JPS61205475A - Production of vinegar having high concentration - Google Patents

Abstract

PURPOSE:To produce concentrated vinegar having the taste and flavor of brewed vinegar and desired acetic acid concentration, by treating a vinegar with pressurized carbon dioxide gas, concentrating the extraction residue with a membrane, and mixing the extracted liquid with the concentrated liquid. CONSTITUTION:The vinegar A is pumped to the extraction column 1 under specific temperature and pressure condition, and the liquified carbon dioxide gas B is introduced into the extraction column 1 in the form of high-pressure carbon dioxide gas of critical point or thereabout. The acetic acid component and the flavoring component, etc. are extracted with the high- pressure carbon dioxide gas in the extraction part 3 and the extract is sent through the upper settler 4, decompressed with the pressure-reducing valve 9 and separated into the carbon dioxide gas and the extracted liquid in the extracted liquid separator 10. The extracted liquid is sent to the mixing tank 20. The extraction residue containing extractable components such as non-volatile acids, amino acids, sugars, etc., is sent through the lower settler 2, decompressed with the pressure-reducing value 13, deaerated with the deaerator 15 to separate carbon dioxide gas, pressurized with the pump 17, sent to the reverse-osmotic separator 18 and separated into the permeated liquid and the concentrated liquid containing the extractable components in concentrated state. The concentrated liquid is sent to the mixing tank 20 and the permeated liquid is recycled to the fermentation step.

Description

DETAILED DESCRIPTION OF THE INVENTION Field of Industrial Application) The present invention relates to a method for producing high-concentration vinegar from normal-concentration vinegar, which can significantly reduce transportation costs and storage equipment, and which does not impair flavor.

(Conventional technology) Vinegar can be roughly divided into two types: brewed vinegar produced using fermentation methods, and synthetic vinegar produced by diluting acetic acid or glacial acetic acid produced using organic synthesis methods with water and adding additives such as seasonings. be.

Most synthetic vinegars have the advantage of being able to obtain vinegar with any acetic acid concentration because glacial acetic acid is diluted with water, but they are avoided due to their poor flavor and the increasing consumer needs for natural and luxury products in recent years. On the other hand, the concentration of acetic acid in brewed vinegar produced by the fermentation method is generally around 5% by weight/volume (hereinafter referred to as "%");
High acidity vinegar of about 5% is also widely commercially available and used in the food industry.

However, even if acetic acid fermentation is carried out using the highest level of modern fermentation technology, the maximum concentration of acetic acid obtained is approximately 20%.
% (see, for example, patent no. 1.212.786).

In this way, most of brewed vinegar is water, and one way to effectively remove this water and obtain highly concentrated table vinegar is to introduce raw vinegar into a distillation column heated to over 100°C under normal pressure. A distillation method that extracts water from the top of the tower and obtains high-concentration vinegar from a distillation can at the bottom of the tower; ■A freeze-thaw method that freezes vinegar and separates crystallized water and concentrated vinegar to obtain concentrated vinegar; ■High pressure A high-pressure carbon dioxide extraction method in which acetic acid is extracted from a dilute acetic acid solution using carbon dioxide [for example, Biotechno
logy and Bioengineering S
ymp, l1h12°249 (1982)).

(Problems to be Solved by the Invention) However, as a method for increasing the concentration of vinegar, the above-mentioned distillation method not only requires a large amount of high-quality energy to distill water, but also the quality of the high-concentration vinegar obtained is brownish. It is colored and has a strange taste and odor, so it cannot be used in food products.During distillation, it is operated at temperatures of 100℃ or higher, so the heat-sensitive components in vinegar decompose. This is thought to be due to the aroma components dissipating.

In addition, (1) the freeze-thaw method requires a large amount of energy to freeze the raw vinegar, but the vinegar components do not change in quality due to heat, and the aroma components are less likely to dissipate, so high-quality, high-concentration vinegar can be obtained. However, it is difficult to separate the ice crystal slurry, and the upper limit of the acetic acid concentration is approximately 50%, making it technically impossible to produce vinegar with a higher concentration.

