CN105779517B - The method of diacylglycerol content during reduction enzyme process esterification deacidification - Google Patents
The method of diacylglycerol content during reduction enzyme process esterification deacidification Download PDFInfo
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Abstract
The present invention provides the method for diacylglycerol content during reducing enzyme process esterification deacidification, will include that the raw material of grease, glycerol and medium-chain fatty acid carries out esterification under the conditions of the method is existing for the catalyst；The medium-chain fatty acid is the medium-chain fatty acid and its derivative that are 6~10 with carbon atom number or their mixture.It can reduce the content of grease diglyceride in esterification process by the method for the invention, shorten the reaction time, be conducive to industrialized production.
Description
Technical field
The invention belongs to edible oil and fat processing technology fields, the specially method of the free fatty acid in removal grease, should
Method can reduce the content of diglyceride in system in esterification process.
Background technique
Acid value is the mark of free fatty acid content in grease, the size of acid value of lipids and raw material, the grease for producing grease
It produces related with the technique of processing, the method for storage and transportation of grease and storing condition etc..Free fatty acid content is excessively high in grease, not only
The hydrolysis that neutral oil can be further speeded up is rancid, and generating penetrating odor influences the flavor of grease, can also make grease to heat and oxygen
Bad stability, promote grease oxidation rancid, and be possible to corrosion refining equipment etc..
Rice oil is a kind of grease extracted from the by-product rice bran generated in rice process, also referred to as rice bran
Oil.Saturated fatty acid content is 23.2g in its every hectogram, and monounsaturated fatty acids content is 42.2g, and polyunsaturated fatty acid contains
Amount is 34.5g, is a kind of natural healthy oil of high-quality close to worldwide nutrition association proposed standard.Rice oil is rich in paddy
Tie up the active skull cap components such as element, vitamin E, tocotrienols, sitosterol.With blood lipid is reduced, cerebral nerve function is adjusted, is resisted
The functions such as aging.
China's rice bran is resourceful, but since there are lipase in rice bran, if rice bran cannot be handled in time, rice
Grease in chaff is easy to by lipase hydrolysis be free fatty acid (FFA), so that the acid value of Rice oil be caused to increase, acid value can
To reach 15-80mgKOH/g, to limit the processing and utilization of Rice oil.
For the Rice oil containing a large amount of free fatty acids, free fatty acid therein esterification can be changed into sweet
Oily three esters are the optimal paths for increasing yield, improving its utilization rate.In esterification process, common esterification process includes chemical ester
Change and two kinds of biological esterification.It is tight to destructions such as active materials in grease such as vitamin E, sterol since chemical esterification needs high temperature
Weight, and the waste water etc. of a large amount of pollution environment can be generated, therefore be difficult to apply in actual production.And biological esterification is to utilize rouge
The high-efficiency catalytic activity of fat enzyme catalytic esterification at low temperatures, while being generated without waste water.Currently used lipase is Novi
Immobilized lipase Novozymes 435, Lipozyme RM IM, the Lipozyme TL IM of letter company.These lipase exist
It can be generated during esterification a certain amount of diglyceride (DAG), and these diglycerides generate the refined oil in later period
Phenomena such as certain adverse effect, such as generation ethylene oxidic ester, emulsification (patent document WO2011002275).Therefore by glycerol two
It is necessary that ester, which is reduced to alap level,.And since the reaction rate of diglyceride and Long carbon chain fatty acid is very slow, often
The method of rule is to extend the reaction time and achieve the purpose that reduce diglyceride.Many scholars study this.
A kind of method that esterification prepares triglycerides is disclosed in patent document WO2013/078187A1.In this method
In, in the case where 435 additive amount of Novozymes is 2%, the diacylglycerol content after reaction 14h in system is still 8.5%.
And when FFA content is 15.5 weight % in embodiment 7, reaction temperature is 75 DEG C, vacuum degree is 7kPa, after reaction 5h in system
The content of diglyceride is up to 19.9%.
Non-patent literature 1 " research of rice bran oil enzyme process esterification deacidification, " Chinese oil ", the 7th phase of volume 30 in 2005,
22-24 pages " in, equally the DAG content in esterification process is studied.When glycerol additive amount is theoretical additive amount, 60
After DEG C reaction 12h in system still containing 10.12% DAG, DAG content, which has no, during subsequent reactions is substantially reduced.
It is 65 DEG C in reaction temperature, enzyme adds using Lipozyme TL IM as catalyst in above-mentioned non-patent literature 1
Dosage is 10%, and the diacylglycerol content after reaction 9.3h in system is still 24.2%.
In " the Biocatalysed synthesis of sn-1,3-diacylglycerol oil of non-patent literature 2
From extra virgin olive oil, (Blasi F, Cossignani L, Simonetti M S, et al., Enzyme
And Microbial Technology, 2007,41 (6): 727-732.) " in using Lipozyme IM as catalyst, In
Reaction temperature is only reduced to about 15% for DAG content in system after 40 DEG C of reactions for 24 hours, needs if being reduced to lower level
Reaction is up to 96h.
It describes in above-mentioned patent and non-patent literature, is contained by diglyceride in various technology controlling and process esterification process
Amount.But glycerol two is reduced in biological esterification reaction process from can be seen that the prior art has the following disadvantages: in above-mentioned document
The time of ester can be very long.The content of diglyceride can be very high during biological esterification in a short time, while the content drop of diester
It is slow at a low speed；And if it is desired to reducing the reaction time that diglyceride then needs to grow very much.Present inventor considered that the above-mentioned prior art
Deficiency can be realized by adding medium-chain fatty acid in biological esterification reaction process in the first of biological esterification reaction process
Phase can in reduction system diglyceride content, and rate it is more common long chain fatty acids reaction rate it is fast, to actual
Industrialized production has great importance.
