Application of accelerated carbonation with a combination of Na2CO3 and CO2 in cement-based solidification/stabilization of heavy metal-bearing sediment

The efficient remediation of heavy metal-bearing sediment has been one of top priorities of ecosystem protection. Cement-based solidification/stabilization (s/s) is an option for reducing the mobility of heavy metals in the sediment and the subsequent hazard for human beings and animals. This work uses sodium carbonate as an internal carbon source of accelerated carbonation and gaseous CO₂ as an external carbon source to overcome deleterious effects of heavy metals on strength development and improve the effectiveness of s/s of heavy metal-bearing sediment. In addition to the compressive strength and porosity measurements, leaching tests followed the Chinese solid waste extraction procedure for leaching toxicity – sulfuric acid and nitric acid method (HJ/T299-2007), German leaching procedure (DIN38414-S4) and US toxicity characteristic leaching procedures (TCLP) have been conducted. The experimental results indicated that the solidified sediment by accelerated carbonation was capable of reaching all performance criteria for the disposal at a Portland cement dosage of 10 wt.% and a solid/water ratio of 1:1. The concentrations of mercury and other heavy metals in the leachates were below 0.10 mg/L and 5 mg/L, respectively, complying with Chinese regulatory level (GB5085-2007). Compared to the hydration, accelerated carbonation improved the compressive strength of the solidified sediment by more than 100% and reduced leaching concentrations of heavy metals significantly. It is considered that accelerated carbonation technology with a combination of Na₂CO₃ and CO₂ may practically apply to cement-based s/s of heavy metal-bearing sediment.     

Factorial experimental design for recovering heavy metals from sludge with ion-exchange resin

Wastewaters containing heavy metals are usually treated by chemical precipitation method in Taiwan. This method can remove heavy metals form wastewaters efficiently, but the resultant heavy metal sludge is classified as hazardous solid waste and becomes another environmental problem. If we can remove heavy metals from sludge, it becomes non-hazardous waste and the treatment cost can be greatly reduced. This study aims at using ion-exchange resin to remove heavy metals such as copper, zinc, cadmium, and chromium from sludge generated by a PCB manufacturing plant. Factorial experimental design methodology was used to study the heavy metal removal efficiency. The total metal concentrations in the sludge, resin, and solution phases were measured respectively after 30 min reaction with varying leaching agents (citric acid and nitric acid); ion-exchange resins (Amberlite IRC-718 and IR-120), and temperatures (50 and 70 degrees C). The experimental results and statistical analysis show that a stronger leaching acid and a higher temperature both favor lower heavy metal residues in the sludge. Two-factors and even three-factor interaction effects on the heavy metal sorption in the resin phase are not negligible. The ion-exchange resin plays an important role in the sludge extraction or metal recovery. Empirical regression models were also obtained and used to predict the heavy metal profiles with satisfactory results.     

Influence of flue gas SO2 on the toxicity of heavy metals in municipal solid waste incinerator fly ash after accelerated carbonation stabilization

The influence of CO₂ content and SO₂ presence on the leaching toxicity of heavy metals in municipal solid waste incinerator (MSWI) fly ash was studied by examining the carbonation reaction of MSWI fly ash with different combinations of simulated incineration flue gases. Compared with raw ash, the leaching solution pH of carbonated ash decreased by almost 1 unit and the leaching concentrations of heavy metals were generally lower, with that of Pb decreasing from 19.45 mg/L (raw ash) to 4.08 mg/L (1# carbonated ash). The presence of SO₂ in the incineration flue gas increased the leaching concentrations of heavy metals from the fly ash to different extents after the carbonation stabilization reaction. The pH of the leaching solution was the main factor influencing the leaching concentrations of heavy metals. The increase in buffer capacity with the pH of carbonated ash caused an increase in heavy metal stability after the carbonation reaction. Accelerated carbonation stabilization of MSWI fly ash could reduce its long-term leaching concentrations (toxicity) of Cu, Pb, Se, and Zn. The leaching concentrations of heavy metals from carbonated ash also likely had better long-term stability than those from raw ash. The presence of SO₂ in the incineration flue gas increased the proportion of exchangeable state species of heavy metals; slightly increased the long-term leaching toxicity of Cu, Pb, Se, and Zn; and reduced the long-term stability of these metals in the fly ash after the carbonation reaction.     

