Revision of the NaBO2–H2O phase diagram for optimized yield in the H2 generation through NaBH4 hydrolysis

The binary phase diagram NaBO₂–H₂O at ambient pressure, which defines the different phase equilibria that could be formed between borates, end-products of NaBH₄ hydrolysis, has been reviewed. Five different solid borates phases have been identified: NaBO₂·4H₂O (Na[B(OH)₄]·2H₂O), NaBO₂·2H₂O (Na[B(OH)₄]), NaBO₂·2/3H₂O (Na₃[B₃O₄(OH)₄]), NaBO₂·1/3H₂O (Na₃[B₃O₅(OH)₂]) and NaBO₂ (Na₃[B₃O₆]), and their thermal stabilities have been studied. The boundaries of the different Liquid + Solid equilibria for the temperature range from −10 to 80 °C have been determined, confirming literature data at low temperature (20–50 °C). Moreover the following eutectic transformation, Liq. → Ice + NaBO₂·4H₂O, occurring at −7 °C, has been determined by DSC. The Liquid–Vapour domain has been studied by ebullioscopy. The invariant transformation Liq. → Vap. + NaBO₂·2/3H₂O has been estimated at 131.6 °C. This knowledge is paramount in the field of hydrogen storage through NaBH₄ hydrolysis, in which borate compounds were obtained as hydrolysis reaction products. As a consequence, the authors propose a comparison with previous NaBO₂–H₂O binary phase diagrams and its consequence related to hydrogen storage through NaBH₄ hydrolysis.     

Study of the influence of the amount of PBI–H3PO4 in the catalytic layer of a high temperature PEMFC

The influence of the amount of polybenzimidazole (PBI)-H₃PO₄ (normalized with respect to the PBI loading, which expressed as C/PBI weight ratio) content in both the anode and cathode has been studied for a PBI-based high temperature proton exchange membrane (PEM) fuel cell. The electrodes prepared with different amounts of PBI have been characterized physically, by measuring the pore size distribution, and visualizing the surface microstructure. Afterwards, the electrochemical behaviour of the electrodes has been evaluated. The catalytic electrochemical activity has been measured by voltamperometry for each electrode prepared with a different PBI content, and the cell performance results have been studied, supported by the impedance spectra, in order to determine the influence of the PBI loading in each electrode. The best results have been achieved with a C/PBI weight ratio of 20, for both the anode and the cathode. A lower C/PBI weight ratio (larger amount of PBI in the catalytic layer) reduced the electrocatalytic activity, and impaired the mass transport processes, due to the large amount of polymer covering the catalyst particle, lowering the cell performance. A higher C/PBI weight ratio (lower amount of PBI in the catalytic layer) reduced the electrocatalytic activity, and slightly increased the ohmic resistance. The low amount of the polymeric ionic carrier PBI–H₃PO₄ limited the proton mobility, despite of the presence of large amounts of “free” H₃PO₄ in the catalytic layer.     

Combustion,performance and emissions of a diesel engine with H2, CH4 and H2–CH4 addition

Experiments were conducted to investigate the combustion and emission characteristics of a diesel engine with addition of hydrogen or methane for dual-fuel operation, and mixtures of hydrogen–methane for tri-fuel operation. The in-cylinder pressure and heat release rate change slightly at low to medium loads but increase dramatically at high load owing to the high combustion temperature and high quantity of pilot diesel fuel which contribute to better combustion of the gaseous fuels. The performance of the engine with tri-fuel operation at 30% load improves with the increase of hydrogen fraction in methane and is always higher than that with dual-fuel operations. Compared with ULSD–CH₄ operation, hydrogen addition in methane contributes to a reduction of CO/CO₂/HC emissions without penalty on NO_x emission. Dual-fuel and tri-fuel operations suppress particle emission to the similar extent. All the gaseous fuels reduce the geometry mean diameter and total number concentration of diesel particulate. Tri-fuel operation with 30% hydrogen addition in methane is observed to be the best fuel in reducing particulate and NO_x emissions at 70 and 90% loads.     

