Influence of Carbonization Conditions on the Properties of Coconut Shell Chars

The changes in chemical, physical, and mechanical properties of fully matured coconut shell chars in relation to carbonization temperature (range: 400–950°C) and time (range: zero–3 h) have been studied. These properties were found to be more susceptible to carbonization temperature than to time. The results indicated an increase in fixed carbon content and true specific gravity of shell chars with rise of carbonization temperature and soak time. The majority of volatilization occurred up to about 800°C. The calorific value of shell char increased sharply with rise of carbonization temperature up to 600°C, and thereafter it decreased to 800°C. The porosity of shell char increased with increase of carbonization temperature up to 600°C followed by a decrease with further rise of temperature up to the range studied. Prolonged soaking at carbonization temperatures of 600, 800, and 950°C, in general, led to slight increases in the porosity and calorific values of resulting shell chars. The results showed that the crushing strength of shell char decreased markedly on increasing the preparation temperature up to 600°C, followed by an increase thereafter. An increase in soaking time at carbonization temperatures of 600, 800, and 950°C also influenced the shell char strength.     

Fixed-Bed Pyrolysis of Hazelnut (Corylus Avellana L.) Bagasse: Influence of Pyrolysis Parameters on Product Yields

Fixed-bed slow pyrolysis experiments have been conducted on a sample of hazelnut bagasse to determine particularly the effects of pyrolysis temperature, heating rate, particle size and sweep gas flow rate on the pyrolysis product yields. The temperature of pyrolysis, heating rate, particle size and sweep gas flow rate were varied in the ranges 350–550° C, 10 and 50° C/min, 0.224–1.800 mm and 50–200 cm³/min, respectively. Under the various pyrolysis conditions applied in the experimental studies, the obtained char, liquid, and gas yield values ranged between 26 and 35 wt%, 23 and 34.40 wt%, and 25 and 32 wt%, respectively. The maximum biooil yield of 34.40% was obtained at the final pyrolysis temperature of 500°C, with a heating rate of 10° C/min, particle size range of 0.425–0.600 mm and a sweep gas flow rate of 150 cm³/min.     

Carbonisation of bagasse in a fixed bed reactor: influence of process variables on char yield and characteristics

Carbonisation experiments on samples of sugar cane bagasse were conducted in a static fixed bed reactor to determine the effect of process variables such as temperature, heating rate, inert sweep gas flow rate and particle size on the yield and composition of solid product char. Experiments were performed to the final temperatures of 250–700°C with heating rates from 5 to 30°C/min with nitrogen sweep gas flow rate of 350 cc/min. Additional tests were aimed at studying the effect of different flow rates of nitrogen sweep gas from 0 to 700 cc/min during carbonization and different particle size fractions of bagasse. The results showed that as the carbonisation temperature was increased, the yield of char decreased. The reduction in yield was rapid up to a final temperature of 500°C and was slower thereafter. The yield of char was relatively insensitive to the changes in heating rate and particle size. Increasing the sweep gas flow rate to 350 cc/min reduced the yield of char. It appears the presence of inert sweep gas reduced secondary reactions which promoted char formation. The proximate analysis of the char suggests that fixed carbon and ash content increased with temperature. The char obtained at temperatures higher than 500°C have high carbon content and is suitable as renewable fuel and for other applications. The carbonization of bagasse has the potential to produce environmental friendly fuels and can assist in reducing deforestation for the production of charcoal.     

Relative reactivity of alkaline extracts of Taiwanese biomass residues toward formaldehyde

Six Taiwanese biomass materials, namely: rice (Oryza sativa L.) hull; rice bran; sugarcane (Saccharum officinarum L.) bagasse; Taiwan acacia (Acacia confusa Merr.) bark; Taiwan acacia foliage; and Taiwan acacia leaf, were extracted with a 22% solution of sodium hydroxide at 95°C for 16 h and at an elevated temperature of 135°C for 4 h. These extracts were reacted with 44% formalin for 2 h at 60 and 80°C, respectively, to investigate their reactivity toward formaldehyde. The free formaldehyde in the reaction mixtures was quantitatively determined by hydroxylamine hydrochloride titration to an end point of pH 4. Extraction temperature, reaction temperature, and type of biomass material were found to significantly influence the reactivity of the extracts with formaldehyde. The 135°C extracts of sugarcane bagasse absorbed the highest amount of formaldehyde while the 95°C extracts of Taiwan acacia foliage absorbed the least amount of formaldehyde.     

