CN110283034A - A method of obtaining high-purity squalene from plant oil deodorizing distillate - Google Patents
A method of obtaining high-purity squalene from plant oil deodorizing distillate Download PDFInfo
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Abstract
The method that the invention discloses a kind of to obtain high-purity squalene from plant oil deodorizing distillate, first carry out plant oil deodorizing distillate (DD oil) to be esterified/transesterification, crystallization and molecular distillation, obtain vitamin E and squalene mixture, the mixture carries out vitamin E absorption by strongly basic anionic resin, loading is carried out to resin with low-alcohol solution, it washes miscellaneous rear obtain and washes miscellaneous oil and efflux, wash it is miscellaneous oil and efflux it is concentrated after pass through saponification, crystallization, filtering, obtain the filtrate for being rich in squalene, filtrate passes through two-stage molecular distillation again, to obtain the squalene of high-purity.The present invention in high volume obtains the squalene of high-purity using the feasible mode of industry from DD oil, it can effectively solve the problems, such as that current squalene scarcity of raw material and the market demand are ever-increasing, vitamin E, fatty acid methyl ester, sterol are had also obtained simultaneously, DD oil resource is made full use of.
Description
Technical field
The invention belongs to the utilization technology fields of plant oil deodorizing distillate, and in particular to a kind of from vegetable oil deodorized
The method of squalene is obtained in distillate.
Background technique
Squalene is a kind of unsaturated straight chain triterpene compound of height, molecular formula C30H50, it is colourless or yellowish
Transparent oily liquid.Squalene has the multiple biological activities such as anti-oxidant, antitumor, anti-infective, rush cardiovascular and cerebrovascular health, in medicine
Using very extensive in product, cosmetics and field of health care products.Squalene source is mainly shark grease at present, at high price, because
This is badly in need of suitable raw material substitution to meet a large amount of market demand.Carrying out synthesis using chemical industry means squalene can yet be regarded as
A kind of effective solution scheme.But due to the particularity of its structure, cause reaction process process longer, and mostly use toxic
Chemical reagent, cause its with it is actual industrialization greatly differ from each other.
Plant oil deodorizing distillate (Deodorizer distillate, abbreviation DD oil) is vegetable oils by being deodorized
After process, the by-product as obtained from distillation and condensation, wherein mainly including fatty acid (30%~70%), glyceride
The ingredients such as (10%~15%), sterol (10%~35%), vitamin E (6%~13%), squalene (1%~3%), these
Ingredient all has very high economic use value.Due to containing squalene in DD oil, obtaining the ingredient from DD oil becomes
The emphasis of scientists study.
It is had been reported that currently, the research for extracting squalene from DD oil also more.Molecular distillation is a kind of based on different molecular
Mean free path difference is to reach the method for separation.Under high vacuum environment, since the mean free path of vapour molecule is greater than
The distance between evaporating surface and condensing surface, so as to be carried out using different component evaporation rate difference in solution to mixture
Separation.It is simple and easy to do due to the method, and facilitate industrialized production, therefore extract the phase of squalene from DD oil using this method
It is many to close patent report.Such as CN102089263A, CN107474093A, CN106890200A, CN105016956A and
Five patents of CN101830770A successively report the method for extracting squalene from DD oil using molecular distillation method.As a result it shows
Show, high yield, low cost and efficient effect can be reached using the method.But due to squalene physicochemical property itself and DD
Remaining substance (vitamin E, sterol) present in oil has similarity, therefore is difficult to reach height by molecular distillation merely
The effect (purity that existing patent is reported is ≤40%) of purifying, can only be as a kind of means of pre-processing.
Due to the continuous development of chromatographic technique, the method for high-purity squalene is obtained also by scientist using column chromatography mode
Use.Silver nitrate silica gel chromatography is then used in CN104262076B, mobile phase is hydrocarbon/ester gradient elution, to obtain
The squalene of high-purity (>=90%).CN105016956A and CN103708992B is then to first pass through anion exchange resin to remove
It is miscellaneous, then squalene is obtained by silica gel or chromatography on alumina mode.It is available using chromatography mode compared to molecularly distilled
The squalene of higher purity.But this method is only using the squalene after the enrichment of remaining method to the more demanding of raw material
(purity 20%~30%) carries out the purity that column chromatography can reach satisfied again；Secondly, silica gel and aluminum oxide column chromatography itself
With consumption organic solvent amount is excessive, column volume containing the sample is limited, column length increase causes column pressure to increase substantially, filler consumption is big and
The problems such as it is difficult to recycle, it is difficult to carry out industrialization promotion, can only realize in laboratory level.
To sum up, the extraction purification at present for squalene in DD oil mainly includes molecular distillation and two kinds of column chromatography.This
Still there are the methods of high efficiency countercurrent chromatography, supercritical extract outside, but these methods are unsatisfactory on practicability, it is difficult to carry out big
The production of batch.Above-mentioned summary is seen, there has been no the suitable techniques for producing high-purity squalene in enormous quantities.In addition, due to DD oil
In with the ingredient of economic value be not only limited to squalene, further include a large amount of fatty acid, glyceride, sterol and vitamin E,
Therefore, the extraction together for considering such components simultaneously is also needed when squalene extracts.
