Search Results (154)

Chemical recycling of polyolefins is essential to mitigate plastic waste accumulation and promote circular economy strategies. Among the various chemical recycling pathways, catalytic pyrolysis, tandem catalyst systems, ethenolysis, hydrocracking, and hydrogenolysis have emerged as promising approaches for converting polyolefin waste into valuable hydrocarbons, including gaseous, liquid, and solid products. This review provides a comprehensive survey of recent research on these methodologies, with a particular focus on the production of light gaseous hydrocarbons (C2–C4), bypassing the intermediate pyrolysis oil stage, potentially reducing contamination issues and simplifying downstream processing. In contrast to conventional reviews focused primarily on liquid products, the present work emphasizes strategies for enhancing the selective production of light gaseous hydrocarbons due to their potential application in circular monomer manufacturing. Aspects such as catalyst selection, reaction conditions, and product distribution are analyzed. Additionally, the current Technology Readiness Level (TRL) of the studied processes and their relative advantages, limitations, and perspectives for industrial applications are discussed. The analysis highlights catalytic pyrolysis with zeolites as the most mature and scalable technological alternative for manufacture of light compounds directly from polyolefin waste, while tandem catalyst systems and ethenolysis constitute promising but still emerging alternatives for targeted gas production. Full article

Spent lithium-ion battery electrolytes contain fluorine-, sulfur-, and phosphorus-bearing toxins, necessitating deep detoxification and directional conversion into C₁–C₆ light hydrocarbons. To elucidate the specific catalytic roles and sequential activation of cathode metals (Li, Ni, Co, Mn), this work systematically deconvolutes their mono- and multi-metallic migration mechanisms over a CaO-ZSM-5* catalyst during vacuum catalytic pyrolysis (530 °C, 100 Pa). Results reveal that Li⁺ and Ni²⁺ dominate C–O bond cleavage in carbonates and CaO-ZSM-5*-assisted decarboxylation and oxygen fixation, significantly increasing the relative hydrocarbon content. Conversely, Co^2/3+ and Mn⁴⁺ release reactive oxygen species, causing deep oxidation of hydrocarbons into CO₂ and antagonizing the targeted conversion. In multi-metallic systems, forming composite metal oxides (M_xN_yO_z) increases the energy barrier for releasing active catalytic ions, hindering carbonate cleavage and leaving unreacted carbonate feedstocks. For detoxification, F and P are effectively immobilized as CaF₂ and Ca₂P₂O₇. The relative content of detected gas-phase nitriles is minimized to <2% due to the strong antagonistic effect of Ni²⁺ on Li⁺-promoted hexanedinitrile cleavage, while sulfur species derived from 1,3-propane sultone are converted to SO₂ and ultimately mineralized as calcium and metal-sulfur salts. Mechanistically, product distributions and crystallographic properties suggest a hypothesized sequential activation model—Li⁺ → Ni²⁺ → Mn⁴⁺—governing reactivity, whereas Co^2/3+ does not participate in the synergistic detoxification and selective upgrading process. This migration–reaction coupling framework provides critical insights for cathode-assisted in situ catalytic pyrolysis and closed-loop electrolyte recycling. Full article

In recent years, accelerated industrialization has made water pollution a major challenge, bisphenol pollutants being one of the most typical examples. Advanced oxidation processes (AOPs) based on peroxymonosulfate (PMS) activation have been applied in environmental remediation due to their broad applicability and high pollutant removal efficiency. The key to AOPs lies in developing low-cost, highly active catalysts. This study utilized waste biomass of baijiu distillers’ grains (DSGs) as precursor to prepare biochar materials for bisphenol pollutant removal. Through high-temperature pyrolysis at 900 °C for 2 h in the presence of NaCl and KCl as activator, biochar-based materials (BC-x) were prepared, which possessed advantageous features of large specific surface area and high nitrogen doping content. When applied for typical bisphenol pollutant removal, the selected BC-900 biochar exhibited almost 100% bisphenol AF (BPAF) removal efficiency after a 30 min adsorption and following a 5 min PMS activation process under reaction conditions of 200 mg L⁻¹ of BC-900, 200 mg L⁻¹ of PMS, and 20 mg L⁻¹ of BPAF. Reactive species of sulfate radicals (SO₄⦁⁻), hydroxyl radicals (⦁OH) and singlet oxygen (¹O₂) were responsible for BPAF degradation, among which ¹O₂ played the major role. Further toxicity prediction of the BPAF degradation intermediate products implied the low ecological risk of the constructed BC-900/PMS catalytic system for BPAF removal. The findings in this study may provide useful guidance for waste biomass conversion and organic contamination remediation in water. Full article

