Modeling microbial growth of dynamic membrane in a biohydrogen production bioreactor

Biohydrogen is renewable and has a huge potential to replace fossil fuels. Understanding mechanisms of controlling microbial processes of the dynamic membrane is critical for effective dark fermentative biohydrogen production in a dynamic membrane bioreactor (DMBR). This paper aims to develop a sophisticated model of biofilm growth, dynamic membrane formation, and dark fermentative hydrogen production within a platform of coupled lattice Boltzmann and cellular automata. The model was validated against the experimental data available and then was applied for the investigation of biohydrogen production in bioreactors under different membrane structures and inlet velocities. The results showed that porous twisted channels in the dynamic membrane could significantly affect biohydrogen extraction and biofilm patterns. In all cases, the dynamic membrane formation has three phases: the initial bacteria deposit, stable biofilm growth, and stable maximum biofilm biomass. The biohydrogen production could increase by 16.4% by optimizing the porous structure and increase 30%–40% of the hydrogen extraction. Inlet velocity also affects biohydrogen extraction in a range of ?28.3%–71.2%. Both porous structure and inlet velocity would be critical operational parameters for continuous biohydrogen production. The present model demonstrated its capability to investigate dark fermentative hydrogen production and its potential applications to porous bioreactors.     

Influence of solids retention time on continuous H2 production using membrane bioreactor

The influence of solids retention time (SRT) on continuous H₂ production in a submerged membrane bioreactor (MBR) was investigated using mixed mesophilic microflora. The bioreactor was continuously operated at the four SRTs of 2, 4, 12.5 and 90 d on a glucose medium under the hydraulic retention time (HRT) of 9 h and the mesophilic condition of 35°C ± 0.5. Stable biogas production with H₂ content of 50.8%–60% was achieved at SRTs ranging from 2 to 12.5 d. No methane gas was observed in monitoring the experimental conditions. The H₂ production increased from 17.62 to 26.1 l-H₂/d when the SRT increased from 2 to 12.5 d, but decreased to 9.1 l-H₂/d at the 90 d SRT. The best H₂ yield, 1.19 mol-H₂/mol-glucose, was observed at the SRT of 2 d and the highest H₂ production rate, 5.8 l-H₂/l/d, was obtained at the SRT of 12.5 d. Stable H₂ production was achieved by maintaining the SRT in the range of 2 - 12.5 d, regardless of the fermentative pathway related to higher lactate production. The decrease in H₂ yield was observed at long SRTs due to the low volatile suspended solids/total suspended solids (VSS/TSS) as well as the high extracellular polymeric substances (EPS) concentrations. These results suggest that the SRT is the key factor enabling sustainable H₂ fermentation in MBR, and that an SLR value of around 1.6 kg-DOC/kg-VSS/d might be the specific condition for achieving optimum H₂ production.     

Effect of cell immobilization,hematite nanoparticles and formation of hydrogen-producing granules on biohydrogen production from sucrose wastewater

This study investigated the effect of granules formation, hematite nanoparticles and biofilm carriers on biohydrogen production from sucrose wastewater in continuous stirring tank reactors operated at 12 h HRT, pH of 5.5 and 35 °C. Granular-based bioreactor was subjected to acid incubation period for 24 h by shifting the pH from 5.5 to 3. Before application of the acid incubation, hydrogen-producing granules (HPGs) diameter and hydrogen production rate (HPR) of 0.5 mm and 4.3 L/L.d, respectively were measured at 10 g-sucrose/L. Application of acid incubation enhanced the granulation process, where the particle size increased to 2.8 mm and higher HPR of 7.8 L/L.d was obtained. Higher sucrose concentration (15–30 g?L) enhanced HPGs diameter and increased the HPR. At 10 g-sucrose/L, addition of hematite nanoparticles increased the HPR to 5.9 L/L.d higher than 3.87 L/L.d measured in control reactor. Biofilm-based reactor showed HPR of 2.48 L/L.d lower than the control reactor.     

