The Potential Role of Ammonia for Hydrogen Storage and Transport: A Critical Review of Challenges and Opportunities

Hydrogen is being included in several decarbonization strategies as a potential contributor in some hard-to-abate applications. Among other challenges, hydrogen storage represents a critical aspect to be addressed, either for stationary storage or for transporting hydrogen over long distances. Ammonia is being proposed as a potential solution for hydrogen storage, as it allows storing hydrogen as a liquid chemical component at mild conditions. Nevertheless, the use of ammonia instead of pure hydrogen faces some challenges, including the health and environmental issues of handling ammonia and the competition with other markets, such as the fertilizer market. In addition, the technical and economic efficiency of single steps, such as ammonia production by means of the Haber–Bosch process, ammonia distribution and storage, and possibly the ammonia cracking process to hydrogen, affects the overall supply chain. The main purpose of this review paper is to shed light on the main aspects related to the use of ammonia as a hydrogen energy carrier, discussing technical, economic and environmental perspectives, with the aim of supporting the international debate on the potential role of ammonia in supporting the development of hydrogen pathways. The analysis also compares ammonia with alternative solutions for the long-distance transport of hydrogen, including liquefied hydrogen and other liquid organic carriers such as methanol

Production and characterization of co-composted biochar and digestate from biomass anaerobic digestion

Biochar, produced through pyrolysis of lignocellulosic biomass, is attracting increasing interest as soil amendment thanks to its potential numerous benefits to agriculture, as well as its ability to sequester carbon in soil. Solid fraction of digestate from anaerobic digestion is a well-known N-rich substrate, most often composted in large and small agro-industrial plants. Co- composting biochar and digestate has the potential to synergistically increase the agronomic value of both components: however, it needs further process and on-field research. The present research work reports on the experimental tests on producing biochar and co-composting various biochar amounts with digestate from biomass anaerobic digestion (product here named COMBI). Biochar was produced by feeding wood chips from chestnut to an innovative oxidative reactor. In order to evaluate the quality of the products obtained by composting and co-composting, correlating this with the final biochar rate in the material, the net organic matter yield, the humified organic matter, the compliance with the European Compost Network Quality Assurance Scheme (ECN-QAS) limits for inorganic pollutants, and the product stabilization and sanitization indexes were investigated. The 11.2% w/w d.b. biochar rate in the initial blend (19.8% w/w d.b final concentration in the co-composted products) offered the best performances and is recommended for further investigation. Additional benefits from co-composting were also assessed, as the reduced dust load that favors safety and health during logistics and use

Thermochemical conversion of microalgae: challenges and opportunities

Research in Advanced Biofuels steadily developed during recent years. A number of highly innovative technologies have been explored at various scale: among these, lignocellulosic ethanol and CTO (Crude Tall Oil)-biofuel technologies already achieved the early-commercial status, while hydrotreating of vegetable oils (HVO, or HEFA) can be considered today fully commercial. However, despite the level of innovation in each specific technological process under consideration, the feedstock maintains a central role in making a biofuel chain really sustainable. In this context, microalgae grown in salt-water and arid areas offers a considerable opportunity for advanced biofuel production: at the same time, however, they also represent a considerable challenge. Processing microalgae in an economic way into a viable and sustainable liquid biofuel (a low-cost mass-produced product) is not trivial. So far, the main attention has been given to cultivating the microorganism, accumulating lipids, extracting the oil, valorising co-products, and treating the algae oil into biodiesel (through esterification) or HEFA (Hydrotreated Esthers and Fatty Acids), this second one representing a very high quality biofuels, almost a drop-in fuel (suitable either for road transport or for aviation), which production exceed 2 Mt y-1 today. However, extracting the algae oil at low cost and at industrial scale is not yet a full industrial mature process, and the still limited market size of algae-to-biofuels makes difficult the development of industrial-scale systems. Nevertheless, another option can be considered, i.e. processing the whole algae into dedicated thermochemical reactors, thus approaching the downstream processing of algae in a completely different way from separation. The present work examines the possible routes for thermochemical conversion of microalgae, distinguishing between dry-processes (namely pyrolysis and gasification) and wet-processes (near critical water hydrothermal liquefaction and hydrothermal gasification). Typical expected elementary composition of major products is given. Main peculiarities of batch versus continuous processing are also discussed from an engineering point of view. Major engineering advantages and challenges in thermochemically conversion of algae are identified and discussed, in view of the production of a transport biofuel. Finally, future perspectives for each route are given in terms of current and expected technological readiness level

The potential role of biomethane for the decarbonization of transport: An analysis of 2030 scenarios in Italy

