Dibenzofuran (DF) is formed from phenol and benzene in combustion gas exhaust streams prior to particle collection equipment. Subsequent chlorination at lower temperatures on particle surfaces is a potential source of chlorinated dibenzofuran (CDF). Gas streams containing 8% O2 and approximately 0.1% DF vapor were passed through particle beds containing copper (II) chloride (0.5% Cu, mass) at temperatures ranging from 200 to 400 °C to investigate the potential for CDF formation during particle collection. Experiment duration was sufficient to provide an excess amount of DF (DF/Cu=3). The efficiency of DF chlorination by CuCl2 and the distribution of CDF products were measured, with effects of temperature, gas velocity, and experiment duration assessed. Results of a more limited investigation of dibenzo-p-dioxin (DD) chlorination by CuCl2 to form chlorinated DD (CDD) products are also presented.
The efficiency of DF/DD chlorination by CuCl2 was high, both in terms of CuCl2 utilization and DF/DD conversion. Total yields of Cl on CDF/CDD products of up to 0.5 mole Cl per mole CuCl2 were observed between 200 and 300 °C; this suggests that nearly 100% CuCl2 was utilized, assuming a conversion of two moles of CuCl2 to CuCl per mole Cl added to DD/DF. In a short duration experiment (DF/Cu=0.3), nearly 100% DF adsorption and conversion to CDF was achieved. The degree of CDF chlorination was strongly dependent on gas velocity. At high gas velocity, corresponding to a gas–particle contact time of 0.3 s, mono-CDF (MCDF) yield was largest, with yields decreasing with increasing CDF chlorination. At low gas velocity, corresponding to a gas–particle contact time of 5 s, octa-CDF yield was largest. DF/DD chlorination was strongly favored at lateral sites, with the predominant CDF/CDD isomers within each homologue group those containing Cl substituents at only the 2,3,7,8 positions. At the higher temperatures and lower gas velocities studied, however, broader isomer distributions, particularly of the less CDD/CDF products, were observed, likely due to preferential destruction of the 2,3,7,8 congeners. 相似文献
Activated carbon (AC) was considered to be an effective sorbent to control mercury in combustion systems. However, its capture
capacity was low and it required a high carbon-to-mercury mass ratio. AC loaded with catalyst showed a high elemental mercury (Hg0)
capture capacity due to large surface area of AC and high oxidization ability of catalyst. In this study, several metal chlorides and metal
oxides were used to promote the sorption capacity of AC. As a result, metal chlorides were better than metal oxides loaded on AC
to remove gaseous mercury. X-ray diffractometer (XRD), thermogravimetric analyzer (TGA) and specific surface area by Brunauer-
Emmett-Teller method (BET) analysis showed the main mechanisms: first, AC had an enormous surface area for loading enough
MClx; second, Cl and MxOy were generated during pyrogenation of MClx; finally, there were lots of active elements such as Cl and
MxOy which could react with elemental mercury and convert it to mercury oxide and mercury chloride. The HgO and HgCl2 might be
released from AC’s porous structure by thermo regeneration. A catalytic chemisorption mechanism predominates the sorption process
of elemental mercury. As Co and Mn were valence variable metal elements, their catalytic effect on Hg0 oxidization may accelerate
both oxidation and halogenation of Hg0. The sorbents loaded with metal chlorides possessed a synergistic function of catalytic effect
of valence variable metal and chlorine oxidation. 相似文献