CN105555715A - 具有去除多价离子的功能的生物电化学系统 - Google Patents

具有去除多价离子的功能的生物电化学系统 Download PDF

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Publication number
CN105555715A
CN105555715A CN201480032301.0A CN201480032301A CN105555715A CN 105555715 A CN105555715 A CN 105555715A CN 201480032301 A CN201480032301 A CN 201480032301A CN 105555715 A CN105555715 A CN 105555715A
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China
Prior art keywords
electrode groove
bioelectrochemical system
anode
electronics
seawater
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Inventor
南珠妍
朴淳哲
金东国
丁湳条
金灿洙
金大熙
黄教植
朴铁镐
左银珍
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KOREA ENERGY TECHNOLOGY INST
Korea Institute of Energy Research KIER
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KOREA ENERGY TECHNOLOGY INST
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Priority claimed from KR1020130065347A external-priority patent/KR101576213B1/ko
Priority claimed from KR1020140026874A external-priority patent/KR101582476B1/ko
Application filed by KOREA ENERGY TECHNOLOGY INST filed Critical KOREA ENERGY TECHNOLOGY INST
Publication of CN105555715A publication Critical patent/CN105555715A/zh
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Abstract

本发明提供一种生物电化学系统，所述生物电化学系统能够去除海水等中存在的多价离子且能够实现电生产。根据本发明的生物电化学系统包括：氧化电极槽，其包括容纳电子的阳极，所述电子为用微生物处理废水中的有机物时所产生的电子；还原电极槽，其包括从所述阳极接收电子的阴极，并且使所述电子与从外部供应的氧和水进行反应，从而生成氢氧化离子，并通过所述氢氧化离子使电解质中的多价离子沉淀；以及阴离子交换膜，其阻止所述电解质中的多价离子向所述氧化电极槽移动。另外，本发明提供一种生物电化学系统，所述生物电化学系统在去除海水等中存在的多价离子的同时，能够生产氢。所述生物电化学系统的特征在于，包括氧化电极槽，其具备附着有电化学活性菌的阳极，并且有机性废水作为基质被注入，从而生成电子；还原电极槽，其具备阴极，并且海水作为电解质被注入，从而在去除多价离子的同时生产氢气；阴离子交换膜，其分离所述氧化电极槽和所述还原电极槽，并且防止所述海水中的多价阳离子向所述氧化电极槽移动；以及电源，其连接于所述阳极和所述阴极之间。

Description

具有去除多价离子的功能的生物电化学系统
技术领域
本发明涉及一种生物电化学系统，更详细地，涉及一种能够去除海水等中存在的多价离子的生物电化学系统。
背景技术
