JP4890825B2 - Method for recovering valuable materials from fermentation broth - Google Patents

Method for recovering valuable materials from fermentation broth Download PDF

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JP4890825B2
JP4890825B2 JP2005276828A JP2005276828A JP4890825B2 JP 4890825 B2 JP4890825 B2 JP 4890825B2 JP 2005276828 A JP2005276828 A JP 2005276828A JP 2005276828 A JP2005276828 A JP 2005276828A JP 4890825 B2 JP4890825 B2 JP 4890825B2
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electrode
valuable
fermentation
fermentation broth
valuable material
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隆之 丸本
修 濱本
睦明 今岡
知樹 小林
俊一郎 西岡
学 大谷
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Mitsui Zosen Environment Engineering Corp
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Description

本発明は、発酵液からの有価物回収方法に関し、詳しくは発酵液から効率的に有価物を回収できる有価物回収方法に関する。   The present invention relates to a valuable material recovery method from a fermentation broth, and more particularly to a valuable resource recovery method capable of efficiently recovering a valuable resource from a fermentation broth.

従来、特許文献１には、発酵液から菌体を凝集分離して有価物を回収するに際し、高価な凝集剤であるキトサンの使用量を低減して経済的に有価物を回収する菌体の凝集分離法が開示されている。この特許文献１の技術は、発酵液にアミジン単位を有するカチオン性高分子凝集剤とキトサンを添加して発酵液中の菌体を凝集分離する方法である。   Conventionally, Patent Document 1 discloses a method of reducing the amount of chitosan that is an expensive flocculant and recovering valuable materials economically when aggregating and separating bacterial cells from a fermentation broth and recovering valuable materials. A coagulation separation method is disclosed. The technique of this patent document 1 is a method of adding a cationic polymer flocculant having an amidine unit and chitosan to a fermentation broth and aggregating and separating cells in the fermentation broth.

特許文献２、３には、発酵液を濃縮して、濃縮液を膜分離によって菌体と有価物に分離し、膜を透過した有価物を回収する方法が開示されている。
特開２００１−１７８４９５号公報 特開平１１−１６９６７１号公報 特開２０００−２１００７２号公報 Patent Documents 2 and 3 disclose a method of concentrating a fermentation broth, separating the concentrated solution into cells and valuables by membrane separation, and recovering valuables that have permeated the membrane.
JP 2001-178495 A JP-A-11-169671 JP 2000-210072

特許文献１に記載の技術は、キトサンの使用量は減るが、高分子凝集剤の使用量は増加するので、結局、凝集剤のコストがかかり、また凝集分離では有価物に反応する凝集剤が限定され、汎用性がない欠点がある。   The technique described in Patent Document 1 reduces the amount of chitosan used, but increases the amount of polymer flocculant used. As a result, the cost of the flocculant is increased, and the flocculant that reacts with valuable substances in the flocculent separation is used. There are drawbacks that are limited and not versatile.

また、有価物回収においては無薬注で行うことが重要であり、有価物中に凝集剤成分を取込むことは好ましくない。   Further, it is important to carry out no chemical injection in the collection of valuable materials, and it is not preferable to incorporate the flocculant component into the valuable materials.

特許文献２、３に記載の技術は、膜分離法であり、以下のような問題がある。一般に、膜分離法は、発酵液を膜で処理するプロセスは有価物回収だけでなく、発酵液（消化液）の処理（下水道や河川放流のための処理）プロセスとしても有効と考えられている。しかし、膜は発酵液に対して、一般に極めて目詰まりを起こしやすく、この点を解決しなければ実用的なプロセスにはならない。この傾向はイオン透析膜、微多孔膜ともに同じである。実際に膜処理装置を組み込んだメタン発酵プロセスが稼動しているが、これは単に固形物をある程度分離する程度の機能しかなく、有価物を回収するという機能までは有していない。むしろ、この膜処理の後段に本発明による有価物回収プロセスを置くことによって、従来からの固形物除去が行えて、有価物回収効率を向上することが可能になる。   The techniques described in Patent Documents 2 and 3 are membrane separation methods and have the following problems. In general, the membrane separation method is considered to be effective not only for recovering valuable materials but also for treating fermented liquor (digested liquid) (processing for sewers and river discharge) as a process for treating the fermented liquor with a membrane. . However, the membrane is generally very clogged with respect to the fermented liquid, and unless this point is solved, it will not be a practical process. This tendency is the same for both ion dialysis membranes and microporous membranes. A methane fermentation process incorporating a membrane treatment apparatus is actually in operation, but this has only a function of separating solids to some extent and does not have a function of recovering valuable materials. Rather, by placing the valuable resource recovery process according to the present invention at the subsequent stage of the membrane treatment, it is possible to remove the solid matter from the prior art and improve the valuable resource recovery efficiency.

