CN112210437A - Method for purifying algae oil - Google Patents
Method for purifying algae oil Download PDFInfo
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- CN112210437A CN112210437A CN202011126530.2A CN202011126530A CN112210437A CN 112210437 A CN112210437 A CN 112210437A CN 202011126530 A CN202011126530 A CN 202011126530A CN 112210437 A CN112210437 A CN 112210437A
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- oil
- alcohol
- water
- water solution
- algae
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- 241000195493 Cryptophyta Species 0.000 title claims abstract description 98
- 238000000034 method Methods 0.000 title claims abstract description 36
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 174
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 131
- 239000003463 adsorbent Substances 0.000 claims abstract description 50
- 239000004519 grease Substances 0.000 claims abstract description 20
- 238000009826 distribution Methods 0.000 claims abstract description 3
- 238000001914 filtration Methods 0.000 claims description 27
- 239000012535 impurity Substances 0.000 claims description 26
- 238000005809 transesterification reaction Methods 0.000 claims description 13
- 239000002253 acid Substances 0.000 claims description 12
- 238000005119 centrifugation Methods 0.000 claims description 12
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 claims description 10
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 10
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 9
- 229910000019 calcium carbonate Inorganic materials 0.000 claims description 5
- AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical compound [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 claims description 3
- 239000000920 calcium hydroxide Substances 0.000 claims description 3
- 229910001861 calcium hydroxide Inorganic materials 0.000 claims description 3
- IDGUHHHQCWSQLU-UHFFFAOYSA-N ethanol;hydrate Chemical compound O.CCO IDGUHHHQCWSQLU-UHFFFAOYSA-N 0.000 claims description 3
- GBMDVOWEEQVZKZ-UHFFFAOYSA-N methanol;hydrate Chemical compound O.OC GBMDVOWEEQVZKZ-UHFFFAOYSA-N 0.000 claims description 3
- 239000002244 precipitate Substances 0.000 claims description 3
- 238000002481 ethanol extraction Methods 0.000 claims description 2
- KIDBBTHHMJOMAU-UHFFFAOYSA-N propan-1-ol;hydrate Chemical compound O.CCCO KIDBBTHHMJOMAU-UHFFFAOYSA-N 0.000 claims description 2
- 239000003921 oil Substances 0.000 description 156
- 235000019441 ethanol Nutrition 0.000 description 75
- 239000000243 solution Substances 0.000 description 73
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 36
- 239000000706 filtrate Substances 0.000 description 31
- 238000000746 purification Methods 0.000 description 24
- JAZBEHYOTPTENJ-JLNKQSITSA-N all-cis-5,8,11,14,17-icosapentaenoic acid Chemical compound CC\C=C/C\C=C/C\C=C/C\C=C/C\C=C/CCCC(O)=O JAZBEHYOTPTENJ-JLNKQSITSA-N 0.000 description 22
- 235000020673 eicosapentaenoic acid Nutrition 0.000 description 21
- 229960005135 eicosapentaenoic acid Drugs 0.000 description 21
- JAZBEHYOTPTENJ-UHFFFAOYSA-N eicosapentaenoic acid Natural products CCC=CCC=CCC=CCC=CCC=CCCCC(O)=O JAZBEHYOTPTENJ-UHFFFAOYSA-N 0.000 description 21
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 18
- 235000020777 polyunsaturated fatty acids Nutrition 0.000 description 16
- 235000014113 dietary fatty acids Nutrition 0.000 description 15
- 229930195729 fatty acid Natural products 0.000 description 15
- 239000000194 fatty acid Substances 0.000 description 15
- 238000003756 stirring Methods 0.000 description 14
- 150000004665 fatty acids Chemical class 0.000 description 13
- 239000000203 mixture Substances 0.000 description 13
- 239000011148 porous material Substances 0.000 description 9
- 239000000047 product Substances 0.000 description 7
- 238000002390 rotary evaporation Methods 0.000 description 7
- MBMBGCFOFBJSGT-KUBAVDMBSA-N all-cis-docosa-4,7,10,13,16,19-hexaenoic acid Chemical compound CC\C=C/C\C=C/C\C=C/C\C=C/C\C=C/C\C=C/CCC(O)=O MBMBGCFOFBJSGT-KUBAVDMBSA-N 0.000 description 6
- 239000001913 cellulose Substances 0.000 description 6
- 229920002678 cellulose Polymers 0.000 description 6
- 238000000605 extraction Methods 0.000 description 6
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 6
- 235000020660 omega-3 fatty acid Nutrition 0.000 description 6
- 229940012843 omega-3 fatty acid Drugs 0.000 description 6
- 239000006014 omega-3 oil Substances 0.000 description 6
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 5
- 230000000694 effects Effects 0.000 description 5
- 239000000725 suspension Substances 0.000 description 5
- 229930186217 Glycolipid Natural products 0.000 description 4
- 150000001298 alcohols Chemical class 0.000 description 4
- 238000004821 distillation Methods 0.000 description 4
- 235000020669 docosahexaenoic acid Nutrition 0.000 description 4
- XLYOFNOQVPJJNP-ZSJDYOACSA-N heavy water Substances [2H]O[2H] XLYOFNOQVPJJNP-ZSJDYOACSA-N 0.000 description 4
- 230000007062 hydrolysis Effects 0.000 description 4
- 238000006460 hydrolysis reaction Methods 0.000 description 4
- 150000002632 lipids Chemical class 0.000 description 4
- 150000003904 phospholipids Chemical class 0.000 description 4
- 150000003839 salts Chemical class 0.000 description 4
- 150000003626 triacylglycerols Chemical class 0.000 description 4
- 241000251468 Actinopterygii Species 0.000 description 3
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 3
- 150000001720 carbohydrates Chemical class 0.000 description 3
- 235000014633 carbohydrates Nutrition 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- 238000007906 compression Methods 0.000 description 3
- 230000006835 compression Effects 0.000 description 3
- 239000010779 crude oil Substances 0.000 description 3
- 238000001514 detection method Methods 0.000 description 3
- 229940090949 docosahexaenoic acid Drugs 0.000 description 3
- -1 etc. Chemical class 0.000 description 3
- 125000004494 ethyl ester group Chemical group 0.000 description 3
- 229910017604 nitric acid Inorganic materials 0.000 description 3
- 239000000049 pigment Substances 0.000 description 3
- 238000002360 preparation method Methods 0.000 description 3
- 102000004169 proteins and genes Human genes 0.000 description 3
- 108090000623 proteins and genes Proteins 0.000 description 3
- 239000001117 sulphuric acid Substances 0.000 description 3
- 235000011149 sulphuric acid Nutrition 0.000 description 3
- HVCOBJNICQPDBP-UHFFFAOYSA-N 3-[3-[3,5-dihydroxy-6-methyl-4-(3,4,5-trihydroxy-6-methyloxan-2-yl)oxyoxan-2-yl]oxydecanoyloxy]decanoic acid;hydrate Chemical compound O.OC1C(OC(CC(=O)OC(CCCCCCC)CC(O)=O)CCCCCCC)OC(C)C(O)C1OC1C(O)C(O)C(O)C(C)O1 HVCOBJNICQPDBP-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 2
- 238000010306 acid treatment Methods 0.000 description 2
- 239000008367 deionised water Substances 0.000 description 2
- 229910021641 deionized water Inorganic materials 0.000 description 2
