CN104711118B - A method of reducing trans-fatty acid - Google Patents
A method of reducing trans-fatty acid Download PDFInfo
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- CN104711118B CN104711118B CN201310689160.7A CN201310689160A CN104711118B CN 104711118 B CN104711118 B CN 104711118B CN 201310689160 A CN201310689160 A CN 201310689160A CN 104711118 B CN104711118 B CN 104711118B
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- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11B—PRODUCING, e.g. BY PRESSING RAW MATERIALS OR BY EXTRACTION FROM WASTE MATERIALS, REFINING OR PRESERVING FATS, FATTY SUBSTANCES, e.g. LANOLIN, FATTY OILS OR WAXES; ESSENTIAL OILS; PERFUMES
- C11B3/00—Refining fats or fatty oils
- C11B3/001—Refining fats or fatty oils by a combination of two or more of the means hereafter
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- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11B—PRODUCING, e.g. BY PRESSING RAW MATERIALS OR BY EXTRACTION FROM WASTE MATERIALS, REFINING OR PRESERVING FATS, FATTY SUBSTANCES, e.g. LANOLIN, FATTY OILS OR WAXES; ESSENTIAL OILS; PERFUMES
- C11B3/00—Refining fats or fatty oils
- C11B3/10—Refining fats or fatty oils by adsorption
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Abstract
The present invention provides a kind of reduction trans-fatty acid, 3- chloro- 1, the method and oil and fat refining method of 2- propylene glycol and its ester, and/or glycidol and its ester, the method includes carrying out column chromatography to decoloration grease, and it is optional carried out after column chromatography the step of 60-150 DEG C of temperature range is deodorized.Method of the invention reduces production energy consumption, the formation that can avoid a series of high temperature deodorization by-products of bring while meeting product index and meeting even more better than the grease edible performance index of traditional diamond-making technique preparation, improves the quality and edible safety of edible oil and fat.
Description
Technical field
The invention belongs to fats and Oils Refining Technology fields, and in particular to a kind of to be deodorized work using column chromatography substitution grease high temperature
Skill, the method to reduce trans-fatty acid.
Background technique
Edible oil obtains everybody extensive concern as necessity a kind of in diet, it provides the same of energy for human body
When also bring a large amount of essential fatty acids, and with introducing some naturals such as vitamin E, phytosterol
Equal nutriments.With rapid economic development, the increasingly raising of people's living standard, while the consumption figure of grease is substantially increased
Attention is also gradually transferred on oil quality by people.Currently, pursuing the edible oil and fat of health, nutrition, safety as disappearing
The person's of expense is highly desirable, and the grease for providing a kind of high-quality becomes inexorable trend [the Han Jinzhi, " soybean oil of oils industry development
The research of novel process for refining ", 2012].
Traditional oil refining process high temperature deodorization is a most important link, is sloughed using high temperature high vacuum condition
The distinctive flavor of grease itself and flavour, and removal is through depickling, in the grease of decolorization there is also micro aldehydes, ketone
[remote rattan Thailand will, the edible oil such as smell of class, hydro carbons, low-molecular-weight fatty acid, the oxide of glyceride and carclazyte, residual solvent
The micro constitutent of rouge, 1992,2 (17): 50-53].By the grease of deodorization processing, effectively changed on color, flavor
It is kind, while the presence of free fatty acid and some oxidation products is had also been removed, the edible safety of grease is improved to a certain extent
Property [M.Victoria Ruiz-M é ndez, Contribution of denaturing and deodorization
Processes of oils to toxic oil syndrome, Chemico-Biological Interactions 2011
(192):142–144]。
But the deodorization of high temperature high vacuum also brings unfavorable one side.During vacuum deodorization, sweet three esters fat inside
Polymerization can be generated between acid molecule or between multiple sweet three ester molecules, general generation dimeric dibasic acid is more, these polymer have
Apparent biology toxicity has certain damaging action to body's immunity, a variety of with cardiovascular disease and diabetes B etc.
Disease related [Cao Wenming, " cytotoxicity of oxidation triacylglycerol polymer ", " food science and technology ", 2012,37 (9): 171-
179].Isomery can also occur under the high temperature conditions for the unsaturated fatty acid in grease, form trans-fatty acid, and human body intake is trans-
Acid can promote low-density protein cholesterol LDL in serum, reduce the high-density protein matter cholesterol HDL in serum, easily lead to
Cardiovascular disease [State of Zhao's will, " trans-fatty acid endangers Research on Problems in fatty foods ", " Chinese food and nutrition ", 2004
(11):16-19].High temperature deodorization also can cause greater loss to natural antioxidant-tocopherol.If soybean oil is at 265 DEG C
Deodorization, tocopherol can lose 43% [Jin Qingzhe, Xie Dan, " growth and decline of micro constitutent and its to edible oil stable state in refining process
Influence ", " Chinese oil ", 2011,36 [6]: 21-24].There are also document report [the Guo Jiaojiao, " detections of chlorine propyl ester in grease
And toxicological experiment research ", 2012；K.O.Wong etc., 3-Monochloropropane-1,2-diol (3-MCPD) in soy
And oyster sauces:Occurrence and dietary intake assessment, Food Control, 2006
(17):408–413；Zhang Li, " side reaction and its control of grease at high temperature ", " Chinese oil ", 2002,27 (3): 22-
24], deodorising process has apparent facilitation for the formation of the pollutant 3-MCPD, glycidol harmful components of grease, this
Also it arouses extensive attention at home and abroad, various countries also one after another expressly provide the highest intake of 3-MCPD, glycidol.