Summary of the invention
The method that the object of the present invention is to provide a kind of to obtain high-purity squalene from plant oil deodorizing distillate, solves
Deodorization distillate efficiently use the problem of, improve prior art present in poor efficiency, high pollution, multi-step the problems such as.
For above-mentioned purpose, the technical solution adopted by the present invention is made of following step:
1, the preliminary concentration of squalene
Plant oil deodorizing distillate is mixed with methanol and carries out esterification and ester exchange reaction, carries out low temperature knot after reaction
Crystalline substance, collects crystal, and remaining liquid phase object is continued by level-one film distillator and second level short-distance distiller distillation purifying, obtained heavy phase
Using three-level short-distance distiller and level Four short-distance distiller distillation purifying, the mixture of squalene and vitamin E is obtained.
2, squalene is separated with vitamin E
It with lower alcohol is by volume that 1:1~1:2 is mixed by the mixture of gained squalene and vitamin E in step 1
It closes, gained mixed liquor is pumped into strongly basic anionic resin exchange column, when content of vitamin E in efflux >=0.5%, in stopping
Sample rinses column bed with lower alcohol, washes after miscellaneous liquid merges with efflux using film distillator in 400~600Pa of vacuum degree, temperature
It is distilled at 110~120 DEG C of degree, charging rate is 30~50L/min, and light phase is pumped into lower alcohol receiving tank, and heavy phase is pumped into slightly
In squalene tank；Wherein the lower alcohol is methanol or ethyl alcohol.
3, thick squalene saponification and crystallization
NaOH the or KOH aqueous solution of heavy phase and mass concentration 15%~30% in thick squalene tank is pressed into quality-volume
Than being mixed for 1kg:1.5~2.5L, reflux saponification 3~5 hours at 60~70 DEG C；After being saponified, extracted with organic solvent
It takes, organic phase crystallize 2~4 hours at 4~10 DEG C after vacuum distillation concentration, filtering, is crystallized and filtrate.
4, the acquisition of high-purity squalene
Gained filtrate in step 3 is subjected to distillation purifying by level-one film distillator and second level short-distance distiller, is obtained
The squalene of purity >=95%, the condition that wherein level-one film distillator distills are as follows: 30~50L/min of charging rate, vacuum degree
100~200Pa, 90~120 DEG C of temperature, the condition of second level short-distance distiller distillation are as follows: 2~8L/min of charging rate, vacuum degree 1
~5Pa, 250~280 DEG C of temperature.
It is preferably 1:4~1:7 according to the volume ratio of plant oil deodorizing distillate and methanol, by vegetable oil in above-mentioned steps 1
Deodorization distillate and methanol pass through high-pressure pump and are pumped into level-one preheater respectively, are mixed in a mixer after being preheated to 45~60 DEG C
It closes, gained mixture is pumped into the tubular type filled with catalyst granules and fixes after second level pre-heater is heated to 290~310 DEG C
Bed reactor, carried out in the case where temperature is 290~310 DEG C, pressure is 15~20MPa esterification and ester exchange reaction, the reaction time 5~
10min；After reaction, for reaction product through gas-liquid separator, flash distillation dryer, light phase flows back to methanol original through cooling de-watering again
Batch can secondary use, heavy phase enter water scrubber and are eluted, and subsequently enter liquid-liquid disc centrifuge and separated, wherein
Water phase is recovered to obtain crude glycerine, and oil passes through Horizontal crystallizer after being mutually precooled to 60~70 DEG C, low whipping speed is 10~15
Turn/min under after gradient crystallisation by cooling, temperature drop to 5~10 DEG C；Material is pumped into horizontal spiral centrifuge after crystallization, centrifugation
The solid crystal obtained afterwards is sterol, and remaining liquid phase material is pumped into level-one film distillator after centrifugation, charging rate is 30~
40L/min is distilled at 100~200Pa of vacuum degree, 140~150 DEG C of temperature, and light phase is pumped into biodiesel receiving tank, weight
Mutually be pumped into second level short-distance distiller, charging rate is 9~12L/min, at 30~40Pa of vacuum degree, 170~180 DEG C of temperature into
Row distillation, light phase are pumped into biodiesel receiving tank, and remaining heavy phase material is pumped into three-level short-distance distiller, 6~8L/ of charging rate
Min is distilled at 5~8Pa of vacuum degree, 230~240 DEG C of temperature, and light phase is pumped into squalene/vitamin E mixing receiving tank,
Heavy phase is pumped into level Four short-distance distiller, and 2~4L/min of charging rate is carried out at 1~2Pa of vacuum degree, 270~280 DEG C of temperature
Distillation, light phase are pumped into squalene/vitamin E mixing receiving tank, obtain the mixture of squalene and vitamin E, remaining heavy phase pump
Enter Residual Oil Tank.
