CN106479682A - Fat or oil composition, Its Preparation Method And Use - Google Patents
Fat or oil composition, Its Preparation Method And Use Download PDFInfo
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Abstract
The present invention relates to fat or oil composition, Its Preparation Method And Use.The preparation method of the fat or oil composition of the present invention, the method include the random step of transesterification that triglycerides is carried out random ester exchange reaction, it is characterised in that there is the compound with hydroxyl in above-mentioned random step of transesterification.The present invention relates to the content of fat or oil composition dialkyl ketone is reduced.
Description
Technical field
The present invention relates to fat or oil composition, Its Preparation Method And Use.In particular it relates to a kind of low dialkyl ketone（DAK）Content 1,3- dioleoyl -2- palmitoyl glyceride（OPO）Composition and preparation method thereof.
Background technology
1,3- dioleoyl -2- palmitoyl glyceride（OPO）It is a kind of structured lipid of new imitation lacto's grease, research shows that baby's formula milk of the intake containing OPO can effectively improve the Energy intaking of baby, soften stool, promote calcium absorption, and can reduce baby crying number of times.Therefore, OPO prepare of great interest and research.Typically, OPO fat or oil composition is carried out acidolysis reaction and prepares by will be enriched in the triglycerides of palmitic acid with oleic acid in the presence of lipase.However, for the content for increasing active ingredient OPO in fat or oil composition, step enzyme method reaction is often inadequate.Need to be combined with other techniques, improve OPO content.
CN101258230 discloses a kind of method for preparing OPO composition, carries out enzymatic interesterification procedure using the palm oil stearin and oleic acid of iodine number 2-12, and increases OPO content by dry fractionation.
CN101679909 discloses a kind of method for producing OPO composition, random ester exchange reaction is carried out by the glyceryl palmitostearate by one or more iodine number between 18-40, so that the content of Sn-2 position palmitic acid in ester exchange grease is improved, and then ester exchange reaction raising OPO content is oriented by enzymatic.
Compared to other techniques, OPO content in OPO composition is improved by random ester exchange reaction, with significant advantage.At present, the most frequently used catalyst of chemically catalyzed interesterification is the alkali alkyl compound with sodium methoxide as representative, this kind of catalyst low price, easily uses, and usage amount is few, and still has higher activity at a lower temperature.However, using inevitably producing dialkyl ketone in the reaction of the chemical catalyst catalytic transesterification（DAK）This kind of accessory substance.DAK also known as two aliphatic ketones（DFK）, it is made up of a series of long-chain fat alkyl ketone, its basic structure is as follows：R-CO-R ', wherein R and R ' represent saturation or undersaturated fatty alkyl.Early in 20 century 70s, someone is found that in margarine to the presence of a certain amount of DAK（Huyghebaert, R., et al. (1970). "La présence des cétones
dans des graisses semblables au beurre." Fette, Seifen, Anstrichmittel
72(4): 289-293.）.
It is reported that, the DAK contained in grease is difficult to remove by refining, and this kind of material can cause grease local flavor unstable, for example, can cause frosting in chocolate application and suppress crystallization.Therefore, in control edible oil and fat, DAK has also been reported containing quantifier elimination.
US5504231 discloses chain fatty acid triglycerides in a kind of low DAK content（MLCT）Preparation method, the method involved by which is esterification between aliphatic acid and monoglyceride, can reduce the content of DAK in product by adding glycerine.
US6303777 discloses a kind of preparation method of the SPE of low DAK content, and which is related to the transesterification reaction between sucrose and alcohol fatty acid ester, controls the content of DAK in product by controlling response parameter.
WO2009012982 discloses a kind of preparation method of low DAK content OPO composition, reduces the content of DAK in product by reducing the water content of grease and the addition of sodium methoxide and reaction time.However, these measures may cause ester exchange reaction to carry out not exclusively, reducing ester exchange rate.Therefore, on the premise of ester exchange rate is ensured, expect to reduce the content of DAK in product as far as possible.
Content of the invention
It is an object of the present invention to provide a kind of preparation method of fat or oil composition, the method includes the random step of transesterification that triglycerides is carried out random ester exchange reaction, it is characterised in that there is the compound with hydroxyl in above-mentioned random step of transesterification.
According to the preparation method of the fat or oil composition of the present invention, the method also includes enzymatic orientation step of transesterification：The step of triglycerides and aliphatic acid or derivatives thereof are oriented ester exchange reaction in the presence of lipase.
According to the preparation method of the fat or oil composition of the present invention, the method also includes：Molecular clock step, the molecular clock step is preferably before enzymatic orientation step of transesterification, or carries out after enzymatic orientation step of transesterification.
According to the triglycerides that the preparation method of the fat or oil composition of the present invention, the triglycerides represent containing useful following formula (1),
In formula (1), R1、R2And R3Each identical or different, R1、R2And R3At least one of represent from the straight or branched that carbon number is 8～30 saturated fatty acid group.
According to the preparation method of the fat or oil composition of the present invention, in formula (1), R1、R2And R3Each identical or different, R1、R2And R3At least one of represent from the linear saturated fatty acids that carbon number is 16～18 group.
According to the preparation method of the fat or oil composition of the present invention, in formula (1), R1、R2And R3At least one of represent from palmitic acid group.
According to the preparation method of the fat or oil composition of the present invention, in formula (1), R1、R2And R3Identical, all represent the group from palmitic acid.
According to the preparation method of the fat or oil composition of the present invention, the triglycerides is plant origin.
According to the preparation method of the fat or oil composition of the present invention, at least one of the triglycerides in the random ester exchange grease of the vegetable oil stearin containing three ester of palmitic acid, the vegetable oil containing three ester of palmitic acid or the vegetable oil containing three ester of palmitic acid.
According to the preparation method of the fat or oil composition of the present invention, the fractionated palm oil that the triglycerides proposes tristearin, the palm oil stearin of random ester exchange, the palm oil of random ester exchange or random ester exchange selected from palm oil stearin, palm oil, fractionated palm oil puies forward at least one in tristearin.
According to the preparation method of the fat or oil composition of the present invention, the random ester exchange is the random ester exchange of chemistry or the random ester exchange of enzyme process.
According to the preparation method of the fat or oil composition of the present invention, the catalyst used in the random ester exchange of the enzyme process is nonspecific lipid enzyme.
According to the preparation method of the fat or oil composition of the present invention, the nonspecific lipid enzyme is Lipozyme TL IM.
According to the preparation method of the fat or oil composition of the present invention, the compound with hydroxyl is selected from least one of ethylene glycol, propane diols, glycerine, glycerin monostearate, trimethylolethane, antierythrite, pentaerythrite, sorbierite or xylitol.
According to the preparation method of the fat or oil composition of the present invention, in terms of the total amount of the triglycerides, the amount of the compound with hydroxyl is 0.01～1.5 weight %.
According to the preparation method of the fat or oil composition of the present invention, in terms of the total amount of the triglycerides, the amount of the compound with hydroxyl is 0.05～1.2 weight %.
According to the preparation method of the fat or oil composition of the present invention, in terms of the total amount of the triglycerides, the amount of the compound with hydroxyl is 0.1～1.0 weight %.
According to the preparation method of the fat or oil composition of the present invention, in terms of the total amount of the triglycerides, the amount of the compound with hydroxyl is 0.2～0.8 weight %.
According to the preparation method of the fat or oil composition of the present invention, at least one of the aliphatic acid in the straight chain unrighted acid of carbon number 16～20.
According to the preparation method of the fat or oil composition of the present invention, at least one of the derivative of fatty acid in the ester of the straight chain unrighted acid of carbon number 16～20.
According to the preparation method of the fat or oil composition of the present invention, at least one of the described aliphatic acid or derivatives thereof in oleic acid, ethyl oleate, methyl oleate, high oleic sunflower oil or high oleic acid palm oil.
According to the preparation method of the fat or oil composition of the present invention, the additional proportion of the triglycerides and the aliphatic acid or derivatives thereof, with weight ratio meter, triglycerides：Aliphatic acid or derivatives thereof is 1：2～5.
According to the preparation method of the fat or oil composition of the present invention, the additional proportion of the triglycerides and the aliphatic acid or derivatives thereof, with weight ratio meter, triglycerides：Aliphatic acid or derivatives thereof is 1：2～4.
