JPH0783687B2 - Method for lowering the seasoning liquid containing high sugar concentration - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION (Industrial field of use) The present invention relates to a method for lowering the seasoning liquid containing a high sugar concentration,
More specifically, it relates to a method for rapidly lowering the seasoning liquid containing high sugar concentration by treating the seasoning liquid containing high sugar concentration with synthetic layered magnesium phyllosilicate.

(Prior art and its problems) In general, brew brew is a generic term for substances that become insoluble due to external factors such as temperature changes and light irradiation conditions during the storage period of the product. It is known to be insolubilization associated with protein denaturation. Seasoning liquid containing rice and rice koji as a main raw material with high sugar concentration, for example, Hon-mirin, fermentable seasoning liquid and mirin-flavored seasoning,
It is said that the above-mentioned water-soluble protein may be an enzyme protein such as oryzinine which is an undegraded protein of rice or amylase derived from rice koji. Since the commercial value of these brewed products is remarkably reduced due to the occurrence of sediment, a process called "deposition reduction" is indispensable in the production process, and a method of removing the causative substance of sediment in advance is performed.

Although persimmon astringent was used as a bottom reducing agent in the conventional orienting lowering process, in the high sugar concentration-containing seasoning liquid, since the liquid is viscous and the liquid specific gravity is large, it was produced when Kakishibu was used alone. Almost no olifloc sedimentation. Therefore, wheat protein etc. are used together with Kakishibu, but it is still 5-10
A day's standing time is necessary.

For the purpose of shortening the time for the thickening step, silica gel is used as a thickening agent, and a method of treating a seasoning liquid containing a high sugar concentration under heating at 50 ° C or higher has been proposed. According to this method, although there is an effect that the tilt lowering step can be shortened, in order to prevent the occurrence of tilt even after long-term storage, it is necessary to treat at a high temperature of about 70 ° C or higher, Therefore, the flavor component of the high-sugar-concentration seasoning liquid may be lost or changed, or the taste component may be altered, resulting in loss of the unique flavor of the high-sugar concentration-containing seasoning liquid. It has the drawback of being easy. Furthermore, since silica gel has the ability to adsorb a wide range of substances, even if it is treated at a relatively low temperature, it will not only contain the causative agent for the occurrence of sediment, but also the aroma and taste components of the high sugar concentration content seasoning liquid. There is also a drawback that it is adsorbed and the flavor of the seasoning liquid is impaired.

(Object of the Invention) The present invention is capable of selectively adsorbing a substance causing causality in a seasoning liquid containing a high sugar concentration, with high performance, and further using a substance having a superior transient property as a depressing agent. , A high-sugar-concentration seasoning liquid having the same flavor and aroma as the high-sugar-concentration seasoning liquid produced using conventional persimmon astringent as a bottom-lowering agent by performing a low-temperature lowering treatment at a relatively low temperature. An object of the present invention is to provide a method for lowering the orientation of the seasoning liquid that can be produced.

(Structure of the Invention) The present invention provides a seasoning liquid containing a high sugar concentration, the main component of which is represented by the following formula Mg ₃ Si ₄ O ₁₀ (OH) ₂ .nH ₂ O (wherein n is a number of 5 or less). It has a composition and the surface spacing is 4.5-4.6Å, 2.5-2.6Å and 1.5
It has an X-ray diffraction peak at ˜1.6 Å, and the following equation is = tan θ ₂ / tan θ ₁ (wherein, θ ₁ is the peak perpendicular and the narrow-angle side peak tangent line at the X-ray diffraction peak with a surface spacing of 4.5 to 4.6 Å). Angle formed, θ ₂
Is the angle formed by the peak perpendicular to the peak and the tangent to the wide-angle side peak) and the stacking irregularity index (Is) is 3.0 or more and 3
A method for lowering a seasoning liquid containing a high sugar concentration, which comprises treating with a synthetic layered magnesium phyllosilicate having a BET specific surface area of 00 m ² / g or more and a methylene blue decolorizing power (JIS K-1470) of 100 ml / g or more. Is.

