Bio-oil from olive oil industry wastes: Pyrolysis of olive residue under different conditions

Olive residues were pyrolysed in a fixed bed reactor under different pyrolysis conditions to determine the role of final temperature, sweeping gas flow rate and steam velocity on the product yields and liquid product composition with a heating rate of 7 °C/min. Final temperature range studied was between 400 and 700 °C and the highest liquid product yield was obtained at 500 °C. Liquid product yield increased significantly under nitrogen and steam atmospheres. Liquid products obtained under the most suitable conditions were characterised by elemental analyses, FT-IR and ¹H-NMR. In addition, column chromatography was employed and the yields of the sub-fractions were calculated. Gas chromatography was achieved on n-pentane fractions. The results show that it is possible to obtain liquid products similar to petroleum from olive residue if the pyrolysis conditions are chosen accordingly.     

Slow pyrolysis of pistachio shell

In this study, pistachio shell is taken as the biomass sample to investigate the effects of pyrolysis temperature on the product yields and composition when slow pyrolysis is applied in a fixed-bed reactor at atmospheric pressure to the temperatures of 300, 400, 500, 550, 700 °C. The maximum liquid yield was attained at about 500–550 °C with a yield of 20.5%. The liquid product obtained under this optimum temperature and solid products obtained at all temperatures were characterized. As well as proximate and elemental analysis for the products were the basic steps for characterization, column chromatography, FT-IR, GC/MS and SEM were used for further characterization. The results showed that liquid and solid products from pistachio shells show similarities with high value conventional fuels.     

Comparative analysis of pyrolysis oils and its subfractions under different atmospheric conditions

In this paper comparative analysis of bio-oils and their subfraction from static, sweeping gas and steam pyrolysis of apricot pulp, a food industry waste, was investigated. Experimental studies were conducted in a well-swept fixed-bed reactor with a heating rate of 5 °C min^{− 1}, to a final pyrolysis temperature of 550 °C. The oil yield which was 22.4% at the static atmosphere reached to the value of 23.2% in the sweeping gas atmosphere by using 100 cm³ min^{− 1} N₂ flow rate. The yield of liquid product in steam pyrolysis was higher (27.2%) than the static and inert gas atmosphere.The elemental analyses of the pyrolysis oils were determined, and the chemical compositions of the oils were investigated using chromatographic and spectroscopic techniques. The liquid products were fractionated into pentane solubles and insolubles (asphaltenes). Pentane solubles were then solvent fractionated into pentane, toluene, and methanol subfractions by fractionated column chromatograpy. The aliphatic subfractions of the oils were then analysed by capillary column gas–liquid chromatography and GC/MS. For further structural analysis, the pyrolysis oils' aliphatic, aromatic and polar subfractions were conducted using FTIR and ¹H NMR spectra.     

Steam pyrolysis of an industrial waste for bio-oil production

Potato skin, a food industry waste, was pyrolysed under three different atmospheres namely static, nitrogen, and steam to produce bio-oil and its derivatives. The oil yield obtained at 550 °C was 24.77% in static atmosphere, whereas it reached to 27.11% in nitrogen atmosphere. Moreover, the use of steam caused a sharp increase of oil yields up to 41.09% with a steam velocity of 1.3 cm s^− 1. TG-DTA analyses were applied on the raw material to investigate the thermal degradation. Liquid products obtained under the most suitable conditions were characterized by elemental analyses, FT-IR and ¹H NMR. In addition, column chromatography was employed to separate the bio-oil into its derivatives. Asphaltene fraction of bio-oil is decreased under steam atmosphere. Gas chromatography was also used to investigate the C distributions. The characterization has shown that the bio-oil obtained under steam atmosphere was more beneficial than those obtained under both static and inert atmospheres. Further comparison of H/C ratios of pyrolysis oils with conventional fuels indicates that the H/C ratios of the oils obtained in this study lie between those of light and heavy petroleum products. It can be concluded that potato skin could be evaluated as a promising biomass candidate of bio-oil production.     

Value-added products from waste: Slow pyrolysis of used polyethylene-lined paper coffee cup waste

The objectives of this study were to examine how to recycle cup waste efficiently and effectively and to determine if cup waste can be converted into liquid, solid, and gas value-added products by slow pyrolysis. The characteristics and potential utilizations of the pyrolysis products were investigated. The study included the effects of temperature, heating rate, and different feedstocks. The yield of pyrolysis oil derived from cup waste increased from 42% at 400°C to 47% at 600°C, while the yield of char decreased from 26% at 400°C to approximately 20% at 600°C. Acetic acid and levoglucosan were identified as the main components of the pyrolysis oil. The char obtained at 500°C was physically activated at 900°C for 3 h with CO₂. The adsorption capacity of the activated char was investigated with model compounds, such as methyl orange, methylene blue, ibuprofen, and acetaminophen. The results showed that the adsorption capacity of the activated char was similar to that of commercial activated carbon produced from peat. The higher heating value of the produced gas stream calculated at 400°C was 19.59 MJ/Nm³. Also, conventional slow pyrolysis (CSP) and microwave-assisted pyrolysis (MAP) technologies were compared to determine the differences in terms of products yields, composition and characteristics of the pyrolysis oil, and their potential applications. The CSP yields higher liquid products than MAP. Also, the pyrolysis oil obtained from the CSP had significantly more levoglucosan and acetic acid compared to that of the MAP.     

