Study of bio-oils and solids from flash pyrolysis of sewage sludges

The aim of this study was to evaluate the production of pyrolysis oil from three types of sewage sludges. The flash pyrolysis was performed at 500 °C, the maximum oil yield was 43.1%, and the water content in bio-oils obtained from secondary sludges was relatively low - 10.3% and 17.0%. GC-MS results showed that pyrolytic bio-oils of studied sludges dominantly contained fatty acids and nitrogenous compounds with potential added value.Obtained solids had high ash content and low calorific value which make them unattractive for use in incineration. FT-IR results showed that solids gave similar IR features as notified alumino silicates; utilization of these solids as adsorbents could be a potential valorization.     

Sulfur transformation during rapid hydropyrolysis of coal under high pressure by using a continuous free fall pyrolyzer☆

The behavior of sulfur transformation during rapid hydropyrolysis of coal was investigated using a pressurized, continuous free fall pyrolyzer under the conditions of temperature ranging from 923 to 1123 K and hydrogen pressure up to 5 MPa. The yields of sulfur converted to gas, tar and char were determined, together with the analyses of sulfur form distributions in coals and chars. The results showed that the decomposition of inorganic sulfur species was affected only by the temperature, while the increases in temperature and hydrogen pressure obviously enhanced the removal of organic sulfur from coal. The extent of organic sulfur removal was proportional to the coal conversion, depending on coal type. A significant retention of gaseous sulfur products by the organic matrix of the char was observed during hydropyrolysis of a Chinese coal above 1023 K, even under the pressurized hydrogen atmosphere. The kinetic analysis indicates that the rate of organic sulfur removal from coal was 0.2th-order with respect to the hydrogen pressure, and the activation energy for total sulfur removal and organic sulfur removal is 17-26 and 13-55 kJ/mol, respectively. The low activation energies suggest that the transformation and removal of sulfur from coal might be controlled by the diffusion and/or thermodynamic equilibrium during hydropyrolysis under the pressurized conditions.     

A green separation process for recovery of healthy oil from pumpkin seed

In this study, pumpkin seeds, called as “Ürgüp Sivrisi” and grown in Cappadocia region, were used as plant materials because of high aroma contents. In the supercritical fluid extraction of pumpkin seed oil, the effect of main process parameters as the particle size (250-2360 μm), the volumetric flow rate of supercritical solvent (0.06-0.30 L/h), the operating pressure (20-50 MPa), the operating temperature (40-70 °C), the type of entrainer (ethanol and n-hexane) and those concentrations (0-10 vol.%) on the extraction yield, the oil solubility and the initial extraction rate were investigated. A cross-over effect for the extraction of pumpkin seed oil using supercritical CO₂ was determined at the operating pressure of 20-30 MPa. The maximum extraction yield obtained with entrainer free was reached 0.50 g oil/g dry seed at 600-1180 μm, 0.12 L/h, 50 MPa and 70 °C for the operation time of 5 h. The maximum extraction yield obtained with ethanol as an entrainer in the experiments was reached 0.54 g oil/g dry seed at the conditions of 600-1180 μm, 0.12 L/h, 30 MPa, 40 °C and 8 vol.% for the operating time of 2 h. The oil compositions were determined by gas chromatography analysis and the results showed that the compositions of pumpkin seed oil which were obtained by means of organic solvent extraction and supercritical fluid extraction were similar. The average oil compositions determined as 9.3 (±0.43)% palmitic acid, 7.5 (±0.6)% stearic acid, 32.3 (±0.6)% oleic acid, 48.1 (±0.6)% linoleic acid and 0.7 (±0.3)% linolenic acid. The morphological changes in the seeds were determined by the scanning electron microscopy analysis.     

Supercritical carbon dioxide extraction of oil from Mexican chia seed (Salvia hispanica L.): Characterization and process optimization

Supercritical carbon dioxide (SC-CO₂) was employed to extract oil rich in omega-3 fatty acids (FAs) from chia seeds, and the physicochemical properties of the oil were determined. A central composite rotatable design was used to analyze the impact of temperature (40 °C, 60 °C and 80 °C), pressure (250 bar, 350 bar and 450 bar) and time (60 min, 150 min and 240 min) on oil extraction yield, and a response surface methodology (RSM) was applied. The extraction time and pressure had the greatest effects on oil. The highest oil yield was 92.8% after 300 min of extraction time at 450 bar. The FA composition varied depending on operating conditions but had a high content of α-linolenic acid (44.4-63.4%) and linoleic acid (19.6-35.0%). The rheological evaluation of the oils indicated a Newtonian behavior. The viscosity of the oil decreased with the increase in temperature following an Arrhenius-type relationship.     

