Distribution equilibrium of mercury (II) chloride between water and air applied to flue gas scrubbing

In the literature, different values of the distribution coefficient KH for HgCl2 between water and air are present in a range that spans more than 3 orders of magnitude. In order to determine if a waste incineration scrubber solution could become saturated with regard to HgCl2, an accurate experimental determination of the distribution constant of HgCl2 at elevated temperatures is needed. In this work, the coefficient has been determined at four different temperatures between 10 and 50 degrees C. The Arrhenius expression obtained is 5.5 x 10(5) x exp[-(8060 +/- 2200)/T] with a corresponding enthalpy for the process HgCl2(aq)<==>HgCl2(g) of 67 +/- 20 kJ/mole. KH at 293 K was found to be approximately 5 x 10(-7) atm M-1, which is in almost perfect agreement with an earlier study. Applying the obtained KH values to waste incineration scrubber conditions shows that no major saturation effect will occur.     

The Adsorptive Capacity of Vapor-Phase Mercury Chloride onto Powdered Activated Carbon Derived from Waste Tires

Abstract

Injection of powdered activated carbon (PAC) upstream of particulate removal devices (such as electrostatic precipitator and baghouses) has been used effectively to remove hazardous air pollutants, particularly mercury-containing pollutants, emitted from combustors and incinerators. Compared with commercial PACs (CPACs), an alternative PAC derived from waste tires (WPAC) was prepared for this study. The equilibrium adsorptive capacity of mercury chloride (HgCl₂) vapor onto the WPAC was further evaluated with a self-designed bench-scale adsorption column system. The adsorption temperatures investigated in the adsorption column were controlled at 25 and 150 °C. The superficial velocity and residence time of the flow were 0.01 m/sec and 4 sec, respectively. The adsorption column tests were run under nitrogen gas flow. Experimental results showed that WPAC with higher Brunauer–Emmett–Teller (BET) surface area could adsorb more HgCl₂ at room temperature. The equilibrium adsorptive capacity of HgCl₂ for WPAC measured in this study was 1.49 × 10^?1 mg HgCl₂/g PAC at 25 °C with an initial HgCl₂ concentration of 25 μg/m³. With the increase of adsorption temperature ≤150 °C, the equilibrium adsorptive capacity of HgCl₂ for WPAC was decreased to 1.×34 10^?1 mg HgCl₂/g PA≤C. Furthermore,WPAC with higher sulfur contents could adsorb even more HgCl₂ because of the reactions between sulfur and Hg²⁺ at 150 °C. It was demonstrated that the mechanisms for adsorbing HgCl₂ onto WPAC were physical adsorption and chemisorption at 25 and 150 °C, respectively. Experimental results also indicated that the apparent overall driving force model appeared to have the good correlation with correlation coefficients (r) >0.998 for HgCl₂ adsorption at 25 and 150 °C. Moreover, the equilibrium adsorptive capacity of HgCl₂ for virgin WPAC was similar to that for CPAC at 25 °C, whereas it was slightly higher for sulfurized WPAC than for CPAC at 150 °C.     

Determination of the Adsorption Isotherm of Vapor-Phase Mercury Chloride on Powdered Activated Carbon Using Thermogravimetric Analysis

Abstract

This study investigated the use of thermogravimetric analysis (TGA) to determine the adsorptive capacity and adsorption isotherm of vapor-phase mercury chloride on powdered activated carbon (PAC). The technique is commonly applied to remove mercury-containing air pollutants from gas streams emitted from municipal solid waste incinerators. An alternative form of powdered activated carbon derived from a pyrolyzed tire char was prepared for use herein. The capacity of waste tire-derived PAC to adsorb vapor-phase HgCl₂ was successfully measured using a self-designed TGA adsorption system. Experimental results showed that the maximum adsorptive capacities of HgCl₂ were 1.75, 0.688, and 0.230 mg of HgCl₂ per gram of powdered activated carbon derived from carbon black at 30, 70, and 150 °C for 500 µg/m³ of HgCl₂, respectively. Four adsorption isotherms obtained using the Langmuir, Freundlich, Redlich-Peterson, and Brunauer–Emmett–Teller (BET) models were used to simulate the adsorption of HgCl₂. The comparison of experimental data associated with the four adsorption isotherms indicated that BET fit the experimental results better than did the other isotherms at 30 °C, whereas the Freundlich isotherm fit the experimental results better at 70 and 150 °C. Furthermore, the calculations of the parameters associated with Langmuir and Freundlich isotherms revealed that the adsorption of HgCl₂ by PAC-derived carbon black favored adsorption at various HgCl₂ concentrations and temperatures.     

