CN108802246A - A kind of nervonic acid process for separation and purification - Google Patents
A kind of nervonic acid process for separation and purification Download PDFInfo
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Abstract
The invention discloses a kind of nervonic acid process for separation and purification, including following operating procedure, 1) obtain neural acid crude；(2) the neural acid crude for obtaining step (1) removes unsaponifiable matter；(3) the neural acid crude for obtaining step (2), it is dissolved in chromatogram flow phase, constant volume, obtains the sample solution that mass concentration is 50-400g/L, above-mentioned sample is repeatedly continuously pumped into 80-120atm to prepare in chromatic spectrum sample feeder, continuous sample introduction separation；(4) sample after separation in step (3) is detected using GC gas-chromatography detection methods；(5) eluent containing nervonic acid that step (3) processing obtains is subjected to low-temperature reduced-pressure revolving, recycling design obtains nervonic acid finished product.The technical program takes ADSORPTION IN A FIXED BED, liquid phase elution, vapor detection mode to be combined, and can be operated to a large amount of neural acid crudes in short cycle, and low energy consumption for entire purification and separation process, by-product effectively can be recycled and be utilized, and waste yield is few.
Description
Technical field
The present invention relates to purification technique fields, and in particular to a kind of nervonic acid process for separation and purification.
Background technology
Nervonic acid also known as turtle acid, the entitled cis-15-tetracosenoic acid of chemistry, is a kind of long-chain unsaturated fatty acid, main
To be present in human brain protein in the form of glycosyl sphingolipid and sphingomyelins, retina, in sperm and nerve fiber.A large amount of medicine cards
Bright, nervonic acid, which has, restores brain cell tip activity, promotes nerve growth and development function, and to cardiovascular and cerebrovascular and itself
Immunodeficiency disease has certain curative effect.Therefore the extraction of nervonic acid has great importance and is worth with application.It is seen at present
Related introduction, including from seaweed plant, turtle oil and turtle brain in extract, but due to raw material resources restrict, cost mistake
It is high, it is difficult to form large-scale production.
In order to solve the problems, such as raw material, also refer to extract nervonic acid from plant in relevant document, such as with ingot
Maple extracts as raw material, and acer truncatum is the deciduous tree that hard maple section hard maple belongs to,《Chinese Plants will》It names as " ingot
Tool " also known as acer monoes.In recent years, to the chemical composition of acer truncatum seed, prospect in medicine, physiology characteristic, the side such as pharmacy characteristic
Face has carried out a series of research, and benevolence oil content 48% is identified to detect 12 kinds of aliphatic acid altogether, and wherein this technology is related to
Neural acid content is 5-6%.
A kind of molecular distillation technique is disclosed in the file that number of patent application is 200710018195.2 from acer truncatum buge oil
Extract nervonic acid preparation method, it using acer truncatum seed as raw material, after pretreatment basic catalyst effect under with it is excessive
Ethyl alcohol carries out esterification, so that the triglycerides in raw material is transformed into fatty-acid ethyl ester, then by croude fatty acids ethyl ester certain
Vacuum pressure is repeatedly distilled at a temperature of, and to obtain neural acetoacetic ester, neural acid product is being obtained after hydrolysis.It is deposited
The problem of be：Complex steps, multiple high temp distillation cause product yield very low, and final products purity is also only capable of reaching
50%, high-content requirement of the market to nervonic acid cannot be met.
One kind is disclosed in the file that number of patent application is 201710680766.2 with Malania Oleifera Oil separating-purifying nervonic acid
Method, including 8 steps, Step 1: saponification：A concentration of 10% lye is added into retort, reaction generates nervonic acid
Sodium salt saponification liquor；Step 2: oil removing；Step 3: acid out：Saponification saline solution is added to acid out tank, stirs lower dropwise addition sulfuric acid to pH
For 6-7, white is precipitated and mixes acid out liquid；Step 4: acid filtering：Acid out liquid will be mixed to be put into the filter pocket for being covered with filter cloth, filter off awns
Nitre liquid removes wastewater disposal basin, collects spare after mixing acid heat water washing air-dries；Step 5: ether dissolved；Step 6: acetone dissolved；Step
Rapid seven, petroleum ether dissolved；Step 8: processing obtains nervonic acid.The present invention is used as using ether, acetone and petroleum ether and is crystallized three times
Solvent, although obtained nervonic acid purity is also only 52% up to 85% neural acid recovering rate, and technique is cumbersome, production
Period is long, and industrial production cost is high.