Bio-oil Production from an Oilseed By-product: Fixed-bed Pyrolysis of Olive Cake

Abstract

A study of pyrolysis of olive cake at the temperature range from 400°C to 700°C has been carried out. The experiments were performed in a laboratory scale tubular reactor under nitrogen atmosphere. The yields of derived gases, liquids, and char were determined in relation to pyrolysis temperature and sweeping gas flow rates, at heating rates of about 300°C min^?1. As the pyrolysis temperature was increased, the percentage mass of char decreased whilst gas product increased. The oil products increased to a maximum value of ～39.4 wt% of dry ash free biomass at a pyrolysis temperature of about 550°C in a nitrogen atmosphere with flow rate of 100 mL min^?1 and with a heating rate of 300°C min^?1. Results showed that the bio-oil obtained under the optimum conditions is a useful substitute for fossil fuels or chemicals.     

Assessment of sugarcane bagasse gasification in supercritical water for hydrogen production

Sugarcane bagasse is one of the major resources of agricultural biomass waste in the world. In this work, supercritical water gasification characteristics of sugarcane bagasse were investigated. The effect of temperature (600–750 °C), concentration (3–12 wt%), residence time (5–20 min) and catalysts (Raney-Ni, K₂CO₃ and Na₂CO₃) on bagasse gasification were studied. A kinetic study on the non-catalytic and Na₂CO₃ catalytic bagasse gasification was conducted to describe the kinetic information of the bagasse gasification reaction. The results showed that a higher reaction temperature, a lower bagasse concentration and a longer residence time could favor the gasification of bagasse, leading to a higher hydrogen yield. Bagasse was nearly completely gasified at 750 °C without using any catalyst and the carbon gasification efficiency could reach up to 96.28%. The addition of employed catalysts remarkably promoted the bagasse gasification reactivity. The maximum hydrogen yield (35.3 mol/kg) was achieved at 650 °C with the Na₂CO₃ loading of 20 wt%. The experimental data fitted well with a homogeneous model based on a Pseudo-first-order reaction hypothesis. The kinetic study showed that Na₂CO₃ catalyst could lower the activation energy E_a of bagasse gasification from 117.88 kJ/mol to 78.25 kJ/mol.     

Comparison of high temperature chars of wheat straw and rice husk with respect to chemistry,morphology and reactivity

Fast pyrolysis of wheat straw and rice husk was carried out in an entrained flow reactor at high-temperatures (1000–1500) °C. The collected char was analyzed using X-ray diffractometry, N₂-adsorption, scanning electron microscopy, particle size analysis with CAMSIZER XT, ²⁹Si and ¹³C solid-state nuclear magnetic resonance spectroscopy and thermogravimetric analysis to investigate the effect of inorganic matter on the char morphology and oxygen reactivity. The silicon compounds were dispersed throughout the turbostratic structure of rice husk char in an amorphous phase with a low melting temperature (≈730 °C), which led to the formation of a glassy char shell, resulting in a preserved particle size and shape of chars. The high alkali content in the wheat straw resulted in higher char reactivity, whereas the lower silicon content caused variations in the char shape from cylindrical to near-spherical char particles. The reactivities of pinewood and rice husk chars were similar with respect to oxidation, indicating less influence of silicon oxides on the char reactivity.     

