Zeolite NaP1 synthesized from municipal solid waste incineration fly ash for photocatalytic degradation of methylene blue.

The disposal of hazardous municipal solid waste incineration (MSWI) fly ash is a challenge nowadays. Recently, the re-utilization of MSWI fly ash by converting it to useful zeolite-containing materials has attracted attention. However, the zeolitic products fabricated from MSWI fly ash are usually of low quality and rarely reported to be applied for photocatalysis. In this study, valuable zeolites (e.g., NaP1) are synthesized from MSWI fly ash via a modified microwave-assisted hydrothermal method. The key parameters for the hydrothermal method including temperature, duration, the amount of additive, and water volume, are investigated and optimized. Specifically, increasing the hydrothermal temperature can promote the synthesis of zeolitic materials; a relatively long hydrothermal duration is essential to accomplish the assembly of zeolites; the addition of Na2SiO3 can increase the precursor for the fabrication of zeolites; the water volume makes little influence on the crystal style of products. Eventually, the hydrothermal condition of 180 °C, 1 h, 0.5 g Na2SiO3, and 10 mL water is suggested based on the energy consumption and the quality of zeolites. The product containing zeolite NaP1 from such a condition is further applied to degrade methylene blue by photocatalysis. The removal rate has reached 96% within 12 h, which dramatically surpasses that of the raw fly ash (38%). Such excellent photocatalytic performance is attributed to the 10-fold increased surface area (24.864 m2 g-1) and active metal elements embedding in the zeolite structures.

Effect of iron nitrate modification on elimination of organic matter from landfill leachate by sludge-based activated carbon.

Sludge-based activated carbons (SACs) prepared from sewage sludge and corn straw, were modified by ferric nitrate, and the unmodified SAC and modified SAC were used as the adsorbing agent to treat the landfill leachate, the elimination capacity for chemical oxygen demand (COD) and organic matter in leachate were studied. Based on this, the physicochemical properties of SACs and the components changes in leachate were analyzed and characterized by X-ray photoelectron spectroscopy and three-dimensional fluorescence spectroscopy. The results showed that under optimal experimental conditions, the elimination capacities of SAC372 for COD, biological oxygen demand over 5 days, and NH4+-N in the leachate were 81.58%, 54.73%, and 69.08%, respectively; while the adsorption capacities of modified SAC for these three substances were 86.25%, 63.51%, and 79.15%, respectively. The ferric nitrate modification improved the ability of SAC to eliminate COD and organic matter from leachate slightly, and made the adsorption occurred easily. The adsorption process of unmodified SAC was dominated by multi-layer adsorption, while the adsorption process of modified SAC was dominated by monolayer adsorption. The mass fraction of Fe (2p) in modified SAC remarkably increased, from 0.70% to 26.01%, organic functional groups certain phase of Fe oxides with different valence states were generated in SAC, which provided a substrate for iron-carbon micro electrolysis. After adsorbed by unmodified SAC and modified SAC adsorption, the total fluorescence intensity of in the leachate increased by 17.01% and 116.84%, respectively. Both two SACs could decompose the humic acid-like substances into aromatic protein organic compounds, and modified SAC could further decompose the soluble microbial byproduct-like substances.

Synthesis of high-quality NaP1 zeolite from municipal solid waste incineration fly ash by microwave-assisted hydrothermal method and its adsorption capacity.

