WO1984000761A1

WO1984000761A1 - Process for purifying and condensing high-molecular polysaccharide extract obtained from sea weed

Info

Publication number: WO1984000761A1
Application number: PCT/JP1983/000261
Authority: WO
Inventors: Masami Kosaka; Kimihiko Takeo
Original assignee: Asahi Chemical Ind
Priority date: 1982-08-10
Filing date: 1983-08-10
Publication date: 1984-03-01
Also published as: DK82684D0; JPS5941303A; DK82684A

Abstract

An aqueous solution of a high-molecular polysaccharide such as carrageenin, agar-agar or alginic acid derivatives is effectively purified and concentrated with a high water permeation rate to a concentration of about 3.0 to about 4.5 wt % by allowing the solution to flow through ultrafiltration hollow body at a shearing speed of 5000 sec-1 or more. Dilution of the aqueous solution with warm water before allowing to flow through the hollow body serves to effectively conduct preliminary filtration usually conducted for removal of sea weed residue in the extract and for removal of colorants due to decrease in viscosity, and the colorants and low-molecular impurities are effectively removed through entrainment by a large amount of water upon ultrafiltration. Thus, a highly pure product which has never been obtained by conventional process is obtained.

Description

Specification ,

Of high molecular polysaccharide extract from seaweed

Purification 'Concentration method

Technical field

TECHNICAL FIELD The present invention relates to a method for efficiently purifying and concentrating a high-molecular-weight polysaccharide extract from seaweed by an over-treatment with an ultrafiltration membrane. More specifically, the present invention relates to an aqueous solution of high molecular polysaccharides such as carrageenan, agar, farceran, and alginic acid derivatives, which are extracts of seaweed forces. , Hollow fibers such as hollow fiber or thin groove type, by flowing under pressure and at a high shear rate into the hollow part of a hollow ultrafiltration membrane] ?, and regarding the method of refinement shrinkage with high water permeability. To do.

Background technology

Seaweeds include red algae, brown algae, green algae, and cyanobacteria. It is the former two types of red algae and brown algae whose extracts are put to practical use in the food and pharmaceutical industry.

The types of high-molecular polysaccharides obtained from red algae include, but are not limited to, carrageenan, agar, and faceralan, and those obtained from brown algae. Alginic acid salts such as sodium alginate, potassium, and ammonium-, and prolonged alcoholic alginate. ¾ Alginic acid ester is known. These high molecular polysaccharides have the following common characteristics.

O PI WIPO (1) These substances extracted from seaweed have high viscosities of several tens to several hundreds of cp even in an aqueous solution with a concentration of about 1 to about 3 weight, and the viscosity depends on the temperature. It has a great nature.

(2) All of them are macromolecular substances, for example, the average molecular weight of ordinary commercially available carrageenan is about 15 to 250000.

(3) It has the flow characteristics of a non-youth fluid.

(4) Extracts from red algae (carrageenan, faceraran, agar) are lamda-type colorants containing about 40 weight% of sulfur dioxide. With the exception of guanines, it has water-gelling properties and forms gels with a gel strength of hundreds or even more when 1 weight of water is added. Moreover, although the above-mentioned lamda-type collagen has no water-gelling property, it has a high viscosity and is useful as a thickener.

(5) Products are advantageously used in the fields of food, cosmetics, pharmaceuticals, etc.

It has many similar properties like this, and even about 1 to 3 weight of diluted water raft extracted from seaweed shows high viscosity, so it is common to these high molecular polysaccharide aqueous solutions. There was a strong demand for a simple and economically efficient refining / concentrating method that can be used.

Below, high molecular weight polysaccharides from seaweed that have been traditionally used The contraction method of the extract will be explained by taking an example of a force laginan, which has been extracted from red algae and whose demand has been increasing in recent years.

Karagian is a seaweed of the red algae, for example, the genus Chondrus Crispus.

Gigar t ina Stellata, Gigarti na Badula It is a high-molecular-weight polysaccharide containing ester sulfate, which is obtained by aging the solution or boiling it in hot water or an aqueous alkaline solution.

What was extracted from seaweed was an aqueous solution of carrageenan with a low degree of dampness, and many methods have been used to make powdery products from it. The manufacturing method is as follows.

(1) Drum drying method

Add ^ -auxiliary material, such as diatomaceous earth, to the extracted aqueous solution of carrageenan at a concentration of 1 to 2 weights of carrageenan, and filter or centrifuge. Separate the aqueous solution of carrageenan as a greed from the seaweed residue using the 璣. This liquid contains impurities such as coloring components in an amount of about 10% by weight based on the solid content, together with the pressure ring.],

^ The liquid is dark brown or dark brown.

In order to remove these impurities, activated carbon or A purification method such as adsorption with an ion-exchange resin is carried out, and then the solution is reduced to the highest concentration possible in a vacuum evaporator, but the aqueous solution of potassium nitrate has a high viscosity even at a low concentration. It is said that there is a limit to the amount of agricultural contraction before and after.

A thin film dryer is brought into contact with a heated dryer or stainless steel belt to dry the condensed liquid, and the hardened material is pulverized.

The feature of this method is that the product can be obtained with relatively simple equipment, but it contains a large amount of impurities depending on the degree of purification, and the drum or stainless steel surface. It is not easy to separate the dried thin film carrageen attached to the base. Inadequate separation and adhesion of the drum surface to the drum surface, and the long-time-heated power magnesium turns yellow, reducing the quality of the product. In addition, there is a method to add tarfine squeeze and high-grade fatty acid monohydrate to prevent sticking, but this will further reduce the product quality.

In general, most of the pressure rings produced by this method are low purity products.