また有価物の回収法で、発酵液を活性炭層やイオン交換樹脂層を通して有価物を回収する吸着法もあるが、共存する固形物や無機イオン等のため、これら吸着法の効率は一般に大きく低下する。例えば、麦焼酎粕からの陰イオン交換樹脂によるクエン酸回収率は、通常５０％を大きく下回る。この原因は共存するより低分子の有機酸（これらは有価物として価値は小さい。）によるものである。メタン発酵液の場合は酢酸や蟻酸が優先的に吸着されて、微量の有価物回収には繋がらない。   There is also an adsorption method that recovers valuable materials through the activated carbon layer or ion-exchange resin layer as a valuable material recovery method, but the efficiency of these adsorption methods is generally greatly reduced due to coexisting solids and inorganic ions. To do. For example, the citric acid recovery rate from an anion exchange resin from wheat shochu is usually well below 50%. This is due to the coexistence of lower molecular organic acids (these are less valuable as valuables). In the case of methane fermentation broth, acetic acid and formic acid are preferentially adsorbed, which does not lead to the recovery of trace amounts of valuable resources.

そこで、本発明は、発酵液から効率的に且つ経済的に有価物を回収できる実用的な発酵液からの有価物回収方法を提供することを課題とする。   Then, this invention makes it a subject to provide the valuable material collection | recovery method from a fermented liquid which can collect | recover valuables efficiently from a fermented liquid economically.

本発明の他の課題は、以下の記載によって明らかとなる。   The other subject of this invention becomes clear by 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）
焼酎発酵蒸留残渣からなる発酵後の懸濁液を電解槽に導入する工程と、該電解槽の電極上に有価物として多価カルボン酸、多価フェノール、アミノ酸の少なくとも一種を析出する電着工程と、該電極上に析出した有価物を分離する分離工程を有することを特徴とする発酵液からの有価物回収方法。
（請求項２）
メタン発酵消化液からなる発酵後の懸濁液を電解槽に導入する工程と、該電解槽の電極上に有価物としてアミノ酸、多価カルボン酸の少なくとも一種を析出する電着工程と、該電極上に析出した有価物を分離する分離工程を有することを特徴とする発酵液からの有価物回収方法。 (Claim 1)
A step of introducing a suspension after fermentation consisting of a shochu fermentation fermentation residue into an electrolytic cell, and an electrodeposition step of depositing at least one of a polyvalent carboxylic acid, a polyhydric phenol, and an amino acid as a valuable material on the electrode of the electrolytic cell And a method for recovering valuable materials from a fermentation broth, comprising a separation step of separating valuable materials deposited on the electrode.
(Claim 2)
A step of introducing a suspension after fermentation consisting of a methane fermentation digestive liquid into an electrolytic cell, an electrodeposition step of depositing at least one of amino acids and polyvalent carboxylic acids as valuable substances on the electrode of the electrolytic cell, and the electrode A method for recovering a valuable material from a fermentation broth, comprising a separation step of separating the valuable material deposited thereon.

（請求項３）
前記電極表面の少なくとも一部が、銀からなることを特徴とする請求項１又は２記載の発酵液からの有価物回収方法。ここで、電極表面の少なくとも一部というのは、不活性もしくは貴金属成分上に銀が塗布あるいはメッキされている状態であり、実プラントにおける電極は、このような銀被膜電極が用いられる。 (Claim 3 )
3. The valuable material recovery method from a fermentation broth according to claim 1, wherein at least a part of the electrode surface is made of silver. Here, at least a part of the electrode surface is a state in which silver is coated or plated on an inert or noble metal component, and such a silver-coated electrode is used as an electrode in an actual plant.

（請求項４）
前記分離工程で分離された有価物を精製する精製工程を有することを特徴とする請求項１〜３の何れかに記載の発酵液からの有価物回収方法。 (Claim 4 )
The method for recovering a valuable material from a fermentation broth according to any one of claims 1 to 3, further comprising a purification step of refining the valuable material separated in the separation step.

