CN112159300A - Method for extracting squalene from plant deodorized distillate - Google Patents
Method for extracting squalene from plant deodorized distillate Download PDFInfo
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- CN112159300A CN112159300A CN202011168092.6A CN202011168092A CN112159300A CN 112159300 A CN112159300 A CN 112159300A CN 202011168092 A CN202011168092 A CN 202011168092A CN 112159300 A CN112159300 A CN 112159300A
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- squalene
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- YYGNTYWPHWGJRM-UHFFFAOYSA-N (6E,10E,14E,18E)-2,6,10,15,19,23-hexamethyltetracosa-2,6,10,14,18,22-hexaene Chemical compound CC(C)=CCCC(C)=CCCC(C)=CCCC=C(C)CCC=C(C)CCC=C(C)C YYGNTYWPHWGJRM-UHFFFAOYSA-N 0.000 title claims abstract description 101
- BHEOSNUKNHRBNM-UHFFFAOYSA-N Tetramethylsqualene Natural products CC(=C)C(C)CCC(=C)C(C)CCC(C)=CCCC=C(C)CCC(C)C(=C)CCC(C)C(C)=C BHEOSNUKNHRBNM-UHFFFAOYSA-N 0.000 title claims abstract description 101
- PRAKJMSDJKAYCZ-UHFFFAOYSA-N dodecahydrosqualene Natural products CC(C)CCCC(C)CCCC(C)CCCCC(C)CCCC(C)CCCC(C)C PRAKJMSDJKAYCZ-UHFFFAOYSA-N 0.000 title claims abstract description 101
- 229940031439 squalene Drugs 0.000 title claims abstract description 101
- TUHBEKDERLKLEC-UHFFFAOYSA-N squalene Natural products CC(=CCCC(=CCCC(=CCCC=C(/C)CCC=C(/C)CC=C(C)C)C)C)C TUHBEKDERLKLEC-UHFFFAOYSA-N 0.000 title claims abstract description 101
- 238000000034 method Methods 0.000 title claims abstract description 62
- 238000006243 chemical reaction Methods 0.000 claims abstract description 29
- 229930182558 Sterol Natural products 0.000 claims abstract description 18
- 150000003432 sterols Chemical class 0.000 claims abstract description 18
- 235000003702 sterols Nutrition 0.000 claims abstract description 18
- 239000011347 resin Substances 0.000 claims abstract description 14
- 229920005989 resin Polymers 0.000 claims abstract description 14
- 238000002425 crystallisation Methods 0.000 claims abstract description 13
- 230000008025 crystallization Effects 0.000 claims abstract description 13
- 239000003960 organic solvent Substances 0.000 claims abstract description 12
- 239000000706 filtrate Substances 0.000 claims abstract description 10
- 238000010438 heat treatment Methods 0.000 claims abstract description 10
- 238000010992 reflux Methods 0.000 claims abstract description 10
- 238000003795 desorption Methods 0.000 claims abstract description 5
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 34
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 24
- 238000011068 loading method Methods 0.000 claims description 21
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 claims description 16
- 238000005406 washing Methods 0.000 claims description 16
- 239000007788 liquid Substances 0.000 claims description 14
- 238000002360 preparation method Methods 0.000 claims description 14
- 239000002904 solvent Substances 0.000 claims description 14
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 14
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 12
- 239000000047 product Substances 0.000 claims description 12
- 235000015112 vegetable and seed oil Nutrition 0.000 claims description 10
- 239000008158 vegetable oil Substances 0.000 claims description 10
- OVYTZAASVAZITK-UHFFFAOYSA-M sodium;ethanol;hydroxide Chemical compound [OH-].[Na+].CCO OVYTZAASVAZITK-UHFFFAOYSA-M 0.000 claims description 9
- 235000019484 Rapeseed oil Nutrition 0.000 claims description 7
- 239000008367 deionised water Substances 0.000 claims description 7
- 229910021641 deionized water Inorganic materials 0.000 claims description 7
- 239000012153 distilled water Substances 0.000 claims description 7
- 238000010828 elution Methods 0.000 claims description 7
- 238000001704 evaporation Methods 0.000 claims description 7
- 230000008020 evaporation Effects 0.000 claims description 7
- 239000004006 olive oil Substances 0.000 claims description 7
- 235000008390 olive oil Nutrition 0.000 claims description 7
- 239000003208 petroleum Substances 0.000 claims description 7
- YLLIGHVCTUPGEH-UHFFFAOYSA-M potassium;ethanol;hydroxide Chemical compound [OH-].[K+].CCO YLLIGHVCTUPGEH-UHFFFAOYSA-M 0.000 claims description 7
- 239000000344 soap Substances 0.000 claims description 7
- 238000003828 vacuum filtration Methods 0.000 claims description 7
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 claims description 6
- 241000196324 Embryophyta Species 0.000 claims description 5
