Pilot-scale studies on the effect of bromine addition on the emissions of chlorinated organic combustion by-products

The addition of brominated organic compounds to the feed of a pilot-scale incinerator burning chlorinated waste has been found previously, under some circumstances, to enhance emissions of volatile and semivolatile organic chlorinated products of incomplete combustion (PICs) including polychlorinated dibenzo-p-dioxins and polychlorinated dibenzofurans (PCDDs/Fs). This phenomenon appears to be sensitive to temperature and combustion conditions. This paper reports on a study to evaluate the emissions of organic combustion by-products while varying amounts of bromine (Br) and chlorine (Cl) are being fed into a pilot-scale incinerator burning surrogate waste materials. The surrogate waste was fed at a constant molar halogen input rate, with varying Br/Cl molar ratios. In these tests, an approximately 30% decrease in the total PCDD/F concentrations due to the addition of Br was observed. This decrease appears to be a decrease only in the chlorinated dioxin and furan species; other halogenated dioxins and furans were formed instead. PCDD/F homologue distribution shifted towards the higher chlorinated species. Perhalogenated or nearly perhalogenated mixed bromo-chloro furans were also observed in quantities that could potentially account for the observed decrease in PCDDs/Fs. This research illustrates the need for careful trial burn planning if Br will be present in the facility's feed-stock during normal operation.     

Comparative environmental analysis of waste brominated plastic thermal treatments

The aim of this research activity is to investigate the environmental impact of different thermal treatments of waste electric and electronic equipment (WEEE), applying a life cycle assessment methodology. Two scenarios were assessed, which both allow the recovery of bromine: (A) the co-combustion of WEEE and green waste in a municipal solid waste combustion plant, and (B) the staged-gasification of WEEE and combustion of produced syngas in gas turbines. Mass and energy balances on the two scenarios were set and the analysis of the life cycle inventory and the life cycle impact assessment were conducted. Two impact assessment methods (Ecoindicator 99 and Impact 2002+) were slightly modified and then used with both scenarios. The results showed that scenario B (staged-gasification) had a potentially smaller environmental impact than scenario A (co-combustion). In particular, the thermal treatment of staged-gasification was more energy efficient than co-combustion, and therefore scenario B performed better than scenario A, mainly in the impact categories of "fossil fuels" and "climate change". Moreover, the results showed that scenario B allows a higher recovery of bromine than scenario A; however, Br recovery leads to environmental benefits for both the scenarios. Finally the study demonstrates that WEEE thermal treatment for energy and matter recovery is an eco-efficient way to dispose of this kind of waste.     

Determination of total chlorine and bromine in solid wastes by sintering and inductively coupled plasma-sector field mass spectrometry

A sample preparation method based on sintering, followed by analysis by inductively coupled plasma-sector field mass spectrometry (ICP-SFMS) for the simultaneous determination of chloride and bromide in diverse and mixed solid wastes, has been evaluated. Samples and reference materials of known composition were mixed with a sintering agent containing Na₂CO₃ and ZnO and placed in an oven at 560 °C for 1 h. After cooling, the residues were leached with water prior to a cation-exchange assisted clean-up. Alternatively, a simple microwave-assisted digestion using only nitric acid was applied for comparison. Thereafter the samples were prepared for quantitative analysis by ICP-SFMS. The sintering method was evaluated by analysis of certified reference materials (CRMs) and by comparison with US EPA Method 5050 and ion chromatography with good agreement. Median RSDs for the sintering method were determined to 10% for both chlorine and bromine, and median recovery to 96% and 97%, respectively. Limits of detection (LODs) were 200 mg/kg for chlorine and 20 mg/kg for bromine. It was concluded that the sintering method is suitable for chlorine and bromine determination in several matrices like sewage sludge, plastics, and edible waste, as well as for waste mixtures. The sintering method was also applied for determination of other elements present in anionic forms, such as sulfur, arsenic, selenium and iodine.     

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.     