A comparison of the emission and impingement heat transfer of LPG–H2 and CH4–H2 premixed flames

Experiments were performed to add hydrogen to liquefied petroleum gas (LPG) and methane (CH₄) to compare the emission and impingement heat transfer behaviors of the resultant LPG–H₂–air and CH₄–H₂–air flames. Results show that as the mole fraction of hydrogen in the fuel mixture was increased from 0% to 50% at equivalence ratio of 1 and Reynolds number of 1500 for both flames, there is an increase in the laminar burning speed, flame temperature and NO_x emission as well as a decrease in the CO emission. Also, as a result of the hydrogen addition and increased flame temperature, impingement heat transfer is enhanced. Comparison shows a more significant change in the laminar burning speed, temperature and CO/NO_x emissions in the CH₄ flames, indicating a stronger effect of hydrogen addition on a lighter hydrocarbon fuel. Comparison also shows that the CH₄ flame at α = 0% has even better heat transfer than the LPG flame at α = 50%, because the longer CH₄ flame configures a wider wall jet layer, which significantly increases the integrated heat transfer rate.     

Energy requirement of HI separation from HI–I2–H2O mixture using electro-electrodialysis and distillation

The separation of HI from HI–I₂–H₂O mixture is an essential subsection of the Iodine–Sulfur (IS) process for thermochemical hydrogen production. The energy requirement of the separation determines, to a large extent, the hydrogen production efficiency of the IS process. In order to examine duty of the separation using electro-electrodialysis (EED) and distillation, a process simulation study was carried out using an analytical model of EED based on ideal membrane properties and properties of the reported EED experiments using a Nafion^® membrane and graphite electrodes. For both of the ideal-membrane case and Nafion-membrane case, effects of the operating parameters on heat duty were estimated, which comprised column pressure, HI molality in the column feed, and the flow rate ratio of the input from Bunsen section to distillate rate. Low column pressure, and high HI molality in the column feed were preferable for the ideal-membrane case; column pressure of 1.0 MPa and optimized HI molality in the column feed were desired for the Nafion-membrane case. The flow rate ratio had little effect on the minimum heat duty in the ideal-membrane case; a value in the vicinity of the lower limit of the flow rate ratio was optimal for the Nafion-membrane case. The difference of the inclination of parameters resulted from the fractional vaporization of the column feed in the ideal-membrane case and weight of the EED cell duty on the total duty due to the membrane voltage drop. The optimization of these parameters was also carried out. The minimum total heat duty of the Nafion-membrane case was 3.07 × 10⁵ J/mol-HI, and that of the ideal-membrane case was 12.5% of this value.     

Interaction in the Ce3Co8Si–H2 system

Interaction of hydrogen with Ce₃Co₈Si intermetallic compound (IMC) has been studied. IMC Ce₃Co₈Si absorbs hydrogen and forms a hydride phase at 11 atm and 50 °C. X-ray analysis of Ce₃Co₈Si H_10.2 saturated hydride phase lattice showed that it has the symmetry of the initial compound and is expanded with strong anisotropy due to increased c parameter. Analysis of hydrogen desorption isotherms in Ce₃Co₈Si–H₂ system has revealed that the decomposition of hydride phase occurred in one stage. The heat of hydride phase formation was calculated on the base of obtained equilibrium pressures data at 50, 60 and 70 °C. The results obtained demonstrate that Ce₃Co₈Si intermetallic compound may be used as reversible accumulator of hydrogen in medium temperatures interval.     

The retardation kinetics of magnetite reduction using H2 and H2–H2O mixtures

Cylindrical compacts of magnetite were isothermally reduced at 773–1273 K with pure H₂ or H₂–H₂O mixtures. The initial reduction rates increased with temperature and partial pressures of H₂ in the H₂–H₂O mixtures. However, with progressing reduction, a dense iron layer formed around the wüstite grains and the rate significantly reduced. In this regime, solid state oxygen diffusion through the dense iron layer was rate limiting. This retardation of reduction occurred at degrees of reduction of 51–89%, depending on the temperature and H₂ partial pressure, which has a linear relationship with the dimensionless kinetic parameter, k₁^mixed/k₂^mixed, (k₁^mixed, k₂^mixed: contribution of gaseous mass transport (GMT) and interfacial chemical reaction (ICR) to the reduction rate, respectively) in the reaction-regime controlled by a combination of both mechanisms. However, under certain conditions (H₂, H₂–10%H₂O, 773 K//H₂–10, 20%H₂O, 873 K//H₂–20%H₂O, 973 K) the retardation was absent because of the formation of a microporous iron layer product.     

