Tri-reforming: A new biogas process for synthesis gas and hydrogen production

In this work biogas valorization – a renewable resource – for synthesis gas and hydrogen generation through dry reforming or tri-reforming (TR) is studied. Several Ni-based catalysts and a bimetallic Rh–Ni catalyst supported on magnesia or alumina modified with oxides like CeO₂ and ZrO₂ were used. For all the experiments, a synthetic biogas (molar composition: 60% CH₄ and 40% CO₂) was fed and the catalytic activities were measured in two different experimental facilities: a bench-scale fixed bed reactor system and a microreactor reaction system, at 1073 K and atmospheric pressure. Those catalysts which achieved high activity and stability in the fixed-bed reactor were impregnated in a microreactor to explore possible process intensification. For TR processes, different steam to carbon ratios, S/C, from 1.0 to 3.0, and O₂/CH₄ ratios of 0.25 and 0.50 were used. The high methane and carbon dioxide conversions reached in the fixed bed reactor were also achieved in the microreactor operating at much higher WHSV. In addition, process intensification improved catalysts stability. Physicochemical characterization of catalyst samples by ICP-OES, N₂ physisorption, H₂ chemisorption, TPR, SEM and XPS showed differences in chemical state, metal–support interactions, average crystallite sizes and redox properties of nickel and rhodium metal particles, indicating the importance of the morphological and surface properties of metal phases in driving the reforming activity.     

Diopside–Ba disilicate glass–ceramic sealants for SOFCs: Enhanced adhesion and thermal stability by Sr for Ca substitution

This article reports on the influence of strontium for calcium substitution in diopside–Ba disilicate glass–ceramics on stabilization thermal parameters and improvement adhesion to interconnect material of SOFCs. Sr replaced 10, 20, 30 and 40% of Ca in the Ca_0.9MgAl_0.1La_0.1Si_1.9O₆ component of the parent glass having the following composition, mol.%: 22.14 CaO, 24.60 MgO, 0.52 BaO, 1.23 Al₂O₃, 1.23 La₂O₃, 47.79 SiO₂, 1.69 B₂O₃, 0.79 NiO. ²⁹Si–MAS–NMR and ²⁷Al MAS–NMR spectra of the glasses revealed irrelevant chemical shifts for silicon and aluminum atoms upon changing the SrO content. T_g decreased and coefficient of thermal expansion (CTE) increased by Sr for Ca substitution in pyroxene glasses. Additionally SrO-containing glasses exhibited a viscosity of ∼10⁶ dPa s at 900 °C, which is suitable for joining of SOFC metallic/ceramic components by glass/glass–ceramic sealing upon stack hermetization. Glass–ceramics revealed long term (up to 1000 h) thermal stability at 900 °C and suitable CTE values (10.0–11.3) × 10⁻⁶ K⁻¹, high electrical resistivity, good adhesion and minimal reactivity with SOFC components.     

Photothermovoltaic effect in a pSi-n(Si2)1 − x − y (ZnSe) x (GaP) y (0 ≤ x ≤ 0.88, 0 ≤ y ≤ 0.09) structure

The results of creating a variband epitaxial (Si₂)_{1 ? x ? y} (ZnSe) _x (GaP) _y layer and observing the photothermovoltaic effect in a pSi-n(Si₂)_{1 ? x ? y} (ZnSe) _x (GaP) _y (0 ≤ x ≤ 0.88, 0 ≤ y ≤ 0.09) heterostructure heated by concentrated solar radiation are detailed. It is shown that the photothermal and thermal voltages in the heterostructure equal 5.8 and 1.2 mV at a temperature of 80°C. The observed relatively high photothermal voltage value is attributed to the possible extrinsic thermophotoelectric effect in the layer of diluted solid solution adjacent to the p-n junction.     