The Chinese patent of CN101760327A discloses a kind of preparing nervonic acid using the rapeseed oil containing nervonic acid as raw material
Method.This method is by the way that rapeseed oil highly pressured hydrolysis is obtained fatty acid mixed, fatty acid mixed rectifying is then obtained nerve
Neural acid crude is finally crystallized to obtain the neural acid product of 95% or more content by organic solvent, and therefrom obtained by acid crude
Take other Long carbon chain aliphatic acid.This method increase the product categories of rapeseed oil deep processing, while using solvent crystallization from length
Nervonic acid is purified in carbon chain fatty acid, to improve the value of the product of rapeseed oil, extends the raw material sources of nervonic acid.It is deposited
The problem of be：Still the unsaponifiable matter containing high level in using rapeseed oil as the neural acid crude that raw material produces, as sterol,
High molecular alcohol, hydrocarbon, pigment and liposoluble vitamin etc., and repeatedly crystallization processes not only result in neural acid recovery
Rate is low, only 20-30%, and production cycle length, energy consumption are high, while the substance other than nervonic acid can only be used as at waste
Reason, not only bad for making full use of for raw material, while also increasing later stage waste processing cost, therefore the technique cannot meet
Industrial scale production requirement.Based on this, this programme is studied and designs a kind of nervonic acid process for separation and purification.
Invention content
One of above-mentioned technical problem of being solved of the invention：Existing nervonic acid exists in process of production produces cumbersome, life
The production period is long, separation purity and the more low technical problem of yield.Based on this, a kind of nervonic acid process for separation and purification is provided, is being obtained
In the case of taking neural acid crude, unsaponifiable matter is deviate from by ADSORPTION IN A FIXED BED, then using in 80-120atm by sample solution
It is pumped into chromatic spectrum sample feeder, quickening detaches the nervonic acid in neural acid crude, and carries out gradient to neural acid crude and wash
It is de-, by neural acid crude nervonic acid and other substances such as erucic acid, lignin acid, behenic acid etc. be effectively separated purification,
Solve the existing nervonic acid technical problems such as low, production cycle length of existing separation purity in process of production.
The present invention is achieved through the following technical solutions：
A kind of nervonic acid process for separation and purification, including following operating procedure,
(1) neural acid crude is obtained；
(2) the neural acid crude for obtaining step (1) removes unsaponifiable matter；
(3) the neural acid crude for obtaining step (1), is dissolved in chromatogram flow phase, constant volume obtains mass concentration respectively
For the sample solution of 50-400g/L, above-mentioned sample is repeatedly continuously pumped into 80-120atm and is prepared in chromatic spectrum sample feeder, continuously
Sample introduction detaches；
(4) sample after separation in step (2) is detected using GC gas-chromatography detection methods；
(5) eluent containing nervonic acid that step (3) processing obtains is subjected to low-temperature reduced-pressure revolving, recycling design obtains
To nervonic acid finished product.
The technical program is mainly for neural acid crude process for separation and purification in the prior art, while by-product high-purity mustard
Acid.Currently used technology is to use rectification and purification, and distilation, the operational means such as dissolved, the period that this method uses is long,
Under the complex situations of same treatment amount, time lengthening 2-3 days, and whole operation process is complicated, waste yield is big, is related to
Operating procedure it is more, it is cumbersome, cause the nervonic acid product purity finally obtained low, the rate of recovery is low.
Based on this, the technical program innovative development is for the ADSORPTION IN A FIXED BED separation of neural acid crude separating-purifying and liquid
The method that phase separation purification is used in conjunction, the method for vapor detection, purification efficiency improve, and entire process cycle shortens, while relative to
The method that other chemical substances use liquid phase purification in the prior art, in operation, neural acid crude sample is introduced into this method
Preparation chromatography is entered back into after fixed bed abjection unsaponifiable matter, prepares the pressure in chromatic spectrum sample feeder, relative to atmospheric operation, is used
The pressure of 80-120atm can accelerate sample to carry out in chromatic spectrum sample feeder, and continuous to detach, accelerans acid sample solution is in liquid phase
Flowing in chromatography shortens the disengaging time of nervonic acid and other impurities, and then obtains good separating effect, after improving separation
The purity of nervonic acid.If pressure is less than 80atm, the flow velocity that nervonic acid crude product solution enters chromatography stream sample device is very slow, separation consumption
Duration, about 48-64h；If pressure is more than 120atm, it is easy industrially the presence of safety and practical feasibility.
