A. Cavalli
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15 records found
1
Catalytic reforming of acetic acid as main primary tar compound from biomass updraft gasifiers
Screening of suitable catalysts and operating conditions
Tar compounds have been defined as Achilles’ heel in biomass gasification. Catalytic reforming solves problems caused by tar by converting them into H2 and CO. Most of the research has focused on secondary and tertiary tar reforming while some information on primary tar can be derived from bio-oil reforming. However, these studies use humidified N2, Ar or He as gas carrier. Therefore, in this work, three catalysts are compared for reforming 40 g/Nm3 acetic acid as main primary tar compound from biomass updraft gasification using simulated biosyngas as gas carrier. The catalysts were tested over a 72 h period between 680 and 750 °C with a gas composition of 35.0 vol% H2O, 2.3 vol% CO, 19.5 vol% CO2, 3.6 vol% CH4, 24.0 vol% H2 and 15.6 vol% N2. Olivine completely converted acetic acid, but a considerable amount of carbonaceous deposits was found on the catalyst and the catalytic activity decreased over time with 0.2 g/Nm3 hydroxyacetone measured in the last day of testing. Dolomite showed promising performances by completely converting acetic acid and accumulating carbonaceous deposits only in the low temperature part of the catalyst bed. The carbonaceous deposits could be suppressed increasing the steam content to 50.1 vol% and the temperature to 900 °C. However, the catalyst became excessively brittle. The metal-based catalyst out-performed the naturally-occurring catalysts by completely converting acetic acid with almost no carbonaceous deposits accumulation. These results are expected to help the further development of tar reformers, and the commercialisation of biomass updraft gasifiers based systems.
Contaminants as particulate matter, sulfur, chlorine and tar should be removed from biosyngas to avoid damaging solid oxide fuel cells. However, there is no sufficient information on tar effect since they might be potentially used as a fuel, or they might cause performance losses and irreversible damages. Therefore, this study aims to assess whether tar can be reformed inside the SOFC and used as fuel. Short-duration experiments were conducted on Ni-GDC cells operating with simulated biosyngas containing different concentrations of representative tar compounds from biomass gasification. While benzene and ethylbenzene could be regarded as additional fuels even at concentrations as high as 15 g/Nm3, naphthalene and phenanthrene act as contaminants for the SOFC electrochemical and catalytic reactions, even at concentrations of 0.3 and 0.05 g/Nm3. However, the effect on these reactions appeared almost completely reversible. Solid carbon deposited on the SOFC ceramic housing in proximity of the inlet. Post-mortem analysis should be performed to asses the tar effect on the cell anode.
Limited overall efficiency and excessive complexity can hinder the competitiveness of biomass gasifier solid oxide fuel cell micro combined heat and power systems. To overcome these problems, hydrocarbons direct internal reforming is analysed as a strategy to increase efficiency and reduce system complexity. To the same end, two biosyngas heating-up strategies are compared: catalytic partial oxidation and afterburner off gases utilization. A comprehensive approach combining thermodynamic equilibrium calculations, experimental measurements, and system modelling was used. The gas cleaning unit should operate at 400 °C to decrease H2S and HCl below 1 ppmv. A tar amount of 120–130 g Nm−3 dry biosyngas for woodchips and 190 g Nm−3 for straw pellets was measured and 2-methoxyphenol, hydroxyacetic acid and hydroxyacetone were selected as representative compounds. With direct internal reforming the cathode air flow rate decreases from approximately 90 kg h−1 to 60 kg h−1. This leads to an increase of around 1% point in electrical efficiency and of even 5–6% points in thermal efficiency. Direct internal tar reforming seems therefore an advantageous strategy. The catalytic partial oxidation unit increases the system overall efficiency but reduces the electric efficiency from roughly 38%–30% and is therefore not advised.
High temperature biosyngas cleaning is more efficient when the end user operates at elevated temperature, as in biomass gasifier solid oxide fuel cell systems. However, there is not much experience with this technology and low temperature gas cleaning is usually adopted. This paper advances current knowledge by presenting the results from the investigation of side reactions catalysed by commercially available sorbents involving biosyngas main components, and the results obtained with the pilot plant developed within the Horizon2020 project “Flexifuel-SOFC”. K2CO3, used for HCl removal, appeared catalytically active towards the water gas shift reaction. Under conditions representative of a real system, the residence time was not sufficient for the gas composition to reach thermodynamic equilibrium. ZnO–CuO, used for H2S removal, showed a catalytic activity significantly higher. Both sorbents seemed not active towards the methanation reaction. The pilot plant tests confirmed the occurrence of the WGS reaction in the HCl removal reactor. The sorbents decreased H2S and HCl below the target value of 1 ppmv for H2S and 5 ppmv for HCl. The catalytic activity of sorbents and the heat released by these reactions should be carefully considered in the design phase of high temperature gas cleaning units.
