Debromination of flame-retarded TV housing plastic waste

The thermal stability and degradation kinetics of TV housing plastic and brominated flame retardants were studied by means of thermogravimetry. The effects of the treatment temperature on the removal rate of Br were investigated using a tube furnace reactor under isothermal and vacuum conditions. The results showed that the weight loss of TV housing plastic was divided into two stages: the thermal degradation of brominated flame retardants mainly occurred at 290°–350°C, and the degradation of the high-impact polystyrene resin mainly occurred at 350°–455°C. Nearly 90% of Br can be removed from TV housing plastic when the treatment temperature exceeds 280°C.     

Conversion of Mixed Low-Density Polyethylene Wastes into Liquid Fuel by Novel CaO/SiO<Subscript>2</Subscript> Catalyst

Plastic wastes disposal can be done by various methods such as landfill, incineration, mechanical and chemical recycling but these are restricted due to some environmental, economic and political problems. Conversion of these plastic wastes into valuable products by degradation is the best option. In the present work waste low density polyethylene was degraded by catalytic process using CaO/SiO₂ as mixed catalyst. The conditions for catalytic degradation were optimized for the production of maximum liquid fuel. It was found that the yield of liquid product was up to 69.10 wt% at optimum condition of temperature (350 °C), time (90 min) and catalyst feed ratio (1:0.4). Liquid fuels obtained from the catalytic degradation were further separated into various fractions by fractional distillation. Composition of liquid fuels was analyzed by FTIR spectroscopy, which showed that the liquid fuels mostly consist of paraffinic and naphthenic hydrocarbons. Different fuel properties such as density, specific gravity, American petroleum institute gravity (API gravity), viscosity, kinematic viscosity, refractive index, refractive intercept and flash point of both the parents and various fractional fuels were determined. All the properties of the obtained fuels are in close agreement with the fuel properties of gasoline, kerosene and diesel. It was found that our catalyst is very much efficient in terms of time, degradation temperature and amount of catalyst.     

Effect of metal chlorides on thermal degradation of (waste) polycarbonate

In this study, we investigated how to treat (waste) polycarbonate efficiently to reduce its degraded residue. The study was carried out in an isothermal reactor under continuous nitrogen flow at atmospheric pressure to pyrolyze polycarbonate (PC) alone and in the presence of metal chloride. Some metal chlorides were shown to be catalytic active for the degradation of PC at 400 degrees C, which increased degradation conversion from 8.5% to more than 58.3%. Among those active metal chlorides, ZnCl2 and SnCl2 can produce higher liquid product yields. Effects such as particle size of PC, temperature, the weight ratio of metal chloride/PC, and degradation time on the degradation conversion of PC without and with these two most active metal chlorides were studied. Results of the liquid product analysis by GC/MS demonstrated the product composition of PC degradation over the metal chlorides is much simpler than that of degradation alone. The main liquid product is phenol, p-isopropylphenol, diphenyl carbonate, and bisphenol A for all cases.     

Characterization of products obtained from pyrolysis and steam gasification of wood waste,RDF, and RPF

Pyrolysis and steam gasification of woody biomass chip (WBC) obtained from construction and demolition wastes, refuse-derived fuel (RDF), and refuse paper and plastic fuel (RPF) were performed at various temperatures using a lab-scale instrument. The gas, liquid, and solid products were examined to determine their generation amounts, properties, and the carbon balance between raw material and products.The amount of product gas and its hydrogen concentration showed a considerable difference depending on pyrolysis and steam gasification at higher temperature. The reaction of steam and solid product, char, contributed to an increase in gas amount and hydrogen concentration. The amount of liquid products generated greatly depended on temperature rather than pyrolysis or steam gasification. The compositions of liquid product varied relying on raw materials used at 500 °C but the polycyclic aromatic hydrocarbons became the major compounds at 900 °C irrespective of the raw materials used. Almost fixed carbon (FC) of raw materials remained as solid products under pyrolysis condition whereas FC started to decompose at 700 °C under steam gasification condition.For WBC, both char utilization by pyrolysis at low temperature (500 °C) and syngas recovery by steam gasification at higher temperature (900 °C) might be practical options. From the results of carbon balance of RDF and RPF, it was confirmed that the carbon conversion to liquid products conspicuously increased as the amount of plastic increased in the raw material. To recover feedstock from RPF, pyrolysis for oil recovery at low temperature (500 °C) might be one of viable options. Steam gasification at 900 °C could be an option but the method of tar reforming (e.g. catalyst utilization) should be considered.     

