Combustible and incombustible speciation of Cl and S in various components of municipal solid waste

Chlorine (Cl) and sulfur (S) in municipal solid waste (MSW) are important reactive elements during combustion. They generate the acidic pollutants HCl and SOx, and, furthermore, produce and suppress organic chlorinated compounds. Nevertheless, few practical reports about Cl and S content in MSW have been published. In combustion and recycling processes, both combustible Cl and S, and incombustible Cl and S species are equally important. This paper presents the results of a comprehensive study about combustible and incombustible Cl and S in MSW components, including kitchen garbage, paper, textiles, wood and leaves, plastics and small chips. By integrating this collected data with data about MSW composition, not only the overall content of Cl and S in MSW, but also the origins of both combustible and incombustible Cl and S were estimated. The average Cl content in bulk MSW was 3.7 g/kg of raw MSW, of which 2.7 and 1.0 g/kg were combustible and incombustible, respectively. The Cl contribution from plastics was 76% and 27% with respect to combustible and incombustible states. The average S content in bulk MSW was 0.81 g/kg of raw MSW, of which 0.46 g/kg was combustible and 0.35 g/kg was incombustible. Combustible S was mainly due to synthetic textiles, while incombustible S was primarily from paper.     

Carbon materials-catalyzed hydroliquefaction of flame-retardant plastics in organic solvents

Flame-retardant plastics, such as desktop and laptop personal computer bodies, could be completely liquefied by carbon materials-catalyzed hydroliquefaction in tetralin without using H₂ as a hydrogen source. Active carbons with larger surface areas (1450–3450 m²/g) acted as superior catalysts in transferring tetralin hydrogens to plastics. On the other hand, carbon blacks and fullerene-rich soot were less active catalysts. Graphite and mesocarbon microbeads did not show any catalytic effects. Benzene, toluene, and ethylbenzene were obtained as recyclable hydrocarbons; their total amounts varied from 4 wt% to 12 wt% depending on the types of plastics and the carbon materials used. Organic bromides such as polybromodioxins were not contained in the gases and oils of the product. Received: July 19, 2000 / Accepted: September 17, 2000     

Trends in Chemical Composition of Wet-only Precipitation at Rural French Monitoring Stations Over the 1990–2003 Period

The long-term monitoring of precipitation and its chemical composition are important for identifying trends in rain quality and for assessing the effectiveness of pollution control strategies. A statistical test has been used to the atmospheric concentrations measured in the French rural monitoring network (MERA) in order to bring out spatio-temporal trends in precipitation quality in France over the period 1990–2003. The non-parametric Mann–Kendall test which has been developed for detecting and estimating monotonic trends in the time series was used and applied in our study at annual values of wet-only precipitation concentrations. The emission data suggest that SO₂ and NO _x emissions decreased (−3.3 and −2.0% year⁻¹, respectively) contrary to NH₃ emissions that increased slightly (+0.2% year⁻¹) over the period 1990–2002 in France. On the national scale, the pH values have a significant decreasing trend of −0.025 ± 0.02 unit pH year⁻¹. and concentrations in precipitation have a significant decreasing trend, −3.0 ± 1.6 and −3.3 ± 0.6% year⁻¹, respectively, corresponding with the downward trends in SO₂ emissions in France (−3.3% year⁻¹). A good correlation (R ² = 0.84) between SO₂ emissions and concentrations was obtained. The decreasing trend of was more significant (−5.4 ± 5.2% year⁻¹) than that of (−1.3 ± 2.4% year⁻¹). Globally, the concentration of the major ions showed a clear downward trend including marine and alkaline ions. In addition, the relative contribution of HNO₃ to acidity precipitation increased by 51% over the studied period.     

Waste plastics recycling by an entrained-flow gasifier

We studied an entrained-flow gasification process which efficiently converts waste plastics to energy at a high energy recovery rate. Waste plastics, after being shredded to <8 mm or <14 mm, were fed into an entrained-flow gasifier with air and oxygen. In the gasifier, organic substances were pyrolyzed, partially combusted, and then converted into synthetic gas (CO, H₂) at a high temperature (over 1600 K). The clarified gasification characteristics were that the lower heat value (LHV) of the product gas was over 4.2 MJ/Nm³ and the cold gas efficiency was approximately 60%. Other inert substances in the wastes such as ashes and metals were melted into slag and condensed on bag filters. The bag filters and a water scrubber removed impurities such as dusts, heavy metals, and hydrogen halides from the product gases. Solid hydrocarbons, which include char and soot, were removed at a hot cyclone and on the bag filters. Received: July 19, 2000 / Accepted: October 3, 2000     