(Function and Effect of the Invention) The cage-lowering agent used in the present invention is a synthetic layered magnesium phyllosilicate having the above-mentioned specific properties,
It has an extremely high adsorptive power not found in natural magnesium phyllosilicates such as talc, and because it has the property of selectively adsorbing the substances that cause ori in the seasoning liquid containing a high sugar concentration. By using an extremely small amount, the high-sugar concentration content seasoning solution can be lowered further at a relatively low temperature such as room temperature. As described later, this is because the synthetic layered magnesium phyllosilicate has a broad X-ray diffraction peak, so that it is a low crystalline or fine crystallite, and has an asymmetric peak, so that the layer This is probably due to the irregular stacking and the structure in which other specific substances easily enter between the layers.

Further, according to the present invention, even if the seasoning liquid lowering step is carried out at a relatively low temperature of about room temperature, it is possible to obtain a sufficient lowering effect, so that persimmon astringent is conventionally used as a lowering agent. Compared with the seasoning liquid produced as described above, there is an effect that the flavor and taste do not change and the seasoning liquid having the same flavor can be produced.

Furthermore, the seasoning solution obtained by the lowering treatment according to the present invention does not give a particular odor based on the synthetic layered magnesium phyllosilicate, or the synthetic layered magnesium phyllosilicate is separated after the lowering treatment. It is also possible to obtain effects such as quick and easy operation.

(Preferred embodiment of the invention) The high sugar concentration-containing seasoning liquid of the present invention has a total sugar content of 30 W / V%.
It includes all liquid seasonings containing the above, and includes, for example, Hon-mirin, fermentable seasoning liquid, mirin-style seasoning and the like. The fermentable seasoning liquid is a liquid seasoning containing rice and / or other grains and koji as the main raw materials and produced through an alcohol fermentation process and having a total sugar content of 30 W / V% or more. Also,
Mirin-style seasoning means total sugar content of 50 W / V% or more, alcohol 1
A liquid seasoning containing V / V% or less, which is produced by brewing or other methods.

The synthetic layered magnesium phyllosilicate having the above-mentioned specific properties, which is used as the depression reducing agent in the present invention, is described in JP-A-61-10020.

That is, the synthetic layered magnesium phyllosilicate in the present invention has a chemical composition represented by the formula Mg ₃ Si ₄ O ₁₀ (OH) ₂ · nH ₂ O (1) as a main component. The water of hydration (nH ₂ O) is usually 5 or less, preferably n is in the range of 0.5 to 3, and the synthetic layered magnesium phyllosilicate has two MgO ₆ octahedral layers sandwiched therebetween. It is mainly composed of a three-layer structure in which a tetrahedral layer of SiO ₄ is sandwiched, and a three-layer structure in which a tetrahedral layer of SiO _{4 and} an octahedral layer of MgO ₆ are layered together is a three-layer structure. It may be contained within a range that does not impair the essence of the structure, and may contain unreacted silica component or magnesium component within a range that satisfies the various characteristics described later.

The synthetic layered magnesium phyllosilicate in the present invention is
It has an X-ray diffraction image specific to the layered structure described above. FIG. 1 of the accompanying drawings shows an X-ray diffraction spectrum of the synthetic layered magnesium phyllosilicate according to the present invention by Cn-Kα radiation. From FIG. 1, the synthetic layered magnesium phyllosilicate in the present invention has a surface spacing of 4.5 to 4.6 Å ([020]).
Surface, corresponding to the [110] plane), 2.5 to 2.6 Å (corresponding to the [200] plane), and 1.5 to 1.6 Å (corresponding to the [110] plane), respectively. It is an X-ray diffraction peak common to natural trioctahedral type layered clay minerals.

