CN106260090A - Non-hydrogenated CBS fat or oil composition and preparation method thereof - Google Patents

Non-hydrogenated CBS fat or oil composition and preparation method thereof Download PDF

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CN106260090A
CN106260090A CN201510258265.6A CN201510258265A CN106260090A CN 106260090 A CN106260090 A CN 106260090A CN 201510258265 A CN201510258265 A CN 201510258265A CN 106260090 A CN106260090 A CN 106260090A
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fat
fats
oils
content
acid
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CN106260090B (en
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姜波
俞建国
张虹
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Wilmar Shanghai Biotechnology Research and Development Center Co Ltd
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Wilmar Shanghai Biotechnology Research and Development Center Co Ltd
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Abstract

The present invention provides a kind of fat or oil composition, it is characterised in that described fat or oil composition fullness in the epigastrium and abdomen be enough to lower condition: content >=87% of (1) TAG, content≤13% of DAG;(2) content of hard fat when 25 DEG C >=60%, when 30 DEG C >=21%, when 35 DEG C≤12%;(3) contain C36 and above XYLa type content of triglyceride is more than 10%, PPO≤68%;Wherein X, Y be carbon number be the satisfied fatty acid of 12~22, La is lauric acid;X, Y, La are on the optional position of triglyceride;P be Palmic acid, O be oleic acid.Fat or oil composition provided by the present invention does not contains trans fatty acid;And it is applied in chocolate have into mould, the superperformance such as release property, mouth fusibleness, fragility, glossiness.

Description

Non-hydrogenated CBS fat or oil composition and preparation method thereof
Technical field
The present invention provides fat or oil composition, its preparation method and the food containing this fat or oil composition.
Background technology
Cocoa butter (cocoa butter) is a kind of natural oil of preparation from cacao bean, is to prepare ingeniously The preferable oils and fats of gram force row's block (chocolate bar).Owing to the raw material production of cocoa butter is by weather The strict restriction of condition, its yield can not meet far away the demand of people, the therefore generation of natural cocoa butter Articles for use arise at the historic moment.According to the glyceride stock used and the difference of processing technique, cocoa butter substitutes Cocoa butter substitute and cacaolike butter can be divided into.Cocoa butter substitute is divided into again lauric (cocoa butter Substitute, CBS) and non-lauric acid type (cocoa butter replacer, CBR) two kinds.
The preparation method of CBS is with palm-kernel oil as primary raw material mostly, palm-kernel oil cooling point is carried, Take its solid fat, make through refine and hydrogenation.The structure of their triglyceride (TAG) is the most not It is same as the TAG structure of cocoa butter, but its physical characteristic, as similar to cocoa butter in fusing point, pre-arcing characterisitics. The chocolate prepared with CBS has the advantages such as technique is simple, hardness good, and fragility is good, mouthfeel Yi Hua. Shortcoming is to have employed HYDROGENATION OF OILS AND FATS technique, and saturated fatty acid content is higher, for chocolate pie block The saturated acid content of CBS is even up to more than 99%.
Hydrogenation process for CBS is to use perhydrogenating technique (full hydrogenation), will not produce Raw trans fatty acid.But overwhelming majority consumer is not comprehensive to hydrogenation technology understanding, easily employing is hydrogenated Oil and fat product prepared by technique is equal to the oil and fat product containing trans fatty acid.Hyper acid for trans fats Absorption can increase the risk suffering from cardiovascular disease, along with the raising of health of people consciousness, major part consumption Food containing hydrogenated oil and fat is compared repulsion by person, is unwilling to buy.
Patent ZL00104510.5 describes a kind of cocoa butter replacer, and this cocoa butter replacer is by Petiolus Trachycarpi Core oil, hydrogenated palm kernel oil, palmkernel stearin and hydrogenated palm kernel oleostearin mix.This Bright still employ hydrogenated oil and fat.
Patent US20090022868 describes a kind of unhydrided confection oil, is contained by least one Lauric oils and fats and at least one non-lauric acid lipid carry out ester exchange acquisition.But this oils and fats is suitable for The products such as chocolate coating (coating), not mentioned at chocolate pie block (chocolate bar) Application.
G.Calliauw et al. describes a kind of 2 steps and divides the method that CBS prepared by palm-kernel oil that puies forward, but not Reveal the physical characteristic such as crystalline rate of palmkernel stearin prepared by the method and its preparing chalk Application performance (G.Calliauw, the I of power row's block.Foubert,et al.production of cocoa butter substitutes via two‐stage static fractionation of palm kernel oil[J],JAOCS, Vol.82,no.11(2005))。
Thus it still remains a need invention one is applicable to chocolate, the particularly non-hydrogenated of chocolate pie block CBS, uses the chocolate of the preparation of this CBS to have rapid Cheng Mo (moulding) simultaneously, excellent The characteristics such as release property (demoulding), mouth fusibleness, fragility (snap), glossiness.
Summary of the invention
Based on drawbacks described above, related personnel of the present invention has done substantial amounts of further investigation work, finds with spy The triglyceride of fixed composition, particular solid content of fatty acid and the specific oils and fats group constituting fatty acid Compound uses as fat, it is thus achieved that the plastic fat of resisting temperature fluctuation, thus completes the present invention.
A first aspect of the present invention, it is provided that a kind of fat or oil composition.
A second aspect of the present invention, it is provided that the second fat or oil composition.
A third aspect of the present invention, it is provided that the preparation method of fat or oil composition.
A fourth aspect of the present invention, it is provided that a kind of food.
