Mussel-inspired polydopamine-modified biochar microsphere for reinforcing polylactic acid composite films: Emphasizing the achievement of excellent thermal and mechanical properties.

Having poor interfacial compatibility between biochar microsphere (BM) and polylactic acid (PLA) should be responsible for the unbalance of composite film strength and toughness. Elucidating the effect of polydopamine (PDA) on BM and BM/PLA composite films is the ultimate goal of this study based on the mussel bionic principle. It was found that the strong adhesion of PDA on the BM surface was achieved, which improved the surface roughness and thermal stability. Also, PDA modification can facilitate crystallization, increase thermal properties, improve interfacial compatibility, and enhance the tensile properties of BM/PLA composite films. Silane-based PDA modified BM/PLA composite film exhibited the best tensile strength, tensile modulus, and elongation at break with 77.95 MPa, 1.87 GPa, and 7.30%. These noteworthy findings, achieving a simultaneous improvement in PLA strength and toughness, hold promising implications for its sustainability.

Catalytic upcycling of waste plastics over nanocellulose derived biochar catalyst for the coupling harvest of hydrogen and liquid fuels.

A powerful simple biochar catalyst derived from nanocellulose was applied to the catalytic upcycling of waste plastics into H2 and liquid fuels for the first time. For the results from model low-density polyethylene (LDPE) pyrolysis, the C8-C16 aliphatics and monocyclic aromatics were dominant constitutes of the liquid product with the yields ranging from 22 to 68 wt%. At the temperature of 500 °C and biochar to LDPE ratio surpassing 3, the LDPE could be completely degraded into liquid and gas without wax production. A wax yield of 16 wt% was observed at the temperature of 450 °C and biochar to LDPE ratio of 4, which was dramatically lower than that (77 wt%) from the absence of biochar at the temperature of 500 °C. Up to 92 vol% of H2 was detected in the gaseous product with a yield of 36 wt%. The lower temperatures and higher biochar to LDPE ratios favored increasing the generation of H2 at the expense of light gas CnHm especially CH4. Moreover, this biochar catalyst was tested effectively to convert the real waste plastics including grocery bags and packaging tray into valuable liquid and H2-enriched gas.

One-step synthesis of biomass-based sulfonated carbon catalyst by direct carbonization-sulfonation for organosolv delignification.

Biomass-based sulfonated carbon catalyst (SCC) was prepared from corncob via direct sulfuric acid carbonization-sulfonation treatment. Central composite design was used to evaluate temperature and time for optimizing SCC yield and sulfonic acid (SO3H) density. The SO3H groups were successfully introduced to the SCC as evidenced by FTIR and sulfur analysis. Numerical optimization results showed that 100 °C and 5.78 h are the optimal conditions for maximizing yield (61.24%) and SO3H density (1.1408 mmol/g). The highest ethanol organosolv lignin (EOL) yield of 63.56% with a substrate yield of 39.08% was achieved at 20% SCC loading in the ethanol organosolv delignification of lignocellulosic biomass. The FTIR spectra of the isolated lignin revealed typical features of G-lignin, indicating that no drastic changes took place in the lignin structure during the process. This study developed a simple one-step preparation method of SCC, which was successfully used as a catalyst in an organosolv delignification of biomass.

Synthesis and characterization of sulfonated activated carbon as a catalyst for bio-jet fuel production from biomass and waste plastics.

Sulfonated activated carbon-based catalysts were prepared by microwaved-assisted carbonization of phosphoric acid activated corncob followed by sulfonation using concentrated sulfuric acid. Sulfonation at different temperatures and times resulted in varied SO3H group density of the SAC catalysts. Sulfonation temperature showed a significant effect on the introduction of SO3H on the AC precursor while time had minor role. The SAC catalysts were characterized by means of N2 sorption analysis (specific surface area, pore-volume, average pore width), FTIR spectroscopy, SEM imaging, and sulfur analysis. The impact of catalysts SO3H density on the product distribution and bio-oil composition from the catalytic co-pyrolysis of Douglas fir and LDPE was evaluated. The highest bio-jet fuels (aromatics and C9-16 alkanes) obtained was 97.51% using the SAC catalyst sulfonated at 100 °C for 5 h. Results showed that SAC has great potential as catalyst in the co-pyrolysis of biomass and plastics for the production of jet-fuel range hydrocarbons.