Summary of the invention
Problems to be solved by the invention
The present invention provide it is a kind of reduction enzyme process esterification deacidification during diacylglycerol content method, it is intended to more quickly drop
In low biological esterification reaction process in system diglyceride content, shorten the reaction time, improve oil yield.
The solution to the problem
First aspect of the present invention be provide it is a kind of reduction enzyme process esterification deacidification during diacylglycerol content method,
Be characterized in that: under the conditions of the method is existing for the catalyst, by the raw material comprising grease, glycerol and medium-chain fatty acid into
Row esterification；The medium-chain fatty acid be with carbon atom number be 6~10 medium-chain fatty acid and its derivative or it
Mixture, the catalyst is preferably lipase, more preferably liquid aliphatic enzyme or hard fat enzyme, more preferably liquid
Lipase.
Alternative plan of the invention be provide it is a kind of reduce acid value of lipids method, it is characterised in that: the method be
Under the conditions of catalyst is existing, esterification will be carried out comprising the raw material of grease, glycerol and medium-chain fatty acid；The middle carbochain
Fatty acid is the medium-chain fatty acid and its derivative that are 6~10 with carbon atom number or their mixture, the catalyst
Preferably lipase, more preferably liquid aliphatic enzyme or hard fat enzyme, more preferably liquid aliphatic enzyme.
According to the first or second scheme of aforementioned present invention, it is characterised in that: the grease is high acid value grease, preferably
Acid value is the high acid value grease of 5~80mgKOH/g, and more preferably one or more of Rice oil, palm oil, fish oil mixes
Object.
According to the scheme of aforementioned present invention, it is characterised in that: dispersing agent, the dispersing agent are added in esterification reaction process
Preferably one of white carbon black, alkaline carclazyte, calcium chloride, florisil or a variety of.
According to the scheme of aforementioned present invention, it is characterised in that: on the basis of the weight of grease, the additive amount of lipase is 1
~10%, preferably 2~7%.
According to the scheme of aforementioned present invention, it is characterised in that: added medium-chain fatty acid and its derivative or it is mixed
The molar ratio for closing diglyceride contained in object and grease is 0.3~2.5:1.
According to the scheme of aforementioned present invention, it is characterised in that: the lipase be liquid aliphatic enzyme or hard fat enzyme, it is excellent
It is selected as liquid aliphatic enzyme.
According to the scheme of aforementioned present invention, it is characterised in that: the molar ratio of free fatty acid and glycerol in grease is 1:1
~3:1.
According to the scheme of aforementioned present invention, it is characterised in that: the content of diglyceride is lower than 12 weight % in reaction system,
Preferably shorter than 10 weight %.
Third program of the invention is the purposes for providing medium-chain fatty acid for reducing acid value of lipids, it is characterised in that:
The medium-chain fatty acid is the medium-chain fatty acid and its derivative that are 6~10 with carbon atom number or their mixture；
Preferably, the molar ratio of or mixtures thereof added medium-chain fatty acid and its derivative and diglyceride contained in grease
For 0.3~2.5:1.
The effect of invention
It is carried out in esterification process using lipase, diacylglycerol content is high in generally existing esterification process, the reaction time
The problems such as long, the present invention mainly are carrying out adding medium-chain fatty acid, Neng Gouxun in lipin deacidifying esterification process using lipase
Diacylglycerol content in fast reduction system improves oil yield, shortens the reaction time.
Specific embodiment
Unless otherwise stated, the various degrees (X%) in the application and the ratio (X:Y) between ingredient are
Based on w/w.
It should be appreciated that the term as used herein " about " (for example, in constituent content and response parameter) is with art technology
Personnel it can be generally understood that meaning explain.Under normal circumstances, term " about " can be understood as positive and negative 5% model of given numerical value
Interior any number is enclosed, for example, about X can represent any number in the range of 95%X to 105%X.
It is also understood that the specific value (for example, in component proportion, reaction temperature and in the reaction time) being presented herein
It can be used as individual numerical value to understand, it should be also appreciated that providing the endpoint value of a certain range, and can be combined with each other and mention
For other ranges.For example, when disclose reaction can carry out 2 it is small when or at 6 hours, reaction, which is also correspondingly disclosed, to be carried out
2-6 hours.
" range " disclosed herein is in the form of lower and upper limit.It can be respectively one or more lower limits and one
Or multiple upper limits.Given range is defined by a selected lower limit and a upper limit.Selected lower and upper limit limit
The boundary of special range is determined.All ranges that can be defined in this way comprising and can combine, i.e., any lower limit
It can combine to form a range with any upper limit.
In the present invention, unless otherwise indicated, between the content range of each component of composition and its preferred scope
It can be combined with each other to form new technical solution.
In the present invention, unless otherwise indicated, " a combination thereof " indicates the multicomponent mixture of each element, such as two
Kind, three kinds, four kinds and until maximum possible multicomponent mixture.
In the present invention, unless otherwise indicated, own " part " and percentage (%) all refers to weight percent.
In the present invention, unless otherwise indicated, the sum of percentage of each component is 100% in all compositions.
In the present invention, unless otherwise indicated, numberical range " a-b " indicates the contracting of any real combinings between a to b
Sketch form shows that wherein a and b is real number.Such as numberical range " 0-10 " expression has all listed between " 0-10 " herein
Whole real numbers, " 0-10 " be these combinations of values breviary indicate.
