Characterization of free radicals by electron spin resonance spectroscopy in biochars from pyrolysis at high heating rates and at high temperatures

The concentration and type of free radicals from the decay (termination stage) of pyrolysis at slow and fast heating rates and at high temperatures (above 1000°C) in biomass char have been studied. A room-temperature electron spin resonance spectroscopy study was conducted on original wood, herbaceous biomass, holocelluloses, lignin and their chars, prepared at high temperatures in a wire mesh reactor, an entrained flow reactor, and a tubular reactor. The radical concentrations in the chars from the decay stage range up between 7·10¹⁶ and 1.5·10¹⁸ spins g⁻¹. The results indicated that the biomass major constituents (cellulose, hemicellulose, lignin) had a minor effect on remaining radical concentrations compared to potassium and silica contents. The higher radical concentrations in the wheat straw chars from the decay stage of pyrolysis in the entrained flow reactor compared to the wood chars were related to the decreased mobility of potassium in the char matrix, leading to the less efficient catalytic effects of potassium on the bond-breaking and radical re-attachments. The high Si levels in the rice husk caused an increase in the char radical concentration compared to the wheat straw because the free radicals were trapped in a char consisting of a molten amorphous silica at heating rates of 10³–10⁴ K s⁻¹. The experimental electron spin resonance spectroscopy spectra were analyzed by fitting to simulated data in order to identify radical types, based on g-values and line widths. The results show that at high temperatures, mostly aliphatic radicals (g = 2.0026–2.0028) and PAH radicals (g = 2.0027–2.0031) were formed.     

Effect of compressive load and particle size on compression characteristics of selected varieties of wheat straw grinds

In this study, the effect of compressive load and particle size on compression characteristics of four varieties (Strongfield, Blackbird, DT773 and DT818) of wheat straw grown at two different fields was investigated. Particle size, bulk and particle densities of all wheat straw samples were determined after grinding. Ground wheat straw samples were densified in a cylindrical die at 90 °C using an Instron testing machine. The wheat straw samples with 9% moisture content were compressed at five levels of compressive pressures (31.6, 63.2, 94.7, 126.4 and 138.9 MPa) and two levels of particle sizes (1.6 and 3.2 mm). Dimensions and mass of all compressed samples were measured to calculate the pellet density. The specific energy required to compress and eject the pellets was calculated from force-displacement data. Applied compressive force and particle size significantly affected the pellet density of wheat straw samples. The pellet density was in the range of 699–1064 kg m⁻³ increasing with pressure and particle size. The total specific energy required for compression and ejection of pellets varied from 4.35 to 33.64 MJ t⁻¹ that increased with compressive load and particle size. Higher compressive forces and particle size increased the durability of pellets to more than 95%. Blackbird variety was the most compressible of the four varieties of wheat straw.     

Physicochemical structure characteristics and intrinsic reactivity of demineralized coal char rapidly pyrolyzed at elevated pressure

This study aims to investigate the effect of pyrolysis pressure on the physical and chemical structure characteristics and reactivity of subbituminous demineralized coal char. The pyrolysis experiments were studied under different pressures using a pressurized drop tube reactor (PDTR). Structural properties of coal chars were investigated by the application of scanning electron microscopy (SEM), nitrogen adsorption analyzer, automatic mercury porosimeter, and Raman spectroscopy, respectively. The Random Pore Model was used to determine kinetic parameters and intrinsic reactivity of chars. The specific pore volume of chars pyrolyzed at 900–1000 °C increased first and then decreased with pyrolysis pressure increasing, and the maximum value of the specific pore volume of chars occurred at 1.0 MPa. The degree of graphitization of chars deepened with the increase of temperature or pressure. Intrinsic activation energy of char-O₂ was within the range of 126–134 kJ/mol. The intrinsic reactivity of char-O₂ reaction showed strong correlation the Raman parameters with the change of pyrolysis conditions, and it suggested that the intrinsic reactivity of char-O₂ reaction was mainly affected by aromatic ring structures rather than pore structures.     

