CN115650943B - Method for enriching polyunsaturated fatty acid ester, squalene, natural vitamin E and phytosterol from plant deodorization distillate - Google Patents
Method for enriching polyunsaturated fatty acid ester, squalene, natural vitamin E and phytosterol from plant deodorization distillate Download PDFInfo
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- CN115650943B CN115650943B CN202211106716.0A CN202211106716A CN115650943B CN 115650943 B CN115650943 B CN 115650943B CN 202211106716 A CN202211106716 A CN 202211106716A CN 115650943 B CN115650943 B CN 115650943B
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- 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 72
- 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 50
- 238000004332 deodorization Methods 0.000 title claims abstract description 42
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims abstract description 48
- 239000004202 carbamide Substances 0.000 claims abstract description 48
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 45
- 238000005886 esterification reaction Methods 0.000 claims abstract description 39
- 239000003995 emulsifying agent Substances 0.000 claims abstract description 37
- 102000004190 Enzymes Human genes 0.000 claims abstract description 28
- 108090000790 Enzymes Proteins 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 19
- 238000002425 crystallisation Methods 0.000 claims abstract description 15
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- 238000004945 emulsification Methods 0.000 claims abstract description 14
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- 238000003825 pressing Methods 0.000 claims abstract description 11
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- 238000010668 complexation reaction Methods 0.000 claims abstract description 7
- 235000015112 vegetable and seed oil Nutrition 0.000 claims description 28
- 239000008158 vegetable oil Substances 0.000 claims description 28
- 235000014113 dietary fatty acids Nutrition 0.000 claims description 22
- 229930195729 fatty acid Natural products 0.000 claims description 22
- 239000000194 fatty acid Substances 0.000 claims description 22
- 238000010438 heat treatment Methods 0.000 claims description 19
- 235000002378 plant sterols Nutrition 0.000 claims description 19
- 238000000199 molecular distillation Methods 0.000 claims description 18
- 238000001704 evaporation Methods 0.000 claims description 16
- 230000008020 evaporation Effects 0.000 claims description 16
- 229940068065 phytosterols Drugs 0.000 claims description 16
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 15
- -1 fatty acid esters Chemical class 0.000 claims description 13
- 230000008569 process Effects 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
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 12
- IDGUHHHQCWSQLU-UHFFFAOYSA-N ethanol;hydrate Chemical compound O.CCO IDGUHHHQCWSQLU-UHFFFAOYSA-N 0.000 claims description 11
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- 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
- 150000001298 alcohols Chemical class 0.000 claims description 3
- 239000013078 crystal Substances 0.000 claims description 3
- 239000012452 mother liquor Substances 0.000 claims description 3
- 239000002904 solvent Substances 0.000 claims description 3
- 238000005406 washing Methods 0.000 claims description 3
- 235000019387 fatty acid methyl ester Nutrition 0.000 abstract description 4
- 230000003301 hydrolyzing effect Effects 0.000 abstract 1
- 241000196324 Embryophyta Species 0.000 description 48
- 238000004519 manufacturing process Methods 0.000 description 9
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- 239000002994 raw material Substances 0.000 description 5
- 150000003432 sterols Chemical class 0.000 description 5
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 4
- 230000002255 enzymatic effect Effects 0.000 description 4
- 238000011085 pressure filtration Methods 0.000 description 4
- 125000005907 alkyl ester group Chemical group 0.000 description 3
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- 125000005456 glyceride group Chemical group 0.000 description 3
- 239000004367 Lipase Substances 0.000 description 2
- 102000004882 Lipase Human genes 0.000 description 2
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- 238000005265 energy consumption Methods 0.000 description 2
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- 125000004494 ethyl ester group Chemical group 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 235000011187 glycerol Nutrition 0.000 description 2
- IPCSVZSSVZVIGE-UHFFFAOYSA-N hexadecanoic acid Chemical compound CCCCCCCCCCCCCCCC(O)=O IPCSVZSSVZVIGE-UHFFFAOYSA-N 0.000 description 2
- 235000019421 lipase Nutrition 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
- 239000007864 aqueous solution Substances 0.000 description 1
- 239000002585 base Substances 0.000 description 1
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- 239000003225 biodiesel Substances 0.000 description 1