Investigation and analysis of proton exchange membrane fuel cell dynamic response characteristics on hydrogen consumption of fuel cell vehicle

The number of working points and response speed are two essential characteristics of proton exchange membrane fuel cell (PEMFC). The improper setting of the number of working points and response speed may reduce the life of PEMFC and increase the hydrogen consumption of the vehicle. This paper explores the impact of the response speed as well as the working points of the PEMFC on the hydrogen consumption in the real-system level. In this paper a dynamic model of the PEMFC system is established and verified by experiments. The model is able to reflect the dynamic response process of PEMFC under a series different number of working points and different response speed. Based on the proposed model, the influence of working points and the response speed of PEMFC on the hydrogen consumption in the vehicle under different driving cycles is analyzed and summarized, for the first time, in the open literature. The results highlight that the hydrogen consumption will decreases in both cases that with the increase of working point number and increase of response speed. However, the reduction range of hydrogen consumption trends to smaller and may reach to an optimal level considering the trade-off between the hydrogen saving and the other costs, for example the control cost. Also, with a more complex driving cycle, the working points and response speed have a greater the impact on the hydrogen consumption in the vehicle applications.     

Effect of gas composition and gas utilisation on the dynamic response of a proton exchange membrane fuel cell

The transient response of a proton exchange membrane fuel cell (PEMFC) was measured for various cathode gas compositions and gas utilisations (fraction of supplied reactant gas which is consumed in the fuel cell reaction). For a PEMFC operated on pure hydrogen and oxygen, the cell voltage response to current steps was fast, with response times in the range 0.01–1 s, depending on the applied current. For a PEMFC supplied with air as cathode gas, an additional relaxation process related to oxygen transport caused a slower response (approximately 0.1–2 s depending on the applied current). Response curves up to approximately 0.01 s were apparently unaffected by gas composition and utilisation and were most likely dominated by capacitive discharge of the double layer and reaction with surplus oxygen residing in the cathode. The utilisation of hydrogen had only a minor effect on the response curves, while the utilisation of air severely influenced the PEMFC dynamics. Results suggested that air flow rates should be high to obtain rapid PEMFC response.     

Effect of operating parameters on dynamic response of water-to-gas membrane humidifier for proton exchange membrane fuel cell vehicle

An analytic multi-dimensional dynamic model of a membrane type humidifier has been developed for the study of transient responses of the humidifier under proton exchange membrane fuel cell vehicle operating conditions. The dynamic responses of heat and mass transfer and fluid flow in a membrane humidifier are mathematically formulated and modeled with a newly developed pseudo-multi-dimensional concept. The model is used to analyze the performance of the humidifier under various operating conditions and the dynamic response of the humidifier under transient operating conditions. The simulation results show that, in the case of the water-to-gas type membrane humidifier modeled in this study, the time constant of water diffusion in the membrane is less than 1 s. Thus, the delay of the response of the humidifier induced by the vapor diffusion in the membrane is not significant in vehicle operation. However, it is also found that the dynamic behavior is mainly due to the thermal resistance and heat capacity of the membrane humidifier.     

Parametric analysis of the steady state and dynamic performance of proton exchange membrane fuel cell models

Proton exchange membrane fuel cells (PEMFCs) are devices that attract the interest for a variety of applications including portable devices, transportation and stationary power. Several models are available in the literature concerning PEMFCs with different modelling approaches. In this paper, two representative dynamic models are examined, one using an electrical equivalent and one based on semi-empirical equations. Moreover, an enhanced model based on semi – empirical equations and a simplified transfer function representation for the dynamic response is proposed. All models can be easily incorporated in power system simulation software. Scope of this paper is to present a parametric analysis method in order to determine the ability of each model to represent accurately the steady – state as well as the slow and fast dynamics of a PEMFC. The influence of each specific parameter is investigated and the tuning procedure is described. Finally, simulation results are presented and the adaptability of all models is evaluated.     