(2) Alcohol precipitation method

Extraction was performed in the same process as the Drum Drying method, and the concentrated liquid was condensed to USP 3 1 '6 0 0 3 "without subjecting the ^ liquid refining operation to shrinking in a vacuum evaporator to about 3 parts by weight. S el ec ti ve

OMPI WIPO E traction of Hydrocolloid Fractions From Sea Plants "Aruha GLICKSMAN" Gum Technology in the Food

Industry "ACADEMIC PRESS (New York) (1 9 6 9)

Approximately 85 weighted engine as described on pages 2-14 to 2-16. Single-alcohol is sprayed in about 2-2.5 times the volume to precipitate and separate the carrageenan. At this time, most of the coloring components and impurities are dissolved in the alcohol, but some of them are also contained in the keratin, so the purity of the product is about 9 3 to 95 5 wt. You can get the thing. It is also suitable for seaweeds containing a large number of components with relatively weak gelling properties, such as Chondrus Crispus]), and has the advantage that it is not restricted by the type of seaweed, but the equipment costs and Energy recovery for alcohol; large and costly.

(3) Gae-Noreless method

Extracted from seaweed, purified the extracted ^ liquid using active or large amount of diatomaceous earth, and then 3 wt.

The concentrated solution, which has been contracted back and forth and cooled, is also described in JP-A No. 5 6-9 5 90 1 `` Gellification manufacturing method of force magnesium with aqueous salt solution ''. In order to form a strong gel by ejecting it into an aqueous solution of an alkali metal salt (for example, an aqueous solution of potassium chloride), wash it thoroughly with water to remove the salt, and then press the machine. Depressurize with and dry.

Ο ΡΙ This method is low in equipment cost and energy cost, but the raw material is seaweed with high gelling ability, such as Eucheunia.

There is a problem that it is limited to Cottonii etc.

Conventionally, uhondrus Crispus was the representative red seaweed seaweed that is the raw material for carrageenan, but the carrageenan obtained from the seaweed was simply coagulated and precipitated in cold water. Since the gel strength is low and it is not suitable for high-level dehydration by pressure, the alcohol precipitation method was often used. Recently, the force magnesium produced from Eucheuma Cottonii, which has been cultivated in the sea near the Philippines, has a high gel strength, and especially, it is ion-exchanged with calcium salt. Gels that have been pre-treated, then coagulated and precipitated have the great advantage that they can be pre-dehydrated by more than 15 weight (wet weight basis) depending on the press.

In either case, a purification S-condensation step is required before gelling, but the extract of carrageenan has a low viscosity and a low viscosity. The efficiency is extremely poor when an aqueous solution extracted with about 1 to 2 weight is added, for example, by adding diatomaceous earth as a super-assistant hao, and the efficiency is extremely low. It was not easy because of the liquid. In addition, adsorption purification using ion-exchange resin has a high cost and has not reached the level of practical application. In addition, the shrinkage due to the vacuum evaporator is about 3 weight at the industrial scale at most, and the energy cost is also large.

OMPI Was

In addition to the above-mentioned manufacturing method, a method of purifying a low-dose carrageenan extract by ultrafiltration and simultaneously concentrating it to a high'concentration 'has been proposed (US Pat. No. 3, 8 5 No. 6,5 6 9 No.). Specifically, this method uses a thin groove type ultrafiltration membrane] ?, and the liquid side is allowed to permeate water and water along with impurities such as color components and low molecular weight substances in the potassium extract. As a result, it is possible to purify and concentrate at the same time by blocking high molecular weight solute on the side of the concentrate. However, according to this method, despite the operation at high temperature and high overpressure, the aqueous solution of keratin honey extracted from seaweed, which has a weak gelling ability, has high strength. Even when concentrating up to about 4 weight, which is easy to form a fine gel, it has a drawback that it is economically difficult to put into practical use due to its low water permeability.

Originally, an aqueous solution of a high-molecular polysaccharide such as carrageenan has a high viscosity as described above, and an aqueous solution of such a high-viscosity is a normal target to be treated by ultrafiltration. Since the viscosity is higher than that of the liquid, the absolute amount of is too small, and at the same time, it is expected that clogging will occur in a short time and the: (F liquid amount will be rapidly decreased. Purification and concentration by ultrafiltration are not considered to be appropriate methods from a practical point of view.In fact, the purification method disclosed in U.S. Pat. In the method of purifying and concentrating the aqueous solution of germanium, IPO with a liquid temperature of about 85 X and an inlet pressure of 5.6 kg / cm ² G Even us to conditions, permeation rate of ^{4 5 (/ 2 'Hr)} , the water permeability unit pressure equivalent is 1 6 (

), But it is extremely insufficient for practical use.

As described above, all of the methods conventionally proposed for the purification and condensation of an aqueous solution of a high molecular polysaccharide extracted from seaweed include all methods such as product purity, economic efficiency, convenience, and reliability. Some are satisfactory, but some are not practically sufficient.

Disclosure of the invention

INDUSTRIAL APPLICABILITY The present invention utilizes an ultrapermeability membrane and a simple apparatus to produce a high-molecular-weight polysaccharide aqueous solution extracted from seaweed at a high cost and a high ^ pressure pressure. To provide an efficient method for refining and condensing.

Immediately, according to the present invention, seaweed is extracted with an aqueous solvent to obtain a high-molecular-weight polysaccharide aqueous solution, which has openings on one end and on the other. , The ultra-hollow hollow body that has an ultrafiltration membrane in its peripheral portion extending in the longitudinal direction is to flow the polymer aqueous solution at a shear rate of 5 000 Sec " ¹ or more in the hollow flow channel. , A method of purifying and contracting the high-polysaccharide aqueous solution into 1 of the ultra-I hypermembrane with high water permeability is provided.