A first aspect of the present invention, it is provided that a kind of fat or oil composition, meets in described fat or oil composition Following condition:
(1) content of TAG is more than or equal to 87%, preferably 90 99.9%, and the content of DAG is less than or equal to 13%, preferably 0 9.1%;
(2) content of hard fat is more than 60% when 25 DEG C, preferably 62 95%, and it is 21% when 30 DEG C Above, preferably 26 70%, it is not higher than 12% when 35 DEG C, preferably 0 10%;
(3) the XYLa type content of triglyceride containing more than C36 is more than 10%, preferably 38 95%, Asymmetrical type triglyceride PPO content is not higher than 68%, and preferably 0 62%;Wherein X, Y are Carbon number is the satisfied fatty acid of 12~22, and La is lauric acid;X, Y, La are at glycerol three On the optional position of ester;P be Palmic acid, O be oleic acid;
In a specific embodiment, in described fat or oil composition, Semen Myristicae bean acid (C14:0, M) contains Amount≤23%, preferably 0 20%, oleic acid content≤21%, preferably 0 15%, stearic acid (C18:0, St) content >=4%, preferably 5 20%.
In another specific embodiment, described fat or oil composition is prepared from by following steps: (1) The compositions comprising monoglyceride and the compositions comprising lauric acid and/or laurate carry out ester exchange and obtain To fat A;(2) the Long carbon chain saturated fatty acid content oils and fats more than 40% is with oleic acid, oleic acid at least A kind of ester or their mixture carry out ester exchange and obtain oils and fats B;(3) fat A is mixed with oils and fats B, Described step (1), (2) can order or backward carry out.
In another specific embodiment, described oils and fats B is containing unsymmetry triglyceride SSO Oils and fats, wherein S be carbon number be the satisfied fatty acid of 12~22, preferably carbon number be 16~18 Satisfied fatty acid, O represents oleic acid.
In another specific embodiment, in described oils and fats B, the content of SSO is 40-100%, preferably 60-100%.
A second aspect of the present invention, it is provided that the second fat or oil composition, described fat or oil composition comprises One or both in fat A, oils and fats B, described fat A is the compositions and bag comprising monoglyceride Ester exchange oils and fats containing lauric acid and/or the compositions of laurate, described oils and fats B is containing asymmetric The oils and fats of property triglyceride SSO, wherein S be carbon number be the satisfied fatty acid of 12~22, preferably Carbon number is the satisfied fatty acid of 16~18, and O represents oleic acid.
In a specific embodiment, described fat A is A/B >=0.1 with the mass ratio of oils and fats B, preferably 0.1-10。
In a specific embodiment, the compositions of monoglyceride and the combination comprising lauric acid or its ester are comprised described in The mass ratio of thing is 2:1-1:3, preferably 1:1.1~1:2.
In a specific embodiment, in described oils and fats B, the content of SSO is 40-100%, preferably 60-100%.
In a specific embodiment, described oils and fats B is that Long carbon chain saturated fatty acid content is more than 40% Oils and fats and oleic acid, at least one ester of oleic acid or the ester exchange oils and fats of their mixture, wherein said Long carbon chain satisfied fatty acid refers to the satisfied fatty acid that carbon number is more than or equal to 16.
In a specific embodiment, the described Long carbon chain saturated fatty acid content oils and fats more than 40% is Petiolus Trachycarpi oil, fractionated palm oil carry tristearin, deep hydrogenation fractionated palm oil carries tristearin, hydrogenated palm oil, Petiolus Trachycarpi Oil point carry palmitin, hydrogenated soybean oil, hydrogenated rapeseed oil, hydrogenated sunflower oil one or more;Described Oleate is one or more in methyl oleate, ethyl oleate, acid isopropyl.
In a specific embodiment, described Long carbon chain saturated fatty acid content more than 40% oils and fats with The weight ratio of oleic acid, at least one ester of oleic acid or their mixture is not less than 1, preferably 2~3.
A third aspect of the present invention, it is provided that the preparation method of a kind of fat or oil composition, described method includes Following steps: the compositions that (1) comprises monoglyceride and the compositions comprising lauric acid and/or laurate Carry out ester exchange and obtain fat A;(2) the Long carbon chain saturated fatty acid content oils and fats more than 40% and oil Acid, at least one ester of oleic acid or their mixture carry out ester exchange and obtain oils and fats B;(3) by fat A Mix with oils and fats B, described step (1), (2) can order or backward carry out.
In a specific embodiment, described oils and fats B is obtained by enzyme process ester exchange, it is preferable that institute State oils and fats B to be obtained by selectivity ester exchange.
A fourth aspect of the present invention, it is provided that a kind of food, containing first, second side in described food Fat or oil composition that face provides or the fat or oil composition prepared according to manufacture method described in the third aspect, or Food described in person uses the fat or oil composition of first, second aspect offer or makes according to described in the third aspect Fat or oil composition prepared by the method for making is made.
In a specific embodiment, described food be preferably chocolate, whipping cream, cake, cookies, Or sandwich beans;More preferably chocolate pie block.
Invention effect
The compositions of the present invention does not contains trans fatty acid, more healthy;
The compositions of the present invention is rapid Cheng Mo (moulding), excellent release property in chocolate (demoulding), the characteristic such as mouth fusibleness, fragility (snap), glossiness.
The preparation method of the present composition is non-hydrogenated technique, and resulting composition does not contains trans fatty acid, contains There is more unsaturated fatty acid, more healthy.
Specific embodiment
" scope " disclosed herein is with lower limit and the form of the upper limit.Can be respectively one or more under Limit, and one or more upper limit.Given range is to be limited by a selected lower limit and a upper limit Fixed.Selected lower limit and the upper limit define the border of special scope.All can carry out by this way The scope limited comprises and can be combined, and the most any lower limit can form one with the combination of any upper limit Scope.Such as, list the scope of 26-70 and 62-95 for special parameter, be interpreted as 24-75 Also expect with the scope of 60-98.If additionally, the minimum zone value 1 and 2 listed, and If listing maximum magnitude value 3,4 and 5, then scope below can all expect: 1-3,1-4, 1-5,2-3,2-4 and 2-5.
