JP2010142203A - Method for producing feed or fertilizer comprising use of fermented residue - Google Patents

Method for producing feed or fertilizer comprising use of fermented residue Download PDF

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JP2010142203A
JP2010142203A JP2008326352A JP2008326352A JP2010142203A JP 2010142203 A JP2010142203 A JP 2010142203A JP 2008326352 A JP2008326352 A JP 2008326352A JP 2008326352 A JP2008326352 A JP 2008326352A JP 2010142203 A JP2010142203 A JP 2010142203A
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fermentation residue
concentrate
fertilizer
shochu
residue
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JP5222124B2 (en
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Osamu Hamamoto
修 浜本
Yoko Miyazaki
陽子 宮崎
Shunichiro Nishioka
俊一郎 西岡
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Mitsui Engineering and Shipbuilding Co Ltd
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    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02A—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE
    • Y02A40/00—Adaptation technologies in agriculture, forestry, livestock or agroalimentary production
    • Y02A40/10—Adaptation technologies in agriculture, forestry, livestock or agroalimentary production in agriculture
    • Y02A40/20—Fertilizers of biological origin, e.g. guano or fertilizers made from animal corpses
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P60/00—Technologies relating to agriculture, livestock or agroalimentary industries
    • Y02P60/80—Food processing, e.g. use of renewable energies or variable speed drives in handling, conveying or stacking
    • Y02P60/87—Re-use of by-products of food processing for fodder production

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  • Treatment Of Sludge (AREA)
  • Fertilizers (AREA)
  • Fodder In General (AREA)

Abstract

<P>PROBLEM TO BE SOLVED: To provide a method for producing feed or fertilizer using fermented residue, by which metal ions are efficiently eliminated from the fermented residue such as distilled spirit lees. <P>SOLUTION: The method for producing feed or fertilizer using fermented residue includes: the concentration process for concentrating the fermented residue to generate fermented residue concentrate; and the metal ion-eliminating process for permeating monovalent cation via cation-exchangeable diaphragm from the side of the fermented residue concentrate produced in the concentration process to eliminate the monovalent cation. Preferably the concentration process includes concentrating solid in the fermentation residue to be at ≥15 wt.%. <P>COPYRIGHT: (C)2010,JPO&INPIT

Description

本発明は発酵残渣を用いた飼料もしくは肥料の製造方法に関し、詳しくは、発酵残渣中から効率良く金属イオンを除去することのできる発酵残渣を用いた飼料もしくは肥料の製造方法に関する。   The present invention relates to a method for producing a feed or fertilizer using a fermentation residue, and in particular, to a method for producing a feed or fertilizer using a fermentation residue that can efficiently remove metal ions from the fermentation residue.

１９９３年に日本を含む多数の国々でロンドン条約（廃棄物その他の投棄による海洋汚染の防止に関する条約）が採択された。発酵蒸留残渣は現在同条約の除外品目として認められているが、現実問題としてはこのまま従来の海洋投棄を継続することは困難な情勢であり、全量陸上処理することを目標に業界での努力がなされてきた。   In 1993, a number of countries, including Japan, adopted the London Convention (the Convention on the Prevention of Marine Pollution from Waste and Other Disposals). Although fermented distillation residues are now recognized as exempted items from the Convention, as a matter of fact, it is difficult to continue the conventional ocean dumping as it is. Has been made.

発酵蒸留残渣、例えば焼酎粕には通常水分と固形分が含まれ、水分は９０重量％以上含まれ、固形分には多量のたんぱく質、でん粉、繊維分等が含まれている。   Fermentation distillation residues, such as shochu, usually contain water and solids, and the water contains 90% by weight or more, and the solids contain a large amount of protein, starch, fiber and the like.

かかる発酵蒸留残渣の陸上処理として焼却処理も考えられるが、焼却設備や助燃剤としての燃料コストの負担が大きくなるため、好ましい手法とは言えない。   Although incineration is also conceivable as a land treatment of such fermentation distillation residue, it is not a preferable method because the burden of fuel costs as incineration equipment and a combustor increases.