This paper aims at evaluating the best allocation of potential biomethane generation for the decarbonization of the transport system, presenting a case study in Italy. The country has some peculiar features, such as several operating biogas plants, additional potential feedstock for biogas/biomethane generation, a well-developed natural gas network and established relevant natural gas uses in different final sectors, including transport. Based on current estimates for sustainable biomethane potential by 2030, ranging from 2.3 to 7.6 billion cubic meters depending on the scenario, the analysis compares technologies for the generation, distribution and final use of biomethane. The results of the analysis confirm the potential interesting contribution of biomethane in decarbonizing the Italian transport system: a billion cubic meters of biomethane can lead to 2.33–4.37 MtCO2e savings, depending on the feedstock mix and the application. On a national basis, annual climate emission savings in 2030 range from 10.0 to 26.7 MtCO2e, depending on the scenario. Additional 3.1–8.1 MtCO2e of emissions can be avoided if the CO2 captured during the biomethane upgrading can be stored or reused. The proposed methodology could be used to extend the analysis to other countries, and to the European context

Design, commissioning and start-up of a new hydrothermal liquefaction continuous pilot unit

Hydrothermal liquefaction (HTL) has been demonstrated to be an effective emerging technology for the conversion of various biomass slurries into valuable biofuels and bioproducts precursors. Many studies have been carried out in batch laboratory-scale apparatus, an effective technique to understand the conversion process applied on several wet materials, from algae to organic wastes and lignocellulosic streams. On the other hand, some examples of continuous system have been implemented and tested worldwide as first step for the industrial scale-up of the technology. This work focuses on the development from the design to the start-up and commissioning of a new continuous HTL unit, established in RE-CORD laboratories. The plant is capable of converting 1-2 kg/hof slurry at about 10 wt.% of biomass to water ratio. The hydrothermal conversion unit comprises a high−pressure slurry feeder, an indirectly heated plug flow reactor, a cooling system, a pressure let-down system and liquid-gas separator. The reactor can reach and keep the converting material at 350 °C at a pressure of 220 bar for a residence time of 5 to 24 min. The solid content can be filtered in-line or separated at the end of the process depending on the physical characteristics of the suspended solid residues. Two different depressurizing system have been designed and implemented in parallel for the continuous discharge of the liquid products, widening the operability of the system to a larger selection of feedstock. The plant commissioning allowed to assess the process analysis in term of heating, pressurizing and reaction control. Flow rate, temperature and pressure profiles along the reaction and cooling zones have been acquired by a National Instrument data acquisition system. The software for data acquisition and for the control of the heaters and the depressurizing system was internally developed with NI LabVieW

Biomass carbonization: process options and economics for small scale forestry farms

Bioenergy represents a unique opportunity for forestry companies to diversify the sources of income and create new stable business opportunities: a large number of initiatives has started in the last decades especially regarding decentralized power generation; nevertheless the conversion of the farmers to energy producers is not a trivial issue. The present work has focused on a possible alternative to biopower generation for forestry farms: the biomass carbonization (i.e. biomass slow pyrolysis). Charcoal making presents good prerequisite conditions for successful biomass based systems in the forestry sector: the system results incentive-independent, the power generation represents the co-product of a different primary production (resulting a real additional income), the plant capital cost is affordable for small scale farmers, operations requires technical skills normally available in the forestry sector and the reliability of the system is proven and credible, reducing the risks contained in business plans based on "number of hours of operation over several years". Moreover charcoal is a well known product, familiar to forestry companies for a very long time, the market is well defined, the technology is known but still offers opportunities for further improvements (in terms of efficiency, costs and environmental impacts), the technology does not present major risk, the investment is well suited to small farmers and the process and technology gives a great opportunity for small scale and local supply chain development. Based on these considerations, the present work investigated the technological opportunities for small scale charcoal making systems. Various process configurations have been examined, focusing on advantages and disadvantages representative of each solution in view of small scale application suitable for the Italian case and a designed pilot plant has been proposed

Policy measures for sustainable sunflower cropping in EU-MED marginal lands amended by biochar: case study in Tuscany, Italy

The aim of this study is to evaluate economic support measures based on current EU policies affecting the profitability of large-scale deployment of biochar for sunflower cultivation in dry marginal lands in Italy, paving the way to large scale carbon sequestration in the EU Mediterranean region. Two cases were considered: i) straight biochar use and ii) biochar in combination with compost (COMBI: 20% biochar and 80% compost mass fraction), at application rates of 5 and 10 Mg ha−1 respectively. Based on realistic estimations of achievable crop-yield performances by biochar and COMBI addition to dry soils, the effect of current policies on the economic viability of biochar deployment and farmers’ income has been investigated. Using a cost-model we identified the required levels of support, in the form of (i) area subsidies for crop cultivation, (ii) tradable carbon certificates (credits), and (iii) REDII-compliant biofuel support for Aviation and Maritime, so to make biochar and sunflower cultivation in EU MED dry marginal lands competitive for sustainable crop-based biofuels. Results show that, by employing existing policy instruments, sufficient income can be generated for famers to recover marginal land, sequester large amount of carbon by BECCS at costs (∼82 € Mg−1 of CO2) falling at or below the typical range of CCS measures, as well as offer additional environmental and socio-economic positive benefits. The combination of currently operational economic mechanisms from the Common Agricultural Policy, the Climate Policy, and the Renewable Energy Directive II can: i) maintain domestic farming activities, ii) support the implementation of biochar projects at local level, iii) contribute to achieve EU and national biofuel targets without generating ILUC impacts and iv) achieve unprecedent potential for carbon sequestration. However, prior to large-scale deployment, targeted on-site R&D actions aimed at validating biochar effects under local conditions (soil, climate, crops) are recommended, together with training and capacity building activities for local farmers

