CN113087586A - Method for extracting multiple active ingredients from deodorized distillate - Google Patents

Method for extracting multiple active ingredients from deodorized distillate Download PDF

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CN113087586A
CN113087586A CN202110353994.5A CN202110353994A CN113087586A CN 113087586 A CN113087586 A CN 113087586A CN 202110353994 A CN202110353994 A CN 202110353994A CN 113087586 A CN113087586 A CN 113087586A
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distillate
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deodorized
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vitamin
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邱建国
梁玉龙
谢杰华
翁庆水
林宜明
钟由源
邓超
郑俊华
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Fujian Glanny Bio-Engineering Co ltd
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Abstract

The invention provides a method for extracting multiple active ingredients from deodorized distillate, which comprises the following steps: s1, adding methanol and lipase into the deodorized distillate to perform esterification reaction; s2, carrying out cold separation on the esterification product and filtering to obtain sterol; s3, carrying out three-stage molecular distillation on the filtrate obtained in the step S2 to obtain a primary vitamin E extract with the content of 10-27 wt%; s4, carrying out five-stage high vacuum rectification on the primary vitamin E extract distilled in the step S3 as a raw material to respectively rectify squalene, soybean vitamin E and alpha vitamin E. The method can extract multiple active ingredients by a set of process, and has simple operation and low cost.

Description

Method for extracting multiple active ingredients from deodorized distillate
Technical Field
The invention relates to a method for extracting multiple active ingredients from deodorized distillate, and belongs to the technical field of deodorized distillate treatment.
Background
The deodorized distillate is vegetable oil leftover produced in the production and refining process of corn oil, rapeseed oil, peanut oil, sunflower seed oil, palm oil and other food oil. Deodorized distillates contain a large amount of useful components. Such as squalene, sterols, vitamin e (ve), and the like. Wherein the VE content is 2-8 wt% (wherein the alpha VE accounts for 20-35 wt%); the sterol content is 2-8 wt%; the acid value is 100 to 140 mgKOH/g.
The extraction of these various active ingredients from deodorized distillates is of great economic value. However, since the components of the deodorized distillate are complex, each active component needs to be purified separately by different processes, and the operation is complex and the cost is high. Furthermore, the conventional extraction method of VE is difficult to purify to more than 50%. In addition, the natural high-purity alpha VE on the market can not be directly extracted from materials, and is prepared by firstly extracting mixed vitamin E, and then converting other 3 types of VE (beta VE, gamma VE and delta VE) into alpha VE through methylation and subsequent hydrotreating, so that the operation is complex and the cost is high.
Disclosure of Invention
The invention provides a method for extracting multiple active ingredients from deodorized distillate, which can simultaneously extract multiple active ingredients by a set of process and can effectively solve the problems.
The invention is realized by the following steps:
a method for extracting multiple active ingredients from deodorized distillate comprises the following steps:
s1, adding methanol and lipase into the deodorized distillate to perform esterification reaction;
s2, carrying out cold separation on the esterification product and filtering to obtain sterol;
s3, carrying out three-stage molecular distillation on the filtrate obtained in the step S2 to obtain a primary vitamin E extract with the content of 10-27 wt%;
s4, carrying out five-stage high vacuum rectification on the primary vitamin E extract distilled in the step S3 as a raw material to respectively rectify squalene, soybean vitamin E and alpha vitamin E.
In a further improvement, the addition amount of the lipase is 0.5-1 wt% of the deodorized distillate, and the addition amount of the methanol is 10-15 wt% of the deodorized distillate.
As a further improvement, the reaction temperature of the esterification reaction is 30-50 ℃, the reaction time is 6-12 h, and the reaction pH is 6.8-7.2.
As a further improvement, the operation of cold separation is that the temperature is reduced by 2 ℃ per hour, the mixture is slowly stirred, and after the temperature is reduced to 8-10 ℃, the heat is preserved and the crystal is grown for 7.5-8.5 hours.
