JPH01197597A - Purification of fatty acid and triglyceride - Google Patents

Abstract

PURPOSE:To separate a fatty acid (alcohol ester) from a triglyceride precisely and economically, by feeding a solution containing both of said fatty acid (alcohol ester) and said triglyceride and an organic solvent to a specified quasi- moving fed. CONSTITUTION:A solution containing both of a triglyceride and a fatty acid (alcohol ester) is fed from a space 19 to a quasi-moving bed composed of an adsorption zone composed of unit packed beds 109-112, a primary purification zone composed of unit packed beds 113-116, an elution zone composed of unit packed beds 105-108 and a secondary purification zone composed of unit packed beds 105-108, wherein each unit packed bed is packed with a hydrophobic synthetic adsorptive resin; an organic solvent as an eluant is fed from a space 11 thereto; these solutions are moved through the quasi-moving bed to perform purification; a purified triglyceride solution is discharged through a space 15; and a purified fatty acid (alcohol ester) solution is discharged through a space 23.

Description

Detailed Description of the Invention [Industrial Field of Application] The present invention is directed to the treatment of triglycerides and fatty acids contained in, for example, oil and fat hydrolysis reaction liquids, oil and fat transesterification reaction liquids, etc., which contain fatty acids or their alcohol esters together with triglycerides. and/or alcohol ester.

[Prior art] Generally, in the oil and fat industry, small amounts of fatty acids or their alcohol esters contained as impurities in raw material oils and fats are separated and removed, or triglycerides and fatty acids contained in the reaction liquid in oil and fat hydrolysis reactions and transesterification reactions are used. It is industrially essential to efficiently separate the alcohol ester and its alcohol ester. For this purpose, conventionally,
The main methods used have been crystallization, distillation, and the use of alkali. However, with the crystallization method, it is difficult to efficiently separate triglycerides and fatty acids or their alcohol esters, and furthermore, on an industrial scale, it is economically disadvantageous because it requires a large refrigerator. On the other hand, the distillation method requires high temperature and high pressure, which requires a large amount of energy, and has the drawback that the triglyceride, fatty acid, or alcohol ester thereof to be treated is subject to thermal denaturation or thermal decomposition. Furthermore, methods using alkali have drawbacks such as insufficient separation efficiency and the need for a dealkalization process after separation of fatty acids.

Therefore, it has been desired to develop a technique that can precisely and economically separate triglycerides from fatty acids and/or their alcohol esters at low temperature and low pressure.

[Structure of the Invention] As a result of various studies conducted by the present inventors on a method for precisely and inexpensively separating fatty acids and/or their alcohol esters from triglycerides, the present inventors found that using a simulated moving bed, hydrophobic By using a synthetic adsorption resin and using an organic solvent as a desorbing agent, triglycerides, fatty acids and/or triglycerides can be separated.

The present inventors have discovered that it is possible to continuously separate alcohol esters or alcohol esters thereof, and have completed the present invention.・The "fatty acids" referred to in the present invention include saturated fatty acids such as capric acid, undecanoic acid, lauric acid, myristic acid, arachidic acid, stearic acid, and palmitic acid, arachidonic acid, eicosapencitric acid, myristoleic acid, and petroselin. It contains all unsaturated fatty acids such as acid, elaidic acid, linoleic acid, lylunic acid, γ-lylunic acid, docosahexaenoic acid, oleic acid, palmitoleic acid, etc., and "alcohol ester" refers to the methyl ester, It includes all lower alcohol esters such as ethyl ester and propyl ester.

Furthermore, the term "triglyceride" as used in the present invention includes all triglycerides, diglycerides, and monoglycerides having the above-mentioned fatty acids as esters.

That is, in the present invention, a raw material liquid is stored in a packed bed in which an adsorbent is housed, and the front end and the rear end are connected by a liquid passage to form an endless packed bed in which liquid circulates in one direction. It consists of introducing a liquid containing a fatty acid and/or its alcohol ester and triglyceride and an organic solvent as a removal liquid, and simultaneously withdrawing a purified triglyceride liquid and a purified fatty acid and/or alcohol ester liquid from the packed bed, The packed bed has (1) an inlet for a liquid containing a fatty acid and/or its alcohol ester and triglyceride as a raw material liquid, (2) an outlet for a purified fatty acid or its alcohol ester, and (3) an organic solvent as a desorption liquid. By arranging the inlet and (4) the triglyceride purified liquid outlet in this order along the direction of fluid flow, and intermittently sequentially moving their positions in the direction of fluid flow within the bed. The present invention provides a method for refining fats and oils, which is characterized by using a simulated moving bed.