Combustion and inorganic bromine emission of waste printed circuit boards in a high temperature furnace

High temperature combustion experiments of waste printed circuit boards (PCBs) were conducted using a lab-scale system featuring a continuously-fed drop tube furnace. Combustion efficiency and the occurrence of inorganic bromine (HBr and Br₂) were systematically studied by monitoring the main combustion products continuously. The influence of furnace temperature (T) was studied from 800 to 1400 °C, the excess air factor (EAF) was varied from 1.2 to 1.9 and the residence time in the high temperature zone (RT_HT) was set at 0.25, 0.5, or 0.75 s.Combustion efficiency depends on temperature, EAF and RT_HT; temperature has the most significant effect. Conversion of organic bromine from flame retardants into HBr and Br₂ depends on temperature and EAF. Temperature has crucial influence over the ratio of HBr to Br₂, whereas oxygen partial pressure plays a minor role. The two forms of inorganic bromine seem substantially to reach thermodynamic equilibrium within 0.25 s. High temperature is required to improve the combustion performance: at 1200 °C or higher, an EAF of 1.3 or more, and a RT_HT exceeding 0.75 s, combustion is quite complete, the CO concentration in flue gas and remained carbon in ash are sufficiently low, and organobrominated compounds are successfully decomposed (more than 99.9%).According to these results, incineration of waste PCBs without preliminary separation and without additives would perform very well under certain conditions; the potential precursors for brominated dioxins formation could be destroyed efficiently. Increasing temperature could decrease the volume percentage ratio of Br₂/HBr in flue gas greatly.     

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.     

Pyrolysis of mixtures of sewage sludge and manure: a comparison of the results obtained in the laboratory (semi-pilot) and in a pilot plant

A pilot-scale pyrolysis process was carried out for the treatment of a mixture of two types of waste, sewage sludge and cattle manure, comparing the results with others obtained under laboratory conditions (semi-pilot scale). The aim of this study was to obtain the energetic valorization of the products. Owing to the specific characteristics of the plant, two products were obtained from the process: gas and carbonized solid. As no liquid fraction was obtained, the gas fraction is a greater percentage made up of both condensable and non-condensable compounds, which were obtained separately at the laboratory scale. The pilot plant was designed so that the gases produced by thermolysis were burnt continuously in a combustion chamber, while the carbonized fraction was fed in batches for co-combustion. To determine composition and combustion ability, the gas and solid products from the pilot process were characterized by chromatographic analysis of the gaseous fraction and chemical analysis and programmed-temperature combustion of the carbonized solid. The composition of the combustion gases, rich in light hydrocarbons, and the carbon present in the carbonized fraction enable the energetic valorization of these products. The combustion gases were subjected to a cleaning process and their composition analysed twice: before and after the gas cleaning treatment. The study led to a positive assessment of the possible use of the process products as fuel, provided that the combustion gases are treated. As most of the sulphur and chlorine from the original waste are mainly concentrated in the solid fraction, the use of char as a fuel will depend on the effectiveness of clean-up techniques for combustion gases. During gas cleansing, neutralizing with sodium bicarbonate proved effective, especially for the acidic compounds HCl, HF and SO(2).     

Emissions from small-scale energy production using co-combustion of biofuel and the dry fraction of household waste

In sparsely populated rural areas, recycling of household waste might not always be the most environmentally advantageous solution due to the total amount of transport involved. In this study, an alternative approach to recycling has been tested using efficient small-scale biofuel boilers for co-combustion of biofuel and high-energy waste. The dry combustible fraction of source-sorted household waste was mixed with the energy crop reed canary-grass (Phalaris Arundinacea L.), and combusted in both a 5-kW pilot scale reactor and a biofuel boiler with 140-180 kW output capacity, in the form of pellets and briquettes, respectively. The chlorine content of the waste fraction was 0.2%, most of which originated from plastics. The HCl emissions exceeded levels stipulated in new EU-directives, but levels of equal magnitude were also generated from combustion of the pure biofuel. Addition of waste to the biofuel did not give any apparent increase in emissions of organic compounds. Dioxin levels were close to stipulated limits. With further refinement of combustion equipment, small-scale co-combustion systems have the potential to comply with emission regulations.     

