Preparation of activated carbons from unburnt coal in bottom ash with KOH activation for liquid-phase adsorption

In this work, unburnt coal (UC) in bottom ash from coal-fired power plants was soaked in KOH solution and activated for 1 h at 780 °C. The yield of activated carbons varied from 47.8 to 54.8% when the KOH/UC weight ratio changed from 2 to 4. Pore properties of these activated carbons including the BET surface area, pore volume, pore size distribution, and pore diameter were characterized based on N₂ adsorption isotherms. It was shown that the isotherms for the adsorption of methylene blue, acid blue 74, and 4-chlorophenol from aqueous solutions on these activated carbons at 30 °C were well fitted by the Langmuir equation (correlation coefficient r² > 0.9968). The adsorption capacities of methylene blue, acid blue 74, and 4-chlorophenol were obtained to be 2.40–2.88, 0.57–1.29, and 2.34–5.62 mmol/g, respectively. Moreover, the adsorption kinetics could be suitably described by the Elovich equation.     

Assessing relocation strategies of urban air quality monitoring stations by GA-based compromise programming

This paper presents a GA-based compromise programming technique for assessing the relocation strategy of urban air quality monitoring network with respect to the multi-objective and multi-pollutant design criteria. While the impact of conservative, quasi-stable, and reactive pollutants are considered in the design principles via a simulation analysis, cost, effectiveness, and efficiency characteristics are postulated in the optimization process. Therefore, technical coverage for illustrating the needs of siting air quality monitoring stations (AQMS) includes both the air quality simulation and optimization modeling analyses in a two-stage analytical framework simultaneously. It starts from determining the spatial interrelationship among those candidate sites using various types of air quality simulation models as an integrated means. And the outputs drawn from the simulation models can then be used as the required inputs in the compromise programming model in order to screen all those siting alternatives that may satisfy the planning goals subject to the essential constraints throughout the multi-objective optimization process. For the illustrating purposes, a series of technical settings for finding the optimal relocation scenarios of AQMS were examined in the case study for the city of Kaohsiung in South Taiwan where the long-term violations of official standards of ozone and particulates turn out to be critical. It not only expresses the ideas of relocation strategy but also indicates how to utilize those alternatives in the decision-making process for improving the functionality of air quality monitoring in the urban environment. Experience gained in this study clearly indicates that the more the number of pollutants and objectives considered simultaneously, the higher the number of candidate sites to be selected in the relocation strategy.     

Field cryofocussing hydride generation applied to the simultaneous multi-elemental determination of alkyl-metal(loid) species in natural waters using ICP-MS detection

Two hydride generation manifold systems, utilizing flow injection and cryotrapping techniques for alkyl-metal(loid) speciation analysis in natural waters, are described in this paper. They provide shipboard capacity for simultaneous derivatization of analytes with NaBH4 and cryotrapping of the generated products in a field packed column at -196 degrees C. The first system is a large-volume hydride generator, using a reagent-injection flow technique as a flow batch type, that has been fully optimized and applied to the simultaneous detection of alkylated species in estuarine waters. The technique permits the analysis of a large volume sample (0.5-11) at a sampling rate of 3 h-1. The second is an online continuous flow hydride generator. A sampling rate of 3-12 h-1 can be achieved with samples of 0.1-0.51. In addition, shipboard operation eliminates major problems related to sample pretreatment, transport and storage. Ultra-trace multi-element determination is finally performed in the laboratory by cryogenic GC hyphenated with ICP-MS. Routine detection limits of 0.5-10 pg (as metal) for 0.51 water samples were achieved for the selected alkyl-metal(loid) species of arsenic, germanium, mercury and tin. Concentrations of various species, obtained from water samples taken from the Rhine estuary, are also presented. These species include alkylated arsenic compounds, other than methyl derivatives, that have been tentatively identified and are reported here for the first time.     

Degradation of anthraquinone dye C.I. Reactive Blue 19 in aqueous solution by ozonation

This study investigated the degradation of anthraquinone reactive dye C.I. Reactive Blue 19 (RB-19) with initial concentration of 100 mg L⁻¹ in aqueous solution by ozone oxidation. The results of UV/VIS and FTIR spectra showed that the anthraquinone structures, nitrogen linkages and amino groups of RB-19 were destroyed under direct ozone reaction. The identification by LC–MS and GC–MS analyses indicated that some organic acids (e.g., phthalic acids) and 1,3-indanone could be the primary degradation products, respectively. The Microtox toxicity of the ozonated RB-19 solution initially increased but subsequently decreased when ozonation time increased. This detoxification accompanied biodegradability enhancement revealed by BOD/COD ratio increasing from 0.15 to 0.33 after 10 min of ozonation.     