Quasi-three dimensional dynamic model of a proton exchange membrane fuel cell for system and controls development

A first principles dynamic model of the physical, chemical, and electrochemical processes at work in a proton exchange membrane fuel cell has been developed. The model solves the dynamic equations that govern the physics, chemistry and electrochemistry for time scales greater than about 10 ms. The dynamic equations are solved for a typical but simplified quasi-three dimensional geometric representation of a single cell repeat unit of a fuel cell stack. The current approach captures spatial and temporal variations in the important physics of heat transfer and water transport in a manner that is simple enough to make the model amenable to PEMFC system simulations and controls development. Comparisons of model results to experimental data indicate that the model can well predict steady state voltage–current relationships as well as the oxygen, water, and nitrogen spatial distribution within the fuel cell. In addition, the model gives dynamic insight into the distribution of current, water flux, species mole fractions, and temperatures within the fuel cell. Finally, a control system test is demonstrated using the simplified dynamic model.     

H2 permeation and its influence on gases through a SAPO-34 zeolite membrane

This work analysed the permeation of binary and ternary H₂-containing mixtures through a SAPO-34 membrane, aiming at investigating how hydrogen influences and its permeation is influenced by the presence of the other gaseous species, such as CO₂ and CH₄. We considered the behaviour of various gas mixtures in terms of permeability and selectivity at various temperatures (25–300 °C), feed pressures (400–1000 kPa) and compositions by means of an already validated mass transport model, which is based on surface and gas translation diffusion. We found that the presence of CO₂ and CH₄ in the H₂-containing mixtures influences in a similar way the H₂ permeation, reducing its permeability of about 80% compared to the single-gas value because of their stronger adsorption. On the other hand, H₂ promotes the permeation of CO₂ and CH₄, causing an increment of their permeability with respect to those as single gases. These combined effects reflected in interesting selectivity values in binary mixture (e.g., CO₂/H₂ about 11 at 25 °C, H₂/CH₄ about 9 at 180 °C), which showed the potential of SAPO-34 membranes in treating of H₂-containing mixtures.     

Experimental study on the dynamic performance of an air-cooled proton exchange membrane fuel cell stack with ultra-thin metal bipolar plate

In this paper, a compact 3 kW air-cooled fuel cell stack consists of 95 single cells with metallic bipolar plate is designed. Compared with graphite bipolar plates, metal stamping bipolar plates are lighter in weight, smaller in size and faster in heat conduction, therefore the transient behaviors of the voltage and temperature of each cell are analyzed. The results show that the heat distribution of the air-cooled fuel cell is very uniform, and the temperature difference between the inlet and outlet of cathode air of the fuel cell is lower than 15 °C. The individual cell voltage uniformity percentage variation value reaches 7% when the drop in the loading current is over 25 A. Moreover, the voltage uniformity variation value is higher than 4% when the loading current output exceeds 35A. Thus, a large drop in loading and a high loading current easily increase the voltage uniformity variation value. Long-term continuous operation has a negative influence on the performance of the stack, especially the last fuel cell near the anode outlet. Anode purging can effectively alleviate the uniformity percentage variation in the voltages. The designed air-cooled fuel cell exhibits good performance and strong environmental adaptability.     

Evaluation of hidden H2-consuming pathways using metabolic flux-based analysis for a fermentative side-stream dynamic membrane bioreactor using untreated seed sludge

This study investigates the performance and hidden hydrogen consuming metabolic pathways of a fermentative side stream dynamic membrane (DM) bioreactor using flux balance analysis (FBA). The bioreactor was inoculated with untreated methanogenic seed sludge. It was found that fouling rate aggravated with increasing COD concentration (10–30 g/L) and was positively correlated to it rather than to the applied solid flux on the DM module. Due to increased fouling rate the hydraulic retention time (HRT) could not be reduced less than 0.82 ± 0.02 d. An increase in the organic loading rate (OLR) led to an increase in H₂ yield from 0.01 to 0.76 mol H₂/mol of sucrose. FBA revealed that homoacetogenesis was the main H₂-consuming pathway at lower OLRs (corresponding to 10 and 15 g COD/L), while for the OLR corresponding to 30 g COD/L, homoacetogens were suppressed. More importantly, caproic acid production pathway was identified for the first time as another H₂-consuming pathway at high OLR which was not significant at lower OLRs during fermentative dynamic membrane bioreactor operations.     

