CN105316107A - Separation method of oleic acid and linoleic acid in tea seed oil - Google Patents
Separation method of oleic acid and linoleic acid in tea seed oil Download PDFInfo
- Publication number
- CN105316107A CN105316107A CN201410312731.XA CN201410312731A CN105316107A CN 105316107 A CN105316107 A CN 105316107A CN 201410312731 A CN201410312731 A CN 201410312731A CN 105316107 A CN105316107 A CN 105316107A
- Authority
- CN
- China
- Prior art keywords
- acid
- urea
- seed oil
- tea seed
- oleic acid
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Landscapes
- Fats And Perfumes (AREA)
Abstract
The invention discloses a separation method of oleic acid and linoleic acid in tea seed oil, which includes the steps of: saponifying and acidifying the tea seed oil to obtain mixed fatty acid; pre-removing saturated fatty acid through a freezing crystallization method; and finally purifying the oleic acid and the linoleic acid through a urea inclusion method. In the method, the saturated fatty acid is separated in a certain degree by means of difference of melting point of the saturated fatty acid and unsaturated fatty acid for the first time, and then saturated and monounsaturated fatty acids are separated from polyunsaturated fatty acids through the urea inclusion to further prepare the oleic acid and the linoleic acid at high purity. Compared with the prior art, synchronous separation of the oleic acid and the linoleic acid in the tea seed oil is achieved. The method not only enriches the oleic acid in the tea seed oil but also separates the linoleic acid, and meanwhile increases the purities of the oleic acid and the linoleic acid. The method solves the problem that only is the oleic acid or the linoleic acid can be separated individually in the prior art and increases the additional value of products and raw material utilization rate.
Description
Technical field
The invention belongs to grease and extract manufacture field, be specifically related to oleic acid and linoleic separation method in a kind of tea seed oil.
Background technology
Tea-seed is the fruit of Theaceae Camellia Plants tea (CamelliaSinensisO.Ktze.), China is the native place of tealeaves, existing tea place area is about 3,200 ten thousand mu, but for a long time only using tealeaves as major industry, tea-seed does not obtain people to be familiar with widely and to pay attention to.In tea seed oil, the ratio of saturated fatty acid, monounsaturated fatty acids, polyunsaturated fatty acid is about 1:1.7:1, comparatively close to the 1:1:1 recommended in the world, is desirable food oils; Long-term edible tea seed oil can reduce hypertension, hyperlipidemia and etc. cardiovascular and cerebrovascular diseases, strengthen body immunity, effectively reduce cholesterol etc.
Tea seed oil is rich in oleic acid and linolic acid, and wherein oleic acid is about more than 50%, and linoleic acid content is about 25%, and oleic acid is a kind of monounsaturated fatty acids, is widely used in plastic plasticizer, and the anti-electric lubricant of wool spinning etc., can be used for cosmetic industry in addition.Linolic acid is a kind of polyunsaturated fatty acid, is the raw material preparing conjugated linolic acid, also can be used for medical.The conventional Oleic Linoleic method that is separated has molecular distillation method, organic solvent method, supercritical extraction, derivative method, absorption method etc., and wherein molecular distillation method and supercritical extraction high cost, energy consumption are large; Organic solvent method is residual noxious solvent easily; And derivative method and the too little experiment small-scale that is only applicable to of absorption method scale are studied.Therefore, need to find more efficiently method to be separated the lipid acid in tea-seed.
Linoleic extraction and separation is disclosed during patent application CN200810154105.7, name are called " extraction of a kind of safflower oil and separation method ", its main technique is: safflower oil saponification, acidifying obtain mixed fatty acid, most of saturated fatty acid and monounsaturated fatty acid lipid acid in urea adduct method removing mixed fatty acid, then molecular distillation method removes the components such as residual solvent, saturated fatty acid, oleic acid, obtains the linolic acid refined; The enrichment and purification method to polyunsaturated fatty acid (PUFA) is disclosed during patent application CN201310221671.6, name are called " a kind of method of enriching and purifying polyunsaturated fatty acid from melon withers seed oil mixed fatty acid ", its main technique is: prepare methyl alcohol-urea-melon and to wither seed oil mixing-in fat acid solution, cooling, standing inclusion, after suction filtration is separated, solvent wash crystallisate, collect filtrate and obtain polyunsaturated fatty acid-methyl alcohol-normal hexane mixed solution, then obtain PUFA by the method for extraction, washing; During patent CN201010212033.4, name are called " the gradient freezing Crystallization Separation method of silkworm chrysalis oil polyunsaturated fatty acid ", also the method adopting urea clathration to extract polyunsaturated fatty acid is protected, its main technique is: ultrasonic extraction silkworm chrysalis oil, saponification, acidifying obtain mixed fatty acid, urea-ethanolic soln inclusion, gradient freezing crystallization obtains the polyunsaturated fatty acid refined; During patent CN201010205773.5, name are called " a kind of method of gathering oleic acid from tea oil "; protect the separation purification method of oleic acid; main technique is: tea-seed oil mixed fatty acid is prepared in tea-seed oil saponification, acidifying; prepare urea-short chain alcohol-mixing-in fat acid solution; freezing and crystallizing inclusion; be separated, urea not inclusion compound acidifying, extraction, wash to obtain oleic acid, destroy urea inclusion and be separated to obtain saturated fatty acid.As can be seen here, although with adopting urea adduct method, have nothing in common with each other to the extracting method of target product in different starting material.
This research team is in the research to tea seed oil composition, according to the feature of tea seed oil composition lipid acid, find in the process be separated, adopt the method that solvent freezing and crystallizing pre-treatment removal saturated fatty acid and urea adduct method combine, first remove a large amount of saturated fatty acids, then make urea molecule form more stable inclusion compound with saturated fatty acid in crystallisation process, form unstable inclusion compound with monounsaturated fatty acids, separate out respectively; And polyunsaturated fatty acid is not easily by urea clathration, therefrom isolate the higher oleic acid of purity and linolic acid, thus achieve oleic acid, linoleic separated in synchronization, and solve tradition and can only isolate oleic acid or a linoleic difficult problem, improve added value of product and raw material availability.