飼料価格の高騰の影響もあいまって、近年、発酵蒸留残渣を家畜飼料として利用する動きが高まっている。   In recent years, there has been an increase in the use of fermented distillation residue as livestock feed, coupled with the impact of soaring feed prices.

焼酎粕は、クエン酸などのオキシカルボン酸類、グルタミン酸などのアミノ酸類、ポリフェノール類などを含有するほか、粗タンパク成分も含まれているので家畜飼料の原料としての価値が高い。しかし、焼酎粕は外気温下で半日乃至一日放置すると腐敗臭が発生し、家畜の嗜好性も低下してしまうため、濃縮することが行われている。   Shochu contains oxycarboxylic acids such as citric acid, amino acids such as glutamic acid, polyphenols, etc., and also contains crude protein components, so it is highly valuable as a raw material for livestock feed. However, if shochu is left for half a day or a day at an outside temperature, a rotting odor is generated and the taste of the livestock is reduced. Therefore, the shochu is concentrated.

焼酎粕はクエン酸や酢酸などの腐敗を防止する成分を比較的多く含有している。そこで、固形分が５〜１０％しかない焼酎粕を濃縮し、粗タンパク量やクエン酸濃度などを上げることによって飼料価値や腐敗防止性（抗菌性）を改善することができる。   Shochu contains a relatively large amount of ingredients such as citric acid and acetic acid that prevent spoilage. Thus, by concentrating shochu containing only 5 to 10% of solid content and increasing the amount of crude protein, the concentration of citric acid, etc., feed value and antiseptic properties (antibacterial properties) can be improved.

黒糖焼酎の焼酎粕は、芋、米、麦などの他の焼酎粕に比べて濃縮が容易であるが、黒糖焼酎の焼酎粕濃縮液には、カリウムが高濃度で含まれており、このカリウム含量の多い飼料を牛等の家畜に与えると、カリウムに対するマグネシウムやカルシウム含量が低くなってしまい、生理障害を引き起こすおそれがある。このため、焼酎粕等の発酵蒸留残渣を濃縮して飼料とする場合は、濃縮液中のカリウムイオン等の金属イオンを除去する必要がある。
特開昭６４−３８１９３号公報 特開２００２−３６２９９０号公報 Shochu of brown sugar shochu is easier to concentrate than other shochu such as rice bran, rice and wheat, but the shochu concentrate of brown sugar shochu contains a high concentration of potassium. If a feed with a high content is given to livestock such as cattle, the content of magnesium or calcium relative to potassium is lowered, which may cause physiological disorders. For this reason, when fermenting distillation residues, such as shochu, are concentrated and used as a feed, it is necessary to remove metal ions, such as potassium ion, in a concentrate.
JP-A-64-38193 JP 2002-362990 A

本発明の課題は、焼酎粕等の発酵残渣中から効率良く金属イオンを除去することのできる発酵残渣を用いた飼料もしくは肥料の製造方法を提供することにある。   The subject of this invention is providing the manufacturing method of the feed or fertilizer using the fermentation residue which can remove a metal ion efficiently from fermentation residues, such as shochu.

また、本発明の他の課題は以下の記載により明らかとなる。   Other problems of the present invention will become apparent from the following description.

上記課題は以下の各発明によって解決される。   The above problems are solved by the following inventions.

（請求項１）
発酵残渣を濃縮して発酵残渣濃縮液を生成する濃縮工程と、前記濃縮工程で得られた発酵残渣濃縮液側から陽イオン交換性の隔膜を介して一価陽イオンを透過、除去する金属イオン除去工程とを有することを特徴とする発酵残渣を用いた飼料もしくは肥料の製造方法。 (Claim 1)
A concentration step for concentrating the fermentation residue to produce a fermentation residue concentrate, and a metal ion that permeates and removes monovalent cations from the fermentation residue concentrate side obtained in the concentration step through a cation-exchangeable diaphragm. A method for producing feed or fertilizer using a fermentation residue, comprising a removal step.

（請求項２）
前記濃縮工程は、前記発酵残渣中の固形分を１５％以上に濃縮することを特徴とする請求項１記載の発酵残渣を用いた飼料もしくは肥料の製造方法。 (Claim 2)
The said concentration process concentrates solid content in the said fermentation residue to 15% or more, The manufacturing method of the feed or fertilizer using the fermentation residue of Claim 1 characterized by the above-mentioned.

