CN104451760A - 一种微生物电解池制氢液的方法 - Google Patents

一种微生物电解池制氢液的方法 Download PDF

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CN104451760A
CN104451760A CN201410708159.9A CN201410708159A CN104451760A CN 104451760 A CN104451760 A CN 104451760A CN 201410708159 A CN201410708159 A CN 201410708159A CN 104451760 A CN104451760 A CN 104451760A
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electrolysis cell
mec
acid
hydrogen production
hydrogen
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金京勋
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SOOCHOW KH BIO SCIENCE&TECHNOLOGY Co Ltd (KHB)
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SOOCHOW KH BIO SCIENCE&TECHNOLOGY Co Ltd (KHB)
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    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
    • C25B1/00—Electrolytic production of inorganic compounds or non-metals
    • C25B1/01—Products
    • C25B1/02—Hydrogen or oxygen
    • C25B1/04—Hydrogen or oxygen by electrolysis of water
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F3/00—Biological treatment of water, waste water, or sewage
    • C02F3/28—Anaerobic digestion processes
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F3/00—Biological treatment of water, waste water, or sewage
    • C02F3/34—Biological treatment of water, waste water, or sewage characterised by the microorganisms used
    • 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
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/30—Hydrogen technology
    • Y02E60/36—Hydrogen production from non-carbon containing sources, e.g. by water electrolysis

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  • Life Sciences & Earth Sciences (AREA)
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  • Microbiology (AREA)
  • Organic Chemistry (AREA)
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  • Inorganic Chemistry (AREA)
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  • Materials Engineering (AREA)
  • Metallurgy (AREA)
  • Preparation Of Compounds By Using Micro-Organisms (AREA)
  • Electrolytic Production Of Non-Metals, Compounds, Apparatuses Therefor (AREA)
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Abstract

本发明公开一种微生物电解池制氢液的方法，向工业废水内充满氮气，用产乙酸菌发酵，调整发酵液pH值为7，C/N为44，添加乙溴乙烷磺酸盐20mmol/L，添加1mL/L营养液。本发明通过优化pH值、C/N和乙溴乙烷磺酸盐浓度，实现制氢液中乙酸、乳酸、丙酸和丁酸浓度分别达到1031.12mg/L、51.32mg/L、84.94mg/L、71.24mg/L，同时对工业废水中COD的去除率可达99％。