A so-called pseudo-moving bed, i.e. a packed bed containing a solid adsorbent and connected between the front and rear ends by a fluid passageway, allowing fluid to circulate within the bed;
A desorbed fluid inlet, an adsorbent fluid outlet, a raw material fluid inlet, and a non-adsorbent fluid outlet are provided along the flow of fluid in the bed, and each fluid is continuously supplied from each inlet and outlet. By sequentially switching each inlet and outlet with those downstream at regular intervals during introduction or withdrawal, the raw material fluid can be divided into components that are relatively easily adsorbed by the solid adsorbent (adsorbate components) and components that are relatively difficult to be adsorbed. The technology for separating components (non-adsorbed components) is well known (Japanese Patent Publication No. 42-15
Examples of the use of such technology include methods for producing fructose (see JP-A-53-88335) and methods for separating maltose (see JP-A-60-67000). It will be done. However, no application examples have been reported yet regarding a method for precisely separating triglycerides from fatty acids and/or their alcohol esters using a simulated moving bed, and it has been considered difficult to apply the method.

The present invention will be explained in more detail below.

The hydrophobic synthetic adsorption resin used in the present invention has a skeleton of a copolymer of styrene and divinylbenzene, such as Amberlite XAD4 manufactured by Rohm and Haas, Duolite 88 manufactured by Sumitomo Chemical Co., Ltd.
61, Diaion HP-10 and I (P-20, manufactured by Mitsubishi Kasei Corporation), but are not limited to these.Also, the particle size of the adsorption resin is not particularly limited, but in order to prevent uneven flow in the bed. It is desirable that the pore size of the adsorption resin is 300 to 600 μm.
Although 50 people is preferable from the viewpoint of material transfer, the number is not particularly limited to this.

The higher the temperature during liquid passage, the higher the separation ability can be obtained, but from the viewpoint of stability of the oil and fat, a temperature of 10 to 60°C is desirable.

As the organic solvent used as a desorbing agent in the present invention, a mixed solvent of a polar solvent and a nonpolar solvent can be used.

Examples of polar solvents include alcohols such as methanol, ethanol, propatool, isopropanol, and butanol; ketones such as acetone, methyl ethyl ketone, and diethyl ketone; ethers such as diethyl ether and tetrahydrofuran; and methylene chloride, chloroform, and DM.
Substances such as FSDMSO are used as non-polar solvents such as saturated aliphatic hydrocarbons such as n-hexane, n-heptane, n-octane, 1so-octane, and n-decane, cycloaliphatic hydrocarbons such as cyclohexane and decalin, benzene, p
- Aromatic hydrocarbons such as xylene, but are not limited to these. The mixing ratio of these polar solvents and non-polar solvents can be appropriately set according to the affinity of triglycerides, fatty acids and/or alcohol esters thereof, and the adsorbent. For example, when using ethanol as a polar solvent and n-hexane as a non-polar solvent, the mixing ratio of both is ethanol/hexane = l/9.
Good separation is achieved with ~3/7. The raw materials triglyceride, fatty acid and/or alcohol ester thereof can be supplied dissolved in the above-mentioned organic solvent, but this is not essential.

Hereinafter, the method of the present invention will be explained in more detail based on the drawings.

FIG. 1 is a schematic diagram of an example of a pseudo moving bed used in the present invention. In Figure 1, the inside of the packed bed, which is the main part of the pseudo moving bed, is divided into 16 unit packed beds.
The number can be suitably determined according to factors such as the composition, concentration and equipment size of the triglycerides and fatty acids and/or their alcohol esters. In FIG. 1, each unit packed bed is filled with a hydrophobic synthetic adsorption resin, and a space is provided between each unit packed bed.

Each space has an inlet for introducing a mixture of triglyceride and a fatty acid or its alcohol ester into the packed bed, an inlet for an organic solvent as a desorption liquid, an outlet for extracting a purified triglyceride solution from the packed bed, and a fatty acid and/or its alcohol. Four types of ester purified liquid extraction ports are open (however, most of them are omitted in FIG. 1). Although the installation of this space is not essential, when the mixed liquid of triglyceride and fatty acid and/or its alcohol ester and the desorbed liquid introduced into the packed bed are introduced into this space, the fluid flowing down and circulating in the bed becomes This is preferable because it can be quickly diffused and mixed into the inside.

In FIG. 1, a mixed solution of triglyceride, a fatty acid and/or an alcohol ester thereof is introduced into a space 19, and an organic solvent is introduced into a space 11 as a desorbing liquid. Further, a purified triglyceride liquid is extracted from the space 15, and a purified liquid of fatty acid or its alcohol ester is extracted from the space 23. Therefore, the packed beds include an adsorption zone consisting of four unit packed beds 109-112, a primary purification zone consisting of four unit packed beds 113-116, a desorption zone consisting of four unit packed beds 101-104, and 4
It consists of four types of zones, each unit packed bed 105 to 108. The action of each zone is equivalent to that of a known simulated moving bed with triglycerides as the adsorbate component and fatty acids and/or alcohol esters thereof as the non-adsorbate component.

