WO2016189333A1 - Procédé de raffinage de l'huile glycéridique comportant un traitement de liquide ionique basique - Google Patents

Procédé de raffinage de l'huile glycéridique comportant un traitement de liquide ionique basique Download PDF

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Publication number
WO2016189333A1
WO2016189333A1 PCT/GB2016/051566 GB2016051566W WO2016189333A1 WO 2016189333 A1 WO2016189333 A1 WO 2016189333A1 GB 2016051566 W GB2016051566 W GB 2016051566W WO 2016189333 A1 WO2016189333 A1 WO 2016189333A1
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Prior art keywords
oil
ionic liquid
basic
process according
glyceride oil
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PCT/GB2016/051566
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English (en)
Inventor
Peter Goodrich
Eoghain O'HARA
Martin Philip Atkins
Christopher Klatt HAMER
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The Queen's University Of Belfast
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Application filed by The Queen's University Of Belfast filed Critical The Queen's University Of Belfast
Priority to CN201680044212.7A priority Critical patent/CN108026476A/zh
Priority to JP2017561967A priority patent/JP2018517038A/ja
Publication of WO2016189333A1 publication Critical patent/WO2016189333A1/fr
Priority to PH12017502157A priority patent/PH12017502157A1/en

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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
    • C11B3/02—Refining fats or fatty oils by chemical reaction
    • C11B3/06—Refining fats or fatty oils by chemical reaction with bases
    • A—HUMAN NECESSITIES
    • A23—FOODS OR FOODSTUFFS; TREATMENT THEREOF, NOT COVERED BY OTHER CLASSES
    • A23D—EDIBLE OILS OR FATS, e.g. MARGARINES, SHORTENINGS, COOKING OILS
    • A23D9/00—Other edible oils or fats, e.g. shortenings, cooking oils
    • A23D9/02—Other edible oils or fats, e.g. shortenings, cooking oils characterised by the production or working-up
    • 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
    • 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
    • C11C—FATTY ACIDS FROM FATS, OILS OR WAXES; CANDLES; FATS, OILS OR FATTY ACIDS BY CHEMICAL MODIFICATION OF FATS, OILS, OR FATTY ACIDS OBTAINED THEREFROM
    • C11C3/00—Fats, oils, or fatty acids by chemical modification of fats, oils, or fatty acids obtained therefrom

Definitions

  • the present invention relates to an improved process for refining glyceride oil which incorporates a basic ionic liquid treatment.
  • the basic ionic liquid treatment prevents or reduces the formation of chloropropanol fatty acid esters and glycidyl fatty acid esters during the overall refining process.
  • the present invention also relates to glyceride oil compositions formed therefrom and uses of the basic ionic liquid.
  • Crude glyceride oils extracted from natural sources typically undergo a variety of refining processes in order to remove unwanted contaminants and improve the organoleptic properties of the oil or other quality parameters depending on the intended use.
  • Glyceride oil refining has in recent years come under increased scrutiny where the oil is intended for human consumption since it has been established that the nature of the refining process and even different cooking practices can lead to the formation of potentially carcinogenic or toxic contaminants.
  • Two groups of known glyceride oil contaminants that have been identified as harmful to human health are chloropropanols and glycidol.
  • Fatty acid esters of chloropropanols and glycidol have been found to accumulate in glyceride oil, particularly refined oil which has been exposed to high temperatures during the refining process. Upon consumption, fatty acid esters of chloropropanols and glycidol are hydrolysed by lipases in the gastrointestinal tract, releasing free chloropropanols and glycidol.
  • Non-esterified chloropropanols can also be present in glyceride oil, including monochloropropandiols, 2-chloro-1 ,3-propanediol (2-MCPD) and 3-chloro-1 ,2-propanediol (3-MCPD), or the corresponding dichloropropanols, 2,3-dichloropropan-1 -ol (2,3-DCP) and 1 ,3-dichloropropan-2-ol (1 ,3-DCP).
  • 3-MCPD has been shown to exhibit in vitro genotoxic carcinogenic effects and a tolerable daily intake (TDI) of 2 g/Kg has now been established across the food industry.
  • Refining of crude lipid-containing glyceride oils typically comprises degumming, bleaching and deodorization, normally with a deacidification step included in the form of either neutralisation with strong base or an extended deodorization to remove any free fatty acids (FFA) present in the oil.
  • Degumming typically involves addition of aqueous acid (citric and/or phosphoric acid) and may also remove other components of the glyceride oil, such as metal ions, at the same time as lipid components. Meanwhile, bleaching with bleaching earth not only reduces the amount of pigments it also absorbs other components of the oil, which can improve organoleptic properties.
  • glyceride oils have been treated with polar solvents as part of liquid- liquid extractions for separating glycerides according to their level of saturation or chain length, as well as for separating mono- and di-glycerides, FFA and glycerol, from triglycerides.
  • Liquid-liquid extractions such as alcohol extractions, are also known as a means for removing polar impurities from glyceride oils.
  • extractions may not be adequate for removing fatty acid esters of chloropropanols and glycidols which are less polar and less volatile than their non-esterified versions.
  • a number of refining processes are now known in the art which aim specifically to remove organochlorine compounds which lead to the formation of chloropropanol fatty acid esters or to prevent their conversion by modifying process conditions.
  • WO 2014/012548 a process is disclosed for lowering the amount of esters of 2- and 3-MCPD formed in refined triglyceride oil by blending with a base, heat treating while passing steam through the oil at reduced pressure and maintaining the degree of interesterification below 60%.
  • This process benefits from a relatively mild heat treatment but involves the addition of free fatty acids (FFA) to the oil to suppress the degree of interesterification.
  • FFA free fatty acids
  • the addition of FFA is thought to negatively impact the organoleptic properties of oil, as well as oil stability, and therefore additional process steps are likely to be required in order to remove FFA after it has been added.
  • a process for removing unwanted propanol components, including free chloropropanols, chloropropanol fatty acid esters, free epoxypropanols, epoxypropanol fatty acid esters, and combinations thereof, from unused triglyceride oil.
  • the process comprises contacting a contaminated oil with a silicate adsorbent selected from the group consisting of magnesium silicate, calcium silicate, aluminum silicate and combinations of these silicates.
  • the oil to be treated is preferably a deodorized contaminated triglyceride oil.