Further, in order to preferably realize the present invention, unsaponifiable matter in neural acid crude is removed in the step (2) and is adopted
Method is：Using solid adsorbent bed, using atlapulgite as stationary phase, under the conditions of 35-60 DEG C of normal pressure, processing speed is
1—10L/min.The solid adsorbent bed, also known as moving bed adsorber are a types of absorber, and the absorber is with activity
Carclazyte is stationary phase, to the unsaponifiable matter in neural acid crude, such as sterol, high molecular alcohol, hydrocarbon, pigment, fat-soluble
Vitamin etc. carries out Adsorption, reduces neural acid crude impurity amount, and atlapulgite described here, the specific substance
It is well known to those skilled in the art.
Further, in order to preferably realize the present invention, chromatographic isolation side is being carried out to sample solution in the step (3)
In method, it is pumped into chromatic spectrum sample feeder, each sample size is 4-8L, 20-60min/ times.
Further, in order to preferably realize the present invention, chromatographic test strip part is in the step (3)：With octadecyl
Silane group silica gel is stationary phase, with arbitrary three kinds of liquid in petroleum ether, n-hexane, ethyl acetate, ethyl alcohol, methanol, purified water
Body is eluted as gradient elution mobile phase with the speed of 1L/min -20L/min.
Further, in order to preferably realize that the present invention, eluent gradient elution program be：0-10min, with petroleum ether：
Ethyl acetate：Purified water ratio is 7：2：1 is eluted, 10-30min, with petroleum ether：Ethyl acetate：Proportion of ethanol is 5：2：
3 are eluted.
In the technical program, in order to by impurity such as unsaponifiable matter, erucic acid in neural acid crude from neural acid crude first
It is eluted out, to improve the purity of nervonic acid, here, mainly being carried out nervonic acid and other impurities using the program of gradient elution
Separation, first with unsaponifiable matter such as sterol, high molecular alcohol, hydrocarbon, pigment and liposoluble vitamin etc. and behenic acid
C220, lignin acid C240Polarity it is different, to which unsaponifiable matter be removed in a manner of adsorbing.
The mobile phase used in the technical program, 0-10min, with petroleum ether：Ethyl acetate：Purified water ratio is 7：2：1
It is eluted, 10-30min, with petroleum ether：Ethyl acetate：Proportion of ethanol is 5：2：3 are eluted.
Petroleum ether, ethyl acetate, purifying aqueous polar size order in mobile phase, purified water > ethyl alcohol > ethyl acetate,
In preceding 10min, eluted according to aforementioned proportion；
And below in 10-30min, with petroleum ether：Ethyl acetate：Proportion of ethanol is 5：2：3 are eluted, polarity size
Sequentially it is：Ethyl alcohol > ethyl acetate > petroleum ethers, it is seen that the mobile phase polarity of 10-30min is less than the mobile phase pole of 0-10min
Property, according to similar compatibility principle, behenic acid, lignin acid, erucic acid solubility in the mobile phase in being dissolved in 0-10min are big,
It is eluted out first, then reduces the polarity of mobile phase, nervonic acid is easily dissolved in the low mobile phase of the polarity, to be eluted
Out, it is finally reached the purpose of neural acid crude purification.
Further, in order to preferably realize that the present invention, eluent gradient elution program be：0-8min, with petroleum ether：
Methanol：Purified water ratio is 5：2：3 are eluted, 8-30min, with petroleum ether：Methanol：N-hexane ratio is 6：3：1 is washed
It is de-.
In the technical program, in order to by impurity such as unsaponifiable matter, erucic acid in neural acid crude, from neural acid crude first
It is eluted out, to improve the purity of nervonic acid, here, mainly being carried out nervonic acid and other impurities using the program of gradient elution
Separation, first with unsaponifiable matter such as sterol, high molecular alcohol, hydrocarbon, pigment and liposoluble vitamin etc. and behenic acid
C220, lignin acid C240Polarity it is different, to which unsaponifiable matter be removed in a manner of adsorbing.
