CN104327954A - Rice bran oil deacidification process based on enzyme method - Google Patents
Rice bran oil deacidification process based on enzyme method Download PDFInfo
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- C11C3/00—Fats, oils, or fatty acids by chemical modification of fats, oils, or fatty acids obtained therefrom
- C11C3/04—Fats, oils, or fatty acids by chemical modification of fats, oils, or fatty acids obtained therefrom by esterification of fats or fatty oils
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Abstract
The invention discloses a rice bran oil deacidification process based on an enzyme method, which is characterized by performing esterification reaction on endogenous phytosterin in rice bran oil (optionally, plus a certain amount of phytosterin (phytosterol)) and free fatty acid in the high-acid-value rice bran oil under the catalytic action of lipase to reduce the acid value of the rice bran oil, thus obtaining a grease product containing phytosterin (phytosterol) fatty acid ester. The method comprises the following steps: mixing rice bran oil, phytosterin (phytosterol) and optional organic solvent ( n-hexane or acetone) according to a certain ratio until the phytosterin (phytosterol) is completely dissolved; proportionally adding lipase, performing enzyme reaction at certain temperature for certain time in an intermittent and semicontinuous reactor until the acid value of the rice bran oil is reduced to 4mg KOH/g or below, and stopping the reaction; and performing subsequent processing: removing and recovering the organic solvent, performing cooling crystallization to remove and recover the unreacted phytosterin (phytosterol), and recovering the lipase, a molecular sieve and the organic solvent for recycling.
Description
Technical field
The present invention relates to a kind of lipin deacidifying processing method, belong to fats and Oils Refining Technology field.
Background technology
Rice pollard oil is a kind of nutritious vegetables oil, has multiple nutrients nourishing function, owing to containing very active lipolytic enzyme in rice bran, contained fat splitting in rice bran can be made under proper condition at short notice to become glycerine and lipid acid.By the restriction of transport and shelf-time between rice bran manufacturing enterprise and Rice pollard oil manufacturing enterprise, the Rice bran crude oil free fatty acid acid number produced reaches more than 15mgKOH/g, and high even reaches 60mgKOH/g.And grease free fatty acid too high levels, not only can produce the local flavor that irritating smell affects grease, the hydrolysis accelerating further neutral oil is become sour, and grease also can be made the poor stability of heat and oxygen, impels grease oxidation rancid, and likely etching apparatus.Therefore further refining is needed to high acid value Rice bran crude oil.Traditional alkali-refining deacidification and physical refining all have certain limitation, are not suitable for the depickling of peracid value rice bran oil.Alkali-refining deacidification needs a large amount of water and pharmaceutical chemicals, and the grease refining consumption caused is large, and causes the loss of the nutritive ingredients such as thiaminogen a large amount of in grease, and the nutritional quality of grease is declined.In addition, a large amount of organic waste water is also produced, contaminate environment.Physical refining method equally also exists for peracid value rice bran oil that refining yield is low, grease accompaniment loses large problem, and the requirement of this technique to equipment is stricter.Esterification deacidification method is under certain vacuum degree and temperature, catalyst catalyzing alcohols and Esterification of Free Fat Acid synthesizing ester, and to reach the object reducing acid value, refining yield is high.Chemical catalyst has certain toxicity, and it is high to consume energy, and by product is more, and after reaction, cast of oil is deepened, and the grease produced is difficult to use in food oils; And enzyme catalysts conditions is gentle, reaction preference is high, and catalytic efficiency is high, and product compares environmental protection, and by can greatly reduce costs the recycling of enzyme, application potential is huge.