Effect of low frequency ultrasonic assisted extraction on the quality of seed oils of Indian origin

The study gives an insight into the effect of low frequency ultrasonic enhancement of solvent extraction on the quality of non-edible oils (Jatropha and Pongamia as model seed varieties) in comparison to conventional methods of extraction i.e. direct reflux or soxhlet extraction using hexane. A series of experiments have been carried out to study the effect of variables; solute to solvent ratio (1:2.5-1:10) and reaction time (30 s-60 min) on the yield of oil. The quality of oil extracted by different methods have been assessed by determining the acid value of oil by ASTM D-974/04 method, a measurement of triglyceride and fatty acid degradation, by the presence of phorbol esters in Jatropha curcas and phenolic compounds in Pongamia oil analyzed using HPLC. Under optimized conditions solute to solvent ratio of 1:10 (w/v), 3 min extraction time yields > 95% pure oil having < 1% FFA in Jatropha curcas and 30 s extraction time in Pongamia seed yields oil with less than 2% FFA in comparison to conventional method of extraction in 16 h.     

Pyrolysis of cellulose, xylan and lignin with the K2CO3 and ZnCl2 addition for bio-oil production

The chemical structure of liquid products of the wood biopolymers, i.e. cellulose, xylan and lignin pyrolysis at 450 °C with and without the 10 wt.% addition of potassium carbonate or zinc chloride was investigated. The yield of liquid products of pyrolysis was in the range of 24-44 wt.% and their form was depending on the chemical structure of pyrolyzed material. The potassium carbonate and zinc chloride addition to biopolymers has also influenced the temperature range of samples decomposition as well as the structure of resulted bio-oils. All bio-oils from biopolymer were dark-brown water-oil emulsions. Contrarily, bio-oils obtained from biopolymer with K₂CO₃ or ZnCl₂ addition were orange liquids with well-separated water and oil phases. All analyses proved that the composition and the quality of bio-oil strongly depends on both the nature of the starting sample and the presence of the additive. The FT-IR analyses of oils showed that oxygen functionalities and hydrocarbons contents highly depend on the type of biopolymer. Results confirmed the significant removal and/or transformation of oxygen containing organic compounds due to the zinc chloride and potassium carbonate presence during pyrolysis process.     

Extraction of oil from chia seeds with supercritical CO2

Chia (Salvia Hispanic, L.) is a crop that was used as food, medicine and paints by the Aztec Indians in Mexico before 1492, and now has a promissory future in several countries. Chia seeds oil is rich in polyunsaturated fatty acids, particularly omega-3 linolenic acid (54-67%) and omega-6 linoleic acid (12-21%) which pose great benefits for human and animal health.The oil extraction from Chia seeds using supercritical CO₂ seems to be a good alternative because it operates at low temperature with good mass-transfer rates and with no solvent residual in the final product.The objective of this work is to evaluate the extraction yield of oil from chia seeds and the concentration of omega-3 and omega-6 acids using supercritical extraction with CO₂ at three pressures: 136, 272, and 408 bar, and three temperatures: 40, 60, and 80 °C.     

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.     

Supercritical carbon dioxide extraction of triglycerides from Jatropha curcas L. seeds

This study examines the effects of pressure, temperature and solvent to solid ratio (SSR) on extraction efficiency of triglycerides from powdered Jatropha seeds by using supercritical carbon dioxide extraction. Supercritical extractions were designed for pressures ranging from 250 to 350 bar, temperatures ranging from 313 to 333 K and SSR values ranging from 65:1 to 125:1. All values were selected using response surface methodology in order to determine their effects on the concentration of triglycerides from the extracted oil. Using 3750 g of carbon dioxide over 5 h, a supercritical carbon dioxide extraction (at 350 bar, 333 K and an SSR value of 125:1) yielded 43.51% oil. The concentration and extraction efficiency (i.e. recovery) of triglycerides in the extract reached 657.1 mg/g and 97.62%, respectively. Changes in pressure presented more effective in increasing the recovery of triglycerides, but both temperature and the SSR value are important in obtaining high concentration of triglycerides from the Jatropha seeds that are useful for biodiesel materials.     

Fixed-bed pyrolysis and hydropyrolysis of sunflower bagasse: Product yields and compositions

Pyrolysis and hydropyrolysis experiments at different temperatures, heating rates and pressures have been conducted on a sample of sunflower pressed bagasse to investigate the effect of particle size, sweep gas velocity, and hydrogen pressure on the product yields and characteristics. In contrast to coal and oil shales, char and oil yields from sunflower pressed bagasse were found to be largely independent of particle size and sweep gas velocity in a Heinze retort with the oil yield of ≈ 40% w/w being the same as that from a well-swept fixed-bed reactor in which a much smaller sample size was used. The use of high hydrogen pressure ( > 50 bar) increased the oil yields by up to ≈ 10% w/w but these increases are much greater when expressed on a carbon basis due to the reduced oxygen contents of the oils. Even at low pressure, it has been estimated that ≈ 40% of the carbon aromatized during pyrolysis.     

