Thermodynamic behavior of rare metals in the melting process of municipal solid waste (MSW) incineration residues

This study aims to identify the thermodynamic behavior of rare metal elements during the melting process of municipal solid waste incineration residues. The fate of several selected rare metal elements was investigated using two approaches: experimental and thermodynamic equilibrium calculation at two actual melting plants. The results revealed that Ag, Bi, Ga, Ge, In, Pd, Sb, Te, and Tl are readily volatilized as chloride and/or gaseous forms and then condensed in melting furnace fly ash. On the other hand, Cr, Ni, Ta, V, and Zr tend to mostly remain in molten slag. Sn is volatilized as SnS (g) under reducing conditions while volatilization is suppressed under oxidizing conditions. Thermodynamically, total volatilization of Mn as MnCl2 (g) occurred with highly available chlorine under oxidizing conditions. However, at the actual plants, only a small proportion was volatilized. As for Co, Mo, and W, no volatilization occurred at the actual plants although the calculations suggest that these elements can form volatile metal chloride and volatilize. Non-equilibrium and heterogeneity of the actual plant melting furnace could explain the discrepancy. This study provided a good qualitative view of the behavior of rare metals in the melting process, but further investigation is required to produce a more accurate simulation and to resolve the discrepancy.     

Regeneration of iron for trichloroethylene reduction by Shewanella alga BrY

Zero valent iron (ZVI), the primary reactive material in several permeable reactive barriers, is often oxidized to ferrous or ferric iron, resulting in decreased reactivity with time. Iron reducing bacteria can reconvert the ferric iron to its ferrous form, prolonging the reduction of chlorinated organic contaminants. In this study, the reduction of Fe(II,III) oxide and Fe(III) oxide by a strain of iron reducing bacteria of the group Shewanella alga BrY(S. alga BrY) was observed in both aqueous and solid phases. S. alga BrY preferentially reduced dissolved ferric iron over the solid ferric iron. In the presence of iron oxide the Fe(II) ions reduced by S. alga BrY efficiently reduced trichloroethylene (TCE). On the other hand, Fe(II) produced by S. alga BrY covered the reactive surfaces of ZVI iron filings and inhibited the reduction of TCE by ZVI. The formation of precipitates on the iron oxide or Fe0 surface was confirmed by scanning electron microscopy. The results suggest that iron-reducing bacteria in the oxidized Fe0 barriers can enhance the removal rate of chlorinated organic compounds and influence on the long-term performance of Fe0 reactive barriers.     

Performance of an electrochemical COD (chemical oxygen demand) sensor with an electrode-surface grinding unit

An electrochemical COD (chemical oxygen demand) sensor using an electrode-surface grinding unit was investigated. The electrolyzing (oxidizing) action of copper on an organic species was used as the basis of the COD measuring sensor. Using a simple three-electrode cell and a surface grinding unit, the organic species is activated by the catalytic action of copper and oxidized at a working electrode, poised at a positive potential. When synthetic wastewater was fed into the system, the measured Coulombic yields were found to be dependent on the COD of the synthetic wastewater. A linear correlation between the Coulombic yields and the COD of the synthetic wastewater was established (10-1000 mg L(-1)) when the electrode-surface grinding procedure was activated briefly at 8 h intervals. When various kinds of wastewater samples obtained from various sewage treatment plants were measured, linear correlations (r(2)> or = 0.92) between the measured EOD (electrochemical oxygen demand) value and COD of the samples were observed. At a practical wastewater treatment plant, the measurement system was successfully operated with high accuracy and good stability over 3 months. These experimental results show that the application of the measurement system would be a rapid and practical method for the determination of COD in water industries.     

Reliable evidences that the removal mechanism of hexavalent chromium by natural biomaterials is adsorption-coupled reduction

For the last few decades, over 200 papers have been published in the Cr(VI) biosorption research field. Most early studies have claimed that Cr(VI) was removed from aqueous phase through an anionic adsorption, but this approach has been lost old original position. It has been newly explained that these findings were misinterpreted due to errors in measuring the concentrations of different chromium species in the aqueous phase, insufficient contact time required for equilibrium and the lack of information about the oxidation state of the chromium bound to biomaterials. Although 'adsorption-coupled reduction' is now widely accepted as the mechanism of Cr(VI) biosorption by natural biomaterials, a number of researchers still believe that Cr(VI) is removed by anionic adsorption onto the biomaterials. Therefore, the objective of this study was to show reliable evidences that the removal mechanism of Cr(VI) by natural biomaterials is 'adsorption-coupled reduction'. Sixteen natural biomaterials were used to study the Cr(VI) biosorption. Not only Cr(VI) but also total Cr in the aqueous phase were analyzed. X-ray photoelectron spectroscope was also used to verify the oxidation state of the chromium bound to the biomaterials. Finally, the removal behavior of Cr(VI) by each biomaterial was described by a kinetic model based on a redox reaction.     

