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

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

Effect of torrefaction pretreatment on the pyrolysis of rubber wood sawdust analyzed by Py-GC/MS

The aim of this study was to investigate the effect of torrefaction on the pyrolysis of rubber wood sawdust (RWS) using pyrolysis–gas chromatography/mass spectrometry (Py-GC/MS). Three typical torrefaction temperatures (200, 250, and 300 °C) and pyrolysis temperatures (450, 500, and 550 °C) were considered. The results suggested that only diethyl phthalate, belonging to esters, was detected at the torrefaction temperatures of 200 and 250 °C, revealing hemicellulose degradation. With the torrefaction temperature of 300 °C, esters, aldehydes, and phenols were detected, suggesting the predominant decomposition of hemicellulose and lignin. The double-shot pyrolysis indicated that the contents of oxy-compounds such as acids and aldehydes in pyrolysis bio-oil decreased with rising torrefaction temperature, implying that increasing torrefaction severity abated oxygen content in the bio-oil. With the torrefaction temperature of 300 °C, relatively more cellulose was retained in the biomass because the carbohydrate content in the pyrolysis bio-oil increased significantly

Economic tradeoff between biochar and bio-oil production via pyrolysis

This paper examines some of the economic tradeoffs in the joint production of biochar and bio-oil from cellulosic biomass. The pyrolysis process can be performed with different final temperatures, and with different heating rates. While most carbonization technologies operating at low heating rates result in higher yields of charcoal, fast pyrolysis is the technology of choice to produce bio-oils. Varying operational and design parameters can change the relative quantity and quality of biochar and bio-oil produced for a given feedstock. These changes in quantity and quality of both products affect the potential revenue from their production and sale. We estimate quadratic production functions for biochar and bio-oil. The results are then used to calculate a product transformation curve that characterizes the yields of bio-oil and biochar that can be produced for a given amount of feedstock, movement along the curve corresponds to changes in temperatures, and it can be used to infer optimal pyrolysis temperature settings for a given ratio of biochar and bio-oil prices.biochar, bio-oil, pyrolysis, biomass conversion, economic tradeoff

Emerging Investigators Series: Pyrolysis Removes Common Microconstituents Triclocarban, Triclosan, and Nonylphenol from Biosolids

Reusing biosolids is vital for the sustainability of wastewater management. Pyrolysis is an anoxic thermal degradation process that can be used to convert biosolids into energy rich py-gas and py-oil, and a beneficial soil amendment, biochar. Batch biosolids pyrolysis (60 minutes) revealed that triclocarban and triclosan were removed (to below quantification limit) at 200 °C and 300 °C, respectively. Substantial removal (\u3e90%) of nonylphenol was achieved at 300 °C as well, but 600 °C was required to remove nonylphenol to below the quantification limit. At 500 °C, the pyrolysis reaction time to remove \u3e90% of microconstituents was less than 5 minutes. Fate studies revealed that microconstituents were both volatilized and thermochemically transformed during pyrolysis; microconstituents with higher vapor pressures were more likely to volatilize and leave the pyrolysis reactor before being transformed than compounds with lower vapor pressures. Reductive dehalogenation products of triclocarban and suspected dehalogenation products of triclosan were identified in py-gas. Application of biosolids-derived biochar to soil in place of biosolids has potential to minimize organic microconstituents discharged to the environment provided appropriate management of py-gas and py-oil

Quantification of polybrominated diphenylethers in oil produced by pyrolysis of flame retarded plastic

In recent years, there has been extensive research into using pyrolysis to convert toxic brominated plastics into safe, bromine free fuels. However, there has been little investigation of the polybrominated diphenyl ethers (PBDE) that are present in the pyrolysis oils. PBDEs are brominated flame retardants that are extremely toxic and are difficult to analyse owing to the existence of 209 different congeners. In this work, the authors have investigated the PBDEs present in the pyrolysis oil of high impact polystyrene which contained decabromodiphenyl ether as a flame retardant. The plastic was pyrolysed in a fluidised bed reactor and the resulting oil was subjected to a rigorous clean-up procedure to remove interfering compounds before the PBDEs were quantified using gas chromatography–mass spectrometry. It was found that the most prominent PBDEs in the oil were 3-monoBDE, 4-monoBDE, 3,49-diBDE, 3,39,4-triBDE and 2,29,4,49,5,69-hexaBDE. The lesser brominated PBDEs were more prevalent than the more heavily brominated PBDEs

Improving the quality of pyrolysis oil from co-firing high-density polyethylene plastic waste and palm empty fruit bunches