Utilization of red mud as catalyst in conversion of waste oil and waste plastics to fuel

The aim of this study was to investigate the possibilities of using a by-product (red mud) from alumina production as a catalyst for recovery of waste. The conversion of waste mineral oil (WMO) and waste mineral oil/municipal waste plastic (WMO/MWP) blends over red mud (RM), a commercial hydrocracking catalyst (silica–alumina), and a commercial hydrotreating catalyst (Ni–Mo/alumina) to fuel has been studied. The effect of the catalyst and the temperature on the product distribution (gas, liquid, and wax) and the properties of liquid products were investigated. In the case of hydrotreatment of WMO, the liquids obtained over RM at both 400° and 425°C had larger amounts of low-boiling hydrocarbons than that of thermal or catalytic treatment with hydrotreating catalyst. Gas chromatography and nuclear magnetic resonance analysis of the liquid products showed that RM had hydrogenation and cracking activity in hydrotreatment of WMO. In coprocessing of WMO with municipal waste plastics, temperature had an important effect as well as the amount of MWP in the blend and the catalyst type. The hydrocracking at 400°C produced no liquid product. In hydrocracking at 425°C, the product distribution varied with catalyst type and MWP amount. The commercial hydrocracking catalyst had more cracking ability in the conversion of WMO/MWP to liquid and gas fuel than RM. In the case of hydrocracking over RM, the largest amount of liquid having satisfactory quality was obtained only from the blend containing 20% MWP.     

Tertiary recycling of PVC-containing plastic waste by copyrolysis with cattle manure

The corrosion from pyrolysis of PVC in plastic waste was reduced by copyrolysis of PVC with cattle manure. The optimization of pyrolysis conditions between PVC and cattle manure was studied via a statistical method, the Box-Behnken model. The pyrolysis reaction was operated in a tubular reactor. Heating rate, reaction temperature and the PVC:cattle manure ratio were optimized in the range of 1-5 degrees C/min, 250-450 degrees C and the ratio of 1:1-1:5, respectively. The suitable conditions which provided the highest HCl reduction efficiency were the lowest heating rate of 1 degrees C/min, the highest reaction temperature of 450 degrees C, and the PVC:cattle manure ratio of 1:5, with reliability of more than 90%. The copyrolysis of the mixture of PVC-containing plastic and cattle manure was operated at optimized conditions and the synergistic effect was studied on product yields. The presence of manure decreased the oil yield by about 17%. The distillation fractions of oil at various boiling points from both the presence and absence of manure were comparable. The BTX concentration decreased rapidly when manure was present and the chlorinated hydrocarbon was reduced by 45%. However, the octane number of the gasoline fraction was not affected by manure and was in the range of 99-100.     

Study on the conversion of waste plastics/petroleum resid mixtures to transportation fuels

Catalytic coprocessing of model and waste plastics with light Arabian crude oil residue was investigated using NiMo/Al₂O₃, ZSM-5, FCC, and hydrocracking catalysts. Reaction systems that were studied included low density polyethylene (LDPE), high density polyethylene (HDPE), polystyrene (PS), and polypropylene (PP). A series of single (plastic/catalyst) and binary (plastic/resid/catalyst) reactions were carried out in a 25-cm³ micro autoclave reactor under different conditions of weight and type of catalyst, duration, pressure, and temperature. The optimum conditions selected for our work were: 1% catalyst by weight of total feedstock weight, 60min reaction time, 8.3Mpa of H₂, and 430°C. The product distribution for the binary system using plastic and petroleum residue provided some encouraging results. High yields of liquid fuels in the boiling range of 100°–480°C and gases were obtained along with a small amount of heavy oils and insoluble material such as gums and coke. In general, this study helps to demonstrate the technical feasibility of upgrading both waste plastics and petroleum resid, as well as an alternative approach to feedstock recycling.     