Description

一种微生物电解池制氢液的方法
技术领域
本发明涉及利用微生物发电技术，具体涉及一种微生物电解池制氢液的方法
背景技术
微生物电解池(microbial electrolysis cell，MEC)，作为新近发展的一种可用于减弱厌氧“发酵障碍”现象的制氢技术近年来受到国内外研究者的广泛重视。借助生物电催化技术，以有机废水为电子供体，通过阳极附着的电活性微生物降解底物释放电子和质子，并在阴极由质子接收电子从而产生H2。当有机物通过丙酮酸途径代谢生成乙酸、丙酸及丁酸等脂肪酸后，在两极附加电压的驱动下，可将发酵末端产物进一步降解并释放质子和电子，从而大幅度提高H2产率。影响MEC产氢效能的主要因素包括额外电压的设定、底物的选择、电极材料的选定以及阴极催化剂的确定。
反应过程主要通过两极的化学反应来完成，其中以乙酸为底物的反应过程如式(1)、式(2)所示。
阳极：CH3COOH+2H2O→CO2+8H++8e-  (1)
阴极：8H++8e-→4H2  (2)
根据能斯特方程，在pH值为7.0时，阴极产生氢气至少需要-410mV的电势，而传统MEC回路产生的电势一般在-300mV左右，所以，为获得氢气，添加在阴阳两极间的电压至少在110mV。在实际MEC运行过程中，考虑到内阻的影响，通常设定电压值在0.2～0.8V之间。
选择合适的底物则对发展MEC制氢工艺至关重要，它将直接决定工艺运行的成本和氢气产率。在MEC中，当复杂碳水化合物经水解生成单糖后，微生物在厌氧条件下通过糖酵解途径将单糖酵解为丙酮酸，随后通过丙酮酸的氧化还原机制平衡辅酶NAD+或NADP+的量，维持微生物的代谢产能过程，从而使得反应自发进行下去。在丙酮酸氧化还原后，产生的末端产物如乙酸、丙酸、丁酸等挥发性脂肪酸，在额外电压的驱动下，可被微生物继续氧化，从而实现厌氧“发酵障碍”现象的减弱。
当前，已开展以甲酸盐、乙酸钠、畜禽废水、发酵出水、工业废水、蛋白质和葡萄糖等为底物进行MEC产氢研究。对于不同的底物类型，由于乙酸钠可直接进入生化反应从而可获得比复合蛋白质等更多的产氢量。
发明内容
鉴于此，本发明目的在于提供一种产氢效率更高的微生物电解池制氢液的方法。
为解决以上技术问题，本发明提供的技术方案是，提供一种微生物电解池制氢液的方法，向工业废水内充满氮气，用产乙酸菌发酵，调整发酵液pH值为7，C/N为44，添加乙溴乙烷磺酸盐20mmol/L，添加1mL/L营养液。
优选地，所述产乙酸菌为醋酸杆菌。
优选地，所述营养液的成分如下：H3BO350mg/L，CuCl230mg/L，MnSO4·H2O50mg/L，(NH4)6Mo7O24·4H2O50mg/L，AlCl350mg/L，CoCl2·6H2O50mg/L，NiCl250mg/L，ZnCl250mg/L。
与现有技术相比，上述技术方案中的一个技术方案具有如下优点：
1、本发明通过优化pH值、C/N和乙溴乙烷磺酸盐浓度，实现高乙酸产率。乙溴乙烷磺酸盐除产甲烷菌外对其它厌氧产酸细菌没有影响，在本发明浓度下，可抑制嗜氢产甲烷菌和嗜乙酸产甲烷菌，且可促进同型乙酸菌的生长，通过水解发酵产酸和同型产乙酸过程来实现厌氧发酵末端产物中乙酸浓度的积累。
2、本发明制氢液中乙酸、乳酸、丙酸和丁酸浓度分别为：1031.12mg/L、51.32mg/L、84.94mg/L、71.24mg/L。
具体实施方式
向工业废水内充满氮气，用产乙酸菌入醋酸杆菌发酵，充氮气有利于降低废水内氧气含量，保证工业废水处于厌氧状态，使之进入厌氧产氢模式。使用磷酸盐缓冲液调整发酵液pH值为7，调整废水中碳、氮比为44，并按照20mmol/L添加乙溴乙烷磺酸盐，按照1mL/L添加营养液，得到制氢液。营养液的成分如下：H3BO350mg/L，CuCl230mg/L，MnSO4·H2O50mg/L，(NH4)6Mo7O24·4H2O50mg/L，AlCl350mg/L，CoCl2·6H2O50mg/L，NiCl250mg/L，ZnCl250mg/L。
本发明制氢液中乙酸、乳酸、丙酸和丁酸浓度分别为：1031.12mg/L、51.32mg/L、84.94mg/L、71.24mg/L。
利用厌氧发酵制氢废液为底物，以乙酸为主要的电子供体，在电解池反应器中，以涂布有Ni纳米颗粒的不锈钢网为阴极，碳布为阳极，最终可获得1.32m3H2/(m3·d)和2.8mLH2/mgCOD的产氢率，以及138％的能量效率，同时对工业废水中COD的去除率可达99％。

Claims (3)

1.一种微生物电解池制氢液的方法，其特征在于，向工业废水内充满氮气，用产乙酸菌发酵，调整发酵液pH值为7，C/N为44，添加乙溴乙烷磺酸盐20mmol/L，添加1mL/L营养液。
2.根据权利要求1所述的微生物电解池制氢液的方法，其特征在于，所述产乙酸菌为醋酸杆菌。
3.根据权利要求1所述的微生物电解池制氢液的方法，其特征在于，所述营养液的成分如下：H3BO350mg/L，CuCl230mg/L，MnSO4·H2O 50mg/L，(NH4)6Mo7O24·4H2O 50mg/L，AlCl350mg/L，CoCl2·6H2O50mg/L，NiCl250mg/L，ZnCl250mg/L。
CN201410708159.9A 2014-11-27 2014-11-27 一种微生物电解池制氢液的方法 Pending CN104451760A (zh)

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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN107761125A (zh) * 2016-08-17 2018-03-06 黄增才 一种微生物电解池制氢液
CN107761126A (zh) * 2016-08-17 2018-03-06 黄增才 一种微生物电解池制氢液

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101550551A (zh) * 2009-04-08 2009-10-07 哈尔滨工业大学 一种利用蛋白质在微生物电解池中产氢的方法
WO2010124147A1 (en) * 2009-04-22 2010-10-28 Qteros, Inc. Compositions and methods for methane production
CN102400169A (zh) * 2011-11-01 2012-04-04 浙江大学 一种碱性微生物电解制氢方法

Patent Citations (3)

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Publication number Priority date Publication date Assignee Title
CN101550551A (zh) * 2009-04-08 2009-10-07 哈尔滨工业大学 一种利用蛋白质在微生物电解池中产氢的方法
WO2010124147A1 (en) * 2009-04-22 2010-10-28 Qteros, Inc. Compositions and methods for methane production
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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN107761125A (zh) * 2016-08-17 2018-03-06 黄增才 一种微生物电解池制氢液
CN107761126A (zh) * 2016-08-17 2018-03-06 黄增才 一种微生物电解池制氢液

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Application publication date: 20150325