Chung-Hsuang Hung

Polychlorinated dibenzo-p-dioxin and dibenzofuran emissions from an industrial park clustered with metallurgical industries

Emissions of polychlorinated dibenzo-p-dioxins and dibenzofurans (PCDD/Fs) from an industrial park operated as Taiwans center of metallurgical industries were investigated. The characteristics of mean PCDD/F I-TEQ concentrations, congener profiles and emission factors of each source were studied over samples of stack flue gases of individual sources. Different characteristics of congener profiles and large variations of emission factors of secondary aluminum smelters (ALSs) were observed. The mean emission factors of electric arc furnaces were comparable to those for ALSs and much greater than those of municipal solid waste incinerators and sinter plants, but still less than that of clinical waste incinerators. Annual PCDD/F emission contribution of each source was estimated, raising critical concerns over the overall PCDD/F emissions from metallurgical processes. The metallurgical industries altogether contributed approximately 98.1% of the total annual emissions, while waste incinerators only 1.9%. The contributions by sinter plants and metallurgical industries to the total annual emissions of the Park were much higher than the corresponding national averages of Taiwan. The combined dioxin emissions from the entire metallurgical processes and their controls should be seriously envisaged by industrial parks devoted to metal productions.

Preparation of Sulfurized Powdered Activated Carbon from Waste Tires Using an Innovative Compositive Impregnation Process

Abstract The objective of this study is to develop an innovative compositive impregnation process for preparing sulfurized powdered activated carbon (PAC) from waste tires. An experimental apparatus, including a pyrolysis and activation system and a sulfur (S) impregnation system, was designed and applied to produce sulfurized PAC with a high specific surface area. Experimental tests involved the pyrolysis, activation, and sulfurization of waste tires. Waste-tire-derived PAC (WPAC) was initially produced in the pyrolysis and activation system. Experimental results indicated that the Brunauer-Emmett-Teller (BET) surface area of WPAC increased, and the average pore radius of WPAC decreased, as water feed rate and activation time increased. In this study, a conventional direct impregnation process was used to prepare the sulfurized PAC by impregnating WPAC with sodium sulfide (Na2S) solution. Furthermore, an innovative compositive impregnation process was developed and then compared with the conventional direct impregnation process. Experimental results showed that the compositive impregnation process produced the sulfurized WPAC with high BET surface area and a high S content. A maximum BET surface area of 886 m2/g and the S content of 2.61% by mass were obtained at 900°C and at the S feed ratio of 2160 mg Na2S/g C. However, the direct impregnation process led to a BET surface area of sulfurized WPAC that decreased significantly as the S content increased.

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.

Enhancing the adsorption of vapor-phase mercury chloride with an innovative composite sulfur-impregnated activated carbon

Mercury chloride (HgCl(2)) is the major mercury derivate emitted from municipal solid waste incinerators, which has high risk to the environment and human health. This study investigated the adsorption of vapor-phase HgCl(2) with an innovative composite sulfurized activated carbon (AC), which was derived from the pyrolysis, activation, and sulfurization of waste tires. The composite sulfur-impregnation process impregnated activated carbon with aqueous-phase sodium sulfide (Na(2)S) and followed with vapor-phase elemental sulfur (S(0)). Thermogravimetric analysis (TGA) was applied to investigate the adsorptive capacity of vapor-phase HgCl(2) using the composite sulfurized AC. The operating parameters included the types of composite sulfurized AC, the adsorption temperature, and the influent HgCl(2) concentration. Experimental results indicated that the sulfur-impregnation process could increase the sulfur content of the sulfurized AC, but decreased its specific surface area. This study further revealed that the composite sulfurized AC impregnated with aqueous-phase Na(2)S and followed with vapor-phase S(0) (Na(2)S+S(0) AC) had much higher saturated adsorptive capacity of HgCl(2) than AC impregnated in the reverse sequence (S(0)+Na(2)S AC). A maximum saturated adsorptive capacity of HgCl(2) up to 5236 μg-HgCl(2)/g-C was observed for the composite Na(2)S+S(0) AC, which was approximately 2.00 and 3.17 times higher than those for the single Na(2)S and S(0) ACs, respectively.