If be not specifically stated, term "an" used in this specification refers to "at least one".
If be not specifically stated, the benchmark of percentage (including weight percent) of the present invention is all the combination
The total weight of object.
In the present invention, if without particularly illustrating, all embodiments mentioned in this article and preferred implementation side
Formula can be combined with each other to form new technical solution.
In the present invention, if without particularly illustrating, all technical characteristics and preferred feature mentioned in this article can
New technical solution is formed to be combined with each other.
In the present invention, if without particularly illustrating, " comprising " mentioned in this article indicates open, is also possible to seal
Enclosed.For example, the " comprising " can indicate can also only can also to include the group listed comprising the other components that do not list
Point.
In the present invention, if without particularly illustrating, specific value and specific substance in embodiment hereof can be with
Other features that part is described herein combine.
Under vacuum conditions, use lipase preferred liquid lipase is catalyst to free fatty acid in grease to this method
While esterification with glycerol, by the way that suitable medium-chain fatty acid is added, diglyceride that can quickly in reduction system
Content shortens the reaction time, and generates Medium-Chain Triglyceride simultaneously.
In the present invention, described " reducing diacylglycerol content during enzyme process esterification deacidification " explains as follows,
I.e. in identical FFA: under the molar ratio of glycerol, after addition medium-chain fatty acid reacted a period of time (such as 2~6 hours)
It is reduced compared with DAG content in the system for not adding medium-chain fatty acid under the same terms.In the present invention, DAG reduced rate is
Refer to identical FFA: under the molar ratio of glycerol, add after the reacted 6h of medium-chain fatty acid with do not add under the same terms
The reduced rate of DAG content in the system of carbon chain fatty acid.
Grease used in the present invention is high acid value grease, preferably acid value be 5-80mgKOH/g high acid value grease.This
It invents the acid value and refers to the milligram number for neutralizing KOH needed for free fatty acid in 1 gram of grease.
The present invention does not have used lipase special requirement, and lipase commonly used in the art can make
With, such as: immobilized lipase Novozymes 435, Lipozyme RM IM, the Lipozyme TL IM of Novozymes Company,
Liquid aliphatic enzyme CALB, Lipase AP15, Lipase PS, Lipase AK, Lipase A6, Lipase F, Lipase
AY30, Lipase G80, and/or Lipase M-10 etc..
First aspect of the present invention be provide it is a kind of reduction enzyme process esterification deacidification during diacylglycerol content method,
Be characterized in that: under the conditions of the method is existing for the catalyst, by the raw material comprising grease, glycerol and medium-chain fatty acid into
Row esterification；The medium-chain fatty acid be with carbon atom number be 6~10 medium-chain fatty acid and its derivative or it
Mixture, the catalyst is preferably lipase, more preferably liquid aliphatic enzyme or hard fat enzyme, more preferably liquid
Lipase.
In specific embodiments of the present invention, the medium-chain fatty acid that the carbon atom number is 6~10 includes but unlimited
In caproic acid, enanthic acid, octanoic acid, n-nonanoic acid, capric acid or derivatives thereof and its mixture.
In the present invention, the grease, glycerol, medium-chain fatty acid addition sequence be arbitrary；Medium-chain fatty acid
And/or the addition time of glycerol can be added when reacting initial or be added after reacting a period of time.
In a specific embodiment of the present invention, carboxyl is contained at least one in described medium-chain fatty acid or derivatives thereof.
In specific embodiments of the present invention, in the medium-chain fatty acid derivative can also comprising hydroxyl, carbonyl,
Ketone group, alkylene, alkynes base, hetero atom such as sulphur, nitrogen, oxygen, one or more functional groups in phosphorus.
In the present invention, the medium-chain fatty acid derivative includes but is not limited to adipic acid, hexenoic acid, hexynic acid, 2-
Nitrogen caproic acid, 3- carbonyl caproic acid.
In specific embodiments of the present invention, described medium-chain fatty acid or derivatives thereof is having for straight chain or branch
Machine molecule.
Alternative plan of the invention be provide it is a kind of reduce acid value of lipids method, it is characterised in that: the method be
Under the conditions of catalyst is existing esterification will be carried out comprising the raw material of grease, glycerol and medium-chain fatty acid；The middle carbochain
Fatty acid is the medium-chain fatty acid and its derivative that are 6~10 with carbon atom number or their mixture, the catalyst
Preferably lipase, more preferably liquid aliphatic enzyme or hard fat enzyme, more preferably liquid aliphatic enzyme.
In specific embodiments of the present invention, the grease is crude oil and/or polished fat.
In specific embodiments of the present invention, the grease is vegetable oil, animal oil or the oil by reaction synthesis
Rouge.The vegetable oil includes but is not limited to soya-bean oil, corn oil, Rice oil, sunflower oil etc. and its mixture；The animal oil packet
Include but be not limited to lard, butter, chicken and duck rouge etc. and its mixture.
In specific embodiments of the present invention, the grease is high acid value grease, and preferably acid value is 5~80mgKOH/
The high acid value grease of g, more preferably one or more of Rice oil, palm oil, fish oil mixture.
According to the scheme of aforementioned present invention, it is characterised in that: dispersing agent, the dispersing agent are added in esterification reaction process
Including but not limited to one of white carbon black, alkaline carclazyte, calcium chloride, florisil or a variety of.
In specific embodiments of the present invention, the florisil includes but is not limited to silicic acid magnesium types adsorbent.
In specific embodiments of the present invention, on the basis of the weight of grease, the additive amount of the dispersing agent is 1-
10%, preferably additive amount is 2-6%.
