JPH0353875A - Purification of mirin - Google Patents

Abstract

PURPOSE:To remove proteins and enzymes from a MIRIN(a sweet sake) to purify the MIRIN is shortened processes without changing a alcohol degree, amino acid degree, etc., of the MIRIN by filtering the MIRIN with a specific selective permselective membrane by a cross flow filtration method. CONSTITUTION:A raw MIRIN prepared by adding malted rice and steamed glutinous rice to SHOCHU(a low class distilled spirit), maturing the mixture and subsequently pressing the matured product, etc., is filtered with a permselective membrane having a dextoran T-70 inhibitions degree of >=70% and a dextran T-10 inhibition degree of <=80% by a cross flow filtration method to purify the objective MIRIN. The raw MIRIN may be filtered with a permselective membrane made from an aromatic polysulfone.

Description

DETAILED DESCRIPTION OF THE INVENTION [Industrial Field of Application] The present invention relates to a method for purifying flavored dairy products using a separation membrane.

[Conventional technology]

There are two types of Ajijo, Honmijo and Honnaji. Honmijo has an extract content of less than 50% when the alcohol content is 13%, and Honnaisho has an extract content of 16% when the alcohol content is 22%. stipulated as less than Honmijo is made by adding rice malt and steamed glutinous rice to shochu, keeping it at 15-20°C, and maturing it for about two months. Honmijo is refined by squeezing and filtering the ajijo moromi, and is a sake quality enhancer. It is adjusted to the above precepts by adding glucose, starch syrup, etc. to adjust the flavor. In addition, hon-naoshi is made by adding shochu to the flavored dairy mash, which is then compressed, filtered, and refined in the same way as hon mirin, and adjusted to the above-mentioned precepts.

Generally, purification steps after press filtration include draining, pasteurization, and final filtration. In the lowering process,
A common method is to adsorb proteins, which are the cause of simmering, onto tannins, but it is difficult to remove proteins with this method in a single operation, and the process is currently repeated several times. . Therefore, simplification of the process and complete protein removal are issues. In addition, in the pasteurization process,
The general purpose is to inactivate enzymes such as α-amylase and protease by heating. However, a large amount of money is consumed in equipment and energy used for heating, so reducing running costs has become an important issue.

As a method to solve these problems and easily reduce running costs, it is possible to replace the conventional purification process with a selective separation membrane. In other words, if it becomes possible to remove proteins and enzymes that cause boiling down using selective separation membranes such as reverse osmosis membranes, loose RO membranes, ultrafiltration membranes, and precision filtration membranes, conventional purification processes can be This can solve problems or reduce running costs. However, it is obvious that with reverse osmosis membranes and loose RO membranes, the pore size of the membrane that separates solutes is too small, so that some of the alcohol content, extract content, etc., which is the main ingredient of ajishu, is removed. Conversely, with microfiltration membranes, the pores of the membrane are too large, allowing proteins and enzymes to be removed to pass through. On the other hand, an ultrafiltration membrane is considered to be the most likely because its pore size is between those of the above separation membranes. However, even in ultrafiltration membranes, there are various membrane pore sizes and filtration methods, and the selection of these affects the quality of purified mirin, so the membrane pore size and filtration method must be appropriately set.

[Problem to be solved by the invention]

As a result of research to solve the above-mentioned problems in the mirin purification process, the present invention has been developed to remove proteins and enzymes in mirin by using a selective separation membrane with an appropriate membrane pore size or a charged separation membrane. Based on this knowledge, we conducted various studies to perfect the present invention. We have developed a method for purifying Ajibutsu that does not change its basic properties, completely removes proteins and enzymes such as α-amylase and protease that cause boiling, and further shortens the purification process. It is about providing.

[Means to solve the problem]

4 The present invention provides a selective separation membrane with a rejection rate of dextran T-70 of 30% or more and a rejection rate of dextran T-10 of 80% or less, or a selective separation membrane with a rejection rate of dextran T500 of 75% and an aromatic polysulfone membrane. The outer surface and pore surface of the porous membrane consists of a charged type component i! having a quaternary abano group and having a crosslinked structure. This is a taste dairy purification method characterized by filtration using an ifI membrane and a cross-flow filtration method.

The ajishu of the present invention is made by adding rice malt and steamed glutinous rice to shochu, and adding shochu to the ajijo moromi, which is kept at about 15 to 20 degrees Celsius and matured for about 2 months, compressed and filtered raw flavor dairy, and aji dairy moromi. It is a raw flavor brewed by adding pressure and filtering.

The characteristics of the selective separation membrane used in the present invention are influenced by the maximum pore size of its surface. The surface is a thin, dense layer on the surface of a membrane that prevents the passage of solutes or suspended particles. The pores on the surface are generally not circular or oval, but often have a complex shape, but the maximum pore diameter in this invention is the length of the longest part of the complex shape observed by electron microscopy. .

