Utilization of laterite ore as an oxygen carrier in chemical looping reforming of methane for syngas production

Growing energy demands in various sectors have resulted in overusing fossil fuel sources and rise in greenhouse gases in the atmosphere. This necessitates the need for reducing greenhouse gases and shifting to cleaner, renewable energy sources like H₂. Chemical looping is one such renewable method to produce clean H₂. The efficiency of this process depends on the oxygen carrier. Generally, oxygen carriers (OC) are transition metal oxides (Fe₂O₃ or NiO) or some complex metal oxides like spinel or perovskites, but usage of these OCs are restricted due to their availability and redox performance. One solution for selecting OCs can be using industrial waste like slag or low-grade ores because of their composition, which consists of metal oxides. One such low-grade ore is Ni-laterite ore or chromite overburden, a mining waste found in the chromite mines of Sukinda (India). In this work, we have focused on utilizing this laterite ore as an OC for the chemical looping reforming of methane to produce syngas. The reactivity analysis of laterite ore with CH₄ was performed in DSC-TG and the reaction products were analyzed in gas chromatography along with microscopy and spectroscopic techniques. Results showed the formation of H₂ and CO gases along with reduced metallic phases. The total H₂ yield at 750 °C is determined to 53.67 (±1.09) ml/g of OC which is comparable or even higher than existing CeO₂ based OCs. Further, thermodynamic calculations are presented to calculate the theoretical yield for our process and compared with the experimental H₂ yield. This study effectively demonstrates the performance of laterite ore as an OC for generating clean and renewable energy through chemical looping technique.     

A strategy of mid-temperature natural gas based chemical looping reforming for hydrogen production

Steam methane reforming (SMR) needs the reaction heat at a temperature above 800 °C provided by the combustion of natural gas and suffers from adverse environmental impact and the hydrogen separated from other chemicals needs extra energy penalty. In order to avoid the expensive cost and high power consumption caused by capturing CO₂ after combustion in SMR, natural gas Chemical Looping Reforming (CLR) is proposed, where the chemical looping combustion of metal oxides replaced the direct combustion of NG to convert natural gas to hydrogen and carbon dioxide. Although CO₂ can be separated with less energy penalty when combustion, CLR still require higher temperature heat for the hydrogen production and cause the poor sintering of oxygen carriers (OC). Here, we report a high-rate hydrogen production and low-energy penalty of strategy by natural gas chemical-looping process with both metallic oxide reduction and metal oxidation coupled with steam. Fe₃O₄ is employed as an oxygen carrier. Different from the common chemical looping reforming, the double side reactions of both the reduction and oxidization enable to provide the hydrogen in the range of 500–600 °C under the atmospheric pressure. Furthermore, the CO₂ is absorbed and captured with reduction reaction simultaneously.Through the thermodynamic analysis and irreversibility analysis of hydrogen production by natural gas via chemical looping reforming at atmospheric pressure, we provide a possibility of hydrogen production from methane at moderate temperature. The reported results in this paper should be viewed as optimistic due to several idealized assumptions: Considering that the chemical looping reaction is carried out at the equilibrium temperature of 500 °C, and complete CO₂ capture can be achieved. It is assumed that the unreacted methane and hydrogen are completely separated by physical adsorption. This paper may have the potential of saving the natural gas consumption required to produce 1 m³ H₂ and reducing the cost of hydrogen production.     

Hydrogen production from phototrophic microorganisms: Reality and perspectives

Hydrogen is a promising alternative to fossil fuel for a source of clean energy due to its high energy content. Some strains of phototrophic microorganisms are known as important object of scientific research and they are being explored to raise biohydrogen (BioH₂) yield. BioH₂ is still not commonly used in industrial area because of the low biomass yield and valuable down streaming process. This article deals with the methods of the hydrogen production with the help of two large groups of phototrophic microorganisms – microalgae and cyanobacteria. Microalgal hydrogen is environmentally friendly alternative to conventional fossil fuels. Algal biomass has been considered as an attractive raw source for hydrogen production. Genetic modified strains of cyanobacteria are used as a perspective object for obtaining hydrogen. The modern photobioreactors and outdoor air systems have been used to obtain the biomass used for hydrogen production. At present time a variety of immobilization matrices and methods are being examined for their suitability to make immobilized H₂ producers.     