According to the scheme of aforementioned present invention, it is characterised in that: on the basis of the weight of grease, the additive amount of lipase is 1
~10%, preferably 2~7%.
According to the scheme of aforementioned present invention, it is characterised in that: added medium-chain fatty acid and its derivative or it is mixed
The molar ratio for closing diglyceride contained in object and grease is 0.3~2.5:1.
According to the scheme of aforementioned present invention, it is characterised in that: the lipase be liquid aliphatic enzyme or hard fat enzyme, it is excellent
It is selected as liquid aliphatic enzyme.
In the present invention, when the lipase used is hard fat enzyme, dispersing agent can not be added.
In specific embodiments of the present invention, the amount of glycerol used is not according in initial grease (esterification occurs)
The amount of free fatty acid determine that the molar ratio of free fatty acid and glycerol in grease is 1:1~3:1.
In specific embodiments of the present invention, the esterification is carried out in the case where being lower than 100mbar, reaction temperature 50-
120℃。
According to the scheme of aforementioned present invention, it is characterised in that: the content of diglyceride is lower than 12 weight % in reaction system,
Preferably shorter than 10 weight %.
Third program of the invention is the purposes provided by medium-chain fatty acid for reducing acid value of lipids, and feature exists
In: the medium-chain fatty acid is the medium-chain fatty acid and its derivative that are 6~10 with carbon atom number or their mixing
Object；Preferably, or mixtures thereof added medium-chain fatty acid and its derivative and diglyceride contained in grease rub
You are than being 0.3~2.5:1.
In specific embodiments of the present invention, the medium-chain fatty acid that the carbon atom number is 6~10 includes but unlimited
In caproic acid, enanthic acid, octanoic acid, n-nonanoic acid, capric acid or derivatives thereof and its mixture.
In specific embodiments of the present invention, in the medium-chain fatty acid derivative comprising hydroxyl, carbonyl, aldehyde radical,
Ketone group, alkylene, alkynes base, hetero atom such as sulphur, nitrogen, oxygen, one or more functional groups in phosphorus.
In specific embodiments of the present invention, described medium-chain fatty acid or derivatives thereof is having for straight chain or branch
Machine molecule.
The embodiment of the present invention using degumming dewaxing Rice oil as raw material, using liquid aliphatic enzymatic free fatty acid with it is sweet
Oil carries out enzyme process esterification, and by adding medium-chain fatty acid in esterification process, system is reduced in esterification process
The content of middle DAG.The specific steps of operation can be described below:
1, mao Rice oil is taken to carry out aquation degumming and freezing dewaxing treatment, degumming that treated dewaxing Rice oil phosphorus content is
140.5ppm, paraffin content are 0.3 weight %；
2, weigh a certain amount of degumming dewaxing Rice oil in reactor, then according to free fatty acid needed for experiment and
The molar ratio of glycerol adds glycerol；
3, according to mass ratio in Rice oil adding liquid lipase, white carbon black and medium-chain fatty acid, be warming up to certain
It is reacted under vacuum conditions after temperature；
4, separately sampled in reaction process, enzyme and grease, the acid value of test sample are centrifugated under 10000rpm revolving speed
Change with diacylglycerol content.
<embodiment>
Degumming dewaxing Rice oil, the dry Rice oil of degumming dewaxing in the present invention: being purchased from Qinhuangdao Jin Hai cereal and oil industry has
Limit company；
In following embodiments of the invention, liquid aliphatic enzyme CALB is commercialization Lipose CALB liquid aliphatic enzyme, is purchased from
Xin Zhong Co., Ltd, Novi.
In following embodiments of the invention,
The detection method of acid value are as follows: GB/T 5530-2005 " animal and plant fat acid value and acidity assaying "
The detection method of DAG content are as follows: AOCS Official Method Cd 11d-96
Embodiment 1 adds medium-chain fatty acid-octanoic acid C8:0；FFA: glycerol=1:1 (mol:mol)；Addition octanoic acid with
The DAG molar ratio initially contained in system is 2.5:1.
Taking 50g acid value is the high acid value Rice oil of 18.92mgKOH/g, glycerol 1.04g is then added, and 1.5g liquid is added
Body fat enzyme CALB (3%), 1.5g white carbon black (3%), 1.74g octanoic acid.After then heating to 80 DEG C vacuum degree be 2KPa
Under reacted, then every 2h sample detection acid value and diacylglycerol content.Different time points sample acid value (AV) and DAG contain
Amount is as shown in the table.Acid value and DAG content when wherein the time is 0h are initial acid value and DAG content (i.e. initial oil in system
Acid value (AV) and DAG content in rouge), similarly hereinafter.
| Time (h) | 0 | 2 | 4 | 6 |
| AV(mgKOH/g) | 30.99 | 3.60 | 2.49 | 2.07 |
| DAG (%) | 6.46 | 9.33 | 10.90 | 11.93 |
Embodiment 2 adds medium-chain fatty acid-capric acid C10:0；FFA: glycerol=1:1 (mol:mol)；The capric acid of addition
It is 2.5:1 with the DAG molar ratio initially contained in system.
