Thermogravimetric and XRD study of the effects of chloride salts on the thermal decomposition of mercury compounds

In this paper, the effects of chloride salt (MgCl₂, CaCl₂ or NaCl) addition on the thermal decomposition of five inorganic mercury compounds (HgCl₂, HgS, Hg(NO₃)₂·H₂O, HgO, and HgSO₄) were investigated by thermogravimetric analysis. Mercury-contaminated soil samples collected from Inner Mongolia were used to verify the results. The desorption temperatures of the mercury compounds increased in the following order: HgCl = HgCl₂ < HgS < Hg(NO₃)₂·H₂O < HgO < HgSO₄. Among the chloride salts, MgCl₂ had the greatest effect on thermal desorption of the mercury compounds, with the greatest reduction in the initial temperature of thermal desorption. After MgCl₂ treatment, the mercury removal rates for the soil were 65.67–81.35 % (sample A), 70.74–84.91 % (sample B), and 69.08 % (sample C). The increase in the mercury removal rate for sample C with addition of MgCl₂ was particularly large (34.96–69.08 %). X-Ray diffraction analysis of white crystals from the thermal desorption with MgCl₂ indicated that MgCl₂ promoted conversion of the mercury compounds in the soil to mercury(II) chloride and dimercury dichloride. This transformation is beneficial for applying thermal desorption to remedy mercury-contaminated soils and treat of mercury containing waste.     

Pyrrolidinium Imides: Promising Ionic Liquids for Direct Capture of Elemental Mercury from Flue Gas

A new approach to vapor phase elemental mercury capture has been explored; this approach exploits an ionic liquid coating layer to oxidize elemental mercury for subsequent immobilization by chelating ligands. The room temperature ionic liquid 1-butyl-1-methyl pyrrolidinium bis(trifluoromethane sulfonyl)imide (P₁₄) was selected for study based on its oxidation potential window, thermal stability, and low vapor pressure. Tests were also completed in which KMnO₄ was added to P₁₄ to form a new ionic liquid, P₁₄–KMnO₄, with a higher oxidation potential. In room-temperature bulk liquid phase capture experiments, 59% of the elemental mercury in the inlet gas was captured using P₁₄ alone; mercury capture using P₁₄–KMnO₄ was quantitative. P₁₄ and P₁₄–KMnO₄ coatings were successfully applied to mesoporous silica substrates and to silica substrates functionalized with mercury chelating ligands. The coating layers were found to be thermally stable up to 300°C. Fixed-bed tests of nonfunctionalized silica coated with P₁₄ showed an elemental mercury uptake of 2.7 mg/g adsorbent at 160°C; at the same temperature, functionalized silica coated with P₁₄–KMnO₄ showed an elemental mercury capacity of at least 7.2 mg/g adsorbent, several times higher than that of activated carbon. The empty bed gas residence time in these tests was 0.04 s. A chelating adsorbent incorporating P₁₄ in the coating layer, may be capable of simultaneous removal of elemental and oxidized mercury from coal combustion flue gases.     

Effect of chlorine on volatilization of Na, K, Pb, and Zn compounds from municipal solid waste during gasification and melting in a shaft-type furnace

In the present work, a shaft-type furnace model in which the furnace column is divided into multiple cells was proposed and equilibrium reaction calculation software was used to describe the model. The model was used to study the effects of gasification and melting conditions such as temperature, oxygen partial pressure, and chlorine content on the volatilization behaviors of the low-boiling-point metals Na, K, Pb, and Zn during the gasification and melting process of municipal solid waste in a shaft-type furnace. Consequently, the volatilization ratios of Na, K, Pb, and Zn compounds in the exhaust gas from a pilot plant shaft-type furnace were found to be in good agreement with the calculation results, and the Na, K, Pb, and Zn compounds were volatilized mainly as metal chlorides in the temperature range up to approximately 1173 K. With a further rise in temperature, these low-boiling point metals were volatilized as metallic forms. It was found that almost 100% of Pb and Zn compounds were volatilized regardless of the chlorine content in municipal solid waste; in contrast, the volatilization rates of Na and K increased when the chlorine content increased. Finally, Na, K, Pb, and Zn compounds were converted from reduced metals to metal chlorides such as NaCl, KCl, PbCl₂, and ZnCl₂ with an increase in the ratio of chlorine to each metal.     

