JPH0670212B2 - Carboxymethylated soy sauce cake, binder using the same, and method for producing the same - Google Patents

Description

TECHNICAL FIELD The present invention relates to carboxymethylated soy sauce cake, a method for producing the same, and uses thereof. This substance is used as a binder for, for example, briquette charcoal and foundry sand. It is what is done.

[Prior Art] Soy sauce cake is used in soy sauce brewing from soy sauce moromi to raw soy sauce.
It is a squeezed cake (residual pickle) obtained by squeezing and filtering, and contains protein, crude fiber, etc. as components, but it has a large amount of salt and a unique odor and is indigestible, so it is used as a part of feed In addition to being used, its use is extremely limited, and various studies have been made on the development of effective use thereof.

As one of the uses of soy sauce cake other than feed, it can be considered to be used as a filler for adhesives. Based on barley bran mixed with mannan, this product is made by adding calcined gypsum to soy sauce cake and heating and crushing it. Method for producing powder for bonding plywood by mixing (JP-A-47-39444) A method for producing a filler for adhesive by heating soy sauce cake by contacting it with saturated steam or superheated steam. (JP-A-55
No. -155073) Method for producing a filler for adhesives by subjecting soy sauce cake to water extraction treatment, followed by drying and crushing (JP-A-55-155074) Soy sauce cake dry powder and a type of water-soluble polymer Alternatively, an adhesive filler containing two or more kinds (Japanese Patent Laid-Open No. 56-151779) is known.

[Problems to be solved by the invention]

Since the soy sauce cake is insoluble, its usage has been limited to the use of the soy sauce cake as described above or the processed and slightly processed soy sauce cake to be dried and crushed to be used as a filler for the adhesive. However, in the present invention, soy sauce cake is subjected to a chemical reaction to make the soy sauce cake water-soluble to impart a caking property, and is used as an industrial caking additive.

[Means for solving problems]

Soy sauce cake produced as a by-product during soy sauce production does not have caking ability because it is insoluble in water, but since it contains fiber in the composition of soy sauce cake, carboxymethylation (hereinafter,
The soy sauce cake is given water-solubility and is used as a binder.

In the present invention, soy sauce cake is a generic term for squeezed cake obtained by pressing and filtering raw soy sauce from soy sauce moromi in soy sauce brewing,
The soy sauce moromi brewing method from which it is derived may be a natural brewing method, a quick brewing method, or a new style brewing method. In addition, it may be one that has been subjected to post-treatment such as pressing or drying, desalting, decolorizing, deodorizing after pressing.

One example of the compositional analysis value of dried soy sauce cake derived from natural brew is water.
7.2%, ash 10.5%, salt 7.7%, total nitrogen 3.9%, crude protein (total N × 6.25) 24.4%, total reducing sugars due to total hydrolysis 35.6% (glucose equivalent), and high performance liquid chromatography. The sugar composition by Grafie is arabinose 4.3
%, Galactose 12.0%, glucose 14.1%, rhamnose trace (root trace), and contains other various amino acids, low molecular weight proteins, polysaccharides and the like.

Further, the CM soy sauce cake of the present invention has an etherification degree of 0.05 to 1.0.
It refers to those which are CMized to mol / 100 g, preferably 0.1 to 0.4 mol / 100 g. If the etherification degree is less than 0.05 mol / 100 g, the water solubility is insufficient, and the etherification degree is 1.0 mol /
If the amount exceeds 100 g, a large amount of expensive reaction chemicals are required, and the economy is poor and it is not practical. Further, the purification treatment after the CM reaction or the preparation with other additives does not matter. Further, in order to be used for a binder, it can be prepared in a form suitable for the purpose.

