JPS58193699A - Purification of sugar liquid - Google Patents

Abstract

(57) [Summary] This bulletin contains application data before electronic filing, so abstract data is not recorded.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a method for removing iron from sugar solution. sugar solution,
Sugar is used as a raw material for soft drinks, fruit juice drinks, lactic acid bacteria drinks, etc., as well as for pharmaceuticals and bread making, as well as for the production of various crushed canned sardines, canned flavored foods, various seasonings, and various pickles. However, the presence of iron is not desirable in these food processing processes. In other words, if iron is mixed in with the sugar solution, it will impair the flavor of the food, promote browning and oxidation of the food, change the color tone of the food, and iron will also interact with the coloring agent to reduce the coloring effect. This causes harmful effects.

In the first place, Kansho starch, potato starch, and corn starch, which are the precursors of these sugars, each contain 20p.
pm, 15 ppn, 25 ppm (7)
Contains iron. Therefore, the food industry is interested in purification processes such as decolorization of sugar solutions as well as processes related to iron removal.
3- Conventionally, activated FA (granulated carbon) filtration method and ion exchange resin method have been used. However, although low temperature treatment is preferred in the ion exchange resin method, it is not easy to efficiently remove a metal such as iron from a viscous sugar solution at low temperatures. Furthermore, the ion exchange resin method has problems such as the use of large amounts of acids and alkalis in the regeneration process.

In view of this situation, the present inventors have conducted various studies, and as a result,
We have discovered a method for removing iron from sugar solutions that can be universally applied to sugar solutions and does not affect the taste or sugar concentration.

That is, according to the present invention, iron in the sugar solution can be removed by making it water-insoluble and hydrophilic.

The number of axes used in the present invention is not particularly limited to 1 as long as it is used in the fields of food, medicine, etc., but the specific number is, for example, 1.

Ba [noisho starch, corn starch 7pun, 1no]
−↓ − Examples include the atomization solution and dextrin solution of JP-A-58-193699 (2).

These sugar solutions are moving! 1 to 5 QW/V% is commonly used (this can be used, and the iron equipment has at least 1 ppm
The above sugar solution C-1'' can also be used for the purpose of iron removal in the present invention.

The water-insoluble tannin preparation according to the present invention is a substance in which a water-insoluble C and hydrophilic polymer (carrier) and a tannin component are bonded through a covalent bond 1.

Product A W is tannin, aminoalkylated tannin.

It can be produced by carboxyalkylated tannins and hydroxylated tannins.

The tannin used in the present invention may be pyrogallol tannin or catechol tannin. Examples of pyrogallol tannins include gallic tannin and pentagram tannin, and examples of catechol tannin include tea.

= 5- Examples include catechol polymers obtained from cacao. Furthermore, the tannins do not necessarily have to be purified; for example, impure tannins such as those commercially available as persimmon tannins may be used.

In addition, as aminoalkylated tannins, carboxyalkylated tannins or hydroxyalkylated tannins,
The tannin is reacted with a cyanogen halide (e.g. cyanogen bromide) or an epoxy compound (e.g. epichlorohydrin) to produce a cyanogen halide activated tannin or an epoxy compound activated tannin, which is then reacted with an alkylene diamine (e.g. ethylene diamine, tetrachlorohydrin). Preferably, those obtained by reacting methylene diamine, hexamethylene diamine, dodecamethylene diamine), aminoalkyl carboxylic acids (e.g., ε-mitsukaproic acid), or aminoalkanols (e.g., 2-aminoethanol) are preferred. It will be done. The reaction between tannins and cyanogen halides (e.g. cyanogen bromide) is carried out at a pH of about 8 to 12.9, for example in a suitable solvent (e.g. water). It can be preferably carried out at a temperature of about 15 to 30°C. The reaction of the thus obtained cyanogen halide activated tannin with gamma-alkylene diamine, aminoalkylcarboxylic acid, aminoalkanol, etc. can be carried out, for example, in a suitable solvent (eg, water).

pH about 8-12. It can be suitably carried out at a temperature of about 15-30'C. On the other hand, tannins and epoxy compounds (
For example, the reaction with epichlorohydrin) can be carried out using a suitable solvent (e.g. epichlorohydrin).
For example, in water), ρt 1 about 9-14, temperature about 30-10
It can be suitably carried out at 0°C. The reaction between the epoxy compound-activated tannin thus obtained and alkylene diamine, aminoalkyl carboxylic acid, etc. is carried out in a suitable solvent (e.g., water) at a pH of about 9-14.1 degrees and about 30-100 degrees.
It can be suitably carried out at ℃. On the other hand, one example of the polymer used in the present invention is a water-insoluble and hydrophilic polymer having in its molecule 11 or more functional groups selected from the group consisting of hydroxyl group, amide group and carboxyl group.

