CN114933529B - Method for separating and preparing high-purity ethyl nervonate from acer truncatum kernel - Google Patents
Method for separating and preparing high-purity ethyl nervonate from acer truncatum kernel Download PDFInfo
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- CN114933529B CN114933529B CN202210530340.XA CN202210530340A CN114933529B CN 114933529 B CN114933529 B CN 114933529B CN 202210530340 A CN202210530340 A CN 202210530340A CN 114933529 B CN114933529 B CN 114933529B
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- ethyl
- nervonate
- acer truncatum
- crude product
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- 241000219226 Acer truncatum Species 0.000 title claims abstract description 95
- CTKJRXIVYBGZEW-QXMHVHEDSA-N ethyl (z)-tetracos-15-enoate Chemical compound CCCCCCCC\C=C/CCCCCCCCCCCCCC(=O)OCC CTKJRXIVYBGZEW-QXMHVHEDSA-N 0.000 title claims abstract description 91
- 238000000034 method Methods 0.000 title claims abstract description 63
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims abstract description 105
- 239000004202 carbamide Substances 0.000 claims abstract description 59
- 239000012043 crude product Substances 0.000 claims abstract description 55
- 235000014113 dietary fatty acids Nutrition 0.000 claims abstract description 41
- 229930195729 fatty acid Natural products 0.000 claims abstract description 41
- 239000000194 fatty acid Substances 0.000 claims abstract description 41
- 238000000199 molecular distillation Methods 0.000 claims abstract description 33
- 238000002425 crystallisation Methods 0.000 claims abstract description 27
- 230000008025 crystallization Effects 0.000 claims abstract description 26
- 239000010779 crude oil Substances 0.000 claims abstract description 24
- 238000000746 purification Methods 0.000 claims abstract description 22
- 239000000047 product Substances 0.000 claims abstract description 15
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 77
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 46
- 235000015112 vegetable and seed oil Nutrition 0.000 claims description 43
- GWHCXVQVJPWHRF-KTKRTIGZSA-N (15Z)-tetracosenoic acid Chemical group CCCCCCCC\C=C/CCCCCCCCCCCCCC(O)=O GWHCXVQVJPWHRF-KTKRTIGZSA-N 0.000 claims description 42
- GWHCXVQVJPWHRF-UHFFFAOYSA-N cis-tetracosenoic acid Natural products CCCCCCCCC=CCCCCCCCCCCCCCC(O)=O GWHCXVQVJPWHRF-UHFFFAOYSA-N 0.000 claims description 42
- XJXROGWVRIJYMO-SJDLZYGOSA-N Nervonic acid Natural products O=C(O)[C@@H](/C=C/CCCCCCCC)CCCCCCCCCCCC XJXROGWVRIJYMO-SJDLZYGOSA-N 0.000 claims description 41
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 36
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 33
- 239000003960 organic solvent Substances 0.000 claims description 26
- 238000005406 washing Methods 0.000 claims description 26
- 235000019441 ethanol Nutrition 0.000 claims description 23
- 238000002156 mixing Methods 0.000 claims description 23
- 239000003208 petroleum Substances 0.000 claims description 23
- 239000000243 solution Substances 0.000 claims description 21
- 150000001875 compounds Chemical class 0.000 claims description 17
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 15
- 238000010992 reflux Methods 0.000 claims description 13
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims description 12
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 12
- 239000002994 raw material Substances 0.000 claims description 12
- 239000012670 alkaline solution Substances 0.000 claims description 10
- 239000003054 catalyst Substances 0.000 claims description 10
- 239000011259 mixed solution Substances 0.000 claims description 10
- 238000000967 suction filtration Methods 0.000 claims description 10
- 239000012535 impurity Substances 0.000 claims description 9
- 238000000605 extraction Methods 0.000 claims description 8
- 238000006243 chemical reaction Methods 0.000 claims description 7
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 6
- 239000006227 byproduct Substances 0.000 claims description 6
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 claims description 6
- 239000003513 alkali Substances 0.000 claims description 2
- 230000035484 reaction time Effects 0.000 claims 2
- 125000004494 ethyl ester group Chemical group 0.000 claims 1
- 230000008569 process Effects 0.000 abstract description 14
- 238000000926 separation method Methods 0.000 abstract description 10
- 230000008901 benefit Effects 0.000 abstract description 5
- 238000003860 storage Methods 0.000 abstract description 2
- 238000005809 transesterification reaction Methods 0.000 abstract description 2
- XIRNKXNNONJFQO-UHFFFAOYSA-N ethyl hexadecanoate Chemical compound CCCCCCCCCCCCCCCC(=O)OCC XIRNKXNNONJFQO-UHFFFAOYSA-N 0.000 description 14
- MVLVMROFTAUDAG-UHFFFAOYSA-N ethyl octadecanoate Chemical compound CCCCCCCCCCCCCCCCCC(=O)OCC MVLVMROFTAUDAG-UHFFFAOYSA-N 0.000 description 14
- 238000001704 evaporation Methods 0.000 description 14
- 239000003921 oil Substances 0.000 description 11
- 235000019198 oils Nutrition 0.000 description 11
- 239000000284 extract Substances 0.000 description 9
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 8
- 239000000203 mixture Substances 0.000 description 8
- 239000008367 deionised water Substances 0.000 description 7
- 229910021641 deionized water Inorganic materials 0.000 description 7
- WFZQLUSOXHIVKL-QXMHVHEDSA-N ethyl (13Z)-docosenoate Chemical compound CCCCCCCC\C=C/CCCCCCCCCCCC(=O)OCC WFZQLUSOXHIVKL-QXMHVHEDSA-N 0.000 description 7
- 229940067592 ethyl palmitate Drugs 0.000 description 7
- 230000008020 evaporation Effects 0.000 description 7
- 238000001914 filtration Methods 0.000 description 6
- 239000000463 material Substances 0.000 description 6
- 240000002234 Allium sativum Species 0.000 description 5
- 238000005352 clarification Methods 0.000 description 5
- 235000013399 edible fruits Nutrition 0.000 description 5
- YBKSMWBLSBAFBQ-UHFFFAOYSA-N ethyl arachidate Chemical compound CCCCCCCCCCCCCCCCCCCC(=O)OCC YBKSMWBLSBAFBQ-UHFFFAOYSA-N 0.000 description 5
- -1 fatty acid ester Chemical class 0.000 description 5
- 239000000706 filtrate Substances 0.000 description 5
- 235000004611 garlic Nutrition 0.000 description 5
- 238000011160 research Methods 0.000 description 5
- 238000002390 rotary evaporation Methods 0.000 description 5
- 239000000126 substance Substances 0.000 description 5
- 241000251730 Chondrichthyes Species 0.000 description 4
- LVGKNOAMLMIIKO-UHFFFAOYSA-N Elaidinsaeure-aethylester Natural products CCCCCCCCC=CCCCCCCCC(=O)OCC LVGKNOAMLMIIKO-UHFFFAOYSA-N 0.000 description 4
- 238000001816 cooling Methods 0.000 description 4
- LVGKNOAMLMIIKO-QXMHVHEDSA-N ethyl oleate Chemical compound CCCCCCCC\C=C/CCCCCCCC(=O)OCC LVGKNOAMLMIIKO-QXMHVHEDSA-N 0.000 description 4
- 229940093471 ethyl oleate Drugs 0.000 description 4
- 150000004665 fatty acids Chemical class 0.000 description 4
- 235000011187 glycerol Nutrition 0.000 description 4
- 239000002253 acid Substances 0.000 description 3
- 230000009286 beneficial effect Effects 0.000 description 3
- 238000011161 development Methods 0.000 description 3
- 230000018109 developmental process Effects 0.000 description 3
