Experimental basic factors in the production of H2 via supercritical water gasification

This study aims to discuss some of the factors that influence the production of hydrogen via the gasification of organic matter in supercritical water. These factors have been investigated based on the reactions of organic matter with relatively simple chemical structures, such as ethanol, glycerol, and glucose. Investigations of these relatively simple organic materials demonstrate the characteristics and trends in the gasification in supercritical water. The results reported in the literature for these organic compounds can also be extrapolated to the reactions of biomass containing ethanol, glucose, (sugar cane industry) and glycerol (biodiesel industry) in supercritical water. Many organic compounds with different levels of molecular complexity can be used to produce hydrogen, which represents an interesting form of energy storage. Supercritical water (T_c ≥ 374 °C, P_c ≥ 22.1 MPa) has unique physical and chemical properties that minimize mass transport limitations, making it an excellent medium for the decomposition of organic compounds. Thus, understanding the key factors that influence organic compound gasification in supercritical water is extremely important. In this study, we summarize some of the key factors involved in these reactions. The main experimental factors were confirmed to be the temperature, concentration of organic matter in the feed, space time/feed rate, catalysts, oxidants, material and design of the reactor, and pressure. In addition, operational challenges, namely, catalyst deactivation and corrosion are mentioned in the text. Furthermore, the operational challenges were discussed, and the state of the art regarding the gasification of ethanol-, glycerol-, and glucose-containing biomass is also presented.     

Carbon sequestration in willow (Salix spp.) plantations on former arable land estimated by repeated field sampling and C budget calculation

Short rotation coppice (SRC) plantations are of interest as producers of biomass for fuel, but also as carbon (C) sinks to mitigate CO₂ emissions. Carbon sequestration in biomass and soil was estimated in 5-year-old replicated SRC plantations with willows (Salix spp.) on former arable land at five sites in Sweden. Total standing C stocks, i.e. C stored in woody biomass above- and belowground, fine root standing crop, litter, and soil organic carbon (SOC) were estimated by repeated field sampling and C budget calculation.Overall, the SRC willow plantations represented a C sink after five years. Estimated increase of total standing C stock was 15% on average compared to pre-planting conditions. There was no change in SOC when including all sites. Analyses within sites revealed a decrease in SOC at one site, although the decrease was compensated for by C stored in willow biomass. After removal of stem biomass, C in other plant pools was sufficient to compensate for the SOC decrease. Remaining C in stumps, stool, and coarse roots was estimated at ca 20% of stem C.There was a discrepancy between SOC sequestration rates from soil sampling and C budget calculation, −2.1–1.0 and 0.15–0.45 Mg ha⁻¹ y⁻¹, respectively. Mineralization of old organic material from previous land-use and input to SOC from understory vegetation were not included in the calculations, which may explain part of the differences. The importance of understory litter in C budgets for young plantations was apparent, as it comprised 24–80% of aboveground litter C.     

Fructose decomposition kinetics in organic acids-enriched high temperature liquid water

Biomass continues to be an important candidate as a renewable resource for energy, chemicals, and feedstock. Decomposition of biomass in high temperature liquid water is a promising technique for producing industrially important chemicals such as 5-hydroxymethylfurfural (5-HMF), furfural, levulinic acid with high efficiency. Hexose, which is the hydrolysis product of cellulose, will be one of the most important starting chemicals in the coming society that is highly dependent on biomass. Taking fructose as a model compound, its decomposition kinetics in organic acids-enriched high temperature liquid water was studied in the temperature range from 180 °C to 220 °C under the pressure of 10 MPa to further improve reaction rate and selectivity of the decomposition reactions. The results showed that the reaction rate is greatly enhanced with the addition of organic acids, especially formic acid. The effects of temperature, residence time, organic acids and their concentrations on the conversion of fructose and yield of 5-HMF were investigated. The evaluated apparent activation energies of fructose decomposition are 126.8 ± 3.3 kJ mol⁻¹ without any catalyst, 112.0 ± 13.7 kJ mol⁻¹ catalyzed with formic acid, and 125.6 ± 3.8 kJ mol⁻¹ catalyzed with acetic acid, respectively, which shows no significant difference.     

