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.     

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.     

Catalytic conversion of Venice lagoon brown marine algae for producing hydrogen-rich gas and valuable biochemical using algal biochar and Ni/SBA-15 catalyst

This study investigated the catalytic behavior of two different types of materials: (i) algal biochar and (ii) 15 wt% Ni impregnated on SBA-15 support (Ni/SBA-15), in the thermochemical decomposition of Venice lagoon brown marine algae (Sargassum). First, non-catalytic pyrolysis tests were conducted in a temperature range of 400–800 °C in a dual-bed slow pyrolysis reactor. The optimum temperature for maximized liquid yield was at the temperature of 700 °C. Biochar catalyst exhibited excellent catalytic activity toward producing aromatic compounds via Diels-Alder-type reactions. However, Ni/SBA-15, because of interconnected pores provided easy passage for reactant and product during the catalytic pyrolysis process and resulted in an improvement in total gas yield (25.87 mmol/g Sargassum) and hydrogen-rich gas production (8.54 mmol/g Sargassum). The catalytic performances of both biochar and Ni/SBA-15 catalysts were compared to biochar-based catalysts derived from red and green macroalgae. High specific surface area, large pore volume, highly ordered pore structure, and narrow pore size distribution make SBA-15 a promising catalyst support in pyrolysis of biomass.     

Biohydrogen production from Imperata cylindrica bio-oil using non-stoichiometric and thermodynamic model

This paper presents a non-stoichiometric and thermodynamic model for steam reforming of Imperata cylindrica bio-oil for biohydrogen production. Thermodynamic analyses of major bio-oil components such as formic acid, propanoic acid, oleic acid, hexadecanoic acid and octanol produced from fast pyrolysis of I. cylindrica was examined. Sensitivity analyses of the operating conditions; temperature (100–1000 °C), pressure (1–10 atm) and steam to fuel ratio (1–10) were determined. The results showed an increase in biohydrogen yield with increasing temperature although the effect of pressure was negligible. Furthermore, increase in steam to fuel ratio favoured biohydrogen production. Maximum yield of 60 ± 10% at 500–810 °C temperature range and steam to fuel ratio 5–9 was obtained for formic acid, propanoic acid and octanol. The heavier components hexadecanoic and oleic acid maximum hydrogen yield are 40% (740 °C and S/F = 9) and 43% (810 °C and S/F = 8) respectively. However, the effect of pressure on biohydrogen yield at the selected reforming temperatures was negligible. Overall, the results of the study demonstrate that the non-stoichiometry and thermodynamic model can successfully predict biohydrogen yield as well as the composition of gas mixtures from the gasification and steam reforming of bio-oil from biomass resources. This will serve as a useful guide for further experimental works and process development.     

Utilization possibilities of Albizia amara as a source of biomass energy for bio-oil in pyrolysis process

Pyrolysis is one of the potential routes to harmless energy and useful chemicals from biomass. The pyrolysis of Albizia amara was studied for determining the main characteristics and quantities of liquid products. Particular investigated process variables were temperature from 350 to 550°C, particle size from 0.6 to 1.25 mm, and heating rate from 10 to 30 °C/min. The maximum bio-oil yield of 48.5 wt% at the pyrolysis temperature of 450°C was obtained at the particle size of 1.0 mm and at the heating rate of 30 °C/min. The bio-oil product was analyzed for physical, elemental, and chemical composition using Fourier transform infrared spectroscopy and gas chromatography spectroscopy. The bio-oil contains mostly phenols, alkanes, alkenes, saturated fatty acids and their derivatives. According to the experimental results, the pyrolysis bio-oil can be used as low-grade fuel having heating value of 18.63 MJ/kg and feedstock for chemical industries.     

Studies on catalytic pyrolysis of empty fruit bunch (EFB) using Taguchi's L9 Orthogonal Array

This paper investigates the effects of four reaction parameters that include type of catalyst, catalyst loading, reaction temperature and nitrogen gas flowrate on the liquid (bio-oil) yield from the catalytic pyrolysis of Empty Fruit Bunch (EFB). The experimental design is based on Taguchi's L9 Orthogonal Array in which the reaction parameters are varied at three levels. The maximum liquid yield is predicted based on systematic experimental runs, and is found to be at 5 wt-% of H-Y catalyst, 500 °C and at nitrogen flowrate of 100 ml min⁻¹. The predicted maximum liquid yield is validated with an experimental run at the corresponding predicted conditions. The bio-oil produced at the optimum reaction condition is characterized and compared with known bio-oil standards in the literature.     

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.     

