Effect of decabromodiphenyl ether and antimony trioxide on controlled pyrolysis of high-impact polystyrene mixed with polyolefins

The controlled pyrolysis of polyethylene/polypropylene/polystyrene mixed with brominated high-impact polystyrene containing decabromodiphenyl ether as a brominated flame-retardant with antimony trioxide as a synergist was performed. The effect of decabromodiphenyl ether and antimony trioxide on the formation of its congeners and their effect on distribution of pyrolysis products were investigated. The controlled pyrolysis significantly affected the decomposition behavior and the formation of products. Analysis with gas chromatograph with electron capture detector confirmed that the bromine content was rich in step 1 (oil 1) liquid products leaving less bromine content in the step 2 (oil 2) liquid products. In the presence of antimony containing samples, the major portion of bromine was observed in the form of antimony bromide and no flame-retardant species were found in oil 1. In the presence of synergist, the step 1 and step 2 oils contain both light and heavy compounds. In the absence of synergist, the heavy compounds in step 1 oil and light compounds in step 2 oils were observed. The presence of antimony bromide was confirmed in the step 1 oils but not in step 2 oils.     

Effect of pressure and temperature on the hydropyrolysis of cotton residue

With growing concerns of fossil fuel resources availability and the volatility of crude oil price, it is becoming imperative day by day to utilize the renewable sources of energy in a sustainable, environment friendly and energy efficient manner. India is the world’s second largest producer of cotton after China. India also has several agricultural and forest residues, and cotton residue is one of the most abundant agricultural residues after rice and wheat residues. The hydropyrolysis of cotton residues has been carried out at various pressures (1, 20 and 40 bar) and temperatures (300, 350, 400 and 450 °C). The effects of temperature and pressure have been studied to understand their yield patterns, and it has been observed that 20 bar pressure and 400 °C are the optimum conditions. The thermogravimetric analysis shows that cotton residue has two significant decomposition temperatures. The SEM, XRD patterns and FT-IR spectra clearly indicate the decomposition of the macromolecular structure of the cotton residue and formation of low molecular weight hydrocarbons suitable for various applications.     

The individual and cumulative effect of brominated flame retardant and polyvinylchloride (PVC) on thermal degradation of acrylonitrile-butadiene-styrene (ABS) copolymer

Acrylonitrile-butadiene-styrene (ABS) copolymers without and with a polybrominated epoxy type flame retardant were thermally degraded at 450 degrees C alone (10 g) and mixed with polyvinylchloride (PVC) (8 g/2 g). Gaseous and liquid products of degradation were analysed by various gas chromatographic methods (GC with TCD, FID, AED, MSD) in order to determine the individual and cumulative effect of bromine and chlorine on the quality and quantity of degradation compounds. It was found that nitrogen, chlorine, bromine and oxygen are present as organic compounds in liquid products, their quantity depends on the pyrolysed polymer or polymer mixture. Bromophenol and dibromophenols were the main brominated compounds that come from the flame retardant. 1-Chloroethylbenzene was the main chlorine compound observed in liquid products. It was also determined that interactions appear at high temperatures during decomposition between the flame retardant, PVC and the ABS copolymer.     

Renewable hydrocarbons through biomass hydropyrolysis process: challenges and opportunities

Considering the current issues of carbon control and the desire to become less dependent on imported oil, the utilization of renewable hydrocarbons for the reduction of CO₂ emission and production of liquid synthetic fuels/chemicals has been proposed by researchers worldwide. Efforts to make chemicals/fuels from renewable resources have escalated over the past few years. Biomass-based renewable hydrocarbons are considered to be one of the sources with the highest potential to contribute to the energy needs of modern society for both developed and developing economies worldwide. Fast pyrolysis is becoming an important thermal route to convert biomass to liquid fuels; however, the raw bio-oils obtained have a number of negative properties such as high acidity, high water content, and variable viscosity over time. To overcome this problem and produce bio-oil of good quality, process of ‘hyropyrolysis’ has been developed. The scope for using pyrolysis under hydrogen pressure and also by process of hydropyrolysis followed by in situ hydroconversion of vapors to give oils with much lower oxygen contents has been reviewed.     

Effect of pressure on the hydropyrolysis of Jatropha seed deoiled cake

The necessity to move towards a sustainable economy is increasing day by day owing to various problems like climate change, increasing crude oil prices, etc. In this line, hydropyrolysis of Jatropha seed deoiled cake has been carried out at various pressures of hydrogen (1, 20, 40 and 52 bar) at 450 °C. With an increase in pressure under the experimental conditions of present study from 1 to 40 bar, the yield of bio-oil is found to have increased and beyond 40 bar the bio-oil yields have decreased. It has been observed that the liquid bio-oil yield is highest at 17 wt% at 40 bar. The FTIR spectrum of the bio-oil and char at 40 bar shows maximum functionality, indicating the clear opening of the macromolecular structure. The EDAX analysis of the hydropyrolysis char obtained at 40 bar pressure show a maximum of 85 wt% carbon and minimum of oxygen 13 wt%.     

