JP5088951B2 - Method for producing water-soluble saccharide raw material from beer-added koji - Google Patents

Method for producing water-soluble saccharide raw material from beer-added koji Download PDF

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JP5088951B2
JP5088951B2 JP2007302610A JP2007302610A JP5088951B2 JP 5088951 B2 JP5088951 B2 JP 5088951B2 JP 2007302610 A JP2007302610 A JP 2007302610A JP 2007302610 A JP2007302610 A JP 2007302610A JP 5088951 B2 JP5088951 B2 JP 5088951B2
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beer
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water
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JP2009124983A (en
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順一 東
哲雄 坂本
清高 大西
巧 河野
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Nippon Steel and Sumikin Chemical Co Ltd
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Description

本発明は、ビール仕込み粕の処理方法に関し、より詳細には、ビール仕込み粕からの液状物製造方法に関する。   The present invention relates to a method for processing beer-added lees, and more particularly to a method for producing a liquid from beer-added lees.

ビールは、麦芽を糖化させたものをろ過して麦芽残さを除去することにより得られる麦汁に、酵母を添加して発酵させることによって製造される。
このビール製造工程において副生する麦芽残さは、ビール仕込み粕あるいはビール粕等と呼ばれ、水分を40%〜80%程度含有するとともに、水を除く残分はリグノセルロース、蛋白質、脂肪質およびシリカ等である。
Beer is produced by adding yeast to fermented wort obtained by filtering saccharified malt to remove malt residues.
The malt residue produced as a by-product in this beer production process is called beer koji or beer koji and contains about 40% to 80% water, and the remainder excluding water is lignocellulose, protein, fat and silica. Etc.

麦芽残さ(以下、これをビール仕込み粕という。)は、日本国全体で年間70万トン以上発生しており、これを排水として放流するためには、高濃度のCOD成分あるいはBOD成分を除去する必要があり、排水処理コストが多大となる。
このため、ビール仕込み粕を飼料化あるいは肥料化することが行われている。
Malt residue (hereinafter referred to as beer-added rice cake) is generated over 700,000 tons per year in Japan as a whole, and in order to discharge it as wastewater, high-concentration COD components or BOD components are removed. This is necessary and the wastewater treatment cost becomes great.
For this reason, beer mashing is made into feed or fertilizer.

しかしながら、ビール仕込み粕を飼料化あるいは肥料化するには、減容化のために、ビール仕込み粕中に大量に含まれる水分を乾燥等の方法で除去することが必要であり、水分除去に多大なエネルギーが必要となる。また、水分除去に手間取るとビール仕込み残渣は腐敗し、悪臭を放つことも考えられる。したがって、早期に処理することが必要である。   However, in order to make beer mash into feed or fertilizer, in order to reduce the volume, it is necessary to remove a large amount of water contained in the beer mash by a method such as drying. Energy is required. In addition, if it takes time to remove moisture, the beer residue may rot and give off a bad odor. Therefore, it is necessary to process early.

そこで、飼料化あるいは肥料化以外のビール仕込み粕の用途開拓が検討されている。   Therefore, the development of beer-added potatoes other than feed or fertilizer is being studied.

例えば、軽度の水熱処理により、具体的には、50〜220℃の温度における飽和水蒸気にビール仕込み粕を10〜30分接触することにより水溶解画分を効率的に得る方法が検討されている(特許文献1参照。)。ここで、水溶解画分の収率、言い換えれば原料(ビール仕込み粕)の可溶化率は60%程度であり、この可溶化率は原料中の有機炭素量に対する水中に溶解した有機炭素量の比率として定義されている。この方法により、ビール仕込み粕を乾燥することなく減容化することができるとされている。
上記の方法によって得られる水溶解画分は、これをいわゆるソフトバイオマス(米国エネルギー庁の定義による用語)としてメタン発酵させてエネルギー源としてのメタンガスを得ることができるとされている。
For example, by mild hydrothermal treatment, specifically, a method for efficiently obtaining a water-soluble fraction by contacting beer-added koji with saturated steam at a temperature of 50 to 220 ° C. for 10 to 30 minutes has been studied. (See Patent Document 1). Here, the yield of the water-soluble fraction, in other words, the solubilization rate of the raw material (beer brewed lees) is about 60%, and this solubilization rate is the amount of organic carbon dissolved in water relative to the amount of organic carbon in the raw material. It is defined as a ratio. According to this method, it is said that the volume of beer-added koji can be reduced without drying.
It is said that the water-soluble fraction obtained by the above method can be subjected to methane fermentation as so-called soft biomass (a term defined by the US Energy Agency) to obtain methane gas as an energy source.

