Co-precipitated Ni–Mg–Al catalysts for hydrogen production by supercritical water gasification of glucose

Supercritical water gasification (SCWG) is a promising process for hydrogen production from biomass. In this study, a series of Ni–Mg–Al catalysts with different Mg/Al molar ratios has been synthesized by a co-precipitation method for hydrogen production by SCWG of glucose. Effects of Mg addition on the catalytic activity, hydrothermal stability and anti-carbon performance of alumina supported nickel catalyst were investigated. The highly dispersed nickel catalysts prepared by co-precipitation could greatly enhance the gasification efficiency of glucose in supercritical water. Among the tested Ni–Mg–Al catalysts, NiMg_0.6Al_1.9 showed the highest catalytic activity with the hydrogen yield of 11.77 mmol/g (912% as that of non-catalytic test). NiMg_0.6Al_1.9 also showed the best hydrothermal stability probably due to the formation of MgAl₂O₄. Mg could efficiently improve the anti-carbon ability of Ni–Al catalyst by inhibiting the formation of graphite carbon. It is also confirmed that MgO supported nickel catalyst is not suitable for SCWG process owing to the difficulty on nickel oxides reduction in the precursors and the phase change of MgO to Mg(OH)₂ under the hydrothermal condition.     

Experimental investigation of a natural zeolite–water adsorption cooling unit

In this study, a thermally driven adsorption cooling unit using natural zeolite–water as the adsorbent–refrigerant pair has been built and its performance investigated experimentally at various evaporator temperatures. The primary components of the cooling unit are a shell and tube adsorbent bed, an evaporator, a condenser, heating and cooling baths, measurement instruments and supplementary system components. The adsorbent bed is considered to enhance the bed’s heat and mass transfer characteristics; the bed consists of an inner vacuum tube filled with zeolite (zeolite tube) inserted into a larger tubular shell. Under the experimental conditions of 45 °C adsorption, 150 °C desorption, 30 °C condenser and 22.5 °C, 15 °C and 10 °C evaporator temperatures, the COP of the adsorption cooling unit is approximately 0.25 and the maximum average volumetric cooling power density (SCP_v) and mass specific cooling power density per kg adsorbent (SCP) of the cooling unit are 5.2 kW/m³ and 7 W/kg, respectively.     

Pyrolysis–gasification of post-consumer municipal solid plastic waste for hydrogen production

Post-consumer plastic waste derived from municipal solid waste was investigated using a two-stage, catalytic steam pyrolysis–gasification process for the production of hydrogen. The three important process parameters of catalyst:plastic ratio, gasification temperature and water injection rate were investigated. Temperature-programmed oxidation (TPO) and scanning electron microscopy (SEM) methods were used to analyse the reacted catalysts. The results showed that there was little influence of catalyst:plastic ratio between the range 0.5 and 2.0 (g/g) on the mass balance and gas composition for the pyrolysis–gasification of waste plastics; this might be due to the effective catalytic activity of the Ni–Mg–Al catalyst. However, increasing the gasification temperature and the water injection rate resulted in an increase of total gas yield and hydrogen production. The coke formation on the catalyst was reduced with increasing use of catalyst; however, a maximum coke formation (9.6 wt.%) was obtained at the gasification temperature of 700 °C when the influence of gasification temperature was investigated. The maximum coke formation was obtained at the water injection rate of 4.74 g h⁻¹, and a more reactive form of coke seemed to be formed on the catalyst with an increase of the water injection rate, according to the TPO experiments.     

Zinc–nickel alloy electrodeposits for water electrolysis

Electrodeposited zinc–nickel alloys of various compositions were prepared. A suitable electrolyte and conditions to produce alloys of various compositions were identified. Alloys produced on electroformed nickel foils were etched in caustic to leach out zinc and to produce the Raney type, porous electro catalytic surface for hydrogen evolution. The electrodes were examined by polarization measurements, to evaluate their Tafel parameters, cyclic voltammetry, to test the change in surface properties on repeated cycling, scanning electron microscopy to identify their microstructure and X-ray diffraction. The catalytic activity as well as the life of the electrode produced from 50% zinc alloy was found to be better than others.     

