Mercury Emissions from a Hazardous Waste Incinerator Equipped with a State-of-the-Art Wet Scrubber

Abstract

Over a six-week period, eleven tests were performed at the U.S. EPA Incineration Research Facility (IRF) in Jefferson, Arkansas to evaluate the fate of trace metals fed to a rotary kiln incinerator equipped with a Calvert Flux-Forcer/Condensation Scrubber pilot plant as the primary air pollution control system (APCS). Test variables were kiln temperature, ranging from 538 °C to 927 °C; waste feed chlorine content, ranging from 0% to 3.4%; and scrubber pressure drop, ranging from 8.2 kPa to 16.9 kPa. Mercury was among the six hazardous constituent trace metals fed to the IRF’s pilotscale rotary kiln incineration system as part of a synthetic waste feed. This paper focuses on the test results solely with respect to mercury.

As expected, mercury behaved as a very volatile metal throughout the tests; it was not detected in any kiln ash samples. Scrubber collection efficiency for mercury ranged from 67% to >99%, averaging 87%; this was somewhat lower than expected and may be attributable to low scrubber loadings.

The ability to collect and analyze representative scrubber water samples appears to have been affected by the waste feed chlorine content; detection of mercury at higher concentrations during high waste-chlorine-content tests is thought to be largely the result of the formation of mercuric chloride, a more water-soluble species, during those tests. As a result, no firm conclusions may be drawn regarding the true impact of waste feed chlorine content on mercury partitioning to the scrubber water. As expected, no significant relationship was observed between kiln exit-gas temperature and mercury partitioning, nor was there a significant relationship with scrubber pressure drop.     

Effect of liquid inhibitors on PCDD/F formation. Prediction of particle-phase PCDD/F concentrations using PLS modelling with gas-phase chlorophenol concentrations as independent variables

Emissions of polychlorinated dibenzo-p-dioxins (PCDDs) and dibenzofurans (PCDFs) from municipal waste incineration are currently a subject of considerable public concern because of their extreme toxicity. PCDD/F formation in incineration processes is being studied widely, but little work has been done on their inhibition. We studied the effect of two liquid inhibitors, sodium ammonium hydrogen phosphate (NAHF) and urea (H2NCONH2), on PCDD/F formation in the combustion of liquid fuel doped with copper and chlorine using a pilot-scale plant. The inhibitors were injected into the flue gas stream at a temperature of 725 degrees C, whereupon both the chlorophenol and PCDD/F concentrations decreased. Particle-phase PCDD/F concentrations in particular decreased by up to 90% with NAHF and 70% with urea, but gas phase reduction took place only with urea. The results suggest that the formation of PCDD/Fs is hindered in the particle phase at the early stages of the PCDD/F formation chain, probably even before precursors such as chlorophenols have been formed. As a consequence, particle-phase PCDD/F concentrations can be predicted by a PLS (partial least-squares) approach with the gas-phase chlorophenol concentrations as independent variables. The structure and partial charges of Cu(+)-urea complex were calculated by the HF/3-21G basis set.     

Thermal Encapsulation of Metals in Superfund Soils

Abstract

Superfund sites frequently contain both heavy metals and organic hazardous waste. If not properly controlled, the metals may be changed to a more leachable form and may also be emitted to the atmosphere via the exhaust stack. This paper documents a batch kiln R&D test program to solve these metal-related problems. It was performed under the U.S. EPA’s SITE (Superfund Innovative Technology Evaluation) Emerging Technology Program. Allis Mineral Systems has developed the Thermal Encapsulation Process. Metals with limits set by EPA’s TCLP (Toxicity Characteristic Leaching Procedure) test and BIF (boiler and industrial furnace) stack emission regulations, such as cadmium, chromium, and lead, are the initial target of this process. This process, while unproven in these areas, may also apply to mixed waste (EPA hazardous waste/low-level radioactive wastes) and may also benefit commercial hazardous waste or Superfund thermal treatment systems. The results of the SITE tests were positive: strong, durable nodules were produced with excellent crush strength and improved resistance to leaching. Feed preparation, particularly control of moisture content, was found to be a key element in initiation of agglomeration. A good correlation was found between decreasing TCLP metals leachate levels and increasing crush strength.     