In the method of the present invention, an aqueous solution of a polycondensate polymer is squeezed into the hollow channel of the ultra-hollow body at a shear rate of 5 000 Sec " ¹ or more.

O PI By flowing at a breaking speed, the chain polymer of the high molecular polysaccharide is broken (by maintaining the gelling ability), and the ultrafiltration at a high water permeability is achieved. It is surprising that the refinement and shrinkage can be achieved efficiently and efficiently.

The reason for this is not clear, but it can be considered as follows. That is, in an aqueous solution of a high molecular polysaccharide obtained by extraction from seaweed, chain polymers are intricately entangled in a string or coil shape, and water is entrapped in them. As a whole, it has a high viscosity, and it is considered that water that is complicatedly entrapped by macromolecules is extremely difficult to release. Moisture or impurities in the released state will not be discharged out of the system as a liquid even if it is in contact with the membrane surface of the ultrafiltration. Therefore, even if a high ^ -E force is applied, at low shear rate of less than 500 Se (less than ¹ ), only low permeation slag is obtained.

The specifications and dimensions of the Amicon's thin-groove ultra ^ super-modules described in the examples of No. 3, 8 5 6, 5 6 9 specifications are the same as those of the same company. Then, the overpressure, the aqueous solution viscosity, and the liquid O viscosity used in the examples were obtained, and then the magnitude of the pressure drop and the circulating fluid flow rate were calculated from the length of the flow path. The shear rate is about 1,00 0 to about 4,00 0 Sec- ¹ .

On the other hand, in the method of the present invention, the aqueous solution of the high molecular polysaccharide was subjected to the medium ultra-extinction at a shear rate of 500 Sec- ^{1 or} higher.

O PI WIPO When flowing through the hollow channel of the membrane] ?, the water and impurities that were entrapped by the high molecular polysaccharide were squeezed to the surface of the high molecular substance! ) It is considered that, after being released, it was released and a large amount of ^ liquid was expelled through the ultra ^ permeabilizer even at a relatively low ^ overpressure force, resulting in high permeability. However, the effect of the present invention cannot be obtained by simply applying a shearing force.For example, a homogenizer having a blade that rotates at a high speed before performing an extreme pass is used. It can be considered that it is passed through, but when stirring at high speed, the chain-like polymer is broken into small pieces and the gelling ability is reduced.

In this way, the aqueous solution of high molecular polysaccharides is flowed at a shearing speed S of 500 0 S ee ^-1 or more, so that the high molecular polysaccharides are subjected to intense shearing stirring to The water and impurities bound by the polymer are squeezed out and released without destroying the chain structure of the polymer, achieving high water permeability. It's surprisingly good that it's not been .50 at all.

As shown in Table 2 of Example 1, which will be described later, or as a graph of this in Fig. 2 and 3 ϋ, as shown in Fig. 3 and ϋ, the flow rate of the aqueous solution of calagen; In the region where the shearing velocity .. is greater than 500 0 S ec " ¹ , the permeability per unit pressure (Fig. 2) or the permeability (Fig. 3) is remarkable. You can see that it is expensive.

A detailed description of the method of the present invention is given below.

ΟΜΡΙ

WIPO Among the seaweeds used in the method of the present invention, preferred are red algae and brown algae as described above, and preferred high molecular weight polysaccharides are carrageenan, agar, and agar. Phosphorus and sodium salts of alginic acid as described above, sodium salts, sodium salts such as ammonium salts, and alginic acid polyprohate. .. Examples include alginic acid derivatives containing ethylene glycol such as glycol monoester.

The aqueous solution of high molecular polysaccharide to be treated in the present invention is prepared by extracting seaweed with water or an aqueous solvent such as KOH'NaOH, Ca (0H) ₂ , NH ₄ OH, Na ₂ C0 ₃ and the like. Obtained. Specifically, although it varies slightly depending on the type of alkaline, generally about 0.1 to 4 weight of dilute aqueous alkaline solution is used, and about 20 to 5 to seaweed (dry weight) is used. Boil it for about 3 to 30 hours at about 85 to 98 X in a bath ratio of 0 times the weight, and then extract it. Further, as the pretreatment, for example, an alkaline treatment with caustic soda containing a reduction ^ such as sulfite or hydrous α-phosphite can be performed. (Japanese Patent Special Publication 4 5-3 9 0 9 7).

The concentration of the high-polysaccharide extract from sea drought treated by the method of the present invention depends on the type or concentration of seaweed or high-molecular-weight polysaccharide, or when using an enzyme. Although different, the concentration of the high-molecular-weight polyaqueous solution obtained by extraction is about 8 to 3 weight. This is usually added to a filter group by adding an'over aid such as diatomaceous earth. During a filtration or a preparative filtration, the seaweed residue that is contaminated with the extract and the fine solids suspended in the liquid are removed. Furthermore, the liquid thus obtained can be subjected to a treatment for removing coloring components or fine low-molecular impurities through a layer filled with activated carbon. For preparatory filtration performed here, a continuous reading type or semi-continuous type filter press, drum filter, centrifuge, etc. that are usually used This is used. Also, a microfilter can be used. These may be used alone or in combination with a microfilter, and after-passing the excess residue liquid with a further filter press.

Then, the high-molecular-weight polysaccharide aqueous solution is applied to the ultrafiltration. In order to carry out the ultrafiltration in the present invention, the above-mentioned aqueous solution of high molecular polysaccharide is used to form an ultrafiltration membrane at the periphery of which one end and the other end each have an opening. Flow under pressure into the hollow flow path of the ultra-hollow body. During the treatment with the ultrafiltration membrane, the shear rate of the aqueous solution of high-polysaccharides in the hollow hollow channel of the ultrafiltration membrane is not less than 5,000 Sec ^-1 , preferably. and rather is 800 0 Sec ^-1 or more, rather than further favored Ru essential requirement der that put the process of this and is the invention to keep the ¹ 0 0 0 0 Sec 1 or more. The upper limit of the shear rate is about 450 0 Sec ^_1 , preferably about 40 000, considering practical overpressure and desired effect.