Trace element partitioning in ashes from boilers firing pure wood or mixtures of solid waste with respect to fuel composition,chlorine content and temperature

Trace element partitioning in solid waste (household waste, industrial waste, waste wood chips and waste mixtures) incineration residues was investigated. Samples of fly ash and bottom ash were collected from six incineration facilities across Sweden including two grate fired and four fluidized bed incinerators, to have a variation in the input fuel composition (from pure biofuel to mixture of waste) and different temperature boiler conditions. As trace element concentrations in the input waste at the same facilities have already been analyzed, the present study focuses on the concentration of trace elements in the waste fuel, their distribution in the incineration residues with respect to chlorine content of waste and combustion temperature.Results indicate that Zn, Cu and Pb are dominating trace elements in the waste fuel. Highly volatile elements mercury and cadmium are mainly found in fly ash in all cases; 2/3 of lead also end up in fly ash while Zn, As and Sb show a large variation in distribution with most of them residing in the fly ash. Lithophilic elements such as copper and chromium are mainly found in bottom ash from grate fired facilities while partition mostly into fly ash from fluidized bed incinerators, especially for plants fuelled by waste wood or ordinary wood chips. There is no specific correlation between input concentration of an element in the waste fuel and fraction partitioned to fly ash. Temperature and chlorine content have significant effects on partitioning characteristics by increasing the formation and vaporization of highly volatile metal chlorides. Zinc and cadmium concentrations in fly ash increase with the incineration temperature.     

Residues characterisation from the fluidised bed combustion of East London’s solid recovered fuel

Waste thermal treatment in Europe is moving towards the utilisation of the combustible output of mechanical, biological treatment (MBT) plants. The standardisation of solid recovered fuels (SRF) is expected to support this trend and increase the amount of the generated combustion residues. In this work, the residues and especially the fly ashes from the fluidised bed combustion (FBC) of East London’s NCV 3, Cl 2, and Hg 1 class SRF, are characterised. The following toxicity indicators have been studied: leachable chlorine, organochlorides expressed as pentachlorobenzene and hexachlorobenzene, and the heavy metals Cu, Cr, Cd, Zn, Ni, and Pb. Furthermore the mineralogical pattern of the ashes has been studied by means of XRD and SEM–EDS. The results suggest that these SRF derived ashes have significantly lower quantities of Cu, Cd, Pb, Zn, leachable Cl, and organochlorides when compared to other literature values from traditional waste thermal treatment applications. This fact highlights the importance of modern separation technologies employed in MBT plants for the removal of components rich in metals and chlorine from the combustible output fraction of SRF resulting to less hazardous residues.     

End-of-life vehicle recycling and automobile shredder residue management in Japan

The Japanese Government introduced the Law on Recycling of End-of-Life Vehicles (ELV Recycling Law) in 2002. This law requires manufacturers to retrieve chlorofluorocarbons (CFCs), airbags, and automobile shredder residue (ASR) from ELVs and to properly recycle the remaining materials. This framework is compared with European ELV directives. Pilot-scale incineration plant testing has revealed a greater formation of by-product persistent organic pollutants (POPs) during the primary combustion of ASR compared to normal municipal solid waste. This may be attributed to the abundance of chlorine, Cu, and Fe in ASR, as Cu and Fe have been found to catalyze the formation of POPs under certain conditions. However, most by-product POPs were destroyed by the secondary combustion, and almost all were removed after flue gas treatment. The direct melting system is a shaft-type gasification and melting technology that has proved effective in many municipal solid waste applications. This system can be applied to ASR recycling for effective decomposition of brominated flame retardants and polybrominated dioxins.     

PCDD/F in source-sorted waste fractions and emissions from their co-combustion with reed canary-grass

The dry combustible fraction of source-sorted household waste, including material that would otherwise be recycled, was mixed with the energy crop reed canary-grass (Phalaris arundinacea L.), and combusted as briquettes in 150 and 600 kW biofuel-boilers without advanced cleaning systems. The source-sorted waste was further sorted and characterized according to its material and chemical contents. The bulk of the waste's chlorine content came from the non-package plastic fraction, whereas 90-95% of summation operator PCDD/F (74-90% of WHO-TEQ) originated from the textile fraction. The sources of the dioxins in the waste fractions are discussed. The balance of dioxin levels was negative, i.e., the amounts of dioxins output in the flue gas were lower than those input in the fuel, except when there were operational disturbances in the combustion. In one of the combustion trials the total levels of dioxins in the flue-gas and ashes were also lower than the input levels. The use of additional cleaning equipment will be needed to ensure that emissions of dioxins and hydrochloric acid will be below legal limits.     

