CN113088402B

CN113088402B - Method for extracting palmitoleic acid ester and linoleate from idesia oil

Info

Publication number: CN113088402B
Application number: CN202110334325.3A
Authority: CN
Inventors: 龙辉; 叶缙桦; 段建利; 吴正奇; 鲁志鹏; 王颖; 徐楚; 方紫君; 余志顺; 周峰; 刘念
Original assignee: Hunan Wanxiang Biotechnology Co ltd
Current assignee: Hunan Wanxiang Biotechnology Co ltd
Priority date: 2021-03-29
Filing date: 2021-03-29
Publication date: 2023-03-17
Anticipated expiration: 2041-03-29
Also published as: CN113088402A

Abstract

The invention relates to the field of natural unsaturated fatty acid extraction and preparation, in particular to a method for extracting palmitoleic acid ester and linoleate from idesia oil; the method comprises the following steps: (1) Performing ester exchange reaction on idesia oil and an alcoholic solution of alkali to obtain fatty acid ester; (2) Performing multi-stage molecular distillation on the fatty acid ester to obtain a light component and a heavy component; (3) And respectively carrying out urea inclusion treatment on the light component and the heavy component. The method of the invention adopts natural grease as raw material to extract the palmitoleic acid ester and the linoleate with high added values, has simple and easy process, is suitable for industrial production, and has promotion effect on the development of related industries. The purity of the palmitoleic acid ester obtained by the method is higher than 90%, the purity of the linoleate is higher than 95%, and the product quality is stable.

Description

Method for extracting palmitoleic acid ester and linoleate from idesia oil

Technical Field

The invention relates to the field of natural unsaturated fatty acid extraction and preparation, in particular to a method for extracting palmitoleic acid ester and linoleate from idesia oil.

Background

The idesia oil is rich in various fatty acids, wherein the content of linoleic acid can reach 60-81%, the content of palmitoleic acid ranges from 3-11%, and the idesia oil is one of a small amount of grease containing palmitoleic acid.

Linoleic acid is the essential fatty acid and the important polyunsaturated fatty acid that were first identified and metabolized in the human body to produce precursors to the omega-6 series of active substances that have important physiological functions in the human body, which are the fatty hormones affecting blood pressure, vascular reactivity, coagulation and the immune system. The normal physiological metabolism can be maintained by taking 6g of linoleic acid every day, and the sufficient intake of the linoleic acid has the effects of cancer prevention and resistance, atherosclerosis resistance, immunity enhancement, bone tissue metabolism promotion and the like.

Palmitoleic acid has more physiological functions, and research by Cao and the like of Harvard university shows that palmitoleic acid and fat binding protein act to form a lipid hormone, so that systemic metabolism is adjusted, fat formation is further influenced, and obesity is caused. The research of fat cells and blood of a type I diabetic patient by Bergman et al finds that palmitoleic acid can influence various blood sugar metabolic enzymes and regulate insulin secretion of the patient. Palmitoleic acid can regulate body metabolism, affect inflammatory markers and PPAR metabolic pathways, and has certain therapeutic effect on inflammation. The study of Yoon et al found that palmitoleic acid can inhibit melanin factors in human cells and improve skin pigmentation. Additional studies have shown that calcium palmitate is very active against the antibacterial activity of Staphylococcus aureus and Propionibacterium acnes, and that calcium palmitate can improve skin smoothness. The palmitoleic acid content is low in general oil crops, the oil commonly used for extracting palmitoleic acid at present comprises seabuckthorn fruit oil, macadamia nut oil and fish oil, and due to the fact that fishery resources are increasingly scarce in recent years and the prices of the seabuckthorn fruit oil and the macadamia nut oil are high, the search for economic and environment-friendly palmitoleic acid raw oil is necessary.

In view of this, the invention is particularly proposed.

Disclosure of Invention

In order to deeply develop the economic benefit of the idesia oil and promote the development of the idesia industry, the invention provides the method for extracting the palmitoleic acid ester and the linoleate from the idesia oil, the purity of the palmitoleic acid ester extracted by the method can reach more than 90 percent, the purity of the linoleate can reach more than 95 percent, and the method is simple in process, low in cost and suitable for industrial production.

