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This research explores the depolymerization of waste polymethyl methacrylate (PMMAW) from dental material in fixed bed semi-batch reactors, focusing on three production scales: laboratory, technical and pilot. The study investigates the thermal degradation mechanism and kinetics of PMMAW through thermogravimetric (TG) and differential scanning calorimetry (DSC) analyses, revealing a two-step degradation process. The heat flow during PMMAW decomposition is measured by DSC, providing essential parameters for designing pyrolysis processes. The results demonstrate the potential of DSC for energetic analysis and process design, with attention to standardization challenges. Material balance analysis across the production scales reveals a temperature gradient across the fixed bed negatively impacting liquid yield and methyl methacrylate (MMA) concentration. Reactor load and power load variables are introduced, demonstrating decreased temperature with increased process scale. The study identifies the influence of temperature on MMA concentration in the liquid fraction, emphasizing the importance of controlling temperature for efficient depolymerization. Furthermore, the research highlights the formation of aromatic hydrocarbons from the remaining char, indicating a shift in liquid composition during the depolymerization process. The study concludes that lower temperatures below 450 °C favor liquid fractions rich in MMA, suggesting the benefits of lower temperatures and slower heating rates in semi-batch depolymerization. The findings contribute to a novel approach for analyzing pyrolysis processes, emphasizing reactor design and economic considerations for recycling viability. Future research aims to refine and standardize the analysis and design protocols for pyrolysis and similar processes. [ABSTRACT FROM AUTHOR]

Hydrothermal processing of biomass may be able to overcome a series of problems associated with the thermochemical conversion of lignocellulosic material into energy and fuels. Investigating the process parameters and an adequate process description is one of the first steps to being able to design and optimize a certain treatment concept. In the present article, we studied process evolution with respect to reaction time in order to evaluate structure changes and kinetics of corn stover decomposition in a hydrothermal reactor. The effect of the biomass-to-H2O ratio was also investigated. A pilot-scale reactor of 18.75 L was used to conduct hydrothermal processing runs at 250 °C at different reaction times (60, 120 and 240 min) and biomass-to-H2O ratios (1:10, 1:15 and 1:20). Solid phase products were characterized by thermogravimetry (TG), scanning electron microscopy (SEM), elemental composition (EDX), crystalline phases by X-ray diffraction (XRD) and surface area (BET). For the experiments with a constant reaction time, the yields of hydro-char, aqueous and gaseous phases varied between 31.08 and 35.82% (wt.), 54.59 and 60.83% (wt.) and 8.08 and 9.58% (wt.), respectively. The yields of hydro-char and gases tend to increase with higher biomass-to-H2O ratios, while aqueous phase yields are lower when using lower ratios. As expected, the yields of liquid and gases are higher when using higher reaction times, but there is a reduction in hydro-char yields. TG showed that 60 min was not enough to completely degrade the corn stover, while 120 and 240 min presented similar results, indicating an optimized time of reaction between 120 and 240 min. SEM images, elemental composition and XRD of hydro-char showed that higher biomass-to-H2O ratios increase the carbonization of corn stover. The surface area analysis of hydro-char obtained at 250 °C, 2.0 °C/min, a biomass-to-H2O ratio of 1:10 and 240 min showed a surface area of 4.35 m2/g, a pore volume of 18.6 mm3/g and an average pore width of 17.08 μm. The kinetic of corn stover degradation or bio-char formation was correlated with a pseudo-first-order exponential model, exhibiting a root-mean-square error (r2) of 1.000, demonstrating that degradation kinetics of corn stover with hot-compressed H2O, expressed as hydro-char formation, is well described by an exponential decay kinetics. [ABSTRACT FROM AUTHOR]

Palm oil is, from an economic, environmental, and social point of view, a vegetable oil with great potential and the state of Pará-Brazil is Brazil's great producer. In addition, soap phase residue or palm oil neutralization sludge (PONS), a byproduct of the neutralization step of the chemical refinement of palm oil, is produced, posing a huge problem for waste disposal and management in the production process of refined palm oil (RPO). In this context, this work aims to systematically investigate the economic analysis of the thermal–catalytic process of crude palm oil (CPO) and palm oil neutralization sludge (PONS). The thermocatalytic processes of CPO and PONS carried out at pilot scale and their economic feasibility were analyzed. The yields of biofuels produced by fractional distillation were also presented. The physicochemical properties of CPO and PONS, as well as those of organic liquid products obtained by the thermal–catalytic process of CPO and PONS were taken into account in the economic analysis. In addition, the chemical composition organic liquid products obtained by thermal–catalytic process of CPO and PONS, as well as its distillation fractions (green gasoline, green kerosene, green light diesel and heavy diesel), used as key factors/indicators on the economic analysis. The analysis of the key factors/indicators from the thermocatalytic processes of CPO and PONS showed economic viability for both crude palm oil (Elaeis guineensis, Jacq) and palm oil neutralization sludge. The minimum fuel selling price (MFSP) obtained in this work for the biofuels was 1.59 USD/L using crude palm oil (CPO) and 1.34 USD/L using palm oil neutralization sludge (PONS). The best breakeven point obtained was of 1.24 USD/L considering the PONS. The sensibility analysis demonstrated that the pyrolysis and distillation yields are the most important variables that affect the minimum fuel-selling price (MFSP) in both economic analyses. [ABSTRACT FROM AUTHOR]