Here, hydrophilicity means that the polymer has the property of being wetted or swollen in water.

-7 Examples of water-insoluble and hydrophilic polymers containing hydroxyl groups in the molecule include polysaccharides such as enzyme, agarose, and cross-linked dextran, or hydroxyalkyl derivatives (e.g., hydroxyl groups). Polysaccharides containing a spacer containing a hydroxyl group such as pilated cross-linked dextran (pilated cross-linked dextran) can be used.

Next, nine examples of water-insoluble and hydrophilic compounds having amino acids in their molecules include aminoalkylated polysaccharides (
(e.g., aminoethylated cellulose, amino/hexylated cellulose, aminohexylated agarose), aminoaralkyl derivatives aa (e.g., aminobenzylated cellulose)
A polysaccharide containing 7 amino groups such as; polyacrylamide; aminoalkylated polyacrylamide (for example, γ-minoethylated polyacrylamide)
Polyacrylamide with a spacer having 7 groups such as polyacrylamide; P-amide vane sylaminopropylated porous glass with a spacer having 7 groups has also been introduced, and fibers such as 8 groups of silk. Scleroproteins - Space-containing amino groups such as aminoalkylated wool (e.g. minohexylated wool) →
Examples include fibrous scleroproteins into which toe has been introduced.

Next, a water-tolerant and hydrophilic polymer having a carboxyl group in the 5z element and [7-c is 6], for example, carboxylated and methylated polymers (e.g., carboxymethylated cellulose, fJ carboxyhexylated agarose, Polymers containing a spacer with a carboxyl group such as carboxymethylated cellulose, carboxydimethylated cross-linked dextran), carboxyalkylated polyacrylamide (e.g. carboxymethylated polyacrylamide) or a spacer with a fulboxyl group Can you name something like polyacrylamide that was introduced?

A water-insoluble tannin preparation is prepared by covalently bonding a tannin compound as described above with a water-insoluble and hydrophilic compound. [For example, Chibata ed., [Immobilized Enzyme J, pH ~ 409-9] Published by Kodansha (March 20, 1975); Yamazaki et al. ed.
Infinity Chromatography J-P19-32. Published by Kodansha (February 1, 1975)], for example, the method described in JP-A-55-39707;

The thus obtained water-insoluble tannin preparation is brought into contact with molasses to remove iron from the sugar solution (this can be carried out by any of the column method, fluidized bed method, or batch method).

For example, when carrying out the column method, fill the column with water-insoluble tannin (g) and 1. After washing with water approximately 10 times the column volume, the sugar solution was passed through.

Collect the 1st one that passed the column by +1. a q rr) r'
Although the liquid speed change speed can be selected at will, it is generally desirable to set it to the space velocity (S V ), I'+45 to 30 Chr-"). Also, the operating temperature should be set quickly. However, it is generally preferable to run at a temperature below 60'C.

In addition, the batch method can be carried out by washing the water-insoluble phosphorus preparation with water approximately 10 times the volume of the preparation, and then adding the sugar solution and stirring. can. The pressing time is preferably about 2 hours, and the operation temperature is preferably 60° C. or lower, as described above.

The sugar solution treated by the powder method can be collected as follows. That is, since the water-insoluble tannin preparation precipitates in a relatively short time, the sugar solution can be collected by collecting the supernatant liquid by decantation or by removing the water-insoluble tannin preparation by filtration.

Furthermore, once used water-insoluble tannin preparations can be regenerated and reused whether used in a column method or a batch method. Regeneration can be easily carried out by contacting the water-insoluble tannin preparation with a dilute acid solution (for example, 0.5N! acid).

According to the method of the present invention, by simply bringing various types of sugar solutions into contact with water-insoluble tannin preparations, iron, which is present in sugars, can be easily removed in a short time. Since the sugar solution can be purified to 0.01pp to 111 or less, it is possible to obtain a sugar solution for use in the production of various foods of good quality with excellent aroma, taste, color tone, etc.

Hereinafter, the present invention will be explained with reference to reference examples and examples.
They do not limit the invention in any way.