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- 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
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- QXJSBBXBKPUZAA-UHFFFAOYSA-N isooleic acid Natural products CCCCCCCC=CCCCCCCCCC(O)=O QXJSBBXBKPUZAA-UHFFFAOYSA-N 0.000 description 1
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- 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
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- 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
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- 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
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Abstract
The invention provides a method for enriching polyunsaturated fatty acid esters, squalene, natural vitamin E and phytosterol from plant deodorization distillate, which comprises the following steps: taking a proper amount of plant deodorization distillate, adding short-chain alcohol and an emulsifying agent or an auxiliary emulsifying agent for emulsification, and adding low-temperature enzyme into the obtained emulsified product for esterification reaction; carrying out gradient freezing crystallization and filter pressing on the product after the esterification reaction to obtain a filter cake and filtrate after the filter pressing, wherein the filter cake comprises phytosterol; rectifying the filtrate in multiple stages to obtain squalene and natural vitamin E, and also to obtain concentrate of polyunsaturated fatty acid ester; and (3) carrying out urea complexation on the concentrate of the polyunsaturated fatty acid ester, urea and ethanol in proportion to obtain high-content polyunsaturated fatty acid ester, and hydrolyzing the polyunsaturated fatty acid ester to obtain the polyunsaturated fatty acid. The present application optimizes the technical disadvantage that the traditional scheme only can 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, in particular to a method for enriching polyunsaturated fatty acid esters, squalene, natural vitamin E and phytosterol from plant deodorization 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 valued and paid attention to in the fields of medicine, food, chemical industry, feed, plant genetic engineering and the like.
A by-product of the deodorization procedure of the vegetable crude oil in the refining process, namely deodorized distillate (DD oil for short, disodorizer distillate), is a distillate collected from the steam distillation of the vegetable oil in the deodorization process, and the yield is about 0.3% -0.6% of the deodorized oil. DD oils often vary in their composition depending on the type of vegetable oil, the source and deodorization process. The DD oil generally comprises 20-80% free fatty acids (mainly including palmitic acid, oleic acid and linoleic acid), 10-30% triglyceride, 5-20% sterol and sterol ester, 0.1-20% natural vitamin E (including tocopherol and tocotrienol), and 5-30% vegetable hydrocarbon (mainly including squalene and its derivatives). DD oil is the main raw material for the current industrial production of natural vitamin E, plant sterols, fatty acids and alkyl esters thereof.
In the prior art, natural vitamin E, plant sterol and biodiesel can only be generally extracted from the vegetable oil deodorization distillate, and polyunsaturated fatty acid, squalene, natural vitamin E and plant sterol can not be simultaneously extracted from the vegetable oil deodorization distillate, so that the raw material utilization rate is low, the extraction efficiency is low and the comprehensive cost is high.
The Chinese patent CN200810049033.X discloses a new method for extracting natural vitamin E, plant sterol and fatty acid methyl ester by enzyme catalysis and molecular distillation, wherein 2 kinds of fatty acid enzymes are needed during the enzymatic esterification in the method, the cost of the lipase is high, the steps are complicated, the subsequent 2 times of molecular distillation are low in separation efficiency, polyunsaturated fatty acid and squalene cannot be simultaneously enriched, and the deodorization distillate of vegetable oil cannot be fully utilized.
Chinese patent CN107012177a discloses a method for catalyzing the esterification reaction of deodorized distillate at low temperature, which has low enzymatic catalytic efficiency, the reaction time is up to 18-36 hours, and secondary enzyme addition is also needed for secondary reaction, thus the production cost is high.
Chinese patent CN107474093a discloses a method for continuously producing VE, sterol, methyl ester, glycerin, squalene and high boiling substances from deodorized distillate, and also, continuously producing VE, sterol, methyl ester, glycerin, squalene and high boiling substances from deodorized distillate by using the processes of enzymatic esterification, cold separation and molecular distillation, wherein the molecular distillation process can only initially separate fatty acid methyl ester, VE, squalene and high boiling substances, and the content of squalene is only 10-20%.