また、例えば、飲食品製造残さであるビール製造残さを粉砕し、粉砕された残さにマイクロ波を照射して温度80〜260℃および圧力2〜35kg/cm、好ましくは、10〜30kg/cmの条件に保つことを特徴とする飲食品製造残さの液化方法が検討されている(特許文献2参照。)。この場合、マイクロ波の照射時間は20秒〜10分間であり、また、マイクロ波を照射する際に、触媒として酸を適宜添加してよいとされ、1%酢酸水溶液が例示されている。
上記の方法によって得られる残さは茶色の液状であり、これは残さに含まれていた繊維質が分解されて低分子化した結果と考えられている。そして、この液化された残さは高温高圧で処理されているために完全に殺菌されているため、食品製造原料や食品添加物として有用であるとされている。
特開2006−305561号公報 特開2004−267115号公報
Moreover, for example, the beer manufacturing residue which is a food-and-beverage-product manufacturing residue is grind | pulverized, and microwaves are irradiated to the grind | pulverized residue, temperature 80-260 degreeC and pressure 2-35-kg / cm < 2 >, Preferably, 10-30 kg / cm A method for liquefying a food and beverage product residue characterized by maintaining the condition 2 has been studied (see Patent Document 2). In this case, the microwave irradiation time is 20 seconds to 10 minutes, and it is said that an acid may be appropriately added as a catalyst when the microwave irradiation is performed, and a 1% aqueous acetic acid solution is exemplified.
The residue obtained by the above method is a brown liquid, which is considered to be the result of degradation of the fiber contained in the residue and the reduction in molecular weight. And since this liquefied residue is completely sterilized because it is processed at high temperature and high pressure, it is said that it is useful as a food production raw material or food additive.
JP 2006-305561 A JP 2004-267115 A

しかしながら、上記したビール仕込み粕の処理方法は、いずれも、比較的高温・高圧で処理するものであり、このため、特許文献1には明記されていないものの、得られる液状物が、ヘミセルロース由来の着色を生じるものと思われる。そして、液状物中に存在するヘミセルロースは、液状物を例えば食品製造原料や食品添加物として利用する際に糖化を阻害し、あるいはまた、エタノール原料として利用する際に反応を阻害するおそれがある。   However, all of the above-described methods for treating beer-added koji are processed at a relatively high temperature and high pressure. For this reason, although not specified in Patent Document 1, the obtained liquid material is derived from hemicellulose. It seems to cause coloring. And hemicellulose which exists in a liquid substance may inhibit saccharification, when using a liquid substance as a food manufacturing raw material or a food additive, for example, or may inhibit reaction when using as a ethanol raw material.

本発明は、上記の課題に鑑みてなされたものであり、ビール仕込み粕を原料として得られる液状物の着色度が低く、これにより液状物を食品製造原料等に好適に利用することができる、ビール仕込み粕からの液状物製造方法を提供することを目的とする。   The present invention has been made in view of the above problems, and the degree of coloring of the liquid material obtained using beer-added koji as a raw material is low, whereby the liquid material can be suitably used as a food production raw material. It aims at providing the manufacturing method of the liquid material from the beer stocking gutter.

本発明に係るビール仕込み粕からの水溶性糖類原料の製造方法は、
水存在下でビール仕込み粕100質量部(乾燥基準)に対して過酸化水素を1質量部〜40質量部配合し、120℃〜200℃の温度条件下で、マイクロ波を3分〜120分照射して固液混合物を得る第一の工程と、
該固液混合物を固液分離して液状物を得る第二の工程と、
該液状物を凍結乾燥する第三の工程と、
を有することを特徴とする。
A method for producing a water-soluble saccharide raw material from beer-mixed koji according to the present invention,
In the presence of water, 1 part by weight to 40 parts by weight of hydrogen peroxide is blended with 100 parts by weight of beer stock (dry basis) , and microwaves are heated at 120 ° C. to 200 ° C. for 3 minutes to 120 minutes. A first step of irradiation to obtain a solid-liquid mixture;
A second step of obtaining a liquid by solid-liquid separation of the solid-liquid mixture;
A third step of freeze-drying the liquid,
It is characterized by having.

