Recent amorphous silicon research results at the Solar Energy Research Institute

Measurements of transport properties and microstructure of hydrogenated amorphous silicon-germanium alloys are reported. Emphasis is placed on the effects of hydrogen dilution of the source gas. The transport properties include photoconductivity, ambipolar diffusion length; the structure was determined from small-angle X-ray scattering.     

A novel approach to ammonia synthesis from hydrogen sulfide

There are a number of shortcomings for currently-available technologies for ammonia production, such as carbon dioxide emissions and water consumption. We simulate a novel model for ammonia production from hydrogen sulfide through membrane technologies. The proposed production process decreases the need for external water and reduces the physical footprint of the plant. The required hydrogen comes from the separation of hydrogen sulfide by electrochemical membrane separation, while the required nitrogen is obtained from separating oxygen from air through an ion transport membrane. 10% of the hydrogen from the electrochemical membrane separation along with the separated oxygen from the ion transport membrane is sent to the solid oxide fuel cell for heat and power generation. This production process operates with a minimal number of processing units and in physical, kinetic, and thermal conditions in which a separation factor of ~99.99% can be attained.     

Mathematical modeling of novel porous transport layer architectures for proton exchange membrane electrolysis cells

Thin foil based porous transport layers (PTLs) that contain highly structured pore arrays have shown promise as anode PTLs in proton exchange membrane electrolysis cells. These novel PTLs, fabricated with advanced manufacturing techniques, produce thin, tunable, multifunctional layers with reduced flow and interfacial resistances and high thermal and electric conductivities. To further optimize their design, it is important to understand their fundamental impact on the transport of protons, electrons, and liquid/vapor mixtures in the electrode. In this work, we develop a two-dimensional multiphysics model to simulate the coupled electrochemistry and multiphase transport in an electrolysis cell operated with the novel PTL architecture. The results show that larger pores improve access of water to the anode catalyst layer, which is beneficial for both the oxygen evolution reaction and membrane hydration. Larger pore sizes also improve oxygen gas transport from the catalyst layer, because generated oxygen gas is forced to travel in-plane through the anode catalyst layer until it reaches a pore opening that is connected to a channel. The discussed results confirm that the proposed thin foil based PTLs are fundamentally different from conventional PTLs, such as felts or layered meshes. The model developed in this work also provides generalizable insight into fundamental PEMEC phenomena, such as the competition between liquid and gas phase transport, membrane hydration and water management, and nonuniform electrochemical reactions, which are processes relevant to all PEMEC designs.     

Optimal dispatch of HCNG penetrated integrated energy system based on modelling of HCNG process

Hydrogen is injected into the existing natural gas network to form hydrogen-rich compressed natural gas (HCNG), effectively addressing the high cost of hydrogen transmission. However, the traditional IES model cannot be used due to the hydrogen injection's effect on gas properties and the vague characteristics of the transport and separation processes. Therefore, this paper proposes an HCNG penetrated integrated energy system (HPIES) optimal dispatching method by comprehensively modelling the injection, transmission, and separation processes of HCNG. An HCNG mass flow rate model considering variable mixing ratio and unknown beginning flow direction is developed to describe the effect of hydrogen injection. Furthermore, the hydrogen separation model is established by introducing a combined membrane and pressure swing adsorption separation process. The tightening McCormick algorithm is proposed to solve quickly HPIES optimal dispatch problem with an acceptable feasibility check. Finally, case studies on the HPIES consisting of IEEE 39-bus power system and 20-node natural gas system validate the effectiveness of the algorithm and model. The results show that the average error is 0.031% for the bilinear term constraint.     

