Characterization of the degradation products of lignocellulosic biomass by using tandem mass spectrometry experiments, model compounds, and quantum chemical calculations.

Biomass-derived degraded lignin and cellulose serve as possible alternatives to fossil fuels for energy and chemical resources. Fast pyrolysis of lignocellulosic biomass generates bio-oil that needs further refinement. However, as pyrolysis causes massive degradation to lignin and cellulose, this process produces very complex mixtures. The same applies to degradation methods other than fast pyrolysis. The ability to identify the degradation products of lignocellulosic biomass is of great importance to be able to optimize methodologies for the conversion of these mixtures to transportation fuels and valuable chemicals. Studies utilizing tandem mass spectrometry have provided invaluable, molecular-level information regarding the identities of compounds in degraded biomass. This review focuses on the molecular-level characterization of fast pyrolysis and other degradation products of lignin and cellulose via tandem mass spectrometry based on collision-activated dissociation (CAD). Many studies discussed here used model compounds to better understand both the ionization chemistry of the degradation products of lignin and cellulose and their ions' CAD reactions in mass spectrometers to develop methods for the structural characterization of the degradation products of lignocellulosic biomass. Further, model compound studies were also carried out to delineate the mechanisms of the fast pyrolysis reactions of lignocellulosic biomass. The above knowledge was used to assign likely structures to many degradation products of lignocellulosic biomass.

Interaction Effects between the Main Components of Protein-Rich Biomass during Microwave-Assisted Pyrolysis.

The interaction effects between the main components (proteins (P), carbohydrates (C), and lipids (L)) of protein-rich biomass during microwave-assisted pyrolysis were investigated in depth with an exploration of individual pyrolysis and copyrolysis (PC, PL, and CL) of model compounds. The average heating rate of P was higher than those of C and L, and the interactions in all copyrolysis groups reduced the max instant heating rate. The synergistic extent (S) of PC and PL for bio-oil yield was 16.78 and 18.24%, respectively, indicating that the interactions promoted the production of bio-oil. Besides, all of the copyrolysis groups exhibited a synergistic effect on biochar production (S = 19.43-28.24%), while inhibiting the gas generation, with S ranging from -20.17 to -6.09%. Regarding the gaseous products, apart from H2, P, C, and L primarily generated CO2, CO, and CH4, respectively. Regarding bio-oil composition, the interactions occurring within PC, PL, and CL exhibited a significantly synergistic effect (S = 47.81-412.96%) on the formation of N-heterocyclics/amides, amides/nitriles, and acids/esters, respectively. Finally, the favorable applicability of the proposed interaction effects was verified with microalgae. This study offers valuable insights for understanding the microwave-assisted pyrolysis of protein-rich biomass, laying the groundwork for further research and process optimization.

Waste-to-energy: Co-pyrolysis of potato peel and macroalgae for biofuels and biochemicals.

Waste-to-energy conversion presents a pivotal strategy for mitigating the energy crisis and curbing environmental pollution. Pyrolysis is a widely embraced thermochemical approach for transforming waste into valuable energy resources. This study delves into the co-pyrolysis of terrestrial biomass (potato peel) and marine biomass (Sargassum angastifolium) to optimize the quantity and quality of the resultant bio-oil and biochar. Initially, thermogravimetric analysis was conducted at varying heating rates (5, 20, and 50 °C/min) to elucidate the thermal degradation behavior of individual samples. Subsequently, comprehensive analyses employing FTIR, XRD, XRF, BET, FE-SEM, and GC-MS were employed to assess the composition and morphology of pyrolysis products. Results demonstrated an augmented bio-oil yield in mixed samples, with the highest yield of 27.1 wt% attained in a composition comprising 75% potato peel and 25% Sargassum angastifolium. As confirmed by GC-MS analysis, mixed samples exhibited reduced acidity, particularly evident in the bio-oil produced from a 75% Sargassum angastifolium blend, which exhibited approximately half the original acidity. FTIR analysis revealed key functional groups on the biochar surface, including O-H, CO, and C-O moieties. XRD and XRF analyses indicated the presence of alkali and alkaline earth metals in the biochar, while BET analysis showed a surface area ranging from 0.64 to 1.60 m2/g. The favorable characteristics of the products highlight the efficacy and cost-effectiveness of co-pyrolyzing terrestrial and marine biomass for the generation of biofuels and value-added commodities.

