CN108026476A - The method of refining of glyceride oil including alkali ionic liquid processing - Google Patents

The method of refining of glyceride oil including alkali ionic liquid processing Download PDF

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Publication number
CN108026476A
CN108026476A CN201680044212.7A CN201680044212A CN108026476A CN 108026476 A CN108026476 A CN 108026476A CN 201680044212 A CN201680044212 A CN 201680044212A CN 108026476 A CN108026476 A CN 108026476A
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oil
ionic liquid
alkali
glyceride oil
alkali ionic
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Inventor
彼得·古德里奇
泰隆·奥哈拉
马丁·菲利普·阿特金斯
克里斯托弗·克拉特·哈默
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Queens University of Belfast
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Queens University of Belfast
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    • 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

Abstract

The present invention relates to a kind of method of improved glyceride oil refining, it includes being handled with alkali ionic liquid.Especially, alkali ionic liquid processing prevent or reduces the formation of chloropropyl alcohol fatty acid ester and glycidol fatty acid ester in whole refining process.The invention further relates to the glyceride oil composition and the purposes of the alkali ionic liquid formed by this method.

Description

The method of refining of glyceride oil including alkali ionic liquid processing
The present invention relates to a kind of method of improved glyceride oil refining, it includes being handled with alkali ionic liquid.Especially Ground, alkali ionic liquid processing prevent or reduce chloropropyl alcohol fatty acid ester and glycidol aliphatic acid in whole refining process The formation of ester.The invention further relates to the glyceride oil composition and the purposes of the alkali ionic liquid formed by this method.
The crude glycerol ester oil extracted from natural resources is usually subjected to various refining process, wherein unwanted to remove Pollutant, to improve the organoleptic attribute of oil product or the quality requirement needed for other intended applications.Glyceride for people's consumption The refining of oil is more and more examined in recent years, because having determined the property of refining process and even not same culinary art Method may all cause potential carcinogenic or toxic pollutant formation.Have confirmed two class glyceride being harmful to human health Oil contaminants are exactly chloropropyl alcohol and glycidol.
It has been found that the fatty acid ester of chloropropyl alcohol and the fatty acid ester of glycidol are accumulated in glyceride oil, particularly exist In refining process in the refined oil of high temperature.After edible, the fatty acid ester of chloropropyl alcohol and the fatty acid ester of glycidol exist By lipase hydrolysis in intestines and stomach, free chloropropyl alcohol and glycidol are discharged.Non-esterified chloropropyl alcohol can also be present in sweet In grease oil, including glycerine monochlorohydrin (monochloropropandiols), the chloro- 1,3-PDs of 2- (2-MCPD) and 3- chloro- 1,2-PD (3-MCPD), or its corresponding dichlorohydrin (dichloropropanols) form exist, and such as respectively 2,3- Dichloro propyl- 1- alcohol (2,3-DCP) and 1,3- dichloros propan-2-ol (1,3-DCP).3-MCPD is shown to be caused with external genetoxic Cancer acts on, and whole food industry is also to it establishes the daily tolerance intake (TDI) of 2 μ g/Kg.Think to be exposed to 3- in vivo MCPD is probably due to the enzymatic hydrolysis of a variety of different chloropropyl alcohol fatty acid esters in human gastrointestinal tract.
Monoglyceride or diglyceride component in glyceride oil form ring acyl-oxygen ion (cyclic by acid promotion Acyloxonium ion) after, with the fatty acid ester of chlorine open loop generation chloropropyl alcohol.Meanwhile the fatty acid ester of glycidol by with The identical ring acyl-oxygen ion of aliphatic acid of chloropropyl alcohol is formed to be formed, simply ring acyl-oxygen ion therein is by deprotonation To form epoxides.
Although have determined the chloropropyl alcohol of trace and glycidol or their fatty acid ester to be likely to be present in some natural Crude glyceride oil in, but now it has been recognized that refining process has formed notable contribution to it.Particularly, glycerine The heat exposure (it is usually necessary to use the steam stripping higher than 220 DEG C) of the deodorising process of ester oil has been observed that it is chlorine in glyceride oil The main reason for propyl alcohol/glycidol fatty acid ester formation, in addition bleaching and degumming step are also found to contribute this.It is hot sudden and violent Dew promotes the formation of glycidol fatty acid ester, while can also cause the thermal decomposition of organic chlorine-containing compound, this is chlorine third again The formation of alcohol provides required chloride sources.
The refining of the rough glyceride oil containing lipid generally includes degumming, bleaching and deodorising process, wherein usually can all wrap One is included with the depickling step carried out in highly basic and/or in the form of extending and be deodorized to remove any free fatty in oil removing (FFA).The typical mode of scouring processes is the aqueous solution (citric acid and/or phosphoric acid) of addition acid, and scouring processes can also remove Other components in glyceride oil, such as metal ion, can also remove lipid components at the same time.Meanwhile carried out with bleaching earth Bleaching process not only reduces the amount of pigment, also absorbs the other compositions in oil, so as to improve organoleptic attribute.
The processing of polar solvent has been carried out to glyceride oil in history.Polar solvent processing is as liquid-liquid extraction A part be used for according to the saturation degree or chain length of glyceride separate glyceride, and from triglycerides separate monoglyceride, Diglyceride, FFA and glycerine.Liquid-liquid extraction, such as alcohol extraction, is also considered as removing the one of polar impurity from glyceride oil Kind means.However, such extraction means may be not enough to remove has lower polarity and lower volatilization than its non-esterified forms The fatty acid ester of chloropropyl alcohol and the fatty acid ester of glycidol of property.The currently known many method of refining in this area, its purpose exist In removing the organochlorine compound of chloropropyl alcohol fatty acid ester is resulted in, or its conversion is prevented by varying process conditions.
In WO2014/012548, a kind of 2-MCPD esters and 3- for reducing and being formed in three ester oil of refined glycerol is disclosed The method of MCPD ester contents, the process employs being blended with alkali, is heat-treated while steam is passed through oil under reduced pressure, and Ester exchange rate is kept to be less than 60%.The advantages of this method, is to employ relatively mild heat treatment, but needs to add into oil Free fatty (FFA) is to suppress ester exchange rate.However, the FFA of addition is considered the organoleptic properties to oil and oil-proofness There is side effect, it is thus possible to need extra processing step to remove the FFA of addition.
In WO2011/005081, disclose one kind and unwanted propyl alcohol is removed from original triglyceride oil Component, including free chloropropyl alcohol, chloropropyl alcohol fatty acid ester, free epoxy prapanol, epoxy prapanol fatty acid ester and combinations thereof Method.This method includes contacting contaminated oil with silicate adsorbent, and silicate adsorbent is selected from magnesium silicate, silicic acid The mixture of calcium, alumina silicate and these silicates.Pending oil is preferably the contaminated triglyceride oil being deodorized.
A kind of method of refining is disclosed in WO2010/063450, its be included in less than 70 DEG C at a temperature of with water to thick Liquefaction carries out degumming, it is not necessary to which acid adding, then carries out wet bleaching and vacuum bleaching in 80-100 DEG C of temperature range.It is reported that The degumming and bleaching carried out by this way reduces 3-MCPD's by removing 3-MCPD and its precursor in whole refining process Formed.
In WO2012/107230, a kind of essence with the 3-MCPD esters reduced and/or glycidol ester content is disclosed The production method of oil refining, it includes making oil undergo following steps successively：(a) blanching step, (b) deodorising step, (c) are finally bleached Step and (d) final deodorising step, wherein final deodorising step (d) at a temperature of than deodorising step (b) low at least 40 DEG C into OK, preferably carried out at a temperature of less than 190 DEG C.
In WO2013/093093, a kind of method that ethylene oxidic ester is removed from vegetable oil is disclosed.This method includes The acid-activated bleaching clay that oil is at least 0.5 oily weight % with weight is contacted, and is deodorized oil at a temperature of less than 200 DEG C At least 30 minutes.But with high-content pigment and in the case of having the oil of taste compound, it is not yet clear that such deodorization is It is no to be adapted to provide for commercially acceptable product.
A kind of method is disclosed in WO2012/169718, discloses one kind by being controlled by means of ion exchange resin For the chlorion included in the water source of refining process, so that the concentration of the 3-MCPD fatty acid esters in table oil be reduced To 0.3ppm or the following method.
In WO2014/042937, a kind of side that glycerine monochlorohydrin and/or glycidol are removed from glycerine is disclosed Method, it includes spent ion exchange resin, is particularly handled with the strong alkali ion exchange resin of OH- form, to reduce a chlorine The content of propane diols.Meanwhile in JP 08-302382, one kind is disclosed by under reduced pressure by fish oil and strong alkalinity anion The method that the mode of exchanger resin contact is deodorized fish oil and decolourizes.