Characterization of metal finishing sludges: influence of the pH

Metal finishing sludges are classified as metal hydroxide hazardous wastes due to the heavy metal release to the environment. This release, commonly determined by compliance lixiviation tests based on the equilibrium conditions at the end of the leaching experiment, is mainly dependent on the pH of the solution. In this work, the leaching behaviour of Cd, Cr, Cu, Fe, Ni, Pb and Zn, of the 32 metal finishing sludges coming from 16 European industrial facilities, and using the distilled water compliance test DIN 38414-S4, have been studied. The concentrations of chromium and copper in the leachates do not follow the solubility evolution of their hydroxide with the pH. The simple assumption of a heavy metal concentration in the leachate directly related to the solubility of the hydroxide is not in good agreement with the experimental results of the distilled water leaching test, probably due to the presence of different species, which can contribute to the metal mobility depending on the sludge composition. An experimental evaluation of the easily available amount of metals in real wastes seems to be necessary for disposal assessment. This paper contains valuable information, from orderly handling metal finishing wastes to the statistical studies of production and management of wastes suggested recently by the Commission of the European Community.     

Study of speciation of metals in an industrial sludge and evaluation of metal chelators for their removal

Leachability and mobility of metals were evaluated in sludge obtained from electroplating industry, using toxicity characteristic leaching procedure (TCLP) and diethylene triamine pentaacetic acid test (DTPA). Sequential leaching procedure was used to determine the chemical fractionation of metals. Further, removal of metals from sludge using various chelators (EDTA, citric acid, siderophore) was evaluated. The leaching test indicated that nickel in the sludge sample exceeded 5 ppm concentration. This categorized the sludge, as a toxic waste. The mobility of the metals in the sludge was in the following order: Ni, Fe, Zn, Cr, Pb. Metals were found to be associated with various fractions of sludge. The metal concentration in the sludge was very high as compared to normal abundance and thus not within the range to be used as a fertilizer. The low removal of metals from the sludge by various chelators may be due to overloading of metals and use of aged sludge rather than artificially contaminated one for the study. The results of this study bring forth the prospect of the use of siderophores for bioremediation, because it is biodegradable and ecofriendly. This can be achieved with further optimization of the method, exploration of more potent siderophores and by inclusion of metal bound sludge fraction specific treatments.     

Effect of NaOH on the vitrification process of waste Ni-Cr sludge

This study investigated the effect of NaOH on the vitrification of electroplating sludge. Ni, the major metal in the electroplating sludge, is the target for recovery in the vitrification. Sludge and encapsulation materials (dolomite, limestone, and cullet) were mixed and various amounts of NaOH were added to serve as a glass modifier and a flux. A vitrification process at 1450 °C separated the molten specimens into slag and ingot. The composition, crystalline characteristics, and leaching characteristics of samples were measured. The results indicate that the recovery of Ni is optimal with a 10% NaOH mass ratio; the recoveries of Fe, Cr, Zn, Cu, and Mn all exhibited similar trends. The results of the toxicity characteristic leaching procedure (TCLP) show that leaching characteristics of the slag meet the requirements of regulation in Taiwan. In addition, a semi-quantitative X-ray diffraction analysis revealed that the main crystalline phase of slag changed from Ca(3)(Si(3)O(9)) to Na(4)Ca(4)(Si(6)O(18)) with a NaOH mass ratio of over 15%, because the Ca(2+) ions were replaced with Na(+) ions during the vitrification process. Na(4)Ca(4)(Si(6)O(18)), a complex mineral which hinders the mobility of metals, accounts for the decrease of metal recovery.     

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.     