Above-mentioned catalyst granules includes calcium oxide, titanium dioxide, manganese dioxide, magnesia, solid mesoporous of zinc oxide
Grain.
In above-mentioned steps 2, preferably by volume by the mixture and lower alcohol of gained squalene and vitamin E in step 1
It is mixed for 1:1~1:1.5, gained mixed liquor is pumped into strongly basic anionic resin exchange column, contains to vitamin E in efflux
When amount >=0.5%, stop loading, rinse column bed with lower alcohol, washes after miscellaneous liquid merges with efflux and existed using film distillator
400~500Pa of vacuum degree, it is distilled at 110~120 DEG C of temperature, charging rate is 30~40L/min, and light phase is pumped into rudimentary
Alcohol receiving tank, heavy phase are pumped into thick squalene tank.
In above-mentioned steps 2, strongly basic anionic resin exchange column end after further being rinsed to lower alcohol with 30~
The rate of 40L/min is passed through carbon dioxide gas and is desorbed, and continues 1~2h, reuses lower alcohol and is eluted, and eluent steams
Vitamin E is obtained after dry.
In above-mentioned steps 2, the preferred macroporous strong basic styrene series anion tree of strongly basic anionic resin exchange column
Ester exchange column.
In above-mentioned steps 3, the organic solvent is n-hexane, hexamethylene, methylene chloride, ethyl acetate, any in ether
It is a kind of.
In above-mentioned steps 3, the condition of concentration is preferably evaporated in vacuo are as follows: 400~600Pa of vacuum degree, 100~110 DEG C of temperature,
It is concentrated into the 1/3~1/4 of original machine phase volume.
In above-mentioned steps 4, preferably level-one film distillator distillation condition are as follows: 30~40L/min of charging rate, vacuum degree
The condition of 100~110 DEG C of 100~150Pa, temperature, preferably second level short-distance distiller distillation are as follows: 2~4L/min of charging rate, true
270~280 DEG C of 1~3Pa of reciprocal of duty cycle, temperature.
Plant oil deodorizing distillate of the present invention is that oil crops are de- after squeezing, degumming, alkali refining, decoloration, dewaxing
Any one in smelly distillate, including soybean oil, olive oil, cottonseed oil, corn oil, rapeseed oil, peanut oil, palm oil or two kinds
Above deodorization distillate.
Beneficial effects of the present invention are as follows:
1, the present invention obtains the squalene of high-purity using the feasible mode of industry from DD oil, gets rid of conventional method
The problems such as " small scale ", " purity is low ", convenient for its large-scale production.
2, the invention proposes a kind of method in high volume obtaining squalene from DD oil, current squalene can effectively be solved
Scarcity of raw material and the ever-increasing problem of the market demand.
3, the present invention to DD oil carry out continuous treatment, obtain including squalene multiple products (vitamin E,
Fatty acid methyl ester, sterol), DD oil resource is made full use of.
Detailed description of the invention
Fig. 1 is process flow chart of the invention.
Fig. 2 is the gas chromatographic detection figure of 1 gained high-purity squalene of embodiment.
Specific embodiment
The present invention is described in more detail with reference to the accompanying drawings and examples, but protection scope of the present invention is not limited only to
These embodiments.
Embodiment 1
Process flow according to figure 1, obtains squalene from plant oil deodorizing distillate, and the specific method is as follows:
1, the preliminary concentration of squalene
It is 1:4 according to the volume ratio of plant oil deodorizing distillate and methanol, soybean oil deodorizer distillate (is contained 49.3%
Free fatty acid, 12.5% glyceride, 26.2% phytosterol, 10.8% vitamin E, 2.2% squalene) it is set respectively with methanol
In in two head tanks, it is pumped into level-one pre-heater respectively by high-pressure pump, enters in mixer after being preheated to 55 DEG C and mixed
It closes, gained mixture is pumped into the tubular type filled with magnesia catalyst particle and fixes after second level pre-heater is heated to 294 DEG C
Bed reactor carries out esterification and ester exchange reaction, and reaction temperature is 300 DEG C, pressure 15MPa, reaction time 5min.Reaction
After, reaction product enters gas-liquid separator and carries out gas-liquid separation, and liquid is pumped into flash distillation dryer and carries out expansion drying, flash distillation
Temperature is 110 DEG C, and light phase flows back to methanol feedstock tank through cooling de-watering again makees secondary use.Remaining heavy phase enters water scrubber progress
Elution, and subsequently enter the separation that liquid-liquid disc centrifuge carries out grease phase, the water phase isolated is recovered obtain it is thick sweet
Oil, oil pass through Messo type Horizontal crystallizer after being mutually precooled to 60 DEG C and carry out gradient crystallisation by cooling.The horizontal knot of Messo type
