CN105132189B - A kind of fine separation method of C18 series and C20~C22 series fatty acid methyl esters - Google Patents
A kind of fine separation method of C18 series and C20~C22 series fatty acid methyl esters Download PDFInfo
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- CN105132189B CN105132189B CN201510478564.0A CN201510478564A CN105132189B CN 105132189 B CN105132189 B CN 105132189B CN 201510478564 A CN201510478564 A CN 201510478564A CN 105132189 B CN105132189 B CN 105132189B
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Abstract
The invention discloses a kind of C18 series and the fine separation methods of C20~C22 series fatty acid methyl esters, this method ionic-liquid catalyst, animal and plant fat is pre-processed, obtained product i.e. biodiesel, for the mixture of a variety of fatty acid methyl esters, then the biodiesel of gained is obtained into C18 fatty acid methyl esters or C20~C22 fatty acid methyl esters by rectification under vacuum, gained fatty acid methyl ester can respectively obtain methyl stearate through the modified silica gel column chromatography purification of silver ion again, methyl oleate and methyl linoleate or methyl eicosapentaenoic acid and Methyl docosahexaenoate.The present invention makes up the blank of the prior art, operating process conveniently, and isolating and purifying between same carbon number difference double key number and the long chain fatty acids methyl esters of thermal sensitivity difference provides operating procedure, lays the foundation for the fine separation of fatty acid methyl ester.
Description
Technical field
The present invention relates to a kind of C18 series and the fine separation methods of C20~C22 series fatty acid methyl esters, especially
Methyl eicosapentaenoic acid, Methyl docosahexaenoate or stearic acid first are therefrom obtained after animal and plant fat is handled
The process for separation and purification of ester, methyl oleate and methyl linoleate.
Background technology
China wide object is rich, ABUNDANT NATUREAL RESOURSES, wherein being even more containing largely to the valuable of people's production and living
Aliphatic acid resource, such as C18 series fatty acids and ω -3, ω -6 unsaturated fatty acid.C18 series fatty acids include mainly
Stearic acid (octadecanoid acid), oleic acid (9- octadecenoic acids) and linoleic acid (9,12- octadecadienoic acid), they are primarily present in
In vegetable fat, it is widely used in the system of auxiliary agent, oil dope, surfactant, lubricant and other organic chemicals
It is standby to wait numerous areas；ω -3, ω -6 unsaturated fatty acid include mainly eicosapentaenoic acid (EPA) and docosahexaenoic acid
(DHA), they are primarily present in fish oil, are both the indispensable important nutrient of human body, wherein eicosapentaenoic
Acid can effectively help to reduce the content of cholesterol and triglycerides, promote saturated fat acid metabolic in human body, to play
Blood viscosity is reduced, blood circulation is promoted, tissue is improved and supplies oxygen and dispelling fatigue；For docosahexaenoic acid, it is to brain
Critically important effect is played in nerve growth development, the development of baby's visual development, child intelligence, while it also has antiallergy, increases
The effects that strong immune.
Comprehensive china natural resources advantage makes full use of existing resource, expands the deep processing of natural resources, reduces the wasting of resources simultaneously
The aliphatic acid of high added value therein is obtained according to fish oil and the separable purification of vegetable fat ingredient feature, can not only be carried
The economic value for rising raw material is worth with prominent in industry of today and healthcare field, even more makes in today of resource anxiety
Resource is adequately utilized, and the grand strategy of overall sustainable development is met.
As described above, middle Long carbon chain aliphatic acid is widely present in animal and plant fat, composition is complicated and mostly with glycerine three
The form of fat exists, and therefore, if wanting to make full use of in aliphatic acid, it need to be made first to carry out the pretreatment of grease, is converted into corresponding
(being usually fatty acid methyl ester) could carry out separating-purifying to corresponding aliphatic acid after aliphatic ester.For long chain fatty acids methyl esters
Separation, common means have traditional rectifying, urea clathrate, supercritical extract and cryogenic freezing crystallization etc., but above method
It is generally separated that purity is not high, is typically only capable to obtain the saturated fatty acid methyl ester class of higher degree and unsaturated fatty acid methyl ester class
Product, and single high purity fatty acid methyl esters can not be almost obtained, particularly with methyl stearate, methyl oleate and linoleic acid first
Ester rarely has people to accomplish.(a) is methyl hexadecanoate (C16 in Fig. 1:0)；(b) it is methyl stearate (C18:0)；(c) it is oleic acid first
Ester (C18:1)；(d) it is methyl linoleate (C18:2), as shown in Figure 1, the difference in the structure of latter three is only one to two
Double bond, this has resulted in the difference very little in physicochemical properties between latter three, and conventional separation means rarely have can be by this
Three kinds of substances are completely isolated；(a) is methyl eicosapentaenoic acid (C20 in Fig. 2:5)；(b) it is docosahexaenoic acid (C22:
6), as shown in Figure 2, methyl eicosapentaenoic acid belongs to the fat of Long carbon chain, how unsaturated key with Methyl docosahexaenoate
Fatty acid methyl esters pass through traditional rectifying and supercritical extract etc. due to the property of the two thermal sensitivity difference under the high temperature conditions itself
Separate mode, it is easy to cause raw material rotten, and the two can hardly be obtained by urea clathrate and cryogenic freezing crystallization
It efficiently separates.In conclusion by methyl stearate, methyl oleate and methyl linoleate or methyl eicosapentaenoic acid and 22
The completely isolated technology for obtaining the very high single fat acid methyl esters of purity of carbon acid methyl esters is rarely reported, this seriously inhibits
The further research and application of high-purity high added value fatty acid methyl ester.
Invention content
In view of the deficiencies of the prior art, it is an object of the present invention to provide a kind of C18 and C20~C22 fatty acid methyl esters
Fine separation method, entire process is concise, easy to operate, and environmentally protective pollution is small, has very much Economic Application foreground.