Summary of the invention
The object of this invention is to provide oleic acid and linoleic separation method in a kind of tea seed oil, realize oleic acid and linoleic separated in synchronization in tea seed oil.
The technical solution used in the present invention is as follows:
Oleic acid and linoleic separation method in a kind of tea seed oil, step is as follows:
(1) preparation of free fatty acids: prepare tea seed oil mixed fatty acid by tea seed oil saponification, acidifying;
(2) saturated fatty acid is removed in the pre-treatment of solvent freeze crystallization: add 1-2 times of anhydrous alcohol solution in above-mentioned mixed fatty acid, low temperature puts 18-24 hour, filters, gets filtrate and add water stratification, get oil reservoir saturated common salt and be washed to neutrality, anhydrous sodium sulfate drying obtains lipid acid;
(3) urea adduct method purifying oleic acid, linolic acid: urea and lower alcohol are that 1:2-4 puts into container according to mass volume ratio, under heating, urea is fully dissolved, make urea-low-alcohol solution, then be that 3-5:1 adds tea seed oil mixed fatty acid according to the mass volume ratio of the mixed fatty acid of urea and step (2) gained, after reflux to clear, be cooled to room temperature, at-8 DEG C-0 DEG C, place 12-18h freezing and crystallizing; Isolate filtrate and urea crystals thing, urea crystals thing adds the layering of hot saturated common salt water dissolution, gets oil-reservoir water and is washed till without till urea, add anhydrous sodium sulfate dehydration, obtains the thick product of oleic acid; Filtrate distillation removing ethanol, with hot saturated common salt water washing, adds anhydrous sodium sulfate dehydration, obtains the linolic acid after separation.
Saponification and the acidifying of the middle tea seed oil of above-mentioned steps (1) can with reference to the preparation technologies of grease mixed fatty acid in prior art.
Preferably, saponification and the acidification technique of the middle tea seed oil of described step (1) are: take tea seed oil, add the NaOH-90% ethanolic soln of 10% of 2-4 times of bulking value, stir and be slowly warming up to 70-75 DEG C, saponification backflow 1-3h, in addition warm water dissolves, regulate pH to 2-3 with 20%HCl, constant temperature stirs 10-20min, stratification, get oil reservoir saturated common salt and be washed to neutrality, anhydrous sodium sulfate drying obtains mixed fatty acid;
Preferably, in described step (2), temperature is 4-8 DEG C, preferably 7 DEG C;
Preferably, in described step (3), lower alcohol is the one in methyl alcohol, ethanol, propyl alcohol, butanols, preferably 95% ethanol.
Further, oleic acid and linoleic separation method in a kind of tea seed oil, step is as follows:
(1) tea seed oil is taken, add the NaOH-90% ethanolic soln of 10% of 3 times of bulking values, stir and be slowly warming up to 75 DEG C, saponification backflow 2h, in addition warm water dissolves, and regulates pH to 2-3 with 20%HCl, constant temperature stirs 15min, stratification, gets oil reservoir saturated common salt and is washed to neutrality, and anhydrous sodium sulfate drying obtains mixed fatty acid;
(2) add 1.5 times of anhydrous alcohol solutions in above-mentioned mixed fatty acid, place 24 hours at 7 DEG C, filter, get filtrate and add water to layering, get oil reservoir saturated common salt and be washed to neutrality, anhydrous sodium sulfate drying obtains lipid acid;
(3) urea and 95% ethanol are that 1:3 puts into container according to mass volume ratio, reflux makes urea fully dissolve, make urea-95% ethanolic soln, then be that 4:1 adds tea seed oil mixed fatty acid according to the mass volume ratio of the mixed fatty acid of urea and step (2) gained, shake up, after reflux to clear, be cooled to room temperature, at-4 DEG C, place 12h freezing and crystallizing; Then explosive decompression suction filtration, isolates filtrate and urea crystals thing, and urea crystals thing adds the saturated common salt water dissolution layering that temperature is 70-80 DEG C, gets oil-reservoir water and is washed till without till urea, add anhydrous sodium sulfate dehydration, obtain the thick product of oleic acid; Filtrate distillation removing ethanol, with hot saturated common salt water washing, adds anhydrous sodium sulfate dehydration, obtains the linolic acid after separation.
First the present invention utilizes saturated fatty acid to carry out certain being separated with unsaturated fatty acids different melting points to saturated fatty acid, saturated, monounsaturated fatty acids are separated with polyunsaturated fatty acid by recycling urea clathration, and then obtain the linoleic plus oleic acid of higher degree.Compared with prior art, achieve tea seed oil oleic acid and linoleic separated in synchronization, while enrichment tea seed oil oleic acid, be also separated linolic acid, and oleic acid and linoleic purity have also been obtained raising, is ideal method for separating and concentrating.
In the oleic acid, linolic acid sepn process of tea seed oil, different separation methods, the consumption of pretreatment mode and urea, the concentration of ethanol and consumption, inclusion temperature, inclusion time have impact in various degree to technique, therefore in order to make those of ordinary skill in the art better understand the present invention, the applicant has carried out series of experiment research, to prove effect of the present invention:
Test example 1 separation method screens
In sepn process, the present inventor designs separation method and selects, and with oleic acid, linoleic acid content for inspection target, takes into full account the impact of each method on separating resulting, has carried out Selection experiment.