According to the preparation method of the fat or oil composition of the present invention, the additional proportion of the triglycerides and the aliphatic acid or derivatives thereof, with weight ratio meter, triglycerides：Aliphatic acid or derivatives thereof is 1：2～3.
According to the preparation method of the fat or oil composition of the present invention, the additional proportion of the triglycerides and the aliphatic acid or derivatives thereof, with weight ratio meter, triglycerides：Aliphatic acid or derivatives thereof is 1：2.
According to the preparation method of the fat or oil composition of the present invention, the lipase is 1,3 specific lipases.
According to the preparation method of the fat or oil composition of the present invention, described 1,3 specific lipases are selected from Lipozyme
RM IM, Lipozyme IM60, Lipozyme IM20, lipase
At least one in SP435, lipase SP382, lipase from candida sp, lipase MC7, Novozym 435, candida antarctica lipase B, R275A lipase or porcine pancreatic lipase or lipase D.
By the fat or oil composition prepared according to the preparation method of the fat or oil composition of the present invention.
According to the fat or oil composition of the present invention, the content of the dialkyl ketone of said composition is less than 10ppm.
It is a further object to provide a kind of preparation method of human milk fat substituted thing, the method includes the random step of transesterification that glycerine three is carried out random ester exchange reaction, it is characterised in that there is the compound with hydroxyl in above-mentioned random step of transesterification.
According to the preparation method of the human milk fat substituted thing of the present invention, the method also includes enzymatic orientation step of transesterification：The step of triglycerides and aliphatic acid or derivatives thereof are oriented ester exchange reaction in the presence of lipase.
According to the preparation method of the human milk fat substituted thing of the present invention, the method also includes：Molecular clock step, the molecular clock step is preferably before enzymatic orientation step of transesterification, or carries out after enzymatic orientation step of transesterification.
According to the triglycerides that the preparation method of the human milk fat substituted thing of the present invention, the triglycerides represent containing useful following formula (1),
In formula (1), R1、R2And R3Each identical or different, R1、R2And R3At least one of represent from the straight or branched that carbon number is 8～30 saturated fatty acid group.
According to the preparation method of the human milk fat substituted thing of the present invention, in formula (1), R1、R2And R3Each identical or different, R1、R2And R3At least one of represent from the linear saturated fatty acids that carbon number is 16～18 group.
According to the preparation method of the human milk fat substituted thing of the present invention, in formula (1), R1、R2And R3At least one of represent from palmitic acid group.
According to the preparation method of the human milk fat substituted thing of the present invention, in formula (1), R1、R2And R3Identical, all represent the group from palmitic acid.
According to the preparation method of the human milk fat substituted thing of the present invention, the triglycerides is plant origin.
According to the preparation method of the human milk fat substituted thing of the present invention, at least one of the triglycerides in the random ester exchange grease of the vegetable oil stearin containing three ester of palmitic acid, the vegetable oil containing three ester of palmitic acid or the vegetable oil containing three ester of palmitic acid.
According to the preparation method of the human milk fat substituted thing of the present invention, the fractionated palm oil that the triglycerides proposes tristearin, the palm oil stearin of random ester exchange, the palm oil of random ester exchange or random ester exchange selected from palm oil stearin, palm oil, fractionated palm oil puies forward at least one in tristearin.
According to the preparation method of the human milk fat substituted thing of the present invention, the random ester exchange is the random ester exchange of chemistry or the random ester exchange of enzyme process.
According to the preparation method of the human milk fat substituted thing of the present invention, the catalyst used in the random ester exchange of the enzyme process is nonspecific lipid enzyme.
According to the preparation method of the human milk fat substituted thing of the present invention, the nonspecific lipid enzyme is Lipozyme TL IM.
According to the preparation method of the human milk fat substituted thing of the present invention, the compound with hydroxyl is selected from least one of ethylene glycol, propane diols, glycerine, glycerin monostearate, trimethylolethane, antierythrite, pentaerythrite, sorbierite or xylitol.
According to the preparation method of the human milk fat substituted thing of the present invention, in terms of the total amount of the triglycerides, the amount of the compound with hydroxyl is 0.01～1.5 weight %.
According to the preparation method of the human milk fat substituted thing of the present invention, in terms of the total amount of the triglycerides, the amount of the compound with hydroxyl is 0.05～1.2 weight %.
According to the preparation method of the human milk fat substituted thing of the present invention, in terms of the total amount of the triglycerides, the amount of the compound with hydroxyl is 0.1～1.0 weight %.
According to the preparation method of the human milk fat substituted thing of the present invention, in terms of the total amount of the triglycerides, the amount of the compound with hydroxyl is 0.2～0.8 weight %.
According to the preparation method of the human milk fat substituted thing of the present invention, at least one of the aliphatic acid in the straight chain unrighted acid of carbon number 16～20.
According to the preparation method of the human milk fat substituted thing of the present invention, at least one of the derivative of fatty acid in the ester of the straight chain unrighted acid of carbon number 16～20.
According to the preparation method of the human milk fat substituted thing of the present invention, at least one of the described aliphatic acid or derivatives thereof in oleic acid, ethyl oleate, methyl oleate, high oleic sunflower oil or high oleic acid palm oil.
According to the preparation method of the human milk fat substituted thing of the present invention, the additional proportion of the triglycerides and the aliphatic acid or derivatives thereof, with weight ratio meter, triglycerides：Aliphatic acid or derivatives thereof is 1：2～5.
According to the preparation method of the human milk fat substituted thing of the present invention, the additional proportion of the triglycerides and the aliphatic acid or derivatives thereof, with weight ratio meter, triglycerides：Aliphatic acid or derivatives thereof is 1：2～4.
According to the preparation method of the human milk fat substituted thing of the present invention, the additional proportion of the triglycerides and the aliphatic acid or derivatives thereof, with weight ratio meter, triglycerides：Aliphatic acid or derivatives thereof is 1：2～3.
According to the preparation method of the human milk fat substituted thing of the present invention, the additional proportion of the triglycerides and the aliphatic acid or derivatives thereof, with weight ratio meter, triglycerides：Aliphatic acid or derivatives thereof is 1：2.
According to the preparation method of the human milk fat substituted thing of the present invention, the lipase is 1,3 specific lipases.
According to the preparation method of the human milk fat substituted thing of the present invention, described 1,3 specific lipases are selected from Lipozyme
RM IM, Lipozyme IM60, Lipozyme IM20, lipase
At least one in SP435, lipase SP382, lipase from candida sp, lipase MC7, Novozym 435, candida antarctica lipase B, R275A lipase or porcine pancreatic lipase or lipase D.
Human milk fat substituted thing prepared by the preparation method according to the human milk fat substituted thing of the present invention.
It is a further object to provide a kind of comprising above-mentioned fat or oil composition or above-mentioned human milk fat substituted thing composition.
It is a further object to provide a kind of comprising above-mentioned fat or oil composition or above-mentioned human milk fat substituted thing food.
It is a further object to provide a kind of baby formula milk powder, which includes above-mentioned fat or oil composition or above-mentioned human milk fat substituted thing.
It is a further object to provide a kind of dispensed food for baby, which includes above-mentioned fat or oil composition or above-mentioned human milk fat substituted thing.
It is a further object to provide a kind of substitute human milk fat composition, which includes above-mentioned fat or oil composition or above-mentioned human milk fat substituted thing.
It is a further object to provide a kind of dietary ingredient, which includes above-mentioned fat or oil composition or above-mentioned human milk fat substituted thing.
It is a further object to provide the purposes of above-mentioned fat or oil composition or above-mentioned human milk fat substituted thing in baby formula milk powder is prepared.
It is a further object to provide the purposes of above-mentioned fat or oil composition or above-mentioned human milk fat substituted thing in dispensed food for baby is prepared.
It is a further object to provide the purposes of above-mentioned fat or oil composition or above-mentioned human milk fat substituted thing in human milk fat substituted product are prepared.
It is a further object to provide the purposes of above-mentioned fat or oil composition or above-mentioned human milk fat substituted thing in dietary ingredient is prepared.
Invention effect
Preparation in accordance with the present invention, in resulting composition, the content of DAK is significantly reduced.The preparation method of the present invention does not affect the reaction process of random ester exchange.The preparation method operating process of the present invention is simple, easily realizes, additive safety, with low cost.The method of the present invention can be used for other chemically catalyzed interesterification products.