The mobile phase used in the technical program, 0-8min, with petroleum ether：Methanol：Purified water ratio is 5：2：3 carry out
Elution, 8-30min, petroleum ether：Methanol：N-hexane ratio is 6：3：1 is eluted.
Petroleum ether, methanol, purifying aqueous polar size order in mobile phase, purified water > methanol > petroleum ethers, preceding
In 8min, eluted according to aforementioned proportion；
And below in 8-30min, with petroleum ether：Methanol：N-hexane ratio is 6：3：1 is eluted, polarity size order
For：Methanol > n-hexane > petroleum ethers, it is seen that the mobile phase polarity of 8-30min is less than the mobile phase polarity of 0-8min, according to
Similar compatibility principle, behenic acid, lignin acid, erucic acid solubility in the mobile phase in being dissolved in 0-8min are big, are washed first
It takes off, then reduces the polarity of mobile phase, nervonic acid is easily dissolved in the low mobile phase of the polarity, to be eluted out, most
Achieve the purpose that neural acid crude purification eventually.
Further, in order to preferably realize that the present invention, eluent gradient elution program be：0-20min, with petroleum ether：
Ethyl alcohol：Purified water ratio is 6：2：2 are eluted, 20-50min, with petroleum ether：Ethyl alcohol：Ethyl acetate ratio is 5：3：2 into
Row elution.
In neural acid crude, such as using rapeseed oil as raw material, the method for preparing nervonic acid, wherein miscellaneous containing long chain fatty acids
Matter, such as erucic acid also contain 45% -70% erucic acid after hydrolyzing, distilling, in crude product.In order to make other substances such as erucic acid,
Lignin acid, behenic acid etc. are efficiently separated with nervonic acid, and when being detached using liquid chromatogram, liquid chromatogram separation condition is：Using
The reversed columns of C18, the mobile phase that when separation uses is arbitrary in petroleum ether, n-hexane, ethyl acetate, ethyl alcohol, methanol, purified water
Three kinds of liquid, and by the way of gradient elution.
In the technical program neural acid crude contain 2%-10% unsaponifiable matter, 50-70% erucic acid C221, 1-3%
Behenic acid C220, 3-10% lignin acid C240And 10% -40% nervonic acid C24 to be purified1, nervonic acid is a kind of
Molecular formula contains the monounsaturated fatty acids of 24 carbon, and erucic acid is a kind of monounsaturated fatty acids containing 22 carbon, behenic acid
Be a kind of saturated fatty acid containing 22 carbon, lignin acid it is a kind of saturated fatty acid containing 24 carbon.Four kinds of sour poles
Property size be C221>C220>C241>C240.This programme utilizes unsaponifiable matter such as sterol, high molecular alcohol, hydrocarbon, pigment
Unsaponifiable matter is removed in the adsorptive selectivity on atlapulgite surface with above-mentioned acid with liposoluble vitamin etc..Utilize above-mentioned four
The polarity difference of kind of acid, reasonably combined different solvents ratio, while increasing using gradient elution the separating degree of sample, reach and carries
The purpose of high separation yield and purity.
The mobile phase used in the technical program, 0-20min, with petroleum ether：Ethyl alcohol：Purified water ratio is 6：2：2 carry out
Elution, 20-50min, with petroleum ether：Ethyl alcohol：Ethyl acetate ratio is 5：3：2 are eluted.
Petroleum ether, ethyl alcohol, purifying aqueous polar size order in mobile phase, from big to small, purified water > ethyl alcohol > acetic acid
Ethyl ester is eluted in preceding 20min according to aforementioned proportion；
And below in 20-50min, with petroleum ether：Ethyl alcohol：Ethyl acetate ratio is 5：3：2 are eluted, polarity size
Sequentially it is：Ethyl alcohol > ethyl acetate > petroleum ethers, it is seen that the mobile phase polarity of 20-50min is less than the mobile phase pole of 0-20min
Property, according to similar compatibility principle, behenic acid, lignin acid, erucic acid solubility in the mobile phase in being dissolved in 0-20min are big,
It is eluted out first, then reduces the polarity of mobile phase, nervonic acid is easily dissolved in the low mobile phase of the polarity, to be eluted
Out.