Kraft lignin fast (catalytic) pyrolysis for the production of high value-added chemicals (HVACs): A techno-economic screening of valorization pathways.

This paper presents a techno-economic analysis (TEA) of six (6) scenarios of the kraft lignin catalytic (CFP) and thermal (TFP) fast pyrolysis towards the production of high value-added chemicals (HVACs) and electric energy, based on experimental data from our previous work. ASPEN PLUS was used to simulate the proposed plants/scenarios and retrofitted custom-based economic models that were developed in Microsoft EXCEL. The results showed that scenarios 1 and 2 in which the produced bio-oil is used as fuel for electricity production are the most cost-deficient. On the other hand, scenarios 3 and 6 that utilize the light bio-oil fraction to recover distinct HVACs, along with the use of heavier fractions for electricity production, have showed a significant investment viability, since profitability measures are high. Furthermore, scenarios 4 and 5 that refer to the recovery of mixtures (fractions) of HVACs, are considered an intermediate investment option due to the reduced cost of separation. All the proposed scenarios have a substantial total capital investment (TCI) which ranges from 135 MM€ (scenario 4) to 380 MM€ (scenario 6) with a Lang factor of 6.08, which shows that the CAPEX results are within reason. As far as the comparison of lignin CFP and TFP goes, it is shown that lignin CFP leads to the production of aromatic and phenolic monomers which have a substantial market value, while TFP can lead to important value-added chemicals with a lower OPEX than CFP. A target of return of investment (ROI) of 32% has been set for the selling prices of the HVACs. In summary, this study aims at listing and assessing a set of economic indicators for industrial size plants that use lignin CFP and TFP towards the production of high value-added chemicals and energy production and to provide simulation data for comparative analysis of three bio-oil separation methods, i.e. distillation, liquid-liquid extraction and moving bed chromatography.

Wastewater-grown microalgae biomass as a source of sustainable aviation fuel: Life cycle assessment comparing hydrothermal routes.

The present paper compared, through life cycle assessment (LCA), the production of aviation biofuel from two hydrothermal routes of microalgae cultivated in wastewater. Hydrothermal liquefaction (HTL) and gasification followed by Fischer-Tropsch synthesis (G + FT) were compared. Both routes included biomass production, hydrotreatment for biofuel upgrading, and product fractionation. Secondary data obtained from the literature were used for the cradle-to-gate LCA. G + FT had a higher impact than HTL in the 18 impact categories assessed, with human carcinogenic toxicity exerting the most harmful pressure on the environment. The catalysts were the inputs that caused the most adverse emissions. The solvent used for bio-oil separation also stood out in terms of impacts. In HTL, emissions for global warming were -51.6 g CO2 eq/MJ, while in G + FT, they were 250 g CO2 eq/MJ. At the Endpoint level, HTL resulted in benefits to human health and ecosystems, while G + FT caused environmental damage in these two categories, as well as in the resources category. In the improvement scenarios, besides considering solid, aqueous, and gaseous products as co-products rather than just as waste/emissions, a 20% reduction in catalyst consumption and 90% recovery were applied. Thus, in HTL, 39.47 kg CO2 eq was avoided, compared to 35.44 kg CO2 eq in the base scenario. In G + FT, emissions decreased from 147.55 kg CO2 eq to the capture of 8.60 kg CO2 eq.

Modulating cultivation regimes of Messastrum gracile SVMIICT7 for biomass productivity integrated with resource recovery via hydrothermal liquefaction.