In the synthetic layered magnesium phyllosilicate of the present invention, the above-mentioned layers are overlapped in parallel, but a certain peculiar irregularity is recognized in the relative position of each layer. FIG. 2 of the accompanying drawings is an enlarged diagram of the diffraction peak near d = 4.5Å in the X-ray diffraction spectrum of FIG. From FIG. 2, this peak shows a relatively asymmetrical peak on the narrow angle side (the side where 2θ is small) and a gentle asymmetric peak on the wide angle side (the side where 2θ is large).
This peak is of interest in structures with regular stacking of layers, and the asymmetric peaks described above indicate that there is some irregularity in the relative position of each layer.

As used herein, the stacking disorder index (Is) of magnesium phyllosilicate is defined as follows. That is, an X-ray diffraction chart as shown in FIG. 2 is obtained by the method described in Reference Example described later. For this peak of d = 4.5-4.6Å,
The maximum inclination peak tangent line a on the narrow angle side and the maximum inclination peak tangent line b on the wide angle side are drawn, and the perpendicular line c is drawn from the intersection of the tangent line a and the tangent line b. Next, the angle θ ₁ between the tangent line a and the perpendicular line c, the tangent line b
The angle θ ₂ between the line and the perpendicular line c is obtained. The stacking irregularity index (Is) is calculated as the value of Is = tan θ ₂ / tan θ ₁ (2). This index (Is) is 1.0 when the peak is completely symmetrical, and becomes larger as the degree of asymmetry increases.

The synthetic layered magnesium phyllosilicate in the present invention is
It has a novel stacking disorder structure in which the stacking disorder index (Is) is 3.0 or more, particularly in the range of 3.5 to 6.0.

The synthetic layered magnesium phyllosilicate in the present invention is
It is also clearly distinguished from the natural layered phyllosilicates. First, in natural phyllosilicate, since many basic three-layer structures are accumulated in the C-axis direction, d = 9 to 15Å [001]
An X-ray diffraction peak peculiar to the surface is shown, but no clear diffraction peak is observed at d = 9 to 15Å in the synthetic layered magnesium phyllosilicate of the present invention. This indicates that there is no regularity in stacking of layers in the C-axis direction. Further, in the case of natural phyllosilicate, the stacking disorder index (Is) is almost 2 or less even if the peak around d = 4.5Å has some asymmetry.

The synthetic layered magnesium phyllosilicate exhibits an extremely large specific surface area and methylene blue decolorizing power which are not observed in any known natural or synthetic phyllosilicate. That is, the synthetic layered magnesium phyllosilicate is 300 m ² / g
Above all, in particular, it has a large BET specific surface area of 500 m ² / g or more, and exhibits a large value of the methylene blue decolorizing power measured by JIS K-1470 of 100 ml / g or more, particularly 250 ml / g or more.

The synthetic layered magnesium phyllosilicate in the present invention is
Method for hydrothermally treating active silicic acid or active aluminosilicic acid obtained by acid treatment of clay mineral and magnesium oxide, hydroxide or compound capable of forming the oxide or hydroxide under reaction conditions Can be manufactured by.

For example, acid clay, bentonite, subbentonite,
The surface index [00] of montmorillonite group clay minerals such as frass earth and beidellite, saponite and other clay minerals
1) with an organic acid such as benzenesulfonic acid or a mineral acid such as sulfuric acid, hydrochloric acid or nitric acid until the X-ray diffraction peak of 1] disappears substantially.
To 300 ° C to generate active silicic acid or active aluminosilicic acid, and magnesium oxide, hydroxide, etc. are made into an aqueous slurry and 110 to 200
The synthetic layered magnesium phyllosilicate can be produced by hydrothermal treatment under pressure at a temperature of ° C.

In the present invention, the synthetic layered magnesium phyllosilicate can be used alone because it has excellent transitivity, or can be used by mixing with a suitable super-auxiliary agent such as diatomaceous earth and white clay. it can. The synthetic layered magnesium phyllosilicate generally has a particle size of 100 mesh or less of Tyler standard sieve, and can be used alone as a powder, or can be used by mixing with the above-mentioned super-auxiliary agent. It is also possible to granulate the mixture with the agent into granules or tablets having an appropriate size before use.

