Improvement of high-rate capability of alkaline Zn–MnO2 battery

Electrolytic dendritic-zinc powders of high surface area are prepared from an alkaline solution by a galvanostatic electrodeposition method. The surface morphology and microstructure of these powders are examined by scanning electron microscopy (SEM) and X-ray diffraction (XRD). Cylindrical AA-size alkaline zinc–manganese dioxide (Zn–MnO₂) batteries made with powders in anode gels are assembled and tested. The electrochemical characteristics of the batteries are evaluated by means of the ac impedance method and the constant-current discharge experiments. It is found that the high-rate performance of cells with dendritic-zinc powders is much better than that of cells with conventional molten-zinc powders.     

H2 production of (CdS–ZnS)–TiO2 supported photocatalytic system

Mixed semiconductor (CdS–ZnS)–TiO₂(1 : 1 : 1) mixture system over different supports like MgO, CaO, γ-Al₂O₃, SiO₂ and modified MgO and CaO, have been prepared, characterized and tested for H₂ production in a S²⁻⧸SO²⁻₃ mixture solution. (CdS–ZnS)–TiO₂(D) over MgO support wherein the TiO₂ taken is from Degussa (D) sample gives 206.7 μmol⧸h of H₂ production and this catalyst sustain the H₂ production rate for longer durations. Dopants like Li₂O, Cs₂O or K₂O make MgO and CaO supports act like super basic oxide when they are doped and in turn increase the photocatalytic activity. The (CdS–ZnS)–TiO₂(I) system wherein the TiO₂ taken from Titanium Isopropoxide, supported on 20 wt% Li₂O doped CaO is found to give 209.8 μmol⧸h rate of H₂ production. Characterization studies like UV-Visible spectra, X-ray Diffraction spectra and Scanning Electron Microscope photographs were taken for all the catalysts and the data generated over these samples is evaluated. A scheme of H₂S photocatalytic decomposition of ZnCdS–TiO₂(D⧸I) over different supports in the presence of S²⁻⧸SO²⁻₃ substrate, is proposed indicating the formation of thiosulfate cycle at this heterojunction. © 1999 International Association for Hydrogen Energy. Published by Elsevier Science Ltd. All rights reserved.     

Recyclable CeO2–ZrO2 and CeO2–TiO2 mixed oxides based Pt catalyst for aqueous-phase reforming of the low-boiling fraction of bio-oil

In this study, a series of CeO₂–ZrO₂ and CeO₂–TiO₂ materials with different composition were prepared, characterized by BET and XRD analysis, and their hydrothermal stability was studied by subjecting the samples to acetic acid solutions at 533 K. All of the materials, especially C1Z1 (50 mol% CeO₂ with 50 mol% ZrO₂) and C1T1 (50 mol% CeO₂ with 50 mol% TiO₂), exhibited excellent stability with no phase transformation and minimal decrease in their specific surface area (SSA) was observed even after 16 h. After being loaded by Pt, these catalysts were used for the aqueous phase reforming (APR) of the low-boiling fraction of bio-oil (LBF) to investigate their catalytic performance. Among these catalysts Pt/C1Z1 and Pt/C1T1 showed superior catalytic activity, probably due to their lowest reduction temperature and the largest amount of O vacancies generated by the reduction of the surface oxygen of well-dispersed CeO₂. Thus, Pt/C1Z1 and Pt/C1T1 were chosen to investigate their recyclability. The catalytic activity and H₂ selectivity of Pt/C1Z1 and Pt/C1T1 can be almost recovered after being calcined in air at 773 K for regeneration. After three cycles, the particle size of Pt/C1Z1 and Pt/C1T1 only experienced a slight increase, while for Pt/Al₂O₃ it increased from 2.9 nm to 7.8 nm. So, compared with Pt/Al₂O₃, the Pt/C1Z1 and Pt/C1T1 catalysts were identified as effective and recyclable candidates for the production of H₂ rich fuel gas from APR of LBF.     

Effects of CaO addition on Ni/CeO2–ZrO2–Al2O3 coated monolith catalysts for steam reforming of N-decane