The esterification deacidification of Chinese of existing food oils focuses mostly in providing acry radical donor with glycerine and Tegin 55G; triglyceride level, triglyceride and monoglyceride is generated with Esterification of Free Fat Acid; or monoglyceride, triglyceride and the free fatty acids generation resterification in oil; although this method can solve the low problem of refining of crude rice bran oil rate; but in grease, add these two kinds of materials and do not meet national relevant laws and regulations, cannot suitability for industrialized production be realized.Since 1999, the U.S., Japan, European Union etc. in succession ratify plant sterol and plant sterol ester is edible material good for health, and its security has obtained the accreditation of the multiple countries and regions, the world comprising China.2010, China allowed plant sterol and plant sterol ester to add in food (Ministry of Health of the People's Republic of China's food safety comprehensive is coordinated and sanitary inspection office, No. 3 new resource food bulletin in 2010) as new resource food.Therefore; be that acry radical donor and Rice pollard oil free fatty acid esterification deacidification meet national legislation with plant sterol; have important practical application of significance; the Rice pollard oil being rich in plant sterol ester is obtained after esterification deacidification; not only solve the problem that refining of crude rice bran oil rate is low, also impart the more trophic function characteristic of Rice pollard oil.
Summary of the invention
The object of this part is some aspects of general introduction embodiments of the invention and briefly introduces some better embodiment.May do in the specification digest and denomination of invention of this part and the application a little simplify or omit with avoid making this part, specification digest and denomination of invention object fuzzy, and this simplification or omit and can not be used for limiting the scope of the invention.
In view of above-mentioned and/or existing with Problems existing in plant sterol and/or the phytostanols high acid value Rice pollard oil intermittent type that is acry radical donor and semi continuous enzyme process deacidifying process, propose the present invention.
Therefore, an object of the present invention is utilizing endogenous plant sterol by enzyme esterification, provide a kind of refining yield high, and the lipin deacidifying method that the tool meeting national relevant laws and regulations has significant practical applications.
For solving the problems of the technologies described above, according to an aspect of the present invention, the invention provides following technical scheme: a kind of Rice pollard oil enzyme process deacidifying process, it utilizes endogenous plant sterol in Rice pollard oil, under lipase-catalyzed effect, be not less than the free fatty acids generation esterification in the Rice pollard oil of 4mgKOH/g with acid value, reduce Rice pollard oil acid value to below 4mgKOH/g, obtain the oil and fat product containing phytosterin fatty acid ester; Wherein, when there is esterification, stir speed (S.S.) 60 ~ 250rpm in reactor, its enzyme addition of described lipase is 1 ~ 10% by percentage to the quality, temperature is 30 ~ 90 DEG C, the molecular sieve dehydration of more than vacuum tightness 0.085MPa dehydration or interpolation 0.05 ~ 0.5g/g oil, reaction times 24 ~ 72h.
As a kind of preferred version of Rice pollard oil enzyme process deacidifying process of the present invention, wherein: described lipase is one or more in immobilized enzyme Lipozyme RM IM, Lipzomye 435, immobilized enzyme Lipozyme TL IM, immobilized enzyme Novozym 435, immobilized enzyme Lipozyme TL 100L, resolvase Lipozyme CAL BL.
As a kind of preferred version of Rice pollard oil enzyme process deacidifying process of the present invention, wherein: also comprise, before the described esterification of generation, a certain amount of organic solvent is added in described Rice pollard oil, described Rice pollard oil and organic solvent proportioning are 1:0.5 ~ 2 (w/v), described organic solvent is normal hexane and acetone, takes the mode of the molecular sieve of interpolation 0.05 ~ 0.5g/g oil to dewater.
As a kind of preferred version of Rice pollard oil enzyme process deacidifying process of the present invention, wherein: described acquisition is containing the oil and fat product of phytosterin fatty acid ester, wherein, the acid value of Rice pollard oil is at below 4mgKOH/g, sterol fatty acid ester content is 4 ~ 36%, content of triglyceride is 50 ~ 80%, and diglyceride content is 5 ~ 15%, and content of monoglyceride is less than 3%.
Therefore, another object of the present invention is to additional plant sterol and/or phytostanols in Rice pollard oil on the basis of endogenous plant sterol, by enzyme esterification, provide a kind of refining yield high, and the lipin deacidifying method that the tool meeting national relevant laws and regulations has significant practical applications.
