Gmbh, 2212 Brunsbuettel, De
EP0507217A1 (fr) 1991-04-03 1992-10-07 W.R. Grace & Co.-Conn. Utilisation d'adsorbants poreux inorganiques traitées avec une base pour l'élimination de contaminants
EP0507424A1 (fr) 1991-04-03 1992-10-07 W.R. Grace & Co.-Conn. Procédé de raffinage physique modifié pour le traitement d'huiles glycéridiques, constituants gras et esters de cire
EP0558173A1 (fr) 1992-02-28 1993-09-01 W.R. Grace & Co.-Conn. Procédé d'élimination de chlorophyle et de corps pigmentés des huiles glycéridiques en utilisant du silice-alumine amorphe
EP0295418B1 (fr) 1987-05-15 1994-08-10 W.R. Grace & Co.-Conn. Procédé d'élimination de la chlorophylle et de corps pigmentés des huiles glycéridiques en utilisant des adsorbants de silice traités à l'acide
WO1994021765A1 (fr) 1993-03-18 1994-09-29 Pq Corporation Procede de reduction des contaminants presents dans des huiles glyceridiques
DE19635730A1 (de) * 1996-09-03 1998-03-05 Sued Chemie Ag Fe- und Al-haltige synthetische Polykieselsäure (silica) zur Behandlung von Ölen
US6245310B1 (en) 1996-10-05 2001-06-12 Rwe-Dea Aktiengesellschaft Fuer Mineraloel Und Chemie Process for the manufacture of dispersible alumino-silicates
EP0931017B1 (fr) 1996-10-05 2003-07-09 SASOL Germany GmbH Mode de fabrication et de dispersion de silicates d'aluminium
WO2004105936A1 (fr) * 2003-05-30 2004-12-09 Süd-Chemie AG Terre decolorante semi-synthetique

Family Cites Families (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE3775008D1 (de) * 1986-11-24 1992-01-16 Unilever Nv Metall-oxid-siliziumdioxid enthaltendes sorbentmittel und dessen verwendung zur oelraffinierung.
GB9104056D0 (en) * 1991-02-27 1991-04-17 Laporte Industries Ltd Adsorbent materials
WO2006131136A1 (fr) * 2005-06-08 2006-12-14 Süd-Chemie AG Argiles a surface riche servant a produire des terres decolorantes, et procede d'activation de ces argiles
DE102005062955A1 (de) * 2005-12-29 2007-07-12 Süd-Chemie AG Natürliches Verfahren zum Bleichen von Ölen

Patent Citations (19)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE1767849A1 (de) * 1968-06-24 1972-04-13 Bitterfeld Chemie Verfahren zur Reinigung von natuerlichen oder synthetischen Fetten,Estern oder Estergemischen
GB1224367A (en) * 1968-08-26 1971-03-10 Bitterfeld Chemie Process for the purification of edible natural and synthetic fats, esters and ester mixtures
US3955004A (en) 1973-08-24 1976-05-04 Lever Brothers Company Glyceride oil treatment with oxide and bleaching earth
US4443379A (en) * 1982-03-17 1984-04-17 Harshaw/Filtrol Partnership Solid bleaching composition for edible oils
US4499196A (en) * 1982-05-04 1985-02-12 Etsuji Yuki Adsorbing deacidifier for oily substances
EP0185182B1 (fr) 1984-12-07 1992-01-22 W.R. Grace & Co.-Conn. Procédé pour raffiner des huiles glycéribiques au moyen de silice amorphe
US4629588A (en) 1984-12-07 1986-12-16 W. R. Grace & Co. Method for refining glyceride oils using amorphous silica
EP0295418B1 (fr) 1987-05-15 1994-08-10 W.R. Grace & Co.-Conn. Procédé d'élimination de la chlorophylle et de corps pigmentés des huiles glycéridiques en utilisant des adsorbants de silice traités à l'acide
EP0340717A2 (fr) 1988-05-06 1989-11-08 W.R. Grace & Co.-Conn. Adsorption et traitement biphases d'huiles de glyceride
DE3839580C1 (fr) 1988-11-24 1990-07-05 Condea Chemie Gmbh, 2212 Brunsbuettel, De
EP0376406A1 (fr) * 1988-12-30 1990-07-04 Unilever N.V. Composition Amorphe, synthétique, macroporeuse de silice alumine et procédé pour raffiner de l'huile glycéridique
EP0507217A1 (fr) 1991-04-03 1992-10-07 W.R. Grace & Co.-Conn. Utilisation d'adsorbants poreux inorganiques traitées avec une base pour l'élimination de contaminants
EP0507424A1 (fr) 1991-04-03 1992-10-07 W.R. Grace & Co.-Conn. Procédé de raffinage physique modifié pour le traitement d'huiles glycéridiques, constituants gras et esters de cire
EP0558173A1 (fr) 1992-02-28 1993-09-01 W.R. Grace & Co.-Conn. Procédé d'élimination de chlorophyle et de corps pigmentés des huiles glycéridiques en utilisant du silice-alumine amorphe
WO1994021765A1 (fr) 1993-03-18 1994-09-29 Pq Corporation Procede de reduction des contaminants presents dans des huiles glyceridiques
DE19635730A1 (de) * 1996-09-03 1998-03-05 Sued Chemie Ag Fe- und Al-haltige synthetische Polykieselsäure (silica) zur Behandlung von Ölen
US6245310B1 (en) 1996-10-05 2001-06-12 Rwe-Dea Aktiengesellschaft Fuer Mineraloel Und Chemie Process for the manufacture of dispersible alumino-silicates
EP0931017B1 (fr) 1996-10-05 2003-07-09 SASOL Germany GmbH Mode de fabrication et de dispersion de silicates d'aluminium
WO2004105936A1 (fr) * 2003-05-30 2004-12-09 Süd-Chemie AG Terre decolorante semi-synthetique