Reference example l +1) Filter pipe Ken 4 (product name manufactured by Toyo Kushisha Co., Ltd.)
25g cooled to 4℃ 12 & sodium hydroxide solution 7
50- for 30 hours, add 1.51' of water and heat at 60°C.
The mixture was stirred for 30 minutes. This and epichlorohydrin 2
50- was added and stirred at 60° C. for 30 hours, the activated cellulose was collected by filtration and thoroughly washed with water. The obtained epichlorohydrin-activated cellulose was mixed with a hexamethylene diamine solution 1/(hexamethylene diamine 6.
257 dissolved in water and adjusted to pH 11) and stirred at 60°C for 2 hours. The produced amyl/hexyl cellulose was collected by filtration and thoroughly washed with water, and then *0.
Suspended in 2sN sodium hydroxide @g1.2sl.

Epichlorohydrin 125- was added to this suspension, and 6
By stirring at 0° C. for 30 minutes, epichlorohydrin-activated ami/hexylcellulose was obtained.

(2) Gobako 9nnin 3L 29) ft water 500 mt
+C dissolved, 0. IN aqueous sodium carbonate solution 12
After adding 5rnl, p
Adjusted to H7.0. Water was added to this solution to make a total volume of 11, and 200 f/(wet ftji) of the epichlorohydrin-activated aminohexylcellulose obtained in (1) above was stirred at Gt/uffiL-45°C for 215 hours.

After the reaction, the solid content was collected by filtration and thoroughly washed with water and 30% acetone to obtain water-insoluble tannin preparation 1.
93 g (wet weight M) was obtained. This wet sample was further freeze-dried to obtain 36.5M' as a dry powder product.

Reference Example 2 (1) Cellulose Powder C (trade name manufactured by Toyo Kushi Co., Ltd.) 10v was mixed with 25% sodium hydroxide aqueous solution 500ml.
After being immersed in water for 30 minutes at 25°C, it was thoroughly washed with water.

Obtained alkali-treated cellulose 13- It was suspended in solution 200- and the pH was adjusted to 11.5.

Cellulose was activated by adding 2.02 g of cyanogen bromide to this suspension (the pH was always 11-11 during the activation reaction).
．． 5 and the reaction temperature was not to exceed 30'C. ). After about 8 minutes, the activated cellulose was collected by filtration and washed with a pre-cooled 0.1M aqueous solution of hydrogen carbonate and water. The obtained cyanogen bromide-activated cellulose was suspended in water/#Ift (pH 10) 250- containing hexamethylene diamine 57-59,
The reaction was allowed to take place at 25°C.

After the reaction was completed, the solid content was collected by filtration and washed with a 0.1M aqueous sodium bicarbonate solution and water to obtain amino-bovine sylated cellulose.

(2) Five-fold tannin was dissolved in water at a ratio of 50% to 11.5%. 2.0y of cyanogen bromide was added to Dma at 20℃, and the reaction was carried out for 8 minutes while maintaining the pl+11 to 11.51 at the same time.The obtained cyanogen bromide activated fivefold tannin solution was It was added to the aminohexylated cellulose obtained in (1) and reacted at 25°C for 2 hours. After the reaction, solid 5)
The water-insoluble tannin 41
32-3 g (wetting amount) was obtained. By further freeze-drying this wet sample, 14.62 was obtained as a dry powder product.

Reference example 3 17! 15 grams of activated Cephalonis 6B (trade name, manufactured by Pharmacia) were washed sequentially with 500 mg of water, 0.5 M sodium chloride solution tgwsoo-, and water 500-. To this was added a solution of 100 mg 1 m of 0.1 M sodium bicarbonate aqueous solution of 5-fold tannin 17, adjusted to poiO, 5 with sodium hydroxide, and reacted at 37°C with shaking for 26 hours. After the O reaction was completed.・Filter out the solid content and add water 11. Charcoal #I! Loose mW(p)1
10) By sequentially washing with 500- and water 11≦, a water-insoluble tannin preparation 40P (wet juta) was obtained.

By further freeze-drying these four wet products, 8y was obtained as a dry powder product.

-1, i- After swelling each ly (dry powder) of the water-insoluble tannin dehiscence prepared by the method of Reference Examples 1 and 2 with distilled water, it was packed into a column with an inner diameter of 1.51 (column g column; 12-). The column was washed with 100 ml of distilled water. This column contains 3(・P) as iron ions.

