Solidification/stabilization of hazardous sludges with Portland cement

Abstract

Studies were conducted to investigate the feasibility and effectiveness of solidification/stabilization of hazardous heavy metal‐laden sludges with portland cement. The results indicated that the sludge properties had a significant effect on the compressive strength of the solidified samples. Additives such as lime, sodium silicate, calcium chloride, and fly ash could enhance the compressive strength and reduce the leachability of heavy metal. Also, leaching studies indicated that stabilization minimized or prevented the release of heavy metals and created a nonhazardous product.     

Solidification/stabilization of electric arc furnace dust using coal fly ash. Analysis of the stabilization process

In this paper, the stabilization of electric arc furnace (EAF) dust containing hazardous metals such as Pb, Cd, Cr or Zn is described. The treatment involves a waste solidification/stabilization (S/S) process, using coal fly ash as the fundamental raw material and main binder. The article also contains a brief review of the most important recent publications related to the use of fly ash as S/S agents.The efficacy of the process has been evaluated mainly through leaching tests on the solidified products and compliance with some imposed leachate limits. The concentration of metals leaching from the S/S products was strongly leachate pH dependent; thus, the final pH of the leachate is the most important variable in reaching the limits and, therefore, in meeting the stabilization goals.In this study, the dependence relationship between the leachate pH and the concentrations of metals in the leachate are analyzed; in some cases, this allows us to estimate the speciation of contaminants in the S/S solids and to understand the mechanism responsible for reduced leachability of heavy metals from solidified wastes.     

Solidification/stabilization of hazardous waste sludge obtained from a chemical industry

In this study, treatment sludge obtained from a chemical-metal finishing industry, which contained potentially toxic heavy metals and organics, was characterized, and the performance of the solidification/stabilization (S/S) of the sludge was discussed. The hazard characteristics of the waste were determined by means of extraction procedure toxicity test and DIN 38414-S4 Test, as defined in both Turkish and USEPA regulations. S/S studies were conducted using Portland cement to solidify the sludge containing high concentrations of total organic carbon, Cr, Cu, Hg, Ni, Pb, and Zn. The waste/binder ratios of 36 sludge specimens were kept between 0/100 and 40/100. The specimens were cured at room temperature for 7, 28, and 90 days. The compressive strengths of the specimens were measured to determine the feasibility of using solidified waste sludge as construction materials. The compressive strength values indicated that specimens could be potentially used as construction materials. The heavy metal and organic contents of the extracts of each specimen were detected in concentrations which were lower than the standard concentrations in EPTox and DIN 38414-S4 leaching procedures for the most part.     

Solidification and stabilization of cadmium ions in sand-cement-clay mixture

This study was carried out to test the ability of a mixture of sand, cement and clay for immobilizing cadmium ions from leaching out into water resources. Various samples with different mass ratios for this mixture were tested to determine their efficiency for adsorbing cadmium. The compressive test, cation exchange capacity (CEC), adsorption equilibrium and leaching test were applied to each sample. The sample that showed the highest cation exchange capacity with 53.1 meq/100 g and compressive strength with 11.05 N/mm2 consists of 25% sand, 50% cement and 25% clay. The equilibrium data for Cd2+ removal using this sample showed a multilayer adsorption, which could be fitted using Brunauer-Emmett-Teller adsorption isotherm model with a regression coefficient of 0.999. The maximum cadmium uptake obtained from this model was 82.618 mg/g solid. The mobility of Cd2+ in acidic solution drawn-off after 18 h of initial mixing was 66.06 mg when the solid sample initially contains 6.0 g Cd2+. This value decreased to 14.33 mg when only 1.0 g Cd2+ was initially spiked in the sample. Introducing clay into this sample enhanced its sorption capacity while the presence of sand and cement enhanced its compressive strength.     

