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WO2010063450A1 - Procédé de réduction de la teneur en 3-mcpd dans des huiles végétales raffinées - Google Patents

Procédé de réduction de la teneur en 3-mcpd dans des huiles végétales raffinées Download PDF

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Publication number
WO2010063450A1
WO2010063450A1 PCT/EP2009/008557 EP2009008557W WO2010063450A1 WO 2010063450 A1 WO2010063450 A1 WO 2010063450A1 EP 2009008557 W EP2009008557 W EP 2009008557W WO 2010063450 A1 WO2010063450 A1 WO 2010063450A1
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WO
WIPO (PCT)
Prior art keywords
oil
bleaching
acid
bleaching earth
degummed
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.)
Ceased
Application number
PCT/EP2009/008557
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German (de)
English (en)
Inventor
Klaus Schurz
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 AG
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Sued Chemie AG
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Filing date
Publication date
Application filed by Sued Chemie AG filed Critical Sued Chemie AG
Priority to EP09771302.8A priority Critical patent/EP2361298B1/fr
Priority to PL09771302T priority patent/PL2361298T3/pl
Priority to DK09771302.8T priority patent/DK2361298T3/en
Priority to ES09771302.8T priority patent/ES2637347T3/es
Publication of WO2010063450A1 publication Critical patent/WO2010063450A1/fr
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11B—PRODUCING, e.g. BY PRESSING RAW MATERIALS OR BY EXTRACTION FROM WASTE MATERIALS, REFINING OR PRESERVING FATS, FATTY SUBSTANCES, e.g. LANOLIN, FATTY OILS OR WAXES; ESSENTIAL OILS; PERFUMES
    • C11B3/00—Refining fats or fatty oils
    • 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
    • C11B3/008—Refining fats or fatty oils by filtration, e.g. including ultra filtration, dialysis
    • 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
    • C11B3/12—Refining fats or fatty oils by distillation
    • C11B3/14—Refining fats or fatty oils by distillation with the use of indifferent gases or vapours, e.g. steam

Definitions

  • the invention relates to a process for refining oils wherein a crude oil is first degummed to obtain a degummed oil, the degummed oil is mixed with a bleaching earth and bleached to obtain a bleached oil which separates the bleaching earth from the bleached oil so that a filter oil is obtained and the filter oil is desorbed.
  • bleaching earths are used to remove turbidity, discoloration or even to remove oxidation accelerators. Adsorptive cleaning significantly improves the taste, color and storage stability of oils and fats.
  • different classes of bleaching earths are used.
  • HPBE High Performance Bleaching Earth.
  • this group comprises acid-reacted montmorillonites, the acid activation being carried out in a complex process by dealuminating the crude clays with concentrated acids at high temperatures, usually at boiling heat. In this process, a bleaching earth product with a very high specific surface area and a large pore volume is obtained.
  • a disadvantage of these highly active bleaching earths is the fact that dealuminating with acid during production results in large quantities of acidic salt-rich waste waters, which can be treated or disposed of only in complex processes.
  • the high costs for waste disposal and the complex production process justify the comparatively high prices of such highly active bleaching earths.
  • NABE Natural Active Bleaching Earth
  • SMBE surface activated systems
  • SMBE surface modified bleaching earth
  • a natural active raw clay with small amounts of acid is applied and thus achieved an "in situ activation".
  • attapulgite and hormite containing have for this process Rohtone proven.
  • These have a very high specific surface area of natural raw materials of about 100 to 180 m 2 / g and a pore volume of about 0.2 to 0.35 ml / g.
  • salts formed in the acid activation or unreacted portions of the acid are not washed out, they remain on the product and are at least partially deposited in the pores.
  • these acid-activated bleaching earths generally do not achieve the same efficiency as achieved by highly active bleaching earths (HPBE) produced by dealuminating with acid.
  • HPBE highly active bleaching earths
  • the simple manufacturing process allows a comparatively low-cost production, with no acid effluents being a particular advantage.
  • a subgroup of the SMBE is the Dry Milled Bleaching Earth (DMBE) .
  • DMBE Dry Milled Bleaching Earth
  • the raw clay is generally treated with an aqueous solution of the acid for the production of the SMBE, whereas for the DMBE a solid acid, mostly citric acid, is used for the activation mull the solid acid together with the raw clay.