（請求項３）
前記金属イオン除去工程は、濃縮液室内に一価イオン交換性の隔膜を有するイオン透析槽を使用し、前記発酵残渣濃縮液を前記濃縮液室内に流通させることにより、前記一価陽イオンを透過、除去することを特徴とする請求項１又は２記載の発酵残渣を用いた飼料もしくは肥料の製造方法。 (Claim 3)
The metal ion removal step uses an ion dialysis tank having a monovalent ion-exchangeable diaphragm in the concentrate chamber, and allows the monovalent cation to permeate by circulating the fermentation residue concentrate in the concentrate chamber. The method for producing feed or fertilizer using the fermentation residue according to claim 1, wherein the fermentation residue is removed.

（請求項４）
前記発酵残渣は、黒糖もしくは芋を原料とする焼酎粕であることを特徴とする請求項１、２又は３記載の発酵残渣を用いた飼料もしくは肥料の製造方法。 (Claim 4)
The method for producing feed or fertilizer using the fermentation residue according to claim 1, wherein the fermentation residue is shochu made from brown sugar or koji.

（請求項５）
前記濃縮工程は、多重効用缶を用いて前記発酵残渣を濃縮することを特徴とする請求項１〜４のいずれかに記載の発酵残渣を用いた飼料もしくは肥料の製造方法。 (Claim 5)
The said concentration process concentrates the said fermentation residue using a multi-effect can, The manufacturing method of the feed or fertilizer using the fermentation residue in any one of Claims 1-4 characterized by the above-mentioned.

本発明によれば、焼酎粕等の発酵残渣中から効率良く金属イオンを除去することのできる発酵残渣を用いた飼料もしくは肥料の製造方法を提供することができる。   ADVANTAGE OF THE INVENTION According to this invention, the manufacturing method of the feed or fertilizer using the fermentation residue which can remove a metal ion efficiently from fermentation residues, such as shochu, can be provided.

以下、本発明の実施の形態を説明する。   Embodiments of the present invention will be described below.

図１は、本発明の一実施形態を示すフローシートである。同図において、１は被処理液である発酵残渣を貯留する貯留タンク、１０は攪拌機である。   FIG. 1 is a flow sheet showing an embodiment of the present invention. In the figure, 1 is a storage tank for storing a fermentation residue that is a liquid to be treated, and 10 is a stirrer.

本発明において発酵残渣には、蒸留酒の製造過程でアルコール分を蒸留した後に残存する固形分を多く含んだ液状物が含まれ、例えば芋焼酎粕、麦焼酎粕、米焼酎粕、黒糖焼酎粕またはこれらの混合物などの焼酎粕や、ウィスキーの醗酵過程で生成する蒸留粕なども含まれる。中でもカリウム（Ｋ）の多い黒糖を原料とする黒糖焼酎粕もしくは芋を原料とする芋焼酎粕が好ましく、特に黒糖焼酎粕が本発明では好ましい。また、本発明の発酵残渣は生ごみメタン発酵残渣であってもよい。ここでは、発酵残渣として黒糖焼酎粕を用いた場合について説明する。   In the present invention, the fermentation residue includes a liquid substance containing a large amount of solids remaining after distillation of the alcohol in the process of producing distilled liquor. For example, shochu shochu, wheat shochu, rice shochu, brown sugar shochu Alternatively, shochu such as a mixture of these, and distilled spirits produced during whiskey fermentation are also included. Of these, brown sugar shochu using brown sugar with a high potassium (K) content or shochu shochu using koji as a raw material is preferred, and brown sugar shochu is particularly preferred in the present invention. The fermentation residue of the present invention may be a garbage methane fermentation residue. Here, the case where brown sugar shochu is used as a fermentation residue will be described.