Parametric gasification process of sugarcane bagasse for syngas production

This research focuses on parametric influence on product distribution and syngas production from conventional gasification. Three experimental parameters at three different levels of temperature (700, 800 and 900 °C), sugarcane bagasse loading (2, 3 and 4 g) and residence time (10, 20 and 30 min) were studied using horizontal axis tubular furnace. Response Surface Methodology supported by central composite design was adopted in order to investigate parameters impact on product distribution (i.e., gas, tar and char) and gaseous products (i.e., H₂, CO, CO₂ and CH₄). The highest H₂ fraction obtained was 42.88 mol% (36.91 g-H₂ kg-biomass⁻¹) at 3 g of sugarcane bagasse loading, 900 °C and 30 min reaction time. The temperature was identified as the most influential parameter followed by reaction time for H₂ production and diminishing the bio-tar and char yields. An increase in sugarcane bagasse loading, on other hand, favored the production of bio-tar, CO₂ and CH₄ production. The statistical analysis verified temperature as most significant (p-value 0.0008) amongst the parameters investigated for sugarcane bagasse biomass gasification.     

Pyrolysis of Some Indigenous Tree Species of Northeast India: Effect of Pyrolysis Temperature and Heating Rate on the Products Yield and Char Quality

Abstract

Seven indigenous tree species of northeast India were pyrolyzed at temperatures ranging from 300°C–800°C with two different heating rates, 3°C/min and 20°C/min, and the effect of heating temperature and heating rate on the products yield and char quality were analyzed and discussed. Among all the species, E. acuminata, M. bombycina and Q. griffithii were found to yield higher percentages of char with better quality, whereas A. lucida yielded the highest percentage of tar.     

Energy Applications of Biomass: Pyrolysis of Apricot Stone

Apricot stone (Prunus armeniaca L.) was pyrolyzed in a directly heated fixed-bed reactor under nitrogen atmosphere. Effects of sweeping gas flow rates and pyrolysis temperature on the pyrolysis of the biomass were also studied. Pyrolysis runs were performed using reactor temperatures between 400°C and 700°C with heating rate of about 300°C min^?1. As the pyrolysis temperature was increased, the percentage mass of char decreased while gas product increased. The product yields were significantly influenced by the process conditions. The bio-oil obtained at 550°C, at which the liquid product yield was maximum, was analyzed. It was characterized by Fourier transform infrared spectroscopy (FT-IR). In addition, the solid and liquid products were analyzed to determine their elemental composition and calorific value. Chemical fractionation of bio-oil showed that only low quantities of hydrocarbons were present, while oxygenated and polar fractions dominated.     

Kinetic characteristics of in-situ char-steam gasification following pyrolysis of a demineralized coal

This study aims to examine the char-steam reactions in-situ, following the pyrolysis process of a demineralized coal in a micro fluidized bed reactor, with particular focuses on gas release and its kinetics characteristics. The main experimental variables were temperatures (925 °C?1075 °C) and steam concentrations (15%–35% H₂O), and the combination of pyrolysis and subsequent gasification in one experiment was achieved switching the atmosphere from pure argon to steam and argon mixture. The results indicate that when temperature was higher than 975 °C, the absolute carbon conversion rate during the char gasification could easily reach 100%. When temperature was 1025 °C and 1075 °C, the carbon conversion rate changed little with steam concentration increasing from 25% to 35%. The activation energy calculated from shrinking core model and random pore model was all between 186 and 194 kJ/mol, and the fitting accuracy of shrinking core model was higher than that of the random pore model in this study. The char reactivity from demineralized coal pyrolysis gradually worsened with decreasing temperature and steam partial pressure. The range of reaction order of steam gasification was 0.49–0.61. Compared to raw coal, the progress of water gas shift reaction (CO + H₂O ? CO₂ + H₂) was hindered during the steam gasification of char obtained from the demineralized coal pyrolysis. Meanwhile, the gas content from the char gasification after the demineralized coal pyrolysis showed a low sensitivity to the change in temperature.     

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.     

