Showing papers on "Pyrolysis published in 2014"

A review on pyrolysis of biomass constituents: Mechanisms and composition of the products obtained from the conversion of cellulose, hemicelluloses and lignin

Abstract: The conversion of biomass by thermochemical means is very promising for the substitution of fossil materials in many energy applications. Given the complexity of biomass the main challenge in its use is to obtain products with high yield and purity. For a better understanding of biomass thermochemical conversion, many authors have studied in TG analyzer or at bed scale the individual pyrolysis of its main constituents (i.e. cellulose, hemicelluloses and lignin). Based on these studies, this original work synthesizes the main steps of conversion and the composition of the products obtained from each constituent. Pyrolysis conversion can be described as the superposition of three main pathways (char formation, depolymerization and fragmentation) and secondary reactions. Lignin, which is composed of many benzene rings, gives the highest char yield and its depolymerization leads to various phenols. The depolymerization of the polysaccharides is a source of anhydro-saccharides and furan compounds. The fragmentation of the different constituents and the secondary reactions produce CO, CO2 and small chain compounds. For temperature higher than 500 °C, the residues obtained from the different constituents present a similar structure, which evolves towards a more condensed polyaromatic form by releasing CH4, CO and H2. As the aromatic rings and their substituent composition have a critical influence on the reactivity of pyrolysis products, a particular attention has been given to their formation. Some mechanisms are proposed to explain the formation of the main products. From the results of this study it is possible to predict the reactivity and energy content of the pyrolysis products and evaluate their potential use as biofuels in renewable applications.

Catalytic fast pyrolysis of lignocellulosic biomass

Abstract: Increasing energy demand, especially in the transportation sector, and soaring CO2 emissions necessitate the exploitation of renewable sources of energy. Despite the large variety of new energy carriers, liquid hydrocarbon still appears to be the most attractive and feasible form of transportation fuel taking into account the energy density, stability and existing infrastructure. Biomass is an abundant, renewable source of energy; however, utilizing it in a cost-effective way is still a substantial challenge. Lignocellulose is composed of three major biopolymers, namely cellulose, hemicellulose and lignin. Fast pyrolysis of biomass is recognized as an efficient and feasible process to selectively convert lignocellulose into a liquid fuel—bio-oil. However bio-oil from fast pyrolysis contains a large amount of oxygen, distributed in hundreds of oxygenates. These oxygenates are the cause of many negative properties, such as low heating value, high corrosiveness, high viscosity, and instability; they also greatly limit the application of bio-oil particularly as transportation fuel. Hydrocarbons derived from biomass are most attractive because of their high energy density and compatibility with the existing infrastructure. Thus, converting lignocellulose into transportation fuels via catalytic fast pyrolysis has attracted much attention. Many studies related to catalytic fast pyrolysis of biomass have been published. The main challenge of this process is the development of active and stable catalysts that can deal with a large variety of decomposition intermediates from lignocellulose. This review starts with the current understanding of the chemistry in fast pyrolysis of lignocellulose and focuses on the development of catalysts in catalytic fast pyrolysis. Recent progress in the experimental studies on catalytic fast pyrolysis of biomass is also summarized with the emphasis on bio-oil yields and quality.

Redox Properties of Plant Biomass-Derived Black Carbon (Biochar)

Abstract: Soils and sediments worldwide contain appreciable amounts of thermally altered organic matter (chars). Chars contain electroactive quinoid functional groups and polycondensed aromatic sheets that were recently shown to be of biogeochemical and envirotechnical relevance. However, so far no systematic investigation of the redox properties of chars formed under different pyrolysis conditions has been performed. Here, using mediated electrochemical analysis, we show that chars made from different feedstock and over a range of pyrolysis conditions are redox-active and reversibly accept and donate up to 2 mmol electrons per gram of char. The analysis of two thermosequences revealed that chars produced at intermediate to high heat treatment temperatures (HTTs) (400–700 °C) show the highest capacities to accept and donate electrons. Combined electrochemical, elemental, and spectroscopic analyses of the thermosequence chars provide evidence that the pool of redox-active moieties is dominated by electron-donating, ...

Biomass derived hard carbon used as a high performance anode material for sodium ion batteries

Abstract: A porous hard carbon material was synthesized by the simple pyrolysis of H3PO4-treated biomass, i.e., pomelo peels, at 700 °C in N2. The as-obtained hard carbon had a 3D connected porous structure and a large specific surface area of 1272 m2 g−1. XPS analysis showed that the carbon material was functionalized by O-containing and P-containing groups. The porous hard carbon was used as an anode for sodium ion batteries and exhibited good cycling stability and rate capability, delivering a capacity of 181 mA h g−1 at 200 mA g−1 after 220 cycles and retaining a capacity of 71 mA h g−1 at 5 A g−1. The sodium storage mechanisms of the porous hard carbon can be explained by Na+ intercalation into the disordered graphene layers, redox reaction of the surface O-containing functional groups and Na+ storage in the nanoscale pores. However, the porous hard carbon demonstrated a low coulombic efficiency of 27%, resulting from the formation of a solid electrolyte interphase film and the side reactions of surface phosphorus groups.