The present study was designed to assess Messastrum gracile SVMIICT7 potential in treating dairy wastewater (autoclaved (ADWW) and raw (DWW)) with relation to nutrient removal, in-vivo Chl-a-based biomass, and bio-oil synthesis. Chlorophyll a fluorescence kinetics revealed improved photochemical efficiency (0.639, Fv/Fm) in M. gracile when grown with DWW. This may be owing to enhanced electron transport being mediated by an effective water-splitting complex at photosystem (PSII) of thylakoids. The increase in ABS/RC observed in DWW can be attributed to the elevated chlorophyll content and reduced light dissipation, as evident by higher values of ETo/RC and a decrease in non-photochemical quenching (NPQ). M. gracile inoculated in DWW had the highest Chl-a-biomass yield (1.8 g L-1) and biomolecules while maximum nutrient removal efficiency was observed in ADWW (83.7% TN and 60.07% TP). M. gracile exhibited substantial bio-oil yield of 29.6% and high calorific value of 37.19 MJ kg-1, predominantly composed of hydrocarbons along with nitrogen and oxygen cyclic compounds. This research offers a thorough investigation into wastewater treatment, illustrating the conversion of algal biomass into valuable energy sources and chemical intermediates within the framework of a biorefinery.

Biofuel from wastewater-grown microalgae: A biorefinery approach using hydrothermal liquefaction and catalyst upgrading.

Third-generation biofuels from microalgae are becoming necessary for sustainable energy. In this context, this study explores the hydrothermal liquefaction (HTL) of microalgae biomass grown in wastewater, consisting of 30% Chlorella vulgaris, 69% Tetradesmus obliquus, and 1% cyanobacteria Limnothrix planctonica, and the subsequent upgrading of the produced bio-oil. The novelty of the work lies in integrating microalgae cultivation in wastewater with HTL in a biorefinery approach, enhanced using a catalyst to upgrade the bio-oil. Different temperatures (300, 325, and 350 °C) and reaction times (15, 30, and 45 min) were tested. The bio-oil upgrading occurred with a Cobalt-Molybdenum (CoMo) catalyst for 1 h at 375 °C. Post-HTL, although the hydrogen-to-carbon (H/C) ratio decreased from 1.70 to 1.38-1.60, the oxygen-to-carbon (O/C) ratio also decreased from 0.39 to 0.079-0.104, and the higher heating value increased from 20.6 to 36.4-38.3 MJ kg-1. Palmitic acid was the main component in all bio-oil samples. The highest bio-oil yield was at 300 °C for 30 min (23.4%). Upgrading increased long-chain hydrocarbons like heptadecane (5%), indicating biofuel potential, though nitrogenous compounds such as hexadecanenitrile suggest a need for further hydrodenitrogenation. Aqueous phase, solid residues, and gas from HTL can be used for applications such as biomass cultivation, bio-hydrogen, valuable chemicals, and materials like carbon composites and cement additives, promoting a circular economy. The study underscores the potential of microalgae-derived bio-oil as sustainable biofuel, although further refinement is needed to meet current fuel standards.

Upgrading of Pyrolysis Bio-Oil by Catalytic Hydrodeoxygenation, a Review Focused on Catalysts, Model Molecules, Deactivation, and Reaction Routes.

Biomass can be converted into energy/fuel by different techniques, such as pyrolysis, gasification, and others. In the case of pyrolysis, biomass can be converted into a crude bio-oil around 50-75% yield. However, the direct use of this crude bio-oil is impractical due to its high content of oxygenated compounds, which provide inferior properties compared to those of fossil-derived bio-oil, such as petroleum. Consequently, bio-oil needs to be upgraded by physical processes (filtration, emulsification, among others) and/or chemical processes (esterification, cracking, hydrodeoxygenation, among others). In contrast, hydrodeoxygenation (HDO) can effectively increase the calorific value and improve the acidity and viscosity of bio-oils through reaction pathways such as cracking, decarbonylation, decarboxylation, hydrocracking, hydrodeoxygenation, and hydrogenation, where catalysts play a crucial role. This article first focuses on the general aspects of biomass, subsequent bio-oil production, its properties, and the various methods of upgrading pyrolytic bio-oil to improve its calorific value, pH, viscosity, degree of deoxygenation (DOD), and other attributes. Secondly, particular emphasis is placed on the process of converting model molecules and bio-oil via HDO using catalysts based on nickel and nickel combined with other active elements. Through these phases, readers can gain a deeper understanding of the HDO process and the reaction mechanisms involved. Finally, the different equipment used to obtain an improved HDO product from bio-oil is discussed, providing valuable insights for the practical application of this reaction in pyrolysis bio-oil production.