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 3
- 239000012071 phase Substances 0.000 description 3
- 239000007787 solid Substances 0.000 description 3
- 238000010025 steaming Methods 0.000 description 3
- GVJHHUAWPYXKBD-UHFFFAOYSA-N (±)-α-Tocopherol Chemical compound OC1=C(C)C(C)=C2OC(CCCC(C)CCCC(C)CCCC(C)C)(C)CCC2=C1C GVJHHUAWPYXKBD-UHFFFAOYSA-N 0.000 description 2
- 235000017060 Arachis glabrata Nutrition 0.000 description 2
- 244000105624 Arachis hypogaea Species 0.000 description 2
- 235000010777 Arachis hypogaea Nutrition 0.000 description 2
- 235000018262 Arachis monticola Nutrition 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical group [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- 241000196324 Embryophyta Species 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- 239000003225 biodiesel Substances 0.000 description 2
- 210000004556 brain Anatomy 0.000 description 2
- 210000005013 brain tissue Anatomy 0.000 description 2
- 238000003763 carbonization Methods 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 238000004821 distillation Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- JIZCYLOUIAIZHQ-UHFFFAOYSA-N ethyl docosenyl Chemical compound CCCCCCCCCCCCCCCCCCCCCC(=O)OCC JIZCYLOUIAIZHQ-UHFFFAOYSA-N 0.000 description 2
- 230000002349 favourable effect Effects 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- AINIZSBLAFHZCP-KHPPLWFESA-N methyl cis-15-tetracosenoate Chemical compound CCCCCCCC\C=C/CCCCCCCCCCCCCC(=O)OC AINIZSBLAFHZCP-KHPPLWFESA-N 0.000 description 2
- 210000002569 neuron Anatomy 0.000 description 2
- 235000020232 peanut Nutrition 0.000 description 2
- 238000001556 precipitation Methods 0.000 description 2
- 230000008439 repair process Effects 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- 210000001519 tissue Anatomy 0.000 description 2
- SPSSULHKWOKEEL-UHFFFAOYSA-N 2,4,6-trinitrotoluene Chemical compound CC1=C([N+]([O-])=O)C=C([N+]([O-])=O)C=C1[N+]([O-])=O SPSSULHKWOKEEL-UHFFFAOYSA-N 0.000 description 1
- 241000208140 Acer Species 0.000 description 1
- 102000004190 Enzymes Human genes 0.000 description 1
- 108090000790 Enzymes Proteins 0.000 description 1
- 241001465754 Metazoa Species 0.000 description 1
- 238000000944 Soxhlet extraction Methods 0.000 description 1
- 229930182558 Sterol Natural products 0.000 description 1
- 229930003427 Vitamin E Natural products 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 210000004204 blood vessel Anatomy 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 230000002490 cerebral effect Effects 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 235000009508 confectionery Nutrition 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 239000002537 cosmetic Substances 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 239000012153 distilled water Substances 0.000 description 1
- 229940079593 drug Drugs 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- FMMOOAYVCKXGMF-MURFETPASA-N ethyl linoleate Chemical compound CCCCC\C=C/C\C=C/CCCCCCCC(=O)OCC FMMOOAYVCKXGMF-MURFETPASA-N 0.000 description 1
- 229940031016 ethyl linoleate Drugs 0.000 description 1
- JYYFMIOPGOFNPK-AGRJPVHOSA-N ethyl linolenate Chemical compound CCOC(=O)CCCCCCC\C=C/C\C=C/C\C=C/CC JYYFMIOPGOFNPK-AGRJPVHOSA-N 0.000 description 1
- JYYFMIOPGOFNPK-UHFFFAOYSA-N ethyl linolenate Natural products CCOC(=O)CCCCCCCC=CCC=CCC=CCC JYYFMIOPGOFNPK-UHFFFAOYSA-N 0.000 description 1
- 229940090028 ethyl linolenate Drugs 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 230000006870 function Effects 0.000 description 1
- WIGCFUFOHFEKBI-UHFFFAOYSA-N gamma-tocopherol Natural products CC(C)CCCC(C)CCCC(C)CCCC1CCC2C(C)C(O)C(C)C(C)C2O1 WIGCFUFOHFEKBI-UHFFFAOYSA-N 0.000 description 1
- 230000036541 health Effects 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- FMMOOAYVCKXGMF-UHFFFAOYSA-N linoleic acid ethyl ester Natural products CCCCCC=CCC=CCCCCCCCC(=O)OCC FMMOOAYVCKXGMF-UHFFFAOYSA-N 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 230000000813 microbial effect Effects 0.000 description 1
- 239000012046 mixed solvent Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 229930014626 natural product Natural products 0.000 description 1
- 210000004126 nerve fiber Anatomy 0.000 description 1
- 210000000944 nerve tissue Anatomy 0.000 description 1
- 239000012074 organic phase Substances 0.000 description 1
- 230000020477 pH reduction Effects 0.000 description 1
- 230000000144 pharmacologic effect Effects 0.000 description 1
- 230000035790 physiological processes and functions Effects 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 238000004321 preservation Methods 0.000 description 1
- 238000003825 pressing Methods 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 230000008929 regeneration Effects 0.000 description 1
- 238000011069 regeneration method Methods 0.000 description 1
- 239000002689 soil Substances 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 150000003432 sterols Chemical class 0.000 description 1
- 235000003702 sterols Nutrition 0.000 description 1
- 230000004083 survival effect Effects 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
- UFTFJSFQGQCHQW-UHFFFAOYSA-N triformin Chemical compound O=COCC(OC=O)COC=O UFTFJSFQGQCHQW-UHFFFAOYSA-N 0.000 description 1
- 125000005457 triglyceride group Chemical group 0.000 description 1
- 239000000015 trinitrotoluene Substances 0.000 description 1
- 229910021642 ultra pure water Inorganic materials 0.000 description 1
- 239000012498 ultrapure water Substances 0.000 description 1
- 229940046009 vitamin E Drugs 0.000 description 1
- 235000019165 vitamin E Nutrition 0.000 description 1
- 239000011709 vitamin E Substances 0.000 description 1
Classifications
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C67/00—Preparation of carboxylic acid esters
- C07C67/08—Preparation of carboxylic acid esters by reacting carboxylic acids or symmetrical anhydrides with the hydroxy or O-metal group of organic compounds
-
- 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
- C07C67/00—Preparation of carboxylic acid esters
- C07C67/48—Separation; Purification; Stabilisation; Use of additives
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C67/00—Preparation of carboxylic acid esters
- C07C67/48—Separation; Purification; Stabilisation; Use of additives
- C07C67/52—Separation; Purification; Stabilisation; Use of additives by change in the physical state, e.g. crystallisation
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C67/00—Preparation of carboxylic acid esters
- C07C67/48—Separation; Purification; Stabilisation; Use of additives
- C07C67/52—Separation; Purification; Stabilisation; Use of additives by change in the physical state, e.g. crystallisation
- C07C67/54—Separation; Purification; Stabilisation; Use of additives by change in the physical state, e.g. crystallisation by distillation
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C67/00—Preparation of carboxylic acid esters
- C07C67/48—Separation; Purification; Stabilisation; Use of additives
- C07C67/58—Separation; Purification; Stabilisation; Use of additives by liquid-liquid treatment