Furthermore, it is not known that the high-pressure carbon dioxide extraction method can be applied to vinegar, which is a food product with a delicate taste and aroma.

In other words, the quality required for high-concentration vinegar as a food product is:
Not only does it have a high acetic acid concentration, but it also lacks flavor components corresponding to each acidity (therefore, it has no commercial value, so the acetic acid used in the chemical industry that can be obtained by such extraction methods The required quality is different.

An object of the present invention is to easily obtain high-concentration vinegar that has the flavor inherent to brewed vinegar and can have an arbitrary acetic acid concentration.

Means for Solving the Problems) That is, the present invention provides a method for producing high-concentration vinegar, which is characterized by including the following steps (a) to (c).

(a) The first step of extracting vinegar using high-pressure carbon dioxide.

(b) A second step of concentrating the raffinate that was not extracted in the first step using a membrane.

(c) A third step of mixing the extract obtained in the first step and the concentrate obtained in the second step to obtain high-concentration vinegar.

Hereinafter, the present invention will be explained in detail step by step.

(a) First step In the first step, vinegar is extracted with high-pressure carbon dioxide to extract the acetic acid component and aroma component in the vinegar as an extract.

Here, high-pressure carbon dioxide refers to the critical temperature of carbon dioxide (
31.1℃) and a temperature near the critical pressure (72.8 atm),
It refers to carbon dioxide under pressure conditions. For example, in the case of vinegar, the pressure is 65 to 300 atm, preferably 70 to 300 atm.
140 atm, temperature 15-40°C, preferably 20-40°C
It is ℃.

Moreover, the flow rate ratio of high-pressure carbon dioxide and raw vinegar at the time of extracting vinegar with high-pressure carbon dioxide is usually 10-100, preferably 13-20 as a weight ratio.

When low-concentration vinegar obtained by a fermentation method is brought into contact with high-pressure carbon dioxide, aromatic components such as acetic acid, ethanol, and trace amounts of ethyl acetate and acetoin are extracted from the vinegar components, and then the system is depressurized and/or Alternatively, an extract in which acetic acid components and aroma components are concentrated can be obtained by increasing the temperature and preferably reducing the pressure of the system to separate gaseous carbon dioxide, acetic acid, aroma components, and (a small amount) water. As described above, a phenomenon occurs in which the acetic acid and aroma components in vinegar are selectively dissolved in high-pressure carbon dioxide, and a small amount of water is further dissolved.

At the same time, a raffinate solution containing extract components such as nonvolatile acids, amino acids, and saccharides among the vinegar components and having water as the main component is obtained.

Here, the first step will be explained in more detail using the phase equilibrium diagram of the acetic acid-water system shown in FIG.

The curve indicated by N in FIG.
It can be seen that under 0wHg, water must be distilled to concentrate acetic acid. Particularly for liquids with low acetic acid concentration, such as fermented vinegar, a large amount of water must be distilled, which is not a good idea. On the other hand, the curve shown in Figure 2 S shows the thermodynamic equilibrium relationship of the carbon dioxide-water monoacetic acid system at a pressure of 80 +r/cdG and a temperature of 25°C, and when carbon dioxide is subtracted from each phase. It is an equilibrium curve.

It can be seen from the curve S that the acetic acid component can be easily concentrated to a high concentration by introducing high pressure carbon dioxide into the system and moving the acetic acid component to the carbon dioxide phase.

Thus, it can be seen that the extraction method using high-pressure carbon dioxide is suitable for concentrating the acetic acid component of vinegar with a low acetic acid concentration, and is much superior to conventional methods.

(b) Second step The raffinate obtained in the first step contains water as the main component, and extract components such as nonvolatile acids, amino acids, and Ws that did not transfer to the carbon dioxide phase in the first step. In this step, this raffinate is concentrated using a membrane.

In addition to the above-mentioned extract components, carbon dioxide is dissolved in the raffinate. Therefore, if left as is, the dissolved carbon dioxide will vaporize when permeating through the membrane, reducing the throughput of the membrane, so it is preferable to sufficiently degas the raffinate before treating it with a membrane separation device.