Decomposition of paper wastes in presence of ceramics and cement raw material

Paper recycling is an environmental important activity that is carried out in all the countries, but during the recycling process a paper waste is produced. Generally these wastes are placed in landfill sites but it is possible to profit it as secondary fuel and raw material in manufacture furnaces.

In this work the combustion of the waste papers with cement and ceramic raw material has been studied with the objective to analyse the interaction of these substances with the emitted pollutants like PAHs and PCDD/Fs.

The results of the study show that the presence of inorganic material produces an increment in the lighter PAH emission but chlorinated compounds are not affected. The PCDD/F emission level found in the combustion of this waste is quite low compared with other wastes subjected to similar conditions.     

Feeding trial on rainbow trout: comparison of dry fish feed and Baltic herring as a source of PCDD/Fs and PCBs

Fish is an important source of dietary intake of polychlorinated dibenzo-p-dioxins and dibenzofurans (PCDD/Fs) and polychlorinated biphenyls (PCBs). To assess bioaccumulation of PCDD/Fs and PCBs in farm-raised fish, rainbow trout were fed with either Baltic herring or dry fish feed. Baltic herring feed had a PCDD/F sum concentration of 125 ng kg(-1) dry weight (d.w.), and dry fish feed contained 18.2 ng kg(-1) d.w. of PCDD/Fs. The PCB concentrations of Baltic herring and dry fish feed were 188 and 48.7 microg kg(-1) d.w., respectively. After feeding with Baltic herring for 4 months, the PCDD/F concentration of the rainbow trout fillet was 27.3 ng kg(-1) fresh weight (f.w.), which was 7.0-fold higher than the initial concentration. The PCDD/F concentration and congener profile in rainbow trout had become almost the same as in Baltic herring. PCDD/Fs were accumulated in the fillet with an efficiency of 21%. Feeding of rainbow trout with dry fish feed resulted in a PCDD/F concentration of 8.08 ng kg(-1) f.w., denoting a 2.1-fold increase from the initial level. The accumulation efficiency was 29%. Time trends in PCB concentrations followed those of PCDD/Fs. After 4 months, the PCB sum concentration in herring-fed rainbow trout was 94.4 pg kg(-1) f.w., whereas in dry fish feed-fed rainbow trout it was 38.6 microg kg(-1) f.w. Accumulation efficiencies of PCBs were higher than those of PCDD/Fs. Based on the accumulated PCDD/F and PCB concentrations, it was estimated that frequent consumption of rainbow trout fed with Baltic herring could lead to a human daily intake that exceeds the recommendation of WHO.     

Catalytic oxidation of gaseous PCDD/Fs with ozone over iron oxide catalysts

Catalytic oxidation of PCDD/Fs (polychlorinated dibenzo-p-dioxins and polychlorinated dibenzofurans) with ozone (catalytic ozonation) over nano-sized iron oxides (denoted as FexOy) was carried out at temperature of 120-180 degrees C. The effects of operating temperature, ozone concentration, space velocity (SV) and water vapor contents on PCDD/F removal and destruction efficiencies via catalytic ozonation were investigated. High activity of the iron oxide catalyst towards PCDD/F decomposition was observed even at low temperatures with the aid of ozone. The PCDD/F removal and destruction efficiencies achieved with FexOy/O3 at 180 degrees C reach 94% and 91%, respectively. In the absence of ozone, the destruction efficiencies of all PCDD/F congeners are below 20% and decrease with increasing chlorination level of PCDD/F congener at lower temperature (120 degrees C). However, in the presence of ozone, the destruction efficiencies of all PCDD/F congeners are over 80% on FexOy/O3 at 180 degrees C. Higher temperature and ozone addition increase the activity of iron oxide for the decomposition of PCDD/Fs. Additionally, in the presence of 5% water vapor, the destruction efficiency of the PCDD/Fs is above 90% even at lower operating temperature (150 degrees C). It indicates that the presence of appropriate amount of water vapor enhances the catalytic activity for the decomposition of gas-phase PCDD/Fs.     