In the present invention, unless otherwise indicated, the content range of each component of compositions and it is excellent Select can be mutually combined between scope and form new technical scheme.
In the present invention, unless otherwise indicated, " a combination thereof " represents that the multicomponent of described each component mixes Compound, such as two kinds, three kinds, four kinds and until the multicomponent mixture of maximum possible.
In the present invention, unless otherwise indicated, all " part " and percent (%) all refers to weight hundred Mark.
In the present invention, unless otherwise indicated, in all compositionss, the percent sum of each component is 100%.
In the present invention, unless otherwise indicated, what numerical range " a-b " represented between a to b is any The breviary of real combinings represents, wherein a and b is real number.Such as numerical range " 0-10 " represents this The most all listing the whole real numbers between " 0-10 " in literary composition, " 0-10 " is the contracting of these combinations of values Sketch form shows.
Without particularly pointing out, the term " a kind of " used by this specification refers to " at least one ".
Without particularly pointing out, the benchmark of percent of the present invention (including percetage by weight) It it is all the gross weight of described compositions.
In this article, except as otherwise noted, ratio or the weight of each component all refers to dry weight.
In the present invention, without particularly explanation, all embodiments mentioned in this article and Preferred implementation can be mutually combined and form new technical scheme.
In the present invention, without particularly explanation, all technical characteristics mentioned in this article and Preferred feature can be mutually combined and form new technical scheme.
In the present invention, without particularly explanation, " including " mentioned in this article represents open, Can also be closed.Such as, described " including " can expression can also comprise other do not listed Element, it is also possible to only include the element listed.
In the present invention, without particularly explanation, the concrete numerical value in embodiment hereof and tool Body material can be combined with other features of part described herein.
A first aspect of the present invention, it is provided that a kind of fat or oil composition.
A second aspect of the present invention, it is provided that the second fat or oil composition.
A third aspect of the present invention, it is provided that the preparation method of fat or oil composition.
A fourth aspect of the present invention, it is provided that a kind of food.
A first aspect of the present invention, it is provided that a kind of fat or oil composition, meets in described fat or oil composition Following condition:
(1) content of TAG is more than or equal to 87%, preferably 90 99.9%, and the content of DAG is less than or equal to 13%, preferably 0 9.1%;
(2) content of hard fat is more than 60% when 25 DEG C, preferably 62 95%, and it is 21% when 30 DEG C Above, preferably 26 70%, it is not higher than 12% when 35 DEG C, preferably 0 10%;
(3) contain C36 and above XYLa type content of triglyceride is more than 10%, preferably 38 95%, Asymmetrical type triglyceride PPO content is not higher than 68%, and preferably 0 62%;Wherein X, Y are carbon atom Number is the satisfied fatty acid of 12~22, and La is lauric acid;X, Y, La are in the optional position of triglyceride On;P be Palmic acid, O be oleic acid.
In the present invention, term " TAG " refers to triglyceride, and term " DAG " refers to glycerol Diester, " C36 and more than " refers to total carbon number is 36 and above triglyceride.
In the present invention, X, Y can be lauric acid, Palmic acid, stearic acid, oleic acid, linoleic acid, Linolenic acid, arachidic acid, behenic acid;X, Y can be the same or different.In the present invention, X, Y Be preferably lauric acid, Palmic acid, stearic acid therein one or more.
In one particular embodiment of the present invention, Semen Myristicae bean acid in described fat or oil composition (C14:0, M) content≤23%, preferably 0 20%, oleic acid content≤21%, preferably 0 15%, stearic acid (C18: 0, St) content >=4%, preferably 5 20%.
In the present invention, the fusing point of described fat or oil composition is 30 37 DEG C;Saturated fatty acid content is 78~100%.
In the present invention, in described fat or oil composition, lauric content is 6~65%.
In the present invention, in described fat or oil composition, the content of trans fatty acid is 0 2%.
In another specific embodiment, described fat or oil composition is prepared from by following steps: (1) The compositions comprising monoglyceride and the compositions comprising lauric acid and/or laurate carry out ester exchange and obtain To fat A;(2) the Long carbon chain saturated fatty acid content oils and fats more than 40% is with oleic acid, oleic acid at least A kind of ester or their mixture carry out ester exchange and obtain oils and fats B;(3) fat A is mixed with oils and fats B, Described step (1), (2) can order or backward carry out.
In another specific embodiment, described oils and fats B is containing unsymmetry triglyceride SSO Oils and fats, wherein S be carbon number be the satisfied fatty acid of 12~22, preferably carbon number be 16~18 Satisfied fatty acid, O represents oleic acid.
In another specific embodiment, in described oils and fats B, the content of SSO is 40-100%, preferably 60-100%.
A second aspect of the present invention, it is provided that the second fat or oil composition, described fat or oil composition comprises oil One or both in fat A, oils and fats B, described fat A is the compositions that comprises monoglyceride and comprise The compositions of lauric acid and/or its ester carries out the oils and fats of ester exchange acquisition, and described oils and fats B is for containing the most right Claim property triglyceride SSO oils and fats, wherein S be carbon number be the satisfied fatty acid of 12~22, excellent The satisfied fatty acid selecting carbon number to be 16~18, O represents oleic acid.
In one particular embodiment of the present invention, monoglyceride in the compositions of monoglyceride is comprised described in Content is more than 90%.
In one particular embodiment of the present invention, comprise described in the compositions of lauric acid and/or its ester The content of lauric acid and/or its ester is more than 90%.
In the present invention, unless specifically indicated, heretofore described monoglyceride refers to that glycerol is former with carbon The straight or branched fatty acid (the preferably linear saturated fatty acids of carbon number 16) of subnumber more than 16 is formed Monoesters, it is also possible to being the more mixture of content of monoglyceride, such as content of monoglyceride is not less than 30%, the most not Less than 40%, preferably not less than 50%, preferably not less than 60%, preferably not less than 70%, it is preferably not less than 80%, the mixture of the glyceride of more desirably not less than 90% (e.g. monoester content 60%, two ester content 35%, The monoglyceride of three ester contents 5%).
