JP5314647B2 - Permeable electrochemical biobarrier and its use - Google Patents
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- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims description 32
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- HKZLPVFGJNLROG-UHFFFAOYSA-M silver monochloride Chemical compound [Cl-].[Ag+] HKZLPVFGJNLROG-UHFFFAOYSA-M 0.000 description 4
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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
- Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
- Y02W10/00—Technologies for wastewater treatment
- Y02W10/10—Biological treatment of water, waste water, or sewage
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- Purification Treatments By Anaerobic Or Anaerobic And Aerobic Bacteria Or Animals (AREA)
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Description
本発明は、透過性電気化学式バイオバリアに関し、特に、いかなる化学薬剤も添加する必要がなく、有機汚染物を効果的に分解して、地下水の汚染の拡散を回避する透過性電気化学式バイオバリアに関する。 The present invention relates to a permeable electrochemical biobarrier, and more particularly to a permeable electrochemical biobarrier that does not require the addition of any chemical agent and effectively decomposes organic contaminants to avoid the diffusion of groundwater contamination. .
いわゆるバイオバリアとは、汚染物が地下水の流れに伴って拡大するのを防止する方法の一つで、ガソリンスタンド、石油精錬所、さらに一部の石油化学工場区等に設置されて、有機汚染物に汚染された地下水が拡散するのを防止する。その使用方式は、汚染された地下水の下流に垂直方向にこの装置を設置することで機能する。 The so-called bio-barrier is one of the methods to prevent contaminants from expanding along with the flow of groundwater. It is installed at gas stations, oil refineries, and some petrochemical plant areas, etc. Prevent the diffusion of contaminated groundwater. Its usage works by installing this device vertically in the downstream of contaminated groundwater.
従来のバイオバリアは、透過性バイオバリアで、その原理は汚染物が前記透過性バイオバリアを流れて通過する時、前記透過性バイオバリアによって阻止され、さらに、物理方式(例、沈殿等)、化学方式(例、酸化、還元等)または生物方式(例、生物的分解作用等)によって汚染物を除去して、汚染された地下水の拡散を防止するものである。 A conventional biobarrier is a permeable biobarrier whose principle is that when contaminants flow through the permeable biobarrier, it is blocked by the permeable biobarrier, and further a physical method (e.g., precipitation, etc.), Contaminants are removed by chemical methods (eg, oxidation, reduction, etc.) or biological methods (eg, biodegradation, etc.) to prevent the diffusion of contaminated groundwater.
しかしながら、物理方式による場合、多くの例で効果が顕著でないという問題が存在する。汚染物の性質は様々に異なるため、全ての汚染物が同様の物理方式によって除去されるのは難しく、手間と物資を費やして残った汚染物を取り除く必要があるという問題があった。また、化学方式によるメカニズムは、有機汚染物を分解する際に反応剤を消耗し切ってしまうため、交換しなければならないという問題があった。そして、生物方式によって分解する場合では、充分な量の電子を受けなければならず、大量の動力を消費して充分な量を供給する必要がある。同時に、物質移動が不均衡であるという現象が発生しやすい。したがって、常に酸化剤(微生物の電子受容体)を補充または追加し続ける必要があり、このため、全体的なコストの増加を招くという問題があった。 However, in the case of using the physical method, there is a problem that the effect is not remarkable in many examples. Since the nature of the contaminants varies, it is difficult to remove all the contaminants by the same physical method, and there is a problem that it is necessary to remove the remaining contaminants by spending labor and materials. In addition, the chemical mechanism has a problem in that it must be replaced because the reactants are exhausted when the organic contaminants are decomposed. And when it decomposes | disassembles by a biological system, it must receive sufficient quantity of electrons, and it is necessary to consume sufficient power and supply sufficient quantity. At the same time, the phenomenon of mass transfer imbalance is likely to occur. Therefore, it is necessary to constantly replenish or add an oxidizing agent (microorganism electron acceptor), which causes an increase in overall cost.
本発明は上記問題点を解決すべくなされたもので、高表面積、高通透性の導電性繊維を利用してバイオバリアを構成し、関連する分解微生物の土壌微生物がバイオバリアに直接付着して生長し、適当な電圧を印加しさえすれば、微生物及び従来の酸化剤を使用することなく、持続的かつ効果的に有機汚染物を分解して地下水が汚染されるのを回避することのできる透過性電気化学式バイオバリアとその使用方法を提供することを目的とする。 The present invention has been made to solve the above-mentioned problems. A biobarrier is constructed using conductive fibers having a high surface area and high permeability, and soil microorganisms of related decomposing microorganisms directly adhere to the biobarrier. It can be sustained and effectively decompose organic pollutants to avoid contaminating groundwater without the use of microorganisms and conventional oxidants, as long as a suitable voltage is applied. It is an object of the present invention to provide a permeable electrochemical biobarrier that can be used and a method of using the same.