State-of-the-Art Review on the Behavior of Bio-Asphalt Binders and Mixtures.

Asphalt binder is the most common material used in road construction. However, the need for more durable and safer pavements requires a better understanding of asphalt's aging mechanisms and how its characteristics can be improved. The current challenge for the road industry is to use renewable materials (i.e., biomaterials not subjected to depletion) as a partial replacement for petroleum-based asphalt, which leads to reducing the carbon footprint. The most promising is to utilize biomaterials following the principles of sustainability in the modification of the asphalt binder. However, to understand whether the application of renewable materials represents a reliable and viable solution or just a research idea, this review covers various techniques for extracting bio-oil and preparing bio-modified asphalt binders, technical aspects including physical properties of different bio-oils, the impact of bio-oil addition on asphalt binder performance, and the compatibility of bio-oils with conventional binders. Key findings indicate that bio-oil can enhance modified asphalt binders' low-temperature performance and aging resistance. However, the effect on high-temperature performance varies based on the bio-oil source and preparation method. The paper concludes that while bio-oils show promise as renewable modifiers for asphalt binders, further research is needed to optimize their use and fully understand their long-term performance implications.

Research progress and future study on physicochemical, nutritional, and structural characteristics of canola and rapeseed feedstocks and co-products from bio-oil processing and nutrient modeling evaluation methods.

This article aims to review research progress and provide future study on physicochemical, nutritional, and molecular structural characteristics of canola and rapeseed feedstocks and co-products from bio-oil processing and nutrient modeling evaluation methods. The review includes Canola oil seed production, utilization and features; Rapeseed oil seed production and canola oil seed import in China; Bio-processing, co-products and conventional evaluation methods; Modeling methods for evaluation of truly absorbed protein supply from canola feedstock and co-products. The article provides our current research in feedstocks and co-products from bio-oil processing which include Characterization of chemical and nutrient profiles and ruminal degradation and intestinal digestion; Revealing intrinsic molecular structures and relationship between the molecular structure spectra features and nutrient supply from feedstocks and co-products using advanced vibrational molecular spectroscopy technique. The study focused on advanced vibrational molecular spectroscopy which can be used as a fast tool to study molecular structure features of feedstock and co-products from bio-oil processing. The article also provides future in depth study areas. This review provides an insight as how to use advanced vibrational molecular spectroscopy for in-depth analysis of the relationship between molecular structure spectral feature and nutrition delivery from canola feedstocks and co-products from bio-oil processing.

Breakdown of biomass for energy applications using microwave pyrolysis: A technological review.

The agricultural industry faces a permanent increase in waste generation, which is associated with the fast-growing population. Due to the environmental hazards, there is a paramount demand for generating electricity and value-added products from renewable sources. The selection of the conversion method is crucial to develop an eco-friendly, efficient and economically viable energy application. This manuscript investigates the influencing factors that affect the quality and yield of the biochar, bio-oil and biogas during the microwave pyrolysis process, evaluating the biomass nature and diverse combinations of operating conditions. The by-product yield depends on the intrinsic physicochemical properties of biomass. Feedstock with high lignin content is favourable for biochar production, and the breakdown of cellulose and hemicellulose leads to higher syngas formation. Biomass with high volatile matter concentration promotes the generation of bio-oil and biogas. The pyrolysis system's conditions of input power, microwave heating suspector, vacuum, reaction temperature, and the processing chamber geometry were influence factors for optimising the energy recovery. Increased input power and microwave susceptor addition lead to high heating rates, which were beneficial for biogas production, but the excess pyrolysis temperature induce a reduction of bio-oil yield.

