CN109908624B - Device and method for separating methyl linolenate based on ionic liquid supported liquid membrane - Google Patents
Device and method for separating methyl linolenate based on ionic liquid supported liquid membrane Download PDFInfo
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Abstract
The invention discloses a device and a method for separating methyl linolenate based on an ionic liquid supported liquid membrane, wherein the device comprises a membrane reactor, a stripping phase delivery pump, a stripping phase tank, a raw material phase delivery pump and a raw material tank, wherein the raw material tank is filled with a raw material liquid containing methyl linolenate, and the stripping phase tank is filled with a stripping solvent; an ionic liquid supporting liquid film is arranged in the membrane reactor and divides the membrane reactor into an upper membrane cavity and a lower membrane cavity; the liquid inlet of the upper film cavity is connected to the liquid outlet of the upper film cavity through a stripping phase delivery pump and a stripping phase tank by pipelines to form a stripping phase pipeline circulating system; the liquid inlet of the lower film cavity is connected to the liquid outlet of the lower film cavity through a raw material phase delivery pump and a raw material tank by pipelines to form a raw material phase pipeline circulating system. The invention adopts Ag+The ionic liquid membrane liquid used as a carrier soaks the hydrophilic base membrane into the ionic liquid supporting liquid membrane, so that high-purity methyl linolenate can be obtained by continuously separating from the vegetable oil methyl ester.
Description
Technical Field
The invention relates to the technical field of production devices for separating and purifying methyl linolenate, in particular to a device and a method for separating methyl linolenate based on an ionic liquid supported liquid membrane.
Background
Linolenic acid is a polyunsaturated fatty acid belonging to the omega-3 series, is a basic substance constituting cell membranes and biological enzymes, has the functions of maintaining lipoprotein balance, regulating cholesterol metabolism and reducing blood pressure and blood fat, is a fatty acid necessary for a human body, but cannot be synthesized by the human body and must be taken from the outside.
Linolenic acid is often present in vegetable oils such as linseed oil, perilla seed oil, Chinese tallow kernel oil, etc. in the form of glyceride together with oleic acid, linoleic acid, palmitic acid, etc. Since the properties between unsaturated fatty acids are similar, differing only in carbon chain length and number of double bonds, there is a great difficulty in separation. The existing methods for separating polyunsaturated fatty acid ester include urea inclusion method, molecular distillation method, freezing crystallization method and silver ion complexation method. These methods are applied to some extent in the separation of polyunsaturated fatty acids, but each of them has problems of high cost, low purity, and complicated operation.
The membrane separation technology has the advantages of high separation effect, low energy consumption, simple and convenient operation and the like, and is widely concerned. The membrane liquid of the immersed supported liquid membrane is adsorbed in micropores of the support body by means of surface tension and capillary action, the raw material phase and the stripping phase flow at two sides of the membrane, and the solute to be separated is transferred from the raw material phase to the stripping phase through the membrane phase, so that the membrane liquid has the advantages of high efficiency, high selectivity, large permeation flux, small membrane liquid consumption and the like.
The ionic liquid is a compound composed of ions, has the excellent characteristics of low vapor pressure, high thermal stability, good dissolving capacity and the like, and can be used as a film liquid phase to obviously improve the stability of a liquid film. The ionic liquid has designability, and inorganic anions and organic cations are adjusted according to actual needs to form a green chemical solvent with unique functions. At present, the utilization of ionic liquid as membrane liquid phase is one of the hot points in the field of supported liquid membrane.
Disclosure of Invention
Aiming at the defects of the prior methyl linolenate separation technology and overcoming the problems in the prior art, the invention aims to provide a device and a method for separating methyl linolenate, which are simple and convenient to operate and high in selectivity.