Specifically, the invention provides the following technical scheme:

the invention provides a method for extracting palmitoleic acid ester and linoleate from idesia oil, which comprises the following steps:

(1) Performing ester exchange reaction on idesia oil and an alcohol solution of alkali to obtain fatty acid ester;

(2) Performing multi-stage molecular distillation on the fatty acid ester to obtain a light component and a heavy component;

(3) And respectively carrying out urea inclusion treatment on the light component and the heavy component.

The invention discovers that catalytic transesterification is carried out on idesia oil and an alcoholic solution of alkali, products obtained by the reaction are subjected to multi-stage molecular distillation to respectively receive a light component and a heavy component, and then the received light component and the received heavy component are respectively subjected to urea inclusion treatment to obtain high-purity palmitoleic acid ester and linoleate.

In order to further improve the purity of the palmitoleic acid ester and the linoleate, the method is optimized, and specifically comprises the following steps:

preferably, the alkali is one or more of sodium hydroxide, potassium hydroxide and sodium ethoxide; the alcohol is one or more of methanol, ethanol and n-butanol;

further, the alkali is sodium hydroxide and/or potassium hydroxide; the alcohol is methanol and/or ethanol;

further, the concentration of the alcoholic solution of the base is 1 to 12:1 (g/L).

Preferably, the transesterification reaction is carried out at 80 to 100 ℃ for 1 to 5 hours.

Preferably, the multistage molecular distillation is five-stage molecular distillation;

wherein, the vacuum degree of the primary molecular distillation is 40-80 pa, and the distillation temperature is 50-90 ℃; the vacuum degree of the secondary molecular distillation is 0.5-25 pa, and the distillation temperature is 80-120 ℃; the vacuum degree of the three-stage molecular distillation is 20-60 pa, and the distillation temperature is 90-130 ℃; the vacuum degree of the four-stage molecular distillation is 0.5-35 pa, and the distillation temperature is 100-155 ℃; the vacuum degree of the five-stage molecular distillation is 0.5-40 pa, and the distillation temperature is 115-155 ℃.

Further, the vacuum degree of the primary molecular distillation is 50-70 pa, and the distillation temperature is 60-80 ℃; the vacuum degree of the secondary molecular distillation is 0.5-15 pa, and the distillation temperature is 90-110 ℃; the vacuum degree of the three-stage molecular distillation is 20-40 pa, and the distillation temperature is 95-125 ℃; the vacuum degree of the four-stage molecular distillation is 0.5-20 pa, and the distillation temperature is 100-130 ℃; the vacuum degree of the five-stage molecular distillation is 0.5-15 pa, and the distillation temperature is 110-130 ℃.

The invention discovers that the C16 fatty acid and the C18 fatty acid in the fatty acid ester can be separated by adopting the specific mode to carry out molecular distillation, lays a foundation for subsequent urea inclusion treatment, and is favorable for improving the purity of the palmitoleic acid ester and the linoleate.

Preferably, the fatty acid ester is subjected to primary molecular distillation, secondary molecular distillation, tertiary molecular distillation, quaternary molecular distillation and quinary molecular distillation in sequence; the light component is obtained by first-stage molecular distillation, and the heavy component is obtained by fifth-stage molecular distillation.

In a specific implementation mode, the fatty acid ester is subjected to primary molecular distillation, the collected light component is the light component, the collected heavy component is subjected to secondary molecular distillation, the collected heavy component is subjected to tertiary molecular distillation, the collected heavy component is subjected to quaternary molecular distillation, and the collected heavy component is subjected to quinary molecular distillation, so that the heavy component is obtained.

Preferably, the urea inclusion treatment is carried out in a solvent, wherein the solvent is one or more of methanol, ethanol, n-butanol, acetone and water; preferably methanol or ethanol.