In the context of this study, it is investigated whether catalytic pyrolysis of post-consumer polypropylene might prove an interesting route to the generation of liquid hydrocarbon materials from plastic waste. The optimum product selectivity can be achieved using the appropriate catalyst. To address this problem, we tested three altered natural zeolites as follows: H-ZN, AT-ZN, and AA-ZN, according to a factorial design which accounts for temperature (400–500 °C), heating rate (10–20 °C per minute), and catalyst loading (5–10 percent by weight). Initially, we verified by thermogravimetric and micro-Raman analyses the thermal behavior of the catalytic systems and the consistency of the polypropylene feedstock. This work confirms that the catalyst assists in initiating the chain-scission process, as changes to the zeolites are responsible for the breakdown of polypropylene at a lower temperature. H-ZN showed high liquid recovery (75.4 wt%), particularly under moderate conditions, as confirmed by product-yield analysis. On the other hand, AT-ZN was more conducive to gas formation and light-fraction production at higher temperatures. H-ZN kept the diesel-range fraction (C12–C20) stable nearly to 51%, according to GC–MS; AT-ZN shifted selectivity to gasoline-range hydrocarbons (C6–C11), up to 57% under severe conditions. AA-ZN showed intermediate behavior. The overall conversion and molecular profile of the liquid products were influenced not only by catalyst acidity, temperature, and their interactions but also by Pearson correlation and ANOVA. The results described above indicate that H-ZN is the most promising catalyst for selective polypropylene-to-diesel conversion and prove that modified natural zeolites are an inexpensive and scalable method for valorizing plastic waste in a circular economy. Full article

This research systematically investigated the catalytic pyrolysis of Arab Heavy (AH) and Arab Light (AL) crude oils using NiO supported on Al₂O₃ or ZSM-5 in a microwave-assisted reactor, with particular emphasis on hydrogen (H₂) generation and value-added chemicals. To understand how both the catalyst and feedstock affect reaction products, gas and liquid products as well as catalyst activity were carefully examined. The production of H₂ and olefins was significantly enhanced by the NiO/Al₂O₃ catalyst, especially when using AL crude. This is most likely due to favorable metal-support interactions that increase the dehydrogenation activity. However, when paired with lighter feedstock, NiO/ZSM-5 greatly increased paraffin production and encouraged light alkane synthesis in both phases. GC-MS and FTIR spectroscopy confirmed that NiO/Al₂O₃ produced liquid products richer in aromatics while also containing a significant fraction of paraffins. Remarkably, the AL over NiO/Al₂O₃ combination showed very little liquid recovery, indicating that gas generation was higher in these reaction conditions. These results showed how H₂ selectivity and hydrocarbon routes in NiO/ZSM-5 and NiO/Al₂O₃ are controlled by various microwave-catalyst interactions. This work further highlights the importance of matching catalyst properties with feedstock type to control product selectivity, with NiO/Al₂O₃ showing particular promise for H₂-focused applications. Full article

The rapid accumulation of plastic and biomass waste has emerged as a major environmental and resource management challenge, driven by increasing global consumption, low recycling efficiency, and the long-term persistence of waste in natural ecosystems. Conventional valorization routes such as pyrolysis, gasification, reforming, and fermentation provide promising pathways for converting waste into fuels and chemicals, yet their industrial deployment remains constrained by thermodynamic limitations, tar formation, catalyst deactivation, high energy demand, and complex downstream separation requirements. Despite increasing research activity, a comprehensive review that systematically addresses membrane reactor (MR) mechanisms, configurations, and their specific applications in the valorization of both plastic and biomass waste remains lacking in the current literature. In recent years, MR technology has attracted increasing attention as a platform for process intensification, integrating reaction and selective separation within a single unit. By enabling in situ product removal, MRs shift reaction equilibria toward higher conversion, selectivity improvement, and a reduction in separation severity and overall energy consumption. This critical review provides a unified and systematic assessment of MR technologies for the valorization of plastic and biomass waste. Reactor configurations, membrane materials, transport mechanisms, and catalytic systems are comprehensively examined, with particular emphasis on hydrogen-selective, oxygen-permeable, and water-selective membranes and their roles in reforming, tar mitigation, and syngas upgrading. The techno-economic and environmental implications of MR integration are critically discussed, together with current technology readiness levels (TRLs) and scale-up challenges. Overall, this review highlights MRs as a versatile and enabling platform for next-generation waste-to-value technologies and outlines their potential role in supporting the transition toward circular, low-carbon fuel and chemical production. Full article