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11B—PRODUCING, e.g. BY PRESSING RAW MATERIALS OR BY EXTRACTION FROM WASTE MATERIALS, REFINING OR PRESERVING FATS, FATTY SUBSTANCES, e.g. LANOLIN, FATTY OILS OR WAXES; ESSENTIAL OILS; PERFUMES
- C11B1/00—Production of fats or fatty oils from raw materials
- C11B1/02—Pretreatment
- C11B1/04—Pretreatment of vegetable raw material
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11B—PRODUCING, e.g. BY PRESSING RAW MATERIALS OR BY EXTRACTION FROM WASTE MATERIALS, REFINING OR PRESERVING FATS, FATTY SUBSTANCES, e.g. LANOLIN, FATTY OILS OR WAXES; ESSENTIAL OILS; PERFUMES
- C11B1/00—Production of fats or fatty oils from raw materials
- C11B1/06—Production of fats or fatty oils from raw materials by pressing
- C11B1/08—Production of fats or fatty oils from raw materials by pressing by hot pressing
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11B—PRODUCING, e.g. BY PRESSING RAW MATERIALS OR BY EXTRACTION FROM WASTE MATERIALS, REFINING OR PRESERVING FATS, FATTY SUBSTANCES, e.g. LANOLIN, FATTY OILS OR WAXES; ESSENTIAL OILS; PERFUMES
- C11B3/00—Refining fats or fatty oils
- C11B3/16—Refining fats or fatty oils by mechanical means
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Life Sciences & Earth Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Wood Science & Technology (AREA)
- Crystallography & Structural Chemistry (AREA)
- Mechanical Engineering (AREA)
- Microbiology (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention relates to a method for separating and preparing high-purity ethyl nervonate from acer truncatum seeds. The method prepares Acer truncatum Bunge crude oil based on Acer truncatum Bunge kernel; then preparing fatty acid ethyl ester through deacidification and transesterification; then urea inclusion is carried out on the fatty acid ethyl ester, and a primary purification crude product of the nervonic acid ethyl ester is obtained through crystallization and separation; performing multistage molecular distillation on the primary ethyl nervonate purification crude product to obtain a secondary ethyl nervonate purification crude product; then urea inclusion is carried out on the secondary ethyl nervonate purification crude product to remove saturated fatty acid ethyl ester, so as to obtain a tertiary ethyl nervonate purification crude product; and finally, carrying out urea inclusion on the crude product purified by the ethyl nervonate for multiple times to obtain the high-purity ethyl nervonate with the purity of more than 90%. The method for purifying the high-purity ethyl nervonate has the advantages that the temperature in the separation process is lower, the components in the system are not easy to crack, the product structure is stable, and the storage and the transportation are facilitated; the method has simple process and low cost, and is suitable for industrialized popularization.
Description
Technical Field
The invention belongs to the technical field of natural product extraction, and relates to a method for separating and preparing high-purity ethyl nervonate from acer truncatum seeds.
Background
Nervonic acid, which was originally found in mammalian shark brain tissue, is also known as shark acid, and has the chemical name cis-15-tetracosenoic acid and the molecular formula C 24 H 46 O 2 The molecular weight is 366.6, the solid is white needle-shaped solid at normal temperature, and the solid is easy to dissolve in organic solvents such as methanol, ethanol and the like and is not easy to dissolve in water.
Nervonic acid is a specific substance which can promote repair and regeneration of damaged nervonic acid tissues and is discovered in the world so far, is an important component of biological membranes, has high content in nerve tissues and brain tissues, and is a natural component of brain nerve fibers and nerve cells. The nervonic acid has various physiological functions beneficial to human bodies, including being capable of promoting the growth and development of human nerve cells and improving the memory of the old; in addition, the nervonic acid can repair, reduce and harden and damage the heart and cerebral vessel wall, restore the elastic activity of the blood vessel, and the like. Along with pharmacological research and analysis of nervonic acid, nervonic acid is widely applied to industries such as medicines, health products, cosmetics and the like.
There are three main aspects to the source of the nervonic acid: one is to prepare the nervonic acid by chemical or microbial synthesis, but the process for synthesizing the nervonic acid is complex, the yield is low, and industrialization cannot be realized; secondly, the nervonic acid is extracted from animal tissues such as shark brain, but the source is limited because the international society prohibits a large amount of killing of the shark; thirdly, the nervonic acid is extracted from plants, and the method is a main source for acquiring the natural nervonic acid. At present, natural nervonic acid raw materials in China comprise garlic fruits, blue-green-grass and acer truncatum. The garlic fruits contain about 62% of nervonic acid, but are listed as national secondary protection plants for a long time, the development and the utilization of the garlic fruits are limited to a certain extent, the acer truncatum as maple, the kernel oil of which contains 5-7% of nervonic acid, and the garlic fruits have wide temperature application range and high soil adaptability, survival rate and preservation rate, and are suitable for large-area planting although the content of nervonic acid is far lower than that of the garlic fruits. The acer truncatum seed kernel has high oil content and high yield and is a high-quality resource for extracting the nervonic acid. The method for extracting nervonic acid and its derivative mainly includes molecular distillation, urea inclusion, low-temperature crystallization, metal salt precipitation, rectification, etc. Chinese patent CN200710018195.2 discloses a method for extracting nervonic acid from acer truncatum seed oil by molecular distillation, which performs six-level molecular distillation to reach about 50% of nervonic acid purity, but has the problems of high molecular distillation stage number, low nervonic acid purity and the like; chinese patent CN200810058474.6 discloses a method for preparing biodiesel and nervonic acid from acer truncatum oil, which comprises rectifying twice to obtain ethyl nervonate with purity up to 46%, wherein the temperature of rectification is up to 200deg.c, and methyl nervonate is easy to carbonize. Chinese patent CN201911002351.5 discloses a Acer truncatum nervonic acid gel candy and a preparation method thereof, adopts a low-temperature crystallization method to purify nervonic acid in Acer truncatum seed oil, and adopts a one-step gradient cooling crystallization mode, wherein the purity of the nervonic acid reaches about 10 percent, and the invention has the problems of low purity of the nervonic acid, complex gradient cooling crystallization process and the like.