また、本発明に係るビール仕込み粕からの液状物製造方法は、好ましくは、前記第二の工程において、ろ過により固液分離することを特徴とする。   In addition, the method for producing a liquid material from beer-added mash according to the present invention is preferably characterized in that in the second step, solid-liquid separation is performed by filtration.

本発明に係るビール仕込み粕からの水溶性糖類原料の製造方法は、水存在下でビール仕込み粕100質量部(乾燥基準)に対して過酸化水素を1質量部〜40質量部配合し、120℃〜200℃の温度条件下で、マイクロ波を3分〜120分照射して固液混合物を得る第一の工程と、該固液混合物を固液分離して液状物を得る第二の工程と、該液状物を凍結乾燥する第三の工程と、を有するため、ビール仕込み粕を原料として得られる液状物の着色度が低く、これにより液状物を食品製造原料等に好適に利用することができる。 120. The method for producing a water-soluble saccharide raw material from beer-added koji according to the present invention comprises blending 1 to 40 parts by mass of hydrogen peroxide with respect to 100 parts by mass (dry basis) of beer-added koji in the presence of water. A first step of obtaining a solid-liquid mixture by irradiating microwaves for 3 minutes to 120 minutes under a temperature condition of from ℃ to 200 ℃, and a second step of obtaining a liquid product by solid-liquid separation of the solid-liquid mixture And a third step of freeze-drying the liquid material, the degree of coloration of the liquid material obtained from beer-added koji is low, and thus the liquid material is suitably used as a raw material for food production, etc. Can do.

本発明の実施の形態について、以下に説明する。   Embodiments of the present invention will be described below.

本実施の形態に係るビール仕込み粕からの液状物製造方法は、水存在下でビール仕込み粕に過酸化水素を配合し、マイクロ波を照射して固液混合物を得る第一の工程と、該固液混合物を固液分離して液状物を得る第二の工程と、を有する。   The method for producing a liquid from beer-added lees according to the present embodiment includes a first step of blending hydrogen peroxide into beer-added lees in the presence of water and irradiating microwaves to obtain a solid-liquid mixture, And a second step of obtaining a liquid material by solid-liquid separation of the solid-liquid mixture.

ビール仕込み粕は、既に説明したように、麦芽を主原料としてビールを製造する工程の副生物として入手することができる。ビール仕込み粕は、水分を40%〜80%程度含有する副生物をそのまま用いてもよく、また、適宜の手段で脱水したものを用いてもよい。また、ビール仕込み粕は、麦芽を原料に含むものである限り、他の原料を併用する、いわゆる発泡酒等を製造する際の残さであってもよい。   As already explained, the beer preparation koji can be obtained as a by-product of the process of producing beer using malt as the main raw material. As the beer brewer's beer, a by-product containing about 40% to 80% of water may be used as it is, or a product dehydrated by an appropriate means may be used. Moreover, as long as malt is included in the raw material, the beer preparation lees may be the residue at the time of manufacturing what is called a sparkling liquor using other raw materials together.

本実施の形態に係るビール仕込み粕からの液状物製造方法は、マイクロ波を照射することで効率的に加熱処理するとともに、その際に、過酸化水素の分解によって生じる酸素の作用を利用することで、ビール仕込み粕を効率的に液状化することができる。
このため、従来技術に比べて、低温・低圧で処理することができ、着色度が低い液状物を得ることができる。これにより、高温反応に伴いヘミセルロース由来の褐色成分が生成し、これが得られる液状物の主成分である糖類の利用過程で阻害要因となっていたと考えられる従来の課題が軽減される。
得られる液状物は、糖類を主成分とするものであり、食品製造原料等として利用できる水溶性糖類原料である。
The method for producing a liquid material from beer-mixed rice cake according to the present embodiment efficiently uses heat treatment by irradiating microwaves, and at that time, utilizes the action of oxygen generated by decomposition of hydrogen peroxide. Thus, the beer brewing can be efficiently liquefied.
For this reason, compared with a prior art, it can process at low temperature and low pressure, and can obtain the liquid substance with a low coloring degree. As a result, a brown component derived from hemicellulose is generated with a high-temperature reaction, and the conventional problems considered to have been an inhibiting factor in the utilization process of saccharides, which are the main components of the liquid material from which this is obtained, are reduced.
The obtained liquid material contains saccharides as a main component and is a water-soluble saccharide raw material that can be used as a food production raw material.