貯留タンク１に貯留された黒糖焼酎粕は、次いで固液分離手段２に送られて固液分離される。固液分離手段２としては、ＭＦ膜（精密ろ過膜）、スクリュープレス、ロータリープレス、真空脱水機、フィルタープレスなどを用いることができ、中でもＭＦ膜やスクリュープレスが好ましい。   The brown sugar shochu stored in the storage tank 1 is then sent to the solid-liquid separation means 2 for solid-liquid separation. As the solid-liquid separation means 2, an MF membrane (microfiltration membrane), a screw press, a rotary press, a vacuum dehydrator, a filter press, or the like can be used. Among them, an MF membrane or a screw press is preferable.

かかる固液分離手段２による固液分離によって黒糖焼酎粕は固形分側と液体分側に分離され、そのうちの液体分側が濃縮手段３に送られ、該濃縮手段３によって濃縮されて黒糖焼酎粕濃縮液（発酵残渣濃縮液）が生成される（濃縮工程）。   By the solid-liquid separation by the solid-liquid separation means 2, the brown sugar shochu is separated into the solid content side and the liquid content side, and the liquid content side is sent to the concentration means 3 and concentrated by the concentration means 3 to concentrate the brown sugar shochu. A liquid (fermentation residue concentrate) is produced (concentration step).

この濃縮手段３に送られる黒糖焼酎粕はスクリーン処理されていることが好ましい。   The brown sugar shochu to be sent to the concentration means 3 is preferably screen-treated.

濃縮手段３としては蒸発缶が好ましく使用でき、蒸発缶としては多重効用缶やスプレー式蒸発缶などを用いることができる。中でも多重効用缶を用いることが好ましく、濃縮度が進むに従い液の粘度が増加してくるため、例えば三井造船株式会社製の減圧強制循環式多重効用型濃縮装置を使用することが好ましい。   As the concentrating means 3, an evaporator can be preferably used. As the evaporator, a multi-effect can, a spray evaporator and the like can be used. Among them, it is preferable to use a multi-effect can, and since the viscosity of the liquid increases as the concentration progresses, it is preferable to use, for example, a reduced-pressure forced circulation multi-effect concentrator made by Mitsui Engineering & Shipbuilding.

この濃縮手段３では、後段の金属イオン除去工程における金属イオンの除去効率（電流効率）を高めるため、黒糖焼酎粕中の固形分濃度（ＴＳ）を１５％以上に濃縮することが好ましく、より好ましくは３０％以上に濃縮することである。この濃縮によってイオン透析の処理量を低減できると共に、透析効率（電流効率）も上げることが可能である。   In this concentration means 3, in order to increase the removal efficiency (current efficiency) of metal ions in the subsequent metal ion removal step, it is preferable to concentrate the solid content concentration (TS) in brown sugar shochu to 15% or more, more preferably. Is to concentrate to 30% or more. This concentration can reduce the amount of ion dialysis, and can also increase dialysis efficiency (current efficiency).

かかる濃縮手段３によって濃縮された黒糖焼酎粕濃縮液は、金属イオン除去装置４に送られ、該金属イオン除去装置４によって、濃縮液中の金属イオン、特にカリウムイオン（Ｋ+）の除去が行われる（金属イオン除去工程）。 The brown sugar shochu concentrate concentrated by the concentration means 3 is sent to the metal ion removing device 4, and the metal ions removing device 4 removes metal ions, particularly potassium ions (K + ) in the concentrated solution. (Metal ion removal step).

本発明において金属イオン除去装置４は、陽イオン交換性の隔膜を介して、濃縮手段３で得られた黒糖焼酎粕濃縮液中から一価陽イオンであるカリウムイオンを透過、除去する。   In this invention, the metal ion removal apparatus 4 permeate | transmits and removes the potassium ion which is a monovalent cation from the brown sugar shochu concentrate obtained by the concentration means 3 through a cation exchange membrane.