Synthesis and characterization of barium doped CaO heterogeneous nanocatalyst for the production of biodiesel from Catharanthus roseus seeds: Kinetics, optimization and performance evaluation.

The exploitation of petroleum derivatives to meet the energy demands of the cutting edge is thought of as impractical because of asset shortage. The current necessitates that the world community improves future energy sources by developing sustainable, ecofriendly alternatives. In this work, biodiesel is produced through the transesterification of Catharanthus roseus seed oil with a barium-doped CaO heterogeneous nanocatalyst. The catalyst characterization is assessed using FTIR, GC-FID, EDAX, XRD, and SEM. The optimum conditions of time (70 min), temperature (58 °C), the molar ratio of methanol: oil is 15:1, and catalyst load (4% w/w) resulted in a conversion of the maximum biodiesel yield of 91.83%. Finally, by using Catharanthus roseus as a feedstock, the low optimal reaction conditions contribute to the development of the economic impact of biodiesel synthesis. Biodiesel blend (B20) containing barium-doped CaO nanoparticles showed better combustion engine performance and lower emissions than fossil fuels.

Pyrolysis of Mixed Date Stones and Pistachio Shells: Identification of Bio-Oil and Utilization of Bio-Char as Activated Carbon Precursor.

Thermal pyrolysis of mixed date stones and pistachio shells in a semi-batch reactor was addressed in this study. The highest yield of liquids (51.20 %) was produced at 500 °C, 90 min, 20 °C/min heating rate, and 50 mesh particle size. Under these conditions, yield of liquid from date stones and pistachio shells separately was 49.12 % and 47.67 %, respectively. The FT-IR results confirmed the presence of multiple oxygen-containing compounds in the bio-oil. Results from GC-MS declared that it was predominately composed of acids (57.57 %), esters (21.35 %), phenols (4.63 5), and alcohols (3.49 5). The obtained biochar was transformed into activated carbon (AC) by the optimized ZnCl2 activation method. The ideal AC was synthesized at 600 °C for 60 min using a 2 : 1 ZnCl2 : biochar impregnation ratio. FESEM and XRD measurements showed that the AC was amorphous. The prepared AC was effective in eliminating dibenzothiophene (DBT) from model fuel (200 ppm DBT/hexane) with a maximum performance 95.26 % at 40 °C for 1h using 0.35 g of the AC. The exhausted AC was regenerated and reutilized 4 times, and removal efficiency reached 88.23 % in the 4th cycle under ideal working conditions.

Study on the Wetting and Permeation Properties of Bio-Oil as Bitumen Rejuvenator.

In order to explore the diffusion and regeneration of bio-oil in aged bitumen, waste cooking oil (WCO), waste wood oil (WWO) and straw liquefied residue oil (SLRO) were selected in this paper. According to the surface wetting theory, the contact angle is obtained by combining laboratory experiments with molecular dynamics (MD) simulation, and the wetting parameters are calculated to evaluate the wetting behavior of bio-oil. The experimental phenomena of the wetting process and the main factors driving wetting are further analyzed. A permeation experiment is designed to obtain the permeation fusion layer (PFL). If the crossover modulus of PFLs changes compared with that of the aged bitumen, it is determined that the bio-oil penetrates the corresponding fusion layer. The results show that the motion of bio-oil included spreading and shrinking processes, and a precursor film played a pivotal role in the transportation of nanodroplets. Higher surface tension, lower viscosity and cohesion can effectively promote the wettability of bio-oil. A higher temperature and a longer permeation time are conducive to the permeation of bio-oil in aged bitumen. WCO with the strongest wettability has the weakest permeability, while WWO has superior permeability and can activate the macromolecules' surface activity, but its wettability is relatively weak. It is necessary to further modify WCO and WWO to be suitable rejuvenators.

