Wood pyrolisys using aspen plus simulation and industrially applicable model

Over the past decades, a great deal of experimental work has been carried out on the development of pyrolysis processes for wood and waste materials. Pyrolysis is an important phenomenon in thermal treatment of wood, therefore, the successful modelling of pyrolysis to predict the rate of volatile evolution is also of great importance. Pyrolysis experiments of waste spruce sawdust were carried out. During the experiment, gaseous products were analysed to determine a change in the gas composition with increasing temperature. Furthermore, the model of pyrolysis was created using Aspen Plus software. Aspects of pyrolysis are discussed with a description of how various temperatures affect the overall reaction rate and the yield of volatile components. The pyrolysis Aspen plus model was compared with the experimental data. It was discovered that the Aspen Plus model, being used by several authors, is not good enough for pyrolysis process description, but it can be used for gasification modelling

Integrating anaerobic digestion and slow pyrolysis improves the product portfolio of a cocoa waste biorefinery

The integration of conversion processes with anaerobic digestion is key to increase value from agricultural waste, like cocoa pod husks, generated in developing countries. The production of one metric ton of cocoa beans generates some 15 metric tonnes of organic waste that is today underutilized. This waste can be converted into added value products by anaerobic digestion, converting part of the cocoa pods to biogas while releasing nutrients, and pyrolysis. Here, we compared different scenarios for anaerobic digestion/slow pyrolysis integration in terms of product portfolio (i.e., biogas, pyrolysis liquids, biochar and pyrolysis gases), energy balance and potential for chemicals production. Slow pyrolysis was performed at 350 degrees C and 500 degrees C on raw cocoa pod husks, as well as on digestates obtained from mono-digestion of cocoa pod husks and co-digestion with cow manure. Anaerobic digestion resulted in 20 to 25 wt% of biogas for mono and co-digestion, respectively. Direct pyrolysis of cocoa pod husks mainly resulted in biochar with a maximum yield of 48 wt%. Anaerobic digestion induced compositional changes in the resulting biochar, pyrolysis liquids and evolved gases after pyrolysis. Pyrolysis of mono-digestatee.g., resulted in a more energy-dense organic phase, rich in valuable phenolics while poorer in light oxygenates that hold a modest value. Our comparison shows that co-digestion/slow pyrolysis at 500 degrees C and mono-digestion/slow pyrolysis at 350 degrees C both present high-potential biorefinery schemes. They can be self-sustaining in terms of energy, while resulting in high quality biochar for nutrient recycling and/or energy recovery, and/or phenolics-rich pyrolysis liquids for further upgrading into biorefinery intermediates

The co-pyrolysis of flame retarded high impact polystyrene and polyolefins

The co-pyrolysis of brominated high impact polystyrene (Br-HIPS) with polyolefins using a fixed bed reactor has been investigated, in particular, the effect that different types brominated aryl compounds and antimony trioxide have on the pyrolysis products. The pyrolysis products were analysed using FT-IR, GC-FID, GC-MS, and GC-ECD. Liquid chromatography was used to separate the oils/waxes so that a more detailed analysis of the aliphatic, aromatic, and polar fractions could be carried out. It was found that interaction occurs between Br-HIPS and polyolefins during co-pyrolysis and that the presence of antimony trioxide influences the pyrolysis mass balance. Analysis of the Br-HIPS + polyolefin co-pyrolysis products showed that the presence of polyolefins led to an increase in the concentration of alkyl and vinyl mono-substituted benzene rings in the pyrolysis oil/wax resulting from Br-HIPS pyrolysis. The presence of Br-HIPS also had an impact on the oil/wax products of polyolefin pyrolysis, particularly on the polyethylene oil/wax composition which converted from being a mixture of 1-alkenes and n-alkanes to mostly n-alkanes. Antimony trioxide had very little impact on the polyolefin wax/oil composition but it did suppress the formation of styrene and alpha-methyl styrene and increase the formation of ethylbenzene and cumene during the pyrolysis of the Br-HIPS

Removal of organobromine compounds from the pyrolysis oils of flame retarded plastics using zeolite catalysts

