CN115650943A - Method for enriching polyunsaturated fatty acid ester, squalene, natural vitamin E and phytosterol from plant deodorized distillate - Google Patents
Method for enriching polyunsaturated fatty acid ester, squalene, natural vitamin E and phytosterol from plant deodorized distillate Download PDFInfo
- Publication number
- CN115650943A CN115650943A CN202211106716.0A CN202211106716A CN115650943A CN 115650943 A CN115650943 A CN 115650943A CN 202211106716 A CN202211106716 A CN 202211106716A CN 115650943 A CN115650943 A CN 115650943A
- Authority
- CN
- China
- Prior art keywords
- fatty acid
- polyunsaturated fatty
- plant
- squalene
- natural vitamin
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 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 title claims abstract description 123
- 235000020777 polyunsaturated fatty acids Nutrition 0.000 title claims abstract description 92
- 150000002148 esters Chemical class 0.000 title claims abstract description 73
- 229930003427 Vitamin E Natural products 0.000 title claims abstract description 61
- 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 title claims abstract description 61
- 235000019165 vitamin E Nutrition 0.000 title claims abstract description 61
- 239000011709 vitamin E Substances 0.000 title claims abstract description 61
- 229940046009 vitamin E Drugs 0.000 title claims abstract description 61
- 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 59
- 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 59
- 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 59
- 229940031439 squalene Drugs 0.000 title claims abstract description 59
- 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 59
- 238000000034 method Methods 0.000 title claims abstract description 52
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 52
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims abstract description 46
- 239000004202 carbamide Substances 0.000 claims abstract description 46
- 238000005886 esterification reaction Methods 0.000 claims abstract description 39
- 102000004190 Enzymes Human genes 0.000 claims abstract description 28
- 108090000790 Enzymes Proteins 0.000 claims abstract description 28
- 239000003995 emulsifying agent Substances 0.000 claims abstract description 28
- 239000000047 product Substances 0.000 claims abstract description 26
- 239000012141 concentrate Substances 0.000 claims abstract description 24
- 239000000706 filtrate Substances 0.000 claims abstract description 20
- 238000004945 emulsification Methods 0.000 claims abstract description 17
- 238000002425 crystallisation Methods 0.000 claims abstract description 15
- 230000008025 crystallization Effects 0.000 claims abstract description 15
- 230000032050 esterification Effects 0.000 claims abstract description 15
- 239000012065 filter cake Substances 0.000 claims abstract description 11
- 230000008014 freezing Effects 0.000 claims abstract description 10
- 238000007710 freezing Methods 0.000 claims abstract description 10
- 238000010668 complexation reaction Methods 0.000 claims abstract description 7
- 235000015112 vegetable and seed oil Nutrition 0.000 claims description 29
- 239000008158 vegetable oil Substances 0.000 claims description 29
- 235000014113 dietary fatty acids Nutrition 0.000 claims description 23
- 229930195729 fatty acid Natural products 0.000 claims description 23
- 239000000194 fatty acid Substances 0.000 claims description 23
- 238000010438 heat treatment Methods 0.000 claims description 21
- 239000000126 substance Substances 0.000 claims description 19
- 238000000199 molecular distillation Methods 0.000 claims description 18
- 230000008569 process Effects 0.000 claims description 18
- 238000001704 evaporation Methods 0.000 claims description 16
- 230000008020 evaporation Effects 0.000 claims description 16
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 15
- -1 fatty acid ester Chemical class 0.000 claims description 15
- 239000007957 coemulsifier Substances 0.000 claims description 13
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 13
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 12
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 12
- 150000004665 fatty acids Chemical class 0.000 claims description 10
- 229940068065 phytosterols Drugs 0.000 claims description 10
- 238000011085 pressure filtration Methods 0.000 claims description 10
- 238000003756 stirring Methods 0.000 claims description 10
- 239000004215 Carbon black (E152) Substances 0.000 claims description 9
- 238000001816 cooling Methods 0.000 claims description 9
- 229930195733 hydrocarbon Natural products 0.000 claims description 9
- 150000002430 hydrocarbons Chemical class 0.000 claims description 9
- 239000000243 solution Substances 0.000 claims description 9
- IDGUHHHQCWSQLU-UHFFFAOYSA-N ethanol;hydrate Chemical compound O.CCO IDGUHHHQCWSQLU-UHFFFAOYSA-N 0.000 claims description 8
- 238000006243 chemical reaction Methods 0.000 claims description 7
- 239000000463 material Substances 0.000 claims description 6
- 150000001299 aldehydes Chemical class 0.000 claims description 4
- 239000007864 aqueous solution Substances 0.000 claims description 4
- 230000008878 coupling Effects 0.000 claims description 4
- 238000010168 coupling process Methods 0.000 claims description 4
- 238000005859 coupling reaction Methods 0.000 claims description 4
- 239000013078 crystal Substances 0.000 claims description 4
- 238000007872 degassing Methods 0.000 claims description 4
- 150000002576 ketones Chemical class 0.000 claims description 4
- 229920000136 polysorbate Polymers 0.000 claims description 4
- 235000013311 vegetables Nutrition 0.000 claims description 4
- 238000004821 distillation Methods 0.000 claims description 3
- 239000012452 mother liquor Substances 0.000 claims description 3
- 238000011084 recovery Methods 0.000 claims description 3
- 238000003828 vacuum filtration Methods 0.000 claims description 3
- 238000005406 washing Methods 0.000 claims description 3
- 150000001298 alcohols Chemical class 0.000 claims description 2
- 230000009467 reduction Effects 0.000 claims description 2
- 238000003825 pressing Methods 0.000 abstract description 5
- 235000019387 fatty acid methyl ester Nutrition 0.000 abstract description 4
- 230000007547 defect Effects 0.000 abstract description 3
- 230000003301 hydrolyzing effect Effects 0.000 abstract 1
- 241000196324 Embryophyta Species 0.000 description 47
- 238000004519 manufacturing process Methods 0.000 description 9
- 239000003921 oil Substances 0.000 description 7
- 235000019198 oils Nutrition 0.000 description 7
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 6
- 229930182558 Sterol Natural products 0.000 description 6
- 150000004702 methyl esters Chemical class 0.000 description 6
- 235000003702 sterols Nutrition 0.000 description 6
- 238000004332 deodorization Methods 0.000 description 5
- 230000002255 enzymatic effect Effects 0.000 description 5
- 235000015097 nutrients Nutrition 0.000 description 5
- 239000002994 raw material Substances 0.000 description 5
- 238000000926 separation method Methods 0.000 description 5
- 150000003432 sterols Chemical class 0.000 description 5
- 239000004367 Lipase Substances 0.000 description 3
- 102000004882 Lipase Human genes 0.000 description 3