As a further improvement, the film scraping temperature of the three-stage molecular distillation is 90-130 ℃; the primary temperature is 100-175 ℃, and the vacuum degree is not more than 120 Pa; the secondary temperature is 100-155 ℃, and the vacuum degree is not more than 30 Pa; the three-stage temperature is 200-250 ℃, and the vacuum degree is not more than 30 Pa.
As a further improvement, the vacuum degree of the high vacuum rectification is not more than 10 Pa; the primary temperature is 200 +/-2 ℃, and the distillate accounts for 10-15 wt% of the raw materials; the secondary temperature is 210-225 ℃, and the distillate accounts for 10-15 wt% of the raw materials; the third-stage temperature is 225-240 ℃, and the distillate accounts for 8-12 wt% of the raw materials; the fourth-stage temperature is 245-260 ℃, and the distillate accounts for 30-40 wt% of the raw materials; the fifth-level temperature is 270 +/-5 ℃, and the distillate accounts for 15-20 wt% of the raw materials.
As a further improvement, the high vacuum rectification secondary distillate is also extracted to obtain squalene.
As a further improvement, the extraction method is as follows: dissolving the secondary distillate by using an extraction solvent, then adding 0.5-1 mol/L sodium hydroxide or potassium hydroxide ethanol solution, and stirring for 0.5-2 h at the temperature of 60-85 ℃; washing with saturated NaCl solution to neutrality; and carrying out reduced pressure distillation to recover the extraction solvent to obtain squalene.
As a further improvement, the extraction solvent is one or more of n-hexane, diethyl ether, petroleum ether and the like.
As a further improvement, the five-stage distillate of the high vacuum rectification is further subjected to resin adsorption and purification to obtain the alpha vitamin E.
The invention has the beneficial effects that:
the method extracts various active ingredients such as sterol by cold separation through a set of process of esterification, cold separation, three-stage molecular distillation and five-stage high vacuum rectification, wherein the second-stage distillation component of the high vacuum rectification is squalene, the fourth-stage distillation component is soybean oil VE, and the fifth-stage distillation component is original high alpha VE, and the method is simple to operate and low in cost.
The method has the advantages that the extraction rate of squalene, sterol and original ecological high alpha VE is high.
The four-stage distillate component of the five-stage high vacuum rectification contains about 50 wt% of VE, wherein the content of alpha VE is about 10%, which is equivalent to that of soybean VE extracted from soybean oil after esterification, cold separation and molecular distillation, and has high value. In addition, the invention has the important significance that the deodorization distillate with fixed acid value can be prepared, and each parameter can be accurately controlled, so that the deodorization distillate can be produced and applied in large scale, and different deodorization distillates from different regions or manufacturers do not need to be tested and the optimal production parameter is determined, so that the time can be greatly saved, and the deodorization distillate can be widely applied to different deodorization distillates from different regions or manufacturers.
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In order to more clearly illustrate the technical solutions of the embodiments of the present invention, the drawings that are required to be used in the embodiments will be briefly described below, it should be understood that the following drawings only illustrate some embodiments of the present invention and therefore should not be considered as limiting the scope, and for those skilled in the art, other related drawings can be obtained according to the drawings without inventive efforts.
FIG. 1 is a flow diagram of a process for extracting multiple active ingredients from deodorized distillates as provided in an embodiment of the present invention.
Detailed Description
In order to make the objects, technical solutions and advantages of the embodiments of the present invention more apparent, the technical solutions of the embodiments of the present invention will be described clearly and completely with reference to the accompanying drawings of the embodiments of the present invention, and it is obvious that the described embodiments are some, but not all embodiments of the present invention. All other embodiments, which can be obtained by a person skilled in the art without any inventive step based on the embodiments of the present invention, are within the scope of the present invention. Thus, the following detailed description of the embodiments of the present invention, presented in the figures, is not intended to limit the scope of the invention, as claimed, but is merely representative of selected embodiments of the invention. All other embodiments, which can be obtained by a person skilled in the art without any inventive step based on the embodiments of the present invention, are within the scope of the present invention.
In the description of the present invention, the terms "first" and "second" are used for descriptive purposes only and are not to be construed as indicating or implying relative importance or implying any number of technical features indicated. Thus, a feature defined as "first" or "second" may explicitly or implicitly include one or more of that feature. In the description of the present invention, "a plurality" means two or more unless specifically defined otherwise.
