JPS59179502A - Preparation of carrageenan - Google Patents

Abstract

PURPOSE:To obtain high-purity carrageenan having improved water dispersibility, by adding a specific amount of a hydrophilic organic solvent to a filtrate of carrageenan extract which is gelatinized by cooling, blending them with stirring, subjecting them to solid-liquid separation. CONSTITUTION:A filtrate of carrageenan extract obtained by extracting it from a red algae (e.g., Eucheuma Cottonii, etc.) followed by filtering it is cooled and gelatinized, preferably crushed coarsely into proper size, blended with 0.8-3.0 times as much a hydrophilic organic solvent (e.g., methanol, etc.) as the filtrate by volume with stirring (preferably for 20min), preferably pressed or centrifuged, and dried to give the desired carrageenan.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a method for producing carrageenan having good dispersibility in water.

Carrageenan is a sulfated galactan contained in red algae, and is generally classified into ni (kappa), λ (lambda),
It is roughly divided into three types: C (iota), gelling property, protein reactivity,
They have different basic properties such as viscosity. In addition, these properties are widely used in the food industry, cosmetics industry, etc. because of their unique properties that differ depending on the cation species bonded to the sulfate group.

The red algae that is the raw material for carrageenan is Eucheuma Spinosum.
, Eucheuma Cotmo
tonll), Contras Chrisvas (Chond)
rus Cr1spus), Gigartina stellata (Oigartina 5tellata), etc. are used. The method for obtaining carrageenan from these red algae is as follows. After washing the red algae with water and pre-treating with acid or alkali as necessary, the red algae is immersed in neutral to slightly alkaline water and heated to 50 to 1 o'clock for 1 to 8 hours for extraction. Next, a filter aid such as diatomaceous earth is added to the extract and filtered, and then the filtrate is dried using a drum dryer to obtain dry carrageenan.

However, this method is economically disadvantageous because it requires a large amount of energy for drying. Furthermore, since water-soluble impurities cannot be removed, a highly pure product cannot be obtained. Gel press method and alcohol precipitation method are known as improved methods.

The gel press method is a method in which liquid F is cooled and turned into a gel, and then pressure is applied from the outside to dehydrate it. This method requires a long time for dehydration, resulting in low productivity and insufficient dehydration effect.Furthermore, there are problems in that cold water soluble laquinan such as λ carrageenan flows out most of the time during compression dehydration. For this reason, a gelling agent is usually used, but the gelling agent remains, making it impossible to obtain a highly pure product. On the other hand, the alcohol precipitation method is a method in which carrageenan is precipitated by adding a hydrophilic organic solvent such as ethanol, inglobanol, etc. to tear fluid. This method has the advantages of being able to dehydrate in a short time, preventing cold water-soluble carrageenan from flowing out, and removing water-soluble impurities, resulting in a highly pure product. It is said to be a manufacturing method.

However, carrageenan obtained by alcohol precipitation has extremely poor dispersibility when dissolved by heating, and tends to form a so-called lump or lumpy state (and is extremely difficult to dissolve).

The present inventors evaluated the dispersibility of carrageenan by the following method. Weigh 2 g of carrageenan powders with particle sizes of 200 to 650 mesh produced by different manufacturing methods. 198m of distilled water at 25℃
1 into a beaker with a capacity of 300 m6, stir with a magnetic stirrer, and set the rotation speed to the minimum required for the vortex to reach the bottom of the beaker. The above-mentioned carrageenan was instantly added to the stirring water and stirred for 60 seconds to obtain a dispersion. The volume (Vml) of the f liquid obtained by passing this dispersion through a 62-mesh sieve and the evaporation residue C of a part of the r liquid
C9/me) is measured, and the dispersibility is calculated from the following formula.

The results are not shown in Table 1.

According to the evaluation by the present inventors, various factors may be considered to determine the dispersibility, but it has been found that the dispersibility is largely dependent on the dehydration method during production.