Brilliant device be it is a kind of with refrigeration and mixing plant horizontal long cylinder, inside be made of 12 concatenated temperature control compartments, setting the 1st every
The temperature of room to the 12nd compartment is followed successively by 60 DEG C, 55 DEG C, 50 DEG C, 45 DEG C, 40 DEG C, 35 DEG C, 30 DEG C, 25 DEG C, 20 DEG C, 15 DEG C, 10
DEG C, 5 DEG C, mixing speed be 15 turns/min.Material after crystallization is pumped into horizontal spiral centrifuge, obtains the steroid that purity is 75.1%
Alcohol crystals, yield 96.9%.Lighter remaining liquid phase material is pumped into level-one film distillator, charging rate 35L/ after centrifugation
Min is distilled at vacuum degree 100Pa, 145 DEG C of temperature, and the light phase that level-one distillation obtains is pumped into biodiesel receiving tank, weight
It is mutually pumped into second level short-distance distiller, charging rate 10L/min is distilled, second level at vacuum degree 30Pa, 175 DEG C of temperature
The light phase that distillation obtains is pumped into biodiesel receiving tank, and remaining heavy phase material is pumped into three-level short-distance distiller, charging rate 7L/
Min is distilled at vacuum degree 5Pa, 235 DEG C of temperature, and the light phase that three-stage distillation obtains is pumped into squalene/vitamin E mixing
Receiving tank, heavy phase are pumped into level Four short-distance distiller, and charging rate 3L/min is distilled at vacuum degree 1Pa, 275 DEG C of temperature,
The light phase that Four-stage distillation obtains is pumped into squalene/vitamin E mixing receiving tank, and remaining heavy phase is pumped into Residual Oil Tank.The level-one is thin
The main component of membrane distiller and second level short-distance distiller distillation gained light phase is fatty acid methyl ester (biodiesel), vitamin E
Content≤0.5%, biodiesel purity are 98.5%, yield 95.0%.The three-level short-distance distiller and level Four short-path distillation
The main component of device distillation gained light phase is vitamin E and squalene, squalene in the light phase that wherein three-level short-path distillation obtains
Content >=30%, level Four short-path distillation obtain heavy phase in squalene content≤0.5%.
2, squalene is separated with vitamin E
By gained squalene and the mixture of vitamin E and the ethyl alcohol of purity >=95% in step 1 be by volume 1:1 into
Row mixing, gained mixed liquor is pumped into D201 macroporous strong basic styrene series resin anion (R.A.) exchange column, to vitamin E in efflux
When content >=0.5%, stop loading.If content of vitamin E >=0.5% in efflux, can pass through repeatedly as material liquid new
D201 macroporous strong basic styrene series resin anion (R.A.) exchange column, until the inside content of vitamin E≤0.5%.Then with three
The ethyl alcohol of purity >=95% of times column volume rinses column bed, by efflux and rinses and washes miscellaneous liquid obtained by column bed (rich in spiny dogfish
The yellow solution of alkene and residual impurity) merge after steamed at vacuum degree 500Pa, 110 DEG C of temperature using film distillator
It evaporates, charging rate 30L/min, light phase is pumped into lower alcohol receiving tank, and heavy phase is pumped into thick squalene tank, and squalene is pure in heavy phase
Degree >=50%.D201 macroporous strong basic styrene series resin anion (R.A.) exchange column end after being rinsed to the ethyl alcohol of purity >=95%
Carbon dioxide gas 1h is passed through with the rate of 30L/min to be desorbed, and the ethyl alcohol of purity >=95% of one times of column volume is reused
It is eluted, eluent obtains vitamin E, purity 97.3%, yield 97.7% after being evaporated.
3, thick squalene saponification and crystallization
The NaOH aqueous solution of heavy phase and mass concentration 20% in thick squalene tank is mixed by quality-volume ratio for 1kg:2L
It closes, reflux saponification 3 hours at 60 DEG C；After being saponified, just with 4 times of volumes of NaOH aqueous solution with mass concentration 20% used
Hexane extracts three times respectively.Merge the organic phase extracted three times, vacuum steaming is carried out in the case where vacuum degree is 500Pa, temperature is 110 DEG C
Concentration is evaporated, the 1/3 of original machine phase volume is concentrated into.Then concentrate is crystallized 2 hours at 10 DEG C, filter, obtain crystallization and
Filtrate, the main component of crystallization are sterol, purity 94.3%.
4, the acquisition of high-purity squalene
Gained filtrate in step 3 is subjected to distillation purifying by level-one film distillator and second level short-distance distiller, wherein
The condition of level-one film distillator distillation are as follows: charging rate 35L/min, vacuum degree 100Pa, 110 DEG C of temperature, second level short-path distillation
The condition of device distillation are as follows: charging rate 2L/min, vacuum degree 5Pa, 250 DEG C of temperature are obtained high-purity squalene (see Fig. 2), pure
Degree 95.1%, yield 91.3%.
