Hydrogen from biomass-production by steam reforming of biomass pyrolysis oil

Thermo-conversion of biomass is one of the leading near-term options for renewable production of hydrogen and has the potential to provide a significant fraction of transportation fuel required in the future. We propose a two-step process that starts with fast pyrolysis of biomass, which generates high yields of a liquid product, bio-oil, followed by catalytic steam reforming of bio-oil to produce hydrogen. A major advantage of such a concept results from the fact that bio-oil is much easier and less expensive to transport than either biomass or hydrogen. Therefore, the processing of biomass and the production of hydrogen can be performed at separate locations, optimized with respect to feedstock supply and to hydrogen distribution infrastructure. This approach makes the process very well suited for both centralized and distributed hydrogen production. This work demonstrates reforming of bio-oil in a bench-scale fluidized bed system and provides hydrogen yields obtained using several commercial and custom-made catalysts.     

High pressure hydropyrolysis of coals by using a continuous free-fall reactor

Rapid hydropyrolysis of coal was carried out at temperatures ranging from 923 to 1123 K and H₂ pressures up to 7 MPa by using a continuous free-fall pyrolyzer. The effects of the reaction conditions on product yields were investigated. Carbon mass balance was fairly good. It was revealed that a large amount of methane was produced due to the hydrogenolysis of higher hydrocarbons and the hydrogasification of char. The influence of pyrolysis temperature was significant on both reactions while H₂ pressure mainly affected the latter. A considerable amount of reactive carbon was formed during hydropyrolysis of coal. It was converted to methane at high temperatures and high H₂ pressures, while the hydrogasification of reactive carbon takes place relatively slowly at low temperatures and low H₂ pressures, resulting in a low overall carbon conversion. The coal conversions observed in the present study were much higher than those obtained with using reactors where the contact between coal particles and H₂ is insufficient.     

Comparison of techniques for the extraction of tobacco seed oil

The yield and fatty acid (FA) composition of the oil obtained from the seeds of a semi‐oriental tobacco (Nicotiana tabacum L.) plant, type Otlja, by various recovery techniques, which are: Soxhlet extraction (SE), maceration (ME), indirect and direct ultrasonic extraction (IUE and DUE, respectively) and cold pressing (CP), were compared. The solvent extractions of ground tobacco seeds (TS) were carried out by n‐hexane, while CP was used to recover the oil from the TS. The highest oil yield (32.9 g/100 g, i.e. 93% of the oil content in the seeds) was achieved by CP. Ultrasonically assisted solvent extractions appear to be inefficient in recovering the oil from the ground TS, as the oil yields were only 45–55% of the oil content, depending on the extraction conditions. Independently of the technique applied, linoleic acid was the major FA of the tobacco seed oil (TSO). The compositions of the TSO extracted by SE, ME, IUE and CP were very similar to each other, and the composition of the TSO recovered by DUE depended on the ultrasonic power input. The content of linoleic acid was reduced, while the content of saturated FA was increased by increasing the ultrasonic power from 5 to 50 W.     

Effects of particle size on the fast pyrolysis of oil mallee woody biomass

This study aims to investigate the effects of biomass particle size (0.18-5.6 mm) on the yield and composition of bio-oil from the pyrolysis of Australian oil mallee woody biomass in a fluidised-bed reactor at 500 °C. The yield of bio-oil decreased as the average biomass particle size was increased from 0.3 to about 1.5 mm. Further increases in biomass particle size did not result in any further decreases in the bio-oil yield. These results are mainly due to the impact of particle size in the production of lignin-derived compounds. Possible inter-particle interactions between bio-oil vapour and char particles or homogeneous reactions in vapour phases were not responsible for the decreases in the bio-oil yield. The bio-oil samples were characterised with thermogravimetric analysis, UV-fluorescence spectroscopy, Karl-Fischer titration as well as precipitation in cold water. It was found that the yields of light bio-oil fractions increased and those of heavy bio-oil fractions decreased with increasing biomass particle size. The formation of pyrolytic water at low temperatures (<500 °C) is not greatly affected by temperature or particle size. It is believed that decreased heating rates experienced by large particles are a major factor responsible for the lower bio-oil yields from large particles and for the changes in the overall composition of resulting oils. Changes in biomass cell structure during grinding may also influence the yield and composition of bio-oil.     