Disclosure of Invention
The invention aims to provide a method for extracting high-purity ethyl nervonate from acer truncatum seeds aiming at the defects of the prior art, so as to solve the problems that the traditional process has high equipment cost, industrialization is difficult to realize, the product purity is low, and carbonization is easy to occur under high-temperature separation conditions.
For this reason, the invention provides a method for separating and preparing high-purity ethyl nervonate from acer truncatum seeds, which comprises the following steps:
step A, taking acer truncatum seeds as raw materials, extracting acer truncatum crude oil, and separating impurities to obtain pure acer truncatum crude oil;
step B, mixing pure Acer truncatum Bunge crude oil with an alkaline solution, reacting, separating byproducts, and washing with water to obtain deacidified Acer truncatum Bunge seed oil;
step C, mixing the deacidified Acer truncatum seed oil with absolute ethyl alcohol, adding an alkaline catalyst, reacting, separating, and washing to obtain fatty acid ethyl ester of the Acer truncatum seed oil;
step D, refluxing the mixed solution of fatty acid ethyl ester of Acer truncatum seed oil, urea and an organic solvent until the solution is clear, crystallizing, performing suction filtration to obtain a primary inclusion compound, and performing water washing, extraction and concentration to obtain a primary refined crude product of nervonic acid ethyl ester;
step E, performing molecular distillation on the primary ethyl nervonate purification crude product, and separating to obtain a secondary ethyl nervonate purification crude product rich in long-carbon-chain fatty acid ethyl ester;
step F, mixing the purified crude product of the secondary ethyl nervonate with urea and an organic solvent, standing for crystallization after the solution is clear and transparent, and carrying out suction filtration to obtain a secondary non-inclusion compound, concentrating, washing, extracting and concentrating to obtain the purified crude product of the tertiary ethyl nervonate;
and G, mixing the purified crude product of the ethyl nervonate for three times with urea and an organic solvent, refluxing the obtained mixed solution to be clear, crystallizing, carrying out suction filtration to obtain a three-time inclusion compound, washing, extracting and concentrating to obtain a phase rich in the ethyl nervonate, and repeating the operation for a plurality of times by taking the phase rich in the ethyl nervonate as a raw material to obtain a finished product rich in the ethyl nervonate.
In some embodiments of the invention, in step B, the alkaline solution is used in an amount of 1wt% to 4wt% based on the weight of acer truncatum seed oil.
In the invention, the alkaline solution is prepared by dissolving alkali into water; preferably, the base is potassium hydroxide and/or sodium hydroxide; further preferably, the concentration of the alkaline solution is 8wt% to 10wt%.
According to the invention, in step B, the temperature of the reaction is 40-60 ℃ and the time of the reaction is 1-5 h.
In some embodiments of the present invention, in the step C, the weight ratio of the deacidified Acer truncatum seed oil to the absolute ethyl alcohol is 1 (0.4-1.2).
In other embodiments of the present invention, in step C, the basic catalyst is used in an amount of 0.1wt% to 1.5wt% based on the weight of the deacidified acer truncatum seed oil.
In the invention, the alkaline catalyst is potassium hydroxide and/or sodium hydroxide.
According to the invention, in step C, the temperature of the reaction is 50-90 ℃ and the time of the reaction is 1-4 hours.
In some embodiments of the invention, in step D, the weight ratio of fatty acid ethyl ester of Acer truncatum seed oil to urea is 1 (0.8-2).
In other embodiments of the present invention, in the step D, the weight-to-volume ratio of the fatty acid ethyl ester of Acer truncatum seed oil to the organic solvent is 1 (10-20) g/mL.
According to the invention, in step D, the temperature of the reflux is 40-90 ℃.
According to the invention, in step D, the crystallization temperature is-10 to 30 ℃ and the crystallization time is 2 to 10 hours.
In some embodiments of the invention, in step F, the weight ratio of the crude product of secondary ethyl nervonate purification to urea is 1 (0.3-2).
In other embodiments of the present invention, in step F, the weight to volume ratio of the crude product of the secondary ethyl nervonate purification to the organic solvent is 1 (6-20) g/mL.
According to the invention, in step F, the crystallization temperature is-10 to 30 ℃ and the crystallization time is 2 to 10 hours.
In some embodiments of the invention, in step G, the weight ratio of the crude product of triple ethyl nervonate purification to urea is 1 (1-3).
In other embodiments of the present invention, in step G, the weight to volume ratio of the crude trinitrotoluene to the organic solvent is 1 (10-35) G/mL.
According to the invention, in step G, the temperature of the reflux is 40-90 ℃.
According to the invention, in step G, the crystallization temperature is-10 to 30 ℃ and the crystallization time is 2 to 10 hours.
In the invention, the organic solvent comprises one or more of methanol, ethanol, ethyl acetate and isopropanol.
In the present invention, in step D, F, G, the extractant used for the extraction includes petroleum ether and/or n-hexane.
In the invention, the content of the ethyl nervonate in the ethyl nervonate finished product is more than or equal to 90wt%.
Compared with the prior art, the invention has the following advantages:
(1) The research selects Acer truncatum kernels as raw materials, has rich resources and high oil content, and has wide development prospect;
(2) The fatty acid ethyl ester is used as a raw material for purification, the separation temperature is lower, the components in a separation process system are not easy to crack, and the obtained nervonic acid ethyl ester has stable structure, is easy to store and transport and has no toxic action on human bodies;
(3) The novel technology of urea inclusion-molecular distillation-urea inclusion combination is adopted innovatively. Firstly, removing ethyl oleate, ethyl linoleate, ethyl linolenate and the like with the total content of more than 50% in raw materials by a urea inclusion method, and simultaneously removing substances such as sterols, vitamin E and the like, so that the treatment capacity of subsequent steps is reduced, the equipment investment is reduced, and the method is easy for industrialized popularization and application;
(4) The urea inclusion method is innovatively utilized to remove saturated fatty acid ethyl ester, erucic acid ethyl ester and the like, and the method has simple equipment and mild conditions, and is easy to realize industrialization;
(5) The process obtains the high-purity ethyl nervonate with the purity of more than 90% through a combined process of urea inclusion and molecular distillation, has a series of advantages of mild operation conditions, low equipment cost, easy realization of industrialization and the like, solves the double problems of high equipment cost and low product purity, and can separate and purify other separated ethyl nervonate or sell for different purposes.
Drawings
In order that the invention may be readily understood, the invention will be described in detail below with reference to the accompanying drawings.
FIG. 1 is a flow chart of the process for extracting high-purity nervonic acid from Acer truncatum seeds by adopting a urea inclusion-molecular distillation-urea inclusion combination process.
Detailed Description
In order that the invention may be readily understood, a detailed description of the invention will be provided below with reference to the accompanying drawings and examples. Before the present invention is described in detail, it is to be understood that this invention is not limited to particular embodiments described. It is also to be understood that the terminology used herein is for the purpose of describing particular embodiments only, and is not intended to be limiting.
