CN113943605B - Winterization and fractionation method for microbial oil - Google Patents
Winterization and fractionation method for microbial oil Download PDFInfo
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- CN113943605B CN113943605B CN202111138251.2A CN202111138251A CN113943605B CN 113943605 B CN113943605 B CN 113943605B CN 202111138251 A CN202111138251 A CN 202111138251A CN 113943605 B CN113943605 B CN 113943605B
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- 238000000034 method Methods 0.000 title claims abstract description 37
- 238000005194 fractionation Methods 0.000 title claims abstract description 32
- 230000000813 microbial effect Effects 0.000 title claims abstract description 17
- 238000001914 filtration Methods 0.000 claims abstract description 78
- 235000014113 dietary fatty acids Nutrition 0.000 claims abstract description 21
- 239000000194 fatty acid Substances 0.000 claims abstract description 21
- 229930195729 fatty acid Natural products 0.000 claims abstract description 21
- 150000004671 saturated fatty acids Chemical class 0.000 claims abstract description 20
- 125000005456 glyceride group Chemical group 0.000 claims abstract description 8
- 239000003921 oil Substances 0.000 claims description 89
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 38
- 239000007787 solid Substances 0.000 claims description 34
- 239000007788 liquid Substances 0.000 claims description 33
- PVNIQBQSYATKKL-UHFFFAOYSA-N tripalmitin Chemical group CCCCCCCCCCCCCCCC(=O)OCC(OC(=O)CCCCCCCCCCCCCCC)COC(=O)CCCCCCCCCCCCCCC PVNIQBQSYATKKL-UHFFFAOYSA-N 0.000 claims description 30
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 claims description 26
- 238000003756 stirring Methods 0.000 claims description 22
- 229910052757 nitrogen Inorganic materials 0.000 claims description 19
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 19
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 18
- IPCSVZSSVZVIGE-UHFFFAOYSA-N palmitic acid group Chemical group C(CCCCCCCCCCCCCCC)(=O)O IPCSVZSSVZVIGE-UHFFFAOYSA-N 0.000 claims description 18
- 229960001947 tripalmitin Drugs 0.000 claims description 14
- 238000001816 cooling Methods 0.000 claims description 13
- 239000004744 fabric Substances 0.000 claims description 12
- 229910052751 metal Inorganic materials 0.000 claims description 11
- 239000002184 metal Substances 0.000 claims description 11
- 239000003054 catalyst Substances 0.000 claims description 10
- 235000021314 Palmitic acid Nutrition 0.000 claims description 9
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 9
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 9
- 235000011187 glycerol Nutrition 0.000 claims description 9
- 238000002156 mixing Methods 0.000 claims description 9
- WQEPLUUGTLDZJY-UHFFFAOYSA-N n-Pentadecanoic acid Natural products CCCCCCCCCCCCCCC(O)=O WQEPLUUGTLDZJY-UHFFFAOYSA-N 0.000 claims description 9
- 239000000377 silicon dioxide Substances 0.000 claims description 9
- 235000012239 silicon dioxide Nutrition 0.000 claims description 8
- WQDUMFSSJAZKTM-UHFFFAOYSA-N Sodium methoxide Chemical compound [Na+].[O-]C WQDUMFSSJAZKTM-UHFFFAOYSA-N 0.000 claims description 6
- 238000006243 chemical reaction Methods 0.000 claims description 6
- 239000006228 supernatant Substances 0.000 claims description 6
- 238000002425 crystallisation Methods 0.000 claims description 5
- 230000008025 crystallization Effects 0.000 claims description 5
- RPDAUEIUDPHABB-UHFFFAOYSA-N potassium ethoxide Chemical compound [K+].CC[O-] RPDAUEIUDPHABB-UHFFFAOYSA-N 0.000 claims description 3
- BDAWXSQJJCIFIK-UHFFFAOYSA-N potassium methoxide Chemical compound [K+].[O-]C BDAWXSQJJCIFIK-UHFFFAOYSA-N 0.000 claims description 3
- QDRKDTQENPPHOJ-UHFFFAOYSA-N sodium ethoxide Chemical compound [Na+].CC[O-] QDRKDTQENPPHOJ-UHFFFAOYSA-N 0.000 claims description 3
- 238000006555 catalytic reaction Methods 0.000 claims description 2
- 238000010438 heat treatment Methods 0.000 claims description 2
- 239000002245 particle Substances 0.000 abstract description 12
- 238000000926 separation method Methods 0.000 abstract description 6
- 239000013078 crystal Substances 0.000 abstract description 5
- 238000011031 large-scale manufacturing process Methods 0.000 abstract 1
- 235000019197 fats Nutrition 0.000 description 38
- 239000000047 product Substances 0.000 description 20
- 238000007789 sealing Methods 0.000 description 19
- 239000011521 glass Substances 0.000 description 18
- 239000004519 grease Substances 0.000 description 13