The Small Unit Cell Reconstructions of SrTiO3 (111)

We analyze the basic structural units of simple reconstructions of the (111) surface of SrTiO3 using density functional calculations. The prime focus is to answer three questions: what is the most appropriate functional to use; how accurate are the energies; what are the dominant low-energy structures and where do they lie on the surface phase diagram. Using test calculations of representative small molecules we compare conventional GGA with higher-order methods such as the TPSS meta-GGA and on-site hybrid methods PBE0 and TPSSh, the later being the most accurate. There are large effects due to reduction of the metal d oxygen sp hybridization when using the hybrid methods which are equivalent to a dynamical GGA+U, which leads to rather substantial improvements in the atomization energies of simple calibration molecules, even though the d-electron density for titanium compounds is rather small. By comparing the errors of the different methods we are able to generate an estimate of the theoretical error, which is about 0.25eV per 1x1 unit cell, with changes of 0.5-1.0 eV per 1x1 cell with the more accurate method relative to conventional GGA. An analysis of the plausible structures reveals an unusual low-energy TiO2-rich configuration with an unexpected distorted trigonal biprismatic structure. This structure can act as a template for layers of either TiO or Ti2O3, consistent with experimental results as well as, in principle, Magnelli phases. The results also suggest that both the fracture surface and the stoichiometric SrTiO3 (111) surface should spontaneously disproportionate into SrO and TiO2 rich domains, and show that there are still surprises to be found for polar oxide surfaces.Comment: 14 pages, 4 Figure

Bio-Hydrocarbons through Catalytic Pyrolysis of Used Cooking Oils: towards sustainable jet and road fuels

Vegetable Oil (VO) is today the most used feedstock for transport biofuel production by transesterification to biodiesel. Other commercial technologies for renewable fuels production are mainly based either on Fischer-Tropsch (FT) synthesis from coal, natural gas and possibly biomass, or hydro treating of vegetable oil (Hydrotreated Vegetable Oil, HVO): this also includes Hydrotreated Renewable Jet fuel, HRJ, Used Cooking Oil (UCO) is a highly sustainable feedstock (based on EC-RED scheme): it is therefore considered as a possible alternative to VOs for greening of air transport and, under proper circumstances, for reducing the feedstock cost component. However, the use of UCO is not trivial in reactors, as catalysts are sensitive to impurities and contaminations, which are typical of waste oils. Moreover, the chemical composition of UCO is variable regionally as well as seasonally, because the type of base-vegetable oils vary with Country and period of the year. In the framework of the ITAKA EU FP7 project, (catalytic) thermochemical conversion of UCO has been considered to obtain an intermediate biofuel suitable for upgrading by hydrotreating. The catalytic conversion of UCO and Fatty Acids were investigated in a 1.5 kg/h pilot unit. UCO, properly filtered and conditioned, was characterized, and then converted in bio-oil by means of thermal and catalytic reactionsunder controlled conditions. The type of catalyst and the reaction conditions, including several parameters such as temperature, reactor geometry, heating rate and residence time, were evaluated, and selected combinations were tested. The bio-oil was characterized in terms of main constituents and hydrocarbons content, and GC-MS and GC-FID analyses were used to qualitatively and quantitatively assess the composition of the fuel

Towards a better understanding of the HTL process of lignin-rich feedstock

Abstract The hydrothermal liquefaction reactions (HTL) in subcritical conditions of a lignin residue has been studied on a lab scale. The starting material was a lignin rich residue co-produced by an industrial plant situated in Northern Italy producing lignocellulosic bioethanol. The reactions were carried out in batch mode using stainless steel autoclaves. The experiments were under the following operating conditions: two different temperatures (300–350 °C), the presence of basis catalysts (NaOH, and NH4OH) in different concentrations and the presence/absence of capping agent 2,6-bis-(1,1-dimethylethyl)-4-methylphenol (BHT). Lignin residue and reaction products were characterized by analytical and spectroscopic techniques such as CHN-S, TGA, GC–MS, EPR, and 1H-NMR with (2,2,6,6-Tetramethylpiperidin-1-yl)oxyl (T.E.M.P.O.). The addition of BHT did not significantly affect the yield of char which is formed by radical way. Spectroscopic analysis indicated that the level of radicals during the reaction was negligible. Therefore, the results obtained experimentally suggest that the reaction takes place via an ionic route while radical species would play a minor role