A direct carbon solid oxide fuel cell fueled with char from wheat straw

Direct carbon solid oxide fuel cell (DC‐SOFC) is a promising technology for electricity generation from biomass with high conversion efficiency and low pollution. Biochar derived from wheat straw is utilized as the fuel of a DC‐SOFC, with cermet of silver and gadolinium‐doped ceria as the material of both cathode and anode and yttrium stabilized zirconia as electrolyte. The output performance of a DC‐SOFC operated on pure wheat straw is 197 mW cm^?2 at 800°C and increases to 258 mW cm^?2 when 5% of Ca, as a catalyst of the Boudouard reaction, is loaded on the wheat straw char. Higher power and fuel conversion utilization are achieved by using Ca as the Boudouard reaction catalyst. X‐ray diffraction, scanning electron microscopy, energy‐dispersive spectrometer, and programmed‐temperature gravimetric experiment are applied to characterize the leaf char. It turns out that the wheat straw char is with porous structure and composed of C, K, Mg, Cl, Fe, and Ca elements. The effects of the Ca catalyst on the Boudouard reaction, the performance of the DC‐SOFCs operated on the wheat straw char, and the economic advantages of the wheat straw char are demonstrated and analyzed in detail.     

Kinetics of rice husk char gasification in an H2O or a CO2 atmosphere

Rice husk gasification has been attracting increasing attention in rice-producing countries, but the technology has not yet achieved optimal efficiency. Only a few studies have reported on the gasification kinetics of rice husk char, and the influence of some important parameters has not yet been investigated. This paper provides an experimental database and kinetic models of gasification of a rice husk char particle in an H₂O or a CO₂ atmosphere. A complete parametric study of rice husk char gasification was performed in a wide range of operating conditions, relevant to those that exist in industrial gasifiers. Two kinetic models were developed to predict the conversion of a particle, taking into account changes in the reactive surface. Results of this study could help researchers and engineers in the design, modeling or optimization of a new efficient rice husk gasifier.     

Potential of bio-hydrogen production from dark fermentation of crop residues: A review

This study provided an estimate of the potential of bio-hydrogen production from dark fermentation of crop residues on a worldwide scale. The different crop residues reviewed included sugarcane tops, leaves and bagasse, corn straw, corn cob and corn stover, wheat straw, rice straw and husk, soybean straw, oil palm trunk and empty fruit bunch, sugar beet pulp, cassava residue, barley straw and sweet sorghum bagasse. Among these crop residues, wheat and rice straws are produced in the highest amount although sugarcane dominates crop production on a worldwide scale. Based on the bio-hydrogen yields reported in literature, estimated worldwide bio-hydrogen potential is highest for untreated rice straw at 58,002 Mm³/year followed by untreated wheat straw at 34,680 Mm³/year. This corresponds to a bio-energy potential of 623 PJ/year and 373 PJ/year for raw rice straw and wheat straw respectively while pre-treatment of the crop residues significantly increases the bio-hydrogen and bio-energy potential. While dark fermentation of crop residues offers a huge bio-energy potential, the process suffers from several constraints that hinder its implementation. As such, coupling of the dark fermentation process with the anaerobic digestion process as a two-stage process seems the most economically viable option for large-scale implementation.     

Influence of pyrolysis pressure on structure and combustion reactivity of Zhundong demineralized coal char

The investigation on evolution of coal char structure during pressurized pyrolysis can reveal the combustion reactivity of coal char in thermal utilization at elevated pressure. In this study, Zhundong subbituminous coal was demineralized and a pressurized drop tube reactor (PDTR) was used to prepare coal char under different temperature and pressure conditions. The physicochemical structures of raw and demineralized coal chars were characterized by the application of nitrogen adsorption analyzer, automatic mercury porosimeter, and Fourier transform infrared spectroscopy (FTIR). The change mechanism of char infrared structure with pyrolysis pressure is revealed on the molecular level in this paper. The results show that the N₂ adsorption quantity of raw coal char increases with the increase of pyrolysis temperature, while that of demineralized coal char decreases. Because of the difference in molecular volume and steric hindrance between aliphatic and aromatic structure in char, the increasing pressure has less inhibition effect on the escape of the former than the latter. With the increase of pyrolysis pressure, the combustion reactivity of char is related to the infrared structure at 700 and 800 °C while to macropore structure at 900 and 1000 °C.     