Supercritical CO2 extraction of dittany oil: Experiments and modelling

The extraction of oil from dittany (Origanum dictamnus) using supercritical carbon dioxide was investigated. The experiments were performed in a bench scale apparatus at the pressures of 100 and 150 bar and at the temperatures of 40 and 60 °C. The effect of the solvent flow rate and the mean particle diameter of dittany on the extraction yield was also investigated at 100 bar and 40 °C. It is shown that the extraction yield increases with pressure, while the increase of temperature and mean particle diameter leads to the opposite effect. Different flow rates of SCCO₂ lead to similar extraction yields. Finally, the overall extraction curves are well correlated by a mass balance model of plug flow, in which the intraparticle diffusion resistance has the controlling role.     

Reactive extraction and in situ esterification of Jatropha curcas L. seeds for the production of biodiesel

Jatropha curcas L. has recently been hailed as the promising feedstock for biodiesel production as it does not compete with food sources. Conventional production of biodiesel from J. curcas L. seeds involve two main processing steps; extraction of oil and subsequent esterification/transesterification to fatty acid methyl esters (FAME). In this study, the feasibility of in situ extraction, esterification and transesterification of J. curcas L. seeds to biodiesel was investigated. It was found that the size of the seed and reaction period effect the yield of FAME and amount of oil extracted significantly. Using seed with size less than 0.355 mm and n-hexane as co-solvent with the following reaction conditions; reaction temperature of 60 °C, reaction period of 24 h, methanol to seed ratio of 7.5 ml/g and 15 wt% of H₂SO₄, the oil extraction efficiency and FAME yield can reached 91.2% and 99.8%, respectively. This single step of reactive extraction process therefore can be a potential route for biodiesel production that reduces processing steps and cost.     

Rapid and catalytic pyrolysis of corn stalks

Non-catalytic and catalytic rapid pyrolysis of corn stalks was studied in a tubular fixed-bed reactor. The optimum operating conditions giving the highest liquid yield was determined as pyrolysis temperature of 500 °C, sweeping gas flow rate of 400 cm³ min^− 1 and heating rate of 500 °C min^− 1. In the catalytic process, rapid pyrolysis of stalks was performed at the optimum conditions with catalysts such as ZSM-5, HY and USY. The highest liquid yield from the catalytic pyrolysis was 27.55% with ZSM-5, while the oil from non-catalytic pyrolysis was 33.30%. In the last part, various spectroscopic and chromatographic methods were applied for characterization of bio-oils. Although catalytic pyrolysis converts the long chains of alkanes and alkenes of the oils into lower weight hydrocarbons, the obtained oil yields were lower than those of non-catalytic pyrolysis. USY catalyst gives the highest amount of aromatics among the catalysts used. Moreover, TG–DTA analyses were applied on raw materials to investigate thermal degradation of corn stalks and calculate the kinetic parameters.     

Hydro-liquefaction of woody biomass in sub- and super-critical ethanol with iron-based catalysts

Hydro-liquefaction of a woody biomass (Jack pine powder) in sub-/super-critical solution of ethanol without and with iron-based catalysts (5 wt% FeS or FeSO₄) was investigated with a stainless steel micro-reactor (10 mL) at temperatures of 473-623 K and an initial pressure of hydrogen varying from 2.0 to 10.0 MPa. Without catalyst, the oil yields were in the range of 17% and 44%, depending on temperature, reaction time and initial pressure of hydrogen. With catalysts, the Oil yields significantly increased while the yields of solid residue and gases and water decreased. A high oil yield of 63% was obtained with FeSO₄ at 623 K and 5 MPa of H₂ for 40 min. The elemental analyses and GC/MS measurements for the Oils revealed that the liquid products have much higher heating values than the crude wood sample and phenolic compounds were dominant in the Oils, irrespective of whether or what catalyst was used.     

