JPS6219210A - Process for separating components - Google Patents

Abstract

PURPOSE:To decrease the amt. of material to be mixed in a process for separating components by a pseudomoving bed process, by dividing at lest one of two fractions discharged as a fraction contg. primarily sorbent component and a fraction contg. primarily nonsorbent component further in the order as it is discharged. CONSTITUTION:Unit packed beds 1001-1024 packed with sorbent having high sorptivity for maltose and space parts 1025-1048 are arranged alternately in the inside of a packed bed 1,000. A feeding pipe 1049 for aq. soln. of aq. maltose syrup, a feeding pipe 1050 of water as desorbing material, a discharging pipe 1051 of liquid contg. a sorptive component (maltose), and a discharging pipe 1052 for liquid contg. nonsorptive component, are provided to each space part, and feeding and discharging of these materials are performed in turns at every fixed interval in each unit packed bed arranged to the down stream succeedingly. A discharging pie 1052 for the nonsorptive component is separated to two branches, which is enabled to be changed over optionally by means of a valve. Thus, more useful, fraction is obtd. in accordance with the change of sugar component.

Description

DETAILED DESCRIPTION OF THE INVENTION (Industrial Application Field) This invention relates to a method for separating components, particularly a liquid containing two or more components, using a sorption method that exhibits selective sorption for the organic components. The present invention relates to an improvement in a method of separating components using a simulated moving bed method using a reagent.

(Prior art and its problems) A pseudo moving bed method is known as a method for separating the components of a liquid containing two or more components. In this pseudo-moving bed component separation method, a large number of unit packed beds filled with a selective sorbent are usually connected in series, with the last unit packed bed being connected to the frontmost unit packed bed. Each unit packed bed is equipped with a device equipped with a supply pipe for the raw material mixture to be treated, a pipe for supplying the desorbing agent before extraction of the non-sorbate component, and a pipe for extracting the sorbate component. In these connected packed beds, there is an adsorption zone from the raw material supply section to the non-sorbate component extraction section, an f# fluorescent zone from the non-sorbate component extraction section to the desorbent supply section, and a desorbent zone. Four zones, a desorption zone from the supply section to the sorbate component extraction section and a backcondensation zone from the sorbate component extraction section to the raw material supply section, are formed in that order from upstream of the fluid flow. is circulated, and the positions of each of the above-mentioned supply parts and extraction parts are intermittently moved in the downstream direction to separate a fraction mainly containing sorbate components and a fraction mainly containing non-sorbate components. This is a chromatographic separation method that involves continuous fractionation, and is considered to be extremely useful industrially as an efficient component separation method. Specific examples to which this component separation method is applied include separation of each component from a mixture of normal hexane and cyclohexane, etc.
Separation of components of mixtures of compounds with similar boiling points such as normal compounds and their isomers in hydrocarbons, alcohols, aldehydes, and ketones, or separation of both components from aqueous solutions containing glucose and fructose, or maltose starch syrup, Separation of polysaccharides greater than malt-st maltotriose is known.

Component separation using the simulated moving bed method is thus performed. Hereinafter, we will take as an example the case of separating maltose starch syrup into an aqueous solution, maltose, and polysaccharides higher than maltotriose. 2.

Maltose starch syrup consists of a mixture of glucose (Class M), Class 2A1, which is mainly composed of maltose, Class 3, which is mainly composed of maltotriose, and Class A+, which is more than maltotetraose. When maltose, the main component, is separated using a simulated moving bed continuous chromatography device, the extraction residual fraction (raffinate fraction) contains:
Along with polysaccharides higher than maltotriose and maltotetraose, a considerable amount of maltose is mixed in. Maltotriose has physical properties such as high hygroscopicity, low sweetness, and low viscosity of an aqueous solution, and is used for applications corresponding to these properties. Therefore, when high-purity maltose is separated using a simulated moving bed separation method using maltose starch syrup as a raw material, the amount of maltose that is mixed into the sugars whose main component is maltotriose, which is a useful component in the extraction residue fraction, is It is preferable if it can be reduced. However, it is difficult to reduce the amount of maltose mixed in from a commercial standpoint. For example, it is possible to reduce the amount of maltose mixed in by reducing the amount of raw material processed per unit volume of sorbent, or by increasing the amount of water supplied as the bath N1 agent (desorbent). Although it is possible, in that case, a very large separation volume is required as an apparatus, and a large amount of separated liquid is condensed, which increases the condensation cost and is not suitable for industrial implementation.