The fine separation method of a kind of C18 series and C20~C22 series fatty acid methyl esters, it includes the following steps：
(1) pretreatment of animal and plant fat, the specific steps are：
(a) it is 1 by mass ratio:2~6:Reaction vessel is added in 10~72 ionic liquid, animal and plant fat and methanol jointly
In；Reaction vessel is placed in 50~80 DEG C of water baths, stir in the container mixed liquor until animal and plant fat and methanol from
Fully reaction generates a variety of fatty acid methyl ester admixtures under the catalytic action of sub- liquid；
(b) after reaction, by the way that separating ionic liquid and a variety of fatty acid methyl ester admixtures is decanted；
(c) by the ionic liquid isolated, rotary evaporation removes a small amount of methanol with after water at 90~150 DEG C, and recycling repeats
It uses；
(2) fatty acid methyl ester crude separation, the specific steps are：
(a) it takes a variety of fatty acid methyl ester admixtures obtained in step (1) to be sent into rectification under vacuum tower reactor and carries out rectifying, tower
Top operating pressure is 100~200Pa, and tower reactor heating power is 100~150W；
(b) rectifying column infinite reflux is 4~10 in the operating reflux ratio of vacuum rectification tower after tower reactor tower top temperature stabilization
Under, collect fatty acid methyl ester product of the rectifying column tower top quality percent purity 98% or more, fatty acid methyl ester production with surge tank
Product are C18 fatty acid methyl esters product or C20~C22 fatty acid methyl esters；
(3) the fine separation of fatty acid methyl ester, the specific steps are：
(a) preparation of column chromatography stationary phase, the specific steps are：
It takes granularity to be placed in container in 200~300 mesh silica gel, absolute ethyl alcohol, silica gel and anhydrous second is then added thereto
The mass ratio of alcohol is 1:3~1:2；Then silica gel forms silica gel suspension with ethyl alcohol in stirring container；By AgNO3Crystal is in dark
Under the conditions of to be dissolved in the volume ratio of ethyl alcohol and water be 7:3~1:In 2 ethanol-water solution, AgNO is obtained3Mass fraction is 10%
~30% AgNO3Ethanol-water solution；AgNO will be dissolved3Ethanol-water solution the above-mentioned silica gel suspension prepared is added
In, 20~40min is stirred under dark condition；It takes out the silver nitrate silica gel suspension mixed and is sent into the appearance that aluminium-foil paper wraps
In device, and the container is connect with Rotary Evaporators, is rotated under conditions of being 0.01~0.1MPa in 70~100 DEG C, vacuum degree
It evaporates 4~5h and removes ethanol-water；Silver nitrate silica gel after removing solvent is placed in 110~120 DEG C of vacuum drying chambers living
Change 16~for 24 hours, modified silica-gel is finally collected in dried for standby in brown bottle；
(b) fatty acid methyl ester finely detaches, the specific steps are：
It takes the silver nitrate-modified silica gel prepared as column chromatography stationary phase, carries out the installation of chromatographic column；It takes in step 2 and obtains
To C18 fatty acid methyl esters or C20~C22 fatty acid methyl ester products be dissolved in n-hexane, pipette fatty acid methyl ester n-hexane
Solution is to silver nitrate-modified silica gel column chromatography upper surface；It is respectively 1%, 3%, 5% acetone-to use acetone volume fraction successively
Hexane solution carries out elution action, elution speed as mobile phase to the chromatographic column for having dosed fatty acid methyl ester n-hexane
For 10~20mL/h, often crosses 40~60min and collect column chromatography effluent progress rotary evaporation recycling design acetone-n-hexane, and
Collect to obtain methyl stearate of the mass percent purity 98% or more, oleic acid first to the product after effluent rotary evaporation
Ester, methyl linoleate, methyl eicosapentaenoic acid or Methyl docosahexaenoate.
Compared with currently existing technology, advantages of the present invention is mainly reflected in：
(1) first, using fish oil, vegetable oil etc. as raw material, esterification and transesterification are carried out with methanol, using ionic liquid
For body as catalyst, a step can obtain pretreatment of raw material product of the acid value less than 2 of high yield, be biodiesel, i.e., more
The mixture of kind fatty acid methyl ester, wherein reaction condition is mild, and ionic-liquid catalyst facilitates recycling and can repeatedly use；
Secondly, rectification under vacuum then by biodiesel oil product is carried out under certain condition obtains C18 fatty acid methyls of the purity 98% or more
Ester (methyl stearate, methyl oleate and methyl linoleate product mix) or C20~C22 fatty acid methyl esters (wherein include 20
Carbon 5 alkene acid methyl esters and Methyl docosahexaenoate), convenience simple to operation；Pass through the modified silica gel column chromatography of stationary phase again
Means are further purified, and can obtain purity respectively in 98% or more methyl stearate, methyl oleate and sub- oil
Sour methyl esters product or methyl eicosapentaenoic acid and Methyl docosahexaenoate.
(2) present invention optimizes integration to the prior art, accomplishes respectively for there is only double bond number differences in structure
Methyl stearate, three kinds of substances of methyl oleate and methyl linoleate and since thermal sensitivity difference does not fit through traditional approach point
From methyl eicosapentaenoic acid finely isolated and purified with Methyl docosahexaenoate, establish for substance of this kind separation field
Fixed certain basis.
Description of the drawings
Fig. 1 is fatty acid methyl ester molecular structure contained in the biodiesel that is prepared by raw material of vegetable fat such as corn oils
Formula；
Fig. 2 be with fish oil etc. be raw material prepare biodiesel contained in high added value fatty acid methyl ester molecular structure
Formula.
Specific implementation mode：
The present invention will be further elaborated by specific case study on implementation below.
The fine separation method of a kind of C18 series and C20~C22 series fatty acid methyl esters, it includes the following steps：
(1) pretreatment of animal and plant fat, the specific steps are：
(a) it is 1 by mass ratio:2~6:Reaction vessel is added in 10~72 ionic liquid, animal and plant fat and methanol jointly
In；Reaction vessel is placed in 50~80 DEG C of water baths, stir in the container mixed liquor until animal and plant fat and methanol from
Fully reaction generates a variety of fatty acid methyl ester admixtures of pretreatment product-under the catalytic action of sub- liquid；
(b) after reaction, by the way that separating ionic liquid and a variety of fatty acid methyl ester admixtures, a variety of aliphatic acid are decanted
Mixtures of methyl esters is biodiesel；
(c) by the ionic liquid isolated, rotary evaporation removes a small amount of methanol with after water at 90~150 DEG C, and recycling repeats
It uses；
(2) fatty acid methyl ester crude separation, the specific steps are：
(a) it takes a variety of fatty acid methyl ester admixtures obtained in step (1) to be sent into rectification under vacuum tower reactor and carries out rectifying, tower
Top operating pressure is 100~200Pa, and tower reactor heating power is 100~150W；
(b) rectifying column infinite reflux is 4~10 in the operating reflux ratio of vacuum rectification tower after tower reactor tower top temperature stabilization
Under, collect fatty acid methyl ester product of the rectifying column tower top quality percent purity 98% or more, fatty acid methyl ester production with surge tank
Product are C18 fatty acid methyl esters product (methyl stearate, methyl oleate and methyl linoleate mixture) or C20~C22 aliphatic acid
Methyl esters (wherein including methyl eicosapentaenoic acid and Methyl docosahexaenoate).
(3) the fine separation of fatty acid methyl ester, the specific steps are：
(a) preparation of column chromatography stationary phase, the specific steps are：
It takes granularity to be placed in container in 200~300 mesh silica gel, absolute ethyl alcohol, silica gel and anhydrous second is then added thereto
The mass ratio of alcohol is 1:3~1:2；Then silica gel forms silica gel suspension with ethyl alcohol in stirring container；By AgNO3Crystal is in dark
Under the conditions of to be dissolved in the volume ratio of ethyl alcohol and water be 7:3~1:In 2 ethanol-water solution, AgNO is obtained3Mass fraction is 10%
~30% AgNO3Ethanol-water solution；AgNO will be dissolved3Ethanol-water solution the above-mentioned silica gel suspension prepared is added
In, 20~40min is stirred under dark condition；It takes out the silver nitrate silica gel suspension mixed and is sent into the appearance that aluminium-foil paper wraps
In device, and the container is connect with Rotary Evaporators, is rotated under conditions of being 0.01~0.1MPa in 70~100 DEG C, vacuum degree
It evaporates 4~5h and removes ethanol-water；Silver nitrate silica gel after removing solvent is placed in 110~120 DEG C of vacuum drying chambers living
Change 16~for 24 hours, modified silica-gel is finally collected in dried for standby in brown bottle.