Monodimensional modeling and experimental study of the dynamic behavior of proton exchange membrane fuel cell stack operating in dead-end mode

The dynamic behavior of a five cells proton exchange membrane fuel cell (PEMFC) stack operating in dead-end mode has been studied at room temperature, both experimentally and by simulation. Its performances in “fresh” and “aged” state have been compared. The cells exhibited two different response times: the first one at about 40 ms, corresponding to the time needed to charge the double-layer capacitance, and the second one at about 15–20 s. The first time response was not affected by the ageing process, despite the decrease of the performances, while the second one was. Our simulations indicated that a high amount of liquid water was present in the stack, even in “fresh” state. This liquid water is at the origin of the performances decrease with ageing, due to its effect on decreasing the actual GDL porosity that in turn cause the starving of the active layer with oxygen. As a consequence, it appears that water management issue in a fuel cell operating in dead-end mode at room temperature mainly consists in avoiding pore flooding instead of providing enough water to maintain membrane conductivity.     

Methane steam reforming in water-deficient conditions on a new Ni-exsolved Ruddlesden-Popper manganite: Coke formation and H2S poisoning

This research deals with the catalytic behavior of the methane steam reforming reaction over a new Ni-exsolved Ruddlesden-Popper manganite during prolonged reaction time (up to 100 h) with special focus on the possible carbon deposition and H₂S poisoning. La_1.5Sr_1.5Mn_1.5Ni_0.5O_7±δ material was synthesized and reduced in diluted hydrogen to induce Ni exsolution. Its catalytic behavior in long reaction times was compared to Ni-impregnated manganite and Ni/YSZ cermet. The catalytic measurements for the steam reforming reaction were carried out at 850 °C in low steam-to-carbon conditions. All materials are susceptible to H₂S poisoning (50 ppm), forming undesired sulfide compounds with damaging impact on their catalytic activity. In contrast, during tests without H₂S, the activity for cermet and impregnated materials drops at relatively short reaction time due to coking formation, as evidenced by TEM and TGA/MS analysis, while the behavior of new exsolved material remains stable throughout the test. This high stability of the new exsolved catalyst over a prolonged reaction time is a noticeable advantage due to its potential use as SOFC anode fed with natural gas free of H₂S.     

The influence of the membrane thickness on the performance and durability of PEFC during dynamic aging

The influence of the membrane thickness on the performance and durability of 25 cm² membrane electrode assembly (MEA) toward dynamic aging test was investigated. The tested MEAs consist of chemically stabilized membranes (AQUIVION™) with thicknesses of 30 and 50 μm, electrocatalyst – 46 %Pt/C (Tanaka) with Pt loadings of 0.25 (anode), 0.45 mg cm⁻² (cathode) and gas diffusion layers 25 BC (SGL Group). The applied dynamic aging procedure is repetitive current cycling between 0.12 A cm⁻² for 40 s and 0.6 A cm⁻² for 20 s. The testing conditions were 80 °C, fully saturated hydrogen and air, total pressure of 2.5 atm abs. The aging procedure was regularly interrupted for evaluating the MEAs' “health” via electrochemical methods and mass spectrometry. The carbon support degradation as a function of the electrode potential, current cycling and supplied gas was studied. The effects of the Pt particles agglomeration and Pt physical loss in the active layer of the cathode on the MEAs performance degradation were individually assessed. The effect of the membrane thicknesses on the performance and durability of the PEFC was established. The reasons and stages of MEAs performance degradation were analyzed.     