ΟΜΗ WIPO Se c " ¹ .

The term "ultra-passing" is used to apply pressure to a solution to block high-molecular substances or colloidal substances with a semipermeable membrane, and to dissolve water and low-molecular substances dissolved in water. Is permeated through a myriad of micropores present on the membrane surface of a semipermeable membrane, and separation, concentration and purification can be achieved at the same time] ?, existing separation methods such as distillation. Method, decompression constriction method, ultracentrifugation method, pressure flotation method, electrolytic flotation method, coagulation sedimentation method, fractional crystallization method, adsorption method, dialysis method, etc. It is said to be effective for shortening. The pore size of the membrane surface is 10 to 100, preferably 20 to 500. Depending on the type of solution, temperature, operating pressure, pH, etc., of the material used to form the film, boron resin, boron resin, or polyacrylic resin can be used. Polyvinyl chloride resin, vinylidene fluoride resin, vinyl chloride resin, etc. are used. For general techniques such as a method for producing an ultrafiltration membrane, refer to U.S. Pat. Nos. 3,871,950 and 4,286,015. In the method of the present invention, there are openings at one end and the other end, respectively. ) An ultra-hollow body having the above-mentioned ultra-permeable membrane is used in the peripheral portion extending in the longitudinal direction, and a specific example thereof is as follows. Immediately, the inner diameter is 0.8 to 1.4 _∞ 0 and the film thickness is 0.1 to 0.5.

-OREA ΟΜΠ WAT It is made into hollow fibers, and the length is adjusted to 0.2 to lm, and several dozen to several thousand fibers are moved to the east to form a multi-pipe type in a plastic or other casing. It is used as a hollow fiber type ultra-super module with a shape like a heat exchanger (C Shell and Tube Heat Exchanger).

Etc. are on the market. The diameter is about 1.24 cm and the length is about 1 mm. The surface of the rod-shaped ceramic or plastic core has a depth of about 0.3 to 8 and a width of about 6 _ra . Six grooves are provided, and an ultrafiltration membrane is wound around the surface of the core material having a hexagonal shape to form a thin groove-like flow path that is long in the vertical direction. A thin-groove type ultra-low-temperature unit composed of dozens of molds formed by pouring the solution to the side and allowing the solution to permeate to the outside of the membrane. There are various types of products (made by Amicon, USA). However, it is used in the present invention! ¾ The shape of the outer ^ peritoneum is not limited to the above.

The shear rate as used in the present invention is expressed by the following equation when the hollow fiber type and the thin groove type are regarded as a cylindrical tube and the thin groove type as a parallel groove, for example.

.40

Hollow fiber type r = — ^

6Q

Thin * type r =

In the above formula

OMH WIPO r: Shear rate C Sec ^-1 ]

Q: Flow rate Tn / sec 3

R: Inner radius of hollow fiber ■ [cm]

w: Thin groove width C cm t: Thin groove thickness C cm

In order to increase the shear rate of high-molecular-weight polysaccharide aqueous solution in the channel, it is the limit of the flat membrane 'high pressure is applied to the membrane to allow the liquid to permeate]? It is desirable to select an ultrafiltration membrane with a small hollow fiber structure or a thin groove structure with a small groove thickness. However, if the inner diameter or groove thickness is reduced, the pressure drop in the flow path increases, and the inlet pressure does not act as ^ overpressure of the liquid, but a sufficient shear rate is obtained. Not obtained. Therefore, it is necessary to reduce the inner diameter or groove thickness, and to select the flow path length that is suitable for the set inner diameter or groove thickness. Generally, in the case of the hollow fiber type ultra ^ permeation membrane, 2 about 0.8 to: L.4 m is preferably used, and in the case of the thin groove type ¾outer membrane, the shape of the groove cross section is about depth. 0.3-0.8 «and a width of about 6 m are preferably used.

When performing ultra-high pressure based on the present invention, the appropriate over pressure is ultra-low: It depends on the material of the transmembrane membrane, but it is about 2 .5 to 5 kg / n ² G, and the outflow pressure is preferably in the range of 0 to 1.0 kg / cm ² G. The temperature of the aqueous solution of the high molecular polysaccharide is 60 to 95 t :, preferably in the range of 70 to 90

O PI WIPO Is suitable. If the liquid temperature is too high, the high molecular weight polysaccharides will be thermally deteriorated, and if the temperature is lower than 60, the aqueous solution will significantly thicken, and in extreme cases, it will gel, which is not preferable.

In order to carry out the present invention, a high molecular polysaccharide extract solution is circulated through a module containing an ultrapermeabilized membrane, and the solution is circulated through the same module repeatedly. It may be a patch-type condensing method for concentrating the high molecular polysaccharide extract, or it may be a continuous concentrating method in which the condensate is successively passed through a plurality of modules. The expression ft can also be reduced.

Thus, according to the method of the present invention, about 0.8 to about 3 parts by weight of the high molecular weight polysaccharide aqueous solution can be easily added to about 3 to 5 parts by weight, preferably about 4 to 4.5 parts by weight. It is possible to squeeze. According to the present invention, at this time, water is removed with a high water permeability, and the coloring components and other low-molecular impurities are removed accordingly, so that the purification can be performed efficiently. Higher degree of dehydration operation gives a high degree of purity of about 92% in terms of purity such as pressure dehydration and electropenetration. By the way, the product density obtained by the conventional drum drying method is low by 90 1o, and the purity obtained by the alcohol precipitation method is 93-95. The equipment cost and energy recovery energy are large, and the cost is high, while there are drawbacks, whereas the method of the present invention is due to its high water permeability.