(b) fatty acid methyl ester finely detaches, the specific steps are：
It takes the silver nitrate-modified silica gel prepared as column chromatography stationary phase, carries out the installation of chromatographic column according to a conventional method；
The content obtained in step 2 is taken to be dissolved in just in 98% or more C18 fatty acid methyl esters or C20~C22 fatty acid methyl ester products
In hexane, fatty acid methyl ester hexane solution is pipetted to silver nitrate-modified silica gel column chromatography upper surface；Acetone volume is used successively
Score be respectively 1%, 3%, 5% acetone-hexane solution as mobile phase to having dosed fatty acid methyl ester n-hexane
Chromatographic column carry out elution action, elution speed be 10~20mL/h, often cross 40~60min collect column chromatography effluent revolved
Turn evaporation recycling design acetone-n-hexane, and gas chromatographic detection is carried out to the product after effluent rotary evaporation and is received respectively
Collect mass percent purity 98% or more methyl stearate, methyl oleate, methyl linoleate, methyl eicosapentaenoic acid or
Person's Methyl docosahexaenoate.
The animal and plant fat includes rich in stearic acid, oleic acid and linoleic animal and plant fat or being rich in 20 light dydrocarbons
Useless fish oil of the high acid value of olefin(e) acid, the algal oil of docosahexaenoic acid, fish oil and acid value more than 2 etc..
The ionic-liquid catalyst is with [BHSO3MIM]HSO4、[(CH2)3SO3HMIM][HSO3] be representative imidazoles
Class with [(CH3CH2)3N(CH2)3SO3H][C7H7O3S] be representative quaternary ammonium salt Bronsted acidic ion liquids, [Bmim]
Br-CuCl2、[Bmim]Br-FeCl3、[Bmim]Br-CuCl、[Bmim]Br-Fe2Cl6、[Bmim]Br-Ni2Cl4For representative
Lewis acidic ion liquids, with [HO3S-(CH2)3-NEt3]Cl-FeCl3、[BSO3HMIM]HSO4-Fe2(SO4)3For representative
Bisgallic acid type ionic liquid, using [BTBD] OH as the alkali ionic liquid of representative, with [PyPS] PW, [TMAPS] PW, [MIMPS] PW
It is arbitrary at least two ionic liquid in the heteropoly acid type ionic liquid of representative and above-mentioned ionic-liquid catalyst with [QPS] PW
Mixture in one kind.
It is 0.5~1.9m that the rectifying column, which uses efficient θ ring fillers or other random packings, packed height,.
Embodiment 1
Raw material used by this example is certain high acid value vegetable oil, and acid is measured through standard GB/T-T5530-2005 methods
Value is 27.7mgKOH/g.
(1) pretreatment of high acid value vegetable oil, the specific steps are：
(a) it is 1 by mass ratio:4:41 ionic liquid [BHSO3MIM]HSO4, high acid value vegetable oil and methanol is added jointly
In reaction vessel；Reaction vessel is placed in 65 DEG C of water baths, stirs mixed liquor in the container until high acid value vegetable oil and first
Alcohol fully reacts under the catalytic action of ionic liquid；
(b) after reaction, by the way that separating ionic liquid and a variety of fatty acid methyl ester admixture pretreatment products is decanted,
A variety of fatty acid methyl ester admixtures are biodiesel；
(c) by the ionic liquid isolated, rotary evaporation removes a small amount of methanol with after water at 130 DEG C, and recycling repeats to make
With；It is 0.96mgKOH/g that obtained biodiesel measures acid value by standard GB/T-T5530-2005 methods.
(2) C18 fatty acid methyl esters crude separation, the specific steps are：
(a) a variety of fatty acid methyl ester admixtures obtained in step (1) is taken to be sent into the rectification under vacuum that packed height is 0.5m
Rectifying is carried out in tower reactor, tower top operating pressure is 100Pa, and tower reactor heating power is 100W；
(b) rectifying column infinite reflux is after tower reactor tower top temperature stabilization, in the case where the operating reflux ratio of vacuum rectification tower is 4, into
Row rectification under vacuum operates, and mass percent purity is collected 98% into gas chromatographic detection in overhead extraction product, and to product
The above C18 fatty acid methyl esters product (methyl stearate, methyl oleate and methyl linoleate mixture).
(3) C18 fatty acid methyl esters finely detach, the specific steps are：
(a) preparation of column chromatography stationary phase, the specific steps are：
It takes granularity to be placed in container in 200 mesh silica gel, absolute ethyl alcohol, the matter of silica gel and absolute ethyl alcohol is then added thereto
Amount is than being 1:3；Then silica gel forms silica gel suspension with ethyl alcohol in stirring container；By AgNO3Crystal dissolves under dark condition
In the volume ratio of ethyl alcohol and water be 3:In 2 ethanol-water solution, AgNO is obtained3The AgNO that mass fraction is 25%3Alcohol-water
Solution；AgNO will be dissolved3Ethanol-water solution be added in the above-mentioned silica gel suspension prepared, stirred under dark condition
30min；It takes out the silver nitrate silica gel suspension mixed to be sent into the container that aluminium-foil paper wraps, and the container and rotation is steamed
Instrument connection is sent out, rotary evaporation 4h removes ethanol-water under conditions of being 0.06MPa in 90 DEG C, vacuum degree；After solvent being removed
Silver nitrate silica gel be placed in 120 DEG C of vacuum drying chambers and activate 16h, modified silica-gel, which is finally collected in drying in brown bottle, waits for
With.
(b) C18 fatty acid methyl esters finely detach, the specific steps are：
It takes the silver nitrate-modified silica gel prepared as column chromatography stationary phase, carries out the installation of chromatographic column according to a conventional method；
It takes the content obtained in step (2) to be dissolved in n-hexane in 98% or more C18 fatty acid methyl esters, is pipetting fatty acid methyl ester just
Hexane solution is to silver nitrate-modified silica gel column chromatography upper surface；The use of acetone volume fraction is respectively successively 1%, 3%, 5%
Acetone-hexane solution carries out elution action as mobile phase to the chromatographic column for having dosed fatty acid methyl ester n-hexane, washes
De- speed is 10mL/h, often crosses 60min and collects column chromatography effluent progress rotary evaporation recycling design acetone-n-hexane, and is right
Product after effluent rotary evaporation carry out gas chromatographic detection and collect respectively mass percent purity 98% or more it is hard
Resin acid methyl esters, methyl oleate and methyl linoleate.
Embodiment 2
Raw material used by this example is Industry Waste palm oil, and acid value is measured through standard GB/T-T5530-2005 methods
For 9.53mgKOH/g.
(1) pretreatment of Industry Waste palm oil, the specific steps are：
(a) it is 1 by mass ratio:3:36 ionic liquid [(CH2)3SO3HMIM][HSO3], Industry Waste palm oil and methanol
It is common to be added in reaction vessel；Reaction vessel is placed in 50 DEG C of water baths, stirs mixed liquor in the container until Industry Waste palm fibre
Palmitic acid oil is fully reacted with methanol under the catalytic action of ionic liquid；
(b) after reaction, by the way that separating ionic liquid and a variety of fatty acid methyl ester admixture pretreatment products is decanted,
A variety of fatty acid methyl ester admixtures are biodiesel；
(c) by the ionic liquid isolated, rotary evaporation removes a small amount of methanol with after water at 90 DEG C, and recycling is reused；
It is 0.82mgKOH/g that obtained biodiesel measures acid value by standard GB/T-T5530-2005 methods.
