State of the art in self-sustaining smoldering for remediation of contaminated soil and disposal of organic waste.

Smoldering combustion applications in energy and environmental fields have attracted increasing research attention in recent years. Smoldering has demonstrated considerable green advantages, such as having a low carbon footprint and being sustainable, for remediation of organic-contaminated soil and disposal of high-moisture, low-calorific value, slurry-type organic waste due to its self-sustaining reaction characteristic. This review aims to analyze and summarize studies on smoldering applications to refine the critical components of applied smoldering systems, key reaction characteristics, and corresponding influencing conditions that affect their effectiveness. Furthermore, the common characteristics and influencing factors of different smoldering application scenarios are compared to provide a comprehensive reference for commercial applications. Thus, this paper specifically includes an overview of the impact of inert porous media, combustible material, and oxidants in applied smoldering systems; a review of the research status of the three key reaction characteristics, including peak temperature, smoldering front propagation velocity, and self-sustainability; a summary of typical influencing factors, disposal material characteristics, and control conditions in the two mainstream application directions, which are remediation of contaminated soil and disposal of organic waste; and a comparative analysis of the common modes of applied smoldering beyond the lab scale. As a technically effective and energy-efficient emerging technology, the prospects of smoldering as a robust treatment process in environmental pollution cleanup are presented.

Distribution of gasification products and emission of heavy metals and dioxins from municipal solid waste at the low temperature pyrolysis stage.

Gasification is widely regarded as one of the most practical, economical, and environmentally friendly waste disposal technologies for municipal solid waste (MSW). The pyrolysis stage (300-500 °C) is crucial for weight loss during MSW gasification, as a considerable amount of organic matter breaks down, producing high-value synthesis gas. This study investigated the product distribution and pollutant emission characteristics within this temperature range and its influencing factors during MSW gasification using a self-designed MSW gasification device. Results indicated that MSW underwent approximately 70% weight loss within this temperature range, yielding low amounts of inorganic and short-chain organic products, with mainly long-chain organic compounds of C16-C34. The atmosphere variation had minimal effect on the elemental composition and content of solid phase products. X-ray fluorescence spectrometry (XRF) and inductively coupled plasma mass spectrometry (ICP-MS) analyses showed that Mn and Zn were the primary components of heavy metal leaching toxicity in solid phase products, with their contents increasing as temperature increased. Synthesis gas showed the highest content of heavy metal As element, reaching a peak at 400 °C. Higher gasification temperature and lower oxygen flow rate significantly reduced the dioxin content and I-TEQ values, with highly chlorinated isomers being the predominant dioxin isomers. Nonetheless, low-chlorinated dioxins accounted for more than 50% of the I-TEQ. This study improves our understanding of the gasification process of MSW.

Characteristics of the pyrolytic products and the pollutant emissions at different operating stages from a pilot waste tire pyrolysis furnace.

Pyrolysis is considered a highly practical, cost-effective, and environment-friendly technology for waste tires disposal. In this study, pyrolysis processes of waste tires were conducted in a pilot scale furnace feeding at 30 kg/h. The properties of pyrolytic products and the distribution patterns of pollutants generated in different operating stages (start-up, steady, and shut-down) were investigated. The pyrolytic gas in the steady state had a high caloric value of 10799 kJ/Nm3, valuable as heating source for pyrolysis. The elements of sulfur and zinc were effectively fixed as ZnS in the pyrolytic carbon. The basic properties of pyrolytic oil were in line with commercial diesel oil except for the lower flash point. Heavy metals were mainly concentrated in the pyrolytic carbon, with slightly higher concentrations in the steady state. Moreover, polycyclic aromatic hydrocarbons (PAHs) and polychlorinated dibenzo-p-dioxins and dibenzofurans (PCDD/Fs) were mainly concentrated in the pyrolytic oil, with predominated low-ring PAHs and high chlorinated PCDD/Fs. The concentrations of PAHs and PCDD/Fs in the gas phase were higher during the start-up stage due to the memory effect, whereas were effectively reduced during the steady stage. The concentration of PAHs in the solid phase was highest during the furnace start-up and lowest in the shut-down stage. In contrast to PAHs, the PCDD/Fs in the solid phase reached their highest concentration during the shut-down stage, which was mainly affected by temperature. The results provide guidance for the reducing of pollutant emissions and the recycling of pyrolytic products.