  • No. 5,151,211 claims a bleaching earth composition
  • a bleaching earth composition comprising a neutral bleaching earth comprising attapulgite and smectite in a ratio in the range of 0.3: 1 to 1.5: 1, the proportion of attapulgite and smectite being at least 65% by weight. % of the bleaching earth corresponds. Furthermore, the cooperation a polyvalent carboxylic acid having an even number of carboxyl groups, which are arranged in pairs, wherein the carboxyl groups can each adopt an eclipsed arrangement.
  • US 6,346,286 D1 claims a bleaching earth composition
  • a bleaching earth composition comprising a mixture of a particulate clay and a particulate polyvalent carboxylic acid wherein the carboxylic acid has a pK a in the range of 1 to 7 and is substantially free of salts of organic acids.
  • the clay has a moisture content of not more than 8% by weight based on the clay.
  • the polyvalent carboxylic acid is contained in a proportion in the range of 1 to 8 wt .-%, based on the composition in this.
  • 6,346,286 B1 describes a bleaching process in which the oil to be bleached is brought into contact with a particulate composition which comprises particles of a clay mineral and particles of at least one organic acid, the organic acid being substantially free of salts of the organic acid.
  • a particulate composition which comprises particles of a clay mineral and particles of at least one organic acid, the organic acid being substantially free of salts of the organic acid.
  • citric acid is mentioned as a suitable organic acid.
  • the refined oil After bleaching, the refined oil should meet certain color, taste and durability requirements. Thus, the oil must not be too dark and, depending on the type of oil, have a yellow to green color. Furthermore, the oil should be preserved over a longer period without taste deterioration, so do not taste rancid.
  • No. 7,179,491 B1 describes a process for bleaching oils, which process does not require any degumming of the oil or the use of alkali or other chemicals, such as acids or bases.
  • the oil is extracted from marine sources, mammals or fish.
  • the crude oil is first degassed in a vacuum. After the vacuum is broken with gaseous nitrogen was first silicic acid is added to the oil and again applied to the reactor vacuum. The vacuum is broken again and bleaching earth is added to the mixture. After vacuum has been re-applied to the reactor, the mixture is bleached. The vacuum is broken again and then the solid components are separated from the bleached oil by filtration.
  • the oil is first degassed after drying and dried, for example, to remove dissolved oxygen. Subsequently, mucilages, in particular phospholipids, are removed.
  • the dried and degassed oil is treated with phosphoric acid and stirred at about 95 ° C and atmospheric pressure for about 15 to 20 minutes.
  • further water is added at the end of the degumming, for example in a proportion of 0.2% by weight.
  • Lecithin phase separated for example by centrifugation.
  • Subsequent bleaching of the degummed oil involves two stages, wet bleaching and vacuum bleaching.
  • wet bleaching the degummed oil is mixed with 0.1 to 0.5% by weight of water and after the oil has been heated to 95 ° C., 0.3 to 2% by weight of bleaching earth is added. The mixture is then stirred at normal pressure for about 20 minutes. Subsequently, a vacuum is applied (for example, 100 mbar) and the oil is stirred for a further 30 minutes at 95 0 C.
  • the spent bleaching earth is separated off, for example by filtering the mixture through a suction filter covered with a paper filter.
  • the oil After bleaching, the oil is still deodorized. For this purpose, superheated steam, which has an outlet temperature of about 240 0 C, passed through the oil to remove free fatty acids as well as unpleasant flavors and odors.
  • the deodorization is carried out in vacuo at a pressure in the range of less than 5 mbar, preferably 1 to 3 mbar.
  • the oil After refining, the oil must meet certain requirements in terms of, for example, color, taste and shelf life. For example, the oil should not appear brown, but depending on the variety have a yellow to green color. A benchmark for this is the Lovibond color number red, which should be as low as possible. To increase the shelf life, the oil should have a very low iron or phosphorus content. Furthermore, the oil should be as insensitive as possible to oxidation in order to prevent the development of a rancid odor and taste.
  • DE 10 2006 035 064 A1 describes a process for bleaching oils and fats, wherein
  • a crude oil derived from a vegetable or animal source the crude oil is heated to a temperature in the range of 35 to 55 0 C; - a bleaching earth is added to the heated crude oil; the heated crude oil is bleached; and the bleaching earth is separated from the bleached crude oil.
  • the method has the advantage that the oil for the addition of Bleaching earth does not have to be heated to high temperatures and the bleaching mass can be reduced.
