JPH01244000A - Method for treating beet sugar liquid - Google Patents

Abstract

PURPOSE:To make it to possible to improve collection efficiency of sucrose and obtain an useful substance by removing betaine, amino acids and salts from a beet sugar liquid, boiling the liquid and then chromatographically separating the resultant molasses into sucrose and other useful substances. CONSTITUTION:A beet sugar liquid is passed through an H type cation exchange resin and an OH type anion exchange resin to remove betaine, amino acids and salts. The resultant sugar liquid is then boiled and separated into crystal sugar and molasses, which are then subjected to regulation of concentration and chromatographically separated into an inositol-enriched fraction, sucrose- enriched fraction and other fractions using a column filled with a sodium type or potassium type cation exchange resin.

Description

[Detailed description of the invention] [Industrial application field] The present invention relates to a method for treating beet sugar solution.

Specifically, the present invention removes betaine, amino acids, and salt from a sugar beet molasses, and then uses a chromatography method to decoct the resulting syrup, and further extracts sucrose and various types of sugar beet molasses. By separating useful substances from
The present invention relates to a method for processing beet sugar solution that can improve the recovery rate of sucrose and obtain useful substances.

[Conventional technology]

As shown in Figure 1, one method for producing beet sugar from sugar beet is to cut the sugar beet, extract the sugar beet liquid in a leaching bath, and then clean it by carbonation or other methods. The exchange resin removes cations, betaine, and amino acids,
Next, anions are removed using an anion exchange resin to obtain a desalted solution.

This desalting solution was concentrated to around BX +o, decolorized with an anion exchange resin, and then boiled with sugar (No. 7 roasted sugar) to obtain No. 7 sugar and No. 7 honey. (No. 2 boiled sugar) Obtain the first sugar and the second sugar.

The No. 2 honey is further roasted with sugar (No. 3 roasted sugar) to obtain No. 3 sugar and No. 3 honey.

The No. 7 sugar, No. 2 sugar, and No. 3 sugar obtained here are mixed to form a product sugar.

No. 3 honey is diluted to around Bxjj, the raffinose it contains is decomposed into sucrose and galactose by melibiase enzyme, and it is roasted again (4 is roasted sugar) to obtain No. 9 sugar and Guban sugar.

Gu Ban Mitsu is further roasted with sugar (No. 5 roasted sugar), and then with J No. sugar! Get honey.

The No. 9 sugar and No. J sugar are dissolved in water and returned to the cleaning process, and the No. 5 sugar is sold externally as feed or a raw material for brewing.

[Problem to be solved by the invention] In this method for producing beet sugar, the problem is that although molasses contains various useful components, it is not possible to utilize them effectively. was there.

On the other hand, the present inventors have invented a method for easily and efficiently separating multiple organic compounds into three fractions using a chromatographic separation method, and have previously filed a patent application (Patent Application No. 6/307).
/23).

As shown in FIGS. 2 and 3, the present inventors have determined that useful components can be separated by fractionating honey obtained by enzymatically treating J honey or No. 3 honey using the above-mentioned chromatographic separation method. The present invention was completed based on the discovery that the recovery rate of sucrose was improved.

[Means to solve the problem]

Generally, when a beet sugar solution is chromatographically separated using a Na-type or Na-type strongly acidic cation exchange resin as an adsorbent, it flows out in the following order.

(1) Ash (inorganic salts) (2) Polysaccharides and their derivatives (3) Raffinose and other trisaccharides (4) Sucrose and other disaccharides (5) Monosaccharides and inositol (6) Betaine and amino acids Sugar beet When industrially chromatographically separating sugar solutions, it is not impossible to separate each of the above six fractions using a single-base method, but with a single-base method, the separation function is poor and the recovery rate of sucrose is low. It is not economically viable due to the low price. Special Public Showa 4t7-23! No. 2, Tokko Akira! The method of 3-2♂Reli No. 93 is an example of this.Since the inositol fraction contains a large amount of sucrose, it is necessary to remove it by fermenting the sugar with yeast or the like.
Inositol cannot be recovered.

