Stabilization and Solidification of Metal-Laden Wastes by Compaction and Magnesium Phosphate-Based Binder

ABSTRACT

Bench-scale and full-scale investigations of waste stabilization and volume reduction were conducted using spiked soil and ash wastes containing heavy metals such as Cd, Cr, Pb, Ni, and Hg. The waste streams were stabilized and solidified using chemically bonded phosphate ceramic (CBPC) binder, and then compacted by either uniaxial or harmonic press for volume reduction. The physical properties of the final waste forms were determined by measuring volume reduction, density, porosity, and compressive strength. The leachability of heavy metals in the final waste forms was determined by a toxicity characteristic leaching procedure (TCLP) test and a 90-day immersion test (ANS 16.1). The structural composition and nature of waste forms were determined by X-ray diffraction (XRD) and scanning electron microscopy (SEM), respectively.

CBPC binder and compaction can achieve 80-wt % waste loading and 39-47% reduction in waste volume. Compressive strength of final waste forms ranged from 1500 to 2000 psi. TCLP testing of waste forms showed that all heavy metals except Hg passed the TCLP limits using the phosphate-based binder. When Na₂S was added to the binder, the waste forms also passed TCLP limits for Hg. Long-term leachability resistance of the final waste forms was achieved for all metals in both soil and ash wastes, and the leachability index was ~14. XRD patterns of waste forms indicated vermiculite in the ash waste was chemically incorporated into the CBPC matrix. SEM showed that waste forms are layered when compacted by uniaxial press and are homogeneous when compacted by harmonic press.     

Stabilization and solidification of metal-laden wastes by compaction and magnesium phosphate-based binder

Bench-scale and full-scale investigations of waste stabilization and volume reduction were conducted using spiked soil and ash wastes containing heavy metals such as Cd, Cr, Pb, Ni, and Hg. The waste streams were stabilized and solidified using chemically bonded phosphate ceramic (CBPC) binder, and then compacted by either uniaxial or harmonic press for volume reduction. The physical properties of the final waste forms were determined by measuring volume reduction, density, porosity, and compressive strength. The leachability of heavy metals in the final waste forms was determined by a toxicity characteristic leaching procedure (TCLP) test and a 90-day immersion test (ANS 16.1). The structural composition and nature of waste forms were determined by X-ray diffraction (XRD) and scanning electron microscopy (SEM), respectively. CBPC binder and compaction can achieve 80-wt% waste loading and 39-47% reduction in waste volume. Compressive strength of final waste forms ranged from 1500 to 2000 psi. TCLP testing of waste forms showed that all heavy metals except Hg passed the TCLP limits using the phosphate-based binder. When Na2S was added to the binder, the waste forms also passed TCLP limits for Hg. Long-term leachability resistance of the final waste forms was achieved for all metals in both soil and ash wastes, and the leachability index was approximately 14. XRD patterns of waste forms indicated vermiculite in the ash waste was chemically incorporated into the CBPC matrix. SEM showed that waste forms are layered when compacted by uniaxial press and are homogeneous when compacted by harmonic press.     

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.     

Limitations of the toxicity characteristic leaching procedure for providing a conservative estimate of landfilled municipal solid waste incineration ash leaching

Limitations of the toxicity characteristic leaching procedure (TCLP) for simulating pollutant leaching from wastes disposed of in full-scale landfills are well understood in the waste management profession; the TCLP solution has a lower pH and greater organic acid content than typical landfill leachate. The TCLP serves its intended regulatory objective, however, as long as a conservative estimate of leaching is provided. Here, we examine TCLP’s ability to represent worst-case leaching conditions for monofilled municipal solid waste incineration (MSWI) ash. A critical examination of TCLP’s applicability to MSWI ash is especially relevant, as ash management at MSWI facilities often centers on passing TCLP, regardless of environmental risk posed by the ash or its recyclability. Multiple batch leaching tests were conducted on different MSWI ash streams: mixed ash, fly ash, and different size fractions of bottom ash. Batch-test results were compared with leachate simulating MSWI ash monofills. The TCLP did not consistently provide the most conservative estimate of leaching, supporting the need to consider alternative methodologies in future regulatory development.