Chlorine promotes antimony volatilization in municipal waste incineration

Antimony volatilization in municipal waste incineration was studied. Two municipal waste samples and antimony(III) oxide (Sb₄O₆) were heated to 500°C and 700°C in an air stream in a quartz furnace. The volatilization of Sb₄O₆ occurred more at 700°C that at 500°C. Conversely, antimony volatilization form municipal waste was stronger at 500°C than at 700°C. This implies that antimony from municipal waste is volatilized as chloride instead of oxide. The chlorine sources for antimony chlorination, a gas-phase reaction involving hydrochloric acid and a solid-phase reaction of inorganic chlorine, e.g., CaCl₂, were compared. Only the solid-phase reaction could offer enough active chlorine to induce chlorination of antimony oxide. Received: July 2, 1998 / Accepted: January 28, 1999     

The feasibility of converting solid waste into refuse-derived fuel 5 via mechanical biological treatment process

The aim of our study was to investigate the feasibility of utilizing solid waste after mechanical biological treatment (MBT) processing at a landfill site in Phitsanulok, Thailand, as refuse-derived fuel 5 (RDF-5). The waste composition, and physical and chemical characteristics of each waste fraction were determined to evaluate the suitability of the waste for recycling and reuse as RDF-5. Results showed that after MBT processing, the solid waste >40 mm in size was observed to have 33.8 MJ/kg of calorific value. The average concentrations of heavy metals were also found to be within the acceptable limit for plastic waste combustion, thus proving that MBT-processed solid waste >40 mm in size has high potential for use as RDF-5. The optimal weight ratio of MBT-processed solid waste and crude oil sludge for transformation into RDF-5 was found to be 80:20. With this optimum ratio, the average calorific values of the RDF-5 were determined to be 47 MJ/kg, with sulfur and chlorine contents of 0.16 and 0.74 %, respectively. The characteristics of the produced RDF-5 could meet the specified ASTM standards in terms of calorific value (>15 MJ/kg), and sulfur and chlorine contents. In addition, the compressive strength of the produced RDF-5 was also found to be suitable for compact storage and transportation without any damage. Finally, the energy production cost from this RDF-5 process was estimated as USD $0.05/kWh.     

Study on chlorine removal from mixture of waste plastics

The recycling of waste plastics that include plastics that contain chlorine, such as polyvinyl chloride, is difficult because the chlorine leads to the corrosion of equipment. Then, the dechlorination method of waste plastics containing chlorine (CCWP) that consists of a series of melt process and hot water process was examined. CCWP was put into the melt process with coal tar (HOB) and converter dust (CD) to inhibit the diffusion of the chlorine-containing gas. The results indicated that iron oxide of the principal element of CD combines with chlorine eliminated from CCWP, and forms water-soluble iron chloride on the melt process. HOB dissolves or adsorbs a part of the chlorine during the melt process, and inhibits the diffusion of the chlorine-containing gas. Approximately 98% of the chlorine in the CCWP reacts with CD and forms iron chloride, which can be extracted on the hot water process.     

Water-soluble characteristics of chlorine in char derived from municipal solid wastes

Chlorine in char derived from municipal solid waste (MSW) was characterized and quantified based on its water solubility: easily water-soluble, hardly water-soluble, and non-water-soluble chlorine. For that, a four-cycle process of water-washing, heating or carbonation were carried out. In order to confirm the characteristics of non-water-soluble chlorine, additional thermal treatment and an alkali-acid washing process were applied to washed char. It was found that a large particle size of char (0.5-1.0 mm) significantly contributed to the amount of non-water-soluble chlorine. Pulverization and HNO3-HF digestion were performed to identify a factor to interfere chlorine release from char with a large particle size. Pulverization was proven ineffective for release of non-water-soluble chlorine, whereas approximately 32% of non-water-soluble chlorine was extracted by HNO3-HF digestion. Therefore, the presence of non-water-soluble chlorine is likely to originate from its chemical property rather than simply from its physical one.     

The separation of waste printed circuit board by dissolving bromine epoxy resin using organic solvent

Separation of waste printed circuit boards (WPCBs) has been a bottleneck in WPCBs resource processing. In this study, the separation of WPCBs was performed using dimethyl sulfoxide (DMSO) as a solvent. Various parameters, which included solid to liquid ratio, temperature, WPCB sizes, and time, were studied to understand the separation of WPCBs by dissolving bromine epoxy resin using DMSO. Experimental results showed that the concentration of dissolving the bromine epoxy resin increased with increasing various parameters. The optimum condition of complete separation of WPCBs was solid to liquid ratio of 1:7 and WPCB sizes of 16 mm² at 145 °C for 60 min. The used DMSO was vapored under the decompression, which obtained the regenerated DMSO and dissolved bromine epoxy resin. This clean and non-polluting technology offers a new way to separate valuable materials from WPCBs and prevent the environmental pollution of waste printed circuit boards effectively.     

