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.     

Preparation of MgCr<Subscript>2</Subscript>O<Subscript>4</Subscript> from waste tannery solution and effect of sulfate,chloride, and calcium on leachability of chromium

This paper presents a study regarding the preparation of MgCr₂O₄ from waste tannery solution, and chromium leaching behavior is also investigated with varying amounts of sulfate, chloride and calcium. The phase transformation, crystallinity index and crystallite diameter were characterized using XRD, FT-IR and thermal analysis. A well-crystallized MgCr₂O₄ was successfully prepared at 1400 °C. The sintering temperature had a major impact on the formation of MgCr₂O₄ compared with sintering time. The MgCr₂O₄ phase was observed initially at 400 °C and its crystallite diameter increased with increasing temperature. The concentration of total chromium leached and Cr(VI) decreased gradually with increasing temperature. The considerable amount of Cr(VI) was found in the leachate at 300–500 °C caused by Cr(VI) intermediary products. Sulfate and chlorine could impact the transformation efficiency of chromium adversely, and chlorine has a more significant effect than sulfate. The presence of calcium disturbed the formation of MgCr₂O₄ and new chromium species (CaCrO₄) appeared, which resulted in a sharp increase in the concentration of leached Cr(VI). Incorporating Cr(III) into the MgCr₂O₄ spinel for reusable products reduced its mobility significantly. This was demonstrated to be a promising strategy for the disposal of chromium containing waste resource.     

Effect of chlorine on volatilization of Na, K, Pb, and Zn compounds from municipal solid waste during gasification and melting in a shaft-type furnace

In the present work, a shaft-type furnace model in which the furnace column is divided into multiple cells was proposed and equilibrium reaction calculation software was used to describe the model. The model was used to study the effects of gasification and melting conditions such as temperature, oxygen partial pressure, and chlorine content on the volatilization behaviors of the low-boiling-point metals Na, K, Pb, and Zn during the gasification and melting process of municipal solid waste in a shaft-type furnace. Consequently, the volatilization ratios of Na, K, Pb, and Zn compounds in the exhaust gas from a pilot plant shaft-type furnace were found to be in good agreement with the calculation results, and the Na, K, Pb, and Zn compounds were volatilized mainly as metal chlorides in the temperature range up to approximately 1173 K. With a further rise in temperature, these low-boiling point metals were volatilized as metallic forms. It was found that almost 100% of Pb and Zn compounds were volatilized regardless of the chlorine content in municipal solid waste; in contrast, the volatilization rates of Na and K increased when the chlorine content increased. Finally, Na, K, Pb, and Zn compounds were converted from reduced metals to metal chlorides such as NaCl, KCl, PbCl₂, and ZnCl₂ with an increase in the ratio of chlorine to each metal.     

Decreased PCDD/F formation when co-firing a waste fuel and biomass in a CFB boiler by addition of sulphates or municipal sewage sludge

Polychlorinated dibenzo-p-dioxins (PCDDs) and polychlorinated dibenzofurans (PCDFs) are formed during waste incineration and in waste-to-energy boilers. Incomplete combustion, too short residence times at low combustion temperatures (<700 °C), incineration of electronic waste and plastic waste containing chlorine are all factors influencing the formation of PCDD/Fs in boilers. The impact of chlorine and catalysing metals (such as copper and iron) in the fuel on PCDD/F formation was studied in a 12 MW_th circulating fluidised bed (CFB) boiler. The PCDD/F concentrations in the raw gas after the convection pass of the boiler and in the fly ashes were compared. The fuel types were a so-called clean biomass with low content of chlorine, biomass with enhanced content of chlorine from supply of PVC, and solid recovered fuel (SRF) which is a waste fuel containing higher concentrations of both chlorine, and catalysing metals. The PCDD/F formation increased for the biomass with enhanced chlorine content and it was significantly reduced in the raw gas as well as in the fly ashes by injection of ammonium sulphate. A link, the alkali chloride track, is demonstrated between the level of alkali chlorides in the gas phase, the chlorine content in the deposits in the convection pass and finally the PCDD/F formation. The formation of PCDD/Fs was also significantly reduced during co-combustion of SRF with municipal sewage sludge (MSS) compared to when SRF was fired without MSS as additional fuel.     