Λτ, In addition, it is advantageous in that it is possible to efficiently obtain a product having a purity comparable to that of the alcohol precipitation method with a simple device and at a low cost.

According to another aspect of the present invention, there is provided a method of diluting the aqueous solution of high molecular polysaccharide with warm water before flowing into the ultrahollow body in the above method.

As described above, the aqueous solution of high molecular polysaccharides extracted from seaweed contains coloring components and various contaminants.Usually, diatomaceous earth and other super-auxiliary agents are added to remove them. I put it on a filter press! ), It is separated by a centrifuge, but the viscosity of the high molecular polysaccharide extract is high, even if it is about 1 weight, and it causes clogging, for example. Since the EE loss is easy and the EE loss is large, frequent disassembly and cleaning are required, and the efficiency of separation remains low in centrifugal separation, which leaves a problem in terms of efficiency.

In addition, there is also a method of adsorbing and removing coloring components or minute impurities from activated carbon: However, this operation is not performed smoothly due to the high viscosity liquid, and special regeneration can be used. In the case of activated carbon, it is not effective because the liquid does not penetrate to the inside of the fine pores of activated carbon.

The aqueous solution of high-f polysaccharides extracted from seaweed can be diluted with warm water to reduce the viscosity of the aqueous solution, and the above-mentioned filter press ^ efficiency and centrifugal separation can be used. Consistency efficiency or decolorization efficiency by activated carbon is significantly increased.

OMPI Rukoto; can be ^.

Conventionally, a high-molecular polysaccharide extraction method can be used by cooling the aqueous solution of high-molecular polysaccharide extraction to form a solid gel and then depressurizing it with a press or the like. The alcohol precipitation method, in which the aqueous solution is condensed with a vacuum evaporator and then added with alcohol to separate the solution, the higher the degree of extraction solution, the higher the degree of gelation and alcohol. When considering that it is easy to divide by using the method, it is possible to efficiently concentrate highly viscous high molecular weight polysaccharide extracts even at low farming levels. When we think about ¾, it seems seemingly meaningless to positively dilute the aqueous solution of high molecular weight polysaccharides extracted from seaweed, and the volume of the solution depends on the dilution. Considering the increase, it may seem like a disadvantage. However, as described above, when a polymeric polysaccharide aqueous solution is flown through the hollow channel of an ultra-hollow body at a shear rate of 500 0 S ec — ¹ or more, extremely high water permeability ^ is obtained. In connection with the basic effects of the present invention, the fact that the extract is diluted before being subjected to the ultrafiltration adds an even greater advantage.

Immediately, the above-mentioned filter press filtration efficiency, centrifugal separation efficiency, and decolorization efficiency by activated carbon, such as preliminary efficiency, are further improved, and the amount of water permeation is increased. Therefore, a large amount of coloring components and low-molecular impurities that are removed along with it are obtained, and a product with high purity is obtained. It is. The product purity obtained by this dilution method is as high as about 95 to 96% or more, and it surpasses that of the alcohol precipitation method, which gives the highest purity among the conventional methods. In addition, this dilution method has the following advantages, that is, when the filter-press method in which an auxiliary agent is used in combination is used as the preparatory method, the combination method is used. The liquor super-assistant that is collected is collected by the rubble cloth and discarded, but at this time, the extract that is adsorbed and retained on the ^ -super-helper agent particle surface or in the particle gap is also discarded. R. At this time, since the high-molecular-weight polysaccharide diffuseness in the extract is low due to the dilution, the amount of useful high-molecular-weight polysaccharide that is discarded along with the vinegar aid is reduced. , Its loss can be reduced.

The degree of dilution is such that the concentration of the high-molecular-weight polysaccharide aqueous solution after dilution is about 0.:! ~ 1.5 wt%, preferably about 0.15-0.6 wt. The power to dilute; At a weight of 1.5 or more, there is no great difference from the commonly extracted a-degree row cattle, and it is difficult to expect the effect of the dilution method. Also, when the amount is 0.1% by weight or less, the amount of liquid is extremely large and a large device is required for handling, which is preferable. It may be possible to extract high-polysaccharides to this extent during the final extraction, but it required a large can due to the large amount of liquid, or a large amount. It requires all resources and is disadvantageous in terms of economic efficiency.

The temperature of the hot water used is high

OMPI WIPO The non-oxidizing temperature is good, generally 60 to 85, and preferably 70 to 851C.

Next, a carrageenan is used as an example of a high molecular weight polysaccharide, and a method for purifying an aqueous solution of a high molecular weight polysaccharide by the above-mentioned dilution method, which is a further preferred embodiment of the present invention, is described. I will explain in detail.

If the aqueous solution of carrageenan extracted with a concentrated amount of carrageenan contains 10% by weight of impurities with respect to the solid content, it should be diluted with warm water to a solids concentration of 0.5% in advance. When the filter press was used to make a filtration, and when the concentration was increased to 4 weight by ultrafiltration, the residual impurities were reduced to, and the product obtained by drying it reached a purity of 96. However, it is possible to obtain a product that is as good as or better than the alcohol precipitation method with inexpensive equipment and low energy cost.

^ Dilution discharged as liquid · Κ is matured and reused as Χ diluted hot water.

In the concentration operation, impurities together with water are used as a liquid to permeate the outer membrane, and high molecular weight collagen is blocked on the side of the contracted liquid in the ultra ^ membrane. It is performed at the same time as the work.

