Characterization of aromatic hydrocarbon formation from pyrolysis of polyethylene-polystyrene mixtures

Design and operating parameters, and cause and effect relationships among feedstocks and products in the pyrolysis of waste polymers are needed if this method of processing is to be used for energy recovery from waste plastics. The purpose of this study was to quantify the effect of various operating factors for the pyrolysis of common polymeric wastes. Experiments were performed using a conventional retort tube as a batch reactor. The operating factors considered were temperature and reaction time at constant heating rate. High density polyethylene (PE) and polystyrene (PS), the most common plastic waste in Korea, were used singly and in mixture.The pyrolysis time for maximum oil production from a PE-PS mixture was shorter than in the case of PE alone, showing an enhancement effect from the PS. The maximum gas production time from PE-PS mixtures was shorter than for PE alone at 500° C; above 600° C, this does not occur. Small aromatic compounds (which can be valuable) are produced at maximum with an 1:1 mixture of PE and PS at 600° C, showing the possibility of process control for the maximum recovery of desirable pyrolysis products. The maximum yield of toluene, xylene, styrene, and 1-propenyl benzene were 8.6, 8.9, 51.0 and 7.4 wt.% of feed for pyrolysis PS at 700° C, respectively. For naphthalene, it was at 700° C with 1:1 PE:PS (by wt.). The maximum recovery was 1.3 wt.%. Diels-Alder theory can explain the formation of aromatic compounds in the pyrolysis products. The yield of these secondary pyrolysis products can be controlled by reaction time, pyrolysis temperature and mixing ratio of plastic wastes in the pyrolysis feed.     

The Evaluation of Mesoporous Materials as Catalyst in Fast Pyrolysis of Wheat Straw

In this study, wheat straw was chosen as a biomass sample and the fast pyrolysis of this sample was carried out with or without catalyst at different conditions in a well-swept fixed-bed reactor. Experiments were carried out in a well-swept tubular fixed-bed reactor with a heating rate of 300°C/min, between pyrolysis temperature ranges 300–800°C in the nitrogen atmosphere. The results indicated that a maximum oil yield of 31.9% was obtained at a pyrolysis temperature of 500°C in non-catalytic procedure. Siliceous and Al-MCM-41 materials were evaluated as potential catalysts in the pyrolysis experiments. Mesoporous materials have large pore dimensions with strong acid sites. These acidic sites catalyze some reactions in pyrolysis. The product yields and the quality of bio-oil were influenced with using MCM-41 materials. The bio-oil yield was reduced, whereas the gas yield increased with using a catalyst in the experiments. An increase in the fractions of pure phenol, alkyl phenols, alkenes+alkanes, carbonyls, aromatic, and cyclic compounds and a decrease in the fractions of methoxy phenols, acids+esters, furans, and alcohols were observed in the presence of Al-MCM-41 material. According to all results, the use of Al-MCM-41 materials as catalyst in the pyrolysis can be suggested to obtain both quality fuels and valuable chemicals.     

The effect of pyrolysis atmosphere on bio-oil yields and structure

A food industry waste, almond shell, was pyrolyzed under three different environment static, nitrogen, and steam to produce bio-oil and its derivatives. The oil yield obtained at pyrolysis temperature of 600°C was 24.23% in a static atmosphere, whereas it increased to 27.25% and 33.05% in nitrogen and steam atmospheres, respectively. The bio-oil obtained under steam atmosphere is very efficient due to the production of high liquid and gas yields. Moreover, co-feeding steam during the pyrolysis altered the bio-oil structure by increasing the aliphatics and reducing the asphaltenes. Moreover, steam treatment also increases H/C and heating value of bio-oils. According to the obtained results, steam pyrolysis is an alternative option for future applications in refineries.     

TGA analysis of tobacco rob pyrolysis and release characteristics of noncondensable gas in a fixed-bed reactor

In this study, the size of tobacco rob (TR) particle was considered as a major factor in determining the mass loss in thermogravimetric analysis (TGA) and product yield and composition at different reactor temperatures in the fixed-bed reactor. The TGA results showed that the conversion rate increased and the activation energy (ranged from 53.29 to 58.25 kJ/mol) decreased with a decrease in particle size. The experiments demonstrated that fuel gas yield (from 0.76 to 0.82 Nm³/kg at 900 °C) increased with a decrease in particle size while char and tar yield decreased. Smaller particle sizes resulted in higher H₂ (25.68%) and CO (27.36%) contents. Minimizing the size of raw materials is an alternative method to improve the gas quality of TR pyrolysis. The increase of gas yield was attributed to the decomposition of char and tar vapor as temperature increased.     