Determination of Room Temperature OH Rate Constants for Acetylene,Ethylene Dichloride,Ethylene Dibromide,p-Dichlorobenzene and Carbon Disulfide

A relative rate procedure was used to measure hydroxyl rate constants at room temperature in the presence of oxygen. The photolysis of methyl nitrite in the presence of nitric oxide was used to generate OH radicals. The rate of loss of the test compounds was measured relative to that of ethane (k_OH = 2.74 × 10^-13 cm³ molec^-1 s^-1). The rates obtained at 297 ± 2 K are: acetylene = (7.8 ± 1.6) × 10^-13 cm³ molec^-1 s^-1,1,2-dichloroethane (2.8 ± Q.6) × 10^-13 cm³ molec^-1 s^-1, 1,2-dibromoethane (2.4 ± 0.5) × 10^-13 cm³ molec^-1 s^-1, p-dichlorobenzene (4.3 ± 0.9) × 10^-13 cm³ molec^-1 s^-1 and carbon disulfide (29 ± 6) × 10^-13 cm³ molec^-1 s^-1. Under a proposed EPA rule, this OH rate determination procedure could be used to determine if a given volatile organic will be subject to control for reduction of photochemical ozone.     

Product Guide/1982

Abstract

An efficient venturi scrubber system making use of heterogeneous nucleation and condensational growth of particles was designed and tested to remove fine particles from the exhaust of a local scrubber where residual SiH₄ gas was abated and lots of fine SiO₂ particles were generated. In front of the venturi scrubber, normal-temperature fine-water mist mixes with high-temperature exhaust gas to cool it to the saturation temperature, allowing submicron particles to grow into micron sizes. The grown particles are then scrubbed efficiently in the venturi scrubber. Test results show that the present venturi scrubber system is effective for removing submicron particles. For SiO₂ particles greater than 0.1 μm, the removal efficiency is greater than 80–90%, depending on particle concentration. The corresponding pressure drop is relatively low. For example, the pressure drop of the venturi scrubber is ～15.4 ± 2.4 cm H₂O when the liquid-to-gas ratio is 1.50 L/m³. A theoretical calculation has been conducted to simulate particle growth process and the removal efficiency of the venturi scrubber. The theoretical results agree with the experimental data reasonably well when SiO₂ particle diameter is greater than 0.1 μm.     

Rate Constants for the Reaction of OH with Halocarbons in the Presence of O2 + N2

Rates of CO₂ production in the reaction CO + OH and CO + OH + halocarbon have been used to determine rate constants for some OH + halocarbon reactions at 29.5°C relative to that of k(CO + OH) = 2.69 × 10^?13 cm³ molecule^?1 sec^?1. The following rate constants were obtained: k(OH + CH₃Cl) = 3.1 ± 0.8, k(OH + CH₂Cl₂) = 2.7 ± 1.0, k(OH + C₂H₅Cl) = 44.0 ± 25, k(OH + CICH₂CH₂CI) = 6.5, (<29) and k(OH + CH₃CCl₃) = 2.1 (<5.7) cm³ molecule^?1 sec^?1 × 10^?14. The k values, CH₂Cl₂ excepted, are in substantial agreement with determinations made in nonoxygen environments. The present results for CH₂Cl₂ are almost certainly in error due to difficulties with the competitive approach used.     

Roadside Particulate Air Pollution in Bangkok

Abstract

Airborne fine particles of PM_2.5-10 and PM_2.5 in Bangkok, Nonthaburi, and Ayutthaya were measured from December 22, 1998, to March 26, 1999, and from November 30, 1999, to December 2, 1999. Almost all the PM₁₀ values in the high-polluted (H) area exceeded the Thailand National Ambient Air Quality Standards (NAAQS) of 120 μg/m³. The low-polluted (L) area showed low PM₁₀ (34–74 μg/m³ in the daytime and 54–89 μg/m³ at night). PM_2.5 in the H area varied between 82 and 143 μg/m³ in the daytime and between 45 and 146 μg/m³ at night. In the L area, PM_2.5 was quite low both day and night and varied between 24 and 54 μg/m³, lower than the U.S. Environmental Protection Agency (EPA) standard (65 μg/m³). The personal exposure results showed a significantly higher proportion of PM_2.5 to PM₁₀ in the H area than in the L area (H = 0.80 ± 0.08 and L = 0.65 ± 0.04).