In addition, exceedingly extending deodorization time to improve oil and fat smoke point and raising temperature being unhelpful to the safety and human health of product.Cause
This, need to find a kind of new oil and fat refining processing method, avoid high temperature deodorization bring adverse effect, improve the edible peace of grease
Quan Xing.
US2012258232A1, which is disclosed, contacts the method for deodorization with vapor to inhibit by-product under a kind of high-temperature pressure-reduction
Formation, such as the reduction of glycidol aliphatic ester (3-MCPD), but bringing into for vapor increases refining energy consumption in the patent,
And there is no have research to the reduction of oil polymers, trans-fatty acid etc. under high temperature to patent the method.
CN200910013118.7 discloses a kind of method of the production of medicinal grease, mainly carries out to deodorization rectifying column
Transformation, is divided into upper, middle and lower segment for tower body, makes material through three sections of rectifying, adjust the process conditions of three sections of rectifying, to adapt to have
There is the separation of the volatile impurity component of different volatile performances to reach medicinal oil index request, but patent the method is not yet
There is the reduction for other harmful components such as trans-fatty acid, polymer under high temperature etc. to have research.
CN201010227935.5 provides a kind of utilize and compounds filler column chromatography technology preparation DHA grease room temperature decoloration side
Method reduces the temperature and time of subsequent deodorizing technology, reduces the formation of trans acids, but not with specific data explanation, institute
The adsorbent species used are more, and to pass through more complicated pretreatment process, and DHA is solvent body in the inventive technique scheme
It was column chromatography, subsequent product needs precipitation, and industrialized production is realized more difficult.
CN200980139300.5 provides the column chromatography technology of a kind of single column or multiple columns of connecting to crude glycerine three
Ester is purified, but the invention product is related to precipitation technique, and realization of industrialization is also more difficult.
From the point of view of existing patent and documents and materials are consulted, the fats and oils processing focus of attention is concentrated mainly on by being deodorized work at present
The change of skill or deodorizing tower reduces a certain by-products content.
The present invention provides a kind of new fats and Oils Refining Technologies, i.e., substitute high temperature deodorizing technology with column chromatography, change and pass
System fat processing method, reduces production energy consumption, meets even more meeting product index better than traditional diamond-making technique preparation
The formation that can avoid a series of high temperature deodorization by-products of bring while grease edible performance index, improves edible oil and fat
Quality and edible safety.
Summary of the invention
It is a primary object of the present invention to substitute grease conventional high-temperature deodorizing technology by column chromatography, high temperature is avoided to be deodorized
The formation of the harmful substance of generation, and pass through oil quality performance indicator prepared by the change to grease conventional machining process
More preferably, edible safety is higher.
Therefore, the present invention provide it is a kind of reduction grease in trans-fatty acid, 3- chlorine-1,2-propylene glycol and its ester, and/or
The method of glycidol and its ester, the method includes carrying out column chromatography to decoloration grease, and it is optional in column layer
The step of deodorization carried out after analysis, it is preferred that the deodorization temperature is 60-150 DEG C, more preferable 60-80 DEG C.
The present invention also provides a kind of oil and fat refining methods, the method includes carrying out column chromatography to decoloration grease,
And the step of optional deodorization carried out after column chromatography, it is preferred that the deodorization temperature is 60-150 DEG C, more preferably
60-80℃。
In method of the invention, the column chromatography is carried out using adsorbent dress column, adsorbent is selected from silica gel, active carbon, silicon
One of magnesium types adsorbent, aluminium oxide, diatomite are a variety of.
In a specific embodiment, compounded using silica gel with active carbon, the two ratio be 1:10~10:1, preferably 1:
4~4:1.
In a specific embodiment, silica gel and active carbon are compounded with the ratio of 1:1, are uniformly mixed.
In a specific embodiment, it is suitable for the invention grease and is selected from soybean oil, corn oil, rice bran oil, palm
One of oil, lard and butter are a variety of.
In a specific embodiment, decoloration grease flows through chromatographic column with the flow velocity of 20~400mL/min.
In a specific embodiment, chromatographic column is that chromatography glass column or stainless steel column, the cylinder of chromatographic column can be arranged
Oxygen.
In a specific embodiment, the method comprise the steps that using metering pump with the flow velocity of 20~400mL/min
Liquid bleached oil is pumped into chromatographic column.
It in a specific embodiment, further include preheating bleached oil (such as the decoloration of solid or semisolid before being pumped into
Oil), the step of obtaining the liquid bleached oil.
In a specific embodiment, column pressure is 0~100bar.
In a specific embodiment, the cylinder of chromatographic column is recycled with water-bath, and the bath temperature is preferably 15~80
℃。
In a specific embodiment, method of the invention further include:
(a) degumming step: degumming medium being added into crude oil, keeps being stirred under vacuum at 50-95 DEG C 30 minutes to 2 small
When, carry out dry degumming；Or degumming medium and pure water are added in crude oil at 50-95 DEG C, it stirs 30 minutes to 5 hours,
Carry out acidification water elution glue；
(b) optional alkali refining step: lye is added at 70-90 DEG C and is reacted with grease；
(c) optional to remove soap step: appropriate hot water to be added at 80-90 DEG C to remove soap stock；With
(d) decolorization process: breaking vacuum and decolorising agent is added after keeping vacuum to be warming up to 80-90 DEG C, then raises temperature to 90-
It 110 DEG C, keeps being stirred under vacuum 30-45 minutes.
The present invention substitutes grease conventional high-temperature deodorizing technology using column chromatography, i.e., on conventional grease refined base,
Column chromatography technology is introduced after link of decolourizing prepares high-quality grease.Process reform grease traditional diamond-making technique, operation temperature
Low, energy consumption is small.