Start-up behaviors of a H2SO4–H2O distillation column for the 50 NL H2/H sulfur–iodine cycle

The sulfur–iodine (SI) cycle to produce hydrogen from water requires a multistage distillation column to concentrate a sulfuric acid solution. To design a concentration process of a sulfuric acid solution that can be applied to the cycle, its static and dynamic simulation is essentially demanded. A 50 NL H₂/h scale SI test facility to be operated under a pressurized environment has been constructed in Korea. This study focuses on the sulfuric acid multi-stage distillation column (SAMDC-50L) for the 50 NL H₂/h SI test facility. The SAMDC-50L was designed and installed in 2012. Based on the design specifications and operation method, a start-up behavior of the SAMDC-50L has been analyzed using the simulation code “KAERI-DySCo”. As a result of the start-up dynamic simulation, it is confirmed that the SAMDC-50L will approach to the steady state value within 30,000 s to fulfill the hydrogen production rate of 50 NL H₂/h. On the other hand, it is expected that the operation time approaching a steady state decreases with an increase in the set point of the condenser temperature until a dew point of the top vapor product and the time required for the transition to the complete steady state is increased with an increasing reflux ratio and reboiler hold-up.     

Synthesis of magnetic Ag3PO4/Ag/NiFe2O4 composites towards super photocatalysis and magnetic separation

The synthesis of Ag₃PO₄/Ag was performed through in-situ deposition and photo-reduction processes with magnetic NiFe₂O₄ nanofibers towards enhanced photocatalysis performance and stability. NiFe₂O₄ inhibit the photoreduction of Ag₃PO₄ into Ag and resulted in high stability. The photocatalytic activity of Ag₃PO₄/Ag/NiFe₂O₄ samples was studied by methylene blue degrading under visible light irradiation. The Ag₃PO₄/Ag/NiFe₂O₄ photocatalyst with NiFe₂O₄ loading of 3% revealed good photocatalytic performance, high stability and quick degradation after 5 cycles. Photoluminescence spectra and photocurrent tests demonstrated that the formation of hetero-junction facilitated the separation of photo-generated carriers. The trapping experiments confirmed that h⁺ and ?OH were active species during the degradation process.     

The HI catalytic decomposition for the lab-scale H2 producing apparatus of the iodine–sulfur thermochemical cycle

The HI decomposition is the key reaction to produce hydrogen in the iodine–sulfur thermochemical cycle. In this paper, the HI catalytic decomposition for the lab-scale H₂ producing apparatus of IS-10 (The H₂ production rate is 10 L/h) in INET (Institute of Nuclear and New Energy Technology, Tsinghua University) was studied. The effects of the different supports (carbon nanotubes, active carbon, carbon molecular sieve, graphite and Al₂O₃), mass of catalyst and reaction temperature on the decomposition of HI were investigated. Also, the fresh and used active carbon supported platinum catalysts were characterized by XRD, BET and TEM. The experiment results showed that the active carbon and carbon molecular sieve had the higher catalytic activity for HI decomposition than other supports. The active carbon was selected to support platinum as the catalyst to catalyze the HI decomposition in the IS-10. In the closed cycle operation, the conversion of HI over the active carbon supported platinum catalyst was more than 20% which was near the thermodynamic equilibrium value. The results of the characterization about the fresh and used active carbon supported platinum catalysts indicated that the specific surface area decreased and the Pt particles size increased, which showed the stability of the catalyst should be improved.     

