Converting Alkali Lignin to Biofuels over NiO/HZSM‐5 Catalysts Using a Two‐Stage Reactor

A series of NiO/HZSM‐5 catalysts were used to convert alkali lignin to hydrocarbon biofuels in a two‐stage catalytic pyrolysis system. The results indicated that all NiO/HZSM‐5 catalysts reduced the content of undesirable phenols, furans, and alcohols of the biofuel compared to non‐catalytic treatment. The NiO/HZSM‐5 catalyst with the lowest amount of NiO generated the highest biofuel yield in all catalytic treatments, and it also produced biofuel with the highest content of hydrocarbons. The emission of carbon oxides (CO and CO₂) increased in the treatments with higher‐NiO loading HZSM‐5 due to the redox reaction between NiO and the oxygenated compounds in the bio‐oil. Ni₂SiO₄ was generated in the used NiO/HZSM‐5 catalysts during the high‐temperature pyrolysis process.     

Study on the nitrogen transformation during the primary pyrolysis of sewage sludge by Py-GC/MS and Py-FTIR

The nitrogen transformation with attention to the intermediates and NO_x precursors has been investigated during the primary pyrolysis of sewage sludge by using Pyrolyzer-gas chromatography/mass spectrometry (Py-GC/MS) and Pyrolyzer-Fourier transform infrared spectrometry (Py-FTIR). A three-stage process of nitrogen transformation during the sewage sludge pyrolysis was suggested. The decomposition of labile protein and inorganic ammonium salt mainly occurred in the first stage (<300 °C), giving rise to a small amount of NH₃. In the second stage (300–600 °C), the macromolecular protein firstly cracked into small molecular amine compounds, and then went through deamination process, contributed to a large release of NH₃. In the third stage (600–900 °C), the amine compounds converted into nitriles, and generated a large amount of HCN, while the formation of NH₃ slowed down accordingly.     

Energy recovery from microalgal biomass via enhanced thermo-chemical process

This work showed that microalgae having low lipid content has high potential for energy recovery via thermo-chemical processes. As an example, Microcystis aeruginosa (M. aeruginosa) was considered and tested. Specifically, this work verified that the growth rate of M. aeruginosa was extremely fast compared to other microalgae (as a factor of ∼10). Moreover, this work investigated the CO₂ co-feed impact on thermo-chemical processes (pyrolysis/gasification) using M. aeruginosa. Introducing CO₂ in the thermo-chemical process as reaction media or feedstock can enhance the efficiency of thermo-chemical processes by expediting the cracking capability of condensable hydrocarbons (tar). The generation of CO was enhanced as a factor of ∼2. Further generation of H₂ could be achieved in the presence of CO₂. Thus, utilizing CO₂ as reaction media or chemical feedstock can modify the end products into environmentally benign and desirable ones. The CO₂ co-feed impact on thermo-chemical processes with lingo-cellulosic biomass can be universally applied.     

Kinetic modeling and simulation: Pyrolysis of Jatropha residue de-oiled cake

An improved kinetic model based on thermal decomposition of biomass constituents, i.e. cellulose, hemicellulose and lignin, is developed in the present study. The model considers the independent parallel reactions of order n producing volatiles and charcoal from each biomass constituent. While estimating the kinetic parameters, the order of degradation of biomass constituents is also checked and found to be matching with the order of degradation reported in the literature. The results of thermo-gravimetric analysis of Jatropha de-oiled cakes are used to find the kinetic parameters. The experimental runs are carried out using a thermo-gravimetric analyzer (TGA 4000, Perkin Elmer). TGA study is performed in a nitrogen atmosphere under non-isothermal conditions at different heating rates and the thermal decomposition profiles are used. The model is simulated using finite difference method to predict the pyrolysis rate. The corresponding parameters of the model are estimated by minimizing the square of the error between the model predicted values of residual weight fraction and the experimental data of thermogravimetry. The minimization of square of the error is performed using non-traditional optimization technique logarithmic differential evolution (LDE).     

Thermochemical processing of meat and bone meal: A review

Since the Bovine Spongiform Encephalopathy crisis, meat and bone meal (MBM) have been considered animal wastes. Nowadays, these animal residues are generally burnt in cement kilns and disposed of in landfills. However, several technologies are being developed in order to achieve energy valorisation of MBM by means of combustion, pyrolysis and gasification. These thermal treatments of MBM will reduce the environmental impact of landfill and, at the same time, take advantage of the MBM heating value (13-30 MJ/kg). The main results of research into combustion, pyrolysis and gasification of MBM show that the products could be used as fertilizer (solid product) and as fuel (gas and liquid products). The present work aims at reviewing the most significant studies about energy valorisation of MBM and the potential application of the products obtained in these thermochemical processes.     

An overview of empty fruit bunch from oil palm as feedstock for bio-oil production

Empty fruit bunch (EFB) from oil palm is one of the potential biomass to produce biofuels like bio-oil due to its abundant supply and favorable physicochemical characteristics. Confirming the assertion, this paper presents an overview of EFB as a feedstock for bio-oil production. The fundamental characteristics of EFB in terms of proximate analysis, ultimate analysis and chemical composition, as well as the recent advances in EFB conversion processes for bio-oil production like pyrolysis and solvolysis are outlined and discussed. A comparison of properties in terms of proximate analysis, ultimate analysis and fuel properties between the bio-oil from EFB and petroleum fuel oil is included. The major challenges and future prospects towards the utilization of EFB as a useful resource for bio-oil production are also addressed.     