The reaction device for separating the methyl linolenate based on the ionic liquid supported liquid membrane is characterized by comprising a membrane reactor, a stripping phase delivery pump, a stripping phase tank, a raw material phase delivery pump and a raw material tank, wherein the raw material tank contains a raw material liquid containing the methyl linolenate, a stripping solvent is contained in the stripping phase tank, and the stripping phase tank and the raw material tank are both arranged below the membrane reactor; an ionic liquid supported liquid membrane for separating the methyl linolenate is arranged in the membrane reactor, and the ionic liquid supported liquid membrane is made of Ag+The membrane reactor is divided into an upper membrane cavity and a lower membrane cavity by an ionic liquid supporting liquid membrane; the liquid inlet of the upper film cavity is connected to the liquid outlet of the upper film cavity through a pipeline by a stripping phase delivery pump and a stripping phase tank in sequence to form a stripping phase pipeline circulating system; the liquid inlet of the lower film cavity is connected to the liquid outlet of the lower film cavity through a raw material phase delivery pump and a raw material tank by pipelines in sequence to form a raw material phase pipeline circulating system.
The reaction device for separating the methyl linolenate based on the ionic liquid supported liquid membrane is characterized in that the membrane reactor comprises a reactor component, the reactor component comprises a polytetrafluoroethylene plate and a small O-shaped ring, the polytetrafluoroethylene plate is provided with a cylindrical groove on the inner side, the small O-shaped ring is embedded into the cylindrical groove in a matched mode, a pair of communicating pore channels for liquid circulation is symmetrically arranged on the bottom surface of the cylindrical groove, and the thickness of the small O-shaped ring is slightly larger than the depth of the cylindrical groove; two polytetrafluoroethylene boards align from top to bottom, closely laminate between the inboard little O type circle of upside polytetrafluoroethylene board and the inboard little O type circle of downside polytetrafluoroethylene board ionic liquid supports the liquid film, and two polytetrafluoroethylene boards press from both sides tight connection fixed again, splice promptly and form membrane reactor.
The reaction device for separating the methyl linolenate based on the ionic liquid supported liquid membrane is characterized in that two opposite sides of the polytetrafluoroethylene plate are respectively provided with a rubber tube in a penetrating manner, and the two rubber tubes are respectively communicated with a pair of communicating pore channels on the bottom surface of the cylindrical groove so as to input and output liquid through the rubber tubes.
The reaction device for separating the methyl linolenate based on the ionic liquid supported liquid membrane is characterized in that the reactor assembly further comprises a large O-shaped ring, an annular groove for embedding the large O-shaped ring is formed in the inner side of the polytetrafluoroethylene plate, and the annular groove is formed in the outer side of the cylindrical groove; the ionic liquid supported liquid membrane is of a wafer structure, the diameter of the ionic liquid supported liquid membrane is the same as the outer diameter of the large O-shaped ring, when the membrane reactor is formed by splicing, the outer side edge of the ionic liquid supported liquid membrane is tightly attached between the large O-shaped ring on the inner side of the upper polytetrafluoroethylene plate and the large O-shaped ring on the inner side of the lower polytetrafluoroethylene plate, and therefore liquid leakage is further prevented.
A method for separating methyl linolenate based on an ionic liquid supported liquid membrane is characterized by comprising the following steps:
1) diluting vegetable oil methyl ester containing methyl linolenate with petroleum ether, and placing into a raw material tank as raw material liquid; taking a mixed solvent of 1-hexene and petroleum ether as a stripping solvent, and placing the stripping solvent into a stripping phase tank;
2) simultaneously operating a stripping phase delivery pump and a raw material phase delivery pump, enabling a stripping solvent in a stripping phase tank to enter an upper membrane cavity of the membrane reactor, then flowing out and returning to the stripping phase tank, enabling a raw material liquid in the raw material tank to enter a lower membrane cavity of the membrane reactor, and then flowing out and returning to the raw material tank, so that the stripping solvent and the raw material liquid respectively circulate and flow in membrane cavities at two sides of an ionic liquid supporting liquid membrane in the membrane reactor in a cross-flow mode; carrying Ag on ionic liquid supported liquid membrane+Under the action of promoting transfer and diffusion, the methyl linolenate enters the stripping solvent from the raw material liquid;
3) and after the separation of the methyl linolenate from the raw material liquid is finished, stopping operating the stripping phase delivery pump and the raw material phase delivery pump, sequentially washing the stripping solvent in the stripping phase tank with a saturated sodium chloride solution and distilled water for 1-3 times, and removing 1-hexene and petroleum ether through rotary evaporation to obtain the final product, namely the methyl linolenate.