Absorption behavior of chlorine and sulfur by Ca(OH)<Subscript>2</Subscript> under simulated conditions with a fluidized bed combustor

This study was carried out to investigate the absorption reaction of chlorine and sulfur with Ca(OH)₂ under simulated conditions related to the co-combustion of refuse-derived fuel and sewage sludge in the fluidized bed combustor, such as high temperature, moisture and a mixing of samples. The combustion experiments were carried out in an electrical furnace with PVC and sulfur powders as the waste samples. High-purity slaked lime powder was used to capture the chlorine and sulfur. The experimental results showed that the removal efficiencies of both chlorine and sulfur were over 90% when the mole ratios of Ca on Cl and S were over 2.5. Furthermore, simultaneous absorption was helpful in improving the removal efficiency of chlorine and sulfur. The presence of chlorine markedly increased the removal efficiency of sulfur. The removal efficiency of chlorine was the highest at 700°C in both independent and simultaneous absorption. The removal efficiency of sulfur increased as the temperature increased, but the removal efficiency of chlorine sharply decreased from 95 to 83% when the moisture content in gases increased from 0 to 20 vol%. These results were confirmed by the combustion test of granular CaCl₂.     

Mechanical properties of incineration bottom ash: The influence of composite species

The mechanical properties, including strength, deformational behavior, and wetting softening phenomena of municipal solid waste incinerator (MSWI) bottom ash are one of the major concerns for reuse applications. However, owing to the complex constituents of municipal solid waste, the properties of MSWI bottom ash are often highly variable. A series of artificial specimens with controlled chemical components were tested in this study. The test results show that the artificial bottom ash possesses the following mechanical characteristics: (1) for the strength, the frictional angles of the bottom ash under dry and saturated conditions vary from 34.8° to 51.1° and 26.0° to 37.2°, respectively; (2) for the deformation, the shear stiffness increases with the normal stress arises and degrades upon increased shearing; (3) significant wetting degradation of the strength and stiffness were observed.The multi-variable regression analysis was conducted to evaluate the associated influence of the chemical components on the strength. Among the evaluated components, Fe₂O₃ and Al₂O₃ are key factors; an increase in either results in higher strength at both dry and saturated conditions. The results were used to propose empirical relationships for ?_dry and ?_sat, expressed in terms of Fe₂O₃ and Al₂O₃. Accordingly, a strength classification chart is proposed for engineering purposes.     

Thermodynamic analysis on heavy metals partitioning impacted by moisture during the MSW incineration

A thermodynamic calculation was carried out to predict the behavior and speciation of heavy metals (HMs), Pb, Zn, Cu, and Cd, during municipal solid waste (MSW) incineration with the different moisture levels. The calculation was based on the minimization of the total Gibbs free energy of the multi-components and multi-phases closed system reaching chemical equilibrium. The calculation also indicated the reaction directions and tendencies of HMs components. The impacts of chlorine additives (No PVC, 1%PVC, and 5%PVC) and moisture on the behavior of HMs were investigated at different temperature levels in the system (750 °C, 950 °C, and 1150 °C). Furthermore, because the incineration temperature falls down with the increase in moisture in waste, the co-influence of moisture and temperature in combusting MSW on the HMs was also studied with the given chlorine (as 1%PVC + 0.5%NaCl). The results showed that in the non-chlorine system, the impact of the moisture on Pb, Zn, and Cu was not significant, and the ratio of compound transformation was less than 10%, except the Cd compounds at 950 °C and 1150 °C. In the system with low chlorine (as 1%PVC) at constant temperature, the chlorides of HMs (Cd, Pb, Zn, and Cu) transferred to oxides, and when the content of chlorine rose up (as 5%PVC), the ratio of the chlorides of HMs (Cd, Pb, Zn, and Cu) transferring to oxides fell down noticeably. When the moisture varied together with the temperature, the Zn and Cu compounds transferred from chlorides to oxides with increase in moisture as well as decrease in temperature. At the temperature of 700–1000 °C, the impact of temperature on Pb and Cd was little and the moisture was the main factor; while at the temperature of 1000–1200 °C, the impact of increase in moisture and decrease in temperature on Pb and Cd was almost equal and reversed.     

