Sulfur Hexafluoride as a Surrogate for Monitoring Hazardous Waste Incinerator Performance

A viable chemical surrogate for monitoring the effectiveness of hazardous waste incinerators must include high thermal stability and low toxicity among its characteristics. The relationship between sulfur hexafluoride (SF₆) and hazardous constituent thermal stability for a mixture of chlorinated hydrocarbons indicates that SF6 has the potential to satisfy the basic requirements of a chemical surrogate for hazardous waste incineration.     

Product Guide/1975

Measurements conducted on full-scale hazardous waste incinerators have occasionally shown a relationship between carbon monoxide (CO) emissions and emissions of toxic organic compounds. In this study, four mixtures of chlorinated C₁ and C₂ hydrocarbons were diluted in commercial-grade heptane and burned in a water-cooled turbulent flame reactor (TFR) under two different excess air levels. No correlation between CO and organic emissions could be discerned. Reasons for this lack of observable correlations are discussed in terms of combustion and chemical reaction kinetic theory.     

Relevance of coplanar PCBs for TEQ emission of fluidized bed incineration and impact of emission control devices

Five fluidized bed incinerators combusting municipal solid waste were assessed for the impact of coplanar PCBs on total TEQ emission. In 17 stack measurements, the coplanar PCBs contributed on average less than 3% to total TEQ with a maximum contribution of 7.5% to total TEQ in one measurement. Differences in the design of the flue gas cooling section did not show an effect on the impact of coplanar PCBs on total TEQ. The effect of emission control devices on the impact of coplanar PCBs on the total TEQ was studied in more detail at one incinerator. The relative contribution of PCBs to total TEQ increased along the flue gas line. This was caused by a slightly higher removal efficiency for TEQ relevant PCDDs/PCDFs compared to coplanar PCBs by the bag filters and a higher destruction efficiency for PCDDs/PCDFs compared to PCBs by the SCR catalyst. Additionally, the removal efficiencies of the emission control devices (bag filters and catalyst) for other chlorinated aromatic compounds which have been proposed as TEQ indicator compounds (polychlorinated benzenes and polychlorinated phenols) were compared with those for PCDDs/PCDFs and coplanar PCBs. Removal efficiencies for polychlorinated benzenes or polychlorinated phenols considerably differed from those of PCDD/PCDF and coplanar PCBs. Implications for TEQ assessments using indicator compounds as proposed in the literature are discussed.     

Removal of carbon dioxide by a spray dryer

With the global warming due to greenhouse effects becoming serious, many efforts are carried out to decrease the emissions of CO2 from the combustion of carbonaceous materials. In Taiwan, there are 19 large-scale municipal solid waste incinerators running and their total emission of CO2 is about 16,950 kton y-1. Spray dryer is the most prevailing air pollution control devise for removing acid gas in waste incineration; however, the performance of spray dryer on the removal of CO2 is seldom studied. This study employs a laboratory-scale spray dryer to investigate the removal efficiency of CO2 under different operating conditions. The evaluated parameters include different absorbents mixed with CaOH2, operating temperature, the concentration of absorbent, and the inlet concentration of CO2. Experimental results show that the best removal efficiency of CO2 by a spray dryer is 48% as the absorbent is 10%NaOH+5%CaOH2 and the operating temperature is 150 degrees C. Comparing this result with previous study shows that the performance of spray dryer is better than traditional NaOH wet scrubber. For NaOH+CaOH2 spray dryer, the removal efficiency of CO2 is decreased with the inlet concentration of CO2 increased and the optimum operating temperature is 150 degrees C. Except NaOH+CaOH2, absorbents DEA+CaOH2, TEA+CaOH2, and single CaOH2 are not effective in removing CO2 by a spray dryer.     

Research Areas for Improved Incineration System Performance

In the past few years, many combustion tests were conducted in full scale operating incinerators. Those test data indicate that certain issues need to be re-evaluated, and point out certain research areas for improved incineration system performance. The issues include incinerability ranking and its relationship with operating temperature; significance of CO monitoring; and significance of products of incomplete combustion emission. The research areas for improvement include waste feed control; oxygen control; expert system; hydrogen halide conversion; submicron particulate formation; and improved air pollution control devices.     