A series of 10 wt%Ni/CeO₂–ZrO₂–Al₂O₃ (10%Ni/CZA) coated monolith catalysts modified by CaO with the addition amount of 1 wt%~7 wt% are prepared by incipient-wetness co-impregnation method. Effects of CaO promoter on the catalytic activity and anti-coking ability of 10%Ni/CZA for steam reforming of n-decane are investigated. The catalysts are characterized by N₂ adsorption-desorption, XRD, SEM-EDS, TEM, NH₃-TPD, XPS, H₂-TPR and Raman. The results show that specific surface area and pore volume of as-prepared catalysts decrease to some extent with the increasing addition of CaO. However, the proper amounts of CaO (≤3 wt%) significantly enhance the catalytic activity in terms of n-decane conversion and H₂ selectivity mainly due to the improved dispersion of NiO particles (precursor of Ni particles). As for anti-coking performance, reducibility of CeO₂ in composite oxide support CZA is promoted by CaO resulting in providing more lattice oxygen, which favors suppressing coke formation. Moreover, the addition of CaO reduces the acidity of 10%Ni/CZA, especially the medium and strong acidity. But far more importantly, a better dispersion of NiO particles obtained by proper amounts of CaO addition is dominant for the lower carbon formation, as well as the higher catalytic activity. For the spent catalysts, amorphous carbon is the main type of coke over 10%Ni–3%CaO/CZA, while abundant filamentous carbon is found over the others.     

Thermodynamic models for H2O–CO2–H2 mixtures in near-critical and supercritical regions of water

The PVTx properties of the H₂O–CO₂–H₂ mixtures have significant applications in the technology of supercritical water gasification of coal. Here, we first carry out the molecular dynamics simulations of the PVTx properties of the H₂O–CO₂–H₂ mixtures in the near-critical and supercritical regions of water to generate 600 datasets at 750–1150 K and 4.0–443.5 MPa. The molar fraction of each composition in the ternary mixtures ranges from 10% to 80%. Later we investigate the applicability of a well-known thermodynamic model for the ternary mixtures, namely the Duan-Møller-Weare equation of state (DMW EOS). It is observed that the DMW EOS shows great potential in the prediction of the PVTx properties of the ternary mixtures. However, it is noted that the mixing parameters describing the binary interactions of H₂O–H₂ and CO₂–H₂ are still unknown in the DMW EOS. By determining the missing mixing parameters using the Levenberg-Marquardt algorithm, the accuracy of the original DMW EOS is improved for the ternary mixtures. Moreover, optimizing the coefficients in the DMW EOS further promotes the accuracy of the model for the H₂O–CO₂–H₂ mixtures. The results from this work may facilitate the development of supercritical water gasification of coal.     

Hydrogen-induced softening of Ti–44Al–6Nb–1Cr–2V alloy during hot deformation

The effect of hydrogen on the hot deformation behavior and microstructural evolution of Ti–44Al–6Nb–1Cr–2V (at.%) alloys were investigated at temperature range of 1373–1523 K under strain rate of 0.01 s^?1. The true stress–strain curves show that the peak stress decreases from 323 MPa to 97 MPa when deformation temperature increases from 1373 K to 1523 K. The peak stress is decreased by 30% after hydrogenation with 2% H, which corresponds to the decrease of deformation temperature by about 50 K, it denotes that hydrogen can promote a solution softening effect in TiAl alloys. This is attributed to hydrogen-promoted the dynamic recrystallization, hydrogen-induced dislocation movement and hydrogen-stabilized the B2 phase. For dynamic recrystallization, the calculated results show that hydrogen accelerates the onset of dynamic recrystallization, which means that hydrogen promotes the dynamic recrystallization kinetics. For dislocation movement, EBSD results show that the fraction of low-density dislocation region increases from 59.6% to 79.7% after hydrogenation with 2% H, which indicates that hydrogen reduces the dislocation tangles and dislocation density. For B2 phase, more softening B2 phases are observed in hydrogenated alloy compared with that in unhydrogenated alloy, which results from hydrogen-promoted the transition of L (α₂/γ) → γ + B2. The positive effect of hydrogen on TiAl alloys provides an effective method to improve the hot workability of TiAl alloys.     

Hydrogen absorption–desorption cycle experiment of Pd–Al2O3 pellets

A series of hydrogen absorption–desorption processes using a pellet form of Pd–Al₂O₃ was repeated up to 1010 cycles. Variations in the amounts and rates of hydrogen absorption and desorption with cycles were determined by means of a constant-volume method. The amounts and rates of absorption and desorption were almost unchanged up to 1010 cycles. The Scanning Electron Microscope pictures and Energy Dispersive Spectroscopy showed no microscopic change on the pellet surface after 1010 cycles. The experimental results assured a high tolerance of the Pd–Al₂O₃ pellet to repetitive absorption–desorption cycles.     

Hydrogen storage properties of Li–Ca–N–H system with different molar ratios of LiNH2/CaH2

In this work, dehydrogenation and rehydrogenation of three LiNH₂/CaH₂ samples with LiNH₂/CaH₂ molar ratio of 2/1, 3/1 and 4/1 were systematically investigated. Remarkable differences were observed in the temperature dependence of hydrogen desorption and subsequent absorption. LiNH₂/CaH₂ in a molar ratio of 2/1 transforms to ternary imide Li₂Ca(NH)₂ after desorbing about 4.5 wt.% H₂ at 350 °C. And it has a reversible hydrogen storage capacity of 2.7 wt.% at 200 °C. As for the LiNH₂/CaH₂ mixture in a molar ratio of 4/1, it transforms to a new compound with a composition of Li₄CaN₄H₆ after being dehydrogenated at 350 °C. The rehydrogenation of both LiCa(NH)₂ and Li₄CaN₄H₆ gives LiNH₂, LiH and the solid solution of 2CaNH–Ca(NH₂)₂.     