Liquid phase equilibrium of phenol extraction from bio-oil produced by biomass pyrolysis using thermodynamic models

Utilization of biomass as a new and renewable energy source is being actively conducted by various parties. One of the technologies for utilizing or converting biomass as an energy source is pyrolysis, to convert biomass into a more valuable product which is bio-oil. Bio-oil is a condensed liquid from the vapor phase of biomass pyrolysis such as coconut shells and coffee shells. Biomass composition consisting of hemicellulose, cellulose, and lignin will oxidize to phenol which is the main content in bio-oil. The total phenolic compounds contained in bio-oil are 47.03% (coconut shell) and 45% (coffee shell). The content of phenol compounds in corrosive bio-oils still quite high, the use of this bio-oil directly will cause various difficulties in the combustion system due to high viscosity, low calorific value, corrosivity, and instability. Phenol compounds have some benefits as one of the compounds for floor cleaners and disinfectants which are contained in bio-oil.The correlation between experimental data and calculations shows that the UNIQUAC Functional-group Activity Coefficients (UNIFAC) equilibrium model can be used to predict the liquid–liquid equilibrium in the phenol extraction process of the coconut shell pyrolysis bio-oil. While the Non-Random Two Liquid (NRTL) equilibrium model can be used to predict liquid–liquid equilibrium in the extraction process of phenol from bio-oil pyrolysis of coffee shells.     

Bio-oil production from oil palm biomass via subcritical and supercritical hydrothermal liquefaction

This paper presents the studies on the liquefaction of three types of oil palm biomass; empty fruit bunch (EFB), palm mesocarp fiber (PMF) and palm kernel shell (PKS) using water at subcritical and supercritical conditions. The effect of temperature (330, 360, 390 °C) and pressure (25, 30, 35 MPa) on bio-oil yields were investigated in the liquefaction process using a Inconel batch reactor. The optimum liquefaction condition of the three types of biomass was found to be at supercritical condition of water i.e. at 390 °C and 25 MPa, with PKS yielding the maximum bio-oil yield of 38.53 wt%, followed by EFB and PMF, with optimum yields of 37.39 wt% and 34.32 wt%, respectively. The chemical compositions of the bio-oils produced at optimum condition were analyzed using GC–MS and phenolic compounds constituted the major portion of the bio-oils, with other minor compounds present such as alcohols, ketones, aromatic hydrocarbons and esters.     

Supercritical extraction of crude oil by methanol- and ethanol-modified carbon dioxide

The effect of ethanol and methanol cosolvents on the extraction yield and kinetics of crude oil originating from the Halfdan field of the North Sea by supercritical carbon dioxide was investigated across a pressure range of 20–60 MPa under a fixed temperature of 60 °C. Results inform that the pure carbon dioxide recovery varied between 43 and 77% while the recovery of the liquid phase of oil ranged between 22 and 56% across the entire pressure range. Using ethanol- and methanol-modified CO₂, the total recovery yield increased significantly averaging an additional 18.2% and 19.4% respectively when compared to pure carbon dioxide. The ethanol addition improved the recovery of the liquid phase of oil averaging 9.6% while the methanol addition improved it to 7.3% across the entire pressure range.Study of the kinetics of extraction process indicated that heavier fractions were extracted faster with the ethanol- compared to the methanol-modified CO₂. GC–MS TIC chromatographic analysis of the extracted oil fractions showed that the extraction of C₁₉-C₃₀ single carbon number groups with the addition of methanol is more dependent on pressure. Predominantly, ethanol addition was more efficient in extraction of C₁₇-C₃₈ single carbon number groups while methanol contributed more in extraction of C₇-C₉ SCN groups.     