Further, when the light component is subjected to urea inclusion treatment, the mass ratio of the light component to the urea to the solvent is 1:0.1 to 5:0.5 to 15; preferably 1:0.5 to 2:3 to 7;

more preferably, the temperature of the urea inclusion treatment is-10 to 20 ℃ (-5 to 10 ℃ being particularly preferable).

Further, when the heavy component is subjected to urea inclusion treatment, the mass ratio of the heavy component to the urea to the solvent is 1:0.5 to 6:0.7 to 15; preferably 1:1 to 4:5 to 10;

more preferably, the temperature of the urea inclusion treatment is-10 to 10 ℃ (-7 to 10 ℃ is particularly preferable).

Preferably, the temperature of the urea complex grease of the light component is-10-20 ℃.

Preferably, the temperature of the urea complex grease of the heavy component is-10 to 10 ℃.

Preferably, after the transesterification reaction is completed, the solvent is recovered under reduced pressure; the temperature of the reduced pressure recovery is 40-90 ℃, and the vacuum degree is-0.02-0.20 MP; preferably, the temperature of the reduced pressure recovery is 40-60 ℃, and the vacuum degree is-0.06-0.09 MP.

The invention has the beneficial effects that:

(1) The method of the invention adopts natural grease as raw material to extract the palmitoleic acid ester and the linoleate with high added values, has simple and easy process, is suitable for industrial production, and has promotion effect on the development of related industries.

(2) The method adopts an environment-friendly molecular distillation technology and a urea inclusion technology, wherein the solvent and urea can be completely recycled, and the process is environment-friendly.

(3) The purity of the palmitoleic acid ester obtained by the method is higher than 90%, the purity of the linoleate is higher than 95%, and the product quality is stable.

Drawings

FIG. 1 is a gas chromatography chromatogram of idesia oil according to the present invention;

FIG. 2 is a gas chromatography chromatogram of palmitoleic acid ester extracted in example 1;

FIG. 3 is a GC analysis of the linoleate extracted in example 1;

FIG. 4 is a gas chromatography chromatogram of palmitoleic acid ester extracted in comparative example 1;

FIG. 5 is a gas chromatography spectrum of linoleate extracted in comparative example 1;

Detailed Description

The following examples are intended to illustrate the invention, but are not intended to limit the scope of the invention.

Unless otherwise specified, the technical means used in the examples are conventional technical means well known to those skilled in the art. Unless otherwise specified, reagents used in examples are commercially available, and "yield" in examples is a mass percentage.

The gas chromatographic analysis patterns of idesia oil referred to in the following examples are shown in figure 1 and table 1; wherein, the product with peak emergence at 15.432min is palmitoleic acid, and the product with peak emergence at 20.368min is linoleic acid.

TABLE 1

Peak#	Name	Ret.Time	Area	Height	Separation	Tailing Fackor	Resolution	Area％
									l	12.652	10262	682	0.000	1.244	0.000	0.0746
2		13.896	3685	375	0.000	1.279	3.651	0.0268
									3	14.639	2217890	131409	1.597	0.000	2.265	16.1169
4		15.432	986929	35822	1.399	0.000	1.430	7.1718
									5	16.038	118455	9183	1.218	0.000	0.000	0.8608
6		16.550	4451	517	1.151	1.169	0.000	0.0323
									7	17.319	33133	2114	1.197	0.869	2.459	0.2408
8		18.060	137241	10666	1.159	1.297	2.085	0.9973
									9	18.823	1412140	90433	1.141	1.563	2.225	10.2617
10		20.368	8518560	354039	1.250	1.826	3.462	61.9024
									11	22.769	203621	6037	1.311	1.714	3.555	1.4797
12		26.000	42914	1497	1.319	1.312	4.082	0.3118
									13	27.651	47851	1599	1.124	1.429	2.114	0.3477
14		30.150	24138	967	1.167	1.688	3.490	0.1754
									Total		13761270	645340				100.0000

Example 1

The embodiment provides a method for extracting palmitoleic acid ester and linoleate from idesia oil, which comprises the following steps:

