Hydrothermal liquefaction is a promising technology for the conversion of a wide range of bio-feedstock into a biocrude; a mixture of chemical compounds that holds the potential for a renewable production of chemicals and fuels. Most research in hydrothermal liquefaction is performed in batch type reactors, although a continuous and energy-efficient operation is paramount for such process to be feasible. In this work an experimental campaign in a continuous bench scale unit is presented. The campaign is based on glycerol-assisted hydrothermal liquefaction of aspen wood carried out with the presence of a homogeneous catalyst at supercritical water conditions, 400 • C and 300 bar. Furthermore, in the experimental campaign a water phase recirculation step is incorporated to evaluate the technical feasibility of such procedure. In total, four batches of approximately 100 kg of feed each were processed successfully at steady state conditions without any observation of system malfunctioning. The biocrude obtained was characterized using several analytical methods to evaluate the feasibility of the process and the quality of the product. Results showed that a high quality biocrude was obtained having a higher heating value of 34.3 MJ/kg. The volatile fraction of the biocrude consisted mostly of compounds having number of carbon atoms in the C 6 -C 12 range similar to gasoline. In terms of process feasibility, it was revealed that total organic carbon (TOC) and ash significantly accumulated in the water phase when such is recirculated for the proceeding batch. After four batches the TOC and the ash mass fraction of the water phase were 136.2 [g/L] and 12.6 [%], respectively. Water phase recirculation showed a slight increase in the biocrude quality in terms on an effective hydrogen-to-carbon ratio, but it showed no effects on the product gas composition or the pH of the water phase. The successful operation demonstrated the technical feasibility of a continuous production of high quality biocrude.
Feedstock pumpability is one of the main obstacles for continuous processing of biomass through hydrothermal liquefaction, due to their tendency to form heterogeneous slurries. In this work a novel strategy is proposed to ensure lignocellulosic feed pumpability in HTL processing, even while applying elevated biomass loadings. In a first stage, a pumpable feed is prepared by an alkaline treatment of coarse wood chips at 180 °C, 120 minutes reaction time and 0.35 NaOH-to-wood ratio. In a subsequent stage the treated feedstock is converted into a bio-crude in a continuously operated 20 kg/h scale unit. In total 100 kg of wood paste with 25 % dry-matter is processed at 400 °C and 30 MPa, demonstrating the usefulness of this two-stage liquefaction strategy. As an additional advantage liquefaction of such pretreated wood shows increased biocrude yields with approximately 10% compared to the case where non-pretreated wood is liquefied.
This paper analyzes the effects of methanol and water vapor on the performance of a high temperature proton exchange membrane fuel cell (HT-PEMFC) at varying temperatures, ranging from 140 C to 180 C. For the study, a H 3 PO 4 e doped polybenzimidazole (PBI) e based membrane electrode assembly (MEA) of 45 cm 2 active surface area from BASF was employed. The study showed overall negligible effects of methanol-water vapor mixture slips on performance, even at relatively low simulated steam methanol reforming conversion of 90%, which corresponds to 3% methanol vapor by volume in the anode gas feed. Temperature on the other hand has significant impact on the performance of an HT-PEMFC. To assess the effects of methanol-water vapor mixture alone, CO 2 and CO are not considered in these tests. The analysis is based on polarization curves and impedance spectra registered for all the test points. After the performance tests, endurance test was performed for 100 h at 90% methanol conversion and an overall degradation rate of À55 mV/ h was recorded.
A major challenge for the implementation of hydrothermal liquefaction (HTL) as a continuous process is the formulation of lignocellulosic feedstock, which is prone to phase separation into water and biomass parts when pressurized. One approach to remedy such phase separation is to reduce the dry matter content; however, as this approach is detrimental to process cost efficiency, designing an appropriate pretreatment step to ensure pumpability at high dry matter content is preferable. This paper evaluated the effect of various pretreatment methods on product distribution and composition resulting from the HTL of willow and proposes short rotation coppice as an alternative biomass feedstock for biofuels production. Alkaline-thermal pretreatment, besides making high dry matter pumpable feedstock slurries, also led to an increase in the production of the bio-crude product with an oxygen content lower than 8wt% and a higher concentration of aromatics and phenolic compounds.
Degradation tests of two phosphoric acid (PA) doped polybenzimidazole (PBI) membrane based high temperature polymer electrolyte membrane (HT-PEM) fuel cells were reported in this paper to investigate the effects of start/stop and the presence of methanol in the fuel to the performance degradation. Continuous tests with H2 and simulated reformate which was composed of H2, water steam and methanol as the fuel were performed on both single cells. 12-h-startup/12-h-shutdown dynamic tests were performed on the first single cell with pure dry H2 as the fuel and on the second single cell with simulated reformate as the fuel. Along with the tests electrochemical techniques such as polarization curves and electrochemical impedance spectroscopy (EIS) were employed to study the degradation mechanisms of the fuel cells. Both single cells showed an increase in the performance in the H2 continuous tests, because of a decrease in the oxygen reduction reaction (ORR) kinetic resistance probably due to the redistribution of PA between the membrane and electrodes. EIS measurement of first fuel cell during the start/stop test showed that the mass transfer resistance and ohmic resistance increased which can be attributed to the corrosion of carbon support in the catalyst layer and degradation of the PBI membrane. During the continuous test with simulated reformate as the fuel the ORR kinetic resistance and mass transfer resistance of both single cells increased. The performance of the second single cell experienced a slight decrease during the start/stop test with simulated reformate as the fuel.
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