Dioxins and furans formation in pilot incineration tests of sewage sludge spiked with organic chlorine

The factors affecting polychlorinated dibenzo-p-dioxins (PCDD) and polychlorinated dibenzofurans (PCDF) formation were studied in sewage sludge incineration tests carried out on a demonstrative plant. The plant includes a circulating fluidised bed furnace (FBF) and a rotary kiln furnace (RKF), operating alternatively. During the tests sewage sludge was spiked with chlorinated hydrocarbons and the operating parameters of the afterburning chamber were varied. PCDD/F were sampled in each test before the bag filter, thus collecting the above contaminants before abatement systems. From the tests it appeared that PCDD/F were always produced in more abundance in the tests carried out by FBF than by RKF. The higher PCDD/F concentrations in the tests by FBF were reached when sewage sludge was spiked with a high dosage of a surrogate organic mixture of chlorinated hydrocarbons and when the afterburning chamber was used only as transit equipment with the burner off. The distribution of the different PCDD/F homologues was compared. P5CDFs were generally the prevalent fraction, with very few exceptions for the tests by RKF at high temperature of the afterburning chamber. As for FBF tests, it was found that the PCDD/F homologue profile depends on the afterburning chamber temperature.     

Flame Temperature in Oil-Fired Fuel-Burning Equipment and its Relationship to Carbonaceous Particulate Emissions

Field tests were conducted on 82 fuel-burning installations ranging from 50 to 500 hp, fired with residual fuel oils. A flame pyrometer was used to measure peak flame temperatures. Coarse particulates were measured by impingement on adhesive paper strips inserted at right angles to the gas flow and fine particulates by filtration of the gas sample through filter paper. Both were evaluated using a standard Bacharach Scale. The tests clearly established that both coarse and fine particulate matter invariably occurred with low flame temperatures but decreased appreciably when peak flame temperatures reached approximately 2650°F; Minimum values were observed at temperatures somewhere between 2750 and 2850°F. This research was conducted as a result of the problem of acid smut and carbonaceous (ceno-sphere) fallout which appears to have increased with the advent of modern high-efficiency low-temperature heating installations and taller, cooler operating chimneys; sudden deluges of particles from the chimney serving large oil-burning plants soil clothing, pit car finishes, and damage nylon stockings and other materials.     

The IMPROVE_A Temperature Protocol for Thermal/Optical Carbon Analysis: Maintaining Consistency with a Long-Term Database

Abstract

Thermally derived carbon fractions including organic carbon (OC) and elemental carbon (EC) have been reported for the U.S. Interagency Monitoring of PROtected Visual Environments (IMPROVE) network since 1987 and have been found useful in source apportionment studies and to evaluate quartz-fiber filter adsorption of organic vapors. The IMPROVE_A temperature protocol defines temperature plateaus for thermally derived carbon fractions of 140 °C for OC1, 280 °C for OC2, 480 °C for OC3, and 580 °C for OC4 in a helium (He) carrier gas and 580 °C for EC1, 740 °C for EC2, and 840 °C for EC3 in a 98% He/2% oxygen (O₂) carrier gas. These temperatures differ from those used previously because new hardware used for the IMPROVE thermal/optical reflectance (IMPROVE_TOR) protocol better represents the sample temperature than did the old hardware. A newly developed temperature calibration method demonstrates that these temperatures better represent sample temperatures in the older units used to quantify IMPROVE carbon fractions from 1987 through 2004. Only the thermal fractions are affected by changes in temperature. The OC and EC by TOR are insensitive to the change in temperature protocol, and therefore the long-term consistency of the IMPROVE database is conserved. A method to detect small quantities of O₂ in the pure He carrier gas shows that O₂ levels above 100 ppmv also affect the comparability of thermal carbon fractions but have little effect on the IMPROVE_TOR split between OC and EC.     

A Study of Catalyst Support Systems for Fume-Abatement of Hydrocarbon Solvents

In a stainless steel pilot plant system, operating with combined thermal incineration and catalytic oxidation, studies have been made of the influence of catalyst-support geometry on abatement efficiency. Catalyst supports tested were ceramic spherical pellets, metal foils, and ceramic honeycomb structures, all with precious metal catalyst. Data obtained cover a range of space velocities from 30,000 to 175,000 scf/hr— cu ft bed and a range of catalytic reactor temperatures from 150 to 450°C. Results show that optimum fume-abatement performance is obtained by combining incineration and catalytic oxidation and that catalyst support geometry has a significant effect on performance.     