Sample A: be called embodiment 1 processing condition in " a kind of method of gathering oleic acid from tea oil " according to CN201010205773.5, name, raw material becomes tea seed oil from camellia seed oil, obtains oleic acid;
Sample B: embodiment 1 processing condition during patent application CN200810154105.7, name are called " extraction of a kind of safflower oil and separation method ", raw material becomes tea seed oil from safflower oil, obtains linolic acid;
Sample C: prepare according to the embodiment of the present invention 1 method;
Sample D: be called embodiment 1 processing condition in " the gradient freezing Crystallization Separation method of silkworm chrysalis oil polyunsaturated fatty acid " according to patent CN201010212033.4, name, raw material becomes tea seed oil from silkworm chrysalis oil, obtain polyunsaturated fatty acid, detect its Linoleic acid;
In aforesaid method, tea seed oil consumption is 100g, and adopt the content of gas chromatography determination lipid acid, concrete steps are: methyl esterification of fatty acid: adopt methanolic method;
Take lipid acid 50mg, add 2.5mol/L sulfuric acid-methanol solution 1mL, in 70 DEG C of heating in water bath 30min, it is to be measured to add 2mL normal hexane extraction esterification product.
Utilize the composition of Agilent 7890A chromatographic fatty acid methyl ester, chromatographic column is DB-23 (60m × 0.25mm × 0.25 μm); Column temperature initial temperature 130 DEG C, keeps 1min; 170 DEG C are risen to 6.5 DEG C/min speed; And then rise to 215 DEG C with 2.75 DEG C/min speed, keep 12min, and then rise to 230 DEG C with 40 DEG C/min speed, keep 3min; Detector is FID, hydrogen flowing quantity 45mL/min, air flow quantity 400mL/min.Lipid acid by with fatty acid methyl ester standard substance retention time Identification, adopt area normalization method calculate oleic acid, linoleic acid content.
The investigation of the object product obtained the results are shown in Table 1.
Table 1 process choice experimental result
| Sample A | Sample B | Sample C | Sample D | |
| Oleic acid content (%) | 50.20 | -- | 55.47 | -- |
| Linoleic acid content (%) | -- | 18.62 | 24.31 | 21.56 |
Upper table can be found out, adopts separation method of the present invention, obtains oleic acid and linolic acid simultaneously; First the present invention utilizes saturated fatty acid to carry out certain being separated with unsaturated fatty acids different melting points to saturated fatty acid in addition, than the extraction and isolation being directly more beneficial to oleic acid with urea adduct method, and simple down-stream can obtain oleic acid and the linolic acid of high-content, is desirable extracting method.
Each processing parameter research in test example 2 urea adduct method
The impact of 2.1 urea lipid acid comparison oleic acid, linolic acid purity and yield
Method: get tea seed oil 100g and be placed in container, according to the step (1) of embodiment 1, (2) carry out pre-treatment and obtain mixed fatty acid, fixing inclusion temperature is-4 DEG C, the inclusion time is 24h, ethanol urea quality is than being 3:1, be 2:1 at urea mixed fatty acid mass ratio, 3:1, 4:1, 5:1, inclusion is carried out under the condition of 6:1, then explosive decompression suction filtration, isolate filtrate and urea crystals thing, urea crystals thing extracts, dewater to obtain oleic acid, filtrate is distilled, washing, dewater to obtain linolic acid, measure linoleic plus oleic acid purity and yield, the results are shown in Table 2.
The impact of table 2 urea lipid acid comparison oleic acid, linolic acid purity and yield
| Urea lipid acid ratio | 2:1 | 3:1 | 4:1 | 5:1 | 6:1 |
| Oleic acid yield (%) | 55.2 | 74.7 | 86.4 | 85.0 | 84.1 |
| Oleic acid purity (%) | 57.6 | 59.1 | 69.1 | 57.8 | 60.0 |
| Linolic acid yield (%) | 75.0 | 69.2 | 44.6 | 37.5 | 22.2 |
| Linolic acid purity (%) | 58.2 | 80.5 | 92.9 | 94.8 | 93.0 |
Result: amount of urea affects larger on linolic acid purity and yield, the above results shows, along with m (urea)/m (lipid acid) value is increased to 4 by 2 in inclusion process, gained linolic acid purity rises to 92.9% by 58.2%, after exceeding this ratio, linolic acid purity is substantially constant, and linolic acid yield increases with urea fatty acid ratio and declines; Oleic acid purity reaches maximum value 69.1% at m (urea)/m (lipid acid) when being 4, and yield is 86.4%.This may be relevant with the principle of urea clathration, and when amount of urea is very few, the inclusion compound framework formed in ethanolic soln is less, causes declining to inclusion degree that is saturated, monounsaturated fatty acids, thus the separation degree of mixed fatty acid Linoleic acid is declined; When amount of urea is more, not only more saturated, monounsaturated fatty acids, by inclusion, makes linolic acid gained purity comparatively large, but linolic acid is also by an inclusion part, and its yield reduces.Consider linolic acid purity and yield and oleic acid purity and yield, select m (urea): m (lipid acid) value is 3-5:1, and the best is 4:1.
The impact of 2.2 ethanol urea comparison oleic acid, linolic acid purity and yield
Method: get tea seed oil 100g and be placed in container, according to the step (1) of embodiment 1, (2) carry out pre-treatment and obtain mixed fatty acid, fixing inclusion temperature is-4 DEG C, the inclusion time is 24h, urea mixed fatty acid mass ratio is 4:1, compare for 2:1 at ethanol contend and urea quality, 3:1, 4:1, 5:1, inclusion is carried out under the condition of 6:1, then explosive decompression suction filtration, isolate filtrate and urea crystals thing, urea crystals thing extracts, dewater to obtain oleic acid, filtrate is distilled, washing, dewater to obtain linolic acid, measure linoleic plus oleic acid purity and yield, the results are shown in Table 3.