(Means for solving the problem) As mentioned above, in the conventional pseudo moving bed type component separation method, the fraction mainly consisting of sorbate components and the unrecoverable In the fractions mainly composed of occupant components, it is unavoidable that components other than the intended components are mixed into each fraction. An object of the present invention is to provide a method for obtaining a separated product with less contaminants, and the purpose is to mainly obtain an astringent component in a component separation method using a simulated moving bed. By turning off the valve, at least one of the two yuzu fractions, which is extracted as the fraction containing 714 real components and the fraction mainly containing non-receivable 714 real components, is added to the effluent. This is achieved by further dividing W into both parts.

The present invention will be explained in detail below, but for ease of understanding, component separation of maltose starch syrup will be used as an example. Figure 1 is a schematic diagram of another example.

In Figure 7, the packed bed (1
The inside of 0θθ) is (/θθ/) ~ (1024t) 4
The unit is divided into packed beds. [In the figure, (1006) to (/(17//) and (/θ/♂
) ~ (/Q2 co] unit packed beds are not shown)
. Each of these unit packed beds contains a salt type cation exchanger which has a large absorption capacity for oligosaccharides such as maltotriose, maltotetraose, and maltopentaose, and maltose. As the cation exchanger, commercially available cation exchanger fecal fat or zeolite can be used. Usually, a strongly acidic cationic resin is used, in which sulfo 711&-M is bonded to a crosslinked copolymer of styrene-divinylbenzene. In order to increase the difference between the adsorption power for maltose and the adsorption power for oligonucleotides νζ of maltotriose or higher, the cation exchanger is usually used in the sodium, potassium, or calcium form.

The maltose starch syrup that is processed usually contains 3 total sugars at a time.
An aqueous solution of 4% to 60M of oligosaccharides containing 0 to 60% by weight of maltotriose in the total sugars is used.

Between each of the unit packed beds (/θoi) to (1ora), there is a space (/θ-ri~() where no filler is filled).
10 da? ) [In the figure, (/θ2?) ~ (1
03 da) and (70 g/) to (10416) (not shown) are provided, and each space sV
C is a supply pipe (i
oda9), and a water supply pipe (1oto
), mainly the collection from each space part 7! A shield pipe for a liquid extraction pipe (103/) containing an i-negative component (maltose) and a liquid extraction pipe (1062) containing a non-sorbent component (polysaccharides of maltotriose or higher) is provided.

By the way, this nonsense! (This may be 9 pipes, or 7 pipes, each of which has a valve and is branched off.) Normally, each space K
e is shown, but illustration is omitted in the drawings. At the point when the functions of these nine pipes are not performed simultaneously in the same space, they are performed at intervals of several unit packed beds as shown in the figure, that is, (10
4t] is the supply of the raw material mixture, (10j2) is the extraction of the fraction containing mainly non-sorbate components, (10r2) is the supply of the desorption agent, and (10ji) is the extraction of the fraction containing mainly the sorbate components. These are removed at fixed time intervals and moved to a unit packed bed on the downstream side of the fluid.

Although it is not essential to install a space (10 pieces 5 ~ IO'l♂), if maltose starch syrup, which is placed in a unit packed bed, is introduced into this space, the liquid that has fallen in the bed will be removed. This is preferable because it can be quickly diffused into the inside.

(10j4t) is a pipe connecting the rear end of the packed bed to the front end, and (/θ!3) is a pump for liquid circulation.

At the time shown in FIG. 1, maltose starch syrup aqueous solution is supplied to the space (io4tz), water as a desorption agent is introduced to the space (7034), and on the other hand, the space (10.2tr)
A liquid containing mainly non-sorbate components is extracted from the space (I
A liquid containing mainly sorbate components is extracted from the O'IO).

Therefore, the total packed bed (1000) is (100/ ) ~ (1
The adsorption zone consists of da unit packed beds of (0o4t), (
A purification zone consisting of two unit packed beds of (1006) to (/Q/ko)', a desorption zone consisting of two unit packed beds of (10/J) to (/θ/6), and a desorption zone consisting of two unit packed beds of (10/J) to (/θ/6); 7)～(102
There are four bands in the AM band, each consisting of two unit packed beds of 4T). The action of each @ region is the same as that of a known pseudo-moving bed in which maltose is the sorption component and oligosaccharides of maltotriose or higher are the non-sorption component. The temperature inside the packed bed is high! -0°C, preferably to-ro°C.

What is the temperature inside the floor? If the θ°C or shi is too high, the sugar solution that is extracted may become colored. See you again! If the temperature is too low, the viscosity of the maltose ice-packed liquid will be high) and the pressure loss in the bed will increase.

