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.     

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.     

Tailoring Cu/Al2O3 catalysts for the catalytic pyrolysis of tomato waste

In this study, pyrolysis of tomato waste has been performed in fixed bed tubular reactor at 500 °C, both in absence and presence of Cu/Al₂O₃ catalyst. The influences of heating rate, catalyst preparation method and catalyst loading on bio-oil yields and properties were examined. According to pyrolysis experiments, the highest bio-oil yield was obtained as 30.31% with a heating rate of 100 °C/min, 5% Cu/Al₂O₃ catalyst loading ratio and co-precipitation method. Results showed that the catalysts have strong positive effect on bio-oil yields. Bio-oil quality obtained from fast catalytic pyrolysis was more favorable than that obtained from non-catalytic and slow catalytic pyrolysis.     

Pyrolysis of Xanthium strumarium in a fixed bed reactor: Effects of boron catalysts and pyrolysis parameters on product yields and character

Pyrolysis of Xanthium strumarium has been performed in a fixed-bed tubular reactor with boron minerals (ulexite, colemanite, and borax) and without catalyst at three different temperatures ranging from 350°C to 550°C with heating rate of 50°C/min. The amounts of bio-oil, bio-char, and gas generated, also the compositions of the resulting bio-oils were identified by GC-MS and FT-IR. The influences of pyrolysis parameters, such as temperature and catalyst on product yields were investigated. Temperature and catalyst were found to be the main factors affecting the conversion of Xanthium strumarium into solid, liquid, and gaseous products. The highest liquid yield (27.97%) including water was obtained with 10% colemanite (Ca₂B₆O₁₁.5H₂O) catalyst at 550°C temperature at a heating rate of 50°C/min when 0.224 > D_p > 0.150 mm particle size raw material and 100 cm³/min of sweeping gas flow rate were used.     

Rice straw as a bio-oil source via pyrolysis and steam pyrolysis

The pyrolysis of rice straw was studied to estimate the effect of pyrolysis conditions on product yields and bio-oil composition when the heating rate was 5 K/min. Pyrolysis temperature, particle size, sweeping gas flow rate and steam velocity were the experimental parameters. Among the four pyrolysis temperatures; namely, 673, 773, 823 and 973 K; 823 K gave the highest bio-oil yield of 27.26%. Six different particle sizes were examined and sample having a particle size of 0.425<D_p<0.85 mm had a bio-oil yield of 27.77%. Nitrogen was used as the sweeping gas with the flow rates of either 50, 100, 200 and 400 ml/min and the highest bio-oil yield was obtained when flow rate was 200 ml/min. The bio-oil yield reached a maximum value of 35.86% with the steam velocity of 2.7 cm/s. Liquid products obtained from pyrolysis, inert atmosphere pyrolysis and steam pyrolysis were then fractionated into aspalthanes and maltanes. The aliphatic subfraction obtained by column chromatography was then analysed by GC/MS. For further structural analysis, the pyrolysis oils were conducted with ¹H-NMR, oils and aliphatic subfractions with FT-IR. The chemical characterisation has shown that the oil obtained from rice straw may be potentially valuable as fuel and chemicals feedstocks.     

Flash pyrolysis of palmyra palm (Borassus flabellifer) using an electrically heated fluidized bed reactor

Agriculture residues such as palmyra fruit bunch are one of the biomass categories that can be utilized for conversion to bio-oil by using pyrolysis process. Flash pyrolysis experiments have been conducted in the electrically heated fluidized bed reactor to determine the effect of pyrolysis temperature, particle size, and sweep gas flow rate on the pyrolysis product yield. In this study the maximum oil yield of 48.2% was achieved at a temperature of 500°C, particle size of 1 mm, and at a sweep gas flow rate of 2 m³/h. The results show that the effects of pyrolysis temperature and particle size on pyrolysis yields are more significant than that of sweep gas flow rate. Bio-oil was identified as a biofuel candidate and it was further upgraded for better-quality biofuel. Various physical and elemental analyses were performed for bio-oil and the same characteristics study was also carried out for biofuel.     

In situ hydrodeoxygenation upgrading of pine sawdust bio-oil to hydrocarbon biofuel using Pd/C catalyst

Hydrodeoxygenation (HDO) is effective for upgrading bio-oil to biofuel. However, the upgrading cost increased due to the high consumption of external hydrogen. In this paper, the hydrogen generated from cheap water using zinc hydrolysis for in situ bio-oil HDO was reported. The effect of different temperatures (200 °C, 250 °C and 300 °C) on bio-oil HDO over Pd/C catalyst was investigated in a batch reactor. The results show that 250 °C yielded biofuel with the highest heating value at 30.17 MJ/kg and the highest hydrocarbons content at 24.09%. Physicochemical properties including heating value, total acid number and chemical compositions of the produced biofuels improved significantly in comparison with that of the original bio-oil.     