Biomass gasification coupled with producer gas cleaning,bottling and HTS catalyst treatment for H2-rich gas production

The aim of the present study is to demonstrate the production of hydrogen-rich fuel gas from J. curcas residue cake. A comprehensive experimental study for the production of hydrogen rich fuel gas from J. curcas residue cake via downdraft gasification followed by high temperature water gas shift catalytic treatment has been carried out. The gasification experiments are performed at different equivalence ratios and performance of the process is reported in terms of producer gas composition & its calorific value, gas production rate and cold gas efficiency. The producer gas is cleaned of tar and particulate matters by passing it through venturi scrubber followed by sand bed filter. The clean producer gas is then compressed at 0.6 MPa and bottled into a gas cylinder. The bottled producer gas and a simulated mixture of producer gas are then subjected to high temperature shift (HTS) catalytic treatment for hydrogen enriched gas production. The effect of three different operating parameters GHSV, steam to CO ratio and reactor temperature on the product gas composition and CO conversion is reported. From the experimental study it is found that, the presence of oxygen in the bottled producer gas has affected the catalyst activity. Moreover, higher concentration of oxygen concentration in the bottled producer gas leads to the instantaneous deactivation of the HTS catalyst.     

Hydrogen production for energy: An overview

Power to hydrogen is a promising solution for storing variable Renewable Energy (RE) to achieve a 100% renewable and sustainable hydrogen economy. The hydrogen-based energy system (energy to hydrogen to energy) comprises four main stages; production, storage, safety and utilisation. The hydrogen-based energy system is presented as four corners (stages) of a square shaped integrated whole to demonstrate the interconnection and interdependency of these main stages. The hydrogen production pathway and specific technology selection are dependent on the type of energy and feedstock available as well as the end-use purity required. Hence, purification technologies are included in the production pathways for system integration, energy storage, utilisation or RE export. Hydrogen production pathways and associated technologies are reviewed in this paper for their interconnection and interdependence on the other corners of the hydrogen square.Despite hydrogen being zero-carbon-emission energy at the end-use point, it depends on the cleanness of the production pathway and the energy used to produce it. Thus, the guarantee of hydrogen origin is essential to consider hydrogen as clean energy. An innovative model is introduced as a hydrogen cleanness index coding for further investigation and development.     

Hydrogen sulphide to hydrogen via H2S methane reformation: Thermodynamics and process scheme assessment

Hydrogen Sulphide Methane Reformation (HSMR) represents a valid alternative for the simultaneous H₂S valorisation and hydrogen production at the industrial scale, without direct CO₂ emissions. The major concerns about the process commercialization are the possible coke formation in the reaction zone and the lack of active and selective catalysts. The study of the thermodynamics is the essential preliminary step for the reaction phenomena understanding. In this work, a deep thermodynamic analysis is performed to explore the system behaviour as a function of temperature, pressure, and inlet feed composition, using the Aspen Plus RGibbs module. In this way, the optimal process operating conditions to avoid carbon lay down can be identified.Assessed the system's thermodynamics, a preliminary process scheme is developed and simulated in Aspen Plus V11.0®, considering hydrogen production and its distribution in pipeline with methane. The process performances are discussed in terms of products' purity and process energy consumptions.     