Table 1 According to the research conducted by the present inventors - The reason why the dispersibility of carrageenan depends on the manufacturing method is because the dispersibility of carrageenan is extremely influenced by the powder surface condition. . In the drum dryer method, the raw material source is extracted and the P liquid obtained by f-filtration is sequentially dried from the surface, and the water inside moves to the vicinity of the surface by diffusion and undergoes drying, so the surface of the dried product is extremely smooth. The surface of dried carrageenan obtained by the gel press method is also smooth for the same reason. However, in the case of the gel press method, the remaining gelling agent has the effect of increasing dispersibility, so it cannot be discussed in parallel.

On the other hand, in the alcohol precipitation method, in order to generally increase the contact between the alcohol and the p-liquid, they are mixed and stirred under high shear conditions, and the resulting precipitate is dried. In this case, since the precipitate contains two or more liquids with different boiling points, for example, if ethanol or ingropanol is used, these alcohols will selectively evaporate during the drying process and the primary It was found that a large number of micropores were distributed especially near the surface due to the evaporation of water. The fact that these differences in surface conditions have a very large effect on the dispersibility of carrageenan powder is explained as follows. Powder with a smooth surface has a slow surface dissolution even when placed in water, so there is little welding of powder particles to each other, and because the powder has a high specific gravity, it quickly sinks into the water - so-called lumps or lumps. No. But-
Powder particles with a long hole surface not only dissolve quickly and easily adhere to each other, but also contain air and have a low apparent specific gravity, making them difficult to submerge in water, resulting in lumps or lumps. exhibit a condition.

The present invention is based on these findings.
This method for producing carrageenan is characterized by mixing with twice the amount of a hydrophilic organic solvent and stirring for one hour, followed by solid-liquid separation.

The red algae may be one that is used as a raw material for the production of carrageenan, such as Euchymata =+).
2. Knee Cue 7 Suhinosum, Contras Crispus, etc. Two or more of these can also be used in combination.

When carrying out the present invention, red algae are washed with water, pretreated with acid or alkali as necessary, and then extracted and filtered by a conventional method. The tear fluid thus obtained is cooled and gelled. F fluid essentially has a gelling property, but its gelling temperature varies depending on the type of raw material source, the carrageenan concentration in the tear fluid, the type and concentration of coexisting salts, etc. For example, if the extract of Euchyuma kotonii is extracted as a liquid and the concentration of carrageenan is 11% by weight, the gelation temperature is 3m degrees at 28°C.
Below, when the carrageenan concentration is 11% by weight in the extract P solution of Eucuma spinosum, the gelation temperature is below 26°C, and the carrageenan concentration is 1.1% by weight in the extract P solution of Contras crispus. In some cases, the gelling concentration is below 12°C.

Next, a hydrophilic organic solvent is added to the cooled and gelled r liquid and mixed and stirred. Appropriately crushing the gelled R liquid prior to this is effective in improving the dehydration and purification effects.

Examples of hydrophilic organic solvents that can be used include lower alcohols such as methanol, ethanol, and inglobanol, acetone, tetrahydrofuran, and dioxane. The amount of the hydrophilic organic solvent to be used is 0.00% of the volume of the gelled P solution.
It is 8 to 3.0 times the amount. If the amount is 0.8 times or less, the dehydration effect will be low, and even if the amount is 6.0 times or more, no increase in the dehydration effect can be expected and it is uneconomical. Further, by continuing stirring for 20 minutes, the water content in the hydrophilic organic solvent becomes a constant value and reaches an equilibrium state, so it is sufficient to continue stirring for 20 minutes. At this time, the water inside the gel diffuses from the surface into
, the surface after drying is extremely smooth. Furthermore, even when the gelled IP solution is treated with a hydrophilic organic solvent, the same purification effect as in the conventional method can be obtained. As a result, carrageenan with good dispersibility and high purity can be obtained. Note that it is effective to remove excess hydrophilic organic solvent by squeezing or centrifugation prior to drying.

The dispersibility of carrageenan produced by the method of the present invention is 8
0 to 90%, and the high sulfuric acid content supports high purity. The present invention provides carrageenan with extremely high added value of high dispersibility and high purity,
This will greatly contribute to the industry.

