Sustainable Hydrogen Production via Sorption Enhanced Reforming of Complex Biorefinery Side Streams in a Fixed Bed Adiabatic Reactor

In this work, sorption enhanced steam reforming is explored as a potential solution for the valorization of gaseous streams recovered from biorefinery hydrogenation processes. The hydrogen content of such streams limits the hydrocarbon conversion in conventional steam reforming due to thermodynamic and kinetic constraints. A previously developed 1D dynamic heterogeneous model of an adiabatic reactor was thus applied to evaluate the effect of H2 dilution on the performance indicators of the sorption enhanced reforming process. The mathematical model analysis highlights that despite of CO2 capture by the sorbent favorably modifies the thermodynamics of syngas production, H2 dilution worsens the performance of the sorption enhanced reforming of model H2/CH4 streams with respect to pure CH4. Results show a drop of 17% for CH4 conversion and a reduction of 15.4% of the captured CO2 on passing from pure methane to a H2/CH4 feed with a 40/60 molar ratio. However, on increasing the heat capacity of the bed, by replacing part of the sorbent with an inert heat carrier, better performances are calculated for the H2/CH4 feed matching the pure CH4 case. The presence of C2+ hydrocarbons is assessed as well and the results show a significant improvement in the reformer’s performance; in the case of a stream composed of H2/CH4/C3H8 with a molar ratio 40/45/15, the total hydrocarbon conversion grows to 92.8%, CO2 capture ratio to 82.6%, and H2 purity to 95.6%. The positive effect is associated with thermal factors that promote the reaction kinetics. Thus, the suitability of the sorption enhanced reforming technology to H2-rich and C-poor streams is strictly composition dependent; by cofeeding of C2+ hydrocarbons, the process turns into a remarkable solution for converting gaseous streams in pure H2

Amides in Bio-oil by Hydrothermal Liquefaction of Organic Wastes: A Mass Spectrometric Study of the Thermochemical Reaction Products of Binary Mixtures of Amino Acids and Fatty Acids

Among biofuels, the bio-oil produced by hydrothermal liquefaction of waste biomass can be considered an alternative to fossil fuels in industry as well as transport and heating compartments. The bio-oil complex composition is directly dependent upon the specific biomass used as feedstock and the process used for the chemical conversion. The coexistence of proteins and lipids can explain, in principle, the high percentage of fatty acid amides found in the produced bio-oil. In the present study, the amides in a sample of bio-oil have been separated by gas chromatography and identified at first on the basis of their electron impact (EI) mass spectra. To distinguish between <i>N</i>-alkyl isomers, standard amides have been synthesized and analyzed. Because the most reasonable origin of fatty acid amides in hydrothermal bio-oils is the condensation reaction between fatty acids and the decarboxylation products of amino acids, a series of model experiments have been carried out by reacting hexadecanoic acid, at high temperature and pressure, with each of the 20 amino acids constitutive of proteins, looking for the formation of fatty acid amides. Remarkably, by such experiments, all of the amides present in the bio-oil have been recognized as hydrothermal coupling compounds of the decomposition products of amino acids with fatty acids, thus allowing for their structural elucidation and, also important, confirming their (bio)­chemical origin