Advanced Concepts in FGD Technology: The SHU Process with Cooling Tower Discharge

The growing awareness of ecological issues in Europe, reinforced by the public debate surrounding acid rain, has led to the enactment of laws and regulations in West Germany relating to emissions from large coal fired combustors.

Flue gas desulfurization (FGD) units have been compulsory for new coal fired power plants in West Germany for about 12 years. The new legislation enacted in 1983, to be met by the middle of 1988, applies not only to new plants but, unlike in the United States, also to. existing power plants (>30MW).

The law currently specifies a residual SO2 emission level of 400 mg/Nm³ (0.311b MM/BTU) for large power plants (>100 MW), but a level of 200 mg/Nm³ (0.15 lb MM/BTU) is already under discussion in some cases. The legally binding emission standards stipulate that none of the daily averages, calculated on the basis of half hour averages may exceed the concentration allowed. SO2 removal efficiencies of 90 percent to 95 percent are normally provided. Since 1983, more than 35,000 MW of retrofit FGD units have been installed in Germany to meet this SO₂ standard.

The regulations also do not allow for the ponding of calcium sulfite scrubber sludge, but stipulate the production of gypsum from limestone slurry processes. Additionally the regulations require flue gases to have a minimum temperature in the stack of 72° C (162°F) after desulfurization. Treated flue gases do not have to be reheated if discharged via a cooling tower.     

Correlation of PCDD/F Emissions with Operating Parameters of Municipal Solid Waste Incinerators

ABSTRACT

Municipal solid waste incinerator (MSWI) operators frequently have expressed the need for an indirect indication of the expected production of PCDD/F and associated abatement procedures through a possible correlation with other real-time data, through using marker pollutants (e.g., penta/hexachlorinated aromatics), or through other indications. Since real-time measurement of PCDD/F is impossible, a correlation of PCDD/F emissions with other operating parameters could help in achieving these goals. Literature data of large-scale MSWIs concerning these correlations are scarce and seldom conclusive. Extensive data of Flemish MSWIs are used to statistically assess possible correlations of PCDD/F and other operating parameters.

The effect of temperature in the electrostatic precipita-tor (ESP) is of major importance. When converting values measured between 180 and 270 °C to a reference temperature of, for example, 230 °C, PCDD/F concentrations achieve nearly constant values, stressing that the major correlating parameter is the temperature of the ESP. High temperatures that enhance de novo synthesis should be avoided.     

Progress in High-Temperature Electrostatic Precipitation

Current-voltage relationships for negative corona are given for a pilot-scale electrostatic precipitator with 3-in. electrode spacing at 80°–1500°F and 35–80 psig. Direct comparison is made with the electrical characteristics for a 1-in. spacing at 1200°F over the same pressure range. Experimental results on both spacing agree well with electrostatic theory. Initial dust removal efficiencies for the pilot-scale precipitator ranged from 90 to 98% at 1460°F and 80 psig, but continuous operation was not achieved owing to excessive thermal expansion of the internal parts of the unit.     

Silica-Enhanced Sorbents for Dry Injection Removal of SO2 from Flue Gas

Novel silica-enhanced lime sorbents were tested in a bench-scale sand-bed reactor for their potential for SO₂ removal from flue gas. Reactor conditions were 64°C (147°F), relative humidity of 60 percent [corresponding to an approach to saturation temperature of 10°C (18°F)], and inlet SO₂ concentration of 500 or 1000 ppm. The sorbents were prepared by pressure hydration of CaO or Ca(OH)₂ with siliceous materials at 100°C (101 kPa) [212°F (14.7 psi)] to 230°C (2793 kPa) [446°F (405 psi)] for 15 min to 4 h. Pressure hydration fostered the formation of a sorbent reactive with SO₂ from fly ash and Ca(OH)₂ in a much shorter time than did atmospheric hydration. The conversion of Ca(OH)₂ in the sand-bed reactor increased with the increasing weight ratio of fly ash to lime and correlated well with B.E.T. surface area, increasing with increasing surface area. The optimum temperature range for the pressure-hydration of fly ash with Ca(OH)₂ was between 110 and 160°C (230 and 320 °F). The pressure hydration of diatomaceous earth with CaO did not offer significant reactivity advantages over atmospheric hydration; however, the rate of enhancement of Ca(OH)₂ conversions was much faster with pressure hydration. Scanning electron microscope (SEM) and x-ray diffraction studies showed solids of different morphology with different fly ash/lime ratios and changing conditions of pressure hydration.     

