PCDD/Fs from a large-scale municipal solid waste incinerator under transient operations: Insight formation pathways and optimal reduction strategies.

Polychlorinated dibenzo-p-dioxin and dibenzofurans (PCDD/Fs) emissions from the transient operation of municipal solid waste incinerators can reach up to 690 ng/Nm3, as measured in this study. To control the extreme emissions to meet the national standard, the formation pathways of PCDD/F were investigated under transient operations (cold start-up, hot start-up, and after start-up) and normal operations. Compared with normal operations, transient operations facilitate the formation of low-chlorinated congeners rather than highly chlorinated congeners. Statistically, for transient operations, strong correlations were found among tetrachlorodibenzo-p-dioxin or tetrachlorodibenzofuran isomers. An abundant carbon matrix is an important carbon source for PCDD formation. Moreover, the comprehensive study revealed that the oxidation of deposited soot is the main source of PCDD/F emissions, relative to de novo synthesis, chlorobenzene-route synthesis, chlorophenol-route synthesis, and chlorination of dibenzo-p-dioxin/dibenzofuran. In addition, the optimal start-up procedure was constructed by analyzing main formation pathways and operating conditions. The relationship between the international toxic quantity (I-TEQ) values (CI-TEQ) and the reaction time can be assigned as CI-TEQ = 11.72t-0.65 (R2 = 0.97) for the circulating fluidized bed. The relationship of CI-TEQ = 4.61t-0.59 (R2 = 0.85) was also proven on the dataset with a grate furnace. Then, the optimal feeding rate of activated carbon was further proposed by the relationship between the reaction time and I-TEQ, and the semi-empirical equation for PCDD/Fs adsorption. Finally, the PCDD/Fs emissions can be reduced to 0.1 ng I-TEQ/Nm3 under transient operations according to the time since start-up.

Online measurement of 1,2,4-trichlorobenzene as dioxin indicator on multi-walled carbon nanotubes.

Polychlorinated dibenzo-p-dioxin and dibenzofuran (PCDD/F) emission is one of main concerns for the secondary pollution of municipal solid waste incinerators (MSWI). For timely response to emission, 1,2,4-trichlorobenzene (1,2,4-TrClBz) as dioxin indicator can be monitored via online measurement techniques. In this study, multi-walled carbon nanotubes (MWCNTs) were investigated for their suitability as a 1,2,4-TrClBz sorbent for MSWI stack gas analysis. The tests include, batch adsorption, continuous adsorption-desorption of 1,2,4-TrClBz via thermal desorption coupled with gas chromatography (TD-GC-ECD), temperature and concentration stability of MWCNTs, and adsorption performance of the system. Thermogravimetric/derivative thermogravimetric (TGA/DTG) analysis reveals that MWCNTs has higher capacity in terms of weight loss (14.34%) to adsorb 1,2,4-TrClBz compared to Tenax TA (9.46%) and also shows fast desorption of adsorbate at temperature of 87 °C compared to Tenax TA (130 °C). Interestingly, carbon nanotubes and Tenax TA gave almost similar adsorption-desorption response, and from TD-GC-ECD analysis it was found that with increasing mass flow of 1,2,4-TrClBz (7.42 × 10-6 - 44.52 × 10-6 mg ml-1) through sorbent traps, average peak areas increased from 2.86 ± 0.02 to 13.54 ± 0.26 for MWCNTs and 2.89 ± 0.02 to 13.38 ± 0.12 for Tenax TA, respectively. The stability of MWCNTs for temperature was 400 °C and for concentration of 1,2,4-TrClBz was 50 ppbv. However, regeneration of sorbent at 100 ppbv (1,2,4-TrClBz) was not possible. TD-GC-ECD system showed high adsorption performance with 3.86% and 3.59% relative standard deviation at 250 °C and 300 °C, respectively. Further Fourier Transform Infrared Spectroscopy (FTIR) analysis confirmed that adsorbate can be fully desorbed at 300 °C.

