Pyrolytic kinetics of sludge from a petrochemical factory wastewater treatment plant--a transition state theory approach

The pyrolysis of hydrocarbon-rich sludge in an oxygen-free environment can provide useful liquefaction products and residues. When applied to sewage sludge, energy and time costs are the major factors that affect the operation. Therefore, it is important to understand how the process is affected by temperature. The pyrolysis kinetics of sludge from a petrochemical factory wastewater treatment plant was studied to reveal the effects of temperature on the reaction rate and the magnitude of deltaH and deltaS of the reaction barrier. Oven-dried sludge samples were pyrolyzed in an isothermal reactor under six different temperatures. The residues were weighed at frequent intervals within a total 30-min experiment period. Data analysis indicated that a first order reaction model could describe the pyrolysis kinetics, across all experimental temperature ranges. When transition state theory was applied, the results indicated that the major reaction barrier came from the entropy term of the activation free energy. Therefore, increasing the pyrolysis temperature to overcome the reaction barrier yielded no apparent improvement, but strategies that reduced the entropy should significantly improve the reaction.     

A METHODOLOGY FOR OUTDOOR RECREATION ANALYSIS IN A STATE WATER RESOURCES PLANNING STUDY1

ABSTRACT: The paper presents a methodology for outdoor recreation analysis in a comprehensive State water resources planning study. This methodology applies to determination of recreation participation desires among the population, allocation of those desires to areas of potential resources within which they must be satisfied, comparison of the areal potential resources against the allocated desires to identify areas having recreational resource deficits or needs, and exploration of alternative solutions to the identified needs. Major elements discussed are: market area, inflow-outflow, resource desire determination and projection, resource desire allocation, facility inventory, resource desire-resource analysis and alternative solutions to identified needs of water-oriented outdoor recreation.     

Effects of chlorides on emissions of toxic compounds in waste incineration: study on partitioning characteristics of heavy metal

Chlorides derived from plastics and food residue content in MSW will affect the formation and partitioning of metal chlorides in the incineration discharges. Our study investigated the effects of waste-derived chlorides on the partitioning of heavy metals in a single-metal combustion system. The results indicate that the heavy metal partitioning behaviors are mainly affected by the presence of chloride, alkaline metals (i.e., Na, K) and moisture in the wastes. The configuration of the metal partitioning is determined by the availability of chlorine, hydrogen, and alkaline metals, or the extent to which the elements may divide from their compounds at a given combustion temperature. The effects of chlorides, including PVC, C2Cl4, FeCl3, NaCl and KCl, were also discussed.     

Improving the Synthesis Gas Quality in Catalytic Gasification of Rice Straw by an Integrated Hot-Gas Cleaning System

This research investigates an enhanced removal rate of tar and trace pollutants (e.g. hydrogen chloride and hydrogen sulfide, H₂S) in the gasification of rice straw, using an integrated in situ tar reduction and hot-gas cleaning technique. The gasification temperature was set at 900°C and equilibrium ratio (ER) was 0.30 in the gasifier. In the in situ tar reduction method, the catalyst, dolomite with an amended ratio of 0–15% was introduced to the gasifier. The integrated hot-gas cleaning system applied a multi-packed tower to remove the tar, sulfur and/or chlorine byproduct in syngas at 250°C. The packed materials composed of zeolite, calcined dolomite and activated carbon. The experimental results indicated that the tar concentration of syngas was approximately 20 g/kg. However, in catalytic gasification with 5% dolomite addition, the tar concentration reduced to 17 g/kg. The tar reduction efficiency was approximately 15% by an in situ dolomite addition. When applying the integrated hot-gas cleanup system, the tar was virtually eliminated. The total tar elimination rate was almost 100% and the cleaned syngas could be applied in other energy utilization equipment. On the other hand, the H₂S and HCl concentration were 101 ppmv and 991 ppmv, respectively. After the integrated syngas cleaning system, the H₂S and HCl were decreased to 7.9 ppmv and 410 ppmv with a removal efficiency of 92.1% and 58.6%, respectively. It can be concluded that combining the in situ method with the integrated syngas cleaning system can effectively reduce the amount of byproduct and enhance the syngas quality in the gasification of rice straw.     