The formation and emission of dioxins in large scale thermal processes

The paper assesses extensive data of PCDD/F measurements on flue gas emissions from thermal processes, including, e.g. municipal solid waste incinerators (MSWIs), combustors of wood and industrial waste, coal fired powerplants and boilers, ferro and non-ferro processes. Numerous investigators have conducted laboratory experiments to assess the formation mechanisms of PCDD/F. The results, obtained from fixed-bed experiments, have been critically evaluated and indicate that de novo synthesis is the dominant mechanism in actual thermal processes where conditions that favour the precursor formation are not experienced. The analysis of PCDD/F profiles from the large scale thermal processes in general, and MSWIs in particular, supports the dominant role of the de novo synthesis, irrespective of the type of thermal process considered. The PCDF/PCDD ratio exceeds 1 and the degree of chlorination points towards the dominant presence of HpCDD and OCDD within the dioxin group, and of PeCDF, HxCDF and HpCDF within the furan group. Since real-time measurement of PCDD/F is impossible, the correlation of PCDD/F emissions with operating parameters and/or emission levels of other more easily measured pollutants could be a tool in predicting the PCDD/F formation levels. Data of Flemish MSWIs were used to statistically assess such correlations. From an evaluation of the data at a given operating temperature, misleading conclusions can be drawn. Only the effect of temperature is evident. After converting all data at a reference temperature of, e.g. 230 degrees C, PCDD/F concentrations achieve nearly constant values, irrespective of the values of other parameters, thus stressing that the major controlling parameter for the PCDD/F emission is the temperature of the ESP. The PCDD/F concentrations increase with temperature in the range up to 280 degrees C. The ESP temperature should be kept preferably between 180 degrees C and 200 degrees C, where de novo synthesis is reduced and where PCDD/Fs are increasingly adsorbed on the fly ash, in line with the standard temperature dependence of adsorption isotherms.     

Characterization of Emissions from a Variable Gasoline/Methanol Fueled Car

In response to the occurrence of the increasingly severe ambient ozone exceedances, regional environmental managers are examining the possibility of a cleaner fuel for automobiles. At this time the leading candidate appears to be methanol. In anticipation of a shift to methanol, flexible-fueled automobiles capable of operating on gasoline and/or methanol are being developed. This study examines both the exhaust and evaporative emissions from a prototype General Motors Variable Fuel Corsica. Results are reported for tests conducted at temperatures of 40°, 75°, and 90° F, and for fuels MO M25, M50, M85, and M100. In addition to regulated emissions and fuel economy, emission rates for methanol, aldehydes, and a large number of hydrocarbon compounds were measured. The data indicate that increasing the fuel's methanol content does not affect the exhaust organic emission rate (calculated in accordance with the regulation) from flexible-fueled cars, but formaldehyde and methanol comprise increasingly greater portions of the organic material while hydrocarbons comprise less. Increasing fuel methanol content has no significant effect on exhaust regulated emission rates (organic material, carbon monoxide, and nitrogen oxides) nor on the composition of total hydrocarbons, except for methane, which increases substantially. The effect of ambient temperature on both exhaust and evaporative emissions is similar to its effect on gasoline cars: organic and carbon monoxide exhaust emissions increase substantially at the lower temperatures, and evaporative emissions increase steadily with increases in temperature.     

Feasibility Demonstration of Electrostatic Precipitation at 1700°F

An experimental high-temperature, high-pressure electrostatic precipitator module has been designed, fabricated and then evaluated in a gaseous environment having the characteristics anticipated for the combustion chamber of a system for generating electric power from the incineration of municipal solid wastes.

Stable positive and negative corona discharges were established in combustion gases from the burning of methanol and air (temperature and pressure approximately 1700°F and 100 psig, respectively) without any apparent deleterious effects due to thermal ionization and/or emission. At gas conditions of about 1700°F and 50 psig, positive polarity energization of the discharge electrode appeared superior to that of negative polarity in terms of voltage level that could be applied and electrical stability.

However, precipitator performance on removal of alumina dust injected under controlled conditions with the methanol fuel, showed negative polarity to be superior to positive polarity at the selected conditions of 1650°F and 100 psig which closely correspond to those required for optimum operation of the gas turbine presently under consideration. Removal efficiencies ranging from 25% for positive polarity to as high as 87% with negative polarity were measured.

In order to check whether materials having a low ionization potential would thermally ionize to such an extent that the voltage-corona current characteristics of the precipitator would be impaired, rendering it ineffective, potassium chloride salt in solution was injected with the fuel. Results indicated that amounts of approximately one part by weight of potassium ion in 2500 to 3000 parts by weight of gas at 1700°F tripled the current measured for a given voltage when compared to non-injection.

Although a limited test program was conducted, sufficient data were obtained to allow preliminary design and sizing of larger scale units.     

