JP3090851B2 - Method for producing tocopherol - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION The present invention relates to a method for producing tocopherol inexpensively and efficiently, and more particularly, to a method for producing a tocopherol from a tocopherol-containing raw material containing a multi-component homolog by using a simulated moving layer. The present invention relates to a method for producing tocopherol for separating and purifying a specific tocopherol component.

[0002]

2. Description of the Related Art In recent years, it has been gradually revealed that active oxygen, lipid peroxide, and the like are deeply involved in adult human diseases and aging phenomena, and therefore, not only in vivo but also in vitro (food) oxidation. The importance of prevention is also being recognized. From such a background, attention has been focused on physiologically active substances such as tocopherol (vitamin E: hereinafter may be abbreviated as “VE”) having strong radical scavenging ability and quencher ability. In particular, tocopherol is highly safe and has various physiological activities that are being elucidated as the effects of vitamin E, so that it is expected that it will continue to play an important role in this field.

It is known that vitamin E is composed of eight homologs. That is, α, β, γ, δ
-Tocopherol and α, β, γ, δ-tocotrienol.

[0004] Among tocopherol homologs, α-tocopherol is effective in vivo due to its strong physiological activity, and is used for medicinal and nutritional purposes.
Although γ, δ-tocopherol has weak physiological activity, it has been widely used as an antioxidant for foods and the like because of its strong antioxidant power. As described above, since the actions of tocopherols in the homologues are different, specific tocopherols separated from the homologues (or specific tocopherols having a common action: hereinafter referred to as "specific groups") It is considered preferable to use a method of separating and purifying tocopherol from a tocopherol-containing material and further separating a specific tocopherol (or a specific group) from other homologues. Typically, a method using a strongly basic anion exchange resin is known.

[0005] This is a tocopherol-containing raw material (generally, a distillate produced as a by-product in the step of deodorizing fats and oils is called "scum".
It is often used as a tocopherol-containing raw material. This raw material is hereinafter referred to as "scum"). After pretreatment such as esterification reaction, saponification extraction, solvent extraction, molecular distillation, and desterol removal to remove impurities, the mixture is strongly anion-exchanged. This method involves passing the solution through a resin, and usually, the raw material is dissolved in a lipophilic solvent, and tocopherol is adsorbed to the strong basic anion exchange resin by passing the solution, and then a lower alcohol or an acidic lower A method is employed in which tocopherol is desorbed from the ion exchange resin by passing alcohol through. As a result, tocopherol homologs in which the adsorption power to the strongly basic anion exchange resin is in the order of δ> β, γ> α are separated. The purification method using this strongly basic anion exchange resin is also widely used because it has the feature that tocopherol can be purified and concentrated at the same time as separating homologs.

[0006]

However, in the above-mentioned method using a strongly basic anion exchange resin, mixing of the lipophilic solvent and the lower alcohol is inevitable since both solvents are passed through.
There is a disadvantage that a large amount of recovery cost is required to separate the lipophilic solvent and the lower alcohol from the mixed solvent.

In addition, an alkaline solution is generally used for regenerating a resin, and an acid is used for desorbing tocopherol. Therefore, there is a problem that the operation is troublesome, and a problem in a working environment is also considered. .

Further, in the method using a strongly basic anion exchange resin, a cycle of adsorption → washing → VE elimination (acid) → regeneration (alkali) → washing → solvent replacement must be repeated, and the process is complicated. There is a fundamental problem that it is difficult to improve productivity because complicated and continuous processing cannot be performed.

The present invention has been made in view of the above points, and an object of the present invention is to remove a specific tocopherol (or a specific tocopherol) from a raw material liquid containing tocopherol without the need for a recovery operation of separating a lipophilic solvent and a lower alcohol. It is an object of the present invention to provide a production method capable of separating and purifying (tocopherol group) almost without impurities.

Another object of the present invention is to provide a simple and highly operable work without performing complicated work such as the above-mentioned (adsorption-washing ...) of the conventional method. An object of the present invention is to provide a production method capable of separating and purifying a specific tocopherol (or a specific group of tocopherols) by a step treatment.

[0011] Still another object of the present invention is to continuously separate and purify a specific tocopherol (or a specific group of tocopherols). It is an object of the present invention to provide a method capable of saving cost and realizing inexpensive manufacturing.