The separation membrane used in the present invention has a rejection rate of 30% or more for Dextran T-70 (average molecular weight 70,000) and a rejection rate of 80% or less for Dextran T-10 (average molecular weight 10,000); Or dextran T-50
0 (average molecular weight 500,000), the material is aromatic polysulfone, and the outer surface and pore surface of the porous membrane have quaternary amino groups and have a crosslinked structure. Membrane is suitable.

The rejection rate of dextran T-500 of 75% is approximately equivalent to the maximum pore diameter of 0.1 μm measured by electron microscopy.If the pore diameter is smaller than this, electron microscopy cannot be measured, so it is usually used as a standard with a known molecular weight. The pore size of the membrane surface is determined by the rejection rate of the substance (usually dextran).

Therefore, the inhibition rate of 80% for Dextran T-10 is a range in which electron microscopy cannot be observed sufficiently, and if the pore size is smaller than this, it will also inhibit sugars and alcohol, which are the main ingredients for flavor creation, and the The purpose of the invention cannot be achieved. In addition, the inhibition rate of dextran T-70 is 30%.
If the pore size becomes larger, it will not be possible to remove the proteins or enzymes that cause the simmering taste.

However, a charged separation membrane that has a rejection rate of 75% for Dextran T-500 has a rejection rate of 0 for Dextran T-10.
%, but because the membrane surface is electrically charged, it has a higher selective blocking function for proteins, enzymes, etc. than conventional membranes, and it also has better heat resistance, chemical resistance, and performance stability than conventional membranes. Since there is little scale adsorption, the permeation flux is stable. Scale generally refers to a layer deposited on the membrane surface, and in the present invention, it refers to the adsorption of poorly soluble substances such as proteins or the like in flavor brewing onto the membrane surface.

Such a charged separation membrane is produced by simultaneously crosslinking the outer surface and narrow surface of a separation membrane made of aromatic borisulfone with chloroalylyl, and further introducing a quaternary ammonium base using a tertiary amine. It is something that

Although there are various methods for filtration using a separation membrane, the present invention uses a cross-flow filtration method. The cross-flow filtration method is a method in which a feed liquid passes through a membrane while flowing over the surface of the membrane, and a permeate from which impurities are removed is obtained.

The method of use in the refining process of the ajijo of the present invention is not particularly limited, but when considering running costs and the effects of the present invention, it is most preferable to use it after the squeeze filtration in the refining process.

〔Effect of the invention〕

We have solved the problems, namely, the complexity of the cooling process, shortened the purification process, and prevented the leakage of proteins and enzymes during the pasteurization process without changing the basic principles such as alcohol content and acetic acids. It can be prevented and completely removed.

The present invention will be explained below with reference to Examples.

Example-1 Raw mirin in the above purification process was used as the filtration stock solution, and the selective separation membrane was manufactured by Pharmacia Fine Chemi.
Hollow fiber selective separation membrane A with a dextran T-70 rejection rate of 30% manufactured by Cal, and dextran T-50
0 rejection rate is 75%, and the outer surface and pore surface of the membrane are cross-linked.
85cffl effective length 50cm), 10L of stock solution,
Filtration temperature 30°C, circulation volume ffil70 ffi/
h, inlet pressure 2.5kg/c+fl, outlet pressure 0. 5
Purified mirin was obtained by internal pressure filtration under the conditions of kg/ci. As a result of the analysis of the strength of the obtained refined miso, as shown in Table 1, it was revealed that it had the same strength as the filtered stock solution.

Next, whether proteins and enzymes were removed by filtration was examined using the following test methods (1) to (5).

(1) Cloudy test sample obtained by adding water and boiling The sample is diluted 3 times with water, heated in boiling water for 5 minutes, cooled with water, and the absorbance at 660 nm is measured.

(2) Cloudy test sample by boiling and heating for 5 minutes, cooled in water, and then 660 nm
Measure the absorbance at

(3) White cloudiness test sample due to persimmon shibu 20d, 10 times diluted persimmon shibu was added at 0.1 intervals. Add up to 5 mfl and measure absorbance at 660 nm.

(4) Residual enzyme amount (α-amylase) According to the analysis method specified by the National Tax Agency, add 10 ml of 1% starch solution to
One sample is added and the transmittance is measured at 670 nm at regular intervals.

(5) Amount of remaining enzyme (protease) Measure the acidic and neutral protease titers according to the analysis method prescribed by the National Tax Agency.

The results according to the test method are shown in Table 2,
According to test methods (1) to (3), it was found that the white turbidity caused by each method was significantly reduced, and it became clear that proteins were removed. Also, test methods (4) to (5)
), it is clear that enzymes such as α-amylase and protease are removed. Therefore, according to the method of the present invention, protein and α, which are the causes of simmered
- It is possible to remove enzymes such as allase and protease.