Further, in order to preferably realize the present invention, chromatographic test strip part is in the step (3)：Octadecyl silicon
The silicagel column of alkane bonded silica gel filling is C18 columns, and C18 column packing grain sizes are 10-40um, internal diameter 100-500mm, column length
500—1000mm。
Further, it in order to preferably realize the present invention, is rotated in the step (5) to containing nervonic acid eluent
When, pressure is 50-100Pa.
Further, it in order to preferably realize the present invention, is rotated in the step (5) to containing nervonic acid eluent
When, temperature is 20-45 DEG C.
Further, in order to preferably realize the present invention, what the middle processing of the step (3) obtained contains nervonic acid eluent
Low-temp low-pressure revolving is carried out, solution is recycled, obtains by-product, purity is more than or equal to 35% erucic acid.Wherein, to containing erucic acid
When eluent is recycled, operating condition：Temperature is 20-45 DEG C, and pressure is 50-100Pa.
The present invention has the advantage that and advantageous effect：
(1) the technical program provides a kind of nervonic acid process for separation and purification, using ADSORPTION IN A FIXED BED, liquid chromatogram mobile
Gradient elution is mutually carried out, the nervonic acid in neural acid crude is efficiently separated with unsaponifiable matter, behenic acid, lignin acid, erucic acid,
And recycle, the rate of recovery effectively improves, and the nervonic acid purity after separation is high.Meanwhile by the implementation of this technique, it can effectively recycle production
Erucic acid in product reduces the waste yield of previous technique.
(2) the technical program takes the mode of ADSORPTION IN A FIXED BED, liquid phase elution, vapor detection to be combined, relative to existing
Technology can carry out a large amount of neural acid crudes in short cycle using processing modes such as distilation, dissolved purification, rectification and purifications
Operation, and low energy consumption for entire purification and separation process, can adapt to technology scale demand.
Description of the drawings
Fig. 1 is neural acid crude 1#GC test maps；
Fig. 2 is neural acid crude 2#GC test maps；
Fig. 3 is neural acid crude 3#GC test maps；
Fig. 4 is the technical program method flow schematic block diagram；
Fig. 5 is that neural acid crude 1# liquid phases elute nervonic acid GC test maps after separation in embodiment 1；
Fig. 6 is that neural acid crude 2# liquid phases elute nervonic acid GC test maps after separation in embodiment 2；
Fig. 7 is that neural acid crude 3# liquid phases elute nervonic acid GC test maps after separation in embodiment 3.
Specific implementation mode
To make the objectives, technical solutions, and advantages of the present invention clearer, with reference to embodiment, the present invention is made
Further to be described in detail, exemplary embodiment of the invention and its explanation are only used for explaining the present invention, are not intended as to this
The restriction of invention.
The rapeseed oil raw material containing nervonic acid is obtained into hydrolysis of passing through, distillation with reference to patent No. CN101760327A
2%-10% unsaponifiable matter, 50-70% erucic acid (C221), the behenic acid (C22 of 1-3%0), 3-10% lignin acid (C240)
Neural acid crude.Each batch raw material GC detected components GC testing results are as follows, as shown in Figure 1, Figure 2, Figure 3 shows,
| Batch number | C160 | C180 | C183 | C220 | C221 | C222 | C240 | C241 | Unsaponifiable matter | It is accumulative |
| 1# | 0.02 | 0.01 | 0.01 | 2.49 | 56.69 | 0.00 | 9.94 | 21.8 | 9.04 | 100 |
| 2# | 0.00 | 0.00 | 0.00 | 2.52 | 60.09 | 0.14 | 3.49 | 30.89 | 2.87 | 100 |
| 3# | 0.72 | 0.44 | 0.00 | 1.74 | 68.13 | 2.24 | 8.54 | 13.21 | 4.48 | 100 |
GC detections are carried out according to the raw material to tri- batches of neural acid crude 1#, 2#, 3#, can be analyzed, neural acid crude
In impurity contain 2%-10% unsaponifiable matter, 50-70% erucic acid C221, 1-3% behenic acid C220, 3-10% wood
Quality acid C240And 10% -40% nervonic acid C24 to be purified1, unsaponifiable matter by atlapulgite Adsorption, and its
Remaining impurity is eluted by eluent gradient due to its polar difference and is come out it according to certain sequentially eluting, according to successively
The sequence being eluted out is：Behenic acid and lignin acid, erucic acid, nervonic acid, according to following way of example to neural acid crude
Carry out separating-purifying.