- 108090001060 Lipase Proteins 0.000 description 3
- 125000005907 alkyl ester group Chemical group 0.000 description 3
- 238000006555 catalytic reaction Methods 0.000 description 3
- 125000005456 glyceride group Chemical group 0.000 description 3
- 235000019421 lipase Nutrition 0.000 description 3
- 239000010773 plant oil Substances 0.000 description 3
- 239000013543 active substance Substances 0.000 description 2
- 230000003197 catalytic effect Effects 0.000 description 2
- 230000000536 complexating effect Effects 0.000 description 2
- 238000005265 energy consumption Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 125000004494 ethyl ester group Chemical group 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- IPCSVZSSVZVIGE-UHFFFAOYSA-N hexadecanoic acid Chemical compound CCCCCCCCCCCCCCCC(O)=O IPCSVZSSVZVIGE-UHFFFAOYSA-N 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 239000001149 (9Z,12Z)-octadeca-9,12-dienoate Substances 0.000 description 1
- WTTJVINHCBCLGX-UHFFFAOYSA-N (9trans,12cis)-methyl linoleate Natural products CCCCCC=CCC=CCCCCCCCC(=O)OC WTTJVINHCBCLGX-UHFFFAOYSA-N 0.000 description 1
- WRIDQFICGBMAFQ-UHFFFAOYSA-N (E)-8-Octadecenoic acid Natural products CCCCCCCCCC=CCCCCCCC(O)=O WRIDQFICGBMAFQ-UHFFFAOYSA-N 0.000 description 1
- GJJVAFUKOBZPCB-UHFFFAOYSA-N 2-methyl-2-(4,8,12-trimethyltrideca-3,7,11-trienyl)-3,4-dihydrochromen-6-ol Chemical compound OC1=CC=C2OC(CCC=C(C)CCC=C(C)CCC=C(C)C)(C)CCC2=C1 GJJVAFUKOBZPCB-UHFFFAOYSA-N 0.000 description 1
- LQJBNNIYVWPHFW-UHFFFAOYSA-N 20:1omega9c fatty acid Natural products CCCCCCCCCCC=CCCCCCCCC(O)=O LQJBNNIYVWPHFW-UHFFFAOYSA-N 0.000 description 1
- LNJCGNRKWOHFFV-UHFFFAOYSA-N 3-(2-hydroxyethylsulfanyl)propanenitrile Chemical compound OCCSCCC#N LNJCGNRKWOHFFV-UHFFFAOYSA-N 0.000 description 1
- QSBYPNXLFMSGKH-UHFFFAOYSA-N 9-Heptadecensaeure Natural products CCCCCCCC=CCCCCCCCC(O)=O QSBYPNXLFMSGKH-UHFFFAOYSA-N 0.000 description 1
- OYHQOLUKZRVURQ-HZJYTTRNSA-N Linoleic acid Chemical compound CCCCC\C=C/C\C=C/CCCCCCCC(O)=O OYHQOLUKZRVURQ-HZJYTTRNSA-N 0.000 description 1
- PKIXXJPMNDDDOS-UHFFFAOYSA-N Methyl linoleate Natural products CCCCC=CCCC=CCCCCCCCC(=O)OC PKIXXJPMNDDDOS-UHFFFAOYSA-N 0.000 description 1
- ZQPPMHVWECSIRJ-UHFFFAOYSA-N Oleic acid Natural products CCCCCCCCC=CCCCCCCCC(O)=O ZQPPMHVWECSIRJ-UHFFFAOYSA-N 0.000 description 1
- 239000005642 Oleic acid Substances 0.000 description 1
- 235000021314 Palmitic acid Nutrition 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 239000010426 asphalt Substances 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000003225 biodiesel Substances 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 238000003889 chemical engineering Methods 0.000 description 1
- 235000005687 corn oil Nutrition 0.000 description 1
- 239000002285 corn oil Substances 0.000 description 1
- 235000012343 cottonseed oil Nutrition 0.000 description 1
- 239000002385 cottonseed oil Substances 0.000 description 1
- 230000001877 deodorizing effect Effects 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000001804 emulsifying effect Effects 0.000 description 1
- FMMOOAYVCKXGMF-MURFETPASA-N ethyl linoleate Chemical compound CCCCC\C=C/C\C=C/CCCCCCCC(=O)OCC FMMOOAYVCKXGMF-MURFETPASA-N 0.000 description 1
- 229940031016 ethyl linoleate Drugs 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- 239000012847 fine chemical Substances 0.000 description 1
- 235000013305 food Nutrition 0.000 description 1
- 235000021588 free fatty acids Nutrition 0.000 description 1
- 238000010353 genetic engineering Methods 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 230000010354 integration Effects 0.000 description 1
- QXJSBBXBKPUZAA-UHFFFAOYSA-N isooleic acid Natural products CCCCCCCC=CCCCCCCCCC(O)=O QXJSBBXBKPUZAA-UHFFFAOYSA-N 0.000 description 1
- 235000020778 linoleic acid Nutrition 0.000 description 1
- OYHQOLUKZRVURQ-IXWMQOLASA-N linoleic acid Natural products CCCCC\C=C/C\C=C\CCCCCCCC(O)=O OYHQOLUKZRVURQ-IXWMQOLASA-N 0.000 description 1
- FMMOOAYVCKXGMF-UHFFFAOYSA-N linoleic acid ethyl ester Natural products CCCCCC=CCC=CCCCCCCCC(=O)OCC FMMOOAYVCKXGMF-UHFFFAOYSA-N 0.000 description 1
- 239000000944 linseed oil Substances 0.000 description 1
- 235000021388 linseed oil Nutrition 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- WQEPLUUGTLDZJY-UHFFFAOYSA-N n-Pentadecanoic acid Natural products CCCCCCCCCCCCCCC(O)=O WQEPLUUGTLDZJY-UHFFFAOYSA-N 0.000 description 1
- ZQPPMHVWECSIRJ-KTKRTIGZSA-N oleic acid Chemical compound CCCCCCCC\C=C/CCCCCCCC(O)=O ZQPPMHVWECSIRJ-KTKRTIGZSA-N 0.000 description 1
- 235000021313 oleic acid Nutrition 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 230000036632 reaction speed Effects 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 238000007670 refining Methods 0.000 description 1
- 239000003813 safflower oil Substances 0.000 description 1
- 238000010517 secondary reaction Methods 0.000 description 1
- 238000010008 shearing Methods 0.000 description 1
- 239000003549 soybean oil Substances 0.000 description 1
- 235000012424 soybean oil Nutrition 0.000 description 1
- 235000020238 sunflower seed Nutrition 0.000 description 1
- 229930003799 tocopherol Natural products 0.000 description 1
- 239000011732 tocopherol Substances 0.000 description 1
- 229960001295 tocopherol Drugs 0.000 description 1
- 235000010384 tocopherol Nutrition 0.000 description 1
- 229930003802 tocotrienol Natural products 0.000 description 1
- 239000011731 tocotrienol Substances 0.000 description 1
- 235000019148 tocotrienols Nutrition 0.000 description 1
- 238000005809 transesterification reaction Methods 0.000 description 1
- UFTFJSFQGQCHQW-UHFFFAOYSA-N triformin Chemical compound O=COCC(OC=O)COC=O UFTFJSFQGQCHQW-UHFFFAOYSA-N 0.000 description 1
- GVJHHUAWPYXKBD-IEOSBIPESA-N α-tocopherol Chemical compound OC1=C(C)C(C)=C2O[C@@](CCC[C@H](C)CCC[C@H](C)CCCC(C)C)(C)CCC2=C1C GVJHHUAWPYXKBD-IEOSBIPESA-N 0.000 description 1
Images
Landscapes
- Fats And Perfumes (AREA)
Abstract
The invention provides a method for enriching polyunsaturated fatty acid esters, squalene, natural vitamin E and phytosterol from plant deodorizer distillate, which comprises the following steps: taking a proper amount of plant deodorized distillate, adding short-chain alcohol and an emulsifier or an auxiliary emulsifier for emulsification, and adding low-temperature enzyme into an obtained emulsified product for esterification; performing gradient freezing crystallization and filter pressing on the product after the esterification reaction to obtain filter cakes and filtrate after filter pressing, wherein the filter cakes comprise phytosterol; performing multi-stage rectification on the filtrate to obtain squalene and natural vitamin E after rectification and also obtain a concentrate of polyunsaturated fatty acid ester; and (3) carrying out urea complexation on the concentrate of the polyunsaturated fatty acid ester, urea and ethanol according to a proportion to obtain the high-content polyunsaturated fatty acid ester, and hydrolyzing the polyunsaturated fatty acid ester to obtain the polyunsaturated fatty acid. The application optimizes the technical defect that the traditional scheme can only extract common fatty acid methyl ester but can not extract polyunsaturated fatty acid ester.
