CN110511136A - A kind of preparation method of punicic acid - Google Patents
A kind of preparation method of punicic acid Download PDFInfo
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- CN110511136A CN110511136A CN201910828356.7A CN201910828356A CN110511136A CN 110511136 A CN110511136 A CN 110511136A CN 201910828356 A CN201910828356 A CN 201910828356A CN 110511136 A CN110511136 A CN 110511136A
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- punicic acid
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- CUXYLFPMQMFGPL-BGDVVUGTSA-N (9Z,11E,13Z)-octadecatrienoic acid Chemical compound CCCC\C=C/C=C/C=C\CCCCCCCC(O)=O CUXYLFPMQMFGPL-BGDVVUGTSA-N 0.000 title claims abstract description 168
- CUXYLFPMQMFGPL-UYWAGRGNSA-N trichosanic acid Natural products CCCCC=C/C=C/C=CCCCCCCCC(=O)O CUXYLFPMQMFGPL-UYWAGRGNSA-N 0.000 title claims abstract description 84
- 238000002360 preparation method Methods 0.000 title claims abstract description 28
- 235000014113 dietary fatty acids Nutrition 0.000 claims abstract description 61
- 229930195729 fatty acid Natural products 0.000 claims abstract description 61
- 239000000194 fatty acid Substances 0.000 claims abstract description 61
- 150000004665 fatty acids Chemical class 0.000 claims abstract description 61
- 235000015112 vegetable and seed oil Nutrition 0.000 claims abstract description 34
- 230000008014 freezing Effects 0.000 claims abstract description 31
- 238000007710 freezing Methods 0.000 claims abstract description 31
- 239000003960 organic solvent Substances 0.000 claims abstract description 19
- 238000004090 dissolution Methods 0.000 claims abstract description 12
- 239000002253 acid Substances 0.000 claims description 52
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 40
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 27
- 238000002425 crystallisation Methods 0.000 claims description 25
- 230000008025 crystallization Effects 0.000 claims description 25
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 claims description 25
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 20
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 19
- 239000000155 melt Substances 0.000 claims description 18
- 241000219991 Lythraceae Species 0.000 claims description 17
- 235000014360 Punica granatum Nutrition 0.000 claims description 17
- 238000001514 detection method Methods 0.000 claims description 14
- 239000003208 petroleum Substances 0.000 claims description 11
- 238000000605 extraction Methods 0.000 claims description 5
- 238000007127 saponification reaction Methods 0.000 claims description 4
- 229960000935 dehydrated alcohol Drugs 0.000 claims description 3
- 230000020477 pH reduction Effects 0.000 claims description 3
- 208000032544 Cicatrix Diseases 0.000 claims description 2
- 231100000241 scar Toxicity 0.000 claims description 2
- 230000037387 scars Effects 0.000 claims description 2
- 239000000463 material Substances 0.000 abstract description 9
- 238000004519 manufacturing process Methods 0.000 abstract description 3
- 150000005671 trienes Chemical class 0.000 description 19
- 238000002390 rotary evaporation Methods 0.000 description 15
- 235000019197 fats Nutrition 0.000 description 11
- 239000012634 fragment Substances 0.000 description 11
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 10
- 239000004202 carbamide Substances 0.000 description 10
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 9
- 238000000034 method Methods 0.000 description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 8
- 235000019441 ethanol Nutrition 0.000 description 7
- 239000007788 liquid Substances 0.000 description 7
- 239000000706 filtrate Substances 0.000 description 6
- 238000001914 filtration Methods 0.000 description 6
- 238000003756 stirring Methods 0.000 description 6
- 229960004756 ethanol Drugs 0.000 description 5
- 150000004671 saturated fatty acids Chemical class 0.000 description 5
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 4
- 239000006210 lotion Substances 0.000 description 4
- 230000008018 melting Effects 0.000 description 4