（請求項５）
前記電極上に析出した有価物を分離する工程が、該電極の極性を電着時と逆転させることを特徴とする請求項１〜４の何れかに記載の発酵液からの有価物回収方法。 (Claim 5 )
The method for recovering a valuable material from a fermentation broth according to any one of claims 1 to 4 , wherein the step of separating the valuable material deposited on the electrode reverses the polarity of the electrode with that during electrodeposition.

本発明によれば、発酵液から効率的に且つ経済的に有価物を回収できる実用的な発酵液からの有価物回収方法を提供することができる。具体的には、電極電位と溶出液の組成によって回収する物質の範囲を選択できる効果がある。   ADVANTAGE OF THE INVENTION According to this invention, the valuable material collection | recovery method from a practical fermented liquid which can collect | recover valuables efficiently and economically from a fermented liquid can be provided. Specifically, there is an effect that the range of substances to be recovered can be selected according to the electrode potential and the composition of the eluate.

以下、本発明の実施の形態を図面に基づいて説明する。   Hereinafter, embodiments of the present invention will be described with reference to the drawings.

図１は本発明の回収方法を実施する装置の一例を示す説明図であり、図に示す装置は電極の電位を例えば反転させて電着と溶出を交互に行うバッチ式（回分式）の回収プロセスを示している。   FIG. 1 is an explanatory view showing an example of an apparatus for carrying out the recovery method of the present invention. The apparatus shown in FIG. 1 is a batch type (batch type) recovery in which the electrode potential is inverted, for example, and electrodeposition and elution are alternately performed. Shows the process.

同図において、１は発酵液導入管であり、２は電解槽である。   In the same figure, 1 is a fermented liquid introduction pipe | tube and 2 is an electrolytic cell.

電解槽２の内部には、電着用電極２０と対極２１を備え、両電極２０、２１の間には必要により隔膜２２が設けられている。２３は回収処理後の発酵液を取り出す排出管である。   Inside the electrolytic cell 2, an electrodeposition electrode 20 and a counter electrode 21 are provided, and a diaphragm 22 is provided between the electrodes 20 and 21 as necessary. 23 is a discharge pipe which takes out the fermented liquor after collection processing.

電着用電極２０に電着された有価物は電極の反転やアルカリ洗浄により、電着された有価物を分離する。分離された電着物は溶出液として外部に取り出されて精製手段で精製される。   The valuables electrodeposited on the electrodeposition electrode 20 are separated by reversing the electrodes or washing with alkali. The separated electrodeposit is taken out as an eluate and purified by a purification means.

図示の例では、有価物を溶出した溶出液は溶出液配管２４を介してタンク２５に貯留され、溶出液ポンプ２６により、図示しない精製手段に輸送される。なお溶出液の一部は溶出液ポンプ２６により電解槽２に返送することができる。   In the illustrated example, the eluate from which valuables have been eluted is stored in the tank 25 via the eluent pipe 24 and is transported to the purification means (not shown) by the eluate pump 26. A part of the eluate can be returned to the electrolytic cell 2 by the eluent pump 26.

本発明において、電着用の電極は、電解液流通型電解槽中の固定極あるいは流動床式の電極、または攪拌式電極（槽内で回転することによって攪拌する形式の電極）などが挙げられる。   In the present invention, examples of the electrodeposition electrode include a fixed electrode or a fluidized bed type electrode in an electrolytic solution flow type electrolytic cell, or an agitation type electrode (an electrode that is agitated by rotating in the cell).

電極の形状としては、平板タイプ、波板タイプ、メッシュタイプなどのほか、流動床式では、球状や導電性活性炭などの形状が挙げられる。   Examples of the shape of the electrode include a flat plate type, a corrugated plate type, and a mesh type, and in the fluidized bed type, there are shapes such as a spherical shape and conductive activated carbon.

対極は、隔膜を挟んで、作用極に対峙させるものや、あるいは無隔膜式のものが挙げられる。電流効率を重視しなくても良い場合は無隔膜式でも十分である。この無隔膜式の場合には膜の目詰まりの問題が回避できる効果がある。図２には無隔膜式の例が示されている。   Examples of the counter electrode include those facing the working electrode with the diaphragm interposed therebetween, and those having no diaphragm. In the case where current efficiency is not important, a diaphragm type is sufficient. In the case of this diaphragm type, there is an effect that the problem of clogging of the membrane can be avoided. FIG. 2 shows an example of a diaphragm type.