Where a range of values is provided, it is understood that each intervening value, between the upper and lower limit of that range and any other stated or intervening value in that stated range, is encompassed within the invention. The upper and lower limits of these smaller ranges may independently be included in the smaller ranges, and are also encompassed within the invention, subject to any specifically excluded limit in the stated range. Where the stated range includes one or both of the limits, ranges excluding either or both of those included limits are also included in the invention.
Unless defined otherwise, all terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention pertains. Although any methods and materials similar or equivalent to those described herein can also be used in the practice or testing of the present invention, the preferred methods and materials are now described.
I, terminology
The term "extractant" as used herein refers to a chemical reagent that forms an extract with the extracted material that is soluble in the organic phase.
The term "high-purity ethyl nervonate" refers to ethyl nervonate which is a nervonate derivative with purity higher than 90%.
The term "clathrate" and "urea clathrate" as used herein may be used interchangeably.
The term "water" as used herein refers to deionized water, distilled water or ultrapure water unless otherwise specified or defined.
II, embodiment
As described above, the method for extracting the nervonic acid and its derivatives mainly includes molecular distillation, urea inclusion, low-temperature crystallization, metal salt precipitation, rectification, etc., but these methods are not satisfactory, for example. Chinese patent CN200710018195.2 adopts six-molecular distillation to extract nervonic acid from Acer truncatum seed oil, the purity of the nervonic acid reaches about 50%, but the problems of high molecular distillation stage number, low purity of the nervonic acid and the like exist; chinese patent CN200810058474.6 takes Acer truncatum oil as raw material to prepare biodiesel and nervonic acid, and the purity of ethyl nervonate reaches 46% after twice rectification, but the temperature of the rectification process is up to 200 ℃, so that the problems of easy carbonization of methyl nervonate and the like exist. The method of low-temperature crystallization is adopted in Chinese patent CN201911002351.5 to purify nervonic acid in acer truncatum seed oil, and the method of primary gradient cooling crystallization is adopted, so that the purity of the nervonic acid reaches about 10 percent, and the method has the problems of low purity of the nervonic acid, complex gradient cooling crystallization process and the like. Therefore, "obtaining a high purity of a nervonic acid or its derivative using mild reaction conditions" has been a problem that one skilled in the art has sought to solve but has not been able to solve. To solve this problem, the present inventors have conducted a great deal of research on a technique for separating and preparing ethyl nervonate from Acer truncatum oil. The invention researches and designs a novel method for separating and preparing high-purity ethyl nervonate from acer truncatum seeds, and the process flow chart of the novel method is shown in figure 1.
As can be seen from fig. 1, the method for preparing high-purity ethyl nervonate from acer truncatum seeds according to the present invention comprises the following steps:
(1) Extracting Acer Truncatum Bunge seed kernel with oil to obtain Acer Truncatum Bunge crude oil, and removing impurities to obtain pure Acer Truncatum Bunge crude oil;
(2) Mixing pure Acer truncatum Bunge crude oil with 8-10wt% alkaline solution, reacting at 40-60deg.C for 1-5 hr, separating by-product, and washing with water to obtain deacidified Acer truncatum Bunge seed oil; the dosage of the alkaline solution is 1 to 4 weight percent of the weight of the acer truncatum seed oil.
(3) Mixing deacidified Acer truncatum seed oil with absolute ethyl alcohol according to the weight ratio of (0.4-1.2), adding an alkaline catalyst (such as potassium hydroxide and/or sodium hydroxide) accounting for 0.1-1.5 wt% of the Acer truncatum seed oil, reacting for 1-4 hours at 50-90 ℃, removing the ethyl alcohol by rotary evaporation, standing for layering, separating the glycerin at the lower layer to obtain an oil layer, washing with water, and evaporating to remove water to obtain fatty acid ethyl ester of the Acer truncatum seed oil;
(4) Mixing the fatty acid ethyl ester of the Acer truncatum seed oil obtained in the step (3) with urea according to the weight ratio of (0.8-2) in an organic solvent, wherein the adding amount of the organic solvent is 1 (10-20) g/mL according to the weight-volume ratio of the fatty acid ethyl ester of the Acer truncatum seed oil to the organic solvent, refluxing the obtained mixed solution to the solution at the temperature of 40-90 ℃ for clarification, transferring to the temperature of minus 10-30 ℃ for crystallization for 2-10 hours, and filtering to obtain a crystal which is a primary inclusion compound, and washing, extracting (e.g. extracting twice), concentrating and the like the primary inclusion compound to obtain a primary ethyl nervonate purified crude product;
(5) Performing molecular distillation (such as secondary molecular distillation) on the primary ethyl nervonate purified crude product obtained in the step (4) at different vacuum degrees and temperatures to remove light components such as ethyl palmitate, ethyl stearate, ethyl arachidate, partial ethyl erucate and the like, wherein the secondary heavy components obtained by separation are secondary ethyl nervonate purified crude products rich in ethyl nervonate, ethyl erucate, ethyl behenate, ethyl pyrolignate and the like and long-carbon chain fatty acid ethyl esters;
(6) Purifying the crude product of the secondary ethyl nervonate obtained in the step (5) and urea according to the weight ratio of 1: (0.3-2) mixing the materials in an organic solvent, wherein the adding amount of the organic solvent is 1 (6-20) g/mL according to the weight-volume ratio of the fatty acid ethyl ester to the organic solvent, transferring the solution to the temperature of minus 10-30 ℃ for crystallization for 2-10 hours after the solution is clear and transparent, filtering to obtain a filtrate which is a secondary non-inclusion compound, and carrying out the steps of rotary evaporation concentration, water washing, extraction, concentration (such as evaporation recovery petroleum ether) and the like on the secondary non-inclusion compound to obtain a tertiary ethyl nervonate purified crude product;
(7) Purifying the crude product of the tertiary ethyl nervonate obtained in the step (6) and urea according to the mass ratio of 1: mixing the above-mentioned materials in organic solvent, adding organic solvent according to the weight-volume ratio of fatty acid ethyl ester and organic solvent (10-35) g/mL, refluxing the mixed liquor at 40-90 deg.C to make it be clear, taking out and transferring it to-10-30 deg.C, crystallizing for 2-10 hr, suction-filtering to obtain three-time inclusion compound, washing with water, extracting (extracting twice) and concentrating so as to obtain the invented product rich in ethyl nervonate. And (3) performing urea inclusion on the product for multiple times (repeating the operation of the step (7)) to obtain the high-purity ethyl nervonate with the purity of more than 90wt%.
According to the method, in the step (1), the method for extracting the acer truncatum seed oil comprises a mechanical pressing method, a Soxhlet extraction method, a subcritical extraction method and a water enzyme method.
In the present invention, the organic solvent includes one or more of methanol, ethanol, ethyl acetate and isopropanol, preferably absolute ethanol and 95% ethanol.