- 238000012360 testing method Methods 0.000 description 10
- 238000007710 freezing Methods 0.000 description 8
- 230000008014 freezing Effects 0.000 description 8
- 239000002585 base Substances 0.000 description 6
- 238000011049 filling Methods 0.000 description 6
- 239000002904 solvent Substances 0.000 description 6
- 238000002360 preparation method Methods 0.000 description 5
- YZXBAPSDXZZRGB-DOFZRALJSA-N arachidonic acid Chemical compound CCCCC\C=C/C\C=C/C\C=C/C\C=C/CCCC(O)=O YZXBAPSDXZZRGB-DOFZRALJSA-N 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- DCXXMTOCNZCJGO-UHFFFAOYSA-N tristearoylglycerol Chemical compound CCCCCCCCCCCCCCCCCC(=O)OCC(OC(=O)CCCCCCCCCCCCCCCCC)COC(=O)CCCCCCCCCCCCCCCCC DCXXMTOCNZCJGO-UHFFFAOYSA-N 0.000 description 4
- 238000009826 distribution Methods 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 150000004665 fatty acids Chemical class 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- 235000021355 Stearic acid Nutrition 0.000 description 2
- 229940114079 arachidonic acid Drugs 0.000 description 2
- 235000021342 arachidonic acid Nutrition 0.000 description 2
- 238000005345 coagulation Methods 0.000 description 2
- 230000015271 coagulation Effects 0.000 description 2
- 239000010779 crude oil Substances 0.000 description 2
- 238000004332 deodorization Methods 0.000 description 2
- 238000009882 destearinating Methods 0.000 description 2
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 description 2
- OQCDKBAXFALNLD-UHFFFAOYSA-N octadecanoic acid Natural products CCCCCCCC(C)CCCCCCCCC(O)=O OQCDKBAXFALNLD-UHFFFAOYSA-N 0.000 description 2
- 238000000746 purification Methods 0.000 description 2
- 239000013049 sediment Substances 0.000 description 2
- 239000008117 stearic acid Substances 0.000 description 2
- 241001052560 Thallis Species 0.000 description 1
- 239000000061 acid fraction Substances 0.000 description 1
- 238000009874 alkali refining Methods 0.000 description 1
- 238000005815 base catalysis Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 125000005313 fatty acid group Chemical group 0.000 description 1
- 238000000855 fermentation Methods 0.000 description 1
- 230000004151 fermentation Effects 0.000 description 1
- 239000012065 filter cake Substances 0.000 description 1
- 239000010419 fine particle Substances 0.000 description 1
- 239000012530 fluid Substances 0.000 description 1
- 230000000887 hydrating effect Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 230000035699 permeability Effects 0.000 description 1
- 235000020777 polyunsaturated fatty acids Nutrition 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 235000003441 saturated fatty acids Nutrition 0.000 description 1
- 238000004062 sedimentation Methods 0.000 description 1
- 238000003807 solvent-free extraction Methods 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 150000003626 triacylglycerols Chemical class 0.000 description 1
- UFTFJSFQGQCHQW-UHFFFAOYSA-N triformin Chemical compound O=COCC(OC=O)COC=O UFTFJSFQGQCHQW-UHFFFAOYSA-N 0.000 description 1
- 235000021122 unsaturated fatty acids Nutrition 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11B—PRODUCING, e.g. BY PRESSING RAW MATERIALS OR BY EXTRACTION FROM WASTE MATERIALS, REFINING OR PRESERVING FATS, FATTY SUBSTANCES, e.g. LANOLIN, FATTY OILS OR WAXES; ESSENTIAL OILS; PERFUMES
- C11B3/00—Refining fats or fatty oils
- C11B3/008—Refining fats or fatty oils by filtration, e.g. including ultra filtration, dialysis
Abstract
The invention provides a method for winterization and fractionation of microbial oil. The winterization and fractionation method of the microbial oil comprises the following steps: 1) Adding trisaturated fatty glyceride into ARA desolventized oil, and then wintering, wherein the mass ratio of the ARA desolventized oil to the trisaturated fatty glyceride is 2:1-1.25:1; the ratio of saturated fatty acid in the trisaturated fatty acid glyceride is not less than 90%; 2) And (5) filtering and separating the plates and frames. The method for winterization and fractionation of microbial oil provided by the invention can form a large number of crystal forms with good stability in ARA desolventized oil in a short time, can keep the particle form for a long time, is convenient for effective separation, can obtain clear and transparent oil products at low temperature after the ARA desolventized oil is subjected to winterization and fractionation once, uses common winterization and fractionation equipment, can be recycled, has less time, and is suitable for large-scale production.