Gasification of refuse derived fuel in a fixed bed reactor for syngas production

Steam gasification of two different refuse derived fuels (RDFs), differing slightly in composition as well as thermal stability, was carried out in a fixed-bed reactor at atmospheric pressure. The proximate and ultimate analyses reveal that carbon and hydrogen are the major components in RDFs. The thermal analysis indicates the presence of cellulose and plastic based materials in RDFs. H2 and CO are found to be the major products, along with CO2 and hydrocarbons resulting from gasification of RDFs. The effect of gasification temperature on H2 and CO selectivities was studied, and the optimum temperature for better H2 and CO selectivity was determined to be 725 degrees C. The calorific value of product gas produced at lower gasification temperature is significantly higher than that of gas produced at higher process temperature. Also, the composition of RDF plays an important role in distribution of products gas. The RDF with more C and H content is found to produce more amounts of CO and H2 under similar experimental conditions. The steam/waste ratio showed a notable effect on the selectivity of syngas as well as calorific value of the resulting product gas. The flow rate of carrier gas did not show any significant effect on products yield or their distribution.     

Temperature-dependent pyrolytic product evolution profile for low-density polyethylene from gas chromatographic study

In this work, a product distribution study from thermal degradation of low-density polyethylene (LDPE) is presented. Thermal degradation of the polymer was investigated under dynamic condition in an inert environment using a thermo-gravimetric analyzer (TGA) coupled with evolved products’ analysis using a gas chromatograph (GC). Fractions evolved at nine different temperatures from 200 to 600 °C were injected into GC for a detailed product analysis. The main objective of the present investigation is to highlight the species-specific evolution profiles of LDPE pyrolyzates (C5–C44) at different stages of its degradation under an inert environment. Pyrograms have been analyzed in terms of amount of different products evolved at various pyrolysis temperatures. Volatile pyrolyzates essentially remain low at low decomposition temperature (200–300 °C) of the polymer, which gradually increase to attain a maximum at maximum decomposition temperature (470 °C) and finally level off at 600 °C. In the mechanistic approach adopted to understand the decomposition mechanism of LDPE, the following reaction types were considered: (a) main chain cleavage to form chain-terminus radicals; (b) intramolecular hydrogen transfer to generate internal radicals; (c) intermolecular hydrogen transfer to form both volatile products and radicals; and (d) β-scission to form both volatiles and terminally unsaturated polymer.     

Catalytic degradation of PP with an Fe/activated carbon catalyst

We investigated the function of Fe and activated carbon (AC) as a catalyst by comparing Fe/AC with Fe/SiO₂ or AC, and also the effect of H₂ as a reaction gas on the product distribution in the catalytic degradation of polypropylene. Supported Fe promotes H₂ consumption to decompose solid residues, and AC support degrades heavy oil to produce light oil. As a result, using Fe/AC as a catalyst gives the maximum yield of the liquid product. For the reaction conditions, with a high reaction temperature or a long reaction time, the product distribution is more influenced by the thermal degradation than by the catalytic degradation. For the amount of Fe to load, 5wt% is the optimum condition in our reaction system. We demonstrated the mechanism of the degradation of polyolefins with hydrogen-capping catalysts.     

Pyrolysis of polyolefins for increasing the yield of monomers' recovery

Pyrolysis of plastic waste is an alternative way of plastic recovery and could be a potential solution for the increasing stream of solid waste. The objective of this work was to increase the yield the gaseous olefins (monomers) as feedstock for polymerization process and to test the applicability of a commercial Ziegler-Natta (Z-N): TiCl(4)/MgCl(2) for cracking a mixture of polyolefins consisted of 46%wt. of low density polyethylene (LDPE), 30%wt. of high density polyethylene (HDPE) and 24%wt. of polypropylene (PP). Two sets of experiments have been carried out at 500 and 650°C via catalytic pyrolysis (1% of Z-N catalyst) and at 650 and 730°C via only-thermal pyrolysis. These experiments have been conducted in a lab-scale, fluidized quartz-bed reactor of a capacity of 1-3kg/h at Hamburg University. The results revealed a strong influence of temperature and presence of catalyst on the product distribution. The ratios of gas/liquid/solid mass fractions via thermal pyrolysis were: 36.9/48.4/15.7%wt. and 42.4/44.7/13.9%wt. at 650 and 730°C while via catalytic pyrolysis were: 6.5/89.0/4.5%wt. and 54.3/41.9/3.8%wt. at 500 and 650°C, respectively. At 650°C the monomer generation increased by 55% up to 23.6%wt. of total pyrolysis products distribution while the catalyst was added. Obtained yields of olefins were compared with the naphtha steam cracking process and other potentially attractive processes for feedstock generation. The concept of closed cycle material flow for polyolefins has been discussed, showing the potential benefits of feedstock recycling in a plastic waste management.     