Study on photocatalytic degradation of gaseous dichloromethane using pure and iron ion-doped TiO2 prepared by the sol-gel method

The synthesis of TiO₂ and Fe–TiO₂ by sol–gel method is demonstrated and characterized. The characterization of TiO₂ and Fe–TiO₂ is performed with instruments, including TGA/DTA, FTIR, UV–Vis, N₂ adsorption and SEM. Dichloromethane is used for the photocatalytic activity test. From the results of dichloromethane photocatalyitc degradation, the calcined temperature of TiO₂ and the presence of water vapor influence the photocatalytic activity. The optimum doping amount of iron ions is 0.005 mol%, and this can enhance the photocatalytic activity, while too great an amount will make the iron ions become recombination centers for the electron–hole pairs and reduce the photocatalytic activity. UV–Vis diffuse reflectance spectra of Fe–TiO₂ show an increase in absorbency in the visible light region with the increase in iron ions doping concentration The intermediate of dichloromethane photodegradation includes CHCl₃, CCl₄, CH₂Cl₂ and COCl₂. The presence of iron ions may reduce the adsorption of Cl element on the surface of the photocatalyst.     

Two-stage biofilter for effective NH3 removal from waste gases containing high concentrations of H2S

A high H2S concentration inhibits nitrification when H2S and NH3 are simultaneously treated in a single biofilter. To improve NH3 removal from waste gases containing concentrated H2S, a two-stage biofilter was designed to solve the problem. In this study, the first biofilter, inoculated with Thiobacillus thioparus, was intended mainly to remove H2S and to reduce the effect of H2S concentration on nitrification in the second biofilter, and the second biofilter, inoculated with Nitrosomonas europaea, was to remove NH3. Extensive studies, which took into account the characteristics of gas removal, the engineering properties of the two biofilters, and biological parameters, were conducted in a 210-day operation. The results showed that an average 98% removal efficiency for H2S and a 100% removal efficiency for NH3 (empty bed retention time = 23-180 sec) were achieved after 70 days. The maximum degradation rate for NH3 was measured as 2.35 g N day(-1) kg of dry granular activated carbon(-1). Inhibition of nitrification was not found in the biofilter. This two-stage biofilter also exhibited good adaptability to shock loading and shutdown periods. Analysis of metabolic product and observation of the bacterial community revealed no obvious acidification or alkalinity phenomena. In addition, a lower moisture content (approximately 40%) for microbial survival and low pressure drop (average 24.39 mm H2O m(-1)) for system operation demonstrated that the two-stage biofilter was energy saving and economic. Thus, the two-stage biofilter is a feasible system to enhance NH3 removal in the concentrated coexistence of H2S.     

Simultaneous removal of NO and SO2 by high-temperature fluidized zero-valent iron processes

A new approach to simultaneously remove nitrogen monoxide (NO) and sulfur dioxide (SO2) by zero valent iron (ZVI) was investigated. Three different parameters, temperature, flux, and ZVI dosage, were tested in fluidized ZVI column studies containing 500 ppmv of NO and SO2, respectively. Under the ZVI dosage of 0.5 g at flux of 0.6 L/cm2 x min for temperature 573 K, there is neither NO nor SO2 reduction. For 623 K and 673 K, complete removal for NO and > 90% removal for SO2 were achieved. For temperatures of 723 K and 773 K, 100% removal was achieved for both NO and SO2. The amounts of NO or SO2 reduction (as milligrams of NO or SO2 per gram ZVI) increased as temperature increased, and linearities were observed with both correlation coefficients > 0.97. Compared with NO, SO2 had earlier breakthrough because of a slower diffusion rate and less reactivity but higher mass reduction because of a higher molecular weight for SO2 (64 g/mol for SO2 and 30 g/mol for NO). At same temperature, both NO and SO2 reductions (as milligrams of NO or SO2 per gram of ZVI) were constant regardless of either flux or ZVI dosage variation, but breakthrough time was affected by both flux and ZVI dosage. A parameter weight of ZVI/flux (W/F) was developed to represent these two parameters at the same time to assess the breakthrough time of NO and SO2. Higher breakthrough time was achieved for higher W/F value. Moreover, interestingly, longer breakthrough time and more NO and SO2 mass reduction were achieved for combined NO and SO2 than individual NO or SO2 treated by ZVI, and both oxidation and reduction reactions occurred instead of a reduction reaction only. Chemical reactions among ZVI/NO, ZVI/ SO2, and ZVI/NO/SO2 were also proposed and verified by X-ray diffraction analyses.     