Improved quartz furnace method for chlorine and sulfur determination in municipal solid waste

 A method of determining the chlorine (Cl) and sulfur (S) in municipal solid waste (MSW) was studied. The quartz furnace method was improved in two ways: recovery from ash by hot extraction with dilute nitric acid, and avoidance of the volatilization of alkali (earth) metal chlorides by setting the sample combustion temperature at 600°C. In a comparison with the bomb method, using nine sets of kitchen garbage and waste plastics, the bomb method yielded a 15%–25% lower value than the improved quartz furnace method. Combustion in the bomb was frequently incomplete, resulting in recovery losses of Cl and S. The average kitchen garbage involved 5.2 mg Cl/g, of which at least 24.1% would be converted to HCl. Plastics contained 23 mg Cl/g generating 88.1% HCl on average. In the same way, kitchen garbage contained 3.0 mg S/g, generating 52.3% SO _x , whereas plastics contained 1.1 mg S/g with 55.1% SO _x formation. Received: March 20, 2002 / Accepted: October 13, 2002     

Mechanisms contributing to the thermal analysis of waste incineration bottom ash and quantification of different carbon species

The focus of this study was to identify the main compounds affecting the weight changes of bottom ash (BA) in conventional loss on ignition (LOI) tests and to obtain a better understanding of the individual processes in heterogeneous (waste) materials such as BA. Evaluations were performed on BA samples from a refuse derived fuel incineration (RDF-I) plant and a hospital waste incineration (HW-I) plant using thermogravimetric analysis and subsequent mass spectrometry (TG–MS) analysis of the gaseous thermal decomposition products. Results of TG–MS analysis on RDF-I BA indicated that the LOI measured at 550 °C was due to moisture evaporation and dehydration of Ca(OH)₂ and hydrocalumite. Results for the HW-I BA showed that LOI at 550 °C was predominantly related to the elemental carbon (EC) content of the sample. Decomposition of CaCO₃ around 700 °C was identified in both materials. In addition, we have identified reaction mechanisms that underestimate the EC and overestimate the CaCO₃ contents of the HW-I BA during TG–MS analyses. These types of artefacts are expected to occur also when conventional LOI methods are adopted, in particular for materials that contain CaO/Ca(OH)₂ in combination with EC and/or organic carbon, such as e.g. municipal solid waste incineration (MSWI) bottom and fly ashes. We suggest that the same mechanisms that we have found (i.e. in situ carbonation) can also occur during combustion of the waste in the incinerator (between 450 and 650 °C) demonstrating that the presence of carbonate in bottom ash is not necessarily indicative for weathering. These results may also give direction to further optimization of waste incineration technologies with regard to stimulating in situ carbonation during incineration and subsequent potential improvement of the leaching behavior of bottom ash.     

The application and evaluation research of coffee residue ash into mortar

Coffee residue is usually regarded as a kind of agriculture waste; as its quantity increases the treatment of coffee residue will become an environmental problem. This research is innovative in that it derives the possibility of recycle application using coffee residue ash for cement replacement. In this research, coffee residue is burned in an electronic oven to three kinds of coffee residue ash at 500, 600 and 700 °C, and then appropriate apparatus is used to check the chemical and physical properties of these three types of coffee residue ash. After a general comparison, this study selected 500 and 600 °C coffee residue ashes with 2, 3, 5, 10 and 15 % cement replacements to make 5 cm³ cube mortar specimen to test different curing ages’ compressive strength. Through measurement and experiment, this research found that the compressive strength decreased by adding 500 or 600 °C coffee residue ash into the mortar. By considering waste reduction and practice application, this research derives that using the 600 °C coffee residue ash with 10 % replacement is better than others application, such using result also can get valuable efficiencies of financial and CO₂ reduction.     

Thermal processing of paper sludge and characterisation of its pyrolysis products

Paper sludge is a waste product from the paper and pulp manufacturing industry that is generally disposed of in landfills. Pyrolysis of paper sludge can potentially provide an option for managing this waste by thermal conversion to higher calorific value fuels, bio-gas, bio-oils and charcoal. This work investigates the properties of paper sludge during pyrolysis and energy required to perform thermal conversion. The products of paper sludge pyrolysis were also investigated to determine their properties and potential energy value. The dominant volatile species of paper sludge pyrolysis at 10 °C/min were found to be CO and CO₂, contributing to almost 25% of the paper sludge dry weight loss at 500 °C. The hydrocarbons (CH₄, C₂H₄, C₂H₆) and hydrogen contributed to only 1% of the total weight loss. The bio-oils collected at 500 °C were primarily comprised of organic acids with the major contribution being linoleic acid, 2,4-decadienal acid and oleic acid. The high acidic content indicates that in order to convert the paper sludge bio-oil to bio-diesel or petrochemicals, further upgrading would be necessary. The charcoal produced at 500 °C had a calorific value of 13.3 MJ/kg.     

