JPS63297485A - Carboxymethylated soy lees, binder using same and production thereof - Google Patents

Abstract

PURPOSE:To obtain the titled soy lees useful as a binder for briquettes, foundry sand, etc., by reaction of soy lees with an alkali and monochloroacetic acid (alkali salt) in a solvent. CONSTITUTION:The objective soy lees can be obtained by reaction of the original soy lees with an alkali and monochloroacetic acid (alkali salt) in water and/or an organic solvent (e.g., an alcohol, ketone, pref. isopropanol).

Description

[Detailed Description of the Invention] [Field of Industrial Application] The present invention relates to carboxymethylated soy sauce lees, a method for producing the same, and its uses, and this substance can be used, for example, as a caking agent for briquette charcoal, foundry sand, etc. It is something that will be done.

[Conventional technology]

Soy sauce lees is used for soy sauce brewing, from light soy sauce to raw soy sauce (liquid).
It is the lees (residue) obtained by pressing and filtering and contains protein, crude fiber, etc., but it has a large amount of salt and a characteristic odor, and is digestible with N, so it is used as some feed. Other than that, its uses are extremely limited, and various ways to develop its effective uses are being studied.

One of the uses of soy sauce lees other than feed is to use it as a filler for adhesives. - A product made by adding calcined gypsum to soy sauce lees and heating and crushing it, based on wheat bran mixed with mannan. (Japanese Unexamined Patent Application Publication No. 47-39444) (1) A method of producing a filler for adhesives by bringing soy sauce lees into contact with saturated steam or superheated steam and heat-treating them. (Unexamined Japanese Patent Publication No. 5
5-155073 Publication) ■ A method of extracting soy sauce lees with water, then drying and pulverizing it to produce a filler for adhesives (Japanese Unexamined Patent Publication No. 55-155074) ■ Soy sauce lees dry powder and water-soluble polymer Filler for adhesives containing one or more substances (JP-A-56-1517)
No. 79) is known.

[Problem that the invention seeks to solve]

Since soy sauce lees is insoluble, its usage has been limited to using soy sauce lees as a filler for adhesives as described above, or by drying and pulverizing the soy sauce lees after some processing. However, in the present invention, soy sauce lees is subjected to a chemical reaction to make the soy sauce lees water-soluble and impart caking performance.

It is intended to be used as an industrial binder.

[Means for solving problems]

Soy sauce lees, which is produced as a by-product during soy sauce production, is insoluble in water and therefore does not have caking properties. However, since the soy sauce lees contains fiber in its composition, it can undergo carboxymethylation (hereinafter referred to as
This reaction (abbreviated as 0M conversion) is carried out to impart water solubility to soy sauce lees and to use it as a binder.

In the present invention, soy sauce lees is a general term for lees obtained by compressing and filtering raw soy sauce from light soy sauce during soy sauce brewing.
The brewing method for soy sauce fumi from which it originates does not matter whether it is a natural brewing method, a quick brewing method, or a new type of brewing method, and it is left to dry after pressing, desalting, and bleaching.

It may be subjected to post-treatment such as deodorization.

An example of the composition analysis of dried soy sauce lees derived from natural brewing is 7.2% moisture, 10.5% ash, 7.7% salt, and 3.0% total nitrogen.
9%, crude protein (total NX 6.25) 24.4%, total reducing sugars due to total hydrolysis (in terms of glucose) 35.6%, and sugar composition determined by high performance liquid chromatography is arabinose 4.3 %, galactose 12
．． 0%, glucose 14.1%, rhamnose trace
(root ball) and contains various other amino acids, low molecular weight proteins, polysaccharides, etc.

In addition, the commercial soy sauce lees of the present invention has a degree of etherification of 0.05.
~1.0 mol/100 g, preferably 0.1-0.4
This refers to 100g of Morph converted to 0M. If the degree of etherification is less than 0.05 mol/100g, water solubility is insufficient, and if the degree of etherification exceeds 1.0 mol/100g, a large amount of expensive reaction chemicals are required, making it uneconomical and practical. Not on point. Furthermore, it does not matter whether it is purified after the lateralization reaction or prepared with other additives. In addition, in order to use it as a binder, it can be prepared in a form suitable for that purpose.