Implications: This paper analyzes the existing hazardous waste regulatory testing requirement for municipal solid waste incinerator (MSWI) ash management to evaluate whether the TCLP serves its intended purpose in providing the most conservative estimate of landfilled MSWI ash. The results will serve as guidance and motivation for policy makers and the regulatory community to reevaluate the TCLP’s application for characterizing MSWI ash leaching in certain disposal scenarios and could promote consideration of alternative testing procedures based upon results of this study. This study serves to promote representative and accurate quantification of leaching risk from MSWI ash.     

Investigations of ash topography/morphology and their relationship with heavy metals leachability

The leachability of heavy metals such as chromium (Cr), lead (Pb) and cadmium (Cd) from the ash material obtained from waste combustion was studied. The effects of ash surface topography and morphology on the leachability of these elements were examined using atomic force microscopy (AFM) and scanning electron microscopy (SEM). The AFM (scan size 10 x 10 microns) and SEM images of the simulated ash pellet obtained at various operating temperatures (1000, 1400 and 1500 degrees C) showed significant microstructural and topographical changes. Ash pellets treated at 1000 degrees C contain porous and non-continuous surface. On the other hand, the ash pellet obtained at higher temperature (1500 degrees C) was found to contain a smooth, continuous and non-porous surface. The AFM height profile studies indicated that the top surface variation of the ash pellet at 1000, 1400 and 1500 degrees C were found to be -40.0 to 25.5, -3.7 to 4.7 and -0.10 to 0.66 nm respectively. The SEM analyses also confirmed the presence of smooth, non-porous outer surface of ash formed at 1500 degrees C. In addition, it also showed the presence of compact and rigid interior for the same ash pellet. The leachability of the heavy metals was determined using standard toxicity characteristic leaching procedure (TCLP) test and the samples were analysed using atomic absorption spectroscopy. The results showed that the TCLP leaching ratios of the heavy metals were Cr = 0.30, Pb = 0.05 and Cd = 0.09 at 1000 degrees C. However, the ash obtained at 1400 degrees C showed negligible heavy metals leaching ratio while at 1500 degrees C no leachability was detected (TCLP concentration dropped to nondetectable levels). The use of high temperature treatment enabled the immobilization of heavy metals in the ash preventing their leaching. Such ash can be considered as a non-hazardous material for reuse or safe disposal.     

Waste Streams,Technology, and State Requirements

Biomedical wastes are generated by hospitals, laboratories, animal research facilities, and by other institutional sources. The disposal of these wastes is coming under critical public scrutiny, and regulations are being promulgated to control their disposal. Incineration is not a final disposal method since it generates a solid residue (ash) which must be buried or otherwise disposed. The incineration process, however, renders the waste non-toxic, non-hazardous, and non-putrescible, and reduces the volume of material for ultimate disposal by an order of magnitude. In some instances, the residue may have high levels of heavy metals; however, this is the exception rather than the rule.     

Dioxins/furans emissions from fluidized bed combustion of salt-laden hog fuel

Polychlorinated dibenzodioxins/furans (PCDD/F) were formed in substantial quantities in a pilot-scale fluidized bed combustor burning salt-laden waste wood, a common fuel for Canadian coastal pulp and paper mills. Formation of PCDD/F increased with increasing chloride content in the feed, and appeared to correlate with the chlorine content in the fly ash. It took a very long time for the ash chlorine content to stabilize, suggesting that chlorine transferred slowly from the flue gas to the ash. The baghouse may contribute largely to formation of the PCDD/F, owing to its temperature range and the potentially long residence time for ash particles. Controlling the baghouse temperature to reduce the PCDD/F formation in the baghouse should be effective in reducing the total emission level. While sulphur addition was found to reduce the emission level by as much as 90%, the emission level was still above the regulated level for the mills burning salt-laden wood under the conditions of the present study. No relation between the emission level and CO concentration in the flue gas was observed.     