The conventional triple-layered sardine using a vacuum evaporator was considered to be the triple limit on an industrial scale, but the operation according to the present invention requires much energy for condensation. To consume

OMPI IPO It can be concentrated efficiently, efficiently and easily to a calorific value of 4 weight ^. If the concentration can be up to 4 weights, gelling can be easily carried out even with the use of sodium hydroxide extracted from seaweed, which has a weak gelling ability, so that it can be handled very easily in the subsequent dehydration step.

In the present invention, the high-molecular-weight polysaccharide extract from seaweed or the high-molecular-weight polysaccharide refined concentrate in the high-molecular-weight polysaccharide purified concentrate, and the high-molecular-weight polysaccharide extract in the present invention, including Examples, are described. The solid content standard purity of the high molecular polysaccharide in the purified solution of high molecular polysaccharide was measured as follows.

(1) Measurement of degree of polymer polysaccharide

9 5 weight I Seo ° b arsenide ⁰ Honoré A Honoré co one Honoré 4 Li Tsu preparative Honoré, stirring ¾ force; al, polysaccharide extract Ah Rui polymer was warmed to 8 0 polymer polysaccharide purification Concentrated liquid 1 is added and the high molecular polysaccharide is made into a fibrous form and allowed to settle. After collecting the fibrous sediment at room temperature, the precipitate obtained is dissolved in 100 times the amount of 80: warm water. The obtained solution is again stirred into 4 5 liters of 9 5 weight-in-proliferanolol to add high-molecular polysaccharides into a fibrous form, which is then taken at room temperature. .. The precipitate obtained is dried at 60 for 24 hours and then weighed. Weight obtained by weighing! : From this, calculate the high molecular polysaccharide concentration as follows.

OMH WIPO W

A (weight? Δ) x 0 0

0 0 0 (^ where A is the macromolecular polysaccharide '

W represents the dry weight of the precipitate.

(2) Measurement of polymer polysaccharide purity (based on solid content) Evaporate the polymer polysaccharide extract or polymer polysaccharide purification solution 1 to dryness, and then dry at 60 for 24 hours. After drying, weigh to obtain solid weight *. On the other hand, after the procedure of alcohol precipitation of the high molecular polysaccharide in the same manner as in (1) above was repeated twice, it was picked up, dried at 60 for 24 hours, and then weighed. Get the weight. From the obtained solid content weight and high molecular weight polysaccharide, the solid content standard purity of the high molecular weight polysaccharides is calculated as follows.

D (

B (weight) = X 100

C (B, Β represents the high molecular polysaccharide ii Si form ^ standard purity; C and D respectively represent the solid content weight and the polymer slag weight.

BEST MODE FOR CARRYING OUT THE INVENTION

The present invention will be described with reference to Examples in order to describe the present invention in more detail, but the scope of the present invention is not limited to these Examples.

FIG. 1 shows the flow chart of the apparatus used for carrying out the ultrafiltration of the polymeric polysaccharide extract from seaweed in this example. The following is a description of the method of the ultrafiltration performed in this example, with reference to FIG.

Undiluted solution tank 1 is a high-molecular-weight polysaccharide extract from seaweed

Add (or diluted extract diluted with water) and pump

2)? It is sent to the filter 13, and the filter 13 removes the suspended matter in the high molecular polysaccharide extract from the seaweed, and then it passes through the inflow pipe 5. Supplied to ultra-i-door excess module 7. At this time, the supply flow rate and the inflow pressure of the high molecular polysaccharide extract from the seaweed to the ultra-permanent module 7 are the flowmeter 4 installed in the inflow pipe 5 and the inflow pressure, respectively. A total of 6 measurements were made. Ultra high molecular weight polysaccharide extract from seaweed while applying pressure

The high-molecular polysaccharide extract from seaweed and the low-molecular-weight impurities in the extract of high-molecular-weight polysaccharides along with water, together with water, are ultra ^ It is discharged through the liquid membrane 1 1 as liquid through the membrane. As a result, the high-molecular-weight polysaccharide extract from seaweed is purified and crimped.

The high molecular polysaccharide extract from the purified and concentrated seaweed is

O PI It was circulated to the stock solution tank 1 through the outflow pipe 9 from the outside 'super module. The outflow pressure of the high molecular polysaccharide extract from the seaweed that had flowed out from the ultrafiltration module care was measured by an outflow pressure gauge 8 installed in the outflow pipe 9. The inflow pressure and flow rate of the high molecular polysaccharide extract from seaweed into the ultra ^ permoule module and the outflow pressure from the ultrapermeable module were adjusted to control valves 10 and 17 respectively. I adjusted it. On the other hand, the broth discharged through the liquor pipe 1 1 due to the ultrafiltration by the ultra-ultramodulation was the high molecular polysaccharide from seaweed in this example. When measuring the water permeability by circulating the extract with the liquid, open the circulation switching valve 1 2 and close the compression switching valve 1 3] ?, Circulation piping

It was circulated to the stock solution tank 1 through 1 4. Further, in the present example, when the high molecular polysaccharide extract from seaweed was concentrated and the hydraulic conductivity was measured from the force, the circulation switch 1 2 was closed and the i¾ compression switching valve 1 3 Each time it was opened, it was led to the ^ liquid tank 16 through the liquid extraction pipe 15. Table 1 shows the specifications of the ultra-perimeter door module 7 used in this example. Table 1 Ultra-super module specifications _ Factory Asahi Kasei Corporation

Model SIT-1013

Membrane type Hollow fiber type

Membrane material Polysulfone

Hollow fiber membrane inner diameter 0.8 β ø

Hollow fiber membrane outer diameter ΙΛπη

Molecular weight cutoff 600 0 0

Number of single threads 400

Mozoule diameter 4

Mozoyule length • 3 4 5 舰

'' Area 0.2 nf

In this example, the viscosity of the aqueous solution of the high-molecular polysaccharide was measured by an E-type viscometer manufactured by Tokyo Keiki Co., Ltd. in Example 1.Example 1 (Eucheuma

Cottoni) -based seaweed is mixed with 1% by weight aqueous solution of calcium hydroxide so that the weight ratio of aqueous solution of calcium hydroxide to the weight of seaweed (dry basis) is 1:20. In addition,

After ripening at 90 X; for about 5 hours, diatomaceous earth was used as a ^ super-assistant, and pressure filtration was performed using a filter press to extract the force. A liquid (aqueous solution) was obtained. The potassium-analan extract had a potassium-analan concentration of 1.67 weight and a viscosity of 21 centigrade (72).