Simulated biomass,environmental impacts and best management practices for long-term switchgrass systems in a semi-arid region

Long-term information on switchgrass (Panicum virgatum L.) as a biomass energy crop grown on marginally saline soil and the associated impacts on soil carbon (C) and nitrogen (N) dynamics, greenhouse gas (GHG) emissions, and best management practices (BMPs) are limited. In this study, we employed the DAYCENT model, based on a 4-year switchgrass field experiment, to evaluate the long-term biomass yield potential and environmental impacts, and further to develop BMPs for switchgrass in a semi-arid region.The model showed that long-term (14-year) annual mean biomass yields were 9.6 and 5.2 Mg ha⁻¹ for irrigated and rainfed switchgrass systems, respectively. The simulated biomass yields correlated well with field-measured biomass with r² values of 0.99 and 0.89 for irrigated and rainfed systems, respectively. Soil organic carbon (SOC) and soil total nitrogen (STN) accumulated rapidly after switchgrass establishment, with mean accrual rates of 0.99–1.13 Mg C ha⁻¹ yr⁻¹ and 0.04–0.08 Mg N ha⁻¹ yr⁻¹, respectively. Based on the outputs of numerous long-term model simulations with variable irrigation water supplies and N rates, the irrigation regime and N rate with the highest yield to input ratio were chosen as BMPs. The DAYCENT model predicted-BMP was irrigating every 14 days at 70% potential evapotranspiration combined with an N rate of 67 kg ha⁻¹ yr⁻¹. Switchgrass established and produced biomass reasonably well in this semi-arid region; however, appropriate irrigation and N fertilization were needed for optimal biomass yield. Switchgrass had a great potential to sequester C into soils with low N₂O emissions while supplying significant quantities of biomass for biofuel synthesis.     

Effect of temperature on the fast pyrolysis of organic-acid leached pinewood; the potential of low temperature pyrolysis

In this paper, we have evaluated the potential of organic acid (mixture of acetic, formic and propionic acid) leaching of biomass and subsequent fast pyrolysis to increase the organic oil, sugars and phenols yield by varying the fluidized bed temperature between 360 °C and 580 °C (360 °C, 430 °C, 480 °C, 530 °C, and 580 °C). The pyrolysis of acid leached pinewood resulted in more organic oil and less water and residue compared to untreated pinewood over the whole temperature range. Below 500 °C the difference was most profound; for acid leached pinewood at 360 °C the organic oil was already 650 g kg⁻¹ pine with a sugar yield of 230 g kg⁻¹ pine. At this low pyrolysis temperature no bed agglomeration was observed for acid leached pine whereas at the higher temperatures tested agglomerates were found, which were identified to be clusters of fluidization sand glued together by sticky pyrolysis products (melt). Low reactor temperatures also favored the production of monomeric phenols, though their absolute yields remained low for both untreated and leached pine (maximum: 23 g kg⁻¹ pine, 80 g kg⁻¹ lignin). GPC, GC/MS and UV-fluorescence spectroscopy showed that acid leaching did not influence significantly the yield and molecular size of the aromatic fraction in the produced pyrolysis oils. Back impregnation of the removed AAEMs into leached biomass revealed that the effects of the applied acid leaching, both with respect to the product yields and bed agglomeration, can be mainly assigned to the removal of AAEMs.     