Description
Technical Field
The invention relates to the technical field of fine chemical engineering, and particularly relates to a method for enriching polyunsaturated fatty acid esters, squalene, natural vitamin E and phytosterol from plant deodorized distillate.
Background
With the rapid development of life science, oil science and engineering technology, vitamin E, sterol, fatty acid methyl ester and squalene are highly regarded and paid attention to in the fields of medicine, food, chemical industry, feed, plant genetic engineering and the like.
A byproduct, namely deodorizer distillate (DD oil for short), generated in the deodorization procedure of the crude vegetable oil in the refining process is distillate collected in the process of distilling the vegetable oil by steam in the deodorization process, and the yield of the distillate is about 0.3 to 0.6 percent of the deodorized oil. DD oils usually have different compositions depending on the kind, source and deodorizing process of the vegetable oil. Generally, DD oil contains free fatty acids (mainly comprising palmitic acid, oleic acid and linoleic acid) 20-80%, triglyceride 10-30%, sterol and sterol ester 5-20%, natural vitamin E (including tocopherol and tocotrienol) 0.1-20%, and plant hydrocarbon (mainly comprising squalene and its derivatives) 5-30%. DD oil is the main raw material for the industrial production of natural vitamin E, phytosterol, fatty acid and alkyl ester thereof at present.
In the prior art, natural vitamin E, phytosterol and biodiesel can only be extracted from deodorized distillate of vegetable oil, and polyunsaturated fatty acid, squalene, natural vitamin E and phytosterol cannot be simultaneously extracted from deodorized distillate of vegetable oil, so that the raw material utilization rate is low, the extraction efficiency is low and the comprehensive cost is high.
Chinese patent CN200810049033.X discloses a novel method for extracting natural vitamin E, phytosterol and fatty acid methyl ester by enzyme catalysis and molecular distillation, wherein 2 kinds of lipase are needed during the enzymatic esterification, the cost of the lipase is high, the steps are complicated, the subsequent 2 times of molecular distillation is carried out, the separation efficiency is low, polyunsaturated fatty acid and squalene cannot be simultaneously enriched, and the deodorized distillate of vegetable oil cannot be fully utilized.
Chinese patent CN107012177A discloses a method for low-temperature catalytic esterification of deodorized distillate, which has low enzymatic catalytic efficiency, the reaction time is up to 18-36 hours, secondary enzyme addition is needed for secondary reaction, and the production cost is high.
Chinese patent CN107474093A discloses a method for continuously producing VE, sterol, methyl ester, glycerol, squalene and high-boiling-point substances from deodorized distillate, wherein VE, sterol, methyl ester, glycerol, squalene and high-boiling-point substances are continuously produced by enzymatic esterification, cold precipitation and molecular distillation processes, the molecular distillation process only can be used for primarily separating fatty acid methyl ester, VE, squalene and high-boiling-point substances, and the content of squalene is only 10-20%.
Disclosure of Invention
Based on the above, the invention aims to provide a method for enriching polyunsaturated fatty acid esters, squalene, natural vitamin E and phytosterol from plant deodorized distillate, which is used for solving the problems of high energy consumption, high pollution, low efficiency and the like in the prior art, and provides a method for simultaneously extracting polyunsaturated fatty acid esters, squalene, natural vitamin E and phytosterol from plant oil deodorized distillate. The method has the advantages of high utilization rate of raw materials, simple operation, mild reaction conditions, low energy consumption, little pollution, high separation degree of active substances, good color and purity of products and remarkable improvement on production efficiency.
The application provides a method for enriching polyunsaturated fatty acid esters, squalene, natural vitamin E and phytosterol from plant deodorizer distillate, which is characterized by comprising the following steps:
taking a proper amount of plant deodorized distillate, adding short-chain alcohol and an emulsifier or a co-emulsifier into the plant deodorized distillate for emulsification, and adding low-temperature enzyme into an obtained emulsified product for esterification;
performing gradient freezing crystallization and filter pressing on a product after the esterification reaction to obtain a filter cake and a filtrate after the filter pressing, wherein the filter cake comprises phytosterol;
carrying out multi-stage rectification on the filtrate to obtain squalene, natural vitamin E and a concentrate of polyunsaturated fatty acid ester;
and (3) carrying out urea complexation on the concentrate of the polyunsaturated fatty acid ester, urea and ethanol according to a proportion to obtain the polyunsaturated fatty acid ester with high content.
According to the method for enriching the polyunsaturated fatty acid ester, the squalene, the natural vitamin E and the phytosterol from the plant deodorized distillate, the polyunsaturated fatty acid, the squalene, the natural vitamin E, the phytosterol and other nutrients are simultaneously extracted from the plant oil deodorized distillate, so that the additional value of the deodorized distillate can be obviously improved, and the production cost of each nutrient is reduced; further, this application adds emulsifier or co-emulsifier and emulsifies to the plant deodorization distillate, to adding low temperature enzyme in the emulsification product that obtains in order to carry out esterification reaction, relative traditional technique, the time of esterification reaction has been reduced, secondly, adopt low temperature enzyme to go on, moreover, this application adopts multistage rectification to the filtrate, molecular distillation in the traditional technique has been replaced, thereby make this application can extract polyunsaturated fatty acid, the technical defect that traditional scheme can only extract methyl ester and can not extract polyunsaturated fatty acid has been optimized, in addition, the plant squalene that obtains, natural vitamin E content is higher, in having solved prior art, can't extract polyunsaturated fatty acid, squalene, natural vitamin E and phytosterol from the plant oil deodorization distillate simultaneously, lead to improving manufacturing cost's technical problem.
In addition, the method for enriching polyunsaturated fatty acid esters, squalene, natural vitamin E and phytosterol from the plant deodorized distillate can also have the following additional technical characteristics:
further, in the step of adding a short-chain alcohol and an emulsifier to the plant deodorizer distillate:
the mass ratio of the short-chain alcohol to the deodorized distillate of the vegetable oil is 12-18%;
the mass ratio of the emulsifier or co-emulsifier to the deodorized distillate of the vegetable oil is 0.1-2%;
the mass ratio of the water to the deodorized distillate of the vegetable oil is 1-4%.
Furthermore, the auxiliary emulsifier generates fatty acid salt through fatty acid reaction, thereby playing a role in emulsification;
further, in the step of adding a short-chain alcohol and an emulsifier or a co-emulsifier to the plant deodorized distillate to perform emulsification, and adding a low-temperature enzyme to the obtained emulsified product to perform an esterification reaction:
the temperature of the emulsification reaction is 25-35 ℃, and low-temperature enzyme is added into the obtained emulsified product at the temperature of 25-35 ℃ to carry out esterification reaction;
the short-chain alcohol comprises one of methanol or ethanol;
the auxiliary emulsifier comprises one of sodium hydroxide or potassium hydroxide;
the emulsifier comprises one of tween and span.