- GRONZTPUWOOUFQ-UHFFFAOYSA-M sodium;methanol;hydroxide Chemical compound [OH-].[Na+].OC GRONZTPUWOOUFQ-UHFFFAOYSA-M 0.000 claims description 5
- 239000003549 soybean oil Substances 0.000 claims description 5
- 235000012424 soybean oil Nutrition 0.000 claims description 5
- 235000019774 Rice Bran oil Nutrition 0.000 claims description 4
- 230000001476 alcoholic effect Effects 0.000 claims description 4
- IDGUHHHQCWSQLU-UHFFFAOYSA-N ethanol;hydrate Chemical compound O.CCO IDGUHHHQCWSQLU-UHFFFAOYSA-N 0.000 claims description 4
- 239000008165 rice bran oil Substances 0.000 claims description 4
- 239000003513 alkali Substances 0.000 claims description 3
- 239000002585 base Substances 0.000 claims description 3
- 239000010495 camellia oil Substances 0.000 claims description 3
- 230000035484 reaction time Effects 0.000 claims description 3
- 150000001875 compounds Chemical class 0.000 claims description 2
- 239000003480 eluent Substances 0.000 claims description 2
- 238000002955 isolation Methods 0.000 claims description 2
- 238000000605 extraction Methods 0.000 abstract description 12
- 239000002994 raw material Substances 0.000 abstract description 11
- 238000010364 biochemical engineering Methods 0.000 abstract description 2
- 238000000638 solvent extraction Methods 0.000 abstract description 2
- 238000004587 chromatography analysis Methods 0.000 abstract 2
- 239000010773 plant oil Substances 0.000 abstract 1
- 239000000243 solution Substances 0.000 description 45
- 238000000926 separation method Methods 0.000 description 19
- 239000007864 aqueous solution Substances 0.000 description 10
- 239000003463 adsorbent Substances 0.000 description 5
- 238000011049 filling Methods 0.000 description 5
- 238000000746 purification Methods 0.000 description 5
- 238000005265 energy consumption Methods 0.000 description 4
- 238000004090 dissolution Methods 0.000 description 3
- 239000003921 oil Substances 0.000 description 3
- 235000019198 oils Nutrition 0.000 description 3
- 238000011084 recovery 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
- 241000251730 Chondrichthyes Species 0.000 description 2
- 206010028980 Neoplasm Diseases 0.000 description 2
- 239000013543 active substance Substances 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 238000000199 molecular distillation Methods 0.000 description 2
- 238000004064 recycling Methods 0.000 description 2
- 239000010686 shark liver oil Substances 0.000 description 2
- 229940069764 shark liver oil Drugs 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 208000024172 Cardiovascular disease Diseases 0.000 description 1
- 241001465754 Metazoa Species 0.000 description 1
- 235000019482 Palm oil Nutrition 0.000 description 1
- 229930003427 Vitamin E Natural products 0.000 description 1
- 239000003242 anti bacterial agent Substances 0.000 description 1
- 238000011021 bench scale process Methods 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 201000011510 cancer Diseases 0.000 description 1
- 208000026106 cerebrovascular disease Diseases 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000002537 cosmetic Substances 0.000 description 1
- 235000020247 cow milk Nutrition 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000004332 deodorization Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 230000002349 favourable effect 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
- 238000009776 industrial production Methods 0.000 description 1
- 208000015181 infectious disease Diseases 0.000 description 1
- 238000011031 large-scale manufacturing process Methods 0.000 description 1
- 210000004185 liver Anatomy 0.000 description 1
- 239000010687 lubricating oil Substances 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 210000000056 organ Anatomy 0.000 description 1
- 239000002540 palm oil Substances 0.000 description 1
- 238000007670 refining Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000007127 saponification reaction Methods 0.000 description 1
- 210000004003 subcutaneous fat Anatomy 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 238000012360 testing method Methods 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
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C7/00—Purification; Separation; Use of additives
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C7/00—Purification; Separation; Use of additives
- C07C7/005—Processes comprising at least two steps in series