Referring to fig. 1, an embodiment of the present invention provides a method for extracting a plurality of active ingredients from deodorized distillate, including the steps of:
s1, adding methanol and lipase to the deodorized distillate to perform an esterification reaction.
S2, carrying out cold separation on the esterification product, and filtering to obtain the sterol.
S3, carrying out three-stage molecular distillation on the filtrate obtained in the step S2 to obtain a primary vitamin E extract with the content of 10-27 wt%.
S4, carrying out five-stage high vacuum rectification on the primary vitamin E extract distilled in the step S3 as a raw material to respectively rectify squalene, soybean vitamin E and alpha vitamin E.
As a further improvement, the deodorized distillate is a non-soybean deodorized distillate, and is selected from corn deodorized distillate, rapeseed deodorized distillate, peanut deodorized distillate, sunflower seed deodorized distillate or palm deodorized distillate. In step S1, since the acid value of different deodorized distillates from different regions or manufacturers is different, it is further necessary to measure the acid value of the same kind of deodorized distillates during the actual production process, and mix and compound the deodorized distillates according to the actually measured value, so as to form the non-soybean deodorized distillate with fixed acid value, which is beneficial to the subsequent processing. Preferably, the deodorized distillate is selected from corn deodorized distillate with acid value of 125-135, rapeseed deodorized distillate, peanut deodorized distillate, sunflower seed deodorized distillate and palm deodorized distillate. In one embodiment, the deodorized distillate is selected from corn oil deodorized distillate with acid value of about 125; in another embodiment, the distillate is selected from rapeseed oil deodorized distillate with acid value of about 130.
In a further improvement, the addition amount of the lipase is 0.5-1 wt% of the deodorized distillate, the addition amount of the methanol is 10-15 wt% of the deodorized distillate, the reaction temperature of the esterification reaction is 30-50 ℃, the reaction time is 6-12 h, and the reaction pH is 6.8-7.2. The esterification reaction can convert fatty acid into fatty acid methyl ester, reduce the boiling point and facilitate the separation from VE during the subsequent molecular distillation.
As a further improvement, the cold separation operation is that the temperature is reduced by 2 ℃ per hour, the mixture is slowly stirred, and after the temperature is reduced to 8-10 ℃, the heat is preserved and the crystal is grown for 7.5-8.5 hours, so that the operation can effectively carry out cold separation on the sterol.
As a further improvement, the film scraping temperature of the three-stage molecular distillation is 90-130 ℃; the primary temperature is 100-175 ℃, and the vacuum degree is not more than 120 Pa; the secondary temperature is 100-155 ℃, and the vacuum degree is not more than 30 Pa; the three-stage temperature is 200-250 ℃, and the vacuum degree is not more than 30 Pa.
As a further improvement, the vacuum degree of the high vacuum rectification is not more than 10 Pa. The primary temperature is 200 +/-2 ℃, and the distillate accounts for 10-15 wt% of the raw materials. The secondary temperature is 210-225 ℃, the distillate accounts for 10-15 wt% of the raw material, and the squalene content in the distillate is 70-80 wt%. The third temperature is 225-240 ℃, the distillate accounts for 8-12 wt% of the raw material, the VE content in the distillate is 20-30 wt%, and the alpha VE content is 1 wt%. The temperature of the fourth stage is 245-260 ℃, the distillate accounts for 30-40 wt% of the raw material, the VE content in the distillate reaches about 50 wt%, wherein the alpha VE content is about 10 wt%, and the value is high, which is equivalent to that of the soybean VE extracted after the soybean oil is subjected to esterification, cold separation and molecular distillation. The fifth-level temperature is 270 +/-5 ℃, the distillate accounts for 15-20 wt% of the raw materials, the VE content in the distillate is about 25 wt%, and the alpha VE content is more than 90 wt%.
