Incineration-source fingerprints and emission spectrums of dioxins with diagnostic application.

Despite increasing waste-to-energy (WtE) capacities, there remain deficiencies in comprehension of 136 kinds of tetra- through octa-chlorinated dibenzo-p-dioxin and dibenzofurans (136 PCDD/Fs) originating from incineration sources. Samples from twenty typical WtE plants, encompassing coal-fired power plants (CPP), grate incinerators (GI), fluidized bed incinerators (FBI), and rotary kilns (RK), yielded extensive PCDD/F datasets. Research was conducted on fingerprint mapping, formation pathways, emission profiles, and diagnostic analysis of PCDD/Fs in WtE plants. Fingerprints revealed a prevalence of TCDF, followed by PeCDF, while CPP and RK respectively generated more PCDD and HxCDD. De novo synthesis was the predominant formation pathway except one plant, where CP-route dominated. DD/DF chlorination also facilitated PCDD/F formation, showing general trends of FBI > GI > CPP > RK. The PCDD/F emission intensities emitted in air pollution control system inlet (APCSI) and outlet (APCSO) followed the statistical sequence of RK > FBI > GI > CPP, with the average I-TEQ concentrations in APCSO reaching 0.18, 0.08, 0.11, and 0.04 ng I-TEQ·Nm-3. Emission spectrum were accordingly formed. Four clusters were segmented for diagnosis analysis, where PCDD/Fs in GI and FBI were similar, grouped as a single cluster. PCDD/Fs in CPP and RK demonstrated distinctive features in TCDD, HxCDD, and HxCDF. The WtE plants exceeding the limit value tended to generate and retain fewer TCDD and TCDF yet had higher fractions of HxCDD and HxCDF. The failure of APCS coupled with the intrinsic source strength of PCDD/Fs directly led to exceedance, highlighting safe operational practices. This study motivated source tracing and precise evaluation of 136 PCDD/Fs based on the revealed fingerprint profiles for WtE processes.

Dioxin emission prediction from a full-scale municipal solid waste incinerator: Deep learning model in time-series input.

The immeasurability of real-time dioxin emissions is the principal limitation to controlling and reducing dioxin emissions in municipal solid waste incineration (MSWI). Existing methods for dioxin emissions prediction are based on machine learning with inadequate dioxin datasets. In this study, the deep learning models are trained through larger online dioxin emissions data from a waste incinerator to predict real-time dioxin emissions. First, data are collected and the operating data are preprocessed. Then, the dioxin emission prediction performance of the machine learning and deep learning models, including long short-term memory (LSTM) and convolutional neural networks (CNN), with normal input and time-series input are compared. We evaluate the applicability of each model and find that the performance of the deep learning models (LSTM and CNN) has improved by 36.5% and 30.4%, respectively, in terms of the mean square error (MSE) with the time-series input. Moreover, through feature analysis, we find that temperature, airflow, and time dimension are considerable for dioxin prediction. The results are meaningful for optimizing the control of dioxins from MSWI.

Influence of different loads on PCDD/F removal by SCR during municipal solid waste incineration.

This study was conducted on a full-scale (500 t/d) municipal solid waste incinerator (MSWI), investigating the influence of different loads on the emission of polychlorinated dibenzodioxins and polychlorinated dibenzofurans (PCDD/Fs) and their removal by selective catalytic reduction (SCR) system. The total concentration of PCDD/Fs at the SCR inlet under 100% load was higher than that under 80% load. The changing loads caused different distribution characteristics of PCDD/Fs at the SCR inlet, and the dominant congeners changed from high-chlorinated PCDDs (80% load) to low-chlorinated PCDFs (100% load). Moreover, the increased load enhanced the removal efficiency of PCDD/Fs by SCR from 17.3% to 64.2%, which was influenced by the inlet PCDD/F distribution and the moisture content. The high-chlorinated PCDD/Fs with the more stable structure were more difficult to be deteriorated and the high moisture content can weaken the catalytic activity of SCR catalysts. Correlation analysis was used to study the relationship between major air pollutants and PCDD/F emissions. The results showed that HCl positively correlated with PCDD/F emission concentrations, while NOx and SO2 negatively correlated. The results of this study can provide a reference for MSWI to operate properly under variable loads.

A new insight into the CaO-induced inhibition pathways on PCDD/F formation: Metal passivation, dechlorination and hydroxide substitution.

Ca-based inhibitors (especially CaO) for PCDD/F (polychlorinated dibenzo-p-dioxin and dibenzofuran) formation are considered as economic inhibitors with low toxicity and strong adsorption of acidic gases (e.g., HCl, Cl2, and SOx), whereas the insight understanding of its inhibition mechanisms is scarcely explored. Herein, CaO was used to inhibit the de novo reaction for PCDD/F formation (250-450 °C). The evolution of key elements (C, Cl, Cu, and Ca) combined with theoretical calculations was systematically investigated. The concentrations and distribution of PCDD/Fs demonstrated the significant inhibition effect of CaO on I-TEQ (international toxic equivalency) concentrations of PCDD/Fs (inhibition efficiencies: > 90 %) and hepta~octa chlorinated congeners (inhibition efficiencies: 51.5-99.8 %). And the conditions (5-10 % CaO, 350 °C) were supposed to be the preferred conditions applied in real MSWIs (municipal solid waste incinerators). CaO significantly suppressed the chlorination of carbon matrix (superficial organic Cl (CCl) reduced from 16.5 % to 6.5-11.3 %) and the formation of unsaturated hydrocarbons or aromatic carbon (superficial CC decreased from 6.7 % to 1.3-2.1 %). Also, CaO promoted the dechlorination of Cu-based catalysts and Cl solidification (e.g., conversion of CuCl2 to CuO, and formation of CaCl2). The dechlorination phenomenon was validated by the dechlorination of highly chlorinated PCDD/F-congeners (via DD/DF chlorination pathways). Density functional theory calculations revealed that CaO facilitated the substitution of Cl by -OH on the benzene ring to inhibit the polycondensation of the chlorobenzene and chlorophenol (Gibbs free energy reduced from +74.83 to -36.62 and - 148.88 kJ/mol), which also indicates the dechlorination effect of CaO on de novo synthesis.