Use of regenerated ferric oxide for CO destruction and suppressing dioxin formation in flue gas in a pilot-scale incinerator

Catalytic destruction of chlorinated compounds is one of the key methods in reducing pollutant emissions. For the purpose of utilizing waste materials, a catalyst was regenerated from ferric ion sludge, obtained from the addition of iron salts to precipitate heavy metals. The sludge was dewatered, heated (800 degrees C for 4 h), and ground into smaller particles. The regenerated ferric oxide particles were then used as the oxidation catalyst to destroy CO formation during the combustion of three chlorinated solvents and to suppress dioxin formation in flue gas in a real waste solvent. In the presence of catalyst, the combustion efficiency (ratio of CO(2) to the sum of CO(2) and CO) for chlorobenzene was more than 98% at 850 degrees C in a pilot-scale incinerator. The destruction and removal efficiencies of chlorobenzene, 2,4-dichlorophenol and trichlorofluoroethane were more than three nines. In the absence of catalysts, the flue gas emission from a real waste could not meet the regulatory dioxin standard of 0.1 ng-TEQ/Nm(3) even with the powdered activated carbon injection. The use of catalyst at either 100 or 300 g/h, however, was able to meet the emission standard.     

Development and Evaluation of a Method to Determine Indicator Microorganisms in Air Emissions and Residue from Medical Waste Incinerators

To allow testing of microbial destruction in medical waste incinerators, methods were developed to determine indicator microorganisms (Bacillus Stearothermophilus spores) in incinerator air emissions and residue. The emission trapping train consisted of a water cooled glass probe and impingers containing a neutral phosphate buffer. In field tests, spores were injected directly into the probe, and results showed that approximately 60 percent of the spores were recovered. Spores were analyzed with adequate precision using a microbial membrane filter unit. Lab experiments indicated that spores were stable in neutral pH phosphate buffer for up to 20 days, and heat shocking samples (heating to 80°C for 20 minutes) reduced spore numbers in acidic or basic buffer. Laboratory tests also showed that 60 to 70 percent of spores initially added to ash were recovered up to 22 days after addition of the spores. In addition, lab tests showed that spores can be effectively recovered from residue test pipes spiked with indicator spores.     

Thermal destruction of benzene

The thermal destruction of benzene in methane/air flue gas is studied experimentally using an atmospheric laminar flow reactor in laboratory scale. The reactor is operated at four different fuel equivalent ratios (phi = 0.06, 0.1,0.5, 3.7), and temperatures in the range from 850 to 973 K and realises a residence time of 5 s. Stable-species concentrations are measured by gas chromatography (GC) and high-pressure liquid chromatography (HPLC), where phenol, acetylene, formaldehyde, acrolein, methane and acetaldehyde are the major hydrocarbon products besides CO and CO2. The augmentation of the temperature from 850 to 973 K increases the benzene conversion rate from 55% to 99%. The experimental results for one fuel equivalent ratio (phi = 0.5) are compared to the benzene model proposed by Emdee et al. (J. Phys. Chem. 92 (1992) 2151-2161). A fair agreement is observed for the benzene consumption and the CO production throughout the temperature range considered here. The small hydrocarbons are not very well matched, which requires further research on the sub-models. Our experimental results on laboratory scale provide a database for the modelling of benzene oxidation in waste incinerators.     

Development and evaluation of a method to determine indicator microorganisms in air emissions and residue from medical waste incinerators.