Embodiment 1：
A kind of nervonic acid process for separation and purification, as shown in figure 4, the above-mentioned neural acid crude 1# of 20kg are taken, in 50 DEG C of items of normal pressure
After being handled by fixed bed (1L/min) under part, it is pumped into collecting tank.
It takes the above-mentioned collections of 2kg to fill interior sample, is separately added into a certain amount of preparation chromatogram flow phase, it is dense to obtain quality for constant volume
Degree prepares the total 20L of sample solution for 50g/L's.Above-mentioned sample is divided 5 times, 4L/ times, 30min/ times, is continuously pumped into high pressure 80atm
It prepares in chromatic spectrum sample feeder, carries out continuous sample introduction separation.
Above-mentioned preparation chromatography selects stainless steel chromatographic column, internal diameter 200mm, length 600mm, with octadecylsilane key
Silica gel is closed, grain size is that 10um-20um is stationary phase, is eluted according to following gradient elution program, 0-10min, with oil
Ether：Ethyl acetate：Purified water ratio is 7：2：1 is eluted, 10-30min, with petroleum ether：Ethyl acetate：Proportion of ethanol is
5：2：3 are eluted, elution flow rate 20L/min.The sample for collecting different retention times carries out low temperature to the sample of day part
Vacuum rotary steam, pressure 50Pa, are carried out at the same time GC tests by 20 DEG C, and the nervonic acid purity of final sample is up to 98.6%, total amount
420g, i.e., neural acid recovering rate are up to 96.3%.The erucic acid purity of by-product is 98.8%, and total amount 1120g, the rate of recovery reaches
98.8%.
Wherein, in the present embodiment, the mobile phase for dissolving neural acid crude is petroleum ether：Ethyl acetate：Purified water ratio is
7：2：1.
And the separating-purifying time is 30min in the present embodiment.
Fig. 5 is in the present embodiment, and neural acid crude 1# liquid phase separations go out nervonic acid GC test maps, nervonic acid after purification
The detection parameters of (nervonic acid 1# is expressed as in collection of illustrative plates) are：
| Component | Retention time | Peak area μ Vs | Peak height μ V | Content % |
| Nervonic acid | 11.337 | 1664669 | 16801 | 98.6 |
Embodiment 2：
A kind of nervonic acid process for separation and purification takes the above-mentioned neural acid crude 2# of 2kg, is separately added into a certain amount of preparation chromatography
Mobile phase, constant volume obtain mass concentration and prepare the total 10L of sample solution for 200g/L.By above-mentioned sample points 2 times, 5L/ times,
It is continuously pumped into high pressure 100atm and prepares in chromatic spectrum sample feeder for 20min/ times, carry out continuous sample introduction separation.
Above-mentioned preparation chromatography selects stainless steel chromatographic column, internal diameter 300mm, length 800mm, with octadecylsilane key
Conjunction silica gel is stationary phase, and grain size 5um-15um carries out gradient elution, 0-8min, with petroleum ether in the following order：Methanol：
Purified water ratio is 5：2：3 are eluted, 8-35min, with petroleum ether：Methanol：N-hexane ratio is 6：3：1 is eluted, and is washed
Separation of flow speed is 10L/min.Low-temperature reduced-pressure revolving, pressure 100Pa are carried out to the sample of day part, temperature is 30 DEG C, then into
Row GC tests, final sample nervonic acid purity are up to 96.1% up to 99.3%, total amount 594g, i.e., neural acid recovering rate.By-product
Erucic acid purity be 98.6%, total amount 1335g, the rate of recovery reaches 98.01%.
Wherein, in the present embodiment, the mobile phase of neural acid crude, specially petroleum ether are dissolved：Methanol：Purified water according to than
Example is 5：2：The liquid that 3 mixing obtain.
The neural acid crude separating-purifying time is 35min in the present embodiment.