The Si and Al in municipal solid waste incineration fly ash (MSWI FA) can be utilized for zeolite fabrication, which can improve the application value of the products. This study focuses on the fabrication of zeolite from MSWI FA by microwave-assisted hydrothermal (MH) treatment. The effects of magnetic stirring time, Na2SiO3 dosage, MH time, and NaOH solution concentration on the crystallization of zeolite NaP1 from MSWI FA are systematically analyzed. The synthetic products are analyzed through spectroscopic and mineralogical methods. The results show that zeolite NaP1 with high crystallinity (51.68 %) can be fabricated by magnetic stirring and MH treatment, and the cation exchange capacity (CEC) of the product can reach a value of 2.58 meq/g, which is approximately 133 times that of the CEC of MSWI FA. The Si/Al ratio plays a decisive role in the zeolite NaP1 synthesis, and a Na2SiO3 dosage of 30 wt% is adopted for zeolite NaP1 fabrication. A NaOH concentration of 1 M is sufficient for zeolite NaP1 synthesis. Additionally, the zeolite NaP1 content is found to obviously increase with increasing MH time from 0.5 h to 2 h. To demonstrate the feasibility of the method provided in this study, the optimal experimental condition is employed for various MSWI FAs, and zeolite NaP1 and analcime are fabricated successfully. The leachability of heavy metals for the synthetic products was evaluated, which met the requirements for pollution control. The BET surface area and total pore volume of zeolite NaP1 fabricated at optimal condition are 61.42 m2/g and 0.44 cm3/g, respectively. The adsorption capacity of zeolite NaP1 for Cu2+ ion and methylene blue are determined to be 84.65 mg/g and 84.55 mg/g, respectively, indicating zeolite NaP1 is a potential adsorbent for cation ion and dyes. This study provides an environmentally friendly scheme for the utilization of MSWI FA.

Comparison of MSWI fly ash from grate-type and circulating fluidized bed incinerators under landfill leachate corrosion scenarios: the long-term leaching behavior and speciation of heavy metals.

In this study, the long-term leaching behaviors of Cd, Cr, Cu, Ni, Pb, and Zn in municipal solid waste incineration (MSWI) fly ash samples from grate-type (GT) and circulating fluidized bed (CFB) incinerators were investigated and compared under the simulated landfill leachate corrosion scenario, which was determined to be more severe than the acid rain corrosion scenario. The total heavy metal contents showed increasing hierarchies of Ni

The influence of redox conditions on aqueous-solid partitioning of arsenic and selenium in a closed coal ash impoundment.

A closed coal ash impoundment case study characterized the effects of field redox conditions on arsenic and selenium partitioning through monitoring of porewater and subsurface gas in conjunction with geochemical speciation modeling. When disposed coal ash materials and porewater were recovered for testing, oxidation led to lower arsenic and higher selenium concentrations in leaching test extracts compared to porewater measurements. Multiple lines of evidence suggest multiple mechanisms of arsenic retention are plausible and the concurrent presence of several redox processes and conditions (e.g., methanogenesis, sulfate reduction, and Fe(III)-reduction) controlled by spatial gradients and dis-equilibrium. Geochemical speciation modeling indicated that, under reducing field conditions, selenium was immobilized through the formation of insoluble precipitates Se(0) or FeSe while arsenic partitioning was affected by a progression of reactions including changes in arsenic speciation, reduction in adsorption due to dissolution and recrystallization of hydrous ferric oxides, and precipitation of arsenic sulfide minerals.

Mechanochemical stabilization of heavy metals in fly ash with additives.

Mechanochemistry, as a non-thermal method showing remarkable degradation for persistent organic pollutants, is extended to stabilize the heavy metals in municipal solid waste incineration (MSWI) fly ash in the present study. The leaching suppression of heavy metals (i.e., Zn, Pb, Cu, Cr, Cd, and Ni) facilitated by five additives during mechanochemical (MC) treatment is systematically investigated, identifying that almost all heavy metals are effectively suppressed with the assistance of either CaO or Ca3(PO4)2. The pH-dependent leaching test further reveals the superiority of Ca3(PO4)2 over CaO for heavy metals stabilization. Moreover, the evolution of heavy metal speciations analysed via an optimized sequential extraction procedure shows that MC treatment with Ca3(PO4)2 significantly reduces the water- and acid-soluble fraction with high mobility from 56.8, 1.39, 12.3, 8.46, 1.13, and 29.5% to 4.96, 0.17, 0.14, 7.36, 0.12, and 0.22%, respectively for Cd, Cr, Cu, Ni, Pb, and Zn. The risk assessment indicates remarkable detoxification of fly ash in terms of heavy metals after MC treatment: the Nemerow pollution index is dramatically decreased from 9.35 (far above 3.0- the threshold of seriously polluted domain) to 0.71 (slightly over 0.7- the threshold of safety domain). Finally, a hypothetical mechanism according with results in this study for MC stabilization of heavy metals in fly ash is proposed as: the conversion of heavy metal compounds from mobile to immobile form through reaction with additives after activated by mechanical energy.