The compositions comprising monoglyceride can be according to need with the specifically used amount or ratio that comprise lauric compositions Monoglyceride to be used and the content of monoglyceride, the lauric acid of needs use and bag in comprising the compositions of monoglyceride Determine containing content lauric in lauric compositions.
In one particular embodiment of the present invention, described fat A is A/B > with the mass ratio of oils and fats B 0.1, preferably 0.1-10.
In another specific embodiment of the present invention, described in comprise monoglyceride compositions with comprise lauric acid and / or the mass ratio of compositions of its ester be 2:1-1:3, preferably 1:1.1~1:2.
In another specific embodiment of the present invention, in described oils and fats B, the content of SSO is 40-100%, preferably 60-100%.
In another specific embodiment of the present invention, described oils and fats B is that Long carbon chain satisfied fatty acid contains The amount oils and fats more than 40% and oleic acid, at least one ester of oleic acid or the ester exchange oils and fats of their mixture, Wherein said Long carbon chain satisfied fatty acid refers to the satisfied fatty acid that carbon number is more than 16.
In another specific embodiment of the present invention, described Long carbon chain saturated fatty acid content is more than 40% Oils and fats be Petiolus Trachycarpi oil, fractionated palm oil carries tristearin, deep hydrogenation fractionated palm oil carries tristearin, hydrogenated palm Oil, fractionated palm oil put forward palmitin, hydrogenated soybean oil, hydrogenated rapeseed oil, the one of hydrogenated sunflower oil or many Kind;Described oleate is one or more in methyl oleate, ethyl oleate, acid isopropyl.
In another specific embodiment of the present invention, described Long carbon chain saturated fatty acid content is more than 40% The weight ratio of oils and fats and oleic acid, at least one ester of oleic acid or their mixture not less than 1, excellent Select 2~3.
A third aspect of the present invention, it is provided that the preparation method of a kind of fat or oil composition, described method includes Following steps: the compositions that (1) comprises monoglyceride is carried out with the compositions comprising lauric acid and/or its ester Ester exchange obtains fat A;(2) Long carbon chain saturated fatty acid content oils and fats and oleic acid more than 40%, At least one ester of oleic acid or their mixture carry out ester exchange and obtain oils and fats B;(3) by fat A and oil Fat B mix, described step (1), (2) can order or backward carry out.
In one particular embodiment of the present invention, comprise the compositions of monoglyceride described in and comprise Laurel The composition quality of acid and/or its ester ratio is for 2:1-1:3, preferably 1:1.1~1:2.
In the present invention, described ester exchange reaction can conventionally be carried out.Described ester exchange Reaction can be carried out in the presence of a catalyst.Described catalyst includes that base catalyst, acidity are urged Agent, biological enzyme agent etc..Wherein, base catalyst include being soluble in alcohol catalyst (as NaOH, KOH, NaOCH3, organic base etc.) and various solid base catalyst;Acidic catalyst Including being soluble in the catalyst (such as sulphuric acid, sulfonic acid etc.) of alcohol and various solid acid catalyst, preferably NaOCH3 (Feldalat NM).The consumption of catalyst is 0.05~2.0 weight % of reaction-ure mixture, excellent Select 0.1 weight %.
Described step of transesterification can also be carried out in the presence of lipase.Described lipase enzyme be non-specially The lipase of one property, can be commercially available enzyme (the such as Lipzoyme TL IM of Novi's letter), it is possible to For the enzyme fermented voluntarily, or for enzyme powder being dissolved in the enzyme liquid of buffer.Described lipase can make It is used for from animal, the lipase of plant, it is possible to use from the lipase of microorganism, as from dredging Lanuginosus spore bacterium (Thermomyces lanuginosus), Rhizopus oryzae (Rhizopus oryzae), rice Rhizomocur miehei (Rhizomucor miehei), antarctic candida (Candida antarctica), aspergillus niger (Aspergillus niger), bulkholderia cepasea (Burkholderia sp.), fold candida (Candida rugosa), Bacillus alcaligenes (Alcaligenes sp.), mucor javanicus (Mucor javanicus), In Rhizopus niveus (Rhizopus niveus), geotrichum candidum (Cryytococcus neoformans) etc. any one Plant or its genetic modification strain.
According to described manufacture method, also include distilling, preferably the product of described esterification Molecular distillation, to remove the step of reaction raw materials, preferably removes monoglyceride, lauric acid and DAG.
Esterification therein, distillation or molecular distillation process, be well known to those skilled in the art, Those skilled in the art can be according to the required purpose reached adjustment design parameter, such as 200 DEG C points Son distillation.
In another specific embodiment of the present invention, described Long carbon chain satisfied fatty acid refers to that carbon containing is former The subnumber satisfied fatty acid not less than 16.
In another specific embodiment of the present invention, Semen Myristicae bean acid in described fat or oil composition (C14: 0, M) content≤23%, preferably 0 20%, oleic acid content≤21%, preferably 0 15%, stearic acid (C18: 0, St) content >=4%, preferably 5 20%.
In another specific embodiment of the present invention, described oleate be methyl oleate, ethyl oleate, One or more in oleic acid propyl ester, acid isopropyl.
In another specific embodiment of the present invention, described oils and fats B is obtained by enzyme process ester exchange, Preferably obtained by selectivity ester exchange.
In another specific embodiment of the present invention, the preparation method of described oils and fats B is in ester exchange After reaction, triglyceride is enriched with and solvent divides the process of putting forward.