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C7/00—Purification; Separation; Use of additives
- C07C7/10—Purification; Separation; Use of additives by extraction, i.e. purification or separation of liquid hydrocarbons with the aid of liquids
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C7/00—Purification; Separation; Use of additives
- C07C7/148—Purification; Separation; Use of additives by treatment giving rise to a chemical modification of at least one compound
Abstract
The invention discloses a method for extracting squalene from plant deodorized distillate, belongs to the technical field of biochemical engineering, and aims to improve the extraction rate and purity of squalene. The method for extracting squalene from plant deodorized distillate provided by the invention is characterized in that plant oil deodorized distillate is used as a raw material, high-purity and high-yield squalene is extracted by a process method combining organic solvent extraction, crystallization and macroporous resin chromatography, the raw material is subjected to heating reflux reaction, unsaponifiable matters obtained by extraction are subjected to crystallization reaction to recover sterol, filtrate is recovered to obtain squalene concentrated solution, and then the squalene is subjected to macroporous resin chromatography and desorption reaction to obtain squalene. The method has the advantages of simple process, low cost, and high extraction rate and purity of squalene.
Description
Technical Field
The invention belongs to the technical field of biochemical engineering, and particularly relates to a method for extracting squalene from plant deodorizer distillate.
Background
Squalene (squalene), also known as triacontahexaene, squalene, is an important chemical active substance mainly present in the liver of sharks. The squalene has good bioactivity, can be used as effective medicine for resisting tumor, cancer and infection, and treating cardiovascular disease and cerebrovascular disease, and can be widely used in cosmetic, antibacterial agent, and lubricating oil. The squalene is a natural active substance and has wide sources, is mainly derived from shark liver oil, is also found in cow milk and lard in small amount, and has certain distribution in human body, such as skin, subcutaneous fat and other organs. The squalene is not only present in animal bodies, but also distributed in plants to a certain extent, and is mostly present in vegetable oil, wherein the content of the squalene in olive oil and rice bran oil is high. The main source of squalene is shark liver oil, and the low reproduction rate and rarity of sharks limit the yield of squalene, so that the search for a new squalene resource and the development of a corresponding extraction method are very important.
At present, relevant researches on extracting squalene from vegetable oil exist, but the process method has more defects, such as:
(1) some processes use vegetable oil as raw material, such as olive oil, palm oil, rapeseed oil, etc., these oils are expensive and do not involve recovery of other useful components while extracting squalene, for example, CN110790626A discloses a method for extracting squalene from rapeseed oil, and CN101597204A discloses a method for extracting high-purity squalene from olive oil, these methods have problems of complicated process and high material and energy consumption, the content of squalene in oil crops and oils is basically below 1 wt%, and the extraction of squalene from these raw materials is costly and uneconomical.
(2) Some processes have complicated and complicated extraction steps, high separation cost and low squalene recovery rate, for example, CN101830770A discloses a method for extracting squalene and simultaneously recovering vitamin E and phytosterol from a vegetable oil deodorized distillate, which comprises multiple steps of saponification, extraction, molecular distillation, cold separation, multi-stage solvent extraction and the like, and has the disadvantages of complicated process, high organic solvent consumption, high separation cost, low squalene recovery rate and the like.
(3) Most of the prior art is preliminarily researched and explored on the basis of laboratory bench scale, and due to various reasons such as harsh conditions, high cost, complex process or no matching equipment, the process is difficult or incapable of realizing real industrial production and only stops at the laboratory bench stage.