Therefore, a method that has been used industrially in recent years is a simulated moving bed chromatographic separation device, but this method can only separate into two fractions.

For example, when separating between (3) and (4) of the above six components, components (5) and (6) are separated in order, so
Usually, 0% of the sugar is fractionated into the sucrose fraction, and the remaining 60% is fractionated into the raffinose fraction.

However, if this is chromatographically separated using the method described in Japanese Patent Application No. Sho-Otsu/-307/23, it can be efficiently separated into three fractions at the same time, so the above six components can be separated into fractions (1) to (3). It can be separated into three fractions: fraction (4) and fractions (5) to (6).

However, if betaine and amino acids are contained in fractions (5) and (6) separated in this way, betaine will precipitate out first when this fraction is concentrated and crystallized.
High purity inositol cannot be obtained.

However, betaine and amino acids can be removed in a desalting step using a cation exchange resin.

Examples of the cation exchange resin used for desalting include styrene-divinylbenzene-based strongly acidic cation exchange resins having a sulfonic acid group as a cross group.

These ion exchange resins may be gel-like ion exchange resins or porous ion exchange resins.

For example, Diamondion SK/B%SK/10, PKu/
4. Examples of anion exchange resins that can be used in the desalting process, such as PK λ0, include Diaion PA30♂ and P
AJ/ko, pA4t/2) SA/ /A, WA2/, W
30 etc. can be mentioned.

Diaion is a registered trademark of Mitsubishi Chemical Industries, Ltd.

When using the above ion exchange resin to remove betaine by passing the beet sugar solution through an H-type cation exchange resin column, it is necessary to remove not only betaine but also amino acids, sodium,
Ions such as potassium and calcium can also be removed, but in the treatment of beet sugar solution in the present invention, the operation of passing the beet sugar solution is discontinued due to leakage of betaine from the cation exchange resin column9. This gives you peace of mind that you can regenerate the used cation exchange resin.

Leakage of betaine can usually be detected using the Reinecke salt method.

The cation exchange resin can be easily regenerated by using an appropriate amount and concentration of mineral acid when regenerating a normal cation exchange resin, but when used in the present invention, It is necessary to first treat a cation exchange resin whose function has decreased with an alkali and then regenerate it into an H-type cation exchange resin using an appropriate amount and concentration of mineral acid.

Examples of the alkali agent used in the alkali treatment include sodium hydroxide, potassium hydroxide, ammonium hydroxide, and the like.

The alkaline treatment of the cation exchange resin is usually performed at the same time as the regeneration of the anion exchange resin.

Regeneration of the anion exchange resin can be carried out, for example, by using a 70% by weight water bath solution of sodium hydroxide at a volumetric rate a,t (// hr ), and the effluent is further passed through a cation exchange resin tower.
Alkali treatment of the cation exchange resin can also be completed at the same time. Alkali-treated cation exchange resin is
It can be thoroughly washed and then regenerated into H-type by using mineral acid.

Examples of mineral acids include hydrochloric acid and sulfuric acid.

As the regeneration conditions, for example, when using an aqueous solution of sulfuric acid, use an equivalent of 720% of the exchange capacity of the cation exchange resin, and increase the capacity rate. The liquid may be passed through the packed tower under conditions of about (//hr).

In this way, the No. 3 honey obtained by passing through an H-type ion exchange resin and an OH-type anion exchange resin to remove betaine, amino acids, and salts, and then repeatedly decocting sugar, or The concentration of the untreated liquid obtained by treating honey with melibiase enzyme is adjusted, and it is processed through a chromatographic separation process.
It is separated into an inositol-enriched fraction, a sucrose-enriched fraction, and other fractions.

In the chromatographic separation step, when performing chromatographic separation by passing the chromatographic feed liquid with the concentration adjusted with the above-mentioned No. 3 honey through a packed column filled with an adsorbent, the adsorbent used for chromatographic separation may be sodium type or A potassium type cation exchange resin is used.

As the cation exchange resin, a styrene-divinylbenzene-based sulfonic acid type strongly acidic cation exchange resin is preferably used.