- 238000002844 melting Methods 0.000 description 4
- 235000021281 monounsaturated fatty acids Nutrition 0.000 description 4
- 238000010992 reflux Methods 0.000 description 4
- 238000005406 washing Methods 0.000 description 4
- WRIDQFICGBMAFQ-UHFFFAOYSA-N (E)-8-Octadecenoic acid Natural products CCCCCCCCCC=CCCCCCCC(O)=O WRIDQFICGBMAFQ-UHFFFAOYSA-N 0.000 description 3
- LQJBNNIYVWPHFW-UHFFFAOYSA-N 20:1omega9c fatty acid Natural products CCCCCCCCCCC=CCCCCCCCC(O)=O LQJBNNIYVWPHFW-UHFFFAOYSA-N 0.000 description 3
- QSBYPNXLFMSGKH-UHFFFAOYSA-N 9-Heptadecensaeure Natural products CCCCCCCC=CCCCCCCCC(O)=O QSBYPNXLFMSGKH-UHFFFAOYSA-N 0.000 description 3
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- OYHQOLUKZRVURQ-HZJYTTRNSA-N Linoleic acid Chemical compound CCCCC\C=C/C\C=C/CCCCCCCC(O)=O OYHQOLUKZRVURQ-HZJYTTRNSA-N 0.000 description 3
- 239000005642 Oleic acid Substances 0.000 description 3
- ZQPPMHVWECSIRJ-UHFFFAOYSA-N Oleic acid Natural products CCCCCCCCC=CCCCCCCCC(O)=O ZQPPMHVWECSIRJ-UHFFFAOYSA-N 0.000 description 3
- 239000003795 chemical substances by application Substances 0.000 description 3
- 239000000284 extract Substances 0.000 description 3
- QXJSBBXBKPUZAA-UHFFFAOYSA-N isooleic acid Natural products CCCCCCCC=CCCCCCCCCC(O)=O QXJSBBXBKPUZAA-UHFFFAOYSA-N 0.000 description 3
- 239000010410 layer Substances 0.000 description 3
- 235000020778 linoleic acid Nutrition 0.000 description 3
- OYHQOLUKZRVURQ-IXWMQOLASA-N linoleic acid Natural products CCCCC\C=C/C\C=C\CCCCCCCC(O)=O OYHQOLUKZRVURQ-IXWMQOLASA-N 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- ZQPPMHVWECSIRJ-KTKRTIGZSA-N oleic acid Chemical compound CCCCCCCC\C=C/CCCCCCCC(O)=O ZQPPMHVWECSIRJ-KTKRTIGZSA-N 0.000 description 3
- 239000012044 organic layer Substances 0.000 description 3
- 239000012074 organic phase Substances 0.000 description 3
- 230000001376 precipitating effect Effects 0.000 description 3
- 238000013517 stratification Methods 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- GHVNFZFCNZKVNT-UHFFFAOYSA-N decanoic acid Chemical compound CCCCCCCCCC(O)=O GHVNFZFCNZKVNT-UHFFFAOYSA-N 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 235000020777 polyunsaturated fatty acids Nutrition 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- OYHQOLUKZRVURQ-NTGFUMLPSA-N (9Z,12Z)-9,10,12,13-tetratritiooctadeca-9,12-dienoic acid Chemical compound C(CCCCCCC\C(=C(/C\C(=C(/CCCCC)\[3H])\[3H])\[3H])\[3H])(=O)O OYHQOLUKZRVURQ-NTGFUMLPSA-N 0.000 description 1
- 239000005632 Capric acid (CAS 334-48-5) Substances 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 208000024172 Cardiovascular disease Diseases 0.000 description 1
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 1
- 239000005977 Ethylene Substances 0.000 description 1
- 230000005526 G1 to G0 transition Effects 0.000 description 1
- 244000207740 Lemna minor Species 0.000 description 1
- 235000006439 Lemna minor Nutrition 0.000 description 1
- 235000001855 Portulaca oleracea Nutrition 0.000 description 1
- 235000021355 Stearic acid Nutrition 0.000 description 1
- 235000019486 Sunflower oil Nutrition 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 150000001335 aliphatic alkanes Chemical class 0.000 description 1
- -1 aliphatic ester Chemical class 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- 230000000844 anti-bacterial effect Effects 0.000 description 1
- 230000003110 anti-inflammatory effect Effects 0.000 description 1
- 239000008280 blood Substances 0.000 description 1
- 210000004369 blood Anatomy 0.000 description 1
- 230000036772 blood pressure Effects 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000012159 carrier gas Substances 0.000 description 1
- 208000026106 cerebrovascular disease Diseases 0.000 description 1
- 230000021615 conjugation Effects 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 230000002526 effect on cardiovascular system Effects 0.000 description 1
- 238000010828 elution Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000012259 ether extract Substances 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 125000005456 glyceride group Chemical group 0.000 description 1
