CN102845537A - Preparation method of human milk fat substitute - Google Patents

Preparation method of human milk fat substitute Download PDF

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CN102845537A
CN102845537A CN2012103090250A CN201210309025A CN102845537A CN 102845537 A CN102845537 A CN 102845537A CN 2012103090250 A CN2012103090250 A CN 2012103090250A CN 201210309025 A CN201210309025 A CN 201210309025A CN 102845537 A CN102845537 A CN 102845537A
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aliphatic acid
human milk
milk fat
oil
grease
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CN102845537B (en
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王兴国
邹孝强
黄健花
金青哲
刘元法
宋志华
刘睿杰
常明
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Jiangnan University
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Abstract

The invention relates to a preparation method of a human milk fat substitute. The method comprises the steps of: step 1) conducting an acid hydrolysis reaction on a raw material of high melting palm stearin subjected to chemical interesterification and alcohol leaching, and an acyl donor of rapeseed oil fatty acid by using Lipozyme RM IM as a catalyst, so as to reduce the total palmitic acid content and increase the relative content of site-two palmitic acid of the raw material; and step 2) deacidifying an intermediate product; and at the same time, calculating the amount of sunflower seed oil, rapeseed oil, palm kernel oil, algae oil and microbial oil added to the intermediate product according to the composition and distribution of fatty acids in human milk fat, by a grease adding model, so as to ensure composition and distribution of fatty acids in a final product meeting requirements of a human milk fat substitute, as well as realize a maximum addition amount. The invention adopts two steps to produce the human milk fat substitute, in order to reduce usage amount of free fatty acids in the acid hydrolysis reaction; meanwhile, two times of oil additions increase yield. Therefore, the invention greatly reduces the cost, and achieves a more than doubled yield compared with a similar products with a similar cost.

Description

A kind of preparation method of human milk fat substitutes
Technical field
The present invention relates to a kind of preparation method of human milk fat substitutes, relate in particular to a kind of method for preparing human milk fat substitutes take palmitic acid tristearin as raw material.
Background technology
Between 3-5%, for the baby provides energy, essential nutriment is such as necessary aliphatic acid, polyunsaturated fatty acid and fat-soluble vitamin etc. greatly for the content of human milk fat.Sweet three fat content in the human milk fat are greatly about more than 98%, and it forms can be along with diet, lactation, race's etc. variation and changing.By the chemical composition of different nursery phase butter oils is analyzed, there are certain rule in composition and the distribution of its aliphatic acid.In human milk, main fatty acid has oleic acid (25-30%), palmitic acid (20-30%), linoleic acid (10-20%), stearic acid (5-9%), myristic acid (4-9%) and laurate (3-7%), linoleic acid with linolenic ratio between 5-15, wherein the palmitic acid of 60-70% is distributed in 2 of sweet three esters, and other unrighted acids mainly are distributed in 1,3.This molecular structure and baby's digestion and metabolism has close relationship.Sweet three esters that are ingested except in stomach by a stomach fat splitting part and (about 30%), other overwhelming majority's fat all is also absorbed at last by the pancreatic lipase hydrolysis in small intestine.Pancreatic lipase is a kind of 1,3 narrow spectrum enzyme, and sweet three esters are hydrolyzed into aliphatic acid and 2-monoglyceride.If any a large amount of saturated fatty acids 1,3, these aliphatic acid will be hydrolyzed, form the soap of indissoluble with calcium ion, so not only reduced the absorption of baby to aliphatic acid, and cause the reduction of calcium absorptivity, also may therefore cause the side effects such as baby's constipation even enteron aisle obstruction simultaneously, be unfavorable for baby's growth.The 2-monoglyceride that hydrolysis obtains can directly be absorbed and again be converted into sweet three fat UPU by small intestinal cell.The pertinent literature report, OPO transport velocity in vivo is higher than POO.Therefore, the special molecular structure of people's butterfat is also significant to the sweet three ester metabolism of baby.In human milk fat, there is a small amount of long carbochain polyunsaturated fatty acid, such as DHA (DHA, n-3), eicosatetraenoic acid (AA, n-6) etc., the content of these aliphatic acid is lower, but the effect important to growing of baby.The content of DHA and AA is respectively 0.32 ± 0.22% and 0.47 ± 0.13% in the human milk, and wherein AA content is about 1.5 times of DHA content.