By passing the degassed raffinate through a membrane separation device,
Extract components such as nonvolatile acids, amino acids, and sugars are concentrated, and the raffinate is separated into a concentrated liquid and a permeated liquid. This concentrated solution is sent to the next step, the third step, for high-concentration vinegar, and the permeate is sent back to the fermentation step or discarded.

Here, a membrane is a selective membrane that allows certain molecules to pass through while others do not. Examples of the membrane materials include cuprophane, recycled cellulose, polyacrylonitrile, polysulfone, aromatic nylon, polyvinylidene fluoride, polybenzimidacylon, sulfonated polysulfone, and sulfonated polyphenylene oxide. etc. can be mentioned.

The operating temperature for membrane separation is usually 5 to 40°C, preferably room temperature, and the operating pressure is usually 2 to 60 kg/cdG,
Preferably it is carried out at 30 to 40 kg/cdG.

(c) Third step In the third step, the extract obtained in the first step and the concentrate obtained in the second step are mixed (adding water as necessary),
Highly concentrated table vinegar of any concentration can be obtained. Thus, the extract obtained in the first step mainly contains acetic acid and aroma components, and the concentrate obtained in the second step contains nonvolatile acids, amino acids, and P! By mixing these extract components, it is possible to obtain flavorful and highly concentrated vinegar with a composition similar to that of ordinary vinegar obtained by fermentation.

Hereinafter, the present invention will be explained in more detail using the drawings. 1st
The figure is an embodiment of the present invention, and is a diagram of the manufacturing process of high-concentration vinegar.

The extraction column 1 is composed of a lower settler 2, an extraction section 3 having trays, packings, etc. therein, and an upper settler 4.

Vinegar A obtained by a fermentation method is adjusted to a predetermined pressure and temperature while passing through a pump 5 and a heater 6, and is sent to an extraction column 1. In addition, the liquefied carbon dioxide B is supplied by a pump 7, a heater 8
While passing through, it becomes high-pressure carbon dioxide near the critical point and is sent to the extraction column 1. Vinegar A and high-pressure carbon dioxide B come into contact with each other in the extraction section 3 of the extraction tower 1, and the acetic acid component, aroma component, etc. of the vinegar components are extracted into the high-pressure carbon dioxide.
Through this process, pulp 9 is reached. This carbon dioxide phase is removed by valve 9
the acetic acid component dissolved in the carbon dioxide phase,
The extract, such as aroma components, is separated from gaseous carbon dioxide in the extract separator 10. The excess gaseous carbon dioxide is
It is either discharged to the outside via tube 11 or recycled into the thread after being recompressed and liquefied by a compressor (not shown). The separated extract is sent through a pipe 12 to a mixing tank 20, which will be described later. Nonvolatile acids, amino acids, and I! that were not extracted by high-pressure carbon dioxide in extraction section 3. ! The raffinate containing extract components such as
leading to. The pressure is reduced in the pulp 13, and the carbon dioxide dissolved in the raffinate is separated and introduced into the deaerator 15 through the pipe 14, where the carbon dioxide is degassed from the raffinate. . The separated carbon dioxide is either discharged to the outside via tube 16 or recycled into the thread after recompression and liquefaction by a compressor (not shown). The raffinate liquid from which carbon dioxide has been separated and removed by the deaerator 15 is pressurized by the pump 17 and then sent to the reverse osmosis membrane separation device 18 . In the reverse osmosis membrane separation device 18, the raffinate liquid is separated into a concentrated liquid in which extract components such as nonvolatile acids, amino acids, T, and E are concentrated, and a permeate liquid. -a! The IN liquid is sent to a mixing tank 20 via a pipe 19. The permeate is also recycled to the fermentation process via tube 21. In the mixing tank 20, highly concentrated vinegar of any concentration is obtained by appropriately mixing the extract and the concentrate.

Effect) The present invention efficiently obtains flavorful and highly concentrated vinegar by skillfully combining the extraction of acetic acid components and aroma components using high-pressure carbon dioxide and the concentration of extract components using a membrane separation method. .