Microwave-assisted synthesis of bifunctional magnetic solid acid for hydrolyzing cellulose to prepare nanocellulose.

The conventional studies on the preparation of nanocellulose used a high concentration of sulfuric acid that is difficult to remove and recover. A biochar-based solid acid with magnetic properties was developed to hydrolyze cellulose to prepare nanocellulose in this work. Two different methods were selected to investigate the properties of the synthesized magnetic carbon-based solid acids. The synthesized catalysts were characterized by SEM, TEM, XRD, NH3-TPD and FT-IR. The experimental results showed that two solid acids by the microwave-assisted synthesis had good magnetic properties by a magnet adsorption. Analysis by SEM and TEM showed that the two solid acids had rich pore structures. According to mineral element analysis, both solid acids contained high sulfur content. The solid acid was an amorphous carbon structural material with a surface rich in active groups. The catalytic activity of the biochar-based solid acids in cellulose hydrolysis to prepare nano-scale cellulosic material was evaluated. It was found that magnetic biochar-based solid acid (MBC-SA1) could achieve a high yield, which produced up to 57.68% for hydrolyzing cellulose into nanometers.

Properties evaluation of biochar/high-density polyethylene composites: Emphasizing the porous structure of biochar by activation.

Activated biochars (AB-0.5, AB-1, AB-1.5, AB-2) prepared under different concentrations of an activating agent were used to manufacturing composites (ABHC-0.5, ABHC-1, ABHC-1.5, ABHC-2) based on high-density polyethylene (HDPE) by compounding and injection molding. Thermal and mechanical properties of the composites were characterized and analyzed. The addition of activated biochars improved the thermal properties of HDPE shown by Differential scanning calorimetry and Thermogravimetric analysis. Additionally, ABHC-0.5 exhibited the best flexural strength (38.66 MPa), flexural modulus (2.46 GPa), tensile strength (32.17 MPa), tensile modulus (1.95 GPa), rigidity, elasticity, creep resistance, and anti-stress relaxation ability due to the best porous structure of AB-0.5. A decrease of mechanical properties was observed in ABHC-1, ABHC-1.5, ABHC-2 compared to ABHC-0.5, which was due to the fact that the porous structure was damaged by an excessive activating agent. The results of this study provided a predictive insight in view of optimizing process parameters and establishing the meaningful relationship between biochar porous structure and its resulting composites.

Production of high-density polyethylene biocomposites from rice husk biochar: Effects of varying pyrolysis temperature.

The novelty of this study is to explore the effect of temperature varied biochar on the properties of biochar/polymers composites. Rice husk biochar (RB) samples were prepared at different pyrolysis temperatures and injection molding was used to prepare RB/high-density polyethylene (HDPE) composites. Additionally, ultimate analysis, X-ray diffraction (XRD), Fourier transform infrared spectroscopy (FTIR), scanning electron microscope (SEM), pore structure characteristics, differential scanning calorimetry (DSC), thermogravimetric analysis (TGA), tensile properties, and dynamic mechanical analysis (DMA) were used to characterize these RB and RB/HDPE composites samples. The results validated that RB obtained at 600 °C showed the highest carbon content, the most complete pore structure, and the largest specific surface area. Moreover, the thermal studies revealed that the addition of RB improved the thermal stability of HDPE. The best tensile strength (26.25 MPa) and Young's modulus (1.87 GPa) were obtained in 500 °C RB/HDPE composites and 600 °C RB/HDPE composites due to their good physical/mechanical interlocking structures shown in SEM. DMA revealed that the stiffness, elasticity, creep resistance and stress relaxation of the composites were improved by the addition of RB. The utilization of temperature varied biochars in biocomposites is important to manage wastes and optimize the properties of biocomposites in terms of reducing production cost and ensuring environmental safety.

Renewable jet-fuel range hydrocarbons production from co-pyrolysis of lignin and soapstock with the activated carbon catalyst.

