Hydrogen production from glycerol steam reforming for low- and high-temperature PEMFCs

This paper presents a thermodynamic study of a glycerol steam reforming process, with the aim of determining the optimal hydrogen production conditions for low- and high-temperature proton exchange membrane fuel cells (LT-PEMFCs and HT-PEMFCs). The results show that for LT-PEMFCs, the optimal temperature and steam to glycerol molar ratio of the glycerol reforming process (consisting of a steam reformer and a water gas shift reactor) are 1000 K and 6, respectively; under these conditions, the maximum hydrogen yield was obtained. Increasing the steam to glycerol ratio over its optimal value insignificantly enhanced the performance of the fuel processor. For HT-PEMFCs, to keep the CO content of the reformate gas within a desired range, the steam reformer can be operated at lower temperatures; however, a high steam to glycerol ratio is required. This requirement results in an increase in the energy consumption for steam generation. To determine the optimal conditions of glycerol steam reforming for HT-PEMFC, both the hydrogen yield and energy requirements were taken into consideration. The operational boundary of the glycerol steam reformer was also explored as a basic tool to design the reforming process for HT-PEMFC.     

Hydrogen and power generation from supercritical water reforming of glycerol and pressurized SOFC integrated system: Use of different CO2 adsorption process

The performance analysis of an integrated system of glycerol supercritical water reforming and pressurized SOFC was presented. The use of different CO₂ adsorption processes that include in situ and ex situ processes was compared to determine the suitable process for hydrogen and power generations. The influence of operating condition, e.g., temperature and pressure of reformer, supercritical water to glycerol (S/G) molar ratio, and calcium oxide to glycerol (CaO/G) molar ratio was examined. Then, the electrical performance of each integrated process was considered with respect to the SOFC conditions comprising temperature, pressure, and current density. The simulation results revealed that both processes have same favourable conditions for temperature and pressure operated at 800 °C and 240 atm, respectively. The suitable S/G and CaO/G molar ratios for in situ process are 10 and 2 whereas those for ex situ process are 20 and 1. Under these conditions, maximum hydrogen can be achieved as 87% and 75% for in situ and ex situ processes, respectively. When both integrated processes are operated at the optimal SOFC conditions as 900 °C, 4 atm, and current density of 10,000 A/m², the SOFC efficiency of 71.56% and 62.12% can provide for in situ and ex situ processes, respectively.     

Maximizing the efficiency of a HT-PEMFC system integrated with glycerol reformer

The efficiency and output power density of an integrated high temperature polymer electrolyte fuel cell system and glycerol reformer are studied. The effects of reformer temperature, steam to carbon ratio (S/C), fuel cell temperature, and anode stoichiometric ratio are examined. An increase in anode stoichiometric ratio will reduce CO poisoning effect at cell’s anode but cause lower fuel utilization towards energy generation. High S/C operation requires large amount of the energy available, however, it will increase anode tolerance to CO poisoning and therefore will lead to enhanced cell performance. Consequently, the optimum gas composition and flow rate is very dependent on cell operating current density and temperature. For example, at low current densities, similar efficiencies were obtained for all the S/C ratio studied range at cell temperature of 423.15 K, however, at cell temperature of 448.15 K, low S/C ratio provided higher efficiency in comparison to high S/C ratio. High S/C is essential when operating the cells at high current densities where CO has considerable impact on cell performance. Optimal conditions that provide the maximum power density at a given efficiency are reported.     