Generation of PCDD/F in fly ash from municipal solid waste incinerators

Fly ash from municipal solid waste incinerators (MSWIs) has been characterized in terms of polychlorinated dibenzyl-p-dioxin and polychlorinated dibenzofuran (PCDD/F) content. Increasing values of PCDD/Fs have been found to correlate with decreasing temperatures of sampling points in flue gas treatment lines of the plants, confirming other researchers' findings about temperature as the major controlling parameter for the PCDD/F formation. Measured PCDD/F ratios show that de novo synthesis is the dominant formation mechanism. The increasing trends of particulate-bound PCDD/Fs can be explained not only through the dominant de novo synthesis process but also considering the adsorption of gaseous PCDD/Fs on fly ash deposits, even outside the typical de novo synthesis temperature ranges. The effective role of a post-combustor unit, imposed by Italian law to destroy PCDD/ Fs, also needs to be carefully reconsidered.     

Emissions behavior and distribution of polychlorinated dibenzo-p-dioxins and furans (PCDD/Fs) from cement kilns in China

The production of cement in China is accompanied by various emissions, such as fine particulate matter, heavy metals, nitrogen oxides, sulfur oxides, carbon dioxide…. Moreover, cement kiln presents a potential health risk to its surroundings, linking to emissions of persistent organic pollutants (POPs), such as polychlorinated dibenzo-p-dioxins and dibenzofurans (PCDD/Fs), in brief dioxins. Flue gas samples were collected from five typical cement kilns during twelve runs and were used to evaluate the levels and distribution of PCDD/Fs in the emissions from cement kilns. The PCDD/Fs concentrations (136 congeners) and I-TEQ values ranged from 2.3 to >40 ng/m³ and 9.3?～?90.8?×?10^?3 ng I-TEQ/m³, respectively, which were lower than the emission standard in China (0.1 ng I-TEQ/m³). In weight units, the dominant congeners were OCDD, 1,2,3,4,6,7,8-HpCDF, and OCDF; 2,3,4,7,8-PeCDF is the largest contributor (36–66 %) to the total I-TEQ value of twelve runs. HxCDF and TCDF were the first two most abundant homologue groups (12–85 and 4–52 %), and the homologue concentration decreased with rising chlorine number for PCDDs. In addition, there was no marked difference in homologue profiles when solid wastes (refuse-derived fuel and municipal solid waste) and hazardous wastes (DDT and POPs) were combusted as supplemental fuels. The use of various supplemental fuels had no obvious effect on the fingerprint of PCDD/F homologues. Moreover, there was no significant difference in levels of PCDD/Fs emission due to the diversity of production capacity, which were consistent with reported previously. Air pollution control device had effect on the homologue profiles, and cement system with electrostatic precipitators (ESP) had more fractions of octachloro congeners to the total.     

Generation of PCDD/F in Fly Ash from Municipal Solid Waste Incinerators

Abstract

Fly ash from municipal solid waste incinerators (MSWIs) has been characterized in terms of polychlorinated dibenzyl-p-dioxin and polychlorinated dibenzofuran (PCDD/F) content. Increasing values of PCDD/Fs have been found to correlate with decreasing temperatures of sampling points in flue gas treatment lines of the plants, confirming other researchers’ findings about temperature as the major controlling parameter for the PCDD/F formation. Measured PCDD/F ratios show that de novo synthesis is the dominant formation mechanism. The increasing trends of particulate-bound PCDD/Fs can be explained not only through the dominant de novo synthesis process but also considering the adsorption of gaseous PCDD/Fs on fly ash deposits, even outside the typical de novo synthesis temperature ranges. The effective role of a post-combustor unit, imposed by Italian law to destroy PCDD/Fs, also needs to be carefully reconsidered.     

