Bio-fuel reforming for solid oxide fuel cell applications. Part 2: Biodiesel

Biodiesel is considered as a renewable hydrogen source for solid oxide fuel cells (SOFCs). This study contributes to a fundamental understanding of biodiesel autothermal reforming (ATR), which has not yet been widely explored in the open literature. Ultra-low sulfur diesel (ULSD) ATR is established as a baseline for this analysis. This work applies a micro-soot meter based on a photo-acoustic method to quantify the condensed carbon from a single-tube reactor, and uses a mass spectrometer to measure the effluent gas composition under different operating conditions (reformer temperature, steam/carbon ratio, oxygen/carbon ratio, and gas hourly space velocity). The key objective is to identify the optimum operating environment for biodiesel ATR with carbon-free deposition and peak hydrogen yield. Thermodynamic analysis based on the method of total Gibbs free energy minimization is used to evaluate the equilibrium composition of effluent from the reformer. The experimental investigations complimented with this theoretical analysis of biodiesel ATR enable effectively optimizing the onboard reforming conditions. This study is one component of a three-part investigation of bio-fuel reforming, also including fuel vaporization and reactant mixing (Part 1) and biodiesel–diesel blends (Part 3).     

Measurement and analysis of carbon formation during diesel reforming for solid oxide fuel cells

Experiments and equilibrium analysis were conducted to study carbon formation during diesel reforming for a solid oxide fuel cell-based auxiliary power unit (APU) application. A photo-acoustic instrument provided direct measurements of solid carbon concentration in the reformer effluent stream, which could be correlated to reformate gas composition (as determined via mass spectrometer) and reformer temperature. These measurements were complimented by equilibrium calculations based upon minimization of total Gibbs free energy. It was determined that oxygen-to-carbon ratio (O/C), fuel utilization fraction and anode recycle fraction all influence the degree of carbon formation, and that once significant carbon concentration is measured, the reformer performance begins to show marked degradation. At a fixed operating point, lowering the reformer temperature produced by far the largest change in effluent carbon concentration. Systematic variation in O/C, fuel utilization and anode recycle revealed the interdependence among reformer temperature, effluent gas composition and carbon concentration, with a strong correlation between carbon and ethylene concentrations observed for [C₂H₄] > 0.8%. After each experiment, baseline reformer performance could be recovered by operation under methane partial oxidation (POx) conditions, indicating that reformer degradation results at least in part from carbon deposition on the reformer catalyst.     

Reinforced composite sealants for solid oxide fuel cell applications

Glass-ceramic sealants are commonly used as joining materials for planar solid oxide fuel cells stacks. Several requirements need to be fulfilled by these materials: beside of electrical insulation and appropriate thermal expansion, a good adhesion on the ceramic and metallic components of a SOFC stack is necessary to form a gas-tight joint. Even though the joining process might have been successful, failures and leaks often occur during the stack operation due to fracture of the brittle material under thermal stresses or during thermal cycling of the components. This study focusses on composite materials consisting of a glass matrix based on the system of BaO-CaO-SiO₂ and various filler materials, e.g. yttria-stabilized zirconia fibres or particles and silver particles. In order to evaluate a possible reinforcing influence of the filler material of the composite, tensile strength tests were carried out on circular butt joints. The highest strength values were found for the composite material with addition of silver particles, followed by the glass matrix itself without any filler addition and the lowest values were measured for the composite with YSZ particles. SEM investigations of cross-sections of the joints elucidated these results by the microstructure of the glass-ceramic sealants.     

Investigation of MnCu0.5Co1.5O4 spinel coated SUS430 interconnect alloy for preventing chromium vaporization in intermediate temperature solid oxide fuel cell

The MnCu_0.5Co_1.5O₄ spinel coating is proposed as a protective coating for SUS430 alloy to improve its oxidation resistance and prevent chromium vaporization. The coated alloy is exposed to dual atmosphere (Air/H₂–3%H₂O) at 750 °C for 200 h, exhibiting a stable spinel structure on the air side, but reduced to MnO, Cu and Co on the fuel side. The coating layer could maintain integrated and dense with a thickness of 13–14 μm. The experiment results shown that the MnCu_0.5Co_1.5O₄ coating is an effective diffusion barrier that can inhibit oxidation and chromium vaporization of metallic interconnect. The relatively low amount of Cr deposition on LSM cathode on coated condition is considered associating with the stable electrochemical performance under current density of 400 mA cm^?2. The above results indicate that MnCu_0.5Co_1.5O₄ spinel is a promising coating for interconnect alloy of solid oxide fuel cell.     