Roadside PM₁₀ was measured simultaneously with the Thailand Pollution Control Department (PCD) monitoring station at the same site and at the intersections where police work. The result from dual simultaneous measurements of PM₁₀ showed a good correlation (correlation coefficient: r = 0.93); however, PM levels near the roadside at the intersections were higher than the concentrations at the monitoring station. The relationship between ambient PM level and actual personal exposures was examined. Correlation coefficients between the general ambient outdoors and personal exposure levels were 0.92 for both PM_2.5 and PM₁₀.

Bangkok air quality data for 1997–2000, including 24-hr average PM₁₀, NO₂, SO₂, and O₃ from eight PCD monitoring stations, were analyzed and validated. The annual arithmetic mean PM₁₀ of the PCD data at the roadside monitoring stations for the last 3 years decreased from 130 to 73 μg/m³, whereas the corresponding levels at the general monitoring stations decreased from 90 to 49 μg/m³. The proportion of days when the level of the 24-hr average PM₁₀ exceeded the NAAQS was between 13 and 26% at roadside stations. PCD data showed PM₁₀ was well correlated with NO₂ but not with SO₂, suggesting that automobile exhaust is the main source of the particulate air pollution. The results obtained from the simultaneous measurement of PM_2.5 and PM₁₀ indicate the potential environmental health hazard of fine particles. In conclusion, Bangkok traffic police were exposed to high levels of automobile-derived particulate air pollution.     

Relationship of Particulate Control,SO2 Removal,and Waste Management

Results with the EPRI 2.5 MW(e) Integrated Environmental Control Pilot Plant (IECPP) indicate the interrelationship of particulate penetration, SO₂ scrubber operation, waste production, and waste properties. Tests compared a fabric filter/wet scrubber and ESP/wet scrubber, the latter operated to simulate 1979 New Source Performance Standards (NSPS), 1971 NSPS, and pre-NSPS ESP units. Tests were conducted with low-sulfur coal producing a flue gas concentration of400ppm; flue gas spiking could be used to increase SO₂ to 2000 ppm. Scrubber waste was dewatered in a thickener and vacuum belt filter (to 55 percent solids content), and mixed with fly ash. The pilot SO₂ scrubber—when preceded by an ESP and forced to operate in zero-discharge—captured less SO₂ than when preceded by a fabric filter. Also, scrubber operation with the ESP produced a greater quantity of waste with difficult handling characteristics, as compared to operation with the fabric filter. These difficulties occurred with particulate penetration above 0.10 lb/MBtu, which could reduce reagent utilization to 80percent. These results are attributable to inhibited limestone dissolution due to accumulation of an aluminum/fluoride compound. For both lowsulfur and simulated high-sulfur test conditions, allowing wastewater discharge to purge aluminum/fluoride content restored performance to design levels. Particulate control efficiency also affected solid waste physical properties. The fabric filter/wet scrubber produced the lowest solid waste permeability (10^?8 cm/s). ESP operation at 1979 NSPS and pre-1971 NSPS ESPs increased solid waste permeability to 10^?7 and 10^?6 cm/s, respectively. These results are meaningful for SO₂ scrubbers both for new plants and for retrofit to units with pre-NSPS ESPs, and could become significant with the increasing trend to restricted water discharge.     

Low Concentration Mercury Sorption Mechanisms and Control by Calcium-Based Sorbents: Application in Coal-Fired Processes

ABSTRACT

The capture of elemental mercury (Hg⁰) and mercuric chloride (HgCl₂) by three types of calcium (Ca)-based sor-bents was examined in this bench-scale study under conditions prevalent in coal-fired utilities. Ca-based sorbent performances were compared with that of an activated carbon. Hg⁰ capture of about 40% (nearly half that of the activated carbon) was achieved by two of the Ca-based sorbents. The presence of sulfur dioxide (SO₂) in the simulated coal combustion flue gas enhanced the Hg⁰ capture from about 10 to 40%. Increasing the temperature in the range of 65-100 °C also caused an increase in the Hg⁰ capture by the two Ca-based sorbents. Mercuric chloride (HgCl₂) capture exhibited a totally different pattern. The presence of SO₂ inhibited the HgCl₂ capture by Ca-based sorbents from about 25 to less than 10%. Increasing the temperature in the studied range also caused a decrease in HgCl₂ capture. Upon further pilot-scale confirmations, the results obtained in this bench-scale study can be used to design and manufacture more cost-effective mercury sorbents to replace conventional sorbents already in use in mercury control.     