Table 2 Table 11-Example-2 Raw flavored dairy products with shochu added were used as a filtration stock solution, and the same filtration treatment as in Example 1 was carried out, and the same tests as in Example-1 were conducted. The results are as shown in Table 3, and it was confirmed that there was no change in the shaki content of mirin.

Additionally, as shown in Table 4, self-turbidity due to protein was reduced, confirming that protein can be removed by the present invention. Therefore, the present invention can be applied to the lowering, pasteurization, and filtration processes of raw flavored dairy products with shochu added, that is, genuine dairy products.

1 2 Table 3 Table 4 Example-3 The same filtration treatment as in Example-1 was performed using the Ajibutsu obtained by draining the raw flavor brewing used in Example-1 as a filtration stock solution. The purified ajijo was evaluated by measuring the amount of residual enzyme using the test method (4) described in Example-1.

The results are shown in Table 5, and it is clear that α-amylase,
Protease can be removed, and the present invention can also be used in place of the pasteurization process and final filtration process.

Table 5 Hibiscus Example-1 Using the filtration stock solution used in Example-3, celite filtration, which is a conventional finishing filtration method, was performed. The filtrate was compared with the filtrate obtained in Example-3. As Celite, Snowlite R and Snowlite No. 2 manufactured by Mouri Filter Industries Co., Ltd. were used together. The comparison method is Aji Dairyu's Terry,
The difference in gloss was observed by absorbance at 660 nm and 430 nm.

The results are shown in Table 6, showing the same absorbance as the filtration stock solution, and it was found that even when a hollow fiber separation membrane was used, the same texture and gloss as conventional Celite filtration could be obtained. Therefore, it has become clear that the present invention can be used in place of Celite filtration, which is the conventional finishing filtration method.

Table 6 Example-4 The filtered stock solution used in Example-2 was filtered and the Ajijo was used as the filtered stock solution, and the same filtration treatment as in Example-1 was performed.

Regarding the obtained filtrate, the amount of residual enzyme was measured by the same test method (4) as in Example 11. The results are shown in Table 7, and it can be seen that the permeability of α-amylase was low and that it was clearly removed. Therefore, it has become clear that the present invention can be applied to the lowering step of the refining process of raw miso with shochu added, that is, the refining process.

Table 7 Comparative Example-2 Using the filtration stock solution used in Example-4, Celite filtration was performed in the same manner as in Comparative Example 1, and the filtrate was compared with the filtrate obtained in Example-4.

The comparison method is the vibration foaming reduction time, and the test method is to put 100ml of Ajijo into a graduated cylinder with a diameter of 32mm and a height of 380mm! I put it in and it vibrates violently up and down,
After the mirin was foamed, it was allowed to stand still, and the time until the foam disappeared was measured.

The results are shown in Table 8, and the present invention made it possible to remove foaming substances from Ajibutsu, which was insufficient with conventional Celite filtration.

Table 8 Comparative Example-3 Using the filtrate obtained by the separation membrane A obtained in Example-1 and the selective separation membrane C having a dextran T-500 rejection rate of 75%, the same procedure as in Example-1 was carried out. The filtrate obtained by the filtration treatment was compared. The comparison method was the same test method as in Example-1. The results are shown in Table 9, and in test methods (1) to (3), the absorbance was high and cloudiness due to protein leakage was observed. It can also be seen that the transmittance according to test method (4) is high and the protease titer according to test method (5) is high. Therefore, it has become clear that when the pore size of the membrane increases, leakage of proteins and enzymes is required, and the effects of the present invention cannot be obtained.

Table 9 Comparative Example-4 Changes in the permeation flow rate of the charged separation membrane during the filtration process of Example 1I and changes in the permeation flux of the selective separation membrane C used in Comparative Example-3 were measured.

The results are shown in FIG. 1, and it can be seen that the permeation flux of the charged separation membrane is more stable than that of the selective separation membrane that has not been subjected to charging treatment. In other words, it can be seen that the charged separation membrane has less scale adsorption and stable membrane performance.

[Brief explanation of drawings]

FIG. 1 is a diagram showing four changes in permeation flow rate in Comparative Example-4. In the figure, the volume reduction rate has the same meaning as the concentration ratio, and is the value obtained by dividing the initial volume of the filtered stock solution by the volume of the retentate after treatment. Further, the permeation flux is a value obtained by dividing the amount of filtrate by the membrane area and the filtration time.

Claims (2)

[Claims] (1) The filtration process is carried out by a cross-flow filtration method using a selective separation membrane that has a rejection rate of 30% or more for Dextran T-70 and a rejection rate of 80% or less for Dextran T-10. A method for refining mirin. (2) A charged separation membrane that has a rejection rate of dextran T-500 of 75% or more, has quaternary amino groups on the outer surface and pore surface of the porous membrane made of aromatic polysulfone, and has a crosslinked structure. 1. A mirin purification method characterized in that the mirin is filtered by a cross-flow filtration method.