Selective catalytic fast pyrolysis of Jatropha curcas residue with metal oxide impregnated activated carbon for upgrading bio-oil

Jatropha curcas waste was subjected to catalytic pyrolysis at 873 K using an analytical pyrolysis–gas chromatography/mass spectrometry in order to investigate the relative effect of various metal oxide/activated carbon (M/AC) catalysts on upgrading bio-oil from fast pyrolysis vapors of Jatropha waste residue. A commercial AC support was impregnated with Ce, Pd, Ru or Ni salts and calcined at 523 K to yield the 5 wt.% M/AC catalysts, which were then evaluated for their catalytic deoxygenation ability and selectivity towards desirable compounds. Without a catalyst, the main vapor products were fatty acids of 60.74% (area of GC/MS chromatogram), while aromatic and aliphatic hydrocarbon compounds were presented at only 11.32%. Catalytic pyrolysis with the AC and the M/AC catalysts reduced the oxygen-containing (including carboxylic acids) products in the pyrolytic vapors from 73.68% (no catalyst) to 1.60–36.25%, with Ce/AC being the most effective catalyst. Increasing the Jatropha waste residue to catalyst (J/C) ratio to 1:10 increased the aromatic and aliphatic hydrocarbon yields in the order of Ce/AC > AC > Pd/AC > Ni/AC, with the highest total hydrocarbon proportion obtained being 86.57%. Thus, these catalysts were effective for deoxygenation of the pyrolysis vapors to form hydrocarbons, with Ce/AC, which promotes aromatics, Pd/AC and Ni/AC as promising catalysts. In addition, only a low yield (0.62–7.80%) of toxic polycyclic aromatic hydrocarbons was obtained in the catalytic fast pyrolysis (highest with AC), which is one advantage of applying these catalysts to the pyrolysis process. The overall performance of these catalysts was acceptable and they can be considered for upgrading bio-oil.     

Multi-response optimization of bio-oil production from catalytic solar pyrolysis of Spirulina platensis

In this work, the solar catalytic pyrolysis of Spirulina platensis microalgae using hydrotalcite as a catalyst was studied to improve the yield and quality of the bio-oil obtained from the algae. The effects of biomass loading, reaction time, and catalyst percentage on the product distribution and bio-oil composition were evaluated. The desirability function was used to identify the pyrolysis conditions that maximize the bio-oil yield and its hydrocarbon content. The experimental results indicated that the catalytic pyrolysis of Spirulina platensis produced considerable solid product content, and high liquid yields were reached in some tests favored by the catalyst presence. The hydrotalcite contributed to increasing the hydrocarbon formation in the bio-oil at lower reaction times, demonstrating the great performance of this catalyst for microalgae pyrolysis. At the optimal conditions, a bio-oil yield of 35.94% with 21.71% hydrocarbon content was achieved.     

Non-catalytic and catalytic pyrolysis of Ulva prolifera macroalgae for production of quality bio-oil

Pyrolysis of Ulva prolifera macroalgae (UM), an aquatic biomass, was carried out in a fixed-bed reactor in the presence of three zeolites based catalysts (ZSM-5, Y-Zeolite and Mordenite) with the different catalyst to biomass ratio. A comparison between non-catalytic and catalytic behavior of ZSM-5, Y-Zeolite and Mordenite catalyst in the conversion of UM showed that is affected by properties of zeolites. Bio-oil yield was increased in the presence of Y-Zeolite while decreased with ZSM-5 and Mordenite catalyst. Maximum bio-oil yield for non-catalytic pyrolysis was (38.5 wt%) and with Y-Zeolite catalyst (41.3 wt%) was obtained at 400 °C respectively. All catalyst showed a higher gas yield. The higher gas yield might be attributed to that catalytic pyrolysis did the secondary cracking of pyrolytic volatiles and promoted the larger small molecules. The chemical components and functional groups present in the pyrolytic bio-oils are identified by GC–MS, FT-IR, ¹H-NMR and elemental analysis techniques. Phenol observed very less percentage in the case of non-catalytic pyrolysis bio-oil (9.9%), whereas catalytic pyrolysis bio-oil showed a higher percentage (16.1%). The higher amount of oxygen present in raw biomass reduced significantly when used catalyst due to the oxygen reacts with carbon and produce (CO and CO₂) and water.     

