Olive bagasse (Olea europea L.) pyrolysis

Olive bagasse (Olea europea L.) was pyrolysed in a fixed-bed reactor. The effects of pyrolysis temperature, heating rate, particle size and sweep gas flow rates on the yields of the products were investigated. Pyrolysis runs were performed using pyrolysis temperatures between 350 and 550 degrees C with heating rates of 10 and 50 degrees C min(-1). The particle size and sweep gas flow rate varied in the ranges 0.224-1.8mm and 50-200 cm3 min(-1), respectively. The bio-oil obtained at 500 degrees C was analysed and at this temperature the liquid product yield was the maximum. The various characteristics of bio-oil obtained under these conditions were identified on the basis of standard test methods. The empirical formula of the bio-oil with heating value of 31.8 MJ kg(-1) was established as CH(1.65)O(0.25)N(0.03). The chemical characterization showed that the bio-oil obtained from olive bagasse may be potentially valuable as a fuel and chemical feedstock.     

Characterization of products from the pyrolysis of rapeseed oil cake

The main aim of this study was to investigate the composition of products from the pyrolysis of rapeseed oil cake in a fixed bed reactor at 400, 450, 500, 700 and 900 degrees C. The gas products mainly consisted of CO(2), CO, CH(4) and H(2)S at 500 degrees C. Empirical formula of bio-oil from the pyrolysis of rapeseed oil cake was CH(1.59)O(0.16)N(0.116)S(0.003) for 500 degrees C. Bio-oils mainly contained oleic acid, 1H-indole, 2,3,5-trimethoxy toluene, toluene, (Z)-9-octadecanamide, psoralene, phenol and phenol derivatives at all pyrolysis temperatures. Both non-aromatic and aromatic hydrocarbon compounds were determined in water phase of liquid product by Headspace-GC analysis. The heating values of bio-chars were found to be similar (24MJkg(-1)) at all pyrolysis temperatures.     

Thermal conversion of elephant grass (Pennisetum purpureum Schum) to bio-gas, bio-oil and charcoal

Elephant grass is an abundant, fast growing plant with significant potential as a renewable energy source and for conversion to higher calorific value fuels. This work investigates thermal conversion of elephant grass to bio-gas, bio-oil and charcoal under two heating rates of 10 and 50 degrees C/min. The energy required to pyrolyse elephant grass was evaluated using computer aided thermal analysis technique, while composition of the resultant bio-gas and bio-oil products were monitored with gas chromatographic and mass spectroscopic techniques. At 500 degrees C, the bio-gas compounds consisted primarily of CO(2) and CO with small amounts of methane and higher hydrocarbon compounds. The heat of combustion of the bio-gas compounds was estimated to be 3.7-7.4 times higher than the heat required to pyrolyse elephant grass under both heating rates, which confirms that the pyrolysis process can be self-maintained. Faster heating rate was found to increase the amount of liquid products by 10%, while charcoal yields remained almost the same at 30%. The bio-oil mainly consisted of organic acids, phthalate esters, benzene compounds and amides. The amount of organic acids and benzene compounds were significantly reduced at 50 degrees C/min, while the yields of phthalate esters and naphthalene compounds increased. The difference in bio-oil composition with increased heating rate is believed to be associated with the reduction of the secondary reactions of pyrolysis, which are more pronounced under lower heating rate.     

Pyrolysis of safflower (Charthamus tinctorius L.) seed press cake: part 1. The effects of pyrolysis parameters on the product yields

Safflower (Charthamus tinctorius L.) seed press cake was pyrolysed in a fixed-bed reactor. The effects of pyrolysis temperature, heating rate and sweep gas flow rates on the yields of the products were investigated. Pyrolysis runs were performed using pyrolysis temperatures between 400 and 600 °C with heating rates of 10, 30 and 50 °C min⁻¹. The obtained bio-char, gas and bio-oil yields ranged between 25 and 34 wt%, 19 and 25 wt%, and 28 and 36 wt%, respectively, at different pyrolysis conditions. The highest liquid yield was obtained at 500 °C pyrolysis temperature with a heating rate of 50 °C min⁻¹ under the sweep gas of N₂ with a flow rate of 100 cm³ min⁻¹. Employing the higher heating rate of 50 °C min⁻¹ results in maximum bio-oil yield, probably due to the decrease in mass transfer limitations. According to the results obtained under the conditions of this study, the effects of pyrolysis temperature and sweep gas flow rate are more significant than the effect of heating rate on the yields.     