Two-stage Sequential Electrochemical Treatment of Nitrate Brine Wastes

Nitrates in concentrated brines can be electrochemically reduced in the cathodic chamber of a split-cell electrochemical reactor with formation of ammonium (and small amounts of nitrite). Fortunately, ammonium may be electrochemically oxidized to nitrogen gas in the anodic reaction chamber if a coupled sequential process is used. The presence of chloride in the brine waste is an important consideration in oxidative electrochemical processes, however, because it cycles through oxidized and reduced states at the electrode surfaces and in the bulk solution. Electrochemical oxidation converts chloride ions to “active chlorine” species with additional oxidizing capability (chlorine, hypochlorous acid and hypochlorite – essentially bleach), as well as to chlorates, depending on the reaction conditions. The production of these active species improves treatment performance in the ammonium oxidation phase since oxidation is no longer limited to the electrode surface. However, the process must be engineered to minimize loss of process efficiency due to parasitic side reactions (chloramines and chlorate). In this study, two-stage batch electrolysis was conducted using a three-electrode (copper anode, platinum-coated titanium cathode, silver/silver chloride reference) electrochemical cell, with the anodic and cathodic chambers separated by a Nafion 117 membrane. Treatment of nitrate and ammonium was tested with and without the presence of chloride in the waste. No significant difference was observed in cathodic nitrate reduction with chloride present or absent. However, the presence of chloride in the solution favored overall soluble nitrogen elimination upon oxidation. Increasing applied current increased production of undesirable byproducts (especially chlorate).     

A chemox treatment for urea‐ and ammonium‐contaminated groundwater

In a pilot project performed at a fertilizer manufacturing facility, a one‐step chemical oxidation technique successfully treated urea‐ and ammonium‐contaminated groundwater. The oxidation reaction occurred in an 1,100‐gallon batch reactor. The contaminated inflow was buffered by the metered addition of sodium bicarbonate solution and subsequently treated with sodium hypochlorite in an 8:1 weight ratio of Cl₂:N. In an instantaneous reaction, the urea and ammo‐nium‐N were completely oxidized to nitrogen gas that was vented to the atmosphere during mixing. The pH of the reactor discharge was ?6.5. Sodium sulfite was used to reduce residual hypochlorite in the reactor effluent to chloride to provide process water with characteristics suitable for discharge. Oxidation rates were similar with different strengths of hypochlorite; however, a 5 to 6 percent sodium hypochlorite (as Cl₂) solution was the most stable. © 2005 Wiley Periodicals, Inc.     

Effects of flue gas composition on the catalytic destruction of chlorinated aromatic compounds with a V-oxide catalyst

When using catalytic flue gas cleaning, several flue gas compounds may influence oxidation reactions of hazardous volatile organic compounds, possibly leading to lower reaction rates and, thus, to an incomplete destruction. Experimental investigations were performed with regard to the influence of selected flue gas compounds, like hydrogen chloride, sulfur dioxide, oxygen, and water vapour, on the catalytic destruction behavior of chlorobenzenes under flue gas cleaning conditions of an incineration plant. For this purpose, a metal oxide catalyst was operated at different temperatures at a space velocity of 3600 h-1 in a laboratory-scale fixed bed reactor with model flue gases, and with real flue gases generated from the TAMARA waste incineration plant. The results obtained from the studies with model flue gas were analyzed with respect to reaction kinetics. These kinetics were applied for comparison with the experimental data gained in the real flue gas.     

Characteristics of mercury desorption from sorbents at elevated temperatures

This study investigated the dynamic desorption characteristics of mercury during the thermal treatment of mercury-loaded sorbents at elevated temperatures under fixed-bed operations. Experiments were carried out in a 25.4 mm ID quartz bed enclosed in an electric furnace. Elemental mercury and mercuric chloride were tested with activated carbon and bauxite. The experimental results indicated that mercury desoption from sorbents was strongly affected by the desorption temperature and the mercury–sorbent pair. Elemental mercury was observed to desorb faster than mercuric chloride and activated carbon appeared to have higher desorption limits than bauxite at low temperatures. A kinetic model considering the mechanisms of surface equilibrium, pore diffusion and external mass transfer was proposed to simulate the observed desorption profiles. The model was found to describe reasonably well the experimental results.     