Description
Technical Field
The invention relates to the technical field of grease separation and purification, in particular to a method for winterization and fractionation of microbial grease.
Background
Microbial oil mainly comprises triglycerides, wherein each component contains fatty acids with different chain lengths and different saturation degrees, various fatty acid groups are combined on a glycerin skeleton through ester bonds, however, the microbial oil rich in polyunsaturated fatty acids is easy to generate flocculent sediment when stored at a lower temperature, and further treatment is needed for the microbial oil, so that solid grease easy to generate flocculent or sediment is separated, and liquid oil is reserved. Because of the large difference in fatty acid structures of different microbial oils, there is a certain complexity in further separating liquid oils.
The arachidonic acid oil is abbreviated as ARA, the fatty acid composition of the ARA has uniqueness, the saturated fatty acid distribution enables the saturated fatty acid distribution to separate solid oil at a low temperature to be lower than 20% or even less, and the saturated fatty acid distribution does not have symmetry, so that crystals which are flocculent and fine in coagulation state can appear in the conventional process for separating solid and liquid oil at a low temperature, longer coagulation time is needed, and the subsequent filtering and separating operation is more difficult, so that the stability of the obtained liquid oil in the storage process is influenced.
In the prior art, a solvent method is generally adopted to cool and purify ARA oil, such as ZL02828043 is added with a solvent such as acetone to help sedimentation of long-chain saturated fatty acid in ARA, but the solvent method needs to obtain a product for desolventizing again, and the method is deviated from the solvent-free extraction and purification technology advocated at present. Meanwhile, in the separation and filtration of microbial oil, the plate-and-frame filtration is widely applied in the actual production process due to the economy and high efficiency, but in the prior art, the plate-and-frame filtration is not effective and economical for obtaining the oil product which still keeps clear and transparent at low temperature after winterizing the microbial oil.
The problem to be solved urgently for separating liquid grease in ARA grease is how to precipitate long-chain saturated fatty acid in ARA grease with low solid fat content in a short time, and the precipitated solid fat can be beneficial to the subsequent separation plate and frame filtration process.
Disclosure of Invention
The invention aims to provide a method for winterization and fractionation of microbial oil, which comprises the following steps:
1) Adding trisaturated fatty glyceride into ARA desolventized oil, and then wintering, wherein the mass ratio of the ARA desolventized oil to the trisaturated fatty glyceride is 2:1-1.25:1; the ratio of saturated fatty acid in the trisaturated fatty acid glyceride is not less than 90%;
2) Filtering and separating the plate frames;
wherein the saturated fatty acid in the trisaturated fatty acid glyceride is long-chain saturated fatty acid with 14-18 carbon atoms.
According to the invention, through a great deal of researches, after the tri-saturated fatty acid glyceride with a specific mass ratio (the ratio of saturated fatty acid is not less than 90%) is added before the winterization step of ARA desolventizing oil requiring plate-and-frame filtration, a great deal of solid fat can be formed and separated out in a short time after winterization. The ARA desolventized oil can be separated and extracted by one-time winterization to obtain a clear and transparent oil product at low temperature.
In the present invention, the trisaturated fatty acid glyceride may be selected from commercially available trisaturated fatty acid glycerides, and may be treated by conventional means as long as the ratio of the corresponding saturated fatty acid in the trisaturated fatty acid glyceride is ensured to be not less than 90%.