Alkali used in the production of CM soy sauce cake includes alkali metal hydroxides such as sodium hydroxide, potassium hydroxide and lithium hydroxide, but sodium hydroxide is mainly used. As the monochloroacetic acid alkali salt, there are alkali metal salts such as sodium monochloroacetic acid and potassium monochloroacetic acid, but sodium monochloroacetic acid is common. As a method for reacting soy sauce cake with an alkali and monochloroacetic acid or an alkali salt of monochloroacetic acid, there are a water medium method performed in an aqueous solution and a solvent method performed in an organic solvent. In the aqueous medium method, monochloroacetic acid or its alkali salt is easily hydrolyzed and the reaction efficiency is low, so the solvent method is preferable.
It is not particularly limited.

First, an example of a method for producing CM-modified soy sauce cake by the water medium method is as follows.

Add soy sauce cake with an alkali such as sodium hydroxide, which is more than twice the mole of monochloroacetic acid used, and add 0.5 at 10-45 ℃.
After thoroughly mixing and stirring for ~ 2 hours, 0.05 ~ for soy sauce cake
Add 2.5 times the amount of monochloroacetic acid and add 2 to 48 at 20 to 50 ℃.
After stirring and reacting for a time, excess alkali is neutralized with an acid such as sulfuric acid, hydrochloric acid or acetic acid to stop the reaction.

When using monochloroacetic acid alkali salt, alkali such as sodium hydroxide is added to soy sauce cake in an amount of at least 1 times the molar amount of monochloroacetic acid alkali salt used, and the reaction is carried out as described above, followed by neutralization with an acid to react. To stop.

After the reaction, add 5 to 50 times the amount of hydrous alcohol such as 60 to 80% methanol to the reaction product, wash and remove the by-products, and then dry and pulverize to obtain water-based CM soy sauce cake. Can be done.

Then, in the method for producing CM-modified soy sauce cake by the solvent method, as the organic solvent, alcohols such as ethanol, butanol, isopropanol, etc., hydrophilic organic solvents such as acetone, ketones such as methyl ethyl ketone, etc. alone or Although a solvent in which benzene, toluene, etc. are mixed can be used, isopropanol, which is currently most commonly used in the production of the solvent-method carboxymethylcellulose sodium salt, is suitable. The method of using isopropanol as the organic solvent will be described in detail. 1 to 10 times the amount of 80 to 95% isopropanol to the raw soy sauce cake and an alkali such as sodium hydroxide at 2 times the mole of monochloroacetic acid used or more are added, After thoroughly mixing and stirring at 10-45 ℃ for 0.5-2 hours, add 0.05-2.5 times the amount of monochloroacetic acid to soy sauce cake, react at 50-80 ℃ for 1-3 hours, and then add excess alkali. Is neutralized with an acid such as sulfuric acid, hydrochloric acid, or acetic acid, and deliquored with a centrifuge or the like.
A solvent-processed CM soy sauce cake can be obtained by adding 5 to 50 times the amount of hydroalcohol such as 60 to 80% methanol for purification, drying and crushing.

When monochloroacetic acid alkali salt is used in the solvent method, the solvent method CM soy sauce is prepared in the same manner as above except that the addition of an alkali such as sodium hydroxide is at least 1 mol of the monochloroacetic acid alkali salt. You can get the lees.

[Action]

The mechanism of action of the present invention is that arabinogalactan, which is a fibrous substance in soy sauce cake, reacts with monochloroacetic acid to be carboxymethylated, so that water solubility is imparted to soy sauce cake and gelatinization occurs even at room temperature. It is used as a binder for substances and inorganic substances.

Although there are many organic and inorganic substances in which the binder is industrially used, since the CM-modified soy sauce cake of the present invention is colored in brown, it is suitable to be used for applications in which the color is not a problem. is there. As such applications, for organic substances, briquette charcoal binder, graphite, activated carbon binder, fertilizer binder, feed binder, etc. are considered, and for inorganic substances, foundry sand binder, powder. Binders for ore briquette and binders for ceramic materials are considered.

Hereinafter, the effects of the CM soy sauce cake of the present invention as a binder will be shown in Examples in the case of powdered coal as a briquette raw material and foundry sand.