Spectroscopic Distribution of Dissolved Organic Matter in a Dam Reservoir Impacted by Turbid Storm Runoff

Spectroscopic characteristics of dissolved organic matter (DOM) in a large dam reservoir were determined using ultraviolet absorbance and fluorescence spectroscopy to investigate spatial distribution of DOM composition after turbid storm runoff. Water samples were collected along a longitudinal axis of the reservoir at three to four depths after a severe storm runoff. Vertical profiles of turbidity data showed that a turbid water layer was located at a middle depth of the entire reservoir. The spectroscopic characteristics of DOM samples in the turbid water layer were similar to those of terrestrial DOM, as demonstrated by the higher specific UV absorbance (SUVA) and the lower fluorescence emission intensity ratio (F ₄₅₀/F ₅₀₀) compared to other surrounding DOM samples in the reservoir. Synchronous fluorescence spectroscopy revealed that higher content of humic-like DOM composition was contained in the turbid water. Fluorescence excitation–emission matrix (EEM) showed that lower content of protein-like aromatic amino acids was present in the turbid water DOM. The highest protein-like fluorescence was typically observed at a bottom layer of each sampling location. The bottom water DOM exhibited extremely high protein-like florescence near the dam site. The particular observation was attributed to the low water temperature and the isolation of the local bottom water due to the upper location of the withdrawal outlet near the dam. Our results suggest that the distribution of DOM composition in a dam reservoir is strongly influenced by the outflow operation, such as selective withdrawal, as well as terrestrial-origin DOM inputs from storm runoff.     

Balancing the energy demand by a resource circulation project in Daejeon,Korea

Demand for sustainable renewable energy is on an increase worldwide, whereas the supply is limited. This paper analyses the feasibility of generating electricity and supplying the surplus steam to Daeduk Industrial Complex, by incinerating the combustible municipal waste generated in Daejeon Metropolitan City. The economic feasibility of surplus biogas generated from the anaerobic digestion of food waste and food waste leachate has been analysed. This study estimated resource circulation facility to supply 23,200 m³/day of biogas generated to Daejeon Combined Heat and Power plant. By 2023, it is expected to supply 25.7 tons of steam per hour all year round. The additional steam demand in Daeduk Industrial Complex is estimated as 101,537 tons/year. Surplus biogas will be supplied through an additional 960-m new installation. The cost of biogas is estimated at 30% of the unit biogas production cost. Daejeon Combined Heat and Power plant expects to make 60% additional profit, and Daeduk Industrial Complex and the communities nearby expect to achieve 10% cost savings. It also reduces the dependence of energy on fossil fuels, contributes to national environmental energy policy in reduction in greenhouse gases, creates competitiveness in local business and reduces corporate tax and generates revenue.     

Gasification characteristics of biomass for tar removal by secondary oxidant injection

Gasification experiments for sawdust were conducted using a fixed bed reactor at 900 °C by varying the secondary oxidant injection ratio to determine the optimal conditions for tar removal along with the enhancement of gasification efficiency. Secondary oxidant was injected as an oxidant at the top zone of the gasifier in varying ratios of 10–30% of the total amount of oxidant. This method was based on the primary method of tar removal and gasification efficiency improvement by thermal cracking of tar. Various gasification performance parameters were evaluated and tar content was estimated by measuring the fluctuation of weight of the activated carbon filter. The results showed that the concentration of tar in the producer gas decreased by injecting the secondary oxidant, even though syngas yield decreased. The recycling potential of the char produced in the gasification experiments was also assessed with the purpose of utilizing char as an adsorbent by determining its surface area and pore volume. The results demonstrated that the char produced from the gasification experiment had similar quality to that of the activated carbon used in this experiment.     

Catalytic upgrading pyrolysis of pine sawdust for bio-oil with metal oxides

The catalytic upgrading pyrolysis of pine sawdust was performed at 500 °C with various metal oxides to improve the quality of the bio-oil. The aim of this study was to investigate the potential of the metal oxides instead of traditional zeolites for catalytic upgrading pyrolysis with the analysis of Gas Chromatograph/Mass Spectrometer. In this study, the used catalysts were Calcium-oxide, Magnesium oxide, Titanium dioxide, and Zeolite (Si/Al?=?80). The influence of catalysts on products yields and compositions were investigated. Most metal oxides can enhance the bio-gas with the bio-oil yields decreased. The metal oxides led to a decrease of Acids, Aldehydes, Ketones and an increase of Furfural, Cresols, Catechols in Furans and Phenolics. Among the catalysts, the MgO catalysts was the most effective to convert the high molecular into lights ones (6.65% Cresols) with yield of 20.48% for Furfural. The deoxygenation reaction in bio-oil was suggested to convert oxygenated compounds into the low molecular weight of the materials (6.39% Guaiacols). Thus, the used metal oxides can improve the quality of bio-oil by decreasing undesirable compounds as well as increasing the desirable compounds with low oxygen contents via deoxygenation reaction.     

Absorption characteristics of potassium carbonate-based solutions with rate promoters and corrosion inhibitors

In this research, absorbents for CO₂ capture were prepared by blending 30 wt% potassium carbonate, 3 wt% of a rate promoter, and 1 wt% of a corrosion inhibitor. Pipecolic acid, sarcosine, and diethanolamine were chosen as rate promoter candidates. Based on a rate promoter screening test for CO₂ loading capacity and absorption rate, pipecolic acid and sarcosine were selected to be used as rate promoters. 1,2,3-benzotriazole and ammonium thiocyanate were chosen as corrosion inhibitors, and they were mixed with a 30 wt% potassium carbonate-based absorbent mixture containing one of the rate promoters. The absorption rates for four absorbent solutions (30 wt% potassium carbonate?+?3 wt% pipecolic acid?+?1 wt% 1,2,3-benzotriazole, 30 wt% potassium carbonate?+?3 wt% pipecolic acid?+?1 wt% ammonium thiocyanate, 30 wt% potassium carbonate?+?3 wt% sarcosine?+?1 wt% 1,2,3-benzotriazole, and 30 wt% potassium carbonate?+?3 wt% sarcosine?+?1 wt% ammonium thiocyanate) were measured, tabulated, and graphically displayed. These types of absorbents can be used for capturing CO₂ under high temperature and pressure conditions, such as those found in coal-fired power plants.