- IPCSVZSSVZVIGE-UHFFFAOYSA-N hexadecanoic acid Chemical compound CCCCCCCCCCCCCCCC(O)=O IPCSVZSSVZVIGE-UHFFFAOYSA-N 0.000 description 1
- 125000004836 hexamethylene group Chemical group [H]C([H])([*:2])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[*:1] 0.000 description 1
- 239000002035 hexane extract Substances 0.000 description 1
- 150000002632 lipids Chemical class 0.000 description 1
- 239000012046 mixed solvent Substances 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 description 1
- OQCDKBAXFALNLD-UHFFFAOYSA-N octadecanoic acid Natural products CCCCCCCC(C)CCCCCCCCC(O)=O OQCDKBAXFALNLD-UHFFFAOYSA-N 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- 235000019198 oils Nutrition 0.000 description 1
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 1
- 230000000144 pharmacologic effect Effects 0.000 description 1
- 230000002265 prevention Effects 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 230000011218 segmentation Effects 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 238000007493 shaping process Methods 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000008117 stearic acid Substances 0.000 description 1
- 239000002600 sunflower oil Substances 0.000 description 1
- 238000003815 supercritical carbon dioxide extraction Methods 0.000 description 1
- 230000009466 transformation Effects 0.000 description 1
- 235000021122 unsaturated fatty acids Nutrition 0.000 description 1
- 150000004670 unsaturated fatty acids Chemical class 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
- C07C51/02—Preparation of carboxylic acids or their salts, halides or anhydrides from salts of carboxylic acids
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
- C07C51/09—Preparation of carboxylic acids or their salts, halides or anhydrides from carboxylic acid esters or lactones
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
- C07C51/42—Separation; Purification; Stabilisation; Use of additives
- C07C51/43—Separation; Purification; Stabilisation; Use of additives by change of the physical state, e.g. crystallisation
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
- C07C51/42—Separation; Purification; Stabilisation; Use of additives
- C07C51/48—Separation; Purification; Stabilisation; Use of additives by liquid-liquid treatment
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Crystallography & Structural Chemistry (AREA)
- Fats And Perfumes (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention discloses a kind of preparation methods of punicic acid, specific preparation process is: taking granada seed oil fatty acid mixed, organic solvent dissolution is added, 0.5~2h is freezed at -30~-10 DEG C, if all freezing to take solid-state frozen material for solid-state, it places at room temperature, Fractional Collections melt, the part melted out rearward are the segment rich in punicic acid, and the segment that will be enriched in punicic acid removes organic solvent up to high purity punicic acid.The present invention, which is reached using punicic acid with the difference of other fatty acid fusing points, separates purpose, has many advantages, such as with short production cycle, high income, at low cost, easy to operate.
Description
Technical field
The present invention relates to the preparation methods of a kind of preparation method of punicic acid, especially high purity punicic acid.
Background technique
Punicic acid is main fatty acid contained in granada seed oil, accounts for 60% or more of fatty acid gross weight.Punicic acid tool
There are reducing blood lipid, blood pressure lowering, prevention cardiovascular and cerebrovascular disease, antibacterial and the multiple efficacies such as anti-inflammatory, is that granada seed oil plays pharmacological action
Most important component.Punicic acid is isolated and purified out from granada seed oil, helps to improve activity and curative effect, agent is taken in reduction
Amount, facilitates preparations shaping.
