Hydrogen production from catalytic reforming of the aqueous fraction of pyrolysis bio-oil with modified Ni–Al catalysts

Hydrogen production from renewable resources has received extensive attention recently for a sustainable and renewable future. In this study, hydrogen was produced from catalytic steam reforming of the aqueous fraction of crude bio-oil, which was obtained from pyrolysis of biomass. Five Ni–Al catalysts modified with Ca, Ce, Mg, Mn and Zn were investigated using a fixed-bed reactor. Optimized process conditions were obtained with a steam reforming temperature of 800 °C and a steam to carbon ratio of 3.54. The life time of the catalysts in terms of stability of hydrogen production and prohibition of coke formation on the surface of the catalyst were carried out with continuous feeding of raw materials for 4 h. The results showed that the Ni–Mg–Al catalyst exhibited the highest stability of hydrogen production (56.46%) among the studied catalysts. In addition, the life-time test of catalytic experiments showed that all the catalysts suffered deactivation at the beginning of the experiment (reduction of hydrogen production), except for the Ni–Mg–Al catalyst; it is suggested that the observation of abundant amorphous carbon formed on the surface of reacted catalysts (temperature programmed oxidation results) may be responsible for the initial reduction of hydrogen production. In addition, the Ni–Ca–Al catalyst showed the lowest hydrogen production (46.58%) at both the early and stabilized stage of catalytic steam reforming of bio-oil.     

Ni–Co bimetallic MgO-based catalysts for hydrogen production via steam reforming of acetic acid from bio-oil

Acetic acid (AC) is a representative compound of bio-oil via fast pyrolysis of biomass, and can be processed for hydrogen production via steam reforming (SR). In the current work, the Ni_xCo_1−xMg₆O_7±δ (x = 0–1) bimetallic catalysts were prepared via co-precipitation and impregnation, and tested in SR of AC. The reaction results indicate that the monometallic catalysts were deactivated obviously in SR, while the Ni_0.2Co_0.8Mg₆O_7±δ bimetallic catalyst performed better in both activity and stability: not only the conversion of AC remained stable near 100%, but also the H₂ yield maintained stable near 3.1 mol-H₂/mol-AC. The results of XRD, BET, XPS, TG and TEM indicate that the high catalytic performance of the Ni_0.2Co_0.8Mg₆O_7±δ catalyst can be attributed to 1) resistance to oxidation of active metals, 2) resistance to coking, and 3) stability of structure and electronic properties.     

A review on the development of supported non-noble metal catalysts for the endothermic high temperature sulfuric acid decomposition step in the Iodine–Sulfur cycle for hydrogen production

The decomposition of sulfuric acid to sulfur dioxide is an important reaction section in both the thermochemical Iodine–Sulfur (IS) cycle and the Hybrid (Hybs) cycle for hydrogen production. This decomposition reaction is a high temperature, highly endothermic reaction whose activation barrier needs to be reduced by a highly active catalyst. The catalysts reported in this reaction are either exorbitantly expensive, synthesized using noble metals, or exhibiting low activity and stability. Hence, the development of non-noble active and stable catalysts in this reaction is a significant challenge. This review comprehensively discusses the recent developments and activity trends of supported non-noble catalysts including their synthesis, activity & stability trends, mechanistic and kinetic aspects. The catalytic activity of nano-catalysts in sulfuric acid decomposition is largely affected by the size of the metal nanoparticles, dispersion, oxygen vacancies, and metal-support interaction. Herein, we report an in-depth theoretical and experimental understanding of the catalytic challenges and solutions that leads to designing a cost-effective, efficient and stable catalyst in this reaction. The role of catalyst support modification for long run stability is also discussed. Further, literature considering reaction kinetics over various catalysts is also reviewed.     

Transformation of biomass into carbon nanofiber for supercapacitor application – A review

This paper starts with a review on challenges and need of improved supercapacitor application, which is then followed by advantages of biomass compared with other materials for use in supercapacitor application. The conversion of biomass into carbon nanofiber using different techniques was extensively reviewed for its advantages and limitations. It was revealed that the materials currently used are yet to be fully sustainable or feasible for energy storage application. In contrast, biomass represents a widely available and sustainable material to be converted into carbon nanofiber for energy storage application. Different techniques were employed for carbon nanofiber production to achieve different objectives, comprising high product yield, feasible diameter adjustment, low electric consumption, and shorter production time. Nevertheless, it was revealed that many key properties of the biomass-derived carbon nanofiber have yet to be fully investigated, as there are still knowledge gaps to be filled for each technique. Thus, more studies are needed to broaden the existing understanding in the key parameters of different techniques in order to develop a highly desirable carbon nanofiber from biomass for sustainable energy storage application.     