〔Example〕

Example 1 A non-dried soy sauce cake (water content 30.0
%) 286g and 50% sodium hydroxide 148g, and add 2 at 20 ℃
After stirring for 70 hours, add 70 g of monochloroacetic acid and 114 g of water and add 20 g.
The mixture was well stirred at ℃ for 2 hours. Then raise the temperature to 40 ° C and
After reacting for a period of time, the pH was neutralized to 7.0 with acetic acid after the reaction was completed.
80% methanol (3 l) was added to the reaction product for purification, and the liquid was dewatered, dried and pulverized to obtain a water medium method CM soy sauce cake A. The analytical values are shown in Table 1, the caking test results of powdered coal for briquettes are shown in Table 2, and the caking test results of foundry sand are shown in Table 3.

Example 2 A soy sauce meal powder (water content: 7.7) was added to a 5 l Werner type kneader.
%) 217 g, isopropanol 437 g, water 77 g, 50% sodium hydroxide 148 g, stirred at 30 ° C. for 1 hour, then added with monochloroacetic acid 70 g and 90% isopropanol 200 g, and reacted at 70 ° C. for 1 hour After cooling, cool to pH 7.
Neutralized to 0. The reaction product was deliquored by a centrifuge, purified by adding 3 l of 75% methanol, deliquored, dried and pulverized again to obtain a solvent-processed CM soy sauce cake B. As in Example 1, the analytical values and the test results of the caking property for powdered coal and foundry sand are shown in Tables 1, 2 and 3, respectively.

In addition, for the caking test of powdered coal for briquettes, 1,2 or 3 parts of a caking agent was added to 100 parts of raw material coal prepared to a predetermined water content in advance, and the mixture was stirred for 5 minutes using a universal mixing stirrer, and then the formwork. Then, a cylindrical specimen having a molding pressure of 50 kg / cm ² , a diameter of 20 mm, and a height of 20 mm was prepared, dried in a hot air dryer at 80 ° C. for 1 hour, and the compressive strength was measured by a uniaxial compression tester. As a binder, a raw material soy sauce cake in addition to the CM-modified soy sauce cake of the present invention and α-starch usually used for this purpose were used for comparison.

The caking test of foundry sand was conducted as follows.
Mix 100 parts of foundry sand (Yayo Silica No. 6) with 8 parts of bentonite (Hotaka mark) and 0.5, 1.0 or 1.5 parts of binder for 1 minute,
Furthermore, add 4 parts of water, knead for 7 minutes with a Simpson mill, and squeeze and squeeze three times with a squeeze compactor, diameter 50mm, height 50m.
A columnar specimen of m was prepared, and the compression strength immediately after molding was tested with a uniaxial compression tester. As the binder, a raw material soy sauce cake in addition to the CM-modified soy sauce cake of the present invention and corn starch which is usually used for this purpose were used for comparison.

[Effects of the Invention] The caking performance of the powdered coal and the molding sand of the CM-modified soy sauce cake according to the present invention is higher than that of the raw material soy sauce cake. In addition, even when compared with the binders that are generally used for each application, they have the same or better caking performance, and it is clear that they are excellent as industrial binders. Is.

─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. ⁵ Identification number Internal reference number FI Technical display location C08L 89/00 LSE 7415-4J C10L 5/14 (72) Inventor Goro Motoko Karako, Choshi-shi, Chiba 10 (56) References, 29, Machicho Japanese Patent Publication Sho 51-9028 (JP, B2)

Claims (3)

[Claims] 1. A carboxymethyl soy sauce cake obtained by carboxymethylating soy sauce cake. 2. A method for producing a carboxymethylated soy sauce cake, which comprises reacting soy sauce cake with alkali and monochloroacetic acid or an alkali salt of monochloroacetic acid in water and / or an organic solvent. 3. A binder containing carboxymethylated soy sauce cake as a main constituent.