The current study aims to investigate the effects of agricultural waste-derived activated carbon catalyst on the jet-fuel range hydrocarbons distribution from raw biomass pyrolysis under the hydrogen donor condition provided by a solid waste. Ex-situ catalytic fast co-pyrolysis of lignin with and without soapstock was carried out using the corn stover-derived activated carbon catalyst in a facile fixed bed reactor. Results showed that the soapstock, as the hydrogen donor, exhibited a positive synergistic effect with lignin on enhancing the production of valuable aromatics in the obtained bio-oil. Additionally, biomass-derived activated carbon catalyst has the robust catalytic ability to convert pyrolysis vapors into high-density jet fuel-ranged aromatic hydrocarbons rather than phenols with the assistance of soapstock solid waste. Results indicated that the proportions of jet-fuel range aromatics increased monotonically with elevating pyrolytic temperatures from 400 to 550 °C, and the optimal lignin/soapstock ratio was 1:2 with regarding the yield of attained bio-oils. The maximum proportion of jet-fuel ranged aromatics (87.8%) and H2 concentration (76.4 vol%) could be achieved with the pyrolytic temperature, lignin/soapstock ratio, and catalyst/feedstock ratio of 550 °C, 2:1, and 1:1, respectively. The current study may provide a novel route of converting solid wastes into value-added jet fuels and hydrogen-enriched fuel gases, which will advance the utilization of renewable biomass.

Microwave-assisted co-pyrolysis of pretreated lignin and soapstock for upgrading liquid oil: Effect of pretreatment parameters on pyrolysis behavior.

The co-pyrolysis of pretreated lignin and soapstock was carried out to upgrade vapors under microwave irradiation. Results showed that the yield of 29.92-42.21 wt% of upgraded liquid oil was achieved under varied pretreatment conditions. Char yield decreased from 32.44 wt% for untreated control to 24.35 wt% for the 150 °C pretreated samples. The increased temperature, irradiation time and acid concentration were conducive to decrease the relative contents of phenols and oxygenates in liquid oils. The main components of the liquid oil were gasoline fraction (mono-aromatics and C5-C12 aliphatics), which ranged from 57.38 to 71.98% under various pretreatment conditions. Meanwhile, the diesel fraction (C12+ aliphatics) ranged from 13.16 to 22.62% from co-pyrolysis of pretreated lignin and soapstock, comparing with 10.18% of C12+ aliphatics from co-pyrolysis of non-pretreated lignin and soapstock. A possible mechanism was proposed for co-pyrolysis of pretreated lignin and soapstock for upgraded liquid oils.

Improving hydrocarbon yield via catalytic fast co-pyrolysis of biomass and plastic over ceria and HZSM-5: An analytical pyrolyzer analysis.

The excessive oxygen content in biomass obstructs the production of high-quality bio-oils. In this work, we developed a tandem catalytic bed (TCB) of CeO2 and HZSM-5 in an analytical pyrolyzer to enhance the hydrocarbon production from co-pyrolysis of corn stover (CS) and LDPE. Results indicated that CeO2 could remove oxygen from acids, aldehydes and methoxy phenols, producing a maximum yield of hydrocarbons of 85% and highest selectivity of monocyclic aromatics of 73% in the TCB. The addition of LDPE exhibited a near-complete elimination of oxygenates, leaving hydrocarbons as the overwhelming products. With increasing LDPE proportion, the yield of aliphatics and the selectivity of BTX kept increasing. An optimum H/Ceff of 0.7 was superior to that reported in literature. Mechanisms consisting of deoxygenation, Diels-Alder reactions, hydrocarbon pool and hydrogen transfer reactions were discussed extensively. Our findings provide an efficient method to produce high-quality biofuels from renewable biomass resources.

A review of catalytic microwave pyrolysis of lignocellulosic biomass for value-added fuel and chemicals.