A distribution of oligosaccharides of maltose and maltotriose is formed in the liquid in the packed bed. a
The degree distribution moves in the downstream direction while retaining its shape. Following this movement, the pipes for injecting maltose starch syrup and water into the packed bed, and the pipes for extracting the sorbate component fraction and non-sorbate component fraction from the packed bed, are sequentially connected to the downstream side. can be switched to each. The switching may be performed simultaneously for all four types of pipes, or may be performed at different times for each pipe. The duration of liquid supply or liquid withdrawal in the same tube varies depending on the size of the unit packed bed, the type of cation exchanger, the speed of the liquid flowing through the bed, etc., but it is usually several minutes to a few minutes. It's a few minutes. Due to this switching, the above-mentioned four types of bands sequentially move their positions in the packed bed. However, the length of each band is always substantially constant. That is, each zone moves while maintaining its size and relative position, and this is repeated intermittently, thereby circulating the packed bed in an endless state.

Under such operating conditions, we investigated in detail the changes in the sugar composition of the non-sorbate fraction from the time when the extraction tube was switched to the next one, and found that immediately after the extraction tube was switched, In this case, the amount of maltose mixed in the effluent is very small, and an effluent with a higher maltotriose content is obtained, and just before the next changeover, the amount of maltose mixed in increases significantly. I found out that it will come. Therefore, if the non-sorbate component fractions were mixed and collected as a single fraction, the sugar composition would be of low quality, and no useful use could be found for the bag. However, if this extracted liquid is divided into two or more fractions in response to the composition change of the extracted liquid during the period from the cutting to the next switching as described above, it is possible to obtain a preferable fraction with a longer -s length. It can be a fraction of the composition.

For this reason, in the present invention, as shown in FIG. The branched pipes (/θj A) and (1062B) can be switched at any time by valves (the figure shows the case where they are branched into one), and the same - extraction and exit positions can be changed within one switching period. According to the change in the sugar composition, the non-sorbable components are divided into two or more parts by switching the valves of the branch pipes.
You can get yourself a more useful sugar composition.

The above-mentioned branch pipe valve switching can be automated by examining the changes in the composition of the extracted liquid over time in advance, operating under the same conditions, and automatically operating the branch pipe valves using a timer. Become.

Although the method of the present invention has been described above for component separation of maltose starch syrup, it can be similarly applied to component separation using other simulated moving bed methods. In those cases, the liquid of class 2a [i.e., the fraction mainly containing sorbate components and % isomerism appears in both compositions containing non-sorbate components, therefore,
We investigated the composition of these liquids and the changes in composition over time during the period from switching the extraction pipe to the next switching, and based on the results,
Either or both of the above two types of liquids can be fractionated into λ or more fractions by the method of the present invention to obtain 11 fractions with −H usefulness.

(Example) Next, an example will be described, but the present invention is not limited to this example r (therefore, it is not limited to this example.
"CH" means "% by weight".

Example glucose 0.7%, maltose 23. ? Using maltose starch syrup with a sugar level of 60, consisting of 6.3% maltotriose and 9.2% polysaccharides higher than maltotetraose, as a raw material, maltose was distributed using the apparatus shown in Figure 2. went.

Type of strong cation exchange resin [Diaion FRK-/
//, manufactured by Mitsubishi Chemical Corporation, Diamond ion is the company's registered trademark] total / 0. r 4t is filled with tl. Each unit packed bed is connected endlessly by a circulation pump (/!/) ~ (/6?), and the fluid passage connecting each unit packed bed is filled with pulp (///) ~ (//♂ ) through the maltose aqueous solution extraction tube (//, pulp (/, 2/) ~ (
/2F) and oligo S of maltotriose or higher (hereinafter simply referred to as oligosaccharide) water /
3θ) and the temperature in the bed of this apparatus was maintained at approximately 7J°C, and the maltose starch syrup and water were supplied at 0.2°C each.・
l/hour and 0.2227 hours, and the values before extraction of the maltose fraction and oligosaccharide fraction were 0.32 t/hour and 0.
．． At 4911 hours, the iAt values of the adsorption zone, purification zone and depletion zone are respectively '
pt, 3317 hours, j, 44tt/hour and 4t, 0jJ
The key was adjusted so that it was 11 o'clock.