Combustion studies of high moisture content waste in a fluidised bed

The combustion of three high moisture content waste materials in a fluidised bed combustor has been investigated and a comparison with co-firing of these materials with coal in the same combustor has been made. Waste materials burnt were olive oil waste, municipal solid waste and potato, which is representative of vegetable waste. Mixtures of up to 20% mass concentration water in the waste were fed to the combustor. Above that value the moisture content was too high to sustain combustion without addition of coal. Measurements of CO, NOx, SO2 temperatures were made and the carbon combustion efficiency evaluated. Co-firing with coal resulted in markedly higher combustion efficiencies with an increase of approximately 10-80% when burning the simulated MSW. However, this was much lower than the value of 93% when coal was burnt on its own. It was also much lower than the value obtained, average 90%, when co-firing potato and olive oil waste with coal and there was little difference in the combustion efficiency between the two types of waste and with increasing moisture content. It was concluded that the high ash content of the simulated MSW 26%, compared with 5% in the other two waste materials resulted in slower burning and consequently the char particles were elutriated from the bed without being fully burnt. In term of gaseous emissions during co-combustion, CO emission is relatively insensitive to change in waste fraction. While emission of SO2 can be reduced as the waste fraction increases as a result of fuel-S dilution. But in terms of percent fuel-S converted, it is actually increased by increasing waste fraction. Emissions of NO and N2O increase slightly with MSW fraction.     

Mechanical-biological waste treatment and the associated occupational hygiene in Finland

A special feature of waste management in Finland has been the emphasis on the source separation of kitchen biowaste (catering waste); more than two-thirds of the Finnish population participates in this separation. Source-separated biowaste is usually treated by composting. The biowaste of about 5% of the population is handled by mechanical-biological treatment. A waste treatment plant at Mustasaari is the only plant in Finland using digestion for kitchen biowaste. For the protection of their employees, the plant owners commissioned a study on environmental factors and occupational hygiene in the plant area. During 1998-2000 the concentrations of dust, microbes and endotoxins and noise levels were investigated to identify possible problems at the plant. Three different work areas were investigated: the pre-processing and crushing hall, the bioreactor hall and the drying hall. Employees were asked about work-related health problems. Some problems with occupational hygiene were identified: concentrations of microbes and endotoxins may increase to levels harmful to health during waste crushing and in the bioreactor hall. Because employees complained of symptoms such as dry cough and rash or itching appearing once or twice a month, it is advisable to use respirator masks (class P3) during dusty working phases. The noise level in the drying hall exceeded the Finnish threshold value of 85 dBA. Qualitatively harmful factors for the health of employees are similar in all closed waste treatment plants in Finland. Quantitatively, however, the situation at the Mustasaari treatment plant is better than at some Finnish dry waste treatment plants. Therefore is reasonable to conclude that mechanical sorting, which produces a dry waste fraction for combustion and a biowaste fraction for anaerobic treatment, is in terms of occupational hygiene better for employees than combined aerobic treatment and dry waste treatment.     

Occupational hygiene in a waste incineration plant

The Turku incineration plant was renovated in 1995 to meet the emission requirements of modern waste combustion facilities. It treats presorted municipal waste from 170,000 residents in the Turku area. In the plant, the incineration process produces several types of by-products having importance in terms of occupational hygiene. Although not obligated by the law, the management of the plant has a keen interest in occupational hygiene at the plant, which was studied from 1998 to 2001. Concentrations of microbes, endotoxins, and dust and the noise level were investigated in three different working areas. Microbe measurements were conducted with a six-stage impactor and using the CAMNEA method. Especially in the measurements of viable fungi and actinomycetes, the six-stage impactor gave better results than the CAMNEA method. Concentrations of bio-aerosols and the level of noise were high enough in the waste bunker to be occasionally harmful to the health of employees. The endotoxin concentration could also be harmful to health in the combustion area, and the noise level there exceeded the Finnish threshold value of 85dBA. The total number of microbes (viable+dead) was high in a few measurements in the crane room. One reason for these high numbers was prior moisture damage, which was repaired in 2000. The use of ear protectors is advised in the bunker area and in the combustion area. Use of respirators (class P3) is advised in the bunker area to prevent the exposure of employees to bio-aerosols.