Studies on the dechlorination and oil-production technology of waste plastics

 Recycle technology for waste plastics containing polyvinyl chloride (PVC) has been developed in the Hokkaido National Industrial Research Institute for the production of solid and liquid fuel, and has established a recycling process which includes a dechlorination process for PVC plastics, and a two-stage catalytic pyrolysis process for plastics using zeolite catalysts. The dechlorination equipment consists of a two-axis screw extruder with a heating element, which can remove chlorine up to 99.9 wt. % from PVC containing plastics as hydrogen chloride. The product had about 44 000 kJ/kg calorific value and was fed into the next oil production process, although it could also be used as a solid fuel. Natural and synthetic zeolite were used as catalysts for the two-stage catalytic process, which produced a light oil with a boiling point which was between those of kerosene and gasoline. The yield of this oil reached 82 wt. %. The chemical type was analyzed using liquid chromatography, and was found to have many aromatic compounds. These technologies make it possible to produce a nonpolluting, high-calorie solid fuel and a liquid fuel very efficiently. Received: July 19, 2000 / Accepted: September 21, 2000     

Characterization of air emissions and residual ash from open burning of electronic wastes during simulated rudimentary recycling operations

Air emissions and residual ash samples were collected and analyzed during experiments of open, uncontrolled combustion of electronic waste (e-waste), simulating practices associated with rudimentary e-waste recycling operations. Circuit boards and insulated wires were handled separately to simulate processes associated with metal recovery. The average emissions of polychlorinated dibenzodioxins and dibenzofurans (PCDD/PCDFs) were 92 ng toxic equivalency (TEQ)/kg [n = 2, relative standard deviation (RSD) = 98%] and 11 900 ng TEQ/kg (n = 3, RSD = 50%) of the initial mass of the circuit boards and insulated wire, respectively. The value for the insulated wire is about 100 times higher than that for backyard barrel burning of domestic waste. The emission concentrations of polybrominated dibenzodioxins and dibenzofurans (PBDD/PBDFs) from the combustion of circuit boards were 100 times higher than for their polychlorinated counterparts. Particulate matter (PM) sampling of the fly ash emissions indicated PM emission factors of approximately 15 and 17 g/kg of the initial mass for the circuit boards and insulated wire, respectively. Fly ash samples from both types of e-waste contained considerable amounts of several metallic elements and halogens; lead concentrations were more than 200 times the United States regulatory limits for municipal waste combustors and 20 times those for secondary lead smelters. Leaching tests of the residual bottom ash showed that lead concentrations exceeded U.S. Environmental Protection Agency landfill limits, designating this ash as a hazardous waste.     

Polyethylene conversion by partial oxidation in supercritical water

This paper gives the results of partial oxidation experiments of polyethylene (PE) in supercritical water (SCW). The experiments were carried out at a reaction temperature of 693K and a reaction time of 30 min using 6 cm³ of a batch-type reactor. The loaded sample weight was 0.3 g and there was 2.52 g water (0.42 g/cm³). The ratio of oxygen atoms to carbon atoms was 0.3. The results show a significant CO formation in O₂–SCW, and the 1-alkene/n-alkane ratio in partial oxidation was higher than that in SCW pyrolysis. These results suggest the possibility of the hydrogenation of hydrocarbon through partial oxidation followed by a water–gas shift reaction. Received: July 19, 2000 / Accepted: September 28, 2000     

Fabric-filter-supported catalyst for removal of harmful solid and gaseous compounds in municipal waste incinerator exhaust gas: characteristics of NO x reduction

We have investigated a fabric-filter-supported catalyst for removing harmful solid and gaseous compounds simultaneously from municipal incinerator exhaust gas. We studied the ways in which the efficiency of NO _x removal is influenced by filter temperature, gas flow rate, and catalyst content. The reduction of the catalyst content by mechanical reverse washing was investigated, and the state of the catalyst supported in the fabric filter was also observed using a scanning electron microscope. The catalyst supported by the fabric filter showed a removal efficiency above 75% when the filter temperature was 200°C, the gas flow rate was 1 m/min, and the catalyst content of the fabric filter was above 300 g/m². The catalyst was supported uniformly on the fibers of the fabric filter, and fine catalyst particles remained on the fibers after mechanical reverse washing. Received: October 15, 1997 / Accepted: March 19, 1999     

Decomposition of mixed plastics consisting of polypropylene and polyethylene terephthalate into oils over titania/silica catalysts