Another object of the present invention is to provide a production method capable of separating and purifying tocopherol without using an acid or alkali solution and capable of operating under a favorable working environment.

[0013]

The features of the method for producing tocopherol according to claim 1 of the present invention are as follows.
In separating and purifying a specific tocopherol (or a specific group of tocopherols) from a raw material fluid containing a plurality of components having different affinities for silica gel and containing a plurality of tocopherol homologs in the components, a plurality of silica gels packed as an adsorbent Of the unit packed towers are connected in an endless series through a switchable fluid supply port and a fluid discharge port provided between the unit packed towers, respectively. A method of supplying a desorbent fluid, or by supplying a fluid in a circulation channel without supplying the desorbent fluid, a plurality of components each having an enrichment from a component having a low affinity for the silica gel to a component having a strong affinity for the silica gel. While forming the adsorption zone sequentially in the circulation channel, the upstream end of the adsorption zone enriched with a component (or a plurality of component groups) having a low affinity is used. A first operation of supplying a raw material fluid and extracting an enriched fraction from a downstream end of an adsorption zone enriched with a predetermined component (or a plurality of component groups) at a position upstream of the raw material fluid supply position; Process and this first
Subsequent to the step, the component remaining in the first step (or a plurality of components) is supplied without supplying the raw material fluid, while supplying a desorbing agent fluid composed of a lipophilic solvent and allowing the fluid to flow in the circulation channel. And b) extracting the enriched fraction from the downstream end of one or two adsorption zones enriched in the group), and extracting the fluid supply position and the fraction after the first step. The position is switched to the downstream side of the fluid flow by one unit packed column, and the process proceeds to the second step. In the second step, the supply position and the fraction of the fluid are set in accordance with the movement of the adsorption zone enriched with each component. The multi-component separation method is performed in which the extraction position is intermittently switched to the downstream side of the fluid flow a plurality of times for each unit packed column, and the first step and the second step are repeated as one cycle.

In the above configuration, when the raw material fluid is a mixed raw material of a homologous tocopherol (α, β, γ, δ) from which impurities have been removed, tocopherols β, γ having an intermediate affinity are prepared in advance in the first step. Tocopherol α is extracted as a component having a low affinity, and tocopherol δ is extracted in a second step. When the raw material fluid is a mixed raw material of a plurality of components including tocopherol, for example, when the components have different affinities for the adsorbent (sterol <tocopherol <other), tocopherols having an intermediate affinity (α, β, γ) , Δ) are extracted as predetermined components in the first step. The homologues of tocopherols (α, β, γ, δ) contained in the extracted component have their affinities of δ> β, γ> α as described above, and are further separated using the above-described method. Alternatively, depending on the difference in affinity, the extracted fraction contains tocopherol α first, then β, γ, and finally δ, and is extracted. By doing so, homologs of tocopherol can be separated and recovered.

In the present invention, hydrophilic silica gel is used as the adsorbent, and the desorbent fluid is selected from lipophilic solvents, that is, hexane, cyclohexane, benzene, toluene, xylene, and alcohols having ₁ to ₆ carbon atoms. Or a mixed solvent of two or more of, for example, an alcohol having C _{1 to} C ₆ + toluene or a mixture of two or more other than alcohols.

The invention according to claim 2 is characterized in that ODS-silica gel is used as the adsorbent to be filled in the unit packed bed, and water and carbon number C ₁ -C are used as the desorbent fluid.
_One or two or more kinds of hydrophilic solvents selected from the alcohols of ( ₃ ) are used. Here, "ODS-silica gel" refers to silica gel in which octadecylsilane is introduced into silanol groups distributed on the surface of silica gel so as to lower the polarity of the silica gel.

A desorbing agent other than the combination of the adsorbent and the desorbing agent, for example, a strong solvent (a desorbing agent having a strong lipophilicity in the case of silica gel, and a desorbing agent having a strong hydrophilicity in the case of ODS-silica gel) When is used, it becomes difficult for all the components contained in the raw material fluid to be adsorbed by the adsorbent, and there is no difference in the moving speed of each component, resulting in poor separation. If a weak solvent is used, the components contained in the undiluted solution are strongly adsorbed by the adsorbent, and the separation becomes poor, so that the components are not desorbed. To desorb, a large amount of desorbed liquid is required.