Relative rate measurements of reactions of unsaturated alcohols with atomic chlorine as a function of temperature

The kinetics of two structurally similar unsaturated alcohols, 3-butene-2-ol and 2-methyl-3-butene-2-ol (MBO232), with Cl atoms have been investigated for the first time, as a function of temperature using a relative method. As far as we know, the present work also provides the first value for 3-buten-2-ol. The coefficient at room temperature was also obtained for 2-propene-1-ol (allyl alcohol). The reactions were investigated using a 400 L Teflon reaction chamber coupled with gas chromatograph-coupled with flame-ionization detection (GC-FID) detection. The experiments were performed at atmospheric pressure and at temperatures between 256 and 298 K in air or nitrogen as the bath gas. The obtained kinetic data were used to derive the Arrhenius expressions, k_MBO232=(2.83±2.50)×10⁻¹⁴ exp (2670±249)/T, k_3-buten-2-ol=(0.65±1.60)×10⁻¹⁵ exp (3656±695)/T (in units of cm³ molecule⁻¹ s⁻¹). Finally, results and atmospheric implications are discussed and compared with the reactivity with OH and NO₃ radicals.     

Impact of Polycyclic Aromatic Hydrocarbon Emissions from Medical Waste Incinerators on the Urban Atmosphere

Abstract

In this study, polycyclic aromatic hydrocarbon (PAH) emissions from two batch-type medical waste incinerators (MWIs), one with a mechanical grate and the other with a fixed grate, both operated by a medical center, were assessed. Both MWIs shared the same air-pollution control devices (APCDs), with an electrostatic precipitator and a wet scrubber installed in series. Results show that when APCDs were used, total PAHs and total benzo- [a]pyrene equivalent (total BaP_eq) emission concentrations of both MWIs were reduced from 2220 to 1870 µg/m³ and 50 to 12.4 µg/m³, respectively. We used the Industrial Source Complex Short Term model (ISCST) to estimate the ground-level concentrations of the residential area and the traffic intersection located at the down-wind side of the two MWIs. For the traffic intersection, we found both total PAHs and total BaP_eq transported from MWIs to both studied areas were not significant. For the residential area, similar results were found when APCDs were used in MWIs. When APCDs were not included, we found that total PAHs transported from MWIs accounted for <12%, but total BaP_eq accounted for >90%, of the on-site measured concentrations. These results suggest that the use of proper APCDs during incineration would significantly reduce the carcinogenic potencies associated with PAH emissions from MWIs to the residential area.     

Kinetics and the mass transfer mechanism of hydrogen sulfide removal by biochar derived from rice hull

The biochar derived from rice hull was evaluated for its abilities to remove hydrogen sulfide (H₂S) from gas phase. The surface area and pH of the biochar were compared. The biochar derived from rice hull was evaluated for its abilities to remove hydrogen sulfide (H₂S) from gas phase. The surface area and pH of the biochar were compared. The different pyrolysis temperature has great influence on the adsorption of H₂S. At the different pyrolysis temperature, the H₂S removal efficiency of rice hull-derived biochar was different. The adsorption capacities of biochar were 2.09 mg·g^–1, 2.65 mg·g^–1, 16.30 mg·g^–1, 20.80 mg·g^–1, and 382.70 mg·g^–1, which their pyrolysis temperatures were 100 °C, 200 °C, 300 °C, 400 °C and 500 °C respectively. Based on the Yoon-Nelson model, it analyzed the mass transfer mechanism of hydrogen sulfide adsorption by biochar.

Implications: The paper focuses on the biochar derived from rice hull–removed hydrogen sulfide (H₂S) from gas phase. The surface area and pH of the biochar were compared. The different pyrolysis temperatures have great influence on the adsorption of H₂S. At the different pyrolysis temperatures, the H₂S removal efficiency of rice hull–derived biohar was different. The adsorption capacities of biochar were 2.09, 2.65, 16.30, 20.80, and 382.70 mg·g^?1, and their pyrolysis temperatures were 100, 200, 300, 400, and 500 °C, respectively. Based on the Yoon-Nelson model, the mass transfer mechanism of hydrogen sulfide adsorption by biochar was analyzed.     