Solidification/stabilization of arsenic containing solid wastes using portland cement, fly ash and polymeric materials

Stabilization/solidification (S/S) is used as a pre-landfill waste treatment technology that aims to make hazardous industrial wastes safe for disposal. Cement-based solidification/stabilization technology is widely used because it offer assurance of chemical stabilization of many contaminants and produce a stable form of waste. The leaching behavior of arsenic from a solidified/stabilized waste was studied to obtain information about their potential environmental risk. Activated alumina (AA) contaminated with arsenic was used as a waste, which was stabilized/solidified (S/S) using ordinary portland cement (C), fly ash (FA), calcium hydroxide (CH) and various polymeric materials such as polystyrene and polymethyl methacrylate (PMMA). Toxicity characteristics leaching procedure (TCLP) and semi-dynamic leach tests were conducted to evaluate the leaching behavior of arsenic. Formations of calcite along with precipitate formation of calcium arsenite were found to be responsible for low leaching of arsenic from the stabilized/solidified samples. Effective diffusivity of arsenic ion from the matrix and leachablity index was also estimated. Minimum leaching of the contaminant was observed in matrix having AA+C+FA+CH due to the formation of calcite.     

Solidification and stabilization of asbestos waste from an automobile brake manufacturing facility using cement

Currently, the generated brake lining waste dust, which contains asbestos as its major component, is disposed of into a secure landfill without any additional treatment. As an alternative to this, solidification/stabilization (S/S) disposal of the dust was investigated using Portland cement alone and Portland cement mixed with activated carbon (AC), as the binders. Toxicity Characteristics Leaching Procedure (TCLP) results on the solidified matrix showed that cement was able to immobilize the heavy metals, Ba, Zn, Cr, Pb, Cu and Fe, to within the limits set by the US EPA for TCLP. Addition of AC to the cement reduced the leaching of heavy metals by an additional 4-24% compared to cement alone. The pH of the TCLP leachate extracted from virgin cement, and from dust treated with cement with or without AC was found to increase to 10.9-12.5 as opposed to an initial value of 4.93 for the TCLP extract for the untreated dust. Results of ANS 16.1 (modified) leach protocol revealed that Ba in cement-treated samples showed the highest leach rate, followed by Zn, Pb, Cr, Cu and Fe. The leach rate of heavy metals decreased with progress in time. Cement mixed with AC exhibited similar leach characteristics, however, the leach rate was lower. The linear relationship between the cumulative fraction leached (CFL) and the square root of leaching time in all cement-based samples indicate that a diffusional process is the controlling transport mechanism for the leaching of the heavy metals. The obtained Leachability Indices (L(i)) of 7.6-9.1 and 8.3-9.5 for cement and cement with AC, respectively, were low but exceeded the guidance value of 6, which clearly indicates that all the heavy metals studied are retained well within solid matrices. Cement-based S/S hardening times increased from 30 to 96 h as the dust content increased from 40 to 70 wt.%. The resulting solid matrices exhibited a compressive strength ranging from 1 to 12 MPa, which was well above the specified limit of 414 kPa for such matrices. An economic analysis indicates that the disposal costs for the dust in the only available secure landfill would increase by 40.3% if one were to go for the cement S/S option. Addition of AC to the cement would escalate this by an additional 43.8%. Although the S/S of brake lining dust using cement effectively immobilized the heavy metals of concern, cost considerations may hinder the commercial adaptation of this technique for waste disposal unless new regulatory demands are implemented.     

Waste-to-energy plant for paper industry sludges disposal: technical-economic study

In this work, a detailed technical-economic analysis of a fluidized bed based waste-to-energy system for disposal of paper manufacturing sludges has been carried out. Specific reference is made to a case study represented by the largest plant in Italy producing recycled paper, with a daily sludge output of about 52t.The adopted plant has been sized for a nominal capacity of 140t per day also allowing the progressive elimination of sludges accumulated in a previously utilized landfill, giving a nominal electrical power output of 3.5MW.The main plant sections have been described and the adopted technical solutions have been outlined. A detailed process and equipment characterization has been carried out leading to a thorough evaluation of capital investment, operating costs and revenues. A differential analysis has been performed with respect to the alternative solution represented by the disposal of untreated sludges in an external landfill in order to highlight the savings obtainable. The economic profitability of the investment has been evaluated regarding several performance indices. The economic evaluation has been completed by a sensitivity and risk analysis in order to assess the effects of uncertainties in the economically significant parameters. Adopting most probable values, the savings obtained with the considered waste-to-energy system are evaluated in the 15--20 million Euro range during the estimated plant life of 15 years with a foreseen pay back time of 4 years. Moreover, many environmental benefits result such as the remediation of existing landfill, the avoidance of new landfills opening and very low air pollutants emissions.     