Reaction Kinetic Model For Optimal Pyrolysis Of Plastic Waste Mixtures

Reaction kinetics at various temperatures for pyrolysis of mixtures of plastic waste [polyethylene(PE) and polystyrene(PS)] are modelled in terms of five types of pyrolysis reaction. The model development is based on the assumption that as plastic wastes are heated in a non-reactive environment they are decomposed homogeneously to various products of gas, oil and char by a first-order rate, irreversible reaction and isothermal condition. Among the five models, the type II model in which the activated polymer exists as an intermediate product is the most accurate in predicting the pyrolysis products of pure PE or pure PS. Also, for mixtures of plastics both type II and IV models can be used to explain the composition of pyrolysis products. Furthermore, from the analysis of variance (ANOVA), the mixing ratio and temperature are shown to be the parameters that have the greatest effect on the pyrolysis reaction of polymer waste mixture. The pyrolysis reaction time for the maximum oil production from PE-PS mixtures is shorter than for PE alone and approaches that of PS alone. Oil production increases with increase of PS content. The optimal temperature for maximum oil production is 600°C for the pyrolysis of 2:8, 5:5 and 1:0 mixtures (w/w) of PE and PS. Oil production for PS alone is constant when the pyrolysis is above 600°C.     

Recovery of glass fibers from glass fiber reinforced plastics by pyrolysis

Fiber-reinforced plastic sheets containing unsaturated polyester cross-linked with styrene, CaCO₃ and glass fibers as fillers were pyrolyzed in a helium and steam atmosphere in order to recover glass fibers and valuable organic pyrolysis products. Glass fibers were separated from CaCO₃ and CaO by dissolving calcium salts in hydrochloric acid. Residual organic material was burnt afterwards. Best results were obtained at a pyrolysis temperature of 600 and 700 °C, resulting in a large liquid fraction high in styrene, leaving little residual organic material on the surface of the glass fibers. At a pyrolysis temperature of 500 °C, the degradation of the polymer matrix was incomplete, and at 900 °C, glass fibers were destroyed in the presence of CaO, leaving CaSiO₃ as a product.     

Pyrolysis process for the treatment of scrap tyres: preliminary experimental results

The aim of this work is the evaluation, on a pilot scale, of scrap tyre pyrolysis process performance and the characteristics of the products under different process parameters, such as temperature, residence time, pressure, etc. In this frame, a series of tests were carried out at varying process temperatures between 550 and 680 degrees C, other parameters being equal. Pyrolysis plant process data are collected by an acquisition system; scrap tyre samples used for the treatment, solid and liquid by-products and produced syngas were analysed through both on-line monitoring (for gas) and laboratory analyses. Results show that process temperature, in the explored range, does not seem to seriously influence the volatilisation reaction yield, at least from a quantitative point of view, while it observably influences the distribution of the volatile fraction (liquid and gas) and by-products characteristics.     

Cardanol Polymerization Under Acid Conditions By Addition And Condensation Reactions

Cashew nut shell liquid (CNSL) is a byproduct of the cashew nut industry and consists predominantly of phenolic compounds that have an side chain with different degrees of unsaturation. Cardanol, one of these components, is biodegradable and widely available. Studies have revealed several polymerization reactions involving cardanol. However, the mechanisms and detailed structures of polymerization reactions have not been explored, although the final product shows different applications. In this work, we evaluated the mechanism and the products structure of the reaction of cardanol with: (i) boron trifluoride diethyl etherate (BF₃O(CH₂CH₃)₂), and (ii) formaldehyde. The characterizations were performed by FTIR, ¹H NMR, SEC and TGA. The results show that the reaction of cardanol with aldehyde produces the expected like-comb structure with a long hydrocarbon pendent chain. Nevertheless, the reaction of cardanol with BF₃O(CH₂CH₃)₂ can exhibits a more complex structure since it was identified aromatic ring linkages, besides the expected polymerization through C=C.     

Thermal Degradation Mechanism of Low-Density Polyethylene Plastic Wastes in Cyclohexane

The thermal LDPE degradation mechanism harnessing a high-pressure autoclave surrounded by a furnace was investigated in this work. Rates of formation of gas, liquid, and solid during degradation of PE plastic wastes in cyclohexane as solvent at 400 and 425°C have been experimentally determined. Four reaction mechanisms have been proposed and tested to estimates of gas, liquid, and solid. Proposed mechanisms are based on the assumption that the reactions are pseudo-first-order with respect to the reacting species. Pseudo-first-order rate constants for each of the indicated mechanistic steps have been calculated by nonlinear regression analysis. The best fit was obtained by model 2 (pure parallel reaction mechanism), and its activation energy was determined.     