(2) C18 fatty acid methyl esters crude separation, the specific steps are：
(a) a variety of fatty acid methyl ester admixtures obtained in step (1) is taken to be sent into the rectification under vacuum that packed height is 0.8m
Rectifying is carried out in tower reactor, tower top operating pressure is 120Pa, and tower reactor heating power is 130W；
(b) rectifying column infinite reflux is after tower reactor tower top temperature stabilization, in the case where the operating reflux ratio of vacuum rectification tower is 7, into
Row rectification under vacuum operates, and mass percent purity is collected 98% into gas chromatographic detection in overhead extraction product, and to product
The above C18 fatty acid methyl esters product (methyl stearate, methyl oleate and methyl linoleate mixture).
(3) C18 fatty acid methyl esters finely detach, the specific steps are：
(a) preparation of column chromatography stationary phase, the specific steps are：
It takes granularity to be placed in container in 200 mesh silica gel, absolute ethyl alcohol, the matter of silica gel and absolute ethyl alcohol is then added thereto
Amount is than being 1:2；Then silica gel forms silica gel suspension with ethyl alcohol in stirring container；By AgNO3Crystal dissolves under dark condition
In the volume ratio of ethyl alcohol and water be 7:In 3 ethanol-water solution, AgNO is obtained3The AgNO that mass fraction is 30%3Alcohol-water
Solution；AgNO will be dissolved3Ethanol-water solution be added in the above-mentioned silica gel suspension prepared, stirred under dark condition
20min；It takes out the silver nitrate silica gel suspension mixed to be sent into the container that aluminium-foil paper wraps, and the container and rotation is steamed
Instrument connection is sent out, rotary evaporation 5h removes ethanol-water under conditions of being 0.01MPa in 70 DEG C, vacuum degree；After solvent being removed
Silver nitrate silica gel be placed in 115 DEG C of vacuum drying chambers and activate 20h, modified silica-gel, which is finally collected in drying in brown bottle, waits for
With.
(b) C18 fatty acid methyl esters finely detach, the specific steps are：
It takes the silver nitrate-modified silica gel prepared as column chromatography stationary phase, carries out the installation of chromatographic column according to a conventional method；
It takes the content obtained in step (2) to be dissolved in n-hexane in 98% or more C18 fatty acid methyl esters, is pipetting fatty acid methyl ester just
Hexane solution is to silver nitrate-modified silica gel column chromatography upper surface；The use of acetone volume fraction is respectively successively 1%, 3%, 5%
Acetone-hexane solution carries out elution action as mobile phase to the chromatographic column for having dosed fatty acid methyl ester n-hexane, washes
De- speed is 15mL/h, often crosses 50min and collects column chromatography effluent progress rotary evaporation recycling design acetone-n-hexane, and is right
Product after effluent rotary evaporation carry out gas chromatographic detection and collect respectively mass percent purity 98% or more it is hard
Resin acid methyl esters, methyl oleate and methyl linoleate.
Embodiment 3
Raw material used by this example is useless high acid value corn oil, and acid is measured through standard GB/T-T5530-2005 methods
Value is 17.8mgKOH/g.
(1) pretreatment of useless high acid value corn oil, the specific steps are：
(a) it is 1 by mass ratio:5:50 ionic liquid [(CH3CH2)3N(CH2)3SO3H][C7H7O3S], useless high acid value it is beautiful
Rice bran oil is added in reaction vessel jointly with methanol；Reaction vessel is placed in 70 DEG C of water baths, it is straight to stir mixed liquor in the container
It is fully reacted under the catalytic action of ionic liquid with methanol to useless high acid value corn oil；
(b) after reaction, by the way that separating ionic liquid and a variety of fatty acid methyl ester admixture pretreatment products is decanted,
A variety of fatty acid methyl ester admixtures are biodiesel；
(c) by the ionic liquid isolated, rotary evaporation removes a small amount of methanol with after water at 140 DEG C, and recycling repeats to make
With；It is 1.12mgKOH/g that obtained biodiesel measures acid value by standard GB/T-T5530-2005 methods.
(2) C18 fatty acid methyl esters crude separation, the specific steps are：
(a) a variety of fatty acid methyl ester admixtures obtained in step (1) is taken to be sent into the rectification under vacuum that packed height is 1.2m
Rectifying is carried out in tower reactor, tower top operating pressure is 140Pa, and tower reactor heating power is 140W；
(b) rectifying column infinite reflux is after tower reactor tower top temperature stabilization, in the case where the operating reflux ratio of vacuum rectification tower is 9, into
Row rectification under vacuum operates, and mass percent purity is collected 98% into gas chromatographic detection in overhead extraction product, and to product
The above C18 fatty acid methyl esters product (methyl stearate, methyl oleate and methyl linoleate mixture).
(3) C18 fatty acid methyl esters finely detach, the specific steps are：
(a) preparation of column chromatography stationary phase, the specific steps are：
It takes granularity to be placed in container in 250 mesh silica gel, absolute ethyl alcohol, the matter of silica gel and absolute ethyl alcohol is then added thereto
Amount is than being 2:5；Then silica gel forms silica gel suspension with ethyl alcohol in stirring container；By AgNO3Crystal dissolves under dark condition
In the volume ratio of ethyl alcohol and water be 1:In 2 ethanol-water solution, AgNO is obtained3The AgNO that mass fraction is 10%3Alcohol-water
Solution；AgNO will be dissolved3Ethanol-water solution be added in the above-mentioned silica gel suspension prepared, stirred under dark condition
40min；It takes out the silver nitrate silica gel suspension mixed to be sent into the container that aluminium-foil paper wraps, and the container and rotation is steamed
Instrument connection is sent out, rotary evaporation 4.5h removes ethanol-water under conditions of being 0.1MPa in 100 DEG C, vacuum degree；Solvent will be removed
Silver nitrate silica gel afterwards is placed in 110 DEG C of vacuum drying chambers and activates for 24 hours, and modified silica-gel, which is finally collected in drying in brown bottle, waits for
With.
(b) C18 fatty acid methyl esters finely detach, the specific steps are：
It takes the silver nitrate-modified silica gel prepared as column chromatography stationary phase, carries out the installation of chromatographic column according to a conventional method；
It takes the content obtained in step (2) to be dissolved in n-hexane in 98% or more C18 fatty acid methyl esters, is pipetting fatty acid methyl ester just
Hexane solution is to silver nitrate-modified silica gel column chromatography upper surface；The use of acetone volume fraction is respectively successively 1%, 3%, 5%
Acetone-hexane solution carries out elution action as mobile phase to the chromatographic column for having dosed fatty acid methyl ester n-hexane, washes
De- speed is 20mL/h, often crosses 60min and collects column chromatography effluent progress rotary evaporation recycling design acetone-n-hexane, and is right
Product after effluent rotary evaporation carry out gas chromatographic detection and collect respectively mass percent purity 98% or more it is hard
Resin acid methyl esters, methyl oleate and methyl linoleate.
Embodiment 4
Raw material used by this example is useless fish oil, and measuring acid value through standard GB/T-T5530-2005 methods is
16.9mgKOH/g。
(1) pretreatment of useless fish oil, the specific steps are：
(a) it is 1 by mass ratio:6:48 ionic liquid [PyPS] PW, useless fish oil and methanol are added in reaction vessel jointly；
Reaction vessel is placed in 80 DEG C of water baths, stir mixed liquor in the container until useless fish oil and methanol ionic liquid catalysis
The lower fully reaction of effect；
(b) after reaction, by the way that separating ionic liquid and a variety of fatty acid methyl ester admixture pretreatment products is decanted,
A variety of fatty acid methyl ester admixtures are biodiesel；
(c) by the ionic liquid isolated, rotary evaporation removes a small amount of methanol with after water at 150 DEG C, and recycling repeats to make
With；It is 1.21mgKOH/g that obtained biodiesel measures acid value by standard GB/T-T5530-2005 methods.