In a preferred embodiment of the present invention, the trisaturated fatty acid glycerides used in the present invention are prepared from glycerol and saturated fatty acids under metal base catalysis. The specific preparation method is preferably as follows: mixing glycerol, saturated fatty acid and metal base catalyst according to the mole ratio of 1 (3-5), introducing nitrogen at 180-190 ℃ to stir and react for 24-48h, cooling to 80-85 ℃, adding water to stir for 1-3h, standing and layering, taking supernatant, adding silicon dioxide, stirring for 1-3h at 80-85 ℃, and filtering. Wherein the water is preferably added in an amount of 50 to 100% by mass of the total mass of the oil in the reaction system. The addition amount of the silicon dioxide is preferably 4-8% of the total mass of oil in the reaction system. Wherein, the metal base catalyst is preferably one of sodium hydroxide, potassium hydroxide, sodium methoxide, potassium methoxide, sodium ethoxide and potassium ethoxide.
In the present invention, "%" is mass percent unless otherwise specified.
In the present invention, the saturated fatty acid in the trisaturated fatty acid glyceride is preferably palmitic acid, and the trisaturated fatty acid glyceride is preferably tripalmitin, wherein the proportion of palmitic acid is not less than 90%. In a preferred embodiment of the present invention, the process for the preparation of tripalmitin for use in the present invention comprises the steps of: mixing glycerol, palmitic acid and a catalyst according to the molar ratio of 1 (3-5), introducing nitrogen at 180-190 ℃ to stir and react for 24-48h, cooling to 80-85 ℃, adding water to stir for 1-3h, standing and layering, taking supernatant, adding silicon dioxide, stirring for 1-3h at 80-85 ℃, and filtering.
In a preferred embodiment of the present invention, the step of winterizing comprises:
heating ARA desolventized oil to 80-85 ℃ under the protection of nitrogen, adding the trisaturated fatty glyceride according to the mass ratio, stirring and mixing, cooling to the crystallization temperature while stirring at the average speed of 0.4-3 ℃/h, and preserving the temperature for more than 16h.
In order to further improve the fractionation effect, the average cooling rate is preferably 0.4 to 1 ℃/h.
In a preferred embodiment of the present invention, the specific steps of "plate and frame filtration and fractionation" in step 2) include:
filtering under the pressure of 1-3 bar by using a plate frame machine, and collecting liquid oil. Wherein, the filter cloth of the plate frame machine is preferably 3000 meshes.
In the method, the unsaturated fatty acid glyceride with a specific mass ratio (the ratio of saturated fatty acid is not less than 90%) is added, so that the filtration pressure can be effectively reduced, and the solid ester can be smoothly separated under the condition of 1-1.5bar preferably. The product obtained starts to develop a cloud point after at least 100 hours. The filter cake layer is better formed under the pressure, can intercept other solid grease with fine particle size, and has better soft grease permeability. The higher the pressure, the more fine the fat is penetrated, affecting the level of fat clarity.
And filtering by a plate frame, collecting liquid oil to obtain the ARA grease subjected to winterization and fractionation, and carrying out subsequent product treatment, such as deodorization and the like, according to production requirements. The remaining solid fat in the plate frame is the trisaturated fatty acid glyceride (preferably tripalmitin) used in the method of the invention, the trisaturated fatty acid glyceride can be repeatedly used after simple treatment, in the actual operation process, in order to purify the trisaturated fatty acid glyceride which is repeatedly used, the solid fat in the plate frame can be heated to 40 ℃ for 8 hours, and then the top of the melted fat is blown out by nitrogen to be used for subsequent deodorization, so that other products are produced, and the remaining solid fat in the plate frame is the purified trisaturated fatty acid glyceride.
The ARA desolventized oil in the present invention is an arachidonic acid-rich triglyceride obtained by a fermentation process. It is well known to those skilled in the art that ARA desolventized oils are typically obtained by extracting dry thalli to obtain crude oil, and then hydrating, alkali refining, decolorizing, desolventizing the crude oil.
The method provided by the invention is particularly suitable for ARA desolventizing oil with a fat fixation ratio of not higher than 20% at normal temperature and low temperature (usually lower than 10 ℃), namely in a preferred embodiment of the invention, the fat fixation ratio of the ARA desolventizing oil is not higher than 20%.