Cesium and strontium sorption by selected tropical and subtropical soils around nuclear facilities

The dynamics of Cs and Sr sorption by soils, especially in the subtropics and tropics, as influenced by soil components are not fully understood. The rates and capacities of Cs and Sr sorption by selected subtropical and tropical soils in Taiwan were investigated to facilitate our understanding of the transformation and dynamics of Cs and Sr in soils developed under highly weathering intensity. The Langmuir isotherms and kinetic rates of Cs and Sr sorption on the Ap1 and Bt1 horizons of the Long-Tan (Lt) and the A and Bt1 horizons of the Kuan-Shan (Kt), Mao-Lin (Tml) and Chi-Lo (Cl) soils were selected for this study. Air-dried soil (<2 mm) samples were reacted with of 7.5 × 10⁻⁵ to 1.88 × 10⁻³ M of CsCl (pH 4.0) or 1.14 × 10⁻⁴ to 2.85 × 10⁻³ M of SrCl₂ (pH 4.0) solutions at 25 °C. The sorption maximum capacity (q_m) of Cs by the Ap1 and Bt1 horizons of the Lt soil (62.24 and 70.70 mmol Cs kg⁻¹ soil) were significantly (p < 0.05) higher than those by the A and Bt1 horizons of the Kt and Cl soils (26.46 and 27.49 mmol Cs kg⁻¹ soil in Kt soil and 34.83 and 29.96 mmol Cs kg⁻¹ soil in Cl soil, respectively), however, the sorption maximum capacity values of the Lt and Tml soils did not show significant differences. The amounts of pyrophosphate extractable Fe (Fe_p) were correlated significantly with the Cs and Sr sorption capacities (for Cs sorption, r² = 0.97, p < 1.0 × 10⁻⁴; for Sr sorption, r² = 0.82, p < 2.0 × 10⁻³). The partition coefficient of radiocesium sorbed on soil showed the following order: Cl soil ? Kt soil > Tml soil > Lt soil. It was due to clay minerals. The second-order kinetic model was applied to the Cs and Sr sorption data. The rate constant of Cs or Sr sorption on the four soils was substantiality increased with increasing temperature. This is attributable to the availability of more energy for bond breaking and bond formation brought about by the higher temperatures. The rate constant of Cs sorption at 308 K was 1.39-2.09 times higher than that at 278 K in the four soils. The activation energy of Cs and Sr sorbed by the four soils ranged from 7.2 to 16.7 kJ mol⁻¹ and from 15.2 to 22.4 kJ mol⁻¹, respectively. Therefore, the limiting step of the Cs⁺ or Sr²⁺ sorption on the soils was diffusion-controlled processes. The reactive components, which are significantly correlated with the Langmuir sorption maxima of Cs and Sr by these soils, substantially influenced their kinetic rates of Cs and Sr sorption. The data indicate that among components of the subtropical and tropical soils studied, short-range ordered sesquioxides especially Al- and Fe-oxides complexed with organics play important roles in influencing their capacity and dynamics of Cs and Sr sorption.     

Seasonal Source-Receptor Relationships in a Petrochemical Industrial District over Northern Taiwan

Abstract

This study investigated the relationships between meteorological data, pollution sources, and receptors over northern Taiwan. During the intensive sampling period in summer 1992, the weather was controlled predominantly by a Pacific subtropical high and by Typhoon Mark. During the other intensive sampling period in winter 1993, while a cold frontal system approached Taiwan, the northeasterly winds prevailed most of the time. The local circulation such as land-sea breeze only developed under weak synoptic environment. Particle concentrations and element composition in winter were higher than in summer. This can be attributed to the high convection of air mass, which leads to the vertical dispersion of pollutants in summer. In addition to the subtropical high pressure, typhoons are frequently accompanied with high-wind speeds and unstable weather conditions that also dilute and eliminate the pollutants. In winter, the prevailing northeasterlies might carry pollutants from Midland China. Furthermore, the anticyclone system develops a stagnant condition that easily leads to pollutant accumulation. In this case, the wind direction affected the source contribution of the receptor and the PM₁₀ displays a higher correlation with coarse and fine particulate than meteorological parameters in summer. In addition, the mixing height shows a high correlation with PM₁₀ in winter.     

