Design of a methanol reformer for on-board production of hydrogen as fuel for a 3 kW High-Temperature Proton Exchange Membrane Fuel Cell power system

The method of Computational Fluid Dynamics is used to predict the process parameters and select the optimum operating regime of a methanol reformer for on-board production of hydrogen as fuel for a 3 kW High-Temperature Proton Exchange Membrane Fuel Cell power system. The analysis uses a three reactions kinetics model for methanol steam reforming, water gas shift and methanol decomposition reactions on Cu/ZnO/Al₂O₃ catalyst. Numerical simulations are performed at single channel level for a range of reformer operating temperatures and values of the molar flow rate of methanol per weight of catalyst at the reformer inlet. Two operating regimes of the fuel processor are selected which offer high methanol conversion rate and high hydrogen production while simultaneously result in a small reformer size and a reformate gas composition that can be tolerated by phosphoric acid-doped high temperature membrane electrode assemblies for proton exchange membrane fuel cells. Based on the results of the numerical simulations, the reactor is sized, and its design is optimized.     

Novel core-shell-like Ni-supported hierarchical beta zeolite catalysts on bioethanol steam reforming

Hierarchical-Beta zeolites have been hydrothermally synthesized by adding a new gemini organic surfactant. The used gemini surfactant play the role of a “pore-forming agents” on the mesoscale, on the same time, providing alkaline environment for the system. With this hierarchical Beta zeolite as the core support, we successfully prepared a shell layer of Ni-containing (22 wt%) petal-like core-shell-like catalyst and applied it to bioethanol steam reforming. At the reaction temperature of 350 °C–550 °C, the conversion rate of ethanol and the selectivity of hydrogen were always above 85% and 70%. After reaction of 100 h on stream at 400 °C, there were not obvious inactivation could be observed on NiNPs/OH-MBeta catalyst.     

Techno-economical evaluations of decarbonized hydrogen production based on direct biogas conversion using thermo-chemical looping cycles

Hydrogen production by biogas conversion represent a promising solution for reduction of fossil CO₂ emissions. In this work, a detailed techno-economic analysis was performed for decarbonized hydrogen production based on biogas conversion using calcium and chemical looping cycles. All evaluated concepts generate 100,000 Nm³/h high purity hydrogen. As reference cases, the biogas steam reforming design without decarbonization and with CO₂ capture by gas-liquid chemical absorption were also considered. The results show that iron-based chemical looping design has higher energy efficiency compared with the gas-liquid absorption case by 2.3 net percentage points as well as a superior carbon capture rate (99% vs. 65%). The calcium looping case shows a lower efficiency than chemical scrubbing, with about 2.5 net percentage points, but the carbon capture rate is higher (95% vs. 65%). The hydrogen production cost increases with decarbonization, the calcium looping shows the most favourable situation (37.14 €/MWh) compared to the non-capture steam reforming case (33 €/MWh) and MDEA and iron looping cases (about 42 €/MWh). The calcium looping case has the lowest CO₂ avoidance cost (10 €/t) followed by iron looping (20 €/t) and MDEA (31 €/t) cases.     

Integrated and inherently safe design and operation of a mobile power generation: Process intensification through microreactor reformer and HT-PEMFC

In the present study, due to various advantages of process miniaturization, the integrated design and operation of a mobile power generation system consisting of a microreactor reformer and a proton exchange membrane fuel cell (PEMFC) are investigated. The hydrogen fuel is supplied through autothermal steam-reforming of methanol in a microreactor leading to a safer, as well as more efficient, and economical operation. A high-temperature polymer membrane fuel cell with external accessories is applied for power generation. Then, simulation-optimization programming is applied for simultaneously optimizing the process design and operation at the same level. The result shows that the implemented procedure ensures the economic and flexible operation of the process while satisfying the safety constraints. The maximum gross power and net power generation are 109.3 and 91.9, respectively, while the cost of hydrogen production reduces from 13 to 20 $/kg to 7.7 $/kg. The fuel (methanol) consumption can be as low as 0.42 L/kWh.     