Through sampling survey, up to the present, the fat substitute in the baby milk powder prescription on the market is simple composite the obtaining through various greases mostly.These fat are only similar with people's butterfat on aliphatic acid forms, and are far from each other aspect fatty acid profile.Therefore, be necessary to find a kind of suitable feedstock and technique to synthesize at aliphatic acid composition and structure and be similar to the fat substitute of people's butterfat, and apply among the prescription of baby milk powder.
Lard is the aliphatic acid composition of occurring in nature existence and sweet three fat that distribution is bordering on human milk fat most, but it contains higher cholesterol, and the while has special religious colony for some and is not suitable for.Contain a large amount of palmitic acids in the palm oil and can minute be carried and be the different palm stearin of palmitic acid content, these palm stearin low prices easily obtain, and are the good raw material sources of producing human milk fat substitutes.The human milk fat substitutes that adopts simultaneously palm stearin to produce is not limited by religion, can be widely used among the baby milk powder prescription.Present technique adopts a step acidolysis tripalmitin to produce human milk fat substitutes mostly, and the aliphatic acid consumption is large in the technique, has increased the difficulty of cost and downstream depickling, and the tripalmitin price is high simultaneously, is difficult to obtain.Therefore adopt palm stearin to reduce production costs on will be very magnanimous as raw material, improve the industrialized possibility of technique.
Summary of the invention
The object of the present invention is to provide a kind of economically viable preparation method take high-melting-point palm stearin (high melting palm stearin, HMPS) as the human milk fat substitutes of raw material.
Raw material involved in the present invention mainly contains 58 degree palm stearin (palm stearin, PS), rapeseed oil (rapeseed oil, RSO), sunflower oil (sunflower oil, SFO), palm-kernel oil (palm kernel oil, PKO) is rich in microbial grease (the microbial oil of AA, MO) and the algae oil (algal oil, AO) that is rich in DHA.The composition of its aliphatic acid distributes as shown in the table:
Table 1 rapeseed oil, sunflower oil, palm-kernel oil, microbial grease, algae oil, 58 degree palm stearins,
The aliphatic acid of high-melting-point palm stearin forms and distributes
Figure BSA00000769539400021
Initial feed involved in the present invention is to pass through the palmitic acid content of chemically catalyzed interesterification at the high-melting-point palm stearin more than 80%.The high-melting-point palm stearin is that employing 58 degree palm stearins are raw material, the palmitic acid content that the process solvent extraction obtains is at the palm stearin more than 80%, its aliphatic acid after dividing in advance forms as shown in table 1, high-melting-point palm stearin through chemically catalyzed interesterification, palmitic acid content on two improves, similar with total palmitic acid content is conducive to improve the Quality and yield of final products.
Initial feed involved in the present invention is to remove because diglyceride and monoglyceride that chemically catalyzed interesterification produces obtain through twice alcohol wash.
Technical scheme of the present invention: a kind of method for preparing human milk fat substitutes take the high-melting-point palm stearin as raw material mainly adopts the high-melting-point palm stearin of first step Lipozyme RM IM enzyme process acidolysis behind chemically catalyzed interesterification to reduce its total palmitic acid, improves the content that two palmitic acids account for total palmitic acid; Intermediate products are after the molecular clock depickling is processed, second step is according to composition and the distribution of people's butterfat aliphatic acid, add a certain proportion of rapeseed oil by the model accurate Calculation, sunflower oil, palm-kernel oil, algae oil and microbial grease are regulated composition and the distribution of the aliphatic acid in the product, finally obtaining that aliphatic acid forms and distributional class is similar under the prerequisite of product of people's butterfat, maximum grease addition is being arranged.Detailed process is as follows:
First step acidolysis high-melting-point palm stearin obtains intermediate products
The high-melting-point palm stearin with the free fatty that derives from rapeseed oil with 1: the molar ratio of 8-12 mixes, and at temperature 50-70 degree, Lipozyme RM IM addition is acidolysis reaction 3-5h under the condition of 8-12%; The mixture of gained obtains total palmitic acid and reduces through the centrifugal enzyme that takes off after the molecular clock depickling, two palmitic acid relative amounts significantly improve intermediate products.Satisfy the requirement of human milk fat substitutes in the distribution of palmitic acid.