- 238000005886 esterification reaction Methods 0.000 description 2
- 235000019197 fats Nutrition 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- 239000012074 organic phase Substances 0.000 description 2
- 238000000053 physical method Methods 0.000 description 2
- 239000013535 sea water Substances 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- UFTFJSFQGQCHQW-UHFFFAOYSA-N triformin Chemical compound O=COCC(OC=O)COC=O UFTFJSFQGQCHQW-UHFFFAOYSA-N 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
- DVSZKTAMJJTWFG-SKCDLICFSA-N (2e,4e,6e,8e,10e,12e)-docosa-2,4,6,8,10,12-hexaenoic acid Chemical compound CCCCCCCCC\C=C\C=C\C=C\C=C\C=C\C=C\C(O)=O DVSZKTAMJJTWFG-SKCDLICFSA-N 0.000 description 1
- GZJLLYHBALOKEX-UHFFFAOYSA-N 6-Ketone, O18-Me-Ussuriedine Natural products CC=CCC=CCC=CCC=CCC=CCC=CCCCC(O)=O GZJLLYHBALOKEX-UHFFFAOYSA-N 0.000 description 1
- UXVMQQNJUSDDNG-UHFFFAOYSA-L Calcium chloride Chemical compound [Cl-].[Cl-].[Ca+2] UXVMQQNJUSDDNG-UHFFFAOYSA-L 0.000 description 1
- ZGTMUACCHSMWAC-UHFFFAOYSA-L EDTA disodium salt (anhydrous) Chemical compound [Na+].[Na+].OC(=O)CN(CC([O-])=O)CCN(CC(O)=O)CC([O-])=O ZGTMUACCHSMWAC-UHFFFAOYSA-L 0.000 description 1
- 229920000064 Ethyl eicosapentaenoic acid Polymers 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 206010061218 Inflammation Diseases 0.000 description 1
- 229910021578 Iron(III) chloride Inorganic materials 0.000 description 1
- 229910004619 Na2MoO4 Inorganic materials 0.000 description 1
- 241000159660 Nannochloropsis oculata Species 0.000 description 1
- 241000224476 Nannochloropsis salina Species 0.000 description 1
- 239000004677 Nylon Substances 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 1
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 239000004480 active ingredient Substances 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 239000008280 blood Substances 0.000 description 1
- 210000004369 blood Anatomy 0.000 description 1
- 230000017531 blood circulation Effects 0.000 description 1
- 238000007664 blowing Methods 0.000 description 1
- 239000001110 calcium chloride Substances 0.000 description 1
- 229910001628 calcium chloride Inorganic materials 0.000 description 1
- 239000004202 carbamide Substances 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- WORJEOGGNQDSOE-UHFFFAOYSA-N chloroform;methanol Chemical compound OC.ClC(Cl)Cl WORJEOGGNQDSOE-UHFFFAOYSA-N 0.000 description 1
- 230000003920 cognitive function Effects 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 238000012217 deletion Methods 0.000 description 1
- 230000037430 deletion Effects 0.000 description 1
- 235000015872 dietary supplement Nutrition 0.000 description 1
- KAUVQQXNCKESLC-UHFFFAOYSA-N docosahexaenoic acid (DHA) Natural products COC(=O)C(C)NOCC1=CC=CC=C1 KAUVQQXNCKESLC-UHFFFAOYSA-N 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 230000002526 effect on cardiovascular system Effects 0.000 description 1
- 239000003344 environmental pollutant Substances 0.000 description 1
- 230000032050 esterification Effects 0.000 description 1
- SSQPWTVBQMWLSZ-AAQCHOMXSA-N ethyl (5Z,8Z,11Z,14Z,17Z)-icosapentaenoate Chemical compound CCOC(=O)CCC\C=C/C\C=C/C\C=C/C\C=C/C\C=C/CC SSQPWTVBQMWLSZ-AAQCHOMXSA-N 0.000 description 1
- 239000004744 fabric Substances 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- 239000012530 fluid Substances 0.000 description 1
- 238000009472 formulation Methods 0.000 description 1
- 235000021588 free fatty acids Nutrition 0.000 description 1
- 239000013505 freshwater Substances 0.000 description 1
- 230000006870 function Effects 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 230000036541 health Effects 0.000 description 1
- 230000007407 health benefit Effects 0.000 description 1
- 238000005286 illumination Methods 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 230000004054 inflammatory process Effects 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- JZMJDSHXVKJFKW-UHFFFAOYSA-N methyl sulfate Chemical compound COS(O)(=O)=O JZMJDSHXVKJFKW-UHFFFAOYSA-N 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 230000004770 neurodegeneration Effects 0.000 description 1
- 208000015122 neurodegenerative disease Diseases 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 229910017464 nitrogen compound Inorganic materials 0.000 description 1
- 150000002830 nitrogen compounds Chemical class 0.000 description 1
- 235000015097 nutrients Nutrition 0.000 description 1
- 229920001778 nylon Polymers 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 231100000719 pollutant Toxicity 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 230000009993 protective function Effects 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 239000011780 sodium chloride Substances 0.000 description 1
- AJPJDKMHJJGVTQ-UHFFFAOYSA-M sodium dihydrogen phosphate Chemical compound [Na+].OP(O)([O-])=O AJPJDKMHJJGVTQ-UHFFFAOYSA-M 0.000 description 1
- 239000011684 sodium molybdate Substances 0.000 description 1
- TVXXNOYZHKPKGW-UHFFFAOYSA-N sodium molybdate (anhydrous) Chemical compound [Na+].[Na+].[O-][Mo]([O-])(=O)=O TVXXNOYZHKPKGW-UHFFFAOYSA-N 0.000 description 1
- 229910000162 sodium phosphate Inorganic materials 0.000 description 1
- 239000002594 sorbent Substances 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 235000003563 vegetarian diet Nutrition 0.000 description 1
Classifications
-
- 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
- C11B3/10—Refining fats or fatty oils by adsorption
-
- 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
- C11B3/001—Refining fats or fatty oils by a combination of two or more of the means hereafter
-
- 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
- C11B3/008—Refining fats or fatty oils by filtration, e.g. including ultra filtration, dialysis
-
- 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
- C11B3/02—Refining fats or fatty oils by chemical reaction
- C11B3/04—Refining fats or fatty oils by chemical reaction with acids
-
- 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
- C11B3/02—Refining fats or fatty oils by chemical reaction
- C11B3/06—Refining fats or fatty oils by chemical reaction with bases
-
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Microbiology (AREA)
- Engineering & Computer Science (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Wood Science & Technology (AREA)
- Organic Chemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Mechanical Engineering (AREA)
- Fats And Perfumes (AREA)
Abstract
The invention relates to a method for purifying algae oil, which comprises the following steps: 1) contacting the algae oil with an alcohol-water solution in the presence of a grease adsorbent, wherein the volume ratio of alcohol to water in the alcohol-water solution is 1:5 to 1:1, so that the algae oil is in oil-drop distribution after being contacted with the alcohol-water solution; 2) separating the oil adsorbent from the alcohol-water solution; and 3) separating the algal oil from the oil adsorbent.