  • WO 2010/063450 a refining process is disclosed which involves degumming of crude oil with water, and without the addition of acids, at a temperature of less than 70 °C followed by wet bleaching and vacuum bleaching at a temperature in the range of 80 to 100 °C. It is reported that degumming and bleaching in this manner reduces 3-MCPD formation as a result of the overall refining process by removing both 3-MCPD and its precursors.
  • a process for the production of a refined oil having a reduced 3- MCPD ester and/or glycidyl ester content comprises subjecting an oil to the following steps, in order: (a) a bleaching step, (b) a deodorization step, (c) a final bleaching step, and (d) a final deodorization step, wherein final deodorization step (d) is carried out at a temperature of at least 40°C lower than deodorization step (b), preferably at a temperature below 190 °C.
  • a method of removing glycidyl esters from a vegetable oil comprises contacting the oil with at least 0.5 % by weight of the oil of an acid-activated bleaching earth and deodorising the oil at a temperature of less than 200°C for a time of at least 30 minutes.
  • a deodorisation would be suitable for providing a commercially acceptable product in the case of oils having high levels of pigments and odiferous compounds.
  • WO 2012/169718 a method is disclosed for reducing the concentration of 3- MCPD fatty acid esters to 0.3 ppm or less in refined edible oil by controlling chloride ions contained in the water source used for the refining process by means of an ion exchange resin.
  • a process for removing monochloropropanediols and/or glycidol from glycerol which includes treatment with ion exchange resins, in particular strong base ion exchange resin in the hydroxyl form, to reduce the level of monochloropropanediol.
  • ion exchange resins in particular strong base ion exchange resin in the hydroxyl form
  • JP 08-302382 a method is disclosed for deodorization and depigmentation of fish oil by contacting with a strongly basic anion-exchange resin under reduced pressure.
  • the present invention is based on the surprising discovery that specifically selected basic ionic liquids comprising a basic anion can be advantageously utilised for preventing or reducing formation of chloropropanol fatty acid esters and/or glycidyl fatty acid esters in glyceride oil, which treatment can be readily integrated into the overall refining process.
  • treatment of glyceride oil with a basic ionic liquid has been found to at least partially remove pigments and odiferous compounds which are typically removed in a separate bleaching step and a high temperature (for example, 240 °C to 270 °C) deodorization step respectively during conventional refining processes.
  • Treatment with a basic ionic liquid has also been found to at least partially degum glyceride oil.
  • Treatment of glyceride oil with basic ionic liquid means that it is possible to use lower temperatures and/or time periods for the deodorization step as part of the overall refining process and less extensive degumming and/or bleaching may be required, if at all. This has the advantage of reducing energy requirements and materials costs associated with the refining process.
  • the present invention provides a process for refining glyceride oil comprising the steps of:
  • ionic liquid comprises a basic anion selected from hydroxide, alkoxide, alkylcarbonate, hydrogen carbonate, carbonate, serinate, prolinate, histidinate, threoninate, valinate, asparaginate, taurinate and lysinate; and a organic quaternary ammonium cation;
  • the glyceride oil does not comprise palm oil.
  • glycosylide oil refers to an oil or fat which comprises triglycerides as the major component thereof.
  • the triglyceride component may be at least 50 wt.% of the glyceride oil.
  • the glyceride oil may also include mono- and/or di-glycerides.
  • the glyceride oil is at least partially obtained from a natural source (for example, a plant, animal or fish/crustacean source) and is also preferably edible.
  • Glyceride oils include vegetable oils, marine oils and animal oils/fats which typically also include phospholipid components in their crude form.
  • Vegetable oils include all plant, nut and seed oils.
  • suitable vegetable oils which may be of use in the present invention include: agai oil, almond oil, beech oil, cashew oil, coconut oil, colza oil, corn oil, cottonseed oil, grapefruit seed oil, grape seed oil, hazelnut oil, hemp oil, lemon oil, macadamia oil, mustard oil, olive oil, orange oil, peanut oil, pecan oil, pine nut oil, pistachio oil, poppyseed oil, rapeseed oil, rice bran oil, safflower oil, sesame oil, soybean oil, sunflower oil, walnut oil and wheat germ oil.
  • vegetable oils are those selected from coconut oil, corn oil, cottonseed oil, groundnut oil, olive oil, rapeseed oil, rice bran oil, safflower oil, soybean oil and sunflower oil.
  • Suitable marine oils include oils derived from the tissues of oily fish or crustaceans (e.g. krill).
  • suitable animal oils/fats include pig fat (lard), duck fat, goose fat, tallow oil, and butter.
  • FFA which may be present in the glyceride oils include monounsaturated, polyunsaturated and saturated FFA.
  • unsaturated FFA include: myristoleic acid, palmitoleic acid, sapienic acid, oleic acid, elaidic acid, vaccenic acid, linoleic acid, linoelaidic acid, a-linolenic acid, arachidonic acid, eicosapentaenoic acid, erucic acid and docosahexaenoic acid.
  • saturated FFA examples include: caprylic acid, capric acid, undecylic acid, lauric acid, tridecylic acid, myristic acid, palmitic acid, margaric acid, stearic acid, nonadecylic acid, arachidic acid, heneicosylic acid, behenic acid, lignoceric acid and cerotic acid.
  • the glyceride oil used in the present invention is a vegetable oil. More preferably, the glyceride oil is a vegetable oil selected from coconut oil, corn oil, cottonseed oil, groundnut oil, olive oil, rapeseed oil, rice bran oil, safflower oil, soybean oil and sunflower oil.
  • palm oil used herein includes oil extracted from the seeds of the soybean (Glycine max).
  • rapeseed oil used herein is synonymous with canola oil and refers to the oil derived from a species of rape plant, for example rapeseed (Brassica napus L.) or field mustard/turnip rape (Brassica rapa subsp. oleifera, syn. B. campestris L).
  • crude glyceride oil is intended to mean glyceride oil which has not undergone refining steps following oil extraction.
  • crude glyceride oil will not have undergone degumming, deacidification, winterisation, bleaching, depigmentation or deodorization.
  • refined used herein in reference to glyceride oil is intended to mean a glyceride oil which has undergone one or more refining steps, such as degumming, deacidification, winterisation, bleaching, depigmentation and/or deodorization.
  • Chloropropanol corresponds to chloropropanols which may, for instance, derive from glycerol and which include monochloropropanol: 2-chloro-1 ,3- propanediol (2-MCPD) and 3-chloro-1 ,2-propanediol (3-MCPD), as well as dichloropropanol: 2,3-dichloropropan-1 -ol (2,3-DCP) and 1 ,3-dichloropropan-2-ol (1 ,3-DCP).