The second step physical mixed is added vegetable oil
Composition and distribution according to people's butterfat aliphatic acid, be oleic acid (25-30%), palmitic acid (20-30%), linoleic acid (10-20%), stearic acid (5-9%), myristic acid (4-9%) and laurate (3-7%), wherein the palmitic acid of 60-70% is distributed in 2 of sweet three esters, and linoleic acid, calculates through model between 5-15 with linolenic ratio, the rapeseed oil that optimization is added in the intermediate product, sunflower oil, palm-kernel oil, the amount of algae oil and microbial grease, make products obtained therefrom in the requirement of satisfying human milk fat substitutes, maximum grease addition is arranged.After adding grease, the computing formula of the aliphatic acid of mixed sweet three esters composition and distribution is as follows in the system:
FA % = Y 1 + Σ i = 2 n Y i X i 1 + Σ i = 2 n X i - - - ( 1 )
sn - 2 FA % = Y 1 ( sn - 2 ) + Σ i = 2 n Y i ( sn - 2 ) X i 1 + Σ i = 2 n X i - - - ( 2 )
sn - 1,3 FA % = 3 × ( Y 1 + Σ i = 2 n Y i X i ) - ( Y 1 ( sn - 2 ) + Σ i = 2 n Y i ( sn - 2 ) X i ) 2 × ( 1 + Σ i = 2 n X i ) - - - ( 3 )
% sn - 2 FA = Y 1 ( sn - 2 ) + Σ i = 2 n Y i ( sn - 2 ) X i 3 ( Y 1 + Σ i = 2 n Y i X i ) × 100 - - - ( 4 )
Y lAnd Y iBe respectively the content of each aliphatic acid of intermediate products and selected grease; Y L (sn-2)And Y I (sn-2)Be respectively the content of two upper each aliphatic acid of intermediate products and selected grease; X iBe the mol ratio of selected grease with intermediate product.The aliphatic acid that can obtain adding triglycerides in the system behind the grease according to above formula forms and distributes.Set up inequality according to the aliphatic acid composition of people's butterfat and the characteristics that distribute, simultaneously according to grease weight formula (5) in the system, employing Matlab R2010a (MathWorks, Natick, Massachusetts) is met the maximum grease addition under the human milk fat substitutes condition.
M = X 1 ( M 1 + Σ i = 2 n X i M i ) - - - ( 5 )
M is the weight of final products; X lIt is the molal quantity of intermediate products; M lThe molecule matter of intermediate products, M iIt is the molecular mass of selected grease.
Beneficial effect of the present invention: the present invention adopts first step acidolysis high-melting-point palm stearin to reduce total palmitic acid content first, improves that two palmitic acid relative amounts and second step add that other greases regulate that method that aliphatic acid form prepares that aliphatic acid forms and distributional class is similar to the substitute of people's butterfat.The present invention has reduced cost dramatically, compares with like product, and under similar cost, product yield doubles above.
The specific embodiment
Embodiment 1
Take by weighing 20g high-melting-point palm stearin in round-bottomed flask, and the same free fatty that derives from rapeseed oil mixes mutually take mol ratio as 1: 10 ratio, add the Lipozyme RM IM (with total substrate restatement) of 10wt% in the mixed system, and under the condition that 60 ℃ waters and stir speed (S.S.) are 250rpm, react 4h.The gained reaction substrate through 4000rpm is centrifugal remove enzyme after, adopt molecular clock to slough aliphatic acid, the molecular clock condition is: evaporating temperature, 185 ℃; Heat exchanger temperature, 60 ℃; Rotating speed, 120rpm; Absolute pressure, it is as shown in the table for the aliphatic acid composition of 2Pa. gained intermediate products and distribution.