The impact of table 3 ethanol urea volume mass comparison oleic acid, linolic acid purity and yield
| Ethanol urea ratio (ml:g) | 1:1 | 2:1 | 3:1 | 4:1 | 5:1 |
| Oleic acid yield (%) | 42.2 | 80.1 | 84.7 | 86.2 | 85.4 |
| Oleic acid purity (%) | 61.2 | 66.4 | 65.0 | 62.4 | 58.3 |
| Linolic acid yield (%) | 20.1 | 21.5 | 44.2 | 39.6 | 23.8 |
| Linolic acid purity (%) | 87.5 | 88.2 | 93.2 | 92.1 | 92.7 |
Result: along with the increase gradually of V (ethanol)/m (urea) value, linolic acid purity increases, and tends to be steady, the rear reduction and linolic acid must take the lead in raising, when ratio is 3, linolic acid yield reaches maximum 44.2%; Oleic acid yield increases with this ratio and raises, and oleic acid purity first raises rear reduction, when V (ethanol)/m (urea) value obtains maximum value 66.4% when being 2.This is because when V (ethanol)/m (urea) is smaller, urea can not dissolve fully, the urea participating in inclusion reaction is less, saturated fatty acid and monounsaturated fatty acids part is caused to residue in linolic acid, purity is lower, along with the increase of ethanol urea quality ratio, have sufficient dissolve with ethanol urea, inclusion reaction can carry out fully.Consider, select ethanol urea quality to be 2-4:1 than scope, preferred alcohol urea quality is than being 3:1.
2.3 inclusion temperature are on the impact of oleic acid, linolic acid purity and yield
Method: get tea seed oil 250g and be placed in container, carry out pre-treatment obtain mixed fatty acid according to the step (1) of embodiment 1, (2), fixing ethanol contend and urea quality are than being 3:1, urea mixed fatty acid mass ratio is 4:1, inclusion 18h at-12 ,-8 ,-4,0,4 DEG C respectively, then explosive decompression suction filtration, isolate filtrate and urea crystals thing, urea crystals thing extracts, dewater to obtain oleic acid, filtrate is distilled, wash, dewater to obtain linolic acid, measure linoleic plus oleic acid purity and yield, the results are shown in Table 4.
Table 4 inclusion temperature is on the impact of oleic acid, linolic acid purity and yield
| Inclusion temperature (DEG C) | -12 | -8 | -4 | 0 | 4 |
| Oleic acid yield (%) | 79.7 | 80.3 | 82.6 | 82.0 | 82.3 |
| Oleic acid purity (%) | 66.2 | 68.0 | 69.6 | 67.5 | 69.3 |
| Linolic acid yield (%) | 25.5 | 29.2 | 47.6 | 42.7 | 30.2 |
| Linolic acid purity (%) | 94.1 | 93.7 | 93.5 | 88.7 | 87.4 |
Result: along with the increase of temperature, oleic acid purity and yield remain unchanged substantially, illustrate that inclusion temperature affects less on oleic acid purity and yield.Linolic acid purity rises with inclusion temperature and declines, comparatively steady at-12--4 DEG C ,-4-4 DEG C of declines; And linolic acid yield first rises with inclusion temperature and declines afterwards, reach maximum value 47.6% at-4 DEG C.Because urea clathration fatty acid response is thermopositive reaction, favors low temperature is in urea clathration saturated fatty acid and oleic acid, and thus during low temperature, linolic acid purity is higher, considers selective temperature scope and is-8 DEG C-0 DEG C, and preferred best inclusion temperature is-4 DEG C.
2.4 inclusion times are on the impact of oleic acid, linolic acid purity and yield
Method: get tea seed oil 250g and be placed in container, according to the step (1) of embodiment 1, (2) carry out pre-treatment and obtain mixed fatty acid, then 5 parts are divided into, be labeled as sample 1-5, fixing ethanol contend and urea quality are than being 3:1, urea mixed fatty acid mass ratio is 4:1, difference inclusion 6 at-4 DEG C, 12, 18, 24, 30h, then explosive decompression suction filtration, isolate filtrate and urea crystals thing, urea crystals thing extracts, dewater to obtain oleic acid, filtrate is distilled, washing, dewater to obtain linolic acid, measure linoleic plus oleic acid purity and yield, the results are shown in Table 5.
The table 5 inclusion time is on the impact of oleic acid, linolic acid purity and yield
| Inclusion time (h) | 6 | 12 | 18 | 24 | 30 |
| Oleic acid yield (%) | 85.1 | 84.7 | 86.4 | 81.9 | 84.7 |
| Oleic acid purity (%) | 68.7 | 69.1 | 67.6 | 65.4 | 68.3 |
| Linolic acid yield (%) | 62.3 | 71.4 | 46.8 | 45.1 | 44.0 |
| Linolic acid purity (%) | 84.7 | 90.2 | 93.8 | 94.6 | 94.9 |
Result: along with the prolongation of inclusion time, oleic acid purity and yield remain unchanged substantially, illustrate that the inclusion time affects less on oleic acid purity and yield.Linolic acid purity increases with the inclusion time and rises, and rises to 94.9% from 84.7%; And linolic acid yield declines with inclusion time lengthening, be down to 44.0% from 62.3%.Urea clathration lipid acid process is comparatively slow, and along with the inclusion time is elongated, in mixed fatty acid, saturated fatty acid and monounsaturated fatty acids are constantly by inclusion, and solution Linoleic acid purity raises; In addition along with inclusion time lengthening, the linolic acid in solution also part, by urea clathration, causes linolic acid yield to decline, therefore considers, and selects inclusion time range to be 12-18 hour, is preferably 12 hours the bests.