The method for separating the methyl linolenate on the basis of the ionic liquid supported liquid membrane is characterized in that in the stripping solvent in the step 1), the mass fraction of 1-hexene is 5-15%, and the preferred mass fraction is 10%; in the step 2), the conveying flow rate of the stripping phase conveying pump is 15-60 mL/min, preferably 40mL/min, and the conveying flow rates of the raw material phase conveying pump and the stripping phase conveying pump are the same.
The method for separating the methyl linolenate based on the ionic liquid supported liquid membrane is characterized in that the concentration of the methyl linolenate in the raw material liquid in the step 1) is 5-40 mg/mL, and preferably 10 mg/mL.
The method for separating the methyl linolenate based on the ionic liquid supported liquid membrane is characterized in that the preparation method of the ionic liquid supported liquid membrane comprises the following steps:
s1: taking hydrophilic imidazole ionic liquid and AgBF4Uniformly mixing in a centrifugal tube, adding 1-hexene serving as a pretreatment agent into the centrifugal tube, oscillating and completely layering the imidazole ionic liquid and the pretreatment agent to obtain a lower ionic liquid phase and an upper pretreatment agent phase;
s2: and (5) uniformly coating the ionic liquid phase on the lower layer in the step (S1) on the nylon membrane, shading and standing for 4-6 min to completely soak the nylon membrane, and slightly wiping off the ionic liquid adhered to the surface of the nylon membrane to obtain the ionic liquid supported liquid membrane.
The method for separating methyl linolenate based on the ionic liquid supported liquid membrane is characterized in that in the step S1, the hydrophilic imidazole ionic liquid is [ C ]2mim][BF4]、[C4mim][BF4]Or [ C8mim][NTF2](ii) a Volume of the imidazole ionic liquid and AgBF4The mass ratio of (A) is 1-5: 1, preferably 2:1, the unit of volume is mL, and the unit of mass is g; in step S1, the volume ratio of the imidazole ionic liquid to 1-hexene is 0.5-2: 1, preferably 1: 1.
The method for separating the methyl linolenate based on the ionic liquid supported liquid membrane is characterized in that the mass fraction of the nylon membrane in the ionic liquid supported liquid membrane prepared in the step S2 is 40-60%.
Compared with the prior art, the invention has the following beneficial effects:
the invention can realize the continuous separation and extraction of the methyl linolenate, adopts the organic nylon membrane, is easy to be infiltrated by hydrophilic ionic liquid, and has better stability and mass transfer performance; when the ionic liquid supported liquid membrane is prepared, only a very small amount of ionic liquid needs to be loaded on the nylon membrane (for example, when a disk-shaped nylon membrane with the diameter of 5cm is adopted, only 0.10-0.15 g of ionic liquid needs to be loaded, so that the loading amount of the ionic liquid is about 40-60%), so that a solvent with high migration promoting carrier content or an extractant with high price and excellent performance can be selected. The stripping solvent adopts 5-15 wt% of 1-hexene-petroleum ether solution. Ag＋The complex reaction is easy to occur with double bonds, and the addition of 1-hexene in the stripping solvent is more beneficial to the back extraction of methyl linolenate from a liquid film, so that the selectivity and the permeation flux of the methyl linolenate are improved. The method is simple to operate, the ionic liquid supported liquid membrane is high in stability, and the method has a wide application prospect in the field of separation of methyl linolenate.
The flow rates of the raw material liquid and the stripping solvent are moderate when the raw material liquid and the stripping solvent flow on two sides of the ionic liquid supported liquid membrane, the permeation flux of the methyl linolenate is low when the flow rate is too low, and the membrane liquid is easy to run off when the flow rate is too high. When the raw material liquid and the stripping solvent flow on two sides of the ionic liquid supported liquid membrane, the extraction and the back extraction of the methyl linolenate are synchronously carried out, so that the continuous separation and purification of the methyl linolenate are realized.
The small O-shaped ring and the large O-shaped ring are arranged on the inner side of the polytetrafluoroethylene plate, so that the condition of liquid leakage can be effectively prevented; and when the upper polytetrafluoroethylene plate and the lower polytetrafluoroethylene plate are clamped, connected and fixed, the ionic liquid supported liquid film is stable under the action of the gaskets of the small O-shaped ring and the large O-shaped ring.
