The proton exchange membrane fuel cell systems using methanolysis of sodium borohydride as a hydrogen source with cobalt catalysts

Constant hydrogen generation via a hydrogen generator is evaluated from the methanolysis of sodium borohydride (NaBH₄) using Co/Al₂O₃ and MnO_x/Al₂O₃ catalysts. Chemical borohydrides coupled with catalysts can be used for compact storage and to create efficient generation systems. Thus, we first report the catalytic activity of MnO_x/Al₂O₃, which is synthesized using the simple wet-impregnation method, for the methanolysis reaction. The results indicate that both catalysts can effectively accelerate the methanolysis reaction and provide constant hydrogen generation rates. Thus, we integrate this hydrogen generation system into a proton exchange membrane fuel cell stack (PEMFC) to determine whether it can be used as a portable power supply. As a result, this fuel cell system operates at 40 W for 1 hr using the hydrogen source supplied from the catalytic methanolysis reaction.     

Biogas upgrading and utilization from ICEs towards stationary molten carbonate fuel cell systems

Biogas production from anaerobic digestion has increased rapidly in the last years, in many parts of the world, mainly due to its local scale disposition and to its potential on greenhouse gases (GHG) emissions mitigation. Biogas can be used as fuel for combined heat and power systems (CHP), in particular for internal combustion engines (ICEs). In recent investigations, fuel cells have been considered as alternative CHP systems. In the present article, two different energy conversion systems are compared: a 1.4 MW class MCFC system, running on pipeline natural gas, and an in situ ICE, running on biogas. In the first case, biogas is considered as a source fuel to obtain upgraded gas to be injected in the natural gas grid. In such scenario, the location of the fuel cell power plant is no longer strictly connected to the anaerobic digester site. Several energy balances are evaluated, considering different upgrading techniques and different biogas methane/carbon dioxide ratios.     

Photodynamic effects of 31 different phthalocyanines on a human keratinocyte cell line

Phthalocyanines (Pcs, colored macromolecular compounds with the ability to generate singlet oxygen) represent a promising group of photosensitizers due to their intense absorption in the red and UV portion of the spectrum which leads to their excitation. In order to characterize possible toxic effects associated with eventual practical use and application of these chemicals, we employed an in vitro cell culture model to evaluate cytotoxic effects of 31 different phthalocyanines using neutral red uptake assay. An immortalized human keratinocyte cell line HaCaT was exposed to the tested chemicals for 2 or 24 h, either with or without illumination in the last 60 min of the exposure period. After 2- or 24-h exposure without illumination, no cytotoxic effects or weak cytotoxic effects were induced by any Pc under the study and EC50 values could not be obtained within the tested concentration ranges (1.25–20 mg L⁻¹ or 0.625–10 mg L⁻¹). On the other hand, exposure to phthalocyanines under illumination induced a significant cytotoxic effect. The most pronounced cytotoxicity was elicited by Pcs previously shown to have high positive charge densities at peripheral parts of substituent groups, which is most likely the factor responsible for the binding of Pc to negatively charged membranes on the cell surface and thus guaranteeing the tight connection necessary for the singlet oxygen attack on the cell surface.     

Electrochemical removal of nitrate using ZVI packed bed bipolar electrolytic cell

The present study investigates the performance of the zero valent iron (ZVI, Fe⁰) packed bed bipolar electrolytic cell for nitrate removal. The packing mixture consists of ZVI as electronically conducting material and silica sand as non-conducting material between main cathode and anode electrodes. In the continuous column experiments for the simulated groundwater (initial nitrate and electrical conductivity of about 30 mg L⁻¹ as N and 300 μS cm⁻¹, respectively), above 99% of nitrate was removed at the applied potential of 600 V with the main anode placed on the bottom of reactor. The influx nitrate was converted to ammonia (20% to maximum 60%) and nitrite (always less than 0.5 mg L⁻¹ as N in the effluent). The optimum packing ratio (v/v) of silica sand to ZVI was found to be 1:1-2:1. Magnetite was observed on the surface of the used ZVI as corrosion product. The reduction at the lower part of the reactor in acidic condition and adsorption at the upper part of the reactor in alkaline condition are the major mechanism of nitrate removal.     