(2) C20~C22 fatty acid methyl esters crude separation, the specific steps are：
(a) a variety of fatty acid methyl ester admixtures obtained in step (1) is taken to be sent into the rectification under vacuum that packed height is 1.6m
Rectifying is carried out in tower reactor, tower top operating pressure is 150Pa, and tower reactor heating power is 125W；
(b) rectifying column infinite reflux is after tower reactor tower top temperature stabilization, in the case where the operating reflux ratio of vacuum rectification tower is 10, into
Row rectification under vacuum operates, and C20 of the purity 98% or more is collected into gas chromatographic detection in overhead extraction product, and to product
~C22 fatty acid methyl esters (wherein including methyl eicosapentaenoic acid and Methyl docosahexaenoate).
(3) C20~C22 fatty acid methyl esters finely detach, the specific steps are：
(a) preparation of column chromatography stationary phase, the specific steps are：
It takes granularity to be placed in container in 300 mesh silica gel, absolute ethyl alcohol, the matter of silica gel and absolute ethyl alcohol is then added thereto
Amount is than being 2:5；Then silica gel forms silica gel suspension with ethyl alcohol in stirring container；By AgNO3Crystal dissolves under dark condition
In the volume ratio of ethyl alcohol and water be 1:In 2 ethanol-water solution, AgNO is obtained3The AgNO that mass fraction is 16%3Alcohol-water
Solution；AgNO will be dissolved3Ethanol-water solution be added in the above-mentioned silica gel suspension prepared, stirred under dark condition
25min；It takes out the silver nitrate silica gel suspension mixed to be sent into the container that aluminium-foil paper wraps, and the container and rotation is steamed
Instrument connection is sent out, rotary evaporation 5h removes ethanol-water under conditions of being 0.05MPa in 90 DEG C, vacuum degree；After solvent being removed
Silver nitrate silica gel be placed in 120 DEG C of vacuum drying chambers and activate for 24 hours, modified silica-gel, which is finally collected in drying in brown bottle, waits for
With.
(b) C20~C22 fatty acid methyl esters finely detach, the specific steps are：
It takes the silver nitrate-modified silica gel prepared as column chromatography stationary phase, carries out the installation of chromatographic column according to a conventional method；
It takes the content obtained in step (2) to be dissolved in n-hexane in 98% or more C20~C22 fatty acid methyl ester products, pipettes fat
Fatty acid methyl esters hexane solution is to silver nitrate-modified silica gel column chromatography upper surface；The use of acetone volume fraction is respectively successively 1%,
3%, 5% acetone-hexane solution washes the chromatographic column for having dosed fatty acid methyl ester n-hexane as mobile phase
De- operation, elution speed 20mL/h often cross 60min and are collecting column chromatography effluent progress rotary evaporation recycling design acetone-just
Hexane, and to after effluent rotary evaporation product carry out gas chromatographic detection and respectively collect purity 98% or more 20
Carbon 5 alkene acid methyl esters and Methyl docosahexaenoate.
Embodiment 5
Raw material used by this example is algal oil, and measuring acid value through standard GB/T-T5530-2005 methods is
2.4mgKOH/g。
(1) pretreatment of algal oil, the specific steps are：
(a) it is 1 by mass ratio:2:10 ionic liquid [HO3S-(CH2)3-NEt3]Cl-FeCl3, algal oil and methanol it is total
With in addition reaction vessel；Reaction vessel is placed in 55 DEG C of water baths, stirs mixed liquor in the container until algal oil and first
Alcohol fully reacts under the catalytic action of ionic liquid；
(b) after reaction, by the way that separating ionic liquid and a variety of fatty acid methyl ester admixture pretreatment products is decanted,
A variety of fatty acid methyl ester admixtures are biodiesel；
(c) by the ionic liquid isolated, rotary evaporation removes a small amount of methanol with after water at 100 DEG C, and recycling repeats to make
With；It is 0.67mgKOH/g that obtained biodiesel measures acid value by standard GB/T-T5530-2005 methods.
(2) C20~C22 fatty acid methyl esters crude separation, the specific steps are：
(a) a variety of fatty acid methyl ester admixtures obtained in step (1) is taken to be sent into the rectification under vacuum that packed height is 1.9m
Rectifying is carried out in tower reactor, tower top operating pressure is 180Pa, and tower reactor heating power is 120W；
(b) rectifying column infinite reflux is after tower reactor tower top temperature stabilization, in the case where the operating reflux ratio of vacuum rectification tower is 5, into
Row rectification under vacuum operates, and C20 of the purity 98% or more is collected into gas chromatographic detection in overhead extraction product, and to product
~C22 fatty acid methyl esters (wherein including methyl eicosapentaenoic acid and Methyl docosahexaenoate).
(3) C20~C22 fatty acid methyl esters finely detach, the specific steps are：
(a) preparation of column chromatography stationary phase, the specific steps are：
It takes granularity to be placed in container in 200 mesh silica gel, absolute ethyl alcohol, the matter of silica gel and absolute ethyl alcohol is then added thereto
Amount is than being 1:3；Then silica gel forms silica gel suspension with ethyl alcohol in stirring container；By AgNO3Crystal dissolves under dark condition
In the volume ratio of ethyl alcohol and water be 3:In 2 ethanol-water solution, AgNO is obtained3The AgNO that mass fraction is 20%3Alcohol-water
Solution；AgNO will be dissolved3Ethanol-water solution be added in the above-mentioned silica gel suspension prepared, stirred under dark condition
25min；It takes out the silver nitrate silica gel suspension mixed to be sent into the container that aluminium-foil paper wraps, and the container and rotation is steamed
Instrument connection is sent out, rotary evaporation 5h removes ethanol-water under conditions of being 0.05MPa in 90 DEG C, vacuum degree；After solvent being removed
Silver nitrate silica gel be placed in 110 DEG C of vacuum drying chambers and activate 16h, modified silica-gel, which is finally collected in drying in brown bottle, waits for
With.
(b) C20~C22 fatty acid methyl esters finely detach, the specific steps are：
It takes the silver nitrate-modified silica gel prepared as column chromatography stationary phase, carries out the installation of chromatographic column according to a conventional method；
It takes the content obtained in step (2) to be dissolved in n-hexane in 98% or more C20~C22 fatty acid methyl ester products, pipettes fat
Fatty acid methyl esters hexane solution is to silver nitrate-modified silica gel column chromatography upper surface；The use of acetone volume fraction is respectively successively 1%,
3%, 5% acetone-hexane solution washes the chromatographic column for having dosed fatty acid methyl ester n-hexane as mobile phase
De- operation, elution speed 15mL/h often cross 50min and are collecting column chromatography effluent progress rotary evaporation recycling design acetone-just
Hexane, and to after effluent rotary evaporation product carry out gas chromatographic detection and respectively collect purity 98% or more 20
Carbon 5 alkene acid methyl esters and Methyl docosahexaenoate.
Embodiment 6
This example uses the algal oil in embodiment 5 as raw material.