Dioxins from thermal and metallurgical processes: recent studies for the iron and steel industry

In thermal metallurgical processes such as iron ore sintering and metal smelting operations, large flows of off-gases are generated. Mainly due to residue recycling in such processes, chlorine and volatile organics are always present in the feed. As a consequence of "de novo" formation, the off-gases from such processes typically contain dioxins in the range 0.3-30 ng I-TEQ/Nm3. So far there are only very few studies about the mechanisms of dioxin formation and destruction in these metallurgical processes. In an European Union (EU) research project "Minimization of dioxins in thermal industrial processes: mechanisms, monitoring and abatement (MINIDIP)", integrated iron and steel plant has been selected as one of the industrial sectors for further investigation. A large number of particulate samples (feed, belt siftings, electrofilter) were collected from the iron ore sintering installations from various steel plants and analyzed for their organochlorocompound contents. Measurable amounts of PCDD/F, PCBz, PCB were found for all samples. The various parameters influencing their de novo synthesis activity were also evaluated in laboratory experiments, and such activity was found to be moderate for samples from the ore sinter belt, but extremely high for some ESP dusts. Fine dust is active in a wide range of temperatures starting at 200 degrees C and declining above 450 degrees C; the optimal temperature for de novo synthesis was found to be around 350 degrees C; some inhibitors, such as triethanolamine, may reduce de novo activity by 50%, and lowering the O2 concentration in the gas stream leads to a much lower amount of PCDD/F formation. On the basis of their relative mass, typical operating conditions and specific activity of the different samples, the regions in the sintering plant where de novo synthesis may take place were tentatively established.     

A Method for Predicting the Effective Volume Resistivity of a Sodium Depleted Fly Ash Layer

Research has been conducted to develop a technique for predicting the effective volume resistivity of a fly ash layer that has been exposed to circumstances leading to a hot-side precipitator problem known as sodium depletion. Eight fly ashes, representing a major portion of U.S. coals, were evaluated by subjecting 0.5 cm ash layers to a continuously applied voltage gradient of 4 kV/cm for periods of time up to 35 days at a temperature of 350°C (662°F). Resistivity was determined at 350°C before the test started and after the long period of applied voltage used to create the sodium depleted situation. In this condition, resistivity was also determined at 280°C (536°F) for an average electric field Intensity of 4 kV/cm and immediately prior to breakdown. This experimental method can be used with any ash sample to estimate resistivity In a sodium depleted condition. But in addition, a correlation resulting from these resistivity data has been developed. This correlation Is combined with an existing technique for predicting resistivity to produce a method for calculating the expected ash layer resistivity after sodium depletion has occurred.     

Asphalt Industry Group,APCA and EPA Conduct Environmental Solution Seminars

The levels of benzo(a)pyrene (BaP) were determined in downtown Caracas in order to have a first approach to the problem related to polycyclic aromatic hydrocarbons in this city. Caracas, the capital city of Venezuela is located 10.30° N and 66.77°E in a valley at an altitude of 996 m above sea level with an average temperature ranging from 18° to 23°C, and two distinctive climatic regimes, a dry and a wet season. The population is approximately 2.5 million with a car density of approximately 1000 vehicles/km² and no industry. The valley is surrounded by mountains, the Avila National Park at the northern edge of the city with peaks of around 2200 m being the most important contribution to the green belt that has been preserved. As far as we know no other studies to determine the levels of BaP have been made in a populated urban area located near the equator.     

HCI Sorption by Dry NaHCO3 for Incinerator Emissions Control

The sorption of hydrochloric acid (HCI) by thermally decomposed sodium bicarbonate (NaHCO₃) was investigated using a fixed-bed reactor containing sorbent particles dispersed in a bed of spherical glass beads. The gas flow rate (68° F and 760 mm Hg) was 0.039 cfm (1.1 liter/min) and the bed had a cross-sectional area of 0.0055 sq. ft. (5.1 sq. cm). The influence of particle diameter (10, 45 and 163 μm), temperature (225, 275, 375, 455, and 550° F), superficial gas velocity (11 and 21 fpm at reactor conditions, 375° F), and Inlet HCI gas concentration (415 ppm and 760 ppm in N₂, 275 and 455° F) were studied. Results showed that HCI sorption increased strongly with increasing temperature but was only weakly dependent on particle diameter, superficial gas velocity, and HCI gas concentration.     