Punicic acid exists in the form of glyceride and phosphatide in granada seed oil, needs first through saponification by granada seed oil
In aliphatic ester be decomposed into fatty acid, the punicic acid of high-purity is further isolated from fatty acid mixed.Common point
It is pillar layer separation from technology, mixture passes through the chromatographic column of opposed polarity, through elution and Fractional Collections, can obtain high-purity
Target compound, disadvantage be time-consuming, target compound is often adsorbed by chromatographic column, leads to low yield；Cross the organic solvent of column
Dosage is big, recycles after need to often recycling.Patent " a method of produce high purity punicic acid " (patent No. ZL
200510012802.5) urea adduct method is used to prepare high purity punicic acid, pass through supercritical carbon dioxide extraction method first
Obtain granada seed oil, then by granada seed oil through saponification, acidification and extraction and etc. obtain granada seed oil fatty acid mixed after processing；
Urea dissolution is added in fatty acid mixed in methyl alcohol, freezes 10h or more, filters, is precipitated as urea-containing saturated fatty acid
And monounsaturated fatty acids, filtrate are punicic acid methanol solution, after removing methanol, pomegranate acid content is up to 92%.Urea clathrate
The principle of method are as follows: urea is easily in conjunction with saturated fatty acid and monounsaturated fatty acids, after chilled, is divided into solid-liquid two condition, solid
In the main conjugate containing urea and saturated fatty acid and monounsaturated fatty acids, be enriched containing two or two or more in filtrate
The polyunsaturated fatty acid of double bond, after removing urea and organic solvent, the content of polyunsaturated fatty acid is significantly improved.This method
Disadvantage are as follows: it is practical also containing the urea dissolved on a small quantity in filtrate, need acidified and extraction process that can remove urea (Zhao
Duckweed waits urea adduct method to study oil engineering to the enrichment of sunflower oil Linoleic acid, 2015,12,31-34.), operation compared with
To be cumbersome, punicic acid loss is larger in extraction process, causes last yield not high.In addition, cooling time is in 10h or more, production
Period is long, and efficiency is relatively low.
It yet there are no the report for separating punicic acid from granada seed oil fatty acid mixed using freezing and crystallizing method.
Summary of the invention
The purpose of the present invention is to provide a kind of time-consumings short, at low cost, high income and high purity punicic acid easy to operate
Preparation method.
The preparation method of punicic acid provided by the invention is: granada seed oil fatty acid mixed taken, organic solvent dissolution is added,
0.5~2h is freezed at -30~-10 DEG C, if all freezing solid-state scars to be taken, placed at room temperature for solid-state, Fractional Collections
Melt, the part melted out rearward are the segment rich in punicic acid, and the segment that will be enriched in punicic acid removes organic solvent up to high
Purity punicic acid.
Further, gained high purity punicic acid is subjected to content detection, it, will be through primary cold if content not up to requires
Freeze high purity punicic acid obtained by crystallization treatment and carry out primary or secondary Freeze crystallization again, until pomegranate acid content reaches and wants
It asks.
Further, the part melted out rearward refers to that last 30%~60% melts out object.
Further, if after granada seed oil fatty acid mixed is dissolved in organic solution and chilled processing, only partially freeze for
Solid-state then filters, and collects the residue on filter up to punicic acid.
Further, the organic solvent is one of acetone, dehydrated alcohol, methanol, n-hexane, petroleum ether or one kind
Above combination.
Further, the additional amount of the organic solvent is 8~20 times of granada seed oil fatty acid mixed weight.
Further, the granada seed oil fatty acid mixed through saponification, acidification, extraction and is removed organic molten by granada seed oil
It is made after agent, comprises the concrete steps that: taking granada seed oil, the KOH- that concentration is 3% to 10% is added in the ratio of 1:10 to 1:20
95% ethanol solution is heated to reflux 1-2h under 70-90 DEG C of water-bath, adds appropriate warm water dissolution saponified, is cooled to room temperature, with acid
PH to 2-4 is adjusted, 10-30 min is stirred, keeps fatty acid sufficiently free, then extract fatty acid therein with organic solvent；It has taken
Solvent layer, it is neutral for being washed with warm water to washing lotion, anhydrous sodium sulfate drying is added, filtration is removed in evaporation on Rotary Evaporators
Go organic solvent to get fatty acid mixed.It is described extract fatty acid organic solvent, be petroleum ether, n-hexane, methylene chloride,
One of ethyl acetate, hexamethylene or more than one combination.