Removing biosyngas contaminants is crucial for the efficient and safe operation of biomass gasifier solid oxide fuel cells systems. Among the contaminants, tar might be considered an additional fuel if converted into H2 and CO in a reformer or directly in the SOFC. However, no sufficient information is available on direct internal tar reforming. The knowledge gained during the 4-years project FlexiFuel-SOFC is presented. The aim of these studies was to determine the possibility to directly reform tar in the SOFC, and to assess the influence that other biosyngas contaminants (i.e., H2S and HCl) can have on the process. Benzene can be regarded as fuel, while naphthalene as a contaminant. Also toluene can be reformed inside the SOFC, but HCl seems to affect the process. Acetic acid is completely converted inside SOFCs and its conversion appears not affected by H2S. However, it causes carbon deposition, mainly in the inlet pipelines.
Integrated biomass gasifier solid oxide fuel cell systems are an alternative to fossil-fuel-based combined heat and power generators. However, biosyngas contaminants represent a bottleneck for small-scale systems. In this work, we present the results of experiments on the effects of H2S, HCl, and acetic acid as model primary tar on Ni-GDC SOFC. First, the effects of 17-128 g/Nm3 dry basis acetic acid were studied. On a second cell, 0.8 and 1.3 ppm(v) H2S were added to the simulated biosyngas anode flow. After a full recovery, the cell was exposed to 42 g/Nm3 acetic acid and 0.8 ppm(v) H2S. On a third cell, 3.4, 20, and 50 ppm(v) HCl were tested and, after a recovery period, 42 g/Nm3 acetic acid and HCl were added. Even 0.8 ppm(v) H2S caused an immediate voltage drop. H2S affected CH4 reforming and water-gas shift reaction. Differently, even 50 ppm(v) HCl appeared not to significantly affect these reactions. Acetic acid increased the cell voltage but caused carbon deposition at the cell inlet. The voltage increase seemed not to be affected by H2S or HCl, and no acetic acid was measured at the cell outlet, indicating that these contaminants do not affect the primary tar conversion.
The diffusion of photovoltaic systems is deterred by the struggle in combining high efficiency and low cost. Nanowire devices have been demonstrated to hold great promise to solve this predicament, but the substrate cost is still an unavoidable obstacle. Repeated nanowire growth on a single substrate is demonstrated by embedding InP nanowires in a polymer layer and removing them from the substrate. Our approach promises cost reduction by using the substrate multiple times. In addition, it provides a pathway to increase the open-circuit voltage by placing a mirror at the backside of the cell.
Nanowire Arrays as Force Sensors with Super-Resolved Localization Position Detection
Application to Optical Measurement of Bacterial Adhesion Forces
The design and application of indium phosphide (InP) nanowire arrays to acquire Xylella fastidiosa bacterial cell vector force maps are discussed. The nanowire deflections are measured with subdiffraction localization confocal laser scanning microscopy (CLSM). The nanowire mechanical stability in air and liquid media as well as methods to average out thermally induced oscillations are investigated. The accuracy of center determination of the CLSM reflected laser intensity profile at nanowire apex is studied using Gaussian fitting and localization microscopy techniques. These results show that the method is reliable for measuring nanowire displacements above ≈25 nm. Corresponding force ranges probed by this method can be customized depending on nanowire geometry and array configuration. The method is applied to explore X. fastidiosa cell adhesion forces on the InP nanowire surface, and in situ probes the effect of N-acetylcysteine on adhered cells. Future perspectives for application of this method in microbiology studies are also outlined.
Charge carrier-selective contacts transform a light-absorbing semiconductor into a photovoltaic device. Current record efficiency solar cells nearly all use advanced heterojunction contacts that simultaneously provide carrier selectivity and contact passivation. One remaining challenge with heterojunction contacts is the tradeoff between better carrier selectivity/contact passivation (thicker layers) and better carrier extraction (thinner layers). Here we demonstrate that the nanowire geometry can remove this tradeoff by utilizing a permanent local gate (molybdenum oxide surface layer) to control the carrier selectivity of an adjacent ohmic metal contact. We show an open-circuit voltage increase for single indium phosphide nanowire solar cells by up to 335 mV, ultimately reaching 835 mV, and a reduction in open-circuit voltage spread from 303 to 105 mV after application of the surface gate. Importantly, reference experiments show that the carriers are not extracted via the molybdenum oxide but the ohmic metal contacts at the wire ends.