Effect of heating rate on the pyrolysis of high-impact polystyrene containing brominated flame retardants: fate of brominated flame retardants

In the case of plastics containing brominated flame retardants, various brominated organic compounds, including polybrominated dibenzodioxins and dibenzofurans, are yielded when they are degraded. In order to reduce the hazard that might be generated during after-live treatment, the behaviour of flame retarded high-impact polystyrene containing decabromo diphenylether and antimony oxide (Sb₂O₃), was investigated using several heating programs. It was found that the separation of the thermal process into two steps divided at 330?°C makes it possible to obtain an oil fraction rich in brominated compounds at low temperatures and an oil fraction depleted in brominated compounds at high temperatures. The low temperature oil contained a high concentration of SbBr₃ and dibromodibenzofurans. Various brominated compounds with a low volatility and 1-bromo-1-phenylethane from the reaction of HBr with styrene were among the substances in the high temperature oil. The concentration of brominated compounds was reduced from 6?wt% for degradation in a single step to below 1?wt% in the high temperature oil in the two step process.     

Development of a catalytic dehalogenation (Cl,Br) process for municipal waste plastic-derived oil

Dehalogenation is a key technology in the feedstock recycling of mixed halogenated waste plastics. In this study, two different methods were used to clarify the effectiveness of our proposed catalytic dehalogenation process using various carbon composites of iron oxides and calcium carbonate as the catalyst/sorbent. The first approach (a two-step process) was to develop a process for the thermal degradation of mixed halogenated waste plastics, and also develop dehalogenation catalysts for the catalytic dehydrochlorination of organic chlorine compounds from mixed plastic-derived oil containing polyvinyl chloride (PVC) using a fixed-bed flow-type reactor. The second approach (a single-step process) was the simultaneous degradation and dehalogenation of chlorinated (PVC) and brominated (plastic containing brominated flame retardant, HIPS–Br) mixed plastics into halogen-free liquid products. We report on a catalytic dehalogenation process for the chlorinated and brominated organic compounds formed by the pyrolysis of PVC and brominated flame retardant (HIPS–Br) mixed waste plastics [(polyethylene (PE), polypropylene (PP), and polystyrene (PS)], and also other plastics. During dehydrohalogenation, the iron- and calcium-based catalysts were transformed into their corresponding halides, which are also very active in the dehydrohalogenation of organic halogenated compounds. The halogen-free plastic-derived oil (PDO) can be used as a fuel oil or feedstock in refineries.     

Effect of polyethylene terephthalate (PET) on the pyrolysis of brominated flame retardant-containing high-impact polystyrene (HIPS-Br)

Pyrolysis of brominated flame retardant-containing high-impact polystyrene (HIPS-Br) was performed at 430°C in the presence of 0.1 wt% of polyethylene terephthalate (PET) in a Pyrex glass reactor. Two different types of brominated flame retardants (decabromodiphenyl ether and decabromodiphenyl ethane) with or without antimony trioxide (as synergist) 5 wt% were used. The presence of PET had a significant effect on the material balance, decreasing the gaseous product and increasing the residue. The type of flame retardant had no effect on the yield of liquid product; however, the presence of Sb resulted in a marked difference in the distribution of decomposition products. Analysis by a gas chromatograph equipped with a flame ionization detector showed that the hydrocarbons were distributed in the range n-C₇ to n-C₂₅ with major peaks at n-C₉ and n-C₁₇. The presence of PET increased the formation of brominated compounds by several times and affected both the type and quantity of polybrominated compounds. The liquid products obtained from the pyrolysis of HIPS-Br/PET have to be treated before they can be used     

Individual and simultaneous degradation of brominated high impact polystyrene and brominated acrylonitrile-butadiene-styrene and removal of heteroelements (Br,N, and O) from degradation oil by multiphase catalytic systems

Brominated high-impact polystyrene (HIPS-Br), which contained decabromodiphenyl ether flame retardant, and brominated acrylonitrile butadiene styrene (ABS-Br), which contained bromine-containing epoxy-type flame retardant, were degraded at 450°C individually and in a 1/1 mixture by a thermal and catalytic procedure using folded sheet mesoporous (FSM) and ZSM-5 zeolite in liquid phase contact mode. The two polymers produced similar degradation oils but at a higher yield for HIPS-Br. However, the composition and distribution of Br-, N-, and O-containing compounds depended on the type of flame retardant in HIPS-Br and ABS-Br. Multiphase catalytic systems consisting of FSM in liquid phase contact mode and various CaH-, FeO-, CoMo-, and NiMo-based catalysts, or combinations of these catalysts, in vapor phase contact mode were used to decrease the amount of heteroatoms (Br, N, and O) in the degradation oils. Each system gave particular results in terms of mass balance and concentrations of heteroatoms. A FSM (liquid phase contact)/CaHC (vapor phase contact) combination was the best catalytic system to remove Br-, N-, and O-containing compounds from degradation oils.