上記目的を達成するために、本発明に係る透過性電気化学式バイオバリアは、地中の地下水に含まれる有機汚染物の拡散を回避するものであって、地中の地下水の流れに対して直交直立させて設置されるところの適当な電圧が印加される少なくとも１個の導電性繊維層（すなわち生物陽極）と、前記導電性繊維層の隣辺に設置される少なくとも１個の陰極と、を備え、もって前記導電性繊維層に付着して成長する土壌微生物によって、前記地下水に含まれる有機汚染物質が分解されるように成したことを特徴とする。このうち、陰極は電荷全体のバランスを取るのに使用される。 In order to achieve the above object, the permeable electrochemical biobarrier according to the present invention avoids the diffusion of organic pollutants contained in the underground water, and is orthogonal to the underground water flow. At least one conductive fiber layer (that is, a biological anode) to which an appropriate voltage to be placed upright is applied, and at least one cathode installed on the adjacent side of the conductive fiber layer; The organic pollutants contained in the groundwater are decomposed by soil microorganisms that grow by adhering to the conductive fiber layer . Of these, the cathode is used to balance the overall charge.
好適な条件は、導電性繊維層が導電性炭繊維、金属繊維またはその組合せから成ることである。 A suitable condition is that the conductive fiber layer is made of conductive carbon fiber, metal fiber or a combination thereof.
さらに理想とする条件は、導電性炭繊維が、導電性活性炭繊維から成り、この導電性活性炭繊維の隣辺に陰極を設置することである。 Furthermore, the ideal condition is that the conductive carbon fiber is made of conductive activated carbon fiber, and a cathode is installed on the side adjacent to the conductive activated carbon fiber.
本発明はまた、透過性電気化学式バイオバリアの使用方法に関し、地中の地下水に含まれる有機汚染物の拡散を透過性電気化学式バイオバリアを使用して回避するものであって、地中の地下水の流れに対して直交直立させて設置されるところの少なくとも１個の導電性繊維層及び前記導電性繊維層の隣辺に設置される少なくとも１個の陰極とを備える透過性電気化学式バイオバリアを提供するステップと、前記透過性電気化学式バイオバリアに適当な電圧を印加するステップと、前記導電性繊維層に設置場所の土壌微生物を付着生長させるステップと、前記土壌微生物により前記有機汚染物質が分解されるステップと、を備えることを特徴とする。このうち、陰極は電荷全体のバランスを取るのに使用される。
The present invention also relates to a method of using a permeable electrochemical biobarrier, which uses a permeable electrochemical biobarrier to avoid the diffusion of organic contaminants contained in the underground groundwater. A permeable electrochemical biobarrier comprising at least one conductive fiber layer installed perpendicularly to the flow of the liquid and at least one cathode installed adjacent to the conductive fiber layer Providing, applying a suitable voltage to the permeable electrochemical biobarrier, attaching and growing soil microorganisms at the installation site on the conductive fiber layer, and decomposing the organic pollutants by the soil microorganisms. And comprising the steps of: Of these, the cathode is used to balance the overall charge.
上記使用方法において、好適な条件は、導電性繊維層が導電性炭繊維、金属繊維またはその組合せから成ることである。 In the above method of use, a preferable condition is that the conductive fiber layer is made of conductive carbon fiber, metal fiber, or a combination thereof.
さらに、上記使用方法において、理想の条件は、導電性炭繊維が、導電性活性炭繊維から成り、前記導電性活性炭繊維の隣辺には陰極を設置することである。 Furthermore, in the above method of use, the ideal condition is that the conductive carbon fiber is made of conductive activated carbon fiber, and a cathode is installed on the adjacent side of the conductive activated carbon fiber.