  • Fatty acid esters of chloropropanols referred to herein correspond to the mono- or di-ester form of the chloropropanols formed from esterification with FFA.
  • Glycidol referred to herein corresponds to 2,3-epoxy-1 -propanol.
  • Fatty acid esters of glycidol referred to herein correspond to the ester form of glycidol formed from esterification of glycidol with FFA.
  • ionic liquid refers to a liquid that is capable of being produced by melting a salt, and when so produced consists solely of ions.
  • An ionic liquid may be formed from a homogeneous substance comprising one species of cation and one species of anion, or it can be composed of more than one species of cation and/or more than one species of anion.
  • an ionic liquid may be composed of more than one species of cation and one species of anion.
  • An ionic liquid may further be composed of one species of cation, and one or more species of anion.
  • an ionic liquid may be composed of more than one species of cation and more than one species of anion.
  • ionic liquid includes compounds having both high melting points and compounds having low melting points, e.g. at or below room temperature.
  • many ionic liquids have melting points below 200 °C, preferably below 150 °C, particularly below 100 °C, around room temperature (15 to 30 °C), or even below 0 °C.
  • Ionic liquids having melting points below around 30 °C are commonly referred to as "room temperature ionic liquids".
  • room temperature ionic liquids the structures of the cation and anion prevent the formation of an ordered crystalline structure and therefore the salt is liquid at room temperature.
  • ionic liquid as used herein also includes "non-classical" ionic liquids which exhibit ionic liquid properties but exist stably only in the presence of a solvent or on a support.
  • basic ionic liquids used in accordance with the present invention include quaternary ammonium hydroxide ionic liquids. These ionic liquids are typically considered to be “non-classical” ionic liquids because Hofmann elimination can make them unstable in neat form. Nevertheless, such ionic liquids are known to exist stably when immobilized on a support (see, for instance, Chem. Commun., 2004, 1096-1097) or in the presence of a solvent, for example an aqueous co-solvent.
  • Basic ionic liquids used in accordance with the present invention also include quaternary ammonium bicarbonate ionic liquids. These ionic liquids are also typically considered to be "non-classical" ionic liquids because they may suffer from Hofmann elimination (although to far less extent than hydroxide based ionic liquids) as well as thermal decomposition of the bicarbonate anion to the carbonate form. Nevertheless, such ionic liquids are known to exist stably in the presence of a solvent, for example an aqueous solvent.
  • a liquid may be used which includes the basic ionic liquid together with a solvent, such as an aqueous solvent. Additional co-solvents, such as an alcohol co- solvent, may also be present.
  • a solvent such as an aqueous solvent.
  • co-solvents such as an alcohol co- solvent
  • Ionic liquids are most widely known as solvents, because of their negligible vapour pressure, temperature stability, low flammability and recyclability, which also make them environmentally friendly. Due to the vast number of anion/cation combinations that are available it is possible to fine-tune the physical properties of the ionic liquid (e.g. melting point, density, viscosity, and miscibility with water or organic solvents) to suit the requirements of a particular application.
  • an "ionic compound comprising the organic quaternary ammonium cation" it is intended to refer to an ionic compound which derives from the basic ionic liquid which is used for contacting the glyceride oil, at least by virtue of the organic quaternary ammonium cation.
  • the ionic compound comprising the organic quaternary ammonium cation may also comprise a chloride anion, as would be expected as a result of the basic ionic liquid undergoing anion exchange.
  • the glyceride oil contains FFA and the ionic compound comprising the organic quaternary ammonium cation also comprises an anion of a fatty acid.
  • the ionic compound which is separated from the treated glyceride oil may also be an ionic liquid as defined herein, which is different to the basic ionic liquid which is used for contacting the glyceride oil initially.
  • the ionic compound comprising the organic quaternary ammonium cation comprises the same anion as the ionic liquid used for contacting the glyceride oil initially, in other words the ionic compound separated from the treated glyceride oil is the same as the ionic liquid used for contacting the glyceride oil initially.
  • the ionic liquids used in the process of the present invention are based on organic quaternary ammonium cations.
  • Organic quaternary ammonium cation used herein is intended to refer to a positively charged ammonium cation wherein the nitrogen atom is bonded only to substituted or unsubstituted Ci to C12 hydrocarbyl groups.
  • hydrocarbyl group refers to a univalent or multi-valent radical derived from a hydrocarbon and may include alkyl, cycloalkyi, alkenyl, alkynyl, or aryl groups.
  • the organic quaternary ammonium cation of the basic ionic liquid is selected from:
  • R a , R b , R c and R d are each independently selected from a Ci to Cs, straight chain or branched alkyl group or a C3 to C & cycloalkyi group; or any two of R a , R b , R c and R d combine to form an alkylene chain -(CH 2 ) q - wherein q is from 3 to 6; and wherein said alkyl or cycloalkyi groups may optionally be substituted by one to three groups selected from: Ci to C 4 alkoxy, C2 to Cs alkoxyalkoxy, C3 to C & cycloalkyi, -OH, -SH, -C0 2 (Ci to C 6 )alkyl, and -OC(0)(Ci to C 6 )alkyl, for example by one to three -OH groups.
  • the organic quaternary ammonium cation of the basic ionic liquid is selected from:
  • R a , R b , R c and R d are each independently selected from a Ci to Cs, straight chain or branched alkyl group; and wherein said alkyl group may optionally be substituted by one to three groups selected from: Ci to C 4 alkoxy, C 2 to C 8 alkoxyalkoxy, C 3 to C 6 cycloalkyl, -OH, -SH, -C0 2 (Ci to C 6 )alkyl, and -OC(0)(Ci to Ce)alkyl, for example by one to three -OH groups.
  • organic quaternary ammonium cation is selected from:
  • R a , R b , R c and R d are each independently selected from a Ci to C 4 , straight chain or branched alkyl group, including C-i, C 2 and C 4 alkyl, wherein at least one of R a , R b , R c or R d is substituted by a single -OH group.
  • the organic quaternary ammonium cation is choline:
  • the basic ionic liquids used for the present invention incorporate basic anions selected from hydroxide, alkoxide, alkylcarbonate, hydrogen carbonate, carbonate, serinate, prolinate, histidinate, threoninate, valinate, asparaginate, taurinate and lysinate. These anions are not merely spectator anions selected by virtue of their ability to confer a certain melting point on the resulting ionic liquid.