For solving the problems of the technologies described above, according to another aspect of the present invention, the invention provides following technical scheme: a kind of Rice pollard oil enzyme process deacidifying process, it is by Rice pollard oil, organic solvent and plant sterol and/or phytostanols mixed dissolution, under lipase-catalyzed effect, the free fatty acids generation esterification in the Rice pollard oil of 4mgKOH/g is not less than with acid value, reduce Rice pollard oil acid value to below 4mgKOH/g, obtain the oil and fat product being rich in plant sterol and/or plant stanol fatty acid ester; Wherein, when there is esterification, stir speed (S.S.) 60 ~ 250rpm in reactor, described lipase enzyme addition is 1 ~ 10% by percentage to the quality, temperature is 30 ~ 90 DEG C, the molecular sieve dehydration of more than vacuum tightness 0.085MPa dehydration or interpolation 0.05 ~ 0.5g/g oil, reaction times 24 ~ 72h.
As a kind of preferred version of Rice pollard oil enzyme process deacidifying process of the present invention, wherein: described lipase is one or more in immobilized enzyme Lipozyme RM IM, immobilized enzyme Lipzomye 435, immobilized enzyme Lipozyme TL IM, immobilized enzyme Novozym 435, immobilized enzyme Lipozyme TL 100L, resolvase Lipozyme CAL BL.
As a kind of preferred version of Rice pollard oil enzyme process deacidifying process of the present invention, wherein: before generation esterification, a certain amount of organic solvent is added in described Rice pollard oil, described Rice pollard oil and organic solvent proportioning are 1:0.5 ~ 2 (w/v), and described organic solvent is normal hexane and acetone.
As a kind of preferred version of Rice pollard oil enzyme process deacidifying process of the present invention, wherein: described by Rice pollard oil, organic solvent and plant sterol and/or phytostanols mixed dissolution, wherein, the addition of plant sterol and/or phytostanols is 1 ~ 28% by percentage to the quality.
As a kind of preferred version of Rice pollard oil enzyme process deacidifying process of the present invention, wherein: described molecular sieve is 3A or 4A molecular sieve.
As a kind of preferred version of Rice pollard oil enzyme process deacidifying process of the present invention, wherein: after obtaining the oil and fat product containing plant sterol and/or plant stanol fatty acid ester, also comprise, subsequent treatment process, it is included in removing and recovery organic solvent in vaporizer, at more than vacuum tightness 0.08Mpa, temperature is 40 ~ 70 DEG C, rotary evaporation removing organic solvent, organic solvent condensation reflux in certain storage within the condenser, or coutroi velocity is directly back in mixing of materials tank, Determination of Residual Organic Solvents≤100ppm, after removing organic solvent, in crystallizer or crystallizer, crystallisation by cooling removes and reclaims unreacted plant sterol and/or phytostanols again, cooling temperature is 0 ~ 5 DEG C, 5 ~ 10 hours cooling times, at this temperature in 3000 ~ 5000rpm frozen centrifugation 2 ~ 5 minutes, be separated and reclaim unreacted plant sterol and/or phytostanols, recovery lipase and molecular sieve are for recycling.
Beneficial effect of the present invention:
The present invention meets the relevant food regulation of country with plant sterol and/or phytostanols for the Esterification of Free Fat Acid depickling in acry radical donor and Rice pollard oil, not only has important actual production meaning, more can give Rice pollard oil more trophic function characteristic.Using lipase as the catalyzer of high-acid value rice bran oil esterification depickling, effectively can promote the carrying out of esterification, acid number can be down to below 4mgKOH/g, mild condition, can not affect grease color, can not destroy the nutritive ingredient in grease, no coupling product, nontoxicity, environmentally safe, by reclaiming and utilizing lipase (molecular sieve, organic solvent) greatly can reduce production cost.
Embodiment
For enabling above-mentioned purpose of the present invention, feature and advantage become apparent more, are described in detail below by the specific embodiment of the present invention.
Set forth a lot of detail in the following description so that fully understand the present invention, but the present invention can also adopt other to be different from alternate manner described here to implement, those skilled in the art can when without prejudice to doing similar popularization when intension of the present invention, therefore the present invention is by the restriction of following public specific embodiment.
High-acid value rice bran oil esterification depickling process of the present invention Rice pollard oil used is hair edible vegetable oil, raw material Rice bran crude oil being removed mechanical impurity through comprising, being come unstuck, dewax, the rice bran hair edible vegetable oil of adsorption bleaching process, acid value is 4 ~ 40mgKOH/g, moisture content less than 0.1%, below phosphorus content 100ppm, color and luster (cell 25.4mm) Huang≤35, red≤6.0.