Embodiment 2
Process flow according to figure 1, obtains squalene from plant oil deodorizing distillate, and the specific method is as follows:
1, the preliminary concentration of squalene
It is 1:4 according to the volume ratio of plant oil deodorizing distillate and methanol, olive oil deodorization distillate (is contained 54.5%
Free fatty acid, 10.1% glyceride, 14.4% phytosterol, 12.5% vitamin E, 3.9% squalene) it is set respectively with methanol
In in two head tanks, it is pumped into level-one pre-heater respectively by high-pressure pump, enters in mixer after being preheated to 50 DEG C and mixed
It closes, gained mixture is pumped into the tubular type filled with magnesia catalyst particle and fixes after second level pre-heater is heated to 300 DEG C
Bed reactor carries out esterification and ester exchange reaction, and reaction temperature is 310 DEG C, pressure 16MPa, reaction time 6min.Reaction
After, reaction product enters gas-liquid separator and carries out gas-liquid separation, and liquid is pumped into flash distillation dryer and carries out expansion drying, flash distillation
Temperature is 110 DEG C, and light phase flows back to methanol feedstock tank through cooling de-watering again makees secondary use.Remaining heavy phase enters water scrubber progress
Elution, and subsequently enter the separation that liquid-liquid disc centrifuge carries out grease phase, the water phase isolated is recovered obtain it is thick sweet
Oil, oil pass through Messo type Horizontal crystallizer after being mutually precooled to 60 DEG C and carry out gradient crystallisation by cooling.The horizontal knot of Messo type
Brilliant device be it is a kind of with refrigeration and mixing plant horizontal long cylinder, inside be made of 12 concatenated temperature control compartments, setting the 1st every
The temperature of room to the 12nd compartment is followed successively by 60 DEG C, 55 DEG C, 50 DEG C, 45 DEG C, 40 DEG C, 35 DEG C, 30 DEG C, 25 DEG C, 20 DEG C, 15 DEG C, 10
DEG C, 5 DEG C, mixing speed be 15 turns/min.Material after crystallization is pumped into horizontal spiral centrifuge, obtains the steroid that purity is 67.1%
Alcohol crystals, yield 94.3%.Lighter remaining liquid phase material is pumped into level-one film distillator, charging rate 40L/ after centrifugation
Min is distilled at vacuum degree 160Pa, 150 DEG C of temperature, and the light phase that level-one distillation obtains is pumped into biodiesel receiving tank, weight
It is mutually pumped into second level short-distance distiller, charging rate 12L/min is distilled, second level at vacuum degree 40Pa, 180 DEG C of temperature
The light phase that distillation obtains is pumped into biodiesel receiving tank, and remaining heavy phase material is pumped into three-level short-distance distiller, charging rate 8L/
Min is distilled at vacuum degree 8Pa, 240 DEG C of temperature, and the light phase that three-stage distillation obtains is pumped into squalene/vitamin E mixing
Receiving tank, heavy phase are pumped into level Four short-distance distiller, and charging rate 3.5L/min is steamed at vacuum degree 1Pa, 280 DEG C of temperature
It evaporates, the light phase that Four-stage distillation obtains is pumped into squalene/vitamin E mixing receiving tank, and remaining heavy phase is pumped into Residual Oil Tank.The level-one
The main component of film distillator and second level short-distance distiller distillation gained light phase is fatty acid methyl ester (biodiesel), vitamin
E content≤0.5%, biodiesel purity are 94.3%, yield 94.0%.The three-level short-distance distiller and level Four short-path distillation
The main component of device distillation gained light phase is vitamin E and squalene, squalene in the light phase that wherein three-level short-path distillation obtains
Content >=30%, level Four short-path distillation obtain heavy phase in squalene content≤0.5%.
2, squalene is separated with vitamin E
It is by volume 1:1.2 by gained squalene in step 1 and the mixture of vitamin E and the ethyl alcohol of purity >=95%
It is mixed, gained mixed liquor is pumped into 201 × 7 macroporous strong basic styrene series resin anion (R.A.) exchange columns, to tie up in efflux
When raw element E content >=0.5%, stopping loading.It, can be repeatedly logical as material liquid if content of vitamin E >=0.5% in efflux
201 × 7 new macroporous strong basic styrene series resin anion (R.A.) exchange columns are crossed, until the inside content of vitamin E≤0.5%.So
Column bed is rinsed with the ethyl alcohol of purity >=95% of three times column volume afterwards, it is (rich by miscellaneous liquid is washed obtained by efflux and flushing column bed
Yellow solution containing squalene and residual impurity) merge after using film distillator at vacuum degree 550Pa, 115 DEG C of temperature
It is distilled, charging rate 35L/min, light phase is pumped into lower alcohol receiving tank, and heavy phase is pumped into thick squalene tank, angle in heavy phase
Squalene purity >=50%；201 × 7 macroporous strong basic styrene series resin anion (R.A.)s after rinsing to the ethyl alcohol of purity >=95% are handed over
Change column end carbon dioxide gas 1h be passed through with the rate of 30L/min and desorbed, reuse the purity of one times of column volume >=
95% ethyl alcohol is eluted, and eluent obtains vitamin E, purity 98.9%, yield 98.1% after being evaporated.