Thermochemical/catalytic co-processing of biomass and solid wastes is a promising route for waste valorization, low-carbon energy recovery, and the co-production of fuels, chemicals, and carbon materials. Conventional pathways, including pyrolysis, gasification, liquefaction, and carbonization, provide the basic framework for mixed-feed conversion. Emerging routes, such as flash Joule heating, microwave-assisted conversion, plasma processing, supercritical water treatment, solar-driven systems, and machine-learning-assisted optimization, further expand opportunities for process intensification and selective upgrading. Owing to feedstock complementarity, including hydrogen donation from plastics, catalytic effects of ash minerals, and interactions among reactive intermediates, co-processing can enhance deoxygenation, hydrogen generation, aromatization, and carbon utilization. Major challenges remain, however, including feedstock heterogeneity, reactor scale-up, catalyst stability, and the limited transferability of laboratory-scale synergy to realistic waste streams. Future progress should therefore focus on continuous validation, mechanistic clarification, and integrated techno-economic, life-cycle, and data-driven assessments. Full article

The development of selective and sustainable catalysts is essential to enable the chemical recycling of mixed plastic waste. In this work, calcium-modified biochars derived from cocoa pod husk (CPH) and palm kernel shell (PKS) were prepared for treating a mixture of poly(ethylene terephthalate) (PET) and poly(lactic acid) (PLA). The aim was to separate the mixture through the PLA methanolysis, while maintaining the PET unreacted for a potential physical recycling. Biochar was ex situ modified with calcium precursor using a value-added concentrate recovered from the hydrothermal treatment of Jatropha fruit husk. Subsequently, a pyrolysis step was further applied to convert the calcium species into CaO, which is the active phase for the methanolysis reaction. Structural, microscopic, and spectroscopic analyses revealed that the carbon matrix strongly influences the evolution and stabilization of calcium phases during pyrolysis and post-treatment. CPH-derived biochars promoted the formation of highly dispersed CaO, whereas PKS favored the growth of larger, less reactive Ca(OH)₂ domains. As a result, the CPH_Ca10 (i.e., 10% desired calcium loading based on CPH-biochar mass) catalyst exhibited superior basicity and catalytic activity, achieving near-complete PLA conversion under mild conditions (90–110 °C) depending on the system with only 2 wt.% catalyst. Importantly, under these mild conditions, PET remained chemically intact, demonstrating the process’s high selectivity and applicability to mixed bioplastic–fossil plastic streams. This study highlights a circular, low-carbon route to producing effective Ca-based catalysts from agricultural residues. It establishes a promising strategy for selective depolymerization and separation in complex plastic waste systems. Full article

This review critically evaluates current PA6 recycling technologies, with a specific focus on caprolactam-oriented chemical recycling pathways, including hydrolysis, pyrolysis, glycolysis, ammonolysis, hydrothermal treatment, ionic-liquid-assisted depolymerization, and microwave-assisted processes. Reported caprolactam yields vary significantly depending on reaction conditions and catalyst systems, ranging from below 60 wt% in conventional hydrolysis to above 90 wt% under optimized catalytic, hydrothermal, or microwave-assisted conditions. Among these approaches, microwave-assisted hydrolysis and catalytic depolymerization have emerged as particularly promising, offering substantially reduced reaction times (minutes rather than hours), improved energy efficiency, and high monomer selectivity at moderate temperatures (typically 200–350 °C). This review integrates kinetic modeling approaches, analytical methods for monitoring depolymerization, and downstream separation considerations that govern monomer purity and recyclability. Key challenges, including energy demand, feedstock contamination, scalability, and economic competitiveness, are critically discussed in relation to industrial implementation. Overall, hydrolysis-based and microwave-assisted chemical recycling routes are the most viable pathways for closed-loop recycling of PA6. Future progress will rely on integrated reaction–separation–repolymerization designs, catalyst optimization, and process intensification to enable sustainable and industrially relevant PA6 circularity. Full article

