TWI648393B - Method for purifying unsaturated fatty acid and purifying linolenic acid - Google Patents

Abstract

A method for purifying unsaturated fatty acids and linolenic acid. Methods of purifying unsaturated fatty acids include providing ethylated linseed oil. Unsaturated fatty acids and saturated fatty acids in ethylated linseed oil were separated by simulated moving bed chromatography to obtain high-purity unsaturated fatty acids containing linoleic acid and linolenic acid.

Description

Method for purifying unsaturated fatty acids and linolenic acid

The present invention relates to a purification method, and more particularly to a method for purifying unsaturated fatty acids and linolenic acid.

Flaxseed, also known as flax seed, belongs to the genus Flax and is an important oil crop. Flaxseed oil is rich in a variety of unsaturated fatty acids, and the content of linolenic acid (LNA) can reach 40% to 60%. Linolenic acid is an essential fatty acid of the human body, also known as vitamin F. It can not only synthesize two other unsaturated fatty acids (docosahexaenoic acid (DHA) and eicosapentaenoic acid (EPA). ), Is also the core substance involved in phospholipid synthesis, metabolism and transformation. Linseed oil is now used as a nutritional additive or functional food ingredient.

The existing separation and purification methods of linseed oil mainly include silver ion complexation method, supercritical carbon dioxide distillation method, molecular distillation method, column chromatography method, adsorption separation method, lipase concentration method, low-temperature crystallization method and urea encapsulation method. Among the above methods, the urea package method has become a preferred purification process for more and more enterprises because of its simple separation equipment, simple and easy operation method, and urea that can be recycled and has less environmental pollution. However, the single urea inclusion method also has disadvantages such as incomplete separation of unsaturated fatty acid components, low yield, and low purity of a single polyunsaturated fatty acid. Silver ion complexation requires the use of a large amount of expensive silver nitrate. Not only is the production cost relatively high, but also it is difficult to recover silver nitrate, which will cause serious pollution. If the operation is not properly controlled, silver nitrate may enter the product.

Therefore, how to find a method to purify high-purity linolenic acid from linseed oil is a problem that researchers are anxious to solve at present.

The invention provides a method for purifying unsaturated fatty acids, which can effectively isolate high-purity unsaturated fatty acids including linoleic acid (LA) and linolenic acid (LNA).

The invention provides a method for purifying linolenic acid, which can effectively isolate high-purity linolenic acid.

An embodiment of the present invention provides a method for purifying unsaturated fatty acids. The method includes the following steps. First, an ethylated linseed oil is provided. Next, the unsaturated fatty acids in the ethylated linseed oil are separated by simulated moving bed chromatography, wherein the separated unsaturated fatty acids include linolenic acid and linoleic acid, wherein the simulated moving bed The chromatography method includes: (i) providing a simulated moving bed, which sequentially includes a first section, a second section, and a third section, wherein the simulated moving bed is composed of a mobile phase and a stationary phase; Composition, the stationary phase particles have pores inside, and the movement relative to the simulated moving bed flows in the same direction from the inlet of the washing end through the first section, the second section, and the Between the third section, the stationary phase is simulated to move in the opposite direction relative to the mobile phase, and the mobile phase is a solvent containing supercritical carbon dioxide and pure ethanol; (ii) the ethylation Linseed oil is injected from the feed inlet between the second section and the third section of the simulated moving bed, and the unsaturated fatty acid moves with the stationary phase to the first section And the extraction end between the second section and Other said mixture of ethyl linseed oil with the movement of said raffinate phase moves to the end of the third section to separate the unsaturated fatty acid.

In an embodiment of the present invention, based on the total amount of the detergent, the content of pure ethanol is, for example, 1 wt% to 8 wt%.

In an embodiment of the present invention, the stationary phase is, for example, random silicon dioxide.

In an embodiment of the present invention, each of the first section, the second section, and the third section includes two columns, and each of the columns is filled with a stationary phase.

In one embodiment of the present invention, the separation conditions used in the above-mentioned simulated moving bed are: the carbon dioxide flow rate is 26.5 kg / hour at the inlet of the scrubbing end, 1.5 kg / hour at the inlet of the feed, and 11.19 kg at the extraction end Per hour and 16.81 kg / hour at the extraction end, and the flow rate of pure ethanol at the inlet of the rinse end is 29.39 ml / min, at the feed inlet is 1.65 ml / min, at the extraction end is 12.44 ml / min, and It is 18.60 ml / min at the raffinate end, and the switching time of the simulated moving bed is 3 minutes 35 seconds to 3 minutes 48 seconds.

In an embodiment of the present invention, the separation conditions used in the above-mentioned simulated moving bed are: the carbon dioxide flow rate is 26.5 kg / hour at the inlet of the scrubbing end, 1.5 kg / hour at the inlet of the feed, and 11.78 kg at the extraction end Per hour and 16.22 kg / hr at the extraction end, and the flow rate of pure ethanol at the inlet of the scrubbing end is 29.39 ml / min, at the feed inlet is 1.65 ml / min, at the extraction end is 13.10 ml / min, and It was 17.94 ml / min at the raffinate end, and the switching time of the simulated moving bed was 3 minutes and 50 seconds to 3 minutes and 53 seconds.

In an embodiment of the present invention, the separation conditions used in the above-mentioned simulated moving bed are: the carbon dioxide flow rate is 26.5 kg / hour at the inlet of the scrubbing end, 0.75 kg / hour at the inlet of the feed, and 11.78 kg at the extraction end Per hour and 15.47 kg / hour at the extract end, and the flow rate of pure ethanol at the inlet of the rinse end is 29.39 ml / min, at the feed inlet is 0.825 ml / min, at the extraction end is 13.10 ml / min, and 17.12 ml / min at the raffinate end, and the switching time of the simulated moving bed is 4 minutes to 4 minutes and 10 seconds.

An embodiment of the present invention provides a method for purifying linolenic acid. The method includes the following steps. First, an ethylated linseed oil is provided. Next, a first simulated moving bed chromatography process is performed to separate the unsaturated fatty acids in the ethylated linseed oil. The separated unsaturated fatty acids include linolenic acid and linoleic acid. The first simulated moving bed The analysis process includes: (i) providing a first simulated moving bed, the first simulated moving bed includes a first section, a second section, and a third section in sequence, wherein the first simulated moving bed is composed of the first mobile phase and It consists of a first stationary phase, and the first stationary phase particles have pores inside. The first movement is in the same direction as the simulated moving bed, and flows from the first washing end inlet through the first section, the second section, and the first section. Between the three sections, the first stationary phase is simulated in the opposite direction relative to the first mobile phase, where the first mobile phase is a detergent containing supercritical carbon dioxide and pure ethanol; (ii) ethylated flaxseed Oil is injected from the first feed inlet between the second section and the third section of the simulated moving bed, and the unsaturated fatty acid moves with the first stationary phase to the first section between the first section and the second section. Extraction and ethylation of linseed oil The other mixtures of the mobile phase are moved to the first raffinate end of the third section with the first mobile phase to separate the unsaturated fatty acids; and a second simulated moving bed chromatography process is performed to separate the linolenic acid in the separated unsaturated fatty acids The second simulated moving bed chromatography process includes: (iii) providing a second simulated moving bed, the second simulated moving bed includes a fourth section, a fifth section, and a sixth section in sequence, in which the first The two simulated moving beds are composed of a second mobile phase and a second stationary phase. The particles of the second stationary phase have pores inside, and the second movement is in the same direction as the second simulated moving bed from the entrance of the second scouring end. Flowing between the fourth, fifth, and sixth sections, the second stationary phase is simulated to move in the opposite direction relative to the second mobile phase, where the second stationary phase is a reversed-phase filler; (iv) The unsaturated fatty acid is injected from the second feed inlet between the fifth section and the sixth section of the second simulated moving bed, and the linolenic acid in the unsaturated fatty acid moves with the second mobile phase to the first section of the sixth section. Second extraction and desaturation The other mixture in the fatty acid moves with the second stationary phase to the second extraction end between the fourth section and the fifth section to separate linolenic acid and linoleic acid.