Description
The application is a divisional application of a patent application with the application date of 2018, 07, 26 and the application number of CN201810837473.5 and the name of a new algae oil purification method.
Technical Field
The invention relates to a method for purifying algae oil.
Background
Polyunsaturated fatty acids (PUFA), such as omega-3 fatty acids, are of great interest for human health. Omega-3 fatty acids, such as eicosapentaenoic acid (EPA) and docosahexaenoic acid (DHA), can reduce the amount of triglycerides in the blood. These polyunsaturated fatty acids also have cardiovascular protective functions, and can prevent and treat inflammation, neurodegenerative diseases, promote cognitive functions, etc. (Sugano, Michihiro, Balanced intake of secreted fatty acids for health benefits. J. Oleo Sci.2001,50(5): 305-. More studies have shown that EPA, but not DHA, is the main component for the above-mentioned effects (Martins JG. EPA but not DHA appeares to be responsive for the effect of omega-3long chain unskilled fatty acid deletion in expression: observation from a method-analysis of random controlled metals. J Am Cold nutrient. 2009 Oct; 28(5): 525-42.; Eclov J et al, EPA, not DHA, present fibers in compression-induced fatty acid: positional roll of free fatty acid 4. Lipid. Dec; 56-12. i. 2297. 10.1194. M034. J. 034. for the purpose of improving blood circulation in expression of fatty acid).
Omega-3 fatty acids are typically derived from marine fish. However, with the decrease of fish resources, the enrichment of fish body pollutants caused by the environment and the like, and more people devote vegetarian diet, the demand for omega-3 fatty acids from plants is increasing. Algal polyunsaturated fatty acids show great potential in plant resources, whether as dietary supplements or as pharmaceuticals. The algae has the advantages that the area occupied by algae cultivation is smaller than that of common land crops, and seawater or fresh water resources can be widely applied.
However, algal oil extracted from algae using ethanol contains a large amount of impurities including salts, carbohydrates, proteins, pigments, etc. due to low selectivity of ethanol. The presence of these impurities, coupled with the presence of omega-3 fatty acids in the algae oil, mainly in the form of triglycerides, glycolipids and phospholipids, makes the algae oil very viscous, which poses a significant obstacle to subsequent purification and concentration, and makes the appearance of the algae oil poor. In large-scale industrial production, the triglycerides, glycolipids and phospholipids are generally converted into a more fluid ethyl ester form by transesterification, followed by subsequent purification and concentration. If desired, the purified and concentrated ethylated omega-3 fatty acids are converted back to their native form, e.g., triglycerides, by transesterification.
Disclosure of Invention
The present disclosure has been made in view of the above-described state of the art, and an object thereof is to provide a method for purifying algal oil capable of improving the purity of polyunsaturated fatty acids contained therein. Specifically, the invention provides a method for purifying algae oil, which comprises the following steps:
1) contacting algae oil with an alcohol-water solution in the presence of a grease adsorbent, wherein the volume ratio of alcohol to water in the alcohol-water solution is 1:5 to 1:1 so that the algae oil is in oil-drop distribution after being contacted with the alcohol-water solution;
2) separating the oil adsorbent from the alcohol-water solution; and is
3) Separating algae oil from the oil adsorbent.
In the purification method according to the present disclosure, algae oil is in the form of oil droplets in an alcohol-water solution having a volume ratio of alcohol to water of 1:5 to 1:1, and has improved work fluidity, and can be sufficiently contacted with the alcohol-water solution, and can be more effectively removed of water-soluble impurities by being separated from the alcohol-water solution by adsorption to a fat adsorbent. After the purification method is used for purifying, the fluidity of the algae oil is greatly improved, and the purity of the contained polyunsaturated fatty acid can be improved.
In addition, in the purification method according to the present disclosure, optionally, the algal oil is crude algal oil extracted from natural dry algae treated with ethanol or esterified algal oil obtained by transesterification with lower alcohol after ethanol extraction.
Further, in the purification method according to the present disclosure, optionally, the alcohol-water solution has a volume ratio of alcohol to water of 1:1, 1:2, 1:3, 1:4, or 1: 5. In this case, the algal oil is in contact with the alcohol-water solution of the specific ratio and distributed in an oil droplet shape, so that the contact area of the algal oil with the alcohol-water solution is increased, thereby enabling water-soluble impurities contained in the algal oil to better enter the alcohol-water solution.
In addition, in the purification method according to the present disclosure, optionally, the grease adsorbent is selected from paper towels or activated carbon.
In addition, in the purification method according to the present disclosure, optionally, the weight ratio of the algal oil to the paper towel is 1:1 to 10: 1.
In addition, in the purification method according to the present disclosure, step 2) may be performed by collecting the oil adsorbent by filtration or centrifugation.