To allow testing of microbial destruction in medical waste incinerators, methods were developed to determine indicator microorganisms (Bacillus Stearothermophilus spores) in incinerator air emissions and residue. The emission trapping train consisted of a water cooled glass probe and impingers containing a neutral phosphate buffer. In field tests, spores were injected directly into the probe, and results showed that approximately 60 percent of the spores were recovered. Spores were analyzed with adequate precision using a microbial membrane filter unit. Lab experiments indicated that spores were stable in neutral pH phosphate buffer for up to 20 days, and heat shocking samples (heating to 80 degrees C for 20 minutes) reduced spore numbers in acidic or basic buffer. Laboratory tests also showed that 60 to 70 percent of spores initially added to ash were recovered up to 22 days after addition of the spores. In addition, lab tests showed that spores can be effectively recovered from residue test pipes spiked with indicator spores.     

An economic evaluation and assessment of environmental impact of the municipal solid waste management system for Taichung City in Taiwan

Municipal solid waste management (MSWM) is an important environmental challenge and subject in urban planning. For sustainable MSWM strategies, the critical management factors to be considered include not only economic efficiency of MSW treatment but also life-cycle assessment of the environmental impact. This paper employed linear programming technique to establish optimal MSWM strategies considering economic efficiency and the air pollutant emissions during the life cycle of a MSWM system, and investigated the correlations between the economical optimization and pollutant emissions. A case study based on real-world MSW operating parameters in Taichung City is also presented. The results showed that the costs, benefits, streams of MSW, and throughputs of incinerators and landfills will be affected if pollution emission reductions are implemented in the MSWM strategies. In addition, the quantity of particulate matter is the best pollutant indicator for the MSWM system performance of emission reduction. In particular, this model will assist the decision maker in drawing up a friendly MSWM strategy for Taichung City in Taiwan.

Implications: Recently, life-cycle assessments of municipal solid waste management (MSWM) strategies have been given more considerations. However, what seems to be lacking is the consideration of economic factors and environmental impacts simultaneously. This work analyzed real-world data to establish optimal MSWM strategies considering economic efficiency and the air pollutant emissions during the life cycle of the MSWM system. The results indicated that the consideration of environmental impacts will affect the costs, benefits, streams of MSW, and throughputs of incinerators and landfills. This work is relevant to public discussion and may establish useful guidelines for the MSWM policies.     

An economic evaluation and assessment of environmental impact of the municipal solid waste management system for Taichung City in Taiwan

Municipal solid waste management (MSWM) is an important environmental challenge and subject in urban planning. For sustainable MSWM strategies, the critical management factors to be considered include not only economic efficiency of MSW treatment but also life-cycle assessment of the environmental impact. This paper employed linear programming technique to establish optimal MSWM strategies considering economic efficiency and the air pollutant emissions during the life cycle of a MSWM system, and investigated the correlations between the economical optimization and pollutant emissions. A case study based on real-world MSW operating parameters in Taichung City is also presented. The results showed that the costs, benefits, streams of MSW, and throughputs of incinerators and landfills will be affected if pollution emission reductions are implemented in the MSWM strategies. In addition, the quantity of particulate matter is the best pollutant indicator for the MSWM system performance of emission reduction. In particular this model will assist the decision maker in drawing up a friendly MSWM strategy for Taichung City in Taiwan. Implications: Recently, life-cycle assessments of municipal solid waste management (MSWM) strategies have been given more considerations. However, what seems to be lacking is the consideration of economic factors and environmental impacts simultaneously. This work analyzed real-world data to establish optimal MSWM strategies considering economic efficiency and the air pollutant emissions during the life cycle of the MSWM system. The results indicated that the consideration of environmental impacts will affect the costs, benefits, streams of MSW, and throughputs of incinerators and landfills. This work is relevant to public discussion and may establish useful guidelines for the MSWM policies.     