Fluoride-immobilized co-processing and resource utilization of aluminum-electrolyzed spent cathode carbon in brick-fired kiln.

Spent cathode carbon (SCC) is hazardous waste from the electrolytic aluminum industry due to its high levels of soluble fluoride, while brick-fired kiln provides the clay and heating conditions needed to immobilize fluoride. However, SCC reusing is still understudied, meanwhile co-processing and resource utilization of SCC in brick-fired kiln were still not reported in the literatures in addition to a Chinese patent of the authors. Here, the effects of firing temperatures, firing time, clay doses and calcium doses on the fluoride-immobilized performance of SCC co-processing were explored in a simulated brick-firing kiln, and their mechanisms were analyzed by SEM and XRD. The results indicated that clay-added co-processing in brick-fired kiln was a preferred choice without required additional additives or operations. The leached fluoride met Chinese standards by clay-added co-processing at ≥ 800 °C/ ≥ 40 g clay/ ≥ 120 min. Clay and calcium-added co-processing in brick-fired kiln was another alternative choice with higher fluoride-immobilization rates. The leached fluoride met Chinese standard (GB5085.3-2007) by clay and calcium-added co-processing at ≥ 500 °C/ ≥ 30 min/ ≥ 5 g clay/ ≥ 0.5 g CaCO3. SEM and XRD indicated that SiO2 in clay reacted with sodium in SCC and formed vitreous analog (Na1.55Al1.55Si0.45O4) to prevent fluoride ion migration and the newly-formed k-Feldspar (K2O.Al2O3.6SiO2) may adsorb fluoride ions in clay-added co-processing. Soluble fluoride NaF in SCC were converted into water-insoluble cuspidine in clay and calcium-added co-processing, in addition to the crystalline phase conversion in clay-added co-processing. Therefore, the risks of finished bricks to human health and the environment were greatly reduced after clay-added or clay and calcium-added treatments.

Systematic study on dynamic pyrolysis behaviors, products, and mechanisms of weathered petroleum-contaminated soil with Fe2O3.

Weathered petroleum-contaminated soil (WPCS) with a high proportion of heavy hydrocarbons is difficult to remediate. Our previous research demonstrated that Fe2O3-assisted pyrolysis was a cost-effective technology for the remediation of WPCS. However, the pyrolysis behaviors, products, and mechanisms of the WPCS with Fe2O3 are still unclear. In this study, a combination of Thermogravimetric-Fourier transform infrared spectroscopy (TG-FTIR) and pyrolysis gas chromatography/mass spectrometry (Py-GC/MS) techniques were used to explore these pyrolysis characteristics. The thermal desorption/degradation of light and heavy hydrocarbons in the WPCS mainly occurred at 200-400 °C and 400-550 °C, respectively. The activation energy of thermal reaction of heavy hydrocarbons was decreased in the presence of Fe2O3 during the WPCS pyrolysis processes. In the process, the released inorganic gaseous products were mainly H2O and CO2, while the released organic gaseous compounds were primarily cycloalkanes, alkanes, acids/esters, alcohols, and aldehydes. Compared with the WPCS pyrolysis without Fe2O3, the yields of gaseous products released during the WPCS pyrolysis with Fe2O3 were reduced significantly, and some gaseous products were even not detected. This phenomenon was contributed by the following two reasons: 1) heavy hydrocarbons in the WPCS were more easily transformed into coke in the presence of Fe2O3 during pyrolysis; 2) some released gaseous products were reacted with Fe2O3 and fixed on the soil particles. Therefore, the WPCS pyrolysis with Fe2O3 can effectively reduce the burden of tail gas treatment. Criado method analysis results suggested that the reaction mechanism of heavy hydrocarbons during the WPCS pyrolysis with Fe2O3 was rendered as the synergic effects of diffusion, order-based, and random nucleation and growth reactions.

Selective production of singlet oxygen from zinc-etching hierarchically porous biochar for sulfamethoxazole degradation.