Physical and chemical characterization of biochars derived from different agricultural residues

Abstract: . Biochar is widely recognized as an efficient tool for carbon sequestration and soil fertility. The understanding of its chemical and physical properties, which are strongly related to the type of the initial material used and pyrolysis conditions, is crucial to identify the most suitable application of biochar in soil. A selection of organic wastes with different characteristics (e.g., rice husk (RH), rice straw (RS), wood chips of apple tree (Malus pumila) (AB), and oak tree (Quercus serrata) (OB)) were pyrolyzed at different temperatures (400, 500, 600, 700, and 800 °C) in order to optimize the physicochemical properties of biochar as a soil amendment. Low-temperature pyrolysis produced high biochar yields; in contrast, high-temperature pyrolysis led to biochars with a high C content, large surface area, and high adsorption characteristics. Biochar obtained at 600 °C leads to a high recalcitrant character, whereas that obtained at 400 °C retains volatile and easily labile compounds. The biochar obtained from rice materials (RH and RS) showed a high yield and unique chemical properties because of the incorporation of silica elements into its chemical structure. The biochar obtained from wood materials (AB and OB) showed high carbon content and a high absorption character.

Effects of feedstock and pyrolysis temperature on biochar adsorption of ammonium and nitrate.

Abstract: Biochar produced by pyrolysis of biomass can be used to counter nitrogen (N) pollution. The present study investigated the effects of feedstock and temperature on characteristics of biochars and their adsorption ability for ammonium N (NH4+-N) and nitrate N (NO3−-N). Twelve biochars were produced from wheat-straw (W-BC), corn-straw (C-BC) and peanut-shell (P-BC) at pyrolysis temperatures of 400, 500, 600 and 700°C. Biochar physical and chemical properties were determined and the biochars were used for N sorption experiments. The results showed that biochar yield and contents of N, hydrogen and oxygen decreased as pyrolysis temperature increased from 400°C to 700°C, whereas contents of ash, pH and carbon increased with greater pyrolysis temperature. All biochars could sorb substantial amounts of NH4+-N, and the sorption characteristics were well fitted to the Freundlich isotherm model. The ability of biochars to adsorb NH4+-N followed: C-BC>P-BC>W-BC, and the adsorption amount decreased with higher pyrolysis temperature. The ability of C-BC to sorb NH4+-N was the highest because it had the largest cation exchange capacity (CEC) among all biochars (e.g., C-BC400 with a CEC of 38.3 cmol kg−1 adsorbed 2.3 mg NH4+-N g−1 in solutions with 50 mg NH4+ L−1). Compared with NH4+-N, none of NO3−-N was adsorbed to biochars at different NO3− concentrations. Instead, some NO3−-N was even released from the biochar materials. We conclude that biochars can be used under conditions where NH4+-N (or NH3) pollution is a concern, but further research is needed in terms of applying biochars to reduce NO3−-N pollution.

Transformation, Morphology, and Dissolution of Silicon and Carbon in Rice Straw-Derived Biochars under Different Pyrolytic Temperatures

Abstract: Biochars are increasingly recognized as environmentally friendly and cheap remediation agents for soil pollution. The roles of silicon in biochars and interactions between silicon and carbon have been neglected in the literature to date, while the transformation, morphology, and dissolution of silicon in Si-rich biochars remain largely unaddressed. In this study, Si-rich biochars derived from rice straw were prepared under 150-700 °C (named RS150-RS700). The transformation and morphology of carbon and silicon in biochar particles were monitored by FTIR, XRD, and SEM-EDX. With increasing pyrolytic temperature, silicon accumulated, and its speciation changed from amorphous to crystalline matter, while the organic matter evolved from aliphatic to aromatic. For rice straw biomass containing amorphous carbon and amorphous silicon, dehydration (<250 °C) made silicic acid polymerize, resulting in a closer integration of carbon and silicon. At medium pyrolysis temperatures (250-350 °C), an intense cracking of carbon components occurred, and, thus, the silicon located in the inside tissue was exposed. At high pyrolysis temperatures (500-700 °C), the biochar became condensed due to the aromatization of carbon and crystallization of silicon. Correspondingly, the carbon release in water significantly decreased, while the silicon release somewhat decreased and then sharply increased with pyrolytic temperature. Along with SEM-EDX images of biochars before and after water washing, we proposed a structural relationship between carbon and silicon in biochars to explain the mutual protection between carbon and silicon under different pyrolysis temperatures, which contribute to the broader understanding of biochar chemistry and structure. The silicon dissolution kinetics suggests that high Si biochars could serve as a novel slow release source of biologically available Si in low Si agricultural soils.