The above method can be implemented in various ways,
For example, as described in JP-A-4-227804, the endless serial circulation flow path is provided so as to be able to circulate and shut off, and the unit fluid containing three or more components having different affinities to the adsorbent is filled with the unit fluid. By flowing through the column, an adsorption band is formed which is sequentially separated from a component having a low affinity for the adsorbent to a component having a strong affinity, and is formed in a manner that a component selected in advance among the components having a low affinity has a higher absorption band. While shutting off the circulation of the system at an upstream position, the raw material fluid is supplied to the system at a position downstream of the shutoff, and a predetermined component of the components forming the adsorption zone upstream of the shutoff position is provided. A first step of extracting substances from the system, and, while circulating the system without supplying a raw material fluid, each component divided into an adsorption zone remaining in the first step is converted into a two-component simulated moving bed. the method of Therefore, the second step of individually extracting each component while supplying the desorbent fluid is referred to as a raw fluid supply position, a desorbent fluid supply position, and a withdrawal position of each fraction. The operation can be repeatedly performed as one cycle while performing the operation of sequentially switching and transferring one unit packed column to the downstream side of the circulation in accordance with the movement of the zone. In the “two-component pseudo moving bed method” performed in the second step, a fluid is circulated in the system by a pump or the like in an endless serial circulation flow path of a number of unit packed towers filled with an adsorbent. Meanwhile, the desorbent fluid is supplied from the upstream of the adsorption zone enriched with a predetermined component, and the enriched fraction is extracted from the downstream of the adsorption zone, and the fraction is circulated sequentially in accordance with the movement of the adsorption zone. This refers to the operation of moving downstream of a stream.

In the second step, the desorbing agent fluid is supplied to the circulation flow path without supplying the raw material fluid, and the desorbent fluid is allowed to flow in the circulation flow path while remaining in the first step. The first step of extracting the enriched fraction from the downstream end of one or two adsorption zones enriched with the component (or a plurality of component groups), and supplying the desorbent fluid to the fluid in the circulation channel. While passing through, each enriched fraction is extracted from the downstream end of the adsorption zone of each component, which is divided into those having weak affinity to those having strong affinity, and the supply position of the desorbent fluid and each enriched fraction The withdrawal position may be divided into a later step in which the extraction position is intermittently switched a plurality of times to the downstream side of the circulating flow in units of one unit packed tower in sequence according to the movement of the adsorption zone.

When the components to be extracted from one extraction port include a plurality of components, they can be extracted as one group without discrimination, and as in the time-series fractionation of the homologs of tocopherol described above. Alternatively, the extraction of a plurality of components can be separated and extracted over time. For example,
For components having different affinities, the three components can be separated by extracting the components in the initial, intermediate, and late stages.

The method of the present invention can be carried out in various modifications in addition to the above-mentioned operations. For example, in the first step, a desorbent fluid may be supplied to the circulation channel system. In this case, it is preferable that the desorbing agent fluid is supplied from the upstream of the adsorption zone where the component having the highest affinity for the adsorbent is distributed. Also, the first
In the process, other components (for example, components having a low affinity) divided into the adsorption zone may be simultaneously extracted from the system.

The apparatus used to carry out the above method is not particularly limited. For example, generally, 4 to 20, preferably 8 to 10 unit packed towers packed with an adsorbent are used. An endless serial circulation channel is formed by using a plurality selected from a plurality of 14, and between each of the unit packed towers in the circulation channel, a liquid supply port and a liquid discharge port that can be switched between open and closed, respectively. And a liquid circulation means such as a pump for liquid circulation provided at an appropriate position in the circulation flow path.

To make the operation of the first step easier, a shutoff valve that can be opened and closed can be provided in the middle of the circulating flow. That is, a shutoff valve is provided in at least one place of a path that sequentially connects the plurality of unit packed towers in the circulation flow path, and the raw material fluid is supplied from a position immediately downstream of the shutoff valve in a state where the shutoff valve is closed, and the affinity is increased. A first step of extracting the tocopherol from immediately upstream of the shutoff valve can be performed while supplying the desorbent fluid to the unit packed tower at a predetermined position to extract the intermediate component (tocopherol).