A study of the stabilization of aluminium titanate

A tialite ceramics (Al₂TiO₅) was synthesized at a temperature of 1500 °C, incorporating CaF₂, La₂O₃, SiO₂ or kaolin and MgO additives. Its thermal stability was investigated by thermocycling in a reducing medium. The batches containing SiO₂ or kaolin additives underwent a decomposition to rutile and corundum. A stabilized ceramic with added MgO was produced. X-ray and electron-probe microanalysis established the presence of Mg/Al, Ti_z/O₄, Al_2–x-y Ti_1+x Mg _y O₅ and Ca_1–x La _x /Al_12–y-z Mg _y Ti _z /O₁₉ solid solutions, which retained their chemical composition after thermocycling in a reducing medium.     

Small hazardous waste generators in developing countries: use of stabilization/solidification process as an economic tool for metal wastewater treatment and appropriate sludge disposal

The aim of this study was to propose a profitable destination for an industrial sludge that can cover the wastewater treatment costs of small waste generators. Optimized stabilization/solidification technology was used to treat hazardous waste from an electroplating industry that is currently released untreated to the environment. The stabilized/solidified (S/S) waste product was used as a raw material to build concrete blocks, to be sold as pavement blocks or used in roadbeds and/or parking lots. The quality of the blocks containing a mixture of cement, lime, clay and waste was evaluated by means of leaching and solubility tests according to the current Brazilian waste regulations. Results showed very low metal leachability and solubility of the block constituents, indicating a low environmental impact. Concerning economic benefits from the S/S process and reuse of the resultant product, the cost of untreated heavy metal-containing sludge disposal to landfill is usually on the order of US$ 150-200 per tonne of waste, while 1tonne of concrete roadbed blocks (with 25% of S/S waste constitution) has a value of around US$ 100. The results of this work showed that the cement, clay and lime-based process of stabilization/solidification of hazardous waste sludge is sufficiently effective and economically viable to stimulate the treatment of wastewater from small industrial waste generators.     

Solidification behavior of PLLA/nHA nanocomposites

As part of a broader effort to establish processing-structure–property relationships in PLLA/nHA, which is currently under consideration for bioresorbable scaffolds for bone repair, hot stage optical microscopy and differential scanning calorimetry have been used to investigate the solidification behavior of a series of medical grade PLLA/nHA nanocomposites. The presence of the nHA resulted in an increase in the number of spherulites per unit volume during isothermal crystallization, but there was a substantial decrease in the spherulite growth rate with increasing nHA content in the temperature range 100–130 °C, argued to be associated with a significant increase in the melt viscosity in the presence of the nHA. The consequences for the global solidification rates and the phase structure of the PLLA/nHA nanocomposites are discussed.     

含砷废渣水泥固化/稳定化技术研究进展

含砷废渣作为一种持久性污染物被广泛关注,固化/稳定化技术是治理含砷废渣的一种行之有效的途径。对硅酸盐水泥基胶凝材料固砷效果以及其固化机理等方面的研究进行了综述,水泥水化过程中产生的大量Ca(OH)_2与可溶性砷酸盐反应生成较为稳定的砷酸钙盐,降低砷的浸出浓度,从而实现砷的有效固化,但其存在污染物包容量小、耐久性差等缺点。本课题组提出了利用地聚物水泥(地聚物材料)固化含砷废渣,通过在地聚物材料水化聚合过程中,以同晶取代的方式实现AsO43-与SiO_4~(4-)、AlO_4~(5-)之间的化学键合,并辅以地聚物材料的高强、耐久性好的优良特性,利用地聚物材料固化含砷废渣实现砷的大容量、持久性地安全稳定固封。     

多组元合金的凝固热力学原理

以发展多元多相合金的凝固理论为目标,探讨了多组元合金自由能描述方法及其凝固过程的热力学平衡条件。多组元合金的自由能是由各组成元素的自由能、原子的组合排列引起熵的变化决定的理想混合自由能和由原子间交互作用引起的附加自由能三部分决定的。其中附加自由能的描述是难点,通常通过实验结果的拟合获得。固相的析出条件可通过自由能最低的热力学原理预测,而固相和液相成分的相关性则可通过化学位相等的热力学原理计算。在实际应用中,可以借鉴相图计算方法进行凝固过程的热力学分析,进而获得相图精细结构的数值计算结果。以Al Mg Si合金为算例,进行了三元合金热力学平衡条件的分析。以该热力学平衡条件计算结果为基础,引入对固相和液相中扩散过程的分析,则可实现多组元合金凝固路径的预测。     