(1) pretreatment of algal oil, the specific steps are：
(a) it is 1 by mass ratio:6:72 ionic liquid [BTBD] OH, algal oil and methanol is added in reaction vessel jointly；
Reaction vessel is placed in 65 DEG C of water baths, stir mixed liquor in the container until algal oil and methanol ionic liquid catalysis
The lower fully reaction of effect；
(b) after reaction, by the way that separating ionic liquid and a variety of fatty acid methyl ester admixture pretreatment products is decanted,
A variety of fatty acid methyl ester admixtures are biodiesel；
(c) by the ionic liquid isolated, rotary evaporation removes a small amount of methanol with after water at 120 DEG C, and recycling repeats to make
With；It is 0.71mgKOH/g that obtained biodiesel measures acid value by standard GB/T-T5530-2005 methods.
(2) C20~C22 fatty acid methyl esters crude separation, the specific steps are：
(a) a variety of fatty acid methyl ester admixtures obtained in step (1) is taken to be sent into the rectification under vacuum that packed height is 1.4m
Rectifying is carried out in tower reactor, tower top operating pressure is 200Pa, and tower reactor heating power is 150W；
(b) rectifying column infinite reflux is after tower reactor tower top temperature stabilization, in the case where the operating reflux ratio of vacuum rectification tower is 10, into
Row rectification under vacuum operates, and mass percent purity is collected 98% into gas chromatographic detection in overhead extraction product, and to product
Above C20~C22 fatty acid methyl esters (wherein including methyl eicosapentaenoic acid and Methyl docosahexaenoate).
(3) C20~C22 fatty acid methyl esters finely detach, the specific steps are：
(a) preparation of column chromatography stationary phase, the specific steps are：
It takes granularity to be placed in container in 200 mesh silica gel, absolute ethyl alcohol, the matter of silica gel and absolute ethyl alcohol is then added thereto
Amount is than being 1:3；Then silica gel forms silica gel suspension with ethyl alcohol in stirring container；By AgNO3Crystal dissolves under dark condition
In the volume ratio of ethyl alcohol and water be 3:In 2 ethanol-water solution, AgNO is obtained3The AgNO that mass fraction is 25%3Alcohol-water
Solution；AgNO will be dissolved3Ethanol-water solution be added in the above-mentioned silica gel suspension prepared, stirred under dark condition
30min；It takes out the silver nitrate silica gel suspension mixed to be sent into the container that aluminium-foil paper wraps, and the container and rotation is steamed
Instrument connection is sent out, rotary evaporation 4h removes ethanol-water under conditions of being 0.05MPa in 90 DEG C, vacuum degree；After solvent being removed
Silver nitrate silica gel be placed in 120 DEG C of vacuum drying chambers and activate 20h, modified silica-gel, which is finally collected in drying in brown bottle, waits for
With.
(b) C20~C22 fatty acid methyl esters finely detach, the specific steps are：
It takes the silver nitrate-modified silica gel prepared as column chromatography stationary phase, carries out the installation of chromatographic column according to a conventional method；
It takes the content obtained in step (2) to be dissolved in n-hexane in 98% or more C20~C22 fatty acid methyl esters, pipettes aliphatic acid
Methyl esters hexane solution is to silver nitrate-modified silica gel column chromatography upper surface；The use of acetone volume fraction is respectively successively 1%, 3%,
5% acetone-hexane solution carries out elution behaviour as mobile phase to the chromatographic column for having dosed fatty acid methyl ester n-hexane
Make, elution speed 10mL/h, often cross 60min and collect column chromatography effluent progress rotary evaporation recycling design acetone-n-hexane,
And gas chromatographic detection is carried out to the product after effluent rotary evaporation and collects mass percent purity respectively 98% or more
Methyl eicosapentaenoic acid and Methyl docosahexaenoate.
Embodiment 7
This example uses the useless fish oil in embodiment 4 as raw material.
(1) pretreatment of useless fish oil, the specific steps are：
(a) it is 1 by mass ratio:6:66 [Bmim] Br-FeCl3With [HO3S-(CH2)3-NEt3]Cl-FeCl3Ionic liquid
Body mixture, useless fish oil and methanol are added in reaction vessel jointly；Reaction vessel is placed in 60 DEG C of water baths, the container is stirred
Middle mixed liquor is until useless fish oil is fully reacted with methanol under the catalytic action of ionic liquid；
(b) after reaction, by the way that separating ionic liquid and a variety of fatty acid methyl ester admixture pretreatment products is decanted,
A variety of fatty acid methyl ester admixtures are biodiesel；
(c) by the ionic liquid isolated, rotary evaporation removes a small amount of methanol with after water at 130 DEG C, and recycling repeats to make
With；It is 0.83mgKOH/g that obtained biodiesel measures acid value by standard GB/T-T5530-2005 methods.
(2) C20~C22 fatty acid methyl esters crude separation, the specific steps are：
(a) a variety of fatty acid methyl ester admixtures obtained in step (1) is taken to be sent into the rectification under vacuum that packed height is 1.6m
Rectifying is carried out in tower reactor, tower top operating pressure is 200Pa, and tower reactor heating power is 150W；
(b) rectifying column infinite reflux is after tower reactor tower top temperature stabilization, in the case where the operating reflux ratio of vacuum rectification tower is 10, into
Row rectification under vacuum operates, and mass percent purity is collected 98% into gas chromatographic detection in overhead extraction product, and to product
Above C20~C22 fatty acid methyl esters (wherein including methyl eicosapentaenoic acid and Methyl docosahexaenoate).
(3) C20~C22 fatty acid methyl esters finely detach, the specific steps are：
(a) preparation of column chromatography stationary phase, the specific steps are：
It takes granularity to be placed in container in 200 mesh silica gel, absolute ethyl alcohol, the matter of silica gel and absolute ethyl alcohol is then added thereto
Amount is than being 1:3；Then silica gel forms silica gel suspension with ethyl alcohol in stirring container；By AgNO3Crystal dissolves under dark condition
In the volume ratio of ethyl alcohol and water be 3:In 2 ethanol-water solution, AgNO is obtained3The AgNO that mass fraction is 25%3Alcohol-water
Solution；AgNO will be dissolved3Ethanol-water solution be added in the above-mentioned silica gel suspension prepared, stirred under dark condition
30min；It takes out the silver nitrate silica gel suspension mixed to be sent into the container that aluminium-foil paper wraps, and the container and rotation is steamed
Instrument connection is sent out, rotary evaporation 4h removes ethanol-water under conditions of being 0.05MPa in 90 DEG C, vacuum degree；After solvent being removed
Silver nitrate silica gel be placed in 120 DEG C of vacuum drying chambers and activate 18h, modified silica-gel, which is finally collected in drying in brown bottle, waits for
With.
(b) C20~C22 fatty acid methyl esters finely detach, the specific steps are：
It takes the silver nitrate-modified silica gel prepared as column chromatography stationary phase, carries out the installation of chromatographic column according to a conventional method；
It takes the content obtained in step (2) to be dissolved in n-hexane in 98% or more C20~C22 fatty acid methyl esters, pipettes aliphatic acid
Methyl esters hexane solution is to silver nitrate-modified silica gel column chromatography upper surface；The use of acetone volume fraction is respectively successively 1%, 3%,
5% acetone-hexane solution carries out elution behaviour as mobile phase to the chromatographic column for having dosed fatty acid methyl ester n-hexane
Make, elution speed 10mL/h, often cross 60min and collect column chromatography effluent progress rotary evaporation recycling design acetone-n-hexane,
And gas chromatographic detection is carried out to the product after effluent rotary evaporation and collects mass percent purity respectively 98% or more
Methyl eicosapentaenoic acid and Methyl docosahexaenoate.