Synthetic natural gas (SNG) liquefaction processes with hydrogen separation

The fact that synthetic natural gas (SNG) contains hydrogen has a great impact on its liquefaction process. Aiming to produce liquefied natural gas (LNG) from SNG, hydrogen separation from SNG through cryogenic processes is studied. A new separation method combining distillation and flash is developed, resulting in higher liquefaction rate than that of distillation under same operating parameters. Process simulations are performed by combining one liquefaction part (a nitrogen expansion process or a mixed refrigerant one) and one distillation part (direct flash, atmospheric distillation, pressurized distillation or the new separation method). Compared to direct flash, distillation can reduce the hydrogen content of products to a very low level, increasing the temperature of products by 8 °C and reducing the unit power consumption by 3%; and, compared to the other three separation ways, the new separation method reduces the unit power consumption by 7–10%. Both nitrogen expansion and SMR liquefaction processes can be integrated with hydrogen separation, but power consumptions for SMR processes are less than those for nitrogen expansion ones.     

Multiphase reactor scale-up for Cu–Cl thermochemical hydrogen production

This paper examines selected design issues associated with reactor scale-up in the thermochemical copper–chlorine (Cu–Cl) cycle of hydrogen production. The thermochemical cycle decomposes water into oxygen and hydrogen, through intermediate copper and chlorine compounds. In this paper, emphasis is focused on the hydrogen, oxygen and hydrolysis reactors. A sedimentation cell for copper separation and HCl gas absorption tower are discussed for the thermochemical hydrogen reactor. A molten salt reactor is investigated for decomposition of an intermediate compound, copper oxychloride (CuO·Cl₂), into oxygen gas and molten cuprous chloride. Scale-up design issues are examined for handling three phases within the molten salt reactor, i.e., solid copper oxychloride particles, liquid (melting salt) and exiting gas (oxygen). Also, different variations of hydrolysis reactions are compared, including 5, 3 and 2-step Cu–Cl cycles that utilize reactive spray drying, instead of separate drying and hydrolysis processes. The spray drying involves evaporation of aqueous feed by mixing the spray and drying streams. Results are presented for the required capacities of feed materials for the multiphase reactors, steam and heat requirements, and other key design parameters for reactor scale-up to a pilot-scale capacity.     

A detailed analysis of ambipolar diffusion in nanostructured metal oxide films

In this paper a transport equation is derived which describes the behaviour of the nanostructured metal oxide films in a photoelectrochemical cell. It is shown that a detailed analysis of the charge compensation mechanism necessarily leads to a transport equation with characteristics similar to but logically distinct from the pure diffusion equation. The studied phenomenon was named ambipolar diffusion in the early 1950s. It takes into account the fact that the diffusion processes of ions and electrons occur at different speeds. A weak electric field therefore couples the processes together to preserve charge neutrality. The electric field in turn affects the transport resulting in a deviation from purely diffusive behaviour. However, this has not been widely recognised in the literature for nanostructured semiconductor films until very recently. In this paper a detailed analysis is presented. It is based on the assumption that the current density is solenoidal. It is shown that application of the ambipolar diffusion model to a photoelectrochemical cell based on a nanostructured metal oxide film leads to an additional term in the transport equation, rather than only a new diffusion coefficient as in earlier work. It is also shown that the boundary conditions interact closely with the equation to form a transport model.     

Stimulatory effect of ascorbate,the alternative electron donor of photosystem II,on the hydrogen production of sulphur-deprived Chlamydomonas reinhardtii

The green alga Chlamydomonas reinhardtii is capable of photoproducing molecular hydrogen following sulphur deprivation, which results in anaerobiosis and a suppression of oxygen evolution and thus an alleviation of the inhibitory effect of oxygen on the hydrogenase. At the same time it transiently maintains a limited supply of electrons arising from photosystem II (PSII) to the hydrogenase (Melis and Happe Plant Physiol 2001; 127:740–748). In this work, using fast chl a fluorescence and P700 measurements, we show that ascorbate (Asc), a naturally occurring PSII alternative electron donor, is capable of donating electrons to PSII in heat-treated and sulphur-deprived cells and this can be significantly accelerated by supplementing the culture with 10 mM Asc. It also enhances, about three-fold, the photoproduction of hydrogen in cells subjected to sulphur deprivation as shown by gas chromatography. Similar stimulation was obtained in the presence of diphenylcarbazide (DPC), an artificial PSII electron donor. Asc and DPC also facilitated the anaerobiosis of cells, probably via super reducing the oxygen evolving complex while feeding electrons to PSII reaction centres and the linear electron transport chain, and ultimately to the hydrogenase – as shown by the significant DCMU-sensitivity of the light-induced Asc- and DPC-dependent re-reduction of P700⁺ and hydrogen evolution.     