In an embodiment of the present invention, based on the total amount of the detergent, the content of pure ethanol is, for example, 1 wt% to 8 wt%.

In an embodiment of the present invention, the stationary phase is, for example, random silicon dioxide.

In an embodiment of the present invention, each of the first section, the second section, and the third section includes two columns, and each of the columns is filled with a stationary phase.

In one embodiment of the present invention, the separation conditions used in the above-mentioned simulated moving bed are: the carbon dioxide flow rate is 26.5 kg / hour at the inlet of the scrubbing end, 1.5 kg / hour at the inlet of the feed, and 11.19 kg at the extraction end Per hour and 16.81 kg / hour at the extraction end, and the flow rate of pure ethanol at the inlet of the rinse end is 29.39 ml / min, at the feed inlet is 1.65 ml / min, at the extraction end is 12.44 ml / min, and It is 18.60 ml / min at the raffinate end, and the switching time of the simulated moving bed is 3 minutes 35 seconds to 3 minutes 48 seconds.

In an embodiment of the present invention, the separation conditions used in the above-mentioned simulated moving bed are: the carbon dioxide flow rate is 26.5 kg / hour at the inlet of the scrubbing end, 1.5 kg / hour at the inlet of the feed, and 11.78 kg at the extraction end Per hour and 16.22 kg / hr at the extraction end, and the flow rate of pure ethanol at the inlet of the scrubbing end is 29.39 ml / min, at the feed inlet is 1.65 ml / min, at the extraction end is 13.10 ml / min, and It was 17.94 ml / min at the raffinate end, and the switching time of the simulated moving bed was 3 minutes and 50 seconds to 3 minutes and 53 seconds.

In an embodiment of the present invention, the separation conditions used in the above-mentioned simulated moving bed are: the carbon dioxide flow rate is 26.5 kg / hour at the inlet of the scrubbing end, 0.75 kg / hour at the inlet of the feed, and 11.78 kg at the extraction end Per hour and 15.47 kg / hour at the extract end, and the flow rate of pure ethanol at the inlet of the rinse end is 29.39 ml / min, at the feed inlet is 0.825 ml / min, at the extraction end is 13.10 ml / min, and 17.12 ml / min at the raffinate end, and the switching time of the simulated moving bed is 4 minutes to 4 minutes and 10 seconds.

In one embodiment of the present invention, the inverse filler is, for example, ODS modified silicon dioxide.

In an embodiment of the present invention, the second mobile phase is, for example, pure ethanol or a 95% ethanol solution.

In an embodiment of the present invention, each of the fourth section, the fifth section, and the sixth section includes two tubular columns, and each of the tubular columns is filled with a second stationary phase.

In an embodiment of the present invention, the separation conditions used in the second simulated moving bed are as follows: the second mobile phase is a 95% ethanol solution, and the flow rate of the 95% ethanol solution is 0.96 ml / min at the inlet of the second washing end. , 0.01 ml / min at the second feed inlet, 0.36 ml / min at the second extraction end, and 0.61 ml / min at the second extraction end, and the switching time of the second simulated moving bed is 6 minutes to 6 minutes and 30 seconds.

In an embodiment of the present invention, the separation conditions used in the second simulated moving bed are as follows: the second mobile phase is pure ethanol, and the flow rate of pure ethanol is 0.96 ml / min at the inlet of the second washing end; The feed inlet is 0.016 ml / min, 0.36 ml / min at the second extraction end and 0.616 ml / min at the second extraction end, and the switching time of the second simulated moving bed is 4 minutes 20 seconds to 4 minutes 30 seconds.

Based on the above, the method for purifying unsaturated fatty acids of the present invention uses simulated moving bed chromatography to separate unsaturated fatty acids containing linolenic acid and linoleic acid from linseed oil, which can not only effectively improve the separation efficiency, but also can obtain high Unsaturated fatty acids containing linolenic acid and linoleic acid in purity. In addition, the linolenic acid purification method of the present invention can further purify linolenic acid from linseed oil by performing a second simulated moving bed chromatography process. Similarly, not only can the separation efficiency be effectively improved, but high purity Linolenic acid.

In order to make the above features and advantages of the present invention more comprehensible, embodiments are hereinafter described in detail with reference to the accompanying drawings.

The method for purifying linolenic acid according to the embodiment of the present invention is a method that can be used to separate and purify linolenic acid and other mixtures from linseed oil. Thereby, high-purity linolenic acid can be obtained.

The following examples are listed to illustrate the details or conditions of the purification method of the present invention, and the following examples are mainly divided into two parts. The first part is the purification of unsaturated fatty acids in linseed oil, and more specifically, the purification of unsaturated fatty acids containing linolenic acid and linoleic acid in linseed oil. Methods for purifying unsaturated fatty acids include: providing ethylated linseed oil; and separating unsaturated fatty acids in ethylated linseed oil by simulated moving bed chromatography, wherein the separated unsaturated fatty acids include linolenic acid As well as linoleic acid.

The second part is the purification of linolenic acid from linseed oil. More specifically, the unsaturated fatty acids containing linolenic acid and linoleic acid are separated from linseed oil, and then the linolenic acid is separated from unsaturated fatty acids. . A method for purifying linolenic acid includes: providing an ethylated linseed oil; performing a first simulated moving bed chromatography process to separate unsaturated fatty acids in the ethylated linseed oil, wherein the separated unsaturated fatty acids include Linolenic acid and linoleic acid; and a second simulated moving bed chromatography process is performed to separate linolenic acid and linoleic acid from the separated unsaturated fatty acids.

The following examples are not intended to limit the protection scope of the present invention. The drawing formulas are schematic diagrams and are for convenience of illustration only, and do not represent methods, conditions, or devices that limit their actuality. Example 1 [ Purification of unsaturated fatty acids ]

In this embodiment, a Supercritical Fluid-Simulated Moving Bed (SF-SMB) device as shown in FIG. 1 may be used to perform a simulated moving bed chromatography method to separate the Saturated fatty acids are purified. FIG. 1 is a pipeline flowchart of a supercritical fluid simulated moving bed device according to an embodiment of the present invention. Referring to FIG. 1, the simulated moving bed 100 includes a first section, a second section, and a third section. In this embodiment, the first section includes two columns C1 and C2, the second section includes three columns C3, C4, and C5, and the third section includes three columns C6, C7, and C8. The above eight pipe strings are connected in series, but the present invention is not limited thereto. In another embodiment, the first section includes two pipe strings, the second section includes two pipe strings, and the third section includes two pipe strings, and the six pipe strings are connected in series.

The simulated moving bed 100 is composed of a mobile phase (not shown) and a stationary phase (not shown). The mobile phase is relative to the simulated mobile bed 100 flowing in the same direction from the inlet D1 of the washing end through the first section, the second section and the third section, and the stationary phase is opposite to the mobile phase. Simulate movement.