OMPI o Put the obtained collagen extract into the stock solution tank 1 of the experimental device shown in Fig. 1, open the circulation switching valve 12 and close the concentration switching valve 13 to close the concentrated liquid. It also circulates in the raw material tank ¹ along with the liquid and ^, and the shear rate (Sec- ¹ :) and permeability

(7 ² * Hr), and shear rate [Sec " ¹ ) and unit pressure

]? Of the water permeability [/ ^ ² · Hr -kg / bin ² ). At this time, the outflow EE (pressure of the concentrated solution) from the ultra-super module 7 is 0.5 kg CTi ² [King of King] (hereinafter, the piezo pressure is expressed as “Zcm ² G”). ), And the inflow EE (feed liquid pressure) into the ultra ^ super-module 7 is changed from 1.0 ^ cm ² G to 3.0 k £ / cm ² G as shown in Table 2. The flow rate of the supply liquid to the ultra-super module 7 was changed. This

Shear rate of the hollow fiber flow path in the module

Table 2 shows (Sec ^_1 ). The permeability at each shear rate [Sec- ¹ ] was obtained by measuring the ^^ amount (for 30 seconds) from the circulating pipe 14. The obtained knots are shown in Table 2 (Experiment I). Shear velocity S [Sec one ¹⁾ and permeability ¾ of the single-position pressure equivalent ^{[^ Xm 2. Hr. ^ /} M the relationship ²⁾ the curve I of FIG. 2, the shear rate (See- ¹⁾ and hydraulic permeability [ The relationship of Zw ² 'Hr) is shown in the curve Ι'in Fig. 3.

The same method as above except that the outflow pressure was kept at 1.0 k ^ / cm ² G and the inflow pressure was changed from 1.5 G to 3.0 k ^ / cm ² G]? The extract solution is passed from the stock solution tank 1 through the ultra ^ supermodule 7 and circulated to the stock solution tank 1.

OMPI WIPO And a water permeability shear rate (Sec one ^{^{_{1) (Z 2 · Η Γ}}} ) and a shear rate of [Se ¹⁾ the unit E Chikarato] 3 water permeability (/ ^ ² · ·

). Table 2 shows the results obtained.

(Experiment ^ II), the curve in Figure 2]! And the curve Γ in Fig. 3.

As is clear from Tables 2, 2 and 3, the permeation rate (Z ² · Hr · Κ 9 Μ ² ) and the permeability (/ ² .Hr) at the unit pressure are When the shear rate of the feed liquid in the hollow fiber flow path is 5,000 Sec ^-1 or more, it markedly improves.

In the above experiment for about 2 hours, no clogging j was found in the hollow fiber.

O PI Experiment .0

L5

2.0

2.5

1.67 21 72 3.0

1.5

2.0

2.5

3.0

* f 'uniformity i. Force is the arithmetic mean of goose pressure and outflow pressure. Forest and pressure are f uniform' / 尸 'excess force.

Example 2

Carrageenan extract similar to that used in Example 1

(Aqueous solution) into the stock solution tank 1 of the experimental equipment shown in Fig. 1, close the circulation switching valve 12 and open the concentration switching valve 13 and put the liquid solution into the liquid tank 16. Then, the concentrate was returned to the stock solution tank 1 and the refinement and contraction of the extract of the karana extract was performed. In this case, the feed liquid temperature is 84, the inflow pressure is 3.5 / CIIL ² G, and the outflow pressure is 1.0 K9 M ² G, and it is placed in the hollow fiber passage in the ultra-turbulent super-module 7. shear rate of feed about 3 0 0 0 0 Se c ¹ of the state to about 5000 Se c "purified down to ¹ 'concentration procedure was rows Tsu name.

Fig. 4 shows the relationship between the concentration and the viscosity of the aqueous solution of potassium lanthanum in the refining process of the aqueous solution of potassium lanthanum described above, as shown in curve IV and The relationship between aqueous solution viscosity and water permeability is shown in curve III in Fig. 4.

The obtained force-refining strength of the condensed liquid was 4%. In addition, the purity of the purified concentrated liquid based on the solid content of potassium was 92%.

Example 3

By the same method as in Example 1, Eucheuma Cotton i type seaweed was boiled. To this, 5.6 times the amount of warm water was added, and the filtration was conducted in the same manner as in Example L. Compared with Example 1, overpressurization was very easy] ?, and it was possible to do it in a short time. Profit

OH IPO The strength and concentration of the diluted strength and strength solution was 0.3 weight and the viscosity was 4 centigrade (7 2 1C).

After warming the above-mentioned dilute aqueous solution of carrageenan to 8 2 1 C, inflow pressure 2.5 K9-ΊΠ ² G, outflow king 1.0 \ / αι ² G, shear rate

When the permeability was determined by the same method as in Example 1 at 3,500 Sec ^-1, it was 280 ^ ym ² 'Hr, which showed a remarkably high permeability.