図２は、かかる金属イオン除去装置４の一例を示している。この金属イオン除去装置４は一般的なイオン透析槽（電気透析槽）を用いた例であり、濃縮液室を構成するイオン透析槽４０の対向する壁面に陽極４１及び陰極４２が対向配置され、その間に、被処理液である黒糖焼酎粕濃縮液を流通させる流路４３と、該黒糖焼酎粕濃縮液中から除去されたカリウムイオンの濃縮液を流通させる流路４４とが交互に配置されており、各流路４３と４４の間にそれぞれ陽イオン交換膜４５と陰イオン交換膜４６とが交互に配置されている。陽極４１及び陰極４２には、チタンに白金等を被覆したエキスパンドメタル等を用いることができる。   FIG. 2 shows an example of such a metal ion removing device 4. This metal ion removing device 4 is an example using a general ion dialysis tank (electrodialysis tank), and an anode 41 and a cathode 42 are disposed opposite to each other on opposite wall surfaces of an ion dialysis tank 40 constituting a concentrate chamber, In the meantime, the channel 43 for circulating the brown sugar shochu concentrate, which is the liquid to be treated, and the channel 44 for circulating the potassium ion concentrate removed from the brown sugar shochu concentrate are alternately arranged. The cation exchange membrane 45 and the anion exchange membrane 46 are alternately arranged between the flow paths 43 and 44, respectively. For the anode 41 and the cathode 42, an expanded metal obtained by coating titanium or the like with platinum or the like can be used.

ここで、陽イオン交換膜４５は、一価の陽イオンを選択的に透過する隔膜が用いられる。このため、陽極４１と陰極４２間に所定の電圧を印加すると、流路４３中を流れる黒糖焼酎粕濃縮液側から陽イオン交換膜４５を介してカリウムイオン（Ｋ+）が、陰極４２側に隣接する流路４４側に透過し、流路４３内の黒糖焼酎粕濃縮液中から除去される。このとき、黒糖焼酎粕濃縮液中の陰イオンも陰イオン交換膜４６を介して陽極４１側に隣接する流路４４側に透過するが、本発明においては黒糖焼酎粕濃縮液中のカリウムイオンが除去されればよく、特に問題はない。 Here, the cation exchange membrane 45 is a diaphragm that selectively transmits monovalent cations. Therefore, when a predetermined voltage is applied between the anode 41 and the cathode 42, potassium ions (K + ) are transferred from the brown sugar shochu concentrate flowing through the flow path 43 through the cation exchange membrane 45 to the cathode 42 side. It permeates to the adjacent channel 44 side and is removed from the brown sugar shochu concentrate in the channel 43. At this time, the anions in the brown sugar shochu concentrate also permeate through the anion exchange membrane 46 to the channel 44 side adjacent to the anode 41 side. There is no particular problem as long as it is removed.

なお、図示しないが、黒糖焼酎粕濃縮液及びカリウムイオンの濃縮液は、それぞれ不図示のポンプによって各流路４３、４４を循環するようになっている。   Although not shown, the brown sugar shochu concentrate and the potassium ion concentrate are circulated through the channels 43 and 44 by pumps (not shown), respectively.

図３は、金属イオン除去装置４の他の例を示している。この金属イオン除去装置４は、陽イオン交換膜４５のみを使用した場合であり、イオン透析槽４０の対向する壁面に陽極４１及び陰極４２が対向配置され、その間に、被処理液である黒糖焼酎粕濃縮液の流路４３と、該黒糖焼酎粕濃縮液中から除去されたカリウムイオンの濃縮液の流路４４とが、間に陽イオン交換膜４５を介して配置された組が複数組設けられている。符号４７は、バイポーラプレート（複極仕切板）である。   FIG. 3 shows another example of the metal ion removing device 4. This metal ion removing device 4 is a case where only a cation exchange membrane 45 is used, and an anode 41 and a cathode 42 are arranged opposite to each other on opposite wall surfaces of the ion dialysis tank 40, and a brown sugar shochu, which is a liquid to be treated, is placed therebetween. A plurality of sets in which the flow path 43 of the cocoon concentrate and the flow path 44 of the concentrated potassium ion solution removed from the brown sugar shochu concentrate are arranged via the cation exchange membrane 45 therebetween are provided. It has been. Reference numeral 47 denotes a bipolar plate (bipolar partition plate).