Each column is filled with a stationary phase with pores inside the particles. In this embodiment, the stationary phase is, for example, irregular silica. However, the present invention is not limited thereto, and the stationary phase may be a conventional stationary phase material. In this embodiment, the mobile phase (or washing agent) is, for example, a washing agent containing supercritical carbon dioxide and an auxiliary solvent. In this embodiment, the auxiliary solvent is pure ethanol (anhydrous ethanol). A detergent containing supercritical carbon dioxide and an auxiliary solvent can be formed by generating high-pressure carbon dioxide with a carbon dioxide liquid pump and mixing with the auxiliary solvent.

Referring again to FIG. 1, the simulated moving bed 100 includes two feeding inlets, namely the sample feeding inlet F1 (that is, the inlet position of the column C6) and the flushing end inlet D1 (that is, the inlet position of the column C1), and includes two The outlets are respectively the extraction end E1 (the exit position of the column C2) and the extraction end R1 (the exit position of the column C8). If the positions of all the inlets and outlets are switched to the next column at the same time after a period of time, the stationary phase movement can be simulated (that is, move to the bottom of Figure 1). For example, the feed inlet is switched from the original position at the inlet of pipe column C6 to the inlet position of pipe column C7, and the other inlets and outlets are also changed to the next pipe column at the same time. The material still flows continuously to the extractive end. If the positions of the inlet and outlet are continuously switched continuously, a continuous downward flow of solids and a recirculation will be formed, so a process of continuous reverse flow contact between solids and supercritical fluid can be achieved.

Since the embodiment of the present invention uses supercritical carbon dioxide as a cleaning agent (mobile phase), a high-pressure carbon dioxide supply source 110 needs to be provided. The simulated moving bed 100 uses a carbon dioxide liquid pump 115 to generate high-pressure carbon dioxide from a carbon dioxide supply source 110 and temporarily stores the carbon dioxide in a high-pressure buffer tank 120. Next, the front-end pressure regulating valve 122 or the rear-end pressure regulating valve 123, a mass flow meter, and a control valve (not shown) are used to control the carbon dioxide flow rate of the feed.

In addition to the control of the mass flow of carbon dioxide, the input of auxiliary solvent is controlled from the input port D2 by the high-performance liquid chromatography pump 125a, and the input of the sample is input from the input port F2 by the high-performance liquid chromatography pump. 125b to control. In detail, after the sample feed is dissolved in the auxiliary solvent, it is input into the simulated moving bed 100 by mixing with carbon dioxide from the input port F2 using the high-performance liquid chromatography pump 125b. Similarly, as a mobile phase, a washing liquid containing supercritical carbon dioxide and an auxiliary solvent is formed by mixing high-pressure carbon dioxide generated by a carbon dioxide liquid pump 115 with an auxiliary solvent input from an input port D2. In addition, the above-mentioned step of mixing the high-pressure carbon dioxide with the auxiliary solvent can be achieved by the mixer 130.

While the supercritical fluid continuously switched the positions of the inlet and the outlet, although the supercritical fluid continued to flow upward (that is, move upwards in FIG. 1), it did not directly circulate back to the position of the column C1. The traditional simulated moving bed device using liquid as the mobile phase often adds a fourth section to regenerate the mobile phase and then directly circulate it back to use. In this embodiment, the regeneration of the supercritical fluid is easily achieved by using a pressure reduction separation method. Therefore, the supercritical fluid flowing from the raffinate end R1 and the extraction end E1 is subjected to a simple pressure reduction of the carbon dioxide after the separation tanks 145a and 145b After vaporization, the carbon dioxide gas can be re-cooled to precipitate the residual auxiliary solvent and solute, and then the purpose of carbon dioxide regeneration can be achieved. This can reduce the use of string in the fourth section, reduce the cost of equipment and the cost of packing requirements.

The carbon dioxide gas recovered from the separation tank 155 is temporarily stored in the working storage tank 160 after being condensed and recovered, and then pre-cooled and pressurized by the carbon dioxide liquid pump 115 and temporarily stored in the high-pressure buffer tank 120, and the rear pressure regulating valve 123 is used. Control its pressure. After moderate pressure adjustment and measurement, the carbon dioxide in the high-pressure buffer tank 120 is injected into the system from the positions of the pipe column C1 and the pipe column C6, respectively, and mixed with a quantitative input auxiliary solvent or a feed solution before injection. After the separation of the simulated moving bed, the two materials exit the system from the extraction end E1 and the extraction residue R1. The supercritical fluid flowing out of the raffinate end R1 first passes through the rear-end pressure regulating valve 123, separates the auxiliary solvent and the solute in the separation tank 145b, and then recovers the carbon dioxide gas. The rear pressure regulator 123 at the R1 outlet of the raffinate end is also responsible for controlling the operating pressure of the entire SF-SMB. The supercritical fluid flowing out of the extraction end E1 is controlled by a mass flow control valve to flow out, and then enters the separation tank 145a to separate the auxiliary solvent and the solute. The carbon dioxide gas flowing out of the extraction tank E1 and the extraction tank R1 separation tank is combined and recycled together.

Next, a method for separating unsaturated fatty acids from linseed oil by using simulated moving bed chromatography will be described below. After providing the simulated moving bed 100 as shown in FIG. 1, the ethylated linseed oil is injected from the feed inlet F1 between the second section and the third section of the simulated moving bed 100 and unsaturated fatty acids are made. Move with the stationary phase to the extraction end E1 between the first section and the second section and make other mixtures (such as saturated fatty acids) in the ethylated linseed oil move with the mobile phase to the third section.端 R1. In order to achieve the above-mentioned separation results, the mobile phase selects a detergent containing supercritical carbon dioxide and pure ethanol. In this embodiment, based on the total amount of the detergent, the content of pure ethanol is 1 wt% to 8 wt%. In one embodiment, the content of pure ethanol is 5% based on the total amount of detergent. [ Analysis method establishment ]

In the analysis method, an Agilent gas chromatography mass spectrometer (GC / MS) (model 7890A / 59770B) was used to analyze the composition of the ethylated linseed oil sample (Hebei Xinqidian Company). The analytical capillary column used was DB -5MS (30 m ^L × 250 μm ^ID ), and use 1.0 ml / min helium as the band gas. The temperature rising conditions of the gas chromatography mass spectrometer were set as follows: the initial temperature was 120 ° C, and the temperature was increased to 10 ° C / min to 210 ° C, and then the temperature was maintained for 10 minutes, and then the temperature was increased to 10 ° C / min to 270 ° C for 12 minutes. The temperature was raised from ℃ / min to 270 ℃ for 6 minutes, the injection volume was 1 μL, and the split was 30: 1.

Figure 2 is a gas chromatographic mass spectrometric analysis of an ethylated linseed oil sample. In FIG. 2, the internal standard IS uses pentadecane at 500 mg / L, and the remaining fatty acids are compared based on the data in the MS database and are shown in FIG. 2. From the GC / MS spectrum, the wave front positions of ethylated linolenic acid, ethylated linoleic acid, ethylated palmitic acid, ethylated oleic acid, and ethylated stearic acid can be clearly read. Based on the results, Is the analysis standard.