The inventor researches find that 95% ethanol is favorable for the rapid dissolution of urea, and can greatly improve the efficiency of urea inclusion.
In the present invention, in the steps (4), (6) and (7), the extractant used for the extraction includes petroleum ether and/or n-hexane, preferably petroleum ether.
The present inventors have found that the main component of the fat is triglyceride, and in order to reduce the influence of the steric hindrance of triglyceride on the separation effect, the fat is generally converted into fatty acid or fatty acid ester before the separation process. Compared with fatty acid, the fatty acid ester has a lower boiling point, is favorable for molecular distillation, rectification and other methods, and prevents the separated system from chemical changes such as cracking due to overhigh temperature. And compared with fatty acid, the fatty acid ester has a carbon chain length, and according to the urea inclusion principle, the longer the carbon chain, the easier the inclusion compound is formed, thereby being beneficial to improving the efficiency of the urea inclusion process. Therefore, when methods such as molecular distillation, urea inclusion and the like are utilized, the fatty acid ester is taken as a raw material to have a great advantage, and the fatty acid ester in the obtained product can be converted into fatty acid through acidification.
The invention provides a method for separating and preparing high-purity ethyl nervonate from acer truncatum seeds, which is a novel process combining urea inclusion and molecular distillation. Firstly, preparing pure Acer truncatum Bunge crude oil by taking Acer truncatum Bunge kernels as raw materials; deacidifying pure Acer truncatum Bunge crude oil, and performing transesterification to prepare fatty acid ethyl ester; mixing fatty acid ethyl ester with urea and an organic solvent, crystallizing and separating to obtain a primary ethyl nervonate purified crude product; performing multistage molecular distillation on the primary ethyl nervonate purification crude product to obtain a secondary ethyl nervonate purification crude product with higher purity; then urea inclusion is carried out on the secondary ethyl nervonate purification crude product to remove saturated fatty acid ethyl ester, and the tertiary ethyl nervonate purification crude product is obtained in filtrate; and finally, carrying out urea inclusion on the crude product purified by the ethyl nervonate for multiple times to finally obtain the high-purity ethyl nervonate with the purity of more than 90%. Compared with the prior art, the invention has the following advantages: the fatty acid ethyl ester obtained by processing the acer truncatum seeds is used as a raw material, the separation temperature is lower, the components in a separation process system are not easy to crack, and the high-purity nervonic acid ethyl ester is obtained by purification, so that the product has a stable structure and is beneficial to storage and transportation; the method creatively provides key steps for removing the saturated fatty acid ethyl ester and the erucic acid ethyl ester by adopting the urea inclusion method, and the whole process is simple to operate, low in equipment cost and suitable for industrial popularization.
II, examples
In order that the invention may be more readily understood, the invention will be further described in detail with reference to the following examples, which are given by way of illustration only and are not limiting in scope of application. The starting materials or components used in the present invention are commercially available or may be prepared by conventional methods unless otherwise specified.
The fatty acid ethyl ester in the acer truncatum seed oil of the experiment is measured by a gas chromatograph (Agilent 8890A, agilent technologies Co., ltd.) with a chromatographic column of DB-FastFame (30 m×0.25mm×0.25 μm). The gas phase analysis method comprises the following steps: the FID temperature is 260 ℃ and the sample inlet temperature is 250 ℃. Heating program: the initial temperature of the chromatographic column was 80℃for 0.5min,40℃/min to 165℃for 1min, and 4℃/min to 230℃for 4min. The split ratio is 100:1, and the sample injection amount is 1 mu L.
Example 1
(1) Washing Acer Truncatum Bunge kernel with water to remove impurities such as residual shell, squeezing with shaft type screw squeezer at 120deg.C to obtain Acer Truncatum Bunge crude oil; centrifuging Acer Truncatum Bunge crude oil at 5500r/min for 10min to remove impurities to obtain clean Acer Truncatum Bunge crude oil;
(2) Mixing Acer truncatum Bunge crude oil with NaOH solution with weight of 2wt% and concentration of 9.42wt% at 60deg.C for 3 hr, separating byproduct, and washing with water to obtain deacidified Acer truncatum Bunge seed oil;
(3) Mixing deacidified Acer truncatum seed oil with absolute ethanol according to the weight ratio of 1:1, adding NaOH catalyst with the weight of 0.25wt% of Acer truncatum seed oil, reacting for 3 hours at 70 ℃, rotationally steaming to remove ethanol, standing for layering, separating glycerin at the lower layer to obtain an oil layer, washing with water, and evaporating to remove water under the condition of the temperature of 80 ℃ and the vacuum degree of 0.05MPa to obtain fatty acid ethyl ester of Acer truncatum seed oil;
(4) Fatty acid ethyl ester obtained in the step (3): urea: ethanol is mixed according to the proportion of 1:1.25:16 g/mL, the mixed solution is refluxed to solution clarification at 50 ℃, transferred to 0 ℃ for crystallization for 5 hours, clathrate crystals are obtained after suction filtration, deionized water at 50 ℃ is added to dissolve urea, the mixture is extracted twice by 60-90 petroleum ether, the extract is combined, petroleum ether is recovered by evaporation, and primary ethyl nervonate purification crude product with the purity of 18.21% is obtained;
(5) Performing two-stage molecular distillation on the primary ethyl nervonate purified crude product obtained in the step (4), and removing short carbon chain fatty acid ethyl esters such as ethyl palmitate, ethyl stearate, ethyl oleate, ethyl arachidate and the like by using one-stage molecular distillation, wherein the distillation temperature is 100 ℃, and the vacuum degree is 0.1Pa; removing ethyl palmitate, ethyl stearate, ethyl arachidate, part of ethyl erucate and the like by secondary molecular distillation, wherein the distillation temperature is 105 ℃, the vacuum degree is 0.1Pa, and obtaining a secondary nervonic acid purification crude product with the purity of 47.47 percent by the two-stage molecular distillation;
(6) Purifying the crude product of the secondary ethyl nervonate obtained in the step (5): urea: ethanol is mixed according to the proportion of 1:0.9:12g/g/mL, the mixture is refluxed to solution clarification at 80 ℃, crystallized for 3 hours at room temperature, filtered to obtain filtrate, ethanol is recovered by rotary evaporation, residual urea is removed by water washing, the extract is extracted twice by 60-90 petroleum ether, the extract is combined, petroleum ether is recovered by evaporation, and a tertiary ethyl nervonate purified crude product with the purity of 46.73% is obtained;
(7) Purifying the tertiary ethyl nervonate obtained in the step (6) to obtain a crude product: urea: ethanol is mixed according to the proportion of 1:1.5:22g/g/mL, the mixture is refluxed to be clear at the temperature of 80 ℃, is taken out and is transferred to be crystallized for 4 hours at the temperature of 0 ℃, the urea inclusion compound is obtained by suction filtration, deionized water at the temperature of 50 ℃ is added to dissolve urea, the mixture is extracted twice by 60-90 petroleum ether, the extracts are combined, the petroleum ether is recovered by evaporation, and the concentrated solution is the product rich in ethyl nervonate. Repeating the step 3 times to obtain ethyl nervonate with purity of 90.1%.
