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.     

Experimental and DFT studies on catalytic reforming of acetic acid for hydrogen production over B-doped Co/Al2O3 catalysts

Steam reforming of bio-oil for hydrogen production is a promising green technology. Acetic acid was used as the bio-oil model compound. Experimental and density functional theory calculations were carried out to study the performance of Co/Al₂O₃ catalysts doped with boron (B) with a 1 wt.%–5 wt.% content. Catalyst characterization by BET, XRD, XPS, NH₃-TPD, H₂-TPR, TEM, and TG-DTG was performed. We found that the catalyst performance improved significantly by B doping. Under the reaction conditions of T = 500 °C, steam-to-carbon ratio (S/C) = 5, and liquid hourly space velocity (LHSV) = 4.3 h^?1, the catalyst with a B doping ratio of 1 wt.% had the highest hydrogen yield of 85% and a maximum acetic acid conversion rate of 95%. The corresponding hydrogen productivity was 0.8 mmol/min. The stability of this catalyst exceeded 29 h. Density functional theory calculations showed that the interactions between the reaction intermediates and the surface were strengthened with B addition.     

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.     

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.     

Catalysts of Ni/α-Al2O3 and Ni/La2O3-αAl2O3 for hydrogen production by steam reforming of bio-oil aqueous fraction with pyrolytic lignin retention

This paper reports on the steam reforming, in continuous regime, of the aqueous fraction of bio-oil obtained by flash pyrolysis of lignocellulosic biomass (sawdust). The reaction system is provided with two steps in series: i) thermal step at 200 °C, for the pyrolytic lignin retention, and ii) reforming in-line of the treated bio-oil in a fluidized bed reactor, in the range 600–800 °C, with space-time between 0.10 and 0.45 g_catalyst h (g_bio-oil)⁻¹. The benefits of incorporating La₂O₃ to the Ni/α-Al₂O₃ catalyst on the kinetic behavior (bio-oil conversion, yield and selectivity of hydrogen) and deactivation were determined. The significant role of temperature in gasifying coke precursors was also analyzed. Complete conversion of bio-oil is achieved with the Ni/La₂O₃-αAl₂O₃ catalyst, at 700 °C and space-time of 0.22 g_catalyst h (g_bio-oil)⁻¹. The catalyst deactivation is low and the hydrogen yield and selectivity achieved are 96% and 70%, respectively.     

Effects of solvents and catalysts in liquefaction of pinewood sawdust for the production of bio-oils

Liquefaction of biomass with proper solvents and catalysts is a promising process to produce liquid biofuels and valuable chemicals. In this study, pinewood sawdust was liquefied in the presence of various supercritical solvents (carbon dioxide, water, acetone, and ethanol) and catalysts (alkali salts and acidic zeolites). The liquid, gas and solid products were analyzed using GC–MS, FT-IR, elemental analyzer, ¹H NMR, ¹³C NMR. The experimental results showed that both solvent and catalyst can significantly improve the liquefaction process by increasing the yield of liquid oil and suppressing the formation of solid residue. K₂CO₃ showed the best performance by doubling the yield of bio oil. Meanwhile, the maximum bio-oil yield (30.8 wt%) and the minimum solid residue yield (28.9 wt%) were obtained when ethanol was employed as the solvent. Solvents can also strongly affect the distribution of liquid products. 2,4,5,7-tetramethyl-phenanthrene and bis(2-ethylhexyl) phthalate were the premier compounds in liquid product as supercritical carbon dioxide is used as solvent while 2-methyl-naphthalene became the main composition when water is used as solvent.     

Optimization and characterization studies on bio-oil production from palm shell by pyrolysis using response surface methodology

In this work palm shell waste was pyrolyzed to produces bio-oil. The effects of several parameters on the pyrolysis efficiency were tested to identify the optimal bio-oil production conditions. The tested parameters include temperature, N₂ flow rate, feed-stock particle size, and reaction time. The experiments were conducted using a fix-bed reactor. The efficient response surface methodology (RSM), with a central composite design (CCD), were used for modeling and optimization the process parameters. The results showed that the second-order polynomial equation explains adequately the non-linear nature of the modeled response. An R² value of 0.9337 indicates a sufficient adjustment of the model with the experimental data. The optimal conditions found to be at the temperature of 500 °C, N₂ flow rate of 2 L/min, particle size of 2 mm and reaction time of 60 min and yield of bio-oil was approximately obtained 46.4 wt %. In addition, Fourier Transform infra-red (FT-IR) spectroscopy and gas chromatography/mass spectrometry (GC-MS) were used to characterize the gained bio-oil under the optimum condition.     

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.     

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.     

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.     

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.     

