Understanding the pyrolysis behavior of agriculture,forest and aquatic biomass: Products distribution and characterization

Pyrolysis studies on agricultural (rice straw), forest (pine) and aquatic (Ulva lactuca) biomass were carried out in a fixed bed reactor at different temperature range of 300–550 °C. The product distributions and their characterization of products were compared among these biomasses. The maximum liquid product yield 29.4, 57.5 and 25.6 wt% obtained at 400, 500 and 400 °C respectively from rice straw (RS), pine (PN) and Ulva lactuca (UL) biomass. However, the higher conversion was observed in the case of pine wood biomass 77.0% at 550 °C. From the GC-MS analysis, it is observed that RS and PN bio-oil mostly composed of derivatives of phenolic compounds, while UL bio-oil composed of cyclopentenone derivatives compounds. The highest higher heating value (HHV) was found in pine bio-oil 34.8 MJ/kg. Also PN pyrolytic bio-oil had higher boiling point differences compounds. The bio-char analysis showed that the PN bio-char is a carbon rich and porous in nature as compared to the RS and UL bio-char.     

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.     

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.     

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.     

Directed regulation of pyridines components in the steam reforming of aqueous bio-oil to H2 production

The steam reforming of aqueous bio-oil is a promising technology for green hydrogen production, yet one of the obstacles is still the cost of production. It was found that under certain conditions, the high-value pyridines components in aqueous bio-oil will be enriched after a reforming hydrogen production reaction, which may become an effective way to improve its economy. In this study, the effects of temperature (700°C–900 °C) and WHSV (10 h⁻¹-30 h⁻¹) on hydrogen production rate and pyridine enrichment rate were investigated. The results show that the highest hydrogen yield of 40.3% was obtained at the initial stage of the reaction at the optimum operating conditions of 850 °C and a WHSV of 15 h⁻¹. Pyridine enrichment in the liquid product collected after the reaction can reach up to 300% at the same time. This study proposed a new route for the co-production of pyridines in the catalytic reforming process of aqueous bio-oil, which is beneficial to the complete quantitative utilization of biomass and improves the economics of bio-oil products.     

Optimization of two bio-oil steam reforming processes for hydrogen production based on thermodynamic analysis

Thermodynamics of hydrogen production from conventional steam reforming (C-SR) and sorption-enhanced steam reforming (SE-SR) of bio-oil was performed under different conditions including reforming temperature, S/C ratio (the mole ratio of steam to carbon in the bio-oil), operating pressure and CaO/C ratio (the mole ratio of CaO to carbon in the bio-oil). Increasing temperature and S/C ratio, and decreasing the operating pressure were favorable to improve the hydrogen yield. Compared to C-SR, SE-SR had the significant advantage of higher hydrogen yield at lower desirable temperature, and showed a significant suppression for carbon formation. However excess CaO (CaO/C > 1) almost had no additional contribution to hydrogen production. Aimed to achieve the maximum utilization of bio-oil with as little energy consumption as possible, the influences of temperature and S/C ratio on the reforming performance (energy requirements and bio-oil consumption per unit volume of hydrogen produced, Q_D/H2 (kJ/Nm³) and Y_Bio-oil/H2 (kg/Nm³)) were comprehensively evaluated using matrix analysis while ensuring the highest hydrogen yield as possible. The optimal operating parameters were confirmed at 650 °C, S/C = 2 for C-SR; and 550 °C, S/C = 2 for SE-SR. Under their respective optimal conditions, the Y_Bio-oil/H2 of SE-SR is significant decreased, by 18.50% compared to that of C-SR, although the Q_D/H2 was slightly increased, just by 7.55%.     

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.     

Effect of synthesis temperature on catalytic activity and coke resistance of Ni/bio-char during CO2 reforming of tar

Understanding how the synthesis parameters affect nickel particle distribution is critical to the synthesis of Ni/bio-char with excellent catalytic performance. In this work, the influence of synthesis temperature on catalytic activity and coke resistance of Ni/bio-char during CO₂ reforming of tar was explored. With the increase of synthesis temperature from 200 °C to 250 °C, the dispersion of nickel precursor into bio-char was promoted, resulting in an increase in crystallite size of metallic nickel particle from 51.98 nm to 62.45 nm. Besides, parts of the metallic nickel particles were oxidized to nickel oxides, providing more lattice oxygen to oxidize the coke deposited on the catalyst. However, further increasing the synthesis temperature to 300 °C would aggravate the oxidation of active nickel particles. The increase in crystallite size of nickel oxide particle from 23.25 nm to 43.38 nm could block the pore structure and hinder the access of reactants, resulting in a drop in the tar conversion rate from 40-51% to 13–27%.     