This study aimed to produce and improve the quality of pyrolysis oil as a source of bioenergy that is made by mixing palm empty fruit bunch (EFB) with high-density polyethylene (HDPE) plastic waste. The slow co-pyrolysis method was employed, and HDPE waste and EFB were fed into the pyrolysis reactor at HDPE amounts of 0, 10, 25, 50, 75, and 100% by weight. The pyrolysis oil product was obtained by co-firing EFB with HDPE using the slow co-pyrolysis method in a fixed bed reactor at 500°C with a flow rate of 750 mL/min and a heating rate of 5°C/min. The chemical compositions of pyrolysis oil were analyzed by gas chromatography-mass spectroscopy. A pyrolysis oil produced by HDPE 100 wt.% was dominated by the chemical compounds of phenols, aromatics, aliphatic, and acids, while for EFB 100 wt.% was dominated with aldehydes, acids, phenols, furan and aliphatic. The addition of HDPE reduced the amount of pyrolysis oil yield, increased the pH, reduced the viscosity, and reduced the oxygen content of the pyrolysis oil. These results proved that the HDPE affected the decrease in pyrolysis oil and the increase in gas production from co-firing HDPE and EFB using the slow co-pyrolysis method

Pyrolysis of brominated feedstock plastic in a fluidised bed reactor

Fire retarded high impact polystyrene has been pyrolysed using a fluidised bed reactor with a sand bed. The yield and composition of the products have been investigated in relation to fluidised bed temperature. The bromine distribution between the products and a detailed analysis of the oils using GC-FID/ECD, GC-MS, FT-ir, and size exclusion chromatography has been carried out. It was found that the majority of the bromine transfers to the pyrolysis oil and the antimony was detected in both the oil and the char. Oil made up over 89.9% of the pyrolysis products. Over 30% of the oil consisted of benzene, toluene, ethylbenzene, styrene and cumene. The pyrolysis gases were mainly hydrocarbons in the C1-C4 range but some HBr and Br2 was detected

Autocatalytic Pyrolysis of Wastewater Biosolids for Product Upgrading

The main goals for sustainable water resource recovery include maximizing energy generation, minimizing adverse environmental impacts, and recovering beneficial resources. Wastewater biosolids pyrolysis is a promising technology that could help facilities reach these goals because it produces biochar that is a valuable soil amendment as well as bio-oil and pyrolysis gas (py-gas) that can be used for energy. The raw bio-oil, however, is corrosive; therefore, employing it as fuel is challenging using standard equipment. A novel pyrolysis process using wastewater biosolids-derived biochar (WB-biochar) as a catalyst was investigated to decrease bio-oil and increase py-gas yield for easier energy recovery. WB-biochar catalyst increased the py-gas yield nearly 2-fold, while decreasing bio-oil production. The catalyzed bio-oil also contained fewer constituents based on GC-MS and GC-FID analyses. The energy shifted from bio-oil to py-gas, indicating the potential for easier on-site energy recovery using the relatively clean py-gas. The metals contained in wastewater biosolids played an important role in upgrading pyrolysis products. The Ca and Fe in WB-biochar reduced bio-oil yield and increased py-gas yield. The py-gas energy increase may be especially useful at water resource recovery facilities that already combust anaerobic digester biogas for energy since it may be possible to blend biogas and py-gas for combined use

Pyrolysis of asphaltenes and biomarkers for the fingerprinting of the _Amoco Cadiz_ oil spill after 23 years

The chemical composition of the petroleum products accidently or deliberately released in the environment varies considerably with time under the action of biological (biodegradation) and physico-chemical (photo-oxidation) processes. It becomes more and more difficult to trace the origin of the oil spilled. A technique widely used for monitoring ancient oil pollutions is the study of oil biomarkers like terpanes and steranes^1,2^. Here we show that the geochemical technique of asphaltenes pyrolysis can be successfully applied to environmental samples. This method allows the reconstitution of the original oil from the asphaltenes fraction of severely degraded oil residues. We applied the two techniques: biomarkers analysis and pyrolysis of asphaltenes to the long-term characterisation of the _Amoco Cadiz_ oil 23 years after the spill in the salt marshes of Ile Grande, Northern Brittany, France. The results show that the oil reached the ultimate degradation stage. The total biodegradation rate was 60% relatively to initial oil. The asphaltenes pyrolysis generated a gas-chromatographic profile very similar to the original _Amoco Cadiz_ oil. In the biomarkers fraction, gas chromatographic/mass spectrometric (GC/MS) analyses demonstrated that terpanes were conserved whereas steranes were partly degraded. We also showed that the class of seco-hopanes biomarkers are conserved and can be used in the long term monitoring of oil pollutions