Pyrolysis of two different biomass samples in a fixed-bed reactor combined with two different catalysts

Pyrolysis of Euphorbia rigida and sesame stalk biomass samples with two selected commercial catalyst, namely DHC-32 and HC-K 1.3Q, have been conducted in a fixed-bed reactor. The effect of different catalysts and their ratio (5, 10 and 20% w/w) and pyrolysis temperature (500 and 750 °C) on the pyrolysis product yields were investigated and the obtained results were compared with similar experiments without catalyst. Bio-oil yield was increased comparing with non-catalytic experiments, at final pyrolysis temperature of 500 °C for both biomass samples and catalysts. In the catalytic experiments; when the temperature reached to 750 °C, although bio-oil product yield was reduced, the gas product yield was increased comparing with non-catalytic experiments.The pyrolysis oils were examined using spectroscopic and chromatographic analyses and then fractioned by column chromatography. Although the aliphatic and aromatic fractions were decreased and polar fraction was increased with catalytic pyrolysis of E. rigida; an opposite trend was observed in the sesame stalk pyrolysis oil, comparing with non-catalytic results.Obtained results were compared with petroleum fractions and determined the possibility of being a potential source of renewable fuels.     

Biofuel production using slow pyrolysis of the straw and stalk of the rapeseed plant

Amongst the renewable alternative energy sources, biomass has a large potential for commercial usage. Pyrolysis is the most important among the thermal conversion processes of biomass. In this study, slow pyrolysis of the straw and stalk of the rapeseed plant was investigated within a tubular reactor under the conditions of static atmosphere, varying temperatures of 350°, 450°, 550° and 650°C and at heating rates of 10°C min⁻¹ and 30°C min⁻¹. The maximum liquid yield was observed to be evolving at 650°C pyrolysis temperature and at a heating rate of 30°C min⁻¹. The various characteristics of pyrolytic oil obtained under these conditions were identified. Following the chemical characterization, the pyrolytic oil originated from the straw and stalk of the rapeseed plant is presented as a biofuel candidate.     

Effect of water vapour and biomass nature on the yield and quality of the pyrolysis products from biomass

Slow pyrolysis/activation of biomass in a flow of steam is studied in laboratory equipment supplied with a fixed bed reactor. Forestry and agricultural residues of different origin are selected as raw materials (birch wood, olive stones, bagasse, pelletised straw and miscanthus). The final pyrolysis temperature is varied in the range 700–800°C and the duration of the activation is 1 or 2 h. The effect of both the nature of the investigated biomass samples and the presence of water vapour on the quality of the pyrolysis products is in the focus of interest of this work. Column chromatography is used to characterize the liquid products. The surface area and the acid–base neutralization capacity of the solid products are determined by the adsorption capacity towards iodine and reactions with EtONa and HCl. The results are compared with those obtained in pyrolysis in inert atmosphere of nitrogen. It is shown that the presence of steam has strong effect on the yield and properties of the products. Significant part of the liquid product is found dissolved in the water phase obtained after condensation of the volatiles. The solid products obtained in the presence of steam have the properties of activated carbons.     

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.     

Pyrolytic characteristics of Jatropha seedshell cake in thermobalance and fluidized bed reactors

Pyrolytic kinetic parameters of Jatropha seedshell cake (JSC) were determined based on reaction mechanism approach under isothermal condition in a thermobalance reactor. Avrami-Erofeev reaction model represents the pyrolysis conversion of JSC waste well with activation energy of 36.4 kJ mol^?1 and frequency factor of 9.18 s^?1. The effects of reaction temperature, gas flow rate and feedstock particle size on the products distribution have been determined in a bubbling fluidized bed reactor. Pyrolytic bio-oil yield increases up to 42 wt% at 500 °C with the mean particle size of 1.7 mm and gas flow rate higher than 3U _mf , where the maximum heating value of bio-oil was obtained. The pyrolytic bio-oil is characterized by more oxygen, lower HHVs, less sulfur and more nitrogen than petroleum fuel oils. The pyrolytic oil showed plateaus around 360 °C in distribution of components’ boiling point due to high yields of fatty acid and glycerides.     