  • the basicity of the anions forming part of the ionic liquids used in conjunction with the present invention is believed to contribute to their ability to remove chloropropanol and glycidol, or their fatty acid esters, from glyceride oil.
  • basic used herein refers to Bransted bases having the ability to react with (neutralise) acids to form salts.
  • the pH range of bases is from above 7.0 to 14.0 when dissolved or suspended in water.
  • the basic anion is selected from alkylcarbonate, hydrogen carbonate, carbonate, hydroxide and alkoxide; preferably hydrogen carbonate, alkylcarbonate and carbonate; and more preferably hydrogen carbonate.
  • the alkyl group may be linear or branched and may be substituted or unsubstituted. In one preferred embodiment, the alkyl group is unsubstituted. In another preferred embodiment, the alkyl group is unbranched. In a more preferred embodiment, the alkyl group is unsubstituted and unbranched.
  • the alkyl group may comprise from 1 to 10 carbon atoms, preferably from 1 to 8 carbon atoms and more preferably form 1 to 4 carbon atoms.
  • the alkyl group may thus be selected from methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl and/or decyl.
  • branched alkyl groups such as iso-propyl, iso- butyl, sec-butyl and/or tert-butyl may also be used.
  • Especially preferred are methyl, ethyl, propyl and butyl.
  • the alkyl group is selected from methyl and ethyl.
  • the basic anion is selected from serinate, prolinate, histidinate, threoninate, valinate, asparaginate, taurinate and lysinate.
  • the basic anion is selected from serinate, lysinate, prolinate, taurinate and threoninate, more preferably from lysinate, prolinate and serinate, most preferably the basic anion is lysinate.
  • the basic ionic liquid used for contacting the glyceride oil in step (i), as well as the ionic compound comprising the organic quaternary ammonium cation separated in step (ii), should have little or no toxicity and/or be readily and substantially separable from the treated oil.
  • a basic ionic liquid comprising a choline cation is particularly suitable for use with the process of the present invention. Choline is a water soluble essential nutrient grouped with the B- complex vitamins which is a precursor to acetylcholine, involved in numerous physiological functions.
  • Choline has particularly low toxicity and excellent biodegradability, making it a natural ingredient that is capable of forming an ionic liquid which is particularly useful in the process of the present invention.
  • the basic ionic liquid is selected from choline bicarbonate:
  • alkyl group is an alkyl group as described hereinbefore; or choline hydroxide:
  • Basic ionic liquids comprising a basic anion selected from serinate, prolinate, histidinate, threoninate, valinate, asparaginate, taurinate and lysinate are also particularly suitable in the process of the present invention due to the particularly low toxicity of these amino acid derivatives.
  • the basic ionic liquid is choline bicarbonate:
  • the basic ionic liquid used in contacting step (i), as well as the ionic compound comprising the organic quaternary ammonium cation separated in step (ii), preferably have low oil solubility and preferentially partition into a non-oil phase, such as an aqueous phase, facilitating their removal from the treated oil. More preferably, the basic ionic liquid is immiscible with the oil. By immiscible with the oil it is meant that the ionic liquid is soluble in the glyceride oil at a concentration of less than 50 ppm, preferably less than 30 ppm, more preferably less than 20 ppm, most preferably, less than 10 ppm, for example, less than 5 ppm. Thus, the solubility of the basic ionic liquid may be tailored so that the basic ionic liquid is immiscible with the oil.
  • the contacting step (i) of the process of the present invention is carried out at a temperature of less than 80 °C, preferably from 25 to 65 °C, more preferably from 35 to 55 °C, for example, 40 °C.
  • a temperature of less than 80 °C preferably from 25 to 65 °C, more preferably from 35 to 55 °C, for example, 40 °C.
  • the contacting step (i) is carried out at a pressure of from 0.1 MPa absolute to 10 MPa absolute (1 bar absolute to 100 bar absolute).
  • the contacting step may be carried out by contacting glyceride oil with the basic ionic liquid in a vessel wherein the resulting mixture is stirred using, for example, a mechanical stirrer, an ultrasonic stirrer, an electromagnetic stirrer or by bubbling an inert gas through the mixture.
  • the basic ionic liquid and the glyceride oil may be contacted in a volume ratio of from greater than 1 :40 to 1 :300, and may be contacted in a mass ratio of from 1 :50, preferably from 1 : 100.
  • the contacting step may last from 1 minute to 60 minutes, preferably 2 to 30 minutes, more preferably, 5 to 20 minutes and most preferably, 8 to 15 minutes.
  • the basic ionic liquid is contacted with the glyceride oil.
  • the basic ionic liquid may added in neat form or as part of a liquid additionally comprising a solvent or mixture of solvents which is/are compatible with the basic ionic liquid and the glyceride oil.
  • a solvent or mixture of solvents may be used to modify the viscosity of the basic ionic liquid as desired.
  • use of a solvent may confer desirable properties on the liquid structure of the liquid based reaction that are particularly suitable for promoting the reaction of the basic ionic liquid.
  • Suitable solvents for this purpose include polar solvents, such as water, or alcohol, for example methanol or ethanol.
  • the glyceride oil is contacted with a liquid comprising the basic ionic liquid and a solvent, wherein the concentration of basic ionic liquid in the liquid is from 15 wt.% to 90 wt.%.
  • the solvent is an aqueous solvent, such as deionised water.
  • the glyceride oil is contacted with a liquid comprising the basic ionic liquid and a solvent, such as an aqueous solvent, and the concentration of basic ionic liquid in the liquid is 50 wt.% to 90 wt.%, for example from 75 wt.% to 85 wt.%.
  • the glyceride oil is contacted with a liquid comprising the basic ionic liquid and a solvent, such as an aqueous solvent, wherein the concentration of basic ionic liquid in the liquid is 15 wt.% to 60 wt.%, preferably from 40 wt.% to 50 wt.%.
  • additional co-solvents may also be present.
  • alcohol co-solvent(s) may also be present, for example, at between 1 wt.% and 20 wt.% of the liquid comprising the basic ionic liquid and aqueous solvent.
  • Separation of the ionic compound comprising the organic quaternary ammonium cation in step (ii) of the process may be carried out by gravity separation (for example, in a settling unit), where the treated glyceride oil is generally the upper phase and the ionic compound comprising the organic quaternary ammonium cation together with any solvent are incorporated in the lower phase in the settling unit.