Porous carbons are appealing low-cost and metal-free catalysts in persulfate-based advanced oxidation processes. In this study, a family of porous biochar catalysts (ZnBC) with different porous structures and surface functionalities are synthesized using a chemical activation agent (ZnCl2). The functional biochars are used to activate persulfate for sulfamethoxazole (SMX) degradation. ZnBC-3 with the highest content of ketonic group (CO, 1.25 at%) exhibits the best oxidation efficiency, attaining a rate constant (kobs) of 0.025 min-1. The correlation coefficient of the density of CO to kobs (R2 = 0.992) is much higher than the linearity of the organic adsorption capacity to kobs (R2 = 0.694), implying that CO is the intrinsic active site for persulfate activation. Moreover, the volume of mesopore (R2 = 0.987), and Zeta potential (R2 = 0.976) are also positive factors in PS adsorption and catalysis. In the mechanistic study, we identified that singlet oxygen is the primary reactive oxygen species. It can attack the -NH2 group aligned to the benzene ring to form dimer products which could be adsorbed on the biochar surface to reach complete removal of the SMX. The optimal pH range is 4-6 which will minimize the electrostatic repulsion between ZnBCs and the reactants. The SMX degradation in ZnBC/PS system was immune to inorganic anions but would compete with organic impurities in the real wastewater. Finally, the biochar catalysts are filled in hydrogel beads and packed in a flow-through packed-bed column. The continuous system yields a high removal efficiency of over 86% for 8 h without decline, this work provided a simple biochar-based persulfate catalyst for complete antibiotics removal in salty conditions.

Biochar cathode: Reinforcing electro-Fenton pathway against four-electron reduction by controlled carbonization and surface chemistry.

Porous biochars have attracted tremendous interests in electrochemical applications. In this study, a family of biochars were prepared from cellulose subject to different carbonization temperatures ranging from 400 to 700 °C, and the biochars were in-situ activated by a molten salt (ZnCl2) to construct a hierarchically porous architecture. The activated porous biochars (ZnBC) were used as a carbocatalyst for electro-Fenton (EF) oxidation of organic contaminants. Results showed that high-temperature carbonization improved the activity of biochar for four-electron oxygen reduction reaction (ORR) due to the rich carbon defects, while the mild-temperature treatment regulated the species and distribution of oxygen functional groups to increase the production of hydrogen peroxide (H2O2) via a selective two-electron ORR pathway. ZnBC-550 was the best cathode material with a high ORR activity without compromise in H2O2 selectivity; a high production rate of H2O2 (796.1 mg/g/h) was attained at -0.25 V vs RHE at pH of 1. Furthermore, Fe(II) addition induced an electro-Fenton system to attain fast decomposition of various organic pollutants at -0.25 V vs RHE (reversible hydrogen electrode) and pH of 3 with a satisfactory mineralization efficiency toward phenolic pollutants. The EF system maintains its excellent stability for 10 cycles. Hydroxyl radicals were identified as the dominant reactive oxygen species based on in situ electron paramagnetic resonance (EPR) analysis and radical quenching tests. This study gains new insights into electrocatalytic H2O2 production over porous biochars and provides a low-cost, robust and high-performance electro-Fenton cathode for wastewater purification.

Enhancing remediation of PAH-contaminated soil through coupling electrical resistance heating using Na2S2O8.

Soil polycyclic aromatic hydrocarbons (PAHs) contamination caused by factory relocations is a serious environmental issue across the world. Electrical resistance heating (ERH) and chemical oxidation are two promising in-situ methods for treating volatile and semi-volatile organic pollutants in contaminated soil. Coupling of ERH and chemical oxidation technologies to improve the remediation efficiency for PAH-contaminated soil was estimated in this study. PAH removal ratio in contaminated soils using ERH treatment were significantly negatively correlated with the boiling point of the pollutants (P = 0.002), and 21.63% (DBA high boiling point) to 71.53% (Nap low boiling point) of PAHs in the contaminated soil were removed in 120 min. With oxidant Na2S2O8 coupling, the removal ratio were increased as more oxidant was added. For one Phe, 35.90% was removed by ERH treatment and increased to 52.90% and 79.42% when 0.05 or 2.5 mmol/g oxidant was added, respectively. PAHs with higher boiling points had more obvious removal ratio, such as Bap, which increased from 23.50% to 85.47% when coupling ERH with Na2S2O8, and Phe which increased from 35.90% to 79.42%. Relationships between boiling points and PAH removal ratio changed with coupled oxidants, indicating a change of mechanism from volatilization to coupling effects of volatilization and oxidation with the introduction of Na2S2O8. A dynamic experiment showed that Na2S2O8 can accelerate 45.50% of the treatment process. The results of this research demonstrated a novel, cost-effective coupling approach for remediating soil contaminated by organic pollutants.