Quick vaporization of sprayed sodium hypochlorite (NaClO(aq)) for simultaneous removal of nitrogen oxides (NOx), sulfur dioxide (SO2), and mercury (Hg0)

Sodium hypochlorite (NaClO) has been widely used as a chemical additive for enhancing nitrogen oxide (NO_x; NO + NO₂), sulfur dioxide (SO₂), and mercury (Hg⁰) removals in a wet scrubber. However, they are each uniquely dependent on NaClO_(aq) pH, hence making the simultaneous control difficult. In order to overcome this weakness, we sprayed low liquid-to-gas (L/G) ratio (0.1 L/Nm³) of NaClO_(aq) to vaporize quickly at 165 °C. Results have shown that the maximized NO_x, SO₂, and Hg⁰ removals can be achieved at the pH range between 4.0 and 6.0. When NO_x and Hg⁰ coexist with SO₂, in addition, their removals are significantly enhanced by reactions with solid and gaseous by-products such as NaClO_(s), NaClO_2(s), OClO, ClO, and Cl species, originated from the reaction between SO₂ and NaClO_(aq). We have also demonstrated the feasibility of this approach in the real flue gases of a combustion plant and observed 50%, 80%, and 60% of NO_x, SO₂, and Hg⁰ removals, respectively. These findings led us to conclude that the spray of NaClO_(aq) at a relatively high temperature at which the sprayed solution can vaporize quickly makes the simultaneous control of NO_x, SO₂, and Hg⁰ possible.

Implications: The simple spray of NaClO_(aq) at temperatures above 165 °C can cause the simultaneous removal of gaseous NO_x, SO₂, and Hg⁰ by its quick vaporization. Their maximized removals are achieved at the pH range between 4.0 and 6.0. NO_x and Hg⁰ removals are also enhanced by gaseous and solid intermediate products generated from the reaction of SO₂ with NaClO_(aq). The feasibility of this approach has been demonstrated in the real flue gases of a combustion plant.     

Inactivation of airborne Enterococcus faecalis and infectious bursal disease virus using a pilot-scale ultraviolet photocatalytic oxidation scrubber

High microbial concentrations and emissions associated with livestock houses raise health and environmental concerns. A pilot-scale ultraviolet photocatalytic oxidation (UV-PCO) scrubber was tested for its efficacy to inactivate aerosolized Enterococcus faecalis and infectious bursal disease virus (IBDV). Microbial reduction was determined by the difference in microbial concentrations measured in the upstream and downstream isolators that were connected to the two ends of the UV-PCO scrubber. Two UV irradiance levels were tested by using one or two UV lamps. The theoretical average UV irradiances were 6,595 µ W cm^?2 with one UV lamp and 12,799 µ W cm^?2 with two UV lamps. At the tested ventilation rate (70 m³ hr^?1), the contact time was 1 sec. Reduction rate and other two indexes (k-value and Z-value) that normalized UV radiation were calculated to describe the extent of microbial inactivation. The UV-PCO scrubber eliminated >99.7% of airborne E. faecalis from the incoming airstream under one UV lamp irradiance, and the reduction was further increased by 0.2–0.3% when the second UV lamp was added. The reduction rate for airborne IBDV was 72.4% with one UV lamp. The calculated k-values were 0.501–0.594 cm² mJ^?1 for airborne E. faecalis and 0.217 cm² mJ^?1 for IBDV. The Z-value of airborne E. faecalis to UV irradiance was 9.3 (±1.6)?×?10^?4 cm² µ W^?1 sec^?1. The results indicate that a UV-PCO scrubber can serve as an effective and efficient technology for inactivating airborne bacteria and virus. Scaling up of the pilot-scale scrubber for field use will require considerations such as design air treatment capacity, UV irradiance level, contact time, dust concentration, susceptibility of target microorganisms, and expected reduction rate.

Implications: This work demonstrated that a UV-PCO scrubber can be used to inactivate animal-associated airborne microorganisms, thus reducing microbial emissions from livestock houses and minimizing the biological impact to ambient environment. The microbial reduction efficiency by the UV-PCO scrubber varied depended on the level of UV irradiation and the target microbial species. The tested viral species (infectious bursal disease virus) was more resistant to the UV-PCO scrubber as compared to its counterpart bacterial species (E. faecalis).     