Parameter Effects and Reaction Pathways of Photoreduction of CO2 over TiO2/SO42– Photocatalyst

Abstract The feasibility of applying a modified acidic photocatalyst (TiO2/SO42–) to reduce carbon dioxide was investigated. The photocatalytic reduction of CO2 was conducted in a bench-scale batch photocatalytic reactor. Three near-UV black lamps with a maximal spectrum wavelength of 365 nm were assembled on the top of the reactor to provide an average irradiation intensity of 2.0 mW/cm2. The TiO2/SO42– photocatalyst was prepared by a modified sol–gel process and coated on stainless steel substrates for the reduction of CO2. Experimental parameters such as reductants, the initial CO2 concentration, and the reaction temperature were investigated. The results indicated that the highest photoreduction rate of CO2 was observed using H2 as a reductant over TiO2/SO42–. The major gaseous products from CO2 photoreduction were carbon monoxide and methane, while other minor products of ethene and ethane were also detected. The photoreduction rate of CO2 was increased with initial CO2 concentration and reaction temperature, which promoted the formation of products. Furthermore, the FT-IR spectra showed that formic acid, methanol, carbonate ions, formaldehyde, and methyl formate formed on the surface of TiO2/SO42– photocatalyst. Two reaction pathways of CO2 photoreduction over TiO2/SO42– were proposed. One reaction pathway described the formation of gaseous products CO, CH4, C2H4, and C2H6. The other reaction pathway formed CO3ads2–, CH3OHads, HCOOads−, HCOOHads, HCOHads, and HCOOCH3ads on the surface of the TiO2/SO42– photocatalyst.

Enhanced photocatalytic oxidation of gaseous elemental mercury by TiO2 in a high temperature environment

The photo-oxidation of Hg(0) in a lab-scale reactor by titanium dioxide (TiO2) coated on the surface of glass beads was investigated at high temperatures. TiO2 was calcinated at four different temperatures of 300 °C, 400 °C, 500 °C and 600 °C (noted as Ti300, Ti400, Ti500 and Ti600) and characterized for its physicochemical properties. The calcinated TiO2 coating on the glass beads was then tested to compare the photo-oxidation efficiencies of Hg(0) with an incident light of 365 nm. The results showed that the oxidation efficiencies of Hg(0) for Ti400 and Ti500 were higher than those of Ti300 and Ti600. To enhance the photo-oxidation efficiency of Hg(0), Ti400 was selected to examine the wave lengths (λ) of 254 nm, 365 nm and visible light with various influent Hg(0) concentrations. The effects of irradiation strength and the presence of oxygen on the photo-oxidation efficiency of Hg(0) were further investigated, respectively. This study revealed that the wave length (λ) of 254 nm could promote the photo-oxidation efficiency of Hg(0) at 140 and 160 °C, while increasing the influent Hg(0) concentration and could enhance the photo-oxidation rate of Hg(0). However, the influence of 5% O2 present in the flue gas for the enhancement of Hg(0) oxidation was limited. Moreover, the intensity of the incident wave length of 365 nm and visible light were demonstrated to boost the photo-oxidation efficiency of Hg(0) effectively.

Photodegradation of diethyl phthalate with PANi/CNT/TiO2 immobilized on glass plate irradiated with visible light and simulated sunlight-effect of synthesized method and pH.

Diethyl phthalate (DEP) is one of the most common phthalates for industrial use and has widely spread in environment. A series of PANi/CNT/TiO2 potocatalysts immobilized on glass plate irradiated with visible light were presented to degrade DEP in this study. The PANi/CNT/TiO2 potocatalysts were fabricated by co-doping with polyaniline (PANi) and two functionalized CNT (CNT-COCl and CNT-COOH) onto TiO2 followed by a hydrothermal synthesis and a sol-gel hydrolysis. Doping of PANi resulted in the absorption edge of the fabricated potocatalysts shifting to 421-437nm and the most distinguished red-shift effect was found in hydrothermal synthesized photocatalysts. The best DEP degradation of 41.5-59.0% and 44.5-67.4% was found in the simulated sunlight system irradiated for 120min for sol-gel hydrolysis PANi/CNT/TiO2 photocatalysts and hydrothermal synthesized ones, respectively. The optimum pH was determined at 5.0 and 7.0 for the two PANi/CNT/TiO2 photocatalysts mentioned above, respectively. The reusability of the sol-gel hydrolyzed photocatalysts up to 5 times was observed no decline in the photodegradation efficiency but less photocatalytic stability of the hydrothermal synthesized ones was found. Meanwhile, the active species of OH radicals generated in the DEP degradation system was identified by free radical scavenging experiments.