Kinetic study of the catalytic reforming of biomass pyrolysis volatiles over a commercial Ni/Al2O3 catalyst

An original kinetic model has been proposed for the reforming of the volatiles derived from biomass fast pyrolysis over a commercial Ni/Al₂O₃ catalyst. The pyrolysis-reforming strategy consists of two in-line steps. The pyrolysis step is performed in a conical spouted bed reactor (CSBR) at 500 °C, and the catalytic steam reforming of the volatiles has been carried out in-line in a fluidized bed reactor. The reforming conditions are as follows: 600, 650 and 700 °C; catalyst mass, 0, 1.6, 3.1, 6.3, 9.4 and 12.5 g; steam/biomass ratio, 4, and; time on stream, up to 120 min. The integration of the kinetic equations has been carried out using a code developed in Matlab. The reaction scheme takes into account the individual steps of steam reforming of bio-oil oxygenated compounds, CH₄ and C₂-C₄ hydrocarbons, and the WGS reaction. Moreover, a kinetic equation for deactivation has been derived, in which the bio-oil oxygenated compounds have been considered as the main coke precursors. The kinetic model allows quantifying the effect reforming conditions (temperature, catalyst mass and time on stream) have on product distribution.     

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.     

Catalytic co‐pyrolysis of Eichhornia Crassipes biomaѕѕ and polyethylene using waste Fe and CaCO3 catalysts

A wild aquatic plant, Eichhornia Crassipes, and polyethylene have been converted into liquid product thermo‐catalytically and cost effectively through co‐pyrolysis using batch steel pyrolyzer. The Fe and CaCO₃ catalysts were obtained as wastes from various mechanical processes. The catalytic process was compared with non‐catalytic pyrolysis. The effect of various reaction conditions was investigated in order to find out the optimized process conditions. It was found that the favorable reaction conditions were 450 °C temperature and 1‐h reaction time at a heating rate of 1 °C/s and 0.4‐mm biomass particle size. The bio‐oil yield was found to be 34.4% and 26.6% using Fe and CaCO₃ respectively with catalysts particle size of 0.4 mm at the optimized reaction conditions and 5 wt% of biomass. The non‐catalytic and catalytic co‐pyrolysis using Fe as catalyst produced 23.9% and 28.7% oil respectively. Thus the efficiency of processes in terms of bio‐oil production was found in order of: Fe > CaCO₃ > non‐catalytic pyrolysis. The GC/MS analysis of n‐hexane extract of bio‐oil shows that Fe catalyst favors formation of aliphatic hydrocarbons while CaCO₃ and non‐catalytic pyrolysis favors formation of aromatic hydrocarbons. Mostly unsaturated aliphatic hydrocarbons were formed in case of co‐pyrolysis reactions. The calorific value of bio‐oil was also measured in order to find out the fuel properties of the products. Copyright © 2016 John Wiley & Sons, Ltd.     

Steam reforming of propionic acid: Thermodynamic analysis of a model compound for hydrogen production from bio-oil

The thermodynamic equilibrium of steam reforming of propionic acid (HPAc) as a bio-oil model compound was studied over a wide range of reaction conditions (T = 500–900 °C, P = 1–10 bar and H₂O/HPAc = 0–4 mol/mol) using non-stoichiometric equilibrium models. The effect of operating conditions on equilibrium conversion, product composition and coke formation was studied. The equilibrium calculations indicate nearly complete conversion of propionic acid under these conditions. Additionally, carbon and methane formation are unfavorable at high temperatures and high steam to carbon (S/C) ratios. The hydrogen yield versus S/C ratio passes a maximum, the value and position of which depends on temperature. The thermodynamic equilibrium results for HPAc fit favorably with experimental data for real bio-oil steam reforming under same reaction conditions.     

Research on Non-Thermal Plasma assisted HZSM-5 online catalytic upgrading bio-oil

In order to improve the quality of bio-oil and reduce the coking and deactivation of HZSM-5 molecular sieve catalyst in the catalytic cracking of bio-oil upgrading process, Non-Thermal Plasma (NTP) assisted HZSM-5 technical scheme was proposed, online upgrading of rape straw vacuum pyrolytic vapors were conducted in a fixed bed reactor to verify the effectiveness of the technology. In the research, the influence of catalyzing temperature, catalyst bed height, discharge power on the physicochemical properties of refined bio-oil were studied, and the yield of refined bio-oil was regarded as evaluation index, response surface methodology was adopted to optimize upgrading processing parameters. Chemical composition of the refined bio-oil which was obtained under optimized parameters was analyzed by GC–MS, and using thermogravimetric analysis, the impact of NTP on catalyst anti-coking property was evaluated. Research results indicates that catalyzing temperature, catalyst bed height and discharge power have significance effect on yield and physicochemical properties of refined bio-oil. With the optimized processing parameters of 392 °C catalyzing temperature, 34 mm catalyst bed height and 23.7 W discharge power, the oxygen content, high heating value and pH of refined bio-oil were respectively 19.79%, 33.14 MJ/kg and 4.98. Compared with original HZSM-5 catalytic upgrading method, the quality of refined bio-oil was improved obviously, and the amount of catalyst coke deposit reduced from 5.88% to 2.14%, the feasibility of NTP assisted HZSM-5 online upgrading bio-oil was confirmed.     