In method provided by the invention, grease color, AV, PV and bad wind are effectively reduced by column chromatography technology
Taste replaces high temperature to be deodorized link, wherein can also be deodorized in conjunction with low temperature to the demanding grease of a small number of flavors further improves
Grease flavor.Grease prepared by this technique is compared with grease prepared by traditional diamond-making technique, color, acid value, peroxide value etc.
Conventional index is more excellent, and edible quality and safety further increase.
The invention avoids the adverse effects that high temperature deodorization generates, and can inhibit trans-fatty acid, 3-MCPD, glycidol and
The formation of polymer etc., and the tocopherol in grease is remained as far as possible, improve grease edible safety.
Specific embodiment
It is a primary object of the present invention to substitute grease conventional high-temperature deodorizing technology by column chromatography, high temperature is avoided to be deodorized
The formation of the harmful substance of generation, and pass through oil quality performance indicator prepared by the change to grease conventional machining process
More preferably, edible safety is higher.
Tomography devices used in the present invention generally include high-pressure delivery pump and pressure-resistant chromatographic column.Pressure-resistant chromatographic column can be layer
Analyse glass column or stainless steel column.High-pressure delivery pump and pressure-resistant chromatographic column are commercially available, such as are matched and separated using Novartis
The delivery pump that the chromatographic column and Dalian Li Wabeng industry Co., Ltd that technology (Shanghai) Co., Ltd. provides provide.
It usually selects and is compounded selected from one or more of silica gel, active carbon, florisil, aluminium oxide, diatomite.
If using 2 kinds of adsorbents, such as silica gel and active carbon, (weight ratio) ratio may be selected to be 1:10~10:1, wherein it is preferred that 4:1~
1:4, more preferable 1:1.If 1~4:1~4:1~4(weight ratio may be selected in ratio using three kinds of adsorbents), it is adsorbed using four kinds
1~4:1~4:1~4~1:4(weight ratio may be selected in agent, ratio), using five kinds of adsorbents, 1~4:1~4:1 is may be selected in ratio
~4:1~4:1~4(weight ratio).If each adsorbent can be loaded on column respectively using two or more adsorbents, or
Person can also first make all adsorbents refill column after evenly mixing.Perfectly even mix.Dry method or wet method dress post may be selected.
Chromatographic column cylinder can nitrogen charging or deoxygenation, cylinder jacketed water-bath circulation.
For Normal Atmospheric Temperature Liquid bleached oil, it can be directly conducted into holding vessel, then pass through metering pump (such as high-pressure delivery
Pump) it is pumped into chromatographic column, in an embodiment of the invention, the chromatographic column is in the chromatographic column of nitrogen charging or deoxygenation.
For room temperature solid or semi-fluid condition vegetable oil or animal oil (bleached oil), can first be preheated, it is ensured that
Grease all melts.Specific preheating temperature is related with specifically used grease, this can be by those skilled in the art in practical behaviour
It is easily grasped in work.For example, bleached oil is usually preheated to 15~80 DEG C, such as 20~60 DEG C.After bleached oil melts, it can will take off
Color oil imports in holding vessel, nitrogen filled protection.Then, the bleached oil of thawing can be pumped by metering pump (such as high-pressure delivery pump)
Optionally in the chromatographic column of nitrogen charging or deoxygenation.Before this, cylinder can be recycled with water-bath, and bath temperature can be controlled in 15~80
℃。
The flow velocity for the bleached oil being pumped into usually may be set to 20~400mL/min, pump pressure and 0~70bar of loine pressure, layer
Analysis column pressure is 0~100bar.These parameters can readily be determined according to actually used bleached oil, chromatographic column etc. and adjustment.
Collecting layer condensate oil sample, can be obtained final product.It can the nitrogen filled protection final product.
In some embodiments, low temperature deodorization processing can further be implemented according to the flavor profile of products obtained therefrom.
In addition, further to remove the glycidol and its ester content in refined oil, also implementable low temperature deodorization processing.
The processing includes being added to be not less than the Citric acid crystal that oil weighs 0.01% in bleached oil.Citric acid crystal can be used various commercially available
The product of acquisition.In general, the 0.01%-30%, preferably 0.1%-20%, more preferably 0.1%-10% of oil weight can be added,
More preferably 0.1%-5%, the more preferably Citric acid crystal of 0.1%-1%.Being suitable for the invention Citric acid crystal can be with
It is the various food grade citric acid crystal being commercially available.
Citric acid solution can also be added in deodorization processing in bleached oil, contain in the citric acid solution of addition not less than oil
Weigh 0.01% citric acid.The citric acid solution of various commercially available acquisitions can be used, oneself can also prepare citric acid solution.Citric acid
It can be the product of various commercially available acquisitions.The mass concentration of citric acid solution is 2-60%, for example, 2-40%, 2-30%, 5-20% are not
Deng.In general, the citric acid solution being added is the 0.01-50%, preferably 0.1-10%, more preferably 0.1%-2% of oil weight.
In deodorization processing, it can usually be passed through nitrogen or water vapour serves as deodorization medium.The vacuum degree for being deodorized processing is usual
Not higher than 25mBarA, such as 1-10mBarA.Deodorization temperature is usually at 150 DEG C hereinafter, for example, 60~150 DEG C, and 60~100 DEG C,
60~80 DEG C are differed.Deodorization time is usually 30-90 minutes.Be deodorized after treatment, can 50 DEG C or less can breaking vacuum, mistake
Filter can be obtained high-quality grease of the invention.
Using the method for the present invention, bleached oil can be used directly and carry out column chromatography.Bleached oil is purchased from market or by normal
The refining techniques of rule obtains.For example, can be used from leach or squeezing process by being extracted in plant and animal, refined decoloration it is de-
Color grease, or mixtures thereof including but not limited to above-mentioned various greases.