Technoeconomics of large-scale clean hydrogen production – A review

Hydrogen is widely used in many industries, yet its role in the clean energy transition goes beyond being an element of these industries. Near-term practical large-scale clean hydrogen production can be made available by involving nuclear, solar, and other renewable energy sources in the process of hydrogen production, and coupling their energy systems to sustainable carbon-free hydrogen technologies. This requires further investigation and assessment of the different alternatives to achieve clean hydrogen using these pathways. This paper assesses the technoeconomics of promising hydrogen technologies that can be coupled to nuclear and solar energy systems for large-scale hydrogen production. It also provides an overview of the design, status and advances of these technologies.     

Metallic and carbonaceous –based catalysts performance in the solar catalytic decomposition of methane for hydrogen and carbon production

Solar catalytic decomposition of methane (SCDM) was investigated in a solar furnace facility with different catalysts. The aim of this exploratory study was to investigate the potential of the catalytic methane decomposition approach providing the reaction heat via solar energy at different experimental conditions. All experiments conducted pointed out to the simultaneous production of a gas phase composed only by hydrogen and un-reacted methane with a solid product deposited into the catalyst particles varying upon the catalysts used: nanostructured carbons either in form of carbon nanofibers (CNF) or multi-walled carbon nanotubes (MWCNT) were obtained with the metallic catalyst whereas amorphous carbon was produced using a carbonaceous catalyst. The use of catalysts in the solar assisted methane decomposition present some advantages as compared to the high temperature non-catalytic solar methane decomposition route, mainly derived from the use of lower temperatures (600–950 °C): SCDM yields higher reaction rates, provides an enhancement in process efficiency, avoids the formation of other hydrocarbons (100% selectivity to H₂) and increases the quality of the carbonaceous product obtained, when compared to the non-catalytic route.     

Hydrogen production from steam gasification of biomass: Influence of process parameters on hydrogen yield – A review

Steam gasification is considered one of the most effective and efficient techniques of generating hydrogen from biomass. Of all the thermochemical processes, steam gasification offers the highest stoichiometric yield of hydrogen. There are several factors which influence the yield of hydrogen in steam gasification. Some of the prominent factors are: biomass type, biomass feed particle size, reaction temperature, steam to biomass ratio, addition of catalyst, sorbent to biomass ratio. This review article focuses on the hydrogen production from biomass via steam gasification and the influence of process parameters on hydrogen yield.     

Analysis of the potential production and the development of bioenergy in the province of Mendoza – Bio-fuels and biomass – Using geographic information systems

In this work, the partial results of the potential production of energy, starting from the biomass and the development of the crops, directed to the production of bio-fuels (Colza and Topinamur) in the North irrigation oasis of Mendoza, Argentina within the National Program of Bio-energy developed by INTA is presented.     

Ni/CeO2/ZSM-5 catalysts for the production of hydrogen from the pyrolysis–gasification of polypropylene

The production of hydrogen from the two-stage pyrolysis–gasification of polypropylene using a Ni/CeO₂/ZSM-5 catalyst has been investigated. Experiments were conducted on CeO₂ loading, calcination temperature and Ni loading of the Ni/CeO₂/ZSM-5 catalyst in relation to hydrogen production. The results indicated that with increasing CeO₂ loading from 5 to 30 wt.% for the 10 wt.% Ni/CeO₂/ZSM-5 catalyst calcined at 750 °C, hydrogen concentration in the gas product and the theoretical potential hydrogen production were decreased from 63.0 to 49.8 vol.% and 50.4 to 21.6 wt.%, respectively. In addition, the amount of coke deposited on the catalyst was reduced from 9.5 to 6.2 wt.%. The calcination temperature had little influence on hydrogen production for the catalyst containing 5 wt.% of CeO₂. However, for the 10 wt.% Ni/CeO₂/ZSM-5 catalyst with a CeO₂ content of 10 or 30 wt.%, the catalytic activities reduced when the calcination temperature was increased from 500 to 750 °C. The SEM results showed that large amounts of filamentous carbons were formed on the surface of the catalysts. The investigation of different Ni content indicates that the Ni/CeO₂/ZSM-5 ((2-10)-5-500) catalyst containing 2 wt.% Ni showed poor catalytic activity in relation to the pyrolysis–gasification of polypropylene according to the theoretical potential H₂ production (7.2 wt.%). Increasing the Ni loading to 5 or 10 wt.% in the Ni/CeO₂/ZSM-5 ((2-10)-5-500) catalyst, high potential hydrogen production was obtained.     