A series of bifunctional hierarchical HZSM-5 catalysts modified with Zn, Ga, Ni, Cr, or Ag were synthesized via impregnation, and their performance in the catalytic fast pyrolysis of walnut shells was systematically evaluated. The influence of the metal species and concentration of NaOH used for desilication (0.20–0.40 mol·L⁻¹) on the yield of light aromatics was assessed. Ga/HZSM-5 and Zn/HZSM-5 exhibited the most pronounced enhancement at 0.35 mol·L⁻¹, significantly outperforming the unmodified HZSM-5. Building on this finding, Zn-Ga bimetallic hierarchical catalysts were developed, and the effect of the Zn:Ga loading ratio (1%:2%, 1.5%:1.5%, 2%:1%) was investigated. The 1%Zn/2%Ga catalyst delivered the highest performance, achieving a total aromatic yield of 3.876 × 10⁴ a.u.·mg⁻¹, with 82% BTX (benzene, toluene, and xylenes) selectivity. The term “a.u.” stands for “arbitrary units,” typically derived from peak area counts obtained through GC-MS analysis. These values represent the relative signal intensity detected by the instrument, rather than absolute quantities of the substance. To more accurately characterize the aromatic hydrocarbon yield, these data are normalized to the yield of aromatic hydrocarbons per unit mass. These findings demonstrate that the combination of Zn-Ga modification and tailored mesoporosity can markedly enhance the production of high-value benzene, toluene, and xylene (BTX) aromatics from lignocellulosic biomass. Full article

Lignin, a complex and heterogeneous polymer, poses significant challenges for effective thermal valorization due to its broad molecular weight distribution and structural diversity. This study systematically compares the effect of lignin’s molecular weight on product distribution under pyrolysis and Ru/C-catalyzed depolymerization conditions. Fractionated lignin samples with distinct molecular weights were subjected to identical thermal and catalytic conversion pathways. Pyrolysis results indicate that, compared with low-molecular-weight (low-MW) lignin, high-molecular-weight (high-MW) lignin more readily generates phenolic compounds, with the relative content of guaiacol increasing by nearly twofold. In contrast, products derived from low-MW lignin contain a higher abundance of unsaturated structures, such as 4-allyl-2,6-dimethoxyphenol, suggesting that side chain cleavage and rearrangement reactions are more pronounced. In contrast, Ru/C-catalyzed depolymerization exhibits a stronger molecular-weight-dependent selectivity, where low-MW lignin is more readily converted into carboxylic acids due to enhanced accessibility of terminal functional groups and reduced structural condensation. This comparative analysis demonstrates that lignin’s molecular weight plays a process-dependent role in governing product distribution, providing guidance for tailored lignin valorization strategies. Full article

The water–energy–carbon (WEC) nexus provides a systems framework for minimizing trade-offs among water security, energy reliability, and carbon mitigation. Within this framework, waste-derived biochar catalysts offer a circular pathway that simultaneously valorizes residues, reduces process energy demand, and supports carbon management through stable carbon storage and catalytic co-benefits. This review consolidates recent advances in biochar-based catalysts engineered from agricultural, industrial, municipal, and sludge-derived wastes, highlighting how feedstock selection and thermochemical processing, namely pyrolysis, hydrothermal carbonization (HTC), and torrefaction, as well as activation and post-modification (heteroatom doping and metal/metal-oxide incorporation) govern structure–property–performance relationships. The synthesized catalysts have been widely applied in water and wastewater treatment, including adsorption–advanced oxidation process (AOP) hybrids, Fenton-like systems, peroxydisulfate/persulfate (PS) and peroxymonosulfate (PMS) activation, photocatalysis, and the removal of emerging contaminants. They have also demonstrated strong potential in energy conversion processes such as the hydrogen evolution reaction (HER), oxygen reduction and evolution reactions (ORR/OER), biomass reforming, and carbon dioxide (CO₂) conversion. In addition, these materials contribute to carbon management through sequestration pathways, avoided emissions, and life cycle assessment (LCA)-based sustainability evaluations. Finally, we propose a WEC-aligned design roadmap integrating techno-economic analysis (TEA), LCA, and scale-up considerations to guide next-generation biochar catalysts toward robust performance in real matrices and deployment-ready systems. Full article