この電極系の少なくとも作用極側に発酵液を導入し、有価物を含む固形物を電極上に析出させて回収する。   Fermentation liquid is introduced into at least the working electrode side of this electrode system, and solids containing valuables are deposited on the electrode and collected.

次に、有価物の精製・回収法例について説明すると、電着させた有価物を含む固形分を、まず、加温下で水酸化ナトリウム水溶液などのアルカリで洗浄して、溶出成分を液側に溶解する。これを中和した後、温度を下げて、有価物を析出させて回収する。   Next, an example of a method for purifying and recovering valuable materials will be described. First, the solid content containing the electrodeposited valuable materials is washed with an alkali such as an aqueous sodium hydroxide solution under heating to bring the eluted components to the liquid side. Dissolve. After neutralizing this, the temperature is lowered, and valuables are deposited and recovered.

回収目的物質に合わせて酸濃度を調整することにより、析出し易さを調節することができ好ましい。さらに溶解・析出を繰り返して、精製度を向上させることなどが可能である。   By adjusting the acid concentration according to the substance to be collected, the easiness of precipitation can be adjusted, which is preferable. Furthermore, it is possible to improve the degree of purification by repeating dissolution and precipitation.

次に、電極への有価物析出例のメカニズムについて説明する。   Next, the mechanism of an example of valuable material deposition on the electrode will be described.

発酵液中の有価物としての有機酸（カルボン酸、オキシカルボン酸、アミノカルボン酸などのカルボン酸；フルボ酸、フミン酸類を含む多価カルボン酸類；フェノール類、多価フェノール類など）は、一般に酸性が強くなるほど溶解性が低減する。   Organic acids (carboxylic acids such as carboxylic acids, oxycarboxylic acids, and aminocarboxylic acids; polycarboxylic acids including fulvic acids and humic acids; phenols, polyhydric phenols, etc.) as valuable substances in the fermentation liquid are generally used. As the acidity increases, the solubility decreases.

電解槽２内の陽極側で酸素発生反応を行う場合、陽極周辺では水酸イオン濃度が低下してｐＨ値が低下する。その結果として、有機酸類の溶解性が低下して、電極面を中心に析出する。これを極性反転やアルカリ洗浄することによって、有機酸類を濃縮液として回収することができる。これをさらに晶析法などによって精製し有価物を回収する。   When the oxygen generation reaction is performed on the anode side in the electrolytic cell 2, the hydroxide ion concentration is lowered and the pH value is lowered around the anode. As a result, the solubility of the organic acids is reduced and precipitates around the electrode surface. By subjecting this to polarity reversal or alkali cleaning, the organic acids can be recovered as a concentrate. This is further purified by a crystallization method or the like to recover valuable materials.

また、銀電極を用いる場合は、電極を若干卑の領域（例えば、＋０.２ＶｖｓＡｇ／ＡｇＣｌ：銀塩化銀基準で＋０．２Ｖ）に維持して有機酸を接触させると、有機酸銀として電極表面に有機酸が析出する。これも極性反転して有機酸を溶出させて、濃縮液を回収することが可能である。   In addition, when a silver electrode is used, if the electrode is kept in a slightly base region (for example, +0.2 V vs Ag / AgCl: +0.2 V on the basis of silver chloride), the surface of the electrode is converted into organic acid silver. An organic acid is deposited on the surface. It is also possible to reverse the polarity to elute the organic acid and recover the concentrated solution.

銅電極も同様の挙動を示し、食品分野などで銅イオンによる汚染が問題になる場合以外は使用できる。   The copper electrode also exhibits the same behavior and can be used except when contamination by copper ions is a problem in the food field.

本発明において、有価物は、次のものが挙げられる。焼酎粕（蒸留残渣）中のクエン酸、りんご酸、コハク酸、乳酸等のほか、アミノ酸としてアルギニン、アスパラギン酸、グルタミン酸など、さらにポリフェノール、ピロガロールなど。食品残渣メタン発酵消化液中のクエン酸等のオキシカルボン酸類、トリプトファン等のアミノ酸類など。   In the present invention, valuable materials include the following. In addition to citric acid, malic acid, succinic acid, lactic acid, etc. in shochu (distilled residue), amino acids such as arginine, aspartic acid, glutamic acid, and polyphenols, pyrogallol, etc. Food residues: Oxycarboxylic acids such as citric acid and amino acids such as tryptophan in methane fermentation digestive fluid.