Potential alternatives of heat and power technology application using rice straw in Thailand

Rice straw could be used for heat and power with the current technologies available in Thailand. The cost of rice straw for power generation at 0.38–0.61 Baht/MJ_e (at rice straw price 930–1500 Baht/t) is not competitive with coal at 0.30 Baht/MJ_e but comparable with other biomass at 0.35–0.53 Baht/MJ_e. However, utilization of rice straw in industrial boilers is a more competitive and flexible option with two alternatives; (1) installing rice straw fired boilers instead of heavy oil fired or natural gas ones when selecting new boilers; and (2) fuel switching from coal to rice straw for existing boilers with cost saving of feedstock supply by 0.01 Baht/MJ_h. Based on its properties (Slagging index, R_s = 0.04; fouling index, R_f = 0.24), rice straw is not expected to have significant operating problems or different emissions compared with wheat straw and rice husk under similar operating conditions.     

Modelling and experimental investigations on gasification of coarse sized coal char particle with steam

The steam gasification characteristics of coal char produced two sub-bituminous coals of different origin have been investigated through modelling and experiments. The gasification experiments are carried out in an Isothermal mass loss apparatus over the temperature range of 800–900 °C using a gas mixture of 65% steam and 35% N₂. A fully transient single particle gasification model, based on the random pore model, is developed incorporating reaction kinetics, heat and mass transport inside the porous char particle and the gas film. Stefan-Maxwell equation and Knudson diffusion are incorporated in the multi-component diffusion of species and pore diffusion. The model is validated with the experimental data of the present authors as well as that reported in the literature. The particle centre temperature is found to increase, then decrease and increase again to reach the reactor temperature finally, and the trend is more prominent for the larger particles. The pore opening phenomenon is more evident in SBC2 char, leading to a final char porosity of 0.65 vis-à-vis 0.52 in SBC1 and making it more reactive. Temporal evolution of contours of carbon conversion and concentration of other gaseous species like steam, H₂O, H₂, CO and CO₂ in the particle are computed to investigate the gasification process. A higher temperature is found to favour both the rate peak and the total production of H₂ for both the chars. The total H₂ production from SBC2 char is found to be 0.0189 mol and 0.0236 mol at 800 and 850 °C, while the same for SBC1 char is0.0232 mol and 0.0290 mol respectively. The reaction follows the shrinking core model at the outset, shifting to the shrinking reactive core model subsequently.     

Study of chemical looping co-gasification (CLCG) of coal and rice husk with an iron-based oxygen carrier via solid–solid reactions

The chemical looping gasification (CLG) is a promising gasification technology for syngas production. It reduces the demand for pure oxygen and heat from outside by the cycle of oxygen carriers. The lattice oxygen is transferred by oxygen carrier like Fe₂O₃ in CLG. Considering the synergy between lignite and rice husk, the chemical looping co-gasification (CLCG) of lignite and rice husk with Fe₂O₃ as oxygen carrier was studied in this work. The mass loss of lignite increased by about 3% with the help of rice husk. Due to the synergetic effect, rice husk developed the pyrolysis of coal in the co-gasification. It is found that the most contributing reaction at around 800 °C–1000 °C in CLG is the gasification of char with Fe₂O₃via solid-solid reactions. The kinetic fitting was used to explore the reaction mechanism of CLCG. The modified random pore model (MRPM) fitted the experimental data well, which confirmed the solid-solid reactions between char and Fe₂O₃, and the synergy between lignite and rice husk in CLCG. Finally, the gas analysis was conducted in a fixed bed system with gas analyzers. It is found that Fe₂O₃ enhanced the concentration of CO and CO₂ in CLG process.     