Pyrolysis of rapeseed in a free fall reactor for production of bio-oil

Pyrolysis experiments of rapeseed (Brassica napus L.) were performed in a free fall reactor at atmospheric pressure under nitrogen atmosphere. The effects of final pyrolysis temperature, particle size and sweep gas flow rate on the yields of products were investigated. The temperature of pyrolysis, particle size and sweep gas flow rate were varied in the ranges of 400—700 °C, −0.224 to 1.8 mm and 50–400 cm³ min⁻¹, respectively. The elemental analysis and calorific value of the bio-oil were determined, and compared with diesel fuel and then the chemical composition of the bio-oil was investigated using chromatographic and spectroscopic techniques (¹H NMR, IR, column chromatography and GC/MS). The chemical characterization has shown that the bio-oil obtained from rapeseed could be use as diesel fuel and chemical feeedstock.     

PRODUCTION OF BIOFUEL FROM SOFT SHELL OF PISTACHIO (PISTACIA VERA L.)

Soft shell of pistachio (Pistacia vera L.) pyrolysis experiments were performed in a fixed-bed reactor to produce bio-oil. The effects of temperature, heating rate, and sweep gas (N₂) flow rates on the yields and compositions of products were investigated. Pyrolysis runs were performed using reactor temperatures between 350° and 500°C with heating rates of 15° and 50°C/min. Nitrogen flow rates varied between 50 and 200 cm³/min and mean particle size was 0.8 mm. The maximum bio-oil yield of 33.18% was obtained in a nitrogen atmosphere with nitrogen flow rate of 150 cm³/min and at 450°C pyrolysis temperature with a heating rate of 50°C/min.The elemental analysis and gross heating value of the bio-oil were determined, and then the chemical composition of the bio-oil was investigated using chromatographic and spectroscopic techniques. The chemical characterization has shown that the bio-oil obtained from soft shell of pistachio can be used as a renewable fuel and chemical feedstock.     

Study on characterization of pyrolysis and hydrolysis products of poly(vinyl chloride) waste

Poly(vinyl chloride) PVC pyrolysis and hydrolysis are conducted in a fixed bed reactor and in an autoclave, respectively, under different operating conditions such as the temperature and time. The product distribution is studied. For the PVC pyrolysis process, the main gas product is HCl (55% at 340°C), there is 9% hydrocarbon gas (C₁–C₅), the liquid product fraction is about 5% (at 340°C), and the solid residue fraction is about 31% (at 340°C). For the hydrolysis process, the main gas product is HCl (55.8% at 240°C) and the solid residue is about 49.6% (at 240°C). The pyrolysis liquid product is analyzed by using gas chromatography with magic‐angle spinning. Aromatic hydrocarbons are the main class (90%), of which the major part is benzene (33%). The residue produced through pyrolysis and hydrolysis is investigated by high‐resolution solid‐state ¹³C‐NMR. These details revealed by the high‐field NMR spectra provide importmant information about the chemical changes in the PVC pyrolysis and hydrolysis process. The mechanism of PVC hydrolysis dechlorination is also discussed. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 90: 3252–3259, 2003     

Liquid fuels and chemicals from pyrolysis of motorcycle tire waste: Product yields,compositions and related properties

In this study, experiments have been conducted on the sample of solid motorcycle tire wastes to determine particularly the effect of temperature, feed size, and apparent vapor residence time on the pyrolysis product yields and their compositions. The maximum liquid yield of 49 wt.% was obtained at a final pyrolysis temperature of 475 °C, feed size 4 cm³, with a residence time of 5 s under N₂ atmosphere in a fixed-bed fire-tube heating reactor system. The pyrolysis liquid products were characterized by elemental analysis and various chromatographic and spectroscopic techniques. Chromatographic and spectroscopic studies on the liquids show that it can be used as liquid fuels and chemical feedstock, with a calorific value of 42.00 MJ/kg and empirical formula of CH_1.27O_0.025N_0.006.     

Fast pyrolysis of cellulose with reactive methane gas in a single-pulse shock tube

A shock tube technique was employed to study the fast pyrolysis of cellulose with methane under conditions of high temperature, high heating rate, short reaction time, and rapid quenching. The effects of temperature, methane atmosphere, and reaction time are investigated. Experiments were carried out at temperatures between 700 and 2200°C in 1% methane (diluted in argon), and comparisons in the yields of major gas products are made with the results obtained in pure argon atmosphere. The total gas yield decreased about 25–30% in methane. The principal gas products—carbon monoxide, carbon dioxide, and acetylene, except ethylene—were significantly decreased in methane as compared to the yields in pure argon. An increase of about 25% in ethylene yield in methane over argon was observed. The onset of the decomposition of cellulose and the evolution of major pyrolysis products were changed with the reaction times, which also affected the amplitude and the distribution of the pyrolysis products. © 1994 John Wiley & Sons, Inc.     