Yield and quality of charcoals from olive mill residues and its stone and pulp fractions: An enhanced comparative study

Pyrolysis is a promising way to upgrade large amounts of residues from olive oil processing into charcoal. Pyrolysis of the stone and pulp fractions needed to be investigated before conclusions could be drawn. We subjected the olive stone fraction, the pulp fraction, and a mixture of the two to dynamic pyrolysis and isothermal pyrolysis at 360°C. We characterized the charcoals resulting from isothermal pyrolysis at 360°C for different durations in terms of the fixed-carbon content (FCC), carbon content (CC), and high heating value (HHV). We found that charcoal yield from the pulp was higher than that from the stones, which were 38.1% and 32.9%, respectively, after pyrolysis for 360 min. This seemingly unexpected result was due to the high contents of ash (6.22%) and extractives (13%) in the pulp, which remained completely and partially undecomposed, respectively, in the charcoals and are accounted for when calculating yields. However, charcoals obtained from the stones were of higher quality than charcoals from the pulp, with lower ash content and higher FCC, CC, and HHV. In particular, the FCC, CC, and HHV after pyrolysis for 360 min were 73.2%, 74.4%, and 30.2 MJ/kg for the stones and only 61.8%, 63.2%, and 25.9 MJ/kg for the pulp, respectively. Depending on the required quality of the final charcoal, our results help decide whether to pyrolyse the entire olive residues or only one of the two fractions, more likely the stones.     

溶剂型聚氨酯涂料废物热解特性及动力学研究

采用TG研究溶剂型聚氨酯涂料废物在不同升温速率、N2气氛影响下的热解特性规律。升温速率取5,10,20,30℃/min;气氛取N2气氛(50 m L/min);实验温度范围为20~800℃。研究表明,随着升温速率的增大,涂料废物热解反应各阶段起始温度、终止温度、最大失重速率温度均向高温方向移动。在500℃时,涂料废物的热分解已基本完成。运用Kissinger法和Flynn-Wall-Ozawa法进行热解动力学分析,得到溶剂型聚氨酯涂料废物热解阶段的表观活化能为196.053 3 kJ/mol。     

Pyrolysis Investigation For Bio-Oil Production From Various Biomass Feedstocks In Thailand

This study investigated the bio-oil production from vacuum pyrolysis of potential biomass feedstocks in Thailand. Experiments were carried out on palm empty fruit bunch, rice straw, rice husk, eucalyptus wood, rubber wood (Hevea Brasiliensis), and Teng wood (Shorea Obtuse) in a lab-scale-fixed bed reactor. The results showed that the product distribution was strongly dependent on temperature and biomass properties. Maximum oil yields, i.e., 50–60 wt %, were reached at 450–550°C. Due to mild temperature, most of alkalis originally present in biomass concentrated in product char, and only traces were detected in oil. Two-third of energy in biomass was in the product oil.     

Pyrolysis of cellulose under catalysis of SAPO-34, ZSM-5, and Y zeolite via the Py-GC/MS method

Bio-oil from pyrolysis of biomass is an important renewable source for liquid fuel and/or for chemicals. However, the application of bio-oil was severely restricted due to its high viscosity, acidity, and low heating value. Hence, it is necessary to upgrade the bio-oil for deoxygenation or for chemicals by catalytic reactions. In this paper, the catalytic behaviors of SAPO-34, ZSM-5, and Y zeolite on pyrolysis of cellulose were investigated via pyrolyzer combined with gas chromatography and mass spectrometer (Py-GC/MS) method in Py-mode. The results showed that ZSM-5 and Y zeolite could promote the conversions of oxygen-containing components to gases, water, aromatics, and phenols. Comparatively, more gas and water were generated under the catalysis of Y zeolite at lower temperatures, while at temperatures above 700°C, the effect of ZSM-5 became more distinct; aromatics were more generated under the catalysis of ZSM-5, while Y zeolite exerted a more distinct role in promoting the formation of phenols. The effect of SAPO-34 caused more water and furfural derivatives, less aromatics and phenols, and exerted a weak influence on gases.     