Taking 50g acid value is the high acid value Rice oil of 18.92mgKOH/g, glycerol 1.04g is then added, and 1.5g liquid is added
Body fat enzyme CALB (3%), 1.5g white carbon black (3%), 2.08g capric acid.After then heating to 80 DEG C vacuum degree be 2KPa
Under reacted, then every 2h sample detection acid value and diacylglycerol content.Different time points sample acid value and DAG content are such as
Shown in following table.
| Time (h) | 0 | 2 | 4 | 6 |
| AV(mgKOH/g) | 30.83 | 3.69 | 2.73 | 2.07 |
| DAG (%) | 6.23 | 9.53 | 11.31 | 12.27 |
Embodiment 3 adds medium-chain fatty acid-caprylic capric mixture；FFA: glycerol=1:1 (mol:mol)；Addition
The DAG molar ratio initially contained in caprylic capric mixture and system is 2.5:1.
Taking 50g acid value is the high acid value Rice oil of 18.92mgKOH/g, glycerol 1.04g is then added, and 1.5g liquid is added
Body fat enzyme CALB (3%), 1.5g white carbon black (3%), the caprylic capric mixture of 1.91g are (sad: capric acid=50:50, quality
Percentage).It is reacted after then heating to 80 DEG C in the case where vacuum degree is 2KPa, then every 2h sample detection acid value and glycerol
Two ester contents.Different time points sample acid value and DAG content are as shown in the table.
| Time (h) | 0 | 2 | 4 | 6 |
| AV(mgKOH/g) | 29.60 | 3.42 | 2.49 | 2.11 |
| DAG (%) | 6.24 | 9.83 | 11.88 | 13.40 |
Embodiment 4 adds medium-chain fatty acid-octanoic acid C8:0；FFA: glycerol=3:1 (mol:mol)；Addition octanoic acid with
The DAG molar ratio initially contained in system is 2.5:1.
Taking 50g acid value is the high acid value Rice oil of 18.92mgKOH/g, glycerol 0.14g is then added, and 1.5g liquid is added
Body fat enzyme CALB (3%), 1.5g white carbon black (3%), 1.74g octanoic acid.After then heating to 80 DEG C vacuum degree be 2KPa
Under reacted, then every 2h sample detection acid value and diacylglycerol content.Different time points sample acid value and DAG content are such as
Shown in following table.
| Time (h) | 0 | 2 | 4 | 6 |
| AV(mgKOH/g) | 30.99 | 13.84 | 11.30 | 9.09 |
| DAG (%) | 6.46 | 6.57 | 6.40 | 5.96 |
Embodiment 5 adds medium-chain fatty acid-octanoic acid C8:0；FFA: glycerol=3:1 (mol:mol)；Addition octanoic acid with
The DAG molar ratio initially contained in system is 1.25:1.
Taking 50g acid value is the high acid value Rice oil of 18.92mgKOH/g, glycerol 0.14g is then added, and 1.5g liquid is added
Body fat enzyme CALB (3%), 1.5g white carbon black (3%), 0.87g octanoic acid.After then heating to 80 DEG C vacuum degree be 2KPa
Under reacted, then every 2h sample detection acid value and diacylglycerol content.Different time points sample acid value and DAG content are such as
Shown in following table.
| Time (h) | 0 | 2 | 4 | 6 |
| AV(mgKOH/g) | 24.96 | 10.49 | 7.42 | 5.72 |
| DAG (%) | 6.46 | 8.62 | 8.53 | 8.19 |
Embodiment 6 adds medium-chain fatty acid-octanoic acid C8:0；FFA: glycerol=3:1 (mol:mol)；Addition octanoic acid with
The DAG molar ratio initially contained in system is 0.625:1.
Taking 50g acid value is the high acid value Rice oil of 18.92mgKOH/g, glycerol 0.14g is then added, and 1.5g liquid is added
Body fat enzyme CALB (3%), 1.5g white carbon black (3%), 0.44g octanoic acid.After then heating to 80 DEG C vacuum degree be 2KPa
Under reacted, then every 2h sample detection acid value and diacylglycerol content.Different time points sample acid value and DAG content are such as
Shown in following table.
| Time (h) | 0 | 2 | 4 | 6 |
| AV(mgKOH/g) | 21.94 | 7.29 | 5.26 | 3.92 |
| DAG (%) | 6.52 | 9.85 | 9.30 | 8.99 |
Embodiment 7 adds medium-chain fatty acid-octanoic acid C8:0；FFA: glycerol=3:1 (mol:mol)；Addition octanoic acid with
The DAG molar ratio initially contained in system is 0.313:1.
Taking 50g acid value is the high acid value Rice oil of 18.92mgKOH/g, glycerol 0.14g is then added, and 1.5g liquid is added
Body fat enzyme CALB (3%), 1.5g white carbon black (3%), 0.22g octanoic acid.After then heating to 80 DEG C vacuum degree be 2KPa
Under reacted, then every 2h sample detection acid value and diacylglycerol content.Different time points sample acid value and DAG content are such as
Shown in following table.
| Time (h) | 0 | 2 | 4 | 6 |
| AV(mgKOH/g) | 20.43 | 7.53 | 5.49 | 4.17 |
| DAG (%) | 6.60 | 10.61 | 10.36 | 9.99 |
Embodiment 8 adds medium-chain fatty acid-capric acid C10:0；FFA: glycerol=3:1 (mol:mol)；The capric acid of addition
It is 2.5:1 with the DAG molar ratio initially contained in system.
Taking 50g acid value is the high acid value Rice oil of 18.92mgKOH/g, glycerol 0.14g is then added, and 1.5g liquid is added
Body fat enzyme CALB (3%), 1.5g white carbon black (3%), 2.08g capric acid.After then heating to 80 DEG C vacuum degree be 2KPa
Under reacted, then every 2h sample detection acid value and diacylglycerol content.Different time points sample acid value and DAG content are such as
Shown in following table.
| Time (h) | 0 | 2 | 4 | 6 |
| AV(mgKOH/g) | 30.83 | 16.51 | 12.58 | 10.34 |
| DAG (%) | 6.23 | 6.72 | 6.53 | 5.98 |
Embodiment 9 adds medium-chain fatty acid-capric acid C10:0；FFA: glycerol=3:1 (mol:mol)；The capric acid of addition
It is 1.25:1 with the DAG molar ratio initially contained in system.
