Catalytic dechlorination of 2,4-dichlorophenol by Pd/Fe bimetallic nanoparticles in the presence of humic acid.

Pd/Fe bimetallic nanoparticles were synthesized for treatment of 2,4-dichlorophenol (2,4-DCP) in the presence of humic acid (HA), in order to understand their applicability for in situ remediation of groundwater. In this case, 2,4-DCP was catalytically dechlorinated to form the final products--phenol (P) via two intermediates, namely o-chlorophenol (o-CP) and p-chlorophenol (p-CP). We demonstrated that the carbon mass balances during the dechlorination were in the range of 82-91%, and other carbons were absorbed on the surface of Pd/Fe bimetallic nanoparticles. Our results suggest the dechlorination reaction of 2,4-DCP by Pd/Fe bimetallic nanoparticles in the presence of HA followed pseudo-first-order kinetics. HA competed for reaction sites on the Pd/Fe bimetallic nanoparticles with 2,4-DCP, and thus reduced the efficiency and rate of the dechlorination of 2,4-DCP. Efficiencies of dechlorination and phenol formations increased significantly as the Pd content increased from 0.10 wt.%, 0.15 wt.% to 0.20 wt.%, the removal percentage of 2,4-DCP increased from 70.4%, 98.4% to 99.4% within 300 min, respectively, the nitrate (NO(3)(-)) content in water also has a significant impact on 2,4-DCP dechlorination efficiency. Our results show that no other intermediates were generated besides Cl(-), o-CP, p-CP and phenol during the catalytic dechlorination of 2,4-DCP.

Hg2+ reduction and re-emission from simulated wet flue gas desulfurization liquors.

In this study, considering that Hg(2+) in wet flue gas desulfurization (FGD) systems can easily be reduced and then released into atmosphere, causing secondary pollution, the researches about Hg(2+) reduction and Hg(0) re-emission mechanism were carried out. The effects of several experimental parameters on the reduction were studied, including initial pH, temperature, and concentrations of Cl(-) and S(IV). Our experimental results indicated that Cl(-) had a restraining effect on the Hg(2+) reduction and Hg(0) re-emission, after 24h reaction, only 20.5% of Hg(2+) was reduced with 100mM Cl(-) in simulated desulfurization solution. Cl(-) can slow Hg(2+) reduction and Hg(0) re-emissions dramatically through changing reaction mechanism, with formation of new intermediate: ClHgSO(3)(-), which can decompose to Hg(0), but much more slowly than Hg(SO(3))(2)(2-) or HgSO(3). Simulating the conditions of the practical application (initial pH 5, T=50 degrees C, S(IV)=5 mM, Cl(-)=100 mM), we also found that Ca(2+), NO(3)(-), F(-), etc. all had obvious effects on reduction rates. Based on the material balance and characteristic of the reactants, the reduction emission mechanism of Hg(2+) has been established, providing theoretical basis for industrial application of mercury control in wet FGD systems.

Factors influencing the dechlorination of 2,4-dichlorophenol by Ni-Fe nanoparticles in the presence of humic acid.

The dechlorination of 2,4-dichlorophenol (2,4-DCP) by Ni-Fe nanoparticles in the presence of humic acid (HA) was investigated to understand the feasibility of using Ni-Fe for the in situ remediation of contaminated groundwater. 2,4-DCP was first adsorbed by Ni-Fe nanoparticles, then quickly reduced to o-chlorophenol (o-CP), p-chlorophenol (p-CP), and finally to phenol (P). However, the introduction of HA decreased the removal percentage of 2,4-DCP, as a result, the phenol production rates dropped from 86% (in the absence of HA) to 29% within 2h. Our data suggested that the dechlorination rate was dependent on a number of factors including Ni-Fe availability, Ni loading percentage over Fe, temperature, pH, and HA concentration. In particular, the removal percentage of 2,4-DCP was determined to be 100, 99, 95, 84 and 69%, for HA concentrations of 0, 5, 10, 30 and 40 mg L(-1), respectively. The kinetic calculations for the dechlorination of 2,4-DCP indicated that k values for 2,4-DCP dechlorination dropped from 0.14, 0.051, 0.039, 0.021 to 0.011 min(-1) with increasing concentrations of HA from 0, 5, 10, 30 to 40 mg L(-1).