As a further improvement, the high vacuum rectification secondary distillate is also extracted to obtain squalene. The extraction method comprises the following steps: dissolving the secondary distillate by using an extraction solvent, then adding 0.5-1 mol/L sodium hydroxide or potassium hydroxide ethanol solution, and stirring for 0.5-2 h at the temperature of 60-85 ℃; washing with saturated NaCl solution to neutrality; and carrying out reduced pressure distillation to recover the extraction solvent to obtain squalene. The extraction solvent is one or more of n-hexane, diethyl ether, petroleum ether, etc. The extraction method can further improve the purity of squalene.
As a further improvement, the five-stage distillate of the high vacuum rectification is further subjected to resin adsorption and purification to obtain the alpha vitamin E. Further improving the purity of the alpha-vitamin E. The resin is strong-base anion resin, the solvent is ethanol, and the resolving agent is carbon dioxide.
The vitamin E in the embodiment of the invention is measured by a method of national standard GB 1886.233-2016.
Example 1
1. Esterification: adopting corn oil deodorized distillate, the indexes are as follows: acid value 125.32, VE content 3.26 wt% (wherein. alpha. VE accounts for 25.17 wt%), sterol content 3.54 wt%, squalene content 2.52 wt%; carrying out lipase-catalyzed esterification reaction, adding 5000Kg of deodorized distillate, 60Kg of 16 wt% NaOH aqueous solution, adding 200Kg of methanol, stirring for 20 minutes, keeping the temperature at 30-50 ℃, and adding 25Kg of lipase; after reacting for 2 hours, adding 200Kg of methanol; continuously reacting for 2 hours, adding 200Kg of methanol, and detecting the acid value after 2 hours, wherein the acid value is lower than 5mgKOH/g, and the reaction is finished; if the acid value is more than 5mgKOH/g, the reaction is continued until the acid value is less than 5 mgKOH/g. The process is to convert fatty acids to fatty acid methyl esters, lower the boiling point, and facilitate separation from VE during subsequent molecular distillation.
2. Cold separation: after the esterification reaction is finished, transferring the mixture to a cold separation kettle, slowly cooling the mixture at a cooling speed of 2 ℃/h, slowly stirring the mixture, cooling the mixture to 8-10 ℃, keeping the temperature, growing the crystals for 8 hours, and performing plate-and-frame filter pressing. This process is for the extraction of phytosterols.
3. Molecular distillation: carrying out molecular distillation on the filtrate subjected to plate-and-frame filter pressing, wherein the molecular distillation parameters are shown in the following table 1:
TABLE 1
Figure BDA0003003001350000071
Figure BDA0003003001350000081
4. The VE primary extract (650Kg, total VE content 23.51 wt%) distilled out of the three stages of molecular distillation was used as the starting material for high vacuum rectification with the parameters as shown in Table 2.
TABLE 2
Figure BDA0003003001350000082
(1) And rectifying the primary VE extract containing 23.51 wt% VE in a rectifying tower at the system pressure of 9pa and the temperature of 200 +/-2 ℃, and collecting 85Kg of front fraction without VE.
(2) And continuously rectifying the mixture at the system pressure of 9pa and the temperature of 215 +/-2 ℃, and collecting 65Kg of crude squalene, wherein the VE content is 1.05 wt% and the squalene content is 76.8 wt%.
(3) And continuously rectifying at the system pressure of 9pa and the temperature of 230 +/-2 ℃, and collecting 80Kg of component (low-VE crude product I) containing 25.26 percent of VE, wherein the content of alpha VE is 1.01 percent by weight.
(4) Continuously rectifying when the system pressure is 9pa and the temperature is 250 +/-2 ℃, and collecting and obtaining 200Kg of component (50VE crude product) containing 50.68 percent VE, wherein the content of alpha VE is 10.33 percent by weight; beta VE1.75wt%, gamma VE61.26wt%, delta VE26.66wt%. The 50.68% VE component is vitamin E having a level of soy vitamin E closest to that of soy vitamin E, and thus can replace existing soy vitamin E. In other words, the process parameters of molecular distillation and high vacuum distillation in example 1 are most suitable for the corn oil deodorized distillate with acid value of 125.32, which can produce vitamin E with content of soybean vitamin E closest to that of soybean vitamin E, thereby replacing the existing soybean vitamin E. In addition, through a large number of comparative tests, the change of acid value, the change of temperature and the system pressure can cause the final produced vitamin E component to have larger difference with the soybean vitamin E. Therefore, the important significance of the invention is that the corn oil deodorized distillate with the fixed acid value of 125.32 can be prepared, and each parameter can be accurately controlled, so that the corn oil deodorized distillate can be produced and applied on a large scale without testing different corn oil deodorized distillates and determining the optimal test parameter. In addition, the invention has another important meaning that the extraction of the soybean vitamin E from non-soybean plants is realized, thereby having wide application prospect.