Disclosure of Invention
The invention aims to improve the extraction rate and the purity of squalene, and provides a method for extracting squalene from plant deodorizer distillate, aiming at solving the problems of difficult process and high process cost, wherein the method comprises the following specific steps:
(1) preparation of unsaponifiable matter: adding the deodorized distillate of vegetable oil into alkaline alcohol solution, heating and refluxing, stopping reaction, washing with distilled water, extracting unsaponifiable matter with organic solvent, removing precipitated soap, and removing solvent with rotary evaporator to obtain unsaponifiable matter;
(2) preparation of squalene concentrated solution: dissolving the unsaponifiable matter obtained in the step (1) by using an organic solvent, carrying out crystallization reaction on the dissolved solution, then carrying out vacuum filtration on a product after the crystallization reaction, recovering sterol to obtain a filtrate, treating the filtrate by using a rotary evaporator, and recovering the solvent to obtain a squalene concentrated solution;
(3) isolation of squalene: and (3) installing a chromatographic column by using a macroporous resin wet method, dissolving the squalene concentrated solution obtained in the step (2) in an ethanol water solution to ensure that the squalene concentration is 10mg/mL, loading the squalene into the chromatographic column, sequentially washing the chromatographic column by using deionized water and the ethanol water solution to obtain a squalene solution, carrying out desorption reaction on the squalene solution obtained after washing, and carrying out reduced pressure evaporation to recover an eluent to obtain a squalene product.
Further limiting, the alcoholic solution of the base in the step (1) is any one of a NaOH-ethanol solution, a KOH-ethanol solution and a NaOH-methanol solution; the organic solvent in the step (1) is n-hexane, diethyl ether or petroleum ether.
Further limiting, the concentration of the alcoholic solution of the alkali in the step (1) is 1.4 mol/L-2.0 mol/L; the material-liquid ratio of the alkali alcohol solution to the deodorized distillate in the step (1) is (2g:1mL) to (4g:1 mL).
Further limiting, the heating reflux reaction temperature in the step (1) is 70-100 ℃, and the reaction time is 1-3 h.
Further limiting, the organic solvent in the step (2) is any one of n-hexane, acetone and n-butanol; the feed-to-liquid ratio of the organic solvent to the unsaponifiable compound in step (2) is (1g:3mL) to (1g:5 mL).
Further limiting, the temperature of the crystallization reaction in the step (2) is-4 ℃ to 4 ℃, and the reaction time is 2h to 5 h.
Further limiting, the height-diameter ratio of the chromatographic column in the step (3) is 5-10.
Further limiting, the sample loading amount in the step (3) is 1.4 BV-1.8 BV, and the sample loading flow rate is 4 BV/h-6 BV/h.
Further limiting, the elution flow rate in the desorption reaction in the step (3) is 4 BV/h-6 BV/h.
Further, the vegetable oil deodorized distillate is any one of a soybean oil deodorized distillate, a rice bran oil deodorized distillate, a rapeseed oil deodorized distillate, a camellia oil deodorized distillate, and an olive oil deodorized distillate.
Has the advantages that:
(1) the cost is low: the method takes the deodorized distillate of the vegetable oil as the raw material, has the advantages of low cost and sufficient sources, and the squalene in the deodorized distillate is once enriched in the refining process, and the content of the squalene is higher, so the deodorized distillate is an ideal raw material for separating and purifying the squalene.
(2) Low energy consumption: the squalene separation and purification method provided by the invention avoids the use of high-energy-consumption equipment such as rectification, molecular distillation and the like, and the separation energy consumption is reduced to a certain extent by the process.
(3) The product quality is high: the squalene product obtained by the method has high purity which is up to 98%, and in addition, because the process steps are less, the loss of squalene in the production flow is reduced, and the product yield is high and can reach more than 95%.
(4) Easy realization of industrialized production: the method for extracting squalene provided by the invention has the advantages of simple process, easiness in operation and easiness in equipment of the process, and is favorable for industrial large-scale production.
Detailed Description
The following examples further illustrate the present invention but are not to be construed as limiting the invention. Modifications and substitutions to methods, procedures, or conditions of the invention may be made without departing from the spirit and substance of the invention.
The test reagents were purchased for commercial use.
The deodorized distillate is a by-product obtained during the deodorization of vegetable oils.
Example 1.
