• Energy Research

High-purity H2 was produced by the sorption enhanced steam reforming (SESR) of acetic acid, a model compound of bio-oil obtained from biomass fast pyrolysis. A fixed bed reactor comprising two sections with different temperature was used to favor the reforming reaction in the high-temperature section, and the water gas shift (WGS) and the CO2 capture reactions along the low-temperature segment. A Pd/Ni-Co hydrotalcite-like material (HT) was used as catalyst and a CaO-based material as CO2 sorbent. High H2 yield (84.4%), with H2 purity of 99.8%, was obtained at atmospheric pressure and 600°C in the above section of the bed followed by a bed temperature of 500°C at the bottom part. A null CO concentration was achieved, while the CH4 and CO2 contents showed very low values (0.15% and 0.02%, respectively). Gobierno del Principado de Asturias (programa predoctoral Severo Ochoa)

The current situation in the energy sector suggests the possibility of using biomass in co-combustion systems as an alternative to other fuels. In the case of the North of Spain the amount of forest residues that is generated guarantees it as a valuable source of energy for the future. However, an effective exploitation of these residues must first overcome a number of serious problems such as transport, storage, handling and pre-treatment, to meet the requirements of the power plants. The aim of this work is to study the influence of storage time on the moisture content and chemical and combustibility properties of pine woodchips. Their combustibility behaviour was evaluated by means of the following tests: heating value, ash composition, slagging/fouling indices, and the combustion profiles obtained from TG analysis. As a result of the weather conditions in the North of Spain open-air storage in the area under study is not suitable for dry pine woodchips, although their combustion behaviour remains practically unaltered. Work carried out with financial support from the Spanish MICINN (Project PS-120000- 2006-3, ECOCOMBOS), and co-financed by the European Regional Development Fund, ERDF. The assistance from staff at La Pereda power plant owned by HUNOSA, is also gratefully acknowledged Peer reviewed

Energy generation from non-hazardous waste streams, which are unfeasible to be reused or recycled, can help overcome some of the problems related to fossil fuel depletion, global increase in energy demand and waste generation management under restricted landfilling. One of the main drawbacks of waste-to-energy strategies is the poor combustion properties of waste, which densification could help to circumvent. This work studies the co-pelletization of refused derived fuel (RDF) and pine sawdust (PIN) in a continuous pilot pellet mill that resembles industrial pelletization. The effect of RDF contents up to 90 wt% on a set of parameters has been assessed: pelletization energy consumption, physical properties (durability, particle and bulk densities), net calorific value and energy density of the obtained pellets. In addition, slagging, fouling and corrosion, phenomena associated with combustion, were estimated from the ash composition. Results showed that obtaining pellets with a low RDF loading (2–9 wt%) was feasible. They accomplished ISO 17225-2 solid biofuels standard for industrial use, and presented low deposition and corrosion risks. On the other hand, pellets with 30–90 wt% RDF were also manufactured and complied with the UNE-EN 15359:2012 solid recovered-fuel standard for energy recovery in incineration and co-incineration plants. All the produced pellets presented durability and net calorific value above 96.9% and 10.7 MJ/kg, respectively. Energy density higher than 10.6 GJ/m3 was obtained for pellet formulations with RDF content up to 50 wt%. It was demonstrated that the blends of RDF and PIN can provide high-quality pellets with a high load of waste material, under the same operational conditions required for PIN pelletization. It is a versatile process that can be tailored to different product requirements depending on the end-use. It promotes energy recovery and generates value out of a waste fraction with no relevant use, adding economic and environmental benefits. This work was carried out with financial support from the Gobierno del Principado de Asturias (PCTI, Ref. IDI/2018/000115), co-financed by the European Regional Development Fund (ERDF) and from the CSIC (Project PIE, Ref. 202080E115). M.V. Gil acknowledges support from a Ramon y Cajal grant (RYC-2017-21937) of the Spanish Government and the Spanish State Research Agency, co-financed by the European Social Fund (ESF). Peer reviewed

This document is the Accepted Manuscript version of a Published Work that appeared in final form in Energy and Fuels, copyright © American Chemical Society after peer review and technical editing by the publisher. To access the final edited and published work see https://doi.org/10.1021/ef100877t The effect of operating conditions (pressure and temperature) on char morphology and structure during coal devolatilization was studied. For this purpose, five different rank coals were selected: a lignite, three bituminous coals, and a semi-anthracite. The coal chars were prepared by devolatilization in a novel pressurized fixed-bed reactor. The pyrolysis experiments were carried out isothermally at temperatures of 800, 900, and 1000 °C and pressures of 1, 5, 10, and 20 atm. The chars obtained from the bituminous coals at elevated pressure experienced a high degree of swelling, whereas those from the lignite and semi-anthracite were hardly affected at all by pressure. The devolatilization temperature did not appear to have any significant effect on char morphology below 1000 °C. The reactivity of the char samples prepared under different pyrolysis conditions was studied by isothermal thermogravimetric analysis at 1000 °C under a steam atmosphere. The chars obtained at elevated pressure were found to be more reactive than those produced at atmospheric pressure. An increase in the pyrolysis temperature led to a decrease in char reactivity. Peer reviewed