  • Separation of the ionic compound comprising the organic quaternary ammonium cation may also be achieved using, for example, a decanter, a hydrocyclone, electrostatic coalesce, a centrifuge or a membrane filter press.
  • the phases are separated using a centrifuge. Contacting and separation steps may be repeated several times, for example 2 to 4 times.
  • the ionic compound comprising the organic quaternary ammonium cation separated in step (ii) is a solid which is precipitated after contacting step (i), for instance, following formation of a quaternary ammonium-FFA salt
  • the solid ionic compound may be separated from the oil by filtration.
  • a polar solvent as described hereinbefore which is immiscible with the oil phase may be added to solubilise the solid salt, following which the salt-containing phase may be separated from the oil by the methods described above.
  • Contacting and separation steps may also be carried out together in a counter- current reaction column.
  • the glyceride oil (hereinafter “oil feed stream”) is generally introduced at or near the bottom of the counter-current reaction column and the basic ionic liquid (hereinafter “ionic liquid feed stream”) at or near the top of the counter- current reaction column.
  • a treated oil phase (hereinafter “product oil stream”) is withdrawn from the top of the column and a phase containing an ionic compound comprising the organic quaternary ammonium cation and solvent when present (hereinafter “secondary stream”) from at or near the bottom thereof.
  • the counter-current reaction column has a sump region for collecting the secondary stream.
  • the oil feed stream is introduced to the counter-current reaction column immediately above the sump region.
  • More than one counter-current reaction column may be employed, for example 2 to 6, preferably 2 to 3 columns arranged in series.
  • the counter-current reaction column is packed with a structured packing material, for example, glass Raschig rings, thereby increasing the flow path for the oil and basic ionic liquid through the column.
  • the counter- current reaction column may contain a plurality of trays.
  • contacting and separating steps are carried out together in a centrifugal contact separator, for example, a centrifugal contact separator as described in US 4,959, 158, US 5,571 ,070, US 5,591 ,340, US 5,762,800, WO 99/12650, and WO 00/29120.
  • Suitable centrifugal contact separators include those supplied by Costner Industries Nevada, Inc.
  • Glyceride oil and the liquid comprising the ionic liquid may be introduced into an annular mixing zone of the centrifugal contact separator.
  • the glyceride oil and the basic ionic liquid are introduced as separate feed streams into the annular mixing zone.
  • the glyceride oil and the basic ionic liquid are rapidly mixed in the annular mixing zone.
  • the resulting mixture is then passed to a separation zone wherein a centrifugal force is applied to the mixture to produce a clean separation of an oil phase and a secondary phase.
  • a plurality of centrifugal contact separators are used in series, preferably, 2 to 6, for example 2 to 3.
  • the oil feed stream is introduced into the first centrifugal contact separator in the series while the basic ionic liquid feed stream is introduced into the last centrifugal contact separator in the series such that oil of progressively decreasing content of, for instance, FFA or free chloride anions is passed from the first through to the last centrifugal contact separator in the series while a basic ionic liquid stream of progressively increasing content of, for instance, quaternary ammonium-FFA salt and/or quaternary ammonium chloride content is passed from the last through to the first centrifugal contact separator in the series.
  • a phase containing an ionic compound comprising the organic quaternary ammonium cation is removed from the first centrifugal contact separator and the treated oil phase is removed from the last centrifugal contact separator in the series.
  • residual basic ionic liquid that is present in the treated glyceride may be recovered by passing the product oil stream through a silica column such that the residual ionic liquid is adsorbed onto the silica column.
  • the adsorbed ionic liquid may then be washed off the silica column using a solvent for the ionic liquid and the ionic liquid may be recovered by driving off the solvent at reduced pressure.
  • the treated glyceride oil may also be passed through a coalescer filter for coalescing fine droplets of non-oil phase liquid, for instance liquid comprising an ionic compound comprising the organic quaternary ammonium cation, so as to produce a continuous phase and facilitate phase separation.
  • a coalescer filter for coalescing fine droplets of non-oil phase liquid, for instance liquid comprising an ionic compound comprising the organic quaternary ammonium cation, so as to produce a continuous phase and facilitate phase separation.
  • the basic ionic liquid used for contact step (i) is used in combination with a solvent
  • the coalescer filter is wetted with the same solvent to improve filtration.
  • the basic ionic liquid may be provided on a support material.
  • Suitable supports for use in the present invention may be selected from silica, alumina, alumina-silica, carbon, activated carbon or a zeolite.
  • the support is silica.
  • the supported form may be provided for contact with the oil as a slurry comprising a suitable solvent, wherein the solvent is as described hereinbefore.
  • contacting and separation steps may also be carried out together by passing the oil through a column packed with the supported ionic liquid (i.e. a packed bed arrangement).
  • a fixed-bed arrangement having a plurality of plates and/or trays may be used.
  • the ionic liquid may be physisorbed or chemisorbed on the support material, and preferably physisorbed.
  • the ionic liquid may be adsorbed onto the support in a basic ionic liquid:support mass ratio of from 10: 1 to 1 : 10, preferably in a basic ionic liquid:support mass ratio of from 1 :2 to 2: 1 .
  • the basic ionic liquid used in accordance with the present invention is capable of preventing or reducing the formation of chloropropanol fatty acid esters and glycidyl fatty acid esters in glyceride oils as a result of subsequent refining steps.
  • reaction mechanisms are believed to be possible as a result of contacting the oil with the basic ionic liquid, which are discussed in further detail below.
  • chloropropanol fatty acid esters and glycidyl fatty acid esters has been found to depend predominantly on: (i) the mono- and di-glyceride content of the glyceride oil; (ii) the chloride content of the glyceride oil; (iii) the proton activity of the glyceride oil; and (iv) the extent of heat exposure during refining.
  • Treatment of glyceride oil with the basic ionic liquid in accordance with the present invention has been found not to affect the mono- and di-glyceride content of the oil and thus it is believed that it is the chloride content and proton activity that are reduced, thereby leading to the prevention or reduction of chloropropanol fatty acid ester and glycidyl fatty acid ester formation during the refining process.
  • anion exchange with free chloride ions is considered to be a means by which the free chloride content of the oil may be reduced.
  • the basicity of the basic ionic liquid may also modify the proton activity of the oil such that glycidyl fatty acid ester formation is also reduced.