Pyrolysis of virgin and waste polypropylene and its mixtures with waste polyethylene and polystyrene

A comparison of waste and virgin polypropylene (PP) plastics under slow pyrolysis conditions is presented. Moreover, mixtures of waste PP with wastes of polyethylene (PE) and polystyrene (PS) were pyrolyzed under the same operating conditions. Not only the impact of waste on degradation products but also impacts of the variations in the mixing ratio were investigated. The thermogravimetric weight loss curves and their derivatives of virgin and waste PP showed differences due to the impurities which are dirt and food residues. The liquid yield distribution concerning the aliphatic, mono-aromatic and poly-aromatic compounds varies as the ratio of PP waste increases in the waste plastic mixtures. In addition to this, the alkene/alkane ratio of gas products shows variations depending on the mixing ratio of wastes.     

Quantitative characterization of recyclable resources dismantled from waste liquid crystal display products

Currently only limited materials, such as common metals and plastics, are recovered from waste flat-panel displays, thus necessitating the development of a comprehensive recycling process. This study aims to establish a statistical database about the types and amounts of valuable resources in waste liquid crystal display (LCD) products. To obtain these data, the waste LCD products were disassembled into four components: plastics, printed circuit boards, metals, and other materials, including their panels, and the weight of each component was measured. Overall, the product weight decreased with increasing manufacturing year regardless of the product screen size; however, the decreasing rate varied from 14 to 73%. The metal weight ratios decreased significantly by 24–31%. Meanwhile, regardless of the manufacturing year, the plastic weight ratios remained almost constant at about 20%. On the other hand, the weight ratio of the other components increased by 26–46% with increasing manufacturing year suggesting that rare-earth metal recycling has become more important. These statistical analyses are expected to contribute to the development of an eco-friendly, high-efficiency dismantling/separation process that will enable higher value recycling and minimal waste disposal.     

Polyalkylphenyl-sulphonic acids with acid groups of variable strength from animal-vegetable wastes

The insoluble organic fraction isolated from rice-hulls residues and animal fecal matter mixture is sulphonated in liquid SO3 at 200 degrees C to a water soluble sulphonate (III). III is compared to the sulphonate (IV) obtained from the same mix after composting. Both products have been found to contain mixtures of molecules with close molecular weight. These molecules consist of a central cicloaliphatic cluster with peripheral pending aromatic chains. III and IV appear to have the same sulphonation degree. However, the latter contains higher concentrations of cicloaliphatic fragments and of amide, phenol and ether bonds, but less carboxylic and amine functional groups. These differences may be reasonably traced back to the starting materials. By comparison with commercial lignosulphonates derived from the paper and pulp industry, the above arylsulphonates are likely candidates for a variety of applications in the chemical industry and in agriculture. We conclude that sulphonation, even under the drastic experimental conditions of this work, does not seem to erase the memory of the parent matter structure. This reaction is capable of upgrading recalcitrant organic matter in vegetable waste residues to an interesting variety of lignosulphonates.     

Evaluation of the biodegradability of copolyesters containing aromatic compounds by investigations of model oligomers

Model oligo esters of terephthalic acid with 1,2-ethanediol, 1,3-propanediol, and 1,4-butanediol have been investigated with regard to their biodegradability in different biological environments. Well-characterized oligomers with weight-average molar masses of from 600 to 2600 g/mol exhibit biodegradation in aqueous systems, soil, and compost at 60°C. SEC investigations showed a fast biological degradation of the oligomer fraction consisting of 1 or 2 repeating units, independent of the diol component used for polycondensation, while polyester oligomers with degrees of polymerization higher than 2 were stable against microbial attack at room temperature in a time frame of 2 months. At 60°C in a compost environment chemical hydrolysis also degrades chains longer than two repeating units, resulting in enhanced degradability of the oligomers. Metabolization of the monomers and the dimers as well by the microorganisms could be confirmed by comparing SEC measurements and carbon balances in a Sturm test experiment. Based on these results degradation characteristics of potential oligomer intermediates resulting from a primary chain scission from copolyesters consisting of aromatic and aliphatic dicarbonic acids can be predicted depending on their composition. These results will have an evident influence on the evaluation of the biodegradability of commercially interesting copolyesters and lead to new ways of tailor-made designing of new biodegradable materials as well.