(5) Continuously rectifying the mixture at the system pressure of 9pa and the temperature of 270 +/-2 ℃, and collecting 120Kg of a component (low-VE crude product II) containing 25.58 percent of VE; wherein the content of alpha VE is 90.45 wt%. 100Kg of residue remained.
(6) Dissolving 65Kg of rectified squalene crude product by 130L of petroleum ether, and then adding 9.25Kg of 1mol/L sodium hydroxide ethanol solution; stirring for 1 hour at 85 ℃; washing with saturated NaCl solution to neutrality; vacuum distillation is carried out to recover the solvent, thus obtaining 49Kg of squalene, the content of which is 95.08 wt% and the yield of which is 93.33%.
(7) And carrying out resin adsorption on the collected component (low-VE crude product II) containing 25.58% of VE: and (3) uniformly mixing the low-VE crude product II and ethanol according to the mass-to-volume ratio of 1:2, adsorbing by using strong-base anion resin, resolving by using carbon dioxide, and recovering ethanol to obtain 33Kg of pure natural original ecological high-alpha VE with the content of 91.58 wt%.
Example 2
1. Esterification: adopting rapeseed oil deodorized distillate, the indexes are as follows: acid value 130.15, VE content 3.42 wt%, alpha VE 35.29 wt%, sterol 3.65 wt%, and squalene 3.05 wt%; carrying out lipase catalysis esterification reaction, adding 5000Kg of deodorized distillate, 60Kg of 16 wt% NaOH aqueous solution, adding 200Kg of methanol, stirring for 20 minutes, keeping the temperature at 30-50 ℃, and adding 25Kg of lipase; after reacting for 2 hours, adding 200Kg of methanol; continuously reacting for 2 hours, adding 200Kg of methanol, and detecting the acid value after 2 hours, wherein the acid value is lower than 5mgKOH/g, and the reaction is finished; if the acid value is more than 5mgKOH/g, the reaction is continued until the acid value is less than 5 mgKOH/g. The process is to convert fatty acids to fatty acid methyl esters, lower the boiling point, and facilitate separation from VE during subsequent molecular distillation.
2. Cold separation: after the esterification reaction is finished, transferring the mixture to a cold separation kettle, slowly cooling the mixture at a cooling speed of 2 ℃/h, slowly stirring the mixture, cooling the mixture to 8-10 ℃, keeping the temperature, growing the crystals for 8 hours, and performing plate-and-frame filter pressing. This process is for the extraction of phytosterols.
3. Molecular distillation: and (3) carrying out molecular distillation on the filtrate subjected to plate-and-frame filter pressing, wherein the molecular distillation parameters are shown in the following table 3:
TABLE 3
Figure BDA0003003001350000101
Figure BDA0003003001350000111
5. The VE primary extract obtained by three-stage distillation in molecular distillation is used as raw material to carry out high vacuum rectification, and the parameters are shown in the following table 4.
TABLE 4
Figure BDA0003003001350000112
1. At a system pressure of 8pa and a temperature of 200 +/-2 ℃, rectifying the VE primary extract containing 24.61 wt% of VE in a rectifying tower, and collecting 80Kg of front fraction without VE.
2. And (3) continuously rectifying at the system pressure of 8pa and the temperature of 220 +/-2 ℃, and collecting 75Kg of squalene crude product, wherein the VE content is 1.15 wt%, and the squalene content is 72.16 wt%.