Mechanical activation of fly ash from MSWI for utilization in cementitious materials.

In the present study, the physicochemical characteristics of municipal solid waste incineration fly ashes (FA) from circulating fluidized bed (CFB) or grate furnaces are studied in detail. It is identified that the CFB FA, containing high amount of Si and Al, has better potential and properties for utilization than the grate FA, which is much richer in chlorides. Mechanical activation (MA) allows amending the properties of CFB FA, thus preparing for its subsequent utilization in cementitious materials. Compared to simple water washing, MA treatment of CFB FA further reduces the residual amount of chlorine in fly ash from 0.72 to 0.33 wt%, giving the possibility of doubling the capacity of cement kiln for fly ash disposal. The improvement in chlorine removal relates to the conversion of FA compounds from a crystalline to an amorphous state, increasing the solubility of sparingly soluble chlorides. During the curing of mortars, traces of aluminum or other nonferrous metals in CFB FA are oxidized, liberating lots of hydrogen gas; this would cause expansion problems and significantly reduce the flexural and compressive strength. MA treatment of CFB FA solves such expansion problems by exhausting these reactions in advance, respectively enhancing flexural and compressive strength from 5.7 and 35.3 MPa to 9.1 and 56.9 MPa, which is comparable to the performance of Ordinary Portland Cement. Finally, an innovative pre-treatment technique for CFB FA, combining wet ball milling and counter-current two-stage water washing, is proposed for facilitating its recycling.

Improving microwave-assisted hydrothermal degradation of PCDD/Fs in fly ash with added Na2HPO4 and water-washing pretreatment.

In this work, microwave-assisted hydrothermal process is applied to the PCDD/F degradation of municipal solid waste incineration (MSWI) fly ash. The effects of water-washing pretreatment and the Na2HPO4 reagent on the degradation efficiency of PCDD/Fs are investigated. The PCDD/F content in MSWI fly ash is detected by high-resolution gas chromatography-mass spectrometry (HRGC/MS). The experimental results show that the efficiency of total PCDD/F degradation increases from 60.6% to 83.3% after water-washing pretreatment, with 5 wt % Na2HPO4 added for 2 h of microwave heating at 220 °C. With more Na2HPO4 (10 wt %), the degradation efficiency of PCDD/Fs reaches 91.8%, and remarkably, the WHO-TEQ is as low as 0.255 ng g-1. Analysis of the degradation pathway of PCDD/Fs indicates that a chlorination reaction happens during the microwave-assisted hydrothermal process, as do dechlorination and destruction reactions. Water-washing effectively weakens the chlorination reaction for the decrease of chlorine in fly ash, which contributes to PCDD/F degradation. The reagent Na2HPO4 has a greater effect on the dechlorination of high-chlorinated congeners. Furthermore, the results indicate that the removal efficiency of PCDDs is higher than that of PCDFs under microwave conditions. Several linear correlations between indicative congener content and I/WHO-TEQ values are summarized. Overall, microwave-assisted hydrothermal process is a promising disposal method and should receive further study for large-scale application.

Formation pathways of PCDD/Fs during the Co-combustion of municipal solid waste and coal.

The co-combustion of simulated municipal solid waste (SMSW) and the coal in a drop-tube furnace is studied in five test cases. The concentration and signature evolution of polychlorinated dibenzo-p-dioxins (PCDD) and -furans (PCDF) in both flue gases and fly ashes are monitored at the level of individual congeners, using statistical methods. Special attention is paid to chlorophenol (CP)-route congeners, 2,3,7,8-substitution, and 1,9-substitution, to reveal the formation pathways of PCDD/Fs and the interaction between SMSW and coal. It is identified that the increase of SMSW proportion alters the major formation pathways from CP-route to chlorophenols/chlorobenzenes condensation and de novo synthesis. The coal-induced carbon enhances the adsorption capacity of fly ash particles for PCDD/Fs, yet facilitates the generation of carbon matrixes and polycyclic aromatic hydrocarbons, both of which will significantly boost the de novo synthesis with the increase of SMSW-induced chlorine and catalytic metals. Further investigations about restricting the participation of chlorine in PCDD/Fs synthesis are essential to increase the treatment capacity of MSW and to reduce the PCDD/Fs emission.