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.     

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.     

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%.     

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.     

Hydrothermal liquefaction of spent coffee grounds in water medium for bio-oil production

Spent coffee grounds (SCG) were liquefied in hot-compressed water to produce crude bio-oil via hydrothermal liquefaction (HTL) in a 100 cm³ stainless-steel autoclave reactor in N₂ atmosphere. We investigated the effects of operating parameters such as retention times (5 min, 10 min, 15 min, 20 min and 25 min), reaction temperatures (200 °C, 225 °C, 250 °C, 275 °C and 300 °C), and water/feedstock mass ratios (5:1, 10:1, 15:1 and 20:1) and initial pressure of process gas (2.0 MPa and 0.5 MPa) on the yield and properties of the resulting crude bio-oil. The highest yield of the crude bio-oil (47.3% mass fraction) was obtained at conditions of 275 °C, 10 min retention time and water/feedstock mass ratio of 20:1 with an initial pressure of 2.0 MPa. The elemental analysis of the produced crude bio-oil revealed that the oil product had a higher heating value (HHV) of 31.0 MJ kg⁻¹, much higher than that of the raw material (20.2 MJ kg⁻¹). GC–MS and FT-IR measurements showed that the main volatile compounds in the crude bio-oil were long chain aliphatic acids and esters.     

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.     

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.     

Fast pyrolysis of date palm biomass using Py-GCMS

Pyrolysis of Date Palm Petiole (DPP) and Date Palm Seed (DPS) biomass was conducted by fast pyrolysis and on-line analysis of the outlet stream by gas chromatography connected to mass spectrometry (Py-GCMS) at different temperatures (450, 500 and 600 °C) in order to study the effect of this variable on the product distribution. The concentration of the components in the volatile stream (bio-oil and non-condensable gases) was greatly influenced by temperature and, to a minor extent, by the content of the biomass components (cellulose, hemicellulose and lignin). The most abundant compound families quantified are acids, anhydrosugars, ketones, furans and phenols. The most abundant compound identified was levoglucosan, which is mainly derived from the degradation of cellulose, with its relative content being as high as 18.3% for DPS pyrolysis at 450 °C and considerably lower for DPP pyrolysis (12.2%). The relative content of acetic acid was as higher as 10.2% at 450 °C for DPP pyrolysis. The knowledge of product composition is crucial for the development of large scale fast pyrolysis units for the valorization of these Tunisian agricultural wastes.     

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.     

Comparative study by GC×GC-TOFMS on the composition of crude and composite-additives bio-oil before and after accelerated aging treatment

In this study, compositions of bio-oil and bio-oil with composite additives before and after accelerated aging treatment were analyzed by two-dimensional gas chromatography with time flight mass spectrometry detector (GC × GC-TOFMS) in order to evaluate the effect of the composite additives on the characteristics of bio-oil. The effects of composite additives on bio-oil components and the changes of the components of the bio-oil with or without accelerated aging treatment were compared. A structured distribution of compounds of classification groups was observed in the two-dimensional space. At a signal-to-noise ratio of 1000, more than 3000 peaks were detected by GC × GC-TOFMS, and more than 340 peaks (relative content > 0.02%) were identified after further analysis. After accelerated aging, the content of various compounds in bio-oil decreased. The content of the classification group and the total content of compounds in the bio-oil with composite additives changed less than that of the crude bio-oil. Before aging, the most abundant substance in bio-oil was 2(5H)-furanone. After aging, the largest content in crude bio-oil is 2(5H)-furanone, and the most abundant substance in the bio-oil with composite additives is Hydroxyacetone. Regardless of whether composite additives are added or not, the component with the highest content before and after aging of bio-oil is ketones. In crude bio-oil, the substance with the most reduced content was phenols, whose content was reduced by 0.51 wt%. The contents of alcohols, esters, furanones, furans and sugars in the bio-oil with composite additives were increased after aging. The maximum increase in content was furanones, whose content was increased by 0.15 wt%. Analysis of bio-oil components showed that high added value compounds existed in bio-oil such as 2(5H)-furanone, Hydroxyacetone and (S)-(+)-2′,3′-Dideoxyribonolactone. The research can provide detailed information on bio-oil composition.     

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.     

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.     

Alkaline treatment for detoxification of acetic acid-rich pyrolytic bio-oil for microalgae fermentation: Effects of alkaline species and the detoxification mechanisms

Bio-oil derived from Pyrolysis of lignocellulosic biomass contains appreciable amounts acetic acid, which can be used as substrate for growing microalgae Chlamydomonas reinhardtii. However, the toxic compounds in the bio-oil inhibit the cell growth. This work is to develop alkaline treatment methods to reduce the toxicity and improve fermentability of acetic acid rich bio-oil. When growing in raw bio-oil without any detoxification treatment, the algae can only tolerate up to 0.1 wt% of bio-oil. Treatment with KOH, NaOH and Ca(OH)₂ significantly reduced the toxicity and consequently improved the fermentability of bio-oil. The bio-oil tolerant level by microalgae depended on the alkali species used. Among the three alkali species, Ca(OH)₂ proved the most effective detoxification reagent. Inhibitory compounds such as furans, phenols, ketones, aldehydes, ethers, esters, alcohols were removed by Ca(OH)₂ treatment through precipitation. The detoxification mechanisms by the Ca(OH)₂ -based treatment were also explored. The synergistic effect of alkaline pH, high temperature, and presence of Ca²⁺ played an important role for the precipitation of those compounds, and the consequent detoxification. Collectively, the results shows alkali, particularly Ca(OH)₂-based, treatment is an effective for reducing the toxicity of the pyrolysis derived bio-oil as fermentative substrate for microalgae growth. The microalgae can tolerant Ca(OH) ₂-treated bio-oil up to 5.5 wt%, which was 55 times higher than algal tolerance level of untreated bio-oil.     