Fig. 6 is in the present embodiment, and neural acid crude 2# liquid phase separations go out nervonic acid GC test maps, nervonic acid after purification
The detection parameters of (nervonic acid 2# is expressed as in collection of illustrative plates) are：
| Component | Retention time | Peak area μ Vs | Peak height μ V | Content % |
| Nervonic acid | 10.786 | 1689746 | 16975 | 99.3 |
Embodiment 3：
A kind of nervonic acid process for separation and purification takes the above-mentioned neural acid crude 2# of 2kg, is separately added into a certain amount of preparation chromatography
Mobile phase, constant volume obtain mass concentration and prepare the total 12.5L of sample solution for 400g/L.Above-mentioned sample is divided 20 times, 28L/
It is secondary, it 15min/ times, is continuously pumped into high pressure 120atm and prepares in chromatic spectrum sample feeder, carry out continuous sample introduction separation.
Above-mentioned preparation chromatography selects stainless steel chromatographic column, internal diameter 300mm, length 500mm, with octadecylsilane key
Silica gel is closed, grain size is that 5um-15um is stationary phase, and gradient elution, 0-20min, with oil are carried out using following mobile phase program
Ether：Ethyl alcohol：Purified water ratio is 6：2：2 are eluted, 20-50min, with petroleum ether：Ethyl alcohol：Ethyl acetate ratio is 5：3：2
It is eluted, elution flow rate 1L/min.Low-temperature reduced-pressure is carried out to the sample of day part and rotates 80Pa, 45 DEG C, is carried out at the same time GC
Test, the nervonic acid purity finally obtained are up to 96.6% up to 99.5%, total amount 255g, i.e., neural acid recovering rate.By-product
Erucic acid purity is 98.9%, and total amount 1342g, the rate of recovery reaches 98.53%.
Wherein, in the present embodiment, the mobile phase of neural acid crude, specially petroleum ether are dissolved：Ethyl alcohol：Ethyl acetate according to
Ratio is 6：3：The liquid that 1 mixing obtains.
The neural acid crude separating-purifying time is 58min in the present embodiment.
Fig. 7 is in the present embodiment, and neural acid crude 3# liquid phase separations go out nervonic acid GC test maps, nervonic acid after purification
The detection parameters of (nervonic acid 3# is expressed as in collection of illustrative plates) are：
| Component | Retention time | Peak area μ Vs | Peak height μ V | Content % |
| Nervonic acid | 10.695 | 1695152 | 16216 | 99.5 |
Comparative example 1：
A method of with Malania Oleifera Oil separating-purifying nervonic acid, including 8 steps, Step 1: saponification：Into retort
A concentration of 10% lye is added, reaction generates neural acid sodium-salt saponification liquor；Step 2: oil removing；Step 3: acid out：By saponification
Saline solution is added to acid out tank, and it is 6-7 to stir lower dropwise addition sulfuric acid to pH, and white is precipitated and mixes acid out liquid；Step 4: acid filtering：It will mix
It is put into the filter pocket for being covered with filter cloth with acid out liquid, filters off saltcake solution and remove wastewater disposal basin, collected spare after mixing acid heat water washing air-dries；
Step 5: ether dissolved；Step 6: acetone dissolved；Step 7: petroleum ether dissolved；Step 8: processing obtains nervonic acid.
The present invention uses ether, acetone and petroleum ether as three subcrystalline solvents, although obtained nervonic acid purity is only
85%, neural acid recovering rate is only 52%, and technique is cumbersome, and the production cycle is 2-3 days, and industrial production cost is high.
Comparative example 2：
A method of preparing nervonic acid using the rapeseed oil containing nervonic acid as raw material, this method is by by rapeseed oil high pressure
Hydrolysis obtains fatty acid mixed, fatty acid mixed rectifying is then obtained neural acid crude, finally by neural acid crude by having
Solvent crystallizes to obtain the neural acid product of 95% or more content, and therefrom obtains other Long carbon chain aliphatic acid.
This method increase the product categories of rapeseed oil deep processing, while using solvent crystallization from Long carbon chain aliphatic acid
Purification nervonic acid extends the raw material sources of nervonic acid to improve the value of the product of rapeseed oil.Itself the problem is that：
Still such as sterol, high molecular alcohol, the carbon of the unsaponifiable matter containing high level in using rapeseed oil as the neural acid crude that raw material produces
Hydrogen compound, pigment and liposoluble vitamin etc., repeatedly crystallization can not effectively remove unsaponifiable matter, and multiple crystallization processes are not
It is very low to only result in product yield, neural acid recovering rate only 20-30%, waste yield is big, and a large amount of erucic acid are not efficiently separated,
It can not directly recycle, and the production cycle grows 2-3 days, energy consumption height, cannot meet industrial scale production requirement.
