Enhanced Bio-BTX Formation by Catalytic Pyrolysis of Glycerol with In Situ Produced Toluene as the Cofeed.

The catalytic coconversion of glycerol and toluene (93/7 wt %) over a technical H-ZSM-5/Al2O3 (60-40 wt %) catalyst was studied, aiming for enhanced production of biobased benzene, toluene, and xylenes (bio-BTX). When using glycerol/toluene cofeed with a mass ratio of 93/7 wt %, a peak BTX carbon yield of 29.7 ± 1.1 C.% (at time on stream (TOS) of 1.5-2.5 h), and an overall BTX carbon yield of 28.7 C.% (during TOS of 8.5 h) were obtained, which are considerably higher than those (19.1 ± 0.4 C.% and 11.0 C.%) for glycerol alone. Synergetic effects when cofeeding toluene on the peak and overall BTX carbon yields were observed and quantified, showing a relative increase of 3.1% and 30.0% for the peak and overall BTX carbon yield (based on the feedstock). These findings indicate that the strategy of cofeeding in situ produced toluene for the conversion of glycerol to aromatics has potential to increase BTX yields. In addition, BTX production on the catalyst (based on the fresh catalyst during the first run for TOS of 8.5 h and without regeneration) is significantly improved to 0.547 ton ton-1catalyst (excluding the 76% of toluene product that is 0.595 ton ton-1catalyst for the recycle in the cofeed) for glycerol/toluene cofeed, which was 0.426 ton ton-1catalyst for glycerol alone. In particular, this self-sufficient toluene product recycling strategy is advantageous for the production and selectivity (relative increase of 84.4% and 43.5% during TOS of 8.5 h) of biobased xylenes.

Characterization and stabilization of incineration fly ash from a new multi-source hazardous waste co-disposal system: field-scale study on solidification and stabilization.

The multi-source hazardous waste co-disposal system, a recent innovation in the industry, offers an efficient approach for hazardous waste disposal. The incineration fly ash (HFA) produced by this system exhibits characteristics distinct from those of typical incineration fly ash, necessitating the use of adjusted disposal methods. This study examined the physicochemical properties, heavy metal content, heavy metal leaching concentration, and dioxin content of HFA generated by the new co-disposal system and compared them with those of conventional municipal waste incineration fly ash. This study investigated the solidification and stabilization of HFA disposal using the organic agent sodium diethyl dithiocarbamate combined with cement on a field scale. The findings revealed significant differences in the structure, composition, and dioxin content of HFA and FA; HFA contained substantially lower levels of dioxins than FA did. Concerning the heavy metal content and leaching; HFA exhibited an unusually high concentration of zinc, surpassing the permitted emission limits, making zinc content a critical consideration in HFA disposal. After stabilization and disposal, the heavy metal leaching and dioxin content of HFA can meet landfill disposal emission standards when a 1% concentration of 10% sodium diethyldithiocarbamate (DDTC) and 150% silicate cement were employed. These results offer valuable insights into the disposal of fly ash resulting from incineration of mixed hazardous waste.

Optimizing performance of iron-rich sludge ash as cost-effective oxygen carrier by calcium-based additive for syngas production from biomass chemical-looping gasification.

Chemical-looping gasification tests were conducted on pine sawdust using thermogravimetric analyzer and horizontal sliding resistance furnace to investigate the regulation effects of calcium-based additive on iron-rich sludge ash oxygen carrier. The impacts of temperature, CaO/C in mole, multiple redox cycles, CaO addition modes on gasification performances were analyzed. The TGA results indicated that the CaO addition could effectively capture CO2 from syngas to from CaCO3, which subsequently decomposed at high temperatures. From in-situ CaO addition experiments, the temperature rise resulted in higher syngas yields, while a decrease in syngas LHV. With the CaO/C growing, the H2 yield grew from 0.103 to 0.256Nm3/kg at 800.0℃, and the CO yield boosted from 0.158 to 0.317Nm3/kg. Multiple redox manifested that the SA oxygen carrier and calcium-based additive kept higher reaction stability. The possible reaction mechanisms showed that the syngas variations from BCLG were influenced by the calcium roles and valence change of iron.

In-depth insight into the effects of intrinsic calcium compounds on the pyrolysis of hazardous petrochemical sludge.