In this embodiment, calibration curves for ethylated linolenic acid and ethylated linoleic acid are prepared, and the response factors obtained are 0.894 and 0.734, respectively. The above calibration curves are combined with fifteen carbon linear alkanes as the internal standard The response factor ( m ) of the product is defined as shown in the following formula 1: (Formula 1) In Formula 1, A and A _is are area of the sample and the standards in the analysis pattern of, C, and C _is a concentration of the sample and the standards, V, and V _is an injection feed liquid sample With the volume of the internal standard. Based on this, it was found that the ratio of linoleic acid to linolenic acid in the ethylated linseed oil sample was 7.90: 1. It can be seen from the graph of FIG. 2 that the separation of linoleic acid from linolenic acid is the easiest. In order to facilitate understanding of the subsequent separation effect of linolenic acid and linoleic acid, the present invention defines the weight part of linolenic acid in the sum of linoleic acid and linolenic acid as purity, and the purity of linolenic acid in the above-mentioned linseed oil sample is 0.888. [ Purity and Recovery of Extraction and Extraction Ends ]

In this embodiment, the definitions of the purity and recovery of the extraction end and the raffinate end are as shown in the following formulas 2 and 3, respectively. (Eq. 2) (Equation 3) In equations 2 and 3, P represents purity, Y represents recovery, C is concentration obtained by regression calculation of GC / MS spectrum, Q is ethanol flow rate, and superscript E and superscript R respectively represent extraction. The ends and the raffinate ends, and the subscripts 18: 3 and 18: 2 respectively represent linolenic acid and linoleic acid. Experimental Example 1 [ Operating Conditions of SF-SMB ]

In Experimental Example 1, an ethylated linseed oil raw material (Hebei Xinqidian Company) was first prepared into a 10.0 g / L ethanol solution. Next, a simulated moving bed tomography method was performed using the supercritical fluid simulated moving bed apparatus shown in FIG. 1. The packed column is an 80 mm DAC column. The packing (stationary phase) used is random silica (Zeoprep60, 40 μm ~ 60 μm, Zeochem), and the packing height is 230 mm. The mobile phase is a detergent containing supercritical carbon dioxide and 5 wt% pure ethanol. The separation conditions are: the temperature is fixed at 50 ° C, the pressure at the outlet of the raffinate end is 121 bar, and the pressure at the inlet of the rinse agent is 130 bar. The flow rate of carbon dioxide at each inlet and outlet is set as follows: the inlet of the scrubbing end is 26.5 kg / hr; the inlet of the feed is 1.5 kg / hr; the extraction end is 11.19 kg / hr (the value calculated using the conservation of mass); the residual end It is 16.81 kg / hour (value inferred from conservation of mass). The flow rate of pure ethanol at the inlet is set as follows: the inlet of the scrubbing end is 29.39 ml / min; the inlet of the feed is 1.65 ml / min; the extraction end is 12.44 ml / min (the value calculated by using mass conservation); The ethanol flow rate was 18.60 ml / min (values extrapolated using mass conservation). In addition, in Experimental Example 1, the valve switching time (3 minutes 35 seconds, 3 minutes 38 seconds, and 3 minutes 48 seconds) on the SF-SMB device was changed at a fixed flow rate at each inlet and outlet, and then the two outlets were observed. Changes in the composition of the sample collected at the sprue.

FIG. 3 is an analysis diagram of the results of separating and purifying unsaturated fatty acids from linseed oil by using simulated moving bed chromatography in an experimental example of the present invention. It can be seen from the results in FIG. 3 that linseed oil and linoleic acid (that is, unsaturated fatty acids) are strongly retentive components, and palmitic acid and stearic acid (that is, saturated fatty acids) are weakly retentive components. When the switching time is 3 minutes 35 seconds and 3 minutes 38 seconds, the unsaturated fatty acids can be effectively separated from the saturated fatty acids, and the recovery rate is close to 100%.

From the above, it can be known that the simulated moving bed in this embodiment uses a washing agent containing supercritical carbon dioxide and pure ethanol as a mobile phase, so the unsaturated fatty acids containing linolenic acid and linoleic acid in the linseed oil can be purified and separated. Experimental example 2

In Experimental Example 2, an ethylated linseed oil raw material (Hebei Xinqidian Company) was first formulated into a 9.823 g / L ethanol solution. Next, a simulated moving bed tomography method was performed using the supercritical fluid simulated moving bed apparatus shown in FIG. 1. The packed column is an 80 mm DAC column. The packing (stationary phase) used is random silica (Zeoprep60, 40 μm ~ 60 μm, Zeochem), and the packing height is 230 mm. The mobile phase is a detergent containing supercritical carbon dioxide and 5 wt% pure ethanol. The separation conditions are: the temperature is fixed at 50 ° C, the pressure at the outlet of the raffinate end is 121 bar, and the pressure at the inlet of the rinse agent is 130 bar. The carbon dioxide flow rate at each inlet and outlet is set as follows: the inlet of the scrubbing end is 26.5 kg / hr; the inlet of the feed is 1.5 kg / hr; the extraction end is 11.78 kg / hr (the value calculated using the conservation of mass); the residual end 16.22 kg / hour (value inferred from conservation of mass). The flow rate of pure ethanol at the feed inlet is set as follows: the inlet of the scrubbing end is 29.39 ml / min; the inlet of the feed is 1.65 ml / min; the extraction end is 13.10 ml / min (the value calculated by using mass conservation); The ethanol flow rate was 17.94 ml / min (values extrapolated from conservation of mass). In addition, in Experimental Example 2, under the condition that the flow rates of the inlets and outlets are fixed, the interval of the valve switching time (3 minutes, 50 seconds and 3 minutes, 53 seconds) on the SF-SMB equipment is changed, and then the samples collected at the two discharge ports The composition changes. The analysis of the results obtained by the simulated moving bed chromatography using the above conditions is shown in FIG. 4. Table 1 shows the results of the content (defined as purity) and recovery calculated from Equation 2 and Equation 3.

Table 1         <TABLE border = "1" borderColor = "# 000000" width = "85%"> <TBODY> <tr> <td> Switching time </ td> <td> Concentration (mg / l) </ td> <td > Purity </ td> <td> Recovery rate </ td> </ tr> <tr> <td> Extraction solution </ td> <td> Extraction solution </ td> <td> P <sub> E </ sub> </ td> <td> P <sub> R </ sub> </ td> <td> Y <sub> E </ sub> </ td> <td> Y <sub> R </ sub> </ td> </ tr> <tr> <td> Linolenic acid </ td> <td> Linoleic acid </ td> <td> Linolenic acid </ td> <td> Linoleic acid </ td > </ tr> <tr> <td> 3 minutes 53 seconds </ td> <td> 723.7 </ td> <td> 67.2 </ td> <td> 756.7 </ td> <td> 133.17 </ td > <td> 0.915 </ td> <td> 0.150 </ td> <td> 0.410 </ td> <td> 0.732 </ td> </ tr> <tr> <td> 3 minutes 50 seconds </ td > <td> 833.0 </ td> <td> 79.9 </ td> <td> 579.5 </ td> <td> 103.0 </ td> <td> 0.912 </ td> <td> 0.151 </ td> < td> 0.511 </ td> <td> 0.64 </ td> </ tr> </ TBODY> </ TABLE>

FIG. 4 is an analysis diagram of a result of separating and purifying unsaturated fatty acids from linseed oil by using simulated moving bed chromatography in an experimental example of the present invention. Please refer to FIG. 4 and Table 1. If the simulated moving bed chromatography is performed under the conditions of the above Experimental Example 2 and operated at a switching time of 3 minutes, 50 seconds to 3 minutes, 53 seconds, the flax in the unsaturated fatty acid at the end is extracted. The acid purity can be increased from 0.888 in the original flaxseed oil to about 0.915. Experimental example 3

