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.     

Thermodynamic analysis of the role of chlorine and sulfur environments during combustion and incineration processes

 In order to control the emission of trace metals from combustion and incineration systems, sorbents and filters are sometimes used. However, the effectiveness of these methods is greatly affected by the volatility of the metals and the way in which they speciate during combustion, and afterwards during condensation, and physical or chemical sorption. Although there has been a lot of research into the mechanisms by which trace metals speciate and subsequently appear in submicron particles, the details of these mechanisms are not yet thoroughly understood. In this study, a chemical equilibrium approach was used to qualitatively determine the speciation of lead, cadmium, and chromium in Cl and S environments. The reaction conditions of sorbents were also tested numerically in order to understand the reaction behavior of metals with sorbents. This article reports the influence of different concentrations of Cl and SO₂ on Pb, Cd, and Cr speciation, as representatives of other trace elements. The partitioning behavior of metals during combustion was also examined for Cl and S. The results obtained indicate that most metals exist in the vapor phase, even at low temperatures, when chlorine is present. However, the addition of SO₂ enhances the formation of the condensed phase, except at extremely high temperatures. This observation was not significant for Cd or Cr. The higher the concentration of Cl the higher the retention of trace metals in the vapor phase, even at low temperatures. Results from comparisons of the reactivities of mixed metals with Cl indicate that the presence of Fe limits the reactivity of most trace metals with Cl except at higher concentrations. In the presence of Fe, alkali metals are the first to react with Cl. If Fe is not present, most trace metals react with Cl, and the activity increases with higher concentrations. On the other hand, the partitioning characteristics of S show that its presence generally means that metals remain in the condensed phase. Sulfur is more reactive with alkali metals than with other trace metals. Received: June 6, 2001 / Accepted: April 30, 2002     

水合改性对钙基吸收剂循环捕集CO2的影响

在钙基吸收剂捕集CO2的过程中，吸收剂转化率会随着循环次数的增加而迅速降低。钙基吸收剂的水合改性作为改善吸收剂循环转化率的主要方法之一受到了国内外学者的广泛关注。总结了目前国内外研究者对不同的吸收剂、循环捕集条件下的水合改性方法的研究成果。结果表明，在循环过程中的不同阶段对吸收剂进行水合处理后得到的效果不同。其中，在碳酸化阶段、煅烧阶段、循环捕集前预处理以及煅烧后对吸收剂水合改性．吸收剂捕集CO2的能力均得到了改善；碳酸化反应后对吸收剂进行水合处理是否对循环吸收有利还存在争议。目前，利用水合改性的方法提高钙基吸收剂循环捕集CO2能力的机理还存在争议，且水合改性后的吸收剂机械性能差以及此方法能耗高的问题尚待解决。     

Behavior of metals in ash melting and gasification-melting of municipal solid waste (MSW)

In this study, metal behavior in ash-melting and municipal solid waste (MSW) gasification-melting facilities were investigated. Eight ash-melting and three MSW gasification-melting facilities with a variety of melting processes and feedstocks were selected. From each facility, melting furnace fly ash (MFA) and molten slag were sampled, and feedstock of the ash-melting processes was also taken. For the ash melting process, the generation rate of MFA was well correlated with the ratio of incineration fly ash (IFA) in feedstock, and this was because MFA was formed mostly by mass transfer from IFA and a limited amount from bottom ash (BA). Distribution ratios of metal elements to MFA were generally determined by volatility of the metal element, but chlorine content in feedstock had a significant effect on Cu and a marginal effect on Pb. Distribution ratio of Zn to MFA was influenced by the oxidizing atmosphere in the furnace. High MFA generation and distribution ratio of non-volatile metals to MFA in gasification-melting facilities was probably caused by carry-over of fine particles to the air pollution control system due to large gas volume. Finally, dilution effect was shown to have a significant effect on metal concentration in MFA.     