  • 3-monochloropropane-1,2-diol can arise in the production of food, e.g. in the production of soy sauce, in baking and toasting, but also in the refining of vegetable oils and fats.
  • 3-MCPD has been shown to be carcinogenic.
  • its mutagenicity could be detected in vitro, but not in vivo.
  • 3-MCPD affects fertility in mammals.
  • 3-MCPD can be present in the centers of life either in free or in bound form, for example in the form of a
  • 3-MCPD was found in different fats and oils.
  • concentration in vegetable fats and oils can range from several hundred to several thousand ppm, calculated as free 3-MCPD.
  • the mechanism by which 3-MCPD is formed during the refining of fats and oils has not yet been fully elucidated.
  • model studies have shown that chloride ions as well as glycerol and mono-, di- and triglycerides are potential starting materials in the formation of 3-MCPD.
  • Bleaching earth is separated from the bleached oil, so that a filter oil is obtained, and the filter oil is deodorized, which leads to the lowest possible formation of 3-MCPD.
  • the degumming of the crude oil is carried out only with water without the addition of acids.
  • the oil is then bleached at a temperature in the range of 80 to 100 0 C, preferably at a temperature of about 95 0 C.
  • the degumming has a significant influence on the concentration of 3-MCPD, which in the refining of oils and fats, bleaching has a significantly lower influence or the addition of bleaching earth lowers the concentration of 3-MCPD in the refined oil or fat after degumming.
  • HPBE highly active bleaching earths
  • water is added to the crude oil and the degumming is carried out without addition of acid at a temperature of less than 70 ° C., and the degummed oil is preferably carried out by an aqueous process
  • Phase is separated, the degummed oil to a temperature in the range of
  • 80 to 100 0 C is heated and to the heated degummed oil, the bleaching earth in an amount of more than 1.5 wt .-% is added, and the bleaching at a temperature in the range of 80 to
  • a crude oil is initially provided in the usual way. This can be obtained, for example, in an oil mill by pressing.
  • the crude oil can also be degassed and dried in the usual way.
  • the crude oil is then mixed with water and stirred at a relatively low temperature.
  • the degumming is preferably carried out in such a way that the crude oil is mixed with water before bleaching.
  • the amount of water added for degumming is preferably less than 15% by weight, more preferably less than 10% by weight. According to one embodiment, the added amount of water is at least 0.2 wt .-%, according to another embodiment, at least 0.5 wt .-% and according to yet another embodiment at least 1% by weight. The percentages are based on the crude oil used.
  • the degumming is carried out without the addition of acids.
  • the degumming is performed at a relatively low temperature of less than 70 0 C, preferably less than 60 0 C, preferably in the range of 35 to 55 ° C, more preferably in the range of 40 to 50 0 C.
  • the treatment time of the oil for degumming is preferably selected in the range of 10 to 30 minutes, more preferably 15 to 25 minutes. After degumming, the
  • Lecithin phase separated from degummed oil for example by centrifugation, decantation or by filtration. If the amount of water is less than 0.5% by weight, removal of the water phase may be omitted. However, it is preferred that even with smaller amounts of water, the water phase is separated from the degummed oil.
  • the degummed oil is heated to a temperature in the range of 80 to 100 0 C, preferably 90 to 98 0 C, preferably about 95 0 C. It has been found that excessively high temperatures in lead lead to an increase in the concentration of 3-MCPD in the refined oil. Overheating of the oil should therefore be avoided.
  • the bleached earth is then added to the heated degummed oil. It has been found that when too low amounts of bleaching earth, the concentration of 3-MCPD or 3-MCPD precursors, which have formed during degumming, can not be reduced sufficiently.
  • the bleaching earth is therefore added to the heated degummed oil in an amount of more than 1.5% by weight, preferably in an amount in the range of from 2.0 to 3.0% by weight, based on the crude oil.
  • bleaching earth has only a low adsorption power for 3-MCPD or its precursors. It was found that 3-MCPD or whose precursors are contained in the oil only in amounts in the ppm range. However, an increase in bleaching amount used for bleaching above 1.5% by weight results in a marked reduction in the amount of 3-MCPD in the refined oil.
  • the oil After adding the bleaching earth to the heated oil, the oil is then bleached in a conventional manner.
  • the bleaching can be done by applying directly after addition of the bleaching earth vacuum, so without having previously given water to the crude oil.