The method comprises the following steps of taking soybean oil deodorized distillate as a raw material, and separating and purifying squalene, wherein the method comprises the following specific operations:
(1) preparation of unsaponifiable matter: adding NaOH-ethanol solution into deodorized soybean oil distillate, wherein the feed-liquid ratio of the NaOH-ethanol solution to the deodorized distillate is 2.5:1(g: mL), the concentration of the NaOH-ethanol solution is 1.5mol/L, heating and refluxing for reaction at 75 ℃ for 1.5h, stopping the reaction, adding distilled water for washing, extracting unsaponifiable matters by using n-hexane for 3 times, placing an extraction phase at 4 ℃, removing precipitated soap, and removing the solvent by using a rotary evaporator to obtain unsaponifiable matters;
(2) preparation of squalene concentrated solution: dissolving unsaponifiable matters by using n-hexane at a material-to-liquid ratio of 1:3.5(g: mL), placing at-2 ℃ for primary crystallization of sterol after dissolution, taking out after 3h, carrying out vacuum filtration to recover the sterol, and recycling the solvent from the filtrate by using a rotary evaporator to obtain squalene concentrated solution after primary separation of the sterol;
(3) macroporous adsorbent resin separation of squalene: and (2) filling the macroporous resin D101 into a column by a wet method, wherein the height-diameter ratio of the chromatographic column is 10, dissolving the squalene concentrated solution obtained in the step (2) into an 85% ethanol aqueous solution, enabling the squalene concentration to be 10mg/mL, loading the squalene into the sample, enabling the loading amount to be 1.6BV and the loading flow rate to be 4BV/h, sequentially washing the squalene by using deionized water, 10%, 30%, 50% and 70% ethanol aqueous solution, desorbing by using petroleum ether, enabling the elution flow rate to be 4BV/h, and recovering the petroleum ether by reduced pressure evaporation to obtain a squalene product with the purity of 98.5%, wherein the yield is 96.8%.
Example 2.
The method comprises the following steps of taking rice bran oil deodorized distillate as a raw material, and carrying out squalene separation and purification, wherein the method comprises the following specific operations:
(1) preparation of unsaponifiable matter: adding NaOH-ethanol solution into deodorized soybean oil distillate, wherein the material-liquid ratio of the NaOH-ethanol solution to the deodorized distillate is 2:1(g: mL), the concentration of the NaOH-ethanol solution is 1.4mol/L, heating and refluxing for reaction at 70 ℃ for 1h, stopping the reaction, adding distilled water for washing, extracting unsaponifiable matters by using ether for 3 times, placing an extraction phase at 4 ℃, removing precipitated soap, and removing the solvent by using a rotary evaporator to obtain unsaponifiable matters;
(2) preparation of squalene concentrated solution: dissolving unsaponifiable matters by using n-hexane at a material-to-liquid ratio of 1:3(g: mL), placing at-4 ℃ for primary crystallization of sterol after dissolution, taking out after 2h, carrying out vacuum filtration to recover the sterol, and recycling the solvent from the filtrate by using a rotary evaporator to obtain squalene concentrated solution after primary separation of the sterol;
(3) macroporous adsorbent resin separation of squalene: and (3) filling the macroporous resin D4020 into a column by a wet method, wherein the height-diameter ratio of the chromatographic column is 8, dissolving the squalene concentrated solution obtained in the step (2) into an 85% ethanol aqueous solution, enabling the concentration of squalene to be 10mg/mL, loading the squalene into the sample, enabling the loading amount to be 1.8BV and the loading flow rate to be 6BV/h, sequentially washing with deionized water, 10%, 30%, 50% and 70% ethanol aqueous solution, desorbing by using petroleum ether, enabling the elution flow rate to be 6BV/h, and recovering the petroleum ether by reduced pressure evaporation to obtain a squalene product with the purity of 98.4%, wherein the yield is 96.0%.
Example 3.
