Hydrogen is a versatile energy vector for a plethora of applications; nevertheless, itsproduction from waste/residues is often overlooked. Gasification and subsequent conversion ofthe raw synthesis gas to hydrogen are an attractive alternative to produce renewable hydrogen. Inthis paper, recent developments in R&D on waste gasification (municipal solid waste, tires, plasticwaste) are summarised, and an overview about suitable gasification processes is given. A literaturesurvey indicated that a broad span of hydrogen relates to productivity depending on the feedstock,ranging from 15 to 300 g H2/kg of feedstock. Suitable gas treatment (upgrading and separation) isalso covered, presenting both direct and indirect (chemical looping) concepts. Hydrogen productionvia gasification offers a high productivity potential. However, regulations, like frame conditions orsubsidies, are necessary to bring the technology into the market.

In this study time-resolved char conversion and alkali release under steam gasification conditions were investigated using a fixed bed reactor. The behaviour of an industrial char and chars produced from straw and furniture waste was investigated. For woody chars, an increase in gasification reactivity is observed together with a notable alkali release as the gasification approaches completion (degree of conversion > 0.8). In contrast, straw char exhibited a decrease in conversion rate and alkali release throughout the gasification process, attributed to the formation of catalytically inactive potassium silicates inhibiting the catalytic role of alkali. Aerosol particles in the 0.01–22 µm size range are emitted during the char conversion. A fraction is formed by nucleation of alkali compounds and other condensable gases. A wide particle distribution that extends over the whole size range is also observed, and the particles are likely to consist of solid char fragments. The study concludes on the importance of alkali release, illustrating the difference in alkali release pattern for high and low ash char.

The conversion of biomass-derived oxygenates over zeolite catalysts constitutes a challenge for the efficient production of bio-based chemicals and fuels due to difficulty in controlling the selectivity and high coke formation of such reactions. This is partly attributed to the microstructure of zeolite catalyst which affects the conversion and selectivity of products derived from biomass-derived oxygenates. In this study, the conversion and deactivation characteristics of three different model oxygenates found in biomass bio-oil (namely, acetol, furfural and guaiacol) over ZSM-5 zeolites of varying acidity, pore and crystal size prepared with bottom-up and top-down approaches were evaluated using a fixed bed microreactor at atmospheric pressure and a space velocity of 5 h−1 at a temperature range of 450–650 °C. Analysis of the experimental results indicates that the optimum temperature for such conversions is in the vicinity of 600 °C allowing for complete conversion of the compounds and high resistance to coking. The mechanisms of those conversions are discussed based on the obtained results. In general, crystal size and mesoporosity induce easier access to active sites improving mass transfer but also alter the location type, and strength of acid sites allowing for higher yields of primary and intermediate products such as olefins.

Bed materials provide efficient heat transfer and catalytic function in the thermochemical conversion of biomass, but their interactions with the fuel remain incompletely understood. In this study, the effects of bed materials on alkali release and fuel conversion during wood pyrolysis and CO2 gasification are investigated by online alkali detection combined with thermogravimetric analysis. The investigated bed materials include silica, sea sand, alumina and the natural ores olivine, ilmenite and dolomite. Only dolomite has a significant effect on fuel mass loss and alkali release during wood pyrolysis, while all bed materials influence char reactivity and alkali release during gasification. Sea sand, alumina and dolomite enhance the char gasification during the whole or most of the gasification process, which is related to alkali migration from the bed materials. All bed materials affect char reactivity and alkali release when the conversion approaches completion, and small amounts of some bed materials reduce the alkali release by an order of magnitude. The findings can be understood based on the chemical composition of the different materials. Silicon-rich materials reduce the levels of catalytically active alkali by formation of stable alkali silicates, and a similar explanation applies for ilmenite that captures alkali efficiently. Magnesium and calcium in contrast promote alkali release through their influence on alkali silicate chemistry. Analysis of char surfaces using scanning electron microscopy with energy dispersive spectroscopy indicates that low amounts of several elements are transferred from the bed material to the char where they may be directly involved in the char conversion process. The transferred elements are specific for each bed material and relates to their chemical composition. Mechanisms for material exchange between bed material and char are discussed.

Fuel blends may be used to meet several operational needs in thermal conversion of biomass waste, including optimization of ash properties and fuel conversion efficiency. In this study, online alkali measurements using surface ionization are employed to study synergistic effects produced by inorganic elements during co-pyrolysis/gasification of wood and straw waste. Synergistic effects on the fuel conversion behavior are not observed during co-pyrolysis, while alkali migration from straw to wood is clearly observed above 600 °C by online alkali monitoring. In contrast, synergistic effects on char conversion and alkali release are substantial during co-gasification. Positive effects on char reactivity during most of the gasification process are attributed to alkali migration from the straw to the wood char, and the most pronounced effect occurs at a gasification temperature of 900 °C and a straw content of 25%. Negative effects on char reactivity are observed at the final gasification stage, which is associated with a significantly reduced alkali release from fuel blends compared to pure wood char. The effect is attributed to the migration of silicon, phosphorus, and aluminum to the wood char, as revealed by scanning electron microscopy with energy dispersive spectroscopy, where the elements react with alkali to form catalytically inactive compounds. The mixing of biofuels is concluded to result in substantial effects on the fuel conversion efficiency, which should be taken into consideration in thermochemical conversion of biomass.