In addition, in the purification method according to the present disclosure, after the oil adsorbent is collected, the oil adsorbent may be washed with water to remove water-soluble impurities.
Additionally, in the purification process contemplated by the present disclosure, optionally, prior to step 1), the algal oil is contacted with dilute acid at room temperature, calcium carbonate, calcium hydroxide or sodium hydroxide is added to neutralize the acid, and the precipitate is removed by filtration or centrifugation. In this case, impurities can be better removed by separating certain kinds of impurities from effective components such as fatty acids in the algal oil.
Additionally, in the purification process contemplated by the present disclosure, optionally, the algal oil is contacted with the dilute acid in the presence of a lower alcohol.
Further, in the purification method to which the present disclosure relates, optionally, the alcohol-water solution is selected from a methanol-water solution, an ethanol-water solution, a propanol-water solution, or a combination thereof.
According to the purification method, the algae oil is placed in the alcohol-water solution with a specific ratio, so that the algae oil is distributed in an oil drop shape, the working fluidity of the algae oil is increased, the contact area of the algae oil and the alcohol-water solution is increased, and water-soluble impurities are better dissolved in the alcohol-water solution; then the algae oil is absorbed in the oil adsorbent, and the oil adsorbent is separated from the alcohol-water solution by filtration or centrifugation, so as to achieve the effect of fully removing water-soluble impurities in the algae oil. The method is not only suitable for natural algae oil with polyunsaturated fatty acid in the form of triglyceride, glycolipid and phospholipid, but also suitable for esterified algae oil obtained by transesterification of lower alcohol such as methanol or ethanol. After treatment by the method of the present invention, the algae oil has an increased total fatty acid content, particularly useful polyunsaturated fatty acids such as EPA, and the algae oil has a greatly improved fluidity.
Detailed Description
The algal oil extracted from microalgae by ethanol contains a large amount of impurities including salts, carbohydrates, proteins, pigments, etc., and fatty acids in algal oil mainly exist in three forms of triglyceride, glycolipid and phospholipid. The superposition of the two factors causes the algae oil to be viscous and nearly solid, which causes certain difficulty in subsequent purification, concentration and the like.
The inventors of the present invention have found that when algal oil is placed in an alcohol-water solution having a volume ratio of alcohol to water of 1:1 or less, the algal oil in a near-solid state is in the form of oil droplets, and fluidity during handling is improved, and the contact area between the algal oil and the alcohol-water solution is increased, so that water-soluble impurities in the algal oil can be more easily dissolved in the alcohol-water solution. This makes it possible to purify algal oil directly and efficiently without transesterification, greatly reducing the flow and cost of the purification process.
By adding an oil adsorbent, for example, a cellulose product such as a paper towel, activated carbon or the like to the alcohol-water solution, fatty acids such as EPA in algal oil are adsorbed on the oil adsorbent. The oil adsorbent is collected by filtration or centrifugation, so that the separation of the effective components of the algae oil, such as polyunsaturated fatty acid, from the alcohol-water solution and the water-soluble impurities contained in the alcohol-water solution is realized. After removing a large amount of impurities, the fluidity of algal oil is improved and the purity of polyunsaturated fatty acids is increased. The better fluidity means that the purity of the grease in the algae oil is high, and the algae oil product is provided with better appearance feeling.
The method of the invention is also suitable for the esterified algae oil after the transesterification treatment of lower alcohol such as methanol or ethanol. The esterified algae oil is also in an oil drop shape in an alcohol-water solution with the volume ratio of alcohol to water being less than 1:1, so that the working fluidity of the algae oil can be further increased, the contact surface of the algae oil and the alcohol-water solution is increased, and water-soluble impurities are better removed.
The algae oil can be extracted by treating the dry algae with ethanol, and the extraction parameters can be adjusted by those skilled in the art according to the needs. In one embodiment, dried algae having a water content of less than 5 wt% is placed in absolute ethanol in a water bath at 80 ℃ and at 20rpm for 2 hours, wherein the ratio of dried algae to absolute ethanol may be 1:20 g/mL.
The ethanol extracted algal oil can be purified by the following process steps:
1) optionally, the algae oil is contacted with dilute acid, calcium carbonate or the like is added to neutralize the acid, and the precipitate is removed by filtration or centrifugation or the like;
2) contacting algae oil with an alcohol-water solution in the presence of a lipid adsorbent;
3) separating the oil adsorbent from the alcohol-water solution;
4) optionally washing the grease adsorbent with water; and
5) separating algae oil from the oil adsorbent.
In the ethanol-extracted algal oil, impurities such as salts, carbohydrates, proteins, and pigments are present. The addition of low concentrations of acid to the algae oil allows certain classes of impurities to be separated from the active ingredients in the algae oil, such as fatty acids, allowing for better removal of impurities. The low concentration acid may be dilute sulfuric acid, dilute hydrochloric acid, dilute nitric acid, and the like. Hydrochloric acid and nitric acid are volatile, hydrochloric acid is too weak in acidity, and nitric acid remains to cause nitrogen compounds in the final product. Therefore, dilute sulfuric acid is the best choice. In order to use a sufficient amount of sulphuric acid while avoiding the occurrence of excessively high concentrations, the algal oil may be contacted with sulphuric acid in the presence of a lower alcohol, such as ethanol, the working concentration of sulphuric acid may be in the range of 0.01-0.1mol/L, for example in the range of 0.036-0.048 mol/L. Due to the low concentration of sulfuric acid, coupled with the temperature control, transesterification of polyunsaturated fatty acids with lower alcohols does not occur even in the presence of alcohols. The original concentration of the added dilute sulfuric acid is not too low, so that more water is brought, and the formulation of the ratio of alcohol-water solution in the subsequent step is difficult. In one embodiment, 45ml of dilute sulfuric acid with a concentration of 3.6mol/L is added to 4.5L of ethanol solution containing about 100g of algal oil, and the mixture is treated at room temperature at 20rpm for 2 hours. After the dilute acid treatment, excessive calcium carbonate, calcium hydroxide and the like are added to neutralize the dilute acid and stop the action of the acid. Insoluble matter can be removed by filtration or centrifugation.