Intermittent type enzyme reaction is carried out in batch-type agitator tank reactor, batch-type or in batches do not add reaction substrate feed liquid, stir speed (S.S.) 60 ~ 250rpm, can add resolvase or immobilized enzyme in reactor, enzyme addition 1 ~ 10%, resolvase temperature of reaction is 30 ~ 60 DEG C, immobilized enzyme temperature of reaction is 50 ~ 90 DEG C, more than vacuum tightness 0.085MPa, 24 ~ 72 hours reaction times, until Rice pollard oil acid value is down to below 4mgKOH/g stopped reaction.Subsequent disposal is included in removing and recovery organic solvent in vaporizer, and in crystallizer or crystallizer, crystallisation by cooling removes and reclaims unreacted plant steroid (alkane) alcohol, reclaims lipase and molecular sieve and organic solvent for recycling.
Semi continuous enzyme reaction is carried out in batch-type agitator tank reactor, be made up of multiple reactors in series, batch-type or in batches do not add reaction substrate feed liquid from first reactor, each reactor stir speed (S.S.) is 60 ~ 250rpm, resolvase or immobilized enzyme can be added in each reactor, enzyme addition 1 ~ 10%, resolvase temperature of reaction is 30 ~ 60 DEG C, immobilized enzyme temperature of reaction is 50 ~ 90 DEG C, add the molecular sieve dehydration of 0.05 ~ 0.5g/g oil, 12 ~ 48 hours reaction times of accumulation, until Rice pollard oil acid value is down to below 4mgKOH/g stopped reaction.Semi continuous reaction and enzyme reaction adopt multiple intermittent reaction to be in series, subsequent disposal is included in removing and recovery organic solvent in vaporizer, in crystallizer or crystallizer, crystallisation by cooling removes and reclaims unreacted plant steroid (alkane) alcohol and recycle technique such as plant steroid (alkane) alcohol and organic solvent etc. and all adopts serialization mode, reclaims lipase and molecular sieve.
Wherein, acid number presses GB/T5530-2005 method mensuration.
The calculation formula of plant steroid (alkane) alcohol amount is in theory:
M＝[(S·M
1·10
-3)/56.1]/NA
M-theoretical plant steroid (alkane) alcohol amount;
S-reaction Rice pollard oil acid number, unit is (mgKOH/g);
M
1rice pollard oil quality is used in-reaction, and unit is (g);
NA-plant steroid (alkane) alcohol every gram mole number, unit is (mol).
The mensuration of color and luster adopts Lovibond spectrophotometry, and three grades and level Four oil employing lovibond test groove 25.4mm, firsts and seconds oil adopts lovibond test groove 133.4mm, and the data of color and luster described in this patent record in 25.4mm cell.
Embodiment 1
Intermittent type enzyme reaction is carried out in batch-type agitator tank reactor, add reaction substrate feed liquid, the Rice pollard oil free fatty acids mixed in mixing of materials tank and the mol ratio of plant sterol are that (Rice pollard oil acid value is 29.311mgKOH/g to 1:1, color and luster Huang 29, red 4.8), stir speed (S.S.) 150rpm, immobilized enzyme Lipozyme RM IM addition 3%, temperature is 70 DEG C, vacuum tightness 0.09MPa, stopped reaction after 60 hours reaction times, centrifugal removing immobilized enzyme, the plant sterol that unreacted is complete is removed in crystallizer, cooling temperature is 4 DEG C, 10 hours cooling times, at this temperature in 5000rpm frozen centrifugation 3 minutes, be separated and obtain the low acid value Rice pollard oil being rich in sterol ester, the recyclable recycling of the plant sterol that immobilized enzyme and crystallization obtain.After reaction, Rice pollard oil acid value is 3.92mgKOH/g, and containing plant sterol ester 25.58%wt, sterol content is 2.39%wt, Tegin 55G content 2.81%wt, DAG content 10.21%wt, sweet three ester content 58.51%wt, color and luster Huang 30, red 4.8.