Unsaturated fatty acid contained in granada seed oil mainly includes oleic acid, linoleic acid and punicic acid, they are 18
Carbon enoic acid contains one, two and three double bond respectively, and ethylene linkage causes intermolecular binding force to increase, freezing point decline, and organic molten
After -10 DEG C or less freezings, through being placed at room temperature for, saturated fatty acid is melted with organic solvent at first because fusing point is higher, is then for agent
Oleic acid containing double bond and the linoleic acid containing two double bonds, finally melting is the punicic acid containing three double bonds, passes through segmentation
The melt of fatty acid mixed and organic solvent is collected, and removes organic solvent rich in pomegranate acid fragment for what is melted out rearward, i.e.,
It can get punicic acid.
The present invention, which is reached using punicic acid with the difference of other fatty acid fusing points, separates purpose, only comprising freezing, fusing and
Except three steps of solvent, cooling time is in 2h hereinafter, having many advantages, such as with short production cycle, high income, at low cost, easy to operate.
Experiments have shown that punicic acid purity can be improved by 78% to 85% or more, through secondary freezing and crystallizing, punicic acid through a freezing and crystallizing
Purity can reach 89% or more (used granada seed oil be homemade, pomegranate acid content is 75% or more).
Detailed description of the invention
Fig. 1 is the GC figure for finally melting out segment in embodiment 1 after a freezing and crystallizing.
Fig. 2 is the GC figure for finally melting out segment in embodiment 1 after secondary freezing and crystallizing.
Fig. 3 is the GC figure for finally melting out segment in embodiment 1 after freezing and crystallizing three times.
In figure: 1, capric acid (internal standard)；2, palmitinic acid；3, linoleic acid；4, oleic acid；5, stearic acid；6, punicic acid；7-9, pomegranate
Acid isomer.
Specific embodiment
For a better understanding of the present invention, present invention is further described in detail combined with specific embodiments below, but this
The protection scope of invention is without being limited thereto.
Embodiment 1
(1) preparation of fatty acid mixed
A. it is derived from granada seed oil processed, the KOH-95% ethanol solution that the concentration for being added 18 times of granada seed oil weight is 3%, In
2h is heated to reflux under 70 DEG C of water-baths；
B. plus in right amount warm water dissolution precipitating (saponified), and salt acid for adjusting pH value to 2 is used, stirring 20min；
C. plus in equal volume n-hexane extracts, and stratification takes upper organic phase；Organic layer is washed in multiple times on a small quantity with water,
It is neutrality to washing lotion；
D. anhydrous sodium sulfate is added, it is stirring while adding, until not agglomerating, stand 30min；Filtrate, rotary evaporation are collected in filtration
N-hexane is removed, granada seed oil fatty acid mixed is obtained；Through GC detection, wherein punicic acid and its C18 conjugated triene acid isomer always contain
Amount is 78.47%.
(2) preparation of punicic acid
A. granada seed oil fatty acid mixed is taken, is weighed, 8 times of fatty acid mixed weight of acetone is added, being sufficiently stirred makes to mix
Fatty acid dissolution is closed, then -30 DEG C of freezing 1h；
B. it will be taken out after the freezing of above-mentioned mixing-in fat acid dissoluting liquid from freezing chamber, being placed in melts it slowly at room temperature, receives
Collect last 40% and melts out object to get rich in pomegranate acid fragment；
C. it will be enriched in pomegranate acid fragment rotary evaporation and remove acetone, obtain the fatty acid mixt rich in punicic acid, examined through GC
It surveys wherein punicic acid and its C18 conjugated triene acid isomer total content is 85.24%；
D. the fatty acid mixt obtained through first time Freeze crystallization is weighed, the acetone of 8 times of its weight is added, into
Second of Freeze crystallization of row, cryogenic temperature and time are identical as first time Freeze crystallization；
E. solid-state frozen material is taken, is melted at room temperature, 50% melts out object after collection, and rotary evaporation removes acetone, must be rich in
The fatty acid mixt of punicic acid, through GC detection, wherein punicic acid and its C18 conjugated triene acid isomer total content are
89.26%；
F. the fatty acid mixt obtained through second of Freeze crystallization is weighed, the acetone of 8 times of its weight is added, into
Row third time Freeze crystallization, cryogenic temperature and time are identical as first time Freeze crystallization；
G. solid-state frozen material is taken, is melted at room temperature, 60% melts out object after collection, and rotary evaporation removes acetone, must be rich in
The fatty acid mixt of punicic acid, through GC detection, wherein punicic acid and its C18 conjugated triene acid isomer total content are
90.71%；
Melt out the determination condition of pomegranate acid content in object with GC detection are as follows: stationary phase be HP-5 capillary column (30m ×
0.32mm × 0.25 μm), carrier gas is high pure nitrogen, column flow 1.2mL/min, split ratio 20:1,270 DEG C of injector temperature,
310 DEG C of fid detector temperature.Capillary column temperature programming: 90 DEG C of beginnings keep 3min, are raised to 180 with the speed of 15 DEG C/min
DEG C, 10min is kept, then be raised to 250 DEG C with the speed of 2.5 DEG C/min.1 μ L of sample volume.