Lignocellulosic biomass is an abundant renewable resource and can be efficiently converted into bio-energy by a bio-refinery. From the various techniques available for biomass thermo-chemical conversion; microwave assisted pyrolysis (MAP) seems to be the very promising. The principles of microwave technology were reviewed and the parameters for the efficient production of bio-oil using microwave technology were summarized. Microwave technology by itself cannot efficiently produce high quality bio-oil products, catalysts are used to improve the reaction conditions and selectivity for valued products during MAP. The catalysts used to optimize MAP are revised in the development of this article. The origins for bio-oils that are phenol rich or hydrocarbon rich are reviewed and their experimental results were summarized. The kinetics of MAP is discussed briefly in the development of the article. Future prospects and scientific development of MAP are also considered in the development of this article.

Bio-oil from fast pyrolysis of lignin: Effects of process and upgrading parameters.

Effects of process parameters on the yield and chemical profile of bio-oil from fast pyrolysis of lignin and the processes for lignin-derived bio-oil upgrading were reviewed. Various process parameters including pyrolysis temperature, reactor types, lignin characteristics, residence time, and feeding rate were discussed and the optimal parameter conditions for improved bio-oil yield and quality were concluded. In terms of lignin-derived bio-oil upgrading, three routes including pretreatment of lignin, catalytic upgrading, and co-pyrolysis of hydrogen-rich materials have been investigated. Zeolite cracking and hydrodeoxygenation (HDO) treatment are two main methods for catalytic upgrading of lignin-derived bio-oil. Factors affecting zeolite activity and the main zeolite catalytic mechanisms for lignin conversion were analyzed. Noble metal-based catalysts and metal sulfide catalysts are normally used as the HDO catalysts and the conversion mechanisms associated with a series of reactions have been proposed.

Thermal behavior and kinetic study for catalytic co-pyrolysis of biomass with plastics.

The present study aims to investigate the thermal decomposition behaviors and kinetics of biomass (cellulose/Douglas fir sawdust) and plastics (LDPE) in a non-catalytic and catalytic co-pyrolysis over ZSM-5 catalyst by using a thermogravimetric analyzer (TGA). It was found that there was a positive synergistic interaction between biomass and plastics according to the difference of weight loss (ΔW), which could decrease the formation of solid residue at the end of the experiment. The first order reaction model well fitted for both non-catalytic and catalytic co-pyrolysis of biomass with plastics. The activation energy (E) of Cellulose-LDPE-Catalyst and DF-LDPE-Catalyst are only 89.51 and 54.51kJ/mol, respectively. The kinetics analysis showed that adding catalyst doesn't change the decomposition mechanism. As a result, the kinetic study on catalytic co-pyrolysis of biomass with plastics was suggested that the catalytic co-pyrolysis is a promising technique that can significantly reduce the energy input.

Optimizing carbon efficiency of jet fuel range alkanes from cellulose co-fed with polyethylene via catalytically combined processes.

Enhanced carbon yields of renewable alkanes for jet fuels were obtained through the catalytic microwave-induced co-pyrolysis and hydrogenation process. The well-promoted ZSM-5 catalyst had high selectivity toward C8-C16 aromatic hydrocarbons. The raw organics with improved carbon yield (∼44%) were more principally lumped in the jet fuel range at the catalytic temperature of 375°C with the LDPE to cellulose (representing waste plastics to lignocellulose) mass ratio of 0.75. It was also observed that the four species of raw organics from the catalytic microwave co-pyrolysis were almost completely converted into saturated hydrocarbons; the hydrogenation process was conducted in the n-heptane medium by using home-made Raney Ni catalyst under a low-severity condition. The overall carbon yield (with regards to co-reactants of cellulose and LDPE) of hydrogenated organics that mostly match jet fuels was sustainably enhanced to above 39%. Meanwhile, ∼90% selectivity toward jet fuel range alkanes was attained.

Bio-based phenols and fuel production from catalytic microwave pyrolysis of lignin by activated carbons.