Elemental Mercury Control by Novel Oxidant and Sorbent in an Entrained-Flow System

An entrained-flow system has been designed and constructed to simulate in-flight mercury capture by sorbents in ducts of coal-fired utility plants. The test conditions of 1.5 s residence time, 140°C temperature, 4.5 ppbv inlet Hg⁰ concentration, and 0–20 lb/MMacf sorbent injection rates were chosen to simulate conditions in the ducts. Novel oxidants developed in previous fixed-bed tests and novel sorbents derived from the novel oxidants were tested for their Hg⁰ capture in the entrained-flow system to examine the possibility of using those sorbents in a full-scale system. Darco-FGD and Darco Hg-LH served as benchmark sorbents with which mercury control capability of the novel oxidants and novel sorbents could be compared. The test results showed that the novel oxidants have remarkable Hg⁰ oxidation capability, and the novel sorbents showed a better performance in Hg⁰ removal than Darco Hg-LH.     

Effects of bed material size distribution, operating conditions and agglomeration phenomenon on heavy metal emission in fluidized bed combustion process

This study investigates the effects of the bed material size distribution, the operating conditions and the agglomeration/defluidization phenomenon on the heavy metal pollutant emissions in the combustion process. After defluidization, the emission concentration of heavy metals increased, because Na may form a low melting eutectic material that enhances bed material adherence. The emission of Cd increased when the feed simulated urban residues contained sodium; however, the presence of Na had no significant effect on the emission of Cr. Furthermore, the Cd emission concentration was low when the material had a Gaussian distribution; however, the decreases in the Cd emission when the bed material had narrow, binary or flat distributions were not significant. The heavy metal Cr showed the same trend. In addition to the operating parameters, the bed material size distribution may influence the heavy metal emissions during combustion processes.     

The effect of chlorine position of chlorinated phenols on their dechlorination kinetics by Fenton's reagent

Chlorine position of chlorophenol isomers has a significant effect on the dechlorination kinetics of monochlorophenols, dichlorophenols, and trichlorophenols during Fenton oxidation. The effects have been evaluated by the rate constants of the dechlorination kinetic model developed in this study. It is found that the dechlorination rate of 3-CP is faster than that of 4-CP, which is faster than that of 2-CP. Since OH and Cl groups on the aromatic ring are ortho and para directors, the directory effect of OH and Cl groups enhances the dechlorination kinetics of 2-CP due to acceleration of the hydroxylation of 2-CP. Therefore, the dechlorination kinetics increases accordingly. For trichlorophenols (TCP), steric hindrance plays an important role during their dechlorination process. Specifically, the closer the chlorine atoms locate with each other on the aromatic ring, the more difficult the dechlorination processes will be. The dechlorination kinetics of dichlorophenols seems to be affected by both directory effect of OH and Cl groups and the effect of steric hindrance of chlorine atoms. The directory effect of OH and Cl groups on trichlorophenols decreases since the chlorine atom occupied the positions which are the most favorable for hydroxyl radical attack.     

膜电解技术处理含氯及重金属的废酸

采用离子交换膜电解技术处理铜冶炼过程产生的含氯及重金属的废酸。考察了废酸处理工艺、电解温度、电解时间、电流密度和催化剂的添加等条件对处理效果的影响。实验结果表明：采用先沉淀重金属后脱氯的废酸处理工艺，氯离子和铜离子的去除效果均较好;当以钛盐为催化剂时，在电解温度为40 ℃、电解时间为2.0 h、电流密度为825 A/m²的最佳工艺条件下，处理后废酸中的氯离子质量浓度为0.22 g/L，氯离子去除率为98.59%，铜离子质量浓度为0.45 g/L，铜离子去除率为95.08%，其他重金属大部分也得到有效去除。净化后的废酸可回用至铜冶炼的生产过程中。     

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.     