The catalytic decomposition of mixed plastics consisting of polypropylene (PP) and polyethylene terephthalate (PET) has been investigated over titania/silica catalysts at 698 K. The yield of oil produced was about 70%, and the large amounts of C₁₈₊ hydrocarbons this contained was from the aromatics in PET. Gas was also produced, including C₃–C₅ hydrocarbons. The carbon-number fractions in the oil was influenced by the PET/(PP + PET) ratios and the catalyst weight. The titania/silica catalysts could be used repeatedly, and after they had been fouled, could be regenerated. From the Fourier Transform Infrared (FT–IR) spectroscopic data of adsorbed pyridine on the catalyst surface, most of the acid sites of the titania/silica catalysts were found to be Lewis sites where the hydride abstracted from PP pyrolysates react with PET pyrolysates to form oil and gas. Received: July 19, 2000 / Accepted: October 20, 2000     

Optimization of thermo-chemical hydrolysis of kitchen wastes

Municipal Solid Wastes (MSWs) in Greece consist mainly of fermentable organic material such as food scraps (～50%) and paper residuals (～20%). The aim of this work was to study the thermo-chemical pretreatment of the kitchen waste (KW) fraction of MSW focusing on biotechnological exploitation of pretreated wastes for biofuel production. A representative sample of municipal food residues was derived by combining weighted amounts of each individual type of residue recognized in daily samples obtained from the University of Patras’ students restaurant located at the Students Residence Hall (Greece). Chemical pretreatment experiments of the representative KW sample were performed using several types of chemical solutions (i.e. H₂SO₄, HCl, NaOH, H₂SO₃) of different solute concentration (0.7%, 1.5%, 3%) at three temperatures (50, 75, 120 °C) and a range of residence times (30–120 min). Optimized results proved that chemical pretreatment of KW, using either 1.12% HCl for 94 min or 1.17% HCl for 86 min (at 100 °C), increased soluble sugars concentration by 120% compared to untreated KW. The increase of soluble sugars was mainly attributed to the mono-sugars glucose and fructose.     

Dehydrochlorination behavior of polyvinyl chloride and utilization of carbon residue: effect of plasticizer and inorganic filler

The dehydrochlorination behavior of plasticizer (DOP) and inorganic filler (CaCO₃) contained in PVC samples and the properties of the activated carbons produced from those carbon residues have been investigated. In the dehydrochlorination process, both additives contributed not only to a decrease in HCl yield but also to the prolonged evolution of HCl. Part of the Cl species were observed to be stabilized as CaCl₂ by reaction with calcium ions when CaCO₃ was added. More than 80% of chlorine removal was achieved in all samples at 533 K. The use of potassium as an activation agent led to the production of activated carbon with a specific surface area greater than 1000 m²/g at the low temperature of 1023 K and assisted also in the elimination of residual Cl species by the formation of KCl during activation. Chemical Feedstock Recycling & Other Innovative Recycling Techniques 6     

Adsorbable organic halides (AOX), AOX formation potential, and PCDDs/DFs in landfill leachate and their removal in water treatment processes

Adsorbable organic halides (AOX) and AOX formation potential (AOXFP) were investigated in 46 landfill lea-chates as potentially toxic parameters. AOX in landfill leachate was within the range <10–2200 μg Cl/l, and AOXFP was within 51–15 000 μg Cl/l. AOX and AOXFP correlated with chemical oxygen demand (COD). AOX discharge from closed landfills was generally lower than that from operating landfills. The molar ratio of AOXFP/total organic carbon (TOC) suggested that organic compounds in a leachate have a double bond every 15–190 carbons under the supposition that one chlorine would add to one double bond. The five landfills discharging high-level AOXFP (>4000 μg Cl/l) were all landfills where sludge had been dumped. The removal efficiencies of three parameters through leachate treatment processes were as follows: polychlorinated dibenzo-dioxins/dibenzo-furans (PCDDs/DFs) > TOC > AOX. PCDDs/DFs were substantially removed at p.p.t. levels, while AOX was hardly removed at relatively low levels. Received: February 14, 2000 / Accepted: January 9, 2001     

Determination of nitrous oxide, methane, and ammonia emissions from a swine waste composting process