Drawings
FIG. 1 is a schematic diagram of the overall structure of a reaction device for separating methyl linolenate based on an ionic liquid supported liquid membrane according to the present invention;
FIG. 2 is a schematic diagram of a split structure of a reaction device for separating methyl linolenate based on an ionic liquid supported liquid membrane;
FIG. 3 is a top view of the inside of a polytetrafluoroethylene sheet of the invention;
in the figure: the device comprises a membrane reactor 1, a polytetrafluoroethylene plate 2, a cylindrical groove 3, a stripping phase delivery pump 4, a stripping phase tank 5, a raw material phase delivery pump 6, a raw material tank 7, a screw through hole 8, a communicating pore channel 9, an annular groove 10, a rubber pipe 11 and a small O-shaped ring 12.
Detailed Description
The present invention is further illustrated by the following examples, which should not be construed as limiting the scope of the invention.
Example (b):
a reaction device for separating methyl linolenate based on an ionic liquid supported liquid membrane comprises a membrane reactor 1, a stripping phase delivery pump 4, a stripping phase tank 5, a raw material phase delivery pump 6 and a raw material tank 7, wherein a raw material liquid containing methyl linolenate is contained in the raw material tank 7, and a stripping solvent is contained in the stripping phase tank 5; an ionic liquid supporting liquid membrane for separating methyl linolenate is arranged in the membrane reactor 1, and the membrane reactor 1 is divided into an upper membrane cavity and a lower membrane cavity by the ionic liquid supporting liquid membrane; the liquid inlet of the upper film cavity is connected to the liquid outlet of the upper film cavity through a pipeline by a stripping phase conveying pump 4 and a stripping phase tank 5 in sequence to form a stripping phase pipeline circulating system; the liquid inlet of the lower film cavity is connected to the liquid outlet of the lower film cavity through a pipeline sequentially through a raw material phase delivery pump 6 and a raw material tank 7 to form a raw material phase pipeline circulating system.
The membrane reactor 1 may be of the following structure: the membrane reactor 1 comprises a reactor component, the reactor component comprises a polytetrafluoroethylene plate 2, a small O-shaped ring 12 and a large O-shaped ring, an annular groove 10 and a cylindrical groove 3 are arranged on the inner side surface of the polytetrafluoroethylene plate 2, and the annular groove 10 is arranged on the outer side of the cylindrical groove 3 and is close to the cylindrical groove 3 (compare with figure 3). The large O-shaped ring is embedded into the annular groove 10 in a matched mode (the annular large O-shaped ring completely seals the annular groove 10), the small O-shaped ring 12 is embedded into the cylindrical groove 3, the thickness of the small O-shaped ring 12 is slightly larger than the depth of the cylindrical groove 3, the thickness of the large O-shaped ring is slightly larger than the depth of the annular groove 10, and the outer diameter of the small O-shaped ring 12 is the same as the inner diameter of the cylindrical groove 3.
The bottom surface of the cylindrical groove 3 is symmetrically provided with a pair of communicating pore channels 9 for circulating liquid, two opposite sides of the polytetrafluoroethylene plate 2 are respectively penetrated by a rubber tube 11, and the two rubber tubes 11 are respectively communicated with the pair of communicating pore channels 9 on the bottom surface of the cylindrical groove 3 so as to input and output liquid through the rubber tubes 11.
And screw through holes 8 are respectively formed at four corners of the polytetrafluoroethylene plate 2. The ionic liquid supporting liquid membrane with a wafer structure is adopted, and the diameter of the ionic liquid supporting liquid membrane is the same as the outer diameter of the large O-shaped ring. When the concatenation forms membrane reactor 1 when, two polytetrafluoroethylene boards 2 align from top to bottom, will ionic liquid supports the liquid film cooperation and places on the big O type circle on downside polytetrafluoroethylene board 2, and two polytetrafluoroethylene boards 2 are tight fixedly connected of clamp again, and the tight fixed mode of connection of clamp is: the two polytetrafluoroethylene plates 2 are clamped tightly by screws passing through screw through holes 8 at four corners of the two polytetrafluoroethylene plates 2. At this time, the ionic liquid supported liquid membrane is stabilized under the clamping and fixing of gaskets of the upper small O-shaped ring 12, the lower small O-shaped ring 12 and the upper large O-shaped ring, and the small O-shaped ring 12 and the large O-shaped ring both play a role in preventing liquid leakage when liquid enters the membrane reactor 1.