Improving Baghouse Performance at the Monticello Generating Station

At the Monticello station, operated by the Texas Utilities Generating Company, lignite coal obtained locally in Titus and Hopkins Counties fuels each of the three units. Units 1 and 2 are identical 575-MW Combustion Engineering (CE) boilers, each of which discharges its effluent to a 36- compartment shake/deflate cleaned baghouse paralleled with four electrostatic precipitators (ESP). Unit 3 is a larger boiler and is followed by an ESP and a scrubber. The Unit 1 and 2 baghouses were designed to clean 80 percent of the flue gas. Since startup, these baghouses have regularly experienced flange-to-flange pressure drops in excess of 10 in. H₂O, with large opacity spikes caused by ash bleeding through the bags after compartment cleanings. Because of higher-than-expected pressure drop, the baghouses receive only about 45-50 percent of the flue gas. Analysis has shown the Monticello lignite ash significantly differs from most other coal ashes. Testing has shown that the Monticello ash is not filtered effectively by many "standard" bag materials. However, this testing indicates that there are fabrics that show promise of eliminating the ash bleedthrough with little pressure drop penalty. Testing has also shown that injection of low concentrations (10-15 ppm) of ammonia (NH₃) into the flue gas significantly decreases ash bleedthrough, so that with NH₃ injection "standard" bag materials may perform adequately. Currently, fullcompartment testing of four fabrics, with and without NH₃ injection, is under way at the Unit 1 baghouse. The research conducted at the Monticello station is reviewed in this paper and the encouraging results from the full-compartment tests are presented.     

Joint US/USSR Test Program for Reducing Fly Ash Resistivity

An electrostatic precipitator preceded by a wet scrubber was tested at the Reftinskaya Power Station. The unit collects a high resistivity fly ash from the combustion of low sulfur Ekibastuz coal. The operating parameters of the precipitator were measured as well as the mass emissions and the in-situ electrical resistivity of the fly ash. Density, particle size distribution, electrical resistivity, and chemical composition were determined for collected samples of the fly ash. The fly ash was also characterized by x-ray diffraction and scanning electron microscopy. When a centrifugal wet wall scrubber was installed ahead of the electrostatic precipitator, the temperature of the flue gas entering the precipitator was decreased and the moisture content increased. The electrical resistivity of the fly ash was attenuated a decade, but not enough to overcome the adverse effects of back corona in the precipitator. Lowering the flue gas temperature to about 85°C by the addition of a venturi scrubber ahead of the centrifugal scrubber reduced the electrical resistivity of the fly ash another decade and allowed the operation of the precipitator without back corona.     

Leachates of municipal solid waste incineration bottom ash from Macao: heavy metal concentrations and genotoxicity

Heavy metals in municipal solid waste incineration bottom ash (MSWIBA) may leach into soil and groundwater and pose long-term risks to the environment. In this study, toxicity characteristic leaching procedure (TCLP) was carried out on the MSWIBA from Macao. Heavy metals in leachates were determined by inductively coupled plasma mass spectrometry (ICP-MS) and inductively coupled plasma atomic emission spectrometry (ICP-AES), and genotoxicity of leachates was also evaluated by micronucleus (MN) assay with Vicia faba root tip cells. The results showed that the concentrations of aluminium (Al), manganese (Mn), cobalt (Co), cadmium (Cd) and mercury (Hg) in the leachates were less than 0.01 mg l(-1), and those of iron (Fe), copper (Cu) and molybdenum (Mo) were less than 0.1 mg l(-1). The concentrations of chromium (Cr), zinc (Zn), selemium (Se), strontium (Sr), barium (Ba) and caesium (Cs) were between 0.11 mg l(-1) and 2.19 mg l(-1). Lead (Pb) concentrations, in particular, reached as high as 19.6 mg l(-1), significantly exceeding the maximum concentration limit (5 mg l(-1) for lead by TCLP). Compared with the negative group, a significant increase of MN frequencies was observed in the leachate-exposed groups (P<0.05). With the increase of heavy metals in the leachates, the toxic effects on the Vicia faba root tip cells increased, implying that heavy metals were the main factors causing the genotoxic effects. Our results suggested that apart from chemical analysis, bioassays like the MN assay of Vicia faba root tip cells should also be included in a battery of tests to assess the eco-environmental risks of bottom ashes before decisions can be made on the utilization, treatment or disposal.     

