JPH1015358A - Production of purified astringent persimmon - Google Patents

Abstract

PROBLEM TO BE SOLVED: To remove an offensive smell by removing a monomeric substance, to freely adjust concn. to obtain not only a conc. product but also a water adjusted product by heating a raw material persimmon tannin squeezed soln. to a specific temp. and circulating said liquid at a specific temp. by using an ultrafiltration film to filter the same at the specific temp. SOLUTION: The raw material squeezed persimmon tannin liquid obtained by squeezing an astringent persimmon is heated and sterilized and, after a heat coagulable substance is coagulated, for example, a transparent filtered liquid is obtained by filtering or centrifugal separation. At this time, temp. is pref. held to 55-100 deg.C, pref., about 70-90 deg.C to be pref. held for about 30sec or more. Next, the transparent filtrate thus obtained is subjected to circulating filtration by using the ultrafiltration membrane to remove a monomeric component. At this time, the liquid temp. is held to 20-95 deg.C, pref., about 30-80 deg.C, further pref. about 40-60 deg.C. As the ultrafiltration film, a polyether sulfone membrane, a polysulfone membrane or a ceramic membrane is pref. used.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention has long been used for the purpose of clarification in the production of sake and other alcoholic beverages, and is used for foods, cosmetics,
The method of purifying persimmon astringent, which is widely used in the papermaking and textile industries, is more specifically a problem of conventional products, that is, it has a peculiar odor and is unsanitary bacterially. The tannin concentration varies depending on the varieties of the persimmon and the harvest time, and there is only a method of blending to supply stable products with a constant tannin concentration, and there is a limit in manufacturing, etc. The present invention relates to a purified persimmon astringent which can produce both a concentrated product and a hydrated product by freely adjusting the tannin concentration, and an inexpensive and efficient production method thereof.

[0002]

2. Description of the Related Art Conventional persimmon astringent manufacturing technology is a method that has been handed down for a long time. First, raw astringent persimmon is squeezed to obtain a juice, which is placed in a container, left at room temperature, and naturally fermented. The sugars in the squeezed juice were assimilated and removed by microorganisms, and then ripened. During this step, volatile organic acids (acetic acid; Mw60, propionic acid; Mw74, butyric acid; Mw8)
8) were produced as by-products, and these were the causes of persimmon astringent odor.
The product was further heat-sterilized (burned) and left to mature at room temperature for usually 2 to 3 years. This product is a product obtained by precipitating and removing other high molecular impurities while leaving a component showing cohesiveness.It contains a large amount of low molecular substances such as organic acids and inorganic substances, so there is a limit in conventional concentration methods. The persimmon astringent concentration as a product was 5 to 6 ° Baume and the tannin titer was about 150. In addition, a long manufacturing period was required.

[0003] The tannin titer referred to herein is a value measured according to a colloid titration method (Analysis by the National Tax Agency, Analytical Method, p337, published by Japan Brewery Association, 1981). That is, the tannin titer is determined by adding a fixed amount of methyl glycol chitosan, which is a positive colloid, to persimmon tannin, which is a negative colloid, and reacting it.The remaining amount of methyl glycol chitosan is titrated with polyvinyl potassium sulfate, which is a negative colloid, and blind. The persimmon tannin content is determined by subtraction from the measured value to determine the amount of persimmon tannin, and is indicated by the titration value of N / 400 potassium potassium sulfate per 1 ml of persimmon juice concentrate.

[0004] Since persimmon juice is produced from natural products, its quality is strictly diversified, and there are differences in properties. Persimmon astringency involves a chemical change during ripening, and also has a different sensual color, fragrance, viscosity, and the like. Even when concentrated under reduced pressure, the peculiar odor cannot be completely removed. Instead of natural fermentation, an improved method has been developed in which persimmon juice is sterilized and then yeast (Saccharomyces bayanus) is added and fermented to assimilate saccharides. In addition, since the sugar composition varies depending on the persimmon production area, harvest year, ripeness, and the like, there is a problem that the assimilation of carbohydrates is not uniform and it is difficult to completely eliminate odor from all raw materials. Moreover, as described above, since there are many impurities containing low molecules, it is impossible to stably produce a product having a high tannin titer by a conventional enrichment method.