Phenanthrene removal and response of bacterial community in the combined system of photocatalysis and PAH-degrading microbial consortium in laboratory system.

This work aimed to study the removal of phenanthrene, change of bacterial community and microbial functions through combined photocatalysis and biodegradation under ultraviolet (UV) and visible light illumination. Results showed that phenanthrene removal was enhanced in combined system irradiated by UV and visible light. High-throughput sequencing of 16S rRNA gene manifested that alpha diversity (richness, evenness and diversity) got promoted and data of relative abundance reported that Planococcaceae as the dominant bacteriawas replaced by Pseudomonadaceae, with some other functional bacteria quickly acclimatizing. Difference analysis indicated that top fifteen genera were generally different significantly (p < 0.001) among two distinct samples, particularly for Pseudomonas on relative abundance. Functional features' regulation suggested that the bacterial community not only protected itself well but also participated in degrading phenanthrene. Selecting suitable degrading microbial consortium from natural environment and understanding deeply on performance of bacterial community contribute to assemble effective and directional combined system.

Eggshell and plant ash addition during the thermal desorption of polycyclic aromatic hydrocarbon-contaminated coke soil for improved removal efficiency and soil quality.

Thermal desorption (TD) technology is the preferred treatment technology for treating soil contaminated by organic compounds. Under laboratory conditions, eggshell and plant ash were studied as additives during thermal desorption to further improve the soil thermal desorption efficiency and the quality of soil after thermal desorption. The results showed that temperature was still an important factor affecting the soil quality and removal efficiency of PAHs (polycyclic aromatic hydrocarbons). The efficiency of the thermal desorption of soil was significantly improved (from 91.7 to 96.6%) by adding two additives, and the agglomeration of the soil was alleviated to some extent according to the decreased amount of large soil particle (100-400 µm). Moreover, the TOC (total organic carbon) and CEC (cation exchange capacity) of the soil were increased. This work suggested that the addition of similar alkaline additives to the soil during thermal desorption might have a positive impact on both thermal desorption behavior and soil quality.

Coupled photocatalytic-bacterial degradation of pyrene: Removal enhancement and bacterial community responses.

Polycyclic aromatic hydrocarbons (PAHs) are a class of pollutants that ubiquitously present in environment and hard to be degraded by microorganisms. Herein, we reported a novel photocatalytic-bacterial coupled removal system to treat PAH-polluted water. Using pyrene as the model pollutant, we demonstrated that the removal percentage of different groups was in order: 63.89% ± 1.03% (Vis-Biological) > 61.27% ± 1.08% (UV-Biological) > 59.58% ± 1.15% (UV) > 57.41% ± 1.13% (Vis) > 6.65% ± 0.72% (Biological) > 1.70% ± 0.34% (Control), showing the coupled system significantly improved the removal percentage of pyrene. Additionally, we observed that the coupled system driven by visible light showed higher removal percentage than UV light, exhibiting a good potential for future application. Sequencing analysis of 16S rRNA genes showed that alpha diversity (richness, evenness and diversity) got promoted and data of the relative abundance showed that Pseudomonadaceae was substituted as the dominant bacteria for Planococcaceae, with some other functional bacteria quickly acclimatizing in the bacterial community. Difference analysis indicated that over half of top fifteen genera were generally different significantly (p < 0.001) among two different samples, and UV light altered structure and composition of bacterial community more than visible light. Functional features' change suggested that the bacterial community not only protected itself but also participated in degrading pyrene. Overall, our study offered a new method for PAH degradation and contributed to further understanding of coupled catalytic-bacterial degradation processes.

Comprehensive diagnosis of PCDD/F emission from three hazardous waste incinerators.