The amounts of harmful gas emissions from the process of composting swine waste were determined using an experimental composting apparatus. Forced aeration (19.2–96.1 l/m³/min) was carried out continuously, and exhaust gases were collected and analyzed periodically. With weekly turning and the addition of a bulking agent in order to decrease the moisture content and increase air permeability, the temperature of most of the contents rose to 70°C and composting was complete within 3–5 weeks. NH₃, CH₄, and N₂O emissions were high in the early stage of composting. About 10%–25% of the nitrogen in the raw material was lost as NH₃ gas during composting. The emission rate of NH₃ mainly depended on the aeration rate, so that as the aeration rate rose, the level of NH₃ emissions increased. The CH₄ and N₂O emissions could be kept lower with adequate treatment at more than 40 l/m³/min aeration. N₂O may be mainly the result of the denitrification of NO _x -N in the additional matured compost used as a composting accelerator. Received: September 11, 1998 / Accepted: November 8, 1999     

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     

Factors affecting the concentration of bisphenol A in leachates from solid waste disposal sites and its fate in treatment processes

 The concentrations of bisphenol A (BPA) contained in landfill leachates from solid waste disposal sites were measured. The concentrations of BPA contained in leachates from industrial waste sites were in the range below the detection limit to 2800 μg/l, while those from municipal sites were in the range 26–8400 μg/l. The leachates from ash-rich sites contained relatively lower concentrations of BPA compared with organic-rich leachates. It is suggested that BPA concentration increases with time after the completion of reclamation in the case of ash-rich sites, whereas the concentration of BPA decreases with time in the case of organic-rich sites. A 7-year survey on a site in Japan showed neither a decrease nor an increase in the concentration of BPA during on-going reclamation. A leachate from a site in the Philippines contained high concentrations of BPA. A slight positive correlation was found between BPA concentrations and total organic carbon (TOC). A major portion of the BPA in leachates was found in dissolved and organic unassociated fractions, which cannot be precipitated by coagulation. More than 99.9% of the BPA contained in raw leachates was removed by a conventional series of treatment processes consisting of biological treatment, coagulation, sedimentation, sand filtration, and activated carbon adsorption. Received: May 29, 2002 / Accepted: October 17, 2002     

Behavior of bromine on the thermal decomposition of paper-based phenolic laminate wastes

We investigated the thermal properties and behavior of bromine on the thermal decomposition of paper-based phenolic laminate wastes containing polybrominated flame retardants. The thermal properties of the phenolic laminate wastes were measured with a thermogravimeter and a conduction-type scanning calorimeter (TG-CSC). The weight loss of the wastes on thermal decomposition was mainly in three phases between 40°C and 600°C. The enthalpy (ΔH) of the thermal decomposition was 104 cal/g. The material balance of the decomposition components was measured with batch-type thermal decomposition equipment. The ratios of carbon residue, liquid, and gas on decomposition at 800°C in a vacuum were 37 wt. %, 48 wt. %, and 15 wt. %, respectively. The bromine contents in the carbon residue and liquid were less than 0.02 wt. % and 10 wt. %, respectively. These results are useful both in the carbonization process of these wastes and in the application of carbon residue as carbon materials. Received: August 11, 2000 / Accepted: March 7, 2001     

Simple removal of dioxins by injecting combustion gas into water

A simple, low-cost method for suppression of dioxins/furans (hereinafter referred to as dioxins) is required because many middle- and, especially, small-scale incinerators have fallen into disuse or have been dismantled because of the high running and system costs of measures for the suppression of dioxins. Therefore, the purpose of the present study was to develop a simple removal method for dioxins from combustion gas and to evaluate the basic removal rate of dioxins. The removal method for suspended matter in a gas mixture (cold model) and dioxins in exhaust gases (hot model) has been investigated by means of gas injection into water, the mechanism of which is that the suspended matter in the gas gathers at the gas–liquid interface. In the cold model, the removal ratio of fine particles (R_P) by gas injection into water was reproduced well by the following equation: R_P (%) = 100 × {1−exp(−0.8 · S_S · t_C)}, where S_S (cm²/cm³) is the specific surface area of bubbles and t_C (s) is the residence time of bubbles in water. The removal ratio of fine particles increased as the product S_s · t_C increased. In a hot model using the exhaust gas from combustion experiments of polyvinyl chloride, the removal ratio of dioxins (R_D) by injecting the exhaust gas into water was estimated by the following equation: R_D (%) = 100 × {1−exp(−0.8 · S_S · t_C · C_D0 ^0.07)}, where C_D0 [ng/cm³ (at standard temperature and pressure)] is the dioxins concentration in the exhaust gas before injection into water. R_D depends greatly on the specific surface area of bubbles and the residence time of the bubbles in water, and only weakly on the dioxins concentration in the exhaust gas. Injection of the exhaust gas into water has been shown to be effective and was evaluated as a simple method for the removal of dioxins from exhaust gas.     