Two-Phase Transport Model for the Pyrolysis Process of a Vertical Wood Cylinder,Including the Surrounding Flow Field

This paper describes a mathematical model for the pyrolysis of a small dry pine wood cylinder. The computational domain is axisymmetric and involves the heating chamber, with the wood cylinder vertically situated in the centre of the chamber. The model simulates the laminar flow around the particle and the laminar flow inside the wood/char matrix by applying a two-phase transport model where the solid wood/char matrix acts as one phase and the various gases produced from the pyrolysis process is assembled in the other phase.

Convective, conductive and thermal radiation transfer modes are included in the model. A two-step pyrolysis reaction scheme is used for the modelling of the conversion from wood to tar and gas. Both the thermal conductivity and the permeability of the wood/char matrix are modelled anisotropically in order to capture the directional differences in heat and mass transport, existing in real wood.

Results from simulations are compared with measurements from literature for the centre core solid temperature and the conversion from wood to char, tar and pyrolysis gas in the particle during heating. The results show very good agreement with the measured temperature profile. The simulated conversion profile shows an overall good agreement with the measurements, however with discrepancies in the early stage of the process. Besides the successful validation with the experimental data, it provides us with all the details of the distribution of the migrating pyrolysis gas and tar, the temperature, the velocity flow field and pressure in the wood/char cylinder.     

Nanocatalyzed biodiesel synthesis from the oily contents of Marine brown alga Dictyota dichotoma

This research article demonstrates biodiesel synthesis through the methanolysis of the oily contents (4.02 ± 0.27% w/w on dried basis) of Dictyota dichotoma collected from the coast of Hawksbay, Pakistan. The metal oxides (CaO, MgO, ZnO, and TiO₂) used as nanocatalysts were refluxed (5% K₂SO₄), calcinated (850 °C) and characterized by Atomic Force Microscopy (AFM) which produced 93.2% w/w FAME (biodiesel) at relatively mild condition (5% catalyst, 65 °C, 3 h, 18:1 molar ratio) using CaO. Whereas, MgO, ZnO, and TiO₂ produced 92.4%, 72.5%, and 31.8% w/w FAME, respectively at elevated condition (225 °C). Thus, CaO was considered to be the best catalyst among the others. This tri-phase reaction require continuous fast mixing and the yield depends on the reaction parameters like catalyst amount, temperature, reaction time and molar ratio (methanol: oil). The reusability of these heterogeneous catalysts simplified the purification step, reduced the waste generation and make the final product technically and economically viable.     

The influence of the precursor and synthesis method on the CO2 capture capacity of carpet waste-based sorbents

Adsorption is one of the most promising technologies for reducing CO₂ emissions and at present several different types of sorbents are being investigated. The use of sorbents obtained from low-cost and abundant precursors (i.e. solid wastes) appears an attractive strategy to adopt because it will contribute to a reduction not only in operational costs but also in the amount of waste that is dumped and burned in landfills every year. Following on from previous studies by the authors, in this work several carbon-based adsorbents were developed from different carpet wastes (pre-consumer and post-consumer wastes) by chemical activation with KOH at various activation temperatures (600–900 °C) and KOH:char impregnation ratios (0.5:1 to 4:1). The prepared materials were characterised by chemical analysis and gas adsorption (N₂, −196 °C; CO₂, 0 °C), and tested for CO₂ adsorption at temperatures of 25 and 100 °C. It was found that both the type of precursor and the conditions of activation (i.e. impregnation ratios, and activation temperatures), had a huge influence on the microporosity of the resultant samples and their CO₂ capture capacities. The carbon-based adsorbent that presented the maximum CO₂ capture capacities at 25 and 100 °C (13.8 wt.% and 3.1 wt.%, respectively), was prepared from a pre-consumer carpet waste and was activated at 700 °C using a KOH:char impregnation ratio of 1:1. This sample showed the highest narrow microporosity volume (0.47 cm³ g⁻¹), thus confirming that only pores of less than 1 nm are effective for CO₂ adsorption at atmospheric pressure.     