The ultrasonically assisted metals recovery treatment of printed circuit board waste sludge by leaching separation

This paper provides a practical technique that realized industrial scale copper and iron separation from printed circuit board (PCB) waste sludge by ultrasonically assisted acid leaching in a low cost, low energy consumption and zero discharge of wastes manner. The separation efficiencies of copper and iron from acid leaching with assistance of ultrasound were compared with the one without assistance of ultrasound and the effects of the leaching procedure, pH value, and ultrasonic strength have been investigated in the paper. With the appropriate leaching procedure, a final pH of 3.0, an ultrasonic generator power of 160 W (in 1 l tank), leaching time of 60 min, leaching efficiencies of copper and iron had reached 97.83% and 1.23%, respectively. Therefore the separation of copper and iron in PCB waste sludge was virtually achieved. The lab results had been successfully applied to the industrial scaled applications in a heavy metal recovery plant in city of Huizhou, China for more than two years. It has great potentials to be used in even the broad metal recovery practices.     

Total concentrations and fractions of Cd, Cr, Pb, Cu, Ni and Zn in sewage sludge from municipal and industrial wastewater treatment plants

Heavy metals are one of the important factors that affect the final disposal of sewage sludge. In this paper, the metal mobility and bioavailability of heavy metals in sewage sludge were studied by using Community Bureau of Reference (BCR) sequential extraction procedure to get more information for the reasonable disposal of sludge. Sewage sludge was collected from five municipal wastewater treatment plants and three industrial wastewater treatment plants. The sludge was examined for and the total concentrations and different chemical fractions of Cd, Cr, Pb, Cu, Ni and Zn. The total metal concentrations of heavy metals in sludge varied greatly. The contents of Zn and Cu were the highest, followed by then Cr, Ni and Pb and the content of Cd was the least. There was no significant difference in total metal concentration between municipal and industrial wastewater treatment plants. Fractions extracted by the BCR sequential procedure were acid soluble/exchangeable, reducible and oxidizable fraction. Sludge pH was found to have profound effect on the chemical fractions of heavy metals. Acidic sludges (Xiamen and Jinlin Petrochemical Group Co., wastewater treatment plant) had higher proportion of the acid soluble/exchangeable fractions than in neutral sludge. In neutral sludges, Pb and Cr were principally distributed in between the oxidizable fraction and the residual fraction; Cu was in the oxidizable fraction; Cd mainly in the residual fraction in municipal wastewater treatment plants and had high percentage of acid soluble/exchangeable and reducible fractions in industrial wastewater treatment plants; Ni and Zn had higher percentage in the acid soluble/exchangeable and the oxidizable fraction.     

Residence Time Distribution of Segregating Sand Particles in a Rotary Drum

Leaching, which is described as the extraction of soluble constituents from a solid by means of a solvent, is an important separation technique in the refining of precious metals from their matte. It is, therefore, important to investigate the extraction behavior of metals from the matte, which is the focus of this study. This study reports the influence of concentration of the solvent (ammonia), leaching temperature, leaching time, and pH on the recovery of nickel and copper from the matte. The elemental composition analysis of the matte indicated that it contains 23% copper, 37% nickel and 1.1% ferrous compound. The analysis also showed that the major mineral phases present in the matte were heazlewoodite (Ni₃S₂), chalcocite (Cu₂S), djurleite (Cu1.9S), and nickel alloy. The leaching parameters studied were concentration of ammonia (1.5, 2.0, 2.5, and 3.0 M), leaching time (0–270 min, at 15 min sampling interval), leaching temperatures (50°C, 60°C, and 70°C), and pH (9.3–11.2). The results obtained revealed that the recovery of nickel and copper from the matte was greatly influenced by the concentration of ammonia, leaching time, leaching temperature, and pH. It was established from this study that the highest dissolution of nickel and copper was obtained at 3 M and 2 M ammonia concentration, respectively. The results also revealed that a decrease in the pH of the solution resulted in a decrease in both nickel and copper recovery, with maximum leaching time of 270 min. It was observed that less than 50% of both nickel and copper was leachable due to the presence of metal alloys. The analyses of the results also showed that as the leaching temperature increased from 50°C to 60°C, the amount of nickel and copper that was recovered from the matte significantly increased. However, there was reduction in the amount of nickel and copper recovered from the matte as the temperature was increased from 60°C to 70°C, due to loss of ammonia by evaporation. The shrinking core model was used to explain the behavior of the recovery of these metals at different temperatures, and both metals were found to be favored by diffusion controlled reaction.     