Behavior of PCNs, PCDDs, PCDFs, and dioxin-like PCBs in the thermal destruction of wastes containing PCNs

In the first known study to characterize the emissions of polychlorinated naphthalenes (PCNs), polychlorinated dibenzo-p-dioxins (PCDDs), polychlorinated dibenzofurans (PCDFs), and dioxin-like polychlorinated biphenyls (dl-PCBs) from the thermal treatment of wastes containing PCNs, the formation and decomposition behavior of these pollutants was investigated both at laboratory scale and at plant scale. Exhaust gas measurements from laboratory-scale combustion of rubber belts containing PCNs (FB belts) were used as the basis for calculations predicting that the incremental dioxin toxic equivalency (TEQ) emissions from municipal solid waste (MSW) incinerators would be less than 0.1 ng/m3 N. In order to directly examine co-incineration of FB belts with MSW and to address potential differences between the laboratory experiment and full-scale MSW incinerators, experiments were conducted using a larger scale thermal treatment test facility with sampling and analysis at several points in the thermal treatment process. Congener specific analysis of PCNs clearly showed that both destruction and synthesis simultaneously occurred during combustion in the kiln. Most of the PCNs were destroyed by secondary combustion, and almost all PCNs were removed after flue gas treatment. Almost all PCDDs/DFs were synthesized as by-products of kiln combustion, most of them were destroyed by the secondary combustion, and almost all dioxins (PCDDs/DFs and dl-PCBs) were removed after flue gas treatment. The TEQ emission levels were less than 0.1 ng/m3 N for all plant-scale tests, and differences in TEQ emission levels were very small. Adding wastes containing PCNs to MSW will not influence thermal treatment emissions to the environment from modern solid waste incinerators.     

Evaporative traffic hydrocarbon emissions,traffic CO and speciated HC traffic emissions from the city of Athens

Quasi-continuous measurements of NO_x, CO and C₅–C₁₂ hydrocarbons made during the MEDCAPHOT-TRACE experiment in a street canyon with heavy traffic load were used to estimate the CO/NO_x and 36 individual NMHC/NO_x traffic emission ratios in the Athens basin. A traffic emission inventory has been compiled for Athens and aspects of this inventory were tested against measurements. The results indicate that although the main features of the 9:00 to 15:00 variations of the NMHC/NO_x and CO/NO_x inventory emission ratios are in agreement with observations, during the rest of the day the fine structure of the variations of these ratios cannot be accurately predicted by the inventory. Comparison of pollutant emission ratios derived from ambient measurements with emission ratios predicted by existing inventories for Athens reveals serious discrepancies. Further, the experimental results and theoretical considerations indicate that the speciation of evaporative emissions changes with increasing ambient temperature in favour of the most volatile HC species, thus changing the speciation of traffic emissions during the course of the day. This is an aspect that is not taken into account in present urban photochemical modelling inventories.     

Particulate Emissions from Apartment House Boilers and Incinerators

The body of information presented in this paper is directed to researchers in stack testing methodology and to those concerned with reduction of emissions through equipment upgrading programs. Extensive testing was done using the U.S. Environmental Protection Agency’s Method 5 stack sampling train to obtain emission factors for existing apartment house boilers and incinerators in the City of New York. In addition to calculating emission factors, stack emission data were examined to compare results of simultaneous emission tests and to compare the dry particulate catch of the sampling train with the total particulate catch which included the impinger catch. Conclusions reached as a result of the testing were that published emission factors for boilers burning moderately high-sulfur residual oil are applicable to New York City boilers burning low-sulfur residual oil. In addition, it was found that the back half of the sampling train—the impinger section—collects a relatively constant amount of material when sampling oil-fired boilers. This may be due to absorption of S0₂ and S0₃ in the impingers and the subsequent formation of sulfuric acid. Comparison of simultaneous boiler tests indicated that the sampling train may be sensitive to variations in operating personnel, sampling conditions, and boiler operation. From tests of on-site incinerators, it was determined that previously published emission factors may be too high for well maintained and properly operated incinerators. The back half particulate catch was found to be relatively large which may have resulted from condensation of unburned organics from the burning waste material.     