Formation pathways, gas-solid partitioning, and reaction kinetics of PCDD/Fs associated with baghouse filters operated at high temperatures: A case study.

The application of the 3T method during combustion (i.e., a Temperature > 850 °C, a residence Time > 2 s, and sufficient Turbulence) can lead to elevated operating temperature in the baghouse filter for the municipal solid waste incineration (MSWI) systems without sufficient heat exchange capacity, which is potentially detrimental to the emission control of polychlorinated dibenzo-p-dioxins and dibenzofurans (PCDD/Fs). Herein, a field study focusing on the distribution and variation of PCDD/Fs in gaseous and solid phases in a baghouse filter with high operating temperature (225-230 °C) was carried out. The concentration of PCDD/Fs in gases at the outlet of the baghouse filter was around 1 order of magnitude higher than that in inlet gases (i.e., noticeable memory effect of PCDD/Fs), because of the significant PCDD/Fs formation in filter fly ash (primarily contributed by the precursor pathway) followed by PCDD/Fs desorption. In addition, the mechanisms and factors resulting in the memory effect of PCDD/Fs were identified based on a laboratory study that carefully investigated the formation and desorption of PCDD/Fs at potential operating temperatures of baghouse filters (i.e., 180, 200, and 225 °C). The temperature was identified as the key factor inducing the memory effect of PCDD/Fs, because: i) PCDD/Fs memory effect was not observed for baghouse filters with low operating temperatures of ~150 °C in previous studies; ii) both the formation and desorption of PCDD/Fs were noticeably favored by rising temperature from 180 to 225 °C; iii) increasing temperature appeared to facilitate the transformation from inorganic Cl to organic Cl and the conversion from aliphatic carbon to aromatic carbon or unsaturated hydrocarbons, both of which were favorable to PCDD/Fs formation; and iv) the release rate of PCDD/Fs from fly ash was exponentially dependent on temperature based on the modeling results of reaction kinetics.

Influence of different kinds of incinerators on PCDD/Fs: a case study of emission and formation pathway.

Few studies focused on the emission of polychlorinated-ρ-dibenzodioxins and dibenzofurans (PCDD/F) from different kinds of waste incinerators. This study was conducted in a full-scale MSW incineration plant to investigate the influence of different incinerator types on PCDD/F. Experimental results indicated that the 2,3,7,8-PCDD/F concentration in the inlet gas of the air pollution control system (APCS) in the studied fluidized bed was higher (2.03 ng I-TEQ/Nm3) than that of the grate (0.77 ng I-TEQ/Nm3). But gas in the outlet of APCS from both incinerators had an approximate concentration, lower than the Chinese emission limit of 0.1 ng I-TEQ/Nm3. Similar distribution patterns were observed for 2,3,7,8-PCDD/Fs, as well as 136 PCDD/F congeners. Specifically, OCDD and 1,2,3,4,6,7,8-HpCDD were major isomer constituents for 2,3,7,8-PCDD/F isomers. In terms of formation pathways, a similar formation mechanism was observed based on fingerprint characteristics of 136 PCDD/F congeners. De novo synthesis was the dominating formation pathway for both incinerators. Meanwhile, DD/DF chlorination was another contributor to PCDD/F formation, which in the fluidized bed was higher. In addition, little correlation (0.009 < R2 < 0.533) between conventional pollutants (HCl, CO, PM) and PCDD/Fs was found, suggesting little high-temperature synthesis observed and verifying the dominance of de novo synthesis.

Emission and migration of PCDD/Fs and major air pollutants from co-processing of sewage sludge in brick kiln.

The annual output of sewage in China is increasing rapidly and continues to grow, so there is an urgent need for a treatment other than landfills. Among various treatment methods, brick production coprocessing of sewage sludge is technically and economically advantageous. The emission characteristics of typical brick kiln coprocessing of sewage sludge with an annual production of 60 million bricks were studied. The major air pollutants and PCDD/Fs in gas and soil were determined. Particulate matter and SO2 contributed most before treatment, with concentrations of (1.017 ± 0.089) × 104 mg/Nm3 and (2.770 ± 0.251) × 103 mg/Nm3, respectively. After cleaning, the average emitted concentrations of major air pollutants were permissive and homogeneous: 58.13 ± 5.51 mg/Nm3 for NOx, 30.15 ± 9.12 mg/Nm3 for HCl, 28.63 ± 14.33 mg/Nm3 for SO2, 23.76 ± 3.31 mg/Nm3 for particulate matter, and 356.8 ± 99.1 for odor. The PCDD/Fs in the exhaust gas and ambient air showed similar distributions and fingerprint characteristics. The annual emission amounts of the PCDD/Fs were 0.265 g/year and 0.0393 g TEQ/year. Moreover, correlation analysis indicated that PCDD/Fs were most relevant to HCl, and particulate matter might be important to SO2 and fluoride. Further relativity studies showed that the brick kiln was a source of PCDD/Fs but not a main source of major air pollutants to the surrounding environment. All the above pollutants from the brick kiln were permissive with relevant national standards. The results could help with pollution inventories for the brick and tile industry and sewage sludge disposal process.