Porous structure and morphology of granular chars from flash and conventional pyrolysis of grape seeds

This work studies the influence of the operating conditions used in the pyrolysis of grape seeds on the morphology and textural properties of the chars resulting. Flash and conventional (283 K min⁻¹ heating rate) pyrolysis have been used within a wide range of temperature (300–1000 °C). The effect of a pretreatment for oil extraction has also been studied. The porous structure of the chars was characterized by adsorption of N₂ at 77 K, Ar at 77 K and 87 K, and CO₂ at 273 K and mercury intrusion porosimetry. The morphology was analyzed by scanning electron microscopy. All the materials prepared revealed an essentially microporous structure, with a poor or even negligible contribution of mesopores. Increasing pyrolysis temperature led to higher specific surface areas and lower pore size. The highest specific surface area values occurred within 700–800 °C, reaching up to 500 m² g⁻¹ with pore sizes in the 0.4–1.1 nm range. No significant morphological changes were observed upon carbonization so that the resulting chars were granular materials of similar size than the starting grape seeds. The hollow core structure of the chars, with most of the material allocated at the periphery of the granules can help to overcome the mass transfer limitations of most common (solid or massive) granular activated carbons. The chars showed a good mechanical strength during attrition tests. These chars can be potential candidates for the preparation of granular carbons molecular sieve or activated carbons raw materials.     

煤焦异相还原NO的实验研究

在U形石英管固定床反应器中实验研究了乌达煤焦对NO的异相还原作用。乌达煤焦在程序升温和快速升温条件下还原NO的实验结果表明,反应温度超过700℃时,NO的还原率开始迅速上升,在实验范围内,温度维持在800～1 000℃,NO的还原率较高。反应区的初始氧气体积分数越高,NO的还原率越低,表明煤焦与氧气的反应和煤焦还原NO的反应之间存在着较强的竞争作用。煤焦粒径越粗、制焦温度越高,NO的还原率越低,表明制焦条件对煤焦还原NO的反应性亦有较大影响。     

Steam gasification of Greek lignite and its chars by co-feeding CO2 toward syngas production with an adjustable H2/CO ratio

Low-rank lignite is among the most abundant and cheap fossil fuels, linked, however, to serious environmental implications when employed as feedstock in conventional thermoelectric power plants. Hence, toward a low-carbon energy transition, the role of coal in world's energy mix should be reconsidered. In this regard, coal gasification for synthesis gas generation and consequently through its upgrade to a variety of value-added chemicals and fuels constitutes a promising alternative. Herein, we thoroughly explored for a first time the steam gasification reactivity of Greek Lignite (LG) and its derived chars obtained by raw LG thermal treatment at 300, 500 and 800 °C. Moreover, the impact of CO₂ addition on H₂O gasifying agent mixtures was also investigated. Both the pristine and char samples were fully characterized by various physicochemical techniques to gain insight into possible structure-gasification relationships. The highest syngas yield was obtained for chars derived after LG thermal treatment at 800 °C, due mainly to their high content in fixed carbon, improved textural properties and high alkali index. Steam gasification of lignite and char samples led to H₂-rich syngas mixtures with a H₂/CO ratio of approximately 3.8. However, upon co-feeding CO₂ and H₂O, the H₂/CO ratio can be suitably adjusted for several potential downstream processes.     