Embodiment 2
Intermittent type enzyme reaction is carried out in batch-type agitator tank reactor, add reaction substrate feed liquid, acry radical donor is the mixture of plant sterol and phytostanols, mixing quality is than being 1:1, the Rice pollard oil free fatty acids mixed in mixing of materials tank and the mol ratio of acry radical donor are that (Rice pollard oil acid value is 29.311mgKOH/g to 1:1, color and luster Huang 29, red 4.8), stir speed (S.S.) 150rpm, immobilized enzyme Lipozyme RM IM addition 3%, temperature is 70 DEG C, vacuum tightness 0.09MPa, stopped reaction after 60 hours reaction times, centrifugal removing immobilized enzyme, plant steroid (alkane) alcohol that unreacted is complete is removed in crystallizer, cooling temperature is 4 DEG C, 10 hours cooling times, at this temperature in 5000rpm frozen centrifugation 3 minutes, separation obtains the low acid value Rice pollard oil being rich in steroid (alkane) alcohol ester, the recyclable recycling of plant steroid (alkane) alcohol that immobilized enzyme and crystallization obtain.After reaction, Rice pollard oil acid value is 3.50mgKOH/g, containing plant sterol ester 11.15%wt, plant stanol ester 14.14%, content of phytosterol is 1.56%wt, phytostanols content 1.02%, Tegin 55G content 2.57%wt, DAG content 12.04%wt, sweet three ester content 55.43%wt, color and luster Huang 30, red 5.0.
Embodiment 3
Intermittent type enzyme reaction is carried out in batch-type agitator tank reactor, add reaction substrate feed liquid, the Rice pollard oil free fatty acids mixed in mixing of materials tank and the mol ratio of phytostanols are that (Rice pollard oil acid value is 29.311mgKOH/g to 1:1, color and luster Huang 29, red 4.8), stir speed (S.S.) 150rpm, immobilized enzyme Novozym 435 addition 3%, temperature is 70 DEG C, vacuum tightness 0.09MPa, stopped reaction after 60 hours reaction times, centrifugal removing immobilized enzyme, the phytostanols that unreacted is complete is removed in crystallizer, cooling temperature is 4 DEG C, 10 hours cooling times, at this temperature in 5000rpm frozen centrifugation 3 minutes, be separated and obtain the low acid value Rice pollard oil being rich in stanol ester, the recyclable recycling of the phytostanols that immobilized enzyme and crystallization obtain.After reaction, Rice pollard oil acid value is 3.41mgKOH/g, and containing plant stanol ester 26.29%wt, stanols content is 2.06%wt, Tegin 55G content 2.49%wt, DAG content 9.47%wt, sweet three ester content 55.68%wt, color and luster Huang 30, red 4.6.
Embodiment 4
Intermittent type enzyme reaction is carried out in batch-type agitator tank reactor, add reaction substrate feed liquid, the Rice pollard oil free fatty acids mixed in mixing of materials tank and the mol ratio of plant sterol are that (Rice pollard oil acid value is 29.311mgKOH/g to 1:1, color and luster Huang 29, red 4.8), acetone addition is 1mL/g oil, pump into after plant sterol dissolves completely in reactor, stir speed (S.S.) 150rpm, immobilized enzyme Lipozyme RM IM addition 3%, temperature is 70 DEG C, 3A molecular sieve addition is 0.1g/g oil, stopped reaction after 64 hours reaction times, centrifugal removing immobilized enzyme, acetone is removed in rotatory evaporator, vacuum tightness 0.085Mpa, temperature is 60 DEG C, rotary evaporation removing organic solvent, organic solvent condensation refluxing in storage within the condenser.The plant sterol that unreacted is complete is removed in crystallizer, cooling temperature is 4 DEG C, 10 hours cooling times, at this temperature in 5000rpm frozen centrifugation 3 minutes, be separated and obtain the low acid value Rice pollard oil being rich in sterol ester, the recyclable recycling of the plant sterol that immobilized enzyme, organic solvent and crystallization obtain.After reaction, Rice pollard oil acid value is 2.79mgKOH/g, and containing plant sterol ester 26.54%wt, sterol content is 1.95%wt, Tegin 55G content 2.42%wt, DAG content 7.96%wt, sweet three ester content 60.11%wt, color and luster Huang 31, red 4.8.