Embodiment 1-3 can be obtained with the analysis of comparative example 1-2, compared with the existing technology nervonic acid process for separation and purification,
The liquid phase elution separation of use, the method for then carrying out vapor detection detach the nervonic acid of acquisition, and purity improves, and the rate of recovery carries
High 69% -75%, the production cycle foreshortens to 1h or even shorter, and can be conducive to industrialization large-scale production.In addition, passing through color
Compose the erucic acid (C22 obtained by separating-purifying1) purity it is also higher (>95%) industrial production raw material can, be directly used as.
Above-described specific implementation mode has carried out further the purpose of the present invention, technical solution and advantageous effect
It is described in detail, it should be understood that the foregoing is merely the specific implementation mode of the present invention, is not intended to limit the present invention
Protection domain, all within the spirits and principles of the present invention, any modification, equivalent substitution, improvement and etc. done should all include
Within protection scope of the present invention.
Claims (9)
1. a kind of nervonic acid process for separation and purification, which is characterized in that including following operating procedure,
(1) neural acid crude is obtained；
(2) the neural acid crude for obtaining step (1) removes unsaponifiable matter；
(3) the neural acid crude for obtaining step (2), is dissolved in chromatogram flow phase, constant volume, and it is 50-to obtain mass concentration
Above-mentioned sample is repeatedly continuously pumped into 80-120atm and prepared in chromatic spectrum sample feeder by the sample solution of 400g/L, continuous sample introduction point
From；
(4) sample after separation in step (3) is detected using GC gas-chromatography detection methods；
(5) eluent containing nervonic acid that step (3) processing obtains is subjected to low-temperature reduced-pressure revolving, recycling design obtains god
Through sour finished product.
2. a kind of nervonic acid process for separation and purification according to claim 1, which is characterized in that removal in the step (2)
The method that unsaponifiable matter uses in neural acid crude for：Using solid adsorbent bed, using atlapulgite as stationary phase, in normal pressure 35-
Under the conditions of 60 DEG C, processing speed is 1-10L/min.
3. a kind of nervonic acid process for separation and purification according to claim 1, which is characterized in that right in the step (3)
Sample solution carry out chromatography separating method in, be pumped into chromatic spectrum sample feeder, each sample size be 4-8L, 20-60min/ times.
4. a kind of nervonic acid process for separation and purification according to claim 1, which is characterized in that chromatography in the step (3)
Testing conditions are：Using octadecylsilane chemically bonded silica as stationary phase, with petroleum ether, n-hexane, ethyl acetate, ethyl alcohol, methanol,
Arbitrary three kinds of liquid in purified water is eluted as gradient elution mobile phase with the speed of 1L/min -20L/min.
5. a kind of nervonic acid process for separation and purification according to claim 4, which is characterized in that eluent gradient elution program
For：0-10min, with petroleum ether：Ethyl acetate：Purified water ratio is 7：2：1 is eluted, 10-30min, with petroleum ether：Second
Acetoacetic ester：Proportion of ethanol is 5：2：3 are eluted.
6. a kind of nervonic acid process for separation and purification according to claim 4, it is characterised in that：Eluent gradient elution program
For：0-8min, with petroleum ether：Methanol：Purified water ratio is 5：2：3 are eluted, 8-30min, with petroleum ether：Methanol：Just
Hexane ratio is 6：3：1 is eluted.
7. a kind of nervonic acid process for separation and purification according to claim 4, it is characterised in that：Eluent gradient elution program
For：0-20min, with petroleum ether：Ethyl alcohol：Purified water ratio is 6：2：2 are eluted, 20-50min, with petroleum ether：Ethyl alcohol：
Ethyl acetate ratio is 5：3：2 are eluted.
8. a kind of nervonic acid process for separation and purification according to claim 4, which is characterized in that chromatography in the step (2)
Testing conditions are：The silicagel column of octadecylsilane chemically bonded silica filling is C18 columns, and C18 column packing grain sizes are 10-40um, interior
Diameter 100-500mm, 500-1000mm of column length.
9. a kind of nervonic acid process for separation and purification according to claim 1, it is characterised in that：To containing in the step (5)
When having nervonic acid eluent to be rotated, pressure is 50-100Pa, and temperature is 20-45 DEG C.
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