この態様でも、黒糖焼酎粕濃縮液及びカリウムイオンの濃縮液を、それぞれ不図示のポンプによって各流路４３、４４を循環させ、その過程で、陽極４１と陰極４２間に印加された電圧によって、流路４３中の黒糖焼酎粕濃縮液側から陽イオン交換膜４５を介して隣接する流路４４にカリウムイオンを透過、除去することができる。   Also in this aspect, brown sugar shochu concentrate and potassium ion concentrate are circulated through the flow paths 43 and 44 by pumps (not shown), respectively, and in the process, the voltage applied between the anode 41 and the cathode 42 Potassium ions can be permeated and removed from the brown sugar shochu concentrate side in the channel 43 to the adjacent channel 44 through the cation exchange membrane 45.

このように陽イオン交換膜を用いて液体中から陽イオンを透過、除去することは一般に知られている技術であるが、本発明では、この陽イオン交換膜を用いてカリウムイオンを透過、除去するに当たり、その前工程として、黒糖焼酎粕を濃縮して黒糖焼酎粕濃縮液としておく点に特徴を有している。黒糖焼酎粕を濃縮液とした上で金属イオンの除去を実施することにより、黒糖焼酎粕に対してそのまま金属イオンの除去を実施するのに比べて、カリウムイオンの除去率が高まり、それだけカリウムイオン除去のための電流効率が高まるようになる。   Although it is a generally known technique to permeate and remove cations from a liquid using a cation exchange membrane as described above, in the present invention, this cation exchange membrane is used to permeate and remove potassium ions. In doing so, it has a feature in that brown sugar shochu is concentrated as a pre-process to prepare a brown sugar shochu concentrate. By removing the metal ions after using brown sugar shochu as a concentrate, the removal rate of potassium ions is higher than the removal of metal ions from brown sugar shochu as it is. The current efficiency for removal increases.

これは本発明者の次のような知見による。すなわち、陽イオン交換膜を使用するイオン透析ではカリウムやナトリウムの他にプロトンも同様に透過し、しかも、プロトンの膜中の透過速度（輸率も関与する）はアルカリ金属イオンよりも通常、一桁以上大きくなる。また、焼酎粕は比較的強い酸性であり、そのため、プロトンの透過量が大きくなって、アルカリ金属除去の電流効率は大きく低下する。焼酎粕のｐＨは４弱程度であり、これは主にクエン酸などの有機酸によるものである。そのため、濃縮した液でもｐＨがあまり低下することはない（プロトン濃度は大きくならない。）。したがって、アルカリ金属イオン除去に関する電流効率は濃縮した液ほど、向上することになる。   This is due to the following knowledge of the present inventors. In other words, in ion dialysis using a cation exchange membrane, protons permeate in the same manner as potassium and sodium, and the proton permeation rate (which also involves the transport number) is usually higher than that of alkali metal ions. Becomes more than an order of magnitude larger. In addition, shochu is a relatively strong acid, so that the amount of proton permeation increases and the current efficiency of alkali metal removal is greatly reduced. The pH of shochu is about 4 or less, which is mainly due to organic acids such as citric acid. Therefore, the pH does not drop much even in a concentrated liquid (the proton concentration does not increase). Therefore, the current efficiency with respect to alkali metal ion removal increases as the concentration of the liquid increases.

このようにしてカリウムイオンが除去された黒糖焼酎粕濃縮液は、家畜の配合飼料として用いられる。   The brown sugar shochu concentrate from which potassium ions have been removed in this way is used as a livestock blended feed.

以上は、発酵残渣として黒糖焼酎粕を用いたが、他の焼酎粕や生ごみメタン発酵残渣の場合も同様にして濃縮液中から一価陽イオンを効率良く除去することができ、得られた濃縮液は配合飼料もしくは肥料として利用することができる。   Above, brown sugar shochu was used as the fermentation residue, but in the case of other shochu and garbage methane fermentation residue as well, monovalent cations could be efficiently removed from the concentrate and obtained. The concentrated liquid can be used as a mixed feed or a fertilizer.

以下に本発明の実施例を説明するが、本発明はかかる実施例によって限定されない。   Examples of the present invention will be described below, but the present invention is not limited to such examples.

試験装置として図４に示す金属イオン除去装置を用い、黒糖焼酎粕からのカリウムイオン除去試験を行った。   The metal ion removal apparatus shown in FIG. 4 was used as a test apparatus, and a potassium ion removal test from brown sugar shochu was performed.