火电厂烟气汞形态转化机理及控制方法

汞是煤中最易挥发的重金属元素之一,燃烧产物中汞的排放为火电厂锅炉汞污染的主流。烟气中的汞主要采用活性炭或者其他吸附剂、飞灰再循环、湿法烟气脱硫装置等手段来去除,但普遍存在吸附剂价格昂贵、经济效应不高,具体脱除效应不明显、仅适用中小型火电厂锅炉等实际问题。为配合脱汞市场,需要在完善测试手段和控制手段的基础上,着重解决多组分污染物联合脱除汞反应的竞争机制和活性/选择性调控规律、吸收剂固体表面物理化学、大容积/大流量反应器内超低浓度污染物的富集/反应机理等关键技术问题。在火电厂烟气零价汞形态转化机理、汞迁移转化动力学模型的研究以及高效价廉吸附剂的开发等方面取得突破,开发具有自主知识产权的新型燃煤电厂烟气中汞排放控制方法。     

Sorbents for CO2 capture from high carbon fly ashes

Fly ashes with high-unburned-carbon content, referred to as fly ash carbons, are an increasing problem for the utility industry, since they cannot be marketed as a cement extender and, therefore, have to be disposed. Previous work has explored the potential development of amine-enriched fly ash carbons for CO(2) capture. However, their performance was lower than that of commercially available sorbents, probably because the samples investigated were not activated prior to impregnation and, therefore, had a very low surface area. Accordingly, the work described here focuses on the development of activated fly ash derived sorbents for CO(2) capture. The samples were steam activated at 850 degrees C, resulting in a significant increase of the surface area (1075m(2)/g). The activated samples were impregnated with different amine compounds, and the resultant samples were tested for CO(2) capture at different temperatures. The CO(2) adsorption of the parent and activated samples is typical of a physical adsorption process. The impregnation process results in a decrease of the surface areas, indicating a blocking of the porosity. The highest adsorption capacity at 30 and 70 degrees C for the amine impregnated activated carbons was probably due to a combination of physical adsorption inherent from the parent sample and chemical adsorption of the loaded amine groups. The CO(2) adsorption capacities for the activated amine impregnated samples are higher than those previously published for fly ash carbons without activation (68.6 vs. 45mg CO(2)/g sorbent).     

The feasibility of converting solid waste into refuse-derived fuel 5 via mechanical biological treatment process

The aim of our study was to investigate the feasibility of utilizing solid waste after mechanical biological treatment (MBT) processing at a landfill site in Phitsanulok, Thailand, as refuse-derived fuel 5 (RDF-5). The waste composition, and physical and chemical characteristics of each waste fraction were determined to evaluate the suitability of the waste for recycling and reuse as RDF-5. Results showed that after MBT processing, the solid waste >40 mm in size was observed to have 33.8 MJ/kg of calorific value. The average concentrations of heavy metals were also found to be within the acceptable limit for plastic waste combustion, thus proving that MBT-processed solid waste >40 mm in size has high potential for use as RDF-5. The optimal weight ratio of MBT-processed solid waste and crude oil sludge for transformation into RDF-5 was found to be 80:20. With this optimum ratio, the average calorific values of the RDF-5 were determined to be 47 MJ/kg, with sulfur and chlorine contents of 0.16 and 0.74 %, respectively. The characteristics of the produced RDF-5 could meet the specified ASTM standards in terms of calorific value (>15 MJ/kg), and sulfur and chlorine contents. In addition, the compressive strength of the produced RDF-5 was also found to be suitable for compact storage and transportation without any damage. Finally, the energy production cost from this RDF-5 process was estimated as USD $0.05/kWh.     

