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.     

Bio‐oil production from rapid pyrolysis of cottonseed cake: product yields and compositions

Fixed‐bed fast pyrolysis experiments have been conducted on a sample of cottonseed cake to determine the effects of pyrolysis temperature, heating rate and sweep gas flow rate on pyrolysis yields and chemical compositions of the product oil. The liquid products and the subfractions of pentane soluble part were characterized by elemental analysis, FT‐IR spectroscopy, ¹H‐NMR spectroscopy and pentane subfraction was analysed by gas chromatography. The maximum oil yield of 34.8% was obtained at final temperature of 550°C with a heating rate of 700°C min^?1 and nitrogen flow rate of 100 cm³ min^?1. Chromatographic and spectroscopic studies on bio‐oil have shown that the oils obtained from cottonseed cake can be used as a renewable fuel and chemical feedstock. Copyright © 2005 John Wiley & Sons, Ltd.     

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.     

Energy production from the pyrolysis of waste biomasses

Pyrolysis of waste biomasses was carried out at the temperatures of 450 and 500°C by heating at 5°C min^?1. Products were collected from emitted gases in a nitrogen purge stream; condensable liquids in the gases were collected by condensation. Gaseous, condensed liquid products and residual solids were collected and analyzed. Condensates were extracted with ether to recover the bio oils (BOs). The maximum liquid yield was obtained from the pyrolysis of soybean oil cake (SBOC) at 500°C with a yield of 60% ca. The BO was higher in the case of SBOC than that of sunflower oil cake (SFOC) at the temperatures of 450 and 500°C. With increasing temperature, bio char yield from the pyrolysis of SFOC decreased, while the liquid yield increased. The increase in temperature did not significantly affect the product distribution for the pyrolysis of SBOC. The compositions of BOs were similar for both SBOC and SFOC. Phenols, phenol derivatives including guaiacols and alkyl‐benzenes were the most common and predominant in BOs from both the pyrolysis of SBOC and SFOC. Carbon dioxide was the major gas product for both SBOC and SFOC. Copyright © 2008 John Wiley & Sons, Ltd.     

Rapid and slow pyrolysis of pistachio shell: effect of pyrolysis conditions on the product yields and characterization of the liquid product

This study reports the experimental results for the pyrolysis of pistachio shell under different conditions in a tubular reactor under a nitrogen flow. For the different conditions of pyrolysis temperature, nitrogen flow rate and heating rate, pyrolysis temperature of 773 K gave the highest bio-oil yield with a value of 27.7% when the heating rate and carrier gas flow rate were chosen as 300 K min⁻¹ and 100 cm³ min⁻¹, respectively. Column chromatography was applied to this bio-oil and its subfractions were characterized by elemental analysis, FT-IR and ¹H-NMR. Aliphatic subfraction was conducted to gas chromatography–mass spectroscopy for further characterization. The results for the characterization show that using pistachio shell as a renewable source to produce valuable liquid products is applicable via pyrolysis. Copyright © 2006 John Wiley & Sons, Ltd.     

Olive residues (cuttings and kernels) rapid pyrolysis product yields and kinetics

A study of pyrolysis of olive residues (cuttings and kernels) at a temperature range from 300 to 600°C, has been carried out. The experiments were performed in a captive sample reactor at atmospheric pressure under helium. The yields of the derived gases, pyrolytic liquids and char were determined in relation to pyrolysis temperature, at heating rates of about 200°C/s.As the pyrolysis temperature was increased the percentage mass of char decreased whilst gas and oil products increased. The oil products increased to a maximum value of ∼30 wt% of dry biomass at about 450–550°C. The major gaseous products are CO and CO₂.A simple first order kinetic model has been applied to the evolution of total losses and gases. Kinetic parameters have been estimated and compared with other reported similar data.     

Experimental analysis of pyrolysis of sewage sludge

Pyrolysis is a thermal process where organic materials such as biomass and oil are decomposed and lighter materials such as gas, vapor, liquid products, and char are produced. The aim of this study was to investigate the pyrolysis behavior of sewage sludge in different operating conditions. Using a fixed bed, the influence of some important parameters such as pyrolysis temperature, heating rate, particle size, and N₂ flow rate on product yields was studied. Results showed that with increase in temperature from 400 to 700°C, the char yield decreased from 30.1 to 7.50%, while the gas yield increased from 35.8 to 52.4%. The gas yield also increased from 46.9 to 49.1% as the heating rate increased from 20 to 60°C/s, while the oil yield increased from 45.2 to 46.8% as heating rate increased to 40°C/s and then the increase leveled off.     