Grease be crude oil in the case where, can first to crude oil carry out various degummings well known in the art, alkali refining, except soap and/
Or the processing such as decoloration." crude oil " refers to come since leaching or squeezing process is by the grease that extracts in plant and animal, including but not
Be limited to, soya-bean oil, sunflower oil, coconut oil, peanut oil, safflower oil, cottonseed oil, rice bran oil, corn oil, olive oil, hydrogenated oil and fat,
Or mixtures thereof the vegetable fat and animal fat such as palm oil, palm-kernel oil.
For example, degumming medium can be added into crude oil, keep being stirred under vacuum 30 minutes to 2 hours at 40-95 DEG C, into
Row dry degumming.Or degumming medium and pure water can be added in crude oil at 40-95 DEG C, it stirs 30 minutes to 5 hours, carries out
It is acidified the processing of water elution glue.It after stirring, can be centrifugated, obtain oily phase.It is preferred that carrying out degumming process using acidification WATER-WASHING METHOD.
Degumming medium usually can be selected from citric acid solution, phosphoric acid solution and degummase.If using degummase, reaction system one
As at 20-80 DEG C, pH 5-6, the time is in 2-4h.When industrial production pH may be suitably adjusted with citric acid (NaOH) buffer
It is worth to 5-6.Degumming medium is usually less than the 0.05wt% of crude oil weight；Water is usually less than the 0.5wt% of crude oil weight.It is logical
Often, degumming medium is not higher than the 2wt% of crude oil weight.Oil weight of the water used in single degumming step not higher than 30wt%, example
Such as within the scope of 0.5-20wt%, 0.5-10wt%, 5-25wt%, the water does not include the water in degumming medium.
If if using acid, the degumming medium is with the total weight of solution, wherein the concentration of acid is not less than 5wt%.Acid
Concentration be normally no higher than 80wt%, such as can be within the scope of 5-65wt%, 10-60wt%, 20-50wt%.
Alkali refining (neutralizing) can be mutually carried out to oil obtained by degumming.Alkali refining step includes that appropriate alkaline liquor is added at 70-90 DEG C
It is reacted with grease.Alkali is alkali commonly used in the art, such as sodium hydroxide solution etc..Those skilled in the art can be according to routine techniques
Means determine caustic dosage.
After alkali refining step, centrifuging and taking light phase can carry out it to handle except soap.It is added except soap step is included at 60-90 DEG C
Appropriate hot water is to remove soap stock.The additional amount of water, can be according to reality within the knowledge that those skilled in the art are grasped
The condition of production is determined.
It should be understood that in the refinery practice of the grease of the prior art, alkali refining step (or neutralization procedure) and except soap step is
Optional step.Therefore, when oil of the invention is crude oil, not necessarily alkali refining and soap step is removed to the processing of crude oil.Ability
Field technique personnel can make appropriate selection according to the quality and its intended applications of crude oil.
The resulting grease of above-mentioned steps can be dried, i.e., at 50 DEG C or more, such as 60-120 DEG C and vacuum
Under be kept stirring upper oil phase 15-30 minutes, oil must be dried.
The oil that can make to obtain to above step mutually carries out decolorization.It can adopt and be taken off with the conventional methods in the field
Color.Breaking vacuum and decolorising agent is added in general, decolorization process includes, after keeping vacuum to be warming up to 80-90 DEG C；It then raises temperature to
It 90-110 DEG C, keeps being stirred under vacuum 30-45 minutes；Then it is filtered to remove decolorising agent.Decolorising agent includes but is not limited to day
Right carclazyte, atlapulgite, active carbon, attapulgite etc.；It is preferred that the acid activation carclazyte of partial neutral, such as sulfuric acid activated carclazyte.It is de-
The additional amount of toner can also be determined according to the actual situation by those skilled in the art.Herein, " partial neutral " or " weak acid
Property " refer to pH between 6.50-6.99.
Present invention will be further explained below with reference to specific examples.It should be understood that these embodiments are merely to illustrate the present invention
Rather than it limits the scope of the invention.In the following examples, the experimental methods for specific conditions are not specified, usually according to conventional strip
Part or according to the normal condition proposed by manufacturer.Unless otherwise stated, otherwise all percentage, ratio, ratio or number is pressed
Poidometer.
Unless otherwise defined, it anticipates known to all professional and scientific terms as used herein and one skilled in the art
Justice is identical.In addition, any method similar to or equal to what is recorded and material can be applied to the method for the present invention.
In following embodiments of the invention, the silica gel used is purchased from Industrial Co., Ltd. of upper marine nation.
In following embodiments of the invention, decoloration soybean oil, degummed soybean oil, the alkali used practices soybean oil, decoloration palm fibre
The reference such as palmitic acid oil Liang Shaohua etc., the influence of Deodorization Technology on Contents of Trans-Fatty Acids in Soybean Oil, Chinese grain and oil journal, the
The phase of volume 23 the 1st, in January, 2008,71-76, in method preparation.
In following embodiments of the invention, the chromatographic column used is matched isolation technics (Shanghai) Co., Ltd. for Novartis and is provided
LC150 type chromatographic column, delivery pump be Dalian Li Wabeng industry Co., Ltd LD4146-010.001-EK2 delivery pump.
In following embodiments, color is measured according to GB/T22460-2008 " measurement of animal and plant fat Lovibond color "；
AV is measured according to GB/T5530-2005 " animal and plant fat acid value and acidity assaying "；PV is according to GB/T5538-2005 " animals and plants
The measurement of oil peroxidation value " measurement；Maximum throughput is by meeting level-one soybean oil in soybean oil national standard (GB1535-2003)
Indices require the maximum chromatography sample size of reception to determine；Trans-fatty acid content is according to trans fats in GB/T22110-2008 food
The measurement gas chromatography measurement of acid；Content of vitamin E is measured according to AOCS Official Method Ce8-89 method.