Taking 50g acid value is the high acid value Rice oil of 18.92mgKOH/g, glycerol 0.14g is then added, and 1.5g liquid is added
Body fat enzyme CALB (3%), 1.5g white carbon black (3%), 1.04g capric acid.After then heating to 80 DEG C vacuum degree be 2KPa
Under reacted, then every 2h sample detection acid value and diacylglycerol content.Different time points sample acid value and DAG content are such as
Shown in following table.
| Time (h) | 0 | 2 | 4 | 6 |
| AV(mgKOH/g) | 24.88 | 10.43 | 7.38 | 5.86 |
| DAG (%) | 6.40 | 8.53 | 8.42 | 8.01 |
Embodiment 10 adds medium-chain fatty acid-capric acid C10:0；FFA: glycerol=3:1 (mol:mol)；The capric acid of addition
It is 0.625:1 with the DAG molar ratio initially contained in system.
Taking 50g acid value is the high acid value Rice oil of 18.92mgKOH/g, glycerol 0.14g is then added, and 1.5g liquid is added
Body fat enzyme CALB (3%), 1.5g white carbon black (3%), 0.52g capric acid.After then heating to 80 DEG C vacuum degree be 2KPa
Under reacted, then every 2h sample detection acid value and diacylglycerol content.Different time points sample acid value and DAG content are such as
Shown in following table.
| Time (h) | 0 | 2 | 4 | 6 |
| AV(mgKOH/g) | 21.91 | 9.40 | 7.15 | 5.59 |
| DAG (%) | 6.46 | 9.44 | 8.92 | 8.31 |
Embodiment 11 adds medium-chain fatty acid-capric acid C10:0；FFA: glycerol=3:1 (mol:mol)；The capric acid of addition
It is 0.313:1 with the DAG molar ratio initially contained in system.
Taking 50g acid value is the high acid value Rice oil of 18.92mgKOH/g, glycerol 0.14g is then added, and 1.5g liquid is added
Body fat enzyme CALB (3%), 1.5g white carbon black (3%), 0.26g capric acid.After then heating to 80 DEG C vacuum degree be 2KPa
Under reacted, then every 2h sample detection acid value and diacylglycerol content.Different time points sample acid value and DAG content are such as
Shown in following table.
| Time (h) | 0 | 2 | 4 | 6 |
| AV(mgKOH/g) | 20.41 | 8.65 | 6.36 | 4.75 |
| DAG (%) | 6.31 | 10.51 | 10.07 | 9.48 |
Embodiment 12 adds medium-chain fatty acid-caproic acid C6:0；FFA: glycerol=3:1 (mol:mol)；The caproic acid of addition
It is 2.5:1 with the DAG molar ratio initially contained in system.
Taking 50g acid value is the high acid value Rice oil of 18.92mgKOH/g, glycerol 0.14g is then added, and 1.5g liquid is added
Body fat enzyme CALB (3%), 1.5g white carbon black (3%), 1.40g caproic acid.After then heating to 80 DEG C vacuum degree be 2KPa
Under reacted, then every 2h sample detection acid value and diacylglycerol content.Different time points sample acid value and DAG content are such as
Shown in following table.
| Time (h) | 0 | 2 | 4 | 6 |
| AV(mgKOH/g) | 30.66 | 6.53 | 4.54 | 3.46 |
| DAG (%) | 6.30 | 6.72 | 7.03 | 6.85 |
Embodiment 13 adds medium-chain fatty acid-octanoic acid C8:0；FFA: glycerol=3:1 (mol:mol)；The octanoic acid of addition
It is 2.5:1 with the DAG molar ratio initially contained in system.
Taking 50g acid value is the high acid value Rice oil of 28.72mgKOH/g, glycerol 0.14g is then added, and 1.5g liquid is added
Body fat enzyme CALB (3%), 1.5g white carbon black (3%), 1.74g octanoic acid.After then heating to 80 DEG C vacuum degree be 2KPa
Under reacted, then every 2h sample detection acid value and diacylglycerol content.Different time points sample acid value and DAG content are such as
Shown in following table.
| Time (h) | 0 | 2 | 4 | 6 |
| AV(mgKOH/g) | 40.35 | 18.69 | 8.27 | 3.04 |
| DAG (%) | 7.20 | 12.72 | 10.72 | 9.68 |
<comparative example>
Comparative example 1 adds Long carbon chain fatty acid-oleic acid C18:1；FFA: glycerol=1:1 (mol:mol)；The oleic acid of addition
It is 2.5:1 with the DAG molar ratio initially contained in system.
Taking 50g acid value is the high acid value Rice oil of 18.92mgKOH/g, glycerol 1.04g is then added, and 1.5g liquid is added
Body fat enzyme CALB (3%), 1.5g white carbon black (3%), 3.41g oleic acid.After then heating to 80 DEG C vacuum degree be 2KPa
Under reacted, then every 2h sample detection acid value and diacylglycerol content.Different time points sample acid value and DAG content are such as
Shown in following table.
| Time (h) | 0 | 2 | 4 | 6 |
| AV(mgKOH/g) | 38.47 | 3.29 | 2.04 | 1.97 |
| DAG (%) | 6.46 | 17.16 | 18.16 | 19.34 |
Comparative example 2 adds Long carbon chain fatty acid-myristic acid C14:0；FFA: glycerol=1:1 (mol:mol)；Addition
The DAG molar ratio initially contained in myristic acid and system is 2.5:1.