After dilute acid treatment, the algae oil is contacted with an alcohol-water solution in the presence of a grease adsorbent, and the volume ratio of alcohol to water in the alcohol-water solution can be below 1: 1. When the algae oil is placed in the alcohol-water solution with the alcohol-water volume ratio, the algae oil is distributed in an oil drop shape, so that the contact area of the algae oil and the alcohol-water solution is increased, water-soluble impurities contained in the algae oil can better enter the alcohol-water solution, the oil drops are gradually adsorbed in the oil adsorbent, and then the adsorbent is separated from the alcohol-water solution through a physical method, so that the effect of removing the water-soluble impurities contained in the algae oil is realized.
The contacting of the algal oil of step 2) with the alcohol-water solution can be carried out, for example, for 2 hours with stirring. The alcohol-water solution may be selected from a methanol-water solution and an ethanol-water solution. In the alcohol-water solution, the volume ratio of alcohol to water is 1:1 or less. In some embodiments, the volume ratio of alcohol to water in the alcohol-water solution can be 1:1 or less, 2:3 or less, or 1:2 or less, and 1:5 or more, 1:4 or more, or 1:3 or more. In some embodiments, the alcohol-water solution has a volume ratio of alcohol to water of 1:1, 1:2, 1:3, 1:4, or 1: 5. The volume ratio of alcohol to water in the alcohol-water solution is not suitable to be too low, otherwise the recycling of ethanol is not facilitated. Therefore, in practical operation, the volume ratio of alcohol to water can be set in the range of 1:1 to 1: 2.
The ratio of algal oil to alcohol-water solution should be in a proper range. When this ratio is too high, the alcohol-water solution may be caused to be insufficient to dissolve all the water-soluble impurities; when the ratio is too low, the amount of alcohol and water used is too large, and the cost is increased. The weight to volume ratio of algal oil to alcohol in step 2) may be in the range of 0.2-0.4g/mL, for example 0.225-0.354g/mL, based on the crude algal oil extracted with ethanol. Since algal oil is extracted by ethanol, if the extraction step is directly carried out to the purification step of the present invention without removal of ethanol, there may be a problem that the ratio of algal oil to alcohol-water solution is too low, the volume of ethanol may be compressed by distillation or the like, and then water may be added according to the amount of ethanol after compression.
The grease adsorbent can be cellulose products, or activated carbon, and the like, and the type and the dosage of the grease adsorbent can be determined by those skilled in the art according to actual needs. In the present invention, the cellulosic product may be a shredded tissue, such as any common household tissue. Cellulose products such as paper towels contain a large amount of cellulose, and the cellulose can adsorb grease and is not dissolved in water and common organic solvents, so that the separation of algae oil and alcohol-water solution is facilitated. In one embodiment, the weight ratio of algae oil to paper towel may be in the range of 1:1-10:1, or a salt thereof.
The oil-and-fat adsorbent having adsorbed algal oil can be separated from the alcohol-water solution by filtration such as filtration under reduced pressure or centrifugation. The oil adsorbent may be washed with water to further remove water-soluble impurities. The oil adsorbed in the oil adsorbent can be dissolved in absolute ethanol, the adsorbent is removed by filtration or centrifugation, and the absolute ethanol is removed by distillation, so as to obtain purified algae oil.
As described above, the method of the present invention is also applicable to esterified algal oils subjected to transesterification with lower alcohols such as methanol or ethanol. The algae oil extracted by processing dry algae with ethanol can be transesterified with lower alcohol under the catalysis of concentrated sulfuric acid at 70 ℃. The transesterification conditions can be set by the person skilled in the art as a function of the circumstances. The lower alcohol can be methanol, ethanol, etc., and is typically ethanol. The esterification reaction can be stopped by adding an excess of calcium carbonate or the like to neutralize the sulfuric acid.
The transesterified algal oil can be purified by the following process steps:
1) contacting the transesterified algal oil with an alcohol-water solution in the presence of a lipid adsorbent;
2) separating the oil adsorbent from the alcohol-water solution;
3) optionally washing the grease adsorbent with water; and
4) the grease is separated from the grease adsorbent.
In step 1), the transesterified algal oil is contacted with an alcohol-water solution in the presence of a lipid adsorbent, and the volume ratio of alcohol to water in the alcohol-water solution can be 1:1 or less. When the transesterified algae oil is placed in the alcohol-water solution with the alcohol-water volume ratio, the transesterified algae oil is distributed in an oil drop shape, so that the contact area of the algae oil and the alcohol-water solution is increased, water-soluble impurities contained in the algae oil better enter the alcohol-water solution, the oil drops are gradually adsorbed in the oil adsorbent, and then the adsorbent is separated from the alcohol-water solution by a physical method, so that the effect of removing the water-soluble impurities contained in the transesterified algae oil is realized. This step can be carried out with stirring for, for example, 2 hours. The alcohol-water solution may be selected from water solutions of lower alcohols such as methanol or ethanol, etc. In the alcohol-water solution, the volume ratio of alcohol to water is 1:1 or less. In some embodiments, the volume ratio of alcohol to water in the alcohol-water solution can be 1:1 or less, 2:3 or less, or 1:2 or less, and 1:5 or more, 1:4 or more, or 1:3 or more. In some embodiments, the alcohol-water solution has a volume ratio of alcohol to water of 1:1, 1:2, 1:3, 1:4, or 1: 5. The volume ratio of alcohol to water may be set in the range of 1:1 to 1:2 in view of the recovery of ethanol.
The ratio of transesterified algal oil to alcohol-water solution should be within a suitable range. When this ratio is too high, the alcohol-water solution may be caused to be insufficient to dissolve all the water-soluble impurities; when the ratio is too low, the amount of alcohol and water used is too large, and the cost is increased. The weight to volume ratio of algal oil to alcohol in step 2) may be in the range of 0.2-0.4g/mL, for example 0.225-0.354g/mL, based on the crude algal oil extracted with ethanol. Since algal oil is extracted by ethanol, if the extraction step directly enters the purification step of the present invention without ethanol removal, there may be a problem that the ratio of algal oil to alcohol-water solution is too low, the volume of ethanol may be compressed by distillation or the like, and then water may be added according to the amount of ethanol after compression.
The grease adsorbent can be cellulose products such as paper towels, activated carbon and the like, and the type and the dosage of the grease adsorbent can be determined by those skilled in the art according to actual needs. In one embodiment, the grease sorbent is a cellulosic product, such as a paper towel, and the weight ratio of algae oil to paper towel can be in the range of 1:1 to 10: 1.
In step 2), the oil-and-fat adsorbent having the transesterified algal oil adsorbed thereon can be separated from the alcohol-water solution by filtration such as filtration under reduced pressure or centrifugation.