The method comprises the following steps of taking rapeseed oil deodorized distillate as a raw material, and carrying out squalene separation and purification, wherein the method comprises the following specific operations:
(1) preparation of unsaponifiable matter: adding a KOH-ethanol solution into deodorized rapeseed oil distillate, wherein the material-liquid ratio of the NaOH-ethanol solution to the deodorized distillate is 3:1(g: mL), the concentration of the KOH-ethanol solution is 1.6mol/L, heating and refluxing for reaction at the reaction temperature of 80 ℃ for 2 hours, adding distilled water for washing after the reaction is stopped, extracting unsaponifiable matters by using petroleum ether for 3 times, placing an extract phase at 4 ℃, removing precipitated soap, and removing a solvent by using a rotary evaporator to obtain unsaponifiable matters;
(2) preparation of squalene concentrated solution: dissolving unsaponifiable matters by using acetone at a material-liquid ratio of 1:4(g: mL), placing at 0 ℃ for primary crystallization of sterol after dissolving, taking out after 3.5h, carrying out vacuum filtration to recover the sterol, and recovering the solvent from the filtrate by using a rotary evaporator to obtain squalene concentrated solution after primary separation of the sterol;
(3) macroporous adsorbent resin separation of squalene: and (2) filling the macroporous resin D4020 into a wet column, wherein the height-diameter ratio of the chromatographic column is 7, dissolving the squalene concentrated solution obtained in the step (2) into an 85% ethanol aqueous solution, enabling the concentration of squalene to be 10mg/mL, loading the squalene into a sample, enabling the loading amount to be 1.7BV and the loading flow rate to be 5BV/h, sequentially washing with deionized water, 10%, 30%, 50% and 70% ethanol aqueous solution, desorbing with diethyl ether, enabling the elution flow rate to be 5BV/h, and recovering the diethyl ether by reduced pressure evaporation to obtain a squalene product with the purity of 98.3%, wherein the yield is 95.2%.
Example 4.
The method comprises the following steps of taking the camellia oil deodorized distillate as a raw material, and carrying out squalene separation and purification, wherein the method comprises the following specific operations:
(1) preparation of unsaponifiable matter: adding a KOH-ethanol solution into deodorized rapeseed oil distillate, wherein the material-liquid ratio of the KOH-ethanol solution to the deodorized distillate is 3.5:1(g: mL), the concentration of the KOH-ethanol solution is 1.7mol/L, heating and refluxing for reaction at the reaction temperature of 85 ℃ for 2.5h, stopping the reaction, adding distilled water for washing, extracting unsaponifiable matters by using n-hexane for 3 times, placing an extraction phase at 4 ℃, removing precipitated soap, and removing a solvent by using a rotary evaporator to obtain unsaponifiable matters;
(2) preparation of squalene concentrated solution: dissolving unsaponifiable matters by using acetone at a material-liquid ratio of 1:4.5(g: mL), placing at 2 ℃ for primary crystallization of sterol after dissolving, taking out after 4 hours, carrying out vacuum filtration to recover the sterol, and recovering the solvent from the filtrate by using a rotary evaporator to obtain squalene concentrated solution after primary separation of the sterol;
(3) macroporous adsorbent resin separation of squalene: and (2) filling the macroporous resin X-5 into a column by a wet method, wherein the height-diameter ratio of the chromatographic column is 6, dissolving the squalene concentrated solution obtained in the step (2) into an 85% ethanol aqueous solution, enabling the squalene concentration to be 10mg/mL, loading the squalene into the sample, enabling the loading amount to be 1.5BV and the loading flow rate to be 4BV/h, sequentially washing the squalene by using deionized water, 10%, 30%, 50% and 70% ethanol aqueous solution, desorbing by using ether, enabling the elution flow rate to be 4BV/h, and recovering the ether by reduced pressure evaporation to obtain a squalene product with the purity of 98.1%, wherein the yield is 95.7%.
Example 5.