Precipitation scavenging of particle-bound contaminants – A case study of PCDD/Fs

Precipitation scavenging of particles is a major mechanism for atmospheric deposition of organic contaminants, but there have been few field studies. We studied precipitation scavenging of PCDD/Fs with the aim of deepening understanding of environmental variables influencing this process. Bulk deposition of PCDD/Fs and their concentrations in ambient air measured at a background site in Sweden were used to calculate precipitation scavenging ratios. Contrary to expectations, increasing scavenging ratios with decreasing degree of chlorination of the PCDD/F congeners were observed when the particle-associated PCDD/F concentrations in air were used for the calculation. This was attributed to differences in temperature and thereby in the gas – particle partitioning of the PCDD/Fs between ground level and clouds where much of the particle scavenging occurs. When the particle-associated PCDD/F concentrations were recalculated for a 10–20 °C lower temperature, the scavenging ratios of the different PCDD/F congeners were similar. Hence differences between ground level and in-cloud temperature should be considered when calculating scavenging ratios from field observations and when modeling this process. The scavenging ratios averaged ～200 000, with lower values when the particle-associated PCDD/F concentration in air was lower. The soot concentration in air was a good predictor of bulk deposition of PCDD/Fs.     

Metal Emissions from Joule-Heated Vitrification Systems

ABSTRACT

Vitrification demonstrations were conducted for surrogates of three inorganic wastewater sludges in a high-temperature, refractory-lined, slurry-fed melter. The total par-ticulate concentrations and melter decontamination factors were determined for selected elements. The decontamination factors were less than 10 for cadmium and lead in all three demonstrations. The decontamination factors for chromium were less than 30 in the two demonstrations using refractories containing chromium, and they were greater than 150 for the demonstrations using refractories without chromium. Except for one demonstration on a surrogate waste with a high sulfate content, decontamination factors were above 80 for the other heavy metals in the demonstrations.     

Evaluation of PCDD/F congener distributions in MWI flue gas treated with SCR catalysts

Partitioning of PCDD/F congeners between gaseous and particulate phases and removal efficiencies of the air pollution control devices (APCDs) for PCDD/Fs at an existing municipal waste incinerator (MWI) in Taiwan are evaluated via stack sampling and analysis. The MWI investigated is equipped with electrostatic precipitators (EP), wet scrubbers (WS) and selective catalytic reduction system (SCR) as APCDs. The average PCDD/F concentration of stack gas is 1.49 ng/N m³, and the International Toxic Equivalent Quantity (I-TEQ) is 0.043 ng-I-TEQ/N m³. The EP increases PCDD/F concentration by 174.0% while the average removal efficiency of WS + SCR system for PCDD/Fs reaches 99.1%. In addition, the PCDF removal efficiency achieved with WS + SCR system (97.1–99.8%) is higher than that for PCDDs (96.5–99.3%). The results obtained on gas/particulate partitioning in flue gas indicate that the particulate-phase PCDD/Fs accounted for 65% at the inlet of EP, 20% at the outlet of EP and 50% at the stack, respectively, of the total PCDD/F concentrations. This study also indicates that as the chlorination level of PCDD/F congeners increases, the percentage of PCDD/Fs existing in gas phase decreases in all flue gas samples.     

Suppressing effect of goethite on PCDD/F and HCB emissions from plastic materials incineration