Catalytic decomposition of biomass tars: use of dolomite and untreated olivine

Although biomass is getting increased attention as a renewable energy source, one of the remaining problems still to be solved is the reduction of the high level of tar present in the product gas from gasification of biomass. The purpose of the present work is to study the activity of olivine and dolomite for tar destruction. Some researchers investigated olivine as bed material for biomass gasification. But it is not yet known how tars behave in the presence of olivine and whether olivine has some activity towards tar destruction. A slipstream from a lab-scale atmospheric bubbling-fluidised-bed gasifier (located at ECN) is passed through a secondary fixed-bed reactor where the additives are placed. For easy understanding, the results are represented in terms of the following tar classes; GC-undetectable tars (class 1), heterocyclic compounds (class 2), aromatic compounds (class 3), light polyaromatic compounds (class 4), heavy polyaromatic compounds (class 5). The general observation is that the conversion of all tar classes increases as the temperature was raised from 800 to 900 °C for both additives. The water-soluble heterocyclic compounds can be easily converted by thermal treatment. At the temperature of 900 °C, the water-soluble heterocyclic compounds are completely converted. A 48% decrease in heavy PAHs is observed with pure sand. Addition of 17 wt% olivine to the sand leads to a 71% decrease of PAHs at 900 °C, whereas addition of 17 wt% (pre-calcined) dolomite converted 90%. Also improvement in conversion of other tar classes is observed when olivine and dolomite are added during hot gas cleaning. A total tar amount of 4.0 g m₀⁻³ could be reduced to 1.5 and 2.2 g m₀⁻³ using dolomite and olivine, respectively, at a temperature of 900 °C. Inspite of this reduction in total tar concentration, a limited impact on the tar dewpoint is observed.     

Catalytic upgrading pyrolysis vapors of Jatropha waste using metal promoted ZSM-5 catalysts: An analytical PY-GC/MS

HZSM-5 with high surface area of 625 m²/g was successfully synthesized by hydrothermal method at 160 °C for 72 h. The metal promoted on HZSM-5 catalyst was prepared by liquid ion exchange method. From XRD results, the addition of metals such as Co and Ni did not change the HZSM-5 structure. The metal/HZSM-5 showed lower crystallinity and surface area than the parent HZSM-5 because of the metal dispersion on the HZSM-5 surface. The metal contents of Co/HZSM-5 and Ni/HZSM-5 detected by EDX were less than 1 wt%. Catalytic fast pyrolysis of Jatropha waste using HZSM-5 and metals/HZSM-5 was investigated in terms of biomass to catalyst ratios (1:0, 1:1, 1:5 and 1:10) and types of metals (Co and Ni). From the results, it can be concluded that both biomass to catalyst ratios and the presence of metals had an effect on the increase in aromatic hydrocarbons yields as well as the decrease in the oxygenated and N-containing compounds. Both Co/HZSM-5 and Ni/HZSM-5 promoted the production of aliphatic compounds. Additionally, the PAHs compounds such as napthalenes and indenes, which caused the formation of coke, could be inhibited by metal/HZSM-5, particularly, Ni/HZSM-5. Among catalysts, Ni/HZSM-5 showed the highest hydrocarbon yield of 97.55% with N-containing compounds remained only 1.78%. The formation of hydrocarbon compounds increased the heating values of bio-oils while the elimination of the undesirable oxygenated compounds such as acids and ketones could alleviate problem regarding acidity and instability in bio oils.     

Optimization of hydrogen production in in-situ catalytic adsorption (ICA) steam gasification based on Response Surface Methodology

The present study investigates the optimization of hydrogen (H₂) production with in-situ catalytic adsorption (ICA) steam gasification by using a pilot-scale fluidized bed gasifier. Two important response variables i.e. H₂ composition (in percent volume fraction, %) and H₂ yield (in g kg⁻¹ of biomass) are optimized with respect to five process variables such as temperature (600 °C–750 °C), steam to biomass mass ratio (1.5–2.5), adsorbent to biomass mass ratio (0.5–1.5), superficial velocity (0.15 m s⁻¹–0.26 m s⁻¹) and biomass particle size (350 μm–2 mm). The optimization study is carried out based on Response Surface Methodology (RSM) using Central Composite Rotatable Design (CCRD) approach. The adsorbent to biomass mass ratio is found to be the most significant process variables that influenced the H₂ composition, whereas temperature and biomass particle size are found to be marginally significant. For H₂ yield, temperature is the most significant process variables followed by steam to biomass mass ratio, adsorbent to biomass mass ratio and biomass particle size. The optimum process conditions are found to be at 675 °C, steam to biomass mass ratio of 2.0, adsorbent to biomass mass ratio of 1.0, superficial velocity of 0.21 m s⁻¹ that is equivalent to 4 times the minimum fluidization velocity, and 1.0 mm–2.0 mm of biomass particle size. The theoretical response variables predicted by the developed model fit well with the experimental results.     