(1) Base catalyzed esterification

Dissolving 600g of sodium hydroxide in 120L of ethanol in a 200L glass reaction kettle, adding 30kg of idesia oil, and carrying out reflux reaction at 90 ℃ for 4 hours; recovering ethanol under reduced pressure; standing and layering to obtain 28.5kg of brown yellow ethyl idesia oil with the yield of 95 percent;

(2) Multistage molecular distillation

The ethyl ester idesia oil is subjected to a molecular distillation processing procedure, and the parameters and results are shown in table 2;

TABLE 2

3.7kg of light components obtained by primary molecular distillation (the content of the palmitoleic acid ester is 55 percent) are collected; 14.8kg of heavy components obtained by five-stage molecular distillation (the content of ethyl linoleate is 86%) are collected;

(3) Inclusion treatment with urea

Putting the light components into a reaction kettle, adding 7.4kg of urea and 22.3kg of 90% ethanol, refluxing and preserving heat for 1 hour at 90 ℃, slowly cooling to-5 ℃, preserving heat and performing suction filtration, taking filtrate, recovering ethanol under reduced pressure, adding a certain amount of dilute hydrochloric acid aqueous solution, washing for three times, and removing solvent residues under reduced pressure to obtain 2.0kg of finished palmitoleate product with the content of 91%;

and (2) putting the heavy component into a reaction kettle, adding 35.5kg of urea and 111.0kg of 90% ethanol, refluxing at 90 ℃ and preserving heat for 1 hour, slowly cooling to 0 ℃, preserving heat and filtering, taking filtrate, recovering ethanol under reduced pressure, adding a certain amount of dilute hydrochloric acid aqueous solution, washing for three times, and removing solvent residues under reduced pressure to obtain a finished product of linoleate, wherein the content of linoleate is 96%.

The palmitoleic acid ester and the linoleate obtained in the example were subjected to gas chromatography; wherein, the gas chromatography spectrum of the palmitoleic acid ester is shown in fig. 2 and table 3, and the gas chromatography spectrum of the linoleate is shown in fig. 3 and table 4.

TABLE 3

TABLE 4

Example 2

(1) Base catalyzed esterification

Dissolving 4kg of potassium hydroxide in 480L of methanol in a 1000L reaction kettle, adding 160kg of idesia oil, and carrying out reflux reaction at 90 ℃ for 5 hours; recovering methanol under reduced pressure; standing and layering to obtain 152kg of brown yellow methyl idesia oil with the yield of 95 percent;

(2) Multistage molecular distillation

The methyl idesia oil is subjected to a molecular distillation processing procedure, and the parameters and the results are shown in table 5;

TABLE 5

Number of stages	Vacuum degree (pa)	Temperature (. Degree. C.)	Yield (%)
				First stage	60	62	13.6
Second stage	2～5	90	12.5
				Three-stage	25	100	10.4
Four stages	20	110	11.6
				Five stages	13	115	46.8

Collecting 20.7kg of light components obtained by primary molecular distillation (the content of the palmitoleate is 50%); 71.1kg of heavy component obtained by five-stage molecular distillation is collected (the content of methyl linoleate is 88%);

(3) Inclusion treatment of urea

Loading the light components into a reaction kettle, adding 50.8kg of urea and 152.4kg of 90% methanol, refluxing and preserving heat for 1 hour at 90 ℃, slowly cooling to-5 ℃, preserving heat and filtering, taking filtrate, recovering methanol under reduced pressure, adding a certain amount of dilute hydrochloric acid aqueous solution, washing for three times, and removing solvent residues under reduced pressure to obtain 11.4kg of finished palmitoleate product with the content of 92%;

and (2) putting the heavy component into a reaction kettle, adding 170.6kg of urea and 533.3kg of 90% methanol, refluxing at 90 ℃ and preserving heat for 1 hour, slowly cooling to 0 ℃, preserving heat and filtering, taking filtrate, recovering methanol under reduced pressure, adding a certain amount of dilute hydrochloric acid aqueous solution, washing for three times, and removing solvent residues under reduced pressure to obtain 46.2kg of a finished linoleate product with the content of 98%.