The membrane reactor 1 is divided into an upper membrane cavity and a lower membrane cavity by the ionic liquid supporting liquid membrane, wherein a cavity is formed by the ionic liquid supporting liquid membrane, a small O-shaped ring 12 on the inner side surface of the upper polytetrafluoroethylene plate 2 and the cylindrical groove 3 in a surrounding mode, and the upper membrane cavity of the membrane reactor 1 is formed. And a cavity enclosed by the ionic liquid supporting liquid film, the small O-shaped ring 12 on the inner side surface of the polytetrafluoroethylene plate 2 at the lower side and the cylindrical groove 3 forms a lower membrane cavity of the membrane reactor 1. The purpose that the rubber tube is penetrated to 2 lateral parts of polytetrafluoroethylene board lies in: when liquid enters the membrane reactor 1, the liquid flows horizontally from the two sides of the ionic liquid supported liquid membrane, so that the liquid is prevented from vertically rushing to the ionic liquid supported liquid membrane.
In the following examples, the cylindrical recess 3 has an inner diameter of 47mm and a height of 2 mm. The outer diameter of the annular groove 10 is 53mm, and the diameter of the ionic liquid supported liquid membrane is 53 mm. The cross-sectional area of the cylindrical groove 3 not covered by the small O-ring 12 is the permeation area of the ionic liquid supported liquid membrane (the permeation area is a circular size with a diameter of 45 mm).
Example 1 (50 mg/mL starting material concentration-40.1 mL/min flow rate- [ C ]4mim]BF4）
1) Preparation of Chinese tallow kernel oil methyl ester raw material
The Chinese tallow kernel oil methyl esterification adopts a known method: weighing 20g of methanol and 1g of KOH, mixing and dissolving, adding into 100g of Chinese tallow kernel oil, stirring and refluxing at 60 ℃ for 1 hour, standing for layering, taking an upper oil layer, washing with water to be neutral, and removing water in vacuum to obtain the Chinese tallow kernel oil methyl ester raw material. The content of the methyl linoleate in the methyl tallow kernel oil raw material is 21.54% by a mass spectrum analyzer and a gas chromatograph.
2) Preparation of ionic liquid membrane liquid
0.5mL of 1-butyl-3-methyl-imidazolium tetrafluoroborate [ C ]4mim]BF4And 0.25g AgBF4Mixing in a centrifuge tube; and adding 0.6mL of 1-hexene serving as a pretreatment agent into a centrifuge tube, oscillating for 5 minutes by using a vortex oscillator, centrifuging for 5 minutes by using a centrifuge, and completely layering an ionic liquid phase and the pretreatment agent phase to obtain a lower extraction phase which is the required ionic liquid membrane liquid.
3) Preparation of ionic liquid supported liquid membrane
Placing a hydrophilic nylon membrane on a watch glass, dripping the prepared ionic liquid membrane on the nylon membrane, uniformly coating the front and back sides of the nylon membrane, and standing for 5 minutes in a shading way to thoroughly soak the membrane; and then, wiping off the residual ionic liquid on the surface of the membrane by using a clean paper towel under light pressure to obtain the required ionic liquid supported liquid membrane.
4) And placing the prepared ionic liquid supported liquid membrane on a polytetrafluoroethylene plate at the lower side, covering the polytetrafluoroethylene plate at the upper side, and clamping the two plates through screws and nuts at four corners.
5) Device for separating methyl linolenate from ionic liquid supported liquid membrane
Clamping the membrane reactor 1 to a position 30cm higher than an experimental table; taking 20mL of 50mg/mL petroleum ether solution of Chinese tallow kernel oil methyl ester as a raw material solution, and placing in a raw material tank 7. 20mL of a 10wt% petroleum ether solution of 1-hexene was taken as a stripping solvent and placed in a stripping phase tank 5. The raw material tank 7, the peeling phase tank 5, the raw material phase delivery pump 6 and the peeling phase delivery pump 4 are all placed on a laboratory bench. Rubber pipes on two sides of a polytetrafluoroethylene plate 2 on the upper side of the membrane reactor 1 are respectively connected with a stripping phase tank 5 and a stripping phase delivery pump 4 through pipelines, and the stripping phase tank 5 is connected with the stripping phase delivery pump 4 through a pipeline to form a stripping phase pipeline circulating system. The rubber pipes on the two sides of the polytetrafluoroethylene plate 2 on the lower side of the membrane reactor 1 are respectively connected with the raw material tank 7 and the raw material phase delivery pump 6 through pipelines, and the raw material tank 7 is connected with the raw material phase delivery pump 6 through a pipeline to form a raw material phase pipeline circulating system.