The raw material fluid of tocopherol used in carrying out the method of the present invention is not particularly limited as long as it contains a homolog of tocopherol.
Typically, the above-mentioned scum (which usually contains about 10% or more of tocopherol) can be used. This scum can be used as it is as a tocopherol raw material in the above-mentioned method, but industrially, in consideration of problems such as contamination of the adsorbent, esterification reaction, saponification extraction, solvent extraction, molecular distillation, It is preferable to use, as a raw material, a fluid from which impurities have been removed by performing a pretreatment such as sterol removal.

According to a third aspect of the present invention, in the second step, the enriched fractions are extracted from the two adsorption zones while supplying the desorbent fluid so that the fluid flow conditions are different. Are divided into a first section, a second section, and a third section in order from the supply position of the desorbent fluid toward the downstream side, and the fluid velocity U in each of these sections is defined as _n is U in the order of the first section to the third section.
_{As 1} , U ₂ and U ₃ , the pseudo moving speed U _S of the adsorbent is (the length of the unit packed tower) / (the fixed time for shifting the positions of the supply of the desorbent fluid and the extraction of each fraction). when a, characterized by operating the U _n / U _S under the following conditions -.

: 1.0 <U ₁ / U _S <10.0 in the first section: 0.3 <U ₂ / U _S <3.0 in the second section: 0.0 in the third section <U ₃ / U _S <2.0 The conditions for these sections are more preferably as follows: 〜 to ″: in the first section, 2.0 <U ₁ / U _S <5.0 ′: in the second section. _{, 0.5 <U 2 / U S} <1.0 ': in the third compartment, it is possible to condition _{0.0 <U 3 / U S <} 1.0.

Each of the above sections is, from the viewpoint of its operation,
The first compartment may be referred to as a desorption operation zone, the second compartment may be referred to as a separation and purification operation zone, and the third compartment may be referred to as a desorbent recovery operation zone. That is, in the above, the role of each section formed in the circulation system is:
In the desorption operation zone of the first section, a desorbent is supplied from outside the system together with the liquid flow in the system from the upstream, the strongly adsorbed component is separated from the adsorbent, and the strongly adsorbed component is recovered downstream. And the separation and purification operation zone of the second zone is a zone for separating and purifying other contaminants while keeping tocopherol at the center of the zone, and the desorbing agent recovery zone of the third zone is In this section, the weakly adsorbed component is adsorbed by the adsorbent to recover the high concentration, and the desorbing agent is collected.

If U ₁ / U _S is less than 1.0, there is a problem that the strongly adsorbed components are not sufficiently desorbed and the strongly adsorbed components are accumulated in the circulation system, lowering the purity of tocopherol. On the other hand, if U ₁ / U _S exceeds 10.0, a desorbing agent more than necessary and necessary for desorbing the strongly adsorbed component from the adsorbent is used, which is not industrially preferable. It is said. If U ₂ / U _S deviates from the above range, tocopherol will not be enriched in the separation and purification zone and will leak out of the outlet of the strongly adsorbed component or the outlet of the weakly adsorbed component, lowering the recovery rate and causing other contaminants. And the purity is also reduced. U ₃ / U _S is
If it is larger than 2.0, the weakly adsorbed components will be distributed throughout the circulation system, and the purity of tocopherol will be reduced.

In the method of the present invention, if the amount of the desorbing agent used is not particularly taken into consideration, the method described in, for example, JP-A-62-91205, in which the desorbing agent recovery zone in the second step is omitted. It can also be implemented by a zone system.

[0030]

DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS An embodiment of the method of the present invention will be described in detail below based on a multi-component separation simulated moving bed apparatus shown in the drawings.

Embodiment 1 FIG. 1 shows an example of an outline of an apparatus used for carrying out the method of the present invention, that is, an apparatus in which twelve unit packed towers are connected endlessly to form a circulation channel. It is shown.