Disclosure of Invention
Based on the problems of high energy consumption, large pollution, low efficiency and the like in the prior art, the invention aims to provide a method for enriching polyunsaturated fatty acid esters, squalene, natural vitamin E and phytosterol from plant deodorization distillate, and provides a method for simultaneously extracting polyunsaturated fatty acid esters, squalene, natural vitamin E and phytosterol from plant deodorization distillate. The method has the advantages of high raw material utilization rate, simple and convenient operation, mild reaction conditions, low energy consumption, little pollution, high separation degree of active substances, good product color and purity, and remarkably improved production efficiency.
The application provides a method for enriching polyunsaturated fatty acid esters, squalene, natural vitamin E and phytosterols from plant deodorization distillate, which is characterized by comprising the following steps:
taking a proper amount of plant deodorization distillate, adding short-chain alcohol and an emulsifying agent or a co-emulsifying agent into the plant deodorization distillate to emulsify, and adding low-temperature enzyme into the obtained emulsified product to perform esterification reaction;
carrying out gradient freezing crystallization and filter pressing on the product after the esterification reaction to obtain a filter cake and filtrate after the filter pressing, wherein the filter cake comprises phytosterol;
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;
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 polyunsaturated fatty acid esters, squalene, natural vitamin E and phytosterol from the plant deodorization distillate, through simultaneously extracting nutrients such as polyunsaturated fatty acids, squalene, natural vitamin E and phytosterol from the plant deodorization distillate, the added value of the deodorization distillate can be obviously improved, and the production cost of each nutrient can be reduced; further, the application adds emulsifying agent or helps the emulsifying agent to emulsify in the plant deodorization distillate, adds low temperature enzyme in order to carry out the esterification reaction to the emulsification product that obtains, compared with the conventional art, reduced the time of esterification reaction, secondly, adopt low temperature enzyme to carry out, furthermore, the application adopts multistage rectification to the filtrate, molecular distillation in the conventional art has been replaced, thereby make the application can draw polyunsaturated fatty acid, the technical defect that traditional scheme can only draw methyl ester and can not draw polyunsaturated fatty acid has been optimized, the plant squalene that obtains in addition, natural vitamin E content is higher, can't draw polyunsaturated fatty acid from the vegetable oil deodorization distillate simultaneously in the prior art, squalene, natural vitamin E and phytosterol, lead to the technical problem that has improved manufacturing cost.
In addition, the method for enriching polyunsaturated fatty acid esters, squalene, natural vitamin E and phytosterol from plant deodorization distillate according to the invention 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 vegetable oil deodorized distillate is 12-18%;
the mass ratio of the emulsifying agent or the auxiliary emulsifying agent to the vegetable oil deodorization distillate is 0.1-2%;
the mass ratio of the water to the vegetable oil deodorized distillate is 1-4%.
Further, the auxiliary emulsifier is fatty acid salt generated by fatty acid reaction, so that the emulsification effect is achieved;
further, in the step of adding a short-chain alcohol and an emulsifier or co-emulsifier to the plant deodorized distillate to perform emulsification, adding a low-temperature enzyme to the obtained emulsified product to perform 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 or span.
Further, in the step of adding a low-temperature enzyme to the resulting emulsified product to perform an esterification reaction:
the mass ratio of the enzyme to the vegetable oil deodorized distillate is 0.2-0.5%, and the esterification reaction is carried out for 4-6 hours.
Further, 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.