A comprehensive review on lignocellulosic biomass biorefinery for sustainable biofuel production

The increasingly severe environmental pollution and energy shortage issues have demanded the production of renewable and sustainable biofuels to replace conventional fossil fuels. Lignocellulosic (LC) biomass as an abundant feedstock for second-generation biofuel production can help overcome the shortcomings of first-generation biofuels related to the “food versus fuel” debate and feedstock availability. Embracing the “circular bioeconomy” concept, an integrated biorefinery platform of LC biomass can be performed by employing different conversion technologies to obtain multiple valuable products. This review provides an overview of the principles and applications of thermochemical processes (pyrolysis, torrefaction, hydrothermal liquefaction, and gasification) and biochemical processes (pretreatment technologies, enzyme hydrolysis, biochemical conversion processes) involved in LC biomass biorefinery for potential biofuel applications. The engineering perspective of LC biofuel production on separate hydrolysis and fermentation (SHF), simultaneous saccharification and fermentation (SSF), simultaneous saccharification and co-fermentation (SSCF), and consolidated bioprocessing (CBP) were also discussed.     

Sustainable biohydrogen production by Chlorella sp. microalgae: A review

The use of fossil fuels is causing a huge environmental impact due to the emission of air pollutants, greenhouse gases, and other ground and water contaminants; also, these fuels are depleting; the world is facing an energy crisis in the years to come if no preventive actions are done. Renewable energies are arising as promising technologies that will complement and even replace conventional fuels shifting the global energy matrix to a cleaner and eco-friendly future. Microalgal biohydrogen is one of those emerging technologies that is showing positive results. This work provides an overview of the key parameters to produce hydrogen from microalgae especially from the genus Chlorella. Current status of chemical and biological hydrogen producing technologies is presented, along with the main metabolic processes for this purpose in microalgae, their characteristic enzymes, several strategies to induce hydrogen production, the key operation parameters and finally providing some remarks about scaling-up and industrial-scale applications.     

A review on pretreatment methods,photobioreactor design and metabolic engineering approaches of algal biomass for enhanced biohydrogen production

The development of alternative fuels has been promoted by the extreme fossil fuel consumption brought on by urbanisation and deteriorating pollution. Due to its high energy and combustible qualities, biohydrogen has been perceived as a potential fuel substitute in dealing with issues related to the rising emission of greenhouse gases and global warming. As a source of carbon sequestration and sustainable renewable energy, biohydrogen synthesis by algae species has been prevalent in research scale. This review focuses on the novel and recent metabolic approaches for enhanced algal based biohydrogen production. Pretreatment methods available and scaling techniques used for enhancing the biohydrogen productivity using algal species have been elaborated in the review. Algal characteristics that make them suitable alternative for biohydrogen production are discussed briefly. Various pretreatment methods such as physical, chemical, biological and thermal are elaborated. In addition, the factors involved in influencing the biohydrogen productivity and the metabolic engineering approaches for modifying the pathway in algae are highlighted. Scaling up of process using different types of photobioreactors such as tubular, flat panel, airlift and stirred tank are reported that briefs about merits and demerits of each photobioreactor.     

Hydrogen technology adoption analysis in Africa using a Doughnut-PESTLE hydrogen model (DPHM)

The hydrogen economy requires the right conditions to produce hydrogen by sustainable routes and provide it to local and international markets for suitable applications. This study evaluated the political, economic, social, technological, legal, and environmental (PESTLE) conditions that can be instrumental in adopting hydrogen technologies most effectively by encapsulating aspects relevant to key stakeholders from hydrogen technology developers through to end-users. For instance, the analysis has shown that countries within a government effectiveness index of 0.5 and ?0.5 are leading the planning of hydrogen economies through strategic cooperation with hydrogen technology developers. Furthermore, the combination of a Doughnut and PESTLE analysis created a novel approach to assessing the adoption of hydrogen technologies while evaluating the impact of the hydrogen economy. For instance, the estimated ammonia demand in 2050 and subsequent anthropogenic nitrogen extraction rate will be about two and a half times more than the 2009 extraction rate.     