Improvements to the UK PCDD/F and PCB atmospheric emission inventory following an emissions measurement programme

PCDD/F data are presented from 75 samples of primary emissions sampled between 1995-97 as part of the compliance monitoring survey undertaken by the UK Environment Agency. Municipal solid waste (MSW), chemical waste and clinical waste incinerators, cement kilns, sinter plants and sewage sludge incinerators were the source categories monitored and reported here. Based on this monitoring programme, the previous national UK emission estimates by Eduljee and Dyke (1) of 560-1100 g I-TEQ a(-1) for 1993 have been revised downwards to 220-660 g I-TEQ a(-1). Despite source reduction measures, MSW incinerators remain a significant source of PCDD/Fs to the atmosphere, contributing between 30-50% of the EPCDD/F I-TEQ emission, rather than the approximately 80% they were estimated to contribute in 1993. 2,3,7,8-substituted PCDD/F congener profile data are presented for some of the source categories and generally support the view that differences in the mixtures ('fingerprints') of PCDD/Fs emitted from different sources are observed. New data on the dioxin-like PCB emissions are presented for cement kilns and sinter plants. These show that TEQ-rated PCBs can make an important contribution to the I-TEQ emitted from certain combustion sources. High concentrations of a full range of PCB congeners/homologues have been measured in the atmosphere close to sintering strands, although the precise source of PCBs from this process remains unclear.     

Practices in dioxin emission reduction by special regulatory enforcement and utilizing advanced control technologies for incinerators in Korea

This study strives to estimate the emission of dioxin and furthermore attempts to find the best technological control methods available for waste incinerators by investigating the emission status thereof. In order to incorporate the Stockholm Convention, a particular stringent law was promulgated in Korea and in recent years incinerators were forced to utilize better technological control. After the enforcement of special dioxin emission regulation in 2003, the average concentration of dioxin emitted from municipal and industrial waste incinerators decreased from 15.25 and 12.86 ng TEQ Nm(-3) to 5.53 and 4.96 ng TEQ Nm(-3) in 2001 and 2004, respectively. Based on test results at commercial plants, several best arranged sets of air pollution control devices (APCDs) were suggested in order to provide guidelines to help operators. These sets included combinations of spray dry absorbers, bag type filters, wet scrubbers, selective catalytic reductions and electrostatic precipitators. Different suggestions and real installations of APCD arrangement were investigated during the years around the regulation in effective. The results were presented depending on the capacity of the incinerators and different waste streams to observe the efforts to reduce dioxin emission by operators of incineration plants. The annual amount of dioxin emission from the incinerators is expected to be 212.5 g-TEQ in 2011 and 234.3g-TEQ in 2015, respectively, compared to 891.6g-TEQ recorded in 2001. The enforcement of new regulation and the installation of better APCDs showed the significant effect on such reduction. This reduction in dioxin emission from incinerators confirmed the nation's commitment to the regulatory requirement set by the Stockholm Convention.     

Development of Instrumentation for Continuous On-line Monitoring of Non-Methane Organic Carbon in Air Emissions

ABSTRACT

Non-methane organic carbon (NMOC) is a measure of total organic carbon in an air emission, excluding that from methane. Thus, it measures the total amount of carbon, irrespective of the structure and functional groups in the molecule. The U.S. Environmental Protection Agency (EPA) Method 25 is used for quantification of NMOC in emission sources and in ambient air. This method involves laboratory analysis of collected air samples and cannot be used for real-time measurements. It is prone to interferences from CO₂, CH₄, and CO, as well as moisture. In this paper, a novel method for continuous, on-line monitoring of NMOC in air emissions and ambient air is presented. Detection limits are at ppb levels, and interference of permanent gases have been eliminated.     