過酸化水素は、過酸化水素水の形で用いることが取り扱い上好適であるが、これに限定するものではない。過酸化水素水を用いる場合は、過酸化水素濃度が35%の市販品を用いてもよく、また、過酸化水素濃度が60%程度の高濃度品を用いてもよいが、水存在下で反応させることを考慮すると、10%程度の濃度のものを用いてもよい。
なお、過酸化水素に変えて、処理の際に酸素を発生する他の化学品を用いることも可能である。
Hydrogen peroxide is preferably used in the form of hydrogen peroxide water in terms of handling, but is not limited thereto. In the case of using hydrogen peroxide water, a commercially available product having a hydrogen peroxide concentration of 35% may be used, or a high concentration product having a hydrogen peroxide concentration of about 60% may be used. In consideration of the reaction, those having a concentration of about 10% may be used.
It is also possible to use other chemicals that generate oxygen during the treatment instead of hydrogen peroxide.

マイクロ波は、周波数を限定するものではなく、例えば、912MHz、2.45GHzあるいは5.8GHz等の商用の周波数を使用することができる。   The frequency of the microwave is not limited, and a commercial frequency such as 912 MHz, 2.45 GHz, or 5.8 GHz can be used.

本実施の形態に係るビール仕込み粕からの液状物製造方法は、上記第一の工程において、好ましくは、ビール仕込み粕100質量部(乾燥基準)に対して過酸化水素を1質量部〜40質量部、より好ましくは、3質量部〜10質量部配合し、120℃〜200℃、より好ましくは、120℃〜150℃の温度条件下で、マイクロ波を3分〜120分照射する。ここで、設定する温度条件に応じて圧力条件が定まり、圧力条件は0.1MPa〜0.4MPaの範囲にある。   In the first step, the method for producing a liquid material from beer-added lees according to the present embodiment is preferably 1 to 40 parts by mass of hydrogen peroxide per 100 parts by mass (dry basis) of beer-added lees. Parts, more preferably 3 parts by mass to 10 parts by mass, and irradiation with microwaves at 120 ° C. to 200 ° C., more preferably 120 ° C. to 150 ° C. for 3 minutes to 120 minutes. Here, the pressure condition is determined according to the temperature condition to be set, and the pressure condition is in the range of 0.1 MPa to 0.4 MPa.

ビール仕込み粕の質量部数は、乾燥基準、すなわち、70℃で恒量に達するまで乾燥器内で乾燥して得られる乾燥物の量をいう。   The number of parts by mass of the beer brewing trough refers to the dry basis, that is, the amount of dried product obtained by drying in a dryer until a constant weight is reached at 70 ° C.

マイクロ波の照射時間は、ビール仕込み粕にマイクロ波を十分に吸収させてセルロースおよびヘミセルロースを多糖類、オリゴ糖および単糖類に好適に変化させるために、3分〜120分であり、より好ましくは、4分〜60分であり、さらに好ましくは、5分〜30分である。   The microwave irradiation time is 3 minutes to 120 minutes, more preferably, in order to sufficiently absorb the microwaves into the beer koji and to change cellulose and hemicellulose into polysaccharides, oligosaccharides and monosaccharides, more preferably It is 4 minutes to 60 minutes, and more preferably 5 minutes to 30 minutes.

本実施の形態に係るビール仕込み粕からの液状物製造方法の上記第二の工程における固液分離の方法は、特に限定するものではなく、例えば遠心法等の適宜の方法を用いることができるが、好ましくは、ろ過法を用い、さらに好ましくは、水可溶性部と水不溶性部を分けるためのデンカテーション法と固形分であるシリカ分を除くためのろ過法を併用する。   The solid-liquid separation method in the second step of the method for producing a liquid material from the beer-added koji according to the present embodiment is not particularly limited, and for example, an appropriate method such as a centrifugal method can be used. Preferably, a filtration method is used, and more preferably, a decantation method for separating the water-soluble part and the water-insoluble part is combined with a filtration method for removing the solid silica component.