Embodiment
Embodiment 1
Oleic acid and linoleic separation method in a kind of tea seed oil, step is as follows:
(1) tea seed oil is taken, add the NaOH-90% ethanolic soln of 10% of 3 times of bulking values, stir and be slowly warming up to 75 DEG C, saponification backflow 2h, in addition warm water dissolves, and regulates pH to 2-3 with 20%HCl, constant temperature stirs 15min, stratification, gets oil reservoir saturated common salt and is washed to neutrality, and anhydrous sodium sulfate drying obtains mixed fatty acid;
(2) add 1.5 times of anhydrous alcohol solutions in above-mentioned mixed fatty acid, place 24 hours at 7 DEG C, filter, get filtrate and add water to layering, get oil reservoir saturated common salt and be washed to neutrality, anhydrous sodium sulfate drying obtains lipid acid;
(3) urea and 95% ethanol are that 1:3 puts into container according to mass volume ratio, reflux makes urea fully dissolve, make urea-95% ethanolic soln, then be that 4:1 adds tea seed oil mixed fatty acid according to the mass volume ratio of the mixed fatty acid of urea and step (2) gained, shake up, after reflux to clear, be cooled to room temperature, at-4 DEG C, place 12h freezing and crystallizing; Then explosive decompression suction filtration, isolates filtrate and urea crystals thing, and urea crystals thing adds the saturated common salt water dissolution layering that temperature is 70-80 DEG C, gets oil-reservoir water and is washed till without till urea, add anhydrous sodium sulfate dehydration, obtain the thick product of oleic acid; Filtrate distillation removing ethanol, with hot saturated common salt water washing, adds anhydrous sodium sulfate dehydration, obtains the linolic acid after separation.
Embodiment 2
Oleic acid and linoleic separation method in a kind of tea seed oil, step is as follows:
(1) tea seed oil is taken, add the NaOH-90% ethanolic soln of 10% of 2 times of bulking values, stir and be slowly warming up to 70 DEG C, saponification backflow 1h, in addition warm water dissolves, and regulates pH to 2-3 with 20%HCl, constant temperature stirs 10min, stratification, gets oil reservoir saturated common salt and is washed to neutrality, and anhydrous sodium sulfate drying obtains mixed fatty acid;
(2) the quality anhydrous alcohol solution such as to add in above-mentioned mixed fatty acid, place 18 hours at 4 DEG C, filter, get filtrate and add water to layering, get oil reservoir saturated common salt and be washed to neutrality, anhydrous sodium sulfate drying obtains lipid acid;
(3) urea and 95% ethanol are that 1:2 puts into container according to mass volume ratio, reflux makes urea fully dissolve, make urea-95% ethanolic soln, then be that 3:1 adds tea seed oil mixed fatty acid according to the mass volume ratio of the mixed fatty acid of urea and step (2) gained, shake up, after reflux to clear, be cooled to room temperature, at-8 DEG C, place 12h freezing and crystallizing; Then explosive decompression suction filtration, isolates filtrate and urea crystals thing, and urea crystals thing adds the saturated common salt water dissolution layering that temperature is 70 DEG C, gets oil-reservoir water and is washed till without till urea, add anhydrous sodium sulfate dehydration, obtain the thick product of oleic acid; Filtrate distillation removing ethanol, with hot saturated common salt water washing, adds anhydrous sodium sulfate dehydration, obtains the linolic acid after separation.
Embodiment 3
Oleic acid and linoleic separation method in a kind of tea seed oil, step is as follows:
(1) tea seed oil is taken, add the NaOH-90% ethanolic soln of 10% of 4 times of bulking values, stir and be slowly warming up to 75 DEG C, saponification backflow 3h, in addition warm water dissolves, and regulates pH to 2-3 with 20%HCl, constant temperature stirs 20min, stratification, gets oil reservoir saturated common salt and is washed to neutrality, and anhydrous sodium sulfate drying obtains mixed fatty acid;
(2) add 2 times of anhydrous alcohol solutions in above-mentioned mixed fatty acid, place 24 hours at 8 DEG C, filter, get filtrate and add water to layering, get oil reservoir saturated common salt and be washed to neutrality, anhydrous sodium sulfate drying obtains lipid acid;
(3) urea and 95% ethanol are that 1:4 puts into container according to mass volume ratio, reflux makes urea fully dissolve, make urea-95% ethanolic soln, then be that 5:1 adds tea seed oil mixed fatty acid according to the mass volume ratio of the mixed fatty acid of urea and step (2) gained, shake up, after reflux to clear, be cooled to room temperature, at 0 DEG C, place 18h freezing and crystallizing; Then explosive decompression suction filtration, isolate filtrate and urea crystals thing, does is it that (used in amounts of water will be write out here for the saturated aqueous common salt of 80 DEG C that urea crystals thing adds temperature?) dissolve layering, get oil-reservoir water and be washed till without till urea, add anhydrous sodium sulfate dehydration, obtain the thick product of oleic acid; Filtrate distillation removing ethanol, with hot saturated common salt water washing, adds anhydrous sodium sulfate dehydration, obtains the linolic acid after separation.
Embodiment 4
Oleic acid and linoleic separation method in a kind of tea seed oil, step is as follows:
(1) tea seed oil is taken, add the NaOH-90% ethanolic soln of 10% of 3 times of bulking values, stir and be slowly warming up to 70 DEG C, saponification backflow 2h, in addition warm water dissolves, and regulates pH to 2-3 with 20%HCl, constant temperature stirs 20min, stratification, gets oil reservoir saturated common salt and is washed to neutrality, and anhydrous sodium sulfate drying obtains mixed fatty acid;
(2) add 1.5 times of anhydrous alcohol solutions in above-mentioned mixed fatty acid, place 21 hours at 5 DEG C, filter, get filtrate and add water to layering, get oil reservoir saturated common salt and be washed to neutrality, anhydrous sodium sulfate drying obtains lipid acid;
(3) urea and methyl alcohol are that 1:3 puts into container according to mass volume ratio, reflux makes urea fully dissolve, make urea-methanol solution, then be that 4:1 adds tea seed oil mixed fatty acid according to the mass volume ratio of the mixed fatty acid of urea and step (2) gained, shake up, after reflux to clear, be cooled to room temperature, at-4 DEG C, place 12h freezing and crystallizing; Then explosive decompression suction filtration, isolates filtrate and urea crystals thing, and urea crystals thing adds the saturated common salt water dissolution layering that temperature is 75 DEG C, gets oil-reservoir water and is washed till without till urea, add anhydrous sodium sulfate dehydration,
Obtain the thick product of oleic acid; Filtrate distillation removing ethanol, with hot saturated common salt water washing, adds anhydrous sodium sulfate dehydration, obtains the linolic acid after separation.