Embodiment 1
It is compounded using silica gel, active carbon with 1:1, is uniformly mixed and is used as adsorbent, dry method is fitted into chromatographic column, uses metering pump
Decoloration soybean oil is squeezed into chromatographic column with the flow velocity of 150mL/min, wherein be pumped and pipeline pressure is 10~20bar, chromatography
Column pressure is 20~30bar, collects oil sample to get prepared oil sample.Chromatography process is not necessarily to nitrogen charging or deoxygenation, without water-bath
It heats, removes in following example and comparative example with the solid greases sample introduction such as the palm oil that decolourizes, operating process is all the same.
Embodiment 2
It is compounded using silica gel, active carbon with 4:1, is uniformly mixed and is used as adsorbent, dry method is fitted into chromatographic column, uses metering pump
Decoloration soybean oil is squeezed into chromatographic column with the flow velocity of 150mL/min, collects oil sample to get prepared oil sample.
Embodiment 3
It is compounded using silica gel, active carbon with 1:4, is uniformly mixed and is used as adsorbent, dry method is fitted into chromatographic column, uses metering pump
Decoloration soybean oil is squeezed into chromatographic column with the flow velocity of 150mL/min, collects oil sample to get prepared oil sample.
Embodiment 4
It is compounded using silica gel, active carbon with 1:1, is uniformly mixed and is used as adsorbent, dry method is fitted into chromatographic column, uses metering pump
Decoloration soybean oil is squeezed into chromatographic column with the flow velocity of 150mL/min, collects oil sample, vacuum is de- under the conditions of 60 DEG C of low temperature 0.3KPa
Smelly 1h cools down up to prepared oil sample.
Embodiment 5
It is compounded using silica gel, active carbon with 1:1, is uniformly mixed and is used as adsorbent, dry method is fitted into chromatographic column, uses metering pump
Decoloration soybean oil is squeezed into chromatographic column with the flow velocity of 150mL/min, collects oil sample, vacuum is de- under the conditions of 80 DEG C of low temperature 0.3KPa
Smelly 1h cools down up to prepared oil sample.
Embodiment 6
It is compounded using silica gel, active carbon with 1:1, is uniformly mixed and is used as adsorbent, dry method is fitted into chromatographic column, cylinder water-bath
Circulating water temperature controls 60 DEG C, cylinder 4bar nitrogen nitrogen charging deoxygenation, and decoloration palm oil is heated to 60 DEG C to whole thawings in advance,
Decoloration palm oil is squeezed into chromatographic column with the flow velocity of 150mL/min with metering pump, collects oil sample to get prepared oil sample.
Embodiment 7
It is compounded using silica gel, active carbon with 1:1, is uniformly mixed and is used as adsorbent, dry method is fitted into chromatographic column, uses metering pump
Soybean oil crude oil is squeezed into chromatographic column with the flow velocity of 150mL/min, collects oil sample to get prepared oil sample.
Embodiment 8
It is compounded using silica gel, active carbon with 1:1, is uniformly mixed and is used as adsorbent, dry method is fitted into chromatographic column, uses metering pump
Degummed soybean oil is squeezed into chromatographic column with the flow velocity of 150mL/min, collects oil sample to get prepared oil sample.
Embodiment 9
It is compounded using silica gel, active carbon with 1:1, is uniformly mixed and is used as adsorbent, dry method is fitted into chromatographic column, uses metering pump
Alkali refining soybean oil is squeezed into chromatographic column with the flow velocity of 150mL/min, collects oil sample to get prepared oil sample.
Embodiment 10
It is compounded using silica gel, active carbon with 1:1, is uniformly mixed and is used as adsorbent, dry method is fitted into chromatographic column, uses metering pump
Decoloration soybean oil is squeezed into chromatographic column with the flow velocity of 50mL/min, collects oil sample to get prepared oil sample.
Embodiment 11
It is compounded using silica gel, active carbon with 1:1, is uniformly mixed and is used as adsorbent, dry method is fitted into chromatographic column, uses metering pump
Decoloration soybean oil is squeezed into chromatographic column with the flow velocity of 300mL/min, collects oil sample to get prepared oil sample.
Comparative example 1
Raw material decoloration soybean oil in embodiment 1, under the conditions of 240 DEG C, vacuum deodorization 2h under the conditions of 0.3KPa, preparation takes off
Smelly soybean oil.
Comparative example 2
Raw material decoloration palm oil in embodiment 2, under the conditions of 260 DEG C, vacuum deodorization 2h under the conditions of 0.3KPa, preparation takes off
Smelly palm oil.
Comparative example 3
Use silica gel as adsorbent, dry method is fitted into chromatographic column, will be decolourized greatly with metering pump with the flow velocity of 150mL/min
Soya-bean oil is squeezed into chromatographic column, collects oil sample to get prepared oil sample.
Comparative example 4
Use active carbon as adsorbent, dry method is fitted into chromatographic column, will be decolourized with metering pump with the flow velocity of 150mL/min
Soybean oil is squeezed into chromatographic column, collects oil sample to get prepared oil sample.
Comparative example 5
Use atlapulgite as adsorbent, dry method is fitted into chromatographic column, will be taken off with metering pump with the flow velocity of 150mL/min
Color soybean oil is squeezed into chromatographic column, collects oil sample to get prepared oil sample.
Comparative example 6
Use aluminium oxide as adsorbent, dry method is fitted into chromatographic column, will be decolourized with metering pump with the flow velocity of 150mL/min
Soybean oil is squeezed into chromatographic column, collects oil sample to get prepared oil sample.