For example, Diaion FRK/3/, FRK/l/, U
BKjJOK%UE3! 20G etc. can be mentioned.

The adsorbent is packed into a packed column to form a packed bed.

This packed column is a packed bed whose front end and rear end are connected by a fluid passage, and a chromatographic system is formed in which fluid is circulated from the front end to the rear end to enable fluid circulation.

The present invention uses such a romato separation system, but two types of raw material fluids are required to operate this separation system.

The third one is a chromatographic feed liquid whose concentration is adjusted appropriately to suit the chromatographic separation system, and the other one is a desorption solution for desorbing substances adsorbed on the adsorbent from the adsorbent. agent (in the case of the present invention, water).

These chromatographic feed solutions and water are fed to the following chromatographic separation step to separate inositol-enriched fractions, sucrose-enriched fractions, and other fractions (in this case, raffinose-enriched fractions). (enriched fraction).

That is, (i) a step of extracting the sucrose-enriched fraction from the rear end of the packed bed while supplying the chromatographic feed liquid from the front end of the packed bed; (11) filling while supplying water from the middle of the packed bed; (iii) extracting the sucrose-enriched fraction from the rear end of the bed;
Circulating the fluid in the bed without supplying the fluid to the packed bed or withdrawing the fluid from the packed bed, (i) filling the zone where sucrose and inositol remaining without being extracted in the step are mixed; (OV) Step of moving the inositol-enriched fraction to the front end of the packed bed while supplying water from the front end of the packed bed; (v) Filling while supplying water from the front end of the packed bed. (v9) circulating the fluid in the bed without supplying the fluid to the packed bed and withdrawing the fluid from the packed bed; This is achieved by repeatedly performing steps (1) to (vi) of the step of moving the zone in which sucrose and other components remaining without being mixed to the front end of the packed bed.

Furthermore, when using an enzyme-treated solution obtained by treating No. 3 honey with melibiase enzyme as a chromatography supply solution, raffinose has already been decomposed, so it is necessary to increase the discharge rate of raffinose, which is difficult to separate from sucrose. Therefore, (i) below
This can also be achieved by repeatedly performing steps to (v).

That is, (1) a step of supplying the chromatographic feed liquid from the front end of the packed bed and extracting a sucrose-enriched fraction from the rear end of the packed bed, (11) supplying fluid to the packed bed and removing the sucrose-enriched fraction from the packed bed. A step in which the fluid in the bed is circulated without drawing out the fluid, and the zone in which sucrose and inositol that remain without being drawn out in the step (1) are mixed is moved to the front end of the packed bed; (iii) filling. Step of extracting the inositol-enriched fraction from the rear end of the packed bed while supplying water from the front end of the bed, OV) While supplying water from the front end of the packed bed, other fractions were enriched from the rear end of the packed bed. (■) A step of extracting the sucrose-enriched fraction from the rear end of the packed bed while supplying water from the front end of the packed bed.

[Effect]

The present invention uses a novel romatoseparation method and an enzyme-treated liquid obtained by removing betaine, amino acids, and salts and then decocting sugar or by further treating with melipiase enzyme. By combining, it is possible to easily separate fractions into sucrose-enriched fractions, inositol-enriched fractions, and other fractions (for example, raffinose-enriched fractions). I think it is now possible to do so.

〔Example〕

Next, the present invention will be further explained with reference to Examples, but the present invention is not limited to these Examples.

Example: During the sugar manufacturing period in 1988, approximately 3,000 tons of sugar beets were cut per day, and the resulting cosettes were then introduced into an extraction device and extracted with hot water at approximately 70°C, resulting in Bx approximately /! of sugar solution was obtained continuously.

The resulting sugar solution was introduced into a cleaning process consisting of carbonation and filtration, and then treated with a strongly acidic cation exchange resin (Diaion P
K! / , < ) and an anion exchange tower filled with a weakly basic anion exchange resin (Diaion WAj0), and a desalted sugar solution with a pure sugar rate of about 29% was obtained. Obtained.