There is still a need for one kind prevents or reduces chloropropyl alcohol fatty acid ester and/or glycidol fatty acid ester shape in glyceride oil Into method, to be capable of providing the product of high value, while save the energy consumption of whole refining process to greatest extent.
The present invention is based on it has surprisingly been found that the alkali ionic liquid comprising alkali anion especially selected can have It is used for the formation for preventing or reducing chloropropyl alcohol fatty acid ester and/or glycidol fatty acid ester in glyceride oil, the processing sharply Can easily it be integrated into overall refining process.
Additionally, it has been found that it can be removed at least in part usually in routine using alkali ionic liquid processing glyceride oil Refining process in single blanching step and high temperature (such as 240 DEG C to 270 DEG C) deodorising step in the pigment that removes and have Taste compound.It has also been found that handle degumming glyceride oil at least in part with alkali ionic liquid.
The deodorising step for the part for being intended as whole refining process with alkali ionic liquid processing glyceride oil can To use relatively low temperature and/or short period, and less comprehensive degumming and/or whitening procedure may be needed.This has The advantages of reducing with the relevant energy requirement of refining process and material cost.
Therefore, in a first aspect, the present invention provides a kind of method of refining of glyceride oil, comprise the following steps：
(i) glyceride oil is contacted to form processed glyceride oil with alkali ionic liquid；Wherein described ionic liquid Body is included selected from hydroxyl, alkoxy radical, alkylcarbonate, bicarbonate radical, carbonate, Ser, proline root, histidine One or more alkali anions in root, threonine root, valine root, aspartate, taurine root and lysine root, And including organic quaternary ammonium cations；
(ii) after glyceride oil is contacted with alkali ionic liquid, by processed glyceride oil and organic quaternary ammonium is included The ionic compound separation of cation；And
(iii) after the separation step, processed glyceride oil is made to carry out at least one further refinement step；
Condition is that glyceride oil does not include palm oil.
Term " glyceride oil " used herein refers to comprising triglycerides as the oily or fatty of its key component.Example Such as, components of triglycerides can be at least 50 weight % of glyceride oil.Glyceride oil further includes monoglyceride and/or glycerine two Ester.Preferably, glyceride oil is at least partly obtained from natural origin (for example, plant, animal or fish/crustacean source), It is and it is also preferable that edible.Glyceride oil includes vegetable oil, marine oil and animal oil/fat, it also typically includes rough The phospholipid fraction of form.
Vegetable oil includes all plants, nut and seed oil.The example bag of suitable vegetable oil for use in the present invention Include：Ah's Sai oil (acai oil), apricot kernel oil, beech-wood tar, cashew nut oil, cocounut oil, rape oil, corn oil, cottonseed oil, grape fruit Seed oil, grape-kernel oil, hazelnut oil, cannabis oil, lemon oil, macadimia nut oil, mustard oil, olive oil, orange oil, peanut oil, English walnut Kernel oil, pine-seed oil, American pistachios oil, poppy seed oil, rapeseed oil, rice bran oil, safflower oil, sesame oil, soybean oil, sunflower oil, core One or more in peach oil and wheat germ oil.Preferably, vegetable oil is selected from cocounut oil, corn oil, cottonseed oil, peanut oil, olive Olive is oily, the one or more in rapeseed oil, rice bran oil, safflower oil, soybean oil and sunflower oil.
Suitable marine oil includes being derived from the oil of the tissue of oily fish or Crustaceans (such as krill).Suitable animal oil/ The example of fat includes pork fat (lard), duck fat fat, goose fat, butter and butter.
The FFA being likely to be present in glyceride oil includes monounsaturated, polynary undersaturated and saturation free-fat Acid.The example of undersaturated free fatty includes：Myristoleic acid, palmitoleic acid, gaidic acid (sapienic Acid), oleic acid, elaidic acid, vaccenic acid, linoleic acid, trans leukotrienes (linoelaidic acid), alpha-linolenic acid, peanut four One or more in olefin(e) acid, eicosapentaenoic acid, erucic acid and docosahexaenoic acid.The free fatty example bag of saturation Include：Octanoic acid, capric acid, undecanoic acid, laurate, tridecanoic acid, myristic acid, palmitic acid, heptadecanoic acid, stearic acid, nonadecylic acid, peanut One or more in acid, heneicosoic acid, behenic acid, tetracosanoic acid and cerinic acid.
Preferably, the glyceride oil for the present invention is vegetable oil.It is highly preferred that glyceride oil is selected from cocounut oil, corn It is one or more in oil, cottonseed oil, peanut oil, olive oil, rapeseed oil, rice bran oil, safflower oil, soybean oil and sunflower oil Vegetable oil.
Terms used herein " soybean oil " includes the oil extracted from the seed of soybean (Glycine max).Make herein Term " palm oil " includes the oil for being at least partly derived from the tree of oil palm category (Elaeis), and the oil palm, which belongs to, forms Palmae category The part of (Arecaceae genera), and including species oil palm (Elaeis guineensis) (African oil palm) and America oil Brown (Elaeis oleifera) (U.S.'s oil palm), or its Hybrid.Therefore palm oil as used herein further includes palm kernel Oil and the palm oil of fractionation, such as palmitic stearin or palm olein cut.Terms used herein " rapeseed oil " and card Nola's oil (canola oil) is synonymous, and refers to the oil from rapeseed plant species, such as rape (Brassica Napus L.) or charlock/turnip type rape (Brassica rapa subsp.oleifera, syn.B campestris L.)。
The term " rough " used herein for being related to glyceride oil is intended to refer to after oil extract not pass through refinement step Glyceride oil.For example, crude glycerol ester oil is without going past degumming, depickling, winterization, bleaching, depigmentation or deodorization.It is used herein " refining " that is related to glyceride oil be intended to refer to experienced one or more refinement steps, such as degumming, depickling, winterization, bleaching, Glyceride oil after depigmentation and/or deodorization.
" chloropropyl alcohol " as referred to herein corresponds to such as chloropropyl alcohol derived from glycerine, it includes a chloropropyl alcohol：2- chloro- 1, Ammediol (2-MCPD) and the chloro- 1,2- propane diols (3-MCPD) of 3- and dichlorohydrin：2,3- dichloro propyl- 1- alcohol (2,3- ) and 1,3- dichloros propan-2-ol (1,3-DCP) DCP.The fatty acid ester of chloropropyl alcohol as referred to herein corresponds to be esterified to be formed with FFA Chloropropyl alcohol single or double ester-formin.
Glycidol mentioned in this article corresponds to 2,3- epoxy -1- propyl alcohol.The fatty acid ester of glycidol corresponds to contracting Water glycerine is esterified the ester-formin for the glycidol to be formed with FFA.
Term " ionic liquid " used herein refers to produce through fused salt, and when such production, Only by from molecular liquid.Ionic liquid can be formed by including a kind of cation and a kind of isotropic body of anion, or Person it can be made of more than one cation and/or more than one anion.Therefore, ionic liquid can be by more than one The cation and a kind of anion of kind are formed.Ionic liquid can be further by a kind of cation and one or more anion Form.Further, ionic liquid can be made of more than one cation and more than one anion.
Term " ionic liquid " includes the compound with dystectic compound and with low melting point, such as fusing point is in Or the compound less than room temperature.Therefore, the fusing point of many ionic liquids is less than 200 DEG C, preferably shorter than 150 DEG C, especially less than 100 DEG C, about room temperature (15 to 30 DEG C), or even lower than 0 DEG C.Ionic liquid of the fusing point below about 30 DEG C is commonly known as " room temperature Ionic liquid ".In ionic liquid at room temperature, the structure of cation and anion prevents the formation of ordered crystal structure, therefore should Salt is liquid at room temperature.
Term " ionic liquid " used herein further includes display ionic liquid character but only in the presence of solvent or is carrying " non-classical " ionic liquid being stabilized on body.For example, alkali ionic liquid used according to the invention further includes hydroxide Quaternary ammonium ion liquid (quaternary ammonium hydroxide ionic liquids).These ionic liquids usually quilt " non-classical " ionic liquid is considered, because hofmann elimination can make them unstable under respective pure form.However, Known such ionic liquid is when being fixed on carrier (for example, see Chem.Commun., 2004,1096-1097) or molten It can be stabilized in the presence of for example water-based cosolvent of agent.Alkali ionic liquid used according to the invention further includes quaternary ammonium carbonic acid Hydrogen salt ionic liquid (quaternary ammonium bicarbonate ionic liquids).These ionic liquids are usual " non-classical " ionic liquid is also considered as, (is based on because they may also undergo hofmann elimination although being far below The degree of the ionic liquid of hydroxide) and bicarbonate anion through being decomposed thermally to form carbonate form.It is well known, however, that this The ionic liquid of sample is stabilized in the presence of solvent such as aqueous solvent.