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.     

Review and model-based analysis of factors influencing soil carbon sequestration under hybrid poplar

The potential for soil carbon (C) sequestration under short-rotation woody crops, like hybrid poplar (Populus spp.), is a significant uncertainty in our understanding of how managed tree plantations might be used to partially offset increasing atmospheric CO₂ concentrations. Through development of a multi-compartment model, we reviewed information from studies on hybrid poplar and analyzed the potential impact of changes in plant traits and nitrogen (N) fertilization on soil C storage. For a hypothetical setting in the southeastern U.S.A., and starting from soils that are relatively depleted in organic matter (2.5 kg C m⁻²), the model predicted an increase in mineral soil C stocks (1.7 kg C m⁻²) over four 7-year rotations of hybrid poplar. However, at the end of the fourth rotation, both cumulative soil C gains and annual rates of soil C accrual (23-93 g C m⁻² yr⁻¹) varied widely depending on fertilization rate, biomass yield, and rates of dead root decomposition (three factors that were examined in a factorial model-based experiment). Our analysis indicated that processes linked to genetically modifiable poplar traits (aboveground biomass production, belowground C allocation, root decomposition) are potential controls on soil C sequestration. Key measures of model performance were sensitive to how aboveground biomass production responded to N fertilization. Site specific properties that were independent of plant traits were also important to predicted soil C accumulation and point to possible genotype x site interactions that may explain contradictory data from both empirical and theoretical studies of C sequestration under hybrid poplar plantations.     

Biomass production and soil nutrients in organic and inorganic fertilized willow biomass production systems

The use of organic waste materials as nutrient sources for willow biomass production is an attractive means to decrease fertilization costs, increase biomass production and reduce greenhouse gas emissions associated with the system. In this study, changes in soil nutrients and biomass production of two willow varieties (Salix miyabeana–SX64 and Salix purpurea–9882-34) in organic and synthetic fertilized systems were compared at three locations in Northeastern U.S.A: Middlebury VT (MID), Delhi NY (DEL) and Fredonia NY (FRE). A 150 and 200 kg available N ha⁻¹ of urea as commercial fertilizer (CF), biosolid compost (BC) and digested dairy manure (DM) and a control (CT0) treatments were applied in June 2008 to the willow which was re-sprouting after coppice. There was no significant difference (p > 0.05) in biomass production among the fertilization treatments at any of the three sites and for either of the varieties. First rotation biomass production of 9882-34 ranged from 9.0 to 11.6 Mg ha⁻¹ yr⁻¹ at DEL, 3.4–8.8 Mg ha⁻¹ yr⁻¹ at MID and 3.5–7.7 Mg ha⁻¹ yr⁻¹ at FRE. For SX64, biomass production ranged from 13.2 to 19.0 Mg ha⁻¹ yr⁻¹ at DEL, 9.0–15.0 Mg ha⁻¹ yr⁻¹ at Mid and 5.5–9.3 Mg ha⁻¹ yr⁻¹ at FRE. SX64 deployed small numbers of large stems and produced more biomass than 9882-34 which deployed large numbers of small stems. Application of BC significantly increased soil N and P levels at MID in both 2008 and 2009 (p < 0.05). At DEL, BC and DM treatments increased soil N, Ca, Mg and OM levels in both 2008 and 2009 (p < 0.05). The fertilization treatments had no significant effect on any soil nutrients at FRE. This study indicates that willow biomass can be produced without fertilizer additions in the first rotation across this range of sites due to the nutrient status of these sites and high internal nutrient cycling in these systems.     