Thermo-chemical conversion of waste rubber seed shell to produce fuel and value-added chemicals

Rubber seed shell (RSS), comprises of 96.67 wt% organic content and 38.6% crystallinity index, was used for the production of biofuel and value-added chemicals through semi-batch pyrolysis. Thermogravimetric analysis (TGA) of RSS at heating rate of 20 °C/min showed R50 value as 12.72%/min at 376.5 °C. The gaseous product evolved during the decomposition of RSS were analyzed through inline Fourier transform infrared (FT-IR) coupled with TGA instrument. The effects of pyrolysis temperatures (350°C-600 °C) and heating rates (10°C/min–40 °C/min) on the product distribution (liquid, gas and bio-char) were investigated. The maximum yield of liquid product (46.14 wt%) and the carbon-rich bio-char (31.92 wt%) were obtained at 550 °C temperature for heating rate of 30 °C/min. The fuel characteristics of produced bio-char such as higher calorific value (34.5 MJ/kg), higher fixed carbon (79.74 wt%), lower ash (1.87 wt%) and lower moisture content (2.11 wt%) suggested its potential to be used as solid fuel. Value-added organic compounds such as acetic acid, phenolic compounds, creosol, pilocarpine, benzene and levoglucosan were identified in the liquid product using gas chromatography. The pH values of liquid products (2.55–3.0) support the presence of organic acids and phenolic fraction. The presence of various functional groups was also identified using FT-IR spectroscopy. In depth analysis of physico-chemical-thermal properties of RSS and obtained products (liquid and bio-char) suggested that RSS can be considered as a suitable feedstock for the production of value added chemicals including fuel.     

Comparison of pyrolysis and hydrothermal liquefaction of Chlamydomonas reinhardtii. Growth studies on the recovered hydrothermal aqueous phase

The production of bio-oil by pyrolysis with a high heating rate (500 K s⁻¹) and hydrothermal liquefaction (HTL) of Chlamydomonas reinhardtii was compared. HTL led to bio-oil yield decreasing from 67% mass fraction at 220 °C to 59% mass fraction at 310 °C whereas the bio-oil yield increased from 53% mass fraction at 400 °C to 60% mass fraction at 550 °C for pyrolysis. Energy ratios (energy produced in the form of bio-oil divided by the energy content of the initial microalgae) between 66% at 220 °C and 90% at 310 °C in HTL were obtained whereas it was in the range 73–83% at 400–550 °C for pyrolysis. The Higher Heating Value of the HTL bio-oil was increasing with the temperature while it was constant for pyrolysis. Microalgae cultivation in aqueous phase produced by HTL was also investigated and showed promising results.     

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.     

Experimental investigation on improvement of storage stability of bio-oil derived from intermediate pyrolysis of Calophyllum inophyllum seed cake

Due to the unstable nature of bio-oil, it becomes mandatory to analyze the changes in physical and chemical properties of the bio-oil during storage to appreciate its chemical instability, for developing stabilization strategies. The present study aims to investigate the oxidative and thermal stability of bio-oil extracted from pyrolyzing Calophyllum inophyllum (CI) deoiled seed cake in a fixed bed reactor at 500 °C under the constant heating rate of 30 °C/min. Each stability analysis method involve an accelerated aging procedure based on standards established by ASTM (D5304 and E2009) and European standard (EN 14112). Fourier Transform Infrared Spectroscopy and Gas Chromatography-Mass Spectrometry were employed to analytically characterize the un-aged and aged bio-oil samples. The results clearly depict that stabilizing Calophyllum inophyllum bio-oil with 10% (w/w) methanol improved its stability than that of the crude sample. Addition of methanol reduced the change in viscosity of bio-oil by 38.55% during accelerated aging process. The oxidation stability index of bio-oil stabilized with methanol was found to be 3.97 h which is in accordance with ASTM D6751. FT-IR and GC-MS results showed an increase in the relative concentration of C-O (carboxylic acids, ethers and esters) and C=O (carbonyl) functional groups in aged bio-oil samples.     

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.     

Characterization of bio-oil and its sub-fractions from pyrolysis of Scenedesmus dimorphus

In the present study, microalgae Scenedesmus dimorphus was reported for pyrolysis in a fixed-bed reactor to determine the effects of temperature on products yield and the chemical compositions of the liquid and solid products. Experiments were carried out at a temperature range of 300–600 °C with heating rate of 40 °C/min and nitrogen flow rate of 100 ml/min. The yield of bio-oil was found to be maximum (39.6%) at the temperature of 500 °C and was further fractionated into n-hexane, toluene, ethyl acetate and methanol sub-fractions by using liquid column chromatography. Various characteristics of bio-oil and its sub-fractions were determined by ¹H NMR, FTIR and GC–MS. The biochar produced as a co-product can be a potential soil amendment with multiple benefits including soil fertility and C-sequestration. The present investigation suggests the suitability of Scenedesmus dimorphus as a potential feedstock for exploitation of energy and biomaterials through pyrolytic conversion.     