The invention also aims to provide a trisaturated fatty acid glyceride for reducing the winterization and fractionation difficulty of microbial oil, and the preparation method of the trisaturated fatty acid glyceride comprises the following steps of:
mixing glycerol, saturated fatty acid and metal base catalyst according to the mole ratio of 1 (3-5), introducing nitrogen at 180-190 ℃ to stir and react for 24-48h, cooling to 80-85 ℃, adding water to stir for 1-3h, standing and layering, taking supernatant, adding silicon dioxide, stirring for 1-3h at 80-85 ℃, and filtering.
In the above scheme, it is preferable to use tripalmitin for reducing the winterization and fractionation difficulty of microbial oil, and the preparation method of tripalmitin comprises the following steps:
mixing glycerol, palmitic acid and a metal catalyst according to the molar ratio of 1 (3-5), introducing nitrogen at 180-190 ℃ to stir and react for 24-48h, cooling to 80-85 ℃, adding water to stir for 1-3h, standing and layering, taking supernatant, adding silicon dioxide, stirring for 1-3h at 80-85 ℃, and filtering to obtain the catalyst.
In the above scheme, the water is preferably added in an amount of 50 to 100% by mass of the total mass of the oil in the reaction system. The addition amount of the silicon dioxide is preferably 4-8% of the total mass of oil in the reaction system. The metal base catalyst may be sodium hydroxide, potassium hydroxide, sodium methoxide, potassium methoxide, sodium ethoxide, or potassium ethoxide.
The invention provides a method for winterization and fractionation of microbial oil, which is particularly suitable for ARA desolventizing oil with solid fat ratio not higher than 20% at normal temperature, can form a large number of crystal forms with good stability in ARA desolventizing oil in a short time, can keep particle forms for a long time, is convenient for effective separation, is a method for purifying the oil, can effectively reduce the difficulty of subsequent plate and frame filtration and fractionation, can obtain clear and transparent oil products at low temperature after the ARA desolventizing oil is subjected to winterization and fractionation once, uses common winterization and fractionation equipment, can be repeatedly recycled, has less use time, and is suitable for mass production. The grease product obtained by the method has excellent clarity, high freezing resistance and easy industrialization.
Detailed Description
The following describes the embodiments of the present invention in further detail with reference to examples. The following examples are illustrative of the invention and are not intended to limit the scope of the invention.
Unless otherwise specified, the preparation method of tripalmitin (PPP) prepared in the examples of the present invention is:
(1) The glycerol and the palmitic acid are selected to prepare high-purity tripalmitin (PPP) under the catalysis of metal base. The two raw materials (glycerin and palmitic acid) and a metal base catalyst are mixed according to the mol ratio of 1:3:3, and nitrogen is introduced at 180 ℃ to stir and react for 24 hours.
(2) Cooling to 80 ℃, adding 85 ℃ pure water with the weight of 50% (w: w) of the mixed oil, stirring for 1h at 80-85 ℃, and standing for layering.
(3) Adding 5% (w: w) silicon dioxide with the weight of oil into the supernatant fluid obtained in the step (2), stirring for 1h at 80-85 ℃, and filtering to obtain tripalmitin PPP with the PPP content of 92% for later use.
Example 1
800kg of ARA refined desolventized oil (solid fat ratio is 18%) with the oil temperature of 85 ℃ is added into 640kg with the oil temperature of 80-85 ℃ to prepare PPP to be mixed for 1h at the rotating speed of 100rpm, and then the mixture is transferred into 2m 3 The winterization tank is cooled at an average speed of 2 ℃/h under the rotation speed of 15rpm, and the temperature is kept for 16h by keeping the rotation speed of 15rpm when the temperature is reduced to 0 ℃.
A plate frame machine provided with 3000 mesh filter cloth through a filtration area of 10 square meters:
(1) When the filtration pressure of 1bar is used, the liquid oil filtration speed is steadily reduced, and the filtration pressure needs to be increased.
(2) 650kg of liquid oil were collected at a maximum filtration pressure of 1.5 bar. 5g of the oil is put into a glass bottle with a sealing cover, is filled with nitrogen for protection and is sealed by an upper cover, is placed into a water area with the temperature of 0 ℃ for testing, and the cloud point of the oil in the bottle begins to appear when the oil is observed for 168 hours; the solid fat obtained in the previous fractionation is hard and hard at room temperature and is not easy to soften, and the particle size is detected to be 150-250 mu m.
Example 2
The method provided in this example is substantially the same as that of example 1, except that the average cooling rate at the time of crystallization is adjusted to 1 deg.c/h.