Production and detailed characterization of bio-oil from fast pyrolysis of palm kernel shell

Bio-oil has been produced from palm kernel shell in a fluidized bed reactor. The process conditions were optimized and the detailed characteristics of bio-oil were carried out. The higher feeding rate and higher gas flow rate attributed to higher bio-oil yield. The maximum mass fraction of biomass (57%) converted to bio-oil at 550 °C when 2 L min⁻¹ of gas and 10 g min⁻¹ of biomass were fed. The bio-oil produced up to 500 °C existed in two distinct phases, while it formed one homogeneous phase when it was produced above 500 °C. The higher heating value of bio-oil produced at 550 °C was found to be 23.48 MJ kg⁻¹. As GC–MS data shows, the area ratio of phenol is the maximum among the area ratio of identified compounds in 550 °C bio-oil. The UV–Fluorescence absorption, which is the indication of aromatic content, is also the highest in 550 °C bio-oil.     

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).     

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.     

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.     

Valorisation of lignocellulosic biomass investigating different pyrolysis temperatures

Presently, sugarcane bagasse (SB) and oat hulls (OH) have a distinctive potential as a renewable source of biomass, due to its global availability, which is advantageous for producing liquid and gaseous fuels by thermochemical processes. Thermo-Catalytic Reforming (TCR) is a pyrolysis based technology for generating energy vectors (char, bio-oil and syngas) from biomass wastes. This work aims to study the conversion of SB and OH into fuels, using TCR in a 2 kg/h continuous pilot-scale reactor at different pyrolysis temperatures. The pyrolysis temperatures were studied at 400, 450 and 500 °C, while the subsequent reforming temperature remained constant at 500 °C. The bio-oil contained the highest calorific value of 33.4 and 33.5 MJ/kg for SB and OH, respectively at 500 °C pyrolysis temperature, which represented a notable increase compared to the raw material calorific value of SB and OH (16.4 and 16.0 MJ/kg, respectively), this was the result of deoxygenation reactions occurring. Furthermore, the increment of the pyrolysis temperature improved the water content, total acid number (TAN), viscosity and density of the bio-oil. The syngas and the biochar properties did not change significantly with the increase of the pyrolysis temperature. In order to use TCR bio-oil as an engine fuel, it is necessary to carry out some upgrading treatments; or blend it with fossil fuels if it is to be used as a transportation fuel. Overall, TCR is a promising future route for the valorisation of lignocellulosic residues to produce energy vectors.     

Bio-fuels from Agricutural Residues

Abstract

Bio-fuels, such as bio-oil, bio-char, and bio-gas, can be obtained from agricultural residues. Agricultural residues are potential renewable energy resources such as biogas from anaerobic digestion, bio-oil from pyrolysis, and bio-char from carbonization and slow pyrolysis processes. Pyrolysis process of agricultural residues are the most common and convenient methods for conversion into bio-oil and bio-char. When the pyrolysis temperature increased, the bio-char yield decreased. The bio-char yield increased with increasing particle size of the sample. The yield of bio-oil from pyrolysis of the samples increased with temperature. Anaerobic biogas production is an effective process for conversion of a broad variety of agricultural biomass to methane to substitute natural gas and medium calorific value gases.     

Reutilization potential of antibiotic wastes via hydrothermal liquefaction (HTL): Bio-oil and aqueous phase characteristics

Hydrothermal liquefaction (HTL) technology was employed to investigate the feasibility of recovering energy from penicillin mycelial waste (PMW) with the help of TG, Py-GC/MS and GC-MS techniques; meanwhile, the nutrients in aqueous phase were also analyzed by spectrophotometry methods. The effects of operating conditions, including hydrothermal temperature (240–300 °C), duration time (20–60 min), total solid ratio (5–15%) and their interactive reactions were concurrently evaluated via response surface methodology. Results demonstrated that operating temperature was found to be the dominant variable affecting the HTL of PMW. Based on the optimal conditions of 298 °C, 60 min and 14.85%, heavy oil derived from PMW was comparable with algal-derived bio-oil as it possessed the highest energy recovery efficiency (42.95%) with a calorie value of 32.84 MJ/kg and a yield of 24.93%. GC/MS results indicated that heavy oil mainly consisted of N-containing compounds (36.73%) and aromatic compounds (31.07%), which might be contributed to the hydrolysis of protein and the aromatization of intermediates, respectively. Besides, more than 65% of nitrogen and 40% of carbon were enriched in aqueous phase, suggesting the possibility of further recycling for algae cultivation, fermentation and anaerobic digestion.     