Embodiment 8
This example uses the Industry Waste palm oil in embodiment 2 as raw material.
(1) pretreatment of Industry Waste palm oil, the specific steps are：
(a) it is 1 by mass ratio:3:36 [(CH2)3SO3HMIM][HSO3] with the ionic liquid mixture of [PyPS] PW,
Industry Waste palm oil is added in reaction vessel jointly with methanol；Reaction vessel is placed in 50 DEG C of water baths, is stirred in the container
Mixed liquor is until Industry Waste palm oil is fully reacted with methanol under the catalytic action of ionic liquid mixture；
(b) after reaction, by the way that separating ionic liquid and a variety of fatty acid methyl ester admixture pretreatment products is decanted,
A variety of fatty acid methyl ester admixtures are biodiesel；
(c) by the ionic liquid isolated, rotary evaporation removes a small amount of methanol with after water at 100 DEG C, and recycling repeats to make
With；It is 0.72mgKOH/g that obtained biodiesel measures acid value by standard GB/T-T5530-2005 methods.
(2) C18 fatty acid methyl esters crude separation, the specific steps are：
(a) a variety of fatty acid methyl ester admixtures obtained in step (1) is taken to be sent into the rectification under vacuum that packed height is 1.0m
Rectifying is carried out in tower reactor, tower top operating pressure is 120Pa, and tower reactor heating power is 130W；
(b) rectifying column infinite reflux is after tower reactor tower top temperature stabilization, in the case where the operating reflux ratio of vacuum rectification tower is 7, into
Row rectification under vacuum operates, and mass percent purity is collected 98% into gas chromatographic detection in overhead extraction product, and to product
The above C18 fatty acid methyl esters product (methyl stearate, methyl oleate and methyl linoleate mixture).
(3) C18 fatty acid methyl esters finely detach, the specific steps are：
(a) preparation of column chromatography stationary phase, the specific steps are：
It takes granularity to be placed in container in 200 mesh silica gel, absolute ethyl alcohol, the matter of silica gel and absolute ethyl alcohol is then added thereto
Amount is than being 1:2；Then silica gel forms silica gel suspension with ethyl alcohol in stirring container；By AgNO3Crystal dissolves under dark condition
In the volume ratio of ethyl alcohol and water be 7:In 3 ethanol-water solution, AgNO is obtained3The AgNO that mass fraction is 30%3Alcohol-water
Solution；AgNO will be dissolved3Ethanol-water solution be added in the above-mentioned silica gel suspension prepared, stirred under dark condition
20min；It takes out the silver nitrate silica gel suspension mixed to be sent into the container that aluminium-foil paper wraps, and the container and rotation is steamed
Instrument connection is sent out, rotary evaporation 5h removes ethanol-water under conditions of being 0.01MPa in 70 DEG C, vacuum degree；After solvent being removed
Silver nitrate silica gel be placed in 115 DEG C of vacuum drying chambers and activate 18h, modified silica-gel, which is finally collected in drying in brown bottle, waits for
With.
(b) C18 fatty acid methyl esters finely detach, the specific steps are：
It takes the silver nitrate-modified silica gel prepared as column chromatography stationary phase, carries out the installation of chromatographic column according to a conventional method；
It takes the content obtained in step (2) to be dissolved in n-hexane in 98% or more C18 fatty acid methyl esters, is pipetting fatty acid methyl ester just
Hexane solution is to silver nitrate-modified silica gel column chromatography upper surface；The use of acetone volume fraction is respectively successively 1%, 3%, 5%
Acetone-hexane solution carries out elution action as mobile phase to the chromatographic column for having dosed fatty acid methyl ester n-hexane, washes
De- speed is 15mL/h, often crosses 40min and collects column chromatography effluent progress rotary evaporation recycling design acetone-n-hexane, and is right
Product after effluent rotary evaporation carry out gas chromatographic detection and collect respectively mass percent purity 98% or more it is hard
Resin acid methyl esters, methyl oleate and methyl linoleate.
Above specific implementation mode has carried out specific description, but content of the present invention to the method for the present invention
Be not restricted to the above case study on implementation, if in the main scope without departing from the present invention, can to experiment condition and method into
The flexible change of row.
Claims (5)
1. the fine separation method of a kind of C18 series and C20~C22 series fatty acid methyl esters, which is characterized in that it includes such as
Lower step：
(1) pretreatment of animal and plant fat, the specific steps are：
(a) it is 1 by mass ratio:2~6:10~72 ionic liquid, animal and plant fat and methanol is added in reaction vessel jointly；
Reaction vessel is placed in 50~80 DEG C of water baths, stirs mixed liquor in the container until animal and plant fat and methanol are in ionic liquid
Fully reaction generates a variety of fatty acid methyl ester admixtures under the catalytic action of body；
(b) after reaction, by the way that separating ionic liquid and a variety of fatty acid methyl ester admixtures is decanted；
(c) by the ionic liquid isolated, rotary evaporation removes a small amount of methanol with after water at 90~150 DEG C, and recycling repeats to make
With；
(2) fatty acid methyl ester crude separation, the specific steps are：
(a) it takes a variety of fatty acid methyl ester admixtures obtained in step (1) to be sent into rectification under vacuum tower reactor and carries out rectifying, tower top behaviour
It is 100~200Pa to make pressure, and tower reactor heating power is 100~150W；
(b) rectifying column infinite reflux, in the case where the operating reflux ratio of vacuum rectification tower is 4~10, is used after tower reactor tower top temperature stabilization
Surge tank collects fatty acid methyl ester product of the rectifying column tower top quality percent purity 98% or more, and fatty acid methyl ester product is
C18 fatty acid methyl esters product or C20~C22 fatty acid methyl esters；
(3) the fine separation of fatty acid methyl ester, the specific steps are：
(a) preparation of column chromatography stationary phase, the specific steps are：
It takes granularity to be placed in container in 200~300 mesh silica gel, is then added absolute ethyl alcohol thereto, silica gel and absolute ethyl alcohol
Mass ratio is 1:3~1:2；Then silica gel forms silica gel suspension with ethyl alcohol in stirring container；By AgNO3Crystal is in dark condition
Under to be dissolved in the volume ratio of ethyl alcohol and water be 7:3~1:In 2 ethanol-water solution, AgNO is obtained3Mass fraction be 10%~
30% AgNO3Ethanol-water solution；AgNO will be dissolved3Ethanol-water solution be added in the above-mentioned silica gel suspension prepared,
20~40min is stirred under dark condition；It takes out the silver nitrate silica gel suspension mixed and is sent into the container that aluminium-foil paper wraps
In, and the container is connect with Rotary Evaporators, it rotates and steams under conditions of being 0.01~0.1MPa in 70~100 DEG C, vacuum degree
It sends out 4~5h and removes ethanol-water；Silver nitrate silica gel after removing solvent is placed in 110~120 DEG C of vacuum drying chambers and is activated
16~for 24 hours, modified silica-gel is finally collected in dried for standby in brown bottle；
(b) fatty acid methyl ester finely detaches, the specific steps are：
It takes the silver nitrate-modified silica gel prepared as column chromatography stationary phase, carries out the installation of chromatographic column；It takes and obtains in step 2
C18 fatty acid methyl esters or C20~C22 fatty acid methyl ester products are dissolved in n-hexane, pipette fatty acid methyl ester hexane solution
To silver nitrate-modified silica gel column chromatography upper surface；Successively use acetone volume fraction be respectively 1%, 3%, 5% acetone-just oneself
Alkane solution carries out elution action, elution speed 10 as mobile phase to the chromatographic column for having dosed fatty acid methyl ester n-hexane
~20mL/h often crosses 40~60min and collects column chromatography effluent progress rotary evaporation recycling design acetone-n-hexane, and convection current
The product gone out after object rotary evaporation is collected to obtain methyl stearate, methyl oleate, Asia of the mass percent purity 98% or more
Methyl oleate, methyl eicosapentaenoic acid or Methyl docosahexaenoate.