Heavy metal speciation and leaching behaviors in cement based solidified/stabilized waste materials

A circuit board printing factory sludge containing high concentrations of copper, zinc and lead was stabilized and solidified (S/S) with different portions of ordinary Portland cement (OPC) and pulverized fly ash (PFA). The chemical speciation and leaching behavior of heavy metals in these cement-based waste materials were studied by different sequential extraction procedures, standard toxicity characteristic leaching procedure (TCLP) and progressive TCLP tests. The sequential extraction results showed that more than 80% of Cu, Pb and Zn were associated with Fraction 2 (weak acid soluble, extracted with 1M NaOAc at pH 5.0 with a solid to liquid ratio of 1:60). This indicated that the heavy metals could exist in the S/S matrix as metal hydrated phases or metal hydroxides precipitating on the surface of calcium silicate hydrates (C-S-H), PFA and sludge particles. The progressive TCLP test results and MINTEQA2 calculation also showed the importance of Cu and Zn oxides during the leaching process. The leaching behaviors of these metals in the S/S waste materials were mainly controlled by the alkaline nature and acid buffering capacity of the S/S matrix. During the progressive TCLP tests, the alkaline conditions and acid buffering capacity of the matrix decreased with the dissolution of calcium hydroxide and C-S-H, therefore, the leaching of heavy metals in the S/S waste materials increased. The leaching of heavy metals in the S/S materials can be considered as a pH dependent and corresponding metal hydroxide solubility controlled process.     

The influence of heavy metals on the polymorphs of dicalcium silicate in the belite-rich clinkers produced from electroplating sludge

The purpose of this study is to utilize an electroplating sludge for belite-rich clinker production and to observe the influence of heavy metals on the polymorphs of dicalcium silicate (C₂S). Belite-rich clinkers prepared with 0.5–2% of NiO, ZnO, CuO, and Cr₂O₃ were used to investigate the individual effects of the heavy metals in question. The Reference Intensity Ratio (RIR) method was employed to determine the weight fractions of γ-C₂S and β-C₂S in the clinkers, and their microstructures were examined by the transmission electron microscopy (TEM). The results showed that nickel, zinc, and chromium have positive effects on β-C₂S stabilization (Cr³⁺ > Ni²⁺ > Zn²⁺), whereas copper has a negative effect. The addition of up to 10% electroplating sludge did not have any negative influence on the formation of C₂S. It was observed that γ-C₂S decreased while β-C₂S increased with a rise in the addition of the electroplating sludge. Moreover, nickel and chromium mainly contributed to stabilizing β-C₂S in the belite-rich clinkers produced from the electroplating sludge.     

Copper recovery and cyanide oxidation by electrowinning from a spent copper-cyanide electroplating electrolyte

Copper-cyanide bleed streams arise from contaminated baths from industrial electroplating processes due to the buildup of impurities during continuous operation. These streams present an elevated concentration of carbonate, cyanide and copper, constituting a heavy hazard, which has to be treated for cyanide destruction and heavy metals removal, according to the local environmental laws. In the Brazilian Mint, bleed streams are treated with sodium hypochlorite, to destroy cyanide and precipitate copper hydroxide, a solid hazardous waste that has to be disposed properly in a landfill or treated for metal recovery. In this paper, a laboratory-scale electrolytic cell was developed to remove the copper from the bleed stream of the electroplating unit of the Brazilian Mint, permitting its reutilization in the plant and decreasing the amount of sludge to waste. Under favorable conditions copper recoveries around 99.9% were achieved, with an energy consumption of about 11 kWh/kg, after a 5-h electrolysis of a bath containing copper and total cyanide concentrations of 26 and 27 g/L, respectively. Additionally, a substantial reduction of the cyanide concentration was also achieved, decreasing the pollution load and final treatment costs.     