In step 3), the fat adsorbent may be washed with water to further remove water-soluble impurities.
In step 4), the transesterified algae oil adsorbed in the oil adsorbent can be dissolved in absolute ethyl alcohol, the adsorbent is removed by filtration or centrifugation, and the absolute ethyl alcohol is removed by distillation, so that purified transesterified algae oil can be obtained.
Example 1 Dry algae preparation
Nannochloropsis salina is grown in artificial seawater containing 22g/L NaCl and 2.44g/L MgSO for 7 days4·7H2O, 0.6g/L KCl, 0.25g/L urea, 0.3g/L CaCl2·2H2O、4.4mg/L NaH2PO4·2H2O、0.1g/L NaHCO3、0.75mg/L Na2EDTA·2H2O、0.097mg/L FeCl3·6H2O、0.5mg/L H3BO3、1mg/LMnSO4、0.05mg/LZnSO4、0.02mg/LCoCl2·6H2O, and 0.1mg/L Na2MoO4·2H2O。
1 ton of algae solution was taken and added with 6M NaOH solution to adjust the pH to 10.5 at which the algae began to settle. After three hours, the aqueous layer was discarded, and the residue was filtered through a Miracloth filter having a pore size of 25 μm to obtain about 1kg of algal mud having a water content of about 80 wt%. The algal mud was treated with ZPG-G spray dryer for 2 hours to obtain 146G of dried algae having a water content of 5 wt% or less.
The method for measuring the water content is as follows: baking the algae mud or algae powder in an oven at 80 ℃ for more than 2 hours until constant weight is achieved; the weight before placing in the oven was compared to the final constant weight and the water content was calculated as (weight before baking-constant weight)/weight before baking 100%.
Example 2 extraction of algal oil
250g of the dried alga prepared in example 1 (containing 6.86% by weight of eicosapentaenoic acid (EPA) and 18.50% of Total Fatty Acids (TFA)) was taken, placed in 2.5L of 94% ethanol, treated in a water bath at 80 ℃ for 2h, and a magnetic stirrer was set at 20 rpm. Thereafter, filtration was performed under reduced pressure (-0.1MPA) using a cloth funnel connected to a suction pump with filter paper (pore size 15-20 μm, Xinxing, qualitative filter paper). The filtered algal bodies were added to 2.5L of 94% ethanol and the above procedure was repeated. The two filtrates were combined to a total volume of about 4.5L and contained about 106.2g of crude algal oil.
1.5L of the filtrate was taken and treated in a rotary evaporator at 70 ℃ until no liquid appeared in the condenser. 35.4g of crude algal oil, having almost no fluidity, containing 14.74 wt% EPA and 33.63 wt% TFA was obtained.
Example 3 purification of algal oil
1.5L of the filtrate from example 2 was taken, 15mL of 3.6mol/L dilute sulfuric acid was added, and the mixture was stirred at room temperature for 2 hours with a magnetic stirrer set at 20 rpm. 10g of CaCO are added3To neutralize the sulfuric acid and stir for an additional 2 h. Filtration was carried out with filter paper (pore size 15-20 μm, Xinxing, qualitative filter paper) to obtain about 1.5L of filtrate. The filtrate was concentrated to 100mL by rotary evaporation (70 ℃, -0.1 MPA). To the resulting suspension was added 5g of shredded paper towels (Vida, each strip of paper towels was approximately 2cm long and 1cm wide). 300mL of water was added with stirring by a magnetic stirrer at 20rpm, and stirring was continued for 2 h. The resulting tissue was collected by filtration through a filter paper (the same as above) under reduced pressure (-0.1MPA), and the tissue was rinsed with 200mL of water to remove water-soluble components from the algal oil. The washed paper towel was placed in 200mL of 100% ethanol, and then filtered with filter paper (same as above) under reduced pressure (-0.1MPA) to obtain a filtrate. The filtered tissue was rinsed with 100mL of 100% ethanol and filtered again. The two filtrates were combined and rotary evaporated at 70 ℃ to give 15.3g of a purified crude oil, better in flowability, containing 31.50 wt% EPA and 64.52 wt% TFA.
The fluidity of the algal oil in this example was greatly improved and the purity of the polyunsaturated fatty acids was improved compared to the unpurified algal oil.
Example 4 transesterification and purification of algal oil
1.5L of the filtrate from example 2 was taken and ethanol was removed by rotary evaporation at 70 ℃ to give 35.4g of crude algal oil. To the crude algal oil were added 70mL of 100% ethanol and 5mL of 98% concentrated sulfuric acid. The magnetic stirrer is set to rotate at 20rpm and the transesterification reaction is carried out for 2h at 70 ℃.20 g of CaCO was added to the reaction3To neutralize the sulfuric acid and stir for an additional 2 h.
Ethanol was added to the reaction solution to a total volume of 500mL for convenient subsequent filtration. Filtration through filter paper (pore size 15-20 μm, Xinxing, qualitative filter paper) gave about 500mL of filtrate. The filtrate was concentrated to 100mL by rotary evaporation (70 ℃, -0.1 MPA). To the resulting suspension was added 5g of paper towels (Vida, each strip of paper towels was approximately 2cm long and 1cm wide). 300mL of water was added with stirring by a magnetic stirrer at 20rpm, and stirring was continued for 2 h. The paper towel was collected by filtration through filter paper (same as above) under reduced pressure (-0.1MPA), and the paper towel was washed with 200mL of water to remove water-soluble components. The washed paper towel was placed in 200mL of 100% ethanol, and filtered with filter paper (same as above) under reduced pressure (-0.1MPA) to obtain a filtrate. The filtered tissue was rinsed with 100mL of 100% ethanol and filtered again. The two filtrates were combined and rotary evaporated at 70 ℃ to give 12.5g of purified fatty acid ethyl ester, better in flowability, containing 38.65 wt% ethylated EPA and 83.45 wt% ethylated TFA.
The purity of the polyunsaturated fatty acids of the algae oil in this example was increased compared to unpurified algae oil.
Example 5 Dry algae preparation
Nannochloropsis oculata was cultured as described in example 1, and dried algae was prepared.
The quality of microalgae varies greatly due to the variation of growth conditions such as illumination. Specifically, the amounts of EPA and TFA contained in the dried algae obtained by the preparation are shown in table 1.