Two-phase flow in a proton exchange membrane electrolyzer visualized in situ by simultaneous neutron radiography and optical imaging

In proton exchange membrane (PEM) electrolyzers, oxygen evolution in the anode and flooding due to water cross-over in the cathode yields two distinct two-phase transport conditions which strongly affect the performance. Two-phase transport in an electrolyzer cell is visualized by simultaneous neutron radiography and optical imaging. Optical and neutron data are used in a complementary manner to aid in understanding the two-phase flow behavior. Two different patterns of gas-bubble evolution and departure are identified: periodic growth/removal of small bubbles vs. prolonged blockage by stagnant large bubbles. In addition, the bubble distribution across the active area is not uniform due to combined effects of buoyancy and proximity to the inlet. The effects of operating parameters such as current density, temperature and water flow rate on the two-phase distribution are investigated. Higher water accumulation is detected in the cathode chamber at higher current density, even though the cathode is purged with a high flow rate of N₂.     

Review and Comparison of Nanofluid Thermal Conductivity and Heat Transfer Enhancements

This study provides a detailed literature review and an assessment of results of the research and development work forming the current status of nanofluid technology for heat transfer applications. Nanofluid technology is a relatively new field, and as such, the supporting studies are not extensive. Specifically, experimental results were reviewed in this study regarding the enhancement of the thermal conductivity and convective heat transfer of nanofluids relative to conventional heat transfer fluids, and assessments were made as to the state-of-the-art of verified parametric trends and magnitudes. Pertinent parameters of particle volume concentration, particle material, particle size, particle shape, base fluid material, temperature, additive, and acidity were considered individually, and experimental results from multiple research groups were used together when assessing results. To this end, published research results from many studies were recast using a common parameter to facilitate comparisons of data among research groups and to identify thermal property and heat transfer trends. The current state of knowledge is presented as well as areas where the data are presently inconclusive or conflicting. Heat transfer enhancement for available nanofluids is shown to be in the 15–40% range, with a few situations resulting in orders of magnitude enhancement.     

Free vibration analysis of a polymer electrolyte membrane fuel cell

A free vibration analysis of a polymer electrolyte membrane fuel cell (PEMFC) is performed by modelling the PEMFC as a 20 cm × 20 cm composite plate structure. The membrane, gas diffusion electrodes, and bi-polar plates are modelled as composite material plies. Energy equations are derived based on Mindlin's plate theory, and natural frequencies and mode shapes of the PEMFC are calculated using finite element modelling. A parametric study is conducted to investigate how the natural frequency varies as a function of thickness, Young's modulus, and density for each component layer. It is observed that increasing the thickness of the bi-polar plates has the most significant effect on the lowest natural frequency, with a 25% increase in thickness resulting in a 17% increase in the natural frequency. The mode shapes of the PEMFC provide insight into the maximum displacement exhibited as well as the stresses experienced by the single cell under vibration conditions that should be considered for transportation and stationary applications. This work provides insight into how the natural frequencies of the PEMFC should be tuned to avoid high amplitude oscillations by modifying the material and geometric properties of individual components.     

Biosorptive removal of Pband Cd onto novel biosorbent: Defatted Carica papaya seeds

Carica papaya seeds, an agricultural waste in Nigeria, were defatted to obtain defatted C. papaya seed biosorbent. The Fourier Transformed Infrared spectrum of defatted C. papaya seed biosorbent suggests the presence of CO, OH of carboxylic acid, lactonic and amide band functional groups. The adsorption of metal ion onto defatted C. papaya seed biosorbent led to small shifts in the IR bands. The adsorption capacity of defatted C. papaya seed biosorbent was evaluated to be 1666.67 mg/g for Pb²⁺ and 1000.00 mg/g for Cd²⁺. In binary metal ion solution, the defatted C. papaya seeds showed decreased adsorption capacity for either metal ion. The influence of different particle sizes was found to have negative impact on the adsorption capacity of C. papaya seed biosorbent in the removal of Pb²⁺ and Cd²⁺ from aqueous solution. The adsorption of both metal ions was observed to follow the Freudlich model better than the Langmuir model suggesting that the adsorption of both metal ions was on multisites on the defatted C. papaya seed biosorbent. The adsorption was found to be highly feasible, spontaneous and exothermic in nature. Optimization results suggests 5 m³ of 100 mg/L of Pb²⁺ and Cd²⁺ requires 43.3 and 49.2 kg of defatted C. papaya seeds to remove 95% of the metal ions from aqueous solution.     