使海水淡水化的方式中，作为膜分离法有反渗透法(ReverseOsmosis：RO)、电渗析法(Electrodialysis：ED)及正渗透法(ForwardOsmosis：FO)等。在膜分离法中，为了延长膜的寿命，并持续维持工序的性能，需要解决因盐类化合物的结晶而在膜的表面形成水垢的问题。因此，在膜分离法中，必须进行用于去除水垢成分的海水预处理。
在海水成分中诱发水垢的物质是一种因浓缩和pH值的变化而在膜表面析出，从而损伤膜的功能的物质。这种物质有碳酸钙(CaCO3)、硫酸钙(CaSO4)、碳酸镁(MgCO3)及硫酸镁(MgSO4)等。为了去除这种诱发水垢的物质而主要使用的使海水淡水化的预处理工序有化学药品投入法和膜分离法(MF、UF)等。化学药品投入法是一种为了防止水垢的析出而在海水中投入阻垢剂(antiscalant)或用于维持低pH的酸(acid)的方法。膜分离法是一种使用微孔滤膜(Microfiltrationmembrane)或超滤膜(Ultrafiltrationmembrane)，从而在淡水化工序的前步骤中去除诱发水垢的离子的方法，但会存在淡水化工序中发生的生成水垢问题会转变成预处理膜工序的问题的局限性。
另外，微生物燃料电池(Microbialfuelcell：MFC)和微生物电解槽(MicrobialElectrolysisCell：MEC)作为生物电化学系统(Bioelectrochemicalsystem：BES)，是一种利用电化学活性菌(Electrochemicallyactivebacteria)进行废水处理的同时，生成电或氢气的装置。微生物燃料电池可以由两个反应槽，即，氧化电极槽(anodechamber)和还原电极槽(cathodechamber)构成，并且两个反应槽被离子交换膜(ionexchangemembrane)分离开。在阳极中，当葡萄糖为基质时所产生的代表性的反应如化学式1所示。在需氧性条件的阴极中产生的代表性的反应如化学式2所示。在氧化电极槽中，有机物被处理，同时生产出电能，并且在还原电极槽中，持续生成OH-，从而溶液的pH会上升。
[化学式1]
C6H12O6+6H2→6CO2+24H++24e-
[化学式2]
O2+4e-+2H2O→4OH-
另一方面，微生物电解槽是一种虽然与微生物燃料电池的结构相似，但是在还原电极槽中不存在氧，并且通过施加一些电能，从而能够生产氢气的装置。在阴极中产生氢气，进而pH会持续上升。与其相关的反应式如化学式3所示。
[化学式3]
2H2O+2e-→H2↑+2OH-
海水因包含大量的离子而导电率高，因此能够在电化学系统中作为电解质使用。当在所述的生物电化学系统的还原电极槽中注入海水时，因微生物燃料电池和微生物电解槽的还原反应而生成电或氢气，并且形成碱，从而能够使海水中的多价阳离子以CaCO3或Mg(OH)2的形态沉淀。通常，以废水处理、电生产及氢气生产作为目的而使用生物电化学系统，但是并没有用于去除包含在海水等中的多价离子的实例。
发明内容
要解决的技术问题
因此，本发明的目的在于，利用微生物和电化学反应来去除海水中的多价离子而不使用投入化学药品或采用附加的分离膜的方法。
另外，本发明的另一目的在于，在去除海水内的多价离子的同时，还对包含有机物的废水进行处理，从而生产电流。
另外，本发明的又一目的在于，在去除海水内的多价离子的同时，对包含有机物的废水进行处理，从而以少的能量生产氢气。
本发明的目的并不限定于上述提及的目的，而可以通过下述的说明来理解没有提及的本发明的其它目的及优点，并通过本发明的实施例而更加明确了解。另外，容易知道本发明的目的及优点可以通过权利要求书中示出的手段及其组合来实现。
技术方案
为了实现上述目的本发明的一特征为，一种能够生产电且去除多价离子的生物电化学系统，所述生物电化学系统包括：氧化电极槽，其包括容纳电子的阳极，所述电子为用微生物处理废水中的有机物时所产生的电子；还原电极槽，其包包括从所述阳极接收电子的阴极，并且使所述电子与从外部供应的氧和水进行反应，从而生成氢氧化离子，并通过所述氢氧化离子使电解质中的多价离子沉淀；以及阴离子交换膜，其阻止所述电解质中的多价阳离子向所述氧化电极槽移动。
优选地，微生物是一种将包含有机物的废水、厌氧性消化流出液、城市污水、工业废水及酸发酵液中的至少一种作为基质利用的电化学活性菌。为了维持电化学活性菌的活性，所述氧化电极槽的pH为中性，并且温度为20℃以上且小于100℃。另外，当所述氧化电极槽的pH小于中性时，所述还原电极槽的沉淀物或化学药品投入到所述氧化电极槽中。阳极为石墨(graphite)或碳(carbon)材料的刷子(brush)或毡子(felt)的形态，阴极包含铂催化剂或代替铂的催化剂。阴极可以为空气阴极(air-cathode)。