Distribution of extractable fractions of heavy metals in sludge during the wastewater treatment process

Sludge samples were collected from different treatment steps of Gaobeidian wastewater treatment plant (WWTP) of Beijing City, PR China, to investigate the distributions of total and chemical fractions of Fe, Mn, Ni, Cu, Zn, Cr, Pb, and Mo in different sludges. The highest total concentrations were found for Fe, Mn, Pb, and Mo in digested sludge (DS), Ni and Cr in thickened sludge (TS), Zn in dewatering sludge (DWS), and Cu in active sludge (AS). The lowest concentrations were observed in AS, except for Cu in TS. Significant differences of total metal concentration were observed between AS and TS (or DS), suggesting that sludge thickening and digesting treatments significantly influenced the total metal concentrations. Fe, Cu, Ni, Cr, Mo, and Pb distributed principally in the residual fraction in all sludges, while Zn and Mn presented in a highly available fraction. For same metal in different sludges, the portion of easily mobile fraction decreased significantly along the wastewater treatment process, and metals in AS presented in the highest available fraction. Organic matter contents, TN, and TP of sludges exhibited a significant positive correlation with the concentrations of exchangeable and reducible fraction of Pb, Mo, Cr, Cu, and Fe, while sludge pH demonstrated significant negative correlations with the concentrations of these metals.     

Cleaning of waste smelter slags and recovery of valuable metals by pressure oxidative leaching

Huge quantities of slag, a waste solid product of pyrometallurgical operations by the metals industry are dumped continuously around the world, posing a potential environmental threat due to entrained values of base metals and sulfur. High temperature pressure oxidative acid leaching of nickel smelter slags was investigated as a process to facilitate slag cleaning and selective dissolution of base metals for economic recovery. Five key parameters, namely temperature, acid addition, oxygen overpressure, solids loading and particle size, were examined on the process performance. Base metal recoveries, acid and oxygen consumptions were accurately measured, and ferrous/ferric iron concentrations were also determined. A highly selective leaching of valuable metals with extractions of >99% for nickel and cobalt, >97% for copper, >91% for zinc and <2.2% for iron was successfully achieved for 20 wt.% acid addition and 25% solids loading at 200-300 kPa O(2) overpressure at 250 degrees C in 2h. The acid consumption was measured to be 38.5 kg H(2)SO(4)/t slag and the oxygen consumption was determined as 84 kg O(2)/t slag which is consistent with the estimated theoretical oxygen consumption. The as-produced residue containing less than 0.01% of base metals, hematite and virtually zero sulfidic sulfur seems to be suitable for safe disposal. The process seems to be able to claim economic recovery of base metals from slags and is reliable and feasible.     

The microwave irradiation effect on copper leaching from sulfide/oxide ores

Increasing the rate and ultimate copper recovery from low-grade copper sources may be the most important problem affecting the economy of copper mining. This present research work is a study on microwave-irradiation application for copper recovery from two main types of copper ores (i.e., oxide and sulfide) was investigated. The results of rolling bottle tests showed that H₂SO₄ consumptions were lower in the pretreated ores in comparison with the conventional leaching tests. Leaching tests in shaking flasks by using the two types of ores showed a significant increase (up to 26% in some cases) in copper recoveries from pretreated ores. Main effective parameters such as irradiation power, ore states in the microwave chamber, and irradiation times were completely studied. To explain the behavior according to the enhanced copper recoveries, some possible mechanisms were discussed.     

Extraction kinetics of heavy metal-containing sludge

In order to remove and recover copper, zinc, cadmium, and chromium from the wastewater treatment sludge generated by an electroplating process, the heavy metal extraction kinetics was studied in a batch reactor using two different extraction agents (nitric and citric acid) at constant agitation speed (150 rpm) and solid to liquid ratio (10 g/L), but varying acid concentrations (0.02-0.10 N), temperatures (25-85 degrees C in nitric acid solution, 25-95 degrees C in citric acid solution), and sludge particle sizes. The shrinking-core model and empirical kinetic model were adopted to analyze the experimental data. Although both models could fit the experimental kinetic data well, the obtained parameters of the shrinking-core model did not show reasonable trends varying with the experimental variables while the empirical model parameters showed significant trends. The experimental and modeling results showed that the metal extraction rates increased with acid concentration, temperature, but decreased with increasing particle size. Nitric acid was found to be more effective than citric acid to extract the heavy metals from the sludge. The extraction activation energies obtained in this study suggested that both a physical diffusion process and a chemical reaction process might play important roles in the overall extraction process.     