In former fatty acid mixed, calculated by peak area ratio, punicic acid and its C18 conjugated triene acid isomer total content are
78.47%, it is 7.47 with internal standard ratio.After a freezing and crystallizing, punicic acid and its C18 conjugated triene acid isomer it is total
Content is 85.24%, is 7.97 (see Fig. 1) with interior target ratio；After secondary freezing and crystallizing, punicic acid and its C18 conjugation three
The total content of olefin(e) acid isomers rises to 89.26%, with interior target ratio 9.67 (see Fig. 2)；After third time Freeze crystallization,
The total content of punicic acid and its C18 conjugated triene acid isomer is 90.71%, is 9.98 (see Fig. 3) with interior target ratio.By scheming
It is found that saturated fatty acid and monounsaturated fatty acids peak height are declined slightly with the increase of Freeze crystallization number, and punicic acid
And its peak height of C18 conjugated triene acid isomer is being stepped up, and shows that its percentage composition and purity are improving.
Embodiment 2
(1) preparation of fatty acid mixed
A. commercially available granada seed oil is taken, the KOH-95% ethanol solution that the concentration for being added 10 times of granada seed oil weight is 8%, In
1.5h is heated to reflux under 80 DEG C of water-baths；
B. plus in right amount warm water dissolves precipitating (saponified), and adjusts pH value to 3 with dilute sulfuric acid, stirs 30min；
C. plus in equal volume petroleum ether extracts, and stratification takes upper organic phase；Organic layer is washed in multiple times on a small quantity with water,
It is neutrality to washing lotion；
D. anhydrous sodium sulfate is added, it is stirring while adding, until not agglomerating, stand 20min；Filtrate, rotary evaporation are collected in filtration
Petroleum ether is removed, granada seed oil fatty acid mixed is obtained；Through GC detection, wherein punicic acid and its C18 conjugated triene acid isomer always contain
Amount is 67.37%；
(2) preparation of punicic acid
A. granada seed oil fatty acid mixed is taken, is weighed, 12 times of fatty acid mixed weight of dehydrated alcohol is added, is sufficiently stirred
Make mixing-in fat acid dissolution, then -10 DEG C of freezing 2h；
B. it will be taken out after the freezing of above-mentioned mixing-in fat acid dissoluting liquid from freezing chamber, mixing-in fat acid dissoluting liquid only partial freeze
For solid-state, filtration takes the solid-state frozen material on filtering layer to get rich in pomegranate acid fragment；
C. it will be enriched in pomegranate acid fragment rotary evaporation and remove ethyl alcohol, obtain the fatty acid mixt rich in punicic acid, examined through GC
It surveys wherein punicic acid and its C18 conjugated triene acid isomer total content is 75%.
The determination condition that GC is detected in the present embodiment is same as Example 1.