Polyethylene (PE) and polyvinyl chloride (PVC) are the leading plastics in total production in the world. The incineration of plastic-based materials forms many chlorinated compounds, such as polychlorinated dibenzo-p-dioxins and polychlorinated dibenzofurans (PCDD/Fs). In this study the addition of goethite (alpha-FeOOH) was investigated to determine its suppressing effect on the emission of PCDD/Fs and hexachlorobenzene (HCB) during the combustion of wastes containing PE and PVC. Goethite was being considered since it acts as a dioxin-suppressing catalyst during incineration. Results showed that incorporation of goethite greatly reduced the generation of PCDD/Fs and HCB in the exhaust gas and fly ash. The concentration of PCDD/Fs in flue gas decreased by 45% for lab-scale and 52% for small incinerator combustion experiments, where the goethite ratios in feed samples were 0.54% and 0.34%, respectively. Under the same conditions, the concentration of HCB in flue gas decreased by 88% and 62%, respectively. The present study showed a possible mechanism of the suppressing effect of the goethite for PCDD/F formation. It is likely that iron chlorides react with particulate carbon to form organo-chlorine compounds and promote PCDD/F formation in the gas phase. XRD analysis of combustion ash revealed that the goethite was partially dehydrated and converted to alpha-Fe(2)O(3) and Fe(3)O(4) but no iron chlorides formation. Therefore the goethite impregnated plastics can contribute the reduction of PCDD/Fs and HCB in the exhaust gas during incineration of MSW.     

PCDD/F formation from oxy-PAH precursors in waste incinerator flyash

The yield of PCDD/F in relation to the presence of oxygenated PAH in model waste incinerator flyash has been investigated in a fixed bed laboratory scale reactor. Experiments were undertaken by thermal treatment of the model flyash at 250 and 350 °C under a simulated flue gas stream for 2 h. After reaction, the PCDD/F content of the reacted flyash and the PCDD/F released into the exhaust gas, and subsequently trapped by XAD-II resin in a down-stream condensation system were analyzed. The PAHs investigated were, dibenzofuran and benzo[b]naphtho[2,3-d]furan and were spiked onto the model flyash as reactant precursors for PCDD/F formation. The results showed significant formation of furans from both of the PAH investigated, however except from some highly chlorinated dioxin congeners, the formation of dioxins was not so common. Benzonaphthofuran was significantly more reactive than dibenzofuran in PCDD/F formation, in spite of the fact that dibenzofuran is structurally more similar to that of PCDD/F. Thus, there was no clear attribution between the chemical structure of PAH used and the formation of PCDD/F. There were considerable differences between the yields of PCDD/F congeners in the gaseous species and those in the reacted flyash under the same operational conditions. The concentration of PCDD/Fs was reduced at the higher reaction temperature of 350 °C; however, the higher temperature resulted in the majority of the PCDD/F formed on the flyash being released into the gas phase.     

Study on the raw fish oil purification from PCDD/F and dl-PCB-industrial tests

The results of tests for the purification of fish oils with activated carbon for industrial use are presented. The optimum parameters for the process of purification (granulation of the activated carbon, its dosage, the oil temperature, and the duration of mixing the oil with activated carbon) were previously established for the laboratory scale. The optimization of the process consisted of selecting purification parameters that would allow for maximum reduction of the toxic polychlorinated dibenzo-para-dioxins and polychlorinated dibenzofurans (PCDD/Fs) content, while retaining the favorable high fatty acid content [C20:5 n−3, eicosapentaenoic acid (EPA) and C22:6 n−3, docosahexaenoic acid (DHA)]. The use of that optimum parameters in industrial conditions confirmed the satisfactory results obtained in laboratory tests. Five types of oil derived from various Baltic fish were purified. Reduction in the PCDD/Fs content was 77.0–93.6% on average, whereas in the dioxin-like polychlorinated biphenyls (dl-PCBs)—it was 42.7–50.5% on average, with insignificant changes in the total amount of EPA and DHA content. Furthermore, a significant reduction in the content of arsenic was noted (by about 62% on average), with insignificant changes in the content of organochlorine pesticides (OCPs), and marker polychlorinated biphenyls (PCBs), polybrominated diphenyl ethers (PBDEs), cadmium, lead, and mercury.Purification provided fish oil having standardized parameters that allow for its use as feed additives, whilst retaining its favorable fatty acid content.     