Embodiment 5
Intermittent type enzyme reaction is carried out in batch-type agitator tank reactor, (Rice pollard oil acid value is 29.311mgKOH/g to high acid value Rice pollard oil, color and luster Huang 29, red 4.8) and plant sterol add in batches, wherein plant sterol and normal hexane dissolve and add in reactor four times at 70 DEG C rear dividing completely, total plant sterol amount and the mol ratio of free fatty acids are 1:1, namely each plant sterol molar weight of adding is 25% of Rice pollard oil free fatty acids molar weight, normal hexane total addition level is 1mL/g oil, adding interval time is 12 hours, stir speed (S.S.) 150rpm, immobilized enzyme Lipozyme 435 addition 3%, temperature is 70 DEG C, 4A molecular sieve addition is 0.1g/g oil, stopped reaction after the 36 hours reaction times of accumulation, centrifugal removing immobilized enzyme, normal hexane is removed in rotatory evaporator, vacuum tightness 0.085Mpa, temperature is 60 DEG C, rotary evaporation removing organic solvent, organic solvent condensation refluxing in storage within the condenser.The plant sterol that unreacted is complete is removed in crystallizer, cooling temperature is 4 DEG C, 10 hours cooling times, at this temperature in 5000rpm frozen centrifugation 3 minutes, being separated and obtaining the low acid value Rice pollard oil being rich in sterol ester, reclaiming lipase and molecular sieve and plant sterol and organic solvent for recycling.This product acid value is 2.28mgKOH/g, and containing plant sterol ester 26.96%wt, sterol content is 1.77%wt, Tegin 55G content 1.92%wt, DAG content 8.24%wt, sweet three ester content 60.04%wt, color and luster Huang 30, red 4.7.
Embodiment 6
Semi continuous enzyme reaction is carried out in batch-type agitator tank reactor, be made up of 4 reactors in series, reaction substrate feed liquid is added from first reactor, the Rice pollard oil mixed in mixing of materials tank and the mol ratio of plant sterol are that (Rice pollard oil acid value is 29.311mgKOH/g to 1:1, color and luster Huang 29, red 4.8), normal hexane addition 1mL/g oil, 4A molecular sieve addition 0.1g/g oil in each reactor, stir speed (S.S.) 150rpm, immobilized enzyme Lipozyme RM IM addition 3%, temperature is 70 DEG C, stopped reaction after 8 hours is reacted in each reactor, filtering immobilized enzyme and molecular sieve pass into next reactor rhythmic reaction, accumulative reaction removes normal hexane after 32 hours again in rotatory evaporator, vacuum tightness 0.085Mpa, temperature is 60 DEG C, rotary evaporation removing organic solvent, organic solvent condensation refluxing in storage within the condenser.The plant sterol that unreacted is complete is removed in crystallizer, cooling temperature is 4 DEG C, 10 hours cooling times, at this temperature in 5000rpm frozen centrifugation 3 minutes, being separated and obtaining the low acid value Rice pollard oil being rich in sterol ester, reclaiming lipase and molecular sieve and plant sterol and organic solvent for recycling.After reaction, Rice pollard oil acid value is 2.34mgKOH/g, and containing plant sterol ester 26.91%wt, sterol content is 1.89%wt, Tegin 55G content 2.11%wt, DAG content 8.93%wt, sweet three ester content 59.02%wt, color and luster Huang 30, red 4.8.