Non-Patent Citations (11)

* Cited by examiner, † Cited by third party
Title
I.P. BARRET; L.G. JOINER; P.P. HAIENDA, J.AM.CHEM.SOC., vol. 73, 1991, pages 373
JAOCS, J. AM, OIL CHEMICAL SOCIETY, vol. 62, no. 4, 1985, pages 753 - 6
JAOCS, J. AM, OIL CHEMICAL SOCIETY, vol. 66, no. 3, 1989, pages 353 - 5
MASLOZHIROVAYA PROMYSHLENNOST, 1977, pages 21 - 3
OILS-FATS-LIPIDS 1995, PROCEEDINGS OF THE WORLD CONGRESS OF THE INTERNATIONAL SOCIETY FOR FAT RESEARCH, 21ST, THE HAGUE, OCT. 1-6, 1995(1996), vol. 1, 1995, pages 129 - 133
OLAJ, SZAPPAN, KOZMETIKA, vol. 42, no. 1, 1993, pages 1 - 6
OLAJ; SZAPPAN, OLAJ,SZAPPAN,KOZMETIKA, vol. 42, no. 2, 1993, pages 51 - 7
PROCEEDINGS OF THE WORLD CONFERENCE ON OILSEED AND EDIBLE OILS PROCESSING, vol. 2, 6 October 1996 (1996-10-06), pages 45 - 46
RIVISTA ITALIANA DELLE SOSTANZE GRASSE, vol. 66, no. 1, 1989, pages 7 - 10
ROLAND E ET AL: "Zeolites", 1 January 2000, ULLMANN'S ENCYCLOPEDIA OF INDUSTRIAL CHEMISTRY, WEINHEIM [U.A.] : WILEY-VCH, DE, PAGE(S) 1 - 31, pages: 1 - 31, XP002577273 *
TLUSZCZE JADALNE, vol. 37, no. 3/4, 2002, pages 133 - 141

Also Published As

Publication number Publication date
EP2483380A1 (fr) 2012-08-08
DE102009043418A1 (de) 2011-04-07

Similar Documents

Publication Publication Date Title
EP2361298B1 (fr) Procédé de réduction de la teneur en 3-mcpd dans des huiles végétales raffinées
EP1893329B1 (fr) Production des terres decolorantes par activation des argiles a surface riche
DE69925277T2 (de) Verfahren und zusammensetzung zur raffinierung von ölen mittels metall-substituiertem silica-xerogel
DE68905318T2 (de) Synthetische, makroporoese, amorphe alumina-kieselerde und verfahren zum raffinieren von glyceridoel.
EP2099561B1 (fr) Procédé d'obtention d'un adsorbant amorphe et de son utilisation dans le raffinement de matières grasses et/ou d'huiles
JP6473661B2 (ja) Ｒｂｄパーム油の脱色方法
US4781864A (en) Process for the removal of chlorophyll, color bodies and phospholipids from glyceride oils using acid-treated silica adsorbents
WO2010013363A1 (fr) Procédé de purification d'huile transestérifiée
DE3851013T2 (de) Verfahren zur Entfernung von Chlorophyll und Pigmentstoffen aus Glycerinölen mit säurebehandelten Silika-Adsorbenzen.
JP6664191B2 (ja) 脱色剤及び脱色剤の製造方法
EP2627744A1 (fr) Procédé d'élimination de composés contenant du phosphore de compositions contenant des triglycérides
WO2007079981A2 (fr) Procédé naturel de blanchiment d'huiles
US4877765A (en) Adsorptive material for the removal of chlorophyll, color bodies and phospholipids from glyceride oils
US5264597A (en) Process for refining glyceride oil using precipitated silica
US6093669A (en) Method for selecting raw material for bleaching clay
EP2483380A1 (fr) Utilisation d'adsorbants à base d'aluminosilicates pour la purification de triglycérides
DE68923515T2 (de) Verfahren zum Raffinieren von glyceridöl.
EP0938375B1 (fr) Acide polysilicique (silice) synthetique contenant du fer et de l'aluminium pour le traitement des huiles
DE10324561A1 (de) Semi-synthetische Bleicherde
DE10356894A1 (de) Oberflächenreiche Tone zur Herstellung von Bleicherden sowie Aktivierungsverfahren dieser Tone
US20230032214A1 (en) Thermally activated bleaching clay product for oil bleaching
JP6618769B2 (ja) 活性白土粒子
DE19607965C2 (de) Verfahren zur Verhinderung der Selbstentzündung gebrauchter, mit brennbaren organischen Stoffen beladener Adsorptionsmittel, danach erhaltene Adsorptionsmittel sowie deren Verwendung
DE102010055969A1 (de) Verfahren zur Aufreinigung von organischen Flüssigkeiten

Legal Events

Date Code Title Description
121 Ep: the epo has been informed by wipo that ep was designated in this application

Ref document number: 10763617

Country of ref document: EP

Kind code of ref document: A1

NENP Non-entry into the national phase

Ref country code: DE

WWE Wipo information: entry into national phase

Ref document number: 2010763617

Country of ref document: EP