Preparation of jet engine range fuel from biomass pyrolysis oil through hydrogenation and its comparison with aviation kerosene

The Bio-oil was produced from the pyrolysis of agricultural wastes (Eucalyptus sawdust) and discarded soybean frying oil. The temperature of the pyrolysis system was initiated at 28°C and increased to 850°C. Atmospheric distillation of crude bio-oil was performed and a fraction at a temperature range 160–240°C (pyrolysis oil) was separated and subjected to GC-MS, ¹H-NMR, TGA and FTIR analysis to identify the different properties and compounds present in pyrolysis oil. It was noticed that there was an abundance of oxygen and nitrogen containing compounds as well as other reactive species in pyrolysis oil. To reduce the amount of these species, the pyrolysis oil was subjected to hydrogenation in the presence of NiMo as a catalyst. After hydrogenation, the atmospheric distillation of hydrogenated bio-oil was performed and another fraction at temperature range 160–240°C (hydrogenated bio-oil) was separated and analyzed by the same techniques. It was noticed that during hydrogenation, more than 60% oxygenated and other reactive species were converted into hydrocarbons. Hydrogenated bio-oil showed very similar physico-chemical properties such as distillation curve, density, viscosity, freezing point, flash point, the presence of hydrocarbons and enthalpy of combustion as aviation kerosene also known as QAV-1.     

Promotional effect of transition metal doping on the properties of KF/CaO catalyst for biodiesel synthesis

A series of heterogeneous KF/CaO catalysts modified with transition metals (lanthanum, cerium, and zirconium) were prepared via wet impregnation method and applied to the trsansesterification process of waste cooking oil (WCO) as feedstock with methanol to biodiesel production. The structure, performance of the solid catalysts was characterized by X-ray diffraction (XRD), temperature programmed desorption of CO₂ (CO₂-TPD), scanning electron microscopy (SEM), and energy-dispersive spectroscopy (EDS). The effect of methanol/oil molar ratio, ¹reaction time, reaction temperature, catalyst amount, and stability was investigated. The results showed that 10 wt% of lanthanum, cerium, and zirconium improved the catalytic activity of KF/CaO catalyst. The maximum catalytic activity using the lanthanum doping of 10wt% on KF/CaO catalyst was reached 98.7% under the optimal reaction condition of methanol/oil molar ratio of 12:1, reaction for 1 h at reaction temperature of 65°C, and 4% (wt/wt oil) catalyst amount. In addition, the FAME yield of KF/CaO/La catalyst remained higher than 95% after 10 cycles. The promotional effect of lanthanum doping could be attributed to the enhancement of the basicity strength of KF/CaO catalyst and block the leach of Ca²⁺ in the transesterification reaction.     

Effect of Fenton pretreatment on anaerobic digestion of olive mill wastewater and olive mill solid waste in mesophilic conditions

The olive mill waste (OMW) generated from olive oil extraction process constitutes a major environmental concern owing to its high organic and mineral matters and acidic pH. Anaerobic digestion (AD) is a main treatment for reducing the organic matter and toxic substances contained in OMW and generating at the same time, energy in the form of biogas. AD of OMW that contains lignocellulose is limited by the rate of hydrolysis due to their recalcitrant structure. This study is devoted to the effect of Fenton process (FP) pretreatment on olive mill wastewater (OMSW) /olive mill solid waste (OMWW) co-digestion to improve their digestibility and in this way the biogas production. The FP pretreatment was performed in batch mode at 25°C, various H₂O₂/[Fe²⁺] ratios (100–1200), catalyst concentration ([Fe²⁺]) ranging from 0.25 to 2 mM, reaction time varying from 30 to150 min, and different pH (3–11). The best performance was obtained with H₂O₂/[Fe²⁺] = 1000, [Fe²⁺] = 1.5 mM, 120 min, and pH 3. Biochemical methane potential (BMP) tests conducted in batch wise digester and at mesophilic conditions (37 °C) showed that cumulative biogas and methane production were higher without FP treatment, and correspond to 699 and 416 mL/g VS, respectively. However, pre-treated OMSW results into an increase of 24% of methane yield. After 30 days of AD, the methane yield was 63%, 54%, and 48%, respectively, for OMSW treated without iron precipitation, with iron precipitation and untreated OMSW sample.     

Use of modified hydroxy-aluminum bentonites for chromium(III) removal from solutions

The retention of chromium(III) from a 2000ppm chromium basic sulfate and tannery waste solution at pH 4.5 using modified hydroxy-aluminum bentonites (OH-Al bentonites) as adsorbents was studied. OH-Al bentonite was prepared by mixing clay with a hydrolyzed commercial chlorohydroxy Al solution. The modified Al bentonites were obtained by (a) a treatment with 0.5M sodium chloride and (b) a treatment with a Na-hexametaphosphate solution (HMP) after adding sodium chloride. The effect of heating the adsorbents at 100, 500, 700 and 800 degrees C on Cr retention as a function of time was also analyzed. Cr retention by modified OH-Al bentonite with HMP increased with time (up to 100mgCr/g) where modified OH-Al bentonite was twice that of untreated bentonite. The relatively high uptake of metal from the salt solution by modified OH-Al bentonite treated at 800 degrees C, in which a complete interlayer collapse occurred, indicated the importance of the contribution of external surface sites to the retention capacity. The maximum Cr uptake from a water waste was 24mg/g, due to interferences and different chromium species in the industrial solution.     