PM<Subscript>10</Subscript> and Ultrafine Particles Counts In-Vehicle and On-Road in the Athens Area

This work presents the first results of a study concerning on-road and in-vehicle exposure to particulate matter in the area of Athens. PM₁₀ concentration measurements were conducted by TSI DustTrak, while driving along routes with different characteristics of traffic density, during September 2003–March 2004. Concurrent measurements of the ultrafine particles (UFPs) number concentration were also conducted, by condensation particle counter during part of the days. Pedestrian exposure to PM₁₀ and UFPs was also studied through stationary measurements on the kerbside of selected roads on November 2003 and February 2004. A major avenue, a heavy-trafficked road across a children hospital and two central roads, one in a residential and one in a commercial area were selected for measurement. The results indicate that every day commuters are exposed to significant concentration levels. Higher exposures were observed in heavy-trafficked areas and during rush hours. Mean PM₁₀ in-vehicle and on-road concentrations ranged from 30–320 μg/m³ and 70–285 μg/m³, respectively. The ultrafine particles number concentrations were in the range of 5.0 × 10⁴–17.3 × 10⁴ particles/cm³ in-vehicle and 3.1 × 10⁴–7.3 × 10⁴ particles/cm³ on the kerbside of a central residential road. Both PM₁₀ and UFPs concentrations presented repeated short-term peak exposures. The results clearly point out the importance of the road microenvironment (in-vehicle and on kerbside) for population exposure in urban areas.     

Characteristics of air pollution in Beijing during sand-dust storm periods

In the Beijing area, March and April have the highest frequency of sand-dust weather. Floating dust, blowing sand, and dust storms, primarily from Mongolia, account for 71%, 20%, and 9% of sand-dust weather, respectively. Ambient air monitoring and analysis of recent meteorological data from Beijing sand-dust storm periods revealed that PM₁₀ mass concentrations during dust storm events remained at 1500 μg m⁻³, which is five to ten times higher than during non-dust storm periods, for fourteen hours on both April 6 and 25, 2000. During the same period, the concentrations in urban areas were comparable to those in suburban areas, while the concentrations of gaseous pollutants, such as SO₂, NO _x , NO₂, and O₃, remained at low levels, owing to strong winds. Furthermore, during sand-dust storm periods, aerosols were created that consisted not only of many coarse particles, but also of a large quantity of fine particles. The PM_2.5 concentration was approximately 230 μg m⁻³, accounting for 28% of the total PM₁₀ mass concentration. Crustal elements accounted for 60–70% of the chemical composition of PM_2.5, and sulfate and nitrate for much less, unlike the chemical composition of PM_2.5 on pollution days, which was primarily composed of sulfates, nitrates, and organic material. Although the very large particle specific surface area provided by dust storms would normally be conducive to heterogeneous reactions, the conversion rate from SO₂ to SO₄ ²⁻ was very low, because the relative humidity, less than 30%, was not high enough.     

Desulfurization of coke oven gas from the coking of coking coal blended with a sorbent and waste plastic

A new way to implement the simultaneous reutilization of solid waste, the desulfurization of coke oven gas (COG), and even the desulfurization of coke by the co-coking of coking coal (CC) and waste plastic (WP) blended with a sorbent is proposed; the evolution of H₂S and the removal efficiency of H₂S from COG during the co-coking process were investigated in a lab-scale cylindrical reactor. The experimental results indicated that for the coking of CC blended with ZnO, Fe₂O₃, or blast furnace dust (BFD) as a sorbent, the instantaneous concentration of H₂S in COG was lower than 500 mg/m³ (which meets the technical specification requirement of the Chinese Cleaner Production Standard–Coking Industry, HJ/T 126-2003) when the molar ratio between the key component of the sorbent and the volatile S in CC or the CC/WP blend, n _Zn+Fe/n _S, was about 1.2 for ZnO and Fe₂O₃, but not for BFD under the same conditions, suggesting that ZnO and Fe₂O₃ are promising sorbents, but that BFD must be treated chemical or thermally before being used as a sorbent because of the size and complicated nature of the influence of its phase/chemical composition on its desulfurization ability. However, for the co-coking of CC and WP blended with ZnO as a sorbent, n _Zn+Fe/n _S must increase to 1.4 and 1.7 for 100/2 and 100/5 blends of CC/WP, respectively, to ensure a satisfactory efficiency for H₂S removal from COG. Part of this paper was presented at the International Symposium on EcoTopia Science 2005 (ISET05), Aug 8–9, 2005, Chikusa-ku, Nagoya, Japan