A concentration distribution of triglycerides and fatty acids and/or their alcohol esters is formed in the liquid in the packed bed, and this concentration distribution moves downstream while maintaining its shape. To follow this movement, there is an inlet for introducing a mixture of triglyceride and fatty acid and/or its alcohol ester or an organic solvent into the packed bed, and an outlet for the purified triglyceride liquid and the purified fatty acid and/or alcohol ester liquid from the packed bed. is sequentially switched to the lower one. The switching may be performed simultaneously for the four types of openings, or may be performed at different times for each opening. The time for which liquid is continued to be introduced or withdrawn from the same opening varies depending on the size of the unit packed bed, the flow rate within the bed, etc., but is usually several minutes to several tens of minutes. By this switching, the four zones described above sequentially move their positions in the packed bed. However, the length of each zone is always approximately constant and maintains its size and relative position as it circulates through the packed bed.

The degree of separation of triglycerides and fatty acids and/or their alcohol esters in a simulated moving bed using a hydrophobic adsorption resin as an adsorbent is influenced by various factors, but the most important factors are the flow rate of the liquid in the bed, This is the time during which liquid is continued to be introduced or withdrawn from the same opening. This means that switching to the downstream openings of the liquid inlet and outlet is equivalent to keeping the positions of the inlet and outlet constant and avoiding moving the hydrophobic adsorption resin upstream. It is also inferred from the fact that the concentration distribution of each component in the bed is formed by interaction with the liquid moving in the upstream direction. Further, this moving speed corresponds to the length (ρ) of each unit packed bed divided by the time (T) for which liquid is continued to be introduced or extracted from the same opening (12/T). As is well known, in order to separate two or more components using a simulated moving bed, the moving velocity of the non-adsorbate component in the packed bed is set to v, >Q/T in the adsorption zone, and >Q/T in the primary purification zone. v+<i2/T, in the desorption zone V,>
C/T, in the secondary purification zone v + > Q /
Let T be the moving velocity of the adsorbate component in the packed bed, V, in the adsorption zone; t vt < 12/T, and V in the primary purification zone.

In the desorption zone, vv>Q/T, and in the secondary purification zone, vt < Q/T. Therefore, the flow rate of the liquid and the time for which the liquid continues to be introduced or withdrawn from the same opening are necessarily determined from these relationships. On the other hand, the movement speed v1 of the non-adsorbate component and the movement speed of the adsorbate component in the packed bed, 2, are determined by the liquid flow rate in the packed bed, but these can be easily measured using a batch-type packed bed. It goes without saying that it can be done.

Next, the present invention will be specifically explained using Examples, but the present invention is not limited thereto.

Example Olive oil and oleic acid were separated using a simulated moving bed consisting of 16 columns each having an inner diameter of 1 cm and a length of 20 cm. The concentrations of olive oil and oleic acid in the raw material liquid were both 209/(l), and they were dissolved in a mixed solvent of ethanol and hexane (ethanol/hexane = 2/8).

A hydrophobic adsorption resin (XAD4 manufactured by Rohm and Haas) was used as the adsorbent, and a mixed solvent of ethanol and hexane (ethanol/hexane-2/8) was used as the desorption liquid.
It was used. The feed rate of the raw material liquid is 1.38 m (77 minutes), the feed rate of the desorbed liquid is 4.27 min/min, and the flow rate of the olive oil purified liquid is 2.83 MQ1 min, and the fatty acid purified liquid is extracted at a flow rate of 2,8311 Q1 min. The raw material liquid and desorbed liquid supply ports and the olive oil purified liquid and oleic acid purified liquid outlet ports were moved every 5 minutes.

As a result, the purified olive oil liquid did not contain any oleic acid and reached a steady state in about 60 minutes, and in the steady state, 97% of the olive oil contained in the raw material liquid was recovered.

[Effects of the Invention] According to the present invention, triglycerides and fatty acids can be precisely separated under mild conditions of low temperature and low pressure. In addition, since the method of the present invention is a continuous operation, it can be easily automated, and an advantage of the simulated moving bed is that the amount of solvent used as the adsorbent and desorbing liquid can be saved. This can be cited as an effect of

[Brief explanation of the drawing]

FIG. 1 is a schematic diagram of a simulated moving bed used in the purification method of the present invention. Patent distributor Kanebuchi Kagaku Kogyo Co., Ltd. Representative Patent attorney Aohaku Ao and one other person Figure 1

Claims (1)

[Claims] 1. A packed bed in which an adsorbent is housed, the front end and the rear end of which are connected by a liquid passage to form an endless structure, and in which liquid circulates in one direction; Introducing a raw material liquid containing a fatty acid and/or its alcohol ester and triglyceride and an organic solvent as a removing agent, and simultaneously withdrawing a purified triglyceride liquid and a purified fatty acid and/or alcohol ester liquid from the packed bed. The packed bed has (1) an inlet for a liquid containing a fatty acid and/or its alcohol ester and triglyceride as a raw material liquid, (2) an outlet for a purified fatty acid or its alcohol ester, and (3) a desorption liquid. The organic solvent inlet and (4) the triglyceride purified liquid outlet are arranged in this order along the direction of fluid flow, and their positions are intermittently moved one after another in the direction of fluid flow within the bed. A method for purifying fatty acids and triglycerides, characterized by using a simulated moving bed comprising: 2. The method according to claim 1, wherein a hydrophobic synthetic adsorption resin is used as the adsorbent.