Promoting effect of biomass ash additives on high-temperature gasification of petroleum coke: Reactivity and kinetic analysis

The effect of biomass ash (rice straw ash (RSA) and cotton straw ash (CSA)) on the gasification reactivity and the evolution of physicochemical structure of petcoke char was investigated. The catalytic effect of CSA was significantly higher than that of RSA, and the catalytic effect of biomass ash was enhanced at lower gasification temperature and for higher blending ratio of biomass ash. The promoting effect of biomass ash was related to the increase of active AAEM content, the decrease of order degree of carbon structure and the development of surface structure in char gasification after biomass ash addition, which was more significant for CSA, at lower temperature and for higher blending ratio. Moreover, the shrinking core model was suitable for char gasification, and the additions of RSA and CSA reduced the activation energy of petcoke char gasification from 199.84 kJ mol⁻¹ to 159.85 kJ mol⁻¹ and 62.75 kJ mol⁻¹, respectively.     

Effects of rice husk particle size on biohydrogen production under solid state fermentation

As a renewable energy source bio-hydrogen production from lignocellulosic wastes is a promising approach which can produce clean fuel with no CO₂ emissions. Utilization of agro-industrial residues in solid state fermentation (SSF) is offering a solution to solid wastes disposal and providing an economical process of value-added products such as hydrogen.In this study three different particle size of rice husk (<2000 μm, <300 μm, <74 μm) was subjected to batch SSF with a Clostridium termitidis: Clostridium intestinale ratio of 5:1. C. termitidis is a cellulolytic microorganism that has the ability to hydrolyze cellulosic substances and C. intestinale is able to grow on glucose having a potential of enhancing hydrogen production when used in the co-culture. 5 g dw rice husk with 75% humidity was used as substrate in SSF under mesophilic conditions. The highest HF Volume (29.26 mL) and the highest yield (5.9 mL H₂ g⁻¹ substrate) were obtained with the smallest particle size (<74 μm). The main metabolites obtained from the fermentation media were acetic, butyric, propionic and lactic acids. The second best production yield (3.99 mL H₂ g⁻¹ substrate) was obtained with the middle particle size (<300 μm) rice husk with a HF of 19.71 mL.     

Multifaceted analysis of products from the intermediate co-pyrolysis of biomass with Tetra Pak waste

This study investigates the co-pyrolysis of two types of biomass (pine bark and wheat straw) with Tetra Pak waste (TPW). The experiments were performed using a fixed-bed reactor equipped with an innovative system, where a sample was rapidly heated to 600 °C before being rapidly cooled. The multifaceted analysis included the determination of the i) physical and chemical properties of the feedstocks and chars, ii) aqueous phase, tars, and waxes, iii) char ignition and burnout temperature, iv) chemical composition of gas, and v) distribution of carbon and hydrogen in the obtained products. The results showed that the addition of TPW to the both types of biomass significantly reduced the char mass and aqueous phase, decreased the carbon, hydrogen, and nitrogen contents of the char, and increased the wax and tar yields retained in the water cooler. Different organic compounds such as alkenes, aromatic hydrocarbons, and acids were found in tars and waxes. The chemical composition of the released gases was detected in situ (by a flue-gas analyser) and ex-situ (using gas chromatography). Changes in the concentrations of H₂, CH₄, CO, CO₂, and C2–C4 were observed. The addition of Tetra Pak to the two types of biomass had an evident and positive effect on the hydrogen content of the pyrolysis gas.     

Gasification reactivity and synergistic effect of conventional and microwave pyrolysis derived algae chars in CO2 atmosphere

This research focuses on the isothermal and non-isothermal CO₂ gasification of an algal (Chlorella) char prepared via two different thermal processing systems, i.e. conventional and microwave-assisted pyrolysis. It was found that chars prepared via microwave irradiation showed higher CO₂ gasification reactivity than that of chars prepared via the conventional method. Meanwhile, the activation energy of microwave char was found to be 127.89 kJ/mol, which was 46.3 kJ/mol lower than that of conventional char, indicating improved reactivity of microwave char. The systematic characterisation of both conventional and microwave chars shows that the higher reactivity of microwave char could be attributed to its large BET surface area, low crystalline index and high active sites. In addition, it was found that microwave heating contributed to high reactivity of chars through generating large amount of primary char, the formation of hot spot and high specific surface area and pore volume. Results of co-gasification under isothermal conditions revealed the existence of greater synergistic effects between coal char and microwave algae char than those of coal char and conventional algae char. Furthermore, based on the relative Rs (average gasification rate), a novel index proposed to quantify the interactions in co-gasification process, Australian coal char/microwave assisted char blend experienced 10% higher interactions compared to Australian coal char/conventional assisted char blend.     