Specific embodiment
The preparation method of fat or oil composition
The preparation method of the fat or oil composition of the present invention, the method include the random step of transesterification that triglycerides is carried out random ester exchange reaction, it is characterised in that there is the compound with hydroxyl in above-mentioned random step of transesterification.
In the preferred embodiment of preparation method of the present invention, the triglycerides that the triglycerides represents containing useful following formula (1),
In formula (1), R1、R2And R3Each identical or different, R1、R2And R3At least one of represent from the straight or branched that carbon number is 8～30 saturated fatty acid group.In preferred formula (1), R1、R2And R3Each identical or different, R1、R2And R3At least one of represent from the linear saturated fatty acids that carbon number is 16～18 group.More preferably in formula (1), R1、R2And R3At least one of represent from palmitic acid group.Further preferably in formula (1), R1、R2And R3Identical, all represent the group from palmitic acid.
In the present invention, the group from aliphatic acid refers to eliminate residue obtained from hydroxyl in aliphatic acid.
In the preferred embodiment of preparation method of the present invention, the triglycerides is plant origin.Triglycerides from plant is selected from least one in the random ester exchange grease of the vegetable oil stearin containing three ester of palmitic acid, the vegetable oil containing three ester of palmitic acid or the vegetable oil containing three ester of palmitic acid.The fractionated palm oil that the triglycerides for being preferably derived from plant proposes tristearin, the palm oil stearin of random ester exchange, the palm oil of random ester exchange or random ester exchange selected from palm oil stearin, palm oil, fractionated palm oil puies forward at least one in tristearin.
In the present invention, the triglycerides can also be obtained as below, and vegetable fat is carried out conventional random ester exchange in the presence of a catalyst, obtain randomization grease.The vegetable fat is selected from Rice oil, sunflower oil, rape oil, palm oil, palm-kernel oil, peanut oil, rapeseed oil, soybean oil, cottonseed oil, safflower seed oil, Purple Perilla Seed Oil, tea-seed oil, olive oil, oleum theobromatis, tallowseed oil, almond oil, apricot kernel oil, bancoul nuts oil, rubber seed oil, corn oil, wheat germ oil, sesame seed oil, Castor oil, oenothera seed oil, hazelnut oil, pumpkin seed oil, nut oil, grape-kernel oil, borage seed oil, Seabuckthorm Seed Oil, tomato seed oil, macadimia nut oil, coconut oil, cocoa butter, at least one in algae oil etc., it is preferred that palm oil.
In the present invention, the randomization ester exchange is the random ester exchange of chemistry or the random ester exchange of enzyme process.
In a preferred embodiment of the invention, the randomization ester exchange is the random ester exchange of chemistry, and the chemical catalyst used in the random ester exchange of chemistry is acidic catalyst or base catalyst；Preferably, the chemical catalyst is NaOH, KOH, NaOCH3, caustic alcohol, organic base, solid base catalyst, sulfuric acid, sulfonic acid or solid acid catalyst；It is highly preferred that the chemical catalyst is NaOH, KOH, NaOCH3, sulfuric acid or sulfonic acid.
In embodiments of the present invention, chemically catalyzed interesterification reaction can pass through, for example, conventionally, mix raw oil material, in terms of the total amount of the triglycerides, 0.05%～0.4 weight % is added, after preferably 0.05%～0.2 weight %, the particularly preferably catalyst of 0.08%～0.1 weight %, under reduced pressure, at 80～160 DEG C stirring 20～90 minutes implementing.After ester exchange reaction terminates, hot water is used（Water temperature is higher than grease fusing point）Or citric acid or phosphate aqueous solution catalyst deactivation, terminate ester exchange reaction.The consumption for continuing increase chemical catalyst can dramatically increase the content of DAK.
In embodiments of the present invention, the randomization ester exchange is the random ester exchange of enzyme process, and the enzyme process ester exchange reaction including but not limited to uses lipase as catalyst.As lipase, it is possible to use lipase powder or the immobilized lipase that lipase powder is fixed on the carriers such as diatomite, ion exchange resin.Lipase used in randomization ester exchange reaction is a lack of site-specific ester exchange reaction, including but not limited to：Lipase from Alcaligenes, the lipase etc. from candida.
In embodiments of the present invention, enzyme process ester exchange reaction can be by, for example, adds lipase powder or the immobilized lipase of 0.02～10 weight % in raw oil material, then at 40～80 DEG C, stirs 0.5～48 hour.After ester exchange reaction terminates, lipase powder or immobilized lipase are removed by filtration etc..
It is preferred that the catalyst used in the random ester exchange of the enzyme process is nonspecific lipid enzyme.The nonspecific lipid enzyme is Lipozyme TL IM.
After the reaction of the random step of transesterification, reactant mixture can be carried out de- soap, drying, decolouring, filtration is washed by conventional method, obtain polished fat.
In a preferred embodiment of the invention, the compound with hydroxyl is selected from least one of ethylene glycol, propane diols, glycerine, glycerin monostearate, trimethylolethane, antierythrite, pentaerythrite, sorbierite or xylitol.
In a preferred embodiment of the invention, in terms of the total amount of the triglycerides, the amount of the compound with hydroxyl is 0.01～1.5 weight %, preferably 0.02～1.4 weight %, more preferably 0.05～1.2 weight %, more preferably 0.1～1.0 weight %, particularly preferred 0.2～0.8 weight %.
In the specific embodiment of the present invention, in terms of the total amount of the triglycerides, the amount of the compound with hydroxyl is 0.1 weight %, 0.2 weight %, 0.4 weight %, 0.5 weight %, 1 weight %.
In a preferred embodiment of the invention, at least one of the aliphatic acid in the straight chain unrighted acid of carbon number 16～20.Palmitoleic acid, oleic acid, linoleic acid, leukotrienes, eicosatrienoic acid, parinaric acid, arachidonic acid, eicosapentaenoic acid etc., preferably palmitoleic acid, oleic acid, linoleic acid, linolenic at least one can be enumerated.
In a preferred embodiment of the invention, at least one of the derivative of fatty acid in the ester of the straight chain unrighted acid of carbon number 16～20.The ester can be the Arrcostab of the carbon number 1～20 of the aliphatic acid of the invention described above, the alkenyl esters of carbon number 2～20, the aryl ester of carbon number 6～20, aralkyl ester of carbon number 7～20 etc..
The Arrcostab can enumerate methyl esters, ethyl ester, propyl ester, butyl ester, pentyl ester, own ester, heptyl ester, monooctyl ester, nonyl ester, last of the ten Heavenly stems ester, hendecane base ester, dodecyl ester, cetyl ester, stearyl etc..The alkenyl esters can enumerate vinyl acetate, propylene, butene esters, amylene ester, hexene ester, heptene ester, octene ester, nonene ester, ubidecarenone, hendecene base ester, laurylene base ester, hexadecylene base ester, octadecylene base ester etc..The aryl ester can enumerate phenylester, naphthyl ester etc..The aralkyl ester can enumerate benzyl ester etc..It is preferred that methyl esters or ethyl ester.
In a preferred embodiment of the invention, at least one of the described aliphatic acid or derivatives thereof in oleic acid, ethyl oleate, methyl oleate, high oleic sunflower oil or high oleic acid palm oil.
In the present invention, described aliphatic acid or derivatives thereof is sometimes referred to as " aliphatic acid of the present invention or derivatives thereof ".
The additional proportion of the aliphatic acid of the triglycerides and the present invention or derivatives thereof, with weight ratio meter, triglycerides：Aliphatic acid of the present invention or derivatives thereof is 1：2～5, preferably 1：2～4, more preferably 1：2～3, further preferred 1：2.
In the preferred embodiment of preparation method of the present invention, also include enzymatic orientation step of transesterification：The step of triglycerides and aliphatic acid or derivatives thereof are oriented ester exchange reaction in the presence of lipase.
In a preferred embodiment of the invention, orientation ester exchange is 1,3 orientations ester exchange of triglycerides.
The lipase is 1,3 specific lipases.Described 1,3 specific lipases are selected from Lipozyme RM IM, Lipozyme
IM60, Lipozyme IM20, lipase SP435, lipase SP382, lipase from candida sp, lipase MC7, Novozym 435, candida antarctica lipase B, R275A
Lipase or porcine pancreatic lipase or lipase D（The lipase D of such as amano enzyme preparation company production）In at least one.