Titanate quantum dots-sensitized Cu2S nanocomposites for superficial H2 production via photocatalytic water splitting

TiO₂ quantum dots-sensitized Cu₂S (Cu₂S/TiO₂) nanocomposites with varying concentration of TiO₂ QDs are synthesized via a facile two-stage hydrothermal-wet impregnation method. X-ray diffraction analysis confirms the formation of Cu₂S and TiO₂with chalcocite and anatase phases, respectively. The observed shoulder-like absorption peaks indicate the UV–visible light-driven properties of the composite. Morphological analysis reveals that the fabricated Cu₂S/TiO₂ composite consists of Cu₂S with a nano rod-like shape (average length and width of ～856 and ～213 nm, respectively) and nanosheets-like structures (average length and width of ～283 and ～289 nm, respectively), whereas the TiO₂ is formed as quantum dots with a size range of 8.2 ± 0.4 nm. Chemical state analysis shows the presence of Cu⁺, S^2?, Ni²⁺, and O^2? in the nanocomposite. The H₂ evolution rate over the optimized photocatalyst is found to be ～45.6 mmol h^?1g^?1_cat under simulated solar irradiation, which is around 5 and 2.4-fold higher than that of the pristine TiO₂ and Cu₂S, respectively. Continuous H₂ production for 30 h is achieved during time-on-stream experiments, demonstrating the excellent stability and durability of the Cu₂S/TiO₂ photocatalyst for large-scale applications.     

A remarkable increase in the adsorbed H2 amount: Influence of pore size distribution on the H2 adsorption capacity of Fe-BTC

Here we show the crucial role of ultramicropores on the adsorbed H₂ amount. By synthesizing Fe-BTCs via a perturbation assisted nanofusion synthesis strategy and by the control of textural porosity via Fe:BTC ratio, BET surface area (1312 m²/g), total pore volume (1.41 cm³/g), and H₂ adsorption capacity (1.10 wt% at 7.6 bar and 298 K) were enhanced by 1.6, 3.1, and 2.6 times, respectively. The reported BET surface area, and the total pore volume are the highest of those reported for Fe-BTC, to date. The enhanced H₂ adsorption capacity of Fe-BTC-3 is attributed to the ultramicropores present in its pore structure. Presence of ultramicropores maximizes van der Waals potential, and the adsorbed H₂ amount increases. By the perturbation assisted nanofusion synthesis strategy and the control over textural porosity, an Fe-BTC that possesses a H₂ adsorption capacity higher than those of reported MOFs with higher BET surface areas has been reported.     

Effect of ZrO2 on the performance of Co–CeO2 catalysts for hydrogen production from waste-derived synthesis gas using high-temperature water gas shift reaction

In this study, highly active and stable CeO₂, ZrO₂, and Zr_(1-x)Ce_(x)O₂-supported Co catalysts were prepared using the co-precipitation method for the high-temperature water gas shift reaction to produce hydrogen from waste-derived synthesis gas. The physicochemical properties of the catalysts were investigated by carrying out Brunauer-Emmet-Teller, X-ray diffraction, CO-chemisorption, Raman spectroscopy, transmission electron microscopy, X-ray photoelectron spectroscopy, and H₂-temperature-programmed reduction measurements. With an increase in the ZrO₂ content, the surface area and reducibility of the catalysts increased, while the interaction between Co and the support and the dispersion of Co deteriorated. The Co–Zr_0.4Ce_0·6O₂ and Co–Zr_0.6Ce_0·4O₂ catalysts showed higher oxygen storage capacity than that of the others because of the distortion of the CeO₂ structure due to the substitution of Ce⁴⁺ by Zr⁴⁺. The Co–Zr_0.6Ce_0·4O₂ catalyst with high reducibility and oxygen storage capacity exhibited the best catalytic performance and stability among all the catalysts investigated in this study.     

The role of oxygen vacancies in the CO2 methanation employing Ni/ZrO2 doped with Ca