另外，本发明的另一特征为，一种利用微生物且能够生产氢气的生物电化学系统，所述生物电化学系统包括：氧化电极槽，其具备附着有电化学活性菌的阳极，并且有机性废水作为基质被注入，从而生成电子；还原电极槽，其具备阴极，并且海水作为电解质被注入，从而生产氢气；阴离子交换膜，其分离所述氧化电极槽和所述还原电极槽，并且防止所述海水中的多价阳离子向所述氧化电极槽移动；以及电源，其连接于所述阳极和所述阴极之间。为了生成氢气，利用直流电源(DCpowersupply)来施加最小为0.3V以上的电压，以使阴极的电势比阳极的电势低，从而能够生产氢气。
优选地，还原电极槽利用通过还原反应生成的OH-离子来使所述海水内的多价阳离子沉淀，从而生成沉淀物。多价阳离子为Ca2+或Mg2+。另外，可以进一步包括将所述还原电极槽的沉淀物或流出水的一部分向所述氧化电极槽移送的工具()。氧化电极槽和还原电极槽均为厌氧性状态。可以具有多个所述阳极。另外，可以进一步包括测定所述有机性废水中的有机物浓度的传感器。
有益效果
如上所述的本发明具有以低的能量以及不需要注入化学药品就能去除作为水垢诱发物质的海水中的多价离子的效果。另外，根据本发明，微生物燃料电池能够去除海水中的多价离子的同时，还能够通过微生物来实现废水处理和电能生产。另外，根据本发明，微生物电解槽能够去除海水内的多价离子的同时，还能够通过微生物来处理废水，从而实现利用少的能量来生产氢气。
附图说明
图1为根据本发明一实施例中作为生物电化学系统的微生物燃料电池的结构图。
图2为表示在图1中示出的微生物燃料电池中进行多价离子去除实验的结果的图表。
图3为根据本发明另一实施例中作为生物电化学系统的微生物电解槽的结构图。
附图标记说明
10：氧化电极槽11：阳极
12：微生物13：氧化电极槽腔室
20：还原电极槽21：阴极
21：阴极30：阴离子交换膜
40：外部电路50：废水
60：海水100：利用微生物的电解装置
102：氧化电极槽104：还原电极槽
106：阴离子交换膜107：氧化电极槽腔室
108：阳极110：电化学活性菌
111：还原电极槽腔室112：阴极
113：电源供应装置114：废水储存设备
116：海水储存设备
具体实施方式
参照附图，并通过后述的详细说明，能够使上述目的、特点及优点更加明确。由此，本发明所属技术领域的技术人员能够容易实施本发明的技术思想。另外，对本发明进行说明时，当认为对与本发明相关的现有技术的具体说明是多余的，并且会干扰本发明的主旨时，将省略对其的详细说明。以下，通过参照附图来对本发明优选的实施例进行详细说明。
图1为本发明一实施例中作为生物电化学系统的微生物燃料电池的结构图。参照图1，微生物燃料电池1包括氧化电极槽10、还原电极槽20和离子交换膜30。氧化电极槽10具备容纳电子的阳极11和腔室13，所述电子为用微生物处理废水中的有机物时所产生的电子。还原电极槽20具备从阳极11接收电子的阴极21和腔室22，并且使从氧化电极槽10接收的电子与从外部供应的氧和水进行反应，从而生成氢氧化离子，并通过该氢氧化离子来使电解质中的多价离子沉淀。所述离子交换膜30为了阻止所述电解质中的多价阳离子向氧化电极槽10移动而由阴离子交换膜构成。
为了微生物12的活性，使氧化电极槽10形成厌氧性条件。在氧化电极槽10中，通过废水储存设备50注入废水。微生物12是一种将包含有机物的废水、厌氧性消化流出液、城市污水、工业废水及酸发酵液等作为基质利用的电化学活性菌。另外，为了维持电化学活性菌的活性，氧化电极槽10的pH为中性，并使温度维持在20℃以上且小于100℃。当氧化电极槽10的pH小于中性时，还原电极槽20的沉淀物或化学药品可以投入到氧化电极槽10中。另外，为了提高氧化电极槽10的导电率，可以将还原电极槽20的沉淀物或流出水的一部分移送到氧化电极槽10。
为了进行还原反应，使包含阴极21的还原电极槽20形成需氧性条件。氧化电极槽10的阳极11和还原电极槽20的阴极21通过外部电路40连接在一起。