The esterification is preferably carried out under heating, and there is no particular limitation for the temperature of heating, as long as not affecting the purpose of the present invention, e.g. 50～80 DEG C, preferably 60 DEG C.
There are special restriction, as long as not affecting the purpose of the present invention, e.g. 0.5～20 hour, preferably 1～10 hour the carrying out time of the esterification.
In the preferred embodiment of preparation method of the present invention, the method also includes：Molecular clock step, the molecular clock step is preferably before enzymatic orientation step of transesterification, or carry out after enzymatic orientation step of transesterification, or after the molecular clock step was carried out before enzymatic orientation step of transesterification, carry out after enzymatic orientation step of transesterification again further.It is preferred that carrying out molecular clock step after enzymatic orientation step of transesterification.
The distillation pressure of molecular clock is 0.2～3Pa, preferably 0.5～2Pa.Vapo(u)rizing temperature presses 130～200 DEG C, preferably 150～190 DEG C.
In the preferred embodiment of the preparation method of the fat or oil composition of the present invention, also include：The step of product being separated with unreacting material after ester exchange reaction.There is no particular limitation for separation method, can enumerate be separated by filtration, the mode such as centrifugation.
In a specific embodiment of the fat or oil composition preparation method of the present invention, in palm oil stearin, the glycerine of 1 weight % in terms of palm oil stearin, is added, random ester exchange is carried out, wherein in terms of palm oil stearin, add the sodium methoxide of 0.4 weight %.
In a specific embodiment of the fat or oil composition preparation method of the present invention, in palm oil stearin, the glycerine of 0.4 weight % in terms of palm oil stearin, is added, random ester exchange is carried out, wherein in terms of palm oil stearin, add the caustic alcohol of 0.24 weight %.
In a specific embodiment of the fat or oil composition preparation method of the present invention, in palm oil stearin, the glycerine of 0.5 weight % in terms of palm oil stearin, is added, random ester exchange is carried out, wherein in terms of palm oil stearin, add the NaOH of 0.2 weight %.
In a specific embodiment of the fat or oil composition preparation method of the present invention, in terms of palm oil, the 1 of 0.1 weight % is added in palm oil, 2- propane diols, carries out random ester exchange, wherein in terms of palm oil, the sodium methoxide of 0.1 weight % is added, the iodine number of the palm oil is 52.
In a specific embodiment of the fat or oil composition preparation method of the present invention, in palm oil, in terms of palm oil, add the monoglyceride of 0.2 weight %, carry out random ester exchange, wherein in terms of palm oil, the sodium methoxide of 0.1 weight % is added, and the iodine number of the palm oil is 52.
In a specific embodiment of the fat or oil composition preparation method of the present invention, in palm oil stearin, the glycerine of 1 weight % in terms of palm oil stearin, is added, carry out random step of transesterification, wherein in terms of palm oil stearin, the sodium methoxide of 0.4 weight % is added；And then molecular clock step is carried out, wherein evaporating temperature is 200 DEG C, absolute pressure 2pa；Subsequently gained molecular clock grease is refined, after obtaining polished fat, polished fat and ethyl oleate are pressed 1:2 part by weight mix, and add the lipase D of 5 weight % of compound lard total amount to carry out enzyme process orientation step of transesterification；Again molecular clock is carried out to this fat or oil composition, evaporating temperature is 180 DEG C, absolute pressure 2pa.
In a specific embodiment of the fat or oil composition preparation method of the present invention, in terms of palm oil, the 1 of 0.1 weight % is added in palm oil, 2- propane diols, carries out random step of transesterification, wherein in terms of palm oil, the sodium methoxide of 0.1 weight % is added, the iodine number of the palm oil is 52；And then molecular clock step is carried out, wherein evaporating temperature is 200 DEG C, absolute pressure 2pa；Subsequently gained molecular clock grease is refined, after obtaining polished fat, polished fat and oleic acid are pressed 1:2 part by weight mix, and add the Lipozyme RM IM of 5 weight % of compound lard total amount to carry out enzyme process orientation step of transesterification；Again molecular clock is carried out to this fat or oil composition, evaporating temperature is 180 DEG C, absolute pressure 2pa.
Fat or oil composition
The fat or oil composition of the present invention can be prepared by the preparation method of the fat or oil composition of the invention described above.The content of the dialkyl ketone of said composition is reduced, preferably shorter than 300ppm, more preferably less than 10ppm.
The preparation method of human milk fat substituted thing
The preparation method of the human milk fat substituted thing of the present invention, the method include the random step of transesterification that triglycerides is carried out random ester exchange reaction, it is characterised in that there is the compound with hydroxyl in above-mentioned random step of transesterification.
In the preferred embodiment of preparation method of the present invention, the triglycerides that the triglycerides represents containing useful following formula (1),
In formula (1), R1、R2And R3Each identical or different, R1、R2And R3At least one of represent from the straight or branched that carbon number is 8～30 saturated fatty acid group.In preferred formula (1), R1、R2And R3Each identical or different, R1、R2And R3At least one of represent from the linear saturated fatty acids that carbon number is 16～18 group.More preferably in formula (1), R1、R2And R3At least one of represent from palmitic acid group.Further preferably in formula (1), R1、R2And R3Identical, all represent the group from palmitic acid.
In the present invention, the group from aliphatic acid refers to eliminate residue obtained from hydroxyl in aliphatic acid.
In the preferred embodiment of preparation method of the present invention, the triglycerides is plant origin.Triglycerides from plant is selected from least one in the random ester exchange grease of the vegetable oil stearin containing three ester of palmitic acid, the vegetable oil containing three ester of palmitic acid or the vegetable oil containing three ester of palmitic acid.The fractionated palm oil that the triglycerides for being preferably derived from plant proposes tristearin, the palm oil stearin of random ester exchange, the palm oil of random ester exchange or random ester exchange selected from palm oil stearin, palm oil, fractionated palm oil puies forward at least one in tristearin.
In the present invention, the triglycerides can also be obtained as below, and vegetable fat is carried out conventional random ester exchange in the presence of a catalyst, obtain randomization grease.The vegetable fat is selected from Rice oil, sunflower oil, rape oil, palm oil, palm-kernel oil, peanut oil, rapeseed oil, soybean oil, cottonseed oil, safflower seed oil, Purple Perilla Seed Oil, tea-seed oil, olive oil, oleum theobromatis, tallowseed oil, almond oil, apricot kernel oil, bancoul nuts oil, rubber seed oil, corn oil, wheat germ oil, sesame seed oil, Castor oil, oenothera seed oil, hazelnut oil, pumpkin seed oil, nut oil, grape-kernel oil, borage seed oil, Seabuckthorm Seed Oil, tomato seed oil, macadimia nut oil, coconut oil, cocoa butter, at least one in algae oil etc., it is preferred that palm oil.
In the present invention, the randomization ester exchange is the random ester exchange of chemistry or the random ester exchange of enzyme process.
In a preferred embodiment of the invention, the randomization ester exchange is the random ester exchange of chemistry, and the chemical catalyst used in the random ester exchange of chemistry is acidic catalyst or base catalyst；Preferably, the chemical catalyst is NaOH, KOH, NaOCH3, caustic alcohol, organic base, solid base catalyst, sulfuric acid, sulfonic acid or solid acid catalyst；It is highly preferred that the chemical catalyst is NaOH, KOH, NaOCH3, sulfuric acid or sulfonic acid.
In embodiments of the present invention, chemically catalyzed interesterification reaction can pass through, for example, conventionally, mix raw oil material, in terms of the total amount of the triglycerides, 0.05%～0.4 weight % is added, after preferably 0.05%～0.2 weight %, the particularly preferably catalyst of 0.08%～0.1 weight %, under reduced pressure, at 80～160 DEG C stirring 20～90 minutes implementing.After ester exchange reaction terminates, hot water is used（Water temperature is higher than grease fusing point）Or citric acid or phosphate aqueous solution catalyst deactivation, terminate ester exchange reaction.The consumption for continuing increase chemical catalyst can dramatically increase the content of DAK.