Regulation of chemical properties of ash and kinetic model construction of Lu’an coal gasification

The objective of this study was to enhance the suitability of Lu’an coal for gasification in large entrained-flow gasifiers currently used by the Lu’an Group Mining Company in its 1.8 million ton per annum coal-based oil synthesis demonstration project. The effect of coal blending and flux addition on the ash fusion temperature (AFT) and gasification reactivity was investigated. CaO, Fe₂O₃, and MgO decreased the AFT of Lu’an coal by 150°C, 73°C, and 68°C, respectively, by a flux addition of up to 7%. Within the range of the experimental investigation, the AFT of Lu’an coal decreased by 3°C for each 1% of Shenmu coal addition. The gradual reduction of mullite and the formation of fayalite and hessonite in blended coal ash decreased the AFT. The addition of a fluxing agent significantly increased the reaction activity of the char, with Fe₂O₃ exhibiting the largest catalytic effect on char gasification. Blending with Shenmu char significantly increased the gasification reactivity. The random pore model best describes the gasification process of Lu’an char, and a kinetic equation for the process was developed on the basis of this model.     

Effect of temperature on Lu’an bituminous char structure evolution in pyrolysis and combustion

In the process of pyrolysis and combustion of coal particles, coal structure evolution will be affected by the ash behavior, which will further affect the char reactivity, especially in the ash melting temperature zone. Lu’an bituminous char and ash samples were prepared at the N₂ and air atmospheres respectively across ash melting temperature. A scanning electron microscope (SEM) was used to observe the morphology of char and ash. The specific surface area (SSA) analyzer and thermogravimetric analyzer were respectively adopted to obtain the pore structure characteristics of the coal chars and combustion parameters. Besides, an X-ray diffractometer (XRD) was applied to investigate the graphitization degree of coal chars prepared at different pyrolysis temperatures. The SEM results indicated that the number density and physical dimension of ash spheres exuded from the char particles both gradually increased with the increasing temperature, thus the coalescence of ash spheres could be observed obviously above 1100°C. Some flocculent materials appeared on the surface of the char particles at 1300°C, and it could be speculated that β-Si₃N₄ was generated in the pyrolysis process under N₂. The SSA of the chars decreased with the increasing pyrolysis temperature. Inside the char particles, the micropore area and its proportion in the SSA also declined as the pyrolysis temperature increased. Furthermore, the constantly increasing pyrolysis temperature also caused the reactivity of char decrease, which is consistent with the results obtained by XRD. The higher combustion temperature resulted in the lower porosity and more fragments of the ash.     

Oxidative catalytic steam gasification of sugarcane bagasse for hydrogen rich syngas production

Reactive Flash Volatilization (RFV) is an emerging thermochemical method to produce tar free hydrogen rich syngas from waste biomass at relatively lower temperature (<900 °C) in a single stage catalytic reactor within a millisecond residence time. Here, we show catalytic RFV of bagasse using Ru, Rh, Pd, or Re promoted Ni/Al₂O₃ catalysts under steam rich and oxygen deficient environment. The optimum reaction conditions were found to be 800 °C, steam to carbon ratio = 1.7 and carbon to oxygen ratio = 0.6. Rh–Ni/Al₂O₃ performed the best, resulting in highest hydrogen concentration in the synthesis gas at 54.8%, with a corresponding yield of 106.4 g-H₂/kg bagasse. A carbon conversion efficiency of 99.96% was achieved using Rh–Ni, followed by Ru–Ni, Pd–Ni, Re–Ni and mono metallic Ni catalyst in that order. Alkali and Alkaline Earth Metal species present in the bagasse ash and char, that deposited on the catalyst, was found to enhance its activity and stability. The hydrogen yield from bagasse was higher than previously reported woody biomass and comparable to the microalgae.     

Gasification of preheated coal: Experiment and thermodynamic equilibrium calculation

A new process integrating a circulating fluidized bed (CFB) reactor and an entrained bed reactor was proposed for gasification of preheated coal. The CFB reactor as a preheater was successfully used in clean coal combustion. In this study, gasification of preheated coal was tested in a bench-scale test rig, which consisted of a CFB preheater and a down flow bed (DFB) gasifier. The effects of operating parameters of the preheater and gasifier were revealed via thermodynamic equilibrium calculations. A stable preheating process was obtained in the CFB preheater at the O₂/C molar ratio of 0.31 and higher gasification reactivity was gained in preheated char owing to the improvement in intrinsic reactivity, specific surface area and total pore volume. Effective gasification of preheated char was achieved in the DFB gasifier at 1100 °C and the total O₂/C molar ratio of 0.67, meanwhile the CO + H₂ yield and carbon conversion increased. Thermodynamic equilibrium calculations revealed when the gasification reaction rates varied little above 1100 °C and the same carbon conversion was achieve in gasifier, lowering the temperature would lead to an increase in cold gas efficiency and a decrease in O₂ demand.     