The conveying flow rates of the raw material phase conveying pump 6 and the stripping phase conveying pump 4 are set to be 40.1mL/min, the two pumps are started simultaneously, and the raw material liquid and the stripping solvent circularly flow through two sides of the ionic liquid supported liquid membrane and can continuously run for tens of hours.
Taking 1mL of stripping solvent from the stripping phase tank 5 per hour for gas chromatography analysis; run 6 hours sample analysis results: the mass content of the methyl linolenate is 77.18%, the concentration is 1.2426mg/mL, and the permeation flux of the methyl linolenate is 0.2254 mg/(cm)2·h)。
Example 2 (100 mg/mL starting material concentration-40.1 mL/min flow — [ C ]4mim][BF4]）
The concentration of the petroleum ether solution of Chinese tallow kernel oil methyl ester is changed to 100mg/mL based on the example 1, and the rest conditions are the same as the example 1.
Taking 1mL of stripping solvent from the stripping phase tank 5 per hour for gas chromatography analysis; 6-hour sampling was performed for analysis results: the mass content of the methyl linolenate is 65.51 percent, the concentration is 0.3821mg/mL, and the permeation flux of the methyl linolenate is 0.0728 mg/(cm)2·h)。
Example 3 (50 mg/mL starting material concentration-40.1 mL/min flow — [ C ]8mim][BF4]）
Variation of the type of ionic liquid on the basis of example 1 to 1-octyl-3-methyl-imidazolium tetrafluoroborate [ C ]8mim]BF4The volume of ionic liquid added was the same as in example 1.
Taking 1mL of stripping solvent from the stripping phase tank 5 per hour for gas chromatography analysis; 6-hour sampling was performed for analysis results: the mass content of the methyl linolenate is 56.30 percent, the concentration of 0.5301mg/mL, and the permeation flux of the methyl linolenate of 0.0979 mg/(cm)2·h)。
Example 4 (50 mg/mL starting material concentration-26.6 mL/min flow [ -C4mim][BF4]）
The flow rates of the raw material phase transfer pump 6 and the stripping phase transfer pump 4 were changed to 26.6mL/min based on example 1, and the other conditions were the same as example 1.
Taking 1mL of stripping solvent from the stripping phase tank 5 per hour for gas chromatographic analysis; 6-hour sampling was performed for analysis results: the mass content of the methyl linolenate is 76.07 percent, the concentration is 0.7117mg/mL, and the permeation flux of the methyl linolenate is 0.1328 mg/(cm)2·h)。
As can be seen from the results of comparing example 1 and example 2, as the concentration of methyl tallowseed oil in the feed solution increases (i.e. as the concentration of methyl linolenate in the feed solution increases), the mass transfer rate of methyl linolenate decreases because: although the increase of the concentration of the raw material is beneficial to improving the mass transfer driving force, the increase of the concentration of the raw material phase increases the solubility of the raw material phase and the liquid film phase, so that the liquid film and the carrier Ag+Is easy to lose, and leads to the reduction of the selectivity of the methyl linolenate.
The experimental results of the comparative example 1 and the example 3 show that the length of the cationic side chain of the ionic liquid is increased, the viscosity is increased, and the overlong substituent generates larger steric hindrance, so that the pi-pi complexation and the hydrogen bonding between the imidazole ring of the ionic liquid and the methyl linolenate are influenced, the diffusion capacity of the methyl linolenate in the liquid membrane is reduced, and the mass transfer rate and the selectivity of the methyl linolenate are reduced. Thus, the type of ionic liquid is important in preparing the ionic liquid supported liquid film.
