Pyrolysis of municipal plastic waste: Chlorine distribution and formation of organic chlorinated compounds.

The release of chlorine during the pyrolysis of actual municipal plastic waste (MPW) was studied. Firstly, thermogravimetry-Fourier transform infrared (TG-FTIR) was analyzed to investigate the chlorine release behavior. Then, the effect of temperature on chlorine migrations was investigated by fast pyrolysis experiments in a fixed bed reactor. Results showed that chlorine released mainly between 241 and 353 °C in the form of HCl or chloroesters during MPW pyrolysis. After pyrolysis, chlorine was mainly distributed in the pyrolytic gas (74.34-82.89 %) and char (10.17-21.29 %). However, the release of chlorine was inhibited due to the melting behavior of MPW at <350 °C. Besides, the relative contents and types of organic chlorinated compounds in liquid products were both decreased with temperature. It was observed that polyethylene terephthalate (PET) was the greatest contributor to the formation of organic chlorinated compounds during MPW pyrolysis. Meanwhile, the pyrolysis of PET was significantly promoted by the HCl released from polyvinyl chloride (PVC). Subsequently, the pathways for the formation of organic chlorinated compounds through the co-pyrolysis of PVC and PET were proposed, including the initial degradation and subsequent chlorination of PET. These findings provided new insights into the release and regulation of chlorine-containing pollutants during actual MPW pyrolysis.

Migration characteristics of chlorine during pyrolysis of municipal solid waste pellets.

The migration process of chlorine during municipal solid waste (MSW) pellets pyrolysis was studied in a fixed bed reactor. Distribution and speciation changes of chlorine at different pyrolysis temperatures were determined by ion chromatography (IC) and X-ray photoelectron spectroscopy (XPS) analyses. Results showed that chlorine was mainly distributed in pyrolysis char (42.36-65.29 %) and gas (26.66-35.03 %) after MSW pellets pyrolysis. With the temperature increasing, chlorine in char and tar was enriched due to the increase of chlorine release and the decrease of product yields, with chlorine concentration increasing to 3498 ppm and 1415 ppm at 800 °C, respectively. Results of chlorine forms analysis indicated that most of the organic-Cl in MSW was released into the volatiles during pyrolysis due to the dissociation of CCl. Inorganic-Cl became the dominant form of chlorine in char after pyrolysis, with the proportion increasing from 46.69 % (raw) to 61.22 % (500 °C), which also suggested that part of organic-Cl was converted into the inorganic-Cl. Notably, the proportions of inorganic-Cl decreased at >600 °C due to the migration of inorganic. In addition, the pyrolysis release behavior of chlorine was affected by the pore structure of char, which could be inhibited by the unprosperous pores in char, especially at low temperatures (<600 °C). These findings provided a reference for the chlorine regulation of MSW pyrolytic products.

Mechanism of the noncatalytic oxidation of soot using in situ transmission electron microscopy.

Soot generation is a major challenge in industries. The elimination of soot is particularly crucial to reduce pollutant emissions and boost carbon conversion. The mechanisms for soot oxidation are complex, with quantified models obtained under in situ conditions still missing. We prepare soot samples via noncatalytic partial oxidation of methane. Various oxidation models are established based on the results of in situ transmission electron microscopy experiments. A quantified maturity parameter is proposed and used to categorize the soot particles according to the nanostructure at various maturity levels, which in turn lead to different oxidation mechanisms. To tackle the challenges in the kinetic analysis of soot aggregates, a simplification model is proposed and soot oxidation rates are quantified. In addition, a special core-shell separation model is revealed through in situ analysis and kinetic studies. In this study, we obtain important quantified models for soot oxidation under in situ conditions.

Syngas Production from Biomass Gasification: Influences of Feedstock Properties, Reactor Type, and Reaction Parameters.