Taking 50g acid value is the high acid value Rice oil of 18.92mgKOH/g, glycerol 1.04g is then added, and 1.5g liquid is added
Body fat enzyme CALB (3%), 1.5g white carbon black (3%), 2.75g myristic acid.It is in vacuum degree after then heating to 80 DEG C
It is reacted under 2KPa, then every 2h sample detection acid value and diacylglycerol content.Different time points sample acid value and DAG contain
Amount is as shown in the table.
| Time (h) | 0 | 2 | 4 | 6 |
| AV(mgKOH/g) | 29.60 | 3.36 | 2.15 | 1.84 |
| DAG (%) | 6.66 | 14.80 | 15.62 | 15.86 |
3 blank of comparative example --- any fatty acid is not added；FFA: glycerol=1:1.
Taking 50g acid value is the high acid value Rice oil of 18.92mgKOH/g, glycerol 1.04g is then added, and 1.5g liquid is added
Body fat enzyme CALB (3%), 1.5g white carbon black (3%).It is reacted after then heating to 80 DEG C in the case where vacuum degree is 2KPa, so
Afterwards every 2h sample detection acid value and diacylglycerol content.Different time points sample acid value and DAG content are as shown in the table.
| Time (h) | 0 | 2 | 4 | 6 |
| AV(mgKOH/g) | 18.92 | 2.09 | 1.97 | 1.92 |
| DAG (%) | 6.74 | 15.33 | 18.09 | 19.13 |
4 blank of comparative example --- any fatty acid is not added；FFA: glycerol=3:1.
Taking 50g acid value is the high acid value Rice oil of 18.92mgKOH/g, glycerol 0.14g is then added, and 1.5g liquid is added
Body fat enzyme CALB (3%), 1.5g white carbon black (3%).It is reacted after then heating to 80 DEG C in the case where vacuum degree is 2KPa, so
Afterwards every 2h sample detection acid value and diacylglycerol content.Different time points sample acid value and DAG content are as shown in the table.
| Time (h) | 0 | 2 | 4 | 6 |
| AV(mgKOH/g) | 18.92 | 8.36 | 5.60 | 4.27 |
| DAG (%) | 6.74 | 10.27 | 11.36 | 10.43 |
Comparative example 5 adds butyric acid-C4:0；FFA: glycerol=3:1 (mol:mol)；Initially contain in the butyric acid and system of addition
Some DAG molar ratios are 2.5:1.
Taking 50g acid value is the high acid value Rice oil of 18.92mgKOH/g, glycerol 0.14g is then added, and 1.5g liquid is added
Body fat enzyme CALB (3%), 1.5g white carbon black (3%), 1.06g butyric acid.After then heating to 80 DEG C in the case where vacuum degree is 2KPa
It is reacted, then every 2h sample detection acid value and diacylglycerol content.Different time points sample acid value and DAG content are as follows
Shown in table.
| Time (h) | 0 | 2 | 4 | 6 |
| AV(mgKOH/g) | 29.60 | 14.48 | 10.58 | 8.94 |
| DAG (%) | 6.55 | 11.42 | 11.52 | 11.10 |
Comparative example 6 uses acid value for the Rice oil of 28.72mgKOH/g, is not added with medium-chain fatty acid；FFA: glycerol=3:
1(mol:mol)。
Taking 50g acid value is the high acid value Rice oil of 28.72mgKOH/g, glycerol 0.14g is then added, and 1.5g liquid is added
Body fat enzyme CALB (3%), 1.5g white carbon black (3%).It is reacted after then heating to 80 DEG C in the case where vacuum degree is 2KPa, so
Afterwards every 2h sample detection acid value and diacylglycerol content.Different time points sample acid value and DAG content are as shown in the table.
| Time (h) | 0 | 2 | 4 | 6 |
| AV(mgKOH/g) | 28.72 | 5.33 | 3.51 | 2.90 |
| DAG (%) | 7.68 | 18.16 | 18.71 | 18.36 |
Embodiment summary summarizes
Influence of the different addition molar ratios of table 1 sad (C8) to DAG content
Influence of the different addition molar ratios of 2 capric acid of table (C10) to DAG content
Influence of the 3 different carbon chain lengths fatty acid of table to DAG content
Table 4 adds influence of the medium-chain fatty acid to DAG content
*: DAG reduced rate refers to identical FFA: under the molar ratio of glycerol, adding the reacted 6h of medium-chain fatty acid
Afterwards with medium-chain fatty acid is not added under the same terms system in DAG content reduced rate.
For above-mentioned all embodiments, it can be found that the medium-chain fatty acid of addition C6-C10 can effectively inhibit esterification de-
The increase for the DAG content that system generates during acid；Medium-chain fatty acid additive amount should according to the content of DAG initial in system into
Row determines that it is preferred that medium-chain fatty acid specifically adds molar ratio are as follows: medium-chain fatty acid: DAG=0.3-2.5:1, preferably 0.6-
2.5:1；It is reduced compared with the content of corresponding comparative example DAG in the case where the embodiment reaction 6h of addition medium-chain fatty acid
4-42.9%.
The foregoing is merely illustrative of the preferred embodiments of the present invention, the substantial technological content model being not intended to limit the invention
It encloses, substantial technological content of the invention is broadly defined in the scope of the claims of application, any technology that other people complete
Entity or method also or a kind of equivalent change, will if identical with defined in the scope of the claims of application
It is considered as being covered by among the scope of the claims.