Modeling of beech wood pellet pyrolysis under concentrated solar radiation

A two-dimensional, unsteady CFD (Computational Fluid Dynamics) single particle model was developed and used to simulate the solar pyrolysis process of beech wood pellets (10 mm in diameter and 5 mm in height). Pseudo-stoichiometric coefficients about the mass fraction of primary tar converted by the reaction into gas and secondary tar were determined at different temperatures and heating rates for the first time. The 2D model predictions were successfully validated with tests performed at 600 °C to 2000 °C final temperature, with 10 and 50 °C/s heating rates. The evolution of the final products and mass losses of pyrolyzed biomass are enhanced with temperature and heating rate. Moreover, the higher the temperature and heating rate, the higher the gas yield. This emphasizes the intra-particle tar secondary reaction into gas for pyrolysis of large size sample under high temperature and heating rate.     

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.     

The characteristics of syngas production from bio-oil dry reforming utilizing the waste heat of granulated blast furnace slag

A two-stage utilization of the waste heat of granulated blast furnace slag (BFS) was proposed, and the characteristics of bio-oil dry reforming under different conditions were investigated. For the bio-oil dry reforming utilizing granulated BFS as the heat carrier, when the temperature was higher than 800 °C, changes in the characteristics as bio-oil conversion and lower heating value (LHV) were not pronounced in response to the increasing temperature. The bio-oil conversion reached its maximum value with a CO₂/C (molar ratio of CO₂ to carbon in bio-oil) of 0.85. When the liquid hourly space velocity (LHSV) was higher than 0.45 h^?1, the bio-oil conversion and LHV dropped quickly as the LHSV increased. At the optimal condition with a temperature of 800 °C, a CO₂/C of 0.85 and an LHSV of 0.45 h^?1, the bio-oil conversion and LHV reached 90.15% and 511.02 kJ per mole of bio-oil, respectively. Granulated BFS could be beneficial for the bio-oil dry reforming process. Combining biomass pyrolysis and bio-oil dry reforming, a feasible industry application utilizing the waste heat of granulated BFS was presented systematically.     

A comparative study on the quality of bioproducts derived from catalytic pyrolysis of green microalgae Spirulina (Arthrospira) plantensis over transition metals supported on HMS-ZSM5 composite

This study investigated three different types of catalysts: Ni/HMS-ZSM5, Fe/HMS-ZSM5, and Ce/HMS-ZSM5 in the thermochemical decomposition of green microalgae Spirulina (Arthrospira) plantensis. First, non-catalytic pyrolysis tests were conducted in a temperature ranges of 400–700 °C in a dual-bed pyrolysis reactor. The optimum temperature for maximized liquid yield was determined as 500 °C. Then, the influence of acid washing on bio-products upgrading was studied at the optimum temperature. Compared to the product yields from the pyrolysis of raw spirulina, a higher bio-oil yield (from 34.488 to 37.778 %wt.) and a lower bio-char yield (from 37 to 35 %wt.) were observed for pretreated spirulina, indicating that pretreatment promoted the formation of bio-oil, while it inhibited the formation of biochar from biomass pyrolysis. Finally, catalytic pyrolysis experiments of pretreated-spirulina resulted that Fe as an active phase in catalyst exhibited excellent catalytic activity, toward producing hydrocarbons and the highest hydrogen yield (3.81 mmol/gr spirulina).     

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%.     

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.     

Bio-oil production from hydrothermal liquefaction of waste Cyanophyta biomass: Influence of process variables and their interactions on the product distributions

Hydrothermal liquefaction (HTL) of waste Cyanophyta biomass at different temperatures (factor A, 260–420 °C), times (factor B, 5–75 min) and algae/water (a/w) ratios (factor C, 0.02–0.3) by single reaction condition and Response Surface Method (RSM) experiments was investigated. By single reaction condition runs, maximum total bio-oil yield (29.24%) was obtained at 350 °C, 60 min and 0.25 a/w ratio. Maximum bio-oil HHV of 40.04 MJ/kg and energy recovery of 51.09% was achieved at 350 °C, 30 min, 0.1 a/w ratio and 350 °C, 60 min, 0.25 a/w ratio, respectively. RSM results indicate that effect of AB interaction was significant on light bio-oil yield. Both AC and AB had more remarkable influence than BC on heavy bio-oil yield and aqueous total organic carbon (TOC) recovery whereas BC was noticeable on ammonia nitrogen (NH₃N) recovery in aqueous products. By model-based optimization of highest bio-oil yield, the highest bio-oil yield reached 31.79%, increasing by 8.72% after RSM optimization, and light and heavy bio-oil yield was 17.44% and 14.35%, respectively. Long-chain alkanes, alkenes, ketones, fatty acids, phenols, benzenes, amides, naphthalenes were the main components in light bio-oil. Some alcohols, phenols and aromatics were primarily found in heavy bio-oil. Solid residue after HTL consisted of numerous microparticles (～5 μm) observed by Scanning Electron Microscopy (SEM). Energy Dispersive Spectrometer (EDS) analysis shows these particles primarily contained C, O, Mg, P and microelements, derived from Cyanophyta cells.