Further, in the step of adding a low-temperature enzyme to the obtained emulsified product to perform an esterification reaction:
the mass ratio of the enzyme to the deodorized distillate of the vegetable oil is 0.2-0.5%, and the esterification reaction is carried out for 4-6 hours.
Further, in the step of performing gradient freezing crystallization and pressure filtration on the product after the esterification reaction:
the temperature reduction speed in the gradient freezing crystallization process is 2-5 ℃/h.
Further, in the step of performing multistage rectification on the filtrate, the multistage rectification method comprises the following steps:
performing 1-stage flash evaporation, namely adding the filtrate into a 1-stage flash evaporation tower, and performing flash evaporation to remove small molecular weight substances under the conditions that the feeding temperature is 100-130 ℃ and the vacuum degree of a system at the top of the tower is 200-2000Pa, wherein the small molecular weight substances comprise water, plant hydrocarbon, fatty acid, aldehyde and ketone;
2, distilling, namely continuously adding the material subjected to flash evaporation and degassing of the 1 st stage into a 2 nd stage rectifying tower, wherein the tower bottom temperature of the rectifying tower is 170-190 ℃, the tower top temperature is 140-160 ℃, the vacuum condition is 50-300Pa, and substances removed from light components in the 2 nd stage rectifying tower comprise C 12 -C 16 Predominantly fatty acid ester, residual C 18 Polyunsaturated fatty acid ester, plant squalene, phytosterol and natural vitamin E;
rectifying in the 3 rd stage, continuously adding the heavy components in the 2 nd stage rectifying tower into the 3 rd stage rectifying tower, heating the tower kettle at 190-210 deg.C, maintaining the tower top at 160-180 deg.C, and vacuum at 50-300Pa to obtain light components in the 3 rd stage rectifying tower 18 Mainly polyunsaturated fatty acid ester, residual plant squalene, phytosterol and natural vitamin E;
rectifying in the 4 th stage, continuously adding the heavy components in the 3 rd stage rectifying tower into the 4 th stage rectifying tower, heating the tower kettle at 220-250 deg.C, maintaining the tower top at 180-210 deg.C, and vacuum at 50-300Pa, wherein the substances removed from the light components in the 4 th stage rectifying tower include plant squalene, part of plant hydrocarbon, C 18 The above fatAcid ester, residual natural vitamin E, phytosterol and partial plant asphalt;
coupling molecular distillation, continuously adding the heavy component after the 4 th-stage rectification into a molecular distillation system, wherein the feeding flow rate is that the heating temperature is kept at 220-240 ℃, the vacuum condition is 1-10Pa, and the light component after the molecular distillation comprises natural vitamin E, phytosterol and residual vegetable pitch.
Further, the step of urea complexing the concentrate of polyunsaturated fatty acid esters with urea and ethanol in a ratio comprising:
dissolving a proper amount of urea in an ethanol water solution, adding the concentrate of the polyunsaturated fatty acid ester, and heating and stirring until the urea is completely dissolved;
and after the urea is completely dissolved, cooling, standing for crystallization, carrying out vacuum filtration, and carrying out reduced pressure recovery, washing and distillation on the filtered mother liquor to obtain the high-content polyunsaturated fatty acid ester.
Further, the mass ratio of the concentrate of polyunsaturated fatty acid esters to the urea is 1:1-3;
the mass ratio of the urea to the ethanol aqueous solution is 1:2-5;
in the ethanol water solution, the volume percentage of water is 1-10%.
Further, after the urea is completely dissolved, cooling to 5-10 ℃, standing in an environment of 4 ℃, and growing the crystals for 6-24 hours.
Further, the step of adding the concentrate of polyunsaturated fatty acid esters and stirring with heating until the urea is completely dissolved comprises:
heating and stirring at 70-80 ℃ until the urea is completely dissolved.
Drawings
FIG. 1 is a flow chart of a process for the enrichment of polyunsaturated fatty acid esters, squalene, natural vitamin E and phytosterols from a plant deodorizer distillate in an example of the present invention.
The following detailed description will further illustrate the invention in conjunction with the above-described figures.
Detailed Description
To facilitate an understanding of the invention, the invention will now be described more fully hereinafter with reference to the accompanying drawings. Several embodiments of the invention are shown in the drawings. This invention may, however, be embodied in many different forms and should not be construed as limited to the embodiments set forth herein. Rather, these embodiments are provided so that this disclosure will be thorough and complete.
Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. The terminology used in the description of the invention herein is for the purpose of describing particular embodiments only and is not intended to be limiting of the invention. As used herein, the term "and/or" includes any and all combinations of one or more of the associated listed items.
In order to solve the technical problems of high production cost and low efficiency caused by the fact that polyunsaturated fatty acid, squalene, natural vitamin E and phytosterol cannot be simultaneously extracted from a deodorized distillate of vegetable oil in the prior art, the application provides a method for simultaneously enriching polyunsaturated fatty acid ester, squalene, natural vitamin E and phytosterol from a deodorized distillate of vegetable oil, so that the application has the following beneficial effects:
1) Through the emulsification pretreatment of raw materials and the enzymatic catalysis esterification and transesterification, one enzyme not only catalyzes fatty acid to be converted into fatty acid ester, but also converts glyceride to fatty acid ester, and has the advantages of high reaction speed, short time, high efficiency and low cost.
2) By utilizing multi-stage continuous rectification, various plant nutrients such as polyunsaturated fatty acid ester, plant squalene, natural vitamin E, phytosterol and the like can be generated at the same time, wherein the content of the polyunsaturated fatty acid ester is between 50 and 70 percent, the content of the plant squalene can be between 30 and 60 percent, the content of the phytosterol is between 40 and 70 percent, and the content of the natural vitamin E can be between 50 and 70 percent.
3) After urea complexation, the content of polyunsaturated fatty acid ester can further reach more than 80-95%, and free polyunsaturated fatty acid can be generated after enzyme method and acid-base hydrolysis.
4) Through process integration, one production line can simultaneously extract and prepare high-quality polyunsaturated fatty acid, plant squalene, phytosterol and natural vitamin E, the production cost is greatly reduced, and the production efficiency is improved.
Specifically, the vegetable oil deodorizer distillate in the application is derived from one or more of soybean oil, cottonseed oil, corn oil, sunflower seed oil, linseed oil and safflower seed oil. The method for enriching polyunsaturated fatty acid esters, squalene, natural vitamin E and phytosterol from plant deodorizer distillate comprises the following steps:
taking a proper amount of plant deodorized distillate, adding short-chain alcohol and an emulsifier or a co-emulsifier into the plant deodorized distillate for emulsification, and adding low-temperature enzyme into an obtained emulsified product for esterification;
performing gradient freezing crystallization and pressure filtration on a product after the esterification reaction to obtain a filter cake and a filtrate after pressure filtration, wherein the filter cake comprises phytosterol;
carrying out multi-stage rectification on the filtrate to obtain squalene and natural vitamin E after rectification and also obtain a concentrate of polyunsaturated fatty acid ester;
and (3) carrying out urea complexation on the concentrate of the polyunsaturated fatty acid ester, urea and ethanol according to a proportion to obtain the polyunsaturated fatty acid ester with high content.
It is further noted that the concentrate of polyunsaturated fatty acid esters includes polyunsaturated fatty acid alkyl esters, the polyunsaturated fatty acid alkyl esters include polyunsaturated fatty acid methyl esters and polyunsaturated fatty acid ethyl esters, the polyunsaturated fatty acid methyl esters include methyl linoleate, and the polyunsaturated fatty acid ethyl esters include ethyl linoleate. The polyunsaturated fatty acid ester is hydrolyzed to obtain the polyunsaturated fatty acid.