Comparative example 7
Use silmag as adsorbent, dry method is fitted into chromatographic column, will with the flow velocity of 150mL/min with metering pump
Decoloration soybean oil is squeezed into chromatographic column, collects oil sample to get prepared oil sample.
Comparative example 8
Use aluminium oxide to compound using 1:1 as adsorbent with silmag, dry method is fitted into chromatographic column, with metering pump with
The flow velocity of 150mL/min squeezes into decoloration soybean oil in chromatographic column, collects oil sample to get prepared oil sample.
Comparative example 9
Use atlapulgite, aluminium oxide and silmag using 1:1:1 ratio compounding as adsorbent, dry method is packed into chromatography
In column, decoloration soybean oil is squeezed into chromatographic column with the flow velocity of 150mL/min with metering pump, collects oil sample to get prepared
Oil sample.
Comparative example 10
Use atlapulgite, aluminium oxide, silica gel, active carbon and silmag using 1:1:1:1:1 ratio compounding as suction
Attached dose, dry method is fitted into chromatographic column, is squeezed into chromatographic column decoloration soybean oil with the flow velocity of 150mL/min with metering pump, is collected
Oil sample is to get prepared oil sample.
Comparative example 11
Successively dry method is packed into silica gel, active carbon to chromatographic column from the bottom up, will be decolourized with metering pump with the flow velocity of 150mL/min
Soybean oil is squeezed into chromatographic column, collects oil sample to get prepared oil sample.
Comparative example 12
Successively dry method is packed into active carbon, silica gel to chromatographic column from the bottom up, will be decolourized with metering pump with the flow velocity of 150mL/min
Soybean oil is squeezed into chromatographic column, collects oil sample to get prepared oil sample.
Comparative example 13
Chromatography column bottom up successively fills 100-200 mesh activated silica gel, diatomite 545 and the active carbon pre-processed
Mixture, diatomite 545 mixture, the 100-200 mesh silica gel that are compounded with sucrose with 1:2 of 1:2 compounding, the original in embodiment 1
Material decoloration soybean oil and n-hexane by volume 1:1 ratio mixing, solvent naphtha is beaten with the flow velocity of 150mL/min with metering pump
Enter in chromatographic column, collects purity nitrogen pressurization (0.1Mpa) rotation recycling n-hexane after oil sample, obtain chromatography soybean oil samples, then 130
DEG C low temperature is deodorized 0.5h, cools down up to prepared oil sample.
Comparative example 14
Chromatography column bottom up successively fills 100-200 mesh activated silica gel, diatomite 545 and the active carbon pre-processed
Mixture, diatomite 545 mixture, the 100-200 mesh silica gel that are compounded with sucrose with 1:2 of 1:2 compounding, the original in embodiment 1
Material decoloration soybean oil, is squeezed into solvent naphtha in chromatographic column with the flow velocity of 150mL/min with metering pump, collects oil sample to get made
Standby oil sample.
The influence of 1 column chromatography of table and deodorizing technology to decoloration soybean oil index
As can be seen from Table 1,60 DEG C after chromatography, 80 DEG C of low temperature deodorizations are compared with without low temperature deodorization, oil sample face
Color and AV are constant, only have extremely faint variation on PV, three kinds of oil samples meet national standard on flavor, wherein through too low
The oil sample flavor of temperature deodorization is slightly good, can be used to prepare a small number of high-quality, to the demanding grease of grease flavor.
It is compounded using 1:1 as filler with silica gel with active carbon, the grease prepared by column chromatography, color, AV, PV etc.
Conventional index lowers the sample for being obviously superior to conventional high-temperature deodorization preparation, and other indexs such as grease transparency and gas flavour
Also meet edible oil national standard.Different fillers, filling mode and different material oil also have shadow for the index of final sample
It ringing, silica gel compounds mixing filling column effect with active carbon with 1:1 and is better than single adsorbent dress column or adsorbent layering dress column, and
And want specific activity carclazyte, aluminium oxide, silmag individually load or it is compound filling as adsorbent effect it is good.Silica gel and work
Property charcoal compounding, silica gel ratio is higher, chromatograph product acid value and peroxide value it is lower, color is relatively deep, conversely, active carbon is got over
Height, color is more shallow, but acid value and peroxide value are higher.From comparative example 3 to comparative example 13, this 11 kinds of filling kinds
It can be seen that silica gel is compounded with active carbon with 1:1 as optimal filler combination with type of feed chromatography oil sample data.
Comparing embodiment 1,10,11, Tomography Velocity is faster, and the indices of grease are poorer, on the contrary, Tomography Velocity is slower,
Adsorbent is more abundant for the absorption of impurity in grease, and grease index is better, but also results in production efficiency reduction accordingly.
Comprehensively consider, can control Tomography Velocity is 20-400mL/min.
Comparing embodiment 1 and comparative example 13, it is found that the method according to disclosed in CN201010227935.5 makes
Up from chromatography column bottom the 100-200 mesh activated silica pre-processed is successively filled with solvent and soybean oil mixing sample introduction
Mixture, the 100-200 that mixture that glue, diatomite 545 are compounded with active carbon 1:2, diatomite 545 are compounded with sucrose with 1:2
Mesh silica gel, the soybean oil obtained by precipitation are compared with grease prepared by the present invention, and the indexs such as color, AV, PV are weaker, together
When comparative example 14 data also further demonstrate that CN201010227935.5 provide filler combination than effect of the present invention
Difference, and be related in this application for the modification before filler use, complicated operation, and filler is too many using type, and
Later period low temperature deodorization temperature is 130-150 DEG C, compares with 60-150 DEG C of low temperature proposed by the present invention deodorization and still provides no advantage against, by
This visible method provided by the invention becomes apparent the adsorption effect of grease impurities, and operates relatively simple.