Example 2
(1) Washing Acer Truncatum Bunge kernel with water to remove impurities such as residual shell, squeezing with shaft type screw squeezer at 120deg.C to obtain Acer Truncatum Bunge crude oil; centrifuging Acer Truncatum Bunge crude oil at 5500r/min for 10min to remove impurities to obtain pure Acer Truncatum Bunge crude oil;
(2) Mixing Acer truncatum Bunge crude oil with NaOH solution with weight of 2wt% and concentration of 9.42wt% at 60deg.C for 3 hr, separating byproduct, and washing with water to obtain deacidified Acer truncatum Bunge seed oil;
(3) Mixing deacidified Acer truncatum seed oil with absolute ethanol in a weight ratio of 1:1, adding NaOH catalyst with a weight of 0.25wt% of Acer truncatum seed oil, reacting at 70 ℃ for 3 hours, steaming to remove ethanol, standing for layering, separating glycerin at the lower layer to obtain an oil layer, washing with water, evaporating at 80 ℃ under a vacuum degree of 0.05MPa to remove water to obtain pure fatty acid ethyl ester of Acer truncatum seed oil;
(4) Fatty acid ethyl ester obtained in the step (3): urea: mixing 95% ethanol according to the proportion of 1:1.25:16 g/mL, refluxing the mixed solution to clarify the solution at 50 ℃, transferring to 0 ℃ for crystallization for 5 hours, filtering to obtain an inclusion compound, adding 50 ℃ deionized water to dissolve urea, extracting twice with 60-90 petroleum ether, combining the extracts, evaporating to recover petroleum ether, and obtaining a primary ethyl nervonate purified crude product with the purity of 18.69%;
(5) Performing two-stage molecular distillation on the primary ethyl nervonate purified crude product obtained in the step (4), wherein the primary molecular distillation is performed to remove short carbon chain fatty acid ethyl esters such as ethyl palmitate, ethyl stearate, ethyl oleate, ethyl peanut mono-dilute acid and the like, the primary molecular distillation temperature is 100 ℃, and the vacuum degree is 0.1Pa; removing ethyl palmitate, ethyl stearate, ethyl arachidate, part of ethyl erucate and the like by secondary molecular distillation, wherein the secondary molecular distillation temperature is 110 ℃, the vacuum degree is 0.1Pa, and obtaining a secondary nervonic acid purified crude product with the purity of 52.5 percent by two-stage molecular distillation;
(6) Purifying the crude product of the secondary ethyl nervonate obtained in the step (5): urea: ethanol is mixed according to the proportion of 1:0.9:12g/g/mL, the mixture is refluxed to solution clarification at 80 ℃, crystallized for 3 hours at room temperature, the filtrate is obtained by suction filtration, the ethanol is recovered by rotary evaporation, the residual urea is removed by water washing, the mixture is extracted twice by 60-90 petroleum ether, the extracts are combined, the petroleum ether is recovered by evaporation, and the purified crude product of the ethyl nervonate with the purity of 50.27% is obtained;
(7) Purifying the tertiary ethyl nervonate obtained in the step (6) to obtain a crude product: urea: ethanol is mixed according to the proportion of 1:1.5:26g/g/mL, the mixed solution is refluxed to be clear at the temperature of 80 ℃, is taken out and is transferred to be crystallized for 4 hours at the temperature of 0 ℃, the urea inclusion compound is obtained by suction filtration, deionized water at the temperature of 50 ℃ is added to dissolve urea, the mixture is extracted twice by 60-90 petroleum ether, the extracting solution is combined, the petroleum ether is recovered by evaporation, and the concentrated solution is the product rich in ethyl nervonate. Repeating the step 3 times to obtain ethyl nervonate with purity of 91.8%.
Example 3
(1) Washing Acer Truncatum Bunge kernel with water to remove impurities such as residual shell; squeezing with a shaft type screw squeezer at 120deg.C to obtain Acer Truncatum Bunge crude oil; centrifuging Acer Truncatum Bunge crude oil at 5500r/min for 10min to remove impurities to obtain pure Acer Truncatum Bunge crude oil;
(2) Mixing Acer truncatum Bunge crude oil with NaOH solution with weight of 2wt% and concentration of 9.42wt% at 60deg.C for 3 hr, separating byproduct, and washing with water to obtain deacidified Acer truncatum Bunge seed oil;
(3) Mixing deacidified Acer truncatum seed oil with absolute ethanol according to a weight ratio of 1:1, adding NaOH catalyst accounting for 0.25wt% of the Acer truncatum seed oil, reacting for 3 hours at 70 ℃, rotationally steaming to remove ethanol, standing for layering, separating glycerin at the lower layer to obtain an oil layer, washing with water, and evaporating to remove water under the conditions of 80 ℃ and 0.05MPa of vacuum degree to obtain pure fatty acid ethyl ester of the Acer truncatum seed oil;
(4) Fatty acid ethyl ester obtained in the step (3): urea: mixing 95% ethanol according to the proportion of 1:1.5:16 g/mL, refluxing the mixed solution to clarify the solution at 50 ℃, transferring to 0 ℃ for crystallization for 5 hours, filtering to obtain an inclusion compound, adding 50 ℃ deionized water to dissolve urea, extracting twice with 60-90 petroleum ether, combining the extract, evaporating to recover petroleum ether, and obtaining a primary ethyl nervonate purified crude product with the purity of 16.01%;
(5) Performing two-stage molecular distillation on the primary ethyl nervonate purified crude product obtained in the step (4), wherein the primary molecular distillation is performed to remove short carbon chain fatty acid ethyl esters such as ethyl palmitate, ethyl stearate, ethyl oleate, ethyl peanut mono-dilute acid and the like, the primary molecular distillation temperature is 100 ℃, and the vacuum degree is 0.1Pa; secondary molecular distillation is carried out to remove ethyl palmitate, ethyl stearate, ethyl arachidate, part of ethyl erucate and the like, the secondary molecular distillation temperature is 115 ℃, the vacuum degree is 0.1Pa, and the secondary nervonic acid purified crude product with the purity of 55 percent is obtained through two-stage molecular distillation;
(6) Purifying the crude product of the secondary ethyl nervonate obtained in the step (5): urea: ethanol is mixed according to the proportion of 1:0.9:12g/g/mL, the mixture is refluxed to solution clarification at 80 ℃, crystallized for 3 hours at room temperature, filtered to obtain filtrate, ethanol is recovered by rotary evaporation, the ethanol is extracted twice by 60-90 petroleum ether, the extracts are combined, petroleum ether is recovered by evaporation, and a crude product of tertiary ethyl nervonate purification with the purity of 53.70 percent is obtained;
(7) Purifying the tertiary ethyl nervonate obtained in the step (6) to obtain a crude product: urea: mixing ethanol and ethyl acetate mixed solvent according to the proportion of 1:1.75:26g/g/mL, refluxing the mixed solution to be clear at the temperature of 80 ℃, taking out and transferring to be crystallized for 4 hours at the temperature of 0 ℃, filtering to obtain a urea inclusion compound, adding 50 ℃ deionized water to dissolve urea, extracting twice with 60-90 petroleum ether, combining the extracting solutions, evaporating and recovering petroleum ether, and obtaining the concentrated solution which is a product rich in ethyl nervonate. Repeating the step 3 times to obtain ethyl nervonate with purity of 90.03%.