Supercritical water gasification of black liquor with wheat straw as the supplementary energy resource

Supercritical water gasification (SCWG) is a new treatment of black liquor (BL) for both energy recovery and pollution management. To provide more energy for the pulp mill, it is proposed to use the pulping raw material as supplementary energy source because it is readily available, inexpensive and renewable. In this study, co-gasification of BL and wheat straw (WS) in supercritical water was investigated. The synergistic effect was observed in the co-gasification because the addition of wheat straw can make better use of the alkali in BL. The maximum improvement of the gasification by the synergistic effect was obtained with the mixing ratio of 1:1. The influences of the temperature (500–750 °C), reaction time (5–40 min), mixture concentration (5.0–19.1 wt%), mixing ratio (0–100%) and the wheat straw particle diameter (74–150 μm) were studied. It was found that the increase of temperature and reaction time, and the decrease of concentration and wheat straw particle size favored the gasification by improving the hydrogen production and gasification efficiency. The highest carbon gasification efficiency of 97.87% was obtained at 750 °C. Meanwhile, the H₂ yield increased from 12.29  mol/kg at 500 °C to 46.02  mol/kg. This study can help to develop a distributed energy system based on SCWG of BL and raw biomass to supply energy for the pulp mill and surrounding communities.     

Effect of Carbonization Temperature on Combustion Reactivity of Bagasse Char

Abstract

The combustion reactivity of bagasse chars was investigated under isothermal conditions at 400°C in air. The bagasse char samples were prepared by carbonizing bagasse in a fixed bed reactor at temperatures between 500°C and 800°C. It was observed that raising the carbonization temperature resulted in a significant decrease in reactivity of bagasse char. This was manifested by the decrease in the values of the maximum reaction rate, average rate based on 50% burnout and conversion achieved in 30 minutes with the increase in carbonization temperature. The decrease in reactivity of bagasse char with carbonization temperature was attributed to changes in the reactive components of bagasse.     

Grinding energy and physical properties of chopped and hammer-milled barley,wheat, oat,and canola straws

In the present study, specific energy for grinding and physical properties of wheat, canola, oat and barley straw grinds were investigated. The initial moisture content of the straw was about 0.13–0.15 (fraction total mass basis). Particle size reduction experiments were conducted in two stages: (1) a chopper without a screen, and (2) a hammer mill using three screen sizes (19.05, 25.4, and 31.75 mm). The lowest grinding energy (1.96 and 2.91 kWh t⁻¹) was recorded for canola straw using a chopper and hammer mill with 19.05-mm screen size, whereas the highest (3.15 and 8.05 kWh t⁻¹) was recorded for barley and oat straws. The physical properties (geometric mean particle diameter, bulk, tapped and particle density, and porosity) of the chopped and hammer-milled wheat, barley, canola, and oat straw grinds measured were in the range of 0.98–4.22 mm, 36–80 kg m⁻³, 49–119 kg m⁻³, 600–1220 kg m⁻³, and 0.9–0.96, respectively. The average mean particle diameter was highest for the chopped wheat straw (4.22-mm) and lowest for the canola grind (0.98-mm). The canola grinds produced using the hammer mill (19.05-mm screen size) had the highest bulk and tapped density of about 80 and 119 kg m⁻³; whereas, the wheat and oat grinds had the lowest of about 58 and 88–90 kg m⁻³. The results indicate that the bulk and tapped densities are inversely proportional to the particle size of the grinds. The flow properties of the grinds calculated are better for chopped straws compared to hammer milled using smaller screen size (19.05 mm).