Column chromatography technology substitutes the refining that traditional deodorizing technology is applicable not only to soybean oil, can also be applied to have compared with Gao Rong
The refining of the palm oil of point, chromatographic technique reduce the indexs such as the color of palm oil, AV, PV obvious.
2 column chromatography technology difference filler of table and the comparison of fill method operating parameter
Note: maximum throughput is that chromatography receives sample no more than national standard level-one soya-bean oil requirement (acid value (mgKOH/g)≤0.20；
Peroxide value (mmol/kg)≤5.0), institute can received maximum sample size..
In table 2, from the point of view of maximum throughput data, silica gel compounded with active carbon 1:1 mix filler than single adsorbent or
The column effect that two kinds of adsorbent layering fillers of person generate is much higher.Comparing embodiment 1 and comparative example 13,14, the present invention mentions
The technique that the chromatographic column column effect of confession is also provided significantly better than comparison patent.In addition, comparing soybean oil crude oil, degummed soybean oil, alkali
Soybean oil, decoloration four kinds of feedstock oil maximum throughputs of soybean oil are refined, raw material oil index is better, and the technology of the present invention maximum throughput is got over
It is more.
The influence of 3 column chromatography of table and deodorizing technology to grease trans-fatty acid content
As can be seen that technical solution of the present invention is avoided that the formation of trans-fatty acid and for crude oil energy from 3 result of table
It further decreases, raw material decoloration soybean oil is compared, and trans-fatty acid content reduces 35.2%.It is de- that comparative example 1,2 is all made of high temperature
Smelly method causes the formation of trans-fatty acid, pair of comparing embodiment 1 and the technical solution using CN201010227935.5
Than embodiment 13 as it can be seen that soya-bean oil is with n-hexane 1:1 mixing sample introduction, although the soybean oil trans-fatty acid content by precipitation preparation is lower than
Common high temperature deodorizing technology, but it is higher than oil sample prepared by the present invention, and risen with decoloration crude oil trans-fatty acid content
Height illustrates that the filler for comparing patent application wants poor compared to the selection absorption for trans acids with the present invention, along with subsequent de-
Molten and low temperature is deodorized link, causes the oil sample trans acids finally prepared higher.
Influence of 4 present invention of table to different material oil trans-fatty acid content
From 4 data of table it is found that the present invention has different degrees of reduction for different material grease trans-fatty acid content, into one
Step illustrates that the technology of the present invention has grease trans acids certain suction-operated.The reduction degree of different material oil trans acids is not
Together, crude oil trans acids reduce minimum, this, which influences column chromatographic effect with impurity content in grease, relationship.
Table 5 compares the influence of column chromatography technology and deodorizing technology to soybean oil oxidation stability and content of vitamin E
From 5 data of table it is found that high temperature deodorising process will lead to soybean oil natural content of vitamin E it is significant under
Drop, and it is not it is obvious that therefore chromatography prepares grease and can retain more natural anti-oxidation that content of vitamin E of the present invention, which reduces,
Agent；By oxidation stability experiment as can be seen that the new fat processing method that chromatography substitutes deodorizing technology is produced for improving
Product oxidation stability also has certain help.
Table 6 compares the influence of column chromatography technology and deodorizing technology to palm oil 3-MCPD, glycidol content
In table 6, deodorising process can cause harmful components 3-MCPD in palm oil, glycidol content to significantly improve, and
Technical solution of the present invention not only can avoid the formation that high temperature causes 3-MCPD, glycidol, can also reduce what glyceride stock was brought into
3-MCPD, glycidol content, wherein method provided by the invention is more aobvious for the reduction of glycidol content in grease
It writes, 0.18mg/kg is reduced to by 1.36mg/kg.
Claims (25)
1. a kind of trans-fatty acid, the chloro- 1,2- propylene glycol of 3- and its ester reduced in grease, and/or glycidol and its ester
Method, which is characterized in that the method includes carrying out column chromatography to decoloration grease, and it is optional after column chromatography
The step of deodorization of progress, wherein carry out the column chromatography using adsorbent, the adsorbent is silica gel and active carbon, described
The weight ratio of silica gel and active carbon is 1:4 ~ 4:1.
2. the method as described in claim 1, which is characterized in that the deodorization temperature is 60-150 DEG C.
3. the method as described in claim 1, which is characterized in that the deodorization temperature is 60-80 DEG C.
4. method as claimed in any one of claims 1-3, which is characterized in that the grease be selected from soybean oil, corn oil,
One of rice bran oil, palm oil, lard and butter are a variety of.
5. method as claimed in any one of claims 1-3, which is characterized in that decoloration grease is with the stream of 20~400mL/min
Speed flows through chromatographic column.
6. method as claimed in any one of claims 1-3, which is characterized in that the chromatographic column be chromatography glass column or
The cylinder of stainless steel column, the chromatographic column can deoxygenation.
7. method as claimed in any one of claims 1-3, which is characterized in that the described method includes:
Liquid bleached oil is pumped into chromatographic column with the flow velocity of 20~400mL/min using metering pump.
8. the method for claim 7, which is characterized in that further include pre- heat decoloring before being pumped into the liquid bleached oil
Oil, the step of obtaining the liquid bleached oil.
9. the method for claim 7, which is characterized in that the column pressure is 0 ~ 100bar.
10. the method for claim 7, which is characterized in that the cylinder of the chromatographic column is recycled using water-bath.
11. method as claimed in claim 10, which is characterized in that the temperature of the water-bath is 15~80 DEG C.