Thermodynamic optimization of biomass gasification for decentralized power generation and Fischer–Tropsch synthesis

In recent years, biomass gasification has emerged as a viable option for decentralized power generation, especially in developing countries. Another potential use of producer gas from biomass gasification is in terms of feedstock for Fischer–Tropsch (FT) synthesis – a process for manufacture of synthetic gasoline and diesel. This paper reports optimization of biomass gasification process for these two applications. Using the non–stoichometric equilibrium model (SOLGASMIX), we have assessed the outcome of gasification process for different combinations of operating conditions. Four key parameters have been used for optimization, viz. biomass type (saw dust, rice husk, bamboo dust), air or equivalence ratio (AR = 0, 0.2, 0.4, 0.6, 0.8 and 1), temperature of gasification (T = 400, 500, 600, 700, 800, 900 and 1000 °C), and gasification medium (air, air–steam 10% mole/mole mixture, air–steam 30%mole/mole mixture). Performance of the gasification process has been assessed with four measures, viz. molar content of H₂ and CO in the producer gas, H₂/CO molar ratio, LHV of producer gas and overall efficiency of gasifier. The optimum sets of operating conditions for gasifier for FT synthesis are: AR = 0.2–0.4, Temp = 800–1000 °C, and gasification medium as air. The optimum sets of operating conditions for decentralized power generation are: AR = 0.3–0.4, Temp = 700–800 °C with gasification medium being air. The thermodynamic model and methodology presented in this work also presents a general framework, which could be extended for optimization of biomass gasification for any other application.     

Thermodynamic properties of ammonia–water mixtures for power-cycle applications

Ammonia–water mixtures have been used as working fluids in absorption–refrigeration cycles for several decades. Their use as multi-component working fluids for power cycles has been investigated recently. The thermodynamic properties required are known or may be calculated at elevated temperatures and pressures. We present a new method for these computations using Gibbs free energies and empirical equations for bubble and dew point temperature to calculate phase equilibria. Comparisons of calculated and experimental data show excellent agreement.     

Supercritical water gasification of sewage sludge and combined cycle for H2 and power production – A thermodynamic study

An integrated system of supercritical water gasification (SCWG) and combined cycle has been developed for H₂ production and power generation. Sewage sludge and lignite coal were selected as raw material in this simulation. The effects of feed concentration (10–30 wt%) and lignite coal addition (0–50 wt%) on syngas yield and H₂ yield were also investigated in the temperature range of 500 °C–700 °C. Several heat exchangers were considered in the proposed integrated system to minimize energy loss. High pressure syngas was expanded by using turbo-expander to produce electricity, resulting in the improvement of the total efficiency. The results showed that the minimum feed concentrations of 14.25 wt%, 18.75 wt%, and 25.50 wt% were required to achieve self-sufficient energy at 500 °C, 600 °C, and 700 °C, respectively. However, the lower feed concentration and higher temperature were preferable for syngas production. The highest syngas and H₂ yield were obtained at 700 °C and 10 wt% feed concentration. The SCWG could produce 178.08 kg syngas from 100 kg feed and 9.06 kg H₂ were obtained after H₂ separation. The total power generation from turbo-expander and combined cycle module was 48.37 kW. By combining SCWG and combined cycle, the total efficiency could reach 63.48%. It worth mentioning that the addition of lignite coal could help reduce the minimum feed concentration to achieve autothermal condition, but did not have significant improvement on H₂ production.     

A water–water preheater and a steam–water heater network: Temperature dynamics

The dynamic simulation of an integrated, double pipe heat exchanger network was validated through experimentation. A steam–water, concentric tube, heat exchanger was coupled to a water–water preheater. When the preheater was configured for cocurrent flow with equal fluid velocities in its annulus and core, Lagrangian-based derivations yielded analytical solutions that accurately predicted observed temperature dynamics. When the preheater was configured for countercurrent flow with distinct fluid velocities in its annulus and core, analytical solutions for the heater and connecting tubing were coupled with Eulerian based numerical solutions for the preheater. Programming used Mathcad. Nonlinear regression analysis of steady state data was used to determine system parameters. The significance of time delays through the integration of unit operations is illustrated.     