また、本実施の形態に係るビール仕込み粕からの液状物製造方法は、上記第二の工程において得られる液状物を凍結乾燥する第三の工程をさらに有すると、熱風乾燥する場合に生じうる、液状物の主成分である水溶性糖類原料の変質を確実に回避することができて、より好ましい。   In addition, the method for producing a liquid from beer-added lees according to the present embodiment may have a third step of freeze-drying the liquid obtained in the second step, which may occur when hot air drying is performed. It is more preferable because alteration of the water-soluble saccharide raw material which is the main component of the liquid material can be surely avoided.

以上説明した本実施の形態に係るビール仕込み粕からの液状物製造方法によれば、ビール仕込み粕を原料として得られる液状物の着色度が低く、これにより液状物を食品製造原料等に好適に利用することができる。着色度が低いことはフルフラール等の酵素阻害物質や発酵阻害物質ができていないことを意味する。   According to the method for producing a liquid material from the beer-added koji according to the present embodiment described above, the color of the liquid material obtained using the beer-made koji as a raw material is low, and thus the liquid material is suitably used as a food production raw material. Can be used. A low coloring degree means that an enzyme inhibitor such as furfural or a fermentation inhibitor is not formed.

本実施の形態に係るビール仕込み粕からの液状物製造方法により得られる液状物は、食品製造原料、食品添加物、家畜の飼料あるいはエタノール原料等の用途に好適に用いることができる。   The liquid obtained by the method for producing a liquid from beer-added koji according to the present embodiment can be suitably used for food production raw materials, food additives, livestock feed, ethanol raw materials and the like.

以上説明した本実施の形態に係る水溶性糖類原料の製造方法に関わらず、本発明は、ビール仕込み粕以外のソフトバイオマス、例えば柑橘類の絞りかす、稲わら、麦わら、そばがら、ライ麦、ひえ、あわ、きび等の穀類の実収穫後の残宰、栗、くるみ、銀杏等の残宰、さらに梅、プラム、杏、桃などの種などに応用可能である。   Regardless of the method for producing the water-soluble saccharide raw material according to the present embodiment described above, the present invention is a soft biomass other than beer-mixed straw, such as citrus pomace, rice straw, straw, buckwheat, rye, koe, It can be applied to residues after harvesting cereals such as awa and acne, residues such as chestnuts, walnuts and ginkgo, and seeds such as plum, plum, apricot and peach.

実施例を挙げて、本発明をさらに説明する。なお、本発明は、以下に説明する実施例に限定されるものではない。   The present invention will be further described with reference to examples. In addition, this invention is not limited to the Example demonstrated below.

(ビール仕込み粕の組成)
以下の組成の脱水したビール仕込み粕を原料に用いた。
ビール仕込み粕は、水分含量4.44±0.1質量%、酸不溶性リグニン含量24.8±1.0質量%、灰分含量(シリカ)3.6±0.1質量%、窒素含量4.31質量%、蛋白質25.8質量%および糖脂質を含む油分12.8質量%である。また、ビール仕込み粕に含まれる中性糖の組成(単位:%)は、表1に示すとおりである。
(Composition of beer brewed rice cake)
A dehydrated beer koji with the following composition was used as a raw material.
The beer-added koji has a moisture content of 4.44 ± 0.1% by mass, an acid-insoluble lignin content of 24.8 ± 1.0% by mass, an ash content (silica) of 3.6 ± 0.1% by mass, and a nitrogen content of 4. 31% by mass, 25.8% by mass of protein, and 12.8% by mass of oil containing glycolipid. Moreover, the composition (unit:%) of the neutral sugar contained in the beer-added koji is as shown in Table 1.