Two flame retarded plastics have been pyrolysed in the presence of two Zeolite catalysts to remove the organobromine compounds from the derived pyrolysis oil. The flame retarded plastics were, acrylonitrile – butadiene – styrene (ABS) that was flame retarded with tetrabromobisphenol A and high-impact-polystyrene (HIPS) that was flame retarded with decabromodiphenyl ether. The two catalysts investigated were Zeolite ZSM-5 and Y-Zeolite. Pyrolysis was carried out in a fixed bed reactor at a final pyrolysis temperature of 440 ºC. The pyrolysis gases were passed immediately to a fixed bed of the catalyst bed. It was found that the presence of Zeolite catalysts increased the amount of gaseous hydrocarbons produced during pyrolysis but decreased the amount of pyrolysis oil produced. In addition, significant quantities of coke were formed on the surface of the catalysts during pyrolysis. The Zeolite catalysts were found to reduce the formation of some valuable pyrolysis products such as styrene and cumene, but other products such as naphthalene were formed instead. The Zeolite catalysts, especially Y-Zeolite, were found to be very effective at removing volatile organobromine compounds. However, they were less effective at removing antimony bromide from the volatile pyrolysis products, although some antimony bromide was found on the surfaces of the spent catalysts

Pyrolysis of Dried Wastewater Biosolids Can Be Energy Positive

Pyrolysis is a thermal process that converts biosolids into biochar (a soil amendment), py-oil and py-gas, which can be energy sources. The objectives of this research were to determine the product yield of dried biosolids during pyrolysis and the energy requirements of pyrolysis. Bench-scale experiments revealed that temperature increases up to 500 °C substantially decreased the fraction of biochar and increased the fraction of py-oil. Py-gas yield increased above 500 °C. The energy required for pyrolysis was approximately 5-fold less than the energy required to dry biosolids (depending on biosolids moisture content), indicating that, if a utility already uses energy to dry biosolids, then pyrolysis does not require a substantial amount of energy. However, if a utility produces wet biosolids, then implementing pyrolysis may be costly because of the energy required to dry the biosolids. The energy content of py-gas and py-oil was always greater than the energy required for pyrolysis

A study of the importance of secondary reactions in char formation and pyrolysis : a dissertation presented in partial fulfilment of the requirements for the degree of Doctor of Philosophy in Process Engineering at Massey University, Manawatū, New Zealand

Anthropogenic climate change, caused primarily by excessive emissions of carbon dioxide, has led to a renewed interest in char, the solid product of pyrolysis. When applied to soil as biochar it can both sequester carbon and improve soil function. To make its manufacture environmentally friendly and economically viable it is important to maximise char yield, which can be done by promoting secondary reactions. This research shows that secondary reactions, which are enhanced by prolonged vapour-phase residence time and concentration, not only increase the char yield but are the source of the majority of the char formed. All four biomass constituents (extractives, cellulose, hemicellulose and lignin) undergo secondary reactions concurrent with primary reactions over the entire pyrolysis range ≈ 140 to 500 °C, which makes it practically impossible to separate them. Secondary char formation was confirmed to be exothermic which affects the overall heat of pyrolysis. Impregnating the feedstock with the elements K, Mg and P, which are plant macro-nutrients naturally present in biomass, resulted in the catalysis of secondary char formation. The results reveal that a first order reaction model does not describe pyrolysis accurately when char formation is enhanced by catalysis and secondary reactions. Secondary char can be enhanced by increasing the particle size but there is a limit due to increased cracking and fracturing of the pyrolysing solid. This limitation is overcome by pyrolysis in an enclosed vessel, termed autogenous pressure pyrolysis, which was discovered to cause significant changes in the volatile pyrolysis products; indicating the co-production of a high quality liquid. This process, however, negatively affects the char properties relevant for biochar like the surface area, similar to self-charring and co-carbonisation of condensed volatile pyrolysis products. To increase research capabilities a unique high temperature/ high pressure reactor (600 °C at 20 MPa) was designed to allow the detailed characterisation of all three pyrolysis product classes under extreme pyrolysis conditions. This was demonstrated to be invaluable for understanding the underlying pyrolysis mechanism and physical processes at play