Numerical analysis of convective and diffusive fuel transports in high-temperature proton-exchange membrane fuel cells

The fuel transports in high-temperature proton-exchange membrane fuel cells have been numerically examined. Both convective and diffusive fuel transports are analyzed in detail. The former is often neglected in straight flow channel configurations while it has been reported to become important for serpentine or interdigitated flow channel configurations. By using a two-dimensional isothermal model, we have performed numerical simulations of a high-temperature proton-exchange membrane fuel cell with a straight flow channel configuration. The present results show that even in a straight flow channel configuration, the convection can play a significant role in fuel transports for the anode side. Examination of the flow field data reveals that the anode gas mixture is transported toward the catalyst layer (CL) whereas the gas mixture in the cathode channel moves away from the reaction site. It is also observed that as the flow moves downstream, the flow rate decreases in the anode channel but increases in the cathode channel. Species transport data are examined in detail by splitting the total flux of fuel transport into convective and diffusive flux components. For oxygen transport in the cathode gas diffusion layer (GDL), diffusion is dominant; in addition, the convective flux has a negative contribution to the total oxygen flux and is negligible compared to the diffusion flux. However, for hydrogen transport to the reaction site, both convection and diffusion are shown to be important processes in the anode GDL. At high cell voltages (i.e., low current densities), it is even observed that the convective contribution to the total hydrogen flux is larger than the diffusive one.     

Measurement of deuterium isotope separation by polymer electrolyte fuel cell stack

Processes for separating hydrogen isotopes are important for future energy applications. Several separation methods are based on electrolytic process; however, electrolysis consumes large amounts of electric energy. In this study, we demonstrate deuterium isotope separation from a mixture of H₂ and D₂ gases using a polymer electrolyte fuel cell stack. To identify the most efficient process, we investigated two flow patterns for the fuel gas, namely, parallel and serial flow. The electrical power of the stacks depended on the flow pattern when a high current was generated. We attribute this dependence on membrane dehydration and water droplet formation in the serial flow, which passed through the single cells in a straight path. However, the stack with the serial path showed a high separation factor (α = 6.6) indicating enrichment of deuterium water during the operation. The long reaction path of the fuel gas contributed to effective separation. The fuel utilization in individual cells suggested the potential for even more effective separation processes by a serial flow path.     

Advances in materials process and separation mechanism of the membrane towards hydrogen separation

The increased demand for a reliable and sustainable renewable energy source encourages the hydrogen-based economy. For the same, membrane separation approaches were reviewed as an advantageous process over contemporary techniques due to the environmentally friendly nature, economically viable pathway, and easily adaptable technology. A comprehensive assessment for the advancements in the type of membranes namely, polymeric and mixed matrix membranes (MMMs) has been delineated in the present article with the fabrication methodologies and associated mechanism for hydrogen separation. In hydrogen separation mechanism of the membrane, depends on the morphology of the membrane (dense or porous). The existence of pores in membranes offers various gas transport mechanisms such as Knudsen diffusion, surface diffusion, capillary condensation, molecular sieving mechanisms were observed, depending on the pore size of membranes and in dense membrane gas transport through the solution-diffusion mechanism. In polymer membrane, hydrogen separation occurs mainly due to solubility and diffusivity of gases. The hydrogen separation mechanism in MMMs is very complex due to the combining effect of polymer and inorganic fillers. So, the gas separation performance of MMMs was evaluated using the modified Maxwell model. Moreover, adequate polymeric material and inorganic fillers have been summarised for MMMs synthesis and highlighting the mechanism for gas transport phenomena in the process. Several types of materials implemented with polymeric matrix examined in the literature, amongst these functionally aligned CNTs with Pd-nanoparticles dispersed in polymer matrix were observed to reveal the best outcome for the hydrogen separation membrane due to the uniform distribution of inorganic material in the matrix. Henceforth, the agglomeration gets reduced promoting hydrogen separation.     