  • the bleaching then takes place as pure vacuum bleaching.
  • the vacuum bleaching is carried out at elevated temperature, more preferably at temperatures of 80 to 110 0 C.
  • the bleaching is carried out in at least two stages, with first wet bleaching and then vacuum equalization.
  • the crude oil is first mixed with water.
  • the amount of water is preferably selected in the range of 0.05 to 1.5 wt .-%, particularly preferably 0.1 to 1 wt .-%.
  • the mixture is then stirred at 80 to 100 ° C., particularly preferably 90 to 95 ° C.
  • the vacuum is carried out at the above conditions, ie preferably at temperatures of 80 to 95 0 C and a pressure in the range of about 100 mbar.
  • the bleaching earth is separated from the bleached oil.
  • conventional methods can be used.
  • the bleaching earth can be allowed to sediment and the supernatant clear oil can be decanted off.
  • the bleached oil is filtered, for example through a paper filter, so that a filter oil is obtained.
  • oil obtained from the bleached oil is referred to as a filter oil, regardless of the method used to separate the bleaching earth.
  • the filter oil is finally deodorized.
  • usual methods are used under the usual conditions.
  • superheated steam is passed through the oil, whereby a Vollraffinat is obtained.
  • the superheated steam preferably has an outlet temperature in the range of 200 to 290 0 C.
  • the deodorization is preferably carried out for a time period of 30 minutes to 2 hours.
  • the deodorization can be carried out in one stage, wherein the outlet temperature of the superheated steam is kept substantially constant.
  • superheated steam is first introduced, which has a temperature in the range of 250 to 290 0 C. This first step is preferably carried out for a period of 20 to 45 minutes.
  • the outlet temperature of the steam is lowered, preferably in a range of 200 to 240 0 C.
  • the superheated steam is then preferably passed through the oil for a further 30 to 120 minutes.
  • deodorization releases 3-MCPD, which the inventors believe to be previously bound in precursors, for example, glycerides or compounds derived therefrom.
  • surface-rich bleaching earths are preferably used.
  • the bleaching earth has a specific surface area of more than 175 m 2 / g, according to another embodiment a specific surface area of more than 220 m 2 / g, and according to another embodiment a specific surface area of more than 300 m 2 / g According to one embodiment, the bleaching earth has a specific surface area of less than 400 m 2 / g.
  • the bleaching earths used in the process according to the invention have a specific pore volume of more than 0.2 ml / g, more preferably more than 0.3 ml / g, particularly preferably a specific pore volume of more than 0.4 ml / g.
  • the bleaching earth has a pore volume of more than 0.45 ml / g and, according to another embodiment, a pore volume of less than 0.95 ml / g.
  • a bleaching earth is selected which has a pore volume in the range of 0.4 to 1.0 ml / g.
  • the specific surface area (BET surface area) and the specific pore volume are determined by means of nitrogen porosimetry according to DIN 66131 and evaluation according to the BJH method.
  • the total pore volume refers to pores with a diameter of 2 to 130 nm.
  • the ion exchange capacity of the bleaching earths is preferably more than 15 meq / 100 g, preferably more than 25 meq / 100 g and in one embodiment more than 40 meq / 100 g.
  • all customary bleaching earths can be used in the process according to the invention.
  • bleaching earth therefore, both natural bleaching earths (NABEs) can be used, as well as acid-activated bleaching earths.
  • NABEs natural bleaching earths
  • SBE surface-activated bleaching earths
  • HPBE highly active bleaching earths
  • the acid activated bleaching earth as a 10% slurry in water, preferably has a pH of less than 5, and more preferably less than 4. In one embodiment, the pH of the slurry is greater than 2. In one embodiment, the slurry has a pH of less than 8.5, and in another embodiment has a pH of less than four. The pH is determined with a pH electrode.
  • SMBE surface-activated bleaching earths
  • acid-activated bleaching earths can be used as acid-activated bleaching earths. These surface-activated bleaching earths are obtained by acid-plating a natural raw clay leaving excess acid on the clay. So no washing step is carried out after the activation. Before activation, the raw clay can be prepared in the usual way and, for example, dried or ground.
  • the surface activation of the raw clay can be carried out by covering the raw clay with a, preferably aqueous, solution of the acid used for the activation.
  • the assignment can be done, for example, by moving the raw clay and the solution of the acid is sprayed onto the raw clay. But there are also other methods possible to apply the solution of the acid to the raw clay, such as soaking.