Pyrolysis characteristics and kinetics of oak trees using thermogravimetric analyzer and micro-tubing reactor

In this work, pyrolysis characteristics were investigated using thermogravimetric analysis (TGA) at heating rates of 5-20 degrees C/min. Most of the materials were decomposed between 330 degrees C and 370 degrees C at each heating rate. The average activation energy was 236.2 kJ/mol when the pyrolytic conversion increased from 5% to 70%. The pyrolysis kinetics of oak trees was also investigated experimentally and mathematically. The experiments were carried out in a tubing reactor at a temperature range of 330-370 degrees C with a reaction time of 2-8 min. A lump model of combined series and parallel reactions for bio-oil and gas formation was proposed. The kinetic parameters were determined by nonlinear least-squares regression from the experimental data. It was found from the reaction kinetic constants that the predominant reaction pathway from the oak trees was to bio-oil formation rather than to gas formation at the investigated temperature range.     

Slow pyrolysis of wood barks from Pinus brutia Ten. and product compositions

Biomass in the form of pine bark (Pinus brutia Ten.) was pyrolysed in an externally heated fixed-bed reactor. The effects of temperature and heating rate on the yields and compositions of the products were investigated. Pyrolysis runs were performed using reactor temperatures between 300 and 500 degrees C with heating rates of 7 and 40 degrees Cmin(-1). The product yields were significantly influenced by the process conditions. The bio-oil obtained at 450 degrees C, at which the liquid product yield was maximum, was analysed. It was characterized by Fourier transform infrared spectroscopy. In addition, the solid and liquid products were analysed 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. The empirical formula of the bio-oil with heating value of 31.03 MJkg(-1) was established as CH(1.43)O(0.332)N(0.0013).     

Production and characterization of pyrolysis liquids from sunflower-pressed bagasse

Pyrolysis experiments on sunflower (Helianthus annus L.)-pressed bagasse were performed in a fixed-bed tubular reactor. The effects of nitrogen flow rate and final pyrolysis temperature on the pyrolysis product yields and chemical compositions were investigated. The maximum bio-oil yield of 52.10 wt.% was obtained in a nitrogen atmosphere with flow rate of 50 ml min(-1) and at a pyrolysis temperature of 550 degrees C with a heating rate of 5 degrees C s(-1). The chemical characterization results showed that the oil obtained from sunflower-pressed bagasse may be a potentially valuable source as fuel or chemical feedstocks.     

Fixed-bed catalytic pyrolysis of cotton-seed cake: effects of pyrolysis temperature, natural zeolite content and sweeping gas flow rate

Catalyzed pyrolysis of cotton-seed cake was studied under different experimental conditions. Variables investigated were pyrolysis temperature, zeolite content and sweeping gas flow rate. Experiments were carried out isothermally. Liquids, gases and char were obtained as products of pyrolysis. The distributions of these products were determined for various contents (1, 5, 10, 20 wt.% of raw material) of zeolite at four different pyrolysis temperatures. The maximum liquid yield obtained was 30.84% at a pyrolysis temperature of 550 degrees C with a sweeping gas flow rate of 100 cm(3) min(-1) in the presence of clinoptilolite (20% based on raw material) as catalyst. The pyrolytic and catalytic liquid products were analysed in detail to determine the predominant chemical classes and the identities of the major compounds present.     

Pyrolysis of grape bagasse: effect of pyrolysis conditions on the product yields and characterization of the liquid product

In this study, pyrolysis of grape bagasse was investigated with the aim to study the product distribution and their chemical compositions and to identify optimum process conditions for maximizing the bio-oil yield. Particular investigated process variables were temperature (350-600 °C), heating rate (10-50 °C/min) and nitrogen gas flow rate (50-200 cm³/min). The maximum oil yield of 27.60% was obtained at the final pyrolysis temperature of 550 °C, sweeping gas flow rate of 100 cm³/min and heating rate of 50 °C/min in a fixed-bed reactor. The elemental analysis and heating value of the bio-oils were determined, and then the chemical composition of the bio-oil was investigated using chromatographic and spectroscopic techniques such as column chromatography, ¹H NMR and FTIR. The fuel properties of the bio-oil such as flash point, viscosity and density were also determined. The bio-oils obtained from grape bagasse were presented as an environmentally friendly feedstock candidate for bio-fuels.     