After the measurement of the water permeability, the dilute aqueous solution of potassium quinanine was purified and contracted to a porosity of 4% by the same method as in Example 2 at the same temperature, inflow pressure, outflow pressure and shear rate as above. The purified raffinate obtained had a purity of 96 in terms of solid content.

Implementation 4

For seaweeds belonging to the red alga Gelidium, water was added so that the weight ratio of water to seaweed weight (dry basis) was 1: 20. After ripening, diatomaceous earth was used as a filtration aid, and pressure filtration was not performed on the filter press to obtain an agar extract (aqueous solution). The agar extract had an agar concentration of 1.5 weight and a rotation of 20 centibodies (72X:).

The obtained agar extract was fed at the same feed temperature and inflow pressure as in Example 2, and the shear rate of the feed in the hollow fiber passage in the ultra ^ supermodule 7 was approximately 1.

OMPI

Cao O The product was purified and concentrated from the state of 300 0 Sec " ¹ to about 500 Sec.

The curve V in Fig. 4 shows the relationship between the agar solution viscosity and the water permeability in the above-mentioned refining of the agar solution.

As is clear from Fig. 4, it was found that the agar extract can be purified and concentrated with a high water permeability as in the case of the Karan-nan extract. ..

Example 5

Seaweed belonging to the genus Laminaria of brown algae was immersed in 0.3 weight of hydrochloric acid at room temperature for about 12 hours to be sufficiently swollen. The swollen seaweed is removed from the hydrochloric acid bath and washed lightly with water, and the ratio of the weight of the aqueous sodium carbonate solution to the weight of the seaweed (dry basis) is 1:40. After adding an aqueous solution of sodium and extracting with warming at 60 mushrooms for 5 hours, diatomaceous earth was used as a mobilizing agent, and pressurization was carried out with a phenol press. A non-sodium alginate extract solution (aqueous solution) was obtained. The sodium alginate extraction solution had an alkalinity level of 0.85 weight ヽ and a viscosity of 70 centigrade (60). After heating the obtained solution of alginic acid oxide to 85 C, the same inflow pressure and outflow pressure as in Example 2 was applied to the inside of the ultrahigh pressure module. From the state where the shear rate of the feeding liquid in the empty fiber channel is about 300 0 0 Sec ' ¹ , it is about 500 0 0.

Purified and reduced until it decreased to Sec " ¹

OMH The permeability at a shear rate of 300 Sec ^-1 is 100 / w ² 'Hr]), and the permeability at a shear rate of 500 Sec * ¹ is 30 A / m, ² ·. It was Η _Γ . The purity of the purified concentrated solution of sodium alginate was 96, which was a very high quality.

Based on the above experiment], the sodium alginate extract can also be purified and condensed at a high water permeability as with the carrageenan extract and the agar extract. There is a sudden change.

Ο ΡΙ Brief description of the drawings

Fig. 1 shows the feet of the device used in this example.

Figure 2 is a graph showing the relationship between the shear rate (Se <T ¹ ) and the permeability per unit pressure (Z ² ΈτΊ / σιιι ² ).

Figure 3 is Ru Da La off der showing the relationship between shear rate (Sec) water permeability and (¼ ² 'Hr).

Figure 4 shows the relationship between the viscosity (cp) of the aqueous solution of potassium nitrate and the water permeability (Z ² 'Hr) [curve]]!), And the viscosity of the aqueous solution of potassium nitrate (cp). It is a graph showing the relationship between the concentration (weight) (curve IV and the relationship between the viscosity of the agar solution (cp) and the permeability (Zm ² -Hr) (curve V)).

O PI WIPO Industrial availability

The method of the present invention is capable of efficiently and simply compressing a high-viscosity high-molecular-weight polysaccharide aqueous solution extracted from seaweed to about 3.0 to 4.5 weight, and at the same time 92 to 9 Since it can be purified to a purity of 6 or higher, it has many uses in the food and pharmaceutical industry, for example, karagi-mono-agar, ferreralan, and algi. High-purity products of high molecular weight polysaccharides such as acid derivatives can be provided at low cost, and their industrial value is high.

Claims

761 35 Request range

1. Seaweed is extracted with an aqueous solvent to obtain a high-molecular-weight polysaccharide aqueous solution, and one end and the other end each have an opening extending in the longitudinal direction. The aqueous solution of the polymeric polysaccharide is placed in the hollow channel of the hollow body.

5 0 0 0 Sec "" At a shear rate of ¹ or more] ?, High

A method of purifying and contracting the aqueous solution of the high molecular polysaccharide to the inside of the ultrafiltration membrane based on the water permeability.

2. A method of claiming in which the high molecular polysaccharide syrup is carrageenan, agar, phacerallan, alginate or alginate ester.

3. The polymer polysaccharide concentration of the polymer polysaccharide aqueous solution is about

Method for Frame 1, which is 0.8 to 3 weight.

4. The polymeric polysaccharide aqueous solution is used as an ultrafiltration membrane hollow body.

Cream 1 method of diluting with warm water before flushing.

5. Dilute with warm water so that the concentration of high-molecular-weight polysaccharides in the aqueous solution is approximately 0.1 to: 1.5 weight.

Frame 4 method.

6. The high molecular weight polymer is a coloran, agar, or far

With seralane, anolenoate or an ester of alginate.

One of the four methods.

7. The high molecular polysaccharide dampness of the aqueous solution of high molecular polysaccharide is about

The method of claim 4, which is 0.8 to 3 weight.

OMPI

WIPO *- 61

36

8. The method of claim 4 in which the diluted high-molecular-weight polysaccharide aqueous solution obtained by dilution is added to the preliminary filtration before flowing into the ultrafiltration hollow body.