Two-stage hydrothermal liquefaction for multilayer plastic valorization

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Multilayer plastic film chemical recycling via sequential hydrothermal liquefaction

Multi-material layered plastic films are used in the food packaging industry due to their excellent properties; however they cannot be mechanically recycled. In this study, a two-stage hydrothermal liquefaction (HTL) process is proposed and tested for chemical recycling of a two-layer film made of LLDPE-PET. Experimental results showed that after a first subcritical stage at 325 ◦C, 94% of terephthalic acid (TPA) is recovered from the PET fraction as a solid and 47% of ethylene glycol in the aqueous phase. The unconverted PE was then used as feedstock for a subsequent supercritical HTL stage at 450 ◦C for 90 min, achieving mass yields of 47% and 29% in a naphtha-gasoline oil and in an alkane-rich gas, respectively. In conclusion, this work proved that a sequential HTL procedure can be used for chemical recycling of multilayer plastics, allowing the recovery of PET monomers to be recycled back to the PET industry and a paraffinic oil and hydrocarbon-rich gas phase that could be used as feedstock for steam cracking to produce virgin materials

Aqueous phase reforming of lignin-rich hydrothermal liquefaction by-products: a study on catalyst deactivation

The water fraction derived from the hydrothermal liquefaction of a lignin-rich feedstock was subjected to aqueous phase reforming to produce hydrogen. Deactivation of the catalyst was observed, and it was ascribed to fouling phenomena caused by phenolic oligomers. Simple aromatics like guaiacol and phenol, as well as in-organics, were proved not to be the cause of the deactivation thanks to the use of a multi-component synthetic mixture. The influence of using activated carbon as a pretreatment was studied, leading to a strong improvement of the performance when it was carried out at high temperature. The extent of deactivation was assessed using aqueous phase reforming of glycolic acid as a model reaction test. The results were found to be correlated with the surface area of the catalyst. A thermal regeneration in inert conditions was evaluated as a mode of catalyst regeneration. While the textural properties were partially recovered, the performance of the catalyst only slightly improved. A spectroscopic analysis of the solids in the aqueous solution was carried out, highlighting the structural similarities between their nature and the lignin residue. The results obtained in this study helped to enlarge the knowledge on the aqueous phase reforming of real complex mixtures, looking at indicators of paramount importance for a possible industrial application such as the stability of the catalyst

Towards the sustainable hydrogen production by catalytic conversion of C-laden biorefinery aqueous streams

An extensive screening of representative molecules of a post-hydrothermal process side stream has been performed with the aim of producing a gas mixture rich in hydrogen by catalytic aqueous phase reforming. The survey enlightens possible routes of valorisation of these by-products, scarcely investigated with other processes so far. The influence of reaction temperature was studied in the 230–270 °C range, looking at both the composition of the gas phase and the characterization of the liquid products. Indeed, the information coming from the condensed phase may provide relevant insights on the components that are not easily reformed, and that should be studied to improve the performance of the process. Binary and ternary mixtures of four selected compounds were tested to investigate synergistic and inhibiting effects, going towards the direction of a real biorefinery stream. The spent alumina-supported catalyst was characterized, outlining possible deactivation mechanisms of the catalytic system, and reused in two successive tests

CO2 conversion into hydrocarbons via modified Fischer-Tropsch synthesis by using bulk iron catalysts combined with zeolites

To effectively address the challenges posed by global warming, a prompt and coordinated effort is necessary to conduct an extensive study aimed at reducing CO2 emissions and overcoming the obstacles presented by expensive and scarce fossil fuel resources. This study primarily focuses on comparing two different methodologies for preparing Na-promoted Fe3O4-based catalysts for the CO2 hydrogenation into hydrocarbon mixtures. Three catalysts were synthesized and tested: two samples were impregnated with a different amount of Na (1 wt% and 5 wt%), while a third one was obtained via coprecipitation with NaOH. As the latter catalyst exhibited the best performance, it was combined with zeolites in two ways: physical mixtures and core-shell structures. MFI-type zeolites were used in both configurations and a conventional structure was compared to a hierarchical one. As a result, mesopores increased successfully both the CO2 conversion from 37% to 40% and the liquid hydrocarbon (C6+) selectivity from 29% to 57%, doubling the C6+ yield. On the other hand, NH3-TPD and XPS measurements demonstrated that the intimate contact between the two materials in the core-shell structures led to the migration of Na from the oxide to the zeolite reducing the concentration of strong acid sites and, consequently, the liquid hydrocarbon yield