TABLE 1 amount of EPA and TFA contained in dried algae
Example 6 extraction of algal oil
250g of each of the dried algae 1 to 3 prepared in example 5 was taken, 5L of absolute ethanol was added, and the mixture was treated in a water bath at 80 ℃ for 2 hours with a magnetic stirrer set at 20 rpm. Thereafter, the mixture was filtered through a filter paper (pore size: 15 to 20 μm, Xinxing, qualitative filter paper) under reduced pressure (-0.1MPA) using a Buchner funnel connected to a suction pump to obtain filtrates of about 4.5L each containing 98.9g, 78g and 67.6g of crude algal oil containing EPA and TFA as shown in Table 2.
TABLE 2 amount of EPA and TFA contained in unpurified crude algal oil
| EPA wt％ | TFA wt％ | |
| Algae 1 | 13.67 | 35.68 |
| Algae 2 | 6.51 | 41.40 |
| Algae 3 | 12.01 | 60.20 |
Example 7 purification of algal oil
4.5L of the filtrate obtained in example 6, two parts of algae 1, and one part of each of algae 2 and algae 3 were taken. 60mL, 45mL and 45mL of 3.6mol/L dilute sulfuric acid were added to each filtrate, and the mixture was stirred at room temperature for 2 hours with a magnetic stirrer set at 20 rpm. 30g of CaCO were added separately3To neutralize the sulfuric acid and stir for an additional 2 h. Filtration was carried out with filter paper (pore size 15-20 μm, Xinxing, qualitative filter paper) to obtain filtrates of about 4.5L each. The filtrate was concentrated to 300mL by rotary evaporation (70 ℃, -0.1 MPA). To each suspension obtained, 50g, 20g and 15g of paper towels (Vida, each strip of paper towels is approximately 2cm long and 1cm wide) were added, respectively. 900mL, 600mL, 1500mL, and 300mL of water were added with stirring at 20rpm of a magnetic stirrer. The paper towel was collected by filtration through filter paper (same as above) under reduced pressure (-0.1 MPA). The paper towel was rinsed with 900mL of water to remove water soluble components. The washed paper towel was placed in 600mL of 100% ethanol, and then filtered with filter paper (same as above) under reduced pressure (-0.1MPA) to obtain a filtrate. The filtered tissue was rinsed with 600mL of 100% ethanol and filtered. The two filtrates were combined and rotary evaporated (70 ℃ C., -0.1MPA) to give 45.9g, 40.60g, 39.0g and 59.4g of purified crude oil with better flowability, which contained EPA and TFA as shown in Table 3.
TABLE 3 amount of EPA and TFA contained in purified algal oil
The fluidity of the algal oil in this example was greatly improved and the purity of the polyunsaturated fatty acids was improved compared to the unpurified algal oil.
Example 8 esterification and purification of algal oil
4.5L of the filtrate obtained in example 6, two parts of algae 1, one part of algae 2 and one part of algae 3 were taken, rotary evaporation was carried out at 70 ℃ and concentrated to 500mL, 14mL of 98% concentrated sulfuric acid was added, and a magnetic stirrer was set at 20rpm and subjected to transesterification reaction at 70 ℃ for 3 hours. 40g of CaCO was added to the reaction3To neutralize the sulfuric acid and stir for an additional 2 h.
Filtration through filter paper (pore size 15-20 μm, Xinxing, qualitative filter paper) gave about 500mL of filtrate. The filtrate was concentrated to 300mL by rotary evaporation (70 ℃, -0.1 MPA). To the resulting suspension were added 10g, 15g, 25g and 15g of paper towels (Vida, each strip of paper towels was approximately 2cm long and 1cm wide), respectively. 900mL, 1500mL, 1200mL, and 300mL of water were added with stirring at 20rpm of a magnetic stirrer. The paper towel was collected by filtration through filter paper (same as above) under reduced pressure (-0.1 MPA). The paper towel was rinsed with 900mL of water to remove water soluble components. The washed paper towel was placed in 600mL of 100% ethanol, and then filtered with filter paper (same as above) under reduced pressure (-0.1MPA) to obtain a filtrate. The filtered tissue was rinsed with 600mL of 100% ethanol and filtered. The two filtrates were combined and rotary evaporated at 70 ℃ to give 37.5g, 34.4g, 50.4g and 50.4g of purified fatty acid ethyl esters with good flowability, which contained EPA ethyl ester and TFA ethyl ester as shown in Table 4.
TABLE 4 amount of EPA and TFA Ethyl esters contained in purified ethylated algae oils
The purity of the polyunsaturated fatty acids of the algae oil in this example was increased compared to unpurified algae oil.
Example 9 extraction of algal oil
3000g of the dried alga 4 prepared in example 5 were taken, added with 24L of absolute ethanol, treated in a water bath at 80 ℃ for 2 hours, and a magnetic stirrer was set at a rotation speed of 20 rpm. Thereafter, filtration through filter paper (pore size 15-20 μm, New Star, qualitative filter paper) under reduced pressure (-0.1MPA) using a Buchner funnel connected to a suction pump gave about 20L of filtrate containing 930g of crude algal oil containing 10.67 wt% EPA and 60.37 wt% TFA.
Example 10 purification of algal oil
20L of the filtrate obtained in example 9 was taken, 200ml of 3.6mol/L dilute sulfuric acid was added to the filtrate, and the mixture was stirred at room temperature for 2 hours with a magnetic stirrer set at 20 rpm. 100g of CaCO are added3To neutralize the sulfuric acid and stir for an additional 2 h. Filtration was performed with filter paper (pore size 15-20 μm, Xinxing, qualitative filter paper) to obtain about 20L volume of filtrate. The filtrate was concentrated to 4mL by rotary evaporation (70 ℃, -0.1 MPA). To the resulting suspension was added 250g of paper towels (Vida, each strip of paper towels was approximately 2cm long and 1cm wide). 4L of water was added with stirring by a magnetic stirrer at 20 rpm. The paper towel was collected by filtration through filter paper (same as above) under reduced pressure (-0.1 MPA). The paper towel was rinsed with 4L of water to remove water-soluble components. The washed paper towel was placed in 4L of 100% ethanol, and then filtered with filter paper (same as above) under reduced pressure (-0.1MPA) to obtain a filtrate. The filtered tissue was rinsed with 4L of 100% ethanol and filtered. The two filtrates were combined and rotary evaporated (70 ℃ C., -0.1MPA) to give 900g of a purified crude oil, better in flowability, containing 12.83 wt% EPA and 67.11 wt% TFA.