In Experimental Example 3, the ethylated linseed oil raw material (Hebei Xinqidian Company) was first formulated into a 9.823 g / L ethanol solution. Next, a simulated moving bed tomography method was performed using the supercritical fluid simulated moving bed apparatus shown in FIG. 1. The packed column is an 80 mm DAC column. The packing (stationary phase) used is random silica (Zeoprep60, 40 μm ~ 60 μm, Zeochem), and the packing height is 230 mm. The mobile phase is a detergent containing supercritical carbon dioxide and 5 wt% pure ethanol. The separation conditions are: the temperature is fixed at 50 ° C, the pressure at the outlet of the raffinate end is 121 bar, and the pressure at the inlet of the rinse agent is 130 bar. The carbon dioxide flow rate at each inlet and outlet is set as follows: the inlet of the scrubbing end is 26.5 kg / hr; the inlet of the feed is 0.75 kg / hr; the extraction end is 11.78 kg / hr (the value calculated using the conservation of mass); the residual end 15.47 kg / hour (value inferred from conservation of mass). The flow rate of pure ethanol at the inlet is set as follows: the inlet of the scrubbing end is 29.39 ml / min; the inlet of the feed is 0.825 ml / min; the extraction end is 13.10 ml / min (the value calculated by using mass conservation); The ethanol flow rate was 17.12 ml / min (values extrapolated using mass conservation). In addition, in Experimental Example 3, the valve switching time (4 minutes, 4 minutes, 05 seconds, and 4 minutes and 10 seconds) on the SF-SMB equipment was changed at a fixed flow rate at each inlet and outlet, and then the two discharge ports were observed. The composition of the collected samples changed. The analysis of the results obtained by the simulated moving bed chromatography using the above conditions is shown in FIG. 5. Table 2 shows the results of the content (defined as purity) and recovery calculated from Equation 2 and Equation 3.

Table 2         <TABLE border = "1" borderColor = "# 000000" width = "85%"> <TBODY> <tr> <td> Switching time </ td> <td> Concentration (mg / l) </ td> <td > Purity </ td> <td> Recovery rate </ td> </ tr> <tr> <td> Extraction solution </ td> <td> Extraction solution </ td> <td> P <sub> E </ sub> </ td> <td> P <sub> R </ sub> </ td> <td> Y <sub> E </ sub> </ td> <td> Y <sub> R </ sub> </ td> </ tr> <tr> <td> Linolenic acid </ td> <td> Linoleic acid </ td> <td> Linolenic acid </ td> <td> Linoleic acid </ td > </ tr> <tr> <td> 4 minutes and 10 seconds </ td> <td> 84.3 </ td> <td> 6.3 </ td> <td> 558.9 </ td> <td> 63.9 </ td > <td> 0.930 </ td> <td> 0.103 </ td> <td> 0.103 </ td> <td> 0.930 </ td> </ tr> <tr> <td> 4 minutes 05 seconds </ td > <td> 138.0 </ td> <td> 10.8 </ td> <td> 490.3 </ td> <td> 73.8 </ td> <td> 0.928 </ td> <td> 0.131 </ td> < td> 0.177 </ td> <td> 0.900 </ td> </ tr> <tr> <td> 4 minutes </ td> <td> 174.6 </ td> <td> 14.7 </ td> <td> 270.1 </ td> <td> 47.5 </ td> <td> 0.922 </ td> <td> 0.149 </ td> <td> 0.330 </ td> <td> 0.810 </ td> </ tr> < / TBODY> </ TABLE>

FIG. 5 is an analysis diagram of the result of separating and purifying unsaturated fatty acids from linseed oil by using simulated moving bed chromatography in an experimental example of the present invention. Please refer to FIG. 5 and Table 2. When the flow rate at the feed end is reduced by half from the conditions of Example 2 and operated at a switching time of 4 minutes to 4 minutes and 10 seconds, the purity of linolenic acid in the unsaturated fatty acid at the extraction end Increased from 0.915 to about 0.930. Experimental Example 4

In Experimental Example 4, the ethylated linseed oil raw material (Hebei Xinqidian Company) was first formulated into ethanol solutions of different concentrations (50 g / l, 100 g / l, 250 g / l). Next, a simulated moving bed tomography method was performed using the supercritical fluid simulated moving bed apparatus shown in FIG. 1. The packed column is an 80 mm DAC column. The packing (stationary phase) used is random silica (Zeoprep60, 40 μm ~ 60 μm, Zeochem), and the packing height is 230 mm. The mobile phase is a detergent containing supercritical carbon dioxide and 5 wt% pure ethanol. The separation conditions are: the temperature is fixed at 50 ° C, the pressure at the outlet of the raffinate end is 121 bar, and the pressure at the inlet of the rinse agent is 130 bar. The carbon dioxide flow rate at each inlet and outlet is set as follows: the inlet of the scrubbing end is 26.5 kg / hr; the inlet of the feed is 0.75 kg / hr; the extraction end is 11.78 kg / hr (the value calculated using the conservation of mass); the residual end 15.47 kg / hour (value inferred from conservation of mass). The flow rate of pure ethanol at the inlet is set as follows: the inlet of the scrubbing end is 29.39 ml / min; the inlet of the feed is 0.825 ml / min; the extraction end is 13.10 ml / min (the value calculated by using mass conservation); The ethanol flow rate was 17.12 ml / min (values extrapolated using mass conservation). In addition, in Experimental Example 4, under the condition that the flow rates of the inlets and outlets are fixed, the valve switching time (3 minutes, 55 seconds, and 4 minutes) on the SF-SMB equipment is shortened correspondingly as the feed concentration increases. The composition of the sample collected at each outlet was changed. Specifically, when the feed concentration is 50 g / L, the switching time is 4 minutes; when the feed concentration is 100 g / L, the switching time is 4 minutes; when the feed concentration is 250 g / L, the switching time is 3 Minutes 55 seconds. The analysis of the results obtained by the simulated moving bed chromatography using the above conditions is shown in FIG. 6. Table 3 shows the results of the content (defined as purity) and recovery calculated from Equation 2 and Equation 3.

table 3         <TABLE border = "1" borderColor = "# 000000" width = "85%"> <TBODY> <tr> <td> Feed concentration (g / l) </ td> <td> Extraction (mg / Liters) </ td> <td> Raffinate (mg / liter) </ td> <td> Purity </ td> <td> Recovery rate </ td> <td> Switching time </ td> </ tr > <tr> <td> Linolenic acid </ td> <td> Linoleic acid </ td> <td> Linolenic acid </ td> <td> Linoleic acid </ td> <td> P <sub> E </ sub> </ td> <td> P <sub> R </ sub> </ td> <td> Y <sub> E </ sub> </ td> <td> Y <sub> R </ sub> </ td> </ tr> <tr> <td> 50 </ td> <td> 148.8 </ td> <td> 17.5 </ td> <td> 171.3 </ td> <td> 24.9 < / td> <td> 0.895 </ td> <td> 0.127 </ td> <td> 0.398 </ td> <td> 0.652 </ td> <td> 4 minutes </ td> </ tr> <tr > <td> 100 </ td> <td> 705.4 </ td> <td> 69.0 </ td> <td> 665.1 </ td> <td> 94.9 </ td> <td> 0.911 </ td> < td> 0.125 </ td> <td> 0.447 </ td> <td> 0.643 </ td> <td> 4 minutes </ td> </ tr> <tr> <td> 250 </ td> <td> 2834 </ td> <td> 230.4 </ td> <td> 2733 </ td> <td> 348.0 </ td> <td> 0.925 </ td> <td> 0.113 </ td> <td> 0.441 < / td> <td> 0.665 </ td> <td> 3 minutes 55 seconds </ td> </ tr> </ TBODY> </ TABLE>

FIG. 6 is an analysis diagram of the result of separating and purifying unsaturated fatty acids from linseed oil by using simulated moving bed chromatography in an experimental example of the present invention. Please refer to FIG. 6 and Table 3. When the feed concentration is increased to 250 g / L, the purity of linolenic acid in the unsaturated fatty acid at the extraction end is still higher than 0.925, and the recovery rate is 0.441. From the above, it can be seen that the simulated moving bed chromatography using a high feed concentration can still purify unsaturated fatty acids with high purity linolenic acid. Therefore, it is speculated that if the ethylated linseed oil raw material is replaced with ethylated linseed A feed solution of seed oil in ethanol should also give unsaturated fatty acids with high purity linolenic acid. Example 2: Purification of linolenic acid

In this embodiment, the purification of linolenic acid can be divided into two separation steps (a first simulated moving bed chromatography process and a second simulated moving bed chromatography process). In the first simulated moving bed chromatography process, a Supercritical Fluid-Simulated Moving Bed (SF-SMB) system is used to perform the simulated moving bed chromatography. In the second simulated moving bed chromatography process, a reversed-phase moving bed (RP-SMB) system is used to perform the simulated moving bed chromatography.