Comparison of non-catalytic and catalytic fast pyrolysis of corncob in a fluidized bed reactor

Fast pyrolysis of corncob with and without catalyst was investigated in a fluidized bed to determine the effects of pyrolysis parameters (temperature, gas flow rate, static bed height and particle size) and a HZSM-5 zeolite catalyst on the product yields and the qualities of the liquid products. The result showed that the optimal conditions for liquid yield (56.8%) were a pyrolysis temperature of 550 degrees C, gas flow rate of 3.4 L/min, static bed height of 10 cm and particle size of 1.0-2.0mm. The presence of the catalyst increased the yields of non-condensable gas, water and coke, while decreased the liquid and char yields. The elemental analysis showed that more than 25% decrease in oxygen content of the collected liquid in the second condenser with HZSM-5 was observed compared with that without catalyst. The H/C, O/C molar ratios and the higher heating value of the oil fraction in the collected liquid with the catalyst were 1.511, 0.149 and 34.6 MJ/kg, respectively. It was indicated that the collected liquid in the second condenser had high qualities and might be used as transport oil.     

Production of pyrolytic liquids from industrial sewage sludges in an induction-heating reactor

With the application of induction-heating, the pyrolytic experiments have been carried out for three sewage sludges from the food processing factories in an externally heated fixed-bed reactor. The thermochemical characteristics of sludge samples were first analyzed. The results indicated that the calorific value had about 15 MJ/kg on an average, suggesting that it had a potential for biomass energy source. However, its nitrogen concentration was relatively high. From the thermogravimetric analysis (TGA) curves, it showed that the pyrolysis reaction can be almost finished in the temperature range of 450-750 degrees C. The yields of resulting liquid and char products from the pyrolysis of sewage sludge were discussed for examining the effects of pyrolysis temperature (500-800 degrees C), heating rate (200-500 degrees C/min), and holding time (1-8 min). Overall, the variation of yield was not so significant in the experimental conditions for three sewage sludges. All results of the resulting liquid products analyzed by elemental analyzer, pH meter, Karl-Fischer moisture titrator and bomb calorimeter were in consistence with those analyses by FTIR spectroscopy. Furthermore, the pyrolysis liquid products contained large amounts of water (>73% by weight) mostly derived from the bound water in the biosludge feedstocks and the condensation reactions during the pyrolysis reaction, and fewer contents of oxygenated hydrocarbons composing of carbonyl and nitrogen-containing groups, resulting in low pH and low calorific values.     

Pyrolysis of Mixed Date Stones and Pistachio Shells: Identification of Bio-Oil and Utilization of Bio-Char as Activated Carbon Precursor

Thermal pyrolysis of mixed date stones and pistachio shells in a semi-batch reactor was addressed in this study. The highest yield of liquids (51.20 %) was produced at 500 °C, 90 min, 20 °C/min heating rate, and 50 mesh particle size. Under these conditions, yield of liquid from date stones and pistachio shells separately was 49.12 % and 47.67 %, respectively. The FT-IR results confirmed the presence of multiple oxygen-containing compounds in the bio-oil. Results from GC–MS declared that it was predominately composed of acids (57.57 %), esters (21.35 %), phenols (4.63 5), and alcohols (3.49 5). The obtained biochar was transformed into activated carbon (AC) by the optimized ZnCl₂ activation method. The ideal AC was synthesized at 600 °C for 60 min using a 2 : 1 ZnCl₂: biochar impregnation ratio. FESEM and XRD measurements showed that the AC was amorphous. The prepared AC was effective in eliminating dibenzothiophene (DBT) from model fuel (200 ppm DBT/hexane) with a maximum performance 95.26 % at 40 °C for 1h using 0.35 g of the AC. The exhausted AC was regenerated and reutilized 4 times, and removal efficiency reached 88.23 % in the 4^th cycle under ideal working conditions.     