[0005]

Therefore, instead of assimilating and removing saccharides by fermentation and concentration under reduced pressure, a solvent extraction method,
Adsorption / separation methods by chromatogram method, ion exchange method, reverse osmosis method, freeze concentration method, etc. were examined, but all were not practical due to some drawbacks. In other words, the solvent extraction method involves a large amount of organic solvent, which poses a danger to the work, the recovery rate is poor and the cost is high in the chromatogram method and the ion exchange method, and the persimmon astringent odor is completely removed in the reverse osmosis method and the freeze concentration method. There were drawbacks such as inability to do so.

SUMMARY OF THE INVENTION The present invention has been made to solve the above-mentioned drawbacks of the prior art, and an object of the present invention is to use an ultrafiltration membrane having a function of sieving a molecular size based on a membrane pore size, and to use water as a solvent. To provide a purified persimmon astringent which can remove odors peculiar to persimmon astringent by removing low molecular substances and obtain a concentrated product and a water-adjusted product by freely adjusting the concentration, and an inexpensive and efficient production method thereof. It is in.

[0007]

Means for Solving the Problems In order to achieve the above object, the present inventors have conducted intensive studies on a method for removing low molecular components of persimmon juice using an ultrafiltration membrane. As a result, the present invention has finally been completed. Was.

That is, according to the present invention, a raw persimmon juice juice solution obtained by squeezing from a persimmon persimmon is heated to 55 to 100 ° C.
A method for producing purified persimmon juice, comprising a step of removing low-molecular components by circulating filtration at 20 to 95 ° C. using an ultrafiltration membrane.

Further, the present invention is characterized in that low molecular components having a molecular weight of 1,000 or less, including volatile organic acids including acetic acid, propionic acid and butyric acid, saccharides including glucose and fructose and inorganic substances are removed. It is refined persimmon astringent.

[0010]

BEST MODE FOR CARRYING OUT THE INVENTION The raw material persimmon juice juice used in the present invention is a raw material persimmon such as Tamura persimmon from Gifu, Tenno persimmon from Kyoto, Atago persimmon from Ehime, Aizu persimmon from Fukushima, etc. First, after finely dividing the persimmon with a Taninaka grinder,
It is obtained by squeezing with a Shoda-type press (screw press) and performing solid-liquid separation. At this time, residue residue generated as a by-product is discarded. The squeezed liquid obtained here contains a large amount of volatile organic acids, inorganic substances, saccharides and the like which cause odor, together with persimmon tannin which is a main component of persimmon astringent.

Next, the thus obtained persimmon juice juice is sterilized by heating to solidify a heat-coagulable substance, and then, for example, filtered or centrifuged to obtain a transparent filtrate. The heating temperature at this time is 55 to 100 ° C, preferably 70 to 90 ° C.
It is preferable to hold for 0 second or more. Since Kakishibu is mainly used as a clarifying agent for sake, it must be sterilized by heating at 55 ° C or higher to prevent the incorporation of burnt bacteria, which is a rot bacterium of sake. In order to sterilize efficiently, it is preferable to hold at 70 ° C. or more for 1 to 2 minutes as instant sterilization.

In the filtration method, diatomaceous earth, which is used as a filter aid, is added to the juice at a rate of 0.2 to 5% of the weight of the juice of the persimmon juice and filtered, or a pre-coated filter is used. Is preferred. In the centrifugal separation method, persimmon juice juice is fed into a bucket rotating at high speed, and solid-liquid separation is continuously performed by centrifugal force generated by rotation. This method is used when diatomaceous earth filtration is difficult.

Next, the thus obtained transparent filtrate is subjected to circulating filtration using an ultrafiltration membrane to remove low molecular components. As the ultrafiltration membrane, cellulose acetate,
Synthetic polymer porous membrane such as polyvinylidene fluoride, polyacrylonitrile, polycarbonate, polyolefin, heat-resistant, pH-resistant and chemical-resistant, heat-sterilizable polyethersulfone or polysulfone membrane, or organic solvent-resistant polyimide membrane And a ceramic film.

The filtration process in ultrafiltration includes:
There are a pressure filtration method, a reduced pressure filtration method, and the like, and the filtration type includes a one-pass type, a multi-stage one-pass type, a circulation type, and the like. A circulation filtration method is preferable for industrially inexpensive and efficient production. The liquid temperature at this time is 20 to 95 ° C, preferably 30 to 95 ° C.
It is kept at 80C, more preferably at 40-60C. By circulating filtration in such a temperature range, the filtration efficiency is good, contamination of various bacteria can be prevented, and damage to the membrane itself can be reduced.