Two-stage anaerobic dry digestion of blue mussel and reed

Blue mussels and reeds were explored as a new biomass type in the Kalmar County of Sweden to improve renewable transport fuel production in the form of biogas. Anaerobic digestion of blue mussels and reeds was performed at a laboratory-scale to evaluate biogas production in a two-stage dry digestion system. The two-stage system consisted of a leach bed reactor and an upflow anaerobic sludge blanket (UASB) reactor. The two-stage system was efficient for the digestion of blue mussels, including shells, and a methane yield of 0.33 m³/kg volatile solids (VS) was obtained. The meat fraction of blue mussels was easily solubilised in the leach bed reactor and the soluble organic materials were rapidly converted in the UASB reactor from which 68% of the methane was produced. However, the digestion of mussels including shells gave low production capacity, which may result in a less economically viable biogas process. A low methane potential, 0.22 m³/kg VS, was obtained in the anaerobic two-stage digestion of reeds after 107 days; however, it was comparable to similar types of biomass, such as straw. About 80% of the methane was produced in the leach bed reactor. Hence, only a leach bed reactor (dry digestion) may be needed to digest reed. The two-stage anaerobic digestion of blue mussels and reeds resulted in an energy potential of 16.6 and 10.7 GWh/year, respectively, from the estimated harvest amounts. Two-stage anaerobic digestion of new organic materials such as blue mussels and reeds can be a promising biomass resource as land-based biomass start to be limited and conflict with food resources can be avoided.     

Effect of fractional condensers on characteristics,compounds distribution and phenols selection of bio-oil from pine sawdust fast pyrolysis

Bio-oil is a multicomponent mixture of more than 400 types of organic compounds, with high water content. Fractionation of bio-oil may be a more efficient approach for primary separation of bio-oil. In this work, to better understand the effect of fractional condensers on bio-oil yield, physicochemical characteristics, compounds distribution and phenols selection during biomass fast pyrolysis process, a semi-automatic controlled fluidized bed reactor biomass fast pyrolysis system with four-stage condensers was developed. Average temperatures of Condensers 1, 2, 3, 4 were 32.39 °C, 26.74 °C, 24.06 °C and 23.68 °C, respectively. And the bio-oil yields of Condenser 1, 2, 3, and 4 were 26.82%, 7.31%, 1.48% and 9.69%, respectively. Bio-oil collected from Condenser 4 had the lowest water content (9.68 wt%), the lowest acidity (pH = 3.67), and the highest HHV (29.2 MJ/kg). The highest relative contents of compounds collected from Condenser 1, 2, 3 and 4 were 1-(4-hydroxy-3-methoxyphenyl)-2-Propanone (6.95%), trans-Isoeugenol (6.63%), Creosol (5.28%), and trans-Isoeugenol (6.69%), respectively. Fractional condensers affected the compounds distribution, but it has a stronger effect on relative heavy compounds (molar mass > 250) and a weaker effect on relative light compounds (molar mass < 200). Fractional condensers were more conducive to the selection of phenols with relative yield of more than 30%. Phenols, acids and furfurans tended to distribute at higher temperature, while alcohols, ethers and hydrocarbons tended to distribute at relative lower temperature, but the difference was small. The research has provided a reference for the production of bio-oil.     