3, thick squalene saponification and crystallization
It is 1kg:2.5L that the NaOH aqueous solution of heavy phase and mass concentration 15% in thick squalene tank, which is pressed quality-volume ratio,
Mixing, reflux saponification 4 hours at 60 DEG C；After being saponified, with 4 times of bodies of NaOH aqueous solution with mass concentration 15% used
Long-pending ethyl acetate extracts three times respectively.Merge the organic phase that extracts three times, in the case where vacuum degree is 500Pa, temperature is 110 DEG C into
Row vacuum distillation concentration, is concentrated into the 1/3 of original machine phase volume.Then concentrate is crystallized 2 hours at 10 DEG C, filters, obtains
To crystallization and filtrate, the main component of crystallization is sterol, purity 92.2%.
4, the acquisition of high-purity squalene
Gained filtrate in step 3 is subjected to distillation purifying by level-one film distillator and second level short-distance distiller, wherein
The condition of level-one film distillator distillation are as follows: charging rate 30L/min, vacuum degree 120Pa, 100 DEG C of temperature, second level short-path distillation
The condition of device distillation are as follows: charging rate 3L/min, vacuum degree 2Pa, 275 DEG C of temperature obtain 96.1% squalene of purity, yield
95.9%.
Embodiment 3
Process flow according to figure 1, obtains squalene from plant oil deodorizing distillate, and the specific method is as follows:
1, the preliminary concentration of squalene
It is 1:4 according to the volume ratio of plant oil deodorizing distillate and methanol, corn oil deodorization distillate (is contained 61.3%
Free fatty acid, 11.0% glyceride, 15.1% phytosterol, 9.9% vitamin E, 1.5% squalene) it is set respectively with methanol
In in two head tanks, it is pumped into level-one pre-heater respectively by high-pressure pump, enters in mixer after being preheated to 48 DEG C and mixed
It closes, gained mixture is pumped into the tubular type filled with magnesia catalyst particle and fixes after second level pre-heater is heated to 300 DEG C
Bed reactor carries out esterification and ester exchange reaction, and reaction temperature is 305 DEG C, pressure 18MPa, reaction time 7min.Reaction
After, reaction product enters gas-liquid separator and carries out gas-liquid separation, and liquid is pumped into flash distillation dryer and carries out expansion drying, flash distillation
Temperature is 110 DEG C, and light phase flows back to methanol feedstock tank through cooling de-watering again makees secondary use.Remaining heavy phase enters water scrubber progress
Elution, and subsequently enter the separation that liquid-liquid disc centrifuge carries out grease phase, the water phase isolated is recovered obtain it is thick sweet
Oil, oil pass through Messo type Horizontal crystallizer after being mutually precooled to 65 DEG C and carry out gradient crystallisation by cooling.The horizontal knot of Messo type
Brilliant device be it is a kind of with refrigeration and mixing plant horizontal long cylinder, inside be made of 12 concatenated temperature control compartments, setting the 1st every
The temperature of room to the 12nd compartment is followed successively by 55 DEG C, 50 DEG C, 46 DEG C, 42 DEG C, 38 DEG C, 34 DEG C, 30 DEG C, 26 DEG C, 22 DEG C, 18 DEG C, 14
DEG C, 10 DEG C, mixing speed be 15 turns/min.Material after crystallization is pumped into horizontal spiral centrifuge, obtaining purity is 71.7%
Sterol crystals, yield 94.0%.Lighter remaining liquid phase material is pumped into level-one film distillator, charging rate 30L/ after centrifugation
Min is distilled at vacuum degree 120Pa, 140 DEG C of temperature, and the light phase that level-one distillation obtains is pumped into biodiesel receiving tank, weight
It is mutually pumped into second level short-distance distiller, charging rate 9L/min is distilled at vacuum degree 35Pa, 180 DEG C of temperature, and second level is steamed
The light phase for evaporating acquisition is pumped into biodiesel receiving tank, and remaining heavy phase material is pumped into three-level short-distance distiller, charging rate 6L/min,
It is distilled at vacuum degree 6Pa, 240 DEG C of temperature, the light phase that three-stage distillation obtains is pumped into squalene/vitamin E mixing and receives
Tank, heavy phase are pumped into level Four short-distance distiller, and charging rate 2.5L/min is distilled at vacuum degree 1.5Pa, 280 DEG C of temperature,
The light phase that Four-stage distillation obtains is pumped into squalene/vitamin E mixing receiving tank, and remaining heavy phase is pumped into Residual Oil Tank.The level-one is thin
The main component of membrane distiller and second level short-distance distiller distillation gained light phase is fatty acid methyl ester (biodiesel), vitamin E
Content≤0.5%, biodiesel purity are 97.2%, yield 95.1%.The three-level short-distance distiller and level Four short-path distillation
The main component of device distillation gained light phase is vitamin E and squalene, squalene in the light phase that wherein three-level short-path distillation obtains
Content >=30%, level Four short-path distillation obtain heavy phase in squalene content≤0.5%.