Production of bioethanol from sugarcane bagasse using yeast strains: A kinetic study

In this study, sugarcane bagasse (2 mm) was pretreated with 2.5% NaOH followed by steaming at 121°C for various time periods. Maximum cellulose content of 81% and delignification of 68.5% were achieved by soaking bagasse in 2.5% NaOH with a residence time of 1 h at room temperature followed by steaming at 121°C for 30 min residence time. The pretreated substrate was analyzed by SEM and FTIR to study the structural modification and functional group of the untreated and pretreated substrates. The pretreated substrate was saccharified by commercial cellulase enzyme depicting 106 µm mesh size of substrate yields maximum saccharification rate. The saccharified material was fermented by Saccharomyces cerevisiae and Pichia stipitis in mono- and co-culture modes. Maximum product yield (Y_p/s) was observed by monoculture using Saccharomyces cerevisiae after 96 h of fermentation period.     

Experimental investigation of the two-phase theory in a fluidized-bed combustor

Though the two-phase theory of fluidization is well-accepted, no direct experimental measurements of the different gas concentrations predicted to occur in bubble and particulate phases could be found in the literature. For the first time, theoretical predictions of these different gas concentrations have been validated experimentally, using a combined oxygen/bubble probe. Based on the two-phase theory, a mathematical model was developed for the combustion of a batch of char particles in a fluidized-bed combustor. The experimental oxygen concentration in the particulate phase as a function of time was well predicted by the model. Slight discrepancies for the bubble phase values were eliminated when low-oxygen-concentration bubbles were excluded from the data, attributed to some char combustion occurring in bubbles being contrary to the model assumption. The temperature difference between char and bed particles (ΔT) was the only adjustable parameter in the model. A value of 20°C fitted the burnoff times measured by visual observation of the top of the bed, for both 5 and 10 g char batch masses. Model predictions of the oxygen concentrations were not sensitive to ΔT during the first half of burnoff, when mass transfer controlled the combustion rate, so the mass transfer processes were predicted correctly by the model effectively with no adjustable parameter. The ΔT value of 20°C was significantly lower than experimental measurements of maximum burning char particle temperatures, reported to be 70°C for the small-diameter bed particles used in this work. The discrepancy was attributed to two factors: (i) the decrease in char particle temperature towards the end of the burnoff, when kinetics significantly affected the combustion rate; and (ii) a lower char particle temperature in the particulate phase than in the bubble phase, with experimental char particle temperature measurements biased towards the higher bubble phase values. It was inferred: (i) that the maximum values of ΔT measured experimentally are too high for calculation of the char particle combustion rate during the kinetic-controlled latter stage of burnoff and (ii) that reported values of the heat transfer coefficient from burning char particles to the particulate phase deduced from these particle temperature measurements may have been underestimated.     

Attrition of lignite char in a spouted bed combustor

The generation of carbon fines by attrition during burning of Thai lignite char has been studied experimentally by means of a 92 mm i.d. continuous spouted bed combustor at different values of spouting gas velocity, bed temperature, and char feed size. Both inert particle size and static bed depth were fixed for all experimental runs. The collected data were used to analyse size distributions of both in-bed particles and elutriated fines, and to generate the suitable correlations for carbon attrition rate. Results obtained showed that attrition rate in the spouted bed is proportional to the excess of gas velocity above the minimum spouting gas velocity and the overall bed carbon surface exposed to attrition. The attrition rate constant is slightly dependent on operating bed temperature. Its values for the char studied were 1.6511 × 10^?6 for 707°C operating bed temperature, and 1.1222 × 10^?6 for 850°C, with the average for all tested runs being 1.224 × 10^?6.