In this embodiment, the supercritical fluid simulated moving bed system uses the same supercritical fluid simulated moving bed equipment as in Embodiment 1 (ie, FIG. 1). Therefore, the same elements are denoted by the same reference numerals, and will not be described repeatedly.

In the present embodiment, the reverse-phase simulated moving bed system includes, for example, the simulated moving bed 200 shown in FIG. 7. FIG. 7 is a configuration design diagram of a simulated moving bed according to an embodiment of the present invention. Referring to FIG. 7, the simulated moving bed 200 includes a fourth section, a fifth section, and a sixth section. In this embodiment, the fourth section includes two pipe columns C1 and C2, the fifth section includes two pipe columns C3 and C4, and the sixth section includes two pipe columns C5 and C6. The above six pipes The columns are connected in series.

The simulated moving bed 200 includes two inlets, which are the sample inlet F3 (that is, the inlet position of the column C5) and the inlet D3 (that is, the inlet position of the column C1), and includes two outlets, respectively It is the extraction end E3 (that is, the column C2 exit position) and the extraction excess end R3 (that is, the column C6 exit position).

In this embodiment, the simulated moving bed 200 has six pipe columns, but the present invention is not limited thereto. In another embodiment, the simulated moving bed 200 has eight columns, wherein the first section includes two columns C1 and C2, the second section includes three columns C3, C4, and C5, and the third section The segment contains 3 columns C6, C7 and C8, and the above 8 columns are connected in series. In this embodiment, the number of pipe columns of the simulated moving bed 200 is different from that of the simulated moving bed 100, but the present invention is not limited thereto. In another embodiment, the number of columns of the simulated moving bed 200 is the same as the number of columns of the simulated moving bed 100.

Next, a method for separating unsaturated fatty acids from linseed oil by using simulated moving bed chromatography will be described below. In the first simulated moving bed chromatography process of this embodiment, the ethylated linseed oil is injected from the feed inlet F1 between the second section and the third section of the simulated moving bed 100, and the linen The unsaturated fatty acids of linoleic acid and linoleic acid move with the stationary phase to the extraction end E1 between the first section and the second section, and other mixtures (such as saturated fatty acids) in the ethylated linseed oil follow the mobile phase. Move to the raffinate end R1 of the third section. In order to achieve the above-mentioned separation results, the mobile phase selects a detergent containing supercritical carbon dioxide and pure ethanol. In this embodiment, based on the total amount of the detergent, the content of pure ethanol is 1 wt% to 8 wt%. In one embodiment, the content of pure ethanol is 5 wt% based on the total amount of detergent.

In order to further separate linolenic acid from unsaturated fatty acids containing linolenic acid and linoleic acid, the unsaturated fatty acids (containing linolenic acid and linoleic acid) collected from the extraction end E1 described above were subjected to a second simulated moving bed chromatography Process. In the second simulated moving bed chromatography process of this embodiment, the unsaturated fatty acids (including linolenic acid and linoleic acid) collected at the extraction end E1 in the first simulated moving bed chromatography process are injected into the simulated mobile Between the fifth section and the sixth section of the bed 200, and the linolenic acid in the unsaturated fatty acid moves with the mobile phase to the raffinate end R3 of the sixth section, and other mixtures of the unsaturated fatty acid follow the stationary phase Move to the extraction end E3 between the fourth section and the fifth section. In order to achieve the above separation results, the reversed phase packing was selected for the stationary phase. The reverse-phase filler is, for example, ODS-modified silica. For example, ODS (Octa Decyl Silane) modified silicon dioxide is, for example, InertSil ODS-3. In this embodiment, the mobile phase is, for example, pure ethanol or a 95% ethanol solution. Experimental example 5 [ Operating conditions of RP-SMB ]

In Experimental Example 5, the separated unsaturated fatty acid having a feed concentration of 250 g / L in Experimental Example 4 was used as the feed for the second simulated moving bed chromatography process, and the above feed was adjusted to 10 g / L. Ethanol solution. In addition, in Experimental Example 5, a simulated moving bed shown in FIG. 7 was used. The packed column size is 4.6 mm × 100 mm), and the packing (stationary phase) used is InertSil ODS-3 (5 μm). The mobile phase was a 95% ethanol solution. The 95% ethanol flow rate of each inlet and outlet is set as follows: the inlet of the scrubbing end is 0.96 ml / min; the inlet of the feed is 0.01 ml / min; the extraction end is 0.36 ml / min; the flow rate of ethanol at the extract end is 0.61 ml / min . In addition, in Experimental Example 5, the valve switching time (6 minutes and 6 minutes and 30 seconds) on the SF-SMB device was changed under the condition of fixed flow rates at each inlet and outlet, and then the composition of the samples collected at the two outlets was observed. Change of switching time. The analysis of the results obtained by the simulated moving bed chromatography using the above conditions is shown in FIG. 8, and the results of the purity and recovery calculated according to Equation 2 and Equation 3 are shown in Table 4.

Table 4         <TABLE border = "1" borderColor = "# 000000" width = "85%"> <TBODY> <tr> <td> Switching time </ td> <td> Concentration (mg / l) </ td> <td > Purity </ td> <td> Recovery rate </ td> </ tr> <tr> <td> Extraction solution </ td> <td> Extraction solution </ td> <td> P <sub> E </ sub> </ td> <td> P <sub> R </ sub> </ td> <td> Y <sub> E </ sub> </ td> <td> Y <sub> R </ sub> </ td> </ tr> <tr> <td> Linolenic acid </ td> <td> Linoleic acid </ td> <td> Linolenic acid </ td> <td> Linoleic acid </ td > </ tr> <tr> <td> 6 minutes and 30 seconds </ td> <td> 17.51 </ td> <td> 2.71 </ td> <td> 4.00 </ td> <td> 0.00 </ td > <td> 0.134 </ td> <td> 1.000 </ td> <td> 1.00 </ td> <td> 0.279 </ td> </ tr> <tr> <td> 6 minutes </ td> < td> 36.62 </ td> <td> 4.08 </ td> <td> 2.96 </ td> <td> 0.00 </ td> <td> 0.100 </ td> <td> 1.000 </ td> <td> 1.00 </ td> <td> 0.120 </ td> </ tr> </ TBODY> </ TABLE>

FIG. 8 is an analysis diagram of the results of separating and purifying linolenic acid from linseed oil by simulated moving bed chromatography in an experimental example of the present invention. Please refer to FIG. 8 and Table 4. Since RP-SMB system is used for purification, linseed oil becomes a weak retention component, so linolenic acid is collected at the raffinate end. In addition, in this embodiment, 95% ethanol is used as a mobile phase and a reversed-phase filler is used as a stationary phase, so the purity of the purified linolenic acid is as high as 100%. Experimental Example 6 [ Operating Conditions of RP-SMB ]