2, squalene is separated with vitamin E
It is by volume 1:1.5 by gained squalene in step 1 and the mixture of vitamin E and the methanol of purity >=95%
It is mixed, gained mixed liquor is pumped into Diaion SA-10A macroporous strong basic styrene series resin anion (R.A.) exchange column, wait flow out
When content of vitamin E in liquid >=0.5%, stop loading.It, can be repeatedly as original if content of vitamin E >=0.5% in efflux
Feed liquid is by new Diaion SA-10A macroporous strong basic styrene series resin anion (R.A.) exchange column, until the inside vitamin E contains
Amount≤0.5%.Column bed is rinsed with the methanol of purity >=95% of three times column volume, efflux is washed with column bed gained is rinsed
Miscellaneous liquid (yellow solution rich in squalene and residual impurity) uses film distillator in vacuum degree 450Pa, temperature after merging
It is distilled at 120 DEG C, charging rate 40L/min, light phase is pumped into lower alcohol receiving tank, and heavy phase is pumped into thick squalene tank,
Squalene purity >=50% in heavy phase.Diaion SA-10A macroporous strong basic benzene second after being rinsed to the methanol of purity >=95%
Alkene series anion resin-column end is passed through carbon dioxide gas 2h with the rate of 30L/min and is desorbed, and reuses one times
The methanol of purity >=95% of column volume is eluted, and eluent obtains vitamin E, purity 99.0%, yield after being evaporated
94.3%.
3, thick squalene saponification and crystallization
The KOH aqueous solution of heavy phase and mass concentration 20% in thick squalene tank is mixed by quality-volume ratio for 1kg:2L
It closes, reflux saponification 5 hours at 70 DEG C；After being saponified, with 5 times of volumes of KOH aqueous solution with mass concentration 20% used
Hexamethylene extract respectively three times.Merge the organic phase extracted three times, is carried out in the case where vacuum degree is 400Pa, temperature is 100 DEG C true
Empty distillation and concentration is concentrated into the 1/4 of original machine phase volume.Then concentrate is crystallized 3 hours at 10 DEG C, filters, is tied
Brilliant and filtrate, the main component of crystallization are sterol, purity 93.7%.
4, the acquisition of high-purity squalene
Gained filtrate in step 3 is subjected to distillation purifying by level-one film distillator and second level short-distance distiller, wherein
The condition of level-one film distillator distillation are as follows: charging rate 30L/min, vacuum degree 130Pa, 110 DEG C of temperature, second level short-path distillation
The condition of device distillation are as follows: charging rate 2L/min, vacuum degree 3Pa, 280 DEG C of temperature obtain 95.4% squalene of purity, yield
93.3%.
Claims (10)
1. a kind of method for obtaining high-purity squalene from plant oil deodorizing distillate, it is characterised in that:
(1) preliminary concentration of squalene
Plant oil deodorizing distillate is mixed with methanol and carries out esterification and ester exchange reaction, carries out low temperature crystallization after reaction,
Crystal is collected, remaining liquid phase object continues to adopt by level-one film distillator and second level short-distance distiller distillation purifying, obtained heavy phase
With three-level short-distance distiller and level Four short-distance distiller distillation purifying, the mixture of squalene and vitamin E is obtained；
(2) squalene is separated with vitamin E
It with the mixture of vitamin E with lower alcohol is by volume that 1:1~1:2 is mixed by gained squalene in step (1),
Gained mixed liquor is pumped into strongly basic anionic resin exchange column, when content of vitamin E in efflux >=0.5%, stops loading,
Column bed is rinsed with lower alcohol, is washed after miscellaneous liquid merges with efflux using film distillator in 400~600Pa of vacuum degree, temperature
It is distilled at 110~120 DEG C, charging rate is 30~50L/min, and light phase is pumped into lower alcohol receiving tank, and heavy phase is pumped into thick angle
In squalene tank；Wherein the lower alcohol is methanol or ethyl alcohol；
(3) thick squalene saponification and crystallization
NaOH or KOH aqueous solution by heavy phase and mass concentration 15%~30% in thick squalene tank is by quality-volume ratio
1kg:1.5~2.5L mixing, reflux saponification 3~5 hours at 60~70 DEG C；It after being saponified, is extracted, is had with organic solvent
Machine mutually crystallize 2~4 hours at 4~10 DEG C after vacuum distillation concentration, filtering, is crystallized and filtrate；
(4) acquisition of high-purity squalene
Gained filtrate in step (3) is subjected to distillation purifying by level-one film distillator and second level short-distance distiller, is obtained pure
The squalene of degree >=95%, the condition that wherein level-one film distillator distills are as follows: 30~50L/min of charging rate, vacuum degree 100
~200Pa, 90~120 DEG C of temperature, the condition of second level short-distance distiller distillation are as follows: 2~8L/min of charging rate, vacuum degree 1~
5Pa, 250~280 DEG C of temperature.
