Stabilization of heavy metals in solid waste and sludge pyrolysis by intercalation-exfoliation modified vermiculite.

Increasing amounts of solid waste and sludge have created many environmental management problems. Pyrolysis can effectively reduce the volume of solid waste and sludge, but there is still the problem of heavy metal contamination, which limits the application of pyrolysis in environmental management. The intercalated-exfoliated modified vermiculite (IEMV) by intercalators of sodium dodecylbenzene sulfonate, hexadecyltrimethylammonium bromide and octadecyltrimethylammonium bromide were used to control the release of Cd, Cr, Cu, Zn and Pb during pyrolysis process of sludge or solid waste. The retention of heavy metals in sludge was generally better than that in solid waste. The IEMV by octadecyltrimethylammonium bromide as the intercalator calcined 800 °C (STAB-800) was the best additive for heavy metal retention, and the retention of Cr, Cu and Zn was significantly better than that of Pb and Cd. Cr, Cu, Zn and Pb were at low risk, while Cd had considerable risk under certain circumstances. New models were proposed to comprehensively evaluate the results of the risk and forms of heavy metals, and the increasing temperature was beneficial in reducing the hazards of heavy metals by the addition of STAB-800. The reaction mechanism of heavy metals with vermiculite was revealed by simulation of reaction sites, Fukui Function and Frontier Molecular Orbital. Thermal activation-intercalated-exfoliated modified vermiculite (T-IEMV) is more reactive and had more active sites for heavy metals. Mg atoms and outermost O atoms are the main atoms for T-IEMV to react with heavy metals. The Cr, Cu and Zn have better adsorption capacity by T-IEMV than Pb and Cd. This study provides a new insight into managing solid waste and sludge and controlling heavy metal environmental pollution.

Effective stabilization of heavy metals in solid waste and sludge pyrolysis using intercalated-exfoliated modified vermiculite: Experiment and simulation study.

Pyrolysis is effective in reducing the volume of solid waste and sludge, and produces less pollutants than incineration and landfill, but the process still suffers from heavy metal pollution. Four types of intercalated-exfoliated modified vermiculite (UIV, DIV, TIV and 3IV) were prepared using urea, dimethylsulfoxide, tributyl phosphate and 3-aminopropyltriethoxysilane as intercalators for the control of Cd, Cr, Cu, Pb and Zn in municipal sewage sludge (MSL), paper mill sludge (PML), municipal domestic waste (MWA) and aged refuse (AFE). The larger the interlayer spacing of the vermiculite, the more favorable the retention of heavy metals. 3IV was the most effective additive, with an average retention of more than 75 % of all heavy metals at 450 ℃ for the four raw materials. Cr, Cu, Pb and Zn were all at low potential ecological risk (Pr), while Cd was moderate or considerable Pr, and the addition of 3IV reduced the Pr. Distribution of intercalators between vermiculite interlayers was haphazard, and interlayer spacing results were close to those of the experiment (except for tributyl phosphate). The reactive electrons mainly flowed from the Highest Occupied Molecular Orbital (HOMO) of vermiculite flakes to the Lower Unoccupied Molecular Orbital (LUMO) of heavy metal chlorides. In contrast, the reactive electrons mostly flowed from the HOMO of heavy metal oxides to the LUMO of vermiculite flakes. Heavy metal oxides were more readily adsorbed on vermiculite flakes than heavy metal chlorides, and the adsorption capacity of Cr and Zn was stronger than that of Cd, Pb and Cu.

Experiment and mechanism study on enrichment of heavy metals during MSW pyrolysis by modified kaolin.

Experiment and mechanism studies on the enrichment of Pb, Cd, Zn, As, and Cr by modified kaolin were investigated during MSW (municipal solid waste) pyrolysis at 450 ~ 650 °C. The results showed that γAlOK(micro- and nano-γAl2O3 by hydrothermal method modified kaolin) was relatively selective for the solid phase enrichment of Cr and As, while CaHPK (CaHPO4 impregnated modified kaolinite) was more advantageous for the adsorption of Pb and Zn, which might be related to the thermal stability of γAl2O3 and the thermal conversion of CaHPO4. Compared with the original kaolin, the adsorption and retention capacity of γAlOK for As was improved by 20 ~ 30%. Moreover, the retention rate of modified kaolin for Cd decreased from 66.75 to 30.30% at 450 ~ 650 ℃, and the effect of temperature on the volatilization of Cd was always greater than the active components on the surface of modified kaolin. In the fluidized bed experiment, the physical mixing of different modified kaolin achieves complementary advantages on the retention capacity of heavy metals. In addition, the ∆E between Ca2P2O7 and PbCl2 is smaller than that of γAl2O3 at 500 ~ 650 °C, i.e., their electron transfer induction is stronger, and therefore more favorable for electron transfer and stable chemical bond formation.