Comprehensive diagnosis of polychlorinated dibenzo-p-dioxin and dibenzofuran (PCDD/F) emissions was systematically conducted on three hazardous waste incinerators (HWIs). Results indicated that PCDD/F mainly existed in the solid phase before the bag filter. This was especially true for higher chlorinated dioxin and furan congeners (hexa-, hepta- and octa-). The aged bag filters tended to increase the gas-phase PCDD/F. Emissions also increased due to PCDD/F desorption from circulated scrubbing solution and plastic packing media used in the wet scrubber. The PCDD/F concentrations were elevated during the start-up process, reaching up to 5.4 times higher than those measured during the normal operating period. The ratios of PCDFs/PCDDs revealed that the surface-catalysed de novo synthesis was the dominant pathway of PCDD/F formation. Installation of more efficient fabric filters, intermittent replacement of circulated scrubbing solution will result in reduced PCDD/F emission. Additionally, 2,3,4,7,8-PeCDF correlated well with the international toxic equivalent quantity (I-TEQ) value, which suggests that 2,3,4,7,8-PeCDF could act as an I-TEQ indicator.

Catalytic decomposition of PCDD/Fs on a V2O5-WO3/nano-TiO2 catalyst: effect of NaCl.

The effect of NaCl addition on the properties, activity, and deactivation of a V2O5-WO3/nano-TiO2 catalyst was investigated during catalytic decomposition of gas-phase polychlorinated dibenzo-p-dioxins and polychlorinated dibenzofurans (PCDD/Fs). The extent of deactivation relates directly to the NaCl loading of the catalyst. Poisoning by sodium neutralizes acid sites, interacts strongly with active VOx species, and reduces the redox capacity of catalysts. In addition, NaCl is also a chlorine source and may actually accelerate the synthesis of new PCDD/Fs. Washing a catalyst with dilute sulfuric acid largely restores catalytic activity, breaking the interaction of Na+ ions and dispersed vanadia and removing Na from the catalyst surface. Consequently, catalyst acidity and redox capacity almost recover. Furthermore, sulfate residues react with surface adsorbed water to generate Brønsted acid sites, ensuing a surge of strong acidity of the catalysts.

Catalytic oxidation of PCDD/F on a V2O5-WO3/TiO2 catalyst: Effect of chlorinated benzenes and chlorinated phenols.

Catalytic oxidation of polychlorinated dibenzo-p-dioxins and dibenzofurans (PCDD/F) is a well-proven technique, applied in a rising number of Municipal Solid Waste Incineration plants, yet the simultaneous and possibly competitive co-oxidation of other compounds, such as chlorinated benzenes (CBz) or phenols (CP), is still poorly documented. In this study, a grinded commercial catalyst (vanadium-tungsten supported on titanium dioxide) was submitted to exploratory testing: the PCDD/F present in a gas test flow were catalytically oxidised (200°C, 10,000h-1), either as such or in the presence of benzene (Bz), monochlorobenzene (MCBz), and 1,2-dichlorobenzene (DCBz) and the effect of these additions on the catalytic destruction of PCDD/F was verified experimentally. Both removal efficiency (RE) and destruction efficiency (DE) declined during the exploratory testing and, importantly, some DCBz even converted into supplemental PCDD/F. Also, the occurrence of carbon deposition negatively influenced catalytic oxidation activity. Regeneration with oxygen or air allowed to remove the deposited carbon and the original catalytic activity was largely restored after calcination. In a second part of this study, the PCDD/F-formation from DCBz, hexachlorobenzene (HCBz), o-monochlorophenol (o-MCP) and pentachlorophenol (PeCP) was demonstrated and tentatively explored. To prepare for further elucidation of the reaction mechanism, a complete isomer-specific analysis was prepared.

The impact of hydrochloric acid on the catalytic destruction behavior of 1,2-dichlorbenzene and PCDD/Fs in the presence of VWTi catalysts.

Catalytic oxidation is regarded an effective technique to control the emissions of chlorinated benzenes (CBzs) and polychlorinated dibenzo-p-dioxins and dibenzofurans (PCDD/Fs) from waste incinerators. Among the numerous factors affecting the degradation efficiency of CBzs and PCDD/Fs, limited attention has been paid to the impact of hydrochloric acid (HCl) present in the flue gas. This study investigates how HCl affects the catalytic degradation of 1,2-dichlorbenzene (1,2-DCBz) at different reaction times and temperature regimes. The results showed that the removal efficiency of 1,2-DCBz, which was achieved by the V2O5/WO3-TiO2 (VWTi) catalyst, decreased the largest by 10% in the presence of HCl. Furthermore, it was found that the increasing concentration of water vapor hindered the degradation efficiency of 1,2-DCBz. No relationship between the process temperature and the destruction efficiency of PCDD/Fs was observed in the presence of HCl. Potential increasing of the removal efficiency of 1,2-DCBz was confirmed by adding different amount of activated carbon (AC) in the presence of HCl.