Ultracompact methane steam reforming reactor based on microwaves susceptible structured catalysts for distributed hydrogen production

Hydrogen is a potential green energy vector. Since the heating of the reforming processes commonly used for its production is obtained by burning hydrocarbons, it has a substantial CO₂ footprint. One of the most critical aspects in the methane steam reforming (MSR) reaction is the heat transfer to the catalytic volume, due to the high heat fluxes required to obtain high methane conversions. Consequently, the reactor has complex geometries, along with the heating medium being characterized by temperatures higher than 1000 °C; expensive construction materials and high reaction volumes are therefore needed, resulting in slow thermal transients. These aspects increase the costs (both operative and fixed) as well as cause a decrease in the whole process efficiency. The heat transfer limitations due to the endothermicity of methane steam reforming reaction could be effectively overcome by microwave (MW) heating. This heating technique, that depends only on the dielectric properties of the materials, can result in an efficient and faster method for transferring heat directly to the catalyst, thus generating the heat directly inside the catalytic volume. In this work, Ni-based catalysts, differing from each other by the Ni loading (7 and 15 wt% with respect to the washcoat) were prepared. The catalysts were characterized by means of several techniques and tested in the MW-assisted methane steam reforming reaction. Furthermore, the energy balance of the entire process was performed to calculate the energy efficiency, making a preliminary evaluation of its feasibility in distributed hydrogen production also possible. The results of the preliminary tests showed that the prepared structured catalysts are very susceptible to the MW radiation, and that in the presence of the MSR reaction, it is possible to make the system reach a temperature of 900 °C. In the same tests, the CH₄ conversion showed a good approach to the thermodynamic equilibrium values starting at temperatures of about 800 °C at a value of gas hourly space velocity (GHSV) of about 5000 h^?1. The energy efficiency of the lab-scale system, calculated as the ratio among the energy absorbed by the system and the energy supplied by the microwaves, was about 50%. Future studies will deal with the microwave reactor optimization, aiming at the increase of the energy efficiency of the system, as well as to obtain a higher CH₄ conversion at lower temperatures and increase the H₂ yield and selectivity.     

The effect of non-uniform temperature on the sorption-enhanced steam methane reforming in a tubular fixed-bed reactor

The effect of non-uniform temperature on the sorption-enhanced steam methane reforming (SE-SMR) in a tubular fixed-bed reactor with a constant wall temperature of 600 °C is investigated numerically by an experimentally verified unsteady two-dimensional model. The reactor uses Ni/Al₂O₃ as the reforming catalyst and CaO as the sorbent. The reaction of SMR is enhanced by removing the CO₂ through the reaction of CaO + CO₂ → CaCO₃ based on the Le Chatelier's principle. A non-uniform temperature distribution instead of a uniform temperature in the reactor appears due to the rapid endothermic reaction of SMR followed by an exothermic reaction of CO₂ sorption. For a small weight hourly space velocity (WHSV) of 0.67 h^?1 before the CO₂ breakthrough, both a low and a high temperature regions exist simultaneously in the catalyst/sorbent bed, and their sizes are enlarged and the temperature distribution is more non-uniform for a larger tube diameter (D). Both the CH₄ conversion and the H₂ molar fraction are slightly increased with the increase of D. Based on the parameters adopted in this work, the CH₄ conversion, the H₂ and CO molar fractions at D = 60 mm are 84.6%, 94.4%, and 0.63%, respectively. After CO₂ breakthrough, the reaction of SMR dominates, and the reactor performance is remarkably reduced due to low reactor temperature.For a higher value of WHSV (4.03 h^?1) before CO₂ breakthrough, both the reaction times for SMR and CO₂ sorption become much shorter. The size of low temperature region becomes larger, and the high temperature region inside the catalyst/sorbent bed doesn't exist for D ≥ 30 mm. The maximum temperature difference inside the catalyst/sorbent bed is greater than 67 °C. Both the CH₄ conversion and H₂ molar fraction are slightly decreased with the increase of D. However, this phenomenon is qualitatively opposite to that for small WHSV of 0.67 h^?1. The CH₄ conversion and H₂ molar fraction at D = 60 mm are 52.6% and 78.7%, respectively, which are much lower than those for WHSV = 0.67 h^?1.     