Application of CuS–ZnS PN junction for photoelectrochemical water splitting

A CuS thin film was prepared by the sulfurization of the electrodeposited copper layer on the FTO substrate using sulfur powder at 400 °C. Surface morphology and structure of the CuS thin film were investigated by scanning electron microscopy and X-ray diffraction. The surface morphology of the CuS thin film was worm-like with the diameter of 70 nm and its crystal structure was hexagonal. Band gap energy of the CuS thin film was obtained as 1.5 eV using absorption spectra. Photoelectrochemical response of the CuS thin film was analyzed under chopped illumination at negative and positive potentials. It showed photoelectrochemical response at negative potentials (ca. 2.6 μA cm^?2 at ?0.4 V vs. Ag/AgCl), but not at positive potentials, which confirmed its p-type semiconductivity. A ZnS thin film was synthesized by spray pyrolysis method and characterized using field emission scanning electron microscopy, X-ray diffraction and UV–vis spectrometer. It was shown that the surface morphology was smooth with the grain size of about 50–150 nm. Also, its crystal structure and band gap energy were hexagonal and 3.72 eV, respectively. In order to obtain PN (positive–negative) junction and increase photoelectrochemical response, the ZnS (n-type semiconductor) thin film was deposited on CuS (p-type semiconductor). Linear scan of elemental composition confirmed the presence of FTO, CuS and ZnS layers. Photoelectrochemical characterization showed more photoresponse than the CuS thin film at negative potentials (13.6 μA cm^?2 at ?0.4 V vs. Ag/AgCl) and no photoresponse at positive potentials. The results confirmed the synthesizing of PN junction at the interface of CuS and ZnS.     

Prediction of wall shear for horizontal annular air–water flow

In this study, non-intrusive pressure drop, liquid base film thickness distribution, and wave behavior measurements have been obtained for 206 horizontal annular two-phase (air–water) flow conditions in 8.8, 15.1, and 26.3 mm ID tubes. Wall shear was correlated to within 8% by a friction factor involving flow quality and gas Reynolds number. This correlation was found to perform better than those available in the literature, including film roughness correlations, two-phase multiplier methods, and pure data fits. Among published relations, the Müller-Steinhagen and Heck correlation was found to be the most accurate, while the Lockhart–Martinelli correlation can be modified to provide reasonable results. The gas friction velocity is found to be similar to the disturbance wave velocity, which suggests that waves are important sources of shear.     

Noble fabrication of Ni–Mo cathode for alkaline water electrolysis and alkaline polymer electrolyte water electrolysis

Among the catalysts for hydrogen evolution reaction (HER) in alkaline media, Ni–Mo turns out to be the most active one. Conventional preparations of Ni–Mo electrode involve repeated spraying of dilute solutions of precursors onto the electrode substrate, which is time-consuming and usually results in cracking and brittle electrodes. Here we report a noble fabrication of Ni–Mo electrode for HER. NiMoO₄ powder was synthesized and used as the precursor. After reduction in H₂ at 500 °C, the NiMoO₄ powder layer was converted to a uniform and robust electrode containing metallic Ni and amorphous Mo(IV) oxides. The distribution of Ni and Mo components in this electrode is naturally uniform, which can maximize the interaction between Ni and Mo and benefit the electrocatalysis. The thus-obtained Ni–Mo electrode exhibits a very high catalytic activity toward the HER: the current density reaches 700 mA/cm² at 150 mV overpotential in 5 M KOH solution at 70 °C. This new fabrication method of Ni–Mo electrode is not only suitable for alkaline water electrolysis (AWE), but also applicable to the alkaline polymer electrolyte water electrolysis (APEWE), an emerging technique for efficient production of H₂.     

Black liquor gasification—consequences for both industry and society

The pulp and paper industry consumes large quantities of biofuels to satisfy process requirements. Biomass is however a limited resource, to be used as effectively as possible. Modern pulping operations have excess internal fuels compared to the amounts needed to satisfy process steam demands. The excess fuel is often used for cogeneration of electric power. If market biofuel availability at a reasonable price is limited, import/export to/from a mill however changes the amount of such biofuel available for alternative users. This work compares different mill powerhouse technologies and CHP plant configurations (including conventional recovery boiler technology and black liquor gasification technology) with respect to electric power output from a given fuel resource. Different process steam demand levels for different representative mill types are considered. The comparison accounts for decreased/increased electricity production in an alternative energy system when biofuel is imported/exported to/from the mill. The results show that black liquor gasification is in all cases considered an attractive powerhouse recovery cycle technology. For moderate values of the marginal electric power generation efficiency for biofuel exported to the reference alternative energy system, excess mill internal biofuel should be used on mill site for gas turbine based CHP power generation. The remaining excess biofuels in market pulp mills should be exported and used in the reference alternative energy system in this case. For integrated pulp and paper mills, biofuel should be imported, but only for cogeneration usage (i.e. condensing power units should be avoided). If biofuel can be used elsewhere for high efficiency CHP power generation, mill internal biofuel should be used exclusively for process heating, and the remainder should be exported.     