In another specific embodiment of the present invention, described solvent divide carry during use solvent be One or more in acetone, normal hexane, ethanol, methanol, the tert-butyl alcohol, normal heptane.
A fourth aspect of the present invention, it is provided that a kind of food, containing first, second side in described food Fat or oil composition that face provides or the fat or oil composition prepared according to manufacture method described in the third aspect, or Food described in person uses the fat or oil composition of first, second aspect offer or makes according to described in the third aspect Fat or oil composition prepared by the method for making is made.
In a specific embodiment, described food be preferably chocolate, whipping cream, cake, cookies, Or sandwich beans;More preferably chocolate pie block.
The food of the present invention include, but not limited to chocolate (such as, sweet chocolate, milk chocolate, half Sweet chocolate, buttermilk chocolate, white chocolate or colored chocolate and polytype chocolate food), Preferably chocolate row's block;Chocolate also includes the chocolate-coated (being coated with chocolate) with chocolate flavouring With other materials playing chocolate substitute effect;Margarine and other things playing margarine substitute effect Matter, chocolate, whipping cream, cake, cookies, sandwich beans etc..
The food of the present invention can conventionally, by by described fat or oil composition and the acceptable load of food Prepared by body contact.
In a preferred embodiment of the invention, cocoa powder, white sugar, the fat or oil composition of the present invention, lecithin With ball mill fine grinding to without grains of sand sense (such as 1 hour);The chocolate mass of gained is placed on baking oven (such as 50 DEG C) After fully melting, chocolate mass is watered in plastic module, after cooling, make chocolate bar.
In a preferred embodiment of the invention, oils and fats and oil phase substance are heated (such as 70 DEG C), stand-by, Oil phase substance includes oils and fats, polysorbate60, sorbester p18, lecithin, sodium stearoyl lactate, propylene glycol fatty acid Ester.Heat after all substances are dissolved, add sodium caseinate and be dispersed in oil, it is thus achieved that oil phase;By glucose Slurry is added to the water, and heats up (such as 65 DEG C~70 DEG C).By xanthan gum, melon glue, microcrystalline Cellulose, sugarcane Being added to the water after the mixing of sugar, salt, dipotassium hydrogen phosphate, stirring (such as 1200 revs/min) to all materials divides Dissipate, it is thus achieved that aqueous phase;Oil phase is slowly added in aqueous phase, 2000 revs/min of stirrings (such as 2000 revs/min, 30min);Homogenizing;Cool down material (such as 2~4 DEG C) with ice cream maker, be put into aging in refrigerator (such as 2~ 4 DEG C, 5h), it is then placed in refrigerator (such as 20 DEG C) storing;Take the plant fresh cream of adfreezing, Thaw (such as 5 DEG C) with warm water and stir to without ice crystal, beating by whipper middling speed (such as 160rpm), Dense to liquid butter retrogradation when beating, lustrous surface disappears, and has soft spike can obtain optimal foam when being formed Structure;Butter piping bag is extruded, places (such as 10 degree, 30 minutes) at baking oven.
In the present invention, described food acceptable carrier includes, but not limited to such as starch, cellulose, Dextrin, butterfat, animal and plant fat such as Oleum sesami, soybean oil, Oleum Arachidis hypogaeae semen, Petiolus Trachycarpi oil, olive oil, Semen Maydis Oil, Oleum Brassicae campestris, Adeps Sus domestica, Adeps Bovis seu Bubali etc., edible glue such as Radix Acaciae senegalis, gelatin, carrageenan, xanthan gum, Guar gum, sodium alginate etc., phospholipid such as lecithin, cephalin etc., baking powder etc., emulsifying agent such as glycerol Fatty acid ester, sucrose fatty acid ester, Span, lecithin etc., antioxidant, coloring agent is fragrant Material etc..
It is described in detail to various aspects of the present invention below in conjunction with embodiment, it is intended to make those skilled in the art The present invention is better understood from, but the scope of the present invention embodiment off guard is limited.
Raw material sources:
Monoglyceride: DMG-CF01, purchased from Jia Li oil chemical industry (Shanghai) Co., Ltd.
Lauric acid: LA-1299, purchased from Feng Yi oil chemistry company limited
Esterified Enzyme: candida antarctica lipase B (CALBL), believe purchased from Novi
Palmkernel stearin: iodine value 6.8, purchased from Southseas Specialty Fats Industrial (Shanghai) Co., Ltd.
Oleic acid: sharp dragon oleic acid OA-7075, purchased from Feng Yi oil chemistry company limited
Non-selective lipase: Lipozyme TL IM believes purchased from Novi
Selected fat enzyme: Lipozyme RMIM, believes purchased from Novi
CBS product: LHK32-03, purchased from Southseas Specialty Fats Industrial (Shanghai) Co., Ltd.
Cocoa powder: low fat cocoa powder, invests (Chinese) company limited purchased from Jia Ji
Defatted milk powder: New Zealand's peace is good
Lecithin: soybean lecithin, purchased from Goldensea Foodstuff Industries Co., Ltd.
White sugar, acetone, ethyl oleate are commercial
Instrument and equipment:
Wiped film molecular distillation equipment: model KDL-5, VTA company of Germany
Ball mill: Wiener W-1-S, WIENER company
Chromatograph of liquid: 1200 type Agilent companies
Gas chromatograph: 7820 type Agilent companies
Detection method:
The detection method of DAG is with reference to AOCS Cd 11d-96 (2009)
The detection method reference AOCS ce5-86 of TAG,
SFC detection method is with reference to AOCS Cd 16b-93.