Simultaneous removal of PCDD/Fs and mercury by activated carbon from a full-scale MSW incinerator in southeast China

This study emphasized on the removal performance of polychlorinated-ρ-dibenzodioxins and dibenzofurans (PCDD/Fs) and mercury by different activated carbon injection (ACI) rates from a full-scale (700 t/d) MSW incinerator. The result exhibited that the emission standard of PCDD/Fs and mercury could be met when the ACI rate reached 50 mg/Nm³ and 30 mg/Nm³, respectively. Lower chlorinated PCDD/Fs and PCDFs showed higher removal efficiencies compared with highly chlorinated PCDD/Fs and PCDDs, which could be attributed to the larger competitiveness of highly volatile congeners in AC adsorption than the lower volatile ones. AC turned out to have different adsorption selectivity for CP-routes PCDD/Fs congeners, among which 1379-TCDD was preferred to be absorbed while others exhibited little or poor selectivity for AC adsorption. The removal efficiency of PCDD/Fs was positively correlated with ACI rate at 99% confidence interval with a linear relationship (R²?=?0.98). Also, the outlet concentration of mercury decreased with the increase of ACI rate in a nearly linear function (R²?=?0.96). These results will be meaningful for the rational use of AC for pollutants control.

     

Variables affecting emissions of PCDD/Fs from uncontrolled combustion of household waste in barrels

The uncontrolled burning of household waste in barrels has recently been implicated as a major source of airborne emissions of polychlorinated dibenzo-p-dioxins and polychlorinated dibenzofurans (PCDD/Fs). A detailed, systematic study to understand the variables affecting emissions of PCDD/Fs from burn barrels was performed. The waste composition, fullness of the barrel, and the combustion conditions within the barrel all contribute significantly to determining the emissions of PCDD/Fs from burn barrels. The study found no statistically significant effect on emissions from the Cl content of waste except at high levels, which are not representative of typical household waste. At these elevated Cl concentrations, the impact of Cl on PCDD/F emissions was found to be independent of the form of the Cl (inorganic or organic). For typical burn conditions, most of the PCDD/F emissions appear to be associated with the later stages of the burn when the waste is smoldering. Polychlorinated biphenyls (PCBs) were also measured for a subset of the tests. For the nominal waste composition, the average emissions were 76.8 ng toxic equivalency units (TEQ)WHO98/kg of waste combusted, which suggests that uncontrolled burning of household waste could be a major source of airborne PCDD/Fs in the United States.     

A study of the influence of sewage sludge fertilization on the concentrations of PCDD/F and PCB in soil and milk

The influence of the agricultural use of sewage sludge on the concentrations of PCBs and PCDD/Fs in soil, feed and milk was investigated on four dairy farms. Evidence of contaminant accumulation in the soil was found on both farms that fertilized with sewage sludge. The concentrations in feed and milk from one of these farms were similar to the concentrations in the matched control, while the concentrations in the samples from the second sludge user were elevated. The study demonstrates that the agricultural use of sewage sludge does under some conditions lead to higher levels of PCBs and PCDD/Fs in food products.     

Utilization of TiO2 deposited on glass plates for removal of metals from aqueous wastes

Glass plates coated with TiO2 were used in a photocatalytic process to collect mercury, lead, copper and cadmium from aqueous solutions containing individual metals and mixtures. Stripping voltammetry, verified to achieve 1-10 ppb detection limits, was used to show that individual metals at concentrations of 1000 to 5200 ppb were reduced to undetectable levels in 3 to 55 min. Capillary electrophoresis (CE) with 8-hydroxyquinoline-5-sulfonic acid as complexing agent was used when appropriate, since it could quantitate all four metals under study in one run although it was less sensitive. It was demonstrated that 100 mL solutions containing 10 ppm of each of the four metals could be treated with a 10 cm2 TiO2-coated plate to leave undetectable metal concentrations in one hour. Stripping voltammetry using carbon electrodes coated with mercury films was estimated to generate daily about 1.1 L of aqueous waste containing 0.1 ppm of each metal. The results indicate the feasibility of assembling an apparatus capable of treating the waste generated by stripping voltammetry to render the latter suitable for routine on-site analyses without environmental concern. Data were also obtained to show the effectiveness in treating silver containing solutions, indicating suitability of the photocatalytic process in treating photographic processing wastes.