Linking valve closure behavior and sodium transport mechanism in freshwater clam Corbicula fluminea in response to copper

Sediment geochemical technique was employed to assess how the sediment records reflect the environmental changes of Jiaozhou Bay, a semi-enclosed bay adjacent to Qingdao, China. In the past hundred years, Jiaozhou Bay has been greatly impacted by human interventions. A dated core sediment by 210Pb chronology was analyzed for trace metals including Li, Cd, Cr, Pb, Cu, Ni, Co, Zn together with C, N, P and BSi. Based on the research, the development of Jiaozhou Bay environment in the past hundred years can be divided into three stages: (1) before the 1980s characterized by relatively low sedimentation rate, weak heavy metal pollution and scarce eutrophication; (2) from the 1980s to 2000, accelerating in the 1990s, during which high sedimentation rates, polluted by heavy metals and the frequent occurrence of red tide; (3) after 2000, the period of the improvement of environment, the whole system has been meliorated including the heavy metal pollution and hypernutrification.     

Removal of humic acid using TiO2 photocatalytic process--fractionation and molecular weight characterisation studies

The photocatalytic removal of humic acid (HA) using TiO₂ under UVA irradiation was examined by monitoring changes in the UV₂₅₄ absorbance, dissolved organic carbon (DOC) concentration, apparent molecular weight distribution, and trihalomethane formation potentials (THMFPs) over treatment time. A resin fractionation technique in which the samples were fractionated into four components: very hydrophobic acids (VHA), slightly hydrophobic acids, hydrophilic charged (CHA) and hydrophilic neutral (NEU) was also employed to elucidate the changes in the chemical nature of the HA components during treatment. The UVA/TiO₂ process was found to be effective in removing more than 80% DOC and 90% UV₂₅₄ absorbance. The THMFPs of samples were decreased to below 20 μg l⁻¹ after treatments, which demonstrate the potential to meet increasingly stringent regulatory level of trihalomethanes in water. Resin fractionation analysis showed that the VHA fraction was decreased considerably as a result of photocatalytic treatments, forming CHA intermediates which were further degraded with increased irradiation time. The NEU fraction, which comprised of non-UV-absorbing low molecular weight compounds, was found to be the most persistent component.     

The effects of FeCl3 on the distribution of the heavy metals Cd, Cu, Cr, and Zn in a simulated multimetal incineration system

Recognizing that waste-derived chlorine can enhance heavy metal emissions by forming volatile metallic chlorides during municipal solid waste (MSW) combustion, and that in Taiwan, FeCl3-containing sewage sludge may either be landfilled or coincinerated with other MSW, this study thus investigated the effects of FeCl3 on the speciation and partitioning of heavy metals in a multimetal incineration system by using a tubular furnace and FeCl3-spiked simulated wastes. The molar ratio of chlorine content to heavy metal content (referred to as the Cl/ M ratio), ranging from 3 to 200, was used as a parameter to evaluate the effects of chlorine on the movement of heavy metals between the incinerator discharges. Results indicate that speciation and partitioning were related to the affinity between the chlorine and the heavy metals and between chlorine and hydrogen in the combustion system. The effectiveness of increasing the Cl/M ratio to the formation potential of metallic chlorides and on the shift of heavy metals from the bottom ash to the fly ash and/or the flue gases was found to have in increasing order as follows: Zn>Cu>Cr, a phenomenon basically reflecting the volatility of the heavy metals and their chlorides formed during combustion.     

Comparisons of metal leachability for various wastes by extraction and leaching methods

The objective of this research was to evaluate three extraction tests, i.e., toxicity characteristic leaching procedures (TCLP), extraction procedure (EP), and American Society for Testing and Materials (ASTM) methods, for their ability to extract metals in chemical sludge and incineration bottom ash, in terms of the precision of analytical results. Typical chemical sludges, including the electroplating and dye-stuff sludges, the municipal solid waste incineration bottom ash, the leather debris, and the steel-mill bottom residue containing Cd, Cr, Cu, Pb, and Zn were prepared for the lysimetry test (dynamic testing) to compare with the extraction results. Results show that for bottom residue and dye-stuff sludge, the concentration of metal leached was almost the same between the lysimetry leaching and the TCLP tests. The metal concentration followed the order: TCLP approximately = EP > ASTM. TCLP and EP exhibited almost the same relative standard deviation (RSD) value. Therefore, the results of the TCLP tests for bottom residue and dye-stuff sludge, which have a low metal content and alkalinity, can be used to estimate the metal concentration leached by typical acid rain in Taiwan; whereas the ASTM extraction test may be a better indicator of the lysimetry test.