Reduction of primary tar vapor from biomass by hot char particles in fixed bed gasification

This study investigated the reduction of primary tar vapor from biomass pyrolysis over a bed of hot char particles, focusing on the effect of different operating conditions and char properties. The char samples were prepared from wood, paddy straw, palm kernel shell, and activated carbon. The primary tar was produced from fir wood by pyrolysis at 500 °C and passed through a reactor filled with char particles with different lengths and temperatures.The tar cracking reactions became active above 700 °C, and the presence of hot char particles promoted more tar reduction compared with thermal cracking alone. The mass yield of the primary tar was reduced from 24.8% by pyrolysis to 13.7% by thermal cracking at 800 °C, and further to 7.7% by hot char particles in a reactor volume of 1.48 cm³/g_wood. In terms of carbon yield, these values correspond to 32.1%, 19.9% and 11.8%, respectively. The tar with smaller molecular weights was quickly decomposed to gases, whereas the heavy tar was resistant to cracking, even when the reactor volume was increased to 6.90 cm³/g_wood. The tar cracking behaviors were similar for four char types despite differences in microscopic surface areas, pore-size distributions, and inorganic contents. The results suggest that creating a tar-cracking zone using char particles situated between the pyrolysis and gasification zones could be helpful in converting the primary tar vapor in a downdraft fixed-bed gasifier, but the degree of conversion is not high enough to eliminate tar issues completely.     

Artisanal and controlled pyrolysis-based biochars differ in biochemical composition,thermal recalcitrance,and biodegradability in soil

Biochar composition and stability is under intense research. Yet the question remains to what extent the current state-of-the-art applies to artisanally charred biomass in tropical regions. We compared kiln and drum based biochars with their counterpart controlled (at 400 °C) slow pyrolysis biochars from coconut shells, rice husks and Palmyra nutshell for their biochemical composition, thermal stability and biodegradability in soil. Thermal behavior of individual organic constituents was quantified by pyrolysis-field ionization mass spectroscopy (Py-FIMS). Comparison of the mass spectra demonstrated higher abundances of either phenols, lignin and carbohydrate monomers or of lipids in the artisanally produced biochars. Hence, relatively more untransformed plant matter was preserved by artisanal charring and also the thermal stability of carbohydrates, alkylaromatics and N-containing compounds was lower for all three feedstocks. This indicates lower prevailing temperatures compared to controlled pyrolysis biochar, at least in parts of the biomass charring in the kilns or drum. Nine-weeks biochar derived C mineralization upon soil incorporation revealed a relatively lower biological stability of the controlled pyrolysis biochars. The proportion of detected ion intensity from thermolabile lower mass signals (<400 °C, m/z < 250) was negatively correlated to the net-biochar derived C mineralization. We hypothesize this fraction to be composite and act both as a C-substrate and at the same time to hold unidentified substances inhibiting microbial activity. Compared to controlled pyrolysis biochar, traditionally charred biomass, i.e. the ‘biochar’ most likely to be actually applied to soil in developing countries, has a heterogeneous thermal and biochemical composition and unpredictable biological stability.     

Partikelform und Porosität von biogenen Pyrolysekoksen

Char particles from pyrolyzed biomass vary in particle size and shape. On average, the particles are more elongated the larger their size. The average size‐specific elongation is almost alike for all investigated samples, i.e. independent from their source material and process. The particle collectives cannot be characterized accurately with classical particle size distributions, which assume spherical particle shape. Accounting for their shape, they can be described more accurately with particle size distributions that are based on an ellipsoid model. The high bulk porosity is mainly attributed to the spaces between particles.     

Mechanical,structural and oxidation resistance enhancement of carbon foam by in situ grown SiC nanowires

A method for processing carbon foams containing both silicon carbide (SiC) nanowires and bulk SiC and silicon nitride (Si3N4) phases has been developed by reaction of powder mixtures containing precursors for carbon, sacrificial template, silicon (Si), short carbon fibers (SCF) and activated carbon (AC). In situ growth of Si nanowires during pyrolysis of the foam at 1000 °C under N2 changed the foam׳s microstructure by covering the porous skeleton inside and out. In situ-grown SiC nanowires were found smoothly curved with diameters ranging around two main modes at 30 and 500 nm while their lengths were up to several tens of micrometers. SCF were found effectively mixed and well-bonded to pore walls. Following density, porosity and pore size distribution analyses, the heat-treated (HT) foam was densified using a chemical vapor infiltration (CVI) process. Thereafter, density increased from 0.62 to 1.30 g/cm³ while flexural strength increased from 29.3 to 49.1 MPa. The latter increase was attributed to the densification process as well as to low surface defects, presence of SCF and coating, by SiC nanowires, of the entire SiC matrix porous structure. The foam׳s oxidation resistance improved significantly from 58 to 84 wt% residual mass of the heat treated and densified sample. The growth mechanism of Si nanowires was supported by the vapor–liquid–solid mechanism developed under pyrolysis conditions of novolac and reducing environment of coal cover.