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We report here on the reductive rearrangement of biomass-derived furfural to cyclopentanone, a promising non-fossil feedstock for fuels and chemicals. An underreported aspect of this reaction is the inevitable formation of heavy byproducts. To mitigate its formation, process condition such as, solvent, catalyst, temperature, acidity, and feed concentration were varied to unravel the chemistry and improve the reaction performance. Water medium was confirmed to play a crucial role, as organic solvents were unable to deliver cyclopentanone or heavy by products. Copper-based catalyst showed the highest selectivity for ring-rearrangement, reaching 50 mol % under the conditions investigated. The main factor influencing the yields of cyclopentanone (CPO), and promote oligomer formation, are the feed concentration and the pH, as high feed concentrations and high acidity facilitate the self-polymerization of furfuryl alcohol (FALC). This was confirmed by dedicated experiments using FALC and the hydroxypentenone intermediate as feed. The concentration challenge could be mitigated by slowly dosing the feed, which increased the desired product yields by 4-12 mol %. Nevertheless, most oligomers appeared to fall in the range of common liquid fuels and could be converted to diesel by hydrodeoxygenation.

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This perspective combines various expertise to develop and analyse the concept of technology cascade for recycling waste plastics with the goal of displacing as much fossil crude oil as possible. It thereby presents archetype recycling technologies with their strengths and weaknesses. It then combines them in various cascades to process a representative plastic mix, and determines how much (fossil) naphtha could be displaced and at which energy consumption. The cascades rely on a limited number of parameters that are fully reported in supplementary information and that were used in a simple and transparent spreadsheet model. The calculated results bust several common myths in plastic recycling, e. g. by prioritizing here recycled volume over recycling efficiency, and prioritizing circular industry over circular products . It unravels the energy cost of solvent-based recycling processes, shows the key role of gasification and the possibility to displace up to 70 % of the fossil feedstock with recycled carbon, a recycling rate that compares well with that aluminium, steel or paper. It suggests that deeper naphtha displacement would require exorbitant amount of energy. It therefore argues for the need to complement recycling with the use of renewable carbon, e. g. based on biomass, to fully defossilise the plastic industry.

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Substituted urea linkages are formed during the production of polyurethane foam. To chemically recycle polyurethane toward its key monomers via depolymerization (i.e., isocyanate), it is essential to break the urea linkages to form the corresponding monomers, namely, an isocyanate and an amine. This work reports the thermal cracking of a model urea compound (1,3-diphenyl urea, DPU) into phenyl isocyanate and aniline in a flow reactor at different temperatures. Experiments were performed at 350-450 °C, with a continuous feed of a solution of 1 wt.% DPU in GVL. In the temperature range studied, high conversion levels of DPU are achieved (70-90 mol%), with high selectivity towards the desired products (close to 100 mol%) and high average mole balance (∼95 mol%) in all cases.

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The predictability of pyrolysis yields and product composition of mixed plastics has been studied. To do so, pyrolysis of virgin polymers (HDPE, LDPE, PP, PS and PET) and eight individual sorting categories from a real waste DKR-350 stream (PE rigid/film, PP rigid/film, PET, PS, multilayer flexibles, and clogged materials) was performed in a batch reactor at 500 °C at laboratory scale. The obtained oil/wax, gas, and solid yields and the composition of oil/wax of those individual feedstocks were used as input of a superposition model to predict the corresponding pyrolysis yields and oil/wax composition of mixed feeds, which were later compared with the experimentally measured product yields from the pyrolysis of those mixed streams. This linear model predicts the oil/wax yield of the mixed streams to a reasonable extent, with a maximum yield deviation (overestimation) of 8 percentage points. However, the presence of significant amounts of PET (above 33 wt%) in the mixed plastic streams negatively impacts the production of the condensable product and promotes the formation of solid products beyond the expected predicted values. Quantification of the type of carbon (aliphatic, aromatic and carbonyl) present in all the oil/wax products was done using 13C NMR spectroscopy. A linear model could also predict the aliphatic carbon yield in the condensable product from plastic waste streams with high accuracy (maximum yield difference of 6 percentage points). However, the aromatic carbon yield could not be predicted, probably due to the observed behavior of PET, which interacts with other polymers to promote solid product formation.

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Diisocyanates, a key monomer in polyurethane, are generally lost during recycling. Polyurethane alcoholysis to carbamate and subsequent cracking to isocyanate represents a promising, phosgene-free recycling route. This work reports the thermal and catalytic cracking of a model carbamate (Methyl N-phenyl carbamate, MPC) to isocyanate (Phenyl isocyanate). Multiple catalysts (ZnO, Bi2O3, Al2O3, and Montmorillonite K-10) were evaluated in a closed system (batch autoclaves) to decompose MPC at temperatures of 160-200 °C, with a thorough analysis of the products and high (≥90%) mole balance. The thermal reaction was very limited at these temperatures, whereas the catalytic reaction led mainly to aniline and urea and seemed to be dominated by water adsorbed on the catalyst surface.

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A novel, low-cost, and fully recyclable thermoplastic material is produced from liquefied lignocellulosic biomass and natural fibers. The matrix, which is the heavy fraction of the liquefaction product, is characterized in terms of molecular weight distribution, density, viscosity, softening point and tensile strength. It is possible to increase the mechanical strength of the matrix by a factor of up to 100 by reinforcing it with flax fibers. Specifically, the tensile strength increased from 0.4 MPa for the non-reinforced matrix, to 55 MPa for the matrix/flax composite with a fiber content of 20 wt %. These values are comparable to conventional thermoplastics, such as poly(methyl methacrylate), polyvinyl chloride, or polystyrene.