Feasibility of palm‐biodiesel fuel for a direct internal reforming solid oxide fuel cell

The feasibility of a direct internal reforming (DIR) solid oxide fuel cell (SOFC) running on wet palm‐biodiesel fuel (BDF) was demonstrated. Simultaneous production of H₂‐rich syngas and electricity from BDF could be achieved. A power density of 0.32 W cm^?2 was obtained at 0.4 A cm^?2 and 800 °C under steam to carbon ratio of 3.5. Subsequent durability testing revealed that a DIR‐SOFC running on wet palm‐BDF exhibited a stable voltage of around 0.8 V at 0.2 A cm^?2 for more than 1 month with a degradation rate of approximately 15 % / 1000 h. The main cause of the degradation was an increase in the ohmic resistance. Copyright © 2012 John Wiley & Sons, Ltd.     

A high performance direct carbon solid oxide fuel cell fueled by Ca-loaded activated carbon

Ca-loaded activated carbon is developed as fuel for direct carbon solid oxide fuel cells (DC-SOFCs), operating without any carrier gas and liquid medium. Ca is loaded on activated carbon through impregnation technique in the form of CaO, which exhibits excellent catalytic activity and significantly promotes the output performance of DC-SOFCs. DC-SOFCs fueled by activated carbon with different Ca loading content (0, 1, 3, 5 and 7 wt. %) are tested and the performances are compared with the DC-SOFC running on the conventional Fe-loaded activated carbon. It is found that the performance of the DC-SOFC with 5 wt. % (373 mW cm^?2) and 7 wt. % (378 mW cm^?2) Ca-loaded activated carbon is significantly higher than that of the cells operated on 5 wt. % Fe-loaded activated carbon, 1 wt. % and 3 wt. % Ca-loaded activated carbon. The discharging time and fuel utilization of the DC-SOFC with 5 wt. % Ca-loaded activated carbon are also the optimal ones among all the cells. The microstructure, element distribution and carbon conversion rate of the Ca-loaded carbon, the impedance spectra of the corresponding DC-SOFCs are measured. The reasons for the reduced fuel utilization of 7 wt. % Ca-loaded carbon fuel are analyzed and the advantage of Ca-loaded carbon for DC-SOFCs is demonstrated in detail.     

Effects of fuel cell anode recycle on catalytic fuel reforming

The presence of steam in the reactant gas of a catalytic fuel reformer decreases the formation of carbon, minimizing catalyst deactivation. However, the operation of the reformer without supplemental water reduces the size, weight, cost, and overall complexity of the system. The work presented here examines experimentally two options for adding steam to the reformer inlet: (I) recycle of a simulated fuel cell anode exit gas (comprised of mainly CO₂, H₂O, and N₂ and some H₂ and CO) and (II) recycle of the reformate from the reformer exit back to the reformer inlet (mainly comprised of H₂, CO, and N₂ and some H₂O and CO₂). As expected, anode gas recycle reduced the carbon formation and increased the hydrogen concentration in the reformate. However, reformer recycle was not as effective due principally to the lower water content in the reformate compared to the anode gas. In fact, reformate recycle showed slightly increased carbon formation compared to no recycle. In an attempt to understand the effects of individual gases in these recycle streams (H₂, CO, CO₂, N₂, and H₂O), individual gas species were independently introduced to the reformer feed.     

A review of numerical modeling of solid oxide fuel cells

The solid oxide fuel cell (SOFC) is one of the most promising fuel cells for direct conversion of chemical energy to electrical energy with the possibility of its use in co-generation systems because of the high temperature waste heat. Various mathematical models have been developed for three geometric configurations (tubular, planar, and monolithic) to solve transport equations coupled with electrochemical processes to describe the reaction kinetics including internal reforming chemistry in SOFCs. In recent years, considerable progress has been made in modeling to improve the design and performance of this type of fuel cells. The numbers of the contributions on this important type of fuels have been increasing rapidly. The objective of this paper is to summarize the present status of the SOFC modeling efforts so that unresolved problems can be identified by the researchers.     

Durability of direct internal reforming of methanol as fuel for solid oxide fuel cell with double-sided cathodes

Direct internal reforming of methanol is applied as fuel for a Ni-YSZ anode-supported solid oxide fuel cell with a flat tube based on double-sided cathodes. It achieves a power density (PD) of 0.25 W/cm² at 0.8 V, reaching about 90% of that is fueled by H₂. And the cell has been operated for more than 120 h by the direct internal reforming of methanol. The durability and apparent advantage for using humidified methanol may lead to widespread applications by direct internal reforming method for this new designed SOFC in the future.     