The aim of this study is to explore catalytic microwave pyrolysis of lignin for renewable phenols and fuels using activated carbon (AC) as a catalyst. A central composite experimental design (CCD) was used to optimize the reaction condition. The effects of reaction temperature and weight hourly space velocity (WHSV, h(-1)) on product yields were investigated. GC/MS analysis showed that the main chemical compounds of bio-oils were phenols, guaiacols, hydrocarbons and esters, most of which were ranged from 71% to 87% of the bio-oils depending on different reaction conditions. Bio-oils with high concentrations of phenol (45% in the bio-oil) were obtained. The calorific value analysis revealed that the high heating values (HHV) of the lignin-derived biochars were from 20.4 to 24.5 MJ/kg in comparison with raw lignin (19 MJ/kg). The reaction mechanism of this process was analyzed.

Catalyzed modified clean fractionation of switchgrass.

Switchgrass was used as a lignocellulosic feedstock for second generation ethanol production, after pretreatment using sulfuric acid-catalyzed modified clean fractionation based on NREL's (National Renewable Energy Laboratory) original procedure. Optimization of temperature, catalyst concentration and solvent composition was performed using Response Surface Methodology, and 59.03 ± 7.01% lignin recovery, 84.85 ± 1.34% glucose, and 44.11 ± 3.44% aqueous fraction xylose yields were obtained at 140.00 °C, 0.46% w/w catalyst concentration, 36.71% w/w ethyl acetate concentration, and 25.00% w/w ethanol concentration. The cellulose fraction did not inhibit the fermentation performance of Saccharomyces cerevisiae and resulted in an ethanol yield of 89.60 ± 2.1%.

Catalytic pyrolysis of microalgae and their three major components: carbohydrates, proteins, and lipids.

To better understand the pyrolysis of microalgae, the different roles of three major components (carbohydrates, proteins, and lipids) were investigated on a pyroprobe. Cellulose, egg whites, and canola oil were employed as the model compounds of the three components, respectively. Non-catalytic pyrolysis was used to identify and quantify some major products and several reaction pathways were proposed for the pyrolysis of each model compound. Catalytic pyrolysis was then carried out with HZSM-5 for the production of aromatic hydrocarbons at different temperatures and catalyst to feed ratios. The aromatic yields of all feedstocks were significantly improved when the catalyst to biomass ratio increased from 1:1 to 5:1. Egg whites had the lowest aromatic yield among the model compounds under all reaction conditions, which suggests that proteins can hardly be converted to aromatics with HZSM-5. Lipids, although only accounted for 12.33% of Chlorella, contributed about 40% of aromatic production from algal biomass.

Production of phenols and biofuels by catalytic microwave pyrolysis of lignocellulosic biomass.

Catalytic microwave pyrolysis of biomass using activated carbon (AC) was investigated to determine the effects of pyrolytic conditions on the yields of phenol and phenolics. Bio-oils with high concentrations of phenol (38.9%) and phenolics (66.9%) were obtained. These levels were higher than those obtained by pyrolysis without AC addition and were closely related to the decomposition of lignin. A high concentration of esters (42.2% in the upgraded bio-oil) was obtained in the presence of Zn powder as catalyst and formic acid/ethanol as reaction medium. Most of the esters identified by GC-MS were long chain fatty acid esters. The high content of phenols and esters obtained in this study can be used as partial replacement of petroleum fuels after separation of oxygenates or as feedstock for organic syntheses in the chemical industry after purification.

Comparative study of organosolv lignin extracted from prairie cordgrass, switchgrass and corn stover.

Lignin extracted from prairie cordgrass, switchgrass, and corn stover (using ethyl acetate-ethanol-water organosolv pretreatment) was analyzed and characterized using several methods. These methods included analysis of purity (by determination of Klason lignin, carbohydrate, and ash contents), solubility (with several organic solvents), phenolic group analysis (ultraviolet ionization difference spectra, and nitrobenzene oxidation), and general functional group analysis (by (1)H NMR). Results showed that all the examined lignin samples were relatively pure (contained over 50% Klason lignin, less than 5% carbohydrate contamination, and less than 3% ash), but switchgrass-derived lignin was observed to be the purest. All the lignins were found to contain high amounts of phenolic groups, while switchgrass-derived lignin was the most phenolic, according to the ionization difference spectra. Nitrobenzene oxidation revealed that all the lignin samples contained available guaiacyl units in high amounts.