A novel process for extraction of tea oil from Camellia oleifera seed kernels by combination of microwave puffing and aqueous enzymatic oil extraction

The objective of this study was to extract the oil from Camellia oleifera seed kernels by aqueous enzymatic oil extraction (AEOE). We describe a novel process for extraction of tea oil preceded by tea saponin extraction from C. oleifera seed kernels. The extraction efficiency obtained with microwave‐assisted extraction (MAE) is very high, which the recovery yield is up to 83% in 30 s and the saponins in camellia seed kernels can be completely removed by the second MAE. Moreover, an important step in the process development has been the pretreatment by microwave puffing of camellia seed kernel residues followed by AEOE increased oil extraction yield from 53% to 95%, which will is comparable to hexane oil extraction yields from plant materials.     

Separation of aromatic components from light cycle oil by solvent extraction

To improve the versatility of light cycle oil (LCO), separation of aromatic compounds from LCO by solvent extraction was investigated. LCO was analyzed to identify 35 components: 19 aromatics and 16 alkanes. The batch liquid–liquid equilibrium extraction of LCO was performed using furfural, sulfolane, and methanol as extraction solvents. In each solvent, the aromatics present in LCO were selectively extracted relative to the alkanes. The separation selectivities of aromatics relative to alkanes were larger in sulfolane than in the other solvents. Among the aromatic components, di- and tricyclic compounds were selectively extracted relative to the monocyclic ones.     

从煤焦油洗油中提取喹啉和异喹啉的研究

从煤焦油洗油中提取高纯度喹啉和异喹啉，考察了萃取剂及其质量分数、pH值对提取率的影响，得出最佳条件：萃取剂为硫酸氢铵，硫酸氢铵质量分数为20％，pH值0．8～1．0，喹啉和异喹啉的提取率大于75％。     

Antioxidant Capacity of Rapeseed Extracts Obtained by Conventional and Ultrasound‐Assisted Extraction

Ultrasound‐assisted extraction (UAE) and conventional solid–liquid extraction were applied to extract total antioxidants from two rapeseed varieties. The antioxidant capacities (AC) of winter and spring rapeseed cultivars were determined by four different analytical methods: ferric reducing antioxidant power (FRAP), cupric reducing antioxidant capacity (CUPRAC), 2,2′‐diphenyl‐1‐picrylhydrazyl (DPPH), 2,2′‐azino‐bis‐3‐ethylbenzothiazoline‐6‐sulfonic acid (ABTS). The average AC of the studied rapeseed cultivars ranged between 4.21–10.03 mmol Trolox (TE)/100 g, 7.82–10.61 mmol TE/100 g, 8.11–51.59 mmol TE/100 g, 22.48–43.13 mmol TE/100 g for FRAP, CUPRAC, DPPH and ABTS methods, respectively. There are positive correlations between total phenolics (TPC = 804–1625 mg sinapic acid (SA)/100 g) and AC of the studied rapeseed extracts (r = 0.2650–0.9931). Results of the principal component analysis (PCA) indicate that there are differences between the total amounts of antioxidants in rapeseed samples extracted by different extraction techniques. Rapeseed extracts obtained after 18 min of ultrasonication revealed the highest content of total antioxidants. The UAE is a very useful, efficient and rapid technique of oilseed samples preparation for determination of AC by different analytical methods.     

Comparison of low‐temperature processes for oil and coenzyme Q10 extraction from mackerel and herring

Among the fat fish species available from Eastern Quebec (Canada), whole Atlantic mackerel (Scomber scombrus) and herring (Clupea harengus) represent abundant fishery resources which are currently under‐utilized. They have relatively high contents of oil and coenzyme Q10 (CoQ10) in their tissues, which could be valuable for nutraceutical applications. Therefore, two low‐temperature extraction processes were compared for the recovery of oil and CoQ10 from these resources, such as enzymatic hydrolysis using Protamex? and supercritical CO₂ (SCO₂) using fish lyophilizates. The results revealed that highest yields of oil and CoQ10 were obtained using the enzymatic hydrolysis process with mackerel. Whatever the process used, CoQ10 concentrations were higher in herring oil, due mainly to a more selective extraction of CoQ10 over that of the oil. The highest CoQ10 recovery rates (extraction efficiencies) were obtained using the enzymatic hydrolysis process with both types of fish, but also the SCO₂ process with herring under some conditions. For mackerel, the lower CoQ10 recovery rates obtained from the SCO₂ process were explained by its more important matrix effect. An economic assessment of both processes revealed that the enzymatic hydrolysis extraction process would be the most promising for up‐scaling the recovery of oil and CoQ10 from these resources.     

