KR100514760B1 - Concentration Method of Glycyrrhizin from Glycyrrhiza Extract Using Polymeric Ultrafiltration or Microfiltration Membrane - Google Patents

Abstract

The present invention passes the licorice extract through a cartridge-type pretreatment filter having a size of 1 to 50 micrometers to remove wood parts, insoluble particles, and various suspended substances present in the licorice extract, and then the fraction molecular weight of about 10,000 to 200,000 daltons ( starch, gums, ash, proteins and sugars present in licorice extract using a polymeric ultrafiltration membrane having a molecular weight cut-off or a microfiltration membrane having a pore size of 0.05 to 0.5 micrometers. The present invention relates to a process for increasing the concentration of glycyrrhizin, an active ingredient widely used in medicine, cosmetics, tobacco flavor, and natural sweeteners by separating and removing impurities.

According to the method of the present invention, by using a polymer ultrafiltration membrane or a microfiltration membrane in concentrating glycyrrhizin from licorice extract, the use of ion exchange resins and adsorptive resins used to reduce the amount of alcohol and to remove various ionic components It can be extremely limited, which simplifies the process and prevents secondary contamination by alcohol, ion exchange resins or adsorbent resins, and also periodically polarizes the filtration membrane to form concentration polarization on the surface of the membrane. And pore fouling of the membrane can be reduced, thereby improving the permeability and economically and efficiently separating and concentrating glycyrrhizin from licorice extract.

Description

Concentration Method of Glycyrrhizin from Glycyrrhiza Extract Using Polymeric Ultrafiltration or Microfiltration Membrane

The present invention relates to a method for concentrating and isolating glycyrrhizin from licorice extract, and more particularly, to a method for separating and concentrating glycyrrhizine to an effective concentration from licorice extract using a polymer ultrafiltration membrane or a microfiltration membrane.

Licorice (Glycyrrhiza uralensis Fisch, Glycyrrhiza glabra L.) is a perennial herb that is a plant belonging to the legumes (Leguminosae), used for medicinal and edible use.Its stem has white short hairs and the root is cylindrical and long and coarse. The outer shell is reddish brown to dark brown. The main components of licorice extract are glycyrrhizin, glycyrrhetic acid, and licoricidin. Among them, glycyrrhizin is the main ingredient of licorice and is 50 times more than sugar and has anti-inflammatory, detoxification and anti-ulcer properties. It is widely used as food, cosmetics, medicines, tobacco flavors, etc. by using properties such as action and surfactant activity.

In order to increase the concentration of glycyrrhizin in licorice extracts, Korean Patent Laid-Open Publication Nos. 2000-49485 and 1998-77716 disclose an extraction process for extracting licorice extract with methanol, a purification and decolorization process using anion exchange resin, and a crystallization process for recrystallization with ethanol. Combination method was used. However, this has a disadvantage that the amount of alcohol is used and impurities such as starch, rubbery, and ash are not sufficiently removed, and an additional process is required for the treatment of licorice residues after extraction. In addition, to remove starch and rubbery or protein after extraction, it is difficult to use various types of filters, to remove them by using an adsorption resin, or to frequently change the elements of the filter, and to frequently wash the resin. In addition, ion exchange resins are used to remove ash, but strong acids or strong alkalis must be used to regenerate the ion exchange resins, causing serious environmental problems as well as adsorbing glycyrazine, an active ingredient in most resins. Rather, it plays a role. Japanese Patent Laid-Open Nos. 56-553398, 57-459800 and 59-20222 describe a method for extracting and purifying licorice root with water and various organic solvents such as methanol, ethanol, butanol, acetone, ether and ethyl ether. However, licorice extract by these methods has a problem of low purity of glycyrrhizin and a complicated process, which makes it impossible to apply the field.The use of a large amount of organic solvent prevents the poor working environment and environmental pollution caused by organic solvents. There are some drawbacks to not coping properly.

Also, in the 105-108 Korean Journal of Film Society 1999 Spring Conference, a paper was used to separate glycyrrhizin using alumina ultrafiltration membrane. They used a pore-size 50 angstrom filtration membrane made of alumina to separate glycyrrhizin, but the alumina filtration membrane had a disadvantage in that its adsorption was so strong that the permeate flow rate was reduced to within 10% of the initial permeate flow rate and lost economic feasibility within 10 minutes of operation. In addition, the pore size of 50 angstroms is too small pore size that is not suitable for the concentration process of glycyrrhizin, such pore size is not suitable because it shows a significantly low permeation flux.

An object of the present invention is to suppress the use of organic solvents and simplify the process by introducing a process using a polymer ultrafiltration membrane or a microfiltration membrane in separating and concentrating glycyrrhizin from licorice extract to solve the problems of the prior art, the use of alcohol By minimizing this, it is to provide an economical and environmentally friendly method for separating and concentrating glycyrrhizin.