Specifically, the low-temperature enzyme esterification is carried out by emulsifying by a high-speed shearing emulsifier at 25-35 ℃ in a certain proportion through short-chain alcohol such as methanol and ethanol, deodorized distillate of vegetable oil, water and emulsifier, adding a certain amount of lipase at the temperature for esterification, and converting fatty acid and glyceride in the deodorized distillate of vegetable oil into fatty acid alkyl ester.
In some alternative embodiments, in the step of adding a short-chain alcohol and an emulsifier or co-emulsifier to the plant deodorizer distillate:
the mass ratio of the short-chain alcohol to the deodorized distillate of the vegetable oil is 12-18%;
the mass ratio of the emulsifier or co-emulsifier to the deodorized distillate of the vegetable oil is 0.1-2%;
the mass ratio of the water to the deodorized distillate of the vegetable oil is 1-4%.
In some optional embodiments, in the step of adding a short-chain alcohol and an emulsifier to the plant deodorizer distillate for emulsification, and adding a low-temperature enzyme to the obtained emulsified product for esterification:
the temperature of the emulsification reaction is 25-35 ℃, and low-temperature enzyme is added into the obtained emulsified product at the temperature of 25-35 ℃ to carry out esterification reaction;
the short-chain alcohol comprises one of methanol or ethanol;
the auxiliary emulsifier comprises one of sodium hydroxide or potassium hydroxide;
the emulsifier comprises one of tween and span.
In some alternative embodiments, in the step of adding a low temperature enzyme to the resulting emulsified product to perform the esterification reaction:
the mass ratio of the enzyme to the deodorized distillate of the vegetable oil is 0.2-0.5%, and the esterification reaction is carried out for 4-6 hours.
In some alternative embodiments, in the step of subjecting the product after the esterification reaction to gradient freeze crystallization and pressure filtration:
the cooling speed in the gradient freezing crystallization process is 2-5 ℃/h.
In some optional embodiments, in the step of subjecting the filtrate to multi-stage rectification, the multi-stage rectification method comprises:
performing 1-stage flash evaporation, namely adding the filtrate into a 1-stage flash evaporation tower, and performing flash evaporation to remove small molecular weight substances under the conditions that the feeding temperature is 100-130 ℃ and the vacuum degree of a system at the top of the tower is 200-2000Pa, wherein the small molecular weight substances comprise water, plant hydrocarbon, fatty acid, aldehyde and ketone;
the 2 nd stage rectification, the material after the 1 st stage flash evaporation and degassing is continuously added into a 2 nd stage rectification tower, the temperature of the tower bottom of the rectification tower is 170-190 ℃, the temperature of the tower top is 140-160 ℃, the vacuum condition is 50-300Pa, and the substances removed from the light components in the 2 nd stage rectification tower comprise C 12 -C 16 Predominantly fatty acid ester, residual C 18 Polyunsaturated fatty acid ester, plant squalene, phytosterol and natural vitamin E;
rectifying in the 3 rd stage, continuously adding the heavy components in the 2 nd stage rectifying tower into the 3 rd stage rectifying tower, heating the tower kettle at 190-210 deg.c, maintaining the tower top at 160-180 deg.c and vacuum condition at 50-300Pa, and obtaining light components in the 3 rd stage rectifying tower to obtain C 18 Mainly polyunsaturated fatty acid ester, residual plant squalene, phytosterol and natural vitamin E;
rectifying in the 4 th stage, continuously adding the heavy components in the 3 rd stage rectifying tower into the 4 th stage rectifying tower, heating the tower kettle at 220-250 deg.C, maintaining the tower top at 180-210 deg.C, and vacuum at 50-300Pa, wherein the substances removed from the light components in the 4 th stage rectifying tower include plant squalene, part of plant hydrocarbon, C 18 The above fatty acid ester, residual natural vitamin E, phytosterol and part of plant pitch;
coupling molecular distillation, continuously adding the heavy component after the 4 th-stage rectification into a molecular distillation system, wherein the feeding flow rate is that the heating temperature is kept at 220-240 ℃, the vacuum condition is 1-10Pa, and the light component after the molecular distillation comprises natural vitamin E, phytosterol and residual vegetable pitch.
In some alternative embodiments, the step of urea complexing the concentrate of polyunsaturated fatty acid esters with urea and ethanol in a ratio comprises:
dissolving a proper amount of urea in an ethanol water solution, adding the concentrate of the polyunsaturated fatty acid ester, heating and stirring until the urea is completely dissolved;
and after the urea is completely dissolved, cooling, standing for crystallization, carrying out vacuum filtration, and carrying out reduced pressure recovery, washing and distillation on the filtered mother liquor to obtain the high-content polyunsaturated fatty acid ester.
In some alternative embodiments, the mass ratio of the concentrate of polyunsaturated fatty acid esters to the urea is 1:1-3;
the mass ratio of the urea to the ethanol aqueous solution is 1:2-5;
in the ethanol water solution, the volume percentage of water is 1-10%.
In some optional embodiments, after the urea is completely dissolved, the temperature is reduced to 5-10 ℃, the mixture is placed in an environment with the temperature of 4 ℃ for standing and crystal growth is carried out for 6-24 hours.
In some alternative embodiments, the step of adding the concentrate of polyunsaturated fatty acid esters followed by stirring with heat until the urea is completely dissolved comprises:
heating and stirring at 70-80 ℃ until the urea is completely dissolved.
The invention adopts enzymatic catalysis esterification to convert fatty acid and glyceride into fatty acid ester, thereby facilitating the subsequent cold separation of phytosterol and the separation of natural vitamin E and squalene. And then, multi-stage continuous rectification is adopted to gradually separate the polyunsaturated fatty acid ester, the plant squalene, the natural vitamin E, the phytosterol and other active substances, the steps are simple and convenient, the separation efficiency is high, the cost is low, and the utilization rate of the raw materials is obviously improved.
In order to facilitate understanding of the invention, several examples of the invention are given below, with reference to fig. 1 for the process flow. This invention may, however, be embodied in many different forms and should not be construed as limited to the embodiments set forth herein. Rather, these embodiments are provided so that this disclosure will be thorough and complete.
Example 1
The method for enriching polyunsaturated fatty acid esters, squalene, natural vitamin E and phytosterol from the plant deodorized distillate in the embodiment comprises the following steps:
s101, taking a proper amount of plant deodorized distillate, adding short-chain alcohol and an emulsifier or a co-emulsifier into the plant deodorized distillate for emulsification, and adding low-temperature enzyme into an obtained emulsified product for esterification.
As a specific example, the temperature of the emulsification reaction is 25-35 ℃, and low-temperature enzyme is added to the obtained emulsified product at 25-35 ℃ to perform esterification reaction, specifically, the mass ratio of the enzyme to the vegetable oil deodorized distillate is 0.2-0.5%, and the esterification reaction lasts for 4-6 hours; short chain alcohols include methanol and ethanol; the emulsifier comprises tween and span, the co-emulsifier comprises one of sodium hydroxide or potassium hydroxide, and further, the co-emulsifier generates fatty acid salt through the reaction of alkali and fatty acid, thereby playing a role in emulsification;
the mass ratio of the short-chain alcohol to the deodorized distillate of the vegetable oil is 12-18%; the mass ratio of the emulsifier or co-emulsifier to the deodorized distillate of the vegetable oil is 0.1-2%; the mass ratio of the water to the deodorized distillate of the vegetable oil is 1-4%.