Valorization of neem seeds biomass to biofuel via non-catalytic and catalytic pyrolysis process: Investigation of catalytic activity of Co-Mo/Al2O3 and Ni-Mo/Al2O3 for biofuel production.

Biofuel production from neem seeds have been evaluated via non-catalytic and catalytic pyrolysis process. Co-Mo/Al2O3 and Ni-Mo/Al2O3 industrial catalysts have been applied in upgrading process of pyrolysis oil to biofuel. The catalytic activity test revealed that these catalysts succeeded in converting fatty acids content of pyrolysis oil into low oxygen content compounds such as alcohols, alkanes, cyclic compounds, and esters via deoxygenation route. Enhancement of temperature and catalyst loading lead to increase of bio-gas production yield, significantly. The highest yield of pyrolysis oil (60.2%) was obtained at 450 °C, heating rate of 40 °C.min-1 via non-catalytic pyrolysis. Using 40% catalyst loading of Ni-Mo/Al2O3, the content of alcohol, cyclic and alkane compounds in the bio-oil were reached 12.65%, 21.74% and 15%, respectively. The highest selectivity using 40% catalyst loading of Co-Mo/Al2O3 catalyst at 450 °C was related to fatty acids (62.5%), esters (18.2%) and alkanes (6.25). It is inferred that the addition of Ni to Mo causes more progress of decarbonylation and decarboxylation reactions, and the addition of Co to Mo generates more ester compounds. Sensitivity analysis indicated that the effect of Ni-Mo/Al2O3 catalyst through catalytic pyrolysis process was more severe than Co-Mo/Al2O3 catalyst.

Sustainable treatment of sewage sludge via plasma-electrolytic liquefaction for bio-friendly production of polyurethane foam.

Safe and green disposal or utilization of sewage sludge (SS) has attracted significant attention as SS is increasingly produced worldwide and emerges as an environmental burden if without proper treatment. In this study, efficient and sustainable treatment of SS was achieved using plasma-electrolytic liquefaction (PEL) with alkaline catalysts including sodium hydroxide (NaOH), sodium carbonate (Na2CO3), and sodium acetate (NaAc) and renewable solvents including polyethylene glycol (PEG) 200 and glycerol. Furthermore, the obtained bio-oil with abundant hydroxyl groups could partially replace polyols derived from fossil energy to synthesize bio-based polyurethane foams (BPUFs) for oil adsorption. The results showed that the Na2CO3 catalyst exhibited better performance and yielded bio-oil with a higher heating value (HHV) of 26.26 MJ/kg, very low nitrogen content (0.14%) and metal ions, and a nearly neutral pH of 7.41, under the optimized conditions. Compared with conventional oil bath liquefaction, PEL can significantly improve the liquefaction efficiency, promote the transfer of metal ions in SS to the solid residue (SR), and facilitate the transfer of nitrogen to the gas phase and SR, thereby upgrading the bio-oil to a certain extent. The BPUFs showed excellent oil adsorption capacity, reusability, and desorption and can play an important role in combating oil spills. The PEL method may provide a green avenue for SS valorization and the comprehensive utilization of the obtained products.

A Review on Catalytic Fast Co-Pyrolysis Using Analytical Py-GC/MS.

Py-GC/MS combines pyrolysis with analytical tools of gas chromatography (GC) and mass spectrometry (MS) and is a quick and highly effective method to analyse the volatiles generated from small amounts of feeds. The review focuses on using zeolites and other catalysts in the fast co-pyrolysis of various feedstocks, including biomass wastes (plants and animals) and municipal waste materials, to improve the yield of specific volatile products. The utilisation of zeolite catalysts, including HZSM-5 and nMFI, results in a synergistic reduction of oxygen and an increase in the hydrocarbon content of pyrolysis products. The literature works also indicate HZSM-5 produced the most bio-oil and had the least coke deposition among the zeolites tested. Other catalysts, such as metals and metal oxides, and feedstocks that act as catalysts (self-catalysis), such as red mud and oil shale, are also discussed in the review. Combining catalysts, such as metal oxides and HZSM-5, further improves the yields of aromatics during co-pyrolysis. The review highlights the need for further research on the kinetics of the processes, optimisation of feed-to-catalyst ratios, and stability of catalysts and products.