In Experimental Example 6, the separated unsaturated fatty acid with a feed concentration of 250 g / L in Experimental Example 4 was used as the feed for the second simulated moving bed chromatography process, and the above feed was adjusted to 10 g / L. Ethanol solution. In addition, in Experimental Example 6, a simulated moving bed shown in FIG. 7 was used. The packed column size is 4.6 mm × 100 mm), and the packing (stationary phase) used is InertSil ODS-3 (5 μm). The mobile phase was a pure ethanol solution. The flow rate of pure ethanol at each inlet and outlet is set as follows: the inlet of the scrubbing end is 0.96 ml / min; the inlet of the feed is 0.016 ml / min; the extraction end is 0.36 ml / min; the flow rate of ethanol at the extract end is 0.616 ml / min. In addition, in Experimental Example 6, the valve switching time (4 minutes 20 seconds, 4 minutes 25 seconds, and 4 minutes 30 seconds) on the SF-SMB equipment was changed under the conditions of fixed flow rates of the inlets and outlets, and then two discharges were observed. The composition of the sample collected in the mouth varies with the switching time. The analysis of the results obtained by the simulated moving bed chromatography using the above conditions is shown in FIG. 9, and the results of the purity and recovery calculated according to Equation 2 and Equation 3 are shown in Table 5.

table 5         <TABLE border = "1" borderColor = "# 000000" width = "85%"> <TBODY> <tr> <td> Switching time </ td> <td> Concentration (mg / l) </ td> <td > Purity </ td> <td> Recovery rate </ td> </ tr> <tr> <td> Extraction solution </ td> <td> Extraction solution </ td> <td> P <sub> E </ sub> </ td> <td> P <sub> R </ sub> </ td> <td> Y <sub> E </ sub> </ td> <td> Y <sub> R </ sub> </ td> </ tr> <tr> <td> Linolenic acid </ td> <td> Linoleic acid </ td> <td> Linolenic acid </ td> <td> Linoleic acid </ td > </ tr> <tr> <td> 4 minutes 30 seconds </ td> <td> 697.3 </ td> <td> 55.7 </ td> <td> 365.2 </ td> <td> 19.5 </ td > <td> 0.074 </ td> <td> 0.949 </ td> <td> 0.873 </ td> <td> 0.150 </ td> </ tr> <tr> <td> 4 minutes 25 seconds </ td > <td> 6543.0 </ td> <td> 433.4 </ td> <td> 431.4 </ td> <td> 27.3 </ td> <td> 0.062 </ td> <td> 0.941 </ td> < td> 0.903 </ td> <td> 0.104 </ td> </ tr> <tr> <td> 4 minutes and 20 seconds </ td> <td> 14170 </ td> <td> 854.8 </ td> < td> 243.9 </ td> <td> 11.4 </ td> <td> 0.057 </ td> <td> 0.955 </ td> <td> 0.978 </ td> <td> 0.028 </ td> </ tr > </ TBODY> </ TABLE>

FIG. 9 is an analysis diagram of the result of separating and purifying linolenic acid from linseed oil by simulated moving bed chromatography in an experimental example of the present invention. Please refer to FIG. 9 and Table 5. Using pure ethanol as the mobile phase and reversed-phase packing as the stationary phase, the purity of the purified linolenic acid is as high as 94.15% to 95.5%.

In summary, the method for purifying unsaturated fatty acids of the present invention can separate the unsaturated fatty acids containing linolenic acid and linoleic acid from linseed oil by applying simulated moving bed chromatography, which can not only effectively improve the separation efficiency, but also High purity unsaturated fatty acids containing linolenic acid and linoleic acid are obtained. In addition, the linolenic acid purification method of the present invention can further purify linolenic acid from linseed oil by performing a second simulated moving bed chromatography process. Similarly, not only can the separation efficiency be effectively improved, but high purity Linolenic acid.

Although the present invention has been disclosed as above with the examples, it is not intended to limit the present invention. Any person with ordinary knowledge in the technical field can make some modifications and retouching without departing from the spirit and scope of the present invention. The protection scope of the present invention shall be determined by the scope of the attached patent application.

100, 200‧‧‧ Simulated Moving Bed

110‧‧‧CO2 supply source

115‧‧‧CO2 liquid pump

120‧‧‧High-pressure buffer tank

122‧‧‧Front end pressure regulator

123‧‧‧ rear pressure regulator

125a, 125b‧‧‧‧High-performance liquid chromatography pump

130‧‧‧ mixer

145a, 145b, 155‧‧‧ separation tank

160‧‧‧Working tank

C1, C2, C3, C4, C5, C6, C7, C8‧‧‧

D1, D3‧‧‧‧Polishing end entrance

D2, F2‧‧‧ input port

E1, E3‧‧‧Extract

F1; F3‧‧‧feed inlet

IS‧‧‧ Internal Standard

R1, R3‧‧‧‧Excess

FIG. 1 is a pipeline flowchart of a supercritical fluid simulated moving bed device according to an embodiment of the present invention. Figure 2 is a gas chromatographic mass spectrometric analysis of an ethylated linseed oil sample. FIG. 3 is an analysis diagram of the results of separating and purifying unsaturated fatty acids from linseed oil by using simulated moving bed chromatography in an experimental example of the present invention. FIG. 4 to FIG. 6 are analysis results of experimental examples of the present invention using simulated moving bed chromatography to separate and purify unsaturated fatty acids from linseed oil. FIG. 7 is a configuration design diagram of a simulated moving bed according to an embodiment of the present invention. FIG. 8 and FIG. 9 are analysis results of the separation and purification of linolenic acid from linseed oil by simulated moving bed chromatography in an experimental example of the present invention.

Claims (16)