Embodiment 3
(1) preparation of fatty acid mixed
A. it is derived from granada seed oil processed, the KOH-95% ethanol solution that the concentration for being added 15 times of granada seed oil weight is 5%, In
2h is heated to reflux under 60 DEG C of water-baths；
B. plus in right amount warm water dissolution precipitating (saponified), and salt acid for adjusting pH value to 2 is used, stirring 10min；
C. plus in equal volume methylene chloride extracts, and stratification takes upper organic phase；It is washed in multiple times on a small quantity with water organic
Layer, until washing lotion is neutrality；
D. anhydrous sodium sulfate is added, it is stirring while adding, until not agglomerating, stand 30min；Filtrate, rotary evaporation are collected in filtration
Methylene chloride is removed, granada seed oil fatty acid mixed is obtained；Through GC detection, wherein punicic acid and its C18 conjugated triene acid isomer are total
Content is 79.2%；
(2) preparation of punicic acid
A. fatty acid mixed is taken, is weighed, 18 times of fatty acid mixed weight of n-hexane is added, being sufficiently stirred makes mixing-in fat
Acid dissolution, then -20 DEG C of freezing 1.5h；
B. it will be taken out after the freezing of above-mentioned mixing-in fat acid dissoluting liquid from freezing chamber, being placed in melts it slowly at room temperature, receives
Collect last 30% and melts out object to get rich in pomegranate acid fragment；
C. it will be enriched in pomegranate acid fragment rotary evaporation and remove n-hexane, the fatty acid mixt rich in punicic acid is obtained, through GC
Wherein punicic acid and its C18 conjugated triene acid isomer total content are 87% for detection；
D. by the fatty acid mixt obtained through first time Freeze crystallization weigh, be added 10 times of its weight just oneself
Alkane carries out second of Freeze crystallization, and cryogenic temperature and time are identical as first time Freeze crystallization；
E. solid-state frozen material is taken, is melted at room temperature, last 60% object that melts out is collected, rotary evaporation removes n-hexane, obtains
Fatty acid mixt rich in punicic acid, through GC detection, wherein punicic acid and its C18 conjugated triene acid isomer total content are
91%.
The determination condition that GC is detected in the present embodiment is same as Example 1.
Embodiment 4
(1) preparation of fatty acid mixed
Preparation process is same as Example 1
(2) preparation of punicic acid
A. fatty acid mixed is taken, is weighed, 5 times of acetone of fatty acid mixed weight and 4 times of methanol is added, being sufficiently stirred makes
Mixing-in fat acid dissolution, then -30 DEG C of freezing 1h；
B. it will be taken out after the freezing of above-mentioned mixing-in fat acid dissoluting liquid from freezing chamber, being placed in melts it slowly at room temperature, receives
Collect last 50% and melts out object to get rich in pomegranate acid fragment；
C. it will be enriched in pomegranate acid fragment rotary evaporation and remove acetone and methanol, obtain the fatty acid mixt rich in punicic acid,
Through GC detection, wherein punicic acid and its C18 conjugated triene acid isomer total content are 78.1%；
D. the fatty acid mixt obtained through first time Freeze crystallization is weighed, the acetone and 4 of 5 times of its weight is added
Methanol again carries out second of Freeze crystallization, and cryogenic temperature and time are identical as first time Freeze crystallization；
E. solid-state frozen material is taken, is melted at room temperature, last 50% object that melts out is collected, rotary evaporation removes acetone and first
Alcohol obtains the fatty acid mixt rich in punicic acid, and through GC detection, wherein punicic acid and its C18 conjugated triene acid isomer always contain
Amount is 84%；
F. the fatty acid mixt obtained through second of Freeze crystallization is weighed, the acetone and 4 of 5 times of its weight is added
Methanol again carries out third time Freeze crystallization, and cryogenic temperature and time are identical as first time Freeze crystallization；
G. solid-state frozen material is taken, is melted at room temperature, last 60% object that melts out is collected, rotary evaporation removes acetone and first
Alcohol obtains the fatty acid mixt rich in punicic acid, and through GC detection, wherein punicic acid and its C18 conjugated triene acid isomer always contain
Amount is 90%.
The determination condition that GC is detected in the present embodiment is same as Example 1.