The mineral content of biomass plays an important role in the gasification rate of biomass-derived char. The understanding and quantification of mineral-related phenomena are thus of importance when considering gasification reactor design. In the present work, the potassium-induced catalytic phenomena during gasification of biomass-derived char have been studied. Char samples with similar structure and different intrinsic potassium content were gasified in a steam atmosphere at a temperature range of 700-800 °C. It was found that for all the samples, irrespective of the temperature and the initial potassium content, there is a critical K/C ratio (5 × 10-3), whereafter the catalytic phenomena prevail. The instantaneous conversion rate of the char is positively correlated with the potassium content and the progressively increasing conversion. The application of the modified random pore model was able to capture the later stages of conversion by the introduction of two additional parameters (c and p). It was found that these constants are not just fitting parameters but that there is an underlying physical significance with c being directly related to the intrinsic potassium content while being temperature independent and with p being temperature dependent.

Online alkali measurements using surface ionization are employed to study alkali release during heating of used industrial fluidized bed materials and gasification of biomass-based char and bed material mixtures. The alkali release from the bed materials starts at 820 °C and increases with temperature, the time a bed material has experienced in an industrial process, and in the presence of CO2. Online alkali measurement during heating of char mixed with used bed material shows significant alkali uptake by the char. Complementary SEM-EDS studies confirm the alkali results and indicate that other important inorganic elements including Si, Mg, and Ca also migrate from the bed material to the char. The migration of elements initially enhances alkali release and char reactivity, but significantly reduces both during the final stage of the gasification. The observed effects on char gasification become more pronounced with increasing amount of bed material and increasing time the material experienced in an industrial process. The ash-layer on the used bed material is concluded to play an important role as a carrier of alkali and other active components. The char and bed material systems are closely connected under operational conditions, and their material exchange has important implications for the thermal conversion. 

The hydrogenation of polyaromatic compounds (PACs) present in mineral oils is of great importance when it comes to the desired product properties and the minimization of health hazards; however, the presence of organonitrogen inhibits the conversion of these compounds. In this study, the inhibition effects of different types of organonitrogen compounds (acridine (ACR) and carbazole (CBZ)-basic and nonbasic organonitrogen) on the hydrodearomatization (HDA) of phenanthrene over a sulfided commercial NiMo/Al2O3 catalyst were investigated in a microflow trickle-bed reactor at a temperature range of 280 to 320 degrees C and at a total pressure of 120 barg. Analysis of the experimental results shows that the hydrogenation of phenanthrene is significantly decreased in the presence of organonitrogen, with acridine showing stronger inhibiting effects. The extent of hydrodenitrogenation (HDN) is shown to correlate with the inhibition degree with a higher extent of HDN being achieved for carbazole than for acridine. Results from co-feeding different nitrogen types (acridine and carbazole) indicate that basic nitrogen is the dominating type of organonitrogen inhibitor. Recovery of catalyst activity in the absence of organonitrogen indicates fully reversible deactivation suggesting that inhibition relates to competitive adsorption and slower reaction rate of HDN compared to HDA.

Potassium and sodium compounds play both positive and negative roles during biomass gasification, but the detailed behavior of alkali metal compounds remain incompletely understood. In this study, alkali release during CO2 gasification of biochar is characterized online with a surface ionization method in combination with thermogravimetric analysis of the char samples undergoing gasification. For wood chars, the alkali release rate follows a slowly decreasing trend as the char conversion proceeds, but increases by up to two orders of magnitude when the conversion approaches completion. In contrast, the alkali release from straw char is 40-50 times higher than observed for wood char and decreases continuously during the whole gasification process. A high temperature and a high CO2 concentration enhance both alkali release and char reactivity. The char preparation method also influences the alkali release from pine char, while the char reactivity is less affected. Alkali release and char reactivity are linked, but other factors including mineral content, surface area and char structure may play important roles for the observed reactivity. The results provide a basis for understanding of alkali behavior during gasification and may help optimize catalytic effects and reduce detrimental issues in biomass gasification.

Customization of pharmaceutical products is a central requirement for personalized medicines. However, the existing processing and supply chain solutions do not support such manufacturing-on-demand approaches. In order to solve this challenge, three-dimensional (3D) printing has been applied for customization of not only the dose and release characteristics, but also appearance of the product (e.g., size and shape). A solution for customization can be realized via non-expert-guided processing of digital designs and drug dose. This study presents a proof-of-concept computational algorithm which calculates the optimal dimensions of grid-like orodispersible films (ODFs), considering the recommended dose. Further, the algorithm exports a digital design file which contains the required ODF configuration. Cannabidiol (CBD) was incorporated in the ODFs, considering the simple correspondence between the recommended dose and the patient's weight. The ODFs were 3D-printed and characterized for their physicochemical, mechanical, disintegration and drug release properties. The algorithm was evaluated for its accuracy on dose estimation, highlighting the reproducibility of individualized ODFs. The in vitro performance was principally affected by the thickness and volume of the grid-like structures. The concept provides an alternative approach that promotes automation in the manufacturing of personalized medications in distributed points of care, such as hospitals and local pharmacies.