  • the activation of the raw clay can be carried out, for example, in aqueous
  • the acid is brought into contact with the crude clay as an aqueous solution.
  • the crude clay which is preferably provided in the form of a powder, in water.
  • the acid is added in concentrated form.
  • the raw clay can also be slurried directly in an aqueous solution of the acid, or the aqueous solution of the acid can be applied to the raw clay.
  • the aqueous acid solution can be, for example, preferably broken or powdered
  • the amount of water is preferably chosen as low as possible and, for example, a concentrated acid or acid solution is used.
  • the amount of acid may preferably be between 1 and 10% by weight, more preferably between 2 and 6% by weight of a strong acid, in particular a mineral acid such as sulfuric acid, based on the anhydrous crude clay (atro). If necessary, excess water can be evaporated and the activated raw clay then ground to the desired fineness. As already explained above, no washing step is required in this embodiment of the method according to the invention. After abandonment of aqueous solution of the acid is only, if necessary, dried until reaching the desired moisture content. Most of the water content of the resulting bleaching earth product is adjusted to a proportion of less than 20 wt .-%, preferably less than 10 wt .-%.
  • the activation can be carried out with both inorganic and organic acids.
  • Suitable inorganic acids are, for example, sulfuric acid, phosphoric acid or else hydrochloric acid.
  • a suitable organic acid is, for example, citric acid.
  • the excess acid and the salts formed during activation are not washed out. Rather, after the task of acid, as usual in the acid activation, preferably no washing step is carried out, but the treated raw clay dried and then ground to the desired particle size.
  • a suitable acid is, for example, citric acid.
  • the grain size is set in the desired range.
  • the amount of acid used for activation is preferably selected to be greater than the ion exchange capacity of the raw clay, preferably in the range of 100 to 140% of the ion exchange capacity of the raw clay.
  • a highly active bleaching earth is preferably used as the acid-activated bleaching earth.
  • These highly active bleaching earths are obtained by extracting a crude clay at elevated temperature, preferably at about boiling heat, with a strong acid. Essentially aluminum ions from the Crisis are detached tall Weg. After extraction, the bleaching earth is separated from the aqueous phase, for example by filtration, and then washed with water. This method is known per se to the person skilled in the art. The highly activated bleaching earth will also be ground to the desired grain size.
  • the grain size or the mean grain size of the bleaching earth should preferably be selected so that a complete and simple separation of the used bleaching earth from the refined product is possible.
  • the mean grain size of the powdered raw clay is selected in a range of 10 to 63 ⁇ m.
  • the fineness is chosen so that on a sieve with a mesh size of 63 microns about 20 to 40 wt .-% of the mixture remain (sieve residue) and on a sieve with a mesh size of 25 microns about 50 to 65 wt .-% of Stay behind. This can be referred to as typical bleaching earth fineness.
  • the inventive method is suitable in itself for the refining of any oils and fats.
  • the method according to the invention is particularly suitable for the refining of vegetable oils.
  • the bleaching process according to the invention is particularly suitable for low-phosphorus oils, which preferably have a phosphorus content of less than 100 ppm.
  • the process according to the invention is suitable for the bleaching of palm oil.
  • the specific surface was carried out on a fully automatic nitrogen porosimeter from Micromeritics, type ASAP 2010, in accordance with DIN 66131.
  • the pore volume was determined using the BJH method (E.P Barrett, L.G. Joyner, P.P. Haienda, J. Am. Chem. Soc. 73 (1951) 373). Pore volumes of certain pore size ranges are determined by adding up incremental pore volumes, which are derived from the evaluation of the pore size ranges
  • Adsorption isotherms are obtained according to BJH.
  • the total pore volume according to the BJH method refers to pores with a diameter of 2 to 130 nm.
  • the sieve is connected to a vacuum cleaner, which sucks all parts which are finer than the sieve through the sieve by means of a suction slot circulating under the sieve bottom.
  • 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 coarser particles remaining on the sieve is determined by differential weighing.
  • a sample of crude palm oil is first heated to the temperature indicated in Table 1 for degumming and then dried and degassed for 15 minutes at 100 mbar. After degassing, the palm oil was added to the amount of 50% phosphoric acid or water indicated in Table 1 and stirred for 15 minutes at ambient pressure.