Solidification study of Cu-based alloys obtained by continuous casting

Commercial production of copper by continuous casting in a wheel-and-band machine, with suitable modifications to induce high undercooling, is considered. Impurities control to a large extent the microstructure and mechanical properties of the ingot. Suitable solute additives in the molten alloy to achieve constitutional supercooling during solidification have been analyzed, with particular emphasis on the presence of lead. Experimental information on the Cu-O-Pb phase diagram has been revised and modeling of the microstructure evolution as a function of several casting parameters is being presented.     

A new method for the kinetic study of cyclization reaction during stabilization of polyacrylonitrile fibers

A new method for the kinetic study of cyclization reaction using the chemical shrinkage was described. The kinetic parameters derived by function fit were used to predict the rate constant at a given temperature and the feasibility of this method was verified by the Kissinger method. The results indicate that the method is feasible and the order of cyclization reaction is relevant to stabilization temperature with an activation energy of 159.11 kJ/mol.     

Assessment of the mineral industry NORM/TENORM disposal in hazardous landfills

The main objective of this paper is to describe the assessment methodology utilised in Brazil, to foresee the performance of industrial landfills to disposal solid wastes containing natural radionuclides arising from milling and metallurgical installations that process ores containing NORM. An integrated methodology is utilized and issues as risk, exposure pathways and the plausible scenarios in which the contaminant can migrate and reach the environment and human beings are addressed. A specific example of the procedure is described and results are presented for actual situations. The model consists of an engineered depository constructed of earthen materials which minimise costs and maintain integrity over long-term. In order to define the landfill characteristics and the potential consequences to the environment, an impact analysis is carried out, considering the engineering aspects of the waste deposit and the exposure pathways by which the contaminant can migrate and reach the environment and human beings. Analytical solutions are used in the computer program in order to obtain fast results.     

Interfacial Thermal Resistance and the Solidification Behavior of the Al/SiCp Composites

The objective of this investigation is to study the effects of applied pressure on the solidification time and interfacial thermal resistance of A356/10% SiC_p during squeeze casting. Samples were prepared for various but constant squeeze pressures up to 130 MPa while maintaining the melt and mold temperatures at 800°C and 400°C, respectively. It was observed that the solidification time was 60 s when no squeeze pressure was applied but it decreased to 42 s when the squeeze pressure was maintained at 130 MPa. The results also showed that the cooling rate increased with squeeze pressure. The solidification time calculated from one-dimensional heat flow theory was found to be close to that obtained from the experimental cooling curves. The interfacial thermal resistance between the mold and the casting was calculated and it decreases when the squeeze pressure increases.     

Fe-B合金非平衡凝固过程的DSC研究

采用DSC技术研究了Fe-B合金冷却速率及试样纯度对其非平衡凝固过程的影响,得到了不同实验条件下过冷度和转变分数的演化结果,并从经典形核理论、非等温结晶动力学等方面进行了分析和讨论.实验结果表明,随冷却速率的增加,过冷度逐渐增大,最大可达409K;在同一冷却速率下,熔体的过冷度随试样纯度的提高也显著增大,并逐渐趋向于一定值.此外,整个非平衡凝固转变时间随过冷度的增大而不断缩短.     

一种测定定向凝固工艺参数的方法

利用连续测定试样顶面温度的方法，方便地测定了向凝固时的温度梯度以及固液界面位置，发现温度梯度受抽拉速度的影响不大，而固液界面的位置抽拉速度影响较大，随着抽拉速度的增大，固液界面位置向下移动。     

A review of solidification/stabilization technology

In hazardous waste management, solidification/stabilization (S/S) is a term normally used to designate a technology employing additives to alter hazardous waste to make it non-hazardous or acceptable for current land disposal requirements. The use of this technology to treat hazardous waste may become more important as regulations restrict the use of land for disposing of hazardous waste. This paper reviews the technology and provides information to help assess its potential role in managing hazardous waste. Information is provided to assist the proper selection, use and evaluation of S/S technologies. Regulatory factors affecting its use are also discussed.