以上、本発明に関して電着法による有価物回収方法について説明したが、上述したように電極の電位を反転させて電着と溶出とを交互に行うことにより有価物を回収してもよいし、また反転によって電着と溶出とを交互に行うに際して、溶出液としてアルカリ水溶液を使用することは好ましい態様である。更に電着と溶出とを交互に行うに際して、反転させずにアルカリ洗浄のみで溶出させることも可能である。   As described above, the valuable material recovery method by the electrodeposition method has been described in relation to the present invention, but the valuable material may be recovered by alternately performing electrodeposition and elution by inverting the potential of the electrode as described above, Moreover, when performing electrodeposition and elution alternately by inversion, it is a preferable aspect to use alkaline aqueous solution as an eluent. Further, when electrodeposition and elution are performed alternately, elution can be performed only by alkali washing without inversion.

この方法では、電極電位と溶出液の組成によって回収する物質の範囲を選択できる効果がある。また共析法によって多価アルコールの回収なども行える効果もある。   This method has an effect that the range of substances to be recovered can be selected according to the electrode potential and the composition of the eluate. There is also an effect that polyhydric alcohol can be recovered by a eutectoid method.

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.

実施例１
白金コーティングチタン網状電極（エックスパンドチタンメタル）に銀を無電解メッキした作用極（２００ｍｍ×３００ｍｍ、単セル）、隔膜として微多孔膜（ＭＦ膜、ユアサコーポレーション社製ユミクロン膜、２００ｍｍ×３００ｍｍ）、対極として白金コーティングチタン網状電極（２００ｍｍ×３００ｍｍ）で構成した液流通型電解槽（作用極室厚さ７ｍｍ）を図１の様に構成し、麦焼酎粕からの有価物回収を行った。 Example 1
A working electrode (200 mm × 300 mm, single cell) obtained by electrolessly plating silver on a platinum-coated titanium mesh electrode (expanded titanium metal), a microporous membrane (MF membrane, Yumicron manufactured by Yuasa Corporation, 200 mm × 300 mm) as a diaphragm, A liquid flow electrolytic cell (working electrode chamber thickness: 7 mm) composed of a platinum-coated titanium mesh electrode (200 mm × 300 mm) as a counter electrode was constructed as shown in FIG. 1 to recover valuable materials from wheat shochu.

電解槽への焼酎粕流通量を毎分１Ｌ（対極室には焼酎粕液を充填）とし、約５０℃にて作用極を陽極とする０．５Ａの通電を行った。２０分後、作用極から液を排除して、溶出液として、ｐＨ６〜８の炭酸ナトリウム水溶液を流通させた。このとき、極性を反転させて、０．２Ａの通電を５分間行った。この回収操作によって得られたクエン酸量は約１３０ｇであり、原液から定量したクエン酸量の約８０％を回収した。   A flow rate of cauterization to the electrolytic cell was 1 liter per minute (the counter electrode chamber was filled with a cautery solution), and 0.5 A energization was performed at about 50 ° C. with the working electrode as the anode. After 20 minutes, the solution was removed from the working electrode, and an aqueous sodium carbonate solution having a pH of 6 to 8 was circulated as an eluent. At this time, the polarity was reversed and a current of 0.2 A was applied for 5 minutes. The amount of citric acid obtained by this recovery operation was about 130 g, and about 80% of the amount of citric acid determined from the stock solution was recovered.

実施例２
上記電解槽の作用極を銅板にして、下記サンプル中の有価物回収を試みた。 Example 2
Using the working electrode of the electrolytic cell as a copper plate, recovery of valuable materials in the following samples was attempted.

（１）サンプルは以下の３種を用意して用いた。
サンプル１：麦焼酎粕にクエン酸を含有する
サンプル２：麦焼酎粕にピロガロールを含有する
サンプル３：メタン消化液に酒石酸を含有する (1) The following three types of samples were prepared and used.
Sample 1: Citric acid in wheat shochu Sample 2: Pyrogallol in wheat shochu Sample 3: Tartaric acid in methane digestive fluid

（２）電着条件は約７Ｖ，０．１ｍＡ／ｃｍ２以下とした。 (2) The electrodeposition conditions were about 7 V and 0.1 mA / cm 2 or less.