The influence of thiourea on copper electrodeposition: Adsorbate identification and effect on electrochemical nucleation

The effect of thiourea on copper deposition onto a copper seed layer from an electrolyte composed of CuSO₄, H₂SO₄, deionized water, and thiourea was investigated. Even in the presence of very low concentrations of thiourea, extremely smooth and bright copper deposits were obtained. From the results of X-ray photoelectron spectroscopy, Auger electron spectroscopy, and electrochemical analyses, thiourea was found to react with copper or copper ions leading to the generation of CuS. CuS adsorption onto the copper seed layer seemed to inhibit the initial nucleation of the copper adions, resulting in the formation of smaller Cu grains compared to those forming in the absence of thiourea. CuS was observed to cover all active sites of the 1 cm² copper seed layer above 0.017 g/L thiourea. The surface roughness as well as the mean grain size of the deposits also approached minimum values above this thiourea concentration. Adsorbed CuS was incorporated into the deposits during electroplating, which was believed to be the major factor for the increased resistivity of the deposits.     

Galvanic sludge metals recovery by pyrometallurgical and hydrometallurgical treatment

This paper reports a study, on laboratory scale, of sulphating roasting to perform a treatment for a selective recovery of valuable metals from galvanic sludge. The target metals were copper, zinc and nickel and the sulphating agent used was pyrite, from coal wastes. The particularity of this treatment is the use of two hazardous wastes as raw material. They are generated in large quantities at coal extraction sites (coal wastes) and at plating shops (galvanic sludge). The wastes were characterized by X-ray fluorescence (XRF), particle size distribution and water contents. The chemical characterization showed sludges with high copper concentration, with more than 14% (dry base). In the roasting step, the galvanic sludge was mixed with pyritic waste and the parameters evaluated were galvanic sludge/pyrite ratio, roasting temperature and roasting time. After roasting, the product of reaction was leached with water in room temperature for 15 min. Considering that other studies have already demonstrated that the pyrometallurgical step determines the process efficiency, this paper only reports the influence of pyrometallurgical parameters. Hydrometallurgical processes will be better evaluated in further studies. The conditions that best reflect a compromise between the valuable metal recover and the economical viability of the process were achieved for 1:0.4 galvanic sludge/pyrite ratio, 90 min of roasting time and 550 degrees C of roasting temperature. These conditions lead to a recovery of 60% zinc, 43% nickel and 50% copper.     

Assessment of alternative management techniques of tank bottom petroleum sludge in Oman

This paper investigated several options for environmentally acceptable management techniques of tank bottom oily sludge. In particular, we tested the applicability of managing the sludge by three options: (1) as a fuel supplement; (2) in solidification; (3) as a road material. Environmental testing included determination of heavy metals concentration; toxic organics concentration and radiological properties. The assessment of tank bottom sludge as a fuel supplement included various properties such as proximate analysis, ultimate analysis and energy content. Solidified sludge mixtures and road application sludge mixtures were subjected to leaching using the toxicity characteristic leaching procedure (TCLP). Tank bottom sludge was characterized as having higher concentrations of lead, zinc, and mercury, but lower concentrations of nickel, copper and chromium in comparison with values reported in the literature. Natural occurring radioactive minerals (NORM) activity values obtained on different sludge samples were very low or negligible compared to a NORM standard value of 100Bq/g. The fuel assessment results indicate that the heating values, the carbon content and the ash content of the sludge samples are comparable with bituminous coal, sewage sludge, meat and bone meal and petroleum coke/coal mixture, but lower than those in car tyres and petroleum coke. The nitrogen content is lower than those fuels mentioned above, while the sulfur content seems comparable with bituminous coal, petroleum coke and a petroleum coke/coal mixture. The apparent lack of leachability of metals from solidification and road material sludge applications suggests that toxic metals and organics introduced to these applications are not readily attacked by weak acid solutions and would not be expected to migrate or dissolved into the water. Thus, in-terms of trace metals and organics, the suggested sludge applications would not be considered hazardous as defined by the TCLP leaching procedure.