On the issue of halophytes as energy plants in saline environment

Presented paper describes findings of original researches on assessment of halophytes in Uzbekistan for biogas production. A range of wild and cultivated plants was investigated. Their development and chemical composition was observed. Good yield of halophytes in marginal environment with low-fertile sandy soils and warm mineralized irrigated water was recognized (14–44 t/ha of green biomass). Chemical content of the biomass was analyzed. Highest total salt accumulation was revealed for Salicornia, Halostachys, Kallidium and Climacoptera (35–50%DM). Suaeda, Atriplex, Kochia, Karelinia and Glycyrrhiza accumulated less amounts of mineral ions (9–26%DM). Plants grown in farm trial contained less mineral compounds as compared with the same species from solonchak (for instance, 31.6% ash versus 46.9% for Climacoptera). Na⁺; Cl⁻; SO₄²⁻ was mainly accumulated in green biomass of halophytes. High nutritional value of the biomass was confirmed. Halophytes contained a big amounts of crude protein (5–13 mg/g DM); cellulose (10.38–20.54 mg/g DM); and lipids (0.5–5.06 mg/g DM). Atriplex, Suaeda and Kochia are recognized as the most nutritional valuable plants. Anaerobic digestion of halophytic biomass was studied in batch-test and continuous mode experiments; 130–366 mL of biogas was produced from 1 g DM of various halophytes at 35 °C; and 269–480 mL – at 55 °C. Taking into consideration current use of different plants, biomass yield and biogas production it is recommended to admit Karelinia caspia as the most promising source of biogas. AD-reactor daily fed by mixture of Karelinia + vegetables/fruit waste (1:1) can produce about 500 mL CH₄/day from 1 L of volume (35 °C; HRT = 20; OLR = 2.65 gVS/L/day).     

Fed-batch operation for bio-H2 production by Rhodopseudomonas palustris (strain 42OL)

Interest in renewable and clean energies such as hydrogen has increased because of the high level of polluting emissions, increasing costs associated with petroleum and the escalating problems of global climate change. In the presence of a light source, a microbial photosynthetic process provides a system for the conversion of some organic compounds into biomass and hydrogen. Using Rhodopseudomonas palustris as a cell-factory, hydrogen photo-evolution was investigated in a photobioreactor (PBR) irradiated either from one or two opposite sides. Irradiating the photobioreactor from only one side, in the presence of malic acid, a reactor hydrogen production of 2.786 l(H₂) PBR⁻¹ was achieved. When the PBR was irradiated from two opposite sides, hydrogen photo-evolution increased to 3.162 l(H₂) PBR⁻¹. Experiments were carried out using inoculum from either the retardation or the exponential growth phases. Using the latter, the highest hydrogen photo-evolution rate based on the bacteriochlorophyll (Bchl) concentration was achieved (3295 μl(H₂) mg (Bchl⁻¹ h⁻¹). The hydrogen to biomass ratio (r_g) was 1.91 l g⁻¹ in the medium containing malic acid and 1.07 l g⁻¹ in that containing acetic acid. It was found that the hydrogen production rate was higher with malic than with acetic acid. Although photobiological hydrogen production cannot furnish alone the greater and greater world requirements of clean renewable energy, it is desirable that photobiological hydrogen technology will grow, in the near future, because photobioreactors for bio-hydrogen production can be positioned in fringe areas without competition with agricultural lands.     

Reduction of tars by dolomite cracking during two-stage gasification of olive cake

The effective implementation of biomass gasification has to overcome some difficulties such as the minimization of tars. On the other hand, with a proper design of experimental conditions, biomass gasification can be directed towards the production of hydrogen. The aim of the present study was to investigate the use of dolomite as catalyst to improve tar removal and hydrogen production by a two-stage steam gasification process, using olive cake as raw material. Fixing the olive cake gasification conditions on the first reactor (900 °C, steam flow rate of 190 mg min⁻¹, O₂ flow rate of 7.5 cm³ min⁻¹), the cracking of tars was prompted by: a) steam gasification (steam flow rate in the range 40-190 mg min⁻¹) at 1000 °C, b) catalytic gasification, using dolomite (5% wt.). It was found that increasing steam flow rate up to 110 mg min⁻¹ involves an increase in hydrogen fraction due to the enhancement of water gas and water gas shift reactions. Also, the influence of dolomite was studied at 800 and 900 °C in a second reactor, finding better results at 800 °C, which gave an hydrogen fraction of 0.51.     