The present inventor has studied the properties of the target raw material persimmon astringent and the operation conditions for ultrafiltration. As a result, the molecular weight of persimmon tannin is about 4500 or more, and it has heat resistance.
It is resistant to low pH (persimmon astringent has a pH of 3-4), has little adhesion of persimmon tannin molecules to the membrane surface, and can be washed with alkali at high temperatures (alkaline washing is most effective for attaching persimmon astringent). I knew I had to be satisfied. As a method of purifying persimmon juice that satisfies these conditions, using a filtration device using an ultrafiltration membrane of a hollow fiber module made of a polyether sulfone membrane, a polysulfone membrane or a ceramic membrane with a molecular weight cut off of 3000 or more, It has been found that circulation filtration by a pressure filtration method is most preferable.

By purifying persimmon astringent using an ultrafiltration membrane as described above, the molecular weight cut off of a large amount of volatile organic acids, inorganic substances, saccharides and the like, which are odor-causing substances dissolved in persimmon astringent, is reduced. Low-molecular substances efficiently permeate through the membrane, while persimmon tannin is blocked by the membrane, and by appropriately concentrating, an odorless persimmon astringent product having a tannin concentration (colloid titer) of 200 or more can be obtained. Further, the obtained persimmon astringent product can be obtained by adjusting the concentration of water or concentration to obtain a desired product in the range of tannin concentration (colloid titer) of the product specification value of 130 or more.

[0017]

EXAMPLES The present invention will be described in more detail with reference to the following Examples, but it should not be construed that the invention is limited thereto. In addition, the tannin titer in the examples is based on
p337 (published by Japan Brewery Association, 1981), and organic acids were analyzed by high performance liquid chromatography (S
him-pack SCR-102H (manufactured by Shimadzu Corporation). The measurement of the odor was performed by a sensory test conducted by 10 panelists. When all 10 people clearly felt the odor, "Persimmon astringent smell" was displayed. When all the 10 people did not clearly sense the odor, "perfect odorless" was displayed. "Was displayed. Further, the tannin recovery rate is calculated by calculating (tannin titer × persimmon juice capacity) before and after ultrafiltration, and calculating 1
00 × [(after ultrafiltration) / (before ultrafiltration)] was calculated and determined.

Example 1 1000 kg of astringent persimmon (Tamura persimmon from Gifu Prefecture, harvested in 1993)
Was obtained using a Shoda-type pressing machine to obtain 600 l of juice. This was heated to 80 ° C. by a plate heater and held for 1 minute.
After burning, 6 Kg of diatomaceous earth was added, and body-aid was performed by stirring, and a filter press (Yabuta type, 90F, 5 m ² )
To obtain a transparent liquid.

300 l of this filtrate (solid content concentration 5%, tannin titer 130, acidity 2.1, pH 3.7) was filled with a hollow fiber module of polyethersulfone membrane (manufactured by Daicel Chemical Industries, Ltd .; molecular weight cut off 10,000). , 89φ × 1129
L × 5, total membrane area 25 m ² ) using an ultrafiltration apparatus at a gauge pressure of 0.8 to 1.2 kg / cm ² at 50 to 60 ° C.
And circulated. Repeat water addition and concentration, 3
After the lapse of time, 3,980 l of the permeate dilute solution and 140 l of the concentrated persimmon juice solution were obtained. The transmission speed at this time is 53.1 l / m ² · hr
Met. Table 1 shows data obtained by comparing the concentrated persimmon astringent product (tannin titer: 260) with the water-adjusted persimmon astringent product (tannin titer: 130) to a persimmon astringent product produced by the conventional method (the above-mentioned transparent liquid). The tannin recovery was 93%.

[0020]

[Table 1]

Example 2 1000 kg of astringent persimmon (Tenno persimmon from Kyoto, harvested in 1991)
Was obtained using a Shoda-type pressing machine to obtain 640 l of juice. This was heated to 90 ° C. by a plate heater and held for 1 minute,
After burning, 7 Kg of diatomaceous earth was added, and body-aid was performed by stirring, and a filter press (Yabuta type, 90F, 5 m ² )
To obtain a transparent liquid.

