H2 production with ultra-low CO selectivity via photocatalytic reforming of methanol on Au/TiO2 catalyst

_H2${\mathrm{H}}_2$ with ultra-low CO concentration was produced via photocatalytic reforming of methanol on Au/_TiO2$\mathrm{Au}/{\mathrm{TiO}}_2$ catalyst. The rate of _H2${\mathrm{H}}_2$ production is greatly increased when the gold particle size is reduced from 10 to smaller than 3 nm. The concentration of CO in _H2${\mathrm{H}}_2$ decreases with reducing the gold particle size of the catalyst. It is suggested that the by-product CO is mostly produced via decomposition of the intermediate formic acid species derived from methanol. The smaller gold particles possibly switch the HCOOH decomposition reaction mainly to _H2${\mathrm{H}}_2$ and _CO2${\mathrm{CO}}_2$ products while suppress the CO and _H2${\mathrm{H}}_2$O products. In addition, some CO may be oxidized to _CO2${\mathrm{CO}}_2$ by photogenerated oxidizing species at the perimeter interface between the small gold particles and _TiO2${\mathrm{TiO}}_2$ under photocatalytic condition.     

Intake charge dilution effects on control of nitric oxide emission in a hydrogen fueled SI engine

Though hydrogen fueled spark ignition engine can operate at high thermal efficiency with almost zero emission of HC and CO, the high level of _NOx${\mathrm{NO}}_x$ poses problems. The high combustion temperature and lean mixtures used are the reasons. In this work, the effect of _N2${\mathrm{N}}_2$, _CO2${\mathrm{CO}}_2$ and hot EGR gas as diluents in the intake charge to suppress NO emission in a manifold injected hydrogen fueled SI engine was studied. Nitrogen as a diluent is not so effective at low loads while inducting smaller amounts, but very effective at higher loads where the mixture becomes richer and the dilution effect (oxygen depletion) is significant. On other hand, carbon dioxide is a good diluent with relatively better thermal effect and diluent effect and effectively controls NO emission at all output regions. However this is at the expense of thermal efficiency. Recirculating hot exhaust gas which contains both _N2${\mathrm{N}}_2$ and steam comes in between _N2${\mathrm{N}}_2$ and _CO2${\mathrm{CO}}_2$ in terms of its effectiveness. On the whole _N2${\mathrm{N}}_2$ is the most effective as it has minimum impact on thermal efficiency for a given level of permissible NO emission. Thus it is felt that cold EGR could be a good option. In all cases, a good control system is necessary to supply correct quantity of diluent.     

Evaluation of conversion efficiency of light to hydrogen energy by Anabaena variabilis

Cyanobacteria provide an efficient system for producing _H2${\mathrm{H}}_2$ from water using solar energy. The energy conversion efficiency can be defined by the ratio of _H2${\mathrm{H}}_2$ produced to the light energy absorbed. An IR and opalescent plate method was used to measure the light energy absorbed. Since cyanobacteria absorb light in the visible range but not in the infrared range, the net amount of light energy absorbed by the cells can be estimated by measuring the IR and visible light intensities transmitted through the biochamber. A rectangular biochamber was used for measuring the conversion efficiency from light energy to _H2${\mathrm{H}}_2$ energy. A quantum meter and radiometer were used to measure the light intensity transmitted through the chamber. Anabaena variabilis was cultured in a BG11 medium with 3.6 mM NaNO₃${}_3$ and the light intensity was 40–50 μmol/m²/s$\mathrm{\mu }\mathrm{mol}/{\mathrm{m}}^2/\mathrm{s}$ in the growth phase and 120–140 μmol/m²/s$\mathrm{\mu }\mathrm{mol}/{\mathrm{m}}^2/\mathrm{s}$ in the _H2${\mathrm{H}}_2$ production phase. The maximum _H2${\mathrm{H}}_2$ production was 50 ml for 40 h and cell density was 1.2 g/l. The _H2${\mathrm{H}}_2$ production rate was 4.1 ml _H2/g${\mathrm{H}}_2/\mathrm{g}$ dry cell weight/h. Based on the light absorbed in the _H2${\mathrm{H}}_2$ production phase, the energy conversion efficiency from light to _H2${\mathrm{H}}_2$ was 1.5% on average and 3.9% at the maximum. Based on the light energy absorbed in the cell growth and _H2${\mathrm{H}}_2$ production phases, the energy conversion efficiency was 1.1% on average.     