高分子除氯剂对水中氯离子的吸附机理

采用高分子除氯剂吸附水中的氯离子,考察了除氯剂投加量、反应时间、反应温度、竞争离子等对氯离子去除率的影响。实验结果表明:随着除氯剂投加量增加,氯离子去除率不断提高;吸附动力学符合拟二级动力学模型,表明化学吸附可能是氯离子吸附过程的速率控制步骤;Elovich模型表明除氯剂表面吸附的氯离子存在非均相扩散的吸附-脱附过程;Freundlich等温吸附模型能更好地描述吸附过程,结合热力学计算表明该过程是一个自发进行的吸热熵增的化学吸附过程,温度越高自发程度越大。     

Behaviour of Cd,Cr, Mn,Ni, Pb,and Zn in sewage sludge incineration by fluidised bed furnace

Cd, Cr, Mn, Ni, Pb, and Zn behaviour during sewage sludge incineration was investigated in seven pilot tests using a circulating fluidised bed furnace. Dewatered sludge at a solids concentration of 15-18% was fed to the furnace either alone (two tests) or spiked with chlorinated organic compounds (five tests). The behaviour of metals in the fluidised bed furnace was studied by comparing metal concentrations in the two main ash streams: ash separated from the cyclone immediately following the fluidised bed furnace, and fly ash recovered in the final bag filter. A metal enrichment factor was defined as the ratio of metal concentration between filter ash and cyclone ash. Only Cd and Pb showed any significant enrichment. Their enrichment factors were mainly affected by chlorine concentration in the feed sludge. To check whether simple equilibrium models may explain and predict metal behaviour, experimental data were compared with percentage of the metal vaporisation in the combustion chamber predicted using a thermodynamic model. Discrepancies between model predictions and experimental results are accounted for by considering that kinetics may be a limiting factor in the formation of metal chloride gaseous species. Due to the very short sludge residence time in the fluidised bed furnace, the gaseous compounds have little chance to evolve completely.     

不同氧化法对模拟聚合物驱废水降黏效果的影响

分别采用UV-Fenton试剂氧化法、次氯酸钙氧化法和二氧化氯氧化法处理模拟聚合物驱废水,考察了各工艺条件对废水降黏效果的影响。实验结果表明:在初始废水pH为7、反应温度为50℃、反应时间为20 min的条件下,UV-Fenton试剂氧化法适宜的H2O2加入量为1 mmol/L,n(H2O2)∶n(Fe2+)=10,处理后废水降黏率达65.7%;次氯酸钙氧化法适宜的次氯酸钙加入量为500 mg/L,处理后废水降黏率达81.7%;二氧化氯氧化法适宜的二氧化氯加入量为100 mg/L,处理后废水降黏率为40.9%。3种氧化法对模拟聚合物驱废水的降黏率大小顺序为:次氯酸钙氧化法>UV-Fenton试剂氧化法>二氧化氯氧化法。     

Study on chlorine removal from mixture of waste plastics

The recycling of waste plastics that include plastics that contain chlorine, such as polyvinyl chloride, is difficult because the chlorine leads to the corrosion of equipment. Then, the dechlorination method of waste plastics containing chlorine (CCWP) that consists of a series of melt process and hot water process was examined. CCWP was put into the melt process with coal tar (HOB) and converter dust (CD) to inhibit the diffusion of the chlorine-containing gas. The results indicated that iron oxide of the principal element of CD combines with chlorine eliminated from CCWP, and forms water-soluble iron chloride on the melt process. HOB dissolves or adsorbs a part of the chlorine during the melt process, and inhibits the diffusion of the chlorine-containing gas. Approximately 98% of the chlorine in the CCWP reacts with CD and forms iron chloride, which can be extracted on the hot water process.     

Absorption behavior of chlorine and sulfur by Ca(OH)<Subscript>2</Subscript> under simulated conditions with a fluidized bed combustor

This study was carried out to investigate the absorption reaction of chlorine and sulfur with Ca(OH)₂ under simulated conditions related to the co-combustion of refuse-derived fuel and sewage sludge in the fluidized bed combustor, such as high temperature, moisture and a mixing of samples. The combustion experiments were carried out in an electrical furnace with PVC and sulfur powders as the waste samples. High-purity slaked lime powder was used to capture the chlorine and sulfur. The experimental results showed that the removal efficiencies of both chlorine and sulfur were over 90% when the mole ratios of Ca on Cl and S were over 2.5. Furthermore, simultaneous absorption was helpful in improving the removal efficiency of chlorine and sulfur. The presence of chlorine markedly increased the removal efficiency of sulfur. The removal efficiency of chlorine was the highest at 700°C in both independent and simultaneous absorption. The removal efficiency of sulfur increased as the temperature increased, but the removal efficiency of chlorine sharply decreased from 95 to 83% when the moisture content in gases increased from 0 to 20 vol%. These results were confirmed by the combustion test of granular CaCl₂.     