Fatyy acids method reference: AOCS Ce lf-96,
The analysis method reference literature (Wei Tingting etc. of the isomerss such as PPO/POP.Series connection silver ion chromatographic column The research of analytical structure triglyceride isomers, Chinese oil [J] 2012,37 (7) 79-81)
The detection method of iodine number is with reference to AOCS Cd 1d-92
Embodiment 1
Weighing 330g monoglyceride and 600g lauric acid in 2000ml flask, under rushing nitrogen protection, evacuation is (true Reciprocal of duty cycle 20mbar) and stir (mixing speed 100rpm) and be heated to 220 DEG C, and after 220 DEG C of reaction 6h It is cooled to 60 DEG C of stopped reaction and obtains Crude CBS.Crude is removed by KDL-5 wiped film molecular distillation equipment Fatty acid in CBS, monoglyceride even partial glycerol diester, collect heavy phase portion and obtain oil sample 1.1.Specifically Condition is as follows, and temperature is 180 DEG C, material flow 200g/h, and blade applicator rotating speed is 120rpm.
Embodiment 2
Weighing 330g monoglyceride and 440g lauric acid in 2000ml flask, under rushing nitrogen protection, evacuation is (true Reciprocal of duty cycle 20mbar) and stir (mixing speed 100rpm) and be heated to 220 DEG C, and after 220 DEG C of reaction 6h It is cooled to 60 DEG C of stopped reaction and obtains Crude CBS.Crude is removed by KDL-5 wiped film molecular distillation equipment Fatty acid in CBS, monoglyceride even partial glycerol diester, collect heavy phase portion and obtain oil sample 1.2.Specifically Condition is as follows, and temperature is 200 DEG C, material flow 170g/h, and blade applicator rotating speed is 120rpm.
Embodiment 3
Weigh 330g monoglyceride and 500g lauric acid in 2000ml flask, be heated with stirring to 70 DEG C, add 55g Esterified Enzyme (Novi's letter commercial enzyme-candida antarctica lipase B (CALBL)) reaction 10h, from The heart separates (centrifugal rotational speed 8000rpm) removing lipase and obtains Crude CBS.By conventional on oil prodution industry Refine means-alkali refining, decolouring, deodorize obtain oil sample 1.3.Actual conditions is as follows: alkali refining (Crude CBS It is heated to adding at 80 DEG C the sodium hydrate aqueous solution of 25% concentration, after stirring reaction 30min, centrifugation), Oil sample after alkali refining (is heated to 90~110 DEG C under vacuum, adds the hargil of oils and fats weight 3%, stirring by decolouring After reaction 30min, it is cooled to 70 DEG C of filtrations), deodorize is (under vacuum stirring inflated with nitrogen, by the oil sample after decolouring It is heated to 210 DEG C, after maintaining 2h, is cooled to 65 DEG C).
Embodiment 4
Weigh oils and fats 1.1 that embodiment 1 obtains with palmkernel stearin (iodine value 6.8) according to 4:1's (w/w) Ratio mixes, it is thus achieved that oil sample 1.4.
Embodiment 5
Weigh oils and fats 1.1 that embodiment 1 obtains and palmkernel stearin (iodine value 6.8) ratio according to 3:2 (w/w) Example mixes, it is thus achieved that oil sample 1.5.
Embodiment 6
Weigh oils and fats 1.3 that embodiment 3 obtains and palmkernel stearin (iodine value 6.8) ratio according to 9:1 (w/w) Mix, it is thus achieved that oil sample 1.6
Embodiment 7
7.1 ester exchange reaction
Fractionated palm oil carries tristearin (iodine value 14.6, palmitic acid content 82%) and is mixed in (1:1.5, w/w) with oleic acid In glass beaker, have 1, under 3 selected fat enzyme Lipozyme RMIM effects, carrying out ester exchange reaction. Enzyme-added in reactor is the 6% of oil weight, and reaction temperature is 60 DEG C, response time 9h, and mixing speed is 60rpm, The reactant mixture I obtained.
7.2 triglyceride enrichments
Mixture I, through decompression distillation, vapo(u)rizing temperature 220 DEG C, removes fatty acid, collects and mixes rich in triglyceride The heavy phase II of thing.
7.3 solvents divide and carry
Heavy phase II and acetone (1 4, w/w) are made into mixture, heat this mixture to clear, are then stirring Mix down (90rpm) and be cooled to 10 DEG C, maintain about 1 hour.10 DEG C filter separate, it is thus achieved that solid part Divide and liquid portion.The liquid portion obtained directly is supplemented the acetone of loss, heats this mixture to clarification thoroughly Bright, the most under agitation it is cooled to 1 DEG C, maintains about 1 hour.Filter at about 1 DEG C and separate, it is thus achieved that Oils and fats 2 is obtained after solid portion precipitation.
Embodiment 8
Petiolus Trachycarpi oil (iodine value 52, palmitic acid content 42%) is mixed with (1:3, w/w) with ethyl oleate, according to reality Execute that the identical reaction condition of example 7 carries out ester exchange, enrichment triglyceride, solvent divide and carry acquisition oils and fats 3.
Embodiment 9
Oils and fats 1.1 mixes acquisition compound lard 1 with oils and fats 2 with the ratio of 3:2 (wt/wt).
Embodiment 10
Oils and fats 1.1 mixes acquisition compound lard 2 with oils and fats 3 with the ratio of 2:3 (wt/wt).
Embodiment 11
Oils and fats 1.1 mixes acquisition compound lard 3. with oils and fats 2 with the ratio of 1:9 (wt/wt)
Embodiment 12
Oils and fats 1.2 mixes acquisition compound lard 4. with oils and fats 2 with the ratio of 9:1 (w/w)
Comparative example 1
According to document (G.Calliauw, I, Foubert, et al.production of cocoa butter substitutes via two-stage static fractionation of palm kernel oil[J], JAOCS, Vol.82, no.11 (2005)) method mentioned prepares palmkernel stearin (PKST, iodine value 5.1) -oil sample A, carries out dry fractionation by the palm-kernel oil (iodine value 18) after refine, and crystallization temperature is 22 DEG C, protects After holding 4h, filter pressing obtains solid oil fraction.