Upgrading of fast pyrolysis bio-oil over Fe modified ZSM-5 catalyst to enhance the formation of phenolic compounds

The present study is aimed to investigate the upgrading of beech sawdust pyrolysis bio-oil through catalytic cracking of its vapors over Fe-modified ZSM-5 zeolite in a fixed bed tubular reactor. The zeolite supported iron catalyst was successfully prepared with varying metal loading ratios (1, 5, 10 wt%) via dry impregnation method and further characterized by BET, XRD, and SEM-EDX techniques. TG/FT-IR/MS analysis was used for the detection of biomass thermal degradation. Product yields of non-catalytic and catalytic pyrolysis experiments were determined and the obtained results show that bio-oil yields decreased in the presence of catalysts. Besides, the bio-oil composition is characterized by GC/MS. It was indicated that the entity of the ZSM-5 and Fe/ZSM-5 catalyst reveal a significant enhancement quality of the pyrolysis products in comparison with non-catalytic experiment. The catalyst increased oxygen removal from the organic phase of bio-oil and further developed the production of desirable products such as phenolics and aromatic compounds.     

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.     

Effect of mineral matter removal on pyrolysis of wood sawdust from an invasive species

Kinetics of the pyrolysis of wood sawdust from the invasive species Parkinsonia aculeata, untreated and demineralized by a mild acid treatment, is comparatively investigated in order to examine the effect of the removal of minerals naturally present in the biomass. Non-isothermal thermogravimetric analysis from room temperature up to 500°C is applied for this purpose. Demineralization shifts the process onset and the maximum degradation rate to higher temperatures, and leads to enhance the activation energy from 56 to 60 kJ mol^–1, pointing to a catalytic role of alkaline and alkaline earth metals in the biomass. Likewise, the three kinds of pyrolysis products (gas, bio-char, and bio-oil) are obtained from experiments performed in a bench-scale installation at 500°C. Yields and physicochemical characteristics of the pyrolysis products are determined. The pronounced reduction in the content of metals in the sawdust leads to increase bio-oil yield in around 10%, the specific surface area of the bio-char, from ≈ 2 to ≈ 74 m² g^–1, and the higher heating value of all the pyrolysis products.     

Hydrothermal liquefaction of macroalgae: Influence of zeolites based catalyst on products

Hydrothermal liquefaction (HTL) of Ulva prolifera macroalgae (UP) was carried out in the presence of three zeolites based catalysts (ZSM-5, Y-Zeolite and Mordenite) with the different weight percentage (10–20 wt%) at 260–300 °C for 15–45 min. A comparison between non-catalytic and catalytic behavior of ZSM-5, Y-Zeolite, and Mordenite in the conversion of Ulva prolifera showed that is affected by properties of zeolites. Maximum bio-oil yield for non-catalytic liquefaction was 16.6 wt% at 280 °C for 15 min. The bio-oil yield increased to 29.3 wt% with ZSM-5 catalyst (15.0 wt%) at 280 °C. The chemical components and functional groups present in the bio-oils are identified by GC-MS, FT-IR, ¹H-NMR, and elemental analysis techniques. Higher heating value (HHV) of bio-oil (32.2–34.8 MJ/kg) obtained when catalyst was used compared to the non-catalytic reaction (21.2 MJ/kg). The higher de-oxygenation occurred in the case of ZSM-5 catalytic liquefaction reaction compared to the other catalyst such as Y-zeolite and mordenite. The maximum percentage of the aromatic proton was observed in bio-oil of ZSM-5 (29.7%) catalyzed reaction and minimum (1.4%) was observed in the non-catalyst reaction bio-oil. The use of zeolites catalyst during the liquefaction, the oxygen content in the bio-oil reduced to 17.7%. Aqueous phase analysis exposed that presence of valuables nutrients.     

Characterization of the physicochemical and structural evolution of biomass particles during combined pyrolysis and CO2 gasification

The combination of pyrolysis and CO₂ gasification was studied to synergistically improve the syngas yield and biochar quality. The subsequent 60-min CO₂ gasification at 800 °C after pyrolysis increased the syngas yield from 23.4% to 40.7% while decreasing the yields of biochar and bio-oil from 27.3% to 17.1% and from 49.3% to 42.2%, respectively. The BET area of the biochar obtained by the subsequent 60-min CO₂ gasification at 800 °C was 384.5 m²/g, compared to 6.8 m²/g for the biochar obtained by the 60-min pyrolysis at 800 °C, and 1.4 m²/g for the raw biomass. The biochar obtained above 500 °C was virtually amorphous.