A plate frame machine provided with 3000 mesh filter cloth through a filtration area of 10 square meters:
(1) At a filtration pressure of 1bar, the liquid oil filtration rate steadily decays slightly without increasing the filtration pressure.
(2) Collecting 544kg of liquid oil under the highest filtering pressure of 1bar, putting 5g of liquid oil into a glass bottle with a sealing cover, filling nitrogen for protection, sealing the glass bottle with the sealing cover, placing the glass bottle in a water area at 0 ℃ for testing, and observing that no cloud point exists in 168 hours; the solid fat obtained in the previous fractionation is hard and hard at room temperature and is not easy to soften, and the particle size is detected to be 240-300 mu m.
Example 3
800kg of ARA refined desolventized oil (solid fat ratio is 18%) with the oil temperature of 85 ℃ is added into 400kg with the oil temperature of 80-85 ℃ at the rotation speed of 100rpm to prepare PPP, mixed for 1h, and then transferred into 2m 3 The winterization tank is cooled at an average speed of 1 ℃/h under the rotation speed of 15rpm, and the temperature is kept for 16h by keeping the rotation speed of 15rpm when the temperature is reduced to 0 ℃.
A plate frame machine provided with 3000 mesh filter cloth through a filtration area of 10 square meters:
(1) At a filtration pressure of 1bar, the liquid oil filtration rate steadily decays slightly without increasing the filtration pressure.
(2) Under the highest filtering pressure of 1bar, 636kg of liquid oil is collected, 5g of liquid oil is taken and put into a glass bottle with a sealing cover, the glass bottle is filled with nitrogen for protection and sealed by an upper cover, and the glass bottle is placed in a water area with the temperature of 0 ℃ for testing, and the cloud point is observed to not appear in 168 hours; the solid fat obtained in the previous fractionation is hard and hard at room temperature and is not easy to soften, and the particle size is detected to be 200-270 mu m.
Example 4
The method provided in this example was substantially the same as that of example 3, except that the average cooling rate at the time of crystallization was adjusted to 0.4 ℃/h.
A plate frame machine provided with 3000 mesh filter cloth through a filtration area of 10 square meters:
(1) At a filtration pressure of 1bar, the liquid oil filtration rate steadily decays slightly without increasing the filtration pressure.
(2) Collecting 628kg of liquid oil under the highest filtering pressure of 1bar, putting 5g of liquid oil into a glass bottle with a sealing cover, filling nitrogen for protection, sealing the glass bottle with the sealing cover, placing the glass bottle in a water area at 0 ℃ for testing, and observing that no cloud point exists in 168 hours; the solid fat obtained in the previous fractionation is hard and hard at room temperature and is not easy to soften, and the particle size is detected to be 280-310 mu m.
Example 5
The method provided in this example is substantially the same as that of example 3, except that: the tripalmitin PPP used in this example was commercially available tripalmitin PPP, and was isolated by solvent fractionation to a palmitic acid fraction of >90%.
A plate frame machine provided with 3000 mesh filter cloth through a filtration area of 10 square meters:
(1) At a filtration pressure of 1bar, the liquid oil filtration rate steadily decays slightly without increasing the filtration pressure.
(2) 628kg of liquid oil were collected at a maximum filtration pressure of 1 bar. 5g of the mixture is put into a glass bottle with a sealing cover, is filled with nitrogen for protection and is sealed by an upper cover, and is placed into a water area at 0 ℃ for testing, and the cloud point is observed to be not appear for 168 hours; the solid fat obtained in the previous step is hard and hard at room temperature and is not easy to soften, and the particle size is detected to be 220-300 mu m.
Example 6
The method provided in this example is substantially the same as that of example 3 except that the tripalmitin PPP used in this example is commercially available tripalmitin PPP, and the fractionation is carried out by a solvent method so that the palmitic acid content thereof is 83%.
A plate frame machine provided with 3000 mesh filter cloth through a filtration area of 10 square meters:
(1) When the filtration pressure of 1bar is used, the liquid oil filtration speed is steadily reduced, and the filtration pressure needs to be increased.