Reduction–melting combined with a Na2CO3 flux recycling process for lead recovery from cathode ray tube funnel glass

With large quantity of flux (Na₂CO₃), lead can be recovered from the funnel glass of waste cathode-ray tubes via reduction–melting at 1000 °C. To reduce flux cost, a technique to recover added flux from the generated oxide phase is also important in order to recycle the flux recovered from the reduction–melting process. In this study, the phase separation of sodium and the crystallization of water-soluble sodium silicates were induced after the reduction–melting process to enhance the leachability of sodium in the oxide phase and to extract the sodium from the phase for the recovery of Na₂CO₃ as flux. A reductive atmosphere promoted the phase separation and crystallization, and the leachability of sodium from the oxide phase was enhanced. The optimum temperature and treatment time for increasing the leachability were 700 °C and 2 h, respectively. After treatment, more than 90% of the sodium in the oxide phase was extracted in water. NaHCO₃ can be recovered by carbonization of the solution containing sodium ions using carbon dioxide gas, decomposed to Na₂CO₃ at 50 °C and recycled for use in the reduction–melting process.     

Chemical Recycling of Polyamide Waste at Various Temperatures and Pressures Using High Pressure Autoclave Technique

Chemical recycling of polyamide waste in water was studied using 0.5 L high pressure autoclave at temperatures of 150, 200, 210, 220,230 and 240 °C and at various pressures of 100, 200, 300, 400, 500, 600 and 700 psi (pound per square inch). Viscosity average molecular weight of the polyamide waste sample was determined by Ostwald method and recorded as 1.928 × 10³. The reaction was found to be first order with velocity constant in order of 10⁻² min⁻¹. The velocity constant and percent conversion of depolymerization reaction at 240 °C and 700 psi pressure were recorded as 2.936 × 10⁻² min⁻¹ and 99.99% respectively. The velocity constant was obtained on the basis of measurement of amine value. Kinetic and thermodynamic parameters such as energy of activation, frequency factor, enthalpy of activation were found to be 10.6 kJ mole⁻¹, 0.3719 min⁻¹ and 6.3 kJ mole⁻¹ respectively, at the optimum conditions for maximum depolymerization of polyamide waste.     

Synthesis of hydrogarnet from molten slag and its hydrogen chloride fixation performance at high temperature

Hydrogarnet was synthesized hydrothermally below 200°C using molten slag obtained from municipal solid waste. For comparison, it was also synthesized using pure-phase CaO–Al₂O₃–SiO₂–H₂O, as reported previously. The structural and textural properties of this material were investigated using various analytical and spectroscopic techniques such as X-ray diffraction, X-ray fluorescence spectrometry, atomic absorption spectrometry (AAS), thermogravimetry/differential thermal analysis, Fourier transform infrared spectroscopy, and scanning electron microscopy. The Cl⁻ fixation ability of hydrogarnet was investigated in the temperature range 500–800°C in a fixed-bed flow reactor using a HCl concentration (1000 p.p.m.v.) similar to that of incinerator exhaust gas. Under these experimental conditions, the hydrogarnet was capable of reducing the HCl gas level to less than 1 p.p.m.v. Analysis of the spent catalyst revealed that the hydrogarnet was being transformed into wadalite and CaCl₂ at high temperatures. The elution test for chromium ions in hydrogarnet obtained from slag was also used, and it was found that chromium ions were not eluted from hydrogarnet. Received: January 27, 2001 / Accepted: October 11, 2001     

Recovery of rare earth elements from waste fluorescent phosphors: Na2O2 molten salt decomposition

In this paper, an efficient recovery of rare earth elements from waste fluorescent phosphors has been reported and the novel process of alkali fusion and acid leaching has been proposed. The experimental results have shown that the key for efficient recycling is the complete dissolution of waste fluorescent phosphors. The Na₂O₂-to-waste mass ratio, calcination temperature and reactive time play considerable roles in rare earth elements extraction during the alkali fusion process. The optimal conditions in terms of temperature, time and Na₂O₂-to-waste mass ratio are 650 °C, 15 min and 2:1, respectively, under which more than 99.5 % rare earth elements are extracted. The possible reaction mechanism of alkali fusion has been proposed.     