Physico-Chemical Modifications Affecting the Activity and Stability of Cu-Based Hybrid Catalysts during the Direct Hydrogenation of Carbon Dioxide into Dimethyl-Ether

The direct hydrogenation of CO2 into dimethyl-ether (DME) has been studied in the presence of ferrierite-based CuZnZr hybrid catalysts. The samples were synthetized with three different techniques and two oxides/zeolite mass ratios. All the samples (calcined and spent) were properly characterized with different physico-chemical techniques for determining the textural and morphological nature of the catalytic surface. The experimental campaign was carried out in a fixed bed reactor at 2.5 MPa and stoichiometric H2/CO2 molar ratio, by varying both the reaction temperature (200–300 °C) and the spatial velocity (6.7–20.0 NL∙gcat−1∙h−1). Activity tests evidenced a superior activity of catalysts at a higher oxides/zeolite weight ratio, with a maximum DME yield as high as 4.5% (58.9 mgDME∙gcat−1∙h−1) exhibited by the sample prepared by gel-oxalate coprecipitation. At lower oxide/zeolite mass ratios, the catalysts prepared by impregnation and coprecipitation exhibited comparable DME productivity, whereas the physically mixed sample showed a high activity in CO2 hydrogenation but a low selectivity toward methanol and DME, ascribed to a minor synergy between the metal-oxide sites and the acid sites of the zeolite. Durability tests highlighted a progressive loss in activity with time on stream, mainly associated to the detrimental modifications under the adopted experimental conditions

Conceptual design and techno-economic assessment of coupled hydrothermal liquefaction and aqueous phase reforming of lignocellulosic residues

Hydrothermal liquefaction is a promising technology for producing renewable advanced biofuels. However, some weaknesses could undermine its large-scale application, such as the significant carbon loss in the aqueous phase (AP) and the necessity of biocrude upgrading. In order to deal with these challenges, in this work the techno-economic feasibility of coupling hydrothermal liquefaction (HTL) with aqueous phase reforming (APR) was evaluated. APR is a catalytic process able to convert water-dissolved oxygenates into a hydrogen-rich gas that can be used for biocrude upgrading. Two cases were proposed, based on different lignocellulosic feedstocks: corn stover (CS) and lignin-rich stream (LRS) from cellulosic ethanol production. HTL-APR plants operating with the same mass flow (3.6 t/h) at 10 wt% solid loading were herein evaluated, resulting in an input size of 20 MW (LRS) and 16.5 MW (CS). Based on experimental and literature data, the mass and energy balances were per- formed; subsequently, the main equipment was designed; finally, the capital and operating costs were evaluated. The analysis showed that the minimum selling prices for the biofuel (0% internal rate of return) were 1.23 (LRS) and 1.27 €/kg (CS). The heat exchangers accounted for most of the fixed capital investment, while electricity and feedstock had the highest impact on the operating costs. The implementation of APR was particularly profitable with CS, as it produced 107% of the hydrogen required for biocrude upgrading. In this case, APR was able to significantly reduce the H2 production cost (1.5 €/kg) making it a competitive technology compared to con- ventional electrolysis

CO Oxidation Over Ceria-Based Catalysts: Comparison of Single and Binary Metal Oxides

Wet air oxidation (WAO) of lignocellulosic biomasses is a promising route for the production of renewable and valuable compounds. In this work, acetovanillone (AV) was selected as lignin model molecule in order to investigate its behavior under the WAO reaction conditions. The experiments were carried out in a pressurized 50 ml batch reactor loaded with NaOH 2M as solvent, the reaction takes 1 h with temperatures ranging from 130 to 190 °C and air pressures between 5 and 30 bar. The perovskite-type mixed oxide LaFeO3 was synthetized and used as heterogeneous catalyst in order to improve the activation of molecular oxygen. Vanillin yield resulted to benefit from high reaction temperature showing a maximum carbon yield of 22%, instead the formation of carboxylic acids from the oxidative degradation of AV largely benefits from high pressure of air, exhibiting an overall carbon yield of 35%. The produced compounds include oxalic, glycolic, lactic, malonic, and levulinic acid