Therefore, in the case of " non-classical " alkali ionic liquid used according to the invention, can use comprising alkalescence from Liquid of the sub- liquid together with solvent such as aqueous solvent.Extra cosolvent, for example, alcohol cosolvent there may also be.Below more The preferred embodiment that ionic liquid is used with solvent combination is discussed in detail.
Ionic liquid is most widely acknowledged as solvent, due to their insignificant steam pressure, temperature stability, Low flammability and recyclability make it that they are environmental-friendly., can since obtainable substantial amounts of Anionic/Cationic combines Adapted to finely tuning the physical property of ionic liquid (for example, fusing point, density, viscosity and miscible with water or organic solvent) The needs of application-specific.
Due to its favourable property, in the past, ionic liquid is already functioned as various organic compounds and polymerization The solvent of thing synthesis.There are many reports to speculate the not same-action that ionic liquid may play when as solvent.S.- I.Ishiguro et al. (Pure Appl.Chem., Vol.82, No.10, page 1927 to page 1941,2010) reports molten Matter-solvent interaction, or the solvation of solute ions or molecule are considered being used as in the reaction of solvent in ionic liquid The key effect of performance.The important function played the reaction in solution the liquid structure of such solvent carries out especially strong Adjust, in the solution, solvent particles are discharged in reaction, are shifted and are contained in bulk liquids structure afterwards.
S.-I.Ishiguro et al. shows that the liquid structure of ionic liquid is heterogeneous, and different from molecular solvent, it may Bring specific solvent properties, and the specific solute reactivity in ionic liquid.However, they recognize, for example, ionic liquid The soda acid property of body, the unsatisfactory establishment for solution chemistry, particularly compared with normal molecular fluid.Cause This, it is difficult to the effect that prediction may be played in the reaction intermediate ion liquid based on particular solution.
When referenced herein " ionic compound for including organic quaternary ammonium cations ", its be intended to refer to be derived from alkalescence from The ionic compound of sub- liquid, alkali ionic liquid at least are used to contact glyceride oil by organic quaternary ammonium cations.One In a little embodiments, the ionic compound comprising organic quaternary ammonium cations can also include cl anion, as alkali ionic liquid Carry out as desired by anion exchange.In other embodiments, glyceride oil includes FFA, and includes organic quaternary ammonium sun The ionic compound of ion also includes the anion of aliphatic acid.Separated ionic compound also may be used from processed glyceride oil To be ionic liquid as herein defined, it is different from being used for the alkali ionic liquid for initially contacting glyceride oil.Into one In the embodiment of step, the ionic compound comprising organic quaternary ammonium cations includes and the ionic liquid for initially contacting glyceride oil The identical anion of body, in other words, glycerine is initially contacted from the separated ionic compound of processed glyceride oil with being used for The ionic liquid of ester oil is identical.
Organic quaternary ammonium cations are based on for the ionic liquid in the method for the present invention.Used herein of " organic quaternary ammonium sun from Son " refers to the ammonium cation of positively charged, wherein nitrogen-atoms and substituted or unsubstituted C1To C12Alkyl is bonded.Term " alkyl " Refer to monovalence or multivalence group derived from hydrocarbon, and alkyl, cycloalkyl, alkenyl, alkynyl or aryl can be included.
Preferably, the organic quaternary ammonium cations of alkali ionic liquid are selected from：
[N(Ra)(Rb)(Rc)(Rd)]+,
Wherein, Ra、Rb、RcAnd RdIt is each independently selected from C1To C8Straight or branched alkyl or C3To C6Cycloalkyl, Or Ra、Rb、RcAnd RdIn any two combine to form alkylidene chain-(CH2)q-, wherein q is from 3 to 6；It is and wherein described Alkyl or cycloalkyl can optionally be substituted by one to three group selected from the following：C1To C4Alkoxy, C2To C8Alkoxy Alkoxy (alkoxyalkoxy), C3To C6Cycloalkyl ,-OH ,-SH ,-CO2(C1To C6) alkyl ,-OC (O) (C1To C6) alkyl, Such as substituted by one to three-OH base.
It is highly preferred that the organic quaternary ammonium cations of alkali ionic liquid are selected from：
[N(Ra)(Rb)(Rc)(Rd)]+,
Wherein, Ra、Rb、RcAnd RdIt is each independently selected from C1To C8Straight or branched alkyl, and wherein described alkyl Optionally substituted by one to three group selected from the following：C1To C4Alkoxy, C2To C8Alkyloxy-alkoxy, C3Extremely C6Cycloalkyl ,-OH ,-SH ,-CO2(C1To C6) alkyl ,-OC (O) (C1To C6) alkyl, such as substituted by one to three-OH base.
It is further preferred that organic quaternary ammonium cations are selected from：
[N(Ra)(Rb)(Rc)(Rd)]+,
Wherein, Ra、Rb、RcAnd RdIt is each independently selected from C1To C4Straight or branched alkyl, including C1、C2And C4Alkyl, Wherein Ra、Rb、RcAnd RdIn at least one substituted by single-OH groups.
Most preferably, organic quaternary ammonium cations are choline：
Alkali ionic liquid for the present invention has selected from hydroxyl, alkoxy radical, alkylcarbonate, bicarbonate radical, carbon Acid group, Ser, proline root, histidine root, threonine root, valine root, aspartate, taurine root and lysine One or more alkali anions in root.These anion are not only to obtain ionic liquid since they are assigned The ability of one fusing point and select look on (spectator) anion.Form the portion for the ionic liquid being used in combination with the present invention The basicity of the anion divided, is considered promoting them to remove chloropropyl alcohol, glycidol and their fat from glyceride oil One or more abilities in acid esters.Term " alkaline " used herein refers to have with acid reaction (neutralization) with forming salt Ability BronstedAlkali.When dissolving or suspending in water, the pH scopes of alkali be higher than 7.0 to 14.0。
In an embodiment of the invention, alkali anion is selected from alkylcarbonate, bicarbonate radical, carbonate, hydrogen One or more in oxygen root and alkoxy radical；The one kind or more being preferably chosen from bicarbonate radical, alkylcarbonate and carbonate Kind；It is more preferably selected from bicarbonate radical.
In the case where alkali anion is selected from alkoxy radical or alkylcarbonate, its alkyl can be straight or branched , and can be substitution or unsubstituted.In one preferred embodiment, alkyl is unsubstituted.Another In a preferred embodiment, alkyl is non-branched.In a preferred embodiment, alkyl be it is unsubstituted and Non-branched.
Alkyl can include 1 to 10 carbon atom, preferably 1 to 8 carbon atom, and more preferably 1 to 4 carbon atom.Alkane Base this can be selected from the one or more in methyl, ethyl, propyl group, butyl, amyl group, hexyl, heptyl, octyl group, nonyl and decyl. It will be understood that branched alkyl can also be used, such as one kind or more in i-propyl, iso-butyl, sec-butyl and tert-butyl Kind.The one or more in methyl, ethyl, propyl group and butyl are particularly preferred.In a preferred embodiment, alkyl Selected from one or both of methyl and ethyl.
In an embodiment of the invention, alkali anion is selected from Ser, proline root, histidine root, Soviet Union One or more in propylhomoserin root, valine root, aspartate, taurine root and lysine root.
In one preferred embodiment of the invention, alkali anion is selected from Ser, lysine root, proline One or more in root, taurine root and threonine root, are more preferably selected from lysine root, proline root and Ser One or more, most preferably, alkali anion is lysine root.
It will be appreciated that in order to make the glyceride oil that the method from the present invention directly obtains be suitable for consumption, used in step (i) In contact glyceride oil alkali ionic liquid and included in step (ii) separated organic quaternary ammonium cations ionization Compound, it should have very little or no toxicity and/or easily substantially separated with processed oil.Comprising choline sun from Method of the alkali ionic liquid of son especially suitable for the present invention.Choline is a kind of water-soluble essential nutrients, it, which is classified as, is Participate in the vitamin B compound (B-complex vitamin) of the precursor of the acetylcholine of many physiological functions.Choline has special Low toxicity and fabulous biological degradability so that it becomes the day that can be formed especially suitable for the method for the present invention ionic liquid Right component.
Therefore, in particularly preferred embodiment of the invention, alkali ionic liquid is selected from Choline Bicarbonate (choline bicarbonate)：
Or selected from alkylcarbonic acid choline (choline alkylcarbonate)：
Alkyl wherein described here is alkyl as described above；
Or selected from bursine (choline hydroxide)：
Comprising selected from Ser, proline root, histidine root, threonine root, valine root, aspartate, ox sulphur The alkali ionic liquid of one or more alkali anions in acid group and lysine root is also especially suitable for the side of the present invention Method, because the toxicity of these amino acid derivativges is especially low.