In this figure, 101 to 112 are ODS-silica gels (average pores 70 °,
A group of unit packed towers (hereinafter, referred to as “columns”) packed with a particle size distribution of 100 to 200 mesh (hereinafter referred to as “columns”) (total of 12 columns). Each end is connected to the top of the next column by a pipe, and the endless connection as a whole. In the circulation passage (circulation system). However, a shut-off valve z12 is provided in the middle of the pipe connecting the column 112 and the column 101, so that the circulation system can be shut off if necessary. 301
Is a supply line for a raw material fluid (hereinafter referred to as “raw liquid f”), which is connected via a supply valve f1 to the top (upstream end) of the column 101 so that the raw liquid f can be supplied. 30
Reference numeral 2 denotes a desorbing agent supply line, and supply valves d1 to d
The desorbing agent D is connected to the column top (upstream end) of each of the columns 101 to 112 through the supply line 12.

Reference numeral 303 denotes a line for extracting a component having a weak affinity (hereinafter, referred to as a "weakly adsorbed component"), and the columns 101 to 11 are connected via extraction valves a1 to a12, respectively.
It is connected so that weakly adsorbed components can be extracted from the lower part (downstream end) of the second column. Reference numeral 304 denotes an extraction line for a component having a strong affinity (hereinafter, referred to as a “strongly adsorbed component”), and the columns 101 to 11 are respectively provided through extraction valves c1 to c12.
2 are connected so that strongly adsorbed components can be extracted therefrom.
Reference numeral 305 denotes an extraction line for an intermediate component having an affinity (hereinafter, referred to as “intermediate component”; tocopherol is the intermediate component in the raw material fluid containing a plurality of components used in this example), and the lower portion of the column 12 through the extraction valve b12. It is connected so that an intermediate component can be extracted from.

A pump for circulating a fluid is provided in the circulation passage, and a control device (not shown) for driving the pump and switching the opening and closing of each valve according to the following predetermined procedure is provided. Is provided.

Next, the operation of the present embodiment using the apparatus having the above configuration will be described.

The first step was performed as follows. That is, the shut-off valve z12 is closed to shut off the circulation system, and at the same time, the undiluted solution f is supplied from the top of the column 101 via the f1 valve, and the desorbing agent D is supplied from the top of the column 106 via the d6 valve. The operation was performed so that the weakly adsorbed components were extracted from the lower part of the column 103 via the a3 valve, and the enriched intermediate component (tocopherol) was extracted from the lower part of the column 112 via the b12 valve.

Following the first step, the second step was performed as follows. That is, an endless connection state is ensured so that the entire circulation and circulation of the circulation system can be performed by opening the shutoff valve z12, and while the desorbing agent D is supplied from the top of the column 107 via the d7 valve, By extracting the weakly adsorbed component from the lower part of the column via the a4 valve and extracting the strongly adsorbed component from the lower part of the column 108 via the c8 valve, the following three sections having different flow rates of the fluid in the circulation system are obtained. Was formed. That is, in the state of FIG. 1, starting from the desorbent supply position (column 107), the column group of 107 to 108 is the first section (desorption operation zone), and the column group of 109 to 104 is downstream. The second section (separation / purification operation zone), and a group of 105 to 106 columns are formed as a third section (desorption agent recovery zone) (this is referred to as a 2-1 step).

In the second step, the opening and closing of the valve is switched at regular intervals, and the desorbing agent supply position and each product withdrawal position are moved by one packed tower in the liquid flow direction, thereby simulating the valve. A typical adsorbent stream was created, and the intermediate component tocopherol was separated and purified. Therefore, in the step next to the step 2-1 (step 2-2), the column group of 108 to 109 is in the first zone (desorption operation zone), and the column group of 110 to 105 is in the second zone (separation / purification operation zone). , 106-1
Column group 07 forms the third section (desorbing agent recovery zone), and this switching operation is repeated 10 times, and the state is returned to the state of the first step by switching the opening and closing of the next valve and shutting off the shutoff valve z12. I let it.

In the present embodiment shown in FIG. 1, the total number of columns is 12, and the number of columns in each zone is set as described above. However, the present invention is not limited to the configuration of this embodiment. Of course.

According to the above apparatus and operation, a stock solution having the composition shown in Table 1 below was separated and purified under the following operating conditions.

Column: 12 (inner diameter: 10 cm, length: 120 cm) Adsorbent: ODS silica gel Desorbing agent: CH ₃ OH / H ₂ O = 98/2 Column temperature: 40 ° C. maintained _{U 1 / U S = 3.6 U} 2 / U S = 1.8 U 3 / U S = 1.1 solution feed quantity 0.04 (L / L-R / h)

[0042]

[Table 1]

In this embodiment, since the difference in affinity with the adsorbent is sterol <VE (δ, γ, β, α-tocopherol) <other, the tocopherol as an intermediate component is supplied to the pipe 305 in the first step. Was extracted from

The results (component composition) of the separation as described above are shown in Table 2 below.