Catalytic pyrolysis of biomass in inert and steam atmospheres

The objective of this study was to investigate thermal conversion of a perennial shrub, Euphorbia rigida biomass sample with catalyst in inert (N₂) and steam atmospheres. Experimental studies were conducted in a well swept fixed bed reactor with a heating rate of 7 °C/min to a final pyrolysis temperature of 550 °C and with a mean particle size of 0.55 mm in order to determine the effect of different atmospheres with various catalyst ratios on pyrolysis yields and characteristics. The catalyst ratios were 5%, 10% and 20% (w/w) under nitrogen atmosphere with flow rates of 50, 100, 200 and 400 cm³/min and steam atmosphere with well-swept velocities of 12, 25 and 52 cm³/min. The optimum oil yield was obtained as 32.1% at the nitrogen flow rate of 200 cm³/min, while it was obtained as 38.6% at steam flow rate of 25 cm³/min when a 10% catalyst by weight according to the biomass was used. Higher oil yields were observed when biomass sample was treated in steam atmosphere than in inert (N₂) atmosphere. The oil composition was then analysed by elemental analyses techniques such as IR and GC-MS. The oil products were also fractionated by column chromatography. The bio-oils obtained at both atmospheres contain mainly n-alkanes and alkenes, aromatic compounds; mainly benzene and derivatives and PAHs, nitrogenated compounds and ketones, carboxylic acids, aldehydes, phenols and triterpenoid compounds. More oxygenated compounds and less substituted alkanes and alkenes were obtained in catalytic pyrolysis of E. rigida in the steam atmosphere. The experimental and chemical characterisation results showed that the oil obtained from perennial shrub, E. rigida can be used as a potential source of renewable fuel and chemical feedstock.     

Experimental and modelling of supercritical oil extraction from rapeseeds and sunflower seeds

The supercritical oil extraction from oleaginous seeds (sunflower and rapeseeds) is presented here through experimental and modelling results. The experimental setup allows an accurate following of the mass of the oil extracted and to derive the experimental influences of pressure, temperature and supercritical CO₂ flowrate on the extraction curves. These parameters are very sensitive and highlight the necessity of precise optimisation of experimental conditions. In order to complete the behaviour of supercritical fluids extraction, an improved modelling is proposed. The modelling basic equations are based on others modelling published previously. In this work, the determination of several parameters comes from correlations and the other constants are fitted with all the experimental results. Thus the modelling is more representative and predictive as other ones. The modelling results present a good agreement with the experimental results, and hence it can be used for the dimensioning of some extraction autoclaves.     

Enhanced extraction of essential oil from Cinnamomum cassia bark by ultrasound assisted hydrodistillation

Cinnamon essential oil with many bioactivities is an important raw material for the production of various chemicals,and the conventional hydrodistillation(HD) for cinnamon oil extraction always require a longer extraction time. In this work, ultrasound-assisted hydrodistillation extraction(UAHDE) technique was employed to enhance the extraction efficiency of essential oils from cinnamon barks. The parameters with significant effects on the essential oil extraction efficiency(ultrasound time, ultrasound power, extraction time, liquid–solid ratio) were optimized, and the proposed UAHDE was compared with the conventional HD extraction in terms of the extraction time, extraction yield, and physicochemical properties of extracted oils. Compared to the HD extraction, the UAHDE resulted in a shorter extraction time and a higher extraction yield. Using GC–MS analysis, the UAHDE provided more valuable essential oil with a high content of the vital trans-cinnamaldehyde compounds compared with the HD. Scanning electron micrograph(SEM) confirmed the efficiency of ultrasound irradiation for cinnamon oil extraction. In addition, the analysis of electric consumption and CO2 emission shows that the UAHDE process is a more economic and environment-friendly approach. Thus, UAHDE is an efficient and green technology for the cinnamon essential oil extraction, which could improve the quantity and quality of cinnamon oils.     