本発明によると、設置場所の土壌微生物が透過性電気化学式バイオバリア上に自然に付着して生長することを利用し、導電性繊維に適当な電圧を印加するだけで微生物の電子受容体となるため、いかなる化学酸化剤の添加も必要とせずに、効果的に有機汚染物の分解を行うことができる。したがって、コスト全体の削減が可能であると同時に、極めて高い地下水の汚染防止効果が期待できる。 According to the present invention, by utilizing the fact that soil microorganisms at the installation site naturally adhere to and grow on the permeable electrochemical biobarrier, it becomes an electron acceptor of microorganisms by simply applying an appropriate voltage to the conductive fibers. Therefore, organic contaminants can be effectively decomposed without the need to add any chemical oxidant. Therefore, it is possible to reduce the overall cost, and at the same time, it can be expected to have a very high groundwater contamination prevention effect.
以下に本発明の好適な実施例を図面に基づいて説明する。 Preferred embodiments of the present invention will be described below with reference to the drawings.
図１において、本発明の透過性電気化学式バイオバリアは、少なくとも１個の導電性繊維層及び少なくとも１個の陰極を備える。導電性繊維層は適当な電圧が印加される。導電性繊維層の材料は、導電性を有するものでさえあれば、特に制限されないが、好適なのは、導電性炭繊維、金属繊維またはその組合せである。本実施例においては、導電性炭繊維は導電性活性炭繊維であり、導電性繊維層は例えば、導電性活性炭繊維層１０で、透過性電気化学式バイオバリアは一層の導電性活性炭繊維層１０及び陰極２０を有する。このうち、導電性活性炭繊維層１０の好適な厚さは約15ｃｍ以内である。陰極２０の材料は、その他の金属材質の棒状物または網状物も可能で、前記導電性活性炭繊維層１０の隣辺に設置される。前記導電性繊維層１０(すなわち陽極)と陰極の設置距離は適当な距離で、好適なのは２０ｍより小さく、さらに理想的なのは1ｍより小さいものだが、ショート現象を回避するために、両極は直接接触してはならない。例えば、導電性活性炭繊維層１０（すなわち陽極）と陰極を海辺に設置する場合、海水の導電性が加わるため、両者の設置距離は２０ｍ離される。
In FIG. 1, the permeable electrochemical biobarrier of the present invention comprises at least one conductive fiber layer and at least one cathode. An appropriate voltage is applied to the conductive fiber layer. The material of the conductive fiber layer is not particularly limited as long as it has conductivity, but conductive carbon fiber, metal fiber, or a combination thereof is preferable. In this embodiment, the conductive carbon fiber is a conductive activated carbon fiber, the conductive fiber layer is, for example, the conductive activated
本発明の、導電性活性炭繊維層１０は、汚染地下水が流れる下流域(図中のＡが地下水の流れる方向を示す)に直立に設置される。さらに、その近隣側辺に陰極２０が設置される。関連する汚染物分解菌は、導電性活性炭繊維層１０の表面に設置場所の分解微生物が直接付着して生長するため、酸化剤を必要とせず、適当な電圧を印加するだけで、汚染物分解菌の生物反応によって発生する電子を導き出し、このバイオバリアの正常な機能を維持する。この場合の好適な電圧は、-10から10ボルトの電圧(参考電極はAg/AgCl)で、さらに理想とする電圧は-0.5から0.5ボルトの電圧（参考電極はAg/AgCl）である。例えば、適当な電圧を超して印加された場合、微生物内部の電子を取り出しすぎて、微生物が死亡したり、関連する汚染物代謝分解速度が遅くなったりする。
The conductive activated
次に、図２及び図３において、電極上の汚染物分解菌は、土壌中に既存する微生物３０である。電極に適当な電圧をかけると、陽極が微生物３０が有機物を分解する過程において受け続ける電子は、外部回路を経て陰極に伝達され、その後、陰極表面において還元反応(例えば、H2等を発生させる)を行なって、電荷全体のバランスを取り、汚染した地下水中の有機汚染物を導電性活性炭繊維１０に進入させた後(Ｂに示した有機汚染物分解の化学反応方向)、酸化剤を使用することなく、順調に微生物３０によって分解されて、二酸化炭素(CO2)を発生させる。
Next, in FIG.2 and FIG.3, the contaminant decomposing bacteria on an electrode are the
実験例１ 現地微生物の分解効果テスト(電極が電子を受ける場合)
本実験例は、ベンゼンを標的有機汚染物(濃度は約350 ppm)とし、汚染された土壌の複合微生物は植種菌源として、実験用フラスコの中で、分解及び生物電流発生テストを行い、電圧0.2 V vs. Ag/AgClを印加すると、実験の過程において、導電性活性炭繊維表面が徐々に生物膜に包まれるのが観察できる。
Experimental example 1 Degradation effect test of local microorganisms (when electrodes receive electrons)
In this experimental example, benzene is the target organic contaminant (concentration is about 350 ppm), the complex microorganisms in the contaminated soil are used as the inoculum, and decomposition and biocurrent generation tests are performed in a laboratory flask. When 0.2 V vs. Ag / AgCl is applied, it can be observed that the surface of the conductive activated carbon fiber is gradually enveloped in the biofilm during the course of the experiment.