Pollutant emissions of burners for steam reformers for residential power supply

The cogeneration of heat and power by means of a fuel cell based CHP unit is a promising option for efficient residential power supply. For most applications natural gas is used as fuel. One main component of such a CHP unit is a fuel processor in order to generate hydrogen from the natural gas with hydrogen thermal power output of about 6 kW. Usually the steam reforming process is used for hydrogen production. In order to meet the heat demand of the endothermic steam reforming process the fuel processor is equipped with a burner, which has to work with natural gas during start up phase and mainly with the low calorific anodic off gas of the fuel cell stack during normal operation.The presented work is focused on aspects of the main pollutant emissions (carbon monoxide and nitrogen oxide) of burners integrated into the reformer. Experimental investigations of two different burners, which were developed and adapted to the steam reformer requirements, in a real fuel processor environment show, that it is possible to operate both burner concepts with high and low calorific gases with very low pollutant emissions in order to compete with emissions of current heating boilers, which are in the range of 15 mg kWh⁻¹ for CO and of 20 mg kWh⁻¹ for NO_x by adjusting suitable excess air ratios in the range of 1.2-1.4.But it is also demonstrated, that the efficiency of the fuel processor is influenced by the excess air ratio. An increase of the air ratio from 1.05 to 1.45 leads to an decrease of the efficiency from 80% to 76%. This results in a conflict of objectives between low pollutant emissions and high system efficiencies. The choice of a suitable burner concept and the definition of a suitable operation strategy can be based on the presented results. Additionally, aspects like fuel processor geometry, flame monitoring, pressure drop in the burner feed gas line as well as in the flue gas duct, investment costs and safety items have also to be considered for the burner selection.     

Auto-ignition of toluene-doped n-heptane and iso-octane/air mixtures: High-pressure shock-tube experiments and kinetics modeling

Toluene is often used as a fluorescent tracer for fuel concentration measurements, but without considering whether it affects the auto-ignition properties of the base fuel. We investigate the auto-ignition of pure toluene and its influence on the auto-ignition of n-heptane and iso-octane/air mixtures under engine-relevant conditions at typical tracer concentrations. Ignition delay times τ_ign were measured behind reflected shock waves in mixtures with air at φ = 1.0 and 0.5 at p = 40 bar, over a temperature range of T = 700–1200 K and compared to numerical results using two different mechanisms. Based on the models, information is derived about the relative influence of toluene on τ_ign on the base fuels as function of temperature. For typical toluene tracer concentrations ?10%, the ignition delay time τ_ign changes by less than 10% in the relevant pressure and temperature range.     

Specific Energy Prediction for Circular Diamond Saw in Cutting Different Types of Rocks Using Multivariable Linear Regression Analysis

Circular diamond saw performance is affected by a variety of factors. The principal factors requiring consideration when predicting cutting rates are the type and operating features of a diamond saw and the rock characteristics. The laboratory experimental tests are carried out on three groups of rocks (16 types) cut with the help of three types of diamond disk saws with different feed rates and cutting depths at constant peripheral velocity. The quantitative determinations of a wide range of textural, mechanical, and intact properties of rocks are also made. The relationship between the specific cutting energy SE _cut of the sawblade operating parameters and rock properties is established. Applying multivariable linear regression analysis, the predictive model of SE _cut is developed based on the rock property data. Models verified by statistical tests prove their practical validity. __________ Translated from Fiziko-Tekhnicheskie Problemy Razrabotki Poleznykh Iskopaemykh, No. 3, pp. 56–80, May–June, 2005.