In very particularly preferred embodiment of the invention, alkali ionic liquid is Choline Bicarbonate：
The alkali ionic liquid that contact procedure (i) uses and included in step (ii) separated organic quaternary ammonium sun from The ionic compound of son preferably has relatively low oil-soluble, and is preferably assigned in non-oil phase such as water phase, so as to promote them Removed from processed oil.It is highly preferred that alkali ionic liquid is unmixing with oil.It is not miscible with oil, it is meant that alkali ion Liquid is with less than 50ppm, preferably smaller than 30ppm, more preferably less than 20ppm, more preferably less than 10ppm, for example, being less than 5ppm Concentration be dissolved in glyceride oil.Therefore, the solubility of alkali ionic liquid is adjusted, so that alkali ionic liquid is not mixed with oil It is molten.
Suitably, the contact procedure (i) of the method for the present invention carries out at a temperature of less than 80 DEG C, preferably 25-65 DEG C, more preferably 35-55 DEG C, such as 40 DEG C.As it will be appreciated, in the case of glyceride oil is semisolid at room temperature, higher temperature is preferred So that glyceride oil is contacted with alkali ionic liquid in liquid form.Suitably, contact procedure (i) is in 0.1MPa absolute pressures Carried out under power (absolute) to 10MPa absolute pressures (1 bar of absolute pressure to 100 bars of absolute pressures).
In some embodiments, contact procedure can be by making glyceride oil be contacted in a reservoir with alkali ionic liquid To carry out, in the above-described container, such as mechanical agitator, ultrasonic stirrer, magnetic stirrer or by by indifferent gas are used Body bubbling is by mixture come the mixture that stirs.
Suitably, alkali ionic liquid and glyceride oil can be with more than 1:40 to 1:300 volume ratio contact, and can With with 1:50, it is preferably 1:100 mass ratio contact.Contact procedure can continue 1 minute to 60 minutes, preferably 2 to 30 minutes, It is further preferred that 5 to 20 minutes, most preferably 8 to 15 minutes.
In contact procedure (i), alkali ionic liquid is contacted with glyceride oil.Alkali ionic liquid can be in pure form Or added as a part for solution, the solution additionally comprises the solvent compatible with alkali ionic liquid and glyceride oil or molten Agent composition.The viscosity of alkali ionic liquid can to change as needed using solvent or solvent mixture.Alternatively, solvent Use can assign the desirable characteristic of liquid structure of the solution based on reaction, it is especially suitable for promoting alkali ion liquid The reaction of body.Suitable solvent for this purpose includes polar solvent, such as water or alcohol, such as methanol or ethanol.
In some embodiments, glyceride oil is contacted with the solution comprising alkali ionic liquid and solvent, wherein solution The concentration of neutral and alkali ionic liquid is 15 weight % to 90 weight %.In the exemplary embodiment, solvent is aqueous solvent, such as Deionized water.
In a preferred embodiment, when the alkali anion of alkali ionic liquid is selected from alkylcarbonate, bicarbonate radical With the one or more in carbonate, particularly when alkali anion is bicarbonate radical, glyceride oil is with including alkali ion The solution of liquid and solvent such as aqueous solvent contacts, and the concentration of solution neutral and alkali ionic liquid is 50 weight % to 90 weights Measure %, such as 75 weight % to 85 weight %.
In a preferred embodiment, when alkali ionic liquid alkali anion in hydroxyl and alkoxy radical one Kind or two kinds, particularly when alkali anion be hydroxyl, glyceride oil with include alkali ionic liquid and solvent such as water The solution contact of solvent, wherein the concentration of solution neutral and alkali ionic liquid is 15 weight % to 60 weight %, preferably 40 weight % To 50 weight %.
In the above-described embodiment, alkali ionic liquid is the part in the mixture being mixed to form with solvent, may be used also With there are extra cosolvent.For example, in the case of using aqueous solvent, there may also be for example, content can be alcohol cosolvent 1 weight % of the liquid comprising alkali ionic liquid and aqueous solvent to 20 weight %.
The ionic compound of separation comprising organic quaternary ammonium cations can pass through gravity point in (ii) this method the step of Carried out from (such as in settler), wherein processed glyceride oil is usually in the phase of upper strata, and include organic quaternary ammonium sun The ionic compound of ion is incorporated into lower floor's phase in settler together with any solvent.Include organic quaternary ammonium cations The separation of ionic compound can also be by using such as decanter, hydrocyclone, electrostatic coagulation, centrifuge or film press filtration Machine is realized.Preferably, phase is separated using centrifuge.Contact procedure and separating step can be repeated several times, such as 2 to 4 times.
After the ionic compound of the separated organic quaternary ammonium cations included in step (ii) is in contact procedure (i) When precipitating the solid formed, for example, after quaternary ammonium salt-FFA salt is formed, solid ion compound can be divided by filtering from oil From.Alternatively, polar solvent unmixing with oil phase as described above can be added with dissolved solid salt, can then pass through above-mentioned side Method separates saliferous phase with oil.
The step that is contacting and separating can also be carried out together in countercurrent reaction tower.Usually by glyceride oil (hereinafter referred to as " oil Feeding flow ") introduced near the bottom of countercurrent reaction tower or bottom, and alkali ionic liquid (is hereinafter referred to as " ionic liquid Body feeding flow ") introduced in countercurrent reaction top of tower or near top.(hereinafter referred to as " the production of processed oil phase is withdrawn from top of tower Thing oil stream "), and withdrawn near bottom or bottom containing the ion for including organic quaternary ammonium cations and solvent (when it is present) The phase (hereinafter referred to as " minor flow ") of compound.Preferably, countercurrent reaction tower has the Chi Qu (sump for being used for collecting minor flow region).Preferably, oily feeding flow is incorporated into the countercurrent reaction tower directly over the area of pond.It can use more than one inverse Flow reaction tower, such as 2 to 6 towers, the tower of preferably 2 to 3 arranged in series.Preferably, countercurrent reaction tower structural filler material, For example, glass Raschig ring (Raschig ring) is filled, the flow path that thus increase oil and alkali ionic liquid pass through tower.It is optional Ground, countercurrent reaction tower can contain multiple tower trays (tray).
In particularly preferred implementation formula, the step that is contacting and separating can be carried out together in centrifugal contact separator, example Such as in US 4,959,158, US 5,571,070, US 5,591,340, US 5,762,800, WO 99/12650 and WO 00/ Centrifugal contact separator described in 29120.Suitable centrifugal contact separator is included by Costner Industries Those of Nevada, Inc. offer.Glyceride oil and solution comprising alkali ionic liquid can be incorporated into centrifugal contact separation The annular mixing zone of device.Preferably, glyceride oil and alkali ionic liquid are incorporated into annular mixing zone as separated feeding flow. Glyceride oil and alkali ionic liquid are quickly mixed in annular mixing zone.The mixture obtained then by Disengagement zone, is dividing From in area, apply centrifugal force to mixture to produce being kept completely separate for oil phase and secondary phase.
Preferably, it is used continuously multiple centrifugal contact separators, preferably 2 to 6, such as 2 to 3.Preferably, oil charging Stream is introduced into first centrifugal contact separator in series, while alkali ionic liquid feeding flow is introduced into series most In the latter centrifugal contact separator, so as to reduce step by step and be as the glyceride oil of FFA or free chlorine anion-content passes through First centrifugal contact separator in row increases such as quaternary ammonium-FFA salt step by step to last centrifugal contact separator And/or the alkali ionic liquid stream of aliquat content by last centrifugal contact separator in series to first Centrifugal contact separator.Therefore, by the phase containing the ionic compound including organic quaternary ammonium cations from first centrifugal contact Removed in separator, and processed oil phase is removed from last centrifugal contact separator in series.
, can be by by product if desired, be present in the remaining alkali ionic liquid in processed glyceride oil Oil stream is recycled by silica column, and so remaining alkali ionic liquid is adsorbed on silica column.Adsorbed Alkali ionic liquid can be eluted then using the solvent for alkali ionic liquid from silica column, and alkalescence Ionic liquid can be recycled by removing solvent under reduced pressure.
Glyceride oil after processing can also agglomerate the fine drop of non-oil phase liquid by coalescent filter, such as containing There is the liquid of the ionic compound including organic quaternary ammonium cations, so as to produce continuous phase and promote to be separated.Preferably, with In the case of the alkali ionic liquid of contact procedure (i) and solvent combination use, coalescent filter can use identical solvent Wetting is filtered with improving.
In some embodiments, alkali ionic liquid can be provided in support materials.For the suitable negative of the present invention Loading can be selected from the one or more in silica, aluminium oxide, alumina silica, carbon, activated carbon and zeolite.It is excellent Selection of land, loaded article are silica.The loaded article form provided can be contacted as the slurries comprising suitable solvent with oil, its Middle solvent is selected from solvent as described above.