To understand the potential effects of intrinsic calcium compounds on sludge pyrolysis, the pyrolysis behavior of petrochemical sludge (PS), calcium carbonate blend PS (CaPS), and decalcified PS (DePS) were investigated using thermogravimetric analysis (TGA) and in-situ Fourier-transform infrared spectroscopy coupled with pyrolysis-gas chromatography and mass spectrometry (Py-GC/MS). The TGA results indicated that decalcification increased and decreased the energy barriers of PS decomposition in ranges 200-350 °C and 350-600 °C, respectively. In contrast, copyrolysis with CaCO3 decreased the activation energy (E) of the pseudoreaction phase 2 (PH2) and altered the mechanism model. Meanwhile, during copyrolysis, char deposition and interaction hindered CaCO3 decomposition. The two-dimensional correlation spectroscopy results, on the other hand, showed that the reaction priority of O-containing groups and CH- vibration of methyl groups were affected by both decalcification and CaCO3 copyrolysis. The Py-GC/MS results indicated that the three sludges mainly released hydrocarbons, N-containing organics, alcohols, aldehydes, and acids. During pyrolysis, CaCO3 also played a neutralization role, which reduced the release of pyrolytic acidic products. In addition, the increase of the pyrolysis temperature increased the hydrocarbon content. This research will guide the industrial application of sludge pyrolysis.

N-doped carbon dots as robust fluorescent probes for the rapid detection of hypochlorite.

Great advances have been made in the development of carbon dot (CD)-based fluorescent materials for the detection of hypochlorite in the past few years. However, developing new CDs with high quantum yield (QY) for the rapid detection of hypochlorite and gaining a deeper insight into the detection mechanism still need to be further investigated. Herein, N-doped carbon dots (NCDs) with high QYs, which can reach as high as 67%, were efficiently prepared employing citric acid and o-phenylenediamine as raw materials. Significantly, the NCDs could act as fluorescent probes for the rapid detection of hypochlorite and the limit of detection is calculated to be as low as 12.6 nM on the basis of fluorescent "on-off" effects upon the addition of hypochlorite. Furthermore, UV-vis absorption spectra, Density Functional Theory (DFT) calculations and kinetic analysis of fluorescence (FL) decay were used to investigate the detection mechanism. The results indicate that the electron transfer (ET) process from NCDs to imine-functionalized NCDs (imine-NCDs) and the higher energy gap of imine-NCDs will facilitate the excited-energy of NCDs to be dissipated in the form of a non-radiative decay procedure, resulting in a static quenching mechanism. Therefore, these observations are useful in deepening the understanding of the hypochlorite induced FL quenching mechanism and thereby developing oxidative stress-related detection materials.

Nitrogen migration in products during the microwave-assisted hydrothermal carbonization of spirulina platensis.

Nitrogen has a vital influence on the properties of the microwave-assisted hydrothermal carbonization (MHTC) products of Spirulina platensis (SP). The effects of hydrothermal temperature (140-220 °C) and time (1-4 h) on the product distribution and nitrogen migration of SP in MHTC were studied. Increasing temperature led to an increase in the carbon content, and a decrease in the nitrogen content in hydrochar. Protein-N was the major nitrogen-containing species in hydrochar. The total nitrogen in liquid phase increased significantly with increasing temperature. Carbon dots were found to be one of the valuable products in the liquid phase. Higher temperatures improved the amine-N level and reduced the quaternary-N content in carbon dots. A close correspondence was found between the N-containing species and the luminescence centers of carbon dots. A possible nitrogen migration mechanism was proposed to provide guidance for the potential application of the products.

Influence of iron-containing petrochemical sludge ash on the pyrolysis of pine wood: Thermal behaviors, thermodynamic analysis, and kinetic parameters.

The pyrolysis characteristics and kinetics of pine wood (PW) with the presence of iron-containing petrochemical sludge ash (PSA) were studied using thermogravimetric analysis at non-isothermal conditions. The thermal conversion of PW with the presence of PSA could be characterized via a three-stage reaction, including the moisture release, pyrolysis reactions and gas-solid reaction, and solid-solid reaction between char and iron oxides. The pyrolysis characteristic parameters analysis showed that the presence of PSA indeed promoted the conversion of PW. Thermodynamic analysis revealed that the Fe2O3 in PSA was characterized by a gradual loss of oxygen during co-pyrolysis. The kinetic parameters were calculated by the Starink method combined with master-plots method. The presence of PSA would decrease the activation energy, and the minimum average value was 167.00 kJ/mol at 15% PSA addition. The most suitable kinetic models for the pyrolysis of PW and its mixtures with PSA were D3 and D4, respectively.