Sequential Toxicity Characteristic Leaching Procedure Research Articles

Leaching and Immobilization Behavior of Zn and Cr from Cement-Based Stabilization/Solidification of Ash Produced from Incineration of Refinery Oily Sludge

In this paper, stabilization/solidification of ash derived from real refinery oily sludge samples was applied using two types of cement (CEM I42.5N and II42.5N) in various additions. Leaching behavior of Cr and Zn was investigated, by means of a five-point sequential Toxicity Characteristic Leaching Procedure (TCLP) test. Sequential TCLP extractions of incinerated refinery sludge samples resulted in very low leachability ( < 0.2 mg/L at 8.6 < pH < 11.6) of heavy metals (Ni, Pb, Co, Cd, Cu, and Fe) after stabilization/solidification with cement, except for Cr (< 40 mg/L at 8.6 < pH < 12.1) and Zn (< 6 mg/L at 8.6 < pH < 12.1). Furthermore, the leaching behavior of Cr and Zn was modeled using the chemical equilibrium program Visual MINTEQ. For that purpose the Diffuse Layer Model (DLM) coupled with 2-pK formalism was employed to model the suspected formation of CaCrO4(s), Cr(VI)-ettringite and zinc hydroxide. The results showed that Cr leachability was mainly controlled by the speciation of Cr(VI) in the al...

Anion Leaching from Refinery Oily Sludge and Ash from Incineration of Oily Sludge Stabilized/Solidified with Cement. Part II. Modeling

This paper presents the modeling of anion leaching (SO4(2-) and CrO4(2-)) from refinery oily sludge and ash produced by incineration of oily sludge, stabilized/solidified (s/s) with two types of cement, 142.5 and 1142.5. Anion leaching was examined using a sequential toxicity characteristic leaching procedure (TCLP) test. To elucidate the mechanisms of sulfate and chromate leaching, we employed Visual MINTEQ, incorporating a multiple-problem setup. Specifically, 10-14 different problems, depending on the pH range of the leachates, were connected together in the same run. Each problem corresponded to one pH value of the leachate and the model run covered the pH range of the five sequential TCLP extractions. This modeling approach was tested using chemical equilibrium with or without sorption onto ferrihydrite. Good agreement between experimental and modeling results was obtained for sulfate leaching from solidified oily sludge and ash, considering surface complexation onto ferrihydrite on top of chemical equilibrium controlled by gypsum at pH <11 and ettringite at pH >11. Chromate leaching was described by chemical equilibrium, controlled by CaCrO4(s) (at pH <11) and Cr(VI)ettringite (at pH >11).

Anion Leaching from Refinery Oily Sludge and Ash from Incineration of Oily Sludge Stabilized/Solidified with Cement. Part I. Experimental Results

This paper presents the leaching behavior of anions (SO4(2-) and CrO4(2-)) from refinery oily sludge and ash produced by incineration of oily sludge, stabilized/solidified (s/s) with two types of cement, 142.5 and 1142.5. Anion leaching was examined using a 5-step sequential toxicity characteristic leaching procedure (TCLP) test. A single TCLP extraction resulted in limited sulfate release (<50 mg/L) for s/s ash and significant sulfate release (<850 mg/L) for s/s oily sludge. Chromate release was <1 mg/L for s/s ash and nondetectable for s/s oily sludge. The sequential TCLP tests resulted in increased leaching for both sulfate and chromate. In general,the increase of liquid-to-solid ratio (TCLP leachant-to-waste ratio) resulted in increased leaching of sulfate from solidified samples compared to untreated oily sludge, ash and cement. In contrast, chromate leaching decreased by s/s process. A qualitatively similar leaching behavior for SO4(2-), even for radically different wastes such as oily sludge and ash, solidified with two different types of cement was observed.

Leaching Behavior of Metals Released from Cement-Stabilized/Solidified Refinery Oily Sludge by Means of Sequential Toxicity Characteristic Leaching Procedure

In this study, stabilization/solidification (S/S) of refinery oily sludge was applied using two types of cement (I and II), in cement-to-waste ratio from 0.1 to 0.7. The leaching behavior of heavy metals was investigated, by means of a five-point sequential toxicity characteristic leaching procedure (TCLP) test. Sequential TCLP was used to provide an improved assessment of long-term contaminant potential leachability, because the acidic leachant is renewed, whereas in the single TCLP, contaminant leachability is limited by the pH neutralization of the alkaline binder. Cement-based S/S of real refinery oily sludge resulted in very low leachability of heavy metals. Pb and Cd were not detected in any TCLP leachate. The maximum leachability of Fe, Zn, and Ni occurred in the pH range between 5.5 and 6.5. The leachability of Cu and Cr increased with increasing pH. Maximum cumulative percentage of Fe, Ni, and Zn leaching after five consecutive TCLP extractions (for worst case conditions, i.e., 10% II42.5) were 0.01, 22, and 1.2%, respectively, on the basis of metal content of each solidified sample. Further, the leaching behavior of Zn and Ni was modeled using the chemical equilibrium program Visual MINTEQ. Using several combinations of suspected solid phases of Zn and Ni hydroxides, carbonates and sulfides, and surface complexation onto ferrihydrite the diffuse double layer model did not accurately describe the leaching behavior of Zn and Ni.

Application of Stabilization/Solidification Technology on Oil Refinery Sludge Contaminated by Heavy Metals

The oily sludge produced by petroleum refineries is classified as a solid hazardous waste, according to European regulations. The objective of this work was to investigate whether stabilization/solidification can be used as a management method for the oily sludge. The sludge samples used originated from a petroleum-storing tank and a centrifuge unit of two Greek refineries. The experiments were designed to study the leachability of the heavy metals Pb, Cr, Cd, Ni, and Cu, which are contained in the sludge, using the Toxicity Characteristic Leaching Procedure (TCLP). Despite the fact that the metals were immobilized in a cement-based environment in the presence of organic load, leaching tests have shown a low metal leachability, less than 5%. Acid Neutralizing Capacity (ANC) tests were employed in order to estimate the acid resistance of the stabilized/solidified waste. In addition to ANC, a sequential TCLP test was employed in order to understand how the pH affects the leachability of Ni from the stabilized/solidified specimen.

Stabilization of high mercury contaminated brine purification sludge

The highly leachable mercury contaminants of brine purification sludge (BPS) generated from the Hg-cell electrolysis process in chlorine production can be stabilized in the treatment procedure employing ferric-lignin derivatives (FLD) (Ligmet™ binder) and Portland cement (PC). The stabilization effectiveness has been examined by time-based multiple toxicity characteristic leaching procedure (TCLP) tests and sequential TCLP tests. In a period of 50 days, the multiple TCLP tests showed a variation of less than 90 μg l −1 for the leachable mercury level, and the sequential TCLP tests for the same sample displayed a declining TCLP mercury level. Based on this study, the stabilization of approximately 2000 t of brine purification sludge has been successfully processed with the ferric-lignin derivatives treatment.