The method comprises the following steps of taking olive oil deodorized distillate as a raw material, and carrying out squalene separation and purification, wherein the method comprises the following specific operations:
(1) preparation of unsaponifiable matter: adding NaOH-methanol solution into deodorized distillate of olive oil, wherein the material-liquid ratio of the NaOH-methanol solution to the deodorized distillate is 4:1(g: mL), the concentration of the NaOH-methanol solution is 2.0mol/L, heating and refluxing for reaction at 100 ℃ for 3h, adding distilled water for washing after the reaction is stopped, extracting unsaponifiable matters by using ether for 3 times, placing an extraction phase at 4 ℃, removing precipitated soap, and removing the solvent by using a rotary evaporator to obtain unsaponifiable matters;
(2) preparation of squalene concentrated solution: dissolving unsaponifiable matters by using n-butanol at a material-to-liquid ratio of 1:5(g: mL), placing at 4 ℃ for primary crystallization of sterol after dissolution, taking out after 5 hours, carrying out vacuum filtration to recover the sterol, and recovering the solvent from the filtrate by using a rotary evaporator to obtain squalene concentrated solution after primary separation of the sterol;
(3) macroporous adsorbent resin separation of squalene: and (2) filling the macroporous resin AB8 into a column by a wet method, wherein the height-diameter ratio of the chromatographic column is 5, dissolving the squalene concentrated solution obtained in the step (2) into an 85% ethanol aqueous solution, enabling the squalene concentration to be 10mg/mL, loading the squalene into the sample, enabling the loading amount to be 1.4BV and the loading flow rate to be 6BV/h, sequentially washing the squalene by using deionized water, 10%, 30%, 50% and 70% ethanol aqueous solution, desorbing by using acetone, enabling the elution flow rate to be 6BV/h, and recovering the acetone by means of reduced pressure evaporation to obtain a squalene product with the purity of 98.2%, wherein the yield is 95.1%.
Claims (10)
1. A method for extracting squalene from plant deodorizer distillate is characterized by comprising the following specific steps of:
(1) preparation of unsaponifiable matter: adding the deodorized distillate of vegetable oil into alkaline alcohol solution, heating and refluxing, stopping reaction, washing with distilled water, extracting unsaponifiable matter with organic solvent, removing precipitated soap, and removing solvent with rotary evaporator to obtain unsaponifiable matter;
(2) preparation of squalene concentrated solution: dissolving the unsaponifiable matter obtained in the step (1) by using an organic solvent, carrying out crystallization reaction on the dissolved solution, then carrying out vacuum filtration on a product after the crystallization reaction, recovering sterol to obtain a filtrate, treating the filtrate by using a rotary evaporator, and recovering the solvent to obtain a squalene concentrated solution;
(3) isolation of squalene: and (3) installing a chromatographic column by using a macroporous resin wet method, dissolving the squalene concentrated solution obtained in the step (2) in an ethanol water solution to ensure that the squalene concentration is 10mg/mL, loading the squalene into the chromatographic column, sequentially washing the chromatographic column by using deionized water and the ethanol water solution to obtain a squalene solution, carrying out desorption reaction on the squalene solution obtained after washing, and carrying out reduced pressure evaporation to recover an eluent to obtain a squalene product.
2. The method according to claim 1, wherein the alcoholic solution of the base in the step (1) is any one of a NaOH-ethanol solution, a KOH-ethanol solution and a NaOH-methanol solution; the organic solvent in the step (1) is n-hexane, diethyl ether or petroleum ether.
3. The method according to claim 1, wherein the concentration of the alcoholic solution of the base in the step (1) is 1.4mol/L to 2.0 mol/L; the material-liquid ratio of the alkali alcohol solution to the deodorized distillate in the step (1) is (2g:1mL) to (4g:1 mL).
4. The method according to claim 1, wherein the heating reflux reaction temperature in the step (1) is 70 ℃ to 100 ℃ and the reaction time is 1h to 3 h.
5. The method according to claim 1, wherein the organic solvent in the step (2) is any one of n-hexane, acetone and n-butanol; the feed-to-liquid ratio of the organic solvent to the unsaponifiable compound in step (2) is (1g:3mL) to (1g:5 mL).
6. The method according to claim 1, wherein the crystallization reaction in step (2) is carried out at a temperature of-4 ℃ to 4 ℃ for a period of 2 hours to 5 hours.
7. The method according to claim 1, wherein the ratio of the height to the diameter of the chromatographic column in the step (3) is 5 to 10.
8. The method according to claim 1, wherein the sample loading amount in the step (3) is 1.4 to 1.8BV and the sample loading flow rate is 4 to 6 BV/h.
9. The method according to claim 1, wherein the elution flow rate in the desorption reaction in the step (3) is 4 to 6 BV/h.
10. The method according to any one of claims 1 to 9, wherein the vegetable oil deodorized distillate is any one of a soybean oil deodorized distillate, a rice bran oil deodorized distillate, a rapeseed oil deodorized distillate, a camellia oil deodorized distillate, and an olive oil deodorized distillate.
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