Embodiment 5
By sample number into spectrum 1-4 obtained for embodiment 1-4, investigate oleic acid yield, oleic acid purity, linolic acid yield, linolic acid purity under each processing parameter condition, the results are shown in Table 6:
Table 6 experimental result
| Oleic acid yield (%) | Oleic acid purity (%) | Linolic acid yield (%) | Linolic acid purity (%) | |
| Sample 1 | 82.30 | 67.5 | 49.71 | 92.77 |
| Sample 2 | 81.43 | 68.2 | 50.62 | 93.32 |
| Sample 3 | 84.17 | 67.4 | 49.10 | 93.07 |
| Sample 4 | 82.46 | 68.7 | 50.42 | 93.14 |
Upper table is known, adopt separation method of the present invention, oleic acid, linoleic yield and purity are all ideal, visible separation method separated in synchronization of the present invention has gone out two kinds of lipid acid, easy, efficient, solve tradition and can only isolate oleic acid or a linoleic difficult problem, improve added value of product and raw material availability.
Claims (5)
1. oleic acid and a linoleic separation method in tea seed oil, step is as follows:
(1) preparation of free fatty acids: prepare tea seed oil mixed fatty acid by tea seed oil saponification, acidifying;
(2) saturated fatty acid is removed in the pre-treatment of solvent freeze crystallization: add 1-2 times of anhydrous alcohol solution in above-mentioned mixed fatty acid, low temperature puts 18-24 hour, filters, gets filtrate and add water stratification, get oil reservoir saturated common salt and be washed to neutrality, anhydrous sodium sulfate drying obtains lipid acid;
(3) urea adduct method purifying oleic acid, linolic acid: urea and lower alcohol put into container according to mass volume ratio 1:2-4, under heating, urea is fully dissolved, make urea-low-alcohol solution, then be that 3-5:1 adds tea seed oil mixed fatty acid according to the mass ratio of the mixed fatty acid of urea and step (2) gained, after reflux is extremely transparent, be cooled to room temperature, at-8 DEG C-0 DEG C, place 12-18h freezing and crystallizing; Isolate filtrate and urea crystals thing, urea crystals thing adds the layering of hot saturated common salt water dissolution, gets oil-reservoir water and is washed till without till urea, add anhydrous sodium sulfate dehydration, obtains the thick product of oleic acid; Filtrate distillation removing ethanol, with hot saturated common salt water washing, adds anhydrous sodium sulfate dehydration, obtains the linolic acid after separation.
2. oleic acid and linoleic separation method in tea seed oil as claimed in claim 1, it is characterized in that: saponification and the acidification technique of the middle tea seed oil of step (1) are: take tea seed oil, add the NaOH-90% ethanolic soln of 10% of 2-4 times of volume, stir and be slowly warming up to 70-75 DEG C, saponification backflow 1-3h, in addition warm water dissolves, pH to 2-3 is regulated with 20%HCl, constant temperature stirs 10-20min, stratification, be washed to neutrality with saturated common salt, anhydrous sodium sulfate drying obtains mixed fatty acid.
3. oleic acid and linoleic separation method in tea seed oil as claimed in claim 1, is characterized in that: in step (2), low temperature is 4-8 DEG C; In step (3), lower alcohol is the one in methyl alcohol, ethanol, propyl alcohol, butanols.
4. oleic acid and linoleic separation method in tea seed oil as claimed in claim 1, is characterized in that: in step (2), low temperature is 7 DEG C; In step (3), lower alcohol is the ethanolic soln of 95%.
5. oleic acid and linoleic separation method in the tea seed oil as described in as arbitrary in claim 1-4, is characterized in that: separation method step is as follows:
(1) tea seed oil is taken, add the NaOH-90% ethanolic soln of 10% of 3 times of bulking values, stir and be slowly warming up to 75 DEG C, saponification backflow 2h, in addition warm water dissolves, and regulates pH to 2-3 with 20%HCl, constant temperature stirs 15min, stratification, gets oil reservoir saturated common salt and is washed to neutrality, and anhydrous sodium sulfate drying obtains mixed fatty acid;
(2) add 1.5 times of anhydrous alcohol solutions in above-mentioned mixed fatty acid, low temperature puts 24 hours, filters, gets filtrate and add water to layering, get oil reservoir saturated common salt and be washed to neutrality, and anhydrous sodium sulfate drying obtains lipid acid;
(3) urea and 95% ethanol are that 1:3 puts into container according to mass volume ratio, reflux makes urea fully dissolve, make urea-95% ethanolic soln, then be that 4:1 adds tea seed oil mixed fatty acid according to the mass ratio of the mixed fatty acid of urea and step (2) gained, shake up, after reflux to clear, be cooled to room temperature, at-4 DEG C, place 12h freezing and crystallizing; Then explosive decompression suction filtration, isolates filtrate and urea crystals thing, and urea crystals thing adds the saturated common salt water dissolution layering that temperature is 70-80 DEG C, gets oil-reservoir water and is washed till without till urea, add anhydrous sodium sulfate dehydration, obtain the thick product of oleic acid; Filtrate distillation removing ethanol, with hot saturated common salt water washing, adds anhydrous sodium sulfate dehydration, obtains the linolic acid after separation.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201410312731.XA CN105316107B (en) | 2014-07-02 | 2014-07-02 | Method for separating oleic acid and linoleic acid from tea seed oil |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201410312731.XA CN105316107B (en) | 2014-07-02 | 2014-07-02 | Method for separating oleic acid and linoleic acid from tea seed oil |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN105316107A true CN105316107A (en) | 2016-02-10 |