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Phosphate fertilizer production from renewable resources like sewage sludge and livestock waste helps to ensure future phosphate supply, while also solving waste management issues. After combustion, the resulting ash contains heavy metals at a restrictively high level, preventing its direct use as fertilizer. In this study, several organic acids and sulfuric acid are used to dissolve phosphates from ash. Acetic, maleic and citric acids perform as expected, but oxalic acid outperforms all, including sulfuric acid. All phosphate is dissolved at pH 4 when using oxalic acid, while pH 2 is needed in the case of sulfuric acid. Furthermore, less of the heavy metals end up in the resulting solution when using oxalic acid. Nearly all calcium is retrieved in the solid residue when oxalic acid is used, pointing towards formation of calcium oxalate, not chelating complexes as often assumed, as the cause of oxalic acid outperforming the other acids in this study.

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Separation of volatile fatty acids (VFAs) from fermented wastewater is challenging, due to low VFA concentrations in mineral-rich streams. As a result, separation capacity and selectivity with traditional solvents and adsorbents are both compromised. In this study, using a complex artificial model solution mimicking real fermented wastewaters, it is shown that a simple and robust adsorption-based separation technique can retain a remarkable capacity and selectivity for VFAs. Four types of polystyrene-divinylbenzene-based resins (primary, secondary, and tertiary amine-functionalized, and nonfunctionalized) were examined as the adsorbents. The presence of chloride, sulfate, and phosphate salts resulted in coadsorption of their acidic forms HCl, H2SO4, and H3PO4 on amine-functionalized adsorbents, and severely reduced the VFA capacity. With the nonfunctionalized adsorbent, almost no mineral acid coadsorption was observed. This together with a high total VFA capacity of up to 76 g/kg in equilibrium with the model solution containing a total VFA concentration of 1 wt % resulted in a very high selectivity for the VFAs. Nitrogen-stripping with various temperature profiles was applied to regenerate the adsorbent, and study the potential for fractionation of the VFAs during regeneration. Butyric acid (HBu) was obtained in mole fractions of up to 0.8 using a stepwise increase in the stripping temperature from 25 °C via 120 to 200 °C. During four successive adsorption-regeneration cycles, no reduction in the adsorption capacity was observed.

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Fermentative bioethanol production from pyrolytic sugars was improved via aromatics removal by liquid-liquid extraction. As solvents, the ionic liquid (IL) trihexyltetradecylphosphonium dicyanamide (P666,14[N(CN)2]) and ethyl acetate (EA) were compared. Two pyrolytic sugar solutions were created from acid-leached and untreated pinewood, with levoglucosan contents (most abundant sugar) of 29.0% and 8.3% (w/w), respectively. In a single stage extraction, 70% of the aromatics were effectively removed by P666,14[N(CN)2] and 50% by EA, while no levoglucosan was extracted. The IL was regenerated by vacuum evaporation (100mbar) at 220°C, followed by extraction of aromatics from fresh pyrolytic sugar solutions. Regenerated IL extracted aromatics with similar extraction efficiency as the fresh IL, and the purified sugar fraction from pretreated pinewood was hydrolyzed to glucose and fermented to ethanol, yielding 0.46g ethanol/(g glucose), close to the theoretical maximum yield.

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We report a process concept for lignocellulose liquefaction in a refinery stream that will be coprocessed with the resulting biocrude and that, therefore, does not require the recovery and recycling of the liquefaction solvent. Light cycle oil and vacuum gas oil were found to be the two most promising solvents. Both refinery streams could provide a liquid yield of 58 C % (64 % energy yield). A techno-economic assessment indicates that the biocrude could be produced at an energy-equivalent crude oil price of 51-64 $ per barrel at a wood cost of 85 $ per dry ton.

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In this study, the feasibility of the gasification of dewatered sewage sludge in supercritical water (SCW) for energy recovery combined with P-recovery from the solid residue generated in this process was investigated. SCWG temperature (400°C, 500°C, 600°C) and residence time (15min, 30min, 60min) were varied to investigate their effects on gas production and the P recovery by acid leaching. The results show that the dry gas composition for this uncatalyzed gasification of sewage sludge in SCW mainly comprised of CO2, CO, CH4, H2, and some C2-C3 compounds. Higher temperatures and longer residence times favored the production of H2 and CH4. After SCWG, more than 95% of the P could be recovered from the solid residue by leaching with acids. SCWG combined with acid leaching seems an effective method for both energy recovery and high P recovery from sewage sludge.

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The liquefaction of lignocellulosic biomass is studied for the production of liquid (transportation) fuels. The process concept uses a product recycle as a liquefaction medium and produces a bio-oil that can be co-processed in a conventional oil refinery. This all is done at medium temperature (≈ 300 °C) and pressure (≈ 60 bar). Solvent-screening experiments showed that oxygenated solvents are preferred as they allow high oil (up to 93% on carbon basis) and low solid yields (≈ 1-2% on carbon basis) and thereby outperform the liquefaction of biomass in compressed water and biomass pyrolysis. The following solvent ranking was obtained: guaiacol>hexanoic acid ≫ n-undecane. The use of wet biomass results in higher oil yields than dry biomass. However, it also results in a higher operating pressure, which would make the process more expensive. Refill experiments were also performed to evaluate the possibility to recycle the oil as the liquefaction medium. The recycled oil appeared to be very effective to liquefy the biomass and even surpassed the start-up solvent guaiacol, but became increasingly heavy and more viscous after each refill and eventually showed a molecular weight distribution that resembles that of refinery vacuum residue.

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