2. the method according to claim 1 for obtaining high-purity squalene from plant oil deodorizing distillate, feature exist
In: it is 1:4~1:7 according to the volume ratio of plant oil deodorizing distillate and methanol, by plant oil deodorizing distillate in step (1)
With methanol level-one preheater is pumped by high-pressure pump respectively, is mixed in a mixer after being preheated to 45~60 DEG C, gained is mixed
Material is closed after second level pre-heater is heated to 290~310 DEG C, is pumped into the tubular fixed-bed reactor filled with catalyst granules,
Esterification and ester exchange reaction, 5~10min of reaction time are carried out in the case where temperature is 290~310 DEG C, pressure is 15~20MPa；Instead
After answering, for reaction product through gas-liquid separator, flash distillation dryer, it is secondary that light phase flows back to methanol feedstock tank through cooling de-watering again
It utilizes, heavy phase enters water scrubber and eluted, and subsequently enters liquid-liquid disc centrifuge and separated, and wherein water phase passes through back
Receipts obtain crude glycerine, and oil passes through Horizontal crystallizer after being mutually precooled to 60~70 DEG C, low whipping speed is under 10~15 turns/min
The gradient crystallisation by cooling after, temperature drop to 5~10 DEG C；Material is pumped into horizontal spiral centrifuge after crystallization, obtains after centrifugation
Solid crystal is sterol, and remaining liquid phase material is pumped into level-one film distillator after centrifugation, and charging rate is 30~40L/min,
100~200Pa of vacuum degree, it is distilled at 140~150 DEG C of temperature, light phase is pumped into biodiesel receiving tank, and heavy phase is pumped into second level
Short-distance distiller, charging rate are 9~12L/min, are distilled at 30~40Pa of vacuum degree, 170~180 DEG C of temperature, gently
It is mutually pumped into biodiesel receiving tank, remaining heavy phase material is pumped into three-level short-distance distiller, 6~8L/min of charging rate, in vacuum
5~8Pa of degree, it is distilled at 230~240 DEG C of temperature, light phase is pumped into squalene/vitamin E mixing receiving tank, and heavy phase is pumped into four
Grade short-distance distiller, 2~4L/min of charging rate are distilled at 1~2Pa of vacuum degree, 270~280 DEG C of temperature, light phase pump
Enter squalene/vitamin E mixing receiving tank, obtains the mixture of squalene and vitamin E, remaining heavy phase is pumped into Residual Oil Tank.
3. the method according to claim 2 for obtaining high-purity squalene from plant oil deodorizing distillate, feature exist
In: the catalyst granules includes the solid mesoporous particles of calcium oxide, titanium dioxide, manganese dioxide, magnesia, zinc oxide.
4. the method according to claim 1 for obtaining high-purity squalene from plant oil deodorizing distillate, feature exist
In: in step (2), mixture and lower alcohol by gained squalene and vitamin E in step (1) are 1:1~1 by volume:
1.5 are mixed, and gained mixed liquor is pumped into strongly basic anionic resin exchange column, to content of vitamin E >=0.5% in efflux
When, stop loading, rinse column bed with lower alcohol, washes after miscellaneous liquid merges with efflux using film distillator in vacuum degree 400
~500Pa, it is distilled at 110~120 DEG C of temperature, charging rate is 30~40L/min, and light phase is pumped into lower alcohol receiving tank,
Heavy phase is pumped into thick squalene tank.
5. the method according to claim 4 for obtaining high-purity squalene from plant oil deodorizing distillate, feature exist
In: the strongly basic anionic resin exchange column end after rinsing to lower alcohol is passed through carbon dioxide with the rate of 30~40L/min
Gas is desorbed, and 1~2h is continued, and is reused lower alcohol and is eluted, and eluent obtains vitamin E after being evaporated.
6. the method according to claim 1 for obtaining high-purity squalene from plant oil deodorizing distillate, feature exist
In: in step (2), the strongly basic anionic resin exchange column is macroporous strong basic styrene series resin anion (R.A.) exchange column.
7. the method according to claim 1 for obtaining high-purity squalene from plant oil deodorizing distillate, feature exist
In: in step (3), the organic solvent is n-hexane, hexamethylene, methylene chloride, ethyl acetate, any one in ether.
8. the method according to claim 1 for obtaining high-purity squalene from plant oil deodorizing distillate, feature exist
In: in step (3), the condition of the vacuum distillation concentration are as follows: 400~600Pa of vacuum degree, is concentrated by 100~110 DEG C of temperature
The 1/3~1/4 of original machine phase volume.
9. the method according to claim 1 for obtaining high-purity squalene from plant oil deodorizing distillate, feature exist
In: in step (4), the condition of the level-one film distillator distillation are as follows: 30~40L/min of charging rate, vacuum degree 100~
100~110 DEG C of 150Pa, temperature, the condition of second level short-distance distiller distillation are as follows: 2~4L/min of charging rate, vacuum degree 1~
270~280 DEG C of 3Pa, temperature.
10. the side of high-purity squalene is obtained in slave plant oil deodorizing distillate described in any one according to claim 1~9
Method, it is characterised in that: the plant oil deodorizing distillate is that oil crops are de- after squeezing, degumming, alkali refining, decoloration, dewaxing
Any one in smelly distillate, including soybean oil, olive oil, cottonseed oil, corn oil, rapeseed oil, peanut oil, palm oil or two kinds
Above deodorization distillate.
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