废轮胎等离子体热解固体产物性质研究

等离子体热解废弃轮胎的产物包括可燃气、固体产物两部分,本文利用工业分析、元素分析、SEM扫描、XPS表面分析、NMR分析等手段考察了等离子体热解固体产物的特性,并与轮胎工业用碳黑做了对比研究。研究结果表明,废轮胎等离子体热解固体产物可作为热解碳黑进行回收利用。     

Recyling of plastic wastes via pyrolysis

Pyrolysis for the simultaneous generation of oils and gases can be convenient to obtain hydrocarbons and even to recover crude petrochemicals or to generate energy from waste plastics. A Gray–King apparatus has been used to pyrolyze waste polyethylene (PE), polystyrene (PS), both separately and with different compositions. Thermogravimetric analysis of waste plastics indicated the critical temperatures, which should be effective for pyrolysis. The chosen heating rate was low in order to achieve higher liquid yields. The results showed that waste PS yielded higher liquid, and waste PE yielded higher gaseous products. The dominant liquid product of PS waste was styrene whereas for waste PE, prophenylbenzene was the dominant pyrolysis product.     

含油污泥热解的影响因素初探＊

以含油污泥"无害化"为目的,考察了温度、升温速率及含水率对热解反应效果的影响。实验结果表明:温度越高,热解剩余残渣率和残渣含油率越低,热解产气率越高;含油污泥中有机质发生热解反应的主要温度为350～500℃和575～625℃,若热解残渣含油率控制在3.0‰以下,热解温度选择600℃较为适宜;升温速率对热解产气率、剩余残渣率和残渣含油率基本无影响,但升温速率越快,热解反应的产气量曲线峰越向前迁移,热解反应的时间缩短;含油污泥含水率越低,则热解产气率及残渣率越高,但含水率对残渣含油率和热解反应时间无影响。     

Ferric-manganese doped sulphated zirconia nanoparticles catalyst for single-step biodiesel production from waste cooking oil: Characterization and optimization

Biodiesel of waste cooking oil origin is gaining attention as a replacement for current fossil fuels, as its low-priced, recycled feedstock shall prevent food source competition, which is estimated to happen with current biodiesel production processes. As a result, waste cooking oil has been claimed to be a highly potential feedstock for biodiesel production. In the present research work, Fe-Mn doped sulphated zirconia catalyst was synthesized and used in simultaneous esterification and transesterification of waste cooking oil to biodiesel synthesis. The catalyst was prepared through the impregnation method and characterized by using XRD, TPD-NH_3, FT-IR, BET, and TEM. Response surface methodology (RSM) in conjunction with the central composite design (CCD) was applied to statistically evaluate and optimize the biodiesel preparation process. It was found that the synthesis of biodiesel achieved an optimum level of 97.2% waste cooking oil methyl ester’s (WCOME’s) yield at the following reaction conditions: methanol/oil molar ratio: 10:1, catalyst concentration: 3.0 wt %, and reaction temperature: 160 °C. The extremely high WCOME’s yield of 97.2% was proved to be due to high acidity, surface area, and large pore diameter; reactants can easily diffuse into the interior pore of the catalyst and allow them to be in contact with active sites that enhance catalytic activity.     

Optimal Absorbent Evaluation for the CO2 Separating Process by Absorption Loading,Desorption Efficiency,Cost, and Environmental Tolerance

The CO₂ absorption capacities of potassium glycinate, potassium sarcosinate (choline, proline), mono-ethanolamine (MEA), and tri-ethanolamine were evaluated to find the optimal absorbent for separating CO₂ from gaseous products by a CO₂ purification process. The absorption loading, desorption efficiency, cost, and environmental tolerance were assessed to select the optimal absorbent. MEA was found to be the optimum absorbent for separating the CO₂ and H₂ mixture in gaseous product. The maximum absorption loading rate was 0.77 mol CO₂ per mol MEA at temperature of 20°C and absorbent concentration of 2.5 mol/L, whereas desorption efficiency was 90% by heating for 3 h at 130°C. MEA was found to be an optimal absorbent for the purification process of CO₂ during gaseous production.