Thermodynamic study of hydrogen production from crude glycerol autothermal reforming for fuel cell applications

This study presents a thermodynamic analysis of hydrogen production from an autothermal reforming of crude glycerol derived from a biodiesel production process. As a composition of crude glycerol depends on feedstock and processes used in biodiesel production, a mixture of glycerol and methanol, major components in crude glycerol, at different ratios was used to investigate its effect on the autothermal reforming process. Equilibrium compositions of reforming gas obtained were determined as a function of temperature, steam to crude glycerol ratio, and oxygen to crude glycerol ratio. The results showed that at isothermal condition, raising operating temperature increases hydrogen yield, whereas increasing steam to crude glycerol and oxygen to crude glycerol ratios causes a reduction of hydrogen concentration. However, high temperature operation also promotes CO formation which would hinder the performance of low-temperature fuel cells. The steam to crude glycerol ratio is a key factor to reduce the extent of CO but a dilution effect of steam should be considered if reforming gas is fed to fuel cells. An increase in the ratio of glycerol to methanol in crude glycerol can increase the amount of hydrogen produced. In addition, an optimal operating condition of glycerol autothermal reforming at a thermoneutral condition that no external heat to sustain the reformer operation is required, was investigated.     

Modeling of an industrial fixed bed reactor based on lumped kinetic models for hydrogenation of pyrolysis gasoline

In this work, a mathematical model of an industrial fixed bed reactor for the catalytic hydrogenation of pyrolysis gasoline produced from olefin production plant is developed based on a lumped kinetic model. A pseudo-homogeneous system for liquid and solid phases and three pseudo-components: diolefins, olefins, and parraffins, are taken into account in the development of the reactor model. Temperature profile and product distribution from real plant data on a gasoline hydrogenation reactor are used to estimate reaction kinetic parameters. The developed model is validated by comparing the results of simulation with those collected from the plant data. From simulation results, it is found that the prediction of significant state variables agrees well with the actual plant data for a wide range of operating conditions; the developed model adequately represents the fixed-bed reactor.     

Electrochemical performance assessment of low-temperature solid oxide fuel cell with YSZ-based and SDC-based electrolytes

In this work, solid oxide fuel cells (SOFCs) based on different electrolytes, i.e., the yttria-stabilized zirconia (YSZ) and the samaria-doped ceria (SDC), were investigated to study their performances at low-temperature operation. The predicted performance of both SOFCs was validated with the experimental results. The verified models were implemented to study the impact of operating conditions, i.e., cell temperature, pressure, thicknesses of cathode, anode, and electrolyte, on their performances. The decrease in the operating temperature from intermediate range (800–900 °C) to low range (550–650 °C) has a considerable effect on the performance of the YSZ-based SOFC as conventional type, which dropped from 0.67–1.40 W/cm² to 0.027–0.13 W/cm². Under the low operating temperature range, the performance of SDC-based SOFC was superior to that of the YSZ-based SOFC, due to the lower ohmic loss. Nevertheless, the SDC-based SOFC has higher concentration overpotentials than the YSZ-based SOFC. The concentration overpotentials of the SDC-based SOFC can be reduced by the thinner anode and cathode thicknesses. In addition, the SDC-based SOFC at low operating temperature with the pressurized operation could significantly improve its power density, about 20% at 2 bar, which was close to that of YSZ-based SOFC at intermediate temperature of 800 °C.     

The use of dilute acetic acid for butyl acetate production in a reactive distillation: Simulation and control studies

The recovery of dilute acetic acid, which is widely found as a by-product in many chemical and petrochemical industries, becomes an important issue due to economic and environmental awareness. In general, separation of acetic acid in aqueous solution by conventional distillation columns is difficult, requiring a column with many stages and high energy consumption. As a result, the primary concern of the present study is the application of reactive distillation as a potential alternative method to recover dilute acetic acid. The direct use of dilute acetic acid as reactant for esterification with butanol to produce butyl acetate in the reactive distillation is investigated. Simulation studies are performed in order to investigate effect of the concentration of dilute acetic acid and key process parameters on the performance of the reactive distillation in terms of acetic acid conversion and butyl acetate production. In addition, three alternative control strategies are studied for the closed loop control of the reactive distillation. The control objective is to maintain the butyl acetate in a bottom product stream at the desired purity of 99.5 wt%.