Mathematical model analysis of Fenton oxidation of landfill leachate

The treatment of concentrated landfill leachate rejected from reverse osmosis (RO) with Fenton process was studied, and the system model was developed through the examination of reaction kinetics. The leachate is typically non-biodegradable with low BOD₅/COD ratio 0.01. The oxidation reactions of Fenton process was found to be a two-stage process, where a fast initial reaction (H₂O₂/Fe²⁺) was followed by a much slower one (H₂O₂/Fe³⁺). A simple and more accurate mathematics model based on COD and TOC removals has been derived successfully to describe the two-stage reaction kinetics. The two corresponding parameters involved in this model have been identified as the initial reaction rate and the maximum oxidation removal efficiency, respectively. It was found to be very useful for evaluating the performance of Fenton system and/or for process design using the two parameters under different experimental conditions.     

Chlorine promotes antimony volatilization in municipal waste incineration

Antimony volatilization in municipal waste incineration was studied. Two municipal waste samples and antimony(III) oxide (Sb₄O₆) were heated to 500°C and 700°C in an air stream in a quartz furnace. The volatilization of Sb₄O₆ occurred more at 700°C that at 500°C. Conversely, antimony volatilization form municipal waste was stronger at 500°C than at 700°C. This implies that antimony from municipal waste is volatilized as chloride instead of oxide. The chlorine sources for antimony chlorination, a gas-phase reaction involving hydrochloric acid and a solid-phase reaction of inorganic chlorine, e.g., CaCl₂, were compared. Only the solid-phase reaction could offer enough active chlorine to induce chlorination of antimony oxide. Received: July 2, 1998 / Accepted: January 28, 1999     

Laboratory studies on the remediation of mercury contaminated soils

Mercury, in contrast to other toxic metals, cycles between the atmosphere, land, and water. During this cycle, it undergoes a series of complex chemical and physical transformations. Because of these transformations, it is found in the environment not only as simple inorganic and organic compounds, but also as complex compounds. As a result, it is difficult to remediate mercury contaminated materials. Laboratory studies were conducted with a mercury contaminated complex waste from an industrial site to evaluate the ability of extractants such as H₂O₂, H₂SO₄ and Na₂S₂O₃ to decontaminate the waste. Up to 87 percent of the total mercury present in the waste was extracted. Mercury was recovered as insoluble mercury sulfide by adding Na₂S solution to the combined filtrates from the H₂O₂ + H₂SO₄ and Na₂S₂O₃ treatment steps. The technique described in this article is capable of recovering mercury in a usable form and can be used as a pretreatment to remediate mercury contaminated waste before laud disposal.     

臭氧氧化法降解聚氯乙烯离心母液废水中3种有机物

以聚氯乙烯离心母液废水中含量较高的3种有机物(聚乙烯醇、异辛醇和α-甲基苯乙烯)作为目标物,考察臭氧氧化工艺对3种有机物的去除效果,同时考察反应时间、臭氧投加量和初始pH对处理效果的影响。实验结果表明,臭氧氧化处理3种废水的最佳反应时间和臭氧投加量分别为:聚乙烯醇25 min,136 mg/L;异辛醇60min,312 mg/L;α-甲基苯乙烯60 min,32 mg/L。在此条件下,3种有机物的去除率分别为98%、85%和95%。此外,碱性条件有助于臭氧氧化工艺对3种有机物的降解。产物分析结果表明,经臭氧氧化,聚乙烯醇断链后进一步反应生成了草酸单乙酯,异辛醇和α-甲基苯乙烯分别生成了和苯乙酮。     

Fate and behavior of selected heavy metals with mercury mass distribution in a fluidized bed sewage sludge incinerator