The Westinghouse Sulfur Cycle for the thermochemical decomposition of water

The Westinghouse Sulfur Cycle is a two-step thermochemical cycle for decomposing water into hydrogen and oxygen. Sulfurous acid and water are reacted electrolytically to produce hydrogen and sulfuric acid. The resultant sulfuric acid is vaporized to produce steam and sulfur trioxide, with the latter compound being subsequently reduced at higher temperatures into sulfur dioxide and oxygen. Following separation of the water and sulfur dioxide for recycle to the electrolyzer, oxygen is available as a process by-product.The cycle has the potential for achieving high thermal efficiencies while using common and inexpensive chemicals. The product hydrogen and oxygen streams are available under pressure and at high purity. As a result, these may be pipelined and used without detrimental environmental effects and without jeopardizing processes which employ the gases.Research has shown that the chemical reactions comprising the cycle proceed at acceptable rates and without the occurrence of side reactions. Conceptual designs and cost estimates indicate that the product gas separations can be done conventionally and economically. This paper discusses the technology supporting the selection of this thermochemical cycle for further development, and potential applications for the hydrogen and oxygen products of the process.     

Two-temperature chemically-non-equilibrium modeling of argon induction plasmas with diatomic gas

A non-equilibrium modeling of argon–oxygen and argon–hydrogen induction thermal plasmas was performed without thermal and chemical equilibrium assumptions. Reaction rates of dissociation and recombination of diatomic gas and ionization were taken into account with two-temperature modeling. A substantial deviation from LTE exists near the torch wall in argon–oxygen induction plasmas under atmospheric pressure, while small deviation in argon–hydrogen plasmas results from the large collision frequency between electrons and hydrogen atoms.     

Membrane separation processes for the benefit of the sulfur–iodine and hybrid sulfur thermochemical cycles

Thermochemical cycles have been proposed as processes for the manufacture of hydrogen from water in which the only other effluent is oxygen. In this paper, membrane-based technologies are described that have the promise of enabling the further development of thermochemical cycle processes. Membranes have been studied for the concentration of hydriodic acid (HI) and sulfuric acid using pervaporation. In this work, Nafion^® and sulfonated poly(ether ether ketone) (SPEEK) membranes have effectively concentrated HI at temperatures as high as 134 °C (407 K) without any significant degradation of transport behavior. Additionally, sulfuric acid has been concentrated using Nafion^® membranes at 100 °C (373 K). Measured fluxes of water and separation factors are commercially competitive and have been characterized with respect to acid concentration in the feed streams. Further, hydrogen permeability is discussed at 300 °C (573 K) with the goal of providing a method for the removal of the product gas from HI in the decomposition step, thus increasing the productivity of the equilibrium-limited reaction.     

Accelerated transfer and separation of charge carriers during the photocatalytic production of hydrogen over Au/ZrO2–TiO2 structures by interfacial energy states

Energy states and surface plasmon resonance (SPR) play an important role in photocatalytic processes and power generation energy, for they improve the separation, transport, and mobility of charge carriers. The creation of Au/semiconductor heterostructures with different amounts of Au forms energy states that can modulate surface plasmon excitation, interfacial charge transport and photocatalytic activity to generate hydrogen. However, the Au loading effect on the interfacial charge transport and photocatalysis of plasmonic Au/semiconductors is unclear. For this reason, in this study, Au/ZrO₂–TiO₂ materials with different Au loadings were synthesized and evaluated in the photocatalytic production of hydrogen. The results confirmed boosted photoactivity with increased gold loading up to 5 wt.%, obtaining four times more hydrogen production than with the base material. The (photo) electrochemical measurements revealed that the Au inclusion provoked the adjustment of Fermi level values associated with the variation of surface energy states at the Au/ZrO₂–TiO₂ interface, which can be related to the modulation of SPR. This phenomenon can be explained by two simultaneous effects: i) the creation of energy states at the Au/ZrO₂–TiO₂ interface that modify the Fermi level to more negative potentials with respect to the base material, in order to have photogenerated electrons with higher reducing power to catalyze the hydrogen production; and ii) the Au metallic nanoparticles with SPR act as electronic reservoirs that extend the life time of photogenerated electron-hole pairs, thus enhancing the separation of charge carriers and the mobility of photogenerated electrons.     