Investigation of oxidation and electrical behavior of AISI 430 steel coated with Mn–Co–CeO2 composite

Ferritic stainless steels, under the working conditions of solid oxide fuel cells, form a chromium oxide layer. This layer has a low electrical conductivity and consequently reduces the efficiency of these energy converters. An action to improve the properties of the connecting plates is to use a conductive and protective layer of coating. In this study, AISI 430 stainless steel was coated with Mn–Co–CeO₂ through electroplating technique. To evaluate the oxidation behavior, isothermal and cyclic oxidation tests were used at 800 °C. Area specific resistance (ASR) of uncoated and coated specimens was also compared as a function of time during oxidation at 800 °C. Coating microstructure and oxidized samples were examined by scanning electron microscopy (SEM) and X-ray diffraction (XRD) device. In isothermal oxidation, uncoated samples had more weight gain than the Mn–Co–CeO₂ coated samples. The coating layer improved oxidation resistance by limiting the diffusion of chromium cation and oxygen anion. The cyclic oxidation results showed that the Mn–Co–CeO₂ coated samples had a very good resistance to cracking and spallation. Also, the results of ASR showed that formation of MnCo₂O₄ and MnFe₂O₄ spinels and also the presence of CeO₂ resulted in reduction of area specific resistance. ASR for samples coated with Mn–Co–CeO₂ and uncoated samples was 12.4 mΩ.cm² and 38.7 mΩ.cm², respectively after 200 h of oxidation at 800 °C.     

Laminar burning velocities and flame characteristics of CO–H2–CO2–O2 mixtures

Laminar burning velocities of CO–H₂–CO₂–O₂ flames were measured by using the outwardly spherical propagating flame method. The effect of large fraction of hydrogen and CO₂ on flame radiation, chemical reaction, and intrinsic flame instability were investigated. Results show that the laminar burning velocities of CO–H₂–CO₂–O₂ mixtures increase with the increase of hydrogen fraction and decrease with the increase of CO₂ fraction. The effect of hydrogen fraction on laminar burning velocity is weakened with the increase of CO₂ fraction. The Davis et al. syngas mechanism can be used to calculate the syngas oxyfuel combustion at low hydrogen and CO₂ fraction but needs to be revised and validated by additional experimental data for the high hydrogen and CO₂ fraction. The radiation of syngas oxyfuel flame is much stronger than that of syngas–air and hydrocarbons–air flame due to the existence of large amount of CO₂ in the flame. The CO₂ acts as an inhibitor in the reaction process of syngas oxyfuel combustion due to the competition of the reactions of H + O₂ = O + OH, CO + OH = CO₂ + H and H + O₂(+M) = HO₂(+M) on H radical. Flame cellular structure is promoted with the increase of hydrogen fraction and is suppressed with the increase of CO₂ fraction due to the combination effect of hydrodynamic and thermal-diffusive instability.     

Suppression of hydrogen–oxygen–nitrogen explosions by fine water mist: Part 2. Mitigation of vented deflagrations

The simultaneous use of water mist and dilution by nitrogen has not been previously considered for the mitigation of hydrogen containing gas explosions and there is little guidance currently available to plant and safety engineers in the nuclear industry. This gap in knowledge is addressed and data reported for the reduction of rates of pressure rise experienced in a vented apparatus. Such information will also be of use in subsequent, separate modelling studies.     

Fabrication and testing of a H2–O2 fuel cell using MoxRuySez

We report the results obtained in the preparation and characterization of Mo_xRu_ySe_z electrocatalysts for oxygen reduction reaction and the design, construction and characterization of a H₂–O₂ fuel cell using Mo_xRu_ySe_z. The catalysts were characterized with respect to their electrocatalytic properties. The fuel cell was designed and built with Mo_xRu_ySe_z supported on carbon as cathode, Pt supported on carbon as anode, and H₂SO₄ as the electrolyte. The fuel cell was tested at room temperature and atmospheric pressure. The H₂–O₂ cell showed an efficiency in the order of 30%.     

Experimental study of the vapour–liquid equilibria of HI–I2–H2O ternary mixtures,Part 2: Experimental results at high temperature and pressure

In order to assess the choice of the sulphur–iodine thermochemical cycle for massive hydrogen production, a precise knowledge of the concentrations of the gaseous species (HI, I₂, and H₂O) in thermodynamic equilibrium with the liquid phase of the HI–I₂–H₂O ternary mixture is required, in a wide range of concentrations and for temperatures and pressures up to 300 °C and 50 bar.     