  • the ionic liquid used in accordance with the present invention has also been found to neutralise FFA present in the oil and form an ionic compound comprising the organic quaternary ammonium cation of the basic ionic liquid used in contact step (i) and the carboxylate anion of FFA.
  • the product of the acid-base reaction between the basic ionic liquid and FFA in the oil may also complex chloride anions and/or chlorine-containing compounds and contribute to their removal from the oil upon separating the quaternary ammonium-FFA salt from the treated oil.
  • the ionic compound comprising the organic quaternary ammonium cation separated in step (ii) of the process may comprise a chloride anion.
  • the ionic compound comprising the organic quaternary ammonium cation which is separated in step (ii) may comprise an anion of a fatty acid.
  • the process of the invention is used to prevent or reduce the formation of chloropropanol fatty acid esters in glyceride oil. More preferably, the process of the invention is used to prevent or reduce the formation of monochloropropanol fatty acid esters in glyceride oil. Most preferably, the process of the invention is used to prevent or reduce the formation of 3-MCPD fatty acid ester in glyceride oil.
  • At least one further refining step is conducted after treatment of the glyceride oil with the basic ionic liquid.
  • the skilled person is aware of the different refining steps typically used in edible oil processing, including for example refining steps discussed in: “Practical Guide to Vegetable Oil Processing", 2008, Monoj K. Gupta, AOCS Press, as well as in the Edible Oil Processing section of the "AOCS Lipid Library” website (lipid!ibrar . aocs.org).
  • the at least one further refining step (iii) may, for instance, be selected from: degumming, bleaching, winterization, depigmentation and deodorisation. Since the heat exposure typically associated with the deodorisation step is known to be responsible for a large increase in the formation of chloropropanol fatty acid esters and glycidol fatty acid esters, the basic ionic liquid treatment preferably precedes deodorisation. Thus, in preferred embodiments, the at least one further refining step according to the process of the present invention comprises deodorisation. In some embodiments, the at least one further refining step (iii) comprises the steps of degumming, bleaching and deodorization.
  • the at least one further refining step (iii) comprises a deodorisation step and the process does not comprise a step of degumming and/or bleaching. Therefore, in exemplary embodiments, the at least one further refining step comprises the steps of degumming and deodorization, but no bleaching. In other exemplary embodiments, the at least one further refining step comprises the steps of bleaching and deodorization, but no degumming step.
  • An additional advantage of the treatment with basic ionic liquid in accordance with the present invention is that the basic ionic liquid has also been found to at least partially remove pigments and odiferous compounds which are typically removed in a high temperature (for example, 240 °C to 270 °C) deodorization step during conventional refining processes.
  • Treatment of glyceride oil with the basic ionic liquid means that lower temperatures and/or time periods can be used for the deodorization step as part of the overall refining process. This has the advantage of reducing the energy requirements of the refining process.
  • Degumming typically involves contacting the oil with aqueous phosphoric acid and/or aqueous citric acid to remove both hydratable and non-hydratable phosphatides (NHP).
  • aqueous phosphoric acid and/or aqueous citric acid is added as a 50 wt% aqueous solution.
  • the aqueous acid is used in an amount of about 0.02 % to about 0.20 % of acid by weight of oil, preferably 0.05 % to about 0.10 % of acid by weight of oil.
  • the degumming step is carried out at a temperature of from about 50 to 1 10 °C, preferably 80 °C to 100 °C, for example 90 °C.
  • the degumming step may suitably last from 5 minutes to 60 minutes, preferably 15 to 45 minutes, more preferably, 20 to 40 minutes, for example 30 minutes.
  • the aqueous phase is separated before the degummed oil is typically dried. Drying of the degummed oil suitably takes place at a temperature of from 80 to 1 10 °C for a suitable time period, for example 20 to 40 min, at reduced pressure, for instance, at 2 to 3 kPa (20 to 30 mbar).
  • glyceride oils with low phosphatide content for example, less than 20 ppm by weight of phosphorus
  • a dry degumming process may be used in which the phosphoric acid or citric acid is added without significant dilution with water (for example, an 85 % acid solution).
  • NHP are converted into phosphatidic acid and a calcium or magnesium bi-phosphate salt which can be removed from the oil in a subsequent bleaching step.
  • dry degumming is known to be less well suited since excessive amounts of bleaching earth are required.
  • Bleaching is incorporated into an edible oil refining process to reduce colour bodies, including chlorophyll, residual soap and gums, trace metals and oxidation products.
  • Bleaching typically involves contacting the oil with an amount of bleaching clay or earth, for example from 0.5 to 5 wt.% clay based on the mass of the oil.
  • Bleaching clays or earths are typically composed of one or more of three types of clay minerals: calcium montmorillonite, attapulgite, and sepiolite. Any suitable bleaching clay or earth may be used in accordance with the present invention, including neutral and acid activated clays (e.g. bentonite).
  • the oil is suitably contacted with bleaching clay for 15 to 45 minutes, preferably 20 to 40 minutes before the earth is separated, typically be filtratio.
  • the oil is typically contacted with bleaching clay or earth at a temperature of from 80 °C to 125 ° C, preferably at a temperature of from 90 ° C to 1 10 ° C.
  • a second stage of the bleaching process is conducted under reduced pressure (“dry bleaching"), for example at 2 to 3 kPa (20 to 30 mbar).
  • Conventional glyceride oil refining processes typically include a FFA neutralisation step with a strong base, for example sodium hydroxide or potassium hydroxide (corresponding to a so called “chemical refining” process).
  • a strong base for example sodium hydroxide or potassium hydroxide
  • deacidification can be achieved by adjusting the deodorisation parameters accordingly to ensure that volatile FFA is removed in that step (a so called “physical refining” process).
  • a disadvantage of a FFA neutralisation step (“chemical refining”) is that it is accompanied by unwanted saponification, lowering triglyeride content, whilst soap formation can lead to substantial neutral oil losses as a result of emulsification.
  • the basic ionic liquid treatment forming part of the refining process of the present invention is effective at neutralising FFA in the oil and may entirely replace a conventional neutralisation step used in a chemical refining process.
  • treatment with the basic ionic liquid has the benefit that it does not lead to saponification of neutral oil.
  • the refining process does not include a neutralisation step with an inorganic base (e.g. sodium hydroxide).
  • FFA present in the oil may be neutralised upon contact with the basic ionic liquid to form a quaternary ammonium-FFA salt.
  • the amount of basic ionic liquid employed in the contacting step is at least stoichiometric with the molar amount of FFA contained in the oil.