In this paper, emission and distribution behavior of six heavy metals (As, Cd, Cr, Ni, Pb, and Hg), particulate matter and mass distribution of mercury within the different streams of a fluidized bed sewage sludge incinerator are presented. At the inlet of air pollution control devices (APCDs); Cd, Cr, Ni and Pb were mainly enriched in coarse particles; comparatively As content was higher in fine particles (<PM_2.5). The concentration of heavy metals in total particulate matter and PM_2.5, at the inlet of APCDs, were in the order of Cr > Ni > Pb > As > Cd. Mercury was almost always distributed in flue gas. Metals, other than mercury, were efficiently removed in APCDs and their concentrations in bottom ash, with fly ash being higher, whereas for that in wastewater, then waste sand was lesser. Overall mercury removal efficiency of APCDs was 98.6 %. More than 83.3 % of mercury was speciated into oxidized form at the inlet of APCDs, attributed by higher chlorine content in sludge. Mercury was mainly distributed in wastewater (78.4 %), wastewater from a spray dry reactor (16.8 %), fly ash in a hopper (3.4 %) and flue gas (1.4 %). This result is one of the first for data to be obtained; more experiments are required to control emission from such sources.     

Novel Mercury Oxidant and Sorbent for Mercury Emissions Control from Coal-fired Power Plants

The authors have successfully developed novel efficient and cost-effective sorbent and oxidant for removing mercury from power plant flue gases. These sorbent and oxidant offer great promise for controlling mercury emissions from coal-fired power plants burning a wide range of coals including bituminous, sub-bituminous, and lignite coals. A preliminary analysis from the bench-scale test results shows that this new sorbent will be thermally more stable and cost-effective in comparison with any promoted mercury sorbents currently available in the marketplace. In addition to the sorbent, an excellent elemental mercury (Hg(0)) oxidant has also been developed, and will enable coal-fired power plants equipped with wet scrubbers to simultaneously control their mercury emissions as well as their sulfur oxides emissions. This will work by converting all elemental mercury to an oxidized form which will be removed by the wet scrubber. This will result in significant cost savings for mercury emissions control to the atmosphere, and will help in keeping electric costs low. The sorbent and oxidant will benefit from the utilization of a waste stream from the printed circuit board (PCB) industry, and would thus be environmentally beneficial to both of the utility and electronics industries. The sorbent also demonstrated thermal stability up to 350°C, suggesting a possibility of an application in pulverized coal-fired power plants equipped with hot-side electrostatic precipitators and coal gasification plants.     

Modeling of mercury sorption by activated carbon in a confined,a semi-fluidized,and a fluidized bed

A process model was developed to simulate elemental mercury sorption by activated carbon in three distinct beds, namely a confined, a semi-fluidized, and a fluidized bed. The model involved the coupling of a kinetic model based on the mechanisms of surface equilibrium and external mass transfer, and a material balance model based on the tank-in-series approach. For surface equilibrium, three different equilibrium laws were used in the model, namely the Henry's Law, the Langmuir isotherm and the Freundlich isotherm. Literature mercury sorption data were used to determine the best-fit values of parameters for these equilibrium expressions. The parameter-fitted model was then used to simulate mercury sorption processes in the three distinct beds. The simulation parameters were mercury concentration, gas flow rate, adsorption temperature and the degree of semi-fluidization. The simulation results have indicated that the model is capable of describing the literature available mercury sorption data. All the three surface equilibrium laws appear to simulate the adsorption profiles equally well mainly because the sorption process occurs in an extremely low concentration range. The simulation results for the three distinct beds have suggested that the confined bed has the best mercury control performance; however, it generates the highest pressure-drop across the bed. A fluidized bed creates the least pressure drop; however, its sorption performance is poor. A semi-fluidized bed offers acceptable performance with affordable pressure-drops and can be a practical candidate for the process.     

Simultaneous capture of metal, sulfur and chlorine by sorbents during fluidized bed incineration

Metal capture experiments were carried out in an atmospheric fluidized bed incinerator to investigate the effect of sulfur and chlorine on metal capture efficiency and the potential for simultaneous capture of metal, sulfur and chlorine by sorbents. In addition to experimental investigation, the effect of sulfur and chlorine on the metal capture process was also theoretically investigated through performing equilibrium calculations based on the minimization of system free energy. The observed results have indicated that, in general, the existence of sulfur and chlorine enhances the efficiency of metal capture especially at low to medium combustion temperatures. The capture mechanisms appear to include particulate scrubbing and chemisorption depending on the type of sorbents. Among the three sorbents tested, calcined limestone is capable of capturing all the three air pollutants simultaneously. The results also indicate that a mixture of the three sorbents, in general, captures more metals than a single sorbent during the process. In addition, the existence of sulfur and chlorine apparently enhances the metal capture process.