为了进行根据本实施例的废水处理，以及去除多价离子，向氧化电极槽10中注入废水，并向还原电极槽20中注入包含多价离子的电解质，例如注入海水。注入到氧化电极槽10中的废水包括城市污水、酸发酵液、厌氧性消化流出液及食品加工废水等含有有机性物质的混合物。另外，为了维持废水中的有机物的适当浓度，可以利用传感器52来监控有机物的浓度。
在氧化电极槽10中，电化学活性菌附着在阳极11上而生长，并且通过氧化废水中的有机物而形成氢离子(H+)和电子(e-)。其中，阳极11为石墨或碳材料，并可以以刷子或毡子的形态形成。生成的电子通过微生物12被传递到阳极11，且该电子通过连接有电阻的外部电路40移动到还原电极槽20，从而产生电。连接在外部电路40的电阻可以设定在1Ω至1000Ω之间。另外，为了生成充分的电子，阳极11可以形成为多个。
另外，如化学式4所示，从氧化电极槽10移动出来的电子，在还原电极槽20中遇到氧和水，从而形成OH-。
[化学式4]
O2+4e-+2H2O→4OH-
在生产电的过程中，在还原电极槽20中生产的OH-使贴附在阴极21表面的海水的pH上升。如化学式5所示，海水中的Ca2+和Mg2+通过形成在阴极21上的OH-而以CaCO3、Mg(OH)2的形态沉淀并被去除。不仅如此，还可以生成Ca2+和Mg2+结合的其它形态的沉淀物。这时，为了防止包含在海水中的阳离子移动到氧化电极槽10，使用阴离子交换膜30。
[化学式5]
Ca2++HCO3 -+OH-→CaCO3↓+H2O
Mg2++2OH-→Mg(OH)2↓
图2为表示在图1中示出的微生物燃料电池1中进行多价离子去除实验的结果的图表。如图2中所示，比较反应前后的多价阳离子的浓度的结果为，Ca2+可以去除96％的Ca2+，Mg2+可以去除55％的Mg2+。
还原电极槽20为了供氧而需要维持需氧性条件，为了减少曝气中所需要的费用，可以使用如图1中所示的阴极21的一面暴露在大气中的形态的空气阴极来代替曝气。阴极21使用耐腐蚀性导电性材料，并且可以镀上铂或代替铂的催化剂而使用。
在还原电极槽20中，为了去除形成在阴极21表面上的水垢层，可以利用漏杓(skimmer)，或用超声波等来震动阴极21，或周期性地向还原电极槽20中喷洒气泡。图3为根据本发明另一实施例中作为生物电化学系统的微生物电解槽100的结构图。如图中所示，微生物电解槽100具有两个腔室，即，氧化电极槽102和还原电极槽104，并且利用阴离子交换膜106来分离开两个腔室102和104。在微生物电解槽100中，在氧化电极槽102中注入废水，在还原电极槽104中注入海水。在阳极108和阴极112之间连接直流电源113。
氧化电极槽102包括腔室107和阳极108，并且使其形成厌氧性条件。在氧化电极槽102中，通过废水储存设备114注入废水。在阳极108上附着电化学活性菌110，并使其生长。电化学活性菌110氧化废水中的有机物，从而生成氢离子(H+)和电子(e-)。生成的电子通过微生物被传递到阳极108，且该电子通过外部电路移动到还原电极槽104。电阻可以设定在1Ω至20Ω之间。
为了电化学活性菌110的活性，需要使pH维持中性，并且使温度维持在25℃以上。氧化电极槽102的pH随着氧化反应的进行而降低，因此为了使pH维持中性，可以将还原电极槽104的沉淀物或流出水的一部分移送到氧化电极槽102。这种沉淀物或流出水的移送从不投入其它添加物也能够提高导电率的方面来说也是有益的。
在氧化电极槽102中，为了生成充分的电子，可以设置多个阳极108。另外，为了提高氧化电极槽102的反应速度，可以以刷型来形成阳极，从而使比表面积最大化。
注入到阳极电极槽102的废水可以为城市污水、酸发酵液、厌氧性消化流出液及食品加工废水等含有有机性物质的混合物。需要使注入到氧化电极槽102中的废水的有机物维持在适当的水平。为此，在废水储存设备114上设置有机物浓度监控传感器115来监控有机物浓度，并且当废水中的有机物浓度在适当水平以下时，需要利用太阳热等来浓缩废水后再注入到氧化电极槽102中。
如果利用直流电源113来施加最小为0.3V以上的电压，以使阴极112的电势比阳极108的电势低，则可以生产氢气。从理论上来说，为了生产氢气，阴极112的电势需要约低于-0.6V。作为电源供应手段，可以采用反向电渗析(Reverseelectrodialysis，RED)或新再生能源来代替直流电源113。
还原电极槽104包括腔室111和阴极112。在还原电极槽104中，通过海水储存设备116注入海水。作为阴极112，使用耐腐蚀性材料，并且镀上铂等的催化剂而使用。