In this case, for example, maltose starch syrup is pulp (/(j@)
At the point when the decoating agent water is supplied through the pulp (/3♂), it is mainly divided into a fraction containing stratiform fractions (hereinafter referred to as product fraction) and a fraction containing mainly non-sorbent fractions. Fractions containing quality components (hereinafter referred to as raffinate fractions) are extracted through pulp (//2) and pulp (/Jj), respectively, and are transferred to a unit packed bed (/θ/
) and (/θ2), the desorption zone, unit packed bed (/θ
3) and (/θ da), an II# contraction zone is formed, an adsorption zone is formed in the unit packed bed (10r) and (106), and a purification zone is formed in the unit packed bed (107) and (/(M)). Each pulp is switched all at once to the downstream pulp every 3 minutes, and each zone goes around the bed in 3 minutes.Here, without dividing the 2 finate fluximine, according to the conventional method. The sugar compositions of the product fraction and raffinate fraction when extracted were as shown in the table below.

Table/ In the above case where the raffinate fraction is not fractionated,
The maltose content of raffinate 7-lactone is higher than that of maltotrione, and it is not necessarily a mixture that has maltotriose as its main component. However, maltose Kanakura cannot be said to be better than maltose starch syrup.

Next, as shown in Figure 1, a branch pipe with three valves is installed in the extraction pipe for the raffinate fraction (in the device shown in the figure, a branch pipe /co (7A, /2OB, /200) is installed in the extraction pipe /20.
). Using this branch pipe, extraction of the raffinate fraction is started by switching the valve, until it is switched to the next pulp downstream! , Divide the extracted fluid extracted in 3 minutes into two or three parts according to the order of outflow according to the passage of time, (/20), ), (/koOB), (
/Oa). This division was performed in the following three ways.

Experiment 1: The total liquid volume of the raffinate fraction that comes out during valve switching is divided into two parts: the first half is 0.00 g, and the latter half is 60 g.

Experiment λ: In the same way, the whole liquid violet was mixed with 0% beef and the second half, 2o
%vc, 2 divisions f.

Experiment 3: Similarly, the total liquid volume was changed to θts in the first half, 4tots in the middle,
The sugar composition of the raffinate fraction when the raffinate fraction is not divided according to the conventional method is useful as shown in the table above. The full-dose content is higher than that of maltotriose, which is made with sugar, but the full-dose content is too small to be evaluated as maltose starch syrup. It has the disadvantage that there are many

However, by dividing the mold into two as shown in Figure 1, i.e., ￥rel/ in the method of the present invention, the maltotriose mold in the first half aO% becomes a larger value, and the maltose in the second half 60q6 also becomes significantly larger than before division. It becomes a large clay, and the divided and collected λ fractions can be made into sugar compositions that can be sufficiently evaluated as a maltotriose mixture and maltose starch syrup, respectively. Similarly, in the experiment on the table,
first half? The maltotriose Kanakura of both O% is higher than when not divided, and the second half of 20-min is an experiment to test the maltose content/Good, 9! , can be increased to In Experiment 3, the raffinate fraction was divided into three parts, and the first half and the second half each had their own characteristics.

(Effects of the invention) (1) In the simulated moving bed component separation method, conventionally, the fraction obtained by separating the sorbate component and the non-sorbent negative component is Although components other than the required components are mixed in, the method of the present invention can suppress the mixing of such undesired components.

(2) In implementing the method of the present invention, a conventional device with slight modifications is used, and the operation is as follows:
There is no need for it to become a particularly busy news.

[Brief explanation of drawings]

FIG. 1 is a schematic diagram of one example of the apparatus used in the method of the present invention, and FIG. 2 is a schematic diagram of another example of the apparatus similarly used. In the figure, (100/) ~ (10or), (10/ko) ~ (
10/7), (/θ23) to (10x4t) are unit packed beds, and (10/) to (/θ?) are also unit packed beds. First calm

Claims (1)

[Claims] (1) Using chromatographic separation, a raw material mixture containing two or more components is continuously fractionated into a fraction containing mainly sorbate components and a fraction containing mainly non-sorbate components. A method for discharging non-sorbing materials from a raw material supply section in a sorbent-packed bed filled with a sorbent having selective sorption properties and having a front end and a rear end connected by a fluid passage. a sorption zone up to the sorbate component extraction section, a purification zone from the non-sorbate component extraction section to the desorbent supply section, a desorption zone from the desorption agent supply section to the sorbate component extraction section, and the above. The fluid is circulated while forming four concentrating zones from the sorbate component extraction section to the raw material supply section in the above order from upstream of the flow of the raw material mixture, and the above raw material supply section and the non-sorbate component are In a pseudo moving bed component separation method that involves intermittently moving the positions of an extraction section, a desorbing agent supply section, and a sorbate component extraction section in the downstream direction, two types of liquids flowing out from the extraction section are A method characterized in that at least one of the fractions is further divided into a plurality of fractions in flow order by switching a valve.