3. Continuously rectifying at the system pressure of 8pa and the temperature of 235 +/-2 ℃, and collecting 60Kg of component (low VE crude product I) containing 25.36 percent of VE, wherein the content of alpha-VE is 1.52 percent by weight.
4. The rectification is continued at the system pressure of 8pa and the temperature of 255 +/-2 ℃, and 220Kg of component (50VE crude product) containing 50.85 percent of VE is collected, wherein the alpha-VE content is 10.51 percent by weight, the beta VE1.78percent by weight, the gamma VE61.35percent by weight and the delta VE26.9percent by weight. The technological parameters of molecular distillation and high vacuum distillation in example 2 are most suitable for rapeseed oil deodorized distillate with acid value of 130.15, which can produce vitamin E with content of soybean vitamin E closest to that of soybean vitamin E, thus being capable of replacing the existing soybean vitamin E. Of course, the composition of vitamin E in example 1 is closer to soy vitamin E than the vitamin composition in example 2 from a practical parameter point of view. In addition, the rapeseed oil deodorized distillate with the fixed acid value of 130.15 is prepared, and each parameter is accurately controlled, so that the rapeseed oil deodorized distillate can be produced and applied in a large scale without testing different rapeseed oil deodorized distillates and determining the optimal test parameters.
5. Continuously rectifying at the system pressure of 8pa and the temperature of 270 +/-2 ℃, and collecting 126Kg of component (low VE crude product II) containing 26.02% of VE; wherein the content of alpha-VE is 92.17 wt%. Leaving 95Kg of residue.
6. Dissolving 75Kg of rectified squalene crude product by using 150L of n-hexane, and then adding 9.25Kg of 1mol/L sodium hydroxide ethanol solution; stirring for 1 hour at 85 ℃; washing with saturated NaCl solution to neutrality; vacuum distilling to recover solvent to obtain squalene 53Kg with content of 95.18 wt% and yield of 93.21%.
7. The fraction collected containing 26.02% VE (crude low VE II) was subjected to resin adsorption: and (3) uniformly mixing the low-VE crude product II and ethanol according to the mass-to-volume ratio of 1:2, adsorbing by using strong-base anion resin, resolving by using carbon dioxide, and recovering ethanol to obtain 36Kg of pure natural original ecological high-alpha VE with the content of 90.81 wt%.
The above description is only a preferred embodiment of the present invention and is not intended to limit the present invention, and various modifications and changes may be made by those skilled in the art. Any modification, equivalent replacement, or improvement made within the spirit and principle of the present invention should be included in the protection scope of the present invention.

Claims (10)

1. A method for extracting a plurality of active ingredients from deodorized distillate is characterized by comprising the following steps:
s1, adding methanol and lipase into the deodorized distillate to perform esterification reaction;
s2, carrying out cold separation on the esterification product and filtering to obtain sterol;
s3, carrying out three-stage molecular distillation on the filtrate obtained in the step S2 to obtain a primary vitamin E extract with the content of 10-27 wt%;
s4, carrying out five-stage high vacuum rectification on the primary vitamin E extract distilled in the step S3 as a raw material to respectively rectify squalene, soybean vitamin E and alpha vitamin E.
2. The method of claim 1, wherein the lipase is added in an amount of 0.5-1 wt% and the methanol is added in an amount of 10-15 wt% based on the deodorized distillate.
3. The method for extracting multiple active ingredients from deodorizer distillate according to claim 1, characterized in that the esterification reaction is carried out at 30-50 ℃ for 6-12 h and at a pH of 6.8-7.2.
4. The method for extracting multiple active ingredients from deodorized distillate according to claim 1, wherein the cold separation is performed by lowering the temperature by 2 ℃ per hour, slowly stirring, lowering the temperature to 8-10 ℃, and then maintaining the temperature for crystal growth for 7.5-8.5 hours.
5. The method for extracting multiple active ingredients from deodorized distillate according to claim 1, characterized in that the wiped film temperature of the three-stage distillation is 90-130 ℃; the primary temperature is 100-175 ℃, and the vacuum degree is not more than 120 Pa; the secondary temperature is 100-155 ℃, and the vacuum degree is not more than 30 Pa; the three-stage temperature is 200-250 ℃, and the vacuum degree is not more than 30 Pa.