Mechanochemical degradation of PCDD/Fs in fly ash within different milling systems.

Two distinct mechanochemical degradation (MCD) methods are adopted to eliminate the polychlorinated dibenzo-p-dioxins and -furans (PCDD/Fs) from fly ash in municipal solid waste incinerators. First, experiments are conducted in a planetary ball mill for selecting suitable additives, and an additive system of SiO2-Al is chosen for its high-efficiency, low-price, and good practicability. The I-TEQ value of PCDD/Fs in washed fly ash decreases dramatically from 6.75 to 0.64 ng I-TEQ/g, after 14 h of milling with 10 wt % SiO2-Al, and dechlorination is identified as the major degradation pathway. Then, this additive is applied in a horizontal ball mill, and the results indicate that the degradation of PCDD/Fs follows the kinetic model established in planetary ball mills. However, longer milling time is required for the same supplied-energy because of the lower energy density of horizontal ball mills, resulting in partial loss of Al reactivity and a lower degradation efficiency of PCDD/Fs. During MCD, the evolution of PCDD/F-signatures is analogous, indicating a similar acting mechanism of all additives in both the two milling systems. Finally, a major dechlorination pathway of PCDD-congeners is proposed based on the signature analysis of congeners synthesized from chlorophenols.

Evolution of PCDD/F-signatures during mechanochemical degradation in municipal solid waste incineration filter ash.

Mechanochemical degradation (MCD) is employed for the dechlorination of polychlorinated dibenzo-p-dioxins (PCDD) and -furans (PCDF) in filter ashes from municipal solid waste incinerators, respectively with the assist of six additive systems. The evolution of PCDD/F-signatures in all eleven samples are systematically monitored and studied at the level of individual congeners, and special attention is paid to CP-route congeners, 2,3,7,8-substitution, 1,9-substitution, and 4,6-PCDF. The PCDD/F-isomers distribution follows an analogous pattern, indicating the similar acting mechanism for all additives: additives transfer electrons to attack the CCl bond and then expulse chlorine. MC dechlorination is not favored for the chlorine on ß-position (2,3,7,8-position). The oxygen with stronger electronegativity in PCDD/Fs negatively influences CCl bond to accept donated electrons, hindering the removal of chlorine on 1,9-position for PCDD, and chlroine on 4,6-position for PCDF. Finally, two fair dechlorination pathways for PCDD and PCDF are respectively proposed based on the detailed analysis of CP-route congeners. The evolution of PCDD-signatures is clear, yet obscure for PCDF-signatures, which still requires further investigations.

Inhibition of de novo synthesis of PCDD/Fs by SO2 in a model system.

The effect of sulfur dioxide (SO(2)) on de novo synthesis of polychlorinated dibenzo-p-dioxins, dibenzofurans (PCDD/F) and biphenyls (PCB) was investigated in model systems containing carbon, activated by cupric chloride (CuCl(2)). Five types of carbons (activated carbon, three types of carbon blacks, and graphite) were used to test the universal character of our results. The influence of SO(2) on speciation and behavior of copper compounds, catalytic oxidation of carbons, and formation of organic chlorine (extractable organic chlorine and non-extractable organic chlorine) was also studied to investigate the inhibition mechanism of SO(2) on de novo synthesis. It was found that SO(2) can sulfate CuCl(2), but does not react with CuO and CuCl(2).CuO in a 10% O(2)/N(2) atmosphere at 300 degrees C. The suppression by SO(2) of organic chlorine (C-Cl) formation also confirmed these findings. It was also found that catalytic oxidation of carbons was strongly suppressed by SO(2). A dramatic decrease in PCDD/Fs formation was observed for all five carbons, while adding SO(2); at the same time the average chlorination level also decreased. However, the inhibiting effect on PCB was less apparent compared with that on PCDD/F. On the basis of the experimental results, the conversion of both cupric and cuprous chloride into the non-reactive sulfate was proposed as inhibition mechanism.