  • the molar ratio of the basic ionic liquid to FFA in the oil may be from 1 : 1 to 10 : 1 , or from 1.5 : 1 to 5 : 1 .
  • the content of FFA in the glyceride oil may be determined prior to treatment with basic ionic liquid using common titration techniques, of which the person of skill in the art is aware.
  • the organic quaternary ammonium cation is selected to provide low melting fatty acid salts with linear C12 to C18 FFAs.
  • Particularly preferred organic quaternary ammonium cations form salts with such FFAs having melting points of less than 100 °C.
  • Such salts may be conveniently separated during separation step (ii) by liquid-liquid separation techniques discussed herein.
  • deodorization corresponds to a stripping process in which an amount of stripping agent is passed through an oil in a distillation apparatus, typically by means of direct injection, at reduced pressure for a period of time so as to vaporize and extract volatile components, such as FFA, aldehydes, ketones, alcohols, hydrocarbons, tocopherols, sterols, and phytosterols.
  • the stripping agent is preferably steam, although other agents such as nitrogen may be used.
  • the amount of stripping agent suitably used is from about 0.5 % to about 5 % by weight of oil.
  • the temperature range of deodorization for the refining process according to the present invention is suitably from 160 °C to 270 °C. Where reference is made herein to the temperature of the deodorization step, this refers to the temperature the oil is heated to before being exposed to the stripping agent.
  • the pressure range of deodorization is suitably from 0.1 to 0.4 kPa (1 to 4 mbar), preferably 0.2-0.3 kPa (2 to 3 mbar). Suitable time periods for deodorization are typically from 30 to 180 minutes, for example 60 to 120 minutes, or 60 to 90 minutes.
  • the skilled person is able to determine a suitable length of deodorization by analysing the appearance and composition of the glyceride oil. For instance, determining the p-anisidine value (AnV) of the oil.
  • the p-anisidine value of an oil is a measure of its oxidative state and, more specifically, provides information regarding the level of secondary oxidation products contained in an oil, although primarily aldehydes such as 2-alkenals and 2,4-dienals.
  • the p-anisidine value (AnV) therefore also gives an indication of the level of oxidation products which are intended to be removed by means of the deodorization step.
  • the AnV is less than 10, preferably less than 5, as determined by AOCS Official Method Cd 18-90.
  • the amount of aldehyde and ketone components of the oil can be determined, which are typically associated with a crude oil's odour, to determine whether sufficient deodorization has taken place.
  • Typical volatile odiferous aldehyde and ketone components of crude or rancid palm oil include: acetaldehyde, benzaldehyde, n-propanal, n-butanal, n-pentanal, n-hexanal, n-octanal, n-nananal, 2- butenal, 3-methylbutanal, 2-methylbutanal, 2-pentenal, 2-hexenal, 2E,4E-decadienal, 2E,4Z-decadienal, 2-butanone, 2-pentanone, 4-methyl-2-pentanone, 2-heptanone, 2- nonanone.
  • each of these components is individually present in a deodorized oil in an amount less than 3 mg/kg of oil, more preferably less than 1 mg/kg of oil, most preferably less than 0.5 mg/kg of oil.
  • the amount of aldehydes and ketones may be readily determined by chromatographic methods, for instance GC-TOFMS or GCxGC-TOFMS.
  • derivatization of aldehydes and ketones may be used to improve chromatographic analysis.
  • aldehydes and ketones may be derivatized with 2,4-dinitrophenylhydrazine (DNPH) under acidic conditions.
  • DNPH 2,4-dinitrophenylhydrazine
  • HPLC-UV analysis can quantify the total amount of aldehydes and ketones which are present in a sample.
  • Conventional deodorisation temperatures are typically in excess of 220 °C, for example 240 °C to 270 °C, and typically operated for 60 to 90 minutes. Where lower than conventional temperatures are used for deodorisation as allowed by the process of the present invention, for example 160 °C to 200 °C, the time periods for deodorization may be lengthened to ensure sufficient deodorization, yet still involve less energy consumption than a conventional deodorization operated at higher temperature, for example 240 °C to 270 °C, for a shorter period. In preferred embodiments, the same or lower than conventional deodorization time periods are used in combination with the lower than conventional deodorization temperature, yet achieve the same extent of deodorization as a result of the preceding basic ionic liquid treatment.
  • the time period for the deodorization may be reduced compared to that which is conventionally used and still achieve a comparable level of deodorization as a result of the preceding the basic ionic liquid treatment.
  • the basic ionic liquid treatment therefore also has the advantage that it may reduce energy consumption during a subsequent deodorization step.
  • by reducing either the temperature or time period of exposure to heat during the deodorization step then side reactions that can lead to undesirable organoleptic properties of the oil, or formation of unwanted, potentially harmful by-products, may also advantageously be reduced.
  • the temperature of the deodorization is from 160 °C to 200 °C, more preferably 170 °C to 190 °C.
  • the time periods over which deodorization is conducted at these temperatures is from 30 to 150 minutes, more preferably 45 to 120 minutes, most preferably 60 to 90 minutes.
  • the basic ionic liquid treatment according to the process of the present invention may suitably be applied to crude glyceride oil which has not undergone any previous refining steps following oil extraction.
  • the process of the present invention may be applied to glyceride oil which has undergone at least one additional refining step prior to treatment with basic ionic liquid.
  • the at least one additional refining step is selected from bleaching and/or degumming.
  • degumming typically involves the addition of citric acid and/or phosphoric acid to remove phospholipids in the oil. It is possible that this step can negatively impact on the proton activity of the oil so as to increase the formation of glycidyl fatty acid esters on exposure to heat.
  • bleaching clay or earth which has been acid activated can be a source of contaminants such as chloride anions, for instance where hydrochloric acid has been used for acid activation. Such acid activated bleaching earth or clay can also modify the proton activity and potentially increase formation of glycidyl fatty acid ester formation on subsequent exposure to heat.
  • degumming precedes the basic ionic liquid treatment since this provides for the proton activity of the oil to be modified by the basic ionic liquid after exposure of the glyceride oil to acid.
  • bleaching particularly where a material comprising a source of chloride anions is used, precedes the basic ionic liquid treatment since this provides the opportunity for such contaminants to be removed by the basic ionic liquid treatment.
  • the basic ionic liquid treatment forming part of the process of the present invention is also capable of at least partially degumming the oil and removing pigments which means that the extent of degumming and bleaching steps can be scaled back, for example, in terms of treatment time or materials.