Upgrading of the liquid fuel from fast pyrolysis of biomass over MoNi/γ-Al2O3 catalysts

The hydrotreatment of bio-oil, which obtained from fast pyrolysis of pine sawdust, was investigated over MoNi/γ-Al₂O₃ catalyst under mild conditions (373 K, 3 MPa hydrogen pressure). Acetic acid was taken as a model compound to investigate the effects of Mo promoter contents and reducing temperatures of catalysts on the catalysts activity under the condition of 473 K and 3 MPa hydrogen pressure. X-ray diffraction and temperature programmed reduction showed that the addition of Mo promoter benefited the uniformity of nickel species and inhibited the formation of NiAl₂O₄ spinel in the catalysts. The GC spectrum of liquid products showed the mechanism of the model reaction. The maximum conversion of acetic acid (33.20%) was attained over 0.06MoNi/γ-Al₂O₃ catalysts being reduced at 873 K. This catalyst was chosen for the upgrading of raw bio-oil. After the upgrading process, the pH value of the bio-oil increased from 2.33 to 2.77. The water content increased from 35.52 wt.% to 41.55 wt.% and the gross calorific value increased from 13.96 MJ/kg to 14.17 MJ/kg. The hydrogen content in the bio-oil increased from 6.25 wt.% to 6.95 wt.%. The product properties of the upgraded bio-oil, particularly the hydrogen content and the acidity were considerably improved. The results of gas chromatography–mass spectrometry analysis showed that both hydrotreatment and esterification had happened over 0.06MoNi/γ-Al₂O₃ (873) catalyst during the upgrading process.     

Supply assessment of forest biomass – A bottom-up approach for Sweden

As there is increasing interest in the use of biomass for energy in Sweden, the potential availability and harvesting costs of forest roundwood, harvesting residues and stumps were estimated up to the year 2069 in 10-year intervals, using a high spatial resolution GIS. In each individual forest area, an average harvesting cost per forest assortment was estimated, based on the geographic and other properties of the area. Using cost structure and resource availability, marginal cost curves were constructed to allow analyses of the effects of changing market conditions and different policy frameworks. Based on geographically explicit data, the results indicated that the average harvesting costs would be 21–24 € m⁻³ for roundwood, depending on the type of harvesting and extraction operation. The corresponding cost estimate for harvesting residues was 23–25 € m⁻³ and 35 € m⁻³ for stumps. The harvesting cost estimates lie on the steeper part of the marginal cost curve, suggesting that increases in the supply of woody biomass can only occur at significantly higher harvesting costs. From a policy perspective, this suggests that subsidies aimed at reducing the harvesting costs will only have limited success in increasing the harvested volumes, given current technology. Therefore, for future development in the supply of forest assortments for energy generation, it is important to consider not only the supply potential, but also the integration of improvements in harvesting and transportation systems.     

Enhanced production of methane through the use of a catalytic Ni–Fe pre-layer in a solid oxide co-electrolyser

A composite cermet consisting in a Ni–Fe alloy and Ce_0.9Gd_0.1O_2-x (CGO) was prepared and used as an electrocatalytic pre-layer in a conventional solid oxide electrolyser (SOEC) for the co-electrolysis of H₂O and CO₂. The electrocatalyst showed two main phases ascribed to trevorite (NiFe₂O₄, 78 wt %) and metallic Ni (22 wt %) and an average crystallite size of 27 nm. The role of the Ni–Fe electrocatalyst in promoting CH₄ formation was analysed by comparing gas-chromatographic and electrochemical results obtained for coated and bare cells. A slight increase of series resistance was observed for the coated cell (0.85 vs 0.53 Ω cm²) at 525 °C. However, the coated cell demonstrated an enhanced CH₄ production in the entire temperature range investigated (525–800 °C). Contrarily to what observed for the bare cell which mainly produced syngas, the coated cell allowed to achieve a high yield of methane (between 67% at 525 °C and 35% at 800 °C) with selectivity to CH₄ between 94% at 525 °C and 51% at 800 °C. The selectivity to CO for the coated cell was relatively low (between 6% at 525 °C and 48% at 800 °C). Whereas, the bare cell showed 98–100% selectivity to CO along the entire temperature range). Durability studies showed the possible occurrence of delamination issues as consequence of carbon formation at the interface between the supporting cathode and the electrolyte as observed from the morphological analysis of SOEC cells after operation.     