  • the aqueous phase was separated off (index "f” in Table 1), for the bleaching the oil was adjusted to the temperature indicated in Table 1 and then the amount of bleaching earth indicated in Table 1 was added.
  • the oil was first bleached for 20 minutes at atmospheric pressure and then for 30 minutes at a reduced pressure of 100 mbar.
  • the oil was filtered hot through a paper filter.
  • the filtered oil was deodorized by first for 30 minutes superheated steam, which had an outlet temperature of 270 0 C, and then for 60 minutes superheated steam, which had an outlet temperature of 240 0 C, passed through the oil.
  • the concentration of 3-MCPD was determined. The results are summarized in Table 1.
  • the bleaching earths used in the examples have the properties listed in Table 2:
  • bleaching earth If a bleaching earth is added after degumming during bleaching, significantly lower concentrations of 3-MCDP are measured in full raffinate.
  • the use of bleaching earth therefore does not increase the concentration of 3-MCPD in the Vollraffinat but adsorbs during the oil refining emerging 3-MCPD or precursors of this compound.

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

L'invention concerne un procédé de raffinage d'huiles, selon lequel une huile brute est tout d'abord démucilaginée, de manière à obtenir une huile démucilaginée, l'huile démucilaginée est mélangée avec une argile décolorante et est décolorée, une huile décolorée étant obtenue, l'argile décolorante est séparée de l'huile décolorée, de manière à obtenir une huile filtrée, et l'huile filtrée est désodorisée. Ledit procédé se caractérise en ce que de l'eau est ajoutée à l'huile brute pour la démucilagination et la démucilagination est réalisée sans ajout d'acide, à une température inférieure à 70 °C, et l'huile démucilaginée est de préférence séparée d'une phase aqueuse, l'huile démucilaginée est portée à une température de l'ordre de 80 à 100 °C et la terre décolorante est ajoutée à l'huile démucilaginée chauffée, en une quantité supérieure à 1,5 % en poids, et la décoloration est réalisée à une température de l'ordre de 80 à 100 °C.
PCT/EP2009/008557 2008-12-02 2009-12-01 Procédé de réduction de la teneur en 3-mcpd dans des huiles végétales raffinées Ceased WO2010063450A1 (fr)

Priority Applications (4)

Application Number Priority Date Filing Date Title
EP09771302.8A EP2361298B1 (fr) 2008-12-02 2009-12-01 Procédé de réduction de la teneur en 3-mcpd dans des huiles végétales raffinées
PL09771302T PL2361298T3 (pl) 2008-12-02 2009-12-01 Sposób zmniejszania zawartości 3-MCPD w rafinowanych olejach roślinnych
DK09771302.8T DK2361298T3 (en) 2008-12-02 2009-12-01 Process for reducing the 3-MCPD content in refined plant oils
ES09771302.8T ES2637347T3 (es) 2008-12-02 2009-12-01 Procedimiento para la reducción del contenido de 3-MCPD en aceites vegetales refinados

Applications Claiming Priority (2)

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DE102008060059.8 2008-12-02
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JP2011174091A (ja) * 2011-06-01 2011-09-08 Showa Sangyo Co Ltd 遊離塩素を除去する工程を設けたパーム油の製造方法
WO2012107230A1 (fr) * 2011-02-10 2012-08-16 Cargill, Incorporated Compositions d'huile
WO2013018412A1 (fr) * 2011-07-29 2013-02-07 日清オイリオグループ株式会社 Composition glycéridique purifiée et son procédé de production
WO2013093093A1 (fr) 2011-12-23 2013-06-27 Loders Croklaan B.V. Procédé de traitement d'une huile végétale
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WO2014081279A1 (fr) 2012-11-21 2014-05-30 Universiti Putra Malaysia Procédé de raffinage d'huile de palme perfectionné