Thermal–mechanical modelling around the cavities of underground coal gasification

Underground coal gasification (UCG) is an efficient method for the conversion of the deep coal resources into energy. This paper is concerned with a feasibility study of the potential of deeply lying coal seams (>1200 m) for the application of UCG combined with subsequent storage of CO₂ for a site located in Bulgaria. A thermal–mechanical coupled model was developed using the ABAQUS software package to predict the heat transfer, the stress distributions around the UCG and the consequent surface subsidence. Material properties of rocks and coal were obtained from existing literature and geomechanical tests which were carried out on samples derived from the demonstration site in Bulgaria. Three days of gasification has been simulated by assigning a moving heat flux on a cell of 2 m × 2 m × 2 m at a velocity of 2 m/day. Results of temperature and stress distribution showed that the developed numerical model was able to simulate the heat propagation and the stress distribution around cavities under a thermal–mechanical coupled loading during the UCG process. Also, the surface subsidence was found to be 0.08 mm after three days of gasification for the case studied. It is anticipated that the results of this paper can be used for the prediction and optimization of the UCG process in deep coal seams.     

CdO–CdS nanocomposites with enhanced photocatalytic activity for hydrogen generation from water

Nanocomposites of CdO–CdS have been prepared in ethylene glycol water mixture followed by heating at 300 °C. TEM and XRD studies confirmed the atomic scale mixing of CdO and CdS nanoparticles, leading to the formation of CdSO₃ phase at the interfacial region between CdO and CdS. Photocatalytic studies for hydrogen generation from water show an enhanced activity for CdO–CdS composites compared to individual components namely CdO or CdS nanoparticles. Based on optical absorption, surface area measurements, steady state and time resolved fluorescence studies, it is established that, enhanced absorption in the visible region, higher surface area and increase in lifetime of the charge carriers are responsible for the observed increase in hydrogen yield from water when composite sample was used as the photocatalyst compared to individual components. The composite sample when combined with Pt as co-catalyst exhibit a large increase in the photocatalytic activity.     

The potential of solar-driven humidification–dehumidification desalination for small-scale decentralized water production

World-wide water scarcity, especially in the developing world, indicates a pressing need to develop inexpensive, decentralized small-scale desalination technologies which use renewable resources of energy. This paper provides a comprehensive review of the state-of-the-art in one of the most promising of these technologies, solar-driven humidification–dehumidification (HDH) desalination. Previous studies have investigated many different variations on the HDH cycle. In this paper, performance parameters which enable comparison of the various versions of the HDH cycle have been defined and evaluated. To better compare these cycles, each has been represented in psychometric coordinates. The principal components of the HDH system are also reviewed and compared, including the humidifier, solar heaters, and dehumidifiers. Particular attention is given to solar air heaters, for which design data is limited; and direct air heating is compared to direct water heating in the cycle assessments. Alternative processes based on the HDH concept are also reviewed and compared. Further, novel proposals for improvement of the HDH cycle are outlined. It is concluded that HDH technology has great promise for decentralized small-scale water production applications, although additional research and development is needed for improving system efficiency and reducing capital cost.     

Ceria–zirconia stabilised tungsten oxides for the production of hydrogen by the methane–water redox cycle

The generation of essentially pure hydrogen through a redox cycle using methane and then water has been investigated for a series of tungsten oxides stabilised by ceria–zirconia. The calcined starting materials were largely monoclinic WO₃ with CeO₂ and ZrO₂ undetectable by XRD. Samples containing 80% and especially 69% WO₃ showed additional XRD lines due to a phase of unknown composition. Temperature programmed reduction to 750 °C in methane converted samples containing WO₃ alone to WC together with small amounts of tungsten metal and a WC_1−x phase. Reoxidation in water at the same temperature then produced CO and H₂ in corresponding amounts. Under the same conditions the 69% WO₃ sample was reduced only as far as WO₂ and reoxidation yielded H₂ largely free of CO. The reoxidation product was not WO₃ but consisted of various non-stoichiometric oxides with composition WO_2+x (x = 0.72, 0.83, etc). The reduction–reoxidation cycle could be repeated many times without loss of hydrogen production efficiency.