The high-sugar concentration-containing seasoning liquid is treated with the synthetic layered magnesium phyllosilicate as a method, after the powder or granules containing the synthetic layered magnesium phyllosilicate is added and mixed to the seasoning liquid, preferably at 10 to 90 ° C. Is a method of stirring the mixture at a temperature of 20 to 70 ° C. for 20 seconds to 30 minutes to lower it, and then separating or settling the powder or granulated product to obtain the purified seasoning liquid. Also, as another method,
In the packed bed of the granulated product containing the synthetic layered magnesium phyllosilicate, the seasoning liquid is maintained at a temperature within the above temperature range and allowed to pass for a residence time within the above time range to perform a lowering treatment and purified as a passing liquid. There is also a method of obtaining the seasoning liquid thus prepared.

In addition, as the seasoning solution depressant, activated carbon can be used together with the synthetic layered magnesium phyllosilicate. The synthetic layered magnesium phyllosilicate and activated carbon partially differ in the kind of the ori generation-causing substance that is easily adsorbed selectively. Therefore, by using the activated carbon together, the amount of the synthetic layered magnesium phyllosilicate used can be reduced. You can It is preferred that the synthetic layered magnesium phyllosilicate and activated carbon are mixed together and optionally used with the above-mentioned super-auxiliary agent, but either one is used in a step treatment method in which it is first contacted with the seasoning solution. Good.

Although the amount of the synthetic layered magnesium phyllosilicate used varies depending on the type of the seasoning liquid and cannot be uniformly determined, it is generally 0.002 to 2 W / V%, preferably 0.01 to 1 W / V% per the amount of the seasoning liquid. Further, the amount ratio of the synthetic layered magnesium phyllosilicate to activated carbon used is 1: 1 by weight.
Hereafter, it is preferably 1: 0.7 to 0.1.

Reference Example (Production of Synthetic Layered Magnesium Phyllosilicate) 250 g of linearly shaped (diameter: 3 mm) 250 g of acid clay produced in Nakajo Town, Niigata Prefecture, was crushed into aluminum, magnesium, Add sulfuric acid equivalent to 3.5 times the gram equivalent of all gram equivalents of basic metal components such as calcium, iron, sodium, potassium and titanium (1.14 gram equivalent / 100 g dry matter), that is, 34% sulfuric acid 700 ml, and add 85 ° C. Acid treatment was carried out by heating in a water bath for 15 hours.
It was washed with water to obtain a cake. 110 a small amount of the cake
After drying at ℃, crushing and quantitative analysis, SiO ₂ content is 92.7%
(110 ° C. dry matter standard). The obtained cake was put in a pot mill, water was added, and wet pulverization was performed together with Korean balls to obtain a slurry containing 15% of SiO ₂ content.

Next, 200 g (SiO ₂ min: 30 g) of the obtained slurry and 22 g of magnesium hydroxide (first-grade reagent) were placed in an autoclave container of 1, and 370 g of water was added, and the mixture was stirred at 500 rpm for 5 minutes at 160 ° C. The hydrothermal synthesis reaction was carried out for an hour. After cooling, the reaction product was taken out and water was separated by filtration.
It was dried at ° C. The dried product was crushed with a small bench sample mill to obtain a white fine powder.

When the obtained white fine powder was analyzed by X-ray diffraction,
It has X-ray diffraction peaks at interplanar spacings of 4.5 to 4.6Å, 2.5 to 2.6Å and 1.5 to 1.6Å, and has a stacking irregularity index (Is) of 4.3 as defined above.
And was a layered magnesium phyllosilicate having a BET specific surface area of 526 m ² / g and a methylene blue decolorizing power of 280 ml / g.

The stacking irregularity index (Is) was calculated by the following method.