稳恒磁场作用下微生物燃料电池的产电特性和电化学阻抗谱分析

对混合菌接种的双室微生物燃料电池加载磁场强度为175 mT的稳恒磁场,利用电化学交流阻抗等电化学分析方法,考察了在磁场作用下微生物燃料电池（MFC）产电性能的变化,分析了磁场对MFC各部分内阻的影响。加载磁场使已启动完成的MFC的产电明显增强,开路电压提高了10%。加载磁场后最大功率密度为2.08 W/m2,大于加载前的1.58 W/m2,表观内阻由170Ω降至80Ω。电化学阻抗谱分析确定了阳极、阴极和全电池的等效电路模型,拟合结果发现阳极极化内阻约为5Ω。加载磁场使MFC的阴极极化内阻由74.98Ω降至56.73Ω。     

炼油废水微生物燃料电池启动及影响因素

以炼油废水为碳源,构建双室填料型微生物燃料电池,考察接种液、外接电阻等电池启动条件,以及电导率、pH值和缓冲溶液强度等溶液性质对电池产电性能的影响。利用微生物燃料处理炼油废水,COD去除率(52±4)%,含油量去除率(81.8±3)%;利用废水中存在的原生菌即可启动电池,但启动期长,外加接种液可快速启动电池;启动时外接电阻的大小对电池稳定运行后的输出功率有明显影响,对电池内阻影响相对较小,当启动外接电阻为2 000Ω,电池输出功率最大,为288 mW/m3;随阳极溶液电导率电池增大,电池内阻降低,输出功率升高;pH值变化对电池阳极电势影响较大,进而影响电池输出,当溶液pH为9时,电池输出电压最大(388 mV),pH过高或过低均不利于电池产电;随着缓冲强度的增大,电池输出电压增大,且PBS缓冲强度的增大可从电导率增大和改善质子传递条件两方面提高电池的输出功率。     

全细胞脂肪酶(菌)对SBR系统中活性污泥性能的影响

将全细胞脂肪酶(菌)以产脂肪酶微生物的形式直接投加到SBR内,与投加野生型酵母菌及空白对照进行比较,研究其对活性污泥性能及含油脂废水处理效果的影响。结果表明,在15～20℃,pH 6.5～7.5,进水油脂浓度2 000 mg/L的条件下,投加一定量全细胞脂肪酶(菌)的SBR系统间歇处理4 d,活性污泥增殖速度加快,是投加野生型酵母菌的1.3倍。静置30 min时活性污泥SV达到45%,SVI为151,MLSS最高可达2 965 mg/L左右,絮凝时间缩短且无污泥膨胀现象。投加全细胞脂肪酶(菌)的SBR系统中,油脂去除率为86.5%,COD去除率为79.5%,与投加野生型酵母菌的SBR系统相比去除率提高了1.3倍。说明投加全细胞脂肪酶(菌)后活性污泥性能增强,油脂废水处理效率提高。     

Metabolism of the14C-labeled herbicide clodinafop-propargyl in plant cell cultures of wheat and tobacco