This work presents the synthesis, characterization, and application of zirconium oxide (ZrO₂)-based catalysts, modified with macro (silica nanospheres, NSP-SiO₂) and mesopore templates (Pluronic 123), impregnated with tungstophosphoric acid (TPA), in the catalytic pyrolysis of tomato agro-industrial residues. The NSP-SiO₂ (SXX) and P123 (PYY) amount mainly influences the ZrO₂SXXPYY-specific surface area (S_BET) and average pore diameter (D_p). ³¹P MAS NMR and FT-IR characterization results show that TPA (H₃PW₁₂O₄₀) was partially transformed into [P₂W₂₁O₇₁]⁶⁻ and [PW₁₁O₃₉]⁷⁻ during the synthesis steps. The acidic properties of ZrO₂SXXPYY samples containing 25 and 50 wt% of TPA (ZrO₂SXXPYYT25 and ZrO₂SXXPYYT50, respectively) are dependent on both the TPA content and the support nature. Bio-oil composition and product selectivity were strongly influenced by the textural and acid-based properties of the catalysts. Notably, non-catalytic pyrolysis favored pathways leading to C2 compounds, with a high content of acetic acid and hydroxyacetone. In contrast, the use of catalysts promoted the formation of higher molecular weight oxygenated compounds (C5–C6), specifically furans, aldehydes, and ketones. Full article

Lignin valorization is a central objective of modern biorefinery research. This study investigates the catalytic depolymerization of two technical lignins, kraft lignin from beech hardwood and natron lignin from annual plants, via two complementary routes: analytical catalytic pyrolysis (Py-GC/MS, 300–600 °C) and hydrogenolysis (250–310 °C, Ru/C, isopropanol/H₂). In Py-GC/MS experiments, noble-metal catalysts on carbon supports (Ru/C, Pd/C, RuPd/C) were screened. Relative compound distributions revealed phenolic derivatives as the dominant products, with Ru/C yielding the highest conversion for lignin from annual plants at 500 °C and Pd/C proving most selective for hardwood lignin at 400 °C. Hydrogenolysis was optimized through a five-level, three-factor central composite design, varying temperature, residence time, and catalyst loading. Lignin conversion ranged from 64 to 83 wt% and bio-oil yield from 69 to 89 wt%. A regression model identified optimal conditions at 295 °C, 32 min, and 17 wt% Ru/C. Catalyst regeneration via solvent washing, H₂O₂ oxidation, and controlled thermal treatment resulted in only an 8% decrease in lignin conversion. The results demonstrate that lignin origin, catalyst type, and depolymerization pathway jointly govern product selectivity, highlighting clear strategies for targeted phenolic compound production. Full article

The increasing energy demand and global dependence on conventional fuels have resulted in severe greenhouse gas (GHG) emissions, necessitating the development of sustainable bioenergy alternatives. Algal is recognized as a promising feedstock for the production of fourth-generation biofuels. This study optimizes catalytic pyrolysis of Arthrospira platensis for bio-oil production via a dual-bed catalyst system of iron-impregnated dolomite (Fe/DM) and a copper-impregnated spent fluid catalytic cracking catalyst (Cu/sFCC). A face-central composite design (FCCD) and response surface methodology (RSM) were used for the delineation of optimal conditions, ensuring that all experimental tests remained within feasible operating conditions of 500–600 °C, a reaction time of 45–75 min, a N₂ flow rate of 50–200 mL/min, and a catalyst loading of 5–20 wt%. The bio-oil yield was maximized at 39.73 ± 2.86 wt% at 500 °C for 45 min, a N₂ flow of 50 mL/min, and 5 wt% catalyst loading to feedstock with a 0.4:0.6 mass ratio of Fe/DM: Cu/sFCC. The dual-catalysts combined Brønsted and Lewis acid sites enhanced the catalytic activity, which promotes the cleavage of carbon–carbon and carbon–hydrogen bonds, including the mechanism of catalytic pathways such as dehydration, decarboxylation, oligomerization, aromatization, and further cracking reactions, and was successful in converting high-molecular-weight molecules into lighter hydrocarbons and significantly improving product selectivity, demonstrating a highly effective pathway for producing high-quality sustainable biofuel. Full article