Comparative example 2.
Oils and fats 650gPKST (iodine value 7) and 350g is prepared according to the method for embodiment in patent US20090022868 2 Palmitic stearin (PST, iodine value 19.8), mixing carries out chemically catalyzed interesterification, and employing Feldalat NM is catalyst, Reaction temperature is 100 DEG C, reacts 30 minutes, obtains oil sample B after refine.
Carry out each oil sample detecting indices as shown in Table 1 and Table 2
The indices testing result of each oil sample of table 1
The indices testing result of each oil sample of table 2
Embodiment 13 application experiment
Carry out chocolate pie block according to following table formula to prepare:
Chocolate pie block manufacturing process:
All materials are put in 60 DEG C of ball mill, drum's speed of rotation 6.5 grades mixing 90min, 3 grades of mixing are set Material is released after 30min.Regulation temperature of charge is 40~45 DEG C, and material is cast in preheated plastic formwork In, scrape off the most rapidly unnecessary material, after vibration, put in 10 DEG C of baking ovens and place cooling certain time, After by template tilt, tapping template all falls to chocolate pie block gently.
With reference to sample:
Use CBS product LHK32-03 (Southseas Specialty Fats Industrial (Shanghai) Co., Ltd.) on market as stated above Prepare chocolate pie block using as with reference to sample.
Sensory evaluation:
Moulding property:
Finger contact chocolate surface is recorded until not adhering to the time of any chocolate on finger in 10 DEG C of baking ovens. Time is the shortest, illustrates that moulding property is the best.
√: the time within 10 minutes,
=: the time at 10~15 minutes,
×: the time is more than 15 minutes.
Release property:
Taking out chocolate and the template of Cheng Mo, slant setting, tapping template is until chocolate pie block is from template gently Come off.
Chocolate the most easily comes off, and illustrates that release property is the best.
√: be easy to the demoulding (hardly with tap or gently tapping template get final product the demoulding),
=: can with the demoulding (need certain force tapping template could the demoulding),
×: demoulding difficulty (needs the ability demoulding of large force tapping template).
Glossiness:
Chocolate pie block after the perusal demoulding,
The complete glossiness of √: chocolate surface is good,
=: chocolate surface has certain gloss,
×: chocolate surface glossiness is poor.
Mouth fusibleness:
After chocolate after the demoulding being placed in climatic chamber (25 DEG C, humidity is 55%) placement 2 days, will be skilful Gram force takes out, and carries out a mouthful fusibleness evaluation.
√: quickly melt in mouth, has nice and cool mouthfeel,
=: in mouth, the thawing time is very fast, but nice and cool mouthfeel is inconspicuous,
×: in mouth, the thawing time is relatively slow, without nice and cool mouthfeel.
Fragility:
After chocolate after the demoulding being placed in climatic chamber (25 DEG C, appropriateness is 55%) placement 2 days, will be skilful Gram force takes out, and breaks disconnected chocolate with hands.
√: chocolate brittleness is fine,
=: chocolate has certain fragility,
×: chocolate brittleness is poor.
Application experiment result is as shown in table 3.
From the experimental result of table 3 it can be seen that oil sample 1.1-1.6 and mixing oil sample 2-4 is relative to oil sample A, B, the reference one-tenth model of sample, demoulding, mouth dissolubility, glossiness and fragility are good.And from table 1,2 Data can be seen that in mixing oil sample, the content of oleic acid is higher than oil sample 1.1-1.6, and the content of satisfied fatty acid is less than Oil sample 1.1-1.6, mixing oil sample is more healthy.
The foregoing is only presently preferred embodiments of the present invention, be not limited to the essence of the present invention Technology contents scope, the substantial technological content of the present invention is broadly to be defined in the claim model of application In enclosing, any technology entities that other people complete or method, if being determined with the right applied for Justice identical, also or the change of a kind of equivalence, is all covered by this claim model by being considered Among enclosing.
The all documents mentioned in the present invention are incorporated as reference the most in this application, just as each piece Document is individually recited as with reference to like that.In addition, it is to be understood that reading the foregoing of the present invention Afterwards, the present invention can be made various changes or modifications by those skilled in the art, and these equivalent form of values are same Sample falls within the application appended claims limited range.

Claims (10)

1. a fat or oil composition, it is characterised in that described fat or oil composition fullness in the epigastrium and abdomen be enough to lower condition:
(1) content of TAG is more than or equal to 87%, and the content of preferably 90-99.9%, DAG is less than or equal to 13%, It is preferably 0-9.1%;
(2) content of hard fat is more than 60% when 25 DEG C, preferably 62-95%, is more than 21% when 30 DEG C, Preferably 26-70%, is not higher than 12% when 35 DEG C, preferably 0-10%;
(3) contain C36 and above XYLa type content of triglyceride is more than 10%, preferably 38-95%, no Triglyceides PPO content is not higher than 68%, preferably 0-62%;Wherein X, Y are that carbon is former Subnumber is the satisfied fatty acid of 12~22, and La is lauric acid;X, Y, La appointing at triglyceride On meaning position;P be Palmic acid, O be oleic acid.
2. fat or oil composition as claimed in claim 1, it is characterised in that Semen Myristicae in described fat or oil composition Bean acid content≤23%, preferably 0-20%, oleic acid content≤21%, preferably 0-15%, stearic acid content >=4%, preferably 5-20%.
3. a fat or oil composition, described fat or oil composition comprises one or more in fat A, oils and fats B, Described fat A is that the compositions containing monoglyceride is carried out with the compositions containing lauric acid and/or its ester The oils and fats that ester exchange obtains, described oils and fats B is the oils and fats containing unsymmetry triglyceride SSO, Wherein S be carbon number be the satisfied fatty acid of 12~22, preferably carbon number be 16~18 full And fatty acid, O represents oleic acid;In the most described oils and fats B, the content of SSO is 40-100%, Preferably 60-100%.