(2) Collecting 635kg of liquid oil under the highest filtering pressure of 1.5bar, putting 5g of liquid oil into a glass bottle with a sealing cover, filling nitrogen for protection, sealing with the upper cover, placing into a water area at 0 ℃ for testing, and observing the cloud point appearing in 120 hours; the solid fat obtained in the previous step is hard and hard at room temperature and is not easy to soften, and the particle size is detected to be 180-260 mu m.
Example 7
The glyceryl tristearate sss used in this example was commercially available and was fractionated by solvent fractionation to give a stearic acid fraction of >90%.
800kg of ARA refined desolventized oil (fat fraction 18%) at 90℃was transferred to 2m at 400kg sss 3 The winterization tank is cooled at the average speed of 1 ℃/h directly under the rotation speed of 15rpm, and the temperature is kept for 16h by keeping the rotation speed of 15rpm when the temperature is reduced to 0 ℃.
A plate frame machine provided with 3000 mesh filter cloth through a filtration area of 10 square meters:
(1) At a filtration pressure of 1bar, the liquid oil filtration rate steadily decays slightly without increasing the filtration pressure.
(2) 560kg of liquid oil were collected at a maximum filtration pressure of 1.0 bar. 5g of the mixture is put into a glass bottle with a sealing cover, is filled with nitrogen for protection and is sealed by an upper cover, and is placed into a water area at 0 ℃ for testing, and the cloud point is observed to be not appear for 168 hours; the solid fat obtained in the previous fractionation is hard and hard at room temperature and is not easy to soften, and the particle size is detected to be 200-250 mu m.
Example 8
The method provided in this example was substantially the same as that of example 1, except that the average cooling rate at the time of crystallization was adjusted to 3 ℃/h.
A plate frame machine provided with 3000 mesh filter cloth through a filtration area of 10 square meters:
(1) When using a filtration pressure of 1bar, the liquid oil filtration rate decays faster in the early stage, and the filtration pressure needs to be increased.
(2) Collecting 685kg of liquid oil under the highest filtering pressure of 2bar, putting 5g into a glass bottle with a sealing cover, filling nitrogen for protection, sealing with the upper cover, placing into a water area at 0 ℃ for testing, and observing the cloud point of grease in the bottle after 5 min; the solid fat separated and extracted in the previous time is soft and easy to melt at room temperature, and the particle size is detected to be 10-70 mu m.
Comparative example 1
800kg of ARA refined desolventized oil (solid fat ratio is 18%) with the oil temperature of 85 ℃ is transferred to 2m in a blending tank 3 The winterization tank is cooled to 0 at an average speed of 1 ℃/h directly under a rotation speed of 15rpmMaintaining the rotation speed at 15rpm for 16h.
A plate frame machine provided with 3000 mesh filter cloth through a filtration area of 10 square meters:
(1) When the filtration pressure of 1bar is used, the liquid oil filtration speed is steadily reduced, and the filtration pressure needs to be increased.
(2) Collecting 650kg of liquid oil under the highest filtering pressure of 2.5bar, putting 5g into a glass bottle with a sealing cover, filling nitrogen for protection, sealing with the upper cover, placing into a water area at 0 ℃ for testing, and observing the cloud point of the grease in the bottle after 5 min; the separated solid fat is soft and easy to melt at room temperature, and the particle size is detected to be 10-70 mu m.
Comparative example 2
800kg of ARA refined desolventized oil (solid fat ratio 20%) with 40kg of prepared PPP at the oil temperature of 85 ℃ is transferred into a 2m blending tank 3 The winterization tank is cooled at the average speed of 0.4 ℃/h directly under the rotation speed of 15rpm, and the temperature is kept for 16h by keeping the rotation speed of 15rpm when the temperature is reduced to 0 ℃.
A plate frame machine provided with 3000 mesh filter cloth through a filtration area of 10 square meters:
(1) When the filtration pressure of 1bar is used, the liquid oil filtration speed is steadily reduced, and the filtration pressure needs to be increased.
(2) Collecting 642kg of liquid oil under the highest filtering pressure of 1.5bar, putting 5g of liquid oil into a glass bottle with a sealing cover, filling nitrogen for protection, sealing the glass bottle with the sealing cover, placing the glass bottle in a water area at 0 ℃ for testing, and observing the cloud point to appear for about 18 hours; the solid fat obtained in the previous step is hard at room temperature but is easy to soften, and the particle size is detected to be 70-250 mu m.