ベンゼンの存在と生物電流の関連性は、図４に示したとおりである。実験初期に140 ppmのベンゼンを加えた時(図４の矢印aで示す)、瞬間電流の発生はない(ベンゼンは直接電極酸化されないことを意味する)。その後電流が徐々に上昇して最高値は100 μＡに達し、最後には300時間後に0 μＡに下がり、その後さらにベンゼンを加えた時(矢印b、c、d(濃度はそれぞれ約350 ppm))、明らかに電流反応現象が見られる。さらに、電流発生の時間が速ければ速いほど、実験全体が終了した後、電極上の生物膜を取り、微生物検証を行なう。分子生物学関連の測定実験を経て、若干の電気発生微生物が大量に培養されているのが明らかになる。各種の証拠により、ベンゼンは直接電極酸化されたのではなく、微生物酸化を通して電流が発生したことがわかる。 The relationship between the presence of benzene and the bioelectric current is as shown in FIG. When 140 ppm of benzene was added at the beginning of the experiment (indicated by arrow a in FIG. 4), there was no instantaneous current generation (meaning that benzene was not directly electrode oxidized). After that, the current gradually increases and reaches the maximum value of 100 μA. Finally, it decreases to 0 μA after 300 hours, and then benzene is added (arrows b, c, d (concentration is about 350 ppm each)) Obviously, a current reaction phenomenon is observed. In addition, the faster the current generation time, the more biofilm on the electrode is taken after the entire experiment is completed, and the microorganism is verified. Through molecular biology-related measurement experiments, it becomes clear that some electrogenic microorganisms are cultured in large quantities. Various evidences show that benzene was not directly electrode oxidized, but an electric current was generated through microbial oxidation.
同時に、上記実験に基づき、本発明のバイオバリア内の微生物は、約350 ppmのベンゼン濃度に適応して激増することが予想される。これは、本発明のフレキシブルな応用性を示すものである。 At the same time, based on the above experiments, the microorganisms in the biobarrier of the present invention are expected to increase dramatically to adapt to a benzene concentration of about 350 ppm. This shows the flexible applicability of the present invention.
実験例２ 透過性電気化学式バイオバリアの模擬土壌カラム検証実験
実験例２は、実験室中において、土壌カラムによって透過性電気化学式バイオバリアの模擬実験を行なったものである。本実施例における土壌カラムの長さは45 cm、内径3 cmで、一層の導電性活性炭繊維層(厚さ15cm)及びプラチナ(Pt)陰極を備え、前記陰極は、前記導電性活性炭繊維層隣側の距離5ｃｍの位置に設置される。実験は連続流方式で行なわれ、水力の停留時間は２日以内である。進流溶液中に含まれる模擬汚染物質は、ベンゼン(benzene)、トルエン(toluene)、エチルベンゼン(ethylbenzene)、キシレン(xylene) (略称BTEX)で、テスト濃度は、それぞれ19524、15383、14981、7257 ppb前後である。その進出流を取り、そのBTEX残量を測定する。結果はBTEXにおいていずれも99%以上の除去効率を有することを示しており、これは、本バイオバリアの優越性を示している。
Experimental Example 2 Permitted Electrochemical Biobarrier Simulated Soil Column Verification Experiment Experimental Example 2 is a permeable electrochemical biobarrier simulated experiment using a soil column in a laboratory. In this example, the soil column has a length of 45 cm and an inner diameter of 3 cm, and is provided with one conductive activated carbon fiber layer (thickness 15 cm) and a platinum (Pt) cathode, and the cathode is adjacent to the conductive activated carbon fiber layer. It is installed at a distance of 5cm on the side. The experiment is conducted in a continuous flow mode, and the hydropower stoppage time is within 2 days. The simulated contaminants contained in the advancing solution are benzene, toluene, ethylbenzene, xylene (abbreviated BTEX), and the test concentrations are 19524, 15383, 14981, and 7257 ppb, respectively. Before and after. Take the progress and measure the remaining BTEX. The results show that all BTEX has a removal efficiency of 99% or more, which indicates the superiority of this biobarrier.