Embodiment 7
Semi continuous enzyme reaction is carried out in batch-type agitator tank reactor, be made up of 5 reactors in series, reaction substrate feed liquid is added from first reactor, the Rice pollard oil mixed in mixing of materials tank and the mol ratio of plant sterol are that (Rice pollard oil acid value is 29.311mgKOH/g to 1:1, color and luster Huang 29, red 4.8), normal hexane addition 1mL/g oil, 4A molecular sieve addition 0.1g/g oil in each reactor, stir speed (S.S.) 150rpm, immobilized enzyme Lipozyme RM IM addition 3%, temperature is 70 DEG C, stopped reaction after 7 hours is reacted in each reactor, filtering immobilized enzyme and molecular sieve pass into next reactor rhythmic reaction, accumulative reaction removes normal hexane after 35 hours again in rotatory evaporator, vacuum tightness 0.085Mpa, temperature is 60 DEG C, rotary evaporation removing organic solvent, organic solvent condensation refluxing in storage within the condenser.The plant sterol that unreacted is complete is removed in crystallizer, cooling temperature is 4 DEG C, 10 hours cooling times, at this temperature in 5000rpm frozen centrifugation 3 minutes, being separated and obtaining the low acid value Rice pollard oil being rich in sterol ester, reclaiming lipase and molecular sieve and plant sterol and organic solvent for recycling.This product acid number is 1.93mgKOH/g, and containing plant sterol ester 27.30%wt, sterol content is 2.33%wt, Tegin 55G content 1.47%wt, DAG content 9.06%wt, sweet three ester content 58.69%wt, color and luster Huang 29, red 4.7.
Embodiment 8
Semi continuous enzyme reaction is carried out in batch-type agitator tank reactor, the Rice pollard oil of question response and the mol ratio of total plant sterol are that (Rice pollard oil acid value is 29.311mgKOH/g to 1:1, color and luster Huang 29, red 4.8), enzyme reaction is made up of 4 reactors in series, and add plant sterol with the time-division 4 batches, each reactor add respectively a collection of plant sterol (plant sterol at 70 DEG C with normal hexane mixed dissolution completely after add in reactor), normal hexane addition is 1mL/g oil, the plant sterol molar weight of adding in each reactor is 25% of Rice pollard oil free fatty acids molar weight, 4A molecular sieve addition 0.1g/g oil in each reactor, stir speed (S.S.) 200rpm, immobilized enzyme Lipozyme RM IM addition 3%, temperature is 70 DEG C, first reactor reaction 3 hours, second reactor reaction 5 hours, 3rd reactor reaction 7 hours, 4th reactor reaction 9 hours, accumulation reaction is stopped reaction after 24 hours, normal hexane is removed in rotatory evaporator, vacuum tightness 0.085Mpa, temperature is 60 DEG C, rotary evaporation removing organic solvent, organic solvent condensation refluxing in storage within the condenser.The plant sterol that unreacted is complete is removed in crystallizer, cooling temperature is 4 DEG C, 10 hours cooling times, at this temperature in 5000rpm frozen centrifugation 3 minutes, being separated and obtaining the low acid value Rice pollard oil being rich in sterol ester, reclaiming lipase and molecular sieve and plant sterol and organic solvent for recycling.This product acid number is 1.43mgKOH/g, and containing plant sterol ester 28.29%wt, sterol content is 2.50%wt, Tegin 55G content 1.32%wt, DAG content 8.41%wt, sweet three ester content 59.18%wt, color and luster Huang 30, red 4.7.
It should be noted that, above embodiment is only in order to illustrate technical scheme of the present invention and unrestricted, although with reference to preferred embodiment to invention has been detailed description, those of ordinary skill in the art is to be understood that, can modify to technical scheme of the present invention or equivalent replacement, and not departing from the spirit and scope of technical solution of the present invention, it all should be encompassed in the middle of right of the present invention.
Claims (10)
1. a Rice pollard oil enzyme process deacidifying process, it is characterized in that: utilize endogenous plant sterol in Rice pollard oil, under lipase-catalyzed effect, the free fatty acids generation esterification in the Rice pollard oil of 4mgKOH/g is not less than with acid value, reduce Rice pollard oil acid value to below 4mgKOH/g, obtain the oil and fat product containing phytosterin fatty acid ester; Wherein,
When there is esterification, stir speed (S.S.) 60 ~ 250rpm in reactor, its enzyme addition of described lipase is 1 ~ 10% by percentage to the quality, and temperature is 30 ~ 90 DEG C, the molecular sieve dehydration of more than vacuum tightness 0.085MPa dehydration or interpolation 0.05 ~ 0.5g/g oil, reaction times 24 ~ 72h.
