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Impregnation of metal catalysts into biomass before thermochemical conversion may provide benefits of increased selective reactivity to obtain desirable products. In this work, coconut shells impregnated with increasing loadings of nickel were successfully prepared using a room-temperature impregnation method using a nickel salt solution at 1 and 2 molar (M) concentrations. The physicochemical characterization of the 2 M impregnated sample revealed the presence of 5.6 wt% of nickel with a particle size of 13.5 nm. The nickel-impregnated samples’ supercritical water gasification (SCWG) was conducted with biomass loading ranging from 20 wt% to 30 wt%, at temperatures between 400 °C and 500 °C, and residence times from 20 to 60 min. Higher nickel loading, higher temperatures and longer reaction times promoted the production of H2 and CO2 up to 15 and 79 mol%. Higher nickel loading also led to an increased Hydrogen Gasification Efficiency value of up to 133%. The analysis of hydrochars suggested that increasing nickel loading enhanced the reduction in nickel ions to the Ni0 nanoparticles, leading to higher H2. Additionally, the chemical composition of the liquid product showed the significant ability of nickel to promote lignin decomposition into phenol, facilitating the phenol hydrogenation reaction and subsequent gas production.

The energy conversion of nickel-impregnated coconut shells using supercritical water has not yet been explored. The impregnation process was conducted at room temperature and a pH of 5.80 for 72 h. Characterization of the prepared sample confirmed the presence of nickel nanoparticles with an average size of 7.15 nm. The gasification of control and impregnated samples was performed at 400–500 °C, biomass loading from 20 to 30 wt% and residence time from 20 to 60 min. The response surface methodology (RSM) approach, with a Box–Behnken method, was used to design the experiments. The optimization model showed that the non-catalytic process at 500 °C, 60 min and 20 wt% of biomass loading could promote an H2 yield of 8.8 mol% and gasification efficiency of 47.6%. The gasification of nickel-impregnated coconut shells showed significantly higher gasification efficiency (58.6%) and hydrogen yield (17.2 mol%) with greater carbon and hydrogen efficiencies (109.4 and 116.9%) when compared to the non-catalytic process. The presence of nickel particles in the biomass matrix as nanocatalysts promoted higher hydrogen production and supercritical water gasification efficiency.

Climate change, the greenhouse effect and fossil fuel extraction have gained a growing interest in research and industrial circles to provide alternative chemicals and fuel synthesis technologies. Carbon dioxide (CO2) hydrogenation to value-added chemicals using hydrogen (H2) from renewable power (solar, wind) offers a unique solution. From this aspect this review describes the various products, namely methane (C1), methanol, ethanol, dimethyl ether (DME) and hydrocarbons (HCs) originating via CO2 hydrogenation reaction. In addition, conventional reactor units for the CO2 hydrogenation process are explained, as well as different types of microreactors with key pathways to determine catalyst activity and selectivity of the value-added chemicals. Finally, limitations between conventional units and microreactors and future directions for CO2 hydrogenation are detailed and discussed. The benefits of such set-ups in providing platforms that could be utilized in the future for major scale-up and industrial operation are also emphasized., Green Open Access added to TU Delft Institutional Repository 'You share, we take care!' - Taverne project https://www.openaccess.nl/en/you-share-we-take-care Otherwise as indicated in the copyright section: the publisher is the copyright holder of this work and the author uses the Dutch legislation to make this work public., ChemE/Catalysis Engineering