以上２つの実験例により、本発明のバイオバリアの優れた効果を知ることができる。したがって、有機汚染物の汚染を受けた地下水下流の位置に本発明のバイオバリアを設置して適当な電圧を印加する(例えば10VAg/AgCl vs.より小さい)だけで、現地の土壌微生物の自然付着生長を利用して、透過性電気化学式バイオバリアに変化させることが可能である。したがって、本発明の操作時には、前記導電性活性炭繊維層に適当な電圧を印加するだけで、いかなる化学薬剤も必要とせずに、順調に有機汚染物を分解することができる。尚、本発明は以上の実施例に限定されるものではなく、本発明の要旨を逸脱しない範囲の設計変更は本発明の権利範囲に含まれる。
From the above two experimental examples, the excellent effect of the biobarrier of the present invention can be known. Therefore, by simply installing the biobarrier of the present invention at a position downstream of groundwater contaminated with organic pollutants and applying an appropriate voltage (for example, smaller than 10VAg / AgCl vs. ), natural adhesion of local soil microorganisms Growth can be transformed into a permeable electrochemical biobarrier. Therefore, during the operation of the present invention, organic contaminants can be decomposed smoothly without applying any chemical agent by simply applying an appropriate voltage to the conductive activated carbon fiber layer. It should be noted that the present invention is not limited to the above embodiments, and design changes within a scope not departing from the gist of the present invention are included in the scope of the right of the present invention.
以上、詳細に説明したように本発明によれば汚染された地下水の流路へ設置し、適当な電圧を印加するだけで、汚染物質を分解する土壌微生物（分解微生物）を受容し、この土壌微生物によって、汚染物質が分解されるので、設置コストとランニングコストの安価な環境汚染防止機器とその方法の分野で好適に用いられるものである。 As described above in detail, according to the present invention, soil microorganisms (decomposing microorganisms) that decompose pollutants can be received by simply installing the contaminated groundwater flow path and applying an appropriate voltage. Since the pollutant is decomposed by the microorganism, it is preferably used in the field of environmental pollution prevention equipment and its method with low installation cost and running cost.
１０ 導電性活性炭繊維層
２０ 陰極
３０ 微生物
Ａ 地下水の流れる方向
a〜d 矢印
Ｂ 有機汚染分解における化学反応方向
10 Conductive activated
a ~ d Arrow B Chemical reaction direction in organic pollution decomposition
Claims (6)
前記地下水の流れに対して直交直立させて設置されるところの適当な電圧が印加される少なくとも１個の導電性繊維層と、
前記導電性繊維層の隣辺に設置される陰極と、
を備え、もって前記導電性繊維層に付着して成長する土壌微生物によって、前記地下水に含まれる有機汚染物質が分解されるように成したことを特徴とする透過性電気化学式バイオバリア。 To avoid the diffusion of organic pollutants in underground groundwater,
At least one conductive fiber layer to which an appropriate voltage is applied that is installed perpendicularly to the groundwater flow; and
A cathode placed on the adjacent side of the conductive fiber layer;
A permeable electrochemical biobarrier characterized in that organic pollutants contained in the groundwater are decomposed by soil microorganisms that grow by adhering to the conductive fiber layer .
地中の地下水の流れに対して直交直立させて設置されるところの少なくとも１個の導電性繊維層及び前記導電性繊維層の隣辺に設置される少なくとも１個の陰極とを備える透過性電気化学式バイオバリアを提供するステップと、
前記透過性電気化学式バイオバリアに適当な電圧を印加するステップと、
前記導電性繊維層に設置場所の土壌微生物を付着生長させるステップと、
前記土壌微生物により前記有機汚染物質が分解させるステップと、
を備えることを特徴とする透過性電気化学式バイオバリアの使用方法。 The use of a permeable electrochemical biobarrier to avoid the diffusion of organic pollutants in underground groundwater,
A permeable electricity comprising at least one conductive fiber layer installed perpendicularly to the groundwater flow in the ground and at least one cathode installed adjacent to the conductive fiber layer Providing a chemical biobarrier; and
Applying an appropriate voltage to the permeable electrochemical biobarrier;
Attaching and growing soil microorganisms at the installation location on the conductive fiber layer;
Decomposing the organic pollutant by the soil microorganisms;
A method for using a permeable electrochemical biobarrier, comprising:
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