Upgrading of liquid fuel from the vacuum pyrolysis of biomass over the Mo–Ni/γ-Al2O3 catalysts

High amounts of acid compounds in bio-oil not only lead to the deleterious properties such as corrosiveness and high acidity, but also set up many obstacles to its wide applications. By hydrotreating the bio-oil under mild conditions, some carboxylic acid compounds could be converted to alcohols which would esterify with the unconverted acids in the bio-oil to produce esters. The properties of the bio-oil could be improved by this method. In the paper, the raw bio-oil was produced by vacuum pyrolysis of pine sawdust. The optimal production conditions were investigated. A series of nickel-based catalysts were prepared. Their catalytic activities were evaluated by upgrading of model compound (glacial acetic acid). Results showed that the reduced Mo–10Ni/γ-Al₂O₃ catalyst had the highest activity with the acetic acid conversion of 33.2%. Upgrading of the raw bio-oil was investigated over reduced Mo–10Ni/γ-Al₂O₃ catalyst. After the upgrading process, the pH value of the bio-oil increased from 2.16 to 2.84. The water content increased from 46.2 wt.% to 58.99 wt.%. The H element content in the bio-oil increased from 6.61 wt.% to 6.93 wt.%. The dynamic viscosity decreased a little. The results of GC–MS spectrometry analysis showed that the ester compounds in the upgraded bio-oil increased by 3 times. It is possible to improve the properties of bio-oil by hydrotreating and esterifying carboxyl group compounds in the bio-oil.     

Sustainability of the four generations of biofuels – A review

Biofuel has emerged as an alternative source of energy to reduce the emissions of greenhouse gases in the atmosphere and combat global warming. Biofuels are classified into first, second, third and fourth generations. Each of the biofuel generations aims to meet the global energy demand while minimizing environmental impacts. Sustainability is defined as meeting the needs of the current generations without jeopardizing the needs of future generations. The aim of sustainability is to ensure continuous growth of the economy while protecting the environment and societal needs. Thus, this paper aims to evaluate the sustainability of these four generations of biofuels. The objectives are to compare the production of biofuel, the net greenhouse gases emissions, and energy efficiency. This study is important in providing information for the policymakers and researchers in the decision-making for the future development of green energy. Each of the biofuel generations shows different benefits and drawbacks. From this study, we conclude that the first generation biofuel has the highest biofuel production and energy efficiency, but is less effective in meeting the goal of reducing the greenhouse gases emission. The third generation biofuel shows the lowest net greenhouse gases emissions, allowing the reduction of greenhouse gases in the atmosphere. However, the energy required for the processing of the third generation biofuel is higher and, this makes it less environmentally friendly as fossil fuels are used to generate electricity. The third and fourth generation feedstocks are the potential sustainable source for the future production of biofuel. However, more studies need to be done to find an alternative low cost for biofuel production while increasing energy efficiency.     

Catalytic steam reforming of bio-oil aqueous fraction for hydrogen production over Ni–Mo supported on modified sepiolite catalysts

Hydrogen will be an important energy carrier in the future and hydrogen production has drawn a great deal of attention to its advantages in efficiency and environmental benefit. Catalytic steam reforming in this study was carried out in a fixed bed tubular reactor with sepiolite catalysts. Sepiolite catalysts modified with nickel (Ni) and molybdenum (Mo) were prepared using the precipitation method. Influential parameters such as temperature, catalyst, steam to carbon ratio (S/C), the feeding space velocity (WHSV), reforming length, and activity of catalyst were investigated and the yields of H₂, CO, CH₄, and CO₂ were obtained. The result of this experiment shows that the acidified sepiolite catalyst with addition of the Ni and Mo greatly improves the activities of catalyst and effectively increases the yield of hydrogen. The favorable reaction condition is as follows: reaction temperature is 700–800 °C; S/C is 16–18; the feeding space velocity is 1.5–2.2 h⁻¹, respectively.     

Effectiveness of dilute oxalic acid pretreatment of Miscanthus × giganteus biomass for ethanol production