A numerical study on the effects of H2 addition in non-premixed turbulent combustion of C3H8–H2–N2 mixture using a steady flamelet approach

This study has been implemented in two sections. At first, the turbulent jet flame of DLR-B is simulated by combining the k–ε turbulence model and a steady flamelet approach. The DLR-B flame under consideration has been experimentally investigated by Meier et al. who obtained velocity and scalar statistics. The fuel jet composition is 33.2% H₂, 22.1% CH₄ and 44.7% N₂ by volume. The jet exit velocity is 63.2 m/s resulting in a Reynolds number of 22,800. Our focus in the first part is to validate the developed numerical code. Comparison with experiments showed good agreement for temperature and species distribution. At the second part, we exchanged methane with propane in the fuel composition whilst maintaining all other operating conditions unchanged. We investigated the effect of hydrogen concentration on C₃H₈–H₂–N₂ mixtures so that propane mole fraction extent is fixed. The hydrogen volume concentration rose from 33.2% up to 73.2%. The achieved consequences revealed that hydrogen addition produces elongated flame with increased levels of radiative heat flux and CO pollutant emission. The latter behavior might be due to quenching of CO oxidation process in the light of excessive cold air downstream of reaction zone.     

Effects of alumina powder characteristics on H2 and H2O2 production yields in γ-radiolysis of water and 0.4 M H2SO4 aqueous solution

The effects of powder characteristics on H₂ and H₂O₂ productions in ⁶⁰Co γ-radiolysis were studied in pure water and in 0.4 M H₂SO₄ aqueous solutions containing alumina powders. In 0.4 M H₂SO₄ solution, the H₂ yields strongly depended on alumina structures and decreased in the order of α > θ > γ-alumina, although the specific surface areas increased as α < θ < γ. The yields increased with increasing specific surface area when compared among α-alumina. In pure water, similar dependence was observed but not as strong as that for 0.4 M H₂SO₄ solution. The H₂O₂ yields were strongly decreased by adding the alumina powders in both water and 0.4 M H₂SO₄ aqueous solution, although the amounts of decrease were almost neither correlated with specific surface areas nor structures. The enhancing H₂ production was discussed in terms of the electron supply from alumina to aqueous solution as well as the adsorption of OH radicals on alumina surfaces.     

Organic-inorganic composite of g-C3N4–SrTiO3:Rh photocatalyst for improved H2 evolution under visible light irradiation

The organic-inorganic composite g-C₃N₄–SrTiO₃:Rh was prepared for the first time as a photocatalyst for hydrogen production and the resulting hydrogen evolution rate under visible light irradiation from aqueous methanol solution was measured. A high hydrogen evolution rate of 223.3 μmol h⁻¹ was achieved by using 0.1 g of as-prepared photocatalyst powder comprised of 20 wt.% g-C₃N₄ 80 wt.% SrTiO₃:Rh (0.3 mol%). The hydrogen evolution rate was greater than that obtained by SrTiO₃:Rh (0.3 mol%) by a factor of 3.24. The quantum efficiency of as-prepared composite photocatalyst was 5.5% at 410 nm for hydrogen evolution. The high activity of the composite photocatalyst for hydrogen evolution stemmed from its electron–hole separation and transportation capabilities due to the hetero-junctions of the organic-inorganic composite materials. The proposed mechanism for the electron–hole separation and hydrogen evolution of the g-C₃N₄–SrTiO₃:Rh composite under visible light irradiation featured the reduced recombination of the photo-generated charge carriers. The doping of Rh ions into the SrTiO₃ has contributed to the high photocatalytic activity by forming a donor level from the valance band to the conduction band.     