In the case where using the alkali ionic liquid being supported, contact procedure and separating step can also be by making oil logical A column (for example, filling bed apparatus) filled with the alkali ionic liquid being supported is crossed to carry out together.Additionally or alternatively, may be used To use the fixed bed device with multiple plates and/or disk.
For in support materials the method for supported ion liquid be it is well known in the art that as example, in US2002/ 0169071st, disclosed in US2002/0198100 and US2008/0306319.Normally, alkali ionic liquid can be inhaled with physics It is attached or be chemisorbed in support materials, preferably physical absorption.In the method for the present invention, alkali ionic liquid can be with 10:1 to 1:10 alkali ionic liquid:Load mass ratio, preferably with 1:2 to 2:1 alkali ionic liquid:Load mass is than absorption On loaded article.
It has been found that alkali ionic liquid used according to the invention can prevent or reduce chloropropyl alcohol fat in glyceride oil The formation of fat acid esters and glycidol fatty acid ester, this is the result of subsequent purification step.Due to oil and alkali ionic liquid The result of contact, it is believed that it is possible to have several reaction mechanisms.This will be discussed in further detail below.
It has been found that the formation of chloropropyl alcohol fatty acid ester and glycidol fatty acid ester depends primarily upon：(i) glyceride oil Monoglyceride and diglyceride content；(ii) chlorinity of glyceride oil；(iii) proton activity of glyceride oil；With (iv) the heat exposure degree in refining process.Alkali ionic liquid processing glyceride oil used according to the invention has been observed that will not The monoglyceride and diacylglycerol content of oil are influenced, is reduced it is taken as that it is chloride content and proton activity, so as to cause The formation of chloropropyl alcohol fatty acid ester and glycidol fatty acid ester is prevented or reduced in refining process.
Inventionwithout being bound to any specific theory, in the possible reaction or interaction of alkali ionic liquid in the oil, with The anion exchange of free chloro ion is considered as that can reduce the means of free chlorine contents in oil.Meanwhile alkali ionic liquid Alkalescence can also change oil proton activity so that the formation of glycidol fatty acid ester also reduces.Such as, it was found that according to Ionic liquid that the present invention uses neutralizes the FFA being present in oil, and formed comprising the alkalescence being used in contact procedure (i) from The ionic compound of the organic quaternary ammonium cations of sub- liquid and the carboxylate anion of FFA.In alkali ionic liquid and oil The product of acid-base reaction between FFA can also be complexed cl anion and/or chlorine-containing compound, and contribute to from processed It is removed from the oil when quaternary ammonium-FFA salt is separated in oil.
Therefore, separated organic quaternary ammonium cations in some embodiments, included in this method the step of (ii) Ionic compound can include cl anion.The glyceride oil of contact is included in the embodiment of FFA in step (i), comprising The ionic compound of separated organic quaternary ammonium cations can include the anion of aliphatic acid in step (ii).
Preferably, method of the invention is used for the formation for preventing or reducing chloropropyl alcohol fatty acid ester in glyceride oil.It is more excellent Selection of land, method of the invention are used for the formation for preventing or reducing a chloropropyl alcohol fatty acid ester in glyceride oil.Most preferably, this hair Bright method is used for the formation for preventing or reducing the 3-MCPD fatty acid esters in glyceride oil.
The method according to the invention, carries out at least one further after glyceride oil is handled with alkali ionic liquid Refinement step.Those skilled in the art will know that different refinement steps usually used in edible oil processing, including for example exist 《The practical guide of vegetable oil processing》In (2008, Monoj K.Gupta, AOCS Press) and " AOCS lipids storehouse " website The refinement step discussed in edible oil processing part (lipidlibrary.aocs.org).
At least one further refinement step (iii) can be selected from：Degumming, bleaching, winterization, depigmentation and One or more in deodorization.It is to cause chloropropyl alcohol fatty acid ester and contracting to be known as usually with the relevant heat exposure of deodorising step The reason for water fatty acid glyceride is largely formed, so alkali ionic liquid processing carries out preferably before deodorization.Therefore, excellent Select in embodiment, at least one further refinement step of the method according to the invention includes deodorization.
In some embodiments, at least one further refinement step (iii) includes degumming, bleaching and deodorization The step of.Alternatively, in other embodiments, at least one further refinement step (iii) includes deodorising step, and And the method does not include degumming and/or blanching step.Therefore, in the exemplary embodiment, it is described at least one further Refinement step includes the step of degumming and deodorization, but does not include bleaching.In other exemplary embodiments of the invention, it is described it is at least one into One step refinement step includes bleaching and deodorising step, but does not include degumming step.
The another advantage for the alkali ionic liquid processing method that the present invention uses is to also found alkali ionic liquid at least Partly remove the pigment that is removed under high temperature (for example, 240 DEG C to 270 DEG C) deodorising step usually in conventional refinery process and There is taste compound.A part for whole refinery practice, deodorising step are intended as with alkali ionic liquid processing glyceride oil Lower temperature and/or shorter time can be used.This has the advantages that the energy requirement for reducing refining process.
Degumming, which is usually directed to, makes oil be contacted with phosphate aqueous solution and/or aqueous citric acid solution so that remove can aquation and nonhydratable Phosphatide (NHP).Normally, citric acid or phosphoric acid are added in the form of the aqueous solution of 50 weight %.Suitably, sour aqueous solution Dosage is about：The weight of acid is about the 0.02 weight % to 0.20 weight % of weight of oil, it is preferable that sour weight is about weight of oil 0.05 weight % to about 0.10 weight %.Suitably, degumming step is at about 50 DEG C to 110 DEG C, preferably 80 DEG C to 100 DEG C of temperature Degree is lower to carry out, such as 90 DEG C.Degumming step can suitably continue 5 minutes to 60 minutes, preferably 15 to 45 minutes, more preferably 20 to 40 minutes, such as 30 minutes.After settling mucus after acid treatment, usually water phase is separated before dry degummed oil.Degummed oil Drying suitably carried out at a temperature of 80 to 110 DEG C and under reduced pressure for example under 2 to 3kPa (20 to 30 millibars) it is suitable Time, such as 20 to 40 minutes.
As it is known by the man skilled in the art, the glyceride for content of phospholipid relatively low (for example, the content of phosphorus is less than 20ppm) Oil, can use dry degumming technique, in the technique, be not required to significantly be diluted with water (for example, 85% when adding phosphoric acid or citric acid Acid solution).NHP is converted into the bis phosphoric acid of the phosphatidic acid that can be removed in subsequent blanching step from oil and calcium or magnesium Salt.For the oil rich in phosphatide, the particularly oil rich in NHP, it is known that dry degumming is less suitable, since it is desired that excessive bleaching Soil.
Bleaching process is attached to during refining raw food oil to reduce chromatoplast, including chlorophyll, remaining aliphatic acid Salt and natural gum, trace metal and oxidation product.Bleaching be usually directed to make it is oily contacted with a certain amount of bleaching clay or soil, such as The clay of the 0.5-5 weight % of quality oil-based.Bleaching clay or soil are normally by following three types of clay mineral In one or more compositions：Ca-montmorillonite, attapulgite and sepiolite.Any suitable drift can be used according to the present invention White clay or soil, including neutral and acid activation clay (such as bentonite).By oil suitably contacted with bleaching clay 15 to 45 minutes, preferably 20 to 40 minutes, then usually separate bleaching clay by filtering.Normally, in 80 DEG C to 125 DEG C of temperature Under degree, preferably at a temperature of 90 DEG C to 110 DEG C, oil is set to be contacted with bleaching clay or soil.What is carried out under atmospheric pressure is initial After contact phase (" wet bleaching "), the second stage of bleaching process carries out (" dry chemicking is white ") under reduced pressure, such as 2 to 3kPa Carried out under (20 to 30 millibars).
Conventional glyceride oil refinery practice is generally included to use in highly basic, such as sodium hydroxide or potassium hydroxide with FFA's Step (corresponds to so-called " chemical refining " process).It is alternatively possible to realize depickling by correspondingly adjusting deodorization parameter, To ensure to remove volatility FFA (so-called " physical refining " process) in this step.FFA neutralization procedures (" chemical refining ") Shortcoming is accompanied by unwanted saponification, so that the content of triglycerides is reduced, simultaneously because emulsification, aliphatic acid The formation of salt can cause the loss of substantial amounts of neutral oil.Form the alkali ionic liquid processing of the method for refining part of the present invention Method is effective for the FFA aspects neutralized in oil, and can be substituted completely in the routine used in chemical refining process And step.Advantageously, handled with alkali ionic liquid with the benefit that will not cause neutral oil saponification.Therefore, the present invention's In preferred embodiment, refining process does not include the neutralization procedure with inorganic base (such as sodium hydroxide).