Further, in the step of subjecting the filtrate to multistage rectification, the method of multistage rectification includes:
the step 1 of flash evaporation, wherein the filtrate is added into a step 1 flash evaporation tower, the feeding temperature is 100-130 ℃, and the low molecular weight substances including moisture, plant hydrocarbon, fatty acid, aldehyde and ketone are removed by flash evaporation under the condition that the vacuum degree of a tower top system is 200-2000 Pa;
2 nd stage distillation, continuously adding the material subjected to 1 st stage flash evaporation and degassing into a 2 nd stage rectifying tower, wherein the temperature of the tower bottom of the rectifying tower is 170-190 ℃, the temperature of the tower top of the rectifying tower is 140-160 ℃, the vacuum condition is 50-300Pa, and the material removed from light components in the 2 nd stage rectifying tower comprises C 12 -C 16 Fatty acid esters of predominantly, residual C 18 Polyunsaturated fatty acid esters, plant squalene, plant sterols and natural vitamin E;
3 rd level rectification, continuously adding heavy components of the 2 nd level rectification tower into the 3 rd level rectification tower, heating the tower kettle to 190-210 ℃, keeping the tower top temperature at 160-180 ℃ and vacuum condition at 50-300Pa, and obtaining C from light components in the 3 rd level rectification tower 18 Polyunsaturated fatty acid esters, residual plant squalene, phytosterols and natural vitamin E as the main components;
4 th stage rectification, continuously adding heavy components of 3 rd stage rectification tower into 4 th stage rectification tower, heating tower bottom at 220-250 deg.C, tower top at 180-210 deg.C and vacuum condition at 50-300Pa, and removing light components in 4 th stage rectification tower including plant squalene, partial plant hydrocarbon and C 18 The fatty acid ester, the residual natural vitamin E, the phytosterol and part of the vegetable pitch;
coupling molecular distillation, continuously adding the heavy component after 4-level distillation 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 molecular distillation comprises natural vitamin E, plant sterol and residual plant asphalt.
Further, the step of urea complexation of the concentrate of polyunsaturated fatty acid esters with urea and ethanol in proportion comprises:
dissolving urea in ethanol water solution, adding the concentrate of polyunsaturated fatty acid ester, heating and stirring until urea is completely dissolved;
after the urea is completely dissolved, cooling, standing for crystallization, vacuum filtering, recovering solvent from mother liquor after the vacuum filtering, washing with water, and distilling to obtain polyunsaturated fatty acid ester with high content.
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 water 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, the temperature is reduced to 5-10 ℃, the urea is placed in an environment of 4 ℃ for standing, and crystal growth is carried out 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 method for enriching polyunsaturated fatty acid esters, squalene, natural vitamin E, and phytosterols from plant deodorizer distillate according to an embodiment of the present invention.
The invention will be further described in the following detailed description in conjunction with the above-described figures.
Detailed Description
In order that the invention may be readily understood, a more complete description of the invention will be rendered by reference to the appended drawings. Several embodiments of the invention are presented in the figures. 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 herein in the description of the invention is for the purpose of describing particular embodiments only and is not intended to be limiting of the invention. The term "and/or" as used herein includes any and all combinations of one or more of the associated listed items.
In order to solve the technical problems that polyunsaturated fatty acid, squalene, natural vitamin E and phytosterol cannot be extracted from vegetable oil deodorization distillate simultaneously in the prior art, so that production cost is high and efficiency is low, the application provides a method for enriching polyunsaturated fatty acid ester, squalene, natural vitamin E and phytosterol from vegetable deodorization distillate simultaneously, which has the following beneficial effects:
1) Through the pretreatment of raw material emulsification, then the enzymatic catalytic esterification and transesterification are adopted, and one enzyme can catalyze the conversion of fatty acid into fatty acid ester and glyceride into fatty acid ester, so that the reaction speed is high, the time is short, the efficiency is high and the cost is low.
2) Multiple stages of continuous rectification are utilized to simultaneously generate multiple plant nutrients such as polyunsaturated fatty acid ester, plant squalene, natural vitamin E, plant sterol and the like, wherein the content of the polyunsaturated fatty acid ester is between 50 and 70 percent, the content of the plant squalene is between 30 and 60 percent, the content of the plant sterol is between 40 and 70 percent, and the content of the natural vitamin E is between 50 and 70 percent.
3) After urea complexation, the content of polyunsaturated fatty acid ester can further reach more than 80-95%, and then free polyunsaturated fatty acid can be generated after enzymatic method and acid-base hydrolysis.
4) Through process integration, one production line can simultaneously extract and prepare high-quality polyunsaturated fatty acid, plant squalene, plant sterol and natural vitamin E, thereby greatly reducing production cost and improving production efficiency.