12. method as claimed in any one of claims 1-3, which is characterized in that the method also includes:
(a) degumming step: degumming medium being added into crude oil, keeps being stirred under vacuum -2 hours 30 minutes at 50-95 DEG C, carry out
Dry degumming；Or degumming medium and pure water are added in crude oil at 50-95 DEG C, it stirs -5 hours 30 minutes, is acidified
Wash degumming；
(b) optional alkali refining step: lye is added at 70-90 DEG C and is reacted with grease；
(c) optional to remove soap step: appropriate hot water to be added at 80-90 DEG C to remove soap stock；With
(d) decolorization process: breaking vacuum and decolorising agent is added after keeping vacuum to be warming up to 80-90 DEG C, then raises temperature to 90-110
DEG C, it keeps being stirred under vacuum 30-45 minutes.
13. a kind of oil and fat refining method, which is characterized in that the method includes carrying out column chromatography to decoloration grease, with
And the step of optional deodorization carried out after column chromatography, wherein carry out the column chromatography, the adsorbent using adsorbent
For uniformly mixed silica gel and active carbon, the weight ratio of the silica gel and active carbon is 1:4 ~ 4:1.
14. method as claimed in claim 13, which is characterized in that the deodorization temperature is 60-150 DEG C.
15. method as claimed in claim 13, which is characterized in that the deodorization temperature is 60-80 DEG C.
16. the method as described in any one of claim 13-15, which is characterized in that the grease is selected from soybean oil, corn
One of oil, rice bran oil, palm oil, lard and butter are a variety of.
17. the method as described in any one of claim 13-15, which is characterized in that decoloration grease is with 20~400mL/min
Flow velocity flow through chromatographic column.
18. the method as described in any one of claim 13-15, which is characterized in that the chromatographic column be chromatography glass column or
The cylinder of person's stainless steel column, the chromatographic column can deoxygenation.
19. the method as described in any one of claim 13-15, which is characterized in that the described method includes:
Liquid bleached oil is pumped into chromatographic column with the flow velocity of 20~400mL/min using metering pump.
20. method as claimed in claim 19, which is characterized in that further include that preheating is de- before being pumped into the liquid bleached oil
The step of color is oily, obtains the liquid bleached oil.
21. method as claimed in claim 19, which is characterized in that the column pressure is 0 ~ 100bar.
22. method as claimed in claim 19, which is characterized in that the cylinder of the chromatographic column is recycled using water-bath.
23. method as claimed in claim 22, which is characterized in that the temperature of the water-bath is 15~80 DEG C.
24. the method as described in any one of claim 13-15, which is characterized in that the method also includes:
(a) degumming step: degumming medium being added into crude oil, keeps being stirred under vacuum -2 hours 30 minutes at 50-95 DEG C, carry out
Dry degumming；Or degumming medium and pure water are added in crude oil at 50-95 DEG C, it stirs -5 hours 30 minutes, is acidified
Wash degumming；
(b) optional alkali refining step: lye is added at 70-90 DEG C and is reacted with grease；
(c) optional to remove soap step: appropriate hot water to be added at 80-90 DEG C to remove soap stock；With
(d) decolorization process: breaking vacuum and decolorising agent is added after keeping vacuum to be warming up to 80-90 DEG C, then raises temperature to 90-110
DEG C, it keeps being stirred under vacuum 30-45 minutes.
25. the grease of the preparation of method described in any one of claim 1-24.
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| CN105053269A (en) * | 2015-07-28 | 2015-11-18 | 华南理工大学 | Method for reducing content of glycidyl ester in edible oil by using adsorbent |
| CN106916630B (en) * | 2015-12-25 | 2021-05-18 | 丰益(上海)生物技术研发中心有限公司 | Method for controlling generation of grease noxious substances |
| CN106701168A (en) * | 2016-12-01 | 2017-05-24 | 成都凯莱力斯发动机有限公司 | Fat for engine |
| CN107090353B (en) * | 2017-05-04 | 2021-03-09 | 辽宁晟麦实业股份有限公司 | Method for reducing content of glycidyl ester in refined vegetable oil |
| CN107460035B (en) * | 2017-09-25 | 2020-05-08 | 嘉必优生物技术（武汉）股份有限公司 | Microbial oil and preparation method thereof |
| CN107418982B (en) * | 2017-09-25 | 2020-05-08 | 嘉必优生物技术（武汉）股份有限公司 | Low-chloropropanol microbial oil and preparation method thereof |
| CN108690727A (en) * | 2018-07-25 | 2018-10-23 | 贵州夜郎古国生物科技有限公司 | A kind of preparation method of oil tea essential oil |
| CN109135920A (en) * | 2018-09-29 | 2019-01-04 | 广州白云山汉方现代药业有限公司 | A kind of acid stripping method of grease |
| CN111349515B (en) * | 2018-12-19 | 2023-06-23 | 丰益(上海)生物技术研发中心有限公司 | Zero-reflection green precise moderate-processing grease composition and preparation method thereof |
| CN111330539B (en) * | 2018-12-19 | 2022-08-26 | 丰益(上海)生物技术研发中心有限公司 | Composite solid adsorbent and method for purifying grease |
| CN110194989B (en) * | 2019-04-23 | 2020-09-08 | 江南大学 | Method for preparing triglyceride oil bases with different chain lengths in batches by purifying vegetable oil |
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| CN111218336A (en) * | 2019-11-28 | 2020-06-02 | 荣海生物科技有限公司 | Method for deodorizing linseed oil at high efficiency and low temperature |
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| CN116286180A (en) * | 2023-03-30 | 2023-06-23 | 广东宝华农业科技股份有限公司 | Low-trans-fatty-acid camellia seed oil and preparation method thereof |
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