| CN105316107B CN105316107B (en) | 2020-03-06 |
Family
ID=55244436
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201410312731.XA Active CN105316107B (en) | 2014-07-02 | 2014-07-02 | Method for separating oleic acid and linoleic acid from tea seed oil |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN105316107B (en) |
Cited By (14)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105753689A (en) * | 2016-03-15 | 2016-07-13 | 宁夏大学 | Method of extracting purified Alpha-linolenic acid from linseed oil |
| CN106831409A (en) * | 2017-03-07 | 2017-06-13 | 辽宁奥克医药辅料股份有限公司 | A kind of preparation method of high-purity oleic acid |
| CN107090357A (en) * | 2017-06-21 | 2017-08-25 | 江苏中兴药业有限公司 | A kind of method of the extraction purification unrighted acid in Silybum Marianum Gaertn Seed Oil |
| CN108251221A (en) * | 2018-04-26 | 2018-07-06 | 孙万成 | A kind of method of purifying branched chain aliphatic acid in butter from yak |
| CN108392440A (en) * | 2018-05-23 | 2018-08-14 | 赣州哈克生物科技有限公司 | A kind of camellia seed skincare oil and its preparation method and application |
| CN108753466A (en) * | 2018-05-24 | 2018-11-06 | 华南理工大学 | A kind of tea oil linoleic acid and its preparation method and application |
| CN108929786A (en) * | 2018-08-08 | 2018-12-04 | 江南大学 | A kind of enrichment method of branched chain fatty acid |
| CN109355138A (en) * | 2017-10-09 | 2019-02-19 | 赣南医学院 | A kind of preparation method, product and its application of tea oil polyunsaturated fatty acid |
| CN110257175A (en) * | 2019-06-20 | 2019-09-20 | 深圳市仙迪化妆品有限公司 | It is a kind of to prepare linoleic method and linoleic application using rose hip oil |
| CN110734810A (en) * | 2019-09-23 | 2020-01-31 | 贵州省亚热带作物研究所 | Purification and enrichment method for omega-7 fatty acid in macadamia nut oil |
| CN112225658A (en) * | 2020-10-12 | 2021-01-15 | 洞口县亿丰农林牧科技有限公司 | Method for extracting oleic acid from tea oil |
| CN112646663A (en) * | 2020-12-15 | 2021-04-13 | 武汉轻工大学 | Method for enriching, separating and purifying linoleic acid in sunflower seed oil |
| CN114181778A (en) * | 2021-11-18 | 2022-03-15 | 南昌大学 | Preparation method of ruminant trans-fatty acid |
| CN116059136A (en) * | 2022-11-22 | 2023-05-05 | 青蛙王子（福建）婴童护理用品有限公司 | Camellia oil product with optimized skin care effect and preparation method and application thereof |
Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2007148889A1 (en) * | 2006-06-22 | 2007-12-27 | E.S.Biotech. Co., Ltd. | Edible plant oils from which saturated fatty acids were removed and manufacturing process thereof |
| CN101525558A (en) * | 2009-03-20 | 2009-09-09 | 中国科学院西北高原生物研究所 | Preparation process of functional polyunsaturated fatty acid in bee pollen |
| CN101744237A (en) * | 2008-12-15 | 2010-06-23 | 天津科技大学 | Method for extracting and separating safflower seed oil |
| CN101845362A (en) * | 2010-06-22 | 2010-09-29 | 中南林业科技大学 | Method for gathering oleic acid from tea-seed oil |
| CN101942357A (en) * | 2010-09-10 | 2011-01-12 | 中国林业科学研究院林产化学工业研究所 | Method for isolating jatropha curcas oil polyunsaturated fatty acids |
| CN103333747A (en) * | 2013-06-05 | 2013-10-02 | 安徽农业大学 | Method for gathering and purifying polyunsaturated fatty acid from mixed fatty acid of trichosanthes seed oil |
-
2014
- 2014-07-02 CN CN201410312731.XA patent/CN105316107B/en active Active
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2007148889A1 (en) * | 2006-06-22 | 2007-12-27 | E.S.Biotech. Co., Ltd. | Edible plant oils from which saturated fatty acids were removed and manufacturing process thereof |
| CN101744237A (en) * | 2008-12-15 | 2010-06-23 | 天津科技大学 | Method for extracting and separating safflower seed oil |
| CN101525558A (en) * | 2009-03-20 | 2009-09-09 | 中国科学院西北高原生物研究所 | Preparation process of functional polyunsaturated fatty acid in bee pollen |
| CN101845362A (en) * | 2010-06-22 | 2010-09-29 | 中南林业科技大学 | Method for gathering oleic acid from tea-seed oil |
| CN101942357A (en) * | 2010-09-10 | 2011-01-12 | 中国林业科学研究院林产化学工业研究所 | Method for isolating jatropha curcas oil polyunsaturated fatty acids |
| CN103333747A (en) * | 2013-06-05 | 2013-10-02 | 安徽农业大学 | Method for gathering and purifying polyunsaturated fatty acid from mixed fatty acid of trichosanthes seed oil |
Non-Patent Citations (3)
| Title |
|---|
| 刘华鼐等: ""茶油中不饱和脂肪酸提纯工艺研究"", 《油脂加工》 * |
| 胡小泓等: ""尿素包合法提纯油茶籽油中油酸的工艺研究"", 《中国油脂》 * |
| 许明塔等: ""尿素包合法制备油茶籽油中油酸的工艺研究"", 《中国粮油学报》 * |
Cited By (17)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105753689A (en) * | 2016-03-15 | 2016-07-13 | 宁夏大学 | Method of extracting purified Alpha-linolenic acid from linseed oil |
| CN105753689B (en) * | 2016-03-15 | 2020-02-07 | 宁夏大学 | Method for extracting and purifying α -linolenic acid from linseed oil |
| CN106831409A (en) * | 2017-03-07 | 2017-06-13 | 辽宁奥克医药辅料股份有限公司 | A kind of preparation method of high-purity oleic acid |