Specifically, the vegetable oil deodorized 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 phytosterols from plant deodorization distillate comprises the following steps:
taking a proper amount of plant deodorization distillate, adding short-chain alcohol and an emulsifying agent or a co-emulsifying agent into the plant deodorization distillate to emulsify, and adding low-temperature enzyme into the obtained emulsified product to perform esterification reaction;
carrying out gradient freezing crystallization and filter pressing on the product after the esterification reaction to obtain a filter cake and filtrate after the filter pressing, wherein the filter cake comprises phytosterol;
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;
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 comprises polyunsaturated fatty acid alkyl esters, polyunsaturated fatty acid alkyl esters comprise polyunsaturated fatty acid methyl esters and polyunsaturated fatty acid ethyl esters, polyunsaturated fatty acid methyl esters comprise methyl linoleate, and polyunsaturated fatty acid ethyl esters comprise ethyl linoleate. The polyunsaturated fatty acid ester is hydrolyzed to obtain polyunsaturated fatty acid.
Specifically, the low-temperature enzyme esterification is carried out by selecting short-chain alcohol such as methanol, ethanol and the like, vegetable oil deodorization distillate, water and emulsifying agent according to a certain proportion, emulsifying by a high-speed shearing emulsifying device at 25-35 ℃, adding a certain amount of lipase for esterification under the temperature condition after the emulsification is finished, and converting fatty acid and glyceride in the vegetable oil deodorization distillate 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 deodorized distillate:
the mass ratio of the short-chain alcohol to the vegetable oil deodorized distillate is 12-18%;
the mass ratio of the emulsifying agent or the auxiliary emulsifying agent to the vegetable oil deodorization distillate is 0.1-2%;
the mass ratio of the water to the vegetable oil deodorized distillate is 1-4%.
In some alternative embodiments, in the step of adding a short chain alcohol and an emulsifier to the plant deodorized distillate for emulsification, a low temperature enzyme is added to the resulting 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.
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 vegetable oil deodorized distillate 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 alternative embodiments, in the step of subjecting the filtrate to multi-stage rectification, the method of multi-stage rectification comprises:
the step 1 of flash evaporation, wherein the filtrate is added into a step 1 flash evaporation tower, the feeding temperature is 100-130 ℃, and the low molecular weight substances including moisture, plant hydrocarbon, fatty acid, aldehyde and ketone are removed by flash evaporation under the condition that the vacuum degree of a tower top system is 200-2000 Pa;
2 nd stage rectification, continuously adding the material subjected to the 1 st stage flash evaporation and degassing into a 2 nd stage rectification tower, wherein the temperature of the tower bottom of the rectification tower is 170-190 ℃, the temperature of the tower top of the rectification tower is 140-160 ℃, the vacuum condition is 50-300Pa, and the material removed from the light components in the 2 nd stage rectification tower comprises C 12 -C 16 Fatty acid esters of predominantly, residual C 18 Polyunsaturated fatty acid esters, plant squalene, plant sterols and natural vitamin E;
3 rd level rectification, continuously adding heavy components of the 2 nd level rectification tower into the 3 rd level rectification tower, and adding the heavy components into the tower kettleHeating at 190-210 deg.c, maintaining the tower top temperature at 160-180 deg.c and vacuum condition at 50-300Pa, and obtaining light component in 3 rd level rectifying tower to obtain C 18 Polyunsaturated fatty acid esters, residual plant squalene, phytosterols and natural vitamin E as the main components;
4 th stage rectification, continuously adding heavy components of 3 rd stage rectification tower into 4 th stage rectification tower, heating tower bottom at 220-250 deg.C, tower top at 180-210 deg.C and vacuum condition at 50-300Pa, and removing light components in 4 th stage rectification tower including plant squalene, partial plant hydrocarbon and C 18 The fatty acid ester, the residual natural vitamin E, the phytosterol and part of the vegetable pitch;
coupling molecular distillation, continuously adding the heavy component after 4-level distillation 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 molecular distillation comprises natural vitamin E, plant sterol and residual plant asphalt.
In some alternative embodiments, the step of urea complexing the concentrate of polyunsaturated fatty acid esters with urea and ethanol in proportions comprises:
dissolving urea in ethanol water solution, adding the concentrate of polyunsaturated fatty acid ester, heating and stirring until urea is completely dissolved;
after the urea is completely dissolved, cooling, standing for crystallization, vacuum filtering, recovering solvent from mother liquor after the vacuum filtering, washing with water, and distilling to obtain polyunsaturated fatty acid ester with high content.
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 water solution is 1:2-5;
in the ethanol water solution, the volume percentage of water is 1-10%.