This object of the present invention is achieved by separating and concentrating glycyrrhizin from licorice extract using a polymer ultrafiltration membrane or a microfiltration membrane.

Licorice extracts are generally highly viscous, and it has been anticipated that it would not be suitable to use a filtration membrane to separate and concentrate glycirigin therefrom, with some attempts to use the separator, but with no effective results. However, the inventors of the present invention, through numerous experiments, do not pass through the filtration membrane even though glycyrizine with a molecular weight of slightly higher than 800 is smaller than the pore size of the molecule, so that glycyrizine does not act independently and works with other substances in licorice extract. Or other substances contaminated the filtration membrane, and based on this, the pore size and filtration membrane material suitable for the separation and concentration of glycyrrhizin were studied, and the pores of the filtration membrane should be considerably larger than the glycyrrhizin molecules. Concentrated in a concentrated solution, the undesired substances are found to accumulate in the permeate through the membrane to complete the invention.

The present invention passes through a cartridge type pretreatment filter having a size of 1 to 50 micrometers in order to remove coarse particles such as wood parts, particulate matter, or insoluble suspended matter present in licorice extract extracted using hot water. The ultrafiltration membrane made of a polymer having a fraction molecular weight of 10,000 to 200,000 Daltons or a microfiltration membrane made of a polymer having a pore size of 0.05 to 0.5 micrometers was used to pass almost all of the low molecular weight substances, ions, etc., which are present independently of each other, It relates to a glycyrrhizin enrichment process that continues operation until the glycyrazine reaches a constant concentration by excluding it, and the material of the polymer filtration membrane is regenerated cellulose, polyacrylonitrile (PAN), polysulfone (Polysulfone). , Polyethersulfone, polybi Preference is given to polyvinylidene fluoride and the like.

Licorice extract that can be treated in the method of the present invention is a diluent for maintaining a low viscosity to be suitable for application to the filtration membrane process as a primary extract extracted with hot water, wherein the dilution ratio is preferably a viscosity of about 30 centipoise or less In order to increase the separation efficiency to 20 centipoise or less, a small amount of C2 to C4 alcohol may be added.

Polymer ultrafiltration membrane or microfiltration membrane that can be used in the present invention is a regenerated cellulose or polyisulfone, polysulfone-based ultrafiltration membrane fractional molecular weight of 10,000 Daltons to 200,000 Daltons, the microfiltration membrane has a pore size of 0.05 to 0.5 microns Meters of preferably 0.2 micrometers can be used, and the shape of the filtration membrane can be preferably a plate-like and tubular membrane, and the transmembrane pressure between the outer surface and the inner surface of the filtration membrane is preferably 0.4 to 5 atm. .

The continuous filtration membrane system as shown in FIG. 1 is used in the method for separating and concentrating glycyrrhizin from the licorice extract of the present invention.

In the continuous filtration membrane system of the present invention, the licorice extract diluent 51 that is introduced passes through the pretreatment filter 52 before being introduced into the feed tank 53, where particulate matter such as wood is removed, and the feed tank 53 is provided. From the feed pump 54 to the polymer ultrafiltration membrane or microfiltration membrane module, that is, the polymer filtration membrane module 56, the ash, low-molecular substances, ions, etc., which are present independently, permeate the filtration membrane, and the permeate 57 of licorice extract It is reused as a diluent or treated and discharged. The concentrated component in the filtration membrane is recycled to the feed tank 53 through the concentrated liquid discharge pipe 58 to condense glycyrrhizin, and when a certain concentration is reached, the operation is stopped and discharged from the feed tank 53 through the discharge pipe 59. Go to product storage. Filtration membrane module inflow and discharge flowmeters (FI1, FI2) were installed to measure the flow rate into and out of the filter membrane module, and permeate discharge flowmeter (FI3) was installed to measure the permeate flow rate. The pressure difference in the filtration membrane was measured by installing the filtration membrane module inflow and discharge pressure gauges (PG1, PG2), respectively, and the pressure gauge (PG3) was installed in the permeate of the filtration membrane to measure the membrane permeation pressure and the backwash pressure. In addition, a back washing apparatus using high pressure nitrogen is installed to reduce the so-called concentration polarization phenomenon in which the removed particles accumulate on the surface of the filtration membrane.

Hereinafter, the present invention will be described in more detail with reference to Examples, but the present invention is not limited thereto.