In embodiments of the present invention, the randomization ester exchange is the random ester exchange of enzyme process, and the enzyme process ester exchange reaction including but not limited to uses lipase as catalyst.As lipase, it is possible to use lipase powder or the immobilized lipase that lipase powder is fixed on the carriers such as diatomite, ion exchange resin.Lipase used in randomization ester exchange reaction is a lack of site-specific ester exchange reaction, including but not limited to：Lipase from Alcaligenes, the lipase etc. from candida.
In embodiments of the present invention, enzyme process ester exchange reaction can be by, for example, adds lipase powder or the immobilized lipase of 0.02～10 weight % in raw oil material, then at 40～80 DEG C, stirs 0.5～48 hour.After ester exchange reaction terminates, lipase powder or immobilized lipase are removed by filtration etc..
It is preferred that the catalyst used in the random ester exchange of the enzyme process is nonspecific lipid enzyme.The nonspecific lipid enzyme is Lipozyme TL IM.
After the reaction of the random step of transesterification, reactant mixture can be carried out de- soap, drying, decolouring, filtration is washed by conventional method, obtain polished fat.
In a preferred embodiment of the invention, the compound with hydroxyl is selected from least one of ethylene glycol, propane diols, glycerine, glycerin monostearate, trimethylolethane, antierythrite, pentaerythrite, sorbierite or xylitol.
In a preferred embodiment of the invention, in terms of the total amount of the triglycerides, the amount of the compound with hydroxyl is 0.01～1.5 weight %, preferably 0.02～1.4 weight %, more preferably 0.05～1.2 weight %, more preferably 0.1～1.0 weight %, particularly preferred 0.2～0.8 weight %.
In the specific embodiment of the present invention, in terms of the total amount of the triglycerides, the amount of the compound with hydroxyl is 0.1 weight %, 0.2 weight %, 0.4 weight %, 0.5 weight %, 1 weight %.
In a preferred embodiment of the invention, at least one of the aliphatic acid in the straight chain unrighted acid of carbon number 16～20.Palmitoleic acid, oleic acid, linoleic acid, leukotrienes, eicosatrienoic acid, parinaric acid, arachidonic acid, eicosapentaenoic acid etc., preferably palmitoleic acid, oleic acid, linoleic acid, linolenic at least one can be enumerated.
In a preferred embodiment of the invention, at least one of the derivative of fatty acid in the ester of the straight chain unrighted acid of carbon number 16～20.The ester can be the Arrcostab of the carbon number 1～20 of the aliphatic acid of the invention described above, the alkenyl esters of carbon number 2～20, the aryl ester of carbon number 6～20, aralkyl ester of carbon number 7～20 etc..
The Arrcostab can enumerate methyl esters, ethyl ester, propyl ester, butyl ester, pentyl ester, own ester, heptyl ester, monooctyl ester, nonyl ester, last of the ten Heavenly stems ester, hendecane base ester, dodecyl ester, cetyl ester, stearyl etc..The alkenyl esters can enumerate vinyl acetate, propylene, butene esters, amylene ester, hexene ester, heptene ester, octene ester, nonene ester, ubidecarenone, hendecene base ester, laurylene base ester, hexadecylene base ester, octadecylene base ester etc..The aryl ester can enumerate phenylester, naphthyl ester etc..The aralkyl ester can enumerate benzyl ester etc..It is preferred that methyl esters or ethyl ester.
In a preferred embodiment of the invention, at least one of the described aliphatic acid or derivatives thereof in oleic acid, ethyl oleate, methyl oleate, high oleic sunflower oil or high oleic acid palm oil.
In the present invention, described aliphatic acid or derivatives thereof is sometimes referred to as " aliphatic acid of the present invention or derivatives thereof "..
The additional proportion of the aliphatic acid of the triglycerides and the present invention or derivatives thereof, with weight ratio meter, triglycerides：Aliphatic acid of the present invention or derivatives thereof is 1：2～5, preferably 1：2～4, more preferably 1：2～3, further preferred 1：2.
In the preferred embodiment of preparation method of the present invention, also include enzymatic orientation step of transesterification：The step of triglycerides and aliphatic acid or derivatives thereof are oriented ester exchange reaction in the presence of lipase.
In a preferred embodiment of the invention, orientation ester exchange is 1,3 orientations ester exchange of triglycerides.
The lipase is 1,3 specific lipases.Described 1,3 specific lipases are selected from Lipozyme RM IM, Lipozyme
IM60, Lipozyme IM20, lipase SP435, lipase SP382, lipase from candida sp, lipase MC7, Novozym 435, candida antarctica lipase B, R275A
Lipase or porcine pancreatic lipase or lipase D（The lipase D of such as amano enzyme preparation company production）In at least one.
The esterification is preferably carried out under heating, and there is no particular limitation for the temperature of heating, as long as not affecting the purpose of the present invention, e.g. 50～80 DEG C, preferably 60 DEG C.
There are special restriction, as long as not affecting the purpose of the present invention, e.g. 0.5～20 hour, preferably 1～10 hour the carrying out time of the esterification.
In the preferred embodiment of preparation method of the present invention, the method also includes：Molecular clock step, the molecular clock step is preferably before enzymatic orientation step of transesterification, or carry out after enzymatic orientation step of transesterification, or after the molecular clock step was carried out before enzymatic orientation step of transesterification, carry out after enzymatic orientation step of transesterification again further.It is preferred that carrying out molecular clock step after enzymatic orientation step of transesterification.
The distillation pressure of molecular clock is 0.2～3Pa, preferably 0.5～2Pa.Vapo(u)rizing temperature presses 130～200 DEG C, preferably 150～190 DEG C.
In the preferred embodiment of the preparation method of the human milk fat substituted thing of the present invention, also include：The step of product being separated with unreacting material after ester exchange reaction.There is no particular limitation for separation method, can enumerate be separated by filtration, the mode such as centrifugation.
In a specific embodiment of the human milk fat substituted thing preparation method of the present invention, in palm oil stearin, the glycerine of 1 weight % in terms of palm oil stearin, is added, random ester exchange is carried out, wherein in terms of palm oil stearin, add the sodium methoxide of 0.4 weight %.
In a specific embodiment of the human milk fat substituted thing preparation method of the present invention, in palm oil stearin, the glycerine of 0.4 weight % in terms of palm oil stearin, is added, carry out random ester exchange, wherein in terms of palm oil stearin, the caustic alcohol of 0.24 weight % is added.
In a specific embodiment of the human milk fat substituted thing preparation method of the present invention, in palm oil stearin, the glycerine of 0.5 weight % in terms of palm oil stearin, is added, carry out random ester exchange, wherein in terms of palm oil stearin, the NaOH of 0.2 weight % is added.
In a specific embodiment of the human milk fat substituted thing preparation method of the present invention, in terms of palm oil, the 1 of 0.1 weight % is added in palm oil, 2- propane diols, carries out random ester exchange, wherein in terms of palm oil, the sodium methoxide of 0.1 weight % is added, the iodine number of the palm oil is 52.
In a specific embodiment of the human milk fat substituted thing preparation method of the present invention, in palm oil, in terms of palm oil, add the monoglyceride of 0.2 weight %, carry out random ester exchange, wherein in terms of palm oil, the sodium methoxide of 0.1 weight % is added, and the iodine number of the palm oil is 52.
In a specific embodiment of the human milk fat substituted thing preparation method of the present invention, in palm oil stearin, the glycerine of 1 weight % in terms of palm oil stearin, is added, carry out random step of transesterification, wherein in terms of palm oil stearin, the sodium methoxide of 0.4 weight % is added；And then molecular clock step is carried out, wherein evaporating temperature is 200 DEG C, absolute pressure 2pa；Subsequently gained molecular clock grease is refined, after obtaining polished fat, polished fat and ethyl oleate are pressed 1:2 part by weight mix, and add the lipase D of 5 weight % of compound lard total amount to carry out enzyme process orientation step of transesterification；Again molecular clock is carried out to this fat or oil composition, evaporating temperature is 180 DEG C, absolute pressure 2pa.
In a specific embodiment of the human milk fat substituted thing preparation method of the present invention, in terms of palm oil, the 1 of 0.1 weight % is added in palm oil, 2- propane diols, carries out random step of transesterification, wherein in terms of palm oil, the sodium methoxide of 0.1 weight % is added, the iodine number of the palm oil is 52；And then molecular clock step is carried out, wherein evaporating temperature is 200 DEG C, absolute pressure 2pa；Subsequently gained molecular clock grease is refined, after obtaining polished fat, polished fat and oleic acid are pressed 1:2 part by weight mix, and add the Lipozyme RM IM of 5 weight % of compound lard total amount to carry out enzyme process orientation step of transesterification；Again molecular clock is carried out to this fat or oil composition, evaporating temperature is 180 DEG C, absolute pressure 2pa.