In some alternative embodiments, after the urea is completely dissolved, the temperature is reduced to 5-10 ℃, and the urea is placed in an environment of 4 ℃ for standing and crystal growth for 6-24 hours.
In some alternative embodiments, the step of adding the concentrate of polyunsaturated fatty acid esters and 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 an enzymatic method to catalyze the esterification, and converts fatty acid and glyceride into fatty acid ester, thereby facilitating the subsequent cold separation of plant sterol and the separation of natural vitamin E and squalene. And then, multistage continuous rectification is adopted to gradually separate polyunsaturated fatty acid esters, plant squalene, natural vitamin E, plant sterols and other active substances, so that the method has the advantages of simple and convenient steps, high separation efficiency, low cost and remarkable improvement of the utilization rate of raw materials.
In order to facilitate understanding of the present invention, several embodiments of the present invention are presented below, and the process flow is shown in FIG. 1. 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 phytosterols from plant deodorization distillate in the embodiment comprises the following steps:
s101, taking a proper amount of plant deodorization distillate, adding short-chain alcohol and an emulsifying agent or a coemulsifier into the plant deodorization distillate to emulsify, and adding low-temperature enzyme into the obtained emulsified product to perform esterification reaction.
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 the temperature of 25-35 ℃ to perform esterification reaction, specifically, the mass ratio of enzyme to vegetable oil deodorized distillate is 0.2-0.5%, and the esterification reaction is carried out for 4-6 hours; short chain alcohols include methanol and ethanol; the emulsifying agent comprises tween and span, the auxiliary emulsifying agent comprises one of sodium hydroxide or potassium hydroxide, and further, the auxiliary emulsifying agent generates fatty acid salt through the reaction of alkali and fatty acid, thereby playing a role of emulsification;
the mass ratio of the short-chain alcohol to the vegetable oil deodorized distillate is 12-18%; the mass ratio of the emulsifying agent or the auxiliary emulsifying agent to the vegetable oil deodorization distillate is 0.1-2%; the mass ratio of the water to the vegetable oil deodorized distillate 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 filtrate after the 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 sterols, specifically, cooling at a speed of 2-5 ℃/h in the gradient freezing crystallization process, and then carrying out filter pressing 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 obtaining the concentrate of polyunsaturated fatty acid ester.
The filter liquor obtained by filter pressing is subjected to multistage rectification, and the method specifically comprises the following steps:
flash evaporation of the 1 st stage, adding the filtrate into a flash evaporation tower of the 1 st stage, wherein the feeding temperature is 100-130 ℃, and the low molecular weight substances including moisture, plant hydrocarbon, fatty acid, aldehyde and ketone are removed by flash evaporation under the condition that the vacuum degree of a tower top system is 200-2000 Pa;
2 nd stage distillation, continuously adding the material subjected to 1 st stage flash evaporation and degassing into a 2 nd stage distillation tower, wherein the temperature of the tower bottom of the distillation tower is 170-190 ℃, the temperature of the tower top of the distillation tower is 140-160 ℃, the vacuum condition is 50-300Pa, and the materials removed from light components in the 2 nd stage distillation tower comprise C 12 -C 16 Fatty acid esters of predominantly, residual C 18 Polyunsaturated fatty acid esters, plant squalene, plant sterols and natural vitamin E;
3 rd level rectification, continuously adding heavy components of the 2 nd level rectification tower into the 3 rd level rectification tower, heating the tower kettle to 190-210 ℃, keeping the tower top temperature at 160-180 ℃ and vacuum condition at 50-300Pa, and obtaining light components in the 3 rd level rectification tower to comprise C 18 Polyunsaturated fatty acid esters, residual plant squalene, phytosterols and natural vitamin E as the main components;
4 th stage rectification, namely continuously adding heavy components of the 3 rd stage rectification tower into the 4 th stage rectification tower, wherein the heating temperature of the tower bottom is 220-250 ℃, and the tower top is provided with a plurality of stages of rectification equipmentMaintaining the temperature at 180-210 deg.C and vacuum condition at 50-300Pa, and removing light components including plant squalene, part of plant hydrocarbon and C in 4-stage rectifying tower 18 The fatty acid ester, the residual natural vitamin E, the phytosterol and part of the vegetable pitch;
coupling molecular distillation, continuously adding the heavy component after 4-level distillation 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 molecular distillation comprises natural vitamin E, plant sterol and residual plant asphalt.