S102, carrying out gradient freezing crystallization and pressure filtration on the product after the esterification reaction to obtain a filter cake and a filtrate after pressure filtration, wherein the filter cake comprises phytosterol.
And (3) carrying out gradient cooling on the esterified liquid after the esterification reaction to crystallize and separate out most of sterol, specifically, carrying out gradient freezing crystallization at a cooling speed of 2-5 ℃/h, and then carrying out pressure filtration to obtain filtrate and a filter cake with the main component of phytosterol.
S103, carrying out multistage rectification on the filtrate to obtain squalene and natural vitamin E after rectification, and also obtaining a concentrate of polyunsaturated fatty acid ester.
Performing multistage rectification on the filtrate obtained by filter pressing, wherein the specific multistage rectification method comprises the following steps:
performing 1-stage flash evaporation, namely adding the filtrate into a 1-stage flash evaporation tower, and performing flash evaporation to remove small molecular weight substances including water, plant hydrocarbon, fatty acid, aldehyde and ketone under the conditions that the feeding temperature is 100-130 ℃ and the vacuum degree of a system at the top of the tower is 200-2000 Pa;
rectifying in the 2 nd stage, continuously adding the material after the 1 st stage flash evaporation and degassing into a 2 nd stage rectifying tower, wherein the tower bottom temperature of the rectifying tower is 170-190 ℃, the tower top temperature is 140-160 ℃, the vacuum condition is 50-300Pa, and substances removed from light components in the 2 nd stage rectifying tower comprise C 12 -C 16 Predominantly fatty acid ester, residual C 18 Polyunsaturated fatty acid ester, plant squalene, phytosterol and natural vitamin E;
rectifying in the 3 rd stage, continuously adding the heavy components in the 2 nd stage rectifying tower into the 3 rd stage rectifying tower, heating the tower kettle at 190-210 deg.C, maintaining the tower top at 160-180 deg.C, and vacuum at 50-300Pa, and obtaining light components in the 3 rd stage rectifying tower 18 Mainly polyunsaturated fatty acid ester, residual plant squalene, phytosterol and natural vitamin E;
rectifying in the 4 th stage, continuously adding the heavy components in the 3 rd stage rectifying tower into the 4 th stage rectifying tower, heating the tower kettle at 220-250 deg.C, maintaining the tower top at 180-210 deg.C, and vacuum at 50-300Pa, wherein the substances removed from the light components in the 4 th stage rectifying tower include plant squalene, part of plant hydrocarbon, C 18 The above fatty acid ester, residual natural vitamin E, phytosterol and part of plant pitch;
coupling molecular distillation, continuously adding the heavy component after the 4 th-stage rectification into a molecular distillation system, wherein the feeding flow rate is that the heating temperature is kept at 220-240 ℃, the vacuum condition is 1-10Pa, and the light component after the molecular distillation comprises natural vitamin E, phytosterol and residual vegetable pitch.
S104, carrying out urea complexation on the concentrate of the polyunsaturated fatty acid ester, urea and ethanol according to a proportion to obtain the polyunsaturated fatty acid ester with high content.
Dissolving a proper amount of urea in an ethanol water solution, adding a light component obtained in the 3 rd-level rectification, heating and stirring at 70-80 ℃ until the urea is completely dissolved, cooling to 5-10 ℃ after the urea is completely dissolved, standing at 4 ℃, and growing crystals for 6-24 hours to obtain the high-content polyunsaturated fatty acid ester.
As a specific example, the mass ratio of concentrate of polyunsaturated fatty acid ester to urea is 1:1-3; the mass ratio of the urea to the ethanol aqueous solution is 1:2-5; in the ethanol water solution, the volume percentage of water is 1-10%.
The following are experimental data obtained by performing 5 sets of experiments by the method to illustrate the process method adopted by the present invention and the effects achieved by the process method, and are specifically shown as follows:
table 1: experimental condition data for experiments carried out in groups 1-5
Table 2: the final product of groups 1-5 has polyunsaturated fatty acid, squalene, natural vitamin E and phytosterol content
As can be seen from tables 1 and 2, the technical solution in the present application can simultaneously enrich polyunsaturated fatty acid esters, squalene, natural vitamin E, and phytosterol from the deodorized distillate of vegetable oil, and can significantly improve the added value of the deodorized distillate and reduce the production cost of each nutrient by simultaneously extracting nutrients such as polyunsaturated fatty acid, squalene, natural vitamin E, and phytosterol from the deodorized distillate of vegetable oil. Further, this application adds the emulsifier in to plant deodorization distillate and emulsifies, to adding low temperature enzyme in the emulsification product that obtains in order to carry out esterification reaction, traditional technology relatively, the time of esterification reaction has been reduced, secondly, adopt low temperature enzyme to go on, moreover, this application adopts multistage rectification to filtrating, has replaced the molecular distillation in the traditional art, thereby make this application can extract polyunsaturated fatty acid, optimized the technical defect that traditional scheme can only extract methyl ester and can not extract polyunsaturated fatty acid and its ester.
In the description herein, references to the description of the term "one embodiment," "some embodiments," "an example," "a specific example," or "some examples," etc., mean that a particular feature, structure, material, or characteristic described in connection with the embodiment or example is included in at least one embodiment or example of the invention. In this specification, the schematic representations of the terms used above do not necessarily refer to the same embodiment or example. Furthermore, the particular features, structures, materials, or characteristics described may be combined in any suitable manner in any one or more embodiments or examples.
The above-mentioned embodiments only express several embodiments of the present invention, and the description thereof is more specific and detailed, but not construed as limiting the scope of the present invention. It should be noted that, for a person skilled in the art, several variations and modifications can be made without departing from the inventive concept, which falls within the scope of the present invention. Therefore, the protection scope of the present patent shall be subject to the appended claims.
Claims (10)
1. A process for the enrichment of polyunsaturated fatty acid esters, squalene, natural vitamin E and phytosterols from plant deodorized distillates, said process comprising:
taking a proper amount of plant deodorized distillate, adding short-chain alcohol and an emulsifier or a co-emulsifier into the plant deodorized distillate for emulsification, and adding low-temperature enzyme into an obtained emulsified product for esterification;
performing gradient freezing crystallization and pressure filtration on a product after the esterification reaction to obtain a filter cake and a filtrate after pressure filtration, wherein the filter cake comprises phytosterol;
carrying out multi-stage rectification on the filtrate to obtain squalene and natural vitamin E after rectification and also obtain a concentrate of polyunsaturated fatty acid ester;
and (3) carrying out urea complexation on the concentrate of the polyunsaturated fatty acid ester, urea and ethanol according to a proportion to obtain the polyunsaturated fatty acid ester with high content.
2. The method of enriching polyunsaturated fatty acid esters, squalene, natural vitamin E and phytosterols from a plant deodorizer distillate according to claim 1, characterized in that in the step of adding short-chain alcohols and emulsifiers to the plant deodorizer distillate:
the mass ratio of the short-chain alcohol to the deodorized distillate of the vegetable oil is 12-18%;
the mass ratio of the emulsifier or co-emulsifier to the deodorized distillate of the vegetable oil is 0.1-2%;
the mass ratio of the water to the deodorized distillate of the vegetable oil is 1-4%.