[0045]

[Table 2]

[0046] <Comparative Example _{1> U 1 / U S =} 10.5, U 2
/ U _s = 3.2, U ₃ / U _s = 2.4, and tocopherol was separated in the same manner as in Example 1 except for the other conditions.
The results are shown in Table 3 below.

[0047]

[Table 3]

<Embodiment 2> FIG. 2 shows an outline of an apparatus used in Embodiment 2, that is, an apparatus in which 12 columns are connected endlessly to form a circulation channel.

In this figure, 101 to 112 are the above-mentioned silica gel (average pore size: 70 °, particle size distribution: 3
(0-60 mesh), each end of which is connected to the top of the next packed tower by a pipe to form an endlessly connected circulation system as a whole. However, 11
A shut-off valve z11 is provided in the middle of the pipe connecting 1 and 112, so that the circulating system can be shut off if necessary.

Reference numeral 301 denotes a stock solution supply line, and a supply valve f
The column 1 is connected so that the undiluted solution f can be supplied to the column 101. Reference numeral 302 denotes a desorbing agent supply line, and the columns 101 to 11 are respectively supplied via supply valves d1 to d12.
The top of the second column is connected so that the desorbing agent D can be supplied.

Reference numeral 303 denotes a line for extracting a weakly adsorbed component, which is connected so that the weakly adsorbed component can be extracted from the lower part of the columns 101 to 112 via extraction valves a1 to a12, respectively. Reference numeral 304 denotes a line for extracting strongly adsorbed components, which is connected to extract strongly adsorbed components from the lower part of the columns 101 to 112 via extraction valves c1 to c12, respectively. An intermediate component (tocopherol) extraction line 305 is connected via an extraction valve b11 so that the intermediate component can be extracted from the lower part of the column 11.

As in the apparatus of the first embodiment, a pump for circulating a fluid is provided in the circulation passage in the apparatus of the present embodiment.
A control device is provided for switching the opening and closing of each valve according to a predetermined procedure described below.

Next, the operation of the present example using the apparatus having the above configuration will be described.

Using this apparatus, the first step was performed as follows. That is, the shut-off valve z11 is closed to shut off the circulation system, the undiluted solution f is supplied from the top of the column 101 via the f1 valve, and d6 is supplied from the top of the column 106.
The desorbent D is supplied through a valve, and the weakly adsorbed component is extracted from the lower part of the column 103 through an a3 valve.
From the lower part of the column 111, an operation was performed to extract the enriched intermediate easily adsorbable component (tocopherol) via the b11 valve.

Following the first step, the second step was performed as follows. That is, the endless column connection state is ensured so that the entire circulation and circulation of the circulation system can be performed by opening the shut-off valve z11, and while the desorbent D is supplied from the top of the column 107 via the d7 valve, By extracting the weakly adsorbed components from the lower part of the column 104 via the a4 valve and extracting the strongly adsorbed components from the lower part of the column 108 via the c8 valve, three sections having different flow speeds are formed in the circulation system. Was. That is, in FIG. 2, starting from the desorbing agent supply position (column 107) and going downstream, the column group of 107 to 108 is the first section (desorption operation zone), and the column group of 109 to 104. Represents a second section (separation and purification operation zone), and a column group of 105 to 106 forms a third section (desorption agent recovery zone) (this is referred to as a 2-1 step).

In the second step, the valve is switched at regular intervals to intermittently move the desorbing agent supply position and each product withdrawal position by one packed tower in the liquid flow direction. As a result, a pseudo adsorbent flow was created, and tocopherol as an intermediate component was separated and purified as described below. Therefore, the next step (2-
In the two steps), the column group of 108 to 109 is in the first section (desorption operation zone), the column group of 110 to 105 is in the second section (separation and purification operation zone), and the column group of 106 to 107 is in the third section ( This switching operation is intermittently repeated 10 times to complete one cycle of operation, and the next step of opening and closing the valve and shutting off the shutoff valve z11 returns to the state of the first step. I put it back.