Thermal Oxidation Kinetics of Selected Organic Compounds

A thermal oxidizer destroys organic pollutants by oxidation to CO₂ and water. Time, temperature, and turbulence, govern the performance of a thermal oxidizer just as they do all other combustion devices. To achieve a desired degree of destruction, a higher temperature allows the use of a shorter residence time and vice versa. For most organics, a thermal oxidizer designed at 1400°-1500°F with 0.1 to 0.3 seconds residence time is normally enough to obtain nearly complete destruction.¹ However, some chemicals require more extreme conditions. These time-temperature requirements can be determined from kinetic rate studies.     

Combustion experiments using pentachlorophenol on a pilot scale and full-scale

Chlorinated phenols are used at many saw mills for impregnation of saw timber. Waste products containing the used compound follow this process. Tests have been performed on pilot and full-scale in order to investigate the possibility of destroying these wastes by combustion.The pilot scale tests with 70 g of pentachlorophenol show that at a transit time of approximately 3 seconds and a combustion temperature of 600°C the unburnt residue was 50 mg/kg fed in pentachlorophenol. At 800°C the residue decreased to 15 mg/kg. No formation of octachlorodioxin could be proved.The full-scale test with a small amount of pentachlorophenol and a large amount of tetrachlorophenol show that at a transit time of approximately 0.9 seconds and a temperature varying during one test between 620–875° (average 760°C), the unburnt residue was 9 mg/kg for tetrachlorophenol and 650 mg/kg for pentachlorophenol. At an increased load the residue increased gradually, being 5.900 mg/kg for tetrachlorophenol and 7.100 mg/kg for pentachlorophenol at a test when the temperature was varied between 460 and 850° (average 620°C). Analyses of chlorinated dioxins show that octachlorodioxin was found in the flue gas at one of the tests. This may indicate a formation.     

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.     

Application of 1D and 2D MFR reactor technology for the isolation of insecticidal and anti-microbial properties from pyrolysis bio-oils

Valuable chemicals can be separated from agricultural residues by chemical or thermochemical processes. The application of pyrolysis has already been demonstrated as an efficient means to produce a liquid with a high concentration of desired product. The objective of this study was to apply an insect and microorganism bioassay-guided approach to separate and isolate pesticidal compounds from bio-oil produced through biomass pyrolysis. Tobacco leaf (Nicotianata bacum), tomato plant (Solanum lycopersicum), and spent coffee (Coffea arabica) grounds were pyrolyzed at 10°C/min from ambient to 565°C using the mechanically fluidized reactor (MFR). With one-dimensional (1D) MFR pyrolysis, the composition of the product vapors varied as the reactor temperature was raised allowing for the selection of the temperature range that corresponds to vapors with a high concentration of pesticidal properties. Further product separation was performed in a fractional condensation train, or 2D MFR pyrolysis, thus allowing for the separation of vapor components according to their condensation temperature. The 300–400°C tobacco and tomato bio-oil cuts from the 1D MFR showed the highest insecticidal and anti-microbial activity compared to the other bio-oil cuts. The 300–350 and 350–400°C bio-oil cuts produced by 2D MFR had the highest insecticidal activity when the bio-oil was collected from the 210°C condenser. The tobacco and tomato bio-oil had similar insecticidal activity (LC₅₀ of 2.1 and 2.2 mg/mL) when the bio-oil was collected in the 210°C condenser from the 300–350°C reactor temperature gases. The 2D MFR does concentrate the pesticidal products compared to the 1D MFR and thus can reduce the need for further separation steps such as solvent extraction.     

Estimation of fluorine and chlorine emissions from Spanish structural ceramic industries. The case study of the Bailén area,Southern Spain

This paper assesses F and Cl emissions as atmospheric pollutants in the Bailén area (southern Spain), originated from the raw material used in structural ceramic industries. The area is one of the most important in Spain, with a daily output over three million pieces. The Bailén area features three categories of industries taking into account F emissions (the most important pollutant from ceramic clays):Group I: Those releasing less than 150 ppm F, which use raw materials with low F contents and/or high proportion of calcite, and fire at about 850°C.Group II: Those releasing 150–300 ppm F, whose raw materials show low calcite percentages and bricks are fired between 850–1050°C.Group III: Those releasing more than 300 ppm F, which use clays containing over 1000 ppm F and firing temperatures around 900°C.The emission rate of F increases with increasing F content in the raw material and firing temperature (particularly when exceeding 1000°C). The calcite and clay mineral contents control the F emissions up to 950°C; on the other hand, a high heating rate hinders fluorine emission to some extent. The emission rate of Cl increases with increasing temperature, but in the most cases chlorine is released at concentrations below 30 ppm.Atmospheric contamination in the Bailén area can reach 3 kg/h of fluorine and up to twice of chlorine emission levels permitted, owing to the massive production of structural clay products.