热烟气气氛下生物质在流化床反应器中快速热解制取生物油

在对操作流化速度进行冷态实验以及流化床温度稳定性进行测试的基础上,研制了新型流化床反应器,并使用玉米秸秆为原料,探究了热烟气气氛下快速热解制取生物油的最佳反应温度以及床料。在最佳热解条件下,对糠醛废弃物、木糖废弃物以及海藻进行了实验研究,得到了各产物产率,并对得到的生物油进行了物理特性分析。结果显示,在最佳操作流速下,当温度为500 ℃时使用白云石为床料可以获得最大生物油产率。4种原料中玉米秸秆的生物油产率最高,达到42.3 wt%。在最佳热解条件下获得了4种物料不同含量的重油和轻质油,其中重油的物理特性差别很小,重油的热值比轻质油的热值高很多。不可冷凝气的高位热值是6.5?8.5 MJ/m3,因此不可冷凝气体可以作为一种燃料气被加以利用。     

Characterization of Bio-oil and Bio-char from Pyrolysis of Palm Oil Wastes

The residues from the palm oil industry are the main contributors to biomass waste in Malaysia, and these wastes require extra attention with respect to handling. The biomass waste is a renewable resource that can potentially be used to produce absorbents, fuels, and chemical feedstocks through the pyrolysis process. In this study, the wastes of palm shell, empty fruit bunches, and mesocarp fiber were characterized and then pyrolyzed in a fixed-bed reactor under the following conditions: a temperature of 500 °C, a nitrogen flow rate of 2 L/min and reaction time of 60 min. After pyrolysis, characterization of the products with an emphasis on the bio-oil and the bio-char was performed using various approaches (including Karl Fischer water-content tests, FTIR, SEM, TGA and CNH/O analyses). The results showed that the pyrolysis of palm oil wastes yielded more bio-oil than bio-char or non-condensable gases. The results also indicated that all of the bio-oils were acidic and contained high levels of oxygen. The bio-oils heating values were low and varied from 10.49 MJ/kg to 14.78 MJ/kg. The heating values of the bio-chars (20–30 MJ/kg) were higher than those of the bio-oils. Among the biomasses studied in this work, palm shell contained the highest level of lignin and showed the highest levels of bio-char yield and fixed and elemental carbon in the raw and bio-char form.     

Pyrolysis of safflower (Charthamus tinctorius L.) seed press cake in a fixed-bed reactor: part 2. Structural characterization of pyrolysis bio-oils

Biomass in the form of agricultural residues is becoming popular among new renewable energy sources, especially given its wide potential and abundant usage. Pyrolysis is the most important process among the thermal conversion processes of biomass. In this study, the various characteristics of bio-oils acquired under different pyrolysis conditions from safflower seed press cake (SPC) were identified. The elemental analyses and calorific values of the bio-oils were determined, and then the chemical compositions of the bio-oils were investigated using chromatographic and spectroscopic techniques such as column chromatography, ¹H NMR, FTIR and GC. The fuel properties of the bio-oil such as kinematic viscosity, flash point, density, water content and ASTM distillation were also determined. Chemical compositions of bio-oils showed that some quantities of hydrocarbons were present, while oxygenated and polar fractions dominated. The bio-oils obtained from safflower seed press cake were presented as an environmentally friendly feedstock candidate for biofuels and chemicals.     

Volatilisation of alkali and alkaline earth metallic species during the pyrolysis of biomass: differences between sugar cane bagasse and cane trash

Sugar cane bagasse and cane trash were pyrolysed in a novel quartz fluidised-bed/fixed-bed reactor. Quantification of the Na, K, Mg and Ca in chars revealed that pyrolysis temperature, heating rate, valence and biomass type were important factors influencing the volatilisation of these alkali and alkaline earth metallic (AAEM) species. Pyrolysis at a slow heating rate (approximately 10 K min(-1)) led to minimal (often <20%) volatilisation of AAEM species from these biomass samples. Fast heating rates (>1000 K s(-1)), encouraging volatile-char interactions with the current reactor configuration, resulted in the volatilisation of around 80% of Na, K, Mg and Ca from bagasse during pyrolysis at 900 degrees C. Similar behaviour was observed for monovalent Na and K with cane trash, but the volatilisation of Mg and Ca from cane trash was always restricted. The difference in Cl content between bagasse and cane trash was not sufficient to fully explain the difference in the volatilisation of Mg and Ca.     