Hydrogen production by steam reforming of bio-oil/bio-ethanol mixtures in a continuous thermal-catalytic process

The feasibility of the steam reforming of bio-oil aqueous fraction and bio-ethanol mixtures has been studied in a continuous process with two in-line steps: thermal step at 300 °C (for the controlled deposition of pyrolytic lignin during the heating of the bio-oil/bio-ethanol feed) followed by steam reforming in a fluidized bed reactor on a Ni/α-Al₂O₃ catalyst. The effect of bio-ethanol content in the feed has been analyzed in both the thermal and reforming steps, and the suitable range of operating conditions (temperature and space-time) has been determined for obtaining a high and steady hydrogen yield. Higher ethanol content in the mixture feed improves the reaction indices and reduces coke deposition. Operating conditions of 700 °C and space-times higher than 0.23 g_catalyst h (g_bio-oil+EtOH)⁻¹ are suitable for attaining almost fully conversion of oxygenates (bio-oil and ethanol) and hydrogen yields above 93%, with low catalyst deactivation.     

Upgraded biofuel from residue biomass by Thermo-Catalytic Reforming and hydrodeoxygenation

Research is focused on the utilisation of waste or residue biomass for bioenergy conversion. A promising conversion technology for the production of liquid biofuels from residue biomass is a process called Thermo-Catalytic Reforming (TCR^®​) which is a combination of prior thermal treatment of the biomass at mild temperatures (intermediate pyrolysis) followed by a second catalytic treatment step at elevated temperatures (reforming). This article focuses on the conversion of TCR^® liquids from digestate as a feedstock for subsequent hydrocarbon production. The generated bio-oil showed a lower heating value of 34.0 MJ kg⁻¹ with an oxygen content of 7.0% and a water content of 2.2%. The bio-oil was hydrodeoxygenated using an industrial NiMo–Al₂O₃ catalyst at temperatures of 503 K–643 K and a pressure of 14 MPa. The hydrodeoxygenated bio-oil reached a lower heating value of 42.3 MJ kg⁻¹ with an oxygen content below 0.8 mg kg⁻¹ and water content of 30 ppm. Product yields and catalyst life give confidence that upgrading of the TCR^®​ bio-oil offers a suitable option to meet the high standards of common fuels.     

Bio-oil catalytic reforming without steam addition: Application to hydrogen production and studies on its mechanism

A novel process for hydrogen production via bio-oil catalytic reforming without steam addition was proposed. The liquid feedstock was a distillation fraction from crude bio-oil molecular distillation. The fraction obtained was enriched with the low-molecular-weight organics (acids, aldehydes, and ketones), and contained nearly all of the water from crude bio-oil. The highest catalytic performance, with a carbon conversion of 95% and a H₂ yield of 135 mg g⁻¹ organics, was obtained by processing the distillate over Ni/Al₂O₃ catalyst at 700 °C. The steam involved in the reforming reaction was derived entirely from the water in the crude bio-oil. The fresh and spent catalysts were characterized by N₂-physisorption, thermogravimetric analysis, and high-resolution transmission electron microscopy. To further understand the reaction mechanisms, symmetric density functional theory calculations for decomposition were performed on four model compounds in bio-oil (acetic acid, hydroxyacetone, furfural, and phenol) over the Ni(111) surface. In addition, the decomposition of H₂O∗ to OH∗ and O∗ and their subsequent steam reforming reactions with carbon precursors (CH∗ and CH₃C∗) were also examined.     

The influence of harvest and storage on the properties of and fast pyrolysis products from Miscanthus x giganteus

The research investigates the fuel property variations associated with the time of harvest and the duration of storage of Miscanthus x giganteus over a one year period. The crop has been harvested at three different times: early (September 2009), conventional (April 2010) and late (June 2010). Once harvested the crop was baled and stored. Biomass properties of samples taken from different storage zones were compared. The thermochemical properties have been investigated using a range of analytical equipment including thermogravimetric analysis (TGA) and pyrolysis-gas chromatography-mass spectrometry (Py-GC-MS). In addition, bio-oil has been produced from the early, conventional and late harvest using a laboratory scale (300 g h⁻¹) fast pyrolysis unit. The potential organic liquid yield (on dry basis, also excluding the reaction water generated) based on the laboratory fast pyrolysis processing undertaken in this study, was found to vary between 2.82 and 3.18 dry t ha⁻¹ for the early and the late harvest respectively. The bio-oil organic yield was reduced by approximately 11% (0.36 t ha⁻¹) between the early and the late harvest. Char yield was also reduced by approximately 18% (0.61 t ha⁻¹). The highest gas yield (18.03%-1.60 t ha⁻¹) was observed for the conventional harvest. Gas chromatography-mass spectrometry (GC-MS) analysis of the bio-oil shows that levoglucosan, methylbenzaldehyde and 1,2-benzenediol all increase as a consequence of delayed harvest. It was also observed that by delaying the harvest time the O:C atomic ratio is reduced and a more carbonaceous feedstock is produced.     