2. Rice pollard oil enzyme process deacidifying process according to claim 1, is characterized in that: described lipase is one or more in immobilized enzyme Lipozyme RM IM, Lipzomye 435, immobilized enzyme Lipozyme TL IM, immobilized enzyme Novozym 435, immobilized enzyme Lipozyme TL 100L, resolvase Lipozyme CAL BL.
3. Rice pollard oil enzyme process deacidifying process according to claim 1, it is characterized in that: also comprise, before the described esterification of generation, a certain amount of organic solvent is added in described Rice pollard oil, described Rice pollard oil and organic solvent proportioning are 1:0.5 ~ 2 (w/v), described organic solvent is normal hexane and acetone, takes the mode of the molecular sieve of interpolation 0.05 ~ 0.5g/g oil to dewater.
4. according to the arbitrary described Rice pollard oil enzyme process deacidifying process of claims 1 to 3, it is characterized in that: described acquisition is containing the oil and fat product of phytosterin fatty acid ester, wherein, the acid value of Rice pollard oil is at below 4mgKOH/g, sterol fatty acid ester content is 4 ~ 36%, content of triglyceride is 50 ~ 80%, and diglyceride content is 5 ~ 15%, and content of monoglyceride is less than 3%.
5. a Rice pollard oil enzyme process deacidifying process, it is characterized in that: by Rice pollard oil, organic solvent and plant sterol and/or phytostanols mixed dissolution, under lipase-catalyzed effect, the free fatty acids generation esterification in the Rice pollard oil of 4mgKOH/g is not less than with acid value, reduce Rice pollard oil acid value to below 4mgKOH/g, obtain the oil and fat product being rich in plant sterol and/or plant stanol fatty acid ester; Wherein,
When there is esterification, stir speed (S.S.) 60 ~ 250rpm in reactor, described lipase enzyme addition is 1 ~ 10% by percentage to the quality, and temperature is 30 ~ 90 DEG C, the molecular sieve dehydration of more than vacuum tightness 0.085MPa dehydration or interpolation 0.05 ~ 0.5g/g oil, reaction times 24 ~ 72h.
6. Rice pollard oil enzyme process deacidifying process according to claim 5, is characterized in that: described lipase is one or more in immobilized enzyme Lipozyme RM IM, immobilized enzyme Lipzomye 435, immobilized enzyme Lipozyme TL IM, immobilized enzyme Novozym 435, immobilized enzyme Lipozyme TL 100L, resolvase Lipozyme CAL BL.
7. the Rice pollard oil enzyme process deacidifying process according to claim 5 or 6, it is characterized in that: before generation esterification, a certain amount of organic solvent is added in described Rice pollard oil, described Rice pollard oil and organic solvent proportioning are 1:0.5 ~ 2 (w/v), and described organic solvent is normal hexane and acetone.
8. Rice pollard oil enzyme process deacidifying process according to claim 5, it is characterized in that: described by Rice pollard oil, organic solvent and plant sterol and/or phytostanols mixed dissolution, wherein, the addition of plant sterol and/or phytostanols is 1 ~ 28% by percentage to the quality.
9. Rice pollard oil enzyme process deacidifying process according to claim 5, is characterized in that: described molecular sieve is 3A or 4A molecular sieve.
10. the Rice pollard oil enzyme process deacidifying process according to claim 5 or 6, is characterized in that: after obtaining the oil and fat product containing plant sterol and/or plant stanol fatty acid ester, also comprise,
Subsequent treatment process, it is included in removing and recovery organic solvent in vaporizer, at more than vacuum tightness 0.08Mpa, temperature is 40 ~ 70 DEG C, rotary evaporation removing organic solvent, organic solvent condensation reflux in certain storage within the condenser, or coutroi velocity is directly back in mixing of materials tank, Determination of Residual Organic Solvents≤100ppm, after removing organic solvent, in crystallizer or crystallizer, crystallisation by cooling removes and reclaims unreacted plant sterol and/or phytostanols again, cooling temperature is 0 ~ 5 DEG C, 5 ~ 10 hours cooling times, at this temperature in 3000 ~ 5000rpm frozen centrifugation 2 ~ 5 minutes, be separated and reclaim unreacted plant sterol and/or phytostanols, recovery lipase and molecular sieve are for recycling.
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