Study of a solid oxide fuel cell fed with n-dodecane reformate. Part II: Effect of the reformate composition

The electrochemical behaviour of a Solid Oxide Fuel Cell (SOFC) fed with n-dodecane reformate is investigated. Experiments are carried out at 800 °C by using a cell consisting of a supporting Ni anode, a thin double layer yttria-stabilised zirconia/yttria-doped ceria electrolyte and a perovskite cathode. A catalytic steam reformer (SR) is used for processing the n-dodecane at 800 °C. The reformer is operated with a steam to carbon (S/C) ratio varying progressively from 3 to 1 and a gas space velocity (GHSV) equal to 16,000 h^?1, in the presence of a RhCeO₂ZrO₂ catalyst. The composition of the reformate gas is determined by gas-chromatography before feeding the stream to the SOFC cell. An endurance test of 300 h for the coupled reformer-SOFC system shows a good stability using a range of S/C values from 3 to 1.5. Electrochemical ac-impedance spectra (EIS) and polarizations curves are carried out during the durability test to study the cell ageing. By decreasing the S/C to 1, an occlusion of the reforming reactor, as a consequence of n-dodecane cracking, occurs. Post-operation scanning electron microscopy analysis (SEM) of the SOFC cell shows that the Ni-based anode is not affected by any relevant deposition of carbon fibres including the inner pores. Whereas, the cracking process, occurring at low S/C values, is essentially involving the catalytic bed and the anode feed pipeline. However, the occurrence of high molecular weight hydrocarbons, already at S/C 1.5, causes a decrease of the cell performance. Accordingly, the best trade-off is achieved with S/C = 2.     

Advanced perovskite anodes for solid oxide fuel cells: A review

Solid oxide fuel cells (SOFCs) are at the frontline of clean energy generation technologies to convert chemical energy to electricity with high efficiency. In recent years, because of their fuel flexibility, multiple fuels are fed in anode, e.g., hydrogen, ammonia, hydrocarbons, solid carbon, etc.; in addition, these fuels are always mixed with a certain amount of H₂S. Perovskite is one of the most important classes of anode materials being investigated in laboratories, these materials to some extent are immune to coke formation and sulfur poisoning when using hydrocarbon fuels, and retain inherent stability upon reduction and oxidation cycling. In this review, recent developments in perovskite anode materials are summarized and future prospects are discussed.     

Model-based development of low-level control strategies for transient operation of solid oxide fuel cell systems

The exploitation of an SOFC-system model to define and test control and energy management strategies is presented. Such a work is motivated by the increasing interest paid to SOFC technology by industries and governments due to its highly appealing potentialities in terms of energy savings, fuel flexibility, cogeneration, low-pollution and low-noise operation.The core part of the model is the SOFC stack, surrounded by a number of auxiliary devices, i.e. air compressor, regulating pressure valves, heat exchangers, pre-reformer and post-burner. Due to the slow thermal dynamics of SOFCs, a set of three lumped-capacity models describes the dynamic response of fuel cell and heat exchangers to any operation change.The dynamic model was used to develop low-level control strategies aimed at guaranteeing targeted performance while keeping stack temperature derivative within safe limits to reduce stack degradation due to thermal stresses. Control strategies for both cold-start and warmed-up operations were implemented by combining feedforward and feedback approaches. Particularly, the main cold-start control action relies on the precise regulation of methane flow towards anode and post-burner via by-pass valves; this strategy is combined with a cathode air-flow adjustment to have a tight control of both stack temperature gradient and warm-up time. Results are presented to show the potentialities of the proposed model-based approach to: (i) serve as a support to control strategies development and (ii) solve the trade-off between fast SOFC cold-start and avoidance of thermal-stress caused damages.     

Fuel utilization and fuel sensitivity of solid oxide fuel cells

Fuel utilization and fuel sensitivity are two important process variables widely used in operation of SOFC cells, stacks, and generators. To illustrate the technical values, the definitions of these two variables as well as practical examples are particularly given in this paper. It is explicitly shown that the oxygen-leakage has a substantial effect on the actual fuel utilization, fuel sensitivity and V-I characteristics. An underestimation of the leakage flux could potentially results in overly consuming fuel and oxidizing Ni-based anode. A fuel sensitivity model is also proposed to help extract the leakage flux information from a fuel sensitivity curve. Finally, the “bending-over” phenomenon observed in the low-current range of a V-I curve measured at constant fuel-utilization is quantitatively coupled with leakage flux.     