Human milk fat substituted thing
The human milk fat substituted thing of the present invention can be prepared by the human milk fat substituted thing preparation method of the invention described above.The content of the dialkyl ketone of the human milk fat substituted thing is reduced, and preferably its DAK content is less than 300ppm, more preferably less than 10ppm.
Food
The present invention provides the food of the fat or oil composition comprising the present invention or human milk fat substituted thing.The food can be selected from babies ' formula milk powder and infant formula, baked goods, including bread, especially biscuit and strudel, dairy products, including milk and milk beverage, ice cream, cereal product, baste, coating, including margarine, oil ＆ fat, bean product, meat products, fried food, confectionery, loaf sugar, candy and chocolate, fast food, beverage and shake bland, instant beverage products, for infants and young and the prepared food for being grown up, including prefabricated cooked food mud and/or pulp, seasoning, cook oil ＆ fat and meat products.
The food of the present invention includes, but it is not limited to, the dispensed food for baby such as dairy products, frying and bakery, meat product, tartar sauce, beverage etc., such as milk, Yoghourt, icecream, milk shake, cheese, milk powder, cream, sterile milk, modulation breast, acidified milk, condensed milk, milk powder, whey powder, PURE WHEY, cheese, processed cheese, baby formula milk powder；Potato chips, fried dough twist；Cake, bread, thin pancake, snow cake, crisp short cakes with sesame, moon cake, sesame seed cake, group, toast, egg roll puff, roasting pudding, egg milk sauce, biscuit, waffle, Egg Tarts, instant noodles, instant-rice, Pizza, buttered tea, saqima, rice grain pattern, rice cake, Zongzi；Meat products：Ham sausage, sausage, Baconic, roast pork, pork luncheon meat, jerky, dried pork slice, cured pork, bacon, sausage；Mayonnaise, crisp sweets, toffee, milk tea, coffee, tea beverage.It is preferred that dispensed food for baby.In the specific embodiment of the present invention, preferred baby formula milk powder.
The food of the present invention conventionally can be prepared by being contacted the fat or oil composition or human milk fat substituted thing with food acceptable carrier.
In the present invention, the food acceptable carrier includes, but it is not limited to, for example starch, cellulose, dextrin, butterfat, animal and plant fat such as sesame oil, soybean oil, peanut oil, palm oil, olive oil, corn oil, rapeseed oil, lard, butter etc., edible glue such as gum arabic, gelatin, carragheen, xanthans, guar gum, sodium alginate etc., phosphatide such as lecithin, cephalin etc., baking powder etc..
In the present invention, term " infant formula " is referred to：Newborn base infant formula or beans base infant formula.
Newborn base infant formula：Refer to newborn class and milk protein preparation as primary raw material, add appropriate vitamin, mineral matter and/or other compositions, the liquid that is only made with physical method production and processing or powder product.It is suitable to normal infant to eat, its energy and nutrient content disclosure satisfy that the normal nutrition needs of 0～6 month infant.
Beans base infant formula：Refer to soybean and soy protein products as primary raw material, add appropriate vitamin, mineral matter and/or other compositions, the liquid that is only made with physical method production and processing or powder product.It is suitable to normal infant to eat, its energy and nutrient content disclosure satisfy that the normal nutrition needs of 0～6 month infant.
In the present invention, term " larger infants and young's formula food " is referred to：With newborn class and milk protein preparation and/or soybean and soy protein products as primary raw material, add appropriate vitamin, mineral matter and/or other auxiliary materials, the liquid that is only made with physical method production and processing or powder product, edible suitable for larger infants and young, its nutrient content can meet normally larger baby（6～12 monthly ages）And child（12～36 monthly ages）Part nutritional need.
The fat or oil composition of the present invention or human milk fat substituted thing can be used in mixed way with cow's milk, sheep breast, milk powder, butterfat etc. according to formula design requirement in the case of infant formula or larger infants and young's formula food is applied to.
In the present invention, " infant " also refers to baby or larger infants and young, and " dispensed food for baby " also refers to infant formula or larger infants and young's formula food.
Purposes
The fat or oil composition of the present invention or human milk fat substituted thing can be used to prepare baby formula milk powder.
The fat or oil composition of the present invention or human milk fat substituted thing can be used to prepare dispensed food for baby.
The fat or oil composition of the present invention or human milk fat substituted thing can be used to prepare human milk fat substituted product.
The fat or oil composition of the present invention or human milk fat substituted thing can be used to prepare dietary ingredient.
The fat or oil composition of the present invention or human milk fat substituted thing can be used to prepare food.The features described above that the present invention is mentioned, or the feature that embodiment is mentioned can be in any combination.All features disclosed in this case specification can be used in combination with any combinations thing form, each feature disclosed in specification, and the alternative characteristics that any can provide identical, impartial or similar purpose replace.Therefore except there is special instruction, disclosed feature is only impartial or similar features general examples.
With reference to specific embodiment, the present invention is expanded on further.It should be understood that these embodiments are only illustrative of the invention and is not intended to limit the scope of the invention.The experimental technique of unreceipted actual conditions in the following example, generally according to normal condition or according to the condition proposed by manufacturer.Unless otherwise indicated, otherwise all of percentage, ratio, ratio or number be by weight.
The unit in percent weight in volume in the present invention is well-known to those skilled in the art, for example, refer to the weight of solute in 100 milliliters of solution.
Unless otherwise defined, all specialties used in text are identical with meaning familiar to one skilled in the art institute with scientific words.Additionally, any method similar or impartial to described content and material are all can be applicable in the inventive method.Preferable implementation described in text is only presented a demonstration with material and is used.
" monoglyceride " is also referred to as " glycerin monostearate " herein." SFC " refers to solid fats content.
Embodiment
Reactant and catalyst in embodiments of the invention all may be from commercially available.Palm oil and palm oil stearin special oil in praising（Shanghai）Co., Ltd, oleic acid oil chemical industry in praising（Shanghai）Co., Ltd, sodium methoxide and caustic alcohol derive from Sigma
Aldrich, lipase D, Lipozyme
RM IM believes that from Novi other chemical reagent such as glycerine derive from Chemical Reagent Co., Ltd., Sinopharm Group.
In product in the embodiment of the present invention, the detection method of DAK content is shown in patent WO2009012982.
Product ester exchange rate in embodiments of the invention is by detection raw material and the change calculations of the solid fat content of product：
Ester exchange rate=（SFC raw material-SFC product）/（SFC raw material-SFC is balanced）×100%
Wherein SFC balance is obtained by determining the product of completely random ester exchange：Feedstock oil is heated to 105 DEG C, control vacuum carries out dehydration 1h in 2 mbar；0.4% sodium methoxide is added, vacuum degree control reacts 30min under 2 mbar at a temperature of 105 DEG C；Add the aqueous citric acid solution of said mixture weight 20%（Concentration 8%）, stir 20min terminating reaction.Cyclic washing is carried out to reactant with hot water, until pH=7, takes off soap.105 DEG C are heated to, vacuum stirring 30min dehydrates and ester exchange offspring is obtained, as the sample of completely random ester exchange.
Embodiment 1
1% glycerine being added in 500g palm oil stearin, heating to 105 DEG C, control vacuum carries out dehydration 1h in 10mbar；0.4% sodium methoxide is added, vacuum degree control reacts 30min under 30mbar at a temperature of 105 DEG C；Add the aqueous citric acid solution of said mixture weight 20%（Concentration 8%）, stir 20min terminating reaction.Cyclic washing is carried out to reactant with hot water, until pH=7, takes off soap.105 DEG C are heated to, vacuum stirring 30min dehydrates and ester exchange grease 1 is obtained, its DAK content of sample analysis and ester exchange rate, the results are shown in Table 1.