2. the method described in accordance with the claim 1 finely detached, it is characterised in that：The animal and plant fat includes rich in tristearin
Acid, oleic acid and linoleic animal and plant fat or rich in eicosapentaenoic acid, the algal oil of docosahexaenoic acid, fish oil with
And the useless fish oil of high acid value of the acid value more than 2.
3. according to the method as claimed in claim 1 or 2 finely detached, it is characterised in that：The ionic liquid be imidazoles from
Sub- liquid, quaternary ammonium salt Bronsted acidic ion liquids, Lewis acidic ion liquids, bisgallic acid type ionic liquid, alkali ion
The liquid either mixture of any one in heteropoly acid type ionic liquid or arbitrary at least two ionic liquid.
4. the method described in accordance with the claim 3 finely detached, it is characterised in that：The glyoxaline ion liquid includes
[BHSO3MIM]HSO4Or [(CH2)3SO3HMIM][HSO3]；The quaternary ammonium salt Bronsted acidic ion liquids include
[(CH3CH2)3N(CH2)3SO3H][C7H7O3S]；The Lewis acidic ion liquids include [Bmim] Br-CuCl2、[Bmim]
Br-FeCl3、[Bmim]Br-CuCl、[Bmim]Br-Fe2Cl6Or [Bmim] Br-Ni2Cl4；The bisgallic acid type ionic liquid
Including [HO3S-(CH2)3-NEt3]Cl-FeCl3Or [BSO3HMIM]HSO4-Fe2(SO4)3；The alkali ionic liquid packet
Include [BTBD] OH；The heteropoly acid type ionic liquid includes [PyPS] PW, [TMAPS] PW, [MIMPS] PW or [QPS] PW.
5. the method finely detached according to claim 4, it is characterised in that：The vacuum rectification tower uses efficient θ rings
Filler or random packing, packed height are 0.5~1.9m.
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| CN105695104B (en) * | 2016-03-29 | 2023-05-09 | 天津大学 | In-tower pumping type high-vacuum rectification method and device for precisely separating C16-C22 fatty acids |
| CN108018100B (en) * | 2016-10-28 | 2020-08-18 | 中国石油化工股份有限公司 | Composition with diesel anti-wear properties, diesel composition and preparation method thereof |
| CN109022118A (en) * | 2018-07-04 | 2018-12-18 | 浙江工商大学 | The extracting method of fish oil and its purification process of EPA in big mesh tuna by-product |
| CN109456838B (en) * | 2018-10-19 | 2021-05-11 | 中国科学院山西煤炭化学研究所 | Method for producing biodiesel and glycerol triacetate |
| CN112574825A (en) * | 2020-11-20 | 2021-03-30 | 余海龙 | Extraction process of high-purity unsaturated fatty acid |
Citations (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1222564A (en) * | 1998-01-05 | 1999-07-14 | 山东禹王制药有限公司 | Industrial production of highly unsaturated fatty acid |
| CN1236773A (en) * | 1999-06-15 | 1999-12-01 | 张其德 | Process for preparing and separating ethyl docosahexenoate and ethyl eicosapentaenoate |
| CN101265185A (en) * | 2008-04-22 | 2008-09-17 | 天津大学 | Process for preparing and separating methyl docosapentaenoate and methyl docosahexenoate |
| CN101456810A (en) * | 2007-12-13 | 2009-06-17 | 中国科学院兰州化学物理研究所 | Method for synthesizing fatty acid ester by ester exchange reaction |
| FR2929621A1 (en) * | 2008-04-08 | 2009-10-09 | Arkema France | Esterifying free fatty acid, useful to prepare bio-diesel, comprises providing a fatty substance comprising free fatty acid, adding alcohol and methane sulfonic acid, conducting esterification reaction, and recovering the fatty substance |
| CN102031202A (en) * | 2010-12-08 | 2011-04-27 | 中国科学院西双版纳热带植物园 | Method for preparing biodiesel under catalysis of ionic liquid |
| CN102180791A (en) * | 2011-04-13 | 2011-09-14 | 天津大学 | Method for separating methyl acetate-methanol mixture by ionic liquid intermittent extractive rectification |
| CN102911795A (en) * | 2012-11-26 | 2013-02-06 | 天津大学 | Method for preparing fish oil ethyl ester by microwave esterification and purifying ethyl eicosapentaenoate |
| CN102978012A (en) * | 2012-11-08 | 2013-03-20 | 江南大学 | Method of biodiesel preparation catalyzed by imidazole anionic type basic ionic liquid |
| CN103396310A (en) * | 2013-07-25 | 2013-11-20 | 浙江大学 | Method for separating and purifying eicosapentaenoic acid ester and docosahexenoic acid ester from micro-algal oil or fish oil |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE602004005010T2 (en) * | 2004-03-31 | 2007-08-09 | Cognis Ip Management Gmbh | Process for the production of fatty acids with the improved properties odor, color and heat stability |
-
2015
- 2015-08-06 CN CN201510478564.0A patent/CN105132189B/en active Active
Patent Citations (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1222564A (en) * | 1998-01-05 | 1999-07-14 | 山东禹王制药有限公司 | Industrial production of highly unsaturated fatty acid |
| CN1236773A (en) * | 1999-06-15 | 1999-12-01 | 张其德 | Process for preparing and separating ethyl docosahexenoate and ethyl eicosapentaenoate |
| CN101456810A (en) * | 2007-12-13 | 2009-06-17 | 中国科学院兰州化学物理研究所 | Method for synthesizing fatty acid ester by ester exchange reaction |
| FR2929621A1 (en) * | 2008-04-08 | 2009-10-09 | Arkema France | Esterifying free fatty acid, useful to prepare bio-diesel, comprises providing a fatty substance comprising free fatty acid, adding alcohol and methane sulfonic acid, conducting esterification reaction, and recovering the fatty substance |
| CN101265185A (en) * | 2008-04-22 | 2008-09-17 | 天津大学 | Process for preparing and separating methyl docosapentaenoate and methyl docosahexenoate |
| CN102031202A (en) * | 2010-12-08 | 2011-04-27 | 中国科学院西双版纳热带植物园 | Method for preparing biodiesel under catalysis of ionic liquid |
| CN102180791A (en) * | 2011-04-13 | 2011-09-14 | 天津大学 | Method for separating methyl acetate-methanol mixture by ionic liquid intermittent extractive rectification |
| CN102978012A (en) * | 2012-11-08 | 2013-03-20 | 江南大学 | Method of biodiesel preparation catalyzed by imidazole anionic type basic ionic liquid |
| CN102911795A (en) * | 2012-11-26 | 2013-02-06 | 天津大学 | Method for preparing fish oil ethyl ester by microwave esterification and purifying ethyl eicosapentaenoate |
| CN103396310A (en) * | 2013-07-25 | 2013-11-20 | 浙江大学 | Method for separating and purifying eicosapentaenoic acid ester and docosahexenoic acid ester from micro-algal oil or fish oil |
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