Dioxin contents in fly ash from large-scale MSW incinerators in Taiwan

In this study, fly ash samples were collected from three municipal waste incinerators (MWI) in Taiwan. These MWIs investigated are equipped with different air pollution control devices (APCDs). Preliminary results indicated that 2,3,7,8-PCDD/Fs homologue patterns of various types of fly ash were quite similar for all three MWIs. Concentrations of higher-chlorinated congeners of PCDDs and PCDFs were remarkably higher than those of lower-chlorinated congeners. In the case of MSW-A, the PCDD/PCDF ratios of ashes were found in the decreasing order for cyclone, boiler and baghouse. The PCDD/PCDF ratios in various types of fly ash of MWI-B was boiler-A < boiler-B < ESP < boiler-C. As for MSW-C, no obvious trend has been observed for PCDD/PCDF ratio. However, the ratio in boiler ash was higher than that in baghouse ash of MWI-A. The dioxin contents in fly ash would increase as the fly ash passed through APCD zones. In other words, the environmental conditions of APCD may actually cause the increase of the dioxin contents in fly ash. The trend for dioxin contents in fly ash collected from three MSW incinerators investigated was MSW-C < MSW-A < MSW-B.     

Performance evaluation of intermediate cover soil barrier for removal of heavy metals in landfill leachate

This pilot-scale study evaluated the use of intermediate cover soil barriers for removing heavy metals in leachate generated from test cells for co-disposed fly ash from municipal solid waste incinerators, ash melting plants, and shredder residue. Cover soil barriers were mixtures of Andisol (volcanic ash soil), waste iron powder, (grinder dust waste from iron foundries), and slag fragments. The cover soil barriers were installed in the test cells' bottom layer. Sorption/desorption is an important process in cover soil bottom barrier for removal of heavy metals in landfill leachate. Salt concentrations such as those of Na, K, and Ca in leachate were extremely high (often greater than 30 gL(-1)) because of high salt content in fly ash from ash melting plants. Concentrations of all heavy metals (nickel, manganese, copper, zinc, lead, and cadmium) in test cell leachates with a cover soil barrier were lower than those of the test cell without a cover soil barrier and were mostly below the discharge limit, probably because of dilution caused by the amount of leachate and heavy metal removal by the cover soil barrier. The cover soil barriers' heavy metal removal efficiency was calculated. About 50% of copper, nickel, and manganese were removed. About 20% of the zinc and boron were removed, but lead and cadmium were removed only slightly. Based on results of calculation of the Langelier saturation index and analyses of core samples, the reactivity of the cover soil barrier apparently decreases because of calcium carbonate precipitation on the cover soil barriers' surfaces.     

Determination of Baghouse Performance from Coal and Ash Properties: Part II

Baghouse performance at utility coal-fired power plants is determined by baghouse design, operating procedures, and the characteristics of the ash that is collected as a dustcake on the fabric filter. The Electric Power Research Institute has conducted laboratory research to identify the fundamental variables that influence baghouse performance. A database was assembled including measured characteristics of coal and dustcake ash, and data describing operating parameters and performance of full-scale and pilotscale baghouses. Predictions of performance can be based on physical characteristics of the ash to be filtered (discussed in Part I of this article), as well as chemical characterizations of the ash, or empirical correlations with the alkali content of the source coal The effects of design and operational variables can be included in these predictions. Baghouse performance can be optimized by exercising proper operating practices and by selecting a filtering fabric and cleaning method matched to the cohesivity of the ash to be collected.     