The ignition,combustion and flame structure of carbon monoxide/hydrogen mixtures. Note 1: Detailed kinetic modeling of syngas combustion also in presence of nitrogen compounds

The kinetic characterization of the _H2/CO${\mathrm{H}}_2/\mathrm{CO}$ system is of interest right now due mainly to its role in sustainable combustion processes. The aim of this paper is to revise and validate a detailed kinetic model of hydrogen and carbon monoxide mixture combustion with particular focus not only on _NOx${\mathrm{NO}}_x$ formation but also on interactions with nitrogen species. Model predictions and experimental measurements are discussed and compared across a wide range of operating conditions. This study moves from the detailed analysis of species profiles in syngas oxidation in flow reactor and laminar premixed flames to global combustion properties (ignition delay times and laminar flame speeds) by referring to a large set of literature data. According to recent literature, the validation of the kinetic scheme confirmed there was a need to slightly modify the kinetic parameters of two relevant _CO2${\mathrm{CO}}_2$ formation reactions (CO+OH=_CO2+H$\mathrm{CO}+\mathrm{OH}={\mathrm{CO}}_2+\mathrm{H}$ and CO+O+M=_CO2+M$\mathrm{CO}+\mathrm{O}+\mathrm{M}={\mathrm{CO}}_2+\mathrm{M}$) and of reaction HONO+OH=_NO2+_H2O$\mathrm{HONO}+\mathrm{OH}={\mathrm{NO}}_2+{\mathrm{H}}_2\mathrm{O}$.     

Development of TiO2-supported nano-RuO2-incorporated catalytic nickel coating for hydrogen evolution reaction

Composite nickel coated steel cathodes were fabricated for hydrogen evolution reaction. _TiO2${\mathrm{TiO}}_2$-supported _RuO2${\mathrm{RuO}}_2$ particles of varying size were incorporated in the electroless coating. The electrodes exhibited high catalytic activity which was dependent on the size of _RuO2${\mathrm{RuO}}_2$ particles incorporated. The smaller the size at nano-level, the higher the catalytic activity. There was enhanced hydrogen adsorption due to high surface roughness and abundant active sites.     

Investigation on the structure and electrochemical properties of the laser sintered La0.7Mg0.3Ni3.5 hydrogen storage alloys

The structure and electrochemical properties of the _{La0.7Mg0.3Ni3.5}${\mathrm{La}}_{0.7}{\mathrm{Mg}}_{0.3}{\mathrm{Ni}}_{3.5}$ alloys laser sintered at different powers were investigated. It is found that all alloys contain three phases _La3MgNi14${\mathrm{La}}_3{\mathrm{MgNi}}_{14}$ with the _Ce2Ni7${\mathrm{Ce}}_2{\mathrm{Ni}}_7$ structure, _LaNi5${\mathrm{LaNi}}_5$ and _LaMgNi4${\mathrm{LaMgNi}}_4$. The abundance of the main phase _La3MgNi14${\mathrm{La}}_3{\mathrm{MgNi}}_{14}$ is 43, 68 and 63 wt%, respectively, when sintering power varies from 1000 to 1200 and 1400 W. The laser sintered _{La0.7Mg0.3Ni3.5}${\mathrm{La}}_{0.7}{\mathrm{Mg}}_{0.3}{\mathrm{Ni}}_{3.5}$ alloys can be activated to their maximum discharge capacity within three cycles. The discharge capacities of those alloys prepared by laser sintering at 1000, 1200 and 1400 W are 324.6, 352.8 and 340.5 mAh/g, respectively. The _{La0.7Mg0.3Ni3.5}${\mathrm{La}}_{0.7}{\mathrm{Mg}}_{0.3}{\mathrm{Ni}}_{3.5}$ alloy laser sintered at 1200 W has a best cyclic stability (_S100=58.4%)$(S_{100}=58.4\%)$ and high-rate dischargeability (_HRD800=79.4%)$({\mathrm{HRD}}_{800}=79.4\%)$ due to the high amount of the main phase _La3MgNi14${\mathrm{La}}_3{\mathrm{MgNi}}_{14}$.     