Design and performance of asymmetric supported membranes for oxygen and hydrogen separation

Producing syngas and hydrogen from biofuels is a promising technology in the modern energy. In this work results of authors’ research aimed at design of supported membranes for oxygen and hydrogen separation are reviewed. Nanocomposites were deposited as thin layers on Ni–Al foam substrates. Oxygen separation membranes were tested in CH₄ selective oxidation/oxi-dry reforming. The hydrogen separation membranes were tested in C₂H₅OH steam reforming. High oxygen/hydrogen fluxes were demonstrated. For oxygen separation membranes syngas yield and methane conversion increase with temperature and contact time. For reactor with hydrogen separation membrane a good performance in ethanol steam reforming was obtained. Hydrogen permeation increases with ethanol inlet concentration, then a slight decrease is observed. The results of tests demonstrated the oxygen/hydrogen permeability promising for the practical application, high catalytic performance and a good thermochemical stability.     

Hydrogen recovery and purification using the solid polymer electrolyte electrolysis cell

A process is described of obtaining high-purity hydrogen characterized by bringing a hydrogen containing gas in contact with a hydrated solid polymer electrolyte cell comprised of a catalytic anode, perfluorocarbon sulfonate ion exchange membrane and a catalytic cathode. Direct current energy is supplied between the electrodes to overcome the internal resistance of the cell, dissociate the hydrogen in the gas-to-be-treated to protons, and drive the protons through the cation membrane for recovery at the opposite electrode. Experimental data on the device indicate very high efficiency and low voltages over the current density range 0–1100 mA cm^–2. Applications of the device are demonstrated for electrochemically pumping hydrogen from a low to a high pressure and separation of hydrogen from an inert gas to provide high-purity hydrogen.     

Dry autothermal reforming of glycerol with in situ hydrogen separation via thermodynamic evaluation

On the basis of the Gibbs free energy minimization principle, the dry autothermal reforming performance of crude glycerol in situ hydrogen separation is investigated via thermodynamic analysis. The impact of hydrogen separation fraction on gas composition in product, carbon formation and reaction heat is studied. It can be found that the hydrogen separation promotes the hydrogen production and hinders methane formation. The hydrogen removal is selective to the reduction of carbon deposition, which improves the carbon formation at a low feed CO₂ to glycerol molar ratio and the impact is reverse for high feed CO₂ to glycerol molar ratio. When the reaction temperature varies from 850 K to 900 K, the required oxygen to glycerol molar ratio of thermal neutral condition is obviously increased from 0.15 to 0.4 with hydrogen removal. Meanwhile, the glycerol impurities evaluation indicates that the syngas yield is significantly reduced with the increase of the glycerol impurities. At a high temperature, the hydrogen removal is in favor of the achievement of autothermal process.     

The turnover times and pool sizes of photosynthetic hydrogen production by green algae

An investigation of the turnover times of photobiological production of hydrogen gas by green algae indicate that the photoreactions associated with molecular hydrogen production have promising properties for solar energy conversion and storage. Our results indicate that (a) the intrinsic kinetic rate capability of the hydrogen photoapparatus in green algae can keep pace with the incidence rate of light quanta, even in full sunlight; (b) the photogenerated electrons for hydrogen production probably lie in the mainstream of the electron transport chain of photosynthesis.These results have been obtained by performing the first measurements on the turnover times and pool sizes of photosynthetic hydrogen production. For the three species of green algae studied, the turnover times range from 0.1 to 3 ms. The turnover time for photosynthetic hydrogen production is, therefore, comparable to that for oxygen production.Rapid multiple flash experiments have been performed which indicate that the immediate source of reductant for photosynthetic hydrogen production is derived from a pool of 5–20 equivalents, depending on the alga. This pool is probably the plastoquinone pool linking the two photosystems of photosynthesis.