Example 1

The licorice extract diluent diluted 10 wt%, 20 wt%, and 30 wt% licorice extract using hot water was equipped with a regenerated cellulose-based ultrafiltration membrane module having a fractional molecular weight of 30,000 Daltons in the filtration membrane system of FIG. 1. The transmittance was measured, and in particular, the operating results at the operating pressure of 1.0 atm and the operating temperature of 25 degrees Celsius are shown in FIG. 2. In case of 10 wt%, the initial permeation flux was about 50 LMH, but the permeation flux decreased with time. 20% by weight showed lower permeation flow rate than 10% by weight, and 30% by weight (15 centipoise of viscosity) showed a lower permeation flow rate, but the rate of decrease of permeation flow rate was decreasing, which is advantageous for long time operation. have. In addition, high performance liquid chromatography (HPLC) was used for component analysis of the licorice extract diluent used as the feed solution and the permeate passed through the filtration membrane, and the results are shown in FIG. 3. In Figure 3 of the present embodiment, glycyrrhizin, peak 22, in any case it can be seen that almost no permeation of the ultrafiltration membrane of 30,000 Daltons.

Example 2

Distilled licorice extract using hot water was prepared in 5% by weight and 10% by weight, and equipped with a polyisulfone ultrafiltration membrane module having a molecular weight of 100,000 Daltons in the filtration membrane system of FIG. 1, operating pressure was 1.0, at an operating temperature of 15 degrees Celsius. The experiments were changed to 1.5, 2.1, 2.5 and 3.0 atm. Experimental time for each operating pressure was about 1 hour to reach a steady state, Table 1 is the permeation flux measured 1 hour after the experiment. When the licorice extract was diluted to 5% by weight, the permeation flux was more than twice higher than when diluted to 10% by weight.

Operating pressure (kgf / ㎠) Permeate Flow Rate (1 / ㎡-hr) 5 wt% 10% by weight 1.0 36.5 18.9 1.5 39.7 21.6 2.1 44.1 24.3 2.5 47.5 27.1 3.0 51.2 29.4

In addition, 5% by weight and 10% by weight licorice extract diluent supplied to the filtration membrane module was analyzed using high performance liquid chromatography to analyze the concentration of glycyrrhizin. It was 14.152 area% for% licorice extract dilution and 16.373 area% for 10 wt% licorice extract diluent. Table 2 shows the concentration of 5% by weight and 10% by weight licorice extract diluent with the filtration membrane, and then the high performance liquid chromatography analysis of the concentrate and the concentration of glycyrrhizin components based thereon. The degree of concentration was calculated as the ratio of the glycyrazine peak areas of the concentrates run at each operating pressure for the glycidazine peak areas 14.152 and 16.373 of the 5 wt% and 10 wt% licorice extract dilutions fed to the separator. In the case of 5% by weight, the concentration ratio gradually decreased from 2.23 to 1.87 as the operating pressure increased, and in the case of 10% by weight, the concentration ratio continued to decrease from 1.73 to 1.40. 5 wt% compared to 10 wt% showed higher concentration ratios for the same operating pressure but in any case was shown to be useful as a method for increasing the content of glycyrizine.

Operating pressure (kgf / ㎠) High Performance Liquid Chromatography Assay 5 wt% 10% by weight area% Concentration area% Concentration 1.0 31.562 2.2302 28.331 1.7303 1.5 28.758 2.0321 24.730 1.5104 2.1 29.322 2.0719 23.524 1.4368 2.5 28.925 2.0439 23.221 1.4182 3.0 26.449 1.8689 22.997 1.4046

Example 3

Diluted licorice extract using hot water was equipped with a polyisulfone microfiltration membrane module having a pore size of 0.2 micrometer in the filtration membrane system of FIG. 1 and tested in the method of [Example 2]. The results are shown in Table 3 and Table 4. It was. The permeation flux in the microfiltration membrane was maintained about 1.5 to 1.6 times higher than the ultrafiltration membrane having a molecular weight of 100,000 Daltons. The rate of permeation flux decreased more rapidly than in [Example 2], but the permeation flux was still high at steady state. However, the concentration ratio was relatively low compared to the ultrafiltration membrane having a molecular weight of 100,000 Daltons, which means that the pores were large and some of the glycyrrhizin component was discharged through the filtration membrane. The degree of glycyrazine release was greater at lower dilution ratios. However, the microfiltration membrane used in this embodiment has an advantage that the concentration time can be shortened by having a very high permeation flux compared to the ultrafiltration membrane having a molecular weight of 100,000 Daltons.

Operating pressure (kgf / ㎠) Permeate Flow Rate (1 / ㎡-hr) 5 wt% 10% by weight 1.0 41.0 25.1 1.5 46.9 28.7 2.1 52.3 31.6 2.5 55.6 35.2 3.0 59.2 38.4

Operating pressure (kgf / ㎠) High Performance Liquid Chromatography Assay 5 wt% 10% by weight area% Concentration area% Concentration 1.0 28.465 2.0114 28.6757 1.7514 1.5 27.919 1.9728 24.4482 1.4932 2.1 28.338 2.0024 24.1104 1.4726 2.5 27.111 1.9157 23.2513 1.4201 3.0 26.669 1.8845 22.8993 1.3986

Example 4

The licorice extract using hot water was diluted to 20% by weight, and a polysulfone tubular microfiltration membrane module having a pore size of 0.2 micrometer was installed in the filtration membrane system of FIG. 1, and was tested by the method of [Example 1], and the permeation flux was almost unchanged. The permeate was collected at steady state and analyzed by high performance liquid chromatography. The area% was 2.73, indicating a relatively low permeability. The change in permeation flux with time is shown in Table 5.