Superior low-temperature hydrogen release from the ball-milled NH3BH3–LiNH2–LiBH4 composite

In the present study, we employed a multi-component combination strategy to constitute an AB/LiNH₂/LiBH₄ composite system. Our study found that mechanically milling the AB/LiNH₂/LiBH₄ mixture in a 1:1:1 molar ratio resulted in the formation of LiNH₂BH₃ (LiAB) and new crystalline phase(s). A spectral study of the post-milled and the relevant samples suggests that the new phase(s) is likely ammoniate(s) with a formula of Li_2−x(NH₃)(NH₂BH₃)_1−x(BH₄) (0 < x < 1). The decomposition behaviors of the Li_2−x(NH₃)(NH₂BH₃)_1−x(BH₄)/xLiAB composite were examined using thermal analysis and volumetric method in a wide temperature range. It was found that the composite exhibited advantageous dehydrogenation properties over LiAB and LiAB·NH₃ at moderate temperatures. For example, it can release ∼7.1 wt% H₂ of purity at temperature as low as 60 °C, with both the dehydrogenation rate and extent far exceeding that of LiAB and LiAB·NH₃. A selectively deuterated composite sample has been prepared and examined to gain insight into the dehydrogenation mechanism of the Li_2−x(NH₃)(NH₂BH₃)_1−x(BH₄)/xLiAB composite. It was found that the LiBH₄ component does not participate in the dehydrogenation reaction at moderate temperatures, but plays a key role in strengthening the coordination of NH₃. This is believed to be a major mechanistic reason for the favorable dehydrogenation property of the composite at moderate temperatures.     

Releasing 9.6 wt% of H2 from Mg(NH2)2–3LiH–NH3BH3 through mechanochemical reaction

Ball milling the mixture of Mg(NH₂)₂, LiH and NH₃BH₃ in a molar ratio of 1:3:1 results in the direct liberation of 9.6 wt% H₂ (11 equiv. H), which is superior to binary systems such as LiH–AB (6 equiv. H), AB–Mg(NH₂)₂ (No H₂ release) and LiH–Mg(NH₂)₂ (4 equiv. H), respectively. The overall dehydrogenation is a three-step process in which LiH firstly reacts with AB to yield LiNH₂BH₃ and LiNH₂BH₃ further reacts with Mg(NH₂)₂ to form LiMgBN₃H₃. LiMgBN₃H₃ subsequently interacts with additional 2 equivalents of LiH to form Li₃BN₂ and MgNH as well as hydrogen.     

Numerical simulations of non-premixed turbulent combustion of CH4–H2 mixtures using the PDF approach

The present work is devoted to the study of non-premixed turbulent combustion with the PDF approach using three turbulence models: k-? model, modified k-? model and RSM model. A detailed kinetic mechanism is used in the numerical simulations. The three turbulence models are compared and evaluated with the experimental data and the numerical results of the literature. The evaluation concludes that the modified k-? is the most appropriate for simulating this kind of flame. A study of the effect of hydrogen addition on methane combustion is performed. Hydrogen addition causes the elevation of combustion temperature, the decreasing of CO and CO₂ mass fractions but leads to the increase of NO mass fraction.     

Adiabatic burning velocity of H2–O2 mixtures diluted with CO2/N2/Ar

Global warming due to CO₂ emissions has led to the projection of hydrogen as an important fuel for future. A lot of research has been going on to design combustion appliances for hydrogen as fuel. This has necessitated fundamental research on combustion characteristics of hydrogen fuel. In this work, a combination of experiments and computational simulations was employed to study the effects of diluents (CO₂, N₂, and Ar) on the laminar burning velocity of premixed hydrogen/oxygen flames using the heat flux method. The experiments were conducted to measure laminar burning velocity for a range of equivalence ratios at atmospheric pressure and temperature (300 K) with reactant mixtures containing varying concentrations of CO₂, N₂, and Ar as diluents. Measured burning velocities were compared with computed results obtained from one-dimensional laminar premixed flame code PREMIX with detailed chemical kinetics and good agreement was obtained. The effectiveness of diluents in reduction of laminar burning velocity for a given diluent concentration is in the increasing order of argon, nitrogen, carbon dioxide. This may be due to increased capabilities either to quench the reaction zone by increased specific heat or due to reduced transport rates. The lean and stoichiometric H₂/O₂/CO₂ flames with 65% CO₂ dilution exhibited cellular flame structures. Detailed three-dimensional simulation was performed to understand lean H₂/O₂/CO₂ cellular flame structure and cell count from computed flame matched well with the experimental cellular flame.     