The Ni/ZrO₂ catalyst doped with Ca and Ni/ZrO₂ were employed in the CO₂ methanation, a reaction which will possibly be used for storing intermittent energy in the future. The catalysts were characterized by X-ray photoelectron spectroscopy (XPS, reduction in situ), X-ray diffraction (XRD, reduction in situ and Rietveld refinement), electron paramagnetic resonance (EPR), temperature-programmed surface reaction, cyclohexane dehydrogenation model reaction, temperature-programmed desorption of CO₂ and chemical analysis. The catalytic behavior of these catalysts in the CO₂ methanation was analyzed employing a conventional catalytic test. Adding Ca to Ni/ZrO₂, the metallic surface area did not change whereas the CO₂ consumption rate almost tripled. The XRD, XPS and EPR analyses showed that Ca⁺² but also some Ni²⁺ are on the ZrO₂ surface lattice of the Ni/CaZrO₂ catalyst. These cations form pairs which are composed of oxygen vacancies and coordinatively unsaturated sites (cus). By increasing the number of these pairs, the CO₂ methanation rate increases. Moreover, the number of active sites of the CO₂ methanation rate limiting step (CO and/or formate species decomposition, rls) is enhanced as well, showing that the rls occurs on the vacancies-cus sites pairs.     

Evaluating influences of impurities on hydrogen production in the reaction of Si with water using Si sludge

Hydrogen has attracted much attention as a next-generation energy resource. Among various technologies, one of the promising approaches for hydrogen production is the use of the reaction between Si and water, which does not require any heat, electricity, and light energy as an input. Notwithstanding the usefulness of Si as a prospective raw material of hydrogen production, the manufacturing process of Si requires a significant amount of energy. Therefore, as an alternative to pure Si, this study used a wasted Si sludge, generated though the manufacturing process of Si wafer, for the direct reuse. Thus, the Si-water reaction for the hydrogen generation was investigated in comparison with pure Si and Si sludge by employing X-ray absorption near edge structure (XANES) to evaluate the feasibility of hydrogen production with the use of Si sludge and to identify the influence of impurities contained in Si sludge. As a result, hydrogen was not produced with the use of Si sludge because of containing Al compound as the impurity. Through the XANES analysis, the formation of SiO(OH)₂ was found as core-shell structure, which potentially would hinder the hydrogen generation.     

Effect of hydrogen flow rate on the synthesis of carbon nanofiber using microwave-assisted chemical vapour deposition with ferrocene as a catalyst

Carbon nanostructure materials are becoming of considerable commercial importance, with interest growing rapidly over the decade since the discovery of carbon nanofibers. In this study, a new novel method is introduced to synthesize the carbon nanofibers by gas-phase, where a single-stage microwave-assisted chemical vapour deposition approach is used with ferrocene as a catalyst and acetylene and hydrogen as precursor gases. Hydrogen flow rate plays a significant role in the formation of carbon nanofibers, as being the carrier and reactant gas in the floating catalyst method. The effect of process parameters such as microwave power, radiation time and gas ratio of C₂H₂/H₂ was investigated statistically. The carbon nanofibers were characterized using scanning and transmission electron microscopy and thermogravimetric analysis. The analysis revealed that the optimized conditions for carbon nanofibers production were microwave power (1000 W), radiation time (35 min) and acetylene/hydrogen ratio (0.8). The field emission scanning electron microscope and transmission electron microscope analyses revealed that the vertical alignment of carbon nanofibers has tens of microns long with a uniform diameter ranging from 115 to 131 nm. High purity of 93% and a high yield of 12 g of CNFs were obtained. These outcomes indicate that identifying the optimal values for process parameters is important for synthesizing high quality and high CNF yield.     

Detonation propagation characteristics of H2/O2/AR in multi-angle bifurcation tubes

The propagation characteristics of the detonation wave in the bifurcated tube with the angular variation range of 30°–90° are simulated with 25% AR as dilution gas for H₂/O₂ mixture fuel at chemical equivalence ratio using the solver DCRFoam built on the OpenFOAM platform. The diffraction and reflection phenomena of detonation waves passing through bifurcation tubes with different angles are studied and analyzed. The results show that the distance from regular reflection to Mach reflection increases with the increase of the bifurcation angle so that after one reflection, the detonation forms three reflection forms with the angle of the different bifurcation tubes. After the first reflection, the detonation waves are more likely to induce the formation of transverse waves in the low-angle bifurcation tube. The lowest collision pressure after the detonation collides with the upper wall to form a secondary reflection occurs in the bifurcation tube between 50° and 60°.     