Comparison of different methods for the determination of the oil content in oilseeds

The investigation and assessment of the oil content of oilseeds are important criteria, especially for the oil milling trade. Standard methods for the determination of the oil content of oilseeds are very time consuming, with extraction periods of 4 to 8 h. Three different oilseeds—rapeseed, sunflower, and soybean—are extracted by supercritical fluid extraction (SFE), accelerated solvent extraction, microwave-assisted extraction, solid fluid vortex extraction, and Soxtherm, and the results are compared with the result of the German Fat Science Society (DGF) standard method B-I 5 (87). Besides, the extracts are analyzed regarding the content of tocopherols as a parameter for mild extraction conditions and the content of diglycerides and free fatty acids as parameters for the content of more polar lipids. The results of the determination of the oil content under optimal conditions are comparable with the results of the DGF standard method B-I 5 (87). There are no significant differences between the different methods. The content of tocopherols is dependent upon the extraction method and the type of oilseed. The highest content is obtained by SFE. The content of diglycerides and free fatty acids varied according to the oilseed.     

Pyrolysis oil upgrading by high pressure thermal treatment

High pressure thermal treatment (HPTT) is a new process developed by BTG and University of Twente with the potential to economically reduce the oxygen and water content of oil obtained by fast pyrolysis (pyrolysis oil), properties that currently complicate its co-processing in standard refineries. During the HPTT process, pyrolysis oil undergoes a phase split yielding a gas phase, an aqueous phase and an oil phase. In this study, HPTT experiments were carried out at different operating conditions in a continuous tubular reactor. Experimental results showed that, with increasing temperature and residence time, the release of gases (mainly CO₂) and the production of water increased, reducing the oxygen content of the oil phase and hence increasing the energy content (from 14.1 to 28.4 MJ/kg) having the temperature a larger effect when compared to the residence time. Using gel permeation chromatography (GPC), an increase of the molecular weight of the oil phase, probably due to polymerisation of the sugars present in pyrolysis oil, was observed. When water was added as solvent to dilute the feed oil, a decrease of the molecular weight of the resulting oil phase was observed. This indicated that the concentration of organic components had a direct effect on the formation of high molecular weight components. In conclusion, during HPTT an oil with lower oxygen and water content with higher energy value was produced, but adverse formation of high molecular weight components was also detected.     

超临界CO_2萃取大豆油的实验研究

采用超临界CO2 萃取技术进行了大豆油的萃取实验。在压力为 2 0～ 30MPa、温度为 30 8～ 32 3K的范围内 ,考察了萃取压力、萃取温度、流体流量和物料预处理方式等条件对出油率的影响。在本文实验范围内 ,大豆油的最佳萃取工艺条件为 :压力 30MPa ,温度 313K ,物料状态为约 0 .4mm厚的大豆片。流体流量只影响萃取速率 ,而不影响最终的出油率     

Supercritical extraction of sunflower seed oil: Experimental data and model validation

In this work experimental results of sunflower seed oil extraction using supercritical CO₂ are presented, together with the outcome obtained by applying to the same data a theoretical model recently developed and further improved here.We performed extraction tests utilizing a supercritical extraction equipment having a volumetric capability of 100 ml; the seeds were milled to obtain different particle sizes (mean diameter between 0.19 and 1.2 mm); the range of pressure investigated was 280–550 bar, the temperature and solvent flow rate were maintained constant at about 40 °C and 10 g/min, respectively.The model accounts for the distinction between broken and intact oil-bearing cells and describes the extraction kinetics similar to the shrinking core models: it allowed satisfactory fitting of the experimental data and permitted to calculate the effective diffusivity of the oil in the seed, which resulted equal to 3 × 10⁻¹¹ m²/s. The reliability of the model is demonstrated by the fact that the value of the effective diffusivity, resulting from model optimization procedures, is similar for the various experimental tests.