The effect of heating rate on yields and compositions of oil products from esparto pyrolysis

Recently, much research has been focused on liquid oil from biomass pyrolysis, which is considered as an alternative to conventional fossil fuels. This paper studies the effect of heating rate on both the yields and the chemical composition of the oil product obtained from pyrolysis of esparto which is the most important biomass in Morocco. The pyrolysis experiments of esparto was performed in a fixed bed reactor under argon atmosphere with different heating rate: 50, 150 and 250°C min^?1. The maximum conversion of esparto in oil of pyrolysis was obtained with fast pyrolysis 68.5% at 550°C. The FT‐IR and ¹H NMR analysis showed that the oil of pyrolysis formed principally by aliphatic compound. The analysis elemental showed that the H/C ratio increase and O/C decrease as the heating rate increase. The PCV improved slightly from 33.5 to 34.8 MJ kg^?1. The oil obtained with higher heating rate has chemical properties similar to diesel that can be used with an economic and environmental advantage. Copyright © 2006 John Wiley & Sons, Ltd.     

Evaluation of influence of two different catalysts on the pyrolysis of laurel (Laurus nobilis L.) extraction residues

Laurel extraction residues with zeolite and alumina catalysts were pyrolyzed in a fixed-bed reactor with a constant heating rate of 10°C min^–1. The final pyrolysis temperature and sweep gas flow rate were kept constant at 500°C and 100 ml min^–1 in all of the experiments, respectively. The influence of catalysts and their ratio (10, 20, 30, 40, and 50% w/w) on the pyrolysis conversion and product yields were investigated in detail. The physicochemical properties of the catalytic bio-oil were determined and compared to those of non-catalytic bio-oil. The catalytic bio-oils were examined using some spectroscopic and chromatographic techniques.     

Pyrolysis of Alternanthera philoxeroides (alligator weed): Effect of pyrolysis parameter on product yield and characterization of liquid product and bio char

In the present work, fast pyrolysis of Alternanthera philoxeroides was evaluated with a focus to study the chemical and physical characteristics of bio-oil produced and to determine its practicability as a transportation fuel. Pyrolysis of A.philoxeroides was conducted inside a semi batch quartz glass reactor to determine the effect of different operating conditions on the pyrolysis product yield. The thermal pyrolysis of A. philoxeroides were performed at a temperature range from 350 to 550 °C at a constant heating rate of 25 °C/min & under nitrogen atmosphere at a flow rate of 0.1 L/min, which yielded a total 40.10 wt.% of bio-oil at 450 °C. Later, some more sets of experiments were also performed to see the effect on pyrolysis product yield with change in operating conditions like varying heating rates (50 °C/min, 75 °C/min & 100 °C/min) and different flow rates of nitrogen (0.2, 0.3, 0.4 & 0.5 L/min). The yield of bio-oil during different heating rate (25, 50, 75 and 100 °C/min) was found to be more (43.15 wt.%) at a constant heating rate of 50 °C/min with 0.2 L/min N₂ gas flow rate and at a fixed pyrolysis temperature of 450 °C. The High Heating Value (HHV) value of bio-oil (8.88 MJ/kg) was very less due to presence of oxygen in the biomass. However, the high heating value of bio-char (20.41 MJ/kg) was more, and has the potential to be used as a solid fuel. The thermal degradation of A. philoxeroides was studied in TGA under inert atmosphere. The characterization of bio-oil was done by elemental analyser (CHNS/O analyser), FT-IR, & GC/MS. The char was characterized by elemental analyser (CHNS/O analysis), SEM, BET and FT-IR techniques. The chemical characterization showed that the bio-oil could be used as a transportation fuel if upgraded or blended with other fuels. The bio-oil can also be used as feedstock for different chemicals. The bio-char obtained from A. philoxeroides can be used for adsorption purposes because of its high surface area.     

Low‐temperature pyrolysis of municipal solid waste: influence of pyrolysis temperature on the characteristics of solid fuel

This paper presents the results of pyrolysis experiments of the mixtures of nine different combustibles municipal solid wastes (MSW's main composition: rice 24.33% and fruits 14.60%). The experiments were carried out in a laboratory‐scale reactor under nitrogen atmosphere at temperature of 300–700°C. The study concentrates on low‐temperature pyrolysis of MSWs and the effect of the pyrolysis temperature on the characteristics of the products (solid fuels) including proximate analysis, volatile content, heating value, ignition temperature and density of the solid fuel. The results indicate that the pyrolysis temperature plays an important role on the characteristics of the solid fuels. The volatile content of the solid fuels decreases with the pyrolysis temperature so that the low‐pyrolysis MSW treating process has advantage for higher heating value of the solid fuel for energy recovery purpose. The heating value is in the range of 23–27 MJ kg^?1, equivalent to the heating value of low‐rank coals. Copyright © 2005 John Wiley & Sons, Ltd.     