Syngas production from CH4 dry reforming over Co–Ni/Al2O3 catalyst: Coupled reaction-deactivation kinetic analysis and the effect of O2 co-feeding on H2:CO ratio

The dry and oxidative dry reforming of CH₄ over alumina-supported Co–Ni catalysts were investigated over 72-h longevity experiments. The deactivation behaviour at low CO₂:CH₄ ratio (≤2) suggests that carbon deposition proceeds via a rapid dehydropolymerisation step resulting in the blockage of active sites and loss in CO₂ consumption. In particular, at high temperatures of 923 K and 973 K, a ‘breakthrough’ point was observed in which deactivation that was previously slow suddenly accelerated, indicating rapid polymerisation of deposited carbon. Only with feed CO₂:CH₄ > 2 or with O₂ co-feeding was coke-induced deactivation eliminated. In particular, O₂ co-feeding gave improved carbon removal, product H₂:CO ratios more suitable for downstream GTL processing and stable catalytic performance. Conversion-time data were adequately fitted to the generalised Levenspiel reaction-deactivation model. Activation energy estimate (66–129 kJ mol⁻¹) was dependent on the CO₂:CH₄ ratio but representative of other hydrocarbon reforming reactions on Ni-based catalysts.     

Pd–Ag thin film membrane for H2 separation. Part 2. Carbon and oxygen diffusion in the presence of CO/CO2 in the feed and effect on the H2 permeability

The effect of CO and CO₂ on the performance and stability of Pd–Ag thin film membranes prepared by electroless plating deposition (EPD) was investigated, observing the presence of dissociation to carbon and oxygen which slowly diffuse in the membrane influencing also H₂ permeability. The effect of the two carbon oxides was investigated both separately and combined in the 400–450 °C temperature range over long-term cumulative experiments (up to over 350 h) on a membrane that already worked for over 350 h in H₂ or H₂–N₂ mixtures. An increase of the H₂ permeation flux was observed feeding only CO₂ in the range 10–20%. This effect was interpreted as deriving from the facilitated H₂ flux caused from oxygen diffusion (deriving from CO₂ dissociation) in the membrane. CO induces instead a partial inhibition on the H₂ flux deriving from the negative effect of CO competitive chemisorption as well as C diffusion in the membrane, which overcome the positive effect associated to oxygen diffusion in the membrane. Carbon and oxygen diffuse through the membrane with a rate two order of magnitude lower than hydrogen, and recombinate at the permeate side forming CO, CO₂ and CH₄ which amount increases with time-on-stream. The effect is reversible and not associated with the creation of cracks or defects in the membrane, as supported by leak tests.     

H2 and CH4 oxidation on Gd0.2Ce0.8O1.9 infiltrated SrMoO3–yttria-stabilized zirconia anode for solid oxide fuel cells

Strontium molybdate (SrMoO₃) as an electronic conductor was incorporated with yttria-stabilized zirconia (YSZ) to form an anode scaffold for solid oxide fuel cells. Gd_0.2Ce_0.8O_1.9 (GDC) nanoparticles were introduced by wet impregnation to complete the Ni-free GDC infiltrated SrMoO₃–YSZ anode fabrication. The effects of SrMoO₃ on the electrode conductivity and GDC infiltration on the catalytic activity were examined. A pronounced performance improvement was observed both on wet H₂ and CH₄ oxidation for the 56 wt.% GDC infiltrated SrMoO₃–YSZ. In particular, the polarization resistance decreased from 8 Ω cm² to 0.5 Ω cm² under wet H₂ (3% H₂O) at 800 °C with the introduction of GDC. Under wet CH₄ at 900 °C, a maximum power density of 160 mW cm⁻² was obtained and no carbon deposition was observed on the anode. It was found that the addition of H₂O in the anode caused an increase of electrode ohmic resistance and a decrease of open circuit voltage. Redox cycling stability was investigated and only a slight drop in cell performance was observed after 5 cycles. These results suggest that GDC infiltrated SrMoO₃–YSZ is a promising anode material for solid oxide fuel cells.