The alkalis used to produce soy sauce lees include sodium hydroxide, hydroxide, and potassium.

There are alkali metal hydroxides such as lithium hydroxide,
Primarily sodium hydroxide is used.

Further, as the alkali salt of monochloroacetate, there are alkali metal salts such as sodium monochloroacetate and potassium monochloroacetate, but sodium monochloroacetate is commonly used. Methods for reacting soy sauce lees with an alkali and monochloroacetic acid or an alkali salt of monochloroacetic acid include an aqueous method in which the reaction is carried out in an aqueous solution, and a solvent method in which the reaction is carried out in an organic solvent.

In the aqueous method, monochloroacetic acid or its alkali salt is easily hydrolyzed and the reaction efficiency is low, so the solvent method is more suitable, but it is not particularly limited.

First, an example of a method for producing CM-formed soy sauce lees using a water-based method will be explained as follows.

Add an alkali such as sodium hydroxide at least twice the mole of monochloroacetic acid used to the soy sauce lees, mix well at 10 to 45°C for 0.5 to 2 hours, and then add 0.05 to Add 2.5 times the amount of monochloroacetic acid,
After the reaction is stirred at ~50°C for 2 to 48 hours, the reaction is stopped by neutralizing the excess alkali with an acid such as sulfuric acid, hydrochloric acid, or acetic acid.

When using an alkali monochloroacetate salt, add an alkali such as sodium hydroxide to the soy sauce lees in an amount of at least 1 times the mole of the alkali monochloroacetate used, and then carry out the reaction as described above, neutralize it with an acid, and react. to stop.

After completion of the reaction, add 5 to 50 times the amount of hydrous alcohol such as 60 to 80% methanol to the reactant, wash and remove by-products, and then dry and crush to obtain commercial soy sauce lees using the water-based method. I can do it.

Next, in the method for producing CM-formed soy sauce lees by a solvent method, the organic solvent is a hydrophilic organic solvent such as alcohols such as ethanol, butanol, and isopropanol, and ketones such as acetone and methyl ethyl ketone, or the like. A mixture of benzene, toluene, etc. can be used, but isopropanol, which is currently most commonly used in the production of carboxymethylcellulose sodium salt by the solvent method, is suitable. In detail, the method of using isopropanol as an organic solvent is to use 80-95% isopropanol in an amount of 1 to 10 times the amount of raw soy sauce lees and an alkali such as sodium hydroxide in an amount of at least twice the mole of monochloroacetic acid used. 0.5 to 2 at 10 to 45℃
After mixing and stirring well for an hour, 0.05 to soy sauce lees
Add 2.5 times the amount of monochloroacetic acid and heat to 50-80℃.
After reacting for 1 to 3 hours, excess alkali is neutralized with an acid such as sulfuric acid, hydrochloric acid, or acetic acid, and the liquid is removed using a centrifuge. Purification is carried out by adding 5 to 50 times the amount of alcohol,
By drying and pulverizing, soy sauce lees made into CM by solvent method can be obtained.

When using alkali monochloroacetate in the solvent method, the same method as above is used except that an alkali such as sodium hydroxide is added in an amount of at least 1 times the mole of the alkali monochloroacetate used. You can get lees.

[Effect]

The mechanism of action of the present invention is that arabinogalactan, which is a fibrous material in soy sauce lees, reacts with monochloroacetic acid and is carboxymethylated, thereby imparting water solubility to the soy sauce lees and gelatinizing it even at room temperature. It is used as a binder for substances and inorganic substances.

There are many organic and inorganic substances for which binders are used industrially, but since the CM4 soy sauce lees of the present invention is colored brown, it is not suitable for use in applications where color is relatively not an issue. be. Examples of such uses include organic substances such as caking agents for briquette charcoal, graphite, activated carbon caking agents, fertilizer caking agents, and feed caking agents, and inorganic substances such as foundry sand caking agents and powder. Possible examples include binders for mineral briquettes and binders for ceramic raw materials.