The obtained desalted sugar solution was concentrated using a Z heavy-duty can to obtain approximately 2 Bx
- Obtain a concentrated sugar solution of O, and use decolorizing resin (Diaion p
AJO/) was passed through to decolorize the mixture, and then boiled with sugar to obtain No. 7 sugar and No. 7 honey. No. 7 honey was further roasted to obtain No. 2 sugar and No. 2 honey. The obtained No. 2 honey was further roasted to obtain No. 3 sugar and No. 3 honey.

The purity of the above process is approximately 200 tons per day? 9.9%
, the product granulated sugar with a color value of about 70 by the AI method, and the first
No. 3 honey with the composition shown in the table as a chromatographic feed solution was obtained. The concentration of this No. 3 honey is Bx7! Met.

The concentration of this No. 3 honey was adjusted to BX + O and used as a chromatography feed solution.

FIG. 2 is a schematic diagram of an apparatus for carrying out a chromatographic separation step in the present invention.

In the figure, / and C indicate a packed bed filled with a sodium-type or potassium-type cation exchange resin as an adsorbent, 3 indicates a storage tank for chromatography supply liquid, and G indicates a storage tank for water (desorbent). 5 and 2 indicate the extraction lines of each fraction, /
θ~/2 indicates a valve, and // indicates a circulation pump, respectively.

In the apparatus shown in FIG. 9 above, the inner diameter J3. ! MR1
Two columns connected in series with a packed bed with a high tacho
Using a rioml adsorbent (Na-type strong acid cation exchange resin, Diaion UBKr10L), the above chromato supply solution was passed through at a volumetric flow rate/2θOrttl/h,
The separation operation was repeated according to the time schedule shown in Table 2 below. The 6 steps shown in Table 2 were repeated per cycle. Since a steady state was reached at the 1st cocycle, samples of each fraction were collected. When analyzed, the results were as shown in Table 1.

When this A fraction λL was vacuum concentrated using a rotary evaporator, the liquid became cloudy before and after Bxto, and inositol began to precipitate.

Furthermore, it was gradually concentrated, and when it reached BXO, the contents were taken out, cooled at 1.2j']-J, and centrifuged. 9. j% inositol white powder/6
．． ．． A liquid sugar having the composition shown in Table 3 below was obtained.

Table 3 Example λ The No. 3 honey obtained in Example/ was adjusted in concentration to BXto,
Add melibiase enzyme to this and heat at 50°C for hr.
The treated enzyme treatment solution was filtered through a filter pre-coated with diatomaceous solution to prepare a chromatography supply solution. The composition of this chromato feed solution is shown in Table 5.

Using the apparatus used in Example (Figure 2), using the above chromatography supply liquid, and using Diaion UB as an adsorbent.
Fill K-630K, capacity flow rate/000111/
h, and the separation operation was repeated in the same manner as in Example 1 according to the time schedule shown in Table 9.

Assuming the 6 steps shown in Table 1 as /cycle, a steady state was reached at the /λ cycle, so samples of each fraction were collected. It was as shown in the table.

Table 1 [Effects of the Invention] Compared to the conventional method for producing beet sugar shown in FIG. 1, the method of the present invention shown in FIGS.
Not only is the process of roasting sugar and roasting sugar omitted, resulting in significant streamlining, but also the majority of the cane sugar remaining in molasses, which was conventionally sold outside, can be recovered as product sugar. It also contributes to improving the ratio.

Furthermore, betaine, amino acids and salts are removed in the desalting process,
By adopting a new chromatographic separation method with good separation performance, it is possible to reduce the betaine and sucrose content to less than 5% in the inositol-enriched fraction, so this fraction can be simply concentrated and By crystallizing, 9 can be easily
2)! -An additional advantage is that the above-mentioned inositol powder and liquid sugar with high utility value can be obtained as by-products.

Furthermore, according to the method of the present invention shown in FIG. 2, in addition to the above-mentioned effects, other fractions are enriched with raffinose. It also becomes possible to obtain pure raffinose as a by-product.