図４において、４００は電解液（カリウムイオン等の濃縮液）、４０１はこの電解液を貯留するイオン透析槽、４０２はチタンに白金を被覆した円筒形状をしたエキスパンドメタルからなる陽極、４０３はチタンに白金を被覆した棒状の陰極である。４０４は陽極４０２の外周に巻き付けられた陽イオン交換膜（有効長５ｃｍ、内径約３ｍｍ）、４０５は陽極４０２と電気的に接続するリード線、４０６は陰極４０３と電気的に接続するリード線である。   In FIG. 4, 400 is an electrolytic solution (concentrated liquid such as potassium ions), 401 is an ion dialysis tank for storing the electrolytic solution, 402 is an anode made of expanded metal in a cylindrical shape in which titanium is coated with platinum, and 403 is titanium. This is a rod-shaped cathode coated with platinum. Reference numeral 404 denotes a cation exchange membrane (effective length: 5 cm, inner diameter: about 3 mm) wound around the outer periphery of the anode 402, 405 denotes a lead wire electrically connected to the anode 402, and 406 denotes a lead wire electrically connected to the cathode 403. is there.

４０７はＴ字管であり、陽イオン交換膜４０４を巻き付けた陽極４０２の下端に液密状に取り付けられている。Ｔ字管４０７の下端部４０７ａは閉塞され、中途部から側方に分岐する分岐部４０７ｂに、イオン透析槽４０１の側壁を貫通して外部に突出する流入管４０８が接続されている。   Reference numeral 407 denotes a T-shaped tube that is liquid-tightly attached to the lower end of the anode 402 around which the cation exchange membrane 404 is wound. The lower end portion 407a of the T-shaped tube 407 is closed, and an inflow tube 408 that penetrates the side wall of the ion dialysis tank 401 and protrudes to the outside is connected to a branch portion 407b that branches sideways from the midway portion.

また、４０９はＴ字管であり、陽イオン交換膜４０４を巻き付けた陽極４０２の上端に液密状に取り付けられている。Ｔ字管４０９の上端部４０９ａは閉塞され、この閉鎖部分を貫通するように上記リード線４０５が挿入されている。Ｔ字管４０９の中途部から側方に分岐する分岐部４０９ｂに、イオン透析槽４０１の側壁を貫通して外部に突出する流出管４１０が接続されている。   Reference numeral 409 denotes a T-shaped tube that is liquid-tightly attached to the upper end of the anode 402 around which the cation exchange membrane 404 is wound. The upper end portion 409a of the T-shaped tube 409 is closed, and the lead wire 405 is inserted so as to penetrate the closed portion. An outflow pipe 410 that penetrates the side wall of the ion dialysis tank 401 and protrudes to the outside is connected to a branch part 409 b that branches from the middle part of the T-shaped pipe 409 to the side.

この試験装置の陽極４０２の内側に、７１０μｍのスクリーン処理を行った未濃縮の黒糖焼酎粕（固形分濃度ＴＳ＝４．５％）と、黒糖焼酎粕濃縮液（固形分濃度ＴＳ＝１５％）を、それぞれ約５ｍＬ／分の流量で流通させ、両極間に約３Ｖの電圧を印加して陽イオン交換膜４０２によってカリウムイオンを除去した。このときの槽温度は１９℃であった。   Inside the anode 402 of this test apparatus, unconcentrated brown sugar shochu (solid content concentration TS = 4.5%) subjected to a screen treatment of 710 μm and brown sugar shochu concentrate (solid content concentration TS = 15%). Were each circulated at a flow rate of about 5 mL / min, and a voltage of about 3 V was applied between the electrodes to remove potassium ions by the cation exchange membrane 402. The tank temperature at this time was 19 degreeC.

Figure 2010142203
Figure 2010142203

その結果、表１に示すように、未濃縮の黒糖焼酎粕中からカリウムイオンが除去される際の電流効率が約１１％であったのに対し、ＴＳ＝１５％まで濃縮した場合、約３８％まで上昇し、濃縮によるカリウムイオンの除去効率の向上効果が確かめられた。   As a result, as shown in Table 1, the current efficiency when potassium ions were removed from unconcentrated brown sugar shochu was about 11%, whereas when concentrated to TS = 15%, about 38%. %, And the effect of improving potassium ion removal efficiency by concentration was confirmed.