典型液氯泄漏危害的ALOHA软件估算

以瞬时泄漏和连续泄漏两种典型液氯泄漏事故为例,分别运用ALOHA软件和公式计算两种方法对液氯泄漏危害进行量化评估。估算结果表明:ALOHA软件对泄漏毒物的危害区域和敏感点毒物浓度的预测结果均具有良好的精度;软件模拟与公式计算的结果对于液氯瞬时泄漏的相对误差仅为7%,对于连续泄漏的相对误差为8%,二者均在可接受范围内。ALOHA软件计算过程简单、表达形象直观,在泄漏事故应急中具实用性。     

氯气泄漏扩散过程及后果评价的研究现状分析

综述了氯气泄漏扩散过程及后果评价的研究成果。从现场试验、实验室模拟和数学模拟三方面分析了氯气泄漏扩散各研究方法的优势和局限性。强调了氯气泄漏扩散后果评价的必要性。指出:必须针对中国特有的一些重气扩散建立专属知识产权的数学模型;不同层次数学模型的精度皆有待于进一步提高;需加强基于特定数学模型的全过程统一界面模拟程序的开发。     

Fundamental study of the behavior of chlorine during the combustion of single RDF

A fundamental study of the combustion characteristics and the de-HCl behavior of a single refuse-derived fuel (RDF) pellet was carried out to explain the de-HCl phenomena of RDF during fluidized bed combustion and to provide data for the development of high efficiency power generation technology using RDF. In this research, combustion and pyrolysis experiments were carried out in an electrical furnace using a series of model and actual RDF samples. The de-HCl capability of Ca(OH)2 in RDF was evaluated by measuring the emission fraction of HCl in the flue gas and the capture fraction of Cl in the residue. It was found that the capture fraction of Cl components in the residue increased from 0 to nearly 70% when the molar ratio of Ca/Cl was changed from 0 to around 13. Apparently, the capture fraction also decreased with increasing oxygen concentration in the feed gas. The devolatilization process of RDF was confirmed to be a very important part of de-HCl process. The effect of temperature profile of the RDF pellet on the de-HCl process, as it varies with the heating rate of RDF and the oxygen concentration in the vicinity of the sample, is discussed.     

Sulfur recirculation for increased electricity production in Waste-to-Energy plants

Sulfur recirculation is a new technology for reducing boiler corrosion and dioxin formation. It was demonstrated in full-scale tests at a Waste to Energy plant in Göteborg (Sweden) during nearly two months of operation. Sulfur was recirculated as sulfuric acid from the flue gas cleaning back to the boiler, thus creating a sulfur loop.The new technology was evaluated by extensive measurement campaigns during operation under normal conditions (reference case) and operation with sulfur recirculation. The chlorine content of both fly ash and boiler ash decreased and the sulfur content increased during the sulfur recirculation tests. The deposit growth and the particle concentration decreased with sulfur recirculation and the dioxin concentration (I-TEQ) of the flue gas was reduced by approximately 25%. Sulfuric acid dew point measurements showed that the sulfuric acid dosage did not lead to elevated SO₃ concentrations, which may otherwise induce low temperature corrosion.In the sulfur recirculation corrosion probe exposures, the corrosion rate decreased for all tested materials (16Mo3, Sanicro 28 and Inconel 625) and material temperatures (450 °C and 525 °C) compared to the reference exposure. The corrosion rates were reduced by 60–90%. Sulfur recirculation prevented the formation of transition metal chlorides at the metal/oxide interface, formation of chromate and reduced the presence of zinc in the corrosion products. Furthermore, measured corrosion rates at 525 °C with sulfur recirculation in operation were similar or lower compared to those measured at 450 °C material temperature in reference conditions, which corresponds to normal operation at normal steam temperatures. This implies that sulfur recirculation allows for higher steam data and electricity production without increasing corrosion.     

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.     

Characterization of metal concentration,heavy metal elution,and desalination behavior of municipal solid waste incineration bottom and grate sifting deposition ash based on particle size

Resource and environmental safety protocols of incineration residues were evaluated by analyzing the metal concentration, heavy metal elution, desalination behavior, and chlorine removal ratio owing to particle size differences between bottom ash (BA) and grate sifting deposition ash (GA). In the total content test, Cl, Zn, and Cr in the incinerator BA exceeded the cement acceptance standard (Cl: 1000 mg/kg; Zn: 1700 mg/kg, and Cr: 170 mg/kg) at almost all of the particle sizes, while Au, Ag, Pd, and Zn had high contents in the GA. When using BA as a construction material, heavy metal elution values and contents are restricted as per the product quality standards based on the Japanese soil pollution control law. Lead within the BA and GA exceeded the standard values for most particle sizes. We predicted that there would be a limit on the elution of K by only washing with water. The removal ratio of total chlorine by particle size was approximately 20–70%, where the effect of the particle size on the removal ratio was small, suggesting that the elution of chlorine was complete in approximately 6 hours. These results contribute to information on the recycling of BA and GA.