S104, urea complexing is carried out on the concentrate of the polyunsaturated fatty acid ester, urea and ethanol according to a proportion, and then the polyunsaturated fatty acid ester with high content is obtained.
Dissolving a proper amount of urea in ethanol water solution, adding the light component obtained in the 3 rd stage rectification, heating and stirring at 70-80 ℃ until the urea is completely dissolved, cooling to 5-10 ℃ after the urea is completely dissolved, standing in an environment of 4 ℃, and crystallizing for 6-24 hours to obtain the polyunsaturated fatty acid ester with high content.
As a specific example, the mass ratio of concentrate of polyunsaturated fatty acid esters to urea is 1:1-3; the mass ratio of urea to ethanol aqueous solution is 1:2-5; in the ethanol water solution, the volume percentage of water is 1-10%.
The following is experimental data obtained by performing 5 groups of experiments by the method, which are used for explaining the process method adopted by the invention and the effect achieved by the process method, and are specifically shown as follows:
table 1: experimental condition data at the time of experiments performed in groups 1 to 5
Table 2: polyunsaturated fatty acid, squalene, natural vitamin E and phytosterol content of the end products of group 1-5
From tables 1 and 2, the technical scheme in the application can simultaneously enrich polyunsaturated fatty acid esters, squalene, natural vitamin E and phytosterol from the vegetable oil deodorization distillate, and can remarkably improve the added value of the deodorization distillate and reduce the production cost of each nutrient by simultaneously extracting the nutrients such as polyunsaturated fatty acids, squalene, natural vitamin E and phytosterol from the vegetable oil deodorization distillate. Further, the emulsifying agent is added into the plant deodorization distillate for emulsification, low-temperature enzyme is added into the obtained emulsified product for esterification reaction, compared with the traditional technology, the time of the esterification reaction is reduced, the low-temperature enzyme is adopted for carrying out, and the filtrate is subjected to multistage rectification, so that the molecular distillation in the traditional technology is replaced, polyunsaturated fatty acid can be extracted, and the technical defect that methyl ester but not polyunsaturated fatty acid and ester thereof can be extracted in the traditional scheme is optimized.
In the description of the present specification, a description referring to terms "one embodiment," "some embodiments," "examples," "specific examples," or "some examples," etc., means 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 present invention. In this specification, schematic representations of the above terms do not necessarily refer to the same embodiments or examples. 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 foregoing examples illustrate only a few embodiments of the invention and are described in detail herein without thereby limiting the scope of the invention. It should be noted that it will be apparent to those skilled in the art that several variations and modifications can be made without departing from the spirit of the invention, which are all within the scope of the invention. Accordingly, the scope of protection of the present invention is to be determined by the appended claims.
Claims (9)
1. A method for enriching polyunsaturated fatty acid esters, squalene, natural vitamin E and phytosterols from plant deodorized distillates, said method comprising:
taking a proper amount of plant deodorization distillate, adding short-chain alcohol and an emulsifying agent or a co-emulsifying agent into the plant deodorization distillate to emulsify, and adding low-temperature enzyme into the obtained emulsified product to perform esterification reaction;
carrying out gradient freezing crystallization and filter pressing on the product after the esterification reaction to obtain a filter cake and filtrate after the filter pressing, wherein the filter cake comprises phytosterol;
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;
urea complexation is carried out on the concentrate of the polyunsaturated fatty acid ester, urea and ethanol according to a proportion, so as to obtain polyunsaturated fatty acid ester with high content;
the multistage rectification method comprises the following steps:
the step 1 of flash evaporation, wherein the filtrate is added into a step 1 flash evaporation tower, the feeding temperature is 100-130 ℃, and the low molecular weight substances including moisture, plant hydrocarbon, fatty acid, aldehyde and ketone are removed by flash evaporation under the condition that the vacuum degree of a tower top system is 200-2000 Pa;