A process dynamic modeling and control framework for performance assessment of Pd/alloy-based membrane reactors used in hydrogen production

In the present study a comprehensive, insightful and practical process dynamic modeling framework is developed in order to analyze and characterize the transient behavior of a Pd/alloy-based (Pd/Au or Pd/Cu) water-gas shift (WGS) membrane reactor. Furthermore, simple process control ideas are proposed aiming at enhancing process system performance by inducing the desirable dynamic characteristics in the response of the controlled process during start-up as well as in the presence of unexpected adverse disturbances (process upset episodes) or operationally favorable set-point changes that reflect new hydrogen production requirements. Finally, the proposed methods are evaluated through detailed simulation studies in an illustrative example involving a Pd/alloy-based WGS membrane reactor that exhibits complex dynamic behavior and is currently used for lab-scale pure hydrogen production and separation.     

Effects of CO and H2 on the formation of N2O via catalytic NO reduction

The formation of N₂O in a mixture of NO, CO, H₂, O₂ and N₂ was investigated experimentally in a tubular-flow reactor containing a catalyst.It was found that the reduction of NO is enhanced by the presences of H₂, and to a lesser extent CO, and that N₂O is formed as a by-product of NH₃ decomposition and NO reduction in the presence of H₂, and through NO reduction in the presence of CO. The main product of NH₃ oxidation is N₂ in addition to the products of NO and N₂O, and the rate of conversion for NH₃ to N₂O is about 10%. The conversion of NO to N₂O is higher in the presence of H₂ than in the presence of CO at lower temperature, and there is a range of temperature in which the formation of N₂O is enhanced in the presence of either H₂ or CO, whereas CO enhances N₂O production from catalytic NO reduction more than H₂ in a CO/H₂/NO/O₂/N₂ gas system.     

Effects of reformate on performance of PBI/H3PO4 proton exchange membrane fuel cell stack

The present study aims to examine the effect of nitrogen and carbon monoxide concentrations as well as the working temperature and the stoichiometry number on the performance of a self-made five-cell high-temperature Proton-exchange membrane fuel cell stack (PEMFC). The concentration of hydrogen in a reformed gas can be varied, and it may contain poisonous substances such as carbon monoxide. Hence, the composition of the fuel gas could affect the performance of the PEMFC. The polarization curve and the electrochemical impedance spectrogram are utilized to examine the behaviors of PEMFC. The cell temperature of 160 °C is found as an optimal working temperature in this study for high-temperature PEMFC. Measured results show that the stoichiometry of the anode gas has a minimal effect on the PEMFC performance. A high percentage of nitrogen makes hydrogen dilute and leads to poor cell performance. When carbon dioxide exceeds 3%, the pt-catalyst was covered with the CO and the cell performance significantly decreased. Finally, a raise of the PEMFC temperature boosted the catalyst energy and improved the detachment of the carbon monoxide and eventually enhanced carbon monoxide tolerance.     

Quantification and evolution on degradation mechanisms of proton exchange membrane fuel cell catalyst layer under dynamic testing conditions

The catalyst layer is one of the core components of the Proton Exchange Membrane Fuel Cell (PEMFC). Studying its degradation mechanism is very important to improve the durability of PEMFC. Therefore, the degradation of the catalyst layer after the 100 h, 225 h, and 650 h durability tests are studied quantitatively in this paper. The results show that the agglomeration of Pt particles is the main reason for the degradation of the catalyst layer in the first 100 h, accounting for 80%. Catalyst dissolution and the loss of proton connectivity caused by the ionomer are the main factors for the degradation of the catalyst layer between 225 and 650 h, which increases from 23% in the initial stage to 46%. In addition, the corrosion degree of the carbon support inside the catalyst layer gradually intensified with the test time. This study reveals the dominant degradation mechanism of the catalyst layer in different degradation stages and the evolution of the whole degradation process, which has important guiding significance for the structural design of the catalyst layer for long-life fuel cells.