Embodiment 5
(1) preparation of fatty acid mixed
Preparation process is same as Example 1
(2) preparation of punicic acid
A. it fatty acid mixed is taken, weighs, 5 times of petroleum ether of fatty acid mixed weight, 4 times of n-hexane and 3 times is added
Acetone, being sufficiently stirred makes mixing-in fat acid dissolution, then -20 DEG C of freezing 2h；
B. it will be taken out after the freezing of above-mentioned mixing-in fat acid dissoluting liquid from freezing chamber, being placed in melts it slowly at room temperature, receives
Collect last 60% and melts out object to get rich in pomegranate acid fragment；
C. it will be enriched in pomegranate acid fragment rotary evaporation and remove petroleum ether, n-hexane and acetone, obtain the fat rich in punicic acid
Acid blend, through GC detection, wherein punicic acid and its C18 conjugated triene acid isomer total content are 79.2%；
D. the fatty acid mixt obtained through first time Freeze crystallization is weighed, 3.5 times of petroleum of its weight is added
Ether, 2.8 times of n-hexanes and 2.1 times of acetone, carry out second of Freeze crystallization, cryogenic temperature and time and freezing for the first time is tied
Crystalline substance processing is identical；
E. solid-state frozen material is taken, is melted at room temperature, last 60% is collected and melts out object, rotary evaporation removes petroleum ether, just
Hexane and acetone obtain the fatty acid mixt rich in punicic acid, detect wherein punicic acid and its C18 conjugated triene acid isomer through GC
Body total content is 85%；
F. the fatty acid mixt obtained through second of Freeze crystallization is weighed, 3.5 times of petroleum of its weight is added
Ether, 2.8 times of n-hexanes and 2.1 times of acetone, carry out third time Freeze crystallization, cryogenic temperature and time and freezing for the first time is tied
Crystalline substance processing is identical；
G. solid-state frozen material is taken, is melted at room temperature, last 60% is collected and melts out object, rotary evaporation removes petroleum ether, just
Hexane and acetone obtain the fatty acid mixt rich in punicic acid, detect wherein punicic acid and its C18 conjugated triene acid isomer through GC
Body total content is 89%.
The determination condition that GC is detected in the present embodiment is same as Example 1.
The above is only the preferred embodiment of the present invention, but scope of protection of the present invention is not limited thereto, any
The transformation and replacement carried out based on technical solution provided by the present invention and inventive concept should all be covered in protection model of the invention
In enclosing.
Claims (7)
1. a kind of preparation method of punicic acid, it is characterised in that: granada seed oil fatty acid mixed is taken, organic solvent dissolution is added,
0.5~2h is freezed at -30~-10 DEG C, if all freezing solid-state scars to be taken, placed at room temperature for solid-state, Fractional Collections
Melt, the part melted out rearward are the segment rich in punicic acid, and the segment that will be enriched in punicic acid removes organic solvent up to high
Purity punicic acid.
2. the preparation method of punicic acid according to claim 1, it is characterised in that: contain gained high purity punicic acid
Amount detection will carry out again primary or two through high purity punicic acid obtained by a Freeze crystallization if content not up to requires
Secondary Freeze crystallization, until pomegranate acid content reaches requirement.
3. the preparation method of punicic acid according to claim 1 or 2, it is characterised in that: the part melted out rearward is
Refer to that last 30%~60% melts out object.
4. the preparation method of punicic acid according to claim 1, it is characterised in that: if granada seed oil fatty acid mixed is dissolved in
After organic solution and chilled processing, only partially freeze then to filter for solid-state, collects the residue on filter up to punicic acid.
5. the preparation method of high purity punicic acid according to claim 1 or 4, it is characterised in that: the granada seed oil is mixed
It closes fatty acid and is made after saponification, acidification, extraction and removing organic solvent by granada seed oil.
6. the preparation method of high purity punicic acid according to claim 1 or 4, it is characterised in that: the organic solvent is
One of acetone, dehydrated alcohol, methanol, n-hexane, petroleum ether or more than one combination.
7. the preparation method of high purity punicic acid according to claim 1 or 4, it is characterised in that: the organic solvent
Additional amount is 8~20 times of granada seed oil fatty acid mixed weight.
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|---|---|---|---|---|
| US20060189817A1 (en) * | 2002-12-18 | 2006-08-24 | Peter Horlacher | Method for producing conjugated linoleic acid |
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| CN102030629A (en) * | 2010-12-02 | 2011-04-27 | 上海麦风微波设备有限公司 | Alpha linolenic acid cryogenic separation and purification method |
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| US20060189817A1 (en) * | 2002-12-18 | 2006-08-24 | Peter Horlacher | Method for producing conjugated linoleic acid |
| CN101386577A (en) * | 2007-09-11 | 2009-03-18 | 河南师范大学 | Purification of conjugate linolenic acid by multi-stage constant temperature crystallization process |
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