本発明の一実施形態を示すフローシートFlow sheet showing an embodiment of the present invention 金属イオン除去装置の一例を示す図The figure which shows an example of a metal ion removal apparatus 金属イオン除去装置の他の一例を示す図The figure which shows another example of a metal ion removal apparatus 実施例に用いた金属イオン除去装置の試験装置を示す図The figure which shows the test apparatus of the metal ion removal apparatus used for the Example

符号の説明Explanation of symbols

１：貯留タンク
１０：攪拌機
２：固液分離装置
３：濃縮装置
４：金属イオン除去装置
４０：イオン透析槽
４１：陽極
４２：陰極
４３、４４：流路
４５：陽イオン交換膜
４６：陰イオン交換膜
４７：バイポーラプレート 1: Storage tank 10: Stirrer 2: Solid-liquid separation device 3: Concentration device 4: Metal ion removal device 40: Ion dialysis tank 41: Anode 42: Cathode 43, 44: Channel 45: Cation exchange membrane 46: Anion Exchange membrane 47: Bipolar plate

Claims (5)

発酵残渣を濃縮して発酵残渣濃縮液を生成する濃縮工程と、前記濃縮工程で得られた発酵残渣濃縮液側から陽イオン交換性の隔膜を介して一価陽イオンを透過、除去する金属イオン除去工程とを有することを特徴とする発酵残渣を用いた飼料もしくは肥料の製造方法。   A concentration step for concentrating the fermentation residue to produce a fermentation residue concentrate, and a metal ion that permeates and removes monovalent cations from the fermentation residue concentrate obtained in the concentration step through a cation-exchangeable membrane. A method for producing feed or fertilizer using a fermentation residue, comprising a removal step. 前記濃縮工程は、前記発酵残渣中の固形分を１５％以上に濃縮することを特徴とする請求項１記載の発酵残渣を用いた飼料もしくは肥料の製造方法。   The said concentration process concentrates solid content in the said fermentation residue to 15% or more, The manufacturing method of the feed or fertilizer using the fermentation residue of Claim 1 characterized by the above-mentioned. 前記金属イオン除去工程は、濃縮液室内に一価イオン交換性の隔膜を有するイオン透析槽を使用し、前記発酵残渣濃縮液を前記濃縮液室内に流通させることにより、前記一価陽イオンを透過、除去することを特徴とする請求項１又は２記載の発酵残渣を用いた飼料もしくは肥料の製造方法。   The metal ion removal step uses an ion dialysis tank having a monovalent ion-exchangeable diaphragm in the concentrate chamber, and allows the monovalent cation to permeate by circulating the fermentation residue concentrate in the concentrate chamber. The method for producing feed or fertilizer using the fermentation residue according to claim 1, wherein the fermentation residue is removed. 前記発酵残渣は、黒糖もしくは芋を原料とする焼酎粕であることを特徴とする請求項１、２又は３記載の発酵残渣を用いた飼料もしくは肥料の製造方法。   The method for producing feed or fertilizer using the fermentation residue according to claim 1, wherein the fermentation residue is shochu made from brown sugar or koji. 前記濃縮工程は、多重効用缶を用いて前記発酵残渣を濃縮することを特徴とする請求項１〜４のいずれかに記載の発酵残渣を用いた飼料もしくは肥料の製造方法。   The said concentration process concentrates the said fermentation residue using a multi-effect can, The manufacturing method of the feed or fertilizer using the fermentation residue in any one of Claims 1-4 characterized by the above-mentioned.
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JP2022125126A (en) * 2018-05-28 2022-08-26 ピアソン キャピタル エンバイロメンタル （ベイジン） リミテッド Efficient methods and compositions for recovery of products from organic acid pretreatment of plant materials

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JPH05285347A (en) * 1992-04-03 1993-11-02 Tokuyama Soda Co Ltd Production of acid and alkali
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