Emergency response plan for boiler explosion with toxic chemical releases at Nan-Kung industrial park in central Taiwan

A large amount of hazardous materials and equipment has been extensively employed to produce useful chemicals for our daily lives, but many serious accidents, such as fires, explosions, toxic releases, and so on, that harm human beings and impact the environment have occurred during preparation, operation, and transportation of these chemicals. On 17 May 2007, a toxic release from a boiler explosion in a chemical firm triggered a large amount of xylene (7 ton), isopropanol (8 ton), phosphorus trichloride (44.7 ton), and dimethyl formamide (DMF) (1.37 ton) to be released to the atmosphere with total damages of 2000 m² level ground. Through concerted efforts from the Yunlin Emergency Response Information Center (YERIC), sponsored by the Environmental Protection Administration (EPA) of Taiwan and other government sectors, this accident was eventually well controlled after 37 h with 107 people being involved in the rescue action. This study could be applied to lessen the degree of hazard for relevant accidents with an emergency response plan (ERP), and, via Fourier transform infrared (FTIR) spectroscopy and photo ionization detector (PID) the toxic concentrations of airborne chemicals that occurred in the industrial area could be analyzed.     

Biofiltration of trimethylamine, dimethylamine, and methylamine by immobilized Paracoccus sp. CP2 and Arthrobacter sp. CP1

A biofilter using granular activated carbon with immobilized Paracoccus sp. CP2 was applied to the elimination of 10–250 ppm of trimethylamine (TMA), dimethylamine (DMA), and methylamine (MA). The results indicated that the system effectively treated MA (>93%), DMA (>90%), and TMA (>85%) under high loading conditions, and the maximum degradation rates were 1.4, 1.2, and 0.9 g-N kg⁻¹ GAC d⁻¹. Among the three different amines treated, TMA was the most difficult to degrade and resulted in ammonia accumulation. Further study on TMA removal showed that the optimal pH was near neutral (6.0–8.0). The supply of high glucose (>0.1%) inhibited TMA removal, maybe due to substrate competition. However, complete TMA degradation was achieved under the co-immobilization of Paracoccus sp. CP2 and Arthrobacter sp. CP1 (96%). Metabolite analysis results demonstrated that the metabolite concentrations decreased by a relatively small 27% while the metabolite apparently increased by heterotrophic nitrification of Arthrobacter sp. CP1 in the co-immobilization biofilter.     

Feasibility study on high-temperature sorption of hydrogen sulfide by natural soils

In this study, seven natural soils were tested for the sorption of hydrogen sulfide from coal gasification gas at high temperature. Results indicate that the LP natural soil has the best performance and the highest sulfur sorption capacity. After extracting free iron oxides, most natural soils have no sorption efficiency. The free iron oxides, therefore, proved to be the major components that react with hydrogen sulfide to form iron sulfides. The sulfur sorption capacity, either determined by EA or breakthrough time, is very close to the theoretical value based on the stoichiometric calculation with the content of free iron oxides. Moreover, the presence of CO is a positive effect while H2 is a negative effect. This can be explained via the water-shift reaction. On the basis of the results of temperature-programmed sulfidation (TPS), the starting temperature for the sorption of hydrogen sulfide is between 623-673 K. From the analyses of temperature-programmed oxidation (TPO) and XPS, the iron polysulfides are the major products and approximately 90% regeneration efficiency can be theoretically achieved while the temperature is controlled higher than 813 K. In the regeneration tests, the results show that the LP natural soil can be regenerated and thus reused after the oxidation process. No significant degeneration occurs on the LP natural soil after five sorption/regeneration cycles. The sulfur sorption capacity of the tenth regenerated soil can be achieved at least 80% compared to the fresh one. The experimental analyzed SO2 concentration from the regeneration process is almost identical to the theoretical calculated equilibrium concentration of the process. Maghemite is the main product after the regeneration process.