Characterization of polycyclic aromatic hydrocarbons (PAHs) on lime spray dryer (LSD) ash using different extraction methods

In this study, traditional Soxhlet, automatic Soxhlet and ultrasonic extraction techniques were employed to determine the speciation and concentration of polycyclic aromatic hydrocarbons (PAHs) on lime spray dryer (LSD) ash samples collected from the baghouse of a spreader stoker boiler. To test the efficiencies of different extraction methods, LSD ash samples were doped with a mixture of 16 US EPA specified PAHs to measure the matrix spike recoveries. The results showed that the spike recoveries of PAHs were different using these three extraction methods with dichloromethane (DCM) as the solvent. Traditional Soxhlet extraction achieved slightly higher recoveries than automatic Soxhlet and ultrasonic extraction. Different solvents including toluene, DCM:acetone (1:1 V/V) and hexane:acetone (1:1 V/V) were further examined to optimize the recovery using ultrasonic extraction. Toluene achieved the highest spike recoveries of PAHs at a spike level of 10 microg kg(-1). When the spike level was increased to 50 microg kg(-1), the spike recoveries of PAHs also correspondingly increased. Although the type and concentration of PAHs detected on LSD ash samples by different extraction methods varied, the concentration of each detected PAH was consistently low, at microg kg(-1) levels.     

Determination of Baghouse Performance from Coal and Ash Properties: Part I

Baghouse performance at utility coal-fired power plants is determined by baghouse design, operating procedures, and the characteristics of the ash that is collected as a dustcake on the fabric filter. The Electric Power Research Institute has conducted laboratory research to identify the fundamental properties of dustcake ash that influence baghouse performance. A database was assembled including measured characteristics of dustcake ash and data describing operating parameters and performance of full-scale and pilot-scale baghouses. Semi-empirical models were developed that describe the effects of particle morphology, particle size, ash cohesivity and ash chemistry on filtering pressure drop and particulate emissions. Cohesivity was identified as the primary ash characteristic affecting baghouse performance. Predictions of performance can be based on physical or chemical characterizations of the ash to be filtered. Part II of this article will discuss the effects of ash and coal chemistry, and baghouse design and operation on performance.     

Arsenic contaminated site at an abandoned copper smelter plant: waste characterization and solidification/stabilization treatment

A preliminary survey of an arsenic contaminated site from an abandoned copper smelting facility and feasibility study of using solidification/stabilization (S/S) process to treat the contaminant waste were undertaken. It was found that the waste, located in the three-flue gas discharge tunnels, contained 2-40% arsenic. The pH of the contaminated waste is extremely low (ranging from 1.8 to 3.6). The X-ray diffraction evidence indicates that the arsenic particles present in the flue gas mainly exist as As(III), or As(2)O(3). The total amount of arsenic contaminated waste is estimated to be 700 ton in the studied area. About 50% of the particle sizes are less than 2 mm. Arsenic is easily extracted from wastes with a variety of leaching solutions. In order to meet the arsenic leaching standard of the toxicity characteristic leaching procedure (TCLP), an extremely high cement dosage is required in the S/S process (cement/waste weight ratio>6). The waste with lower particle size having higher specific surface area exhibits somewhat positive effect on the S/S performance. The use of fly ash from municipal waste incinerators, in conjunction with the reduced amount of cement, is able to meet the TCLP arsenic and lead standards. The use of lime alone could meet the TCLP arsenic standard, but lead leaching concentrations exceeded leaching Pb standard. The results of semi-dynamic leaching tests of some solidified samples indicate higher accumulated arsenic leaching concentrations after only a few leachant renewals.     