Hydrogen production employing Cu(BDC) metal–organic framework support in methanol steam reforming process within monolithic micro-reactors

Cu(BDC) metal–organic framework (MOF) was used as a support for the copper (Cu) catalyst applied in the methanol steam reforming (MSR) process at low temperatures (130–250 °C) with a feed WHSV = 9.2 h^?1 within the monolithic reactor. Also, the effects of diverse promoters were examined on the catalytic activities of the Cu/X–Cu(BDC) (X = Ce, Zn, Gd, Sm, La, Y, Pr) catalysts. Results showed that the Ce/Sm–Cu(BDC) supports exhibited highest activities, lowest reduction temperatures and largest specific surface areas, which caused highest distributions of the active copper metal nanoparticles on the supports. The reactor tests displayed that the activities of Cu/X–Cu(BDC) (X = Ce, Zn, Gd, Sm, La, Y, Pr) catalysts followed the order X = Ce > Sm > Y > La > Pr > Cu(BDC) > Zn > Gd. The highest activities of Ce and Sm containing catalysts were attributed to the presence of CeO₂ and Sm₂O₃ caused the oxygen vacancies on the catalyst surface which had positive effects on the methanol reforming process. The time-on-stream stability tests showed the highest resistance of the Cu/Ce–Cu(BDC) catalyst to the carbon formation during 32 h. Consequently, the Cu/Ce–Cu(BDC) with the highest stability, methanol conversion and carbon monoxide selectivity could be used in practical industrial applications.     

Tungsten(VI) oxide supported rhodium nanoparticles: Highly active catalysts in hydrogen generation from ammonia borane

Herein, we report the use of tungsten(VI) oxide (WO₃) as support for Rh⁰ nanoparticles. The resulting Rh⁰/WO₃ nanoparticles are highly active and stable catalysts in H₂ generation from the hydrolysis of ammonia borane (AB). We present the results of our investigation on the particle size distribution, catalytic activity and stability of Rh⁰/WO₃ catalysts with 0.5%, 1.0%, 2.0% wt. Rh loadings in the hydrolysis reaction. The results reveal that Rh⁰/WO₃ (0.5% wt. Rh) is very promising catalyst providing a turnover frequency of 749 min^?1 in releasing 3.0 equivalent H₂ per mole of AB from the hydrolysis at 25.0 °C. The high catalytic activity of Rh⁰/WO₃ catalyst is attributed to the reducible nature of support. The report covers the results of kinetics study as well as comparative investigation of activity, recyclability, and reusability of colloidal(0) nanoparticles and Rh⁰/WO₃ (0.5 % wt. Rh) catalyst in the hydrolysis reaction.     

Production of hydrogen from methanol steam reforming using CuPd/ZrO2 catalysts – Influence of the catalytic surface on methanol conversion and CO selectivity

Electricity generation for mobile applications by proton exchange membrane fuel cells (PEMFCs) is typically hindered by the low volumetric energy density of hydrogen. Nevertheless, nearly pure hydrogen can be generated in-situ from methanol steam reforming (MSR), with Cu-based catalysts being the most common MSR catalysts. Cu-based catalysts display high catalytic performance, even at low temperatures (ca. 250 °C), but are easily deactivated. On the other hand, Pd-based catalysts are very stable but show poor MSR selectivity, producing high concentrations of CO as by-product. This work studies bimetallic catalysts where Cu was added as a promoter to increase MSR selectivity of Pd. Specifically, the surface composition was tuned by different sequences of Cu and Pd impregnation on a monoclinic ZrO₂ support. Both methanol conversion and MSR selectivity were higher for the catalyst with a CuPd-rich surface compared to the catalyst with a Pd-rich surface. Characterization analysis indicate that the higher MSR selectivity results from a strong interaction between the two metals when Pd is impregnated first (likely an alloy). This sequence also resulted in better metallic dispersion on the support, leading to higher methanol conversion. A H₂ production rate of 86.3 mmol h^?1 g^?1 was achieved at low temperature (220 °C) for the best performing catalyst.