According to the above apparatus and operation, a stock solution having the composition shown in Table 4 below was separated and purified under the following operating conditions.

Column: 12 (inner diameter: 10 cm, length: 120 cm) Adsorbent: silica gel Desorbing agent: toluene / i-propanol = 99.5 /
It maintained 0.5 column temperature inside _{··· 40 ℃ U 1 / U S} = 4.5 U 2 / U S = 0.9 U 3 / U S = 0.7 solution feed quantity 0.03 (L / L -R / h)

[0059]

[Table 4]

In this embodiment, the difference in affinity with the adsorbent is sterol> VE (δ, γ, β, α-tocopherol)> others, so that tocopherol as an intermediate component is supplied to the pipe 305 in the first step. Was extracted from

The results (component composition) of the separation as described above are shown in Table 5 below.

[0062]

[Table 5]

[0063] <Comparative Example _{2> U 1 / U S =} 10.2, U 2
/ U _S = 3.2, U ₃ / U _S = 2.9, and tocopherol was separated in the same manner as in Example 2 except for the other conditions.
The results are shown in Table 6 below.

[0064]

[Table 6]

[0065]

As described above, according to the first or second aspect of the invention, the following effects can be obtained.

A specific tocopherol (or group) can be obtained from a raw material liquid containing tocopherol without the need of a conventional recovery operation of separating a lipophilic solvent for passing a raw material and a lower alcohol for removing tocopherol. )
Can be separated and purified with almost no impurities.

The conventional method (adsorption-washing -...)
The specific tocopherol (or group) can be separated and purified by a simple and easy-to-operate process without performing the complicated work of (...).

A specific tocopherol (or group) can be continuously separated and purified instead of a batch type.

The above-mentioned effects can reduce the equipment cost and the operating cost, and can produce a specific tocopherol (or group) with high purity and at a low cost.

Further, in addition to the above effects, since tocopherol can be separated and purified without using an acid and alkali solution, the working environment can be improved.

According to the third and fourth aspects of the present invention, further effects can be obtained in addition to the above effects.

: Tocopherol can be continuously produced with high purity, high concentration and high recovery.

[Brief description of the drawings]

FIG. 1 is a diagram showing a schematic configuration of an apparatus used in a first embodiment of a method of the present invention;

FIG. 2 is a diagram showing a schematic configuration of an apparatus used in a first embodiment of the method of the present invention.

[Explanation of symbols]

101 to 112: column, 301: stock solution supply line, 302: desorbent supply line, 303: weakly adsorbed component extraction line, 304: strongly adsorbed component extraction line, 305 ... Intermediate component extraction line, a1-a
12 ... extraction valve, b12 ... extraction valve, c1
... c12 ... withdrawal valve, d1 to d12 ... supply valve, z11, z12 ... shutoff valve.

Continued on the front page (72) Inventor Takeo Yotsuka 56 Shinko, Mihama-ku, Chiba-shi, Chiba RIKEN Vitamin Co., Ltd. Chiba Plant (72) Inventor Kohei Sato 1-4-9 Kawagishi, Toda-shi, Saitama Organo Stock Inside the Corporate Research Institute (72) Inventor Kikuzo Kaneko 5-6-1 Hongo, Bunkyo-ku, Tokyo Organo Corporation (72) Inventor Naoto Yamashita 5-5-16-Hongo, Bunkyo-ku, Tokyo Organo Corporation (56) References JP-A-4-227804 (JP, A) (58) Fields investigated (Int. Cl. ⁷ , DB name) C07D 311/72

Claims (4)