The influence of temperature and heating rate on the slow pyrolysis of biomass

The slow pyrolysis of biomass in the form of pine wood was investigated in a static batch reactor at pyrolysis temperatures from 300 to 720°C and heating rates from 5 to 80 K min⁻¹. The compositions and properties of the derived gases, pyrolytic oils and solid char were determined in relation to pyrolysis temperatures and heating rates. In addition, the wood and the major components of the wood—cellulose, hemicellulose and lignin—were pyrolysed in a thermogravimetric analyser (TGA) under the same experimental conditions as in the static batch reactor. The static batch reactor results showed that as the pyrolysis temperature was increased, the percentage mass of solid char decreased, while gas and oil products increased. There was a small effect of heating rate on product yield. The lower temperature regime of decomposition of wood showed that mainly H₂O, CO₂ and CO were evolved and at the higher temperature regime, the main decomposition products were oil, H₂O, H₂, hydrocarbon gases and lower concentrations of CO and CO₂. Fourier transformation infra-red spectroscopy and elemental analysis of the oils showed they were highly oxygenated. The TGA results for wood showed two main regimes of weight loss, the lower temperature regime could be correlated with the decomposition of hemicellulose and the initial stages of cellulose decomposition whilst the upper temperature regime correlated mainly with the later stages of cellulose decomposition. Lignin thermal decomposition occurred throughout the temperature range of pyrolysis.     

Highly efficient Co/NC catalyst derived from ZIF-67 for hydrogen generation through ammonia decomposition

Small-size cobalt nanoparticles (NPs) distributed on nitrogen doped carbon support (Co/NC-X) were prepared by pyrolysis of ZIF-67 at various temperatures (X = 500, 600,700 and 800 °C) in nitrogen atmosphere and utilized as catalysts for hydrogen production through ammonia decomposition. Characterizations of the catalysts including XRD, HRTEM, XPS, H₂-TPR, CO₂-TPD, etc., were conducted for structure analysis. The N–C plate obtained from pyrolysis was coated with Co NPs to hinder its aggregation, which made the Co NPs dispersed evenly and increased their dispersion. The calcination temperature and the strong base of the support can adjust the strength of Co–N bond. The activity of the Co/NC-X catalysts is attributed to the high content of Co⁰ and the moderate Co–N bond strength. The ammonia decomposition activity of Co/NC-X catalysts in this paper is higher than many reported Co-based catalysts. Co/NC-600 catalyst demonstrates an ammonia conversion of 80% at 500 °C with a space velocity of 30,000 ml g_cat^?1 h^?1, corresponding to a hydrogen production rate of 26.8 mmol H₂ g_cat^?1 min^?1. The work provides insight for the development of highly active cobalt-based catalysts for hydrogen production through ammonia decomposition.     

Experimental investigation of pyrolysis process of woody biomass mixture

This paper describes an experimental investigation of pyrolysis of woody biomass mixture. The mixture consists of oak, beech, fir, cherry, walnut and linden wood chips with equal mass fractions. During the experiment, the sample mass inside the reactor was 10 g with a particle diameter of 5-10 mm. The sample in the reactor was heated in the temperature range of 24-650℃. Average sample heating rates in the reactor were 21, 30 and 54 ℃/min. The sample mass before, during and after pyrolysis was determined using a digital scale. Experimental results of the sample mass change indicate that the highest yield of pyrolytic gas was achieved at the temperature slightly above 650℃ and ranged from 77 to 85%, while char yield ranged from 15 to 23%. Heating rate has sig- nificant influence on the pyrolytic gas and char yields. It was determined that higher pyrolysis temperatures and heating rates induce higher yields of pyrolytic gas, while the char mass reduces. Condensation of pyrolytic gas at the end of the pyrolysis process at 650℃ produced 2.4-2.72 g of liquid phase. The results obtained represent a starting basis for determining material and heat balance of pyrolysis process as well as woody biomass pyrolysis equipment.     

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.     

Kinetic study and thermal analysis of the pyrolysis of non-edible oilseed powders by thermogravimetric and differential scanning calorimetric analysis

This work reports the kinetic study of the pyrolysis of four non-edible oil seeds such as Mahua, Karanja, Niger and Linseed conducted at a heating rate of 5, 10 and 15 °C min⁻¹ under nitrogen atmosphere. The relation between kinetic parameters and degradation rate was observed with respect to temperature and heating rate. The results indicated that the kinetic parameters were very close to each other and directly proportional to temperature and heating rate. The comparison of kinetic parameters related to heating rate concluded that heating rate had a direct affinity towards activation energy and pre-exponential factor. The TG-DTG analysis indicated three stages of thermal degradation during pyrolysis of the oil seeds whereas DSC analysis point towards the endothermic and exothermic pathway of pyrolysis. The presence of hemicelluloses, cellulose and lignin was determined on the basis of degradation temperature and their respective functional groups in the seeds observed by FTIR analysis.     