Numerical simulation of intermediate-temperature direct-internal-reforming planar solid oxide fuel cell

A numerical model for an anode-supported intermediate-temperature direct-internal-reforming planar solid oxide fuel cell (SOFC) was developed. In this model, the volume-averaging method is applied to the flow passages in the SOFC by assuming that a porous material is inserted in the passages as a current collector. This treatment reduces the computational time and cost by avoiding a full three-dimensional simulation while maintaining the ability to solve the flow and pressure fields in the streamwise and spanwise directions. In this model, quasi-three-dimensional multicomponent gas flow fields, the temperature field, and the electric potential/current fields were simultaneously solved. The steam-reforming reaction using methane, the water-gas shift reaction, and the electrochemical reactions of hydrogen and carbon monoxide were taken into account. It was found that the endothermic steam-reforming reaction led to a reduction in the local temperature near the inlet and limited the electrochemical reaction rates therein. Computational results indicated that the local temperature and current density distributions can be controlled by tuning the pre-reforming rate. It was also found that a small amount of heat loss from the sidewall can cause significant nonuniformity in the flow and thermal fields in the spanwise direction.     

Application of biochar derived from used cigarette filters in direct carbon solid oxide fuel cell

As a typical waste, used cigarette filters (UCFs) are difficult to biodegrade and harmful to the environment. The direct carbon solid oxide fuel cell (DC-SOFC) is an energy conversion device that can utilize carbon directly, including biochar, as fuel. We report a superior DC-SOFC powered by Fe-loaded UCF biochar in this paper. The microstructure and composition are characterized, indicating that the UCF biochar is micron-sized and contains metal elements such as K and Ca that are beneficial to the performance of DC-SOFC. The peak power density of the cell fueled by pure UCF biochar is 308 mW cm^?2 and increases to 341 mW cm^?2 after loading Fe as the catalyst, which is comparable to that of the cell with Fe-loaded activated carbon (368 mW cm^?2). It proves the feasibility of the UCF biochar as fuel for DC-SOFCs, providing a theoretical basis and technical demonstration for the disposal and transformation of solid waste.     

A novel direct carbon fuel cell by approach of tubular solid oxide fuel cells

A direct carbon fuel cell based on a conventional anode-supported tubular solid oxide fuel cell, which consisted of a NiO-YSZ anode support tube, a NiO-ScSZ anode functional layer, a ScSZ electrolyte film, and a LSM-ScSZ cathode, has been successfully achieved. It used the carbon black as fuel and oxygen as the oxidant, and a preliminary examination of the DCFC has been carried out. The cell generated an acceptable performance with the maximum power densities of 104, 75, and 47 mW cm⁻² at 850, 800, and 750 °C, respectively. These results demonstrate the feasibility for carbon directly converting to electricity in tubular solid oxide fuel cells.     

Feasibility assessment of a container ship applying ammonia cracker-integrated solid oxide fuel cell technology

The maritime industry has entered its pathway of decarbonization. To achieve the IMO's ambitious goals of an absolute emissions reduction of 50% by 2050, and a 70% carbon intensity reduction by 2050 compared to the 2008 level, various options for the adoption of technologies and alternative fuels are considered by the market stakeholders.Ammonia, one of the most promising alternative marine fuels has long been considered to reduce carbon emissions. And solid oxide fuel cell is expected to transform ship propulsion technology in the future due to its high utilization of fuels. In this paper, a feasibility study is performed to assess the application of an ammonia cracker-integrated solid oxide fuel cell (hereafter as Ammonia SOFC) system on an ocean-going vessel through a detailed CAPEX, FuelEX, OPEX, Carbon tax, and carbon emission analysis. Comparison is made with direct ammonia, LNG and conventional fuels fired heat engines. The result concludes that it can be economically viable to apply to deep-sea shipping, compared to other marine fuels and propulsion technologies.     

Study on proton-conducting solid oxide fuel cells with a conventional nickel cermet anode operating on dimethyl ether

This study investigates dimethyl ether (DME) as a potential fuel for proton-conducting SOFCs with a conventional nickel cermet anode and a BaZr_0.4Ce_0.4Y_0.2O_3−δ (BZCY4) electrolyte. A catalytic test demonstrates that the sintered Ni + BZCY4 anode has an acceptable catalytic activity for the decomposition and steam reforming of DME with CO, CH₄ and CO₂ as the only gaseous carbon-containing products. An O₂-TPO analysis demonstrates the presence of a large amount of coke formation over the anode catalyst when operating on pure DME, which is effectively suppressed by introducing steam into the fuel gas. The selectivity towards CH₄ is also obviously reduced. Peak power densities of 252, 280 and 374 mW cm⁻² are achieved for the cells operating on pure DME, a DME + H₂O gas mixture (1:3) and hydrogen at 700 °C, respectively. After the test, the cell operating on pure DME is seriously cracked whereas the cell operating on DME + H₂O maintains its original integrity. A lower power output is obtained for the cell operating on DME + H₂O than on H₂ at low temperature, which is mainly due to the increased electrode polarization resistance. The selection of a better proton-conducting phase in the anode is critical to further increase the cell power output.