4. fat or oil composition as claimed in claim 3, it is characterised in that described fat A is with oils and fats B's Mass ratio is A/B >=0.1, preferably 0.1-10, more preferably 0.5-9.
5. fat or oil composition as claimed in claim 3, it is characterised in that described in comprise the combination of monoglyceride Thing is 2:1-1:3, preferably 1:1.1~1:2 with the mass ratio of the compositions comprising lauric acid or its ester.
6. fat or oil composition as claimed in claim 3, its feature in, described oils and fats B is that Long carbon chain is saturated The content of fatty acid oils and fats more than 40% and oleic acid, at least one ester of oleic acid or their mixture Ester exchange oils and fats;Preferably, described ester exchange is enzyme process ester exchange, it is highly preferred that described ester is handed over It is changed to selectivity ester exchange.
7. fat or oil composition as claimed in claim 6, it is characterised in that described Long carbon chain satisfied fatty acid The content oils and fats more than 40% is Petiolus Trachycarpi oil, fractionated palm oil carries tristearin, deep hydrogenation fractionated palm oil carries Tristearin, hydrogenated palm oil, fractionated palm oil carry palmitin, hydrogenated soybean oil, hydrogenated rapeseed oil, hydrogenation certain herbaceous plants with big flowers One or more of flower seed oil;Described oleate is methyl oleate, ethyl oleate, acid isopropyl In one or more.
8. fat or oil composition as claimed in claim 6, it is characterised in that described Long carbon chain satisfied fatty acid The content oils and fats more than 40% and oleic acid, at least one ester of oleic acid or the weight of their mixture Ratio not less than 1, preferably 2~3.
9. a preparation method for fat or oil composition, including: the compositions that (1) comprises monoglyceride with comprise Laurel The compositions of acid and/or its ester carries out ester exchange and obtains fat A;(2) Long carbon chain saturated fatty acid content Oils and fats more than 40% carries out ester exchange with oleic acid, at least one ester of oleic acid or their mixture and obtains To oils and fats B;(3) fat A is mixed with oils and fats B;Preferably, described oils and fats B is through enzyme process ester exchange Obtain, it is highly preferred that described oils and fats B chosen property ester exchange obtains.
10. a food, it contains in claim 1~8 fat or oil composition described in any one or right is wanted Ask fat or oil composition prepared by manufacture method described in 9, described food be preferably chocolate, whipping cream, Cake, cookies or sandwich beans;More preferably chocolate pie block.
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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN111374186A (en) * 2018-12-28 2020-07-07 丰益(上海)生物技术研发中心有限公司 Fat and oil composition for chocolate

Citations (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1085390A (en) * 1992-05-22 1994-04-20 尤尼利弗公司 The fat blend of bloom-inhibiting
EP1731594A1 (en) * 2005-06-09 2006-12-13 Fuji Oil Europe Non-hydrogenated fat composition and its use
WO2007039020A1 (en) * 2005-09-26 2007-04-12 Unilever N.V. Non-hydrogenated hardstock fat
JP2008086268A (en) * 2006-10-03 2008-04-17 Fuji Oil Co Ltd Cream oil and fat, and cream using the same
CN101460063A (en) * 2006-06-02 2009-06-17 普瑞图斯股份有限公司 Method to stabilize the crystallization of a blend of fat and oil containing more than 10% cocoa butter and having a low trans fat content
CN101926391A (en) * 2008-12-18 2010-12-29 花王株式会社 Hard fat and chocolate
WO2013132285A1 (en) * 2012-03-09 2013-09-12 Team Foods Colombia S.A. Cocoa butter substitute
CN103533840A (en) * 2011-05-25 2014-01-22 不二制油株式会社 Fat composition for chocolate
EP2839750A1 (en) * 2013-08-22 2015-02-25 Loders Croklaan B.V. Fat composition

Patent Citations (11)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1085390A (en) * 1992-05-22 1994-04-20 尤尼利弗公司 The fat blend of bloom-inhibiting
EP1731594A1 (en) * 2005-06-09 2006-12-13 Fuji Oil Europe Non-hydrogenated fat composition and its use
WO2007039020A1 (en) * 2005-09-26 2007-04-12 Unilever N.V. Non-hydrogenated hardstock fat
EP1931211A1 (en) * 2005-09-26 2008-06-18 Unilever N.V. Non-hydrogenated hardstock fat
CN101460063A (en) * 2006-06-02 2009-06-17 普瑞图斯股份有限公司 Method to stabilize the crystallization of a blend of fat and oil containing more than 10% cocoa butter and having a low trans fat content
JP2008086268A (en) * 2006-10-03 2008-04-17 Fuji Oil Co Ltd Cream oil and fat, and cream using the same
CN101926391A (en) * 2008-12-18 2010-12-29 花王株式会社 Hard fat and chocolate
CN103533840A (en) * 2011-05-25 2014-01-22 不二制油株式会社 Fat composition for chocolate
WO2013132285A1 (en) * 2012-03-09 2013-09-12 Team Foods Colombia S.A. Cocoa butter substitute
WO2013132284A1 (en) * 2012-03-09 2013-09-12 Cruz Adriana Fernanda Cocoa butter substitute
EP2839750A1 (en) * 2013-08-22 2015-02-25 Loders Croklaan B.V. Fat composition

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
徐斌等: "糖果及巧克力专用油脂的制备探讨 ", 《中国油脂》 *

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN111374186A (en) * 2018-12-28 2020-07-07 丰益(上海)生物技术研发中心有限公司 Fat and oil composition for chocolate
CN111374186B (en) * 2018-12-28 2023-04-07 丰益(上海)生物技术研发中心有限公司 Fat and oil composition for chocolate

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