Investigation of Pyrolysis Kinetics of Humic Acids from Low Rank Anatolian Coal by Thermal Analysis

Abstract

Thermogravimetric analysis (TGA) of humic acid samples from low rank Anatolian (east of Turkey, Bingol) coal were investigated under atmospheric pressure. The samples were subjected for the decomposition of organic matter ambient to 800°C at four different heating rates (5, 10, 15, and 20°C min^?1). The humic acid samples were started at decomposition between 170–206°C and amount of residues varied 55–60% according to heating rate. Each of samples was showed a single step mass loss. TG/DTG data of samples were analyzed to determine activation energy values by Coats and Redfern method and Arrhenius method. Activation energy values are similar obtained from Coats and Redfern method and Arrhenius method and varied from 25 to 29 kJ mol^?1.     

Hydrogen from empty cotton boll agro-waste via thermochemical route and feasibility study of operating an IC engine in continuous mode

Hydrogen can be cited as prospective source of clean power. In this work hydrogen rich syn-gas generated from the agro-waste, empty cotton bolls was injected into an IC engine in continuous mode along with gasoline. At the air-fuel ratio of 23.40, specific fuel consumption of 0.35 kg kWh^?1, the engine could be operated with higher efficiency than with gasoline alone. A distinct reduction in emission characteristics could also be seen. Empty cotton bolls derived after removal of cotton from the flower in field, was first studied for fuel properties. The reasonably high heating value (HHV) of 17.54 MJ kg^?1 suggested that it could be a precursor to hydrogen via two stepped thermo-chemical process. The first step involved slow pyrolysis of the biomass at 500 °C for 60 min at a heating rate of 10 °C min^?1 yielding 39.71% bio-char by weight. The C, H, N, S and O contents of the produced bio-char was 59.91, 2.91, 0.72, 0.47 and 35.99% respectively and its HHV was 26.7 MJ kg^?1. Steam gasification of this bio-char, at 700 °C and water flowrate of 7 mL min^?1 exhibited maximum hydrogen yield of 67.42% (v/v) in the syn-gas mixture. Subsequent enrichment of the gas using ethanolamine/ethylene diamine and KMnO₄ solutions resulted in more than 90% (v/v) hydrogen in the combustible gas mixture and the test engine could be effectively operated.     

Comparison of catalytic and noncatalytic pyrolysis and product yields of some waste biomass species

The products obtained by fast pyrolysis of biomass can be used as an energy source or chemical raw material. In this study, samples of hazelnut shells, tea bush, and hazelnut knot selected as waste biomass were from the cities of Trabzon and Rize in the Eastern Black Sea Region. Firstly, the waste biomass samples were granulated into four different particle sizes by milling and sieving operations. Fast pyrolysis of the samples with specific mixing rates was carried out in a fixed bed reactor. Additionally, 2 wt% vanadium (V) oxide (V₂O₅) was used as catalyst to maximize the yield of pyrolysis liquid products. The influence of temperature, heating rate, and particle size on fast pyrolysis yields under both catalytic and noncatalytic conditions were investigated and compared. While the amount of liquid product increased with the addition of catalyst, the amount of solid products decreased. It has been found that the temperature and heating rate parameters are very effective in liquid product yield. In all experiments, the maximum liquid yield was acquired at the same heating rate of 450°C min^?1 and the temperature of 450°C with particle size of 0.5 to 1.0 mm. The maximum pyrolysis liquid (bio‐oil) was obtained with catalytic pyrolysis, and this value was 60.58 wt%.     

Fixed-bed pyrolysis of safflower seed: influence of pyrolysis parameters on product yields and compositions

Fixed-bed slow pyrolysis experiments have been conducted on a sample of safflower seed to determine particularly the effects of pyrolysis temperature, heating rate, particle size and sweep gas flow rate on the pyrolysis product yields and their chemical compositions. The maximum oil yield of 44% was obtained at the final pyrolysis temperature of 500°C, particle size range of +0.425–1.25 mm, with heating rate of 5°C min⁻¹ and sweep gas (N₂) flow rate of 100 cm³ min⁻¹ in a fixed-bed lab-scale reactor. Chromatographic and spectroscopic studies on the pyrolytic oil showed that the oil obtained from safflower seed can be used as a renewable fuel and chemical feedstock with a calorific value of 41.0 MJ/kg and empirical formula of CH_1.92O_0.11N_0.02.