Synthesis and hydrogen storage properties of carbon nanotubes

Multi-walled carbon nanotubes (MWNT) have been synthesized by chemical vapor decomposition of acetylene over rare-earth (RE) based _AB2${\mathrm{AB}}_2$ alloy hydride catalysts. The _AB2${\mathrm{AB}}_2$ alloy hydride catalysts have been prepared by hydrogen decrepitation technique and characterized by scanning electron microscopy. The advantage of this novel method of obtaining catalysts has been discussed. The as-grown carbon nanotubes were purified by acid and heat treatments and characterized using powder X-ray diffraction, transmission electron microscopy, scanning electron microscopy, thermo gravimetric analysis and Raman spectroscopy. Hydrogen adsorption measurements were carried out on as-prepared and purified MWNT in the temperature range of 143–373 K and pressure range of 10–100 bar using a high pressure hydrogen adsorption setup and the results have been discussed. A maximum hydrogen storage capacity of 3.5 wt% is obtained for purified MWNT prepared with _DyNi2${\mathrm{DyNi}}_2$ alloy hydride catalyst at 143 K and 75 bar.     

Hydrogen energy from coupled waste gasification and cement production—a thermochemical concept study

A plant concept for hydrogen production from waste gasification coupled with cement manufacturing is presented. Hot precalcined cement meal, from the operating cement process, is used as heat carrier to provide energy required by the parallel arranged gasifier. The amount of CaO present in the cement meal operates simultaneously as an effective in situ _CO2${\mathrm{CO}}_2$-sorbent. First, a practical case study was devised to be able to perform simulations for estimation of expected hydrogen yield. The influence of different operation parameters of the gasifier and the hydrogen separation unit (steam-to-fuel ratio, pyrolysis temperature, PSA efficiency) was studied based on chemical equilibrium calculations. The simulation results indicate, that the coupling provides advantages for both processes. The production of a hydrogen-rich gas via thermal gasification benefits from the continuously available fresh CaO, which improves fuel conversion reactions and captures _CO2${\mathrm{CO}}_2$ in situ. High-calorific streams from gasification process remaining after hydrogen separation may substitute fossil fuels needed for cement process. For a steam/fuel ratio of 0.3 and a PSA efficiency of 0.7, the calculated hydrogen energy yield is 46% of fuel energy input.     

A new gaseous and combustible form of water

In this paper we present, apparently for the first time, various measurements on a mixture of hydrogen and oxygen called HHO gas produced via a new electrolyzer (international patents pending by Hydrogen Technologies Applications, Inc. of Clearwater, Florida), which mixture is distinctly different than the Brown and other known gases. The measurements herein reported suggest the existence in the HHO gas of stable clusters composed of H and O atoms, their dimers H–O, and their molecules _H2${\mathrm{H}}_2$, _O2${\mathrm{O}}_2$ and _H2O${\mathrm{H}}_2\mathrm{O}$ whose bond cannot entirely be of valence type. Numerous anomalous experimental measurements on the HHO gas are reported in this paper for the first time. To reach their preliminary, yet plausible interpretation, we introduce the working hypothesis that the clusters constituting the HHO gas constitute another realization of a recently discovered new chemical species called for certain technical reasons magnecules   as well as to distinguish them from the conventional “molecules” [Santilli RM. Foundations of hadronic chemistry with applications to new clean energies and fuels. Boston, Dordrecht, London: Kluwer Academic Publisher; 2001]. It is indicated that the creation of the gaseous and combustible HHO from distilled water at atmospheric temperature and pressure occurs via a process structurally different than evaporation or separation, thus suggesting the existence of a new form of water, apparently introduced in this paper for the first time, with the structure (H×H)$(\mathrm{H}\times \mathrm{H})$–O where “×$\times$” represents the new magnecular bond and “-$-$” the conventional molecular bond. The transition from the conventional H–O–H species to the new (H×H)$(\mathrm{H}\times \mathrm{H})$–O species is predicted by a change of the electric polarization of water caused by the electrolyzer. When H–O–H is liquid, the new species (H×H)$(\mathrm{H}\times \mathrm{H})$–O can only be gaseous, thus explaining the transition of state without evaporation or separation energy. Finally, the new species (H×H)$(\mathrm{H}\times \mathrm{H})$–O is predicted to be unstable and decay into H×H$\mathrm{H}\times \mathrm{H}$ and O, by permitting a plausible interpretation of the anomalous constituents of the HHO gas as well as its anomalous behavior. Samples of the new HHO gas are available at no cost for independent verifications, including guidelines for the detection of the new species.     