The comparison of fossil carbon fraction and greenhouse gas emissions through an analysis of exhaust gases from urban solid waste incineration facilities

In this study, in order to understand accurate calculation of greenhouse gas emissions of urban solid waste incineration facilities, which are major waste incineration facilities, and problems likely to occur at this time, emissions were calculated by classifying calculation methods into 3 types. For the comparison of calculation methods, the waste characteristics ratio, dry substance content by waste characteristics, carbon content in dry substance, and ¹²C content were analyzed; and in particular, CO₂ concentration in incineration gases and ¹²C content were analyzed together. In this study, 3 types of calculation methods were made through the assay value, and by using each calculation method, emissions of urban solid waste incineration facilities were calculated then compared. As a result of comparison, with Calculation Method A, which used the default value as presented in the IPCC guidelines, greenhouse gas emissions were calculated for the urban solid waste incineration facilities A and B at 244.43 ton CO₂/day and 322.09 ton CO₂/day, respectively. Hence, it showed a lot of difference from Calculation Methods B and C, which used the assay value of this study. It is determined that this was because the default value as presented in IPCC, as the world average value, could not reflect the characteristics of urban solid waste incineration facilities. Calculation Method B indicated 163.31 ton CO₂/day and 230.34 ton CO₂/day respectively for the urban solid waste incineration facilities A and B; also, Calculation Method C indicated 151.79 ton CO₂/day and 218.99 ton CO₂/day, respectively.

Implications: This study intends to compare greenhouse gas emissions calculated using ¹²C content default value provided by the IPCC (Intergovernmental Panel on Climate Change) with greenhouse gas emissions calculated using ¹²C content and waste assay value that can reflect the characteristics of the target urban solid waste incineration facilities. Also, the concentration and ¹²C content were calculated by directly collecting incineration gases of the target urban solid waste incineration facilities, and greenhouse gas emissions of the target urban solid waste incineration facilities through this survey were compared with greenhouse gas emissions, which used the previously calculated assay value of solid waste.     

IMR-MS on-line measurements in the exhaust gas of a municipal solid waste incineration pilot plant (Tamara)

The major inorganic components identified by ion-molecule reaction mass spectrometry (IMR-MS) raw gas measurements performed at the TAMARA facility include O₂, H₂O, CO₂, HCl, SO₂ and NO Higher concentrations of organic components, i.e. organic substance amounts > 10 m:1/m³ are not observed during normal operation. The concentrations of acetic and formic acids measured in the raw gas by the IMR-MS method range between “not detectable” (i.e. < 0.5 mg/Nm³) and 5 mg/Nm³. A relationship to the incineration parameters has not yet been established In case of operation failures, which are indicated by a CO increase, other organic compounds, e.g. acetaldehyde or benzene can be identified by the IMR-MS method Hence, the results obtained by IMR-MS in on-line emission control of a waste incineration gas are far more precise than the FID values. By IMR-MS measurements above the waste bed, a multitude of strong signals are recorded, which indicates the presence of a number of organic compounds in high concentrations (10 – 10000 mg/Nm³). A quantification during a “snapshot” has been accomplished for benzene (4000 mg/Nm³) and toluene (300 mg/Nm³).     

Performance of a Semi-Industrial Scale Gasification Process for the Destruction of Polychlorinated Biphenyls

Abstract

A semi-industrial scale test was conducted to thermally treat mixtures of spent oil and askarels at a concentration of 50,000 ppm and 100,000 ppm of polychlorinated biphenyls (PCBs) under a reductive atmosphere. In average, the dry-basis composition of the synthesis gas (syngas) obtained from the gasification process was: hydrogen 46%, CO 34%, CO₂ 18%, and CH₄ 0.8%. PCBs, polychlorinated dibenzo-p-dioxins, and polychlorinated dibenzofurans (PCDDs/PCDFs) in the gas stream were analyzed by high-resolution gas chromatography (GC)-mass spec-trometry. The coplanar PCBs congeners 77, 105, 118, 156/157, and 167 were detected in the syngas at concentrations <2 ×10^?7 mg/m³ (at 298 K, 1 atm, dry basis, 7% O₂). The chlorine released in the destruction of the PCBs was transformed to hydrogen chloride and separated from the gas by an alkaline wet scrubber. The concentration of PCBs in the water leaving the scrubber was below the detection limit of 0.002 mg/L, whereas the destruction and removal efficiency was >99.9999% for both tests conducted. The concentration of PCDDs/PCDFs in the syngas were 8.1 ×10^?6 ng-toxic equivalent (TEQ)/m³ and 7.1 × 10^?6 ng-TEQ/m³ (at 298 K, 1 atm, dry basis, 7% O₂) for the tests at 50,000 ppm and 100,000 ppm PCBs, respectively. The only PCDD/F congener detected in the gas was the octachloro-dibenzo-p-dioxin, which has a toxic equivalent factor of 0.001. The results obtained for other pollutants (e.g., metals and particulate matter) meet the maximum allowed emission limits according to Mexican, U.S., and European regulations for the thermal treatment of hazardous waste (excluding CO, which is a major component of the syngas, and total hydrocarbons, which mainly represent the presence of CH₄).     