Investigating the Effect of Operational Variables on the Yield, Characterization, and Properties of End-of-Life Olive Stone Biomass Pyrolysis Products.

In recent years, biomass has emerged as a promising raw material to produce various products, including hydrocarbons, platform chemicals, and fuels. However, a more comprehensive evaluation of the potential production of desirable value-added products and chemical intermediates is required. For these reasons, this study aimed to investigate the impact of various operating parameters on the pyrolysis of end-of-life olive stone, an agriculture and food industry waste, using a tubular quartz reactor operated at 773 K. The results revealed that the product compositions were comparable under batch or semi-batch nitrogen feeding conditions and with reaction times of 1 or 3 h. The product distribution and composition were significantly influenced by changes in the heating rate from 5 to 50 K min-1, while the effect of changing the biomass particle size from 0.3 to 5 mm was negligible in the semi-batch test. This work provides a comprehensive understanding of the relationship between pyrolysis operational parameters and obtained product distribution and composition. Moreover, the results confirmed the possible exploitation of end-of-life olive stone waste to produce high-added value compounds in the zero-waste strategy and biorefinery concept.

Hydrodeoxygenation of Oxygenates Derived from Biomass Pyrolysis Using Titanium Dioxide-Supported Cobalt Catalysts.

Bio-oil upgrading to produce biofuels and chemicals has become an attractive topic over the past decade. However, the design of cost- and performance-effective catalysts for commercial-scale production remains a challenge. Herein, commercial titania (TiO2) was used as the support of cobalt (Co)-based catalysts (Co/TiO2) due to its low cost, high availability, and practicability for commercialization in the future. The Co/TiO2 catalysts were made with two different forms of TiO2 (anatase [TiO2-A] and rutile [TiO2-R]) and comparatively evaluated in the hydrodeoxygenation (HDO) of 4-propylguaicol (4PG), a lignin-derived model compound. Both Co/TiO2 catalysts promoted the HDO of 4PG following a similar pathway, but the Co/TiO2-R catalyst exhibited a higher activity in the early stages of the reaction due to the formation of abundant Ti3+ species, as detected by X-ray photoelectron spectroscopy (XPS) and hydrogen-temperature programed reduction (H2-TPR) analyses. On the other hand, the Co/TiO2-A catalyst possessed a higher acidity that enhanced propylcyclohexane production at prolonged reaction times. In terms of reusability, the Co/TiO2-A catalyst showed a higher stability (less Co leaching) and reusability compared to Co/TiO2-R, as confirmed by transmission electron microscopy (TEM) and inductively coupled plasma optical emission spectroscopy (ICP-OES) analyses. The HDO of the real bio-oil derived from pyrolysis of Leucaena leucocephala revealed that the Co/TiO2-A catalyst could convert high oxygenated aromatics (methoxyphenols, dimethoxyphenols, and benzenediols) to phenols and enhanced the phenols content, hinting at its potential to produce green chemicals from bio-feedstock.

Hydrothermal liquefaction of sewage sludge anaerobic digestate for bio-oil production: Screening the effects of temperature, residence time and KOH catalyst.

Due to sewage sludge being an abundant biobased resource, and with the number of biogas plants utilizing sewage sludge increasing, digested sewage sludge (DSS) is a promising feedstock for producing bio-oil. This study uses DSS from a biogas plant to produce bio-oil in a hydrothermal liquefaction process adjusting time from 2 to 6 hours, temperature from 280 to 380°C and the presence of a base as a depolymerization agent and potential catalyst. High conversion yields are obtained, with the maximum of 58 wt% on a dry, ash free basis and an energy recovery of up to 94%. The oils contain compounds with a potential for utilization as biofuels and building blocks, especially fatty acids as biodiesel feedstock and biobased phenols, glycols and aliphatic alcohols.