Example 3

The embodiment provides a method for extracting palmitoleic acid ester and linoleate from idesia oil, which comprises the following steps of:

(1) Base catalyzed esterification

Dissolving 4.3kg of sodium hydroxide in 400L of ethanol in a 1000L reaction kettle, adding 200kg of idesia oil, and carrying out reflux reaction at 90 ℃ for 5 hours; recovering ethanol under reduced pressure; standing and layering to obtain 190kg of brown yellow ethyl idesia oil with the yield of 95 percent;

(2) Multistage molecular distillation

The ethyl ester idesia oil is subjected to a molecular distillation processing procedure, and the parameters and results are shown in table 6;

TABLE 6

Number of stages	Vacuum degree (pa)	Temperature (. Degree. C.)	Yield (%)
				First stage	55	60	13.5
Second stage	2	110	15.4
				Three-stage	25	110	6.5
Four stages	15	115	12.2
				Five stages	10	120	50.1

Collecting 25.6kg of light components obtained by primary molecular distillation (the content of the palmitoleic acid ester is 53%); 95.2kg of heavy component obtained by five-stage molecular distillation is collected (the content of ethyl linoleate is 85%);

(3) Inclusion treatment of urea

Putting the light components into a reaction kettle, adding 51.2kg of urea and 153.6g of 90% ethanol, refluxing and preserving heat at 90 ℃ for 1 hour, slowly cooling to-5 ℃, preserving heat and filtering, taking filtrate, recovering ethanol under reduced pressure, adding a certain amount of dilute hydrochloric acid aqueous solution, washing for three times, and removing solvent residues under reduced pressure to obtain 13.8kg of finished palmitoleate with the content of 93%;

and (2) putting the heavy component into a reaction kettle, adding 228.5kg of urea and 714.0kg of 90% ethanol, refluxing at 90 ℃ and preserving heat for 1 hour, slowly cooling to 0 ℃, preserving heat and filtering, taking filtrate, recovering ethanol under reduced pressure, adding a certain amount of dilute hydrochloric acid aqueous solution, washing for three times, and removing solvent residues under reduced pressure to obtain 58.8kg of a finished linoleate product with the content of 99%.

Comparative example 1

This comparative example provides a process for extracting palmitoleic and linoleic acid esters from idesia oil, differing from example 1 only in that: the conventional rectification equipment is adopted for carrying out multiple rectification to replace multi-stage molecular distillation equipment, and the ethyl ester idesia oil is processed.

0.8kg of finished palmitoleate obtained in the comparative example, with the content of 74 percent; 6.4kg of the obtained linoleate finished product with the content of 89 percent.

The palmitoleic acid ester and the linoleate obtained in the comparative example are subjected to gas chromatography analysis; among them, the gas chromatography spectrum of palmitoleic acid ester is shown in fig. 4 and table 7, and the gas chromatography spectrum of linoleate is shown in fig. 5 and table 8.

TABLE 7

Peak#	Ret.Time	Area	Heieht	k′	Separation	Tailing Factor	Resolution	Area％
									1	12.435	32616	10718	0.000	0.000	1.030	0.000	0.2142
2	15.132	159986	41036	0.217	0.000	1.000	29.467	1.0508
									3	17.674	6075	1282	0.421	1.943	1.016	22.111	0.0399
4	18.924	157528	24489	0.522	1.238	0.932	8.324	1.0346
									5	19.922	9213	997	0.602	1.154	0.000	4.769	0.0605
6	20.189	8381	1144	0.624	1.036	0.000	0.000	0.0550
									7	20.605	11308229	1184620	0.657	1.054	0.588	0.000	74.2712
8	20.777	140963	30873	0.671	1.021	0.000	0.902	0.9258
									9	22.739	19831	2370	0.829	1.235	1.418	12.269	0.1302
10	25.460	3038368	372798	1.047	1.264	0.663	13.009	19.9557
									11	25.627	189996	34467	1.061	1.013	0.000	0.907	1.2479
12	27.829	140814	20055	1.238	1.167	0.988	13.125	0.9249
									13	30.876	7200	1013	1.483	1.198	1.048	16.019	0.0473
14	31.220	6384	872	1.511	1.019	0.994	1.777	0.0419
									Total		15225584	1726734					100.0000