320 liters of this filtrate (solid content 8%, tannin titer 160, acidity 1.8, pH 3.9) was filled with a polysulfone membrane hollow fiber module (manufactured by Kuraray Co., Ltd .; molecular weight cut off: 13000, 114φ × 1100 L) × 5, 0.8 to 1.2K using an ultrafiltration apparatus having a total membrane area of 25 m ² )
Circulation was performed while maintaining the temperature at 45 to 55 ° C. at a g / cm ² gauge pressure. Water addition and concentration were repeated, and after 3 hours, 3370 l of a permeate dilute solution and 150 l of a concentrated persimmon juice were obtained. The transmission speed at this time was 44.9 l / m ² · hr. Table 2 shows data obtained by comparing the concentrated persimmon astringent product (tannin titer: 320) with the water-adjusted persimmon astringent product (tannin titer: 160) to a persimmon astringent product produced by the conventional method (the above-mentioned transparent liquid).
The tannin recovery was 94%.

[0023]

[Table 2]

Example 3 1000 kg of astringent persimmon (Atago persimmon from Ehime Prefecture, harvested in 1992)
Using a Shoda-type pressing machine, 620 l of a juice was obtained. This was heated to 70 ° C. by a plate heater and held for 2 minutes.
After burning, 7 Kg of diatomaceous earth was added, and body-aid was performed by stirring, and a filter press (Yabuta type, 90F, 5 m ² )
To obtain a transparent liquid.

310 l of this filtrate (solid content concentration 6%, tannin titer 140, acidity 1.5, pH 4.1) was used as a hollow fiber module of polysulfone membrane (manufactured by Kuraray Co., Ltd .; molecular weight cut off: 13000, 114φ × 1100 L) × 5, 0.8 to 1.2K using an ultrafiltration apparatus having a total membrane area of 25 m ² )
Circulation was performed while maintaining the temperature at 45 to 55 ° C. at a g / cm ² gauge pressure. Water and concentration were repeated, and after 3 hours, 3440 l of a dilute permeate and 200 l of a concentrated persimmon juice were obtained. The transmission speed at this time was 45.9 l / m ² · hr. Table 3 shows data obtained by comparing the concentrated persimmon astringent product (tannin titer: 200) with the water-adjusted persimmon astringent product (tannin titer: 140) by a conventional method.
The tannin recovery was 92%.

[0026]

[Table 3]

Example 4 Astringent persimmon (Aizu persimmon from Fukushima, harvested in 1994) 1000 kg
Was obtained using a Shoda-type pressing machine to obtain 600 l of juice. This was heated to 90 ° C. by a plate heater and held for 1 minute,
After burning, 6 Kg of diatomaceous earth was added, and body-aid was performed by stirring, and a filter press (Yabuta type, 90F, 5 m ² )
To obtain a transparent liquid.

3 liters of this filtrate (solid content 7%, tannin titer 100, acidity 1.3, pH 4.2) was mixed with a ceramic membrane monolith module (manufactured by NGK Insulators, Ltd .; molecular weight cut off: 10,000, 30φ / 4φ-). 19,1000L x 1
Using an ultrafiltration apparatus having a total membrane area of 0.24 m ² ) at a gauge pressure of 0.8 to 1.2 kg / cm ² at 50 to 60 ° C.
And circulated. Repeat water addition and concentration, 3
After a lapse of time, 36 l of a permeate dilute solution and 1.4 l of a concentrated persimmon juice solution were obtained. At this time, the transmission speed was 50.0 l / m ² · hr. Table 4 shows data obtained by comparing the concentrated persimmon astringent product (tannin titer: 200) with the water-adjusted persimmon astringent product (tannin titer: 100) by a conventional method. The tannin recovery was 93%.

[0029]

[Table 4]

Example 5 1000 Kg of astringent persimmon (Tenno persimmon from Kyoto, harvested in 1995)
Using a Shoda-type pressing machine, 590 l of a juice was obtained. This was heated to 80 ° C. by a plate heater and held for 1 minute.
After burning, centrifuge (ADS: manufactured by Saito Centrifuge Co., Ltd .: ADS)
-3001CS, 5.5kw, 7300rpm) to obtain a transparent liquid.

This liquid (solid concentration 9%, tannin titer 1
290 l of a polyethersulfone membrane hollow fiber module (manufactured by Daicel Chemical Industries, Ltd .; fractional molecular weight: 30,000, 89φ × 1129)
L × 5, total membrane area 25 m ² ) using an ultrafiltration apparatus at a gauge pressure of 0.8 to 1.2 kg / cm ² at 40 to 50 ° C.
And circulated. Repeat water addition and concentration, 3
After a lapse of time, 3170 l of a permeate diluted liquid and 200 l of a concentrated persimmon juice liquid were obtained. The transmission speed at this time is 42.3 l / m ² · hr
Met. Table 5 shows data obtained by comparing the concentrated persimmon astringent product (tannin titer: 200) with the water-adjusted persimmon astringent product (tannin titer: 160) to a persimmon astringent product (the above-mentioned transparent liquid) by a conventional method. The tannin recovery was 86%.