All references mentioned in the present invention is incorporated herein by reference, independent just as each document
It is incorporated as with reference to such.In addition, it should also be understood that, those skilled in the art can be right after having read above content of the invention
The present invention makes various changes or modifications, and these equivalent forms also fall within the scope of the appended claims of the present application.
Claims (14)
1. a kind of method of diacylglycerol content during reduction enzyme process esterification deacidification, it is characterised in that: the method is to urge
Under the conditions of agent is existing, esterification will be carried out comprising the raw material of grease, glycerol and medium-chain fatty acid；The middle carbochain rouge
Fat acid be with carbon atom number be 6~10 medium-chain fatty acid and its derivative or their mixture, the catalyst be
Lipase, the derivative include one or more functional groups in hydroxyl, carbonyl, ketone group, alkylene, alkynes base, hetero atom,
The molar ratio of or mixtures thereof added medium-chain fatty acid and its derivative and diglyceride contained in grease is 0.3~
2.5:1。
2. a kind of method for reducing acid value of lipids, it is characterised in that: under the conditions of the method is existing for the catalyst, will include
The raw material of grease, glycerol and medium-chain fatty acid carries out esterification；The medium-chain fatty acid be with carbon atom number be 6~
10 medium-chain fatty acid and its derivative or their mixture, the catalyst are lipase, and the derivative includes hydroxyl
Base, carbonyl, ketone group, alkylene, alkynes base, one or more functional groups in hetero atom, added medium-chain fatty acid and
The molar ratio of or mixtures thereof its derivative and diglyceride contained in grease is 0.3~2.5:1.
3. method according to claim 1 or claim 2, it is characterised in that: the catalyst is liquid aliphatic enzyme or hard fat
Enzyme.
4. method according to claim 3, it is characterised in that: the catalyst is liquid aliphatic enzyme.
5. method according to claim 1 or claim 2, it is characterised in that: the grease is the peracid that acid value is 5~80mgKOH/g
Valence grease.
6. method according to claim 1 or claim 2, it is characterised in that: the grease is Rice oil, palm oil, one in fish oil
Kind or several mixtures.
7. method according to claim 1 or claim 2, it is characterised in that: dispersing agent, the dispersion are added in esterification reaction process
Agent is one of white carbon black, alkaline carclazyte, calcium chloride, florisil or a variety of.
8. method according to claim 1 or claim 2, it is characterised in that: on the basis of the weight of grease, the additive amount of lipase is
1~10%.
9. method according to claim 8, it is characterised in that: on the basis of the weight of grease, the additive amount of lipase is 2~
7%.
10. method according to claim 1 or claim 2, it is characterised in that: at least contain in described medium-chain fatty acid or derivatives thereof
There is a carboxyl.
11. method according to claim 1 or claim 2, it is characterised in that: the molar ratio of free fatty acid and glycerol in grease is
1:1~3:1.
12. method according to claim 1 or claim 2, it is characterised in that: the content of diglyceride is lower than 12 weights in reaction system
Measure %.
13. method according to claim 12, it is characterised in that: the content of diglyceride is lower than 10 weights in reaction system
Measure %.
14. medium-chain fatty acid is for reducing the purposes of acid value of lipids, it is characterised in that: the medium-chain fatty acid is with carbon
The medium-chain fatty acid and its derivative or their mixture that atomicity is 6~10, the derivative include hydroxyl, carbonyl,
Ketone group, alkylene, alkynes base, one or more functional groups in hetero atom, added medium-chain fatty acid and its derivative
Or mixtures thereof with the molar ratio of diglyceride contained in grease be 0.3~2.5:1.
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| WO2024079301A1 (en) * | 2022-10-14 | 2024-04-18 | Novozymes A/S | Process for selective hydrolysis of diglycerides in an oil/fat with aid of candida antarctica lipase b |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101736047A (en) * | 2010-02-01 | 2010-06-16 | 国家粮食局科学研究院 | Method for preparing functional grease by enzyme catalysis and modificaiton on tea oil |
| CN101979625A (en) * | 2010-11-03 | 2011-02-23 | 江南大学 | Method for synthesizing triglyceride with medium/long-chain structure by catalyzing ester exchange through enzyme |
| CN103119172A (en) * | 2010-06-18 | 2013-05-22 | 布特马斯先进生物燃料有限责任公司 | Extraction solvents derived from oil for alcohol removal in extractive fermentation |
-
2014
- 2014-12-22 CN CN201410830587.9A patent/CN105779517B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101736047A (en) * | 2010-02-01 | 2010-06-16 | 国家粮食局科学研究院 | Method for preparing functional grease by enzyme catalysis and modificaiton on tea oil |
| CN103119172A (en) * | 2010-06-18 | 2013-05-22 | 布特马斯先进生物燃料有限责任公司 | Extraction solvents derived from oil for alcohol removal in extractive fermentation |
| CN101979625A (en) * | 2010-11-03 | 2011-02-23 | 江南大学 | Method for synthesizing triglyceride with medium/long-chain structure by catalyzing ester exchange through enzyme |
Non-Patent Citations (1)
| Title |
|---|
| 米糠油酶法酯化脱酸的研究;杨博 等;《中国油脂》;20050720;22-24 * |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2024079301A1 (en) * | 2022-10-14 | 2024-04-18 | Novozymes A/S | Process for selective hydrolysis of diglycerides in an oil/fat with aid of candida antarctica lipase b |
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