A method for purifying unsaturated fatty acids, comprising: providing ethylated linseed oil; and separating the unsaturated fatty acids in the ethylated linseed oil by simulated moving bed chromatography, wherein the separated said Unsaturated fatty acids include linolenic acid and linoleic acid, wherein the simulated moving bed chromatography method includes: providing a simulated moving bed, the simulated moving bed sequentially including a first section, a second section, and a third section, Wherein the simulated moving bed is composed of a mobile phase and a stationary phase, the stationary phase particles have pores inside, and the movement flows through the inlet of the washing end in the same direction relative to the simulated moving bed. Between the first section, the second section, and the third section, the stationary phase is simulated to move in a reverse direction relative to the mobile phase, and the mobile phase includes supercritical carbon dioxide and pure ethanol Cleaning agent, wherein each of the first section, the second section, and the third section includes 2 columns, 3 columns, and 3 columns, and each column is filled with Said stationary phase; said ethylating Hemp seed oil is injected from the feed inlet between the second section and the third section of the simulated moving bed, and the unsaturated fatty acid moves with the stationary phase to the first section The extraction end between the second section and the other mixture in the ethylated linseed oil moves with the mobile phase to the extraction end of the third section to separate the saturated fatty acid. The method for purifying unsaturated fatty acids according to item 1 of the scope of the patent application, wherein the content of the pure ethanol is 1 wt% to 8 wt% based on the total amount of the detergent. The method for purifying unsaturated fatty acids according to item 1 of the scope of patent application, wherein the stationary phase is random silica. The method for purifying unsaturated fatty acids according to item 1 of the scope of patent application, wherein the separation conditions used in the simulated moving bed are: the flow rate of carbon dioxide at the inlet of the scrubbing end is 26.5 kg / hour, at the inlet of the feed 1.5 kg / h, 11.19 kg / h at the extraction end and 16.81 kg / h at the extraction end, and the flow rate of pure ethanol at the inlet of the scrubbing end was 29.39 ml / min, at The feed inlet is 1.65 ml / min, 12.44 ml / min at the extraction end and 18.60 ml / min at the extract end, and the switching time of the simulated moving bed is 3 minutes 35 seconds to 3 minutes and 48 seconds. The method for purifying unsaturated fatty acids according to item 1 of the scope of patent application, wherein the separation conditions used in the simulated moving bed are: the flow rate of carbon dioxide at the inlet of the scrubbing end is 26.5 kg / hour, at the inlet of the feed 1.5 kg / hour, 11.78 kg / hour at the extraction end and 16.22 kg / hour at the extraction end, and the flow rate of pure ethanol at the inlet of the scrubbing end was 29.39 ml / minute, at The feed inlet is 1.65 ml / min, 13.10 ml / min at the extraction end and 17.94 ml / min at the rest end, and the switching time of the simulated moving bed is 3 minutes and 50 seconds to 3 minutes and 53 seconds. The method for purifying unsaturated fatty acids according to item 1 of the scope of patent application, wherein the separation conditions used in the simulated moving bed are: the flow rate of carbon dioxide at the inlet of the scrubbing end is 26.5 kg / hour, at the inlet of the feed 0.75 kg / hour at the extraction end, 11.78 kg / hour at the extraction end, and 15.47 kg / hour at the extraction end, and the flow rate of pure ethanol was 29.39 ml / min at the inlet of the scrubbing end, at The feed inlet is 0.825 ml / min, 13.10 ml / min at the extraction end and 17.12 ml / min at the rest end, and the switching time of the simulated moving bed is 4 minutes to 4 minutes 10 seconds. A method for purifying linolenic acid includes: providing ethylated linseed oil; performing a first simulated moving bed chromatography process to separate unsaturated fatty acids in the ethylated linseed oil, wherein the separated The unsaturated fatty acid includes linolenic acid and linoleic acid. The first simulated moving bed chromatography process includes: providing a first simulated moving bed, and the first simulated moving bed includes a first section and a second section in sequence. Segment and third segment, wherein the first simulated moving bed is composed of a first mobile phase and a first stationary phase, the first stationary phase particles have pores inside, and the first movement is relative to the In the simulated moving bed, the first stationary phase flows through the first section, the second section, and the third section from the inlet of the first washing end in the same direction. The first mobile phase simulates a movement in the opposite direction, wherein the first mobile phase is a detergent containing supercritical carbon dioxide and pure ethanol, wherein the first section, the second section, and the third section Sections each contain 2 columns and 3 tubes And three tube columns, each of which is filled with the first stationary phase; the ethylated linseed oil is injected into the second section of the simulated moving bed and the Between the third segment, and moving the unsaturated fatty acid with the first stationary phase to a first extraction end between the first segment and the second segment and causing the B The other mixture in the esterified linseed oil moves with the first mobile phase to the first raffinate end of the third section to separate the unsaturated fatty acids; and performs a second simulated moving bed chromatography process, To separate the linolenic acid in the separated unsaturated fatty acids, the second simulated moving bed chromatography process includes: providing a second simulated moving bed, and the second simulated moving bed sequentially includes a fourth Section, the fifth section, and the sixth section, wherein the second simulated moving bed is composed of a second mobile phase and a second stationary phase, and the second stationary phase particles have pores inside, and the first The two moves relative to the second simulated moving bed are flushed from the second direction in the same direction. The inlet flows between the fourth section, the fifth section, and the sixth section, and the second stationary phase is simulated to move in a reverse direction relative to the second mobile phase, wherein the The second stationary phase is a reversed-phase packing, wherein each of the fourth section, the fifth section, and the sixth section includes two columns, and each of the columns is filled with the second stationary phase. ; Injecting the unsaturated fatty acid from the second feed inlet between the fifth section and the sixth section of the second simulated moving bed, and allowing linolenic acid in the unsaturated fatty acid to follow The second mobile phase moves to the second raffinate end of the sixth section, and causes the other mixture in the unsaturated fatty acid to move with the second stationary phase to the fourth section and The second extraction end between the fifth sections to separate linolenic acid from linoleic acid. The method for purifying linolenic acid according to item 7 in the scope of the patent application, wherein the content of the pure ethanol in the rinse agent is 1 wt% to 8 wt% based on the total amount of the rinse agent. The method for purifying linolenic acid according to item 7 of the scope of patent application, wherein the first stationary phase is random silica. The method for purifying linolenic acid according to item 7 of the scope of the patent application, wherein the separation conditions used in the first simulated moving bed are: the flow rate of carbon dioxide at the inlet of the first scouring end is 26.5 kg / hour, The first feed inlet is 1.5 kg / hr, 11.19 kg / hr at the first extraction end and 16.81 kg / hr at the first extraction end, and the flow rate of the pure ethanol is at the first The inlet of the rinse end is 29.39 ml / min, 1.65 ml / min at the first feed inlet, 12.44 ml / min at the first extraction end, and 18.60 ml / min at the first raffinate end Minutes, and the switching time of the first simulated moving bed is 3 minutes 35 seconds to 3 minutes 48 seconds. The method for purifying linolenic acid according to item 7 in the scope of the patent application, wherein the separation conditions used in the simulated moving bed are: the flow rate of carbon dioxide at the inlet of the first scrubbing end is 26.5 kg / hour, The feed inlet is 1.5 kg / hr, 11.78 kg / hr at the first extraction end and 16.22 kg / hr at the first extraction end, and the flow rate of the pure ethanol is at the first rinse The end inlet is 29.39 ml / min, the first feed inlet is 1.65 ml / min, the first extraction end is 13.10 ml / min, and the first raffinate end is 17.94 ml / min, And the switching time of the first simulated moving bed is 3 minutes and 50 seconds to 3 minutes and 53 seconds. The method for purifying linolenic acid according to item 7 of the scope of the patent application, wherein the separation conditions used in the first simulated moving bed are: the flow rate of carbon dioxide at the inlet of the first scrubbing end is 26.5 kg / hour, The first feed inlet is 0.75 kg / hr, 11.78 kg / hr at the first extraction end and 15.47 kg / hr at the first extraction end, and the flow rate of the pure ethanol is at the first The inlet of the rinse end is 29.39 ml / min, 0.825 ml / min at the first feed inlet, 13.10 ml / min at the first extraction end, and 17.12 ml / min at the first raffinate end Minutes, and the switching time of the first simulated moving bed is 4 minutes to 4 minutes and 10 seconds. The method for purifying linolenic acid according to item 7 of the scope of patent application, wherein the reversed-phase filler comprises ODS-modified silica. The method for purifying linolenic acid according to item 7 of the patent application scope, wherein the second mobile phase comprises pure ethanol or a 95% ethanol solution. The method for purifying linolenic acid according to item 7 of the scope of the patent application, wherein the separation conditions used in the second simulated moving bed are: the second mobile phase is a 95% ethanol solution, and the flow rate of the 95% ethanol solution 0.96 ml / min at the second inlet, 0.01 ml / min at the second inlet, 0.36 ml / min at the second extraction end, and at the second raffinate The end is 0.61 ml / min, and the switching time of the second simulated moving bed is 6 minutes to 6 minutes and 30 seconds. The method for purifying linolenic acid according to item 7 in the scope of the patent application, wherein the separation conditions used in the second simulated moving bed are: the second mobile phase is the pure ethanol, and the flow rate of the pure ethanol is The inlet of the second washing end is 0.96 ml / min, 0.016 ml / min at the second feed inlet, 0.36 ml / min at the second extraction end, and 0.616 ml / min, and the switching time of the second simulated moving bed is 4 minutes and 20 seconds to 4 minutes and 30 seconds.