Hydrogen generation from liquid phase catalytic reforming of sugar solutions using metal-supported catalysts

Most of the hydrogen production processes are designed for large-scale industrial uses and are not suitable for a compact hydrogen device to be used in systems like solid polymer fuel cells. Integrating the reaction step, the gas purification and the heat supply can lead to small-scale hydrogen production systems. The aim of this research is to study the influence of several reaction parameters on hydrogen production using liquid phase reforming of sugar solution over Pt, Pd, and Ni supported on nanostructured supports. It was found that the desired catalytic pathway for _H2${\mathrm{H}}_2$ production involves cleavage of C–C, C–H and O–H bonds that adsorb on the catalyst surface. Thus a good catalyst for production of _H2${\mathrm{H}}_2$ by liquid-phase reforming must facilitate C–C bond cleavage and promote removal of adsorbed CO species by the water–gas shift reaction, but the catalyst must not facilitate C–O bond cleavage and hydrogenation of CO or _CO2${\mathrm{CO}}_2$. Apart from studying various catalysts, a commercial Pt/γ$\gamma$-alumina catalyst was used to study the effect of temperature at three different temperatures of 458, 473 and 493 K. Some of the spent catalysts were characterised using TGA, SEM and XRD to study coke deposition. The amorphous and organised form of coke was found on the surface of the catalyst.     

Kinetic study on nonisothermal dehydrogenation of TiH2 powders

The nonisothermal dehydrogenation of TiH₂ powders was studied using thermogravimetry and differential scanning calorimetry. The reaction model was established by estimating the activation energy. The results show the nonisothermal dehydrogenation occurred in a four-step process. The hydrogen released from the TiH_1.5∼2$\text{Ti}{\mathrm{H}}_{1.5\sim 2}$ phase in the first step, which led to the decrease of activation energy. The second step was derived from the formation of βH${\beta }_H$ in δ$\delta$ phase and the reaction model was Phase boundary reaction. In the third step, the hydrogen started to release from the βH${\beta }_H$ phase, and then the βH→αH${\beta }_{\mathrm{H}}\to {\alpha }_{\mathrm{H}}$ phase transformation happened. So the activation energy Eα$E_{\alpha }$ underwent a decrease followed by a quick increase. The fourth step corresponded to the formation of αH${\alpha }_H$ in βH${\beta }_H$ phase, and the slight oxidation resulted in the small fluctuation of activation energy.     

Some technical issues of zero-emission coal technology

A concept of zero-emission coal technology, proposed by ZECA Corporation, is presented and discussed. The process can produce electricity at 60–70% efficiency with zero emission to the atmosphere. The carbon dioxide is produced as concentrated, clean stream, which is easy to sequestrate. The process uses CaO/_CaCO3$\mathrm{CaO}/{\mathrm{CaCO}}_3$ reaction to enhance hydrogen production and to separate carbon dioxide. Hydrogen feeds a stack of solid oxide fuel cells (SOFCs), which produce electricity. High-temperature byproduct heat from the SOFC drives the calcination reaction, which restores CaO. Unfortunately, the possible realization of the process may encounter various technical difficulties mainly connected with requirements for the SOFC (very high operating temperature, high sulfur tolerance, integrated heat exchanger) and CaO/_CaCO3$\mathrm{CaO}/{\mathrm{CaCO}}_3$ process (the decrease of the performance with increasing number of cycles and problematic heat transport into calcination vessel).     

Autothermal sorption-enhanced steam reforming of bio-oil/biogas mixture and energy generation by fuel cells: Concept analysis and process simulation

A concept of sorption-enhanced steam reforming of bio-oil/biogas for electricity and heat generation by phosphoric acid fuel cells is investigated. The process is modeled using SIMSCI Pro II process simulator. Sorptive removal of the carbon dioxide from the reaction site results in low CO and _CO2${\mathrm{CO}}_2$ concentrations (<1%$<1\%$) in the reformate, as a result it can be used in the phosphoric acid fuel cell without any further fuel cleanup. High hydrogen concentration and calorific value of the reformate enable the operation of the fuel cell at a high-efficiency mode despite of the high carbon/hydrogen ratio of the bio-fuel. Addition of biogas to the reformer enables autothermal operation of the reformer, as well as significantly improves the efficiency of the process. The simulation shows that the overall efficiency of the proposed system is compatible with the efficiency of the system using “classical” steam reforming of the fuel. The process exhibits 6% lower electrical efficiency compared to the system utilizing natural gas, and 4.6% higher efficiency compared to a system using bio-oil as a fuel.