The FFA being present in oil can be neutralized when being contacted with alkali ionic liquid to form quaternary ammonium salt-FFA salt. In preferred embodiment, the mole of the FFA contained by the amount and oil of the alkali ionic liquid used in contact procedure is at least It is stoichiometric ratio.For example, the molar ratio of alkali ionic liquid and FFA in oil can be 1:1 to 10:1, or 1.5:1 to 5: 1.Those skilled in the art know that the content of FFA can use conventional drop before alkali ionic liquid processing in glyceride oil Determine technology measure.It is, for example, possible to use phenolphthalein indicator titrates sodium hydroxide to measure the FFA contents of glyceride oil.
In a preferred embodiment, organic quaternary ammonium cations are selected to provide with linear C12To C18Free fatty Low melting point soap.It is particularly preferred that organic quaternary ammonium cations are less than 100 DEG C of free fatty forming salt with fusing point. Such salt can easily be separated during separating step (ii) by the liquid-liquid separation technology being discussed herein.
As it is known by the man skilled in the art, deodorization corresponds to stripping process, usually make a certain amount of vapour by being directly injected into Propose agent and flow through oil in distilling apparatus, flow through a period of time under reduced pressure to vaporize and extract volatile component, such as FFA, aldehyde Class, ketone, alcohols, hydro carbons, tocopherols, sterol and phytosterol.Steam stripping agent is preferably steam, but can also use other vapour Carry agent such as nitrogen.The suitable amount of the steam stripping agent used is about the 0.5% to about 5% of weight of oil.
Deodorization temperature scope in refining process according to the present invention is suitably 160 DEG C to 270 DEG C.Deodorization is referred to herein During the temperature of step, this refers to oil in the temperature being heated to before steam stripping agent.The pressure limit of deodorization is suitably 0.1 to 0.4kPa (1 to 4 millibar), preferably 0.2 to 0.3kPa (2 to 3 millibars).The right times of deodorization are usually 30 to 180 points Clock, such as 60 to 120 minutes or 60 to 90 minutes.
Those skilled in the art can determine suitable deodorization time length by analyzing appearance and the composition of glyceride oil It is short.For example, determine the P-anisidine value (AnV) of oil.The P-anisidine value of oil is measuring for its oxidation state, and more specifically Say, it provides the information on contained secondary oxidation product level in oil, although mainly aldehydes such as 2- chains olefine aldehydr and 2,4- Two olefine aldehydrs.Therefore P-anisidine value (AnV) also gives the instruction for the content for being intended to the oxidation product removed by deodorising step. For example, as determined by AOCS official method Cd 18-90, for example, when AnV is less than 10, preferably smaller than 5, it is possible to achieve order The deodorising effect of people's satisfaction.
Additionally or alternatively, it may be determined that oily aldehydes and the amount of ketone component, it is usually related with the smell of raw oil, with Determine whether to have occurred that sufficient deodorization.The flavored aldehydes of common volatility of rough palm oil or the palm oil that becomes sour and Ketone component includes：Acetaldehyde, benzaldehyde, positive propionic aldehyde, n-butanal, valeraldehyde, n-hexyl aldehyde, n-octaldehyde, n-nonyl aldehyde, 2- crotonaldehydes, 3- methylbutyraldehyds, 2 methyl butyraldehyde, 2- pentenals, 2- hexenoic aldehydes, 2E, 4E- decadienals, 2E, 4Z- decadienals, 2- butanone, 2 pentanone, 4-methyl-2 pentanone, 2-HEPTANONE, methyl n-heptyl ketone.Preferably, each in these components is independently with less than 3mg/ Kg oil, more preferably less than 1mg/kg oil, the amount of more preferably less than 0.5mg/kg oil are present in deodorised oil.
The amount of aldehydes and ketone can be determined easily by chromatographic process, such as GC-TOFMS or GCxGC-TOFMS.Can The derivatization of selection of land, aldehydes and ketone can be used for improving chromatography.For example, as it is known that aldehydes and ketone can be in acid condition With 2,4 dinitrophenyl hydrazine (DNPH) derivatization.The reagent is not reacted with carboxylic acid or ester, therefore is analyzed from glyceride oil sample Present in these components influences.After derivatization, HPLC-UV analyses can be with aldehydes present in quantitative analysis sample and ketone Total amount.
Conventional deodorization temperature is usually more than 220 DEG C, such as 240 DEG C to 270 DEG C, usually carries out 60 to 90 minutes.Such as exist Permitted in these embodiments of the present invention, present invention deodorization can use the temperature lower than ordinary temperature, such as 160 DEG C To 200 DEG C, the time of deodorization can extend to ensure enough deodorizations, but still for example exist at a higher temperature than conventional The deodorization operation that the shorter time is carried out at 240 DEG C to 270 DEG C is related to less energy expenditure.
In a preferred embodiment, it can use and compare identical or shorter time and combination with conventional deodorization time Using than conventional deodorization temperature lower temperature, due to alkali ionic liquid processing before, embodiment of the present invention also may be used To reach identical deodorization degree.In other preferred embodiments, deodorising step in refining process of the invention can be with Use the conventional temperature for deodorising step, such as 240 DEG C to 270 DEG C, compared with being routinely deodorized the time used, the present invention Time of deodorization can reduce, due to alkali ionic liquid processing before, the present invention still reaches comparable levels of deodorization Effect.
Therefore alkali ionic liquid processing also has the advantages that energy expenditure can be reduced during subsequent deodorising step. In addition, temperature or time by reducing the exposure to heat during deodorising step, it is possibility to have oil may be caused by reducing sharply Undesirable organoleptic properties or form the side reaction of undesired, potentially harmful accessory substance.
In particularly preferred embodiments, at least one further refinement step bag of the method according to the invention In the case of including deodorization, the temperature of deodorization is 160 DEG C to 200 DEG C, more preferably 170 DEG C to 190 DEG C.Preferably, in these temperature The lower time being deodorized will be 30 to 150 minutes, more preferably 45 to 120 minutes, be most preferably 60 to 90 minutes.
The alkali ionic liquid processing of the method according to the invention can be adapted for not undergoing any elder generation after extract oil The crude glyceride oil of preceding refinement step.Alternatively, the method for the present invention can be adapted for handling with alkali ionic liquid The glyceride oil of at least one extra refinement step is had gone through before.Preferably, at least one extra refining Step is selected from bleaching and/or degumming.
As described above, degumming generally includes to add citric acid and/or phosphoric acid with except the phosphatide in deoiling.The step is possible to Have a negative impact to the proton activity of oil, so as to increase the formation of glycidol fatty acid ester when exposed to heat.Equally To know, the bleaching clay or soil of acid activation are probably the source of pollutant, such as the source of cl anion, such as In the case that hydrochloric acid has been used to acid activation.The bleaching earth or clay of this acid activation can also change proton activity, and may The formation of glycidol fatty acid ester can be increased when being subsequently exposed to heat.
Therefore, in some embodiments it is preferred that ground carries out degumming before alkali ionic liquid processing, because this causes In glyceride oil, the proton activity of oil is changed by alkali ionic liquid after acid.In some embodiments, particularly In the case of using the material comprising cl anion source, preferably bleached before alkali ionic liquid processing, because This provides the chance for being handled by alkali ionic liquid and removing this pollutant.
Advantageously, it has been found that, the alkali ionic liquid processing method for forming the part of the method for the present invention can also Make degumming of oil at least in part and remove depigmentation, it means that the degree of degumming and blanching step can reduce, such as just handle It can reduce for time or material.As described above, the alkali ionic liquid processing method for forming the method for the present invention part is kept away The single FFA neutralization procedures used in chemical refining process are exempted from.Meanwhile form the alkalescence of the part of the method for the present invention Ionic liquid processing method may also can reduce the energy expenditure in deodorising step.
Alkali ionic liquid processing method used according to the invention is intended to avoid using ion exchange resin and ultrafiltration membrane Etc. depollution thing of making a return journey, this can be significantly reduced refines relevant material cost with glyceride oil.Therefore, in preferred embodiment In, method of refining as described herein does not include spent ion exchange resin or ultrafiltration membrane treatment glyceride oil.
In some embodiments, if desired, the alkali ionic liquid used in contact procedure (i) can pass through Regeneration technology is regenerated from the ionic compound (wherein these salt are different) for the organic quaternary ammonium cations isolated comprising step (ii), So as to which alkali ionic liquid is recycled in the method for refining of the present invention.For example, regenerative process can include anion exchange Or cation-exchange step is to obtain the alkali ionic liquid for including required alkali anion as described above.
In one embodiment, regenerative process includes by choline-FFA salt forming alkali ionic liquid, wherein, it is alkaline from Sub- liquid is Choline Bicarbonate, is comprised the following steps：
(a) choline-FFA salt is contacted with carbonic acid；With
(b) Choline Bicarbonate is obtained from reaction mixture.