[0032]

[Table 5]

Example 6 With respect to the effectiveness as a liquor clarifying agent, a persimmon lowering test was carried out on sake brewed sake, split water, and burned sake using the persimmon astringent products described in Table 1, and a comparative study was conducted. Ori lowering test, sake production technology (published by Japan Brewery Association, p30
9 to 315, 1985), the results of the conventional method, the method of the present invention (adjusted water product), and the method of the present invention (concentrated product) are shown in Tables 6, 7, and 8, respectively.

[0034]

[Table 6]

[0035]

[Table 7]

[0036]

[Table 8]

Example 7 For the effectiveness as a liquor clarifying agent, the persimmon astringent products described in Table 2 were used to carry out a mirin-ripened moromi, squeezed, and mirin-drinking test after burning, and a comparative study was conducted. The lowering test is based on sake production technology (published by Japan Brewery Association)
309-315 (Showa 60)), the results of the conventional method, the method of the present invention (hydrolyzed product) and the method of the present invention (concentrated product) are shown in Tables 9, 10 and 11, respectively.

[0038]

[Table 9]

[0039]

[Table 10]

[0040]

[Table 11]

[0041]

The method of the present invention focuses on the difference in the specific molecular weight between persimmon tannin, which is the main component of persimmon astringent, and other components (volatile organic acids, etc.), and demonstrates heat resistance, pH resistance, and chemical resistance. By using a polyether sulfone membrane or a hollow fiber module of a polysulfone membrane, and a membrane separation system using a ceramic membrane, an odorless persimmon tannin can be easily and efficiently separated and purified. Even when added in a large amount as a fining agent (food additive), it is expected to be widely used in the food industry in the future, without impairing the flavor of alcoholic beverages (food) and also from the environmental and sanitary viewpoints. Furthermore, development is proceeding widely not only in fining agents (food additives) but also in other industrial fields, and it is considered that the value of persimmon astringent as a natural material will increase.

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[Procedure amendment]

[Submission date] March 28, 1997

[Procedure amendment 1]

[Document name to be amended] Statement

[Correction target item name] Claims

[Correction method] Change

[Correction contents]

[Claims]

[Procedure amendment 2]

[Document name to be amended] Statement

[Correction target item name] 0008

[Correction method] Change

[Correction contents]

That is, according to the present invention, the raw material persimmon juice juice liquid obtained by squeezing from persimmon persimmon is preferably at 55 to 100 ° C. , more preferably.
Or 70-90 ° C. , and the liquid is heated using an ultrafiltration membrane, preferably at 20-95 ° C. , more preferably
A method for producing a purified persimmon juice, comprising a step of removing low molecular components together with water by circulating filtration at 40 to 60 ° C.

Claims (8)

[Claims] 1. A raw material persimmon juice juice solution obtained by squeezing juice from astringent persimmon is heated to 55 to 100 ° C., and the solution is circulated and filtered at 20 to 95 ° C. using an ultrafiltration membrane. ,
A method for producing purified persimmon juice, comprising a step of removing low molecular components. 2. A tannin concentration (colloid titer) of 200
The method for producing purified persimmon juice according to claim 1, further comprising a concentration step. 3. A tannin concentration (colloid titer) of 130
The method for producing a purified persimmon juice according to claim 1 or 2, comprising a step of concentrating or adjusting the water content within the above range. 4. The method according to claim 1, wherein a polyethersulfone membrane, a polysulfone membrane or a ceramic membrane is used as the ultrafiltration membrane. 5. The method for producing a purified persimmon juice according to claim 1, wherein the ultrafiltration membrane has a molecular weight cut off of 3,000 or more. 6. Heat the persimmon juice juice to 70-90 ° C.
The circulating filtration is performed at 0 to 60 ° C.
5. The method for producing a purified persimmon juice according to any one of the above items 5. 7. A purified persimmon juice wherein low-molecular components having a molecular weight of 1000 or less, including volatile organic acids including acetic acid, propionic acid, and butyric acid, saccharides including glucose and fructose, and inorganic substances are removed. 8. The tannin concentration (colloid titer) is 130.
The purified persimmon juice according to claim 7, which is concentrated or adjusted for water.