AbstractHigh yield of high‐purity H2 from acetic acid, a model compound of bio‐oil obtained from the fast pyrolysis of biomass, was produced by sorption‐enhanced steam reforming (SESR). An oxygen carrier was introduced into a chemical loop (CL) coupled to the cyclical SESR process to supply heat in situ for the endothermic sorbent regeneration to increase the energy efficiency of the process. A new multifunctional 1 %Pd/20 %Ni–20 %Co catalyst was developed for use both as oxygen carrier in the CL and as reforming catalyst in the SESR whereas a CaO‐based material was used as CO2 sorbent. In the sorbent–air regeneration step, the Ni–Co atoms in the catalyst undergo strong exothermic oxidation reactions that provide heat for the CaO decarbonation. The addition of Pd to the Ni–Co catalyst makes the catalyst active throughout the whole SESR–CL cycle. Pd significantly promotes the reduction of Ni–Co oxides to metallic Ni–Co during the reforming stage, which avoids the need for a reduction step after regeneration. H2 yield above 90 % and H2 purity above 99.2 vol % were obtained.

The ignition behavior of coal and biomass blends was assessed in air and oxy-firing conditions in an entrained flow reactor. Four coals of different rank, an anthracite, a semi-anthracite, and two high-volatile bituminous coals, were tested in air and O2/CO2 (21–35% O2) environments. For all the coals, deterioration in ignition properties was observed in the 21%O2/79%CO2 atmosphere in comparison with air. However, the ignition properties were enhanced when the oxygen concentration in the O2/CO2 mixture was increased. Coal and biomass blends of a semi-anthracite and a high-volatile bituminous coal with 10 and 20 wt% of olive residue were also used in the ignition experiments under air and oxy-firing conditions. The ignition behavior of the coals improved as the additions of biomass increased both in air and oxy-firing conditions. In particular, the effect of biomass blending was more noticeable in the ignition of the high rank coal. Since industrial oxy-coal combustion with a wet recycle would result in higher concentrations of H2O(v), the effect of steam addition on ignition behavior was also studied. A worsening in ignition behavior was observed when steam was added to the oxy-fuel combustion atmospheres, although an increase in the steam concentration from 10 to 20% did not produce any significant difference in the ignition characteristics of the fuels. This work was carried out with financial support from the Spanish MICINN (Project PS-120000-2005-2) co-financed by the European Regional Development Fund. L.A. and M.V.G. acknowledge funding from the CSIC JAE programs, co-financed by the European Social Fund. J.R. acknowledges funding from the Government of the Principado de Asturias (Severo Ochoa program), respectively. Support from the CSIC (PIE 201080E09) is gratefully acknowledged. Peer reviewed

H2 production from biogas (60%CH4 + 40%CO2) by sorption enhanced steam reforming (SESR) was thermodynamically and experimentally studied in a fluidized bed reactor. Biogas is an interesting renewable biomass resource for hydrogen production due to its sustainable nature. SESR combines the catalytic reforming reaction of biogas with simultaneous CO2 removal in a single step. A Pd/Ni–Co hydrotalcite-like material (HT) was used as catalyst and dolomite as CO2 sorbent. The effects of temperature (550–800 °C), steam/CH4 molar ratio (2–6) and gas hourly space velocity (GHSV) (492–3937 mL CH4 gcat−1 h−1) on the process performance were evaluated. CO2 in biogas was effectively removed by the sorbent from the gas phase at 550–700 °C, without influencing the reforming process. H2 yield increased with temperature from 550 to 650 °C, but H2 concentration decreased at temperatures higher than 600 °C, requiring a tradeoff between both parameters to select an optimum operating temperature. H2 purity of 98.4 vol% was obtained at 550–600 °C and H2 yield of 92.7% was reached at 650 °C. Higher steam/CH4 ratios enhance the process, whereas higher space velocities decrease H2 yield. Results demonstrate that high-purity high-yield biohydrogen can be produced by the SESR of a renewable biomass resource as biogas. The authors thank Franefoss Miljøkalk A/S (Norway) for supplying Arctic dolomite. This work was carried out with financial support from the Spanish MICINN (Project ENE2017-83530-R) and from the Gobierno del Principado de Asturias (PCTI, Ref. IDI/2018/000115), both co-financed by the European Regional Development Fund (ERDF). M.V. Gil acknowledges support from a Ramón y Cajal grant (RYC-2017-21937) of the Spanish Government, co-financed by the European Social Fund (ESF). Peer reviewed