Preferably, step (a) passes through the aqueous solution and CO that make to include choline-FFA salt2Contact (such as by by CO2Bubbling Pass through aqueous solution) carry out.
Preferably, step (b) is preferably by making step (mixture of (a) and solvent that can be miscible with Choline Bicarbonate Contact and solvent is isolated from Choline Bicarbonate to carry out.
Present invention also offers the purposes of alkali ionic liquid as described above, by making oil and alkali before heating stepses Property ionic liquid contact, for chloropropyl alcohol fatty acid ester and/or contracting in glyceride oil to be prevented or reduced during heating stepses The formation of water fatty acid glyceride.Heating stepses for example can correspond to oil being heated to above such as 150 DEG C, 200 DEG C or very To 250 DEG C of temperature.Would generally be it is contemplated that largely forming the fatty acid ester of chloropropyl alcohol and/or glycidol in glyceride oil.Cause This heating steps can form a part for deodorising step.
Preferably, alkali ionic liquid is used for the formation for preventing or reducing chloropropyl alcohol fatty acid ester in glyceride oil.It is more excellent Selection of land, alkali ionic liquid are used for the formation for preventing or reducing a chloropropyl alcohol fatty acid ester.Most preferably, alkali ionic liquid is used In the formation for preventing or reducing 3-MCPD fatty acid esters in glyceride oil.It is related to the anion and cation of alkali ionic liquid The preferred embodiment of the other aspects of the present invention of property and the property of glyceride oil is equally applicable to this of the present invention Aspect.For example, ionic liquid is preferably Choline Bicarbonate.
R.Wei β haar " are measuring total 3- chloropropanes -1,2- two in edible oil by using sodium methoxide cracking MCPD esters Described in alcohol (3-MCPD) " (Eur.J.Lipid Sci.Technol. (2008) 110,183-186) in measure glyceride oil The analysis method of MCPD concentration.Revised Germany's fat 18 (10) (German Standard of science association (DGF) standard method C-III Method 2010) also provide horizontal appropriate method for determining MCPD or its fatty acid ester, and definite glycidol or Indirect method existing for its fatty acid ester.Such as J Am Oil Chem Soc.Jan 2011；88(1):1-14 reports, for true The direct method for determining chloropropyl alcohol and glycidol and the content of their fatty acid ester includes the use of liquid chromatogram-flight time matter Compose (LC-TOFMS).
Invention described above embodiment can be combined with any other compatible embodiment to form the present invention's Further embodiment.As it will appreciated by a person of ordinary skill, all aspects of the invention can be used for processing and Refined palm Oil or the glyceride oil mixture comprising palm oil.In instantiation, present invention also contemplates that method described herein, wherein sweet Grease oil is made of comprising palm oil or palm oil, and wherein the method further includes regeneration step as described above.
The present invention will be illustrated by the following examples now.
Embodiment
Measure the acid number (mg KOH/g oil) of glyceride oil and the conventional method of FFA (weight %) content.
Measure the acid number (mg KOH/g oil) of glyceride oil and the conventional method of FFA (weight %) content.
0.5ml phenolphthalein is added into the beaker containing 60ml isopropanols.The mixture is heated until boiling, and adds and contains There is the isopropanol of 0.02M potassium hydroxide, until faint pink colour continues about 10 seconds.
0.200g palm oil samples are added into vial, are then dissolved in the above-mentioned hot aqueous isopropanols of 50ml In.The 25ml droppers that obtained solution is 0.1ml with scale are titrated and stirred with 0.02M potassium hydroxide solutions, until phenolphthalein The terminal of indicator, i.e., until pink colour continues at least 30 seconds.
Then acid number (mg KOH/g oil) is calculated using following formula：
56.1×N×V/m
Wherein：
56.1 be the molecular weight (Mr) of potassium hydroxide；
V is the volume (ml) of potassium hydroxide solution used；
N is the equivalent concentration of potassium hydroxide solution；With
M is the quality (g) of glyceride oil sample.
Once it is determined that acid number, it is possible to derive the content of FFA.For purpose disclosed by the invention, FFA contents are determined Justice is mass percent, while assumes that FFA is that the equivalent of palmitic acid (Mr=256g/mol) and oleic acid (Mr=282g/mol) is mixed Compound, obtains average molecular weight as 269 grams/mol.The oil of FFA with 1 weight % contains:The oleic acid and palmitic acid of 0.01g/ The amount of the oil per 1g, the oleic acid and palmitic acid is equivalent to 3.171 × 10-5Mole (be 0.01/269).Calculate and be used to neutralize the amount Oleic acid and palmitic acid needed for KOH amount (i.e. acid number-AV) for 2.086mg KOH/g oil (i.e. 3.171 × 10-5×56.1)。 Therefore FFA contents (weight %) are calculated according to the following formula：
FFA contents (weight %)=acid number × 0.479
Embodiment 1：The ionic liquid processing of corn oil
The FFA contents of analysis corn oil (10g) and with tristearin acid doping to obtain the FFA contents of 5 weight %.By doping Oil samples are heated to 60 DEG C, then add 0.363g Choline Bicarbonate solution (in H2Concentration is 80w/w% in O, by Britain Sigma-Aldrich is provided).Quick stirring mixture 30 minutes, is then centrifuged 2 minutes with 4400rpm.
Upper oil phase is removed and analyzes FFA contents.It the results are provided in table 1 below.
Embodiment 2：The ionic liquid processing of olive oil
The method for repeating embodiment 1, except the present embodiment using olive oil sample replaces corn oil.It the results are provided in following table In 1.
Embodiment 3：The ionic liquid processing of castor oil
The method for repeating embodiment 1, except the present embodiment using castor-oil plant oil samples replaces corn oil, the results are provided in following table In 1.
Embodiment 4：The ionic liquid processing of rapeseed oil (canola oil)
The method for repeating embodiment 1, except the present embodiment using vegetable seed oil samples replaces corn oil, the results are provided in following table In 1.
Embodiment 5：The ionic liquid processing of milk butter
The method for repeating embodiment 1, except the present embodiment using butter sample replaces corn oil.It the results are provided in table 1 below In.
Table 1
Table 1 the result shows that, alkali ionic liquid processing can from it is a variety of oil in remove FFA.In addition, result table Bright, alkali ionic liquid processing can reduce the proton activity of oil.It has been found that the property is the chlorine in subsequent deodorising step The important accelerating agent that propyl alcohol fatty acid ester and glycidol fatty acid ester are formed.
, will be above-mentioned processed every under the flowing of steam (water of 1 mass %/hour) when in the case where depressurizing (0.1kPa) When a kind of oil then heats 90 minutes in flask (having heating mantle) at 260 DEG C, find MCPD fatty acid esters and shrink sweet The level (using standard method DGF-C-VI 18, part A and DGF standard methods C-VI 17 (10) measure) of oil and fat acid esters with Being compared without ionic liquid processing doped with the level observed in stearic oil samples significantly reduces.
Embodiment 6：The ionic liquid processing of milk butter
1.5g butter is placed in sample bottle, uncombined 3-MCPD is then adulterated and (is carried by Britain Sigma-Aldrich For).Gained mixture is stirred at 40 DEG C 3 it is small when to ensure that oil and dopant are sufficiently mixed, it is then determined that dopant in oil Concentration.Then by Choline Bicarbonate (100mg, in H2Concentration is 80w/w% in O, is provided by Britain Sigma-Aldrich) Add into oil/doping agent composition, and gained mixture stirred at 40 DEG C about 12 it is small when.Then by mixture with 2500rpm is centrifuged 10 minutes.Then upper oil phase is removed, takes a small amount of oil phase sample to be analyzed.It the results are provided in table 2 below.
Embodiment 7：The ionic liquid processing of corn oil
The method for repeating embodiment 6, except the present embodiment using corn oil replaces butter, at room temperature with choline bicarbonate Salt is mixed and contacted.It the results are provided in table 2 below.
Embodiment 8：The ionic liquid processing of olive oil
The method for repeating embodiment 6, except the present embodiment using olive oil replaces butter, at room temperature with choline bicarbonate Salt is mixed and contacted.It the results are provided in table 2 below.
Table 2
Method for analyzing oil is that R.Wei β haar propose " to crack MCPD esters by using sodium methoxide to measure edible oil In total 3- chloropropanes -1,2- glycol (3-MCPD) " (Eur.J.Lipid Sci.Technol. (2008) 110,183-186). This method is related to extraction 3-MCPD, with boronic acid derivative, is then analyzed using GC-MS (by deuterium-labeled internal standard (3- MCPD-d5) be added in each sample).
The calibration curve that deuterium-labeled 3-MCPD, increased standard solution is indicated using addition carries out quantitative analysis.From Sub- m/z 147 (3-MCPD) and 150 (3-MCPD-d of m/z5) it is object ion.Ion m/z 196 (3-MCPD) and m/z 201 (3-MCPD-d5) it is qualitative ion.The detection of this method is limited to 0.15mg/kg.