Effect of Pyrolysis on the Removal of Antibiotic Resistance Genes and Class I Integrons from Municipal Wastewater Biosolids

Wastewater biosolids represent a significant reservoir of antibiotic resistance genes (ARGs). While current biosolids treatment technologies can reduce ARG levels in residual wastewater biosolids, observed removal rates vary substantially. Pyrolysis is an anoxic thermal degradation process that can be used to convert biosolids into energy rich products including py-gas and py-oil, and a beneficial soil amendment, biochar. Batch pyrolysis experiments conducted on municipal biosolids revealed that the 16S rRNA gene, the ARGs erm(B), sul1, tet(L), tet(O), and the integrase gene of class 1 integrons (intI1) were significantly reduced at pyrolysis temperatures ranging from 300–700 °C, as determined by quantitative polymerase chain reaction (qPCR). Pyrolysis of biosolids at 500 °C and higher resulted in approximately 6-log removal of the bacterial 16S rRNA gene. ARGs with the highest observed removals were sul1 and tet(O), which had observed reductions of 4.62 and 4.04-log, respectively. Pyrolysis reaction time had a significant impact on 16S rRNA, ARG and intI1 levels. A pyrolysis residence time of 5 minutes at 500 °C reduced all genes to below detection limits. These results demonstrate that pyrolysis could be implemented as a biosolids polishing treatment technology to substantially decrease the abundance of total bacteria (i.e., 16S rRNA), ARGs and intI1 prior to land application of municipal biosolids

Pyrolysis-GC×GC-TOFMS to characterize carbonaceous chondrites

Using pyrolysis-GCxGC-TOFMS to analyze organic carbon in carbonaceous chondrites gives a massive increase in both sensitivity and structural information from samples when compared to traditional Py-GC-MS

Potential of short wavelength laser ablation of organic materials

Although the literature contains several articles on UV laser ablation of synthetic polymers [1] and human tissue for surgical applications, to our knowledge there is no published record on organic geochemical applications for UV laser pyrolysis–gas chromatography–mass spectrometry (LA-GC-MS). In this study we have demonstrated the use of a 213 nm UV laser beam for ablating kerogens and organic rich rocks to liberate and analyse hydrocarbon signatures and compared the results against IR laser pyrolysis and traditional Py-GC-MS. It is possible to equate laser wavelength to electron volts where 1064 nm (IR) = 1.2 eV and 213 nm (UV) = 5.8 eV. Most chemical bonds have an energy between 2-4 eV and C-C bonds are ~3.6 eV. Organic materials can absorb radiation from a UV laser and chemical bonds can be cleaved cleanly by complex photochemical pathways by a single photon [2]. Ablation occurs with almost no heating of the sample and hence the term laser ablation instead of pyrolysis. Visible or IR lasers have insufficient energy to break bonds with a single photon this results in the heating of sample by the absobtion of energy into the vibrational modes of the molecule which can then result in pyrolysis. A solvent-extracted kerogen consisting mainly of higher plant material (Brownie Butte, Montanna, ~ 70 Ma) was used for initial experiments. A number of other samples have also been analysed. Laser ablation work was performed off-line in a static helium cell followed by solvent extraction of the laser cell. Separate analysis of the same samples using a more traditional flash pyrolysis approach was performed with a CDS pyroprobe and IR laser pyrolysis [3] for comparative purposes. As can be seen in Fig 1 UV laser ablation is able to liberate relatively high molecular weight fragments with no alkenes or other pyrolysis artefacts detected. SEM images of ablation pits indicate there is no obvious thermal alteration of the sample. The results of the pyrolysis techniques (on-line and IR laser pyrolysis) are similar and display a number of artefacts related to the pyrolysis process. Laser ablation of a number of samples has also shown that the distributions of biomarkers are comparable with the solvent extracts. Product yields although not quantified appear to be much higher than traditional pyrolysis technique