Flash pyrolysis of coals: behaviour of three coals in a 20 kg h−1 fluidized-bed pyrolyser

Flash pyrolysis of Loy Yang brown coal, and Liddell and Millmerran bituminous coals has been studied using a fluidized-bed reactor with a nominal throughput of 20 kg h^?1. The apparatus and its performance are described. The yields of tar and hydrocarbon gases are reported for each coal in relation to pyrolysis temperature, as also are analytical data on the pyrolysis products. The peak tar yields for the dry, ash-free Loy Yang and Millmerran coals were respectively 23% wt/wt (at ≈ 580 °C) and 35% wt/wt (at $\text{\$}\text{?}$600 °C). The tar yield from Liddell coal was 31% wt/wt at ≈ 580 °C. Hydro-carbon gases were produced in notable quantities during flash pyrolysis; e.g. Millmerran coal at 810 °C gave 6% wt/wt (daf) methane, 0.9% wt/wt ethane, 6% wt/wt ethylene, and 2.5% wt/wt propylene. The atomic $\text{H}\text{C}$ ratios and the absolute levels of hydrogen in product tars and chars decreased steadily with increasing pyrolysis temperature.     

Kinetic study of fast pyrolysis of sawdust in a conical spouted bed reactor in the range 400–500 °C

An original reactor (a conical spouted bed reactor) is used for the kinetic study of Pinus insignis sawdust pyrolysis in the range 400–500 °C under the usual conditions of this reactor for pyrolysis in a continuous regime. The equipment meets the requirements for pyrolysis kinetic study (bed isothermality, high mass and heat transfer between phases and short residence time of gaseous products). The results of yield of products are evidence of the good performance of the conical spouted bed reactor for obtaining a liquid product, with a maximum yield of 70 wt% in the range 440–460 °C. © 2001 Society of Chemical Industry     

Fixed-bed pyrolysis of cotton stalk for liquid and solid products

The pyrolysis of cotton stalk was studied for determining the main characteristics and quantities of liquid and solid products. Particular variables investigated were temperature (from 400 °C to 700 °C), particle sizes (from 0.25 mm to 1.8 mm) and nitrogen gas flow rate (from 50 and 400 cm³/min). All experiments were performed at a heating rate of 7 °C/min. The results showed that particle size and nitrogen flow rate did not exert a significant influence, whereas temperature was very significant. The liquid products and the subfractions of pentane-soluble fraction were characterized by elemental analysis, FT-IR spectroscopy, ¹H-NMR spectroscopy, and the pentane subfraction was analysed by gas chromatography. The characterization of char was performed in terms of its elemental composition, surface area and FT-IR spectroscopy. The H/C and O/C ratios of the chars decreased with the rise in the temperature. FT-IR showed that results the hydroxyl and carbonyl functionalities were lost at high temperatures. According to the experimental results the liquid products can be used as liquid fuels, whereas the solid products can be transformed to activated carbon for adsorption processes.     

废旧电路板真空热解

采用热重分析仪和固定床热解反应器对废旧电路板进行了低真空条件下的热分解实验.研究了混合废旧电路板在真空下的降解特性、热解动力学以及热解条件对热解产品产率的影响,并讨论了真空和氮气条件下电路板热解的差异.实验结果表明真空降低了电路板热解的表观活化能,提高了热解产物的挥发性,减少了二次裂解反应,因而真空有利于提高液体产品的产率,降低气体和固体产品的产率.废旧电路板的真空热解液体产品主要由酚、烷基酚、双酚A、水以及各种溴酚构成,液体中总溴高达13.47％,其中一半左右以有机溴的形式存在,因此液体产品适合用于分离提取化工原料而不宜用于作燃料.     

Co-pyrolysis of petroleum based waste HDPE,poly-lactic-acid biopolymer and organic waste

Waste pyrolysis is widely investigated, but less information is available about their co-pyrolysis. The present paper discloses the waste pyrolysis and co-pyrolysis in batch reactor at 400 °C, 450 °C and 500 °C. The effect of the raw materials and temperature to the product was investigated. Product yield was increased and the quality (composition, contaminants, etc.) improved by co-pyrolysis. Gas and pyrolysis oil yields increased as function of temperature. Higher ratio of organic waste/petroleum based plastic waste resulted in lower yields of volatile hydrocarbons. Concentrations of oxygen containing products and contaminants are significantly changed with temperature or adding of HDPE into raw materials.