在还原电极槽104中，通过化学式6的反应来生成氢气，因此，需要包括氢气捕获装置(未图示)。产生的氢气可以用于去除海水中的粒子性物质。
[化学式6]
2H2O+2e-→H2↑+2OH-
通过在阴极112中形成的OH-，并通过化学式7的反应，使海水中的Ca2+和Mg2+等的多价阳离子沉淀，从而形成沉淀物。沉淀物不仅为CaCO3、Mg(OH)2，还可以为Ca2+和Mg2+结合的形态的沉淀物。沉淀物可以在后续工序中与肥料提取正渗透(fertiliserDrawnForwardOsmosis，FDFO)联合使用，从而用作沉淀物肥料。
[化学式7]
Ca2++HCO3 -+OH-→CaCO3↓+H2O
Mg2++2OH-→Mg(OH)2↓
如果沉淀物附着在阴极112上，则难以引起还原反应，因此需要对阴极112进行去垢(scaling)处理。为此，可以利用漏杓，或对阴极112施加震动或超声波，或周期性地向阴极112喷洒气泡。
还原电极槽104和氧化电极槽102通过阴离子交换膜106分离开。用阴离子交换膜106来分离氧化电极槽102和还原电极槽104的原因在于，为了防止包含在海水中的阳离子移动到氧化电极槽102。对于阴离子交换膜104的表面，也需要利用漏杓，或施加震动或超声波，或周期性地喷洒气泡来进行去垢处理。
如上所述的本发明，对于本发明所属技术领域的技术人员来说，在没有超出本发明的技术思想的范围内，可以进行各种取代、变形及变更，因此本发明并不限定于前述的实施例及附图。

Claims (15)

1.一种生物电化学系统，所述生物电化学系统用于去除多价离子，其特征在于，所述生物电化学系统包括氧化电极槽，其包括容纳电子的阳极，所述电子为用微生物处理废水中的有机物时所产生的电子；还原电极槽，其包括从所述阳极接收电子的阴极，并且使所述电子与从外部供应的氧和水进行反应，从而生成氢氧化离子，并通过所述氢氧化离子使电解质中的多价离子沉淀；以及阴离子交换膜，其阻止所述电解质中的多价阳离子向所述氧化电极槽移动。
2.根据权利要求1所述的生物电化学系统，其特征在于，所述微生物为电化学活性菌。
3.根据权利要求2所述的生物电化学系统，其特征在于，为了维持电化学活性菌的活性，所述氧化电极槽的pH为中性，温度为20℃以上且小于100℃。
4.根据权利要求3所述的生物电化学系统，其特征在于，当所述氧化电极槽的pH小于中性时，所述还原电极槽的沉淀物或化学药品投入到所述氧化电极槽中。
5.根据权利要求1所述的生物电化学系统，其特征在于，所述阳极形成为多个，从而增加电子的生成。
6.根据权利要求1所述的生物电化学系统，其特征在于，所述阳极为石墨(graphite)或碳(carbon)材料的刷子(brush)或毡子(felt)的形态。
7.根据权利要求1所述的生物电化学系统，其特征在于，所述阴极包含铂催化剂或代替铂的催化剂。
8.根据权利要求1所述的生物电化学系统，其特征在于，所述阴极为空气阴极(air-cathode)。
9.根据权利要求1所述的生物电化学系统，其特征在于，所述还原电极槽为需氧性状态。
10.一种生物电化学系统，其特征在于，所述生物电化学系统包括：氧化电极槽，其具备附着有电化学活性菌的阳极，并且有机性废水作为基质被注入，从而生成电子；还原电极槽，其具备阴极，并且海水作为电解质被注入，从而生产氢气；阴离子交换膜，其分离所述氧化电极槽和所述还原电极槽，并且防止所述海水中的多价阳离子向所述氧化电极槽移动；以及电源，其连接于所述阳极和所述阴极之间。
11.根据权利要求10所述的生物电化学系统，其特征在于，所述还原电极槽利用通过还原反应生成的OH-离子来使所述海水中的多价阳离子沉淀，从而生成沉淀物。
12.根据权利要求11所述的生物电化学系统，其特征在于，所述生物电化学系统进一步包含将所述还原电极槽的沉淀物或流出水的一部分向所述氧化电极槽移送的工具。
13.根据权利要求10所述的生物电化学系统，其特征在于，所述氧化电极槽和所述还原电极槽均为厌氧性状态。
14.根据权利要求10所述的生物电化学系统，其特征在于，所述阳极为多个。
15.根据权利要求10所述的生物电化学系统，其特征在于，所述生物电化学系统进一步包括测定所述有机性废水中的有机物浓度的传感器。
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