Microalgae as a renewable fuel source: Fast pyrolysis of Scenedesmus sp.

Herein we report the fast pyrolysis of dried, ground Scenedesmus sp. at two different reactor scales. Pyrolysis was performed at 480 °C and 1 bar in both an isothermal spouted bed reactor and a dynamic pyrolysis-GC/MS unit, each with 2 s vapor residence times. Bio-oil products were characterized on the basis of GC-MS, simulated distillation GC, elemental analysis, calorific content and total acid number. The ratio of crude oil: char obtained from the spouted bed reactor was 3.76 by weight, the average calorific content of the oil being 18.4 MJ/kg. The average total acid number (68 mg KOH/g) was lower than typical bio-oil produced via wood pyrolysis. Simulated distillation results indicated that a significant proportion of the oil corresponded to the boiling range typical for heavy gas oil (343 °C–524 °C). Elemental analysis showed the oil contained an average of 27.6 wt.% oxygen and 8.6 wt.% nitrogen, the relatively high nitrogen content being a consequence of the high protein content of the algae. According to GC-MS data, the oil consisted of various hydrocarbons as well as oxygenated and nitrogenous species, including indoles, fatty acids and amides. Pyrolysis-GC-MS was also performed on Scenedesmus sp. in order to provide insights into the nature of the primary pyrolysis products.     

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.     

Catalytic hydropyrolysis of crop straws with different biochemical composition

In this study, four kinds of straws with different biochemical compositions, including soybean straw (SS), peanut straw (PS), rice straw (RS), and corn straw (CS), were subjected to catalytic hydropyrolysis (HyPy) to explore the influence of biochemical composition on the products distribution and properties of the pyrolysis oil. The HyPy reactions were performed at 400 °C for 2 h with added 10 wt% Pd/C and 4 MPa H₂. During the HyPy, hydrogen and catalyst broke the coating structure and hydrogen bond between cellulose (CL) and hemicellulose (HCL), and thus significantly weakened the biochemical composition effect on the yield and elemental composition of the bio-oil. The bio-oil yield varied between 11.75 wt% and 13.05 wt%, and the C, H, N, O, and S content fell into the following ranges of 82.06–85.15 wt%, 9.24–9.61 wt%, 1.18–1.43 wt%, 4.62–7.86 wt%, 45–130 ppm, respectively. Biochemical composition of straw, especially the mass ratio of CL to HCL (m_CL/m_HCL), markedly influenced the molecular composition of the bio-oil. Hydrocarbons (20.15–46.66%) and phenolic compounds (17.01–47.98%) accounted for the vast majority of the identified compounds. SS and PS with higher m_CL/m_HCL (1.92 and 1.80, respectively) tended to produce bio-oils with more aromatics (22.63% and 20.70%, respectively) and fewer phenolic compounds (17.01% and 22.56%, respectively).     

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.     

Potentiality of combined catalyst for high quality bio-oil production from catalytic pyrolysis of pinewood using an analytical Py-GC/MS and fixed bed reactor

The aim of this study was to investigate the potential of combined catalyst (ZSM-5 and CaO) for high quality bio-oil production from the catalytic pyrolysis of pinewood sawdust that was performed in Py-GC/MS and fixed bed reactor at 500 °C. In Py-GC/MS, the maximum yield of aromatic hydrocarbon was 36 wt% at biomass to combined catalyst ratio of 1:4 where the mass ratio of ZSM-5 to CaO in the combined catalyst was 4:1. An increasing trend of phenolic compounds was observed with an increasing amount of CaO, whereas the highest yield of phenolic compounds (31 wt%) was recorded at biomass to combined catalyst ratio of 1:4 (ZSM-5: CaO - 4:1). Large molecule compounds could be found to crack into small molecules over CaO and then undergo further reactions over zeolites. The water content, higher heating value, and acidity of bio-oil from the fixed bed reactor were 21%, 24.27 MJkg⁻¹, and 4.1, respectively, which indicates that the quality of obtained bio-oil meets the liquid biofuel standard ASTM D7544-12 for grade G biofuel. This research will provide a significant reference to produce a high-quality bio-oil from the catalytic pyrolysis of woody biomass over the combined catalyst at different mass ratios of biomass to catalyst.     

Study of bio-oil and bio-char production from algae by slow pyrolysis

This study examined bio-oil and bio-char fuel produced from Spirulina Sp. by slow pyrolysis. A thermogravimetric analyser (TGA) was used to investigate the pyrolytic characteristics and essential components of algae. It was found that the temperature for the maximum degradation, 322 °C, is lower than that of other biomass. With our fixed-bed reactor, 125 g of dried Spirulina Sp. algae was fed under a nitrogen atmosphere until the temperature reached a set temperature between 450 and 600 °C. It was found that the suitable temperature to obtain bio-char and bio-oil were at approximately 500 and 550 °C respectively. The bio-oil components were identified by a gas chromatography/mass spectrometry (GC–MS). The saturated functional carbon of the bio-oil was in a range of heavy naphtha, kerosene and diesel oil. The energy consumption ratio (ECR) of bio-oil and bio-char was calculated, and the net energy output was positive. The ECR had an average value of 0.49.     

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.