This work aims to investigate the effect of process temperature and catalyst content by pyrolysis and thermal catalytic cracking of (organic matter + paper) fraction from municipal household solid waste (MHSW) on the yields of reaction products (bio-oil, bio-char, H2O, and gas), acid value, chemical composition of bio-oils, and characterization of bio-chars in laboratory scale. The collecting sectors of MHSW in the municipality of Belém-Pará-Brazil were chosen based on geographic and socio-economic database. The MHSW collected and transported to the segregation area. The gravimetric analysis of MHSW was carried out and the fractions (Paper, Cardboard, Tetra Pack, Hard Plastic, Soft Plastic, Metal, Glass, Organic Matter, and Inert) were separated. The selected organic matter and paper were submitted to pre-treatment of crushing, drying, and sieving. The experiments carried out at 400, 450, and 475 °C and 1.0 atmosphere, and at 475 °C and 1.0 atmosphere, using 5.0, 10.0, and 15.0% (wt.) Ca(OH)2, in batch mode. The bio-oil was characterized for acid value. The chemical functions present in bio-oil were identified by FT-IR and the composition was identified by GC-MS. The bio-char was characterized by SEM, FT-IR, and XRD. The variance in mass (wt.%) for organic fractions of municipal household solid waste (OFMHSW), between 56.21 and 67.45% (wt.), lies with the interval of 56% (wt.) and 64% (wt.) of OFMHSW for middle- and low-income countries. The pyrolysis of MHSW fraction (organic matter + paper) shows bio-oil yields between 2.63 and 9.41% (wt.), aqueous phase yields between 28.58 and 35.08% (wt.), solid phase yields between 35.29 and 45.75% (wt.), and gas yields between 16.54 and 26.72% (wt.). The bio-oil yield increases with pyrolysis temperature. For the catalytic cracking, the bio-oil and gas yields increase slightly with CaO content, while that of bio-char decreases, and the H2O phase remains constant. The GC-MS of liquid reaction products identified the presence of hydrocarbons (alkanes, alkenes, alkynes, cycloalkanes, and aromatics) and oxygenates (carboxylic acids, ketones, esters, alcohols, phenols, and aldehydes), as well as compounds containing nitrogen, including amides and amines. The acidity of bio-oil decreases with increasing process temperature and with aid Ca(OH)2 as a catalyst. The concentration of hydrocarbons in bio-oil increases with increasing Ca(OH)2-to-OFMHSW fraction ratio due to the catalytic deoxygenation of fatty acid molecules, by means of decarboxylation/decarbonylation, producing aliphatic and aromatic hydrocarbons. [ABSTRACT FROM AUTHOR]

Radiotherapy (RT) is a relatively safe and established treatment for cancer, where the goal is to kill tumoral cells with the lowest toxicity to healthy tissues. Using it for disorders involving cell loss is counterintuitive. However, ionizing radiation has a hormetic nature: it can have deleterious or beneficial effects depending on how it is applied. Current evidence indicates that radiation could be a promising treatment for neurodegenerative disorders involving protein misfolding and amyloidogenesis, such as Alzheimer's or Parkinson's diseases. Low-dose RT can trigger antioxidant, anti-inflammatory and tissue regeneration responses. RT has been used to treat peripheral amyloidosis, which is very similar to other neurodegenerative disorders from a molecular perspective. Ionizing radiation prevents amyloid formation and other hallmarks in cell cultures, animal models and pilot clinical trials. Although some hypotheses have been formulated, the mechanism of action of RT on systemic amyloid deposits is still unclear, and uncertainty remains regarding its impact in the central nervous system. However, new RT modalities such as low-dose RT, FLASH, proton therapy or nanoparticle-enhanced RT could increase biological effects while reducing toxicity. Current evidence indicates that the potential of RT to treat neurodegeneration should be further explored. [ABSTRACT FROM AUTHOR]