It is in table 2 the result shows that alkali ionic liquid processing can be removed from the oil substantial amounts of organochlorine compound, such as 3-MCPD is in itself.Therefore, ionic liquid processing can go to dechlorination source from oil, and chlorine source is related to as discussed above subsequent Deodorising step in chloropropyl alcohol fatty acid ester formation.

Claims (26)

1. a kind of method of refining of glyceride oil, comprises the following steps：
(i) glyceride oil is contacted to form processed glyceride oil with alkali ionic liquid；Wherein described ionic liquid bag Containing selected from hydroxyl, alkoxy radical, alkylcarbonate, bicarbonate radical, carbonate, Ser, proline root, histidine root, Soviet Union One or more alkali anions in propylhomoserin root, valine root, aspartate, taurine root and lysine root, and Include organic quaternary ammonium cations；
(ii) after the glyceride oil is contacted with the alkali ionic liquid, by treated glyceride oil with comprising The ionic compound separation of organic quaternary ammonium cations；With
(iii) after the separation step, treated glyceride oil is made to carry out at least one further refinement step；
Condition is that the glyceride oil does not include palm oil.
2. the method as described in claim 1, it is characterised in that at least one further refinement step is included selected from de- One or more in glue, bleaching, winterization, depigmentation and deodorization；Preferably, at least one further refinement step bag Include deodorization.
3. method as claimed in claim 2, it is characterised in that at least one further refinement step includes deodorization and walks Suddenly, steam stripped deodorising step is preferably directed to, the deodorising step carries out at a temperature of 160 to 270 DEG C, preferably at 160 DEG C Carry out at a temperature of to 240 DEG C, more preferably carried out at a temperature of 170 DEG C to 190 DEG C.
4. the method according to any one of the preceding claims, it is characterised in that the method further includes middle use in step (i) At least one extra refinement step for the glyceride oil that alkali ionic liquid processing carries out before, it is preferable that it is described extremely A few extra refinement step is selected from bleaching and/or degumming.
5. method as claimed in claim 4, it is characterised in that at least one extra refinement step be with bleaching earth into Capable blanching step, the bleaching earth include cl anion source, such as the bleaching earth of hydrochloric acid activation.
6. such as the method any one of claim 1-3, it is characterised in that at least one further refinement step (iii) deodorising step is included, and the method does not include degumming and/or blanching step.
7. the method according to any one of the preceding claims, it is characterised in that separated ionization in the step (ii) Compound includes one or more cl anions.
8. such as the method any one of claim 1-6, it is characterised in that separated ion combination in the step (ii) Thing includes the anion of free fatty.
9. the method according to any one of the preceding claims, it is characterised in that the contact procedure is in the temperature less than 80 DEG C Degree is lower to carry out, and preferably carries out at a temperature of 25 DEG C to 65 DEG C, is more preferably carried out at a temperature of 35 DEG C to 55 DEG C.
10. the method according to any one of the preceding claims, it is characterised in that the organic quaternary ammonium of the alkali ionic liquid Cation is selected from：
[N(Ra)(Rb)(Rc)(Rd)]+,
Wherein, Ra、Rb、RcAnd RdIt is each independently selected from C1To C8Straight or branched alkyl or C3To C6Cycloalkyl, or Ra、Rb、RcAnd RdIn any two combine to form alkylidene chain-(CH2)q-, wherein q is from 3 to 6；And wherein described alkyl Or cycloalkyl can optionally be substituted by one to three group selected from the following：C1To C4Alkoxy, C2To C8Alkoxy alcoxyl Base, C3To C6Cycloalkyl ,-OH ,-SH ,-CO2(C1To C6) alkyl ,-OC (O) (C1To C6) alkyl, such as by one to three-OH base Substitution.
11. method as claimed in claim 10, it is characterised in that the organic quaternary ammonium cations choosing of the alkali ionic liquid From：
[N(Ra)(Rb)(Rc)(Rd)]+,
Wherein, Ra、Rb、RcAnd RdIt is each independently selected from C1To C8Straight or branched alkyl, and wherein described alkyl can appoint Selection of land is substituted by one to three group selected from the following：C1To C4Alkoxy, C2To C8Alkyloxy-alkoxy, C3To C6Ring Alkyl ,-OH ,-SH ,-CO2(C1To C6) alkyl ,-OC (O) (C1To C6) alkyl, such as substituted by one to three-OH base.
12. method as claimed in claim 11, it is characterised in that the organic quaternary ammonium cations choosing of the alkali ionic liquid From：
[N(Ra)(Rb)(Rc)(Rd)]+,
Wherein, Ra、Rb、RcAnd RdIt is each independently selected from C1To C4Straight or branched alkyl, including C1、C2And C4Alkyl, wherein Ra、Rb、RcAnd RdIn at least one substituted by single-OH groups.
13. method as claimed in claim 12, it is characterised in that the organic quaternary ammonium cations are choline：
14. the method according to any one of the preceding claims, it is characterised in that the alkali anion is selected from alkylcarbonic acid One or more in root, bicarbonate radical and carbonate, preferably described alkali anion is bicarbonate radical.
15. method as claimed in claim 14, it is characterised in that be used to contact the glyceride oil in the step (i) Alkali ionic liquid is Choline Bicarbonate：
16. such as the method any one of claim 1-13, it is characterised in that the alkali anion be selected from hydroxyl and One or both of alkoxy radical；Preferably, the alkali anion is hydroxyl.
17. the method described in claim 16, it is characterised in that be used to contact the glyceride oil in the step (i) Alkali ionic liquid is bursine：
18. the method according to any one of the preceding claims, it is characterised in that the glyceride oil is with including alkali ion The solution of liquid and solvent contacts, such as the solvent is aqueous solvent, and the concentration of alkali ionic liquid is described in the solution 15 weight % to 90 weight %.
19. the method as described in claims 14 or 15, it is characterised in that the glyceride oil with comprising alkali ionic liquid and The solution contact of solvent, such as the solvent is aqueous solvent, the concentration of alkali ionic liquid described in the solution is 50 weights % to 90 weight % is measured, is preferably 75 weight % to 85 weight %.
20. the method as described in claim 16 or 17, it is characterised in that the glyceride oil with comprising alkali ionic liquid and The solution contact of solvent, such as the solvent is aqueous solvent, the concentration of the solution neutral and alkali ionic liquid for 15 weight % extremely 60 weight %, preferably 40 weight % are to 50 weight %.
21. method as claimed in claim 15, it is characterised in that the glyceride oil for contact includes free fatty, from The separated ionic compound of glyceride oil is choline-free-fat hydrochlorate, and wherein the method is further included is from processing The ionic compound that the glyceride oil crossed is isolated regenerates Choline Bicarbonate alkali ionic liquid, the regeneration method bag Include following steps：
(a) choline-free-fat hydrochlorate is contacted with carbonic acid；With
(b) Choline Bicarbonate is obtained from reaction mixture.
22. method as claimed in claim 21, it is characterised in that the step of the renovation process (a) by make comprising choline- The aqueous solution and CO of free-fat hydrochlorate2Contact to carry out.
23. the method according to any one of the preceding claims, it is characterised in that the glyceride oil is vegetable oil；It is preferred that Ground, the vegetable oil are selected from cocounut oil, corn oil, cottonseed oil, peanut oil, olive oil, rapeseed oil, rice bran oil, safflower oil, soybean oil With the one or more in sunflower oil.
24. a kind of purposes of alkali ionic liquid, by making glyceride oil be contacted with alkali ionic liquid before heating stepses, For chloropropyl alcohol fatty acid ester in glyceride oil and/or glycidol fatty acid ester to be prevented or reduced during heating stepses Formed；Condition is that the glyceride oil does not include palm oil；The alkali ionic liquid is included selected from hydroxyl, alkoxy radical, alkane Base carbonate, bicarbonate radical, carbonate, Ser, proline root, histidine root, threonine root, valine root, asparagus fern ammonia One or more alkali anions in acid group, taurine root and lysine root, and include organic quaternary ammonium cations.
25. purposes as claimed in claim 24, it is characterised in that the glyceride oil such as claim 23 is defined, and/or The alkali ionic liquid such as any one of claim 10-17 is defined.
26. the purposes as described in claim 24 or 25, it is characterised in that the alkali ionic liquid is used to prevent or reduce sweet The formation of a chloropropyl alcohol fatty acid ester and/or glycidol fatty acid ester in grease oil；It is highly preferred that the alkali ionic liquid For preventing or reducing the formation of a chloropropyl alcohol fatty acid ester in glyceride oil；Most preferably, the alkali ionic liquid is used for Prevent or reduce the formation of 3-MCPD fatty acid esters in glyceride oil.
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