The aliphatic acid of table 2 intermediate products forms and distributes
Aliphatic acid total sn-2 %sn-2 a sn-1,3 b
C12:0 0.3 0.1 11.1 0.4
C14:0 0.4 0.1 8.3 0.6
C16:0 39.6 83.7 70.5 17.6
C18:0 3.5 2.4 22.9 4.1
C18:1n-9 36.6 10.2 9.3 49.8
C18:2n-6 14.6 2.7 6.2 20.6
C18:3n-6 4.8 0.6 4.2 6.9
Mean molecule quantity 846.9
a2 aliphatic acid account for the percentage of TFA, computing formula be sn-2 * 100%/(3 * total).
bThe composition of aliphatic acid on 1,3 position, computing formula are (3 * total-sn-2)/2.
Get the 10g intermediate products and regulate aliphatic acid and form and distribute to wherein adding other greases, add various greases amount calculate gained by model optimization.According to products obtained therefrom and selected sunflower oil (x1), rapeseed oil (x2), palm-kernel oil (x3), composition and the distribution of the aliphatic acid of algae oil (x4) and microbial grease (x5), structure satisfies the inequality that people's butterfat aliphatic acid forms and distributes, and sets up object function as follows:
M=(846.9+870.3*x1+870.6*x2+696.4*x3+890.5*x4+869.6*x5)*0.0118;
Laurate:
0.3+1.3*x1+0.9*x2+55.7*x3>=3*(1+x1+x2+x3);
0.4+1.3*x1+0.9*x2+55.7*x3<=10*(1+x1+x2+x3);
Palmitic acid:
39.6+6.8*x1+6.7*x2+6.4*x3<=30*(1+x1+x2+x3);
39.6+6.8*x1+6.7*x2+6.4*x3>=20*(1+x1+x2+x3);
Oleic acid:
36.6+25.4*x1+58.1*x2+10.2*x3>=25*(1+x1+x2+x3);
36.6+25.4*x1+58.1*x2+10.2*x3<=35*(1+x1+x2+x3);
Linoleic acid:
14.6+59.0*x1+22.5*x2+2.1*x3>=10*(1+x1+x2+x3);
14.6+59.0*x1+22.5*x2+2.1*x3<=20*(1+x1+x2+x3);
Linoleic acid is with linolenic ratio:
14.6+59.0*x1+22.5*x2+2.1*x3>=5*(4.8+0.6*x1+7.8*x2);
14.6+59.0*x1+22.5*x2+2.1*x3<=15*(4.8+0.6*x1+7.8*x2);
The relative amount of palmitic acid:
0.6*(39.6+6.8*x1+6.7*x2+6.4*x3)<=83.7;
DHA:
42*x4>=(1+x1+x2+x3+x4+x5)*0.2;
Eicosapentaenoic acid:
49*x5>=(1+x1+x2+x3+x4+x5)*0.4.
By Matlab R2010a function is optimized processing, the mol ratio that is met condition and can obtains the various greases of maximum addition is: intermediate products: sunflower oil: rapeseed oil: palm-kernel oil: algae oil: microbial grease=1: 0.28: 0.40: 0.36: 0.015: 0.017, the addition of each grease is respectively sunflower oil with this understanding, 2.8g; Rapeseed oil, 4.1g; Palm-kernel oil, 3.0g; Algae oil, 0.16; Microbial grease 0.17g, the gross mass of the human milk fat substitutes that obtains is: it is as shown in the table for the aliphatic acid composition of 20.3g. products obtained therefrom and distribution:
The aliphatic acid of table 3 human milk fat substitutes forms and distributes
Aliphatic acid total sn-2 %sn-2 sn-1,3
C8:0 0.7 0.1 4.8 1.0
C10:0 0.8 0.2 8.3 1.1
C12:0 9.6 6.9 24.0 11.0
C14:0 3.5 3.0 28.6 3.8
C16:0 23.5 43.1 61.1 13.7
C18:0 3.4 1.4 13.7 4.4
C18:1n-9 34.6 22.8 22.0 40.5
C18:2n-6 19.1 19.0 33.2 19.2
C18:3n-6 3.7 2.3 20.7 4.4
C20:4n-6 0.4 0.4 30.0 0.4
C22:5n-3 0.1 0.1 26.7 0.1
C22:6n-3 0.3 0.3 35.6 0.3
Embodiment 2
Take by weighing 20g high-melting-point palm stearin in round-bottomed flask, and the same free fatty that derives from rapeseed oil mixes mutually take mol ratio as 1: 12 ratio, add the Lipozyme RM IM (with total substrate restatement) of 8wt% in the mixed system, and under the condition that 65 ℃ waters and stir speed (S.S.) are 250rpm, react 3h.The gained reaction substrate through 4000rpm is centrifugal remove enzyme after, adopt molecular clock to slough aliphatic acid, the molecular clock condition is: evaporating temperature, 185 ℃; Heat exchanger temperature, 60 ℃; Rotating speed, 120rpm; Absolute pressure, the aliphatic acid of 2Pa. gained intermediate products forms and distributes as shown in the table.