In the embodiment 1, the yield of the soft fat product is 81.3%, the highest filtration pressure of 1.5bar is needed for fractionation, and the product is mixed with solid fat and has weak freezing resistance; the yield of the soft fat product in the example 2 is 68%, the yield of the product is reduced due to the larger PPP addition amount, but the product has no solid fat which can be formed at 0 ℃ and has strong freezing resistance; the yield of the soft fat product of the embodiment 3 is 79.5%, the solid fat crystal grains are large and are easy to filter and press, the highest filtering pressure of 1bar is only needed for fractionation, and the freezing resistance is strong. The yield of the soft grease product in the embodiment 4 is 78.5%, and the product also has the characteristic of strong freezing resistance, but the cooling rate is reduced, so that the working hour capacity is affected. Example 5 provides a slightly poorer effect than examples 3 and 4. The tripalmitin added in example 6 was of lower purity and had smaller grains during winterization and required increased pressure to be effective for filtration. Example 7 used glycerol tristearate sss with a stearic acid ratio >90% and was slightly less effective than glycerol tripalmitate. The yield of the soft fat product of example 8 was 104.4%, and the fractionation required a maximum filtration pressure of 2bar due to the presence of fine solid fat grains, and the freezing resistance was poor due to the solid fat mixed in the product. The comparative example 1 has smaller grains, and the separation effect is poor when the grains are separated by higher pressure, so that the cloud point appears in the freezing resistance experiment. The yield of the soft fat product in comparative example 2 is 80.3%, and the fractionation requires a maximum filtration pressure of 1.5bar due to the existence of fine solid fat crystal grains, and the product is mixed with a small amount of solid fat and has general freezing resistance.
Finally, the method of the present invention is only a preferred embodiment and is not intended to limit the scope of the present invention. Any modification, equivalent replacement, improvement, etc. made within the spirit and principle of the present invention should be included in the protection scope of the present invention.
Claims (8)
1. The winterization and fractionation method for the microbial oil is characterized by comprising the following steps of:
1) Adding trisaturated fatty glyceride into ARA desolventized oil, and then wintering, wherein the mass ratio of the ARA desolventized oil to the trisaturated fatty glyceride is 2:1-1.25:1; the ratio of saturated fatty acid in the trisaturated fatty acid glyceride is not less than 90%; the winterization method specifically comprises the following steps:
heating ARA desolventized oil to 80-85 ℃ under the protection of nitrogen, adding the trisaturated fatty glyceride according to the mass ratio, stirring and mixing, cooling to the crystallization temperature while stirring at the average speed of 0.4-1 ℃/h, and preserving the temperature for more than 16 hours;
2) Filtering and separating the plate frames;
wherein the saturated fatty acid in the tri-saturated fatty acid glyceride is palmitic acid; the trisaturated fatty acid glyceride is tripalmitin.
2. The method according to claim 1, wherein the trisaturated fatty acid glyceride is produced from glycerin and a saturated fatty acid under the catalysis of a metal base.
3. The method according to claim 2, wherein the method for preparing the trisaturated fatty acid glyceride comprises the steps of:
mixing glycerol, saturated fatty acid and metal base catalyst according to the mole ratio of 1 (3-5), introducing nitrogen at 180-190 ℃ to stir and react for 24-48h, cooling to 80-90 ℃, adding water to stir for 1-3h, standing and layering, taking supernatant, adding silicon dioxide, stirring for 1-3h at 80-90 ℃, and filtering.
4. A method according to claim 3, wherein the water is added in an amount of 50 to 100% of the total mass of oil in the reaction system, and the silica is added in an amount of 4 to 8% of the total mass of oil in the reaction system.
5. The method according to claim 3 or 4, wherein the metal base catalyst is one or more of sodium hydroxide, potassium hydroxide, sodium methoxide, potassium methoxide, sodium ethoxide, and potassium ethoxide.
6. The method of claim 1, wherein the ARA desolventizing oil has a fat solids fraction of no more than 20%.
7. The method according to claim 1, wherein the specific step of "plate-and-frame filtration fractionation" in step 2) comprises:
and filtering by using a plate frame machine under the highest filtering pressure of 1-3 bar, and collecting liquid oil.
8. The method of claim 7, wherein the filter cloth of the frame machine is 3000 mesh.
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| WO2014007254A1 (en) * | 2012-07-03 | 2014-01-09 | 不二製油株式会社 | Method for promoting crystallization of fats and oils |
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