Copper stabilization in beneficial use of waterworks sludge and copper-laden electroplating sludge for ceramic materials

A promising strategy for effectively incorporating metal-containing waste materials into a variety of ceramic products was devised in this study. Elemental analysis confirmed that copper was the predominant metal component in the collected electroplating sludge, and aluminum was the predominant constituent of waterworks sludge collected in Hong Kong. The use of waterworks sludge as an aluminum-rich precursor material to facilitate copper stabilization under thermal conditions provides a promising waste-to-resource strategy. When sintering the mixture of copper sludge and the 900 °C calcined waterworks sludge, the CuAl₂O₄ spinel phase was first detected at 650 °C and became the predominant product phase at temperatures higher than 850 °C. Quantification of the XRD pattern using the Rietveld refinement method revealed that the weight of the CuAl₂O₄ spinel phase reached over 50% at 850 °C. The strong signals of the CuAl₂O₄ phase continued until the temperature reached 1150 °C, and further sintering initiated the generation of the other copper-hosting phases (CuAlO₂, Cu₂O, and CuO). The copper stabilization effect was evaluated by the copper leachability of the CuAl₂O₄ and CuO via the prolonged leaching experiments at a pH value of 4.9. The leaching results showed that the CuAl₂O₄ phase was superior to the CuAlO₂ and CuO phases for immobilizing hazardous copper over longer leaching periods. The findings clearly indicate that spinel formation is the most crucial metal stabilization mechanism when sintering multiphase copper sludge with aluminum-rich waterworks sludge, and suggest a promising and reliable technique for reusing both types of sludge waste for ceramic materials.     

Pore structure and adsorption properties of carbonized material prepared from waste paper

We have already reported the adsorptivity and pore structure of activated carbon made from waste newspaper in order to use the waste paper for purposes other than paper-making stock. However, manufacturing the activated carbon may not necessarily be an advantageous method based on environmental concerns and the effective use of the resource because the reaction during the activating process is endothermic and the amount of carbon consumed is significant. Here, we examine the pore structure and adsorption properties of waste newspaper used as an adsorbent in the form of a carbonized material. Waste newspaper was carbonized for 2 h in the temperature range 400°–1000°C. The specific surface area of the carbonized material obtained, 418 m²/g, was highest for the sample carbonized at 800°C, which was equal to or greater than that of commercially available charcoal. Moreover, the iodine adsorption number of 581 mg/g was the highest and the rate of adsorption was the fastest for the sample carbonized at 800°C. However, the humidity control capability was highest for the material carbonized at 600°–700°C. It has been determined that it is advantageous to carbonize waste paper at 800°C in order to use the carbonized material as an adsorbent, while carbonization at 600°–700°C is more advantageous for use as a humidity control material. Received: June 23, 2000 / Accepted: January 17, 2001     

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.     

The behaviors of H2, CH4, C2H4 and C3H6 from the decomposition of polypropylene by NiO/Si–Al catalyst

The purpose of this study was to investigate the possibility of light gases produced from polypropylene, specifically hydrogen. In particular, we examined the effect of operating conditions on gaseous product and compositions in the catalytic cracking of polypropylene. We also characterized the gaseous product generated from polypropylene cracking. The feedstock (2.0 g) mixed with NiO/SiO₂–Al₂O₃ (Si–Al) was used, under non-isothermal conditions at low temperature range between 380 and 500 °C. Argon gas was used to carry the pyrolyzed gas, and the gas collected in a tedlar bag was analyzed for its behavior. We observed the behavior of major gases (H₂, CH₄, C₂H₄ and C₃H₆, etc.) according to reaction time and temperature. Finally, the effect of reaction conditions on evolved gases from catalytic cracking of polypropylene was analyzed.     

Production of gaseous fuel from refuse plastic fuel via co-pyrolysis using low-quality coal and catalytic steam gasification

In this study, refuse plastic fuel (RPF) was copyrolyzed with low-quality coal and was gasified in the presence of a metal catalyst and steam. Some metal catalysts, such as Ni, NiO, and Mg, and mixtures of these with base promoters such as Al₂O₃ and Fe₂O₃ were employed in the pyrolysis and gasification processes to convert the synthesis gas into more valuable fuel gas. The operating temperatures for the pyrolysis and gasification were between 700° and 1000°C. The experimental parameters were the operating temperature, catalyst type, basic promoter type, and steam injection amount. Solid fuel samples (5 g) were fed into a semibatch-type quartz tube reactor when the reactor reached the designated temperature. The synthesis gas was analyzed by gas chromatography. The use of low-quality coal as fuel in co-pyrolysis with RPF was explored. For the co-pyrolysis of RPF and low-quality coal, the effectiveness of the catalysts for fuel gas production followed the order Mg > NiO > Ni. In catalytic gasification of RPF, the addition of Al₂O₃ seemed to reduce the activity of the corresponding catalysts Ni and Mg. The maximum fuel gas yield (92.6%) was attained when Mg/Fe₂O₃ was used in steam gasification at 1000°C.