Determination of organic silicon compounds in biogas from wastewater treatments plants,landfills, and co-digestion plants

The study determined the organic silicon compounds in biogases from landfills, wastewater treatment plants (WWTPs), and biogas plants processing different organic material. The aim was to provide information for gas utilisation applications, as siloxanes are reported to shorten the life time of engines when biogas is used for energy production. In total, 48 samples were measured. The total concentration of organic silicon compounds in landfill and WWTP gases varied from 77 to 2460 μg/m³ while the concentrations in biogases from biogas plants varied from 24 to 820 μg/m³. The total concentration of organic silicon compounds was lowest (24 μg/m³) in the biogas plant processing grass and maize, and highest (2460 μg/m³) in one of the studied WWTP. The most common compounds in WWTPs and in biogas plants processing also sewage sludge were D4 and D5 while in landfills the most common compounds were D4 and L2 followed by trimethyl silanol. The effect of condensation of biogas on concentrations of organic silicon compounds was studied in one of the landfills and a negligible effect on concentrations was detected.     

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.     

From piggery wastewater nutrients to biogas: Microalgae biomass revalorization through anaerobic digestion

Microalgae grown in swine wastewater were used as a promising strategy to produce renewable energy by coupling wastewater bioremediation and biomass revalorization. The efficiency of a microalgae consortium treating swine slurry at different temperature (15 and 23 °C) and illumination periods (11 and 14 h) was assessed for biomass growth and nutrient removal at two NH₄⁺ initial concentrations (80 and 250 mg L⁻¹ NH₄⁺). Favourable culture conditions (23 °C and 14 h of illumination) and high ammonium loads resulted in higher biomass production and greater nutrients removal rates. The initial N–NH₄⁺ load determined the removal mechanism, thus ammonia stripping and nitrogen uptake accounted similarly in the case of high NH₄⁺ load, while nitrogen uptake prevailed at low NH₄⁺ load. Under favourable conditions, nitrogen availability in the media determined the composition of the biomass. In this context, carbohydrate-rich biomass was obtained in batch mode while semi-continuous operation resulted in protein-rich biomass. The revalorization of the resultant biomass was evaluated for biogas production. Methane yields in the range of 106–146 and 171 ml CH₄ g COD⁻¹ were obtained for the biomasses grown in batch and semi-continuous mode, respectively. Biomass grown under favourable conditions resulted in higher methane yields and closer to the theoretically achievable.     

Associated effects of storage and mechanical pre-treatments of microalgae biomass on biomethane yields in anaerobic digestion

The pre-treatment of microalgae cell walls is known to be a key factor to enhance methane (CH₄) yields during anaerobic digestion. This study investigated the combined effects of two different biomass storage methods and physical pre-treatments on the anaerobic digestion for three different microalgae species. Acutodesmus obliquus, Chlorella vulgaris and Chlorella emersonii were cultivated in 80 L sleevebag photobioreactors (batch mode), and then subjected to different storage (cooling and freezing) and pre-treatment methods prior to anaerobic digestion using the biochemical methane potential (BMP) test. A. obliquus was selected to evaluate pre-treatment methods for further experimentation. Significantly higher CH₄ yields of cooled (4 °C) A. obliquus biomass were achieved through ultrasonication (+53% CH₄) and wet-milling (+51% CH₄). These methods were then applied in follow-up experiments to cooled (4 °C) biomass of C. emersonii and A. obliquus. Ultrasonication again led to significantly higher CH₄ yields for A. obliquus biomass (323 dm³ kg⁻¹ CH₄ yield calculated at standard gas conditions of 273 K, and 101.5 kPa per unit volatile solids, +41% CH₄), and C. emersonii biomass (308 dm³ kg⁻¹; +35% CH₄). In a third experiment series, frozen A. obliquus and C. vulgaris biomass were thawed prior to pre-treatment and BMP-testing. Among all BMP tests, the highest CH₄ yields were achieved with untreated, freeze-thawed C. vulgaris biomass (406 dm³ kg⁻¹); pre-treatment did not enhance CH₄ yields for C. vulgaris, but for A. obliquus (ultrasonication +20%). Pre-treatment was more effective for cooled than freeze-thawed microalgal biomass and combined effects acted strain dependently.