Production of green aromatics and olefins by catalytic cracking of oxygenate compounds derived from biomass pyrolysis: A review

Abstract: The concern for depletion of fossil fuels and their growing environmental threats necessitates to develop efficient techniques for utilization of biomass as an alternative fuel source which is renewable and environmentally safe. Catalytic cracking of biomass pyrolysis derived feedstock could be an economical process for production of high value added chemicals which are currently obtained from fossil fuels. However, promotion of reaction selectivity toward valuable chemicals is a great challenge in this process. Coke formation in catalytic cracking of biomass pyrolysis vapors/bio-oil is a competing reaction with production of valuable hydrocarbons like aromatics and olefins. Coke is one major undesired product of this process which its high yield is due to low hydrogen to carbon effective ratio of biomass and in turn low hydrogen content in hydrocarbon pool inside catalyst. Catalytic cracking of biomass pyrolysis vapors/bio-oil is a highly shape selective reaction with strong dependency on catalyst acidity and reaction conditions. This paper, for the first time, reviews the effects of catalyst properties and reaction conditions on reaction selectivity toward aromatics and olefins in catalytic cracking of biomass pyrolysis vapors/bio-oil and bio-oil model compounds.

In-situ catalytic conversion of tar using rice husk char-supported nickel-iron catalysts for biomass pyrolysis/gasification

Abstract: This paper aims to propose an effective tar conversion approach during biomass pyrolysis via in-situ dry reforming over rice husk (RH) char and char-supported Ni-Fe catalysts. Utilizing high pyrolysis temperature, tar from biomass pyrolysis could be removed effectively in the gasifier by mixing with the char-supported catalysts, simplifying the follow-up tar removal process. Under the optimized conditions, the conversion efficiencies of condensable tar can reach about 92.3% and 93% using Ni-Fe char (without calcination) and Ni char (with calcination), respectively. It is noteworthy that the condensable tar could be catalytically transformed into the non-condensable tar or small molecule gases resulting in the heating value increase of gaseous products to benefit of the power generation systems. Compared with the other catalysts preparation methods, Ni–Fe char exhibited more advantages of convenient and energy-saving. In the presence of catalysts, the concentration of CO2 (vol.%) was reduced slightly, while the CO concentration (vol.%) increased greatly because of dry reforming. Due to carbon loss, parts of RH char-supported catalysts (C-SiO2 catalysts) could be converted into SiO2-based catalysts because of high-content amorphous nano-sized SiO2 in RH char. In addition, partial metal oxides or ions via carbon (i.e., biochar) and gas (i.e., H2, CO) in-situ reduction were transformed into metallic states contributing to the enhancement of tar conversion. Therefore, RH char plays two significant roles during the process of biomass pyrolysis. On one hand, it works as an intermediate reductant to reduce the metal oxides and CO2; on the other hand, it can be considered as an adsorptive-support to adsorb metal ions and tar. After that, the char-supported catalysts could be used for tar conversion. In particular, since the metal catalysts still remain in the solid residues, the pyrolysis char could be regenerated via thermal regeneration using waste heat or gasified into syngas directly.

Pyrolysis of Cellulose under Ammonia Leads to Nitrogen-Doped Nanoporous Carbon Generated through Methane Formation

Abstract: Here, we present a simple one-step fabrication methodology for nitrogen-doped (N-doped) nanoporous carbon membranes via annealing cellulose filter paper under NH3. We found that nitrogen doping (up to 10.3 at %) occurs during cellulose pyrolysis under NH3 at as low as 550 °C. At 700 °C or above, N-doped carbon further reacts with NH3, resulting in a large surface area (up to 1973.3 m2/g). We discovered that the doped nitrogen, in fact, plays an important role in the reaction, leading to carbon gasification. CH4 was experimentally detected by mass spectrometry as a product in the reaction between N-doped carbon and NH3. When compared to conventional activated carbon (1533.6 m2/g), the N-doped nanoporous carbon (1326.5 m2/g) exhibits more than double the unit area capacitance (90 vs 41 mF/m2).