2 nd stage rectification, continuously adding the material subjected to the 1 st stage flash evaporation and degassing into a 2 nd stage rectification tower, wherein the temperature of the tower bottom of the rectification tower is 170-190 ℃, the temperature of the tower top of the rectification tower is 140-160 ℃, the vacuum condition is 50-300Pa, and the materials removed by light components in the 2 nd stage rectification tower comprise fatty acid esters mainly containing C12-C16, residual C18 polyunsaturated fatty acid esters, plant squalene, plant sterols and natural vitamin E;
3 rd level rectification, namely continuously adding heavy components of the 2 nd level rectification tower into the 3 rd level rectification tower, heating the tower bottom at 190-210 ℃, keeping the tower top at 160-180 ℃ and the vacuum condition at 50-300Pa, and obtaining polyunsaturated fatty acid esters mainly containing C18, residual plant squalene, plant sterols and natural vitamin E from light components in the 3 rd level rectification tower;
4 th level rectification, namely continuously adding heavy components of the 3 rd level rectification tower into the 4 th level rectification tower, wherein the tower bottom heating temperature is 220-250 ℃, the tower top temperature is kept at 180-210 ℃, the vacuum condition is 50-300Pa, and substances removed from light components in the 4 th level rectification tower comprise plant squalene, partial plant hydrocarbon, fatty acid ester with more than C18, residual natural vitamin E, plant sterol and partial plant asphalt;
coupling molecular distillation, continuously adding the heavy component after 4-level distillation 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 molecular distillation comprises natural vitamin E, plant sterol and residual plant asphalt.
2. The method of 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 adding short chain alcohols and emulsifiers to the plant deodorizer distillate:
the mass ratio of the short-chain alcohol to the vegetable oil deodorized distillate is 12-18%;
the mass ratio of the emulsifying agent or the auxiliary emulsifying agent to the vegetable oil deodorization distillate is 0.1-2%;
the mass ratio of the water to the vegetable oil deodorized distillate is 1-4%.
3. The method for enriching polyunsaturated fatty acid esters, squalene, natural vitamin E and phytosterols from plant deodorizer distillate according to claim 1, wherein short chain alcohols and emulsifiers are added to the plant deodorizer distillate for emulsification and low temperature enzymes are added to the resulting emulsified product for 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 or span.
4. The method for enriching polyunsaturated fatty acid esters, squalene, natural vitamin E and phytosterols from plant deodorized distillate according to claim 1 characterized in that in the step of adding a low temperature enzyme to the resulting emulsified product for esterification:
the mass ratio of the enzyme to the vegetable oil deodorized distillate 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 deodorized distillates according to claim 1, characterized in that in the step of subjecting the product after esterification reaction to gradient freeze crystallization and filter pressing:
the cooling speed in the gradient freezing crystallization process is 2-5 ℃/h.
6. The method of enriching polyunsaturated fatty acid esters, squalene, natural vitamin E and phytosterols from plant deodorized distillates according to claim 1 characterized in that the step of urea complexation of the concentrate of polyunsaturated fatty acid esters with urea and ethanol comprises:
dissolving urea in ethanol water solution, adding the concentrate of polyunsaturated fatty acid ester, heating and stirring until urea is completely dissolved;
after the urea is completely dissolved, cooling, standing for crystallization, vacuum filtering, recovering solvent from mother liquor after the vacuum filtering, washing with water, and distilling to obtain polyunsaturated fatty acid ester with high content.
7. The method for enriching polyunsaturated fatty acid esters, squalene, natural vitamin E and phytosterols from plant deodorized distillate according to claim 1 or 6,
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 water solution is 1:2-5;
in the ethanol water solution, the volume percentage of water is 1-10%.
8. The method for enriching polyunsaturated fatty acid esters, squalene, natural vitamin E and phytosterols from plant deodorized distillate according to claim 1 or 6,
cooling to 5-10deg.C after the urea is completely dissolved, standing at 4deg.C, and growing crystal for 6-24 hr.
9. The method of enriching polyunsaturated fatty acid esters, squalene, natural vitamin E and phytosterols from plant deodorized distillates according to claim 6 wherein the step of adding a concentrate of the polyunsaturated fatty acid esters and stirring with heat until the urea is completely dissolved comprises:
heating and stirring at 70-80 ℃ until the urea is completely dissolved.
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