Figure 0005088951
Figure 0005088951

(液状物の製造実施例1)
上記のビール仕込み粕3.0gと、10%過酸化水素水30mLをマイクロ波照射装置(Microsynth、周波数2.45GHz、最大出力1kW、マイルストーンゼネラル社製)に配置した高圧反応管(フッ素樹脂製、容量50mL、マイルストーンゼネラル社製)に入れ、0.27MPaの圧力下、2分間かけて130℃に昇温した後、5分間マイクロ波を照射した。高圧反応管を冷却した後、N0.3のろ紙を用いてろ過し、液状物と残渣を分離した。
得られた液状物(水可溶化画分料)はそのまま凍結乾燥し、質量を測定した。液状物は、総質量が1.50gであり、ビール仕込み粕3.0gに対する可溶化率は仕込み基準で50.1%であった。また、得られた液状物は無色透明であった。
(Liquid Production Example 1)
A high-pressure reaction tube (made of fluororesin), in which 3.0 g of the above-mentioned beer charge and 30 mL of 10% hydrogen peroxide water are placed in a microwave irradiation device (Microsynth, frequency 2.45 GHz, maximum output 1 kW, manufactured by Milestone General) In a volume of 50 mL, manufactured by Milestone General Co., Ltd., heated to 130 ° C. over 2 minutes under a pressure of 0.27 MPa, and then irradiated with microwaves for 5 minutes. After cooling the high pressure reaction tube, it was filtered using N0.3 filter paper to separate the liquid and the residue.
The obtained liquid (water-solubilized fraction) was lyophilized as it was, and the mass was measured. The liquid material had a total mass of 1.50 g, and the solubilization rate with respect to 3.0 g of the beer-added koji was 50.1% on the basis of preparation. Further, the obtained liquid was colorless and transparent.

(液状物の製造実施例2)
反応温度(マイクロ波照射時の温度)を140℃としたほかは、実施例1と同様の方法で液状物を得た。実施例1と同様の方法で測定した可溶化率は61.6%であった。また、得られた液状物は得られた液状物は無色透明であった。
(Liquid Production Example 2)
A liquid material was obtained in the same manner as in Example 1 except that the reaction temperature (temperature during microwave irradiation) was 140 ° C. The solubilization rate measured by the same method as in Example 1 was 61.6%. Moreover, the obtained liquid substance was colorless and transparent.

(液状物の製造比較例)
100〜220℃の範囲で、10℃刻みで温度を変えて、それぞれ5分間保持して加熱反応させたほかは、実施例1と同様の方法で温度条件ごとの液状物を得た。実施例1と同様の方法で測定した可溶化率の最大値は、温度200℃で反応させたときの47.5%であった。150℃での反応物は、薄い茶色を帯び、反応温度の上昇と共に茶色が濃くなってゆき、200℃を過ぎると液は褐色を帯びていた。
(Production comparative example of liquid material)
A liquid material for each temperature condition was obtained in the same manner as in Example 1 except that the temperature was changed in increments of 10 ° C. in the range of 100 to 220 ° C., and each was held for 5 minutes to cause a heating reaction. The maximum value of the solubilization rate measured by the same method as in Example 1 was 47.5% when reacted at a temperature of 200 ° C. The reaction product at 150 ° C. had a light brown color, and the brown color became darker as the reaction temperature increased, and after 200 ° C., the liquid became brown.

Claims (2)

水存在下でビール仕込み粕100質量部(乾燥基準)に対して過酸化水素を1質量部〜40質量部配合し、120℃〜200℃の温度条件下で、マイクロ波を3分〜120分照射して固液混合物を得る第一の工程と、
該固液混合物を固液分離して液状物を得る第二の工程と、
該液状物を凍結乾燥する第三の工程と、
を有することを特徴とするビール仕込み粕からの水溶性糖類原料の製造方法。
In the presence of water, 1 part by weight to 40 parts by weight of hydrogen peroxide is blended with 100 parts by weight of beer stock (dry basis) , and microwaves are heated at 120 ° C. to 200 ° C. for 3 minutes to 120 minutes. A first step of irradiation to obtain a solid-liquid mixture;
A second step of obtaining a liquid by solid-liquid separation of the solid-liquid mixture;
A third step of freeze-drying the liquid,
A method for producing a water-soluble saccharide raw material from beer-added koji.
前記第二の工程において、ろ過により固液分離することを特徴とする請求項1記載のビール仕込み粕からの水溶性糖類原料の製造方法。The method for producing a water-soluble saccharide raw material from beer-added koji according to claim 1, wherein in the second step, solid-liquid separation is performed by filtration.
JP2007302610A 2007-11-22 2007-11-22 Method for producing water-soluble saccharide raw material from beer-added koji Expired - Fee Related JP5088951B2 (en)

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