Effects of Pore Structure on Performance of An Activated-Carbon Supercapacitor Electrode Recycled from Scrap Waste Tires

Abstract: It is important to address the challenges posed with the ever-increasing demand for energy supply and environmental sustainability. Activated carbon, which is the common material for commercial supercapacitor electrodes, is currently derived from petroleum-based precursors. This paper presents an effective synthetic method that utilizes waste tires as the precursor to prepare the activated carbon electrodes by the pyrolysis and chemical activation processes. Adjusting the activation parameters can tailor multiple physical properties of the resulting activated carbon, which in turns tunes the performance of the activated carbon electrode. Statistical multiple linear regression and stepwise regression methods are employed to investigate the dependence of the specific capacitance and the rate capability upon the physical properties (such as porosity) of the activated carbon electrode. The specific capacitance of activated carbon electrode is controlled by the micropore volume but independent of the mesopores...

Catalytic Conversion of Nonfood Woody Biomass Solids to Organic Liquids

Abstract: This Account outlines recent efforts in our laboratories addressing a fundamental challenge of sustainability chemistry, the effective utilization of biomass for production of chemicals and fuels. Efficient methods for converting renewable biomass solids to chemicals and liquid fuels would reduce society's dependence on nonrenewable petroleum resources while easing the atmospheric carbon dioxide burden. The major nonfood component of biomass is lignocellulose, a matrix of the biopolymers cellulose, hemicellulose, and lignin. New approaches are needed to effect facile conversion of lignocellulose solids to liquid fuels and to other chemical precursors without the formation of intractable side products and with sufficient specificity to give economically sustainable product streams. We have devised a novel catalytic system whereby the renewable feedstocks cellulose, organosolv lignin, and even lignocellulose composites such as sawdust are transformed into organic liquids. The reaction medium is supercritical methanol (sc-MeOH), while the catalyst is a copper-doped porous metal oxide (PMO) prepared from inexpensive, Earth-abundant starting materials. This transformation occurs in a single stage reactor operating at 300-320 °C and 160-220 bar. The reducing equivalents for these transformations are derived by the reforming of MeOH (to H2 and CO), which thereby serves as a "liquid syngas" in the present case. Water generated by deoxygenation processes is quickly removed by the water-gas shift reaction. The Cu-doped PMO serves multiple purposes, catalyzing substrate hydrogenolysis and hydrogenation as well as the methanol reforming and shift reactions. This one-pot "UCSB process" is quantitative, giving little or no biochar residual. Provided is an overview of these catalysis studies beginning with reactions of the model compound dihydrobenzofuran that help define the key processes occurring. The initial step is phenyl-ether bond hydrogenolysis, and this is followed by aromatic ring hydrogenation. The complete catalytic disassembly of the more complex organosolv lignin to monomeric units, largely propyl-cyclohexanol derivatives is then described. Operational indices based on (1)H NMR analysis are also presented that facilitate holistic evaluation of these product streams that within several hours consist largely of propyl-cyclohexanol derivatives. Lastly, we describe the application of this methodology with several types of wood (pine sawdust, etc.) and with cellulose fibers. The product distribution, albeit still complex, displays unprecedented selectivity toward the production of aliphatic alcohols and methylated derivatives thereof. These observations clearly indicate that the Cu-doped solid metal oxide catalyst combined with sc-MeOH is capable of breaking down the complex biomass derived substrates to markedly deoxygenated monomeric units with increased hydrogen content. Possible implementations of this promising system on a larger scale are discussed.

Catalytic fast pyrolysis of biomass with mesoporous ZSM-5 zeolites prepared by desilication with NaOH solutions

Abstract: This study investigated the effects of desilication of ZSM-5 zeolite on its catalytic properties in catalytic fast pyrolysis (CFP) of lignocellulosic biomass. A series of mesoporous ZSM-5 zeolites were prepared by desilication of a conventional microporous ZSM-5 zeolite with NaOH solutions of varying concentrations (0.1–0.5 M). The creation of mesopores improved the diffusion property of the desilicated ZSM-5 zeolites and their catalytic activity for cracking bulky oxygenates (e.g., syringols derived from the lignin component of biomass). Consequently, the desilicated zeolites produced more aromatic hydrocarbons (carbon yields of 26.2–30.2%) and less coke (39.9–41.2%) in CFP of beech wood than the parent microporous ZSM-5 (23.2% aromatics and 44.4% coke). The highest aromatic yield (30.2%) and lowest coke yield (39.9%) were obtained in CFP of beech wood with mildly desilicated zeolite treated with 0.3 M NaOH solution. However, desilication with a greater concentration, 0.5 M NaOH, decreased the aromatic yield to 26.2% due to a considerable loss of microporosity in the severely desilicated zeolite. The results indicate that carefully controlled desilication of zeolite can improve the conversion of lignocellulose to valuable aromatic hydrocarbons and decrease the formation of undesired coke, thus improving the product distribution in CFP of lignocellulose.