  • the basic ionic liquid treatment forming part of the process of the present invention obviates a separate FFA neutralisation step used in a chemical refining process.
  • the basic ionic liquid treatment forming part of the process of the present invention may also be capable of reducing energy consumption in a deodorization step.
  • the basic ionic liquid treatment used in accordance with the present invention is intended to obviate the use of ion exchange resins and ultrafiltration membranes and the like for removing contaminants which can contribute significantly to the materials costs associated with glyceride oil refining.
  • the refining processes described herein do not comprise treatment of the glyceride oil with ion exchange resins or ultrafiltration membranes.
  • the basic ionic liquid used in contact step (i) may be regenerated from the ionic compound comprising the organic quaternary ammonium cation separated in step (ii) (where these salts are different) by means of a regeneration process in order to recycle the basic ionic liquid to the refining process of the invention, if desired.
  • a regeneration process may comprise anion or cation exchange steps to obtain a basic ionic liquid comprising the desired basic anion as described hereinbefore.
  • the regeneration process comprises forming a basic ionic liquid which is choline bicarbonate from a choline-FFA salt; comprising the steps of:
  • step (b) obtaining choline bicarbonate from the reaction mixture.
  • step (a) is performed by contacting an aqueous solution comprising the choline-FFA salt with C0 2 (e.g. by bubbling C0 2 through the aqueous solution).
  • step (b) is performed by contacting the mixture of step (a) with a solvent which is miscible with choline bicarbonate and separating the solvent from choline bicarbonate.
  • the present invention also provides a use of a basic ionic liquid as described hereinbefore for preventing or reducing formation of fatty acid esters of chloropropanol and/or glycidol in glyceride oil during a heating step by contacting the oil with the basic ionic liquid prior to the heating step.
  • the heating step may, for instance, correspond to heating the oil to temperatures in excess of, for example, 150 °C, 200 °C or even 250 °C, where substantial formation of fatty acid esters of chloropropanol and/or glycidol in glyceride oil would normally be expected.
  • the heating step may therefore form part of a deodorization step.
  • the basic ionic liquid is used to prevent or reduce the formation of chloropropanol fatty acid esters in the glyceride oil. More preferably, the basic ionic liquid is used to prevent or reduce formation of monochloropropanol fatty acid esters. Most preferably, the ionic liquid is used to prevent or reduce the formation of 3- MCPD fatty acid ester in the glyceride oil.
  • the ionic liquid is choline bicarbonate.
  • Embodiments of the invention described hereinbefore may be combined with any other compatible embodiments to form further embodiments of the invention.
  • all aspects of the present invention may be applied to the treatment and refining of palm oil or glyceride oil mixtures comprising palm oil.
  • the present invention also covers processes described herein wherein the glyceride oil comprises or consists of palm oil where the process further comprises a regeneration step as described hereinbefore.
  • V is the volume (ml) of potassium hydroxide solution used
  • N is the normality of the potassium hydroxide solution
  • m is the mass (g) of the glyceride oil sample.
  • the FFA content may be derived.
  • Oil with an FFA of 1 wt.% contains 0.01 g of oleic/palmitic acid per 1 g of oil, which amount of oleic/palmitic acid corresponds to 3.171 x 10 "5 mol (0.01/269).
  • Example 1 Ionic liquid treatment of corn oil
  • Corn oil (10 g) was analysed for its FFA content and doped with stearic acid to give an FFA content of 5 wt.%.
  • the doped oil was sample was heated to 60 °C before 0.363g of a choline bicarbonate solution (80 w/w% in H 2 O supplied by Sigma-Aldrich UK) was added. The mixture was rapidly stirred for 30 minutes before being centrifuged at 4400 rpm for 2 minutes. The upper oil phase was removed and analysed for FFA content. Results are provided in Table 1 below.
  • Example 1 The method of Example 1 was repeated except that an olive oil sample was used in place of corn oil. Results are provided in Table 1 below.
  • Example 1 The method of Example 1 was repeated except that a castor oil sample was used in place of corn oil. Results are provided in Table 1 below.
  • Example 4 Ionic liquid treatment of rapeseed (canola) oil
  • Example 1 The method of Example 1 was repeated except that a rapeseed oil sample was used in place of corn oil. Results are provided in Table 1 below.
  • Example 5 Ionic liquid treatment of cow's milk butter
  • Example 1 The method of Example 1 was repeated except that a butter sample was used in place of corn oil. Results are provided in Table 1 below.
  • the results of Table 1 demonstrate that the basic ionic liquid treatment is capable of removing FFA from a variety of different oils. Furthermore, the results demonstrate that the basic ionic liquid treatment is capable of lowering the proton activity of the oil. This property has been found to be a significant promotor of chloropropanol fatty acid ester and glycidyl fatty acid ester formation in a subsequent deodorization step.
  • Example 6 ionic liquid treatment of cow's milk butter
  • Example 7 ionic liquid treatment of corn oil
  • Example 8 ionic liquid treatment of olive oil
  • Example 6 The method of Example 6 was repeated except that corn oil was used in place of butter and the mixing and contacting with choline bicarbonate was conducted at room temperature. Results are provided in Table 2 below. Table 2
  • Quantitative analysis was carried out using a calibration curve with increasing standard solutions spiked with deuterium-labelled 3-MCPD.
  • the ions m/z 147 (3- MCPD) and m/z 150 (3-MCPD-d 5 ) were the target ions.
  • Ions at m/z 196 (3-MCPD) and m/z 201 (3-MCPD-d 5 ) were the qualifiers.
  • the detection limit of this methodology is 0.15 mg/kg.

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Abstract

La présente invention concerne un procédé amélioré de raffinage de l'huile glycéridique qui incorpore un traitement de liquide ionique basique. En particulier, le traitement de liquide ionique basique empêche ou réduit la formation des esters d'acide gras de chloropropanols et des esters d'acides gras glycidiliques pendant l'ensemble du processus de raffinage. La présente invention concerne également des compositions d'huile glycéridique formées à partir de celle-ci et des utilisations du liquide ionique basique.
PCT/GB2016/051566 2015-05-27 2016-05-27 Procédé de raffinage de l'huile glycéridique comportant un traitement de liquide ionique basique WO2016189333A1 (fr)

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GB201509084D0 (en) 2015-07-08
AR104799A1 (es) 2017-08-16

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