6. The method of extracting multiple active ingredients from deodorizer distillate according to claim 1 characterized in that the vacuum degree of said high-vacuum rectification is not more than 10 Pa; the primary temperature is 200 +/-2 ℃, and the distillate accounts for 10-15 wt% of the raw materials; the secondary temperature is 210-225 ℃, and the distillate accounts for 10-15 wt% of the raw materials; the third-stage temperature is 225-240 ℃, and the distillate accounts for 8-12 wt% of the raw materials; the fourth-stage temperature is 245-260 ℃, and the distillate accounts for 30-40 wt% of the raw materials; the fifth-level temperature is 270 +/-5 ℃, and the distillate accounts for 15-20 wt% of the raw materials.
7. Method for extracting multiple active ingredients from a deodorised distillate according to claim 7, characterised in that the extraction method is: dissolving the secondary distillate by using an extraction solvent, then adding 0.5-1 mol/L sodium hydroxide or potassium hydroxide ethanol solution, and stirring for 0.5-2 h at the temperature of 60-85 ℃; washing with saturated NaCl solution to neutrality; and carrying out reduced pressure distillation to recover the extraction solvent to obtain squalene.
8. The method of extracting multiple active ingredients from deodorizer distillate according to claim 8 characterized by that the extraction solvent is one or more of n-hexane, diethyl ether, petroleum ether, etc.
9. The method for extracting multiple active ingredients from deodorized distillate according to claim 7, characterized in that the high vacuum rectified fifth distillate is further subjected to resin adsorption purification to obtain alpha-tocopherol.
10. The method according to claim 7, wherein the deodorized distillate is selected from corn deodorized distillate having an acid value of 125 to 135, rapeseed deodorized distillate, peanut deodorized distillate, sunflower seed deodorized distillate, and palm deodorized distillate.
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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN115650943A (en) * 2022-09-13 2023-01-31 宜春大海龟生命科学有限公司 Method for enriching polyunsaturated fatty acid ester, squalene, natural vitamin E and phytosterol from plant deodorized distillate
CN117096550A (en) * 2023-10-19 2023-11-21 珙县华洁危险废物治理有限责任公司成都分公司 Method for recovering oil-containing waste film from wet lithium battery diaphragm by dropping liquid

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN105367370A (en) * 2014-08-27 2016-03-02 浙江医药股份有限公司新昌制药厂 Method of extracting squalene from bottom sediment with natural vitamin E extracted
CN106317007A (en) * 2015-06-15 2017-01-11 浙江医药股份有限公司新昌制药厂 Method for recovery of d-alpha-tocopherol from natural vitamin E leftover material
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

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN105367370A (en) * 2014-08-27 2016-03-02 浙江医药股份有限公司新昌制药厂 Method of extracting squalene from bottom sediment with natural vitamin E extracted
CN106317007A (en) * 2015-06-15 2017-01-11 浙江医药股份有限公司新昌制药厂 Method for recovery of d-alpha-tocopherol from natural vitamin E leftover material
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

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
代志凯等: "大豆油脱臭馏出物中同时提取角鲨烯、生育酚和植物甾醇的工艺研究" *

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN115650943A (en) * 2022-09-13 2023-01-31 宜春大海龟生命科学有限公司 Method for enriching polyunsaturated fatty acid ester, squalene, natural vitamin E and phytosterol from plant deodorized distillate
CN115650943B (en) * 2022-09-13 2024-02-27 宜春大海龟生命科学股份有限公司 Method for enriching polyunsaturated fatty acid ester, squalene, natural vitamin E and phytosterol from plant deodorization distillate
CN117096550A (en) * 2023-10-19 2023-11-21 珙县华洁危险废物治理有限责任公司成都分公司 Method for recovering oil-containing waste film from wet lithium battery diaphragm by dropping liquid
CN117096550B (en) * 2023-10-19 2024-01-26 珙县华洁危险废物治理有限责任公司成都分公司 Method for recovering oil-containing waste film from wet lithium battery diaphragm by dropping liquid

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