The fluidity of the algal oil in this example was greatly improved and the purity of the polyunsaturated fatty acids was improved compared to the unpurified algal oil.
Determination of fatty acid composition in dried algae
0.100g of the dried algae of example 1 or 5 was weighed into a 50mL glass hydrolysis tube (with a lid), 21mL of chloroform-methanol mixture (2:1, v/v) was added, and the mixture was shaken for 12 hours at 200r/min in a shaker. The hydrolysis tube was removed from the shaker, placed in a water bath at 60 ℃ and blown dry with nitrogen, then 10mL of 5% methanolic sulfate solution (95mL methanol +5mL sulfuric acid) was added and placed in a water bath at 100 ℃ for 1 h. The hydrolysis tube was removed from the water bath, cooled, then 2mL n-hexane was added, mixed well, and an appropriate amount of deionized water was added to stratify the solution. The upper organic phase was passed through a 0.22 μm organic membrane (nylon, brand: agilent) and loaded into a sample bottle, which was placed on a GC sample tray, and was ready for testing.
The GC detection instrument is Agilent 7890B, an FID detector, a chromatographic column: agilent 19091J-413 HP-530 m 0.32mm 0.25 μm. Sample introduction volume: 1 μ L, injection port temperature: at 250 ℃ without splitting. Temperature programming: 60 deg.C (0min) -270 deg.C (31.25min) @8 deg.C/min, 5min, 270 deg.C (31.25min) -280 deg.C (38.25min) @2 deg.C/min, 2 min. The detector temperature is 280 ℃, the air flow is 400mL/min, the hydrogen gas flow is 30mL/min, and the tail gas blowing flow is 31.5 mL/min.
Determination of fatty acid composition in non-transesterified algal oil
After distilling off any ethanol present, 0.05g of the algal oil of example 2, 3, 6, 7, 9 or 10 was weighed out, and then 10mL of 5% methanol sulfate solution was added thereto in a water bath at 100 ℃ for 1 hour. Taking out the hydrolysis tube, cooling, adding 5mL of n-hexane, mixing, adding a proper amount of deionized water for layering, putting the upper organic phase into a sample bottle after passing through a 0.22 mu m organic film, putting the bottle on a GC sample tray, and waiting for detection.
The compositional measurements were performed using the same instruments and parameters described above.
Determination of fatty acid composition in transesterified algal oil
After distilling off the ethanol which may be present, 0.05g of the algal oil of example 4 or 8 was weighed out, and then dissolved in n-hexane to a volume of 10 mL. After passing through a 0.22 μm organic film, the mixture was put into a sample bottle and put on a GC sample plate to wait for detection.
The compositional measurements were performed using the same instruments and parameters described above.
The present invention has been described with reference to the above specific embodiments, but these embodiments do not limit the scope of the present invention. The scope of protection of the invention is defined by the appended claims.
Claims (10)
1. A method of purifying algal oil, the method of purifying comprising:
1) contacting the algae oil with an alcohol-water solution in the presence of a grease adsorbent, wherein the volume ratio of alcohol to water in the alcohol-water solution is 1:5 to 1:1, so that the algae oil is in oil-drop distribution after being contacted with the alcohol-water solution;
2) separating the oil adsorbent from the alcohol-water solution; and is
3) Separating the algae oil from the oil adsorbent.
2. The method according to claim 1, wherein the algal oil is crude algal oil extracted from natural dry algae treated with ethanol or esterified algal oil obtained by transesterification with lower alcohol after ethanol extraction.
3. The method of claim 1, wherein the alcohol-water solution has a volume ratio of alcohol to water of 1:1, 1:2, 1:3, 1:4, or 1: 5.
4. The method of claim 1, wherein the grease adsorbent is selected from paper towels or activated carbon.
5. The method of claim 1 or 4, wherein the oil adsorbent is a paper towel, and the weight ratio of the algae oil to the paper towel is 1:1-10: 1.
6. The method of claim 1, wherein step 2) is performed by collecting the grease adsorbent by filtration or centrifugation.
7. The method of claim 6, wherein after collecting the grease adsorbent, the grease adsorbent is washed with water to remove water-soluble impurities.
8. The process of claim 1, wherein prior to step 1), the algal oil is contacted with dilute acid at room temperature and the acid is neutralized by adding calcium carbonate, calcium hydroxide or sodium hydroxide and the precipitate is removed by filtration or centrifugation.
9. The process of claim 8, wherein the algal oil is contacted with the dilute acid in the presence of a lower alcohol.
10. The method of claim 1, wherein the alcohol-water solution is selected from a methanol-water solution, an ethanol-water solution, a propanol-water solution, or a combination thereof.
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| CN117343792A (en) * | 2023-10-30 | 2024-01-05 | 临沂友康生物科技有限公司 | Algae oil purification equipment and purification method thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102746947A (en) * | 2012-07-18 | 2012-10-24 | 福建华尔康生物科技有限公司 | Method for separating and purifying DHA (docosahexaenoic acid) and saturated fatty acid from schizochytrium limacinum oil |
| CN103937604A (en) * | 2014-04-08 | 2014-07-23 | 北京化工大学 | Method for extracting oil in microalgae |
| CN104059773A (en) * | 2014-07-02 | 2014-09-24 | 华南理工大学 | Method for wet extraction of purified microalgae oil |
| CN107760440A (en) * | 2017-12-07 | 2018-03-06 | 河西学院 | A kind of method of purification of microalgae grease |
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Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102746947A (en) * | 2012-07-18 | 2012-10-24 | 福建华尔康生物科技有限公司 | Method for separating and purifying DHA (docosahexaenoic acid) and saturated fatty acid from schizochytrium limacinum oil |
| CN103937604A (en) * | 2014-04-08 | 2014-07-23 | 北京化工大学 | Method for extracting oil in microalgae |
| CN104059773A (en) * | 2014-07-02 | 2014-09-24 | 华南理工大学 | Method for wet extraction of purified microalgae oil |
| CN107760440A (en) * | 2017-12-07 | 2018-03-06 | 河西学院 | A kind of method of purification of microalgae grease |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN117343792A (en) * | 2023-10-30 | 2024-01-05 | 临沂友康生物科技有限公司 | Algae oil purification equipment and purification method thereof |
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| CN112210437B (en) | 2023-10-13 |
| CN110760376B (en) | 2020-11-13 |
| CN110760376A (en) | 2020-02-07 |
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