The metabolism of ¹⁴C-clodinafop-propargyl (CfP) was examined in cell cultures of wheat (Triticum aestivum L. cv. ‘Heines Koga II’) and tobacco (Nicotiana tabacum L.). Besides the non-transgenic tobacco culture, cultures transformed separately with cDNA of human cytochrome P450-monooxygenases (P450s) CYP1A1, CYP1A2, CYP3A4, CYP2B6 and CYP2C19 were examined. Experiments with wheat were executed in the presence and absence of safener cloquintocet-mexyl (CqM). After 48 h of incubation, only about 10% of applied ¹⁴C was found in media (both tobacco and wheat). Non-extractable residues of ¹⁴C-CfP in wheat cells were 16.54% (without CqM) and 30.87% (with CqM). In all tobacco cultures, 82.41–92.46% of applied radioactivity was recovered in cell extracts. In contrast to wheat, non-extractable residues amounted only to 1.50–2.82%. As determined by radio-thin layer chromatography (TLC) and -high-performance liquid chromatography (HPLC), the parent CfP was not found in the cell extracts of wheat; in tobacco cell extracts, only traces of CfP were detected. After a hydrolysis of assumed carbohydrate conjugates of CfP derived polar ¹⁴C-labeled compounds, TLC and HPLC analysis showed that in wheat, a more complex pattern of metabolites of CfP were observed as compared to all tobacco cultures. In hydrolysates resulting from wheat, the identity of three primary products was confirmed by means of GC-EI-MS: free acid clodinafop (Cf), hydroxy-Cf hydroxylated at the pyridinyl moiety, and 4-(5-chloro-3-fluoropyridin-2-yloxy)phenol. In hydrolysates derived from all tobacco cultures, main metabolite was Cf besides only traces of further unidentified products. Differences among the different tobacco cultures (non-transgenic, transgenic) did not emerge. According to kinetics of disappearance of primary metabolite Cf as well as formation of polar soluble products and non-extractable residues, metabolization of CfP proceeded at a noticeably higher rate in wheat cells treated with safener CqM than in cells without CqM treatment. Thus, these results indicated a stimulation of CfP's metabolism by CqM, although metabolic profiles observed in CqM treated and non-treated cells (after hydrolysis) were qualitatively similar. The findings obtained from all tobacco cultures suggested that with the exception of ester cleavage to Cf, CfP cannot be metabolized by tobacco itself or by the human P450s examined.     

胞外多聚物在厌氧污泥颗粒化成核过程中的特性

以模拟啤酒废水为底物在IC反应器中进行厌氧污泥颗粒化培养,并对污泥颗粒化过程中胞外多聚物(EPS)的主要成分变化及其与细胞表面疏水性和Zeta电位之间的相互关系进行分析,以此来阐述EPS对污泥颗粒化成核的作用。研究结果表明,好氧剩余污泥在经过56 d的培养后,平均粒径由接种时的54.72μm增长到103.46μm,实现了厌氧污泥颗粒化成核过程;EPS蛋白质含量(PN)在颗粒化过程中逐渐由接种时的18.1 mg/g增至54.3 mg/g,而EPS多糖含量(PS)则无明显变化;此外,PN/PS与污泥平均粒径、细胞表面疏水性(RH)以及Zeta电位之间呈正相关关系,相关系数分别为0.9727、0.9593和0.9274。由此可推测:厌氧污泥颗粒化成核过程的主要作用成分为胞外蛋白质,其可以改变污泥细胞表面疏水性和Zeta电位,从而在厌氧污泥颗粒化过程中有着重要的促进作用。     

一体式MFC-好氧MBR运行效果及膜污染特性

膜生物反应器（MBR）是一种高效的污水处理工艺,而微生物燃料电池（MFC）能利用N0i作为电子受体进行脱氮。为解决膜生物反应器（MBR）脱氮效率低和膜污染问题,建立了一套能够进行脱氮、有效抑制膜污染的一体式MFC-好氧MBR新工艺。以开路MFC—MBR反应器为对照,对耦合系统中污水处理效果、膜污染情况进行研究。研究表明,2套系统的COD去除率均超过88％,对NH4-N的去除均达到99％。闭路MFC—MBR系统TN去除率达到69．4％,高于开路系统的55．3％。混合液的MLVSS／MLSS稳定在88％左右,同时耦合系统能够改善污泥混合液的性质,zeta电位的绝对值和粘度较开路系统有所减少,污泥颗粒平均体积粒径（233．482μm）较开路系统（94．877μm）有明显增加,膜清洗周期延长了41．17％。