Characterization of the liquid and solid products obtained from the oxidative pyrolysis of meat and bone meal in a pilot-scale fluidised bed plant

Pyrolysis of meat and bone meal material has been studied in an auto-thermal pilot scale unit with a fluidised bed reactor based on Bioware Technology. The heating value of the bio-oil samples is around 33-36 MJ/kg, whilst the nitrogen content is between 7.3 wt.% and 9.0 wt.%. Liquid fractionation with solvents of the bio-oil has been carried out. Chemical analyses of the fractions have shown that the main components in the bio-oil samples are alkanes, alkenes, oxygenated components (as alcohols) and nitrogen compounds (as nitriles) which are identified in the water insoluble fraction. Knowing the chemical composition of the bio-oils is important for assessing possible chemical and pharmaceutical applications of these bio-oils. The char samples have a notable ash content (63 wt.% to 77 wt.%) and its high Ca content could make it suitable for use as a catalyst in gasification processes.     

Optimization of supercritical carbon dioxide extraction of Passiflora seed oil

This study investigates extraction of Passiflora seed oil by using supercritical carbon dioxide. Artificial neural network (ANN) and response surface methodology (RSM) were applied for modeling and the prediction of the oil extraction yield. Moreover, process optimization were carried out by using both methods to predict the best operating conditions, which resulted in the maximum extraction yield of the Passiflora seed oil. The maximum extraction yield of Passiflora seed oil was estimated by ANN to be 26.55% under the operational conditions of temperature 56.5 °C, pressure 23.3 MPa, and the extraction time 3.72 h; whereas the optimum oil extraction yield was 25.76% applying the operational circumstances of temperature 55.9 °C, pressure 25.8 MPa, and the extraction time 3.95 h by RSM method. In addition, mean-squared-error (MSE) and relative error methods were utilized to compare the predicted values of the oil extraction yield obtained from both models with the experimental data. The results of the comparison reveal the superiority of ANN model compared to RSM model.     

Effect of moisture and particle size on the extractability of oils from seeds with supercritical CO2

Moisture level and particle size of soybeans, peanuts and cottonseed were correlated with the extraction rate and yield of oil when extracted with supercritical carbon dioxide (SC-CO₂) at a constant temperature (50 C) and pressure (8000 psig). The rate of extraction and ultimate oil yields were quite low with cracked soybeans. However, good extraction rates and nearly theoretical oil yields were obtained from ground or thinly flaked (<0.010″) seeds. Moisture levels between 3% and 12% had little effect on extracability. Oil composition was not influenced by either parameter. Scanning electron microscopy was used to study seed structure before and after extraction with SC-CO₂. Micrographs of SC-CO₂-extracted seeds were similar to hexane-extracted seeds. Presented at the AOCS Meeting, May 1983, Chicago.     

Thermochemical liquefaction characteristics of microalgae in sub- and supercritical ethanol

Thermochemical liquefaction characteristics of Spirulina, a kind of high-protein microalgae, were investigated with the sub- and supercritical ethanol as solvent in a 1000 mL autoclave. The influences of various liquefaction parameters on the yields of products (bio-oil and residue) from the liquefaction of Spirulina were studied, such as the reaction temperature (T), the S/L ratio (R₁, solid: Spirulina, liquid: ethanol), the solvent filling ratio (R₂) and the type and dosage of catalyst. Without catalyst, the bio-oil yields were in the range of 35.4 wt.% and 45.3 wt.% depending on the changes of T, R₁ and R₂. And the bio-oil yields increased generally with increasing T and R₂, while the bio-oil yields reduced with increasing R₁. The FeS catalyst was certified to be an ideal catalyst for the liquefaction of Spirulina microalgae for its advantages on promoting bio-oil production and suppressing the formation of residue. The optimal dosage of catalyst (FeS) was ranging from 5-7 wt.%. The elemental analyses and FT-IR and GC-MS measurements for the bio-oils revealed that the liquid products have much higher heating values than the crude Spirulina sample and fatty acid ethyl ester compounds were dominant in the bio-oils, irrespective of whether catalyst was used.     

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.     

Recovery of triglycerides from used frying oil by extraction with liquid and supercritical ethane

The extraction of triglycerides from used frying oil with liquid and supercritical ethane has been studied in a semibatch system at different temperatures (25-80 °C) and pressures (150-250 kg/cm²). It has been found that isobaric decreases of temperature and isothermal increases of pressure lead to both increasing extraction yields and decreasing separation efficiencies. Lipid fractions recovered in the high density region had acceptable concentrations of polar compounds.Results with ethane have been compared to those reported for CO₂ in earlier works. At similar reduced densities of the solvents, oil solubility in ethane was higher than in CO₂, being the separation efficiency of polar fractions slightly better when using ethane.The extraction process was further analyzed in a packed countercurrent column. At optimum conditions (250 kg/cm², 25 °C, and solvent-to-oil ratio 45 g:g) about 85% of the triglycerides were recovered, being 11.2% the polar content of the triglyceride fraction recovered.