The aliphatic acid of table 4 intermediate products forms and distributes
Aliphatic acid total sn-2 %sn-2 sn-1,3
C12:0 0.3 0.1 11.1 0.4
C14:0 0.4 0.1 8.3 0.6
C16:0 38.1 83.1 72.7 15.6
C18:0 3.3 2.1 21.2 3.9
C18:1n-9 37.3 11.7 10.5 50.1
C18:2n-6 15.6 2.4 5.1 22.2
C18:3n-6 5.0 0.5 3.3 7.3
Mean molecule quantity 852.2
Get the 10g intermediate products and regulate aliphatic acid and form to wherein adding other greases, add various greases amount calculate gained by model optimization.According to products obtained therefrom and selected sunflower oil (x1), rapeseed oil (x2), palm-kernel oil (x3), composition and the distribution of the aliphatic acid of algae oil (x4) and microbial grease (x5), structure satisfies the inequality that human milk fat acid forms and distributes, and sets up object function as follows:
M=(852.9+870.3*x1+870.6*x2+696.4*x3+890.5*x4+869.6*x5)*0.0117;
Laurate:
0.3+1.3*x1+0.9*x2+55.7*x3>=3*(1+x1+x2+x3);
0.4+1.3*x1+0.9*x2+55.7*x3<=10*(1+x1+x2+x3);
Palmitic acid:
38.1+6.8*x1+6.7*x2+6.4*x3<=30*(1+x1+x2+x3);
38.1+6.8*x1+6.7*x2+6.4*x3>=20*(1+x1+x2+x3);
Oleic acid:
37.3+25.4*x1+58.1*x2+10.2*x3>=25*(1+x1+x2+x3);
37.3+25.4*x1+58.1*x2+10.2*x3<=35*(1+x1+x2+x3);
Linoleic acid:
15.6+59.0*x1+22.5*x2+2.1*x3>=10*(1+x1+x2+x3);
15.6+59.0*x1+22.5*x2+2.1*x3<=20*(1+x1+x2+x3);
Linoleic acid is with linolenic ratio:
15.6+59.0*x1+22.5*x2+2.1*x3>=5*(5.0+0.6*x1+7.8*x2);
15.6+59.0*x1+22.5*x2+2.1*x3<=15*(5.0+0.6*x1+7.8*x2);
The relative amount of palmitic acid:
0.6*(38.1+6.8*x1+6.7*x2+6.4*x3)<=83.7;
DHA:
42*x4>=(1+x1+x2+x3+x4+x5)*0.2;
Eicosatetraenoic acid:
49*x5>=(1+x1+x2+x3+x4+x5)*0.4.