| CN106831409B (en) * | 2017-03-07 | 2019-08-06 | 辽宁奥克医药辅料股份有限公司 | A kind of preparation method of high-purity oleic acid |
| CN107090357A (en) * | 2017-06-21 | 2017-08-25 | 江苏中兴药业有限公司 | A kind of method of the extraction purification unrighted acid in Silybum Marianum Gaertn Seed Oil |
| CN109355138A (en) * | 2017-10-09 | 2019-02-19 | 赣南医学院 | A kind of preparation method, product and its application of tea oil polyunsaturated fatty acid |
| CN108251221A (en) * | 2018-04-26 | 2018-07-06 | 孙万成 | A kind of method of purifying branched chain aliphatic acid in butter from yak |
| CN108392440A (en) * | 2018-05-23 | 2018-08-14 | 赣州哈克生物科技有限公司 | A kind of camellia seed skincare oil and its preparation method and application |
| CN108753466A (en) * | 2018-05-24 | 2018-11-06 | 华南理工大学 | A kind of tea oil linoleic acid and its preparation method and application |
| CN108753466B (en) * | 2018-05-24 | 2021-06-08 | 华南理工大学 | Tea oil linoleic acid and preparation method and application thereof |
| CN108929786A (en) * | 2018-08-08 | 2018-12-04 | 江南大学 | A kind of enrichment method of branched chain fatty acid |
| CN110257175A (en) * | 2019-06-20 | 2019-09-20 | 深圳市仙迪化妆品有限公司 | It is a kind of to prepare linoleic method and linoleic application using rose hip oil |
| CN110734810A (en) * | 2019-09-23 | 2020-01-31 | 贵州省亚热带作物研究所 | Purification and enrichment method for omega-7 fatty acid in macadamia nut oil |
| CN112225658A (en) * | 2020-10-12 | 2021-01-15 | 洞口县亿丰农林牧科技有限公司 | Method for extracting oleic acid from tea oil |
| CN112646663A (en) * | 2020-12-15 | 2021-04-13 | 武汉轻工大学 | Method for enriching, separating and purifying linoleic acid in sunflower seed oil |
| CN114181778A (en) * | 2021-11-18 | 2022-03-15 | 南昌大学 | Preparation method of ruminant trans-fatty acid |
| CN116059136A (en) * | 2022-11-22 | 2023-05-05 | 青蛙王子（福建）婴童护理用品有限公司 | Camellia oil product with optimized skin care effect and preparation method and application thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| CN105316107B (en) | 2020-03-06 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN105316107A (en) | Separation method of oleic acid and linoleic acid in tea seed oil | |
| CN101921254B (en) | Method for extracting natural vitamin E from blackberry seeds | |
| CN101928642B (en) | Method for extracting and separating spice and medicinal components from whole plants of Dendranthema indicum | |
| CN107057852B (en) | Preparation method of unsaturated fatty acid tea oil | |
| CN102311882A (en) | Extraction method for unsaturated fatty acid | |
| CN103467432B (en) | A kind of method extracting vitamin E from deodorizer distillate of idesia polycarpa oil | |
| CN101440115A (en) | Method for extracting oryzanol | |
| CN101774997B (en) | Method for completely and continuously extracting natural vitamin E and phytosterol | |
| CN103305332A (en) | Method for separating and gathering 1,3-dioleate-2-palmitic acid triglyceride by using dry coupling solvent method | |
| CN102628003A (en) | Method for extracting purified alpha-linolenic acid from linseed oil | |
| CN107586253B (en) | Method for preparing linoleic acid | |
| CN102311881B (en) | Method for extracting mixed aliphatic acid from abdominal fat of foie gras | |
| CN105237339B (en) | The method that n-octacosanol is extracted by raw material of sugar refinery mix indicator technique | |
| CN103864656B (en) | The method of astaxanthin one ester of astaxanthin odd-numbered fatty acid one ester is rich in preparation | |
| CN101948459B (en) | Method for extracting osthole from traditional Chinese medicine fructus cnidii | |
| CN103588855B (en) | A kind of method of plant sterol of purifying from deodorization distillate | |
| CN107603743A (en) | A kind of extracting method of sunflower seed dregs biowax and application | |
| CN106890199A (en) | Extract method and the medicine containing squalene of plant source spiny dogfish ene compositions and its preparation method and application | |
| CN104710492A (en) | Method for extracting androstenedione in bi-liquid phases system | |
| CN107162910A (en) | The method that high-purity EPA EE are prepared from fish oil | |
| CN102731598A (en) | Comprehensive utilization method of dried orange peel strips | |
| CN106890200A (en) | Extract method and the medicine containing squalene of plant source spiny dogfish ene compositions and its preparation method and application | |
| CN101575553B (en) | Method for classifying partial glyceride with low freezing point | |
| CN109528784A (en) | A method of extracting 4,4 '-dimethylsterols of preparation from shea butter | |
| Kaviani et al. | Comparing different extraction methods of sesame oil |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| CB02 | Change of applicant information | ||
| CB02 | Change of applicant information |
Address after: 564100 green food industrial park, Meitan County, Guizhou, Zunyi Province, 101 floor 1, building 6, clear ecology science and Technology Park Applicant after: Guizhou qianchazhiguang Biotechnology Co., Ltd Applicant after: Wang Xiaoqin Address before: 564100 green food industrial park, Meitan County, Guizhou, Zunyi Province, 101 floor 1, building 6, clear ecology science and Technology Park Applicant before: Zhou Yiqing bio tech ltd, Guizhou Applicant before: Wang Xiaoqin |
|
| GR01 | Patent grant | ||
| GR01 | Patent grant |