     

Effects of chemical composition of fly ash on efficiency of metal separation in ash-melting of municipal solid waste

In the process of metal separation by ash-melting, Fe and Cu in the incineration residue remain in the melting furnace as molten metal, whereas Pb and Zn in the residue are volatilized. This study investigated the effects of the chemical composition of incineration fly ash on the metal-separation efficiency of the ash-melting process. Incineration fly ash with different chemical compositions was melted with bottom ash in a lab-scale reactor, and the efficiency with which Pb and Zn were volatilized preventing the volatilization of Fe and Cu was evaluated. In addition, the behavior of these metals was simulated by thermodynamic equilibrium calculations. Depending on the exhaust gas treatment system used in the incinerator, the relationships among Na, K, and Cl concentrations in the incineration fly ash differed, which affected the efficiency of the metal separation. The amounts of Fe and Cu volatilized decreased by the decrease in the molar ratio of Cl to Na and K in the ash, promoting metal separation. The thermodynamic simulation predicted that the chlorination volatilization of Fe and Cu was prevented by the decrease in the molar ratio, as mentioned before. By melting incineration fly ash with the low molar ratio in a non-oxidative atmosphere, most of the Pb and Zn in the ash were volatilized leaving behind Fe and Cu.     

Heavy metal removal from contaminated sludge for land application: a review

In recent years, various methods for heavy metal removal from sewage sludge have been extensively studied in order to minimize the prospective health risks of sludge during land application. In this paper, a comparative review and critical analysis of the application of chemical extraction, bioleaching, electroreclamation, and supercritical fluid extraction (SFE), in removing heavy metals from contaminated sludges is presented. Moreover, speciation studies, which can indicate ease of leachability of the different forms of heavy metals in sludge, are also presented. Experimental studies revealed a broad range in metal extraction efficiencies of the different extraction technologies. Acid treatment seemed to effectively remove Cd, attaining as much as 100% removal for some studies, as compared to bioleaching. SFE also gave higher removal efficiency than bioleaching. Cr, Pb and Ni seemed to be also effectively removed by the acid treatment. For the removal of Cu, Mn and Zn, the bioleaching process seemed to be appropriate with maximum removal efficiencies of 91%, 93% and 96% for the three metals, respectively, and as high as 64% minimum removal efficiency for Zn. The SFE process also gave good results for Cu, Mn and Zn removal. Electroreclamation exhibited better removal efficiency for Mn, but is still inferior to acid treatment and bioleaching processes. For chemical extraction, because of the adverse impacts that can result from the use of inorganic acids and complexing agents, interest can be directed more toward utilizing organic acids as extracting agents because of their biodegradability and capability to remove metals at mildly acidic condition, hence requiring less acid. The bioleaching process, although it seems to give a higher yield of metal extraction with lower chemical cost than chemical extraction, may be limited by the inability of the system to cope with the natural environmental conditions, requires strict monitoring of aeration rate and temperature and has applicability to only low sludge solids concentration. A full-scale study would be useful to better assess the efficiency of the process. The electroreclamation technology is limited by its relatively higher energy consumption and limited applicability to sludge. The SFE method, on the other hand, is limited by the complexity of the process and the cost of ligands suitable for effective metal extraction. Both of these technologies are still in their early stage of application and hence there is a need for further basic and applied studies. Finally, the common advantage for almost all treatment technologies studied is that the extraction efficiencies for some metals are high enough to remove metals from sludge to levels suitable for land application.