By Matlab R2010a function is optimized processing, the mol ratio that is met condition and can obtains the various oil of maximum addition is: intermediate products: sunflower oil: rapeseed oil: palm-kernel oil: algae oil: microbial grease=1: 0.24: 0.28: 0.31: 0.009: 0.015, the addition of each grease is respectively sunflower oil with this understanding, 2.4g; Rapeseed oil, 2.8g; Palm-kernel oil, 2.5g; Algae oil, 0.1; Microbial grease 0.15g, the gross mass of the human milk fat substitutes that obtains is: the aliphatic acid of 18.0g. products obtained therefrom forms and distributes as shown in the table:
The aliphatic acid of table 5 human milk fat substitutes forms and distributes
Aliphatic acid total sn-2 %sn-2 sn-1,3
C8:0 0.7 0.1 2.3 1.1
C10:0 0.8 0.2 6.9 1.1
C12:0 9.8 7.1 24.3 11.1
C14:0 3.2 2.7 28.9 3.4
C16:0 23.8 46.8 65.6 12.3
C18:0 3.1 1.5 16.2 3.9
C18:1n-9 33.9 22.2 21.8 39.8
C18:2n-6 19.8 16.7 28.1 21.3
C18:3n-3 4.0 1.8 15.0 5.1
C20:4n-6 0.4 0.4 31.2 0.4
C22:5n-3 0.1 0.1 29.7 0.1
C22:6n-3 0.2 0.2 37.9 0.2

Claims (5)

1. the preparation method of a human milk fat substitutes is characterized in that adopting two-step method, i.e. the high-melting-point palm stearin of first step Lipozyme RM IM enzyme process acidolysis after chemically catalyzed interesterification and alcohol wash; After intermediate products are processed through the molecular clock depickling, second step calculates by model according to composition and the distribution of people's butterfat aliphatic acid, adds a certain proportion of other greases, the aliphatic acid of regulating in the product forms and distribution, finally obtains aliphatic acid composition and distributional class and is similar to human milk fat substitutes.
2. the preparation method of human milk fat substitutes according to claim 1 is characterized in that raw materials used is that 58 degree palm stearins divide through solvents and carry chemically catalyzed interesterification, the high-melting-point palm stearin that obtains after the alcohol wash.
3. the preparation method of human milk fat substitutes according to claim 1, it is characterized in that adopting the high-melting-point palm stearin of the treated mistake of first step Lipozyme RM IM enzyme process acidolysis, acidolysis uses fatty acid source in rapeseed oil, acidolysis condition is: high-melting-point palm stearin and aliphatic acid mol ratio 1: 8-12, reaction temperature is the 50-70 degree, Lipozyme RM IM addition is 8-12%, and the reaction time is 3-5h;
4. the preparation method of human milk fat substitutes according to claim 1 is characterized in that the used initiation material of second step is the product after the first step reactant molecule distillation depickling.
5. the preparation method of human milk fat substitutes according to claim 1, the grease that it is characterized in that second step interpolation usefulness is sunflower oil, rapeseed oil, palm-kernel oil, the algae oil that is rich in the microbial grease of AA and is rich in DHA, adding proportion forms and distribution according to the aliphatic acid of people's butterfat, adds model by grease and determines.After adding grease, the aliphatic acid of product forms and the computing formula of distribution is:
FA % = Y 1 + Σ i = 2 n Y i X i 1 + Σ i = 2 n X i - - - ( 1 )
sn - 2 FA % = Y 1 ( sn - 2 ) + Σ i = 2 n Y i ( sn - 2 ) X i 1 + Σ i = 2 n X i - - - ( 2 )
sn - 1,3 FA % = 3 × ( Y 1 + Σ i = 2 n Y i X i ) - ( Y 1 ( sn - 2 ) + Σ i = 2 n Y i ( sn - 2 ) X i ) 2 × ( 1 + Σ i = 2 n X i ) - - - ( 3 )
% sn - 2 FA = Y 1 ( sn - 2 ) + Σ i = 2 n Y i ( sn - 2 ) X i 3 ( Y 1 + Σ i = 2 n Y i X i ) × 100 - - - ( 4 )
Y lAnd Y iBe respectively the content of each aliphatic acid of intermediate products and selected grease, Y L (sn-2)And Y I (sn-2)Be respectively the content of two upper each aliphatic acid of intermediate products and selected grease, X iBe the mol ratio of selected grease with intermediate product, the aliphatic acid that can obtain adding triglycerides in the system behind the grease according to above formula forms and distributes, set up inequality according to the aliphatic acid composition of people's butterfat and the characteristics that distribute, adopt Matlab R2010a (MathWorks, Natick, Massachusetts) obtain the maximum grease addition of sufficient condition:
M = X 1 ( M 1 + Σ i = 2 n X i M i ) - - - ( 5 )
M is the weight of final products; X lIt is the molal quantity of intermediate products; M lThe molecule matter of intermediate products, M iIt is the molecular mass of selected grease.
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