[Brief explanation of the drawing]

FIG. 1 is a diagram showing a conventional process for processing sugar beet, FIGS. 2 and 3 are diagrams showing a process for processing beet sugar according to the present invention, and FIG. FIG. 2 is a schematic diagram of the device for performing the operation. / and co ・・・・・・・・・・・・・・・ Packed bed 3 ・・・・・・・・・・・・・・・・・・・・・
・・・・・・・・・ Chromato supply liquid tank ・・
・・・・・・・・・・・・・・・・・・・・・・・・
・・・・Aquarium 5-7 ・・・・・・・・・・・・・・・
...... Extraction line 10~/7...
・・・・・・・・・・・・ Pulp/L! ″・・・
・・・・・・・・・・・・・・・・・・・・・・・・
Circulation pump applicant: Mitsubishi Kasei Techno Engineers Zazu Co., Ltd. (and 7 others)

Claims (5)

[Claims] (1) Pass the beet sugar solution through an H-type cation exchange resin and an OH-type anion exchange resin to remove betaine, amino acids, and salt, and then decoct the sugar and separate it into crystalline sugar and shaken honey. 1 step, and the chromatographic feed solution obtained by adjusting the concentration of shimitsu is separated into an inositol-enriched fraction and a sucrose-enriched fraction using a sodium-type or potassium-type cation exchange resin as an adsorbent. A method for treating a beet sugar solution, characterized in that the second step is chromatographic separation into fractions and other fractions, and the first step and the second step are combined. (2) The method for treating a sugar beet liquid according to claim 1, characterized in that the H-type cation exchange resin is an H-type cation exchange resin regenerated with an alkali and an acid. Method. (3) The method for treating a sugar beet solution according to claim 1, wherein the other fraction is a raffinose-enriched fraction. (4) In the method for treating a beet sugar solution as set forth in claim 2 or 3, the second step of chromatographic separation is performed using a cation exchange resin packed with a sodium type or potassium type cation exchange resin as an adsorbent. The chromatographic separation system consists of a bed, the front end and the rear end of which are connected by a fluid passage, and the fluid is circulated from the front end to the rear end of the packed bed to enable fluid circulation. (i) extracting the sucrose-enriched fraction from the rear end of the packed bed while supplying the chromatographic feed liquid from the front end of the packed bed; (ii) supplying water from the middle of the packed bed while withdrawing the sucrose-enriched fraction from the rear end; (iii) circulating the fluid in the bed without supplying the fluid to the packed bed and withdrawing the fluid from the packed bed; (i) (iv) a step in which a zone containing a mixture of sucrose and inositol remaining without being extracted in the process is moved to the front end of the packed bed; (iv) inositol is enriched from the rear end of the packed bed while supplying water from the front end of the packed bed; (v) extracting other fractions from the rear end of the packed bed while supplying water from the front end of the packed bed; (vi) supplying fluid to and from the packed bed; (i) circulating the fluid in the bed without extracting the fluid, and (v) moving the zone in which sucrose and other components remaining without being extracted in the step are mixed to the front end of the packed bed; A method characterized by repeatedly performing steps ) to (vi). (5) In the method for treating a beet sugar solution as set forth in claim 2 or 3, the second step of chromatographic separation is performed using a sodium-type or potassium-type cation exchange resin filled as an adsorbent. The chromatographic separation system consists of a bed, the front end and the rear end of which are connected by a fluid passage, and the fluid is circulated from the front end to the rear end of the packed bed to enable fluid circulation. , (i) supplying the chromatographic feed liquid from the front end of the packed bed and extracting the sucrose-enriched fraction from the rear end of the packed bed; (ii) supplying the fluid to the packed bed and removing the sucrose-enriched fraction from the packed bed; Circulating the fluid in the bed without extracting the fluid; (i) moving the zone in which sucrose and inositol that remain without being extracted in the step are mixed to the front end of the packed bed; (iii) filling. (iv) extracting the inositol-enriched fraction from the rear end of the packed bed while supplying water from the front end of the bed; (iv) withdrawing other fractions from the rear end of the packed bed while supplying water from the front end of the packed bed; (v) extracting the sucrose-enriched fraction from the rear end of the packed bed while supplying water from the front end of the packed bed, steps (i) to (v) are repeated. how to.