Effects of the Invention) As described above, according to the present invention, when producing high-concentration vinegar, heating energy is not required unlike the conventional distillation method, so it is energy saving and easy to produce. In addition, the obtained high-concentration vinegar can be adjusted to any concentration and can be of high quality with flavor, and can be used in a very wide range of fields where vinegar is used.

Example) EXAMPLES Hereinafter, the present invention will be explained in more detail with reference to Examples.

Example 1 According to the manufacturing process diagram shown in FIG. 1, high-concentration vinegar was manufactured using vinegar with a 15% acetic acid concentration obtained by fermentation as raw vinegar. The operating conditions of the extraction column 1 and the reverse osmosis membrane separation device 18 are as follows.

■Temperature: 25℃ Pressure: 80kg/cjG Flow rate ratio (weight ratio) of high-pressure carbon dioxide and raw vinegar;], 6
．． 7"1B 1 Membrane; Synthetic polymer composite membrane made of polysulfone resin; Pressure; 4
0 kg/cAG Temperature: 25°C Table 1 shows the analytical values of high concentration vinegar and raw vinegar when high concentration vinegar was produced under the above operating conditions.

Table 1 Note: Products a, b, and c are obtained by mixing the extract from the first step and the concentrate from the second step so that the acid concentrations are the same.

As is clear from Table 1, according to the present invention, it is possible to easily produce high-concentration vinegar with an acetic acid concentration of 50% or more, which is considered impossible by the freeze-thaw method.

Next, the raw vinegar and the high-concentration vinegar produced in this example were each diluted to an acetic acid concentration of 5.0%, and a sensory evaluation was performed using a three-point discrimination test. The results are shown in Table 2.

Table 2 *) There is a significant difference at a 5% risk rate.

From Table 2, products a and b cannot be sensually distinguished from raw vinegar. Product C could not be distinguished from the raw vinegar in terms of aroma, but it was possible to distinguish the taste.

However, when the taste was corrected by adding a small amount of complex amino acids and glucose to Product C, a vinegar that was sensory-wise almost the same as the raw vinegar in aroma and taste was obtained.

Example of Use Powdered vinegar was manufactured using the raw vinegar used in Example 1 and the product obtained in Example 1. The combination recipe is shown below.

Kankin missing 1 (for powdered vinegar using raw vinegar) Raw vinegar (acetic acid concentration 15%) 10 kg dextrin
8 kg anhydrous sodium acetate
0.5-Juryoshi 1 (for powdered vinegar using product) Product B (acetic acid concentration 60%) 5 kg Dextrin 4 kg Anhydrous sodium acetate 1 kg Using the Lab 1) manufactured by Co., Ltd., the chamber temperature was
When dried under ℃ conditions, the powdered vinegar using the raw vinegar weighed approximately 9.5 kg (acetic acid concentration 15.0%), and the powdered vinegar using the finished product weighed approximately 7.5 kg (acetic acid concentration 37.5%). was gotten.

Next, dissolve each vinegar powder in water to make the acetic acid concentration 5%.
After making it into an aqueous solution, we subjected it to sensory evaluation, and found that the powdered vinegar using the product had a more natural aroma and taste.
It turned out to be clearly superior.

[Brief explanation of drawings]

FIG. 1 is a process diagram for producing high-concentration vinegar according to one embodiment of the present invention, and FIG. 2 is a phase equilibrium diagram of an acetic acid-water system. l; Extraction column 10; Separator 15: Deaerator 18; Reverse osmosis membrane separation device 20; Mixing tank Patent applicant Nakano Suten Co., Ltd. Mitsubishi Kakoki Co., Ltd. agent Patent attorney Ryutan Shirai l Figure 15 #Out tower lO; Separator I5; Deaerator ta; Pass through 9 and 5 20;

Claims (1)

[Claims] (1) A method for producing high-concentration vinegar, characterized by including the following steps (a) to (c). (a) The first step of extracting vinegar using high-pressure carbon dioxide. (b) A second step of concentrating the raffinate that was not extracted in the first step using a membrane. (c) A third step of mixing the extract obtained in the first step and the concentrate obtained in the second step to obtain high-concentration vinegar.