Synthesis of heat exchanger networks featuring a minimum number of constrained-size shells of 1–2 type

In chemical plants requiring a high number of heat exchangers, standard sizes are established so that most of the services can be satisfied through arrays of a limited number of different standard-type units. If such an industrial practice is not taken into account during the heat recovery network synthesis task, the optimality of the proposed design could be doubtful. This paper addresses the HENS problem allocating multiple constrained-size shells rather than a single one to accomplish a heat match. Two cases are considered: (a) pure countercurrent exchangers and (b) shell-and-tube exchangers of 1–2 type. The neighbor-based HENS framework of Galli and Cerdá (1998) has been generalized in order to adopt a more realistic fixed-cost target, i.e. the overall number of constrained-size shells. Therefore, new 0–1 variables have been defined to stand for the additional shells needed to get both, a shell size below the specified upper bound, and simultaneously, an F_T correction factor above the threshold value everywhere. The resulting MILP problem formulation is now able to find network structures reaching the heat recovery target, under some structural constraints on the network design specified by the user, at near-minimum capital cost. The proposed algorithmic approach has been successfully applied to the solution of a couple of example problems and produced significant capital cost savings compared with prior HENS techniques.     

Study of Ni/CeO2–ZnO catalysts in the production of H2 from acetone steam reforming

This paper reports the study of new Ni/ZnO-based catalysts for hydrogen production from substoichiometric acetone steam reforming (ASR). The effect of CeO₂ introduction is analyzed regarding the catalytic behavior and carbon deposits formation. ASR was studied at 600 °C using a steam/carbon ratio S/C = 1. Ni/xCeZnO (x = 10, 20, 30 CeO₂ wt %) catalysts showed a better performance than the bare Ni/ZnO. Ni/xCeZnO generated a lower amount and less ordered carbon deposits than Ni/ZnO. The higher the CeO₂ content in Ni/xCeZnO, the lower the amount of carbon deposits in the post-reaction catalyst. The highest H₂ production under ASR at the experimental conditions used was achieved for the Ni/xCeZnO catalysts. In-situ DRIFTS-MS experiments under ESR conditions showed different reaction pathways over Ni/20CeZnO and Ni/ZnO catalysts.     

Effect of Y element on cyclic stability of A2B7 -type La–Y–Ni-based hydrogen storage alloy

The La_3-xY_xNi_9.7Mn_0.5Al_0.3 (x = 1, 1.5, 1.75, 2, 2.25, 2.5) alloys were prepared by magnetic suspension induction melting method and annealed at 1273 K for 24 h. The alloys were tested using electrochemical measurements, X-ray diffraction (XRD) and scanning electron microscope with energy-dispersive X-ray diffraction spectroscope (SEM-EDS). With the increase of Y content, the main phase of the alloys changed from Gd₂Co₇ phase to Ce₂Ni₇ phase, and Ce₂Ni₇ phase increased gradually. The maximum discharge capacity of alloys increased from 279.3 mA h/g (x = 1) to 383.8 mA h/g (x = 2.5). The high-rate dischargeabilitiy at the discharge current density of 1200 mA/g increased from 56.98% (x = 1) to 83.76% (x = 2.5). The maximum capacity retention rate first increased from 50.13% (x = 1) to 69.43% (x = 2), and then decreased to 21.35% (x = 2.5). The results showed that the structural stability of the alloys was improved due to the increase of Y content. However, with the increase of Y content, the corrosion, pulverization, and the dissolution of Al element aggravated, which deteriorated the cyclic stability of the alloy electrodes.     

Study on the characteristics of evaporation–atomization–combustion of biodiesel

A great deal of research is being carried out on renewable diesel fuels. The number of raw materials (especially waste, animal, and vegetable oils), production technologies, and additives of biodiesel is increasing. In our work, a evaporation–atomization–combustion system consisting of a biomass liquid fuel was designed to produce a laminar premixed flame for studying the combustion–emission characteristics of biodiesel. The combustion characteristics of biodiesel including flame height, flame front area, flame speed, and OH total signal intensity were studied by planar laser-induced fluorescence of OH (OH-PLIF). The emission characteristics of biodiesel (CO, CO₂, and NO) were studied with a flue gas analyzer. The experimental results showed that the flame height, flame front area, flame speed, and the OH total signal intensity changed with the equivalence ratio (Φ). The relationship between the OH radical intensity and the emission of CO/CO₂ was obtained from the OH-PLIF average signal intensity. The [CO]/[CO₂] ratio decreased with the OH-PLIF average signal intensity. Finally, we obtained the relationship between the OH-PLIF average signal intensity and the NO emissions.