Example 1 Eukyuma kotoni was immersed in water with a pH of 8 and heated to 80°C.
After heating and extraction for 6 hours, the mixture was filtered by a conventional method to obtain a clear JJ liquid with a carrageenan concentration of 1.2%. Using this tear fluid, carrageenan powder was produced by the following method.

Ten stones of sample IA SP liquid were dried at 90° C. using a drum dryer and ground to obtain a powder having a particle size of 200 to 650 mesh (drum dryer method).

Sample IB: 40% potassium chloride in 10ffl of 1 solution
9 was added thereto, heated and dissolved, cooled to 25°C to gel, and then coarsely crushed to a size of 15 x 10 x 10 mm. This gel was incubated at a pressure of 20 kg/cm2 for 1 hour, then at a pressure of 50 kg/cm2.
After pressing at a pressure of kg,/cn+2 for 60 minutes, it was dried at 90° C. for 45 minutes and crushed to obtain a powder having a particle size of 200 to 350 mesh (gel press method).

Sample 1C: 10.8 of the Δcoliquid was used without cooling and gelling, 60 stones of isopropanol was added thereto, and the mixture was stirred for 20 minutes.
The resulting precipitate was squeezed at a pressure of 30 kg7 cm2 for 60 minutes, dried at 90°C for 45 minutes, and crushed to give 20 kg.
A powder containing 5F grains of 0 to 650 mesh was obtained (
alcohol precipitation method).

Ten swamps of sample rDHHp solution were cooled to 10° C. to form a gel, and then coarsely crushed into a size of 5×10×10 mm. 20 ffl of isopropanol was added thereto and stirred for 20 minutes.

Next, it was squeezed for 60 minutes at a pressure of 30 kg/cm2, dried at -90°C for 45 minutes, and crushed to a
A powder having a particle size of 650 mesosius was obtained (method according to the invention).

Sample 1E2: Processed in the same manner as Sample 1D except that 5 ml of inpropanol was used in 10 ml of P solution.

As a result, dehydration was insufficient and pressing was impossible.

Sample 1F was treated in the same manner as Sample 1D except that Improper Tool 30N was used for 10 volumes of the two-liquid to obtain powder having a particle size of 200 to 650 mesh (method of the present invention).

The results of evaluating the yield, dispersibility, sulfate group content, and appearance after drying of these samples are shown in Table 2, and it is known that they are excellent in all respects.

Example 2 The drum dryer method (Sample 2A), the gel press method (Sample 2B), the alcohol precipitation method (Sample 2C), and the method of the present invention (Samples 2D, 2E, 2F) were carried out in the same manner as in Example 1 using Eucuma spinozum. We attempted to manufacture products by dehydrating and drying and pulverizing. However, the gel press method is virtually impossible to implement, and sample 2E could not be obtained for the same reason as Example 1.

Table 2 shows the results of evaluating the yield, dispersibility, sulfuric acid content, and appearance after drying for each sample.

It is known that the products produced by the method of the invention (2D and 2F) are superior in all respects.

Example 6 Using Chondrus Crispus, the Drumtom-Year method (Sample 3A), gel press method (Sample 6b), alcohol precipitation method (Sample 6C), and the method of the present invention (Samples 6D, 3E, 3F) and pulverized to try to manufacture a product. As a result, Sample 6E was evaluated for the same buried O/Y1 views as in Example 1, and the results are shown in Table 2. It is known that the products (3D, 3F) according to the method of the present invention (, /C) are superior in all respects.

Table 2 Note: Samples 1B and 6B contain 1D% and 11% potassium chloride.
Contains %.

Applicant: Mitsubishi Acetate Co., Ltd. Agent: Patent Attorney Masao Kobayashi

Claims (1)

[Claims] Production of carrageenan characterized by mixing and stirring a cooled gelled carrageenan extraction solution F with a hydrophilic organic solvent in an amount of 0.8 to 3.0 times the volume of the extraction solution F, and then performing solid-liquid separation. Law.