As can be seen from the results of the experiments of comparative example 1 and example 4, the flow rates of the raw material liquid and the stripping solvent were increased, the external diffusion resistance of fatty acid methyl ester was decreased, and the mass transfer rates of the respective components and methyl linolenate and Ag were maintained while the internal diffusion resistance in the liquid film was maintained+The complexation and decomplexing rate of the linolenic acid is increased, and the mass transfer rate and the selectivity of the linolenic acid methyl ester are improved.
The statements in this specification merely set forth a list of implementations of the inventive concept and the scope of the present invention should not be construed as limited to the particular forms set forth in the examples.
Claims (11)
1. A method for separating methyl linolenate based on an ionic liquid supported liquid membrane is characterized by comprising the following steps:
1) diluting vegetable oil methyl ester containing methyl linolenate with petroleum ether, and placing into a stock tank (7) as stock solution; taking a mixed solvent of 1-hexene and petroleum ether as a stripping solvent, and placing the stripping solvent in a stripping phase tank (5);
2) simultaneously operating a stripping phase delivery pump (4) and a raw material phase delivery pump (6), enabling a stripping solvent in a stripping phase tank (5) to enter an upper membrane cavity of the membrane reactor (1), then flowing out and returning to the stripping phase tank (5), enabling a raw material liquid in a raw material tank (7) to enter a lower membrane cavity of the membrane reactor (1), and then flowing out and returning to the raw material tank (7), so that the stripping solvent and the raw material liquid respectively circulate and flow in membrane cavities at two sides of an ionic liquid supporting liquid membrane in the membrane reactor (1) in a cross-flow mode; carrying Ag on ionic liquid supported liquid membrane+Under the action of promoting transfer and diffusion, the methyl linolenate enters the stripping solvent from the raw material liquid;
after the separation of the methyl linolenate from the raw material liquid is finished, stopping operating the stripping phase delivery pump (4) and the raw material phase delivery pump (6), washing the stripping solvent in the stripping phase tank (5) with a saturated sodium chloride solution and distilled water for 1-3 times, and removing 1-hexene and petroleum ether through rotary evaporation to obtain a final product, namely the methyl linolenate;
the preparation method of the ionic liquid supported liquid membrane comprises the following steps:
s1: taking hydrophilic imidazole ionic liquid and AgBF4Uniformly mixing in a centrifugal tube, adding 1-hexene serving as a pretreatment agent into the centrifugal tube, oscillating and completely layering the imidazole ionic liquid and the pretreatment agent to obtain a lower ionic liquid phase and an upper pretreatment agent phase;
s2: uniformly coating the ionic liquid phase on the lower layer in the step S1 on a nylon membrane, shading and standing for 4-6 min to completely soak the nylon membrane, and slightly wiping off the ionic liquid adhered to the surface of the nylon membrane to obtain the ionic liquid supported liquid membrane;
a reaction device for separating methyl linolenate based on an ionic liquid supported liquid membrane comprises a membrane reactor (1), a stripping phase delivery pump (4), a stripping phase tank (5), a raw material phase delivery pump (6) and a raw material tank (7), wherein the raw material tank (7) is filled with a raw material liquid containing methyl linolenate, the stripping phase tank (5) is filled with a stripping solvent, and the stripping phase tank (5) and the raw material tank (7) are both arranged below the membrane reactor (1);
an ionic liquid supported liquid membrane for separating the methyl linolenate is arranged in the membrane reactor (1), and the ionic liquid supported liquid membrane is made of Ag+The membrane reactor is characterized by comprising a hydrophilic ionic liquid membrane as a carrier, wherein the membrane reactor (1) is divided into an upper membrane cavity and a lower membrane cavity by an ionic liquid supporting liquid membrane; the liquid inlet of the upper film cavity is connected to the liquid outlet of the upper film cavity through a pipeline by a stripping phase conveying pump (4) and a stripping phase tank (5) in sequence to form a stripping phase pipeline circulating system; the liquid inlet of the lower film cavity is connected to the liquid outlet of the lower film cavity through a pipeline sequentially through a raw material phase delivery pump (6) and a raw material tank (7) to form a raw material phase pipeline circulating system.