Comparative example 1a
500g palm oil stearin is heated to 105 DEG C, control vacuum carries out dehydration 1h in 10mbar；0.4% sodium methoxide is added, vacuum degree control reacts 30min under 30mbar at a temperature of 105 DEG C；Add the aqueous citric acid solution of said mixture weight 20%（Concentration 8%）, stir 20min terminating reaction.Cyclic washing is carried out to reactant with hot water, until pH=7, takes off soap.105 DEG C are heated to, vacuum stirring 30min dehydrates and ester exchange grease 2 is obtained, its DAK content of sample analysis and ester exchange rate, the results are shown in Table 1.
Comparative example 1b
500g palm oil stearin is heated to 105 DEG C, control vacuum carries out dehydration 1h in 10mbar；0.4% sodium methoxide is added, vacuum degree control reacts 30min under 30mbar at a temperature of 105 DEG C；Add 1% glycerine, high-temperature is risen to 170 DEG C, react 10min, obtain ester exchange grease 3 under vacuum condition, its DAK content of sample analysis and ester exchange rate, the results are shown in Table 1.
Comparative example 1c
500g palm oil stearin is heated to 170 DEG C, control vacuum after keeping 1h, is obtained grease 4, its DAK content and ester exchange rate is measured by sampling, the results are shown in Table 1 in 10mbar.
Comparative example 1d
500g palm oil stearin is heated to 170 DEG C, control vacuum after keeping 1h, is added 1% glycerine, keeping temperature and vacuum, after reaction 10min, grease 5 obtained, its DAK content and ester exchange rate is measured by sampling, the results are shown in Table 1 in 10mbar.
Table 1
| Numbering | DAK content（ppm） | Ester exchange rate（%） |
| Ester exchange grease 1 | 682.5 | 102.3 |
| Ester exchange grease 2 | 973.2 | 99.1 |
| Ester exchange grease 3 | 946.4 | 99.5 |
| Grease 4 | Do not detect | 0 |
| Grease 5 | Do not detect | 0 |
Above-described embodiment shows that DAK is mainly derived from the side reaction in the ester-exchange reaction of this kind of chemical catalyst catalysis of sodium methoxide.If there is no catalyst in system, DAK is nearly free under the high temperature conditions, while ester exchange reaction can not be produced.Additionally, adding this kind of material of glycerine effectively suppress the yield of DAK in course of reaction before the reaction starts.However, adding glycerine after ester exchange reaction terminates, by pyroreaction, the reduction to DAK is not almost acted on.
Embodiment 2
0.4% glycerine being added in 500g palm oil stearin, heating to 105 DEG C, control vacuum carries out dehydration 1h in 10mbar；0.2% caustic alcohol is added, vacuum degree control reacts 30min under 10mbar at a temperature of 90 DEG C；Add the aqueous citric acid solution of said mixture weight 20%（Concentration 8%）, stir 20min terminating reaction.Cyclic washing is carried out to reactant with hot water, until pH=7, takes off soap.105 DEG C are heated to, vacuum stirring 30min dehydrates and ester exchange grease 6 is obtained, its DAK content of sample analysis and ester exchange rate, the results are shown in Table 2.
Comparative example 2
500g palm oil stearin is heated to 105 DEG C, control vacuum carries out dehydration 1h in 10mbar；0.2% caustic alcohol is added, vacuum degree control reacts 30min under 10mbar at a temperature of 90 DEG C；Add the aqueous citric acid solution of said mixture weight 20%（Concentration 8%）, stir 20min terminating reaction.Cyclic washing is carried out to reactant with hot water, until pH=7, takes off soap.105 DEG C are heated to, vacuum stirring 30min dehydrates and ester exchange grease 7 is obtained, its DAK content of sample analysis and ester exchange rate, the results are shown in Table 2.
Embodiment 3
0.5% glycerine being added in 500g palm oil stearin, heating to 105 DEG C, control vacuum carries out dehydration 1h in 10mbar；0.2% NaOH is added, vacuum degree control reacts 60min under 10mbar at a temperature of 120 DEG C；Add the aqueous citric acid solution of said mixture weight 20%（Concentration 8%）, stir 20min terminating reaction.Cyclic washing is carried out to reactant with hot water, until pH=7, takes off soap.105 DEG C are heated to, vacuum stirring 30min dehydrates and ester exchange grease 8 is obtained, its DAK content of sample analysis and ester exchange rate, the results are shown in Table 2.
Table 2
| Numbering | DAK content（ppm） | Ester exchange rate（%） |
| Ester exchange grease 6 | 122.5 | 103 |
| Ester exchange grease 7 | 231.3 | 100.7 |
| Ester exchange grease 8 | 68.6 | 96.8 |
Embodiment 4
0.1% 1,2-PD is added in 500g palm oil (iodine number IV=52), 105 DEG C are heated to, control vacuum carries out dehydration 1h in 10mbar；0.1% sodium methoxide is added, vacuum degree control reacts 30min under 10mbar at a temperature of 80 DEG C；Add the aqueous citric acid solution of said mixture weight 20%（Concentration 8%）, stir 20min terminating reaction.Cyclic washing is carried out to reactant with hot water, until pH=7, takes off soap.105 DEG C are heated to, vacuum stirring 30min dehydrates and ester exchange grease 9 is obtained, its DAK content of sample analysis and ester exchange rate, the results are shown in Table 3.
Embodiment 5
0.2% monoglyceride is added in 500g palm oil (iodine number IV=52), 105 DEG C are heated to, control vacuum carries out dehydration 1h in 10mbar；0.1% sodium methoxide is added, vacuum degree control reacts 30min under 10mbar at a temperature of 80 DEG C；Add the aqueous citric acid solution of said mixture weight 20%（Concentration 8%）, stir 20min terminating reaction.Cyclic washing is carried out to reactant with hot water, until pH=7, takes off soap.105 DEG C are heated to, vacuum stirring 30min dehydrates and ester exchange grease 10 is obtained, its DAK content of sample analysis and ester exchange rate, the results are shown in Table 3.
Comparative example 4
By 500g palm oil（Iodine number IV=52）105 DEG C are heated to, control vacuum carries out dehydration 1h in 10mbar；0.1% sodium methoxide is added, vacuum degree control reacts 30min under 10mbar at a temperature of 80 DEG C；Add the aqueous citric acid solution of said mixture weight 20%（Concentration 8%）, stir 20min terminating reaction.Cyclic washing is carried out to reactant with hot water, until pH=7, takes off soap.105 DEG C are heated to, vacuum stirring 30min dehydrates and ester exchange grease 11 is obtained, its DAK content of sample analysis and ester exchange rate, the results are shown in Table 3.
Table 3
| Numbering | DAK content（ppm） | Ester exchange rate（%） |
| Ester exchange grease 9 | 20.7 | 106.4 |
| Ester exchange grease 10 | 25.2 | 97 |
| Ester exchange grease 11 | 50.5 | 98.6 |
Embodiment 6
Ester exchange grease 1 in embodiment 1 is carried out molecular clock, evaporating temperature is 200 DEG C, 40 DEG C of heat exchanger temperature, rotating speed 250rpm, absolute pressure 2pa.Collect heavy phase and molecular clock grease 1 is obtained, DAK content is determined, the results are shown in Table 4.
2% atlapulgite of weight is added in above-mentioned molecular clock grease 1, at 110 DEG C, keep 30min to be decolourized, be filtrated to get grease after decolouring.Grease is heated to 240 DEG C, 2mbar and nitrogen are advertised down and deodorization 3h is carried out, and obtain polished fat 1.200g polished fat 1 and ethyl oleate are pressed 1:2 ratios mix, the lipase D of compound lard total amount 5% is added to carry out enzyme process orientation ester exchange, reaction temperature is 60 DEG C, filter after reaction 5h and dezymotize, fat or oil composition is obtained, molecular clock is carried out to this fat or oil composition, evaporating temperature is 180 DEG C, 50 DEG C of heat exchanger temperature, rotating speed 250rpm, absolute pressure 2pa.Collect heavy phase and OPO composition 1 is obtained, DAK content is determined, the results are shown in Table 4.
Comparative example 5
The ester exchange grease 2 of comparative example 1a is added 2% atlapulgite of weight, at 110 DEG C, is kept 30min to be decolourized, is filtrated to get grease after decolouring.Grease is heated to 240 DEG C, 2mbar and nitrogen are advertised down and deodorization 3h is carried out, and obtain polished fat 2.200g polished fat 2 and ethyl oleate are pressed 1:2 ratios mix, the lipase D of compound lard weight 5% is added to carry out enzyme process orientation ester exchange, reaction temperature is 60 DEG C, filter after reaction 5h and dezymotize, fat or oil composition is obtained, molecular clock is carried out to this fat or oil composition, evaporating temperature is 180 DEG C, 50 DEG C of heat exchanger temperature, rotating speed 250rpm, absolute pressure 2pa.Collect heavy phase and OPO composition 2 is obtained, DAK content is determined, the results are shown in Table 4.