3. The method for enriching polyunsaturated fatty acid esters, squalene, natural vitamin E and phytosterols from a plant deodorized distillate according to claim 1, characterized in that in the step of adding a short-chain alcohol and an emulsifier to the plant deodorized distillate for emulsification, and adding a low-temperature enzyme to the obtained emulsified product for esterification:
the temperature of the emulsification reaction is 25-35 ℃, and low-temperature enzyme is added into the obtained emulsified product at the temperature of 25-35 ℃ to carry out esterification reaction;
the short-chain alcohol comprises one of methanol or ethanol;
the auxiliary emulsifier comprises one of sodium hydroxide or potassium hydroxide;
the emulsifier comprises one of tween or span.
4. The method for the enrichment of polyunsaturated fatty acid esters, squalene, natural vitamin E and phytosterols from plant deodorizer distillates according to claim 1, characterized in that in the step of adding low temperature enzymes to the obtained emulsified product to carry out the esterification reaction:
the mass ratio of the enzyme to the deodorized distillate of the vegetable oil is 0.2-0.5%, and the esterification reaction is carried out for 4-6 hours.
5. The method for enriching polyunsaturated fatty acid esters, squalene, natural vitamin E and phytosterols from plant deodorizer distillate according to claim 1, characterized in that in the step of subjecting the product after esterification to gradient freeze crystallization and pressure filtration:
the temperature reduction speed in the gradient freezing crystallization process is 2-5 ℃/h.
6. The method for enriching polyunsaturated fatty acid esters, squalene, natural vitamin E and phytosterols from a plant deodorizer distillate according to claim 1, characterized in that in the step of subjecting the filtrate to multi-stage rectification, the multi-stage rectification method comprises:
performing 1-stage flash evaporation, namely adding the filtrate into a 1-stage flash evaporation tower, and performing flash evaporation to remove small molecular weight substances under the conditions that the feeding temperature is 100-130 ℃ and the vacuum degree of a system at the top of the tower is 200-2000Pa, wherein the small molecular weight substances comprise water, plant hydrocarbon, fatty acid, aldehyde and ketone;
the 2 nd stage rectification, the material after the 1 st stage flash evaporation and degassing is continuously added into a 2 nd stage rectification tower, the temperature of the tower bottom of the rectification tower is 170-190 ℃, the temperature of the tower top is 140-160 ℃, the vacuum condition is 50-300Pa, and the substances removed from the light components in the 2 nd stage rectification tower comprise C 12 -C 16 Predominantly fatty acid ester, residual C 18 Polyunsaturated fatty acid ester, plant squalene, phytosterol and natural vitamin E;
rectifying in the 3 rd stage, continuously adding the heavy components in the 2 nd stage rectifying tower into the 3 rd stage rectifying tower, heating the tower kettle at 190-210 deg.C, maintaining the tower top at 160-180 deg.C, and vacuum at 50-300Pa to obtain light components in the 3 rd stage rectifying tower 18 Mainly polyunsaturated fatty acid ester, residual plant squalene, phytosterol and natural vitamin E;
rectifying in the 4 th stage, continuously adding the heavy components in the 3 rd stage rectifying tower into the 4 th stage rectifying tower, heating the tower kettle at 220-250 deg.C, maintaining the tower top at 180-210 deg.C, and vacuum at 50-300Pa, wherein the substances removed from the light components in the 4 th stage rectifying tower include plant squalene, part of plant hydrocarbon, C 18 The above fatty acid ester, residual natural vitamin E, phytosterol and part of plant pitch;
coupling molecular distillation, continuously adding the heavy component after the 4 th-stage rectification into a molecular distillation system, wherein the feeding flow rate is that the heating temperature is kept at 220-240 ℃, the vacuum condition is 1-10Pa, and the light component after the molecular distillation comprises natural vitamin E, phytosterol and residual vegetable pitch.
7. The process for the enrichment of polyunsaturated fatty acid esters, squalene, natural vitamin E and phytosterols from plant deodorizer distillates according to claim 1, characterized in that the step of urea complexation of said concentrate of polyunsaturated fatty acid esters with urea and ethanol in proportions comprises:
dissolving a proper amount of urea in an ethanol water solution, adding the concentrate of the polyunsaturated fatty acid ester, and heating and stirring until the urea is completely dissolved;
and after the urea is completely dissolved, cooling, standing for crystallization, carrying out vacuum filtration, and carrying out reduced pressure recovery, washing and distillation on the filtered mother liquor to obtain the high-content polyunsaturated fatty acid ester.
8. The process of enriching polyunsaturated fatty acid esters, squalene, natural vitamin E and phytosterols from plant deodorized distillate according to claim 1 or 7,
the mass ratio of the concentrate of the polyunsaturated fatty acid ester to the urea is 1:1-3;
the mass ratio of the urea to the ethanol aqueous solution is 1:2-5;
in the ethanol water solution, the volume percentage of water is 1-10%.
9. The method of enriching polyunsaturated fatty acid esters, squalene, natural vitamin E and phytosterols from a plant deodorizer distillate according to claim 1 or 7,
after the urea is completely dissolved, cooling to 5-10 ℃, standing in an environment of 4 ℃, and growing crystals for 6-24h.
10. The method of claim 7, wherein the step of adding the concentrate of polyunsaturated fatty acid esters and heating and stirring until the urea is completely dissolved comprises:
heating and stirring at 70-80 ℃ until the urea is completely dissolved.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202211106716.0A CN115650943B (en) | 2022-09-13 | 2022-09-13 | Method for enriching polyunsaturated fatty acid ester, squalene, natural vitamin E and phytosterol from plant deodorization distillate |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202211106716.0A CN115650943B (en) | 2022-09-13 | 2022-09-13 | Method for enriching polyunsaturated fatty acid ester, squalene, natural vitamin E and phytosterol from plant deodorization distillate |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN115650943A true CN115650943A (en) | 2023-01-31 |
| CN115650943B CN115650943B (en) | 2024-02-27 |
Family
ID=84984260
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202211106716.0A Active CN115650943B (en) | 2022-09-13 | 2022-09-13 | Method for enriching polyunsaturated fatty acid ester, squalene, natural vitamin E and phytosterol from plant deodorization distillate |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN115650943B (en) |
Citations (13)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2004043685A (en) * | 2002-07-12 | 2004-02-12 | Riken Vitamin Co Ltd | Production method for purified product of sterol fatty acid ester, purified product of sterol fatty acid ester, and its use |
| US20050250953A1 (en) * | 2002-08-20 | 2005-11-10 | May Choo Y | Extraction of palm vitamin E, phytosterols and squalene from palm oil |
| US20080015367A1 (en) * | 2006-07-11 | 2008-01-17 | Wiley Organics, Inc. | Process for isolating phytosterols and tocopherols from deodorizer distillate |