2. The method for separating methyl linolenate based on an ionic liquid supported liquid membrane according to claim 1, wherein the membrane reactor (1) comprises a reactor component, the reactor component comprises a polytetrafluoroethylene plate (2) provided with a cylindrical groove (3) on the inner side and a small O-ring (12) matched and embedded in the cylindrical groove (3), the bottom surface of the cylindrical groove (3) is symmetrically provided with a pair of communicating pore channels (9) for circulating liquid, and the thickness of the small O-ring (12) is slightly larger than the depth of the cylindrical groove (3); two polytetrafluoroethylene boards (2) align from top to bottom, closely laminate between the little O type circle (12) of upside polytetrafluoroethylene board (2) inboard and the little O type circle (12) of downside polytetrafluoroethylene board (2) inboard ionic liquid supports the liquid film, and two polytetrafluoroethylene boards (2) are pressed from both sides tight connection again and are fixed, splice promptly and form membrane reactor (1).
3. The method for separating methyl linolenate based on an ionic liquid supported liquid membrane according to claim 2, wherein two rubber tubes (11) are respectively arranged on two opposite sides of the polytetrafluoroethylene plate (2) in a penetrating manner, and the two rubber tubes (11) are respectively communicated with a pair of communicating pore channels (9) on the bottom surface of the cylindrical groove (3) so as to input and output liquid through the rubber tubes (11).
4. The method for separating methyl linolenate on the basis of an ionic liquid supported liquid membrane according to claim 2, wherein the reactor assembly further comprises a large O-ring, the inner side of the polytetrafluoroethylene plate (2) is provided with an annular groove (10) for embedding the large O-ring, and the annular groove (10) is arranged on the outer side of the cylindrical groove (3); the ionic liquid supports the liquid membrane and is the disk structure, and the diameter that ionic liquid supported the liquid membrane is the same with the external diameter of big O type circle, forms when the concatenation membrane reactor (1), the outside edge of ionic liquid supports the liquid membrane closely fits between the big O type circle of upside polytetrafluoroethylene board (2) inboard and the big O type circle of downside polytetrafluoroethylene board (2) inboard to further prevent the weeping condition.
5. The method for separating the methyl linolenate on the basis of the ionic liquid supported liquid membrane according to claim 1, wherein in the stripping solvent in the step 1), the mass fraction of 1-hexene is 5-15%; in the step 2), the conveying flow rate of the stripping phase conveying pump (4) is 15-60 mL/min, and the conveying flow rates of the raw material phase conveying pump (6) and the stripping phase conveying pump (4) are the same.
6. The method for separating the methyl linolenate on the basis of the ionic liquid supported liquid membrane according to claim 5, wherein in the stripping solvent of the step 1), the mass fraction of the 1-hexene is 10%; in the step 2), the conveying flow rate of the stripping phase conveying pump (4) is 40 mL/min.
7. The method for separating the methyl linolenate based on the ionic liquid supported liquid membrane as claimed in claim 1, wherein the concentration of the methyl linolenate in the raw material liquid in the step 1) is 5-40 mg/mL.
8. The method for separating the methyl linolenate on the basis of the ionic liquid supported liquid membrane according to claim 7, wherein the concentration of the methyl linolenate in the feed solution in the step 1) is 10 mg/mL.
9. The method for separating methyl linolenate on the basis of the ionic liquid supported liquid membrane according to claim 1, wherein in step S1, the hydrophilic imidazole-based ionic liquid is [ C ]2mim][BF4]、[C4mim][BF4]Or [ C8mim][NTF2](ii) a Volume of the imidazole ionic liquid and AgBF4The mass ratio of (A) to (B) is 1-5: 1, the unit of volume is mL, and the unit of mass is g; in the step S1, the volume ratio of the imidazole ionic liquid to 1-hexene is 0.5-2: 1.
10. The method for separating methyl linolenate on the basis of the ionic liquid supported liquid membrane according to claim 9, wherein the volume of the imidazole-based ionic liquid and the AgBF are set according to the4The mass ratio of (A) to (B) is 2:1, the unit of volume is mL, and the unit of mass is g; in step S1, the volume ratio of the imidazole-based ionic liquid to 1-hexene is 1: 1.
11. The method for separating methyl linolenate based on the ionic liquid supported liquid membrane of claim 1, wherein the ionic liquid supported liquid membrane prepared in step S2 comprises 40-60% by weight of nylon membrane.
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