Air Quality Measurements from the Fresno Supersite

ABSTRACT

The Fresno Supersite intends to 1) evaluate non-routine monitoring methods, establishing their comparability with existing methods and their applicability to air quality planning, exposure assessment, and health effects studies; 2) provide a better understanding of aerosol characteristics, behavior, and sources to assist regulatory agencies in developing standards and strategies that protect public health; and 3) support studies that evaluate relationships between aerosol properties, co-factors, and observed health end-points. Supersite observables include in-situ, continuous, short-duration measurements of 1) PM_2.5, PM₁₀, and coarse (PM₁₀ minus PM_2.5) mass; 2) PM_2.5 SO₄ ^-2, NO₃ ^-, carbon, light absorption, and light extinction; 3) numbers of particles in discrete size bins ranging from 0.01 to ~10μm; 4) criteria pollutant gases (O₃, CO, NO_x); 5) reactive gases (NO₂, NO_y, HNO₃, peroxyacetyl nitrate [PAN], NH₃); and 6) single particle characterization by time-of-flight mass spectrometry. Field sampling and laboratory analysis are applied for gaseous and particulate organic compounds (light hydrocarbons, heavy hydrocarbons, carbonyls, polycyclic aromatic hydrocarbons [PAH], and other semi-volatiles), and PM_2.5 mass, elements, ions, and carbon. Observables common to other Supersites are 1) daily PM_2.5 24-hr average mass with Federal Reference Method (FRM) samplers; 2) continuous hourly and 5-min average PM_2.5 and PM₁₀ mass with beta attenuation monitors (BAM) and tapered element oscillating microbalances (TEOM); 3) PM_2.5 chemical specia-tion with a U.S. Environmental Protection Agency (EPA) speciation monitor and protocol; 4) coarse particle mass by dichotomous sampler and difference between PM₁₀ and PM_2.5 BAM and TEOM measurements; 5) coarse particle chemical composition; and 6) high sensitivity and time resolution scalar and vector wind speed, wind direction, temperature, relative humidity, barometric pressure, and solar radiation. The Fresno Supersite is coordinated with health and toxicological studies that will use these data in establishing relationships with asthma, other respiratory disease, and cardiovascular changes in human and animal subjects.     

Evaluation of Canisters for Measuring Emissions of Volatile Organic Air Pollutants from Hazardous Waste Incineration

Regulation to control air emissions of toxic organic compounds require the collection and analysis of effluent gas from low level sources such as hazardous waste incinerators. The standard SW- 846 Method specifies the use of Tenax and Tenax/charcoal adsorbent traps for collection of volatile organics from incinerators. This study evaluates passivated stainless steel canisters as an alternative to adsorbent traps to eliminate some of the problems associated with adsorbent sampling. Initially the stability of 18 nonpolar, volatile organic compounds was determined in Summa-treated stainless steel canisters with greater than 100 ppmv HCI and saturated with water vapor. All 18 components were stable for a twoweek period; however, an Interference caused a 10-fold increase In the FID response of trlchloroethylene, toluene, and chlorobenzene. No Interference of the ECD response was found for any of the 11 compounds detected with the ECD including trlchloroethylene. A pilot scale incinerator was sampled using canisters, and the destruction efficiency of 1,1,1-trichloroethane was determined at a concentration of less than 0.5 ppbv while determining 1,1-dichloroethylene, the major product of Incomplete combustion, at a concentration of 8000 ppbv from the same sample.     

Removal of PCDD/F from Incinerator Flue Gases by Entrained-Phase Adsorption

Abstract

The emission abatement of polychlorinated dioxins and furans (PCDD/F) issued from municipal solid waste incineration is growing in importance because of more stringent emission standards and general concern about their toxic characteristics. These substances cannot be separated by conventional gas cleanup processes but are successfully removed through adsorption onto carbonaceous materials. The simplest technique is the entrained-phase injection of pulverized adsorbents in the flue gas, followed by fabric filter separation. The various related techniques are briefly reviewed here. Operating conditions and results obtained from Flemish MSWIs are given. The results illustrate the excellent overall removal efficiency. Furans are adsorbed to a slightly higher extent than dioxins.

PCDD/F removal by carbonaceous adsorbents is thereafter modeled from first principles for the contribution of both entrained-phase (η₁) and cake filtration (η₂) to the overall efficiency (η_T). Application of the model equations and comparison of measured and predicted overall efficiencies for the Flemish municipal solid waste incinerators (MSWIs) demonstrate that the approach is meaningful and that the dominant parameters are the operating temperature, the dosage and activity of adsorbent, and the fraction of adsorbent in the filter cake. The model equations enable the MSWI operators to predict the adsorption efficiencies for any combination of operating parameters and to assess the sensitivity of the process to varying operating conditions.