Syngas from biomass gasification can be used in downstream process industries such as city gas, hydrogen production, etc. In this review, the effects of biomass feedstock properties, and gasification reaction conditions (temperature, gasifier type, etc.) on syngas properties are systematically reviewed. In summary, the cracking and reforming of volatile fractions in the gasification process and the catalytic effect of alkali and alkaline earth metals in the ash on the gasification have a direct impact on the syngas yield. And biomass pretreatment (i.e., terrifying/hydrothermal carbonization) can reduce the moisture content, which can effectively reduce the energy required for gasification and enhance the calorific value and syngas yield further. The fixed-bed gasifiers produce lower amounts of syngas. The concentration of H2 is significantly increased by adding steam as a gasification agent. Additionally higher gasification temperatures produce more syngas, and an equivalence ratio of about 0.2-0.3 is considered suitable for gasification. For the influence of feedstock on syngas, this paper not only reviews the feedstock properties (volatile, ash, moisture) but also compares the influence of two pretreatments on syngas yield and proposes that the combination of torrefaction/hydrothermal carbonization and a multistage air bed gasifier is an important research direction to improve the combustible components of syngas. In addition to the summary of commonly used single gasification agents, two or more gasification agents on the concentration of syngas components are also discussed in the gasification parameters, and it is suggested that further research into the use of more than one gasification agent is also important for future syngas production.

Iron valence state evolution and hydrochar properties under hydrothermal carbonization of dyeing sludge.

Iron (Fe) migration mechanisms and hydrochar properties in dyeing sludge hydrothermal carbonization (HTC) are important topics in wastewater treatment. HTC treatment of sludge produces wastewater containing Fe so it is necessary to study the migration behavior of Fe during HTC treatment. This study investigated the basic properties and Fe migration behavior of hydrochar during HTC treatment supplemented with nitric acid (HNO3). The results showed that the carbonization degree and yield of hydrochar treated with the HNO3 solution (HHC) were much lower than those of hydrochar treated with ultrapure water (WHC). The variation of total Fe (TF) concentration indicated that the decomposition of organic material and dissolution of minerals in the aqueous release of Fe during the liquid phase, led to much lower TF concentrations compared to the original dyeing sludge. Fe release was further enhanced with the addition of HNO3 and increase of temperature, rendering a much lower TF concentration of the HHC compared to the WHC. The variations of Fe3+ and Fe2+ concentrations indicated that the HTC-treated hydrochar contained more Fe2+, caused by Fe3+ reduction with hydroxyl methyl-furfural and glucose in the liquid and subsequent Fe2+/Fe3+ transferral to the solid hydrochar phase. X-ray diffraction (XRD) showed that the main Fe content in WHC was FeO(OH), while HHC contained mainly Fe(SO4)(OH)•2H2O and Fe3O4. XPS and XRF showed that Fe could more easily enter the internal pores of the hydrochar instead of being deposited on the surface. This study provided more insights on Fe migration behavior during HTC treatment.

Effect of Structural Optimization of Scrubbing Cooling Rings on Vertical Falling Film Flow Characteristics.

In order to study the influence of the structural optimization of the scrubbing cooling ring in the scrubbing cooling chamber on the flow characteristics of the vertical falling film, the flow characteristics of the turbulent falling film in the rising section of the development region at different internal platform heights of the scrubbing cooling ring and a high Reynolds number were studied by FLUENT software. First, the correctness of the model was verified by the maximum error of simulation and experimental results of no more than 9.836%. Then, the distribution of liquid film thickness (δ), velocity (V), and turbulence intensity (I z) at 0° of the tube in the axial direction x = 0-500 mm were calculated and obtained when the platform height (H) was 0-30 mm and the liquid film Reynolds number (Re l) = 1.1541 × 104-3.4623 × 104. The results showed that δ in the entrance region increased sharply due to the "jet" effect with solid wall constraints formed by the structure of the water inlet pipe and the scrubbing cooling ring. On the contrary, the liquid film in the fully developed region showed a stable fluctuation trend due to the weakening of the "jet" effect. When H = 30 mm, the change of δ was relatively stable and the change of I z was small, indicating that this platform height is conducive to the stable and uniform distribution of the liquid film. In addition, when Re l < 1.1541 × 104, the liquid film was unstable due to the low flow rate and insufficient cohesion of the liquid film, but V increased slightly. In addition, with the increase of Re l, δ did not change significantly along the axial direction, that is, the Plateau-Rayleigh hindered the growth of δ. Finally, the empirical formula for δ applicable to Re l = 1.1541 × 104-3.4623 × 104 at the axial fixed position was fitted for the first time.

Pretreatment, modification and applications of sewage sludge-derived biochar for resource recovery- A review.

With the quick increase in industrialization and urbanization, a mass of