In this work, a techno-economic assessment of the production of bio-oil, coke and gas, via thermo-catalytic pyrolysis followed by distillation, is accomplished. The raw materials were two solid wastes: lipid-based material (residual fat/scum from a fat retention box from the University Restaurant at the Federal University of Pará—UFPA) and a lignin-cellulosic material of açaí seed (Euterpe oleracea Mart.). From the literature, a review is made of the physicochemical analysis of the raw materials, of the bio-oil, and of the chemical composition of the biofuels produced (kerosene, light diesel, and heavy diesel). The bio-oil yields for each experiment of pyrolysis and distillation are also presented and compared with the literature. The economic indicators for the evaluation of the most viable cracking (pyrolysis) and distillation process of bio-oils were: (a) the simple payback criterion, (b) discounted payback, (c) net present value (NPV), (d) internal rate of return (IRR), and (e) index of profitability (IP). The analysis of the indicators showed the economic viability of the lipid-based material and unfeasibility for the açai seed (Euterpe oleracea Mart.). The breakeven point obtained was 1.28 USD/L and the minimum fuel selling price (MFSP) obtained in this work for the biofuels was 1.34 USD/L). The sensibility analysis demonstrated that the pyrolysis and distillation yields are the most important variables to affect the minimum fuel selling price (MFSP). [ABSTRACT FROM AUTHOR]

This work investigated the influence of the reaction time and catalyst-to-residual fat ratio by catalytic upgrading from pyrolysis vapors of residual fat at 400 °C and 1.0 atmosphere, on the yields of reaction products, physicochemical properties (density, kinematic viscosity, and acid value) and chemical composition of bio-oils, over a catalyst fixed-bed reactor of activated carbon pellets impregnated with 10.0 M NaOH, in semi-pilot scale. The experiments were carried out at 400 °C and 1.0 atmosphere, using a process schema consisting of a thermal cracking reactor of 2.0 L coupled to a catalyst fixed-bed reactor of 53 mL, without catalyst and using 5.0%, 7.5%, and 10.0% (wt.) activated carbon pellets impregnated with 10.0 M NaOH, in batch mode. Results show yields of bio-oil decreasing with increasing catalyst-to-tallow ratio. The GC-MS of liquid reaction products identified the presence of hydrocarbons (alkanes, alkenes, ring-containing alkanes, ring-containing alkenes, and aromatics) and oxygenates (carboxylic acids, ketones, esters, alcohols, and aldehydes). For all the pyrolysis and catalytic cracking experiments, the hydrocarbon selectivity in bio-oil increases with increasing reaction time, while those of oxygenates decrease, reaching concentrations of hydrocarbons up to 95.35% (area). [ABSTRACT FROM AUTHOR]

In this work, the influence of temperature on textural, morphological, and crystalline characterization of bio-adsorbents produced by hydrothermal carbonization (HTC) of corn stover was systematically investigated. HTC was conducted at 175, 200, 225, and 250 °C, 240 min, heating rate of 2.0 °C/min, and biomass-to-H2O proportion of 1:10, using a reactor of 18.927 L. The textural, morphological, crystalline, and elemental characterization of hydro-chars was analyzed by TG/DTG/DTA, SEM, EDX, XRD, BET, and elemental analysis. With increasing process temperature, the carbon content increased and that of oxygen and hydrogen diminished, as indicated by elemental analysis (C, N, H, and S). TG/DTG analysis showed that higher temperatures favor the thermal stability of hydro-chars. The hydro-char obtained at 250 °C presented the highest thermal stability. SEM images of hydro-chars obtained at 175 and 200 °C indicated a rigid and well-organized fiber structure, demonstrating that temperature had almost no effect on the biomass structure. On the other hand, SEM images of hydro-chars obtained at 225 and 250 °C indicated that hydro-char structure consists of agglomerated micro-spheres and heterogeneous structures with nonuniform geometry (fragmentation), indicating that cellulose and hemi-cellulose were decomposed. EDX analysis showed that carbon content of hydro-chars increases and that of oxygen diminish, as process temperature increases. The diffractograms (XRD) identified the occurrence of peaks of higher intensity of graphite (C) as the temperature increased, as well as a decrease of peaks intensity for crystalline cellulose, demonstrating that higher temperatures favor the formation of crystalline-phase graphite (C). The BET analysis showed 4.35 m2/g surface area, pore volume of 0.0186 cm3/g, and average pore width of 17.08 μm. The solid phase product (bio-adsorbent) obtained by hydrothermal processing of corn stover at 250 °C, 240 min, and biomass/H2O proportion of 1:10, was activated chemically with 2.0 M NaOH and 2.0 M HCl solutions to investigate the adsorption of CH3COOH. The influence of initial acetic acid concentrations (1.0, 2.0, 3.0, and 4.0 mg/mL) was investigated. The kinetics of adsorption were investigated at different times (30, 60, 120, 240, 480, and 960 s). The adsorption isotherms showed that chemically activated hydro-chars were able to recover acetic acid from aqueous solutions. In addition, activation of hydro-char with NaOH was more effective than that with HCl. [ABSTRACT FROM AUTHOR]