Comparative analyses of catalytic degradation of PCDD/Fs in the laboratory vs. industrial conditions.

This study investigates the efficiencies and mechanisms of the catalytic degradation of polychlorinated dibenzo-p-dioxins and furans (PCDD/Fs) first, in simulated laboratory conditions and then, in a commercial municipal solid waste incineration (MSWI) plant. Five commercially available V2O5-WO3/TiO2 (VWTi) catalysts were tested. The degradation efficiency of PCDD/Fs in the simulated flue gas ranged 22.8-91.7% and was generally higher than that in the MSWI flue gas of 8.0-85.4%. The degradation efficiency of PCDD/Fs in the real flue gas of the MSWI plant was largely hindered by the complex composition of the flue gas, which could not be completely reproduced in the simulated laboratory conditions. Furthermore, the degradation of the higher chlorinated PCDD/Fs was easier compared to the lower chlorinated ones in the presence of the VWTi catalysts, which was primarily driven by the tendency of the higher chlorinated PCDD/Fs to be adsorbed on the surface of the catalyst and further destructed due to their lower vapor pressure. In addition, powdered catalysts should be preferred over the honeycomb shaped ones as they exposed higher PCDD/Fs degradation efficiencies under equal reaction conditions. The chemical composition and a range of the relevant to the study properties of the catalysts, such as surface area, crystallinity, oxidation ability, and surface acidity, were analyzed. The study ultimately supports the identification of the preferred characteristics of the VWTi catalysts for the most efficient degradation of toxic PCDD/Fs and elucidates the corresponding deactivation reasons of the catalysts.

Catalytic oxidation of 1,2-DCBz over V2O5/TiO2-CNTs: effect of CNT diameter and surface functional groups.

A series of V2O5/TiO2-carbon nanotube (CNT) catalysts were prepared and tested to decompose gaseous 1,2-dichlorobenzene (1,2-DCBz). Several physicochemical methods, including nitrogen adsorption, scanning electron microscopy (SEM), transmission electron microscopy (TEM), X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS) and H2 temperature-programmed reduction (TPR) were employed to characterise their physicochemical properties. To better understand the effect of CNT properties on the reactivity of V2O5/TiO2-CNT catalysts, the 1,2-DCBz residue remaining in the off-gas and on the catalyst surface were both collected and analysed. The results indicate that the outer diameter and the surface functional groups (hydroxide radical and carboxyl) of CNTs significantly influence upon the catalytic activity of CNT-containing V2O5/TiO2 catalysts: the CNT outer diameter mainly affects the aggregation of CNTs and the π-π interaction between the benzene ring and CNTs, while the introduction of -OH and -COOH groups by acid treatment can further enlarge specific surface area (SSA) and contribute to a higher average oxidation state of vanadium (V aos) and supplemental surface chemisorbed oxygen (Oads). In addition, the enhanced mobility of lattice oxygen (Olatt) also improves the oxidation ability of the catalysts.

Municipal solid waste incineration in China and the issue of acidification: A review.

In China, incineration is essential for reducing the volume of municipal solid waste arising in its numerous megacities. The evolution of incinerator capacity has been huge, yet it creates strong opposition from a small, but vocal part of the population. The characteristics of Chinese municipal solid waste are analysed and data presented on its calorific value and composition. These are not so favourable for incineration, since the sustained use of auxiliary fuel is necessary for ensuring adequate combustion temperatures. Also, the emission standard for acid gases is more lenient in China than in the European Union, so special attention should be paid to the issue of acidification arising from flue gas. Next, the techniques used in flue gas cleaning in China are reviewed and the acidification potential by cleaned flue gas is estimated. Still, acidification induced by municipal solid waste incinerators remains marginal compared with the effects of coal-fired power plants.