WO2015174822A1 (fr) 2014-05-16 2015-11-19 Sime Darby Malaysia Berhad Procédé de raffinage d'un produit d'huile de fruit de palmier brute
EP2640813B1 (fr) 2010-11-19 2016-06-01 Loders Croklaan B.V. Procédé de fabrication d'une huile végétale raffinée
EP2874501B1 (fr) 2012-07-18 2016-07-20 Aak Ab Réduction de composés de mcpd dans l'huile végétale raffinée pour aliments
EP2594625B1 (fr) 2010-07-16 2016-11-16 Wilmar (shanghai) Biotechnology Research & Development Center Co., Ltd. Procédé d'ajustement de la teneur du 3-chloro-1,2-propanediol ou d'esters de celui-ci dans des huiles et des matières grasses
EP2449071B1 (fr) 2009-06-30 2017-12-13 Sime Darby Malaysia Berhad Procédé de production de fractions d'huile de palme ne contenant quasiment pas d'esters d'acides gras de 3-monochloropropanediol
WO2018156013A1 (fr) 2017-02-21 2018-08-30 Sime Darby Plantation Berhad Procédé de production d'huile de fruit de palmier raffinée
US10150933B2 (en) 2015-05-27 2018-12-11 Evonik Degussa Gmbh Process for removing metal from a metal-containing glyceride oil comprising a basic quaternary ammonium salt treatment
US10221374B2 (en) 2015-05-27 2019-03-05 Evonik Degussa Gmbh Process for refining glyceride oil comprising a basic quaternary ammonium salt treatment
US10301572B1 (en) 2017-11-10 2019-05-28 Evonik Degussa Gmbh Process for extracting fatty acids from triglyceride oils
US10316268B2 (en) 2015-05-27 2019-06-11 The Queen's University Of Belfast Process for removing chloropropanols and/or glycidol, or their fatty acid esters, from glyceride oil, and an improved glyceride oil refining process comprising the same
WO2019217223A1 (fr) 2018-05-07 2019-11-14 Arisdyne Systems, Inc. Procédés de production d'huile de palme raffinée avec formation réduite de 3-mcpd
EP3321348B1 (fr) 2017-08-23 2019-12-18 Bunge Loders Croklaan B.V. Procédé de raffinage d'huile végétale avec suppression des impuretés indésirables
CN111683536A (zh) * 2018-02-07 2020-09-18 嘉吉公司 不含不期望的污染物的液态油
CN111683537A (zh) * 2018-02-07 2020-09-18 嘉吉公司 无不需要的污染物的棕榈油
WO2021239797A1 (fr) * 2020-05-28 2021-12-02 Société des Produits Nestlé S.A. Prévention de la formation de mcpd par lavage à température élevée
US12384984B2 (en) 2019-11-15 2025-08-12 Societe Des Produits Nestle S.A. Prevention of MCPD formation by auxiliary degumming

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PL238351B1 (pl) 2018-08-27 2021-08-09 Komagra Spolka Z Ograniczona Odpowiedzialnoscia Sposób wytwarzania rafinowanego oleju jadalnego o niskiej zawartości niepożądanych 3-MPCD, 2-MPCD oraz glicydów
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WO2011040539A1 (fr) * 2009-09-30 2011-04-07 不二製油株式会社 Procédés de réduction des chloropropanols et d'une de leurs substances formatives, l'ester d'acide gras de glycidol, contenus dans les huiles glycéridiques
EP2594625B1 (fr) 2010-07-16 2016-11-16 Wilmar (shanghai) Biotechnology Research & Development Center Co., Ltd. Procédé d'ajustement de la teneur du 3-chloro-1,2-propanediol ou d'esters de celui-ci dans des huiles et des matières grasses
EP2640813B1 (fr) 2010-11-19 2016-06-01 Loders Croklaan B.V. Procédé de fabrication d'une huile végétale raffinée
EP3070154B2 (fr) † 2010-11-19 2025-04-16 Bunge Loders Croklaan B.V. Procédé de production d'huile végétale raffinée
EP3070154B1 (fr) 2010-11-19 2018-06-20 Loders Croklaan B.V. Procédé de production d'huile végétale raffinée
CN103369972A (zh) * 2011-02-10 2013-10-23 卡吉尔公司 油组合物
US12349693B2 (en) 2011-02-10 2025-07-08 Cargill, Incorporated Oil compositions
WO2012107230A1 (fr) * 2011-02-10 2012-08-16 Cargill, Incorporated Compositions d'huile
RU2599643C2 (ru) * 2011-02-10 2016-10-10 Карджилл, Инкорпорейтед Масляные композиции