Comparative techno-economic analysis of biohydrogen production via bio-oil gasification and bio-oil reforming

This paper evaluates the economic feasibility of biohydrogen production via two bio-oil processing pathways: bio-oil gasification and bio-oil reforming. Both pathways employ fast pyrolysis to produce bio-oil from biomass stock. The two pathways are modeled using Aspen Plus^® for a 2000 t d⁻¹ facility. Equipment sizing and cost calculations are based on Aspen Economic Evaluation® software. Biohydrogen production capacity at the facility is 147 t d⁻¹ for the bio-oil gasification pathway and 160 t d⁻¹ for the bio-oil reforming pathway. The biomass-to-fuel energy efficiencies are 47% and 84% for the bio-oil gasification and bio-oil reforming pathways, respectively. Total capital investment (TCI) is 435 million dollars for the bio-oil gasification pathway and is 333 million dollars for the bio-oil reforming pathway. Internal rates of return (IRR) are 8.4% and 18.6% for facilities employing the bio-oil gasification and bio-oil reforming pathways, respectively. Sensitivity analysis demonstrates that biohydrogen price, biohydrogen yield, fixed capital investment (FCI), bio-oil yield, and biomass cost have the greatest impacts on facility IRR. Monte-Carlo analysis shows that bio-oil reforming is more economically attractive than bio-oil gasification for biohydrogen production.     

Sustainable hydrogen production from steam reforming of bio-oil model compound based on carbon deposition/elimination

Steam reforming of crude bio-oil or some heavy component present in bio-oil is a great challenge for sustainable hydrogen production due to the extensive coke formation and catalyst deactivation. Catalyst regeneration will be an unavoidable operation in this process. In this paper, m-cresol (a model compound derived from bio-oil) was steam reformed on commercial Ni-based catalyst. Two conventional carbon elimination methods for coked catalyst were applied and the results showed that sustainable hydrogen production can be obtained based on carbon deposition/elimination. The carbon deposition can be gasified easily under certain temperature. The activity of regenerated catalyst samples can be nearly recovered as the fresh ones. Under the reaction conditions of 850 °C and steam to carbon ratio 5:1, >66% hydrogen mole fraction, >81% hydrogen yield, and >97% carbon conversion can be achieved based on regenerated catalyst. Catalyst characterization indicated that the loss of active metal can be considered as the main reason for tiny activity drop. Ni redispersion and Fe contamination may be another two factors that influence catalyst activity.     

Utilization possibilities of palm shell as a source of biomass energy in Malaysia by producing bio-oil in pyrolysis process

Agriculture residues such as palm shell are one of the biomass categories that can be utilized for conversion to bio-oil by using pyrolysis process. Palm shells were pyrolyzed in a fluidized-bed reactor at 400, 500, 600, 700 and 800 °C with N₂ as carrier gas at flow rate 1, 2, 3, 4 and 5 L/min. The objective of the present work is to determine the effects of temperature, flow rate of N₂, particle size and reaction time on the optimization of production of renewable bio-oil from palm shell. According to this study the maximum yield of bio-oil (47.3 wt%) can be obtained, working at the medium level for the operation temperature (500 °C) and 2 L/min of N₂ flow rate at 60 min reaction time. Temperature is the most important factor, having a significant positive effect on yield product of bio-oil. The oil was characterized by Fourier Transform infra-red (FT-IR) spectroscopy and gas chromatography/mass spectrometry (GC-MS) techniques.     

Optimisation of bio-oil production by hydrothermal liquefaction of agro-industrial residues: Blackcurrant pomace (Ribes nigrum L.) as an example

This work reports bio-oil production by hydrothermal liquefaction of blackcurrant pomace (Ribes nigrum L.), a fruit residue obtained after berry pressing. The bio-oil has a higher heating value of 35.9 MJ kg⁻¹ and low ash content, which makes it suitable for energy applications. We report the influence of process parameters on yields and carbon distribution between products: temperature (563–608 K), holding time (0–240 min), mass fraction of dry biomass in the slurry (0.05–0.29), and initial pH (3.1–12.8) by adding sodium hydroxide (NaOH). Depending on the experiments, the bio-oil accounts for at least 24% mass fraction of the initial dry biomass, while char yields ranges from 24 to 40%. A temperature of 583 K enhances the bio-oil yield, up to 30%, while holding time does not have a significant influence on the results. Increasing biomass concentrations decreases bio-oil yields from 29% to 24%. Adding sodium hydroxide decreases the char yield from 35% at pH = 3.1 (without NaOH) to 24% at pH = 12.8. It also increases the bio-oil yield and carbon transfer to the aqueous phase. Thermogravimetric analysis shows that a 43% mass fraction of the bio-oil boils in the medium naphtha petroleum fraction range. The bio-oil is highly acidic and unsaturated, and its dynamic viscosity is high (1.7 Pa s at 298 K), underlining the need for further upgrading before any use for fuel applications.