(57) [Claims] 1. A plurality of unit packed towers filled with silica gel as an adsorbent are connected in an endless series via a fluid supply port and a fluid outlet which can be opened and closed, respectively, provided between these unit packed towers. A specific tocopherol (or a plurality of tocopherol groups) is passed through the circulation channel through a feed fluid containing a plurality of components having different affinity for the silica gel and containing a plurality of tocopherol homologues in the components. ) Is separated from other components and recovered, wherein a fluid having a low affinity for the silica gel is removed from the component having a low affinity for the silica gel by supplying a fluid in a circulation channel with or without supplying a desorbent fluid. A plurality of enriched adsorption zones are sequentially formed in the circulation channel while forming a plurality of enriched adsorption zones, and the enriched adsorption zone (or a plurality of component groups) having low affinity is enriched. The raw material fluid is supplied from the upstream end of the zone, and the enriched fraction is extracted from the downstream end of the adsorption zone where a predetermined component (or a plurality of component groups) is enriched at a position upstream of the raw material fluid supply position. A first step of performing an operation, and, following the first step, one or two or more kinds selected from hexane, cyclohexane, benzene, toluene, xylene, and an alcohol having ₁ to ₆ carbon atoms without supplying a raw material fluid. One or two components enriched in the component (or a plurality of component groups) remaining in the first step while supplying a desorbing agent fluid composed of a lipophilic solvent and allowing the fluid to flow through the circulation channel. And a second step of extracting the enriched fraction from the downstream ends of the two adsorption zones, respectively, after the first step, the supply position of the fluid and the extraction position of the fraction are one unit downstream of the fluid flow. Switch for packed tower 2
In the second step, the supply position of the fluid and the extraction position of the fraction are intermittently arranged one unit packed column downstream of the fluid flow in accordance with the movement of the adsorption zone enriched with each component. The first step and the second step are switched a plurality of times
A method for producing tocopherol, which is repeated as a cycle. 2. A plurality of unit packed towers filled with ODS-silica gel as an adsorbent are connected in an endless series via a fluid supply port and a fluid discharge port which can be opened and closed, respectively, provided between these unit packed towers. By passing a feed fluid containing a plurality of components having different affinities for the ODS-silica gel and containing a plurality of homologs of tocopherol into the components, a specific tocopherol (or Separating and recovering a plurality of tocopherols) from other components, comprising supplying a desorbent fluid or flowing a fluid in a circulation flow path without supplying a desorbent fluid, thereby obtaining an affinity for the ODS-silica gel. While forming a plurality of adsorption zones in which the weak component to the strong component are each enriched in the circulation channel, the components having weak affinity (or a plurality of The raw material fluid is supplied from the upstream end of the adsorption zone enriched with the component group), and the downstream side of the adsorption zone enriched with the predetermined component (or a plurality of component groups) at a position upstream of the raw material fluid supply position. A first step of performing an operation of extracting the enriched fraction from the end; and, following the first step, one or two selected from water and an alcohol having ₁ to ₃ carbon atoms without supplying a raw material fluid. One or more of the components (or a plurality of component groups) remaining in the first step are enriched while supplying the desorbent fluid composed of the above hydrophilic solution and allowing the fluid to flow through the circulation channel. A second step of extracting the enriched fractions from the downstream ends of the two adsorption zones, respectively, after the first step, the fluid supply position and the fraction extraction position are located downstream of the fluid flow. Switching by unit packed tower
In the second step, the supply position of the fluid and the extraction position of the fraction are intermittently arranged one unit packed column downstream of the fluid flow in accordance with the movement of the adsorption zone enriched with each component. The first step and the second step are switched a plurality of times
A method for producing tocopherol, which is repeated as a cycle. 3. The method according to claim 1, wherein the enriched fractions are extracted from the two adsorption zones while supplying the desorbent fluid, so that the fluid flow states are different. One of the partition part, the downstream sequentially first compartment as a base point the feed position of the release agent fluid, and a second compartment and a third compartment, the fluid velocity U _n in each of these compartments the first compartment, second in the order of 3 sections as _{U 1, U 2, U 3} , the supply and the position of extraction of each fraction of the pseudo moving speed U _S (the length of a packing bed unit) / (desorbent fluid adsorbent when a certain time) to transition, U _n / U _S tocopherol manufacturing method according to claim 1 or 2, characterized in that operating under the following conditions -: the first section, 1.0 < U ₁ / U _S <10.0: the second _{compartment, 0.3 <U 2 / U S} <3.0: third district _{In, 0.0 <U 3 / U S} <2.0. 4. The method of claim 3, the manufacturing method of tocopherol, characterized by operating a U _n / U _S under the following conditions' ~ '': In the first compartment, 2.0 <U ₁ / U _S <5.0 ': in the second _{compartment, 0.5 <U 2 / U S} <1.0': in the third _{compartment, 0.0 <U 3 / U S} <1.0.