It should be noted that the above-described embodiments are only for explaining the present invention and do not constitute any limitation of the present invention. The invention has been described with reference to exemplary embodiments, but it is understood that the words which have been used are words of description and illustration, rather than words of limitation. Modifications may be made to the invention as defined in the appended claims, and the invention may be modified without departing from the scope and spirit of the invention. Although the invention is described herein with reference to particular means, materials and embodiments, the invention is not intended to be limited to the particulars disclosed herein, as the invention extends to all other means and applications which perform the same function.
Claims (11)
1. A method for separating and preparing high-purity ethyl nervonate from acer truncatum kernel, comprising the following steps:
step A, taking acer truncatum seeds as raw materials, extracting acer truncatum crude oil, and separating impurities to obtain pure acer truncatum crude oil;
step B, mixing pure Acer truncatum Bunge crude oil with an alkaline solution, reacting, separating byproducts, and washing with water to obtain deacidified Acer truncatum Bunge seed oil;
step C, mixing the deacidified Acer truncatum seed oil with absolute ethyl alcohol, adding an alkaline catalyst, reacting, separating, and washing to obtain fatty acid ethyl ester of the Acer truncatum seed oil;
step D, refluxing the mixed solution of fatty acid ethyl ester of Acer truncatum seed oil, urea and an organic solvent until the solution is clear, crystallizing, performing suction filtration to obtain a primary inclusion compound, and performing water washing, extraction and concentration to obtain a primary refined crude product of nervonic acid ethyl ester;
e, performing secondary molecular distillation on the primary ethyl nervonate purification crude product, and separating to obtain a secondary ethyl nervonate purification crude product rich in long carbon chain fatty acid ethyl ester;
step F, mixing the purified crude product of the secondary ethyl nervonate with urea and an organic solvent, standing for crystallization after the solution is clear and transparent, and carrying out suction filtration to obtain a secondary non-inclusion compound, concentrating, washing, extracting and concentrating to obtain the purified crude product of the tertiary ethyl nervonate;
step G, mixing the purified crude product of the ethyl nervonate for three times with urea and an organic solvent, refluxing the obtained mixed solution to be clear, crystallizing, carrying out suction filtration to obtain a third inclusion compound, washing, extracting and concentrating to obtain a phase rich in the ethyl nervonate, and repeating the operation for a plurality of times by taking the phase rich in the ethyl nervonate as a raw material to obtain a finished product rich in the ethyl nervonate;
in the step D, the weight ratio of the fatty acid ethyl ester of the acer truncatum seed oil to the urea is 1 (0.8-1.5); the weight-volume ratio of the fatty acid ethyl ester of the acer truncatum seed oil to the organic solvent is 1 (10-16) g/mL;
in the step F, the weight ratio of the purified crude product of the secondary ethyl nervonate to urea is 1 (0.3-0.9); the weight-volume ratio of the secondary ethyl nervonate purification crude product to the organic solvent is 1 (6-12) g/mL;
in the step G, the weight ratio of the crude product purified by the ethyl ester of the tertiary nervonate to the urea is 1 (1-1.75); the weight-volume ratio of the crude product of the tertiary nervonic acid to the organic solvent is 1 (10-26) g/mL.
2. The method according to claim 1, wherein in the step B, the alkaline solution is used in an amount of 1 to 4wt% based on the weight of the acer truncatum seed oil; the temperature of the reaction is 40-60 ℃, and the reaction time is 1-5 h.
3. The method according to claim 2, wherein in step B, the alkaline solution is prepared from alkali-soluble water; the alkali is potassium hydroxide and/or sodium hydroxide; the concentration of the alkaline solution is 8-10wt%.
4. The method according to claim 1, wherein in the step C, the weight ratio of the deacidified acer truncatum seed oil to the absolute ethyl alcohol is 1 (0.4-1.2); the temperature of the reaction is 50-90 ℃, and the reaction time is 1-4 h.
5. The method according to claim 4, wherein in the step C, the amount of the basic catalyst is 0.1 to 1.5wt% of the weight of the deacidified Acer truncatum seed oil; the alkaline catalyst is potassium hydroxide and/or sodium hydroxide.
6. The method according to claim 1, wherein in step D, the temperature of the reflux is 40-90 ℃; the temperature of the crystallization is-10-30 ℃, and the time of the crystallization is 2-10 h.
7. The method according to claim 1, wherein in step F, the crystallization is performed at a temperature of-10 to 30 ℃ for a time of 2 to 10 hours.
8. The method according to claim 1, wherein in step G, the temperature of the reflux is 40-90 ℃; and/or the temperature of the crystallization is-10-30 ℃, and the time of the crystallization is 2-10 h.
9. The method of claim 1, wherein the organic solvent comprises one or more of methanol, ethanol, ethyl acetate, and isopropanol.
10. The method according to claim 1, wherein in step D, F, G the extractant used for the extraction comprises petroleum ether and/or n-hexane.
11. The method according to any one of claims 1 to 10, wherein the ethyl nervonate content of the ethyl nervonate product is greater than or equal to 90wt%.
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|---|---|---|---|---|
| CN101486647A (en) * | 2009-02-11 | 2009-07-22 | 中国科学院山西煤炭化学研究所 | Method for extracting nervonate from nervonate and eruciate mixer |
| CN108863764A (en) * | 2018-07-20 | 2018-11-23 | 李明龙 | A kind of improvement memory improves the nervonic acid piece preparation method of sleep quality |
| CN111848341A (en) * | 2020-07-20 | 2020-10-30 | 齐鲁工业大学 | Method for separating and purifying nervonic acid in acer truncatum buge oil by combining molecular distillation with urea inclusion method |
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2022
- 2022-05-16 CN CN202210530340.XA patent/CN114933529B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101486647A (en) * | 2009-02-11 | 2009-07-22 | 中国科学院山西煤炭化学研究所 | Method for extracting nervonate from nervonate and eruciate mixer |
| CN108863764A (en) * | 2018-07-20 | 2018-11-23 | 李明龙 | A kind of improvement memory improves the nervonic acid piece preparation method of sleep quality |
| CN111848341A (en) * | 2020-07-20 | 2020-10-30 | 齐鲁工业大学 | Method for separating and purifying nervonic acid in acer truncatum buge oil by combining molecular distillation with urea inclusion method |
Non-Patent Citations (1)
| Title |
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| 张元等.元宝枫油中神经酸乙酯的分离提纯.中国油脂.2010,第35卷(第1期),第28-31页. * |
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