| CN101225414A (en) * | 2008-01-09 | 2008-07-23 | 河南工业大学 | Novel method for extracting natural vitamin E, phytosterol, fatty acid methyl ester by enzyme catalysis and molecular distillation |
| CN102089263A (en) * | 2008-07-07 | 2011-06-08 | 索菲姆公司 | Process for the extraction of squalene, sterols and vitamin e contained in condensates of physical refining and/or in distillates of deodorization of plant oils |
| CN103483305A (en) * | 2013-09-25 | 2014-01-01 | 潘见 | Method for gathering/recovering VE (Vitamins E), squalene and polyunsaturated fatty acids from deodorized distillate of plant oil |
| CN103571633A (en) * | 2013-11-15 | 2014-02-12 | 潘见 | Esterification-ultrahigh pressure crystallization separation method for distillate of vegetable oil |
| CN106187980A (en) * | 2016-07-15 | 2016-12-07 | 武汉藤欣生物工程有限公司 | Natural low content vitamin E is that raw material extracts natural Vitamin E and the method and apparatus of Squalene |
| CN107474093A (en) * | 2017-08-23 | 2017-12-15 | 福建省格兰尼生物工程股份有限公司 | A kind of deodorization distillate continuous production VE, sterol, methyl esters, glycerine, the method for squalene and high-boiling components |
| CN107778277A (en) * | 2016-08-24 | 2018-03-09 | 丰益(上海)生物技术研发中心有限公司 | The method for reclaiming squalene, vitamin E and/or sterol |
| CN108299373A (en) * | 2018-05-07 | 2018-07-20 | 宜春大海龟生命科学有限公司 | The method that natural VE is extracted from rice bran oil deodorization distillate |
| CN112941126A (en) * | 2021-04-01 | 2021-06-11 | 福建省格兰尼生物工程股份有限公司 | Method for extracting soybean vitamin E from non-soybean deodorized distillate |
| CN113087586A (en) * | 2021-04-01 | 2021-07-09 | 福建省格兰尼生物工程股份有限公司 | Method for extracting multiple active ingredients from deodorized distillate |
-
2022
- 2022-09-13 CN CN202211106716.0A patent/CN115650943B/en active Active
Patent Citations (13)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2004043685A (en) * | 2002-07-12 | 2004-02-12 | Riken Vitamin Co Ltd | Production method for purified product of sterol fatty acid ester, purified product of sterol fatty acid ester, and its use |
| US20050250953A1 (en) * | 2002-08-20 | 2005-11-10 | May Choo Y | Extraction of palm vitamin E, phytosterols and squalene from palm oil |
| US20080015367A1 (en) * | 2006-07-11 | 2008-01-17 | Wiley Organics, Inc. | Process for isolating phytosterols and tocopherols from deodorizer distillate |
| CN101225414A (en) * | 2008-01-09 | 2008-07-23 | 河南工业大学 | Novel method for extracting natural vitamin E, phytosterol, fatty acid methyl ester by enzyme catalysis and molecular distillation |
| CN102089263A (en) * | 2008-07-07 | 2011-06-08 | 索菲姆公司 | Process for the extraction of squalene, sterols and vitamin e contained in condensates of physical refining and/or in distillates of deodorization of plant oils |
| CN103483305A (en) * | 2013-09-25 | 2014-01-01 | 潘见 | Method for gathering/recovering VE (Vitamins E), squalene and polyunsaturated fatty acids from deodorized distillate of plant oil |
| CN103571633A (en) * | 2013-11-15 | 2014-02-12 | 潘见 | Esterification-ultrahigh pressure crystallization separation method for distillate of vegetable oil |
| CN106187980A (en) * | 2016-07-15 | 2016-12-07 | 武汉藤欣生物工程有限公司 | Natural low content vitamin E is that raw material extracts natural Vitamin E and the method and apparatus of Squalene |
| CN107778277A (en) * | 2016-08-24 | 2018-03-09 | 丰益(上海)生物技术研发中心有限公司 | The method for reclaiming squalene, vitamin E and/or sterol |
| CN107474093A (en) * | 2017-08-23 | 2017-12-15 | 福建省格兰尼生物工程股份有限公司 | A kind of deodorization distillate continuous production VE, sterol, methyl esters, glycerine, the method for squalene and high-boiling components |
| CN108299373A (en) * | 2018-05-07 | 2018-07-20 | 宜春大海龟生命科学有限公司 | The method that natural VE is extracted from rice bran oil deodorization distillate |
| CN112941126A (en) * | 2021-04-01 | 2021-06-11 | 福建省格兰尼生物工程股份有限公司 | Method for extracting soybean vitamin E from non-soybean deodorized distillate |
| CN113087586A (en) * | 2021-04-01 | 2021-07-09 | 福建省格兰尼生物工程股份有限公司 | Method for extracting multiple active ingredients from deodorized distillate |
Also Published As
| Publication number | Publication date |
|---|---|
| CN115650943B (en) | 2024-02-27 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| US8268595B2 (en) | Integrated methods for processing palm fruit bunches | |
| EP2114851B1 (en) | Process for separating saturated and unsaturated fatty acids | |
| CN101688150A (en) | Biodiesel production | |
| AU2021201921B2 (en) | Polyunsaturated fatty acid triglyceride and preparation and uses thereof | |
| CN101092344B (en) | Method for extracting nervonic acid from oil of Mono Maple by using technique of molecular distillation | |
| EP1809755B1 (en) | Biodiesel production from soapstock | |
| US5710030A (en) | Process for preparing fuels, fuel substitutes, and fuel supplements from renewable resources | |
| CN106977582A (en) | A kind of method of Hydrolysis kinetics phytosterol in deodorization distillate | |
| CN105001297A (en) | Method for extracting phytosterol from plant pitch | |
| CN101033243A (en) | Method of coproducting phytosterol, biological diesel oil and vitamin E | |
| CN102268464B (en) | Method for producing diglyceride with rice bran oil of high acid value | |
| CN1844319A (en) | Process for preparing bio- diesel oil by conversion of subcritical - supercritical fluid | |
| CN107216253A (en) | A kind of utilization enzyme-chemically United Technologies extract the production method of VE, sterol from soybean oil deodorizer distillate | |
| CN1966614A (en) | Method for preparing biological diesel fuel | |
| CN115650943B (en) | Method for enriching polyunsaturated fatty acid ester, squalene, natural vitamin E and phytosterol from plant deodorization distillate | |
| CN102352400B (en) | Method for producing phytosterol from deodorized distillate of vegetable fat obtained by microbial fermentation | |
| CN113481248B (en) | Method for preparing 1, 3-dioleoyl-2-palmitic acid triglyceride | |
| CN113337551B (en) | Preparation method of structural triglyceride | |
| CN1563399A (en) | New technique for extracting vitamin C and sterol from distillation of deodorizing vegetable oil | |
| KR102411079B1 (en) | Method for preparing of bio-diesel and fatty acid using microalgae oil | |
| CN112195199A (en) | Production method of 1, 3-dioleoyl-2-palmitic acid triglyceride | |
| CN113584094B (en) | Preparation method of triglyceride with 1,3 unsaturated-2-saturated fatty acid structure based on milk fat | |
| CN116287036B (en) | Method for producing 1, 3-dioleoyl 2-palmitoyl glycerol | |
| CN113621660B (en) | Preparation method of structural lipid for regulating lipid composition of infant formula milk powder | |
| CN116949105A (en) | Method and device for preparing high diglyceride camellia oil by enzyme catalysis of subcritical system |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| CB02 | Change of applicant information | ||
| CB02 | Change of applicant information |
Country or region after: China Address after: 336000 pharmaceutical industry park, Yuanzhou District, Jiangxi, Yichun Applicant after: YiChun Dahaigui Life Science Co.,Ltd. Applicant after: Wuhan Mingde biochemistry Co.,Ltd. Address before: 336000 pharmaceutical industry park, Yuanzhou District, Jiangxi, Yichun Applicant before: YICHUN DAHAIGUI LIFE SCIENCE Co.,Ltd. Country or region before: China Applicant before: Wuhan Mingde biochemistry Co.,Ltd. |
|
| GR01 | Patent grant | ||
| GR01 | Patent grant |