Table 4
| Numbering | DAK content（ppm） |
| Ester exchange grease 1 | 682.5 |
| Molecular clock grease 1 | 457.8 |
| Polished fat 1 | 435.7 |
| OPO composition 1 | 278.1 |
| Ester exchange grease 2 | 973.2 |
| Polished fat 2 | 922.5 |
| OPO composition 2 | 654.3 |
Embodiment 7
Ester exchange grease 9 in embodiment 4 is carried out molecular clock, evaporating temperature is 200 DEG C, 40 DEG C of heat exchanger temperature, rotating speed 250rpm, absolute pressure 2pa.Collect heavy phase and molecular clock grease 2 is obtained, DAK content is determined, the results are shown in Table 5.
2% atlapulgite of weight is added in the grease after above-mentioned molecular clock, at 110 DEG C, keep 30min to be decolourized, be filtrated to get grease after decolouring.Grease is heated to 240 DEG C, 2mbar and nitrogen are advertised down and deodorization 3h is carried out, and obtain polished fat 3.This polished fat of 200g and oleic acid are pressed 1:2 ratios mix, the Lipozyme RM IM of compound lard total amount 5% is added to carry out enzyme process orientation ester exchange, reaction temperature is 60 DEG C, filter after reaction 5h and dezymotize, fat or oil composition is obtained, molecular clock is carried out to this fat or oil composition and sloughs remaining aliphatic acid, evaporating temperature is 180 DEG C, 50 DEG C of heat exchanger temperature, rotating speed 250rpm, absolute pressure 2pa.Collect heavy phase and OPO composition 3 is obtained, DAK content is determined, the results are shown in Table 5.
Table 5
| Numbering | DAK content（ppm） |
| Ester exchange grease 9 | 20.7 |
| Molecular clock grease 2 | 11.8 |
| Polished fat 3 | 10.5 |
| OPO composition 3 | 3.1 |
The process described in embodiment 8 is carried out to ester exchange grease 10, and the DAK content in the OPO composition 4 of acquisition is also smaller than 10ppm.
Above embodiment shows that add the high boiling substance containing hydroxyl during chemically catalyzed interesterification, such as glycerine, propane diols, monoglyceride etc., can significantly reduce the content of DAK in product, and ensure that ester exchange reaction is unaffected.Additionally, the DAK material produced during chemically catalyzed interesterification is difficult to be removed by traditional refining process, but the DAK formed by the removal that molecular clock can be by a relatively large margin.The method provided using the present invention prepares OPO composition, and its DAK content can be significantly reduced, and preferably its DAK content reduces by more than 50, and preferably its DAK content is less than 300ppm, and more preferably its DAK content is less than 10ppm.Meanwhile, the method for the present invention can be suitably used for the chemically catalyzed interesterification reaction of different material, control the content of DAK in its product.
The foregoing is only presently preferred embodiments of the present invention, it is not limited to the substantial technological context of the present invention, the substantial technological content of the present invention is broadly defined in the right of application, any technology entities that other people complete or method, if identical with defined in the right of application, also or a kind of equivalent change, will all be considered to be covered by among the right.
Claims (14)
1. a kind of preparation method of fat or oil composition, the method include the random step of transesterification that triglycerides is carried out random ester exchange reaction, it is characterised in that there is the compound with hydroxyl in above-mentioned random step of transesterification.
2. a kind of preparation method of human milk fat substituted thing, the method include the random step of transesterification that triglycerides is carried out random ester exchange reaction, it is characterised in that there is the compound with hydroxyl in above-mentioned random step of transesterification.
3. preparation method according to claim 1 and 2, the method also include enzymatic orientation step of transesterification：The step of triglycerides and aliphatic acid or derivatives thereof are oriented ester exchange reaction in the presence of lipase, and/or molecular clock step, the molecular clock step is preferably before enzymatic orientation step of transesterification, or carries out after enzymatic orientation step of transesterification.
4. the preparation method according to claims 1 to 3 any one, the triglycerides that the triglycerides represents containing useful following formula (1),
In formula (1), R1、R2And R3Each identical or different, R1、R2And R3At least one of represent from the straight or branched that carbon number is 8～30 saturated fatty acid group, it is preferred that R1、R2And R3At least one of represent from the linear saturated fatty acids that carbon number is 16～18 group, more preferably R1、R2And R3At least one of represent from palmitic acid group, particularly preferred R1、R2And R3Identical, all represent the group from palmitic acid.
5. the preparation method according to Claims 1 to 4 any one, the triglycerides is plant origin, it is preferred that the triglycerides is selected from the vegetable oil stearin containing three ester of palmitic acid, at least one in the random ester exchange grease of the vegetable oil containing three ester of palmitic acid or the vegetable oil containing three ester of palmitic acid, more preferably described triglycerides is selected from palm oil stearin, palm oil, fractionated palm oil carries tristearin, the palm oil stearin of random ester exchange, the random palm oil of ester exchange or the fractionated palm oil of random ester exchange put forward at least one in tristearin.
6. the preparation method according to Claims 1 to 5 any one, it is the random step of transesterification of chemistry in the random step of transesterification, wherein chemical catalyst is acidic catalyst or base catalyst, it is preferable that the chemical catalyst is NaOH, KOH, NaOCH3, caustic alcohol, organic base, solid base catalyst, sulfuric acid, sulfonic acid or solid acid catalyst；It is highly preferred that the chemical catalyst is NaOH, KOH, NaOCH3, sulfuric acid or sulfonic acid, it is preferred that in terms of the total amount of the triglycerides, add 0.05%～0.4 weight %, particularly preferably preferably 0.05%～0.2 weight %, the catalyst of 0.08%～0.1 weight %.
7. the preparation method according to claim 1～6 any one, the compound with hydroxyl are selected from least one of ethylene glycol, propane diols, glycerine, glycerin monostearate, trimethylolethane, antierythrite, pentaerythrite, sorbierite or xylitol.
8. the preparation method according to claim 1～7 any one, in terms of the total amount of the triglycerides, the amount of the compound with hydroxyl is 0.01～1.5 weight %, preferably 0.05～1.2 weight %, more preferably 0.1～1.0 weight %, particularly preferably 0.2～0.8 weight %.
9. the preparation method according to claim 3～8 any one, at least one of the aliphatic acid in the straight chain unrighted acid of carbon number 16～20, it is preferred that at least one of the derivative of fatty acid in the ester of the straight chain unrighted acid of carbon number 16～20, at least one of the more preferably described aliphatic acid or derivatives thereof in oleic acid, ethyl oleate, methyl oleate, high oleic sunflower oil or high oleic acid palm oil.
10. the preparation method according to claim 3～9 any one, the additional proportion of the triglycerides and the aliphatic acid or derivatives thereof, with weight ratio meter, triglycerides：Aliphatic acid or derivatives thereof is 1：2～5, preferably 1：2～4, more preferably 1：2～3, particularly preferably 1：2.
11. preparation methods according to claim 3～10 any one, the lipase is 1,3 specific lipases, preferably, described 1,3 specific lipases are selected from Lipozyme RM IM, Lipozyme IM60, Lipozyme IM20, lipase SP435, lipase SP382, lipase from candida sp, lipase MC7, Novozym 435, candida antarctica lipase B, R275A lipase or porcine pancreatic lipase or at least one in lipase D.
12. fat or oil compositions prepared by the preparation method described in claim 1～11 any one or human milk fat substituted thing, the content of preferably wherein dialkyl ketone are less than 300ppm, are more preferably less than 10ppm.
A kind of 13. fat or oil compositions comprising described in claim 12 or the composition of human milk fat substituted thing, it is preferred that the composition is food, more preferably baby formula milk powder, dispensed food for baby, substitute human milk fat composition or dietary ingredient.
Fat or oil composition or human milk fat substituted thing described in 14. claims 12 preparing baby formula milk powder or dispensed food for baby or human milk fat substituted product or the purposes in dietary ingredient.
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