The effect of the CM-formed soy sauce lees of the present invention as a caking agent will be shown below in Examples using powdered charcoal and foundry sand as raw materials for briquettes.

〔Example〕

Example 1 Undried soy sauce lees (moisture 30
．． 0%) 286 g and 148 g of 50% sodium hydroxide
After stirring at 20°C for 2 hours, add monochloroacetic acid.
70 g and 114 g of water were added and stirred well at 20° C. for another 2 hours. Next, the temperature was raised to 40°C, and the reaction was carried out for 24 hours. After the reaction was completed, the pH was neutralized to 7.0 with acetic acid.

This reaction product was purified by adding 80% methanol 3Q, and after diluting, it was dried and pulverized to obtain soy sauce lees A made into CM using aqueous medium method. The analytical values are shown in Table 1, the results of the caking test for powdered charcoal for briquettes are shown in Table 2, and the results of the caking test for foundry sand are shown in Table 3.

Example 2 Dry soy sauce lees powder (moisture 7
．． 7%) 217g and isopropanol 437g.

Add 77 g of water and 148 g of 50% sodium hydroxide, stir at 30°C for 1 hour, and then add 70 g of monochloroacetic acid.
was dissolved in 200 g of 90% isopropanol and reacted at 70°C for 1 hour. After cooling, the pH was adjusted to 7.
After deliquifying the 0 reactant neutralized to 0 using a centrifuge.

Purification was performed by adding 75% methanol 3Q, and the mixture was again deliquified, dried, and pulverized to obtain CM-formed soy sauce lees B obtained by the solvent method. As in Example 1, the analysis values and the test results of caking properties for powdered coal and foundry sand are shown in Tables 1, 2 and 3, respectively.

In addition, the caking property test of powdered charcoal for briquettes was carried out by adding 1, 2 or 3 parts of a caking agent to 100 parts of raw coal that had been prepared to a predetermined moisture content, and stirring for 5 minutes using a universal mixer. Packed into a mold with a molding pressure of 50 kg/a#, a diameter of 20 m, and a height of 20 nm.
A cylindrical specimen was prepared, and after drying in a hot air dryer at 80° C. for 1 hour, the compressive strength was measured using a uniaxial compression tester. As the binder, in addition to the commercialized soy sauce lees of the present invention, raw soy sauce lees,
α-starch, which is commonly used for this purpose, was used for comparison.

A caking test for foundry sand was conducted as follows.

Mix 100 parts of foundry sand (Yayoi silica sand No. 6) with 8 parts of bentonite (Hotaka Serushi) and 1.5 parts of binder O, S, T, O or 1.5 parts for 1 minute, then add 4 parts of water and make Simpson Knead in a mill for 7 minutes, pound and harden three times in a molding machine to make a cylindrical specimen with a diameter of 50I and a height of 50mm, and the compressive strength immediately after molding is ll1l! Tested on I compression testing machine. As the binder, in addition to the soy sauce lees of the present invention, raw soy sauce lees,
Cornstarch, which is commonly used for this purpose, was used for comparison.

Table 1 Analytical values of Kaihua soy sauce lees Table 2 Powdered charcoal caking performance of Kaihua soy sauce lees Table 3 CM
Casting sand caking performance of chemical soy sauce lees (bentonite 8%, moisture 4
%) [Effects of the Invention] The caking performance of the powdered charcoal and foundry sand of the CM-formed soy sauce lees according to the present invention is higher than that of the raw soy sauce lees. Furthermore, when compared with binders commonly used in various applications, it has the same or better caking performance, making it clear that it is an excellent industrial binder. It is.

Patent applicant: Sanyo Kokusaku Pulp Co., Ltd. ,・　,) ・：、L、、r

Claims (1)

[Claims] 1. Carboxymethylated soy sauce lees obtained by carboxymethylating soy sauce lees. 2. A method for producing carboxymethylated soy sauce lees, which comprises reacting soy sauce lees with an alkali and monochloroacetic acid, or an alkali salt of monochloroacetic acid in water and/or an organic solvent. 3. A binder whose main component is carboxymethylated soy sauce lees.