Spray-dry desulfurization of flue gas from heavy oil combustion

An experimental investigation on sulfur dioxide removal in a pilot-scale spray dryer from the flue gas generated by combustion of low-sulfur (S) heavy oil is reported. A limewater slurry was sprayed through an ultrasonic two-fluid atomizer in the spray-dry chamber, and the spent sorbent was collected downstream in a pulse-jet baghouse together with fly ash. Flue gas was sampled at different points to measure the desulfurization efficiency after both the spray-dry chamber and the baghouse. Parametric tests were performed to study the effect of the following variables: gas inlet temperature, difference between gas outlet temperature and adiabatic saturation temperature, lime-to-S ratio, and average size of lime particles in the slurry. Results indicated that spray drying is an effective technology for the desulfurization of low-S fuel oil flue gas, provided operating conditions are chosen carefully. In particular, the lowest gas inlet and outlet temperatures compatible with baghouse operation should be selected, as should a sufficiently high lime-to-S ratio. The attainment of a small lime particle size in the slurry is critical for obtaining a high desulfurization efficiency. A previously presented spray-dry flue gas desulfurization model was used to simulate the pilot-scale desulfurization tests, to check the ability of the model to predict the S capture data and its usefulness as a design tool, minimizing the need for pilot-scale experimentation. Comparison between model and experimental results was fairly good for the whole range of calcium/S ratios considered.     

Feedstock quality and growth of bioenergy crops fertilized with sewage sludge

Sewage sludge is rich in essential plant nutrients, but its use is restricted for crop production due to the pollutants it contains, such as metalloids and heavy metals. Sludge is also very sticky and compact. Therefore, the objectives of this work were to evaluate (1) the impact of various amounts of sludge on bioenergy crop productivity and quality and (2) the use of peat as an adjuvant to reduce the stickiness, density and nutrient richness of the sludge. Three different applications of sludge were examined, high, low (50% of high) and low mixed with an equal volume of peat. The sludge-peat mix increased significantly leaf area and biomass accumulation of maize and hemp. High sludge and sludge-peat mix applications increased significantly the leaf area and biomass accumulation as well as the net photosynthesis of oilseed rape. High sludge application resulted in the highest heavy metal and metalloid accumulation in maize and hemp. Sludge-peat mix resulted in the highest heavy metal and metalloid accumulation in oilseed rape. However, the sludge-peat mix application provided the best feedstock quality in all three crops, since chloride, silicon and sulfur concentrations and ash content in plant material were the lowest of the three sludge treatments.     

2种浸出方法对水泥熟料的适用性比较

采用2种不同类型的代表性浸出方法:TCLP和NEN7371对不同重金属含量及不同烧制条件下所得水泥熟料进行浸出实验.结果表明,NEN7371方法下各样品中所有受试重金属几乎均有检出,大部分重金属的浸出率均高于10%;重金属的浸出浓度与其在熟料样品中含量的趋势对应性较好;TCLP方法下各样品中的受试重金属均只有部分检出,且浸出率一般在0.5%左右,浸出浓度很低,仪器检测误差较大.说明在考察水泥熟料中重金属的浸出特性时,NEN7371方法的适用性相对更好.     

典型建筑固体废弃物再生骨料对环保砖性能的影响

随着我国城市化和工业化进程的快速推进,城市建设产生大量的建筑废弃物,燃煤电厂产生大量炉底渣,建筑固废的处置在城市可持续发展过程中备受关注。以建筑垃圾再生骨料、炉底渣和石粉等区域特色的骨料制备环保砖,系统考察了骨料对环保砖力学性能的影响。实验结果表明,再生骨料的种类对环保砖抗压强度的影响显著。再生骨料中混凝土的增加,环保砖抗压强度逐渐增加;而再生骨料中粘土砖含量的增加,环保砖抗压强度明显降低。环保砖抗压强度随炉底渣的含量增加而降低,石粉对环保砖抗压强度有提升作用。