Diffraction angle (2θ) 19.5 ° ~ 19.7 obtained by X-ray diffraction
Draw the peak tangents (a, b) so that the absolute values of the slopes are maximum on the narrow and wide angles of the ° peak. Next, the perpendicular c is dropped from the intersection of the narrow-angle peak tangent a and the wide-angle peak tangent b, and the angle θ ₁ and the tangent b between the tangent a and the perpendicular c are made.
And the angle θ ₂ formed by the perpendicular line c.

The stacking irregularity index (Is) is calculated by the following formula.

The methylene blue decolorizing power was determined by the method specified in JIS K-1470 Activated Carbon Test Method.

Control Example Mochi steamed rice (1.4 kg), rice koji (400 g), 36% alcohol (2 l) and starch syrup (1.7 kg) were mixed and aged at 30 ° C. for 30 days, and a liquid obtained by solid-liquid separation was used as a test sample mirin.

To 300 ml of the test sample mirin, 0.3 ml of persimmon astringent juice and 40 mg of the purified protein oritol (manufactured by Nikken Chemical Co., Ltd.) were added and mixed with stirring.

Example 1. While maintaining 1.0 L of the test sample mirin at 30 ° C. and stirring it with a stirrer, 0.5 g of the synthetic layered magnesium phyllosilicate obtained in the reference example was added and stirred for 30 seconds, then immediately separated and separated. I got 1.0 liter of mirin. This was subjected to a storage test at 40 ° C. for 5 months, but no occurrence of sediment was observed.

Example 2. Instead of 0.5 g of synthetic layered magnesium phyllosilicate, 0.4 g of the same synthetic layered magnesium phyllosilicate and activated carbon of 0.
The same procedure as in Example 1 was carried out except that a mixture with 1 g was used to obtain 1.0 l of hon mirin. This was subjected to a storage test at 40 ° C. for 5 months, but no occurrence of sediment was observed.

Sensory evaluation Using the mirin and the control mirin obtained in each example as a sample, a sensory evaluation of their flavors was performed by a panel consisting of 10 women by the paired comparison method. The results are shown in Table 1. The numbers in Table 1 indicate the number of panelists who responded that the sample in the left vertical column had a better flavor than the sample in the horizontal column.

From the results shown in Table 1, it is clear that the Hon-Mirin obtained by the method of the present invention has no significant difference in flavor as compared with the Hon-Mirin obtained by using persimmon astringent as a flavor-lowering agent. .

[Brief description of drawings]

FIG. 1 is an X-ray diffraction spectrum by a synthetic layered magnesium phyllosilicate Cu-Kα ray produced in Reference Example. FIG. 2 shows d = 4 in the X-ray diffraction spectrum of FIG.
It is the line diagram which expanded the diffraction peak near 5Å, and illustrates how to obtain θ ₁ and θ ₂ for calculating the stacking disorder index (Is).

Claims (2)

[Claims] 1. A seasoning liquid containing a high sugar concentration, wherein the main component has a composition represented by the following formula Mg ₃ Si ₄ O ₁₀ (OH) ₂ .nH ₂ O (wherein n is a number of 5 or less). , Surface spacing 4.5 to 4.6Å, 2.5 to 2.6Å and 1.5
There is an X-ray diffraction peak at ~ 1.6Å, and the following equation is = tan θ ₂ / tan θ ₁ (where θ ₁ is the peak perpendicular and the narrow-angle side peak tangent line at the X-ray diffraction peak with a surface spacing of 4.5 to 4.6Å) The angle formed by and θ ₂
Is the angle formed by the peak perpendicular to the peak and the tangent to the wide-angle side peak) and the stacking irregularity index (Is) is 3.0 or more and 3
A method for lowering a seasoning liquid containing a high sugar concentration, which comprises treating with a synthetic layered magnesium phyllosilicate having a BET specific surface area of 00 m ² / g or more and a methylene blue decolorizing power (JIS K-1470) of 100 ml / g or more. . 2. The method according to claim 1, wherein the synthetic layered magnesium phyllosilicate is treated together with activated carbon.