Effect of phenols extraction on the behavior of Ni-spinel derived catalyst for raw bio-oil steam reforming

Alkyl-phenols and hydroxy- or methoxy-phenols (e.g., catechols, guaiacols and syringols) tend to polymerize into carbonaceous structures, causing clogging of reaction equipment and high coke deposition during bio-oil steam reforming (SR). In this work, removal of these phenolic compounds from raw bio-oil was addressed by accelerated aging and liquid-liquid extraction methods. The solvent-anti-solvent extraction with dichloromethane and water was suitable for obtaining a treated bio-oil appropriate for SR. The effect that phenols extraction has on the stability and regenerability of a NiAl₂O₄ spinel catalyst was studied by conducting reaction-regeneration cycles. Operating conditions were: 700 °C; S/C, 6; space-time, 0.15 g_catalysth/g_bio-oil (reaction step), and in situ coke combustion at 850 °C for 4 h (regeneration step). Fresh, deactivated and regenerated catalyst samples were analyzed by temperature programmed oxidation (TPO), temperature programmed reduction (TPR) and X-ray diffraction (XRD). Stability of the Ni-spinel derived catalyst was significantly improved by removing phenols due to attenuation of both coke deposition and Ni sintering. Regenerability of this catalyst was also slightly improved when reforming the treated bio-oil.     

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.     

Production of crude bio-oil via direct liquefaction of spent K-Cups

Spent K-Cups were liquefied into crude bio-oil in a water-ethanol co-solvent mixture and reaction conditions were optimized using response surface methodology (RSM) with a central composite design (CCD). The effects of three independent variables on the yield of crude bio-oil were examined, including the reaction temperature (varied from 255 °C to 350 °C), reaction time (varied from 0 min to 25 min) and solvent/feedstock mass ratio (varied from 2:1 to 12:1). The optimum reaction conditions identified were 276 °C, 3 min, and solvent/feedstock mass ratio of 11:1, giving a mass fraction yield of crude bio-oil of 60.0%. The overall carbon recovery at the optimum conditions was 93% in mass fraction. The effects of catalyst addition (NaOH and H₂SO₄) on the yield of crude bio-oil were also investigated under the optimized reaction conditions. The results revealed that the presence of NaOH promoted the decomposition of feedstock and significantly enhanced the bio-oil production and liquefaction efficiency, whereas the addition of H₂SO₄ resulted in a negative impact on the liquefaction process, decreasing the yield of crude bio-oil.     

Comparative study on pyrolysis and catalytic pyrolysis upgrading of biomass model compounds: Thermochemical behaviors,kinetics, and aromatic hydrocarbon formation

In order to understand the pyrolysis mechanism, reaction kinetic and product properties of biomass and select suitable agricultural and forestry residues for the generation desired products, the pyrolysis and catalytic pyrolysis characteristics of three main components (hemicellulose, cellulose, and lignin) of biomass were investigated using a thermogravimetric analyzer (TGA) with a fixed-bed reactor. Fourier transform infrared spectroscopy (FTIR) and elemental analysis were used for further characterization. The results showed that: the thermal stability of hemicellulose was the worst, while that of cellulose was higher with a narrow range of pyrolysis temperatures. Lignin decomposed over a wider range of temperatures and generated a higher char yield. After catalytic pyrolysis over HZSM-5 catalyst, the conversion ratio increased. The ratio for the three components was in the following order: lignincellulose < biomass < xylan. The Starink method was introduced to analyze the thermal reaction kinetics, activation energy (Ea), and the pre-exponential factor (A). The addition of HZSM-5 improved the reactivity and decreased the activation energy in the following order: xylan (30.54%) > biomass(15.41%) > lignin (14.75%) > cellulose (6.73%). The pyrolysis of cellulose gave the highest yield of bio-oil rich in levoglucosan and other anhydrosugars with minimal coke formation. Xylan gave a high gas yield and moderate yield of bio-oil rich in furfural, while lignin gave the highest solid residue and produced the lowest yield of bio-oil that was rich in phenolic compounds. After catalytic pyrolysis, xylan gave the highest yield of monocyclic aromatic hydrocarbons, 76.40%, and showed selectivity for benzene and toluene. Cellulose showed higher selectivity for xylene and naphthalene; however, lignin showed enhanced for selectivity of C10 + polycyclic aromatic hydrocarbons. Thus, catalytic pyrolysis method can effectively improve the properties of bio-oil and bio-char.     

Optimization study of sub/supercritical water liquefication of lignite: Fast liquefaction for high bio-oil yield

Sub/supercritical water liquefication (SCWL) is a water-based thermochemical technology as well as an environmentally friendly treatment by converting wet feedstock into bioenergy. In the present study, a systematic investigation of SCWL of lignite was carried out covering a temperature range between 320 and 440 °C when residence time increased from 5 min to 40 min. The highest bio-oil oil yield of 34.3% with solid residue of 52.7% was obtained at 440 °C for 5 min. Phenol derivatives, carboxylic acids, long chain hydrocarbons, ketones, and naphthalene were the main bio-oil composition through FTIR and GC-MS analysis. Gas yields and their exact compositions were also determined and CO₂ was the dominate gas product but the percentage of CH₄ became significant at severe SCWL conditions. A conclusion was drawn that fast liquefaction (e.g. 5 min) at relative higher temperature (e.g. 400 °C) which avoid excessive gasification and repolymerization reactions was an optimization strategy for high yield bio-oil production from SCWL of lignite.