In the present study the effect of temperature, reaction time and dilute oxalic acid (OA) concentration during steam-pretreatment of Miscanthus × gigantueus has been evaluated using the combined severity factor (CS). At the highest CS glucan and lignin content in the water insoluble fraction (WIF) increased, while xylan content decreased. While glucose recovery in the water soluble fraction (WSF) was found at low concentration when mild CS were used (≤5.0 g L⁻¹ at CS ≤ 2.17), xylose and arabinose concentrations were higher at low-mild CS (1.58–2.17) with a concentration peak at CS 2.03 (39.9 and 3.2 g L⁻¹ for xylose and arabinose, respectively). The decrease in pentoses coincided with inhibitory formation in the WSF, namely acetic acid, furfural, HMF and phenolic compounds. Glucan conversion rose from 46.1% at CS 1.54 to 91.2% at CS 2.76. Likewise, maximum ethanol concentration was achieved at CS 2.76, corresponding to 20.2 g L⁻¹ and a volumetric ethanol productivity of 0.28 g L⁻¹ h⁻¹. Negative correlations have been found between xylan vs. glucan conversion and xylan vs. ethanol production, suggesting that decreasing the xylan content in WIF increases both saccharification rate and ethanol concentration (R² 0.91 and R² 0.93, respectively). On the other hand, a positive correlation was found between ethanol production and glucan conversion (R² 0.93). Fermentation of WSF by Scheffersomyces (Pichia) stipitis CBS 6054 at CS 1.54 produced 12.1 g L⁻¹ of ethanol after 96 h incubation with a volumetric ethanol productivity of 0.13 g L⁻¹ h⁻¹.     

Hydrogen production via catalytic gasification of ethanol. A mechanism proposal over copper–nickel catalysts

Ethanol gasification using Cu–Ni–K/γ-Al₂O₃ catalysts was studied. The reaction was carried out at a low temperature (300°C) and atmospheric pressure. The influence of the diffusional effects, the residence time and the water/ethanol molar ratio in the feed on the ethanol conversion and on the product distribution was analysed. Additional experiments were performed with monometallic catalysts, such as Cu–K/γ-Al₂O₃ and Ni–K/γ-Al₂O₃ catalysts.Ethanol gasification is favoured by a diminution of the diffusional resistances, high residence time and low water to ethanol feed ratio. A probable reaction mechanism is postulated, which is consistent with the experimental results and let identify the function of each metal (copper and nickel).     

Chromium deposition and poisoning of cathodes of solid oxide fuel cells – A review

Intermediate temperature solid oxide fuel cells (IT-SOFCs) using chromia-forming alloy interconnect requires the development of cathode not only with high electrochemical activity but also with the high resistance or tolerance towards Cr deposition and poisoning. This is due to the fact that, at SOFC operating temperatures, volatile Cr species are generated over the chromia scale, poisoning the cathodes such as (La,Sr)MnO₃ (LSM) and (La,Sr)(Co,Fe)O₃ (LSCF) and causing a rapid degradation of the cell performance. Thus, a fundamental understanding of the interaction between the Fe–Cr alloys and SOFC cathode is essential for the development of high performance and stable SOFCs. The objective of this paper is to critically review the progress and particularly the work done in the last 10 years in this important area. The mechanism and kinetics of the Cr deposition and Cr poisoning process on the cathodes of SOFCs are discussed. Chromium deposition at SOFC cathodes is most likely dominated by the chemical reduction of high valence Cr species, facilitated by the nucleation agents on the electrode and electrolyte surface and/or at the electrode/electrolyte interface, i.e., the nucleation theory. The driving force behind the nucleation theory is the surface segregation and migration of cationic species on the surface of perovskite oxide cathodes. Overwhelming evidences indicate that the surface segregation plays a critical role in the Cr deposition. The prospect of the development in the Cr-tolerant cathodes for SOFCs is presented.     

Scenarios for biofuel demands,biomass production and land use – The case of Denmark

The land potential for producing biomass for bioenergy purposes has been highly debated in recent years. The present paper analyses the possibilities and consequences for land use and agricultural production of biofuel production in Denmark based on domestic wheat and rape under specific scenario conditions for the period 2010–2030. The potential is assessed for a situation where policy targets for renewable energy carriers in the transport sector is reached using biofuels, and where second generation ethanol increasingly substitutes first generation ethanol.Three scenarios are developed and evaluated: a baseline, an alternative scenario allowing continuous growth in the now dominant livestock branch and a biofuel scenario assuming that efforts to achieve self-sufficiency in biofuel displaces part of the domestic production of fodder.Results show that the biofuel demand could be met in 2020; but only if current rape oil production is used to satisfy local bio-diesel demand. It would also imply that the Danish bio-diesel export currently supplying a minor part of the German fuel market would seize. In 2030, however, only about 60 percent of the biofuel demand would be covered by self-sufficiency. If biofuels were to displace animal production to make up for this, a reduction of the pig production between 10 and 20 percent would result. Efficiency increases across production branches would allow the animal production to continue un-affected if about half of the rape oil produced for other purposes is utilized.     

Effects of phosphoric acid additions on the behaviour of the lead—acid cell: A review

The electrochemical behaviour of a lead—acid cell changes significantly after the addition of small amounts of phosphoric acid (H₃PO₄). The o