Sunflower shells utilization for energetic purposes in an integrated approach of energy crops: laboratory study pyrolysis and kinetics

Sunflower is a traditional crop which can be used for the production of bioenergy and liquid biofuels. A study of the pyrolytic behaviour of sunflower residues at temperatures from 300 to 600 degrees C has been carried out. The experiments were performed in a captive sample reactor under atmospheric pressure and helium as sweeping gas. The yields of the derived pyrolysis products were determined in relation to temperature, with constant sweeping gas flow of 50 cm3 min(-1) and heating rate of 40 degrees Cs(-1). The maximum gas yield of around 53 wt.% was obtained at 500 degrees C, whereas maximum oil yield of about 21 wt.% was obtained at 400 degrees C. A simple first order kinetic model has been applied for the devolatilization of biomass. Kinetic constants have been estimated: E=78.15 kJ mol(-1); k(0)=1.03 x 10(3)s(-1).     

Microwave induced pyrolysis of oil palm biomass

The purpose of this paper was to carry out microwave induced pyrolysis of oil palm biomass (shell and fibers) with the help of char as microwave absorber (MA). Rapid heating and yield of microwave pyrolysis products such as bio-oil, char, and gas was found to depend on the ratio of biomass to microwave absorber. Temperature profiles revealed the heating characteristics of the biomass materials which can rapidly heat-up to high temperature within seconds in presence of MA. Some characterization of pyrolysis products was also presented. The advantage of this technique includes substantial reduction in consumption of energy, time and cost in order to produce bio-oil from biomass materials. Large biomass particle size can be used directly in microwave heating, thus saving grinding as well as moisture removal cost. A synergistic effect was found in using MA with oil palm biomass.     

Pyrolysis of groundnut de-oiled cake and characterization of the liquid product

Renewable biomass is considered as an important energy resource all over the world and for an agriculture based economy like that of India, the future prospects of being able to convert widely available biomass materials into various forms of fuel is most attractive. In this study, pyrolysis of groundnut de-oiled cake was investigated with an aim of studying the physical and chemical characteristics of the bio-fuel produced and to determine its feasibility as a commercial fuel. Thermal pyrolysis of groundnut de-oiled cake was done in a semi-batch reactor at a temperature range of 200-500 °C and at a heating rate of 20 °C/min. The chemical analysis of the bio-fuel showed the presence of functional groups such as alkanes, alkenes, alkynes, aldehydes, ketones, carboxylic acids, esters, amines, nitriles, nitro compounds and aromatics rings. The physical properties of the bio-fuel obtained were close to that of diesel and petrol.     

Pyrolysis of glycerol for the production of hydrogen or syn gas

Biodiesel has high potential as alternative liquid transportation fuel because it is renewable and CO(2) neutral, and has similar properties as diesel fuel. Glycerol is a by-product obtained during the production of biodiesel. Canadian government has planned to produce 500 million litres of biodiesel by 2010. An increase in biodiesel production would decrease the market price of glycerol. The objective of this study is to pyrolyse glycerol for the production of clean fuels such as H(2) or a feedstock such as syn gas for additional transportation fuel via Fisher-Tropsch synthesis. The pyrolysis of glycerol was carried out at various flow rates of N(2) (30-70 mL/min), temperatures (650-800 degrees C) and types and sizes of packing material in a tubular reactor at atmospheric pressure. The products were mostly gas, essentially consisting of CO, H(2), CO(2), CH(4) and C(2)H(4). It was observed that temperature, carrier flow rates and particle diameter of packing material had profound effects on the conversion of glycerol as well as product distribution. Composition of product gas ranged between syn gas 70-93 mol%, CH(4) 3-15 mol% and C(2)H(4) 2-12 mol% and heating value ranged from 13 to 22 MJ/m(3). This study indicates that the bio-glycerol has potential in making syn gas and medium heating value gases.