Surface Functional Characteristics (C, O, S) of Waste Tire-Derived Carbon Black before and after Steam Activation

Abstract The effects of steam activation on the surface functional characteristics of waste tire-derived carbon black were investigated. Two carbon-based materials, powdered carbon black (PCB) and PCB-derived powdered activated carbon (PCB-PAC), were selected for this study. A stainless steel tubular oven was used to activate the PCB at an activation temperature of 900 °C and 1 atm using steam as an activating reagent. X-ray photoelectron spectroscopy (XPS) was adopted to measure the surface composition and chemical structure of carbon surface. Various elemental spectra (C, O, and S) of each carbon sample were further deconvoluted by peak synthesis. Results showed that the surfaces of PCB and PCB-PAC consisted mainly of COC and C—O. The PCB-PAC surface had a higher percentage of oxygenated functional groups (C═O and O—C═O) than PCB. The O1s spectra show that the oxygen detected on the PCB surface was mainly bonded to carbon (C—O), whereas the oxygen on the PCB-PAC surface could be bonded to hydrogen (O—H) and carbon (C—O). Sulfur on the surface of PCB consisted of 58.9 wt% zinc sulfide (ZnS) and 41.1 wt% S═C═S, whereas that on the surfaces of PCB-PAC consisted mainly of S═C═S. Furthermore, the increase of oxygen content from 9.6% (PCB) to 11.9% (PCB-PAC) resulted in the increase of the pH values of PCB-PAC after steam activation.

Influence of Sea-Land Breezes on the Tempospatial Distribution of Atmospheric Aerosols over Coastal Region

ABSTRACT The influence of sea-land breezes (SLBs) on the spatial distribution and temporal variation of particulate matter (PM) in the atmosphere was investigated over coastal Taiwan. PM was simultaneously sampled at inland and offshore locations during three intensive sampling periods. The intensive PM sampling protocol was continuously conducted over a 48-hr period. During this time, PM2.5 and PM2.5–10 (PM with aerodynamic diameters ≤2.5 μm and between 2.5 and 10 μm, respectively) were simultaneously measured with dichotomous samplers at four sites (two inland and two offshore sites) and PM10 (PM with aerodynamic diameters ≤10 μm) was measured with β-ray monitors at these same 4 sites and at 10 sites of the Taiwan Air Quality Monitoring Network. PM sampling on a mobile air quality monitoring boat was further conducted along the coastline to collect offshore PM using a β-ray monitor and a dichotomous sampler. Data obtained from the inland sites (n = 12) and offshore sites (n = 2) were applied to plot the PM10 concentration contour using Surfer software. This study also used a three-dimensional meteorological model (Pennsylvania State University/National Center for Atmospheric Research Meteorological Model 5) and the Comprehensive Air Quality Model with Extensions to simulate surface wind fields and spatial distribution of PM10 over the coastal region during the intensive sampling periods. Spatial distribution of PM10 concentration was further used in investigating the influence of SLBs on the transport of PM10 over the coastal region. Field measurement and model simulation results showed that PM10 was trans ported back and forth across the coastline. In particular, a high PM10 concentration was observed at the inland sites during the day because of sea breezes, whereas a high PM10 concentration was detected offshore at night because of land breezes. This study revealed that the accumulation of PM in the near-ocean region because of SLBs influenced the tempospatial distribution of PM10 over the coastal region. IMPLICATIONS Model simulation and field measurements show that PM was transported back and forth across the coastline because of SLBs and that this regularly influenced the tempospatial distribution of PM10 over the coastal region. A high PM10 concentration was observed at the inland sites because of daytime onshore breezes, whereas a high PM10concentration was detected over the ocean because of nighttime offshore breezes. The implications of these results suggest that relevant authorities should work to prevent pollution episodes by reducing regional PM emissions that lead to stagnant or recirculating air under specific weather conditions.

Determination of the adsorptive capacity and 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.