TABLE 8

Peak#	Ret.Time	Area	Height	k′	Separation	TailingFactor	Resolution	Area％
									1	19.909	6473	1103	0.000	0.000	1.145	0.000	0.0269
2	21.386	23276	4136	0.074	0.000	1.055	9.817	0.0966
									3	23.813	5497	816	0.196	2.643	1.136	14.816	0.0228
4	26.619	2490408	200808	0.337	1.719	0.693	10.662	10.3329
									5	26.843	48676	5757	0.348	1.033	0.000	0.000	0.2020
6	28.561	39109	2256	0.435	1.248	0.000	0.000	0.1623
									7	29.398	21459929	1207210	0.477	1.097	0.546	1.581	89.0386
8	31.930	22673	3355	0.604	1.267	0.000	7.598	0.0941
									9	42.845	5773	762	1.152	1.908	0.000	57.227	0.0240
Total		24101814	1426203					100.0000

Although the invention has been described in detail hereinabove by way of general description, specific embodiments and experiments, it will be apparent to those skilled in the art that many modifications and improvements can be made thereto based on the invention. Accordingly, such modifications and improvements are intended to be within the scope of the invention as claimed.

Claims

1. A method for extracting palmitoleic acid ester and linoleate from idesia oil is characterized by comprising the following steps:

(1) Performing ester exchange reaction on idesia oil and an alcoholic solution of alkali to obtain fatty acid ester;

(2) Sequentially carrying out primary molecular distillation, secondary molecular distillation, tertiary molecular distillation, quaternary molecular distillation and quinary molecular distillation on the fatty acid ester to obtain a light component and a heavy component; the light component is obtained by first-stage molecular distillation, and the heavy component is obtained by fifth-stage molecular distillation; the vacuum degree of the primary molecular distillation is 55 to 60Pa, and the distillation temperature is 60 to 62 ℃; the vacuum degree of the secondary molecular distillation is 2 to 5Pa, and the distillation temperature is 90 to 110 ℃; the vacuum degree of the tertiary molecular distillation is 25Pa, and the distillation temperature is 100-110 ℃; the vacuum degree of the four-stage molecular distillation is 15 to 20Pa, and the distillation temperature is 110 to 115 ℃; the vacuum degree of the five-grade molecular distillation is 10 to 13Pa, and the distillation temperature is 115 to 120 ℃;

2. The method according to claim 1, wherein the base is sodium hydroxide and/or potassium hydroxide; the alcohol is methanol and/or ethanol;

the concentration of the alcoholic solution of the alkali is 1 to 12:1 g/L.

3. The method according to claim 1 or 2, wherein the urea inclusion treatment is carried out in a solvent which is one or more of methanol, ethanol, n-butanol, acetone, water.

4. The method according to claim 3, wherein when the light fraction is subjected to a urea inclusion treatment, the mass ratio of the light fraction to the urea and the solvent is 1:0.1 to 5:0.5 to 15;

the temperature of the urea inclusion treatment is-10 to 20 ℃.

5. The method according to claim 3, wherein when the heavy component is subjected to the urea inclusion treatment, the mass ratio of the heavy component to the urea and the solvent is 1:0.5 to 6:0.7 to 15;

the temperature of the urea inclusion treatment is-10 to 10 ℃.

6. The method as claimed in claim 4, wherein the temperature of the light-component urea complex grease is from-10 to 20 ℃.

7. The method according to claim 5, wherein the temperature of the urea complex grease with heavy components is-10 to 10 ℃.

8. The method according to claim 1, wherein after the completion of the transesterification reaction, the solvent is recovered under reduced pressure; the temperature of the reduced pressure recovery is 40 to 90 ℃, and the vacuum degree is-0.02 to-0.20 MPa.