Effect of ammonia concentration on hythane (H2 and CH4) production in two-phase anaerobic digestion

Co-production of hydrogen and methane by two-phase anaerobic digestion (AD) may offer a sustainable solution for the centralized treatment of food waste (FW), while ammonia accumulation is potentially encountered. A mesophilic two-phase AD was investigated for hydrogen and methane production from FW at varying ammonia concentrations. The process achieved a hydrogen yield of 47.7 mL/g VS and a methane yield of 335 mL/g VS by optimizing the organic loading rate (OLR) and recirculation ratio. Total ammonia nitrogen (TAN) concentration of 4044 mg/L corresponded to a threshold in the hydrogen reactor, above which ammonia would initiate inhibition of hydrogenogenesis and acidogenesis. Methane yield was recovered in the methane reactor after acute inhibiting effects of TAN below 5800 mg/L, while TAN above 6200 mg/L caused chronic inhibition of methanogens. Adjusting hydraulic retention time (HRT) and recirculation ratio in hydrogen and methane reactors reduced TAN to 960 and 2105 mg/L respectively, resulting in successful recovery was achieved in the hydrogen reactor but not in the methane reactor. The two-phase AD for methane and hydrogen production can be a promising solution for ammonia accumulation in AD from FW.     

Polyaniline sensitized Pt@TiO2 for visible-light-driven H2 generation

Polyaniline is a typical conducting polymer with high migration electron rate, good stability, eco-friendly properties, and high absorption coefficients for visible light. In the present study, polyaniline decorated Pt@TiO₂ for visible light-driven H₂ generation is reported for the first time. The above-mentioned nanocomposite is prepared through a simple oxidative-polymerization and characterized by infrared spectroscopy, transmission electron microscopy, X–ray diffraction, thermogravimetric analysis, and ultraviolet–visible diffuse reflectance spectra. Polyaniline modification improves the absorption of the nanocomposite in visible light region via a photosensitization effect similar to dye–sensitization but does not influence the crystal structure and size of Pt@TiO₂. The polyaniline modified Pt@TiO₂ exhibits a remarkable visible light activity (61.8 μmol h⁻¹ g⁻¹) and good stability for H₂ generation (with an average apparent quantum yield of 10.1%) with thioglycolic acid as an electron donor. This work provides new insights into using conducting polymers, including polyaniline, as a sensitizer to modify Pt@TiO₂ for visible-light hydrogen generation.     

Simultaneous biohydrogen (H2) and bioplastic (poly-β-hydroxybutyrate-PHB) productions under dark,photo, and subsequent dark and photo fermentation utilizing various wastes

The present study is focused on bio hydrogen (H₂) and bioplastic (i.e., poly-β-hydroxybutyrate; PHB) productions utilizing various wastes under dark fermentation, photo fermentation and subsequent dark-photo fermentation. Potential bio H₂ and PHB producing microbes were enriched and isolated. The effects of substrate (rice husk hydrolysate, rice straw hydrolysate, dairy industry wastewater, and rice mill wastewater) concentration (10–100%) and pH (5.5–8.0) were examined in the batch mode under the dark and photo fermentation conditions. Using 100% rice straw hydrolysate at pH 7, the maximum bio H₂ (1.53 ± 0.04 mol H₂/mol glucose) and PHB (9.8 ± 0.14 g/L) were produced under dark fermentation condition by Bacillus cereus. In the subsequent dark-photo fermentation, the highest amounts of bio H₂ and PHB were recorded utilizing 100% rice straw hydrolysate (1.82 ± 0.01 mol H₂/mol glucose and 19.15 ± 0.25 g/L PHB) at a pH of 7.0 using Bacillus cereus (KR809374) and Rhodopseudomonas rutila. The subsequent dark-photo fermentative bio H₂ and PHB productions obtained using renewable biomass (i.e., rice husk hydrolysate and rice straw hydrolysate) can be considered with respect to the sustainable management of global energy sources and environmental issues.