Grape composition containing ferrous ammonium sulfate (degrees; 30<) #solution SV = 15 (!tr') r
It flowed down at Da degree. The effluent was fractionated into 100 fractions, and the iron contained in each fraction was measured. The results are shown in Table 1, and it was found that all water-insoluble tannin preparations according to the present invention adsorbed iron well. In addition, iron emplacement was performed using atomic absorption method and α, Q! Both colorimetric methods using '-dipyridyl were used.

JP-A-58-193699 (5) 1st friend (Removal of iron from foreign fleas made of various water-insoluble tannins-Ii:)
*FFHII (G: Water-insoluble tannin preparation of Reference Example 1 Water-insoluble tannin product prepared by the method of Reference Example 1)
(Dry powder) was swollen with distilled water, packed into one column (column volume: 121R1), and washed with distilled water. An isomerized slime containing 5 ppm of iron sulfate as iron ions was allowed to flow down the column at a rate of 5v=1°5 (hr").

The effluent was fractionated into 100-unit fractions to measure the iron adsorption capacity of the water-insoluble tannin preparation. The dock was as shown in Table 2, and it was confirmed that the amount of iron plate deposited on the tannin side was about 3.2 times the amount of iron ions per gram.

7- Table 2 (Iron absorption 11ffi/:I of water-insoluble tannin preparations) Experimental example 3 After washing the column used in Experimental example 2 with distilled water,
．． It was regenerated by flushing with 2N hydrochloric acid 100wJiSV=10(j+r') and washing with water. Thereafter, a re-adsorption test was conducted in exactly the same manner as in Experimental Example 2. The results are shown in Table 3, and the iron adsorption capacity did not decrease at all even after the regeneration treatment.

-1+- Table 3 (Iron absorption capacity of water-insoluble tannin preparations)
Actual Example 1 34 After filling a water-soluble 10% solid wet immobilized tannin 307 prepared by the method of Example 1 into a column with a jacket tube (column volume: 60*J), 17 rounds each of 31 were washed with water. did. The pH, iron content, and glucose content of the pruned bamboo before and after treatment were measured to examine the treatment effects. In addition, the physical properties of this saccharified solution were also shown. As shown in Table 1, n
All of the iron in the chemical solution could be removed extremely significantly.

*Specific gravity and viscosity are at so℃. The viscosity was measured with an Ostwide meter. For specific gravity, a 70-type specific gravity needle was used.

Measured with a pyrorefractive needle. 20'Ct Koteshi! It was calculated using the same refractive index as III.

Practical Example 2 The water-insoluble IQ solids wet measurement immobilized tannin 305' prepared by the method of Reference Example 1 was packed into a column with a jacket material (column volume: 60 sJ), and then watered and incubated at 50°C for 6 hours.
00-d/hr (S V = 10) (Fl)f
fiA flowed down. p++ of saccharified solution before and after passing through the column
, iron content was measured and treatment effects were investigated.

*Specific gravity and viscosity are values at 50℃.

■Measured using a refractometer. It was calculated as having the same refractive index as sucrose at 20°C.

As shown in the table above, the iron concentration in the sugar solution could be significantly lowered.

Example 3 Water-insoluble 10% solid immobilized tannin 307 prepared by the method of Reference Example 2 was washed with water, filtered, thoroughly drained, and heated to 95°C to obtain a solid content of 10. %
Dextrin solution 31 was added thereto, stirred at 95°C for 15 minutes, and then filtered. When we measured the iron concentration after immobilized tannin treatment + 111, it was 86 ppb before treatment and 39 ppb after treatment.
It was b.

H]

Claims (2)

[Claims] (1) Iron in the sugar solution is removed by bringing the sugar solution into contact with a water-insoluble tannin preparation in which a water-insoluble and hydrophilic polymer and a tannin component are bonded by covalent bonds. How to purify sugar solution. (2) The water-insoluble tannin preparation is a polymer containing one or more functional groups selected from the group consisting of hydroxyl group, amino group, and carboxyl group in the needle, and tannin, amide/alkylated tannin, carboxyalkylated tannin, and hydrogel. The purification method according to claim 1, wherein the tannin compound selected from the group consisting of dialkylated tannins is a substance bound through multiple covalent bonds. The purification method according to claim 12 or 2, which is a saccharification solution such as starch syrup, various types of sugar syrup, isomerized sugar solution, fructose belly, white spring, etc., or a dextrin solution.