AU2012216164B2 (en) * 2011-02-10 2016-01-07 Cargill, Incorporated Oil compositions
CN103458699A (zh) * 2011-03-25 2013-12-18 雀巢产品技术援助有限公司 由洗涤过的粗植物性油生产精炼植物性油
JP2011174091A (ja) * 2011-06-01 2011-09-08 Showa Sangyo Co Ltd 遊離塩素を除去する工程を設けたパーム油の製造方法
EP2738243B1 (fr) 2011-07-29 2016-10-05 The Nisshin Oillio Group, Ltd. Composition glycéridique purifiée et son procédé de production
WO2013018412A1 (fr) * 2011-07-29 2013-02-07 日清オイリオグループ株式会社 Composition glycéridique purifiée et son procédé de production
JP5216942B1 (ja) * 2011-07-29 2013-06-19 日清オイリオグループ株式会社 精製グリセリド組成物及び該精製グリセリド組成物の製造方法
EP3502219A1 (fr) 2011-12-23 2019-06-26 Bunge Loders Croklaan B.V. Procédé de traitement d'une huile végétale
US9217120B2 (en) 2011-12-23 2015-12-22 Loders Croklann B.V. Method of treating a vegetable oil
WO2013093093A1 (fr) 2011-12-23 2013-06-27 Loders Croklaan B.V. Procédé de traitement d'une huile végétale
EP2874501B1 (fr) 2012-07-18 2016-07-20 Aak Ab Réduction de composés de mcpd dans l'huile végétale raffinée pour aliments
WO2014081279A1 (fr) 2012-11-21 2014-05-30 Universiti Putra Malaysia Procédé de raffinage d'huile de palme perfectionné
CN103525548B (zh) * 2013-11-06 2014-10-01 江南大学 一种用于降低植物油中氯源及3-氯-1,2-丙二醇酯前体物质含量的脱胶方法
CN103525548A (zh) * 2013-11-06 2014-01-22 江南大学 一种用于降低植物油中氯源及3-氯-1,2-丙二醇酯前体物质含量的脱胶方法
WO2015174820A1 (fr) 2014-05-16 2015-11-19 Sime Darby Malaysia Berhad Procédé de raffinage d'un produit d'huile de fruit de palme brute
WO2015174822A1 (fr) 2014-05-16 2015-11-19 Sime Darby Malaysia Berhad Procédé de raffinage d'un produit d'huile de fruit de palmier brute
US10150933B2 (en) 2015-05-27 2018-12-11 Evonik Degussa Gmbh Process for removing metal from a metal-containing glyceride oil comprising a basic quaternary ammonium salt treatment
US10221374B2 (en) 2015-05-27 2019-03-05 Evonik Degussa Gmbh Process for refining glyceride oil comprising a basic quaternary ammonium salt treatment
US10316268B2 (en) 2015-05-27 2019-06-11 The Queen's University Of Belfast Process for removing chloropropanols and/or glycidol, or their fatty acid esters, from glyceride oil, and an improved glyceride oil refining process comprising the same
WO2018156013A1 (fr) 2017-02-21 2018-08-30 Sime Darby Plantation Berhad Procédé de production d'huile de fruit de palmier raffinée
US11421183B2 (en) 2017-08-23 2022-08-23 Bunge Loders Croklaan B.V. Process for refining vegetable oil with suppression of unwanted impurities
EP3321348B1 (fr) 2017-08-23 2019-12-18 Bunge Loders Croklaan B.V. Procédé de raffinage d'huile végétale avec suppression des impuretés indésirables
US10301572B1 (en) 2017-11-10 2019-05-28 Evonik Degussa Gmbh Process for extracting fatty acids from triglyceride oils
CN111683536A (zh) * 2018-02-07 2020-09-18 嘉吉公司 不含不期望的污染物的液态油
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US11634657B2 (en) 2018-05-07 2023-04-25 Arisdyne Systems, Inc. Method for refined palm oil production with reduced 3-MCPD formation
US12195697B2 (en) 2018-05-07 2025-01-14 Arisdyne Systems, Inc. Method for refined palm oil production with reduced 3-MCPD formation
WO2019217223A1 (fr) 2018-05-07 2019-11-14 Arisdyne Systems, Inc. Procédés de production d'huile de palme raffinée avec formation réduite de 3-mcpd
US12384984B2 (en) 2019-11-15 2025-08-12 Societe Des Produits Nestle S.A. Prevention of MCPD formation by auxiliary degumming
WO2021239797A1 (fr) * 2020-05-28 2021-12-02 Société des Produits Nestlé S.A. Prévention de la formation de mcpd par lavage à température élevée

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ES2637347T3 (es) 2017-10-11
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