Driving time (seconds) Permeate Flow Rate (1 / ㎡-hr) 60 21.2 600 19.1 1200 16.7 1800 14.6 2100 13.9 3000 13.2

Comparative Example 1

The alumina tubular nanofiltration membrane module having a pore size of 50 angstroms was mounted in the filtration membrane system of FIG. 1 and tested by the method of [Example 4], but the filtration membrane contamination occurred seriously, and as a result, the membrane permeation flow rate was the same as in the above examples. No results were obtained. As a result of analyzing the permeate by high performance liquid chromatography, the area% was 0.28, and the permeation was not good, and the permeation flux with time decreased very rapidly as shown in Table 6, which lost economic feasibility within ten minutes. This rapid decrease in permeation rate seems to be due to membrane fouling and concentration polarization due to strong physical bonding between the surface of the membrane and the licorice extract.

Driving time (seconds) Permeate Flow Rate (1 / ㎡-hr) 60 8.2 600 6.9 1200 4.1 1800 3.0 2100 1.4 3000 0.6

According to the method of the present invention, it is possible to remove impurities from the extract extracted with hot water from licorice and to easily increase the content of the required active ingredients such as glycyrrhizine, limited to the content of glycyrrhizine, but as the content of glycyrrhizine increases It can be extended to pharmaceuticals, cosmetics, tobacco flavors, and natural sweeteners.

In addition, according to the method of the present invention, by concentrating glycyrrhizine using a polymer filtration membrane, it is possible to prevent the deterioration of the working environment due to the use of the organic solvent and to minimize the environmental problems, the ion exchange resin process used to remove ions Since it can be omitted, the process can be simplified to reduce the production cost, and there is no need for the use of strong acids and strong alkalis for the regeneration of the ion exchange resin, so as not to cause pollution problems.

1 is a schematic view showing a filtration membrane system manufactured and used in the present invention.

2 is an ultrafiltration membrane module having a molecular weight of 30,000 Daltons of fractional molecular weight of regenerated cellulose (Regenerated Cellulose) after diluting licorice extract to 10 wt%, 20 wt% and 30 wt%, respectively, at an operating pressure of 1 atmosphere at a temperature of 25 degrees Celsius. When separated by the filtration membrane system of Figure 1 is a graph showing the permeation flux over time.

Figure 3 is a graph showing the results of analyzing the licorice extract diluent used as a feed solution and the permeate passed through the filtration membrane using high performance liquid chromatography (HPLC) when separating the glycyrrhizin from the licorice extract by the method of FIG.

<Description of Symbols for Main Parts of Drawings>

51: licorice extract diluent 52: pretreatment filter

53: feed tank 54: feed pump

55: bypass tube 56: polymer filtration membrane module

57: permeate 58: concentrate discharge pipe

59: discharge pipe FI1: filtration membrane module inflow flow meter

FI2: filtration membrane module discharge flow meter FI3: permeate discharge flow meter

PG1: filtration membrane module inlet pressure gauge PG2: filtration membrane module outlet pressure gauge

PG3: permeate pressure gauge V1, V2: flow rate and pressure regulating valve

V3, V4: Permeate Discharge Valve V5: Concentrate Discharge Valve

Claims (5)

In the method of concentrating glycyrrhizin from licorice extract, a molecular weight cut-off of a polymer ultrafiltration membrane of 10,000 to 200,000 Daltons or a polymer microfiltration membrane having a pore size of 0.05 to 0.5 micrometer is used. And permeate the independent low molecular weight material, ions, ash, and the like to separate and remove from the licorice extract to concentrate glycyrrhizin. The material of claim 1, wherein the filtration membrane is made of any one of regenerated cellulose, polyethersulfone, polyvinylidenefluoride, polyacrylonitrile, and polysulfone polymer. A method for concentrating glycyrrhizin from a single licorice extract. The method of claim 1, wherein the licorice extract is a method for concentrating glycyrrhizin from a licorice extract which is diluted to have a viscosity of 30 centipoise or less. The method according to any one of claims 1 to 3, wherein the glycyrazine is concentrated from the licorice extract whose transmembrane pressure is 0.4 to 5 atm. The method of claim 1, wherein the method comprises concentrating glycyrrhizin from the licorice extract comprising a pretreatment process to remove coarse matter through a cartridge type pretreatment filter of 1 to 50 micrometers in size.