Hg Reactions in the Presence of Chlorine Species: Homogeneous Gas Phase and Heterogeneous Gas-Solid Phase

Abstract

The kinetics of Hg chlorination (with HCl) was studied using a flow reactor system with an online Hg analyzer, and speciation sampling using a set of impingers. Kinetic parameters, such as reaction order (α), overall rate constant (k′ ), and activation energy (E _a), were estimated based on the simple overall reaction pathway. The reaction order with respect to C _Hg, k′, and E _a were found to be 1.55, 5.07 x 10^-2exp(-1939.68/T) [(μg/m³)^-0.55(s)^-1], and 16.13 [kJ/mol], respectively. The effect of chlorine species (HCl, CH₂Cl₂) on the in situ Hg capture method previously de-veloped²⁸ was also investigated. The efficiency of capture of Hg by this in situ method was higher than 98% in the presence of chlorine species. Furthermore, under certain conditions, the presence of chlorine enhanced the removal of elemental Hg by additional gas-phase oxidation.     

Emissions of Polychlorinated Dibenzo-p-Dioxins and Dibenzofurans from Various Industrial Sources

Abstract

This study characterized the emissions of polychlorinated dibenzo-p-dioxins (PCDDs) and polychlorinated dibenzofurans (PCDFs) from the stack flue gases of 17 industrial sources, which were classified into 10 categories. The results show that the mean PCDD/PCDF concentration of secondary zinc smelter (Zn-S) and secondary copper smelter (Cu-S) is 2.44 ng international toxic equivalent (I-TEQ)/Nm³ (N represents normal conditions at 0 °C, 760 mmHg), which was found to be significantly greater than that of industrial waste incinerators (mean concentration = 0.15 ng I-TEQ/Nm³). These results imply that the controlling of secondary metallurgical melting processes is more important than industrial waste incineration for the reduction of PCDD/PCDF emissions. The mean emission factors of cement production, Zn-S and Cu-S, are 0.052, 1.99, and 1.73 μg I-TEQ/t product, respectively. For industrial waste incineration, the mean emission factors of waste rubber, waste liquor, waste sludge, industrial waste solid (IWI)-1, IWI-2, IWI-3, and IWI-4 are 0.752, 0.435, 0.760, 6.64, 1.67, 2.38, and 0.094 μg I-TEQ/t feed, respectively. Most of the PCDD/PCDF emission factors established in this study are less than those reported in previous studies, which could be because of the more stringent regulations for PCDD/PCDF emissions in recent years.     

Loading Effect Correction for Real-Time Aethalometer Measurements of Fresh Diesel Soot

Abstract

In this study, a correction was developed for the aethalometer to measure real-time black carbon (BC) concentrations in an environment dominated by fresh diesel soot. The relationship between the actual mass-specific absorption coefficient for BC and the BC-dependent attenuation coefficients was determined from experiments conducted in a diesel exposure chamber that provided constant concentrations of fine particulate matter (PM; PM_2.5; PM <2.5 µm in aerodynamic diameter) from diesel exhaust. The aethalometer reported BC concentrations decreasing with time from 48.1 to 31.5 µg m^?3when exposed to constant PM_2.5concentrations of 55 ± 1 µg m^?3and b_scat= 95 ± 3 Mm^?1from diesel exhaust. This apparent decrease in reported light-absorbing PM concentration was used to derive a correction K(ATN) for loading of strong light-absorbing particles onto or into the aethalometer filter tape, which was a function of attenuation of light at 880 nm by the embedded particles.