（３）分離工程
電圧反転させ、希アンモニア溶液で分離された有価物を溶出した。 (3) Separation process The voltage was inverted, and valuables separated with dilute ammonia solution were eluted.

（４）回収確認法
サンプル１：硝酸銀水溶液の還元（加熱）によってクエン酸を確認した。
サンプル２：溶出液の１９０ｎｍ吸収ピークでピロガロールの回収を確認した。
サンプル３：硝酸銀水溶液の還元によって酒石酸を確認した。 (4) Recovery confirmation method Sample 1: Citric acid was confirmed by reduction (heating) of an aqueous silver nitrate solution.
Sample 2: Recovery of pyrogallol was confirmed at the 190 nm absorption peak of the eluate.
Sample 3: Tartaric acid was confirmed by reduction of an aqueous silver nitrate solution.

（５）結果
サンプル１、２、３の各々について、有価物であるクエン酸、ピロガロール、酒石酸の回収を確認できた。 (5) Results For each of Samples 1, 2, and 3, recovery of valuable citric acid, pyrogallol, and tartaric acid was confirmed.

本発明の回収方法を実施する装置の一例を示す説明図Explanatory drawing which shows an example of the apparatus which enforces the collection | recovery method of this invention 本発明の回収方法を実施する装置の他の例を示す説明図Explanatory drawing which shows the other example of the apparatus which enforces the collection | recovery method of this invention

符号の説明Explanation of symbols

１：発酵液導入管
２：電解槽
２０：電着用電極
２１：対極
２２：隔膜
２３：排出管
２４：溶出液配管
２５：タンク
２６：溶出液ポンプ 1: Fermentation liquid introduction pipe 2: Electrolysis tank 20: Electrodeposition electrode 21: Counter electrode 22: Diaphragm 23: Discharge pipe 24: Eluate pipe 25: Tank 26: Eluate pump

Claims (5)

焼酎発酵蒸留残渣からなる発酵後の懸濁液を電解槽に導入する工程と、該電解槽の電極上に有価物として多価カルボン酸、多価フェノール、アミノ酸の少なくとも一種を析出する電着工程と、該電極上に析出した有価物を分離する分離工程を有することを特徴とする発酵液からの有価物回収方法。 A step of introducing a suspension after fermentation consisting of a shochu fermentation fermentation residue into an electrolytic cell, and an electrodeposition step of depositing at least one of a polyvalent carboxylic acid, a polyhydric phenol, and an amino acid as a valuable material on the electrode of the electrolytic cell And a method for recovering valuable materials from a fermentation broth, comprising a separation step of separating valuable materials deposited on the electrode. メタン発酵消化液からなる発酵後の懸濁液を電解槽に導入する工程と、該電解槽の電極上に有価物としてアミノ酸、多価カルボン酸の少なくとも一種を析出する電着工程と、該電極上に析出した有価物を分離する分離工程を有することを特徴とする発酵液からの有価物回収方法。 A step of introducing a suspension after fermentation consisting of a methane fermentation digestive liquid into an electrolytic cell, an electrodeposition step of depositing at least one of amino acids and polyvalent carboxylic acids as valuable substances on the electrode of the electrolytic cell, and the electrode A method for recovering a valuable material from a fermentation broth, comprising a separation step of separating the valuable material deposited thereon. 前記電極表面の少なくとも一部が、銀からなることを特徴とする請求項１又は２記載の発酵液からの有価物回収方法。 3. The valuable material recovery method from a fermentation broth according to claim 1, wherein at least a part of the electrode surface is made of silver. 前記分離工程で分離された有価物を精製する精製工程を有することを特徴とする請求項１〜３の何れかに記載の発酵液からの有価物回収方法。 The method for recovering a valuable material from a fermentation broth according to any one of claims 1 to 3, further comprising a purification step of refining the valuable material separated in the separation step. 前記電極上に析出した有価物を分離する工程が、該電極の極性を電着時と逆転させることを特徴とする請求項１〜４の何れかに記載の発酵液からの有価物回収方法。 The method for recovering a valuable material from a fermentation broth according to any one of claims 1 to 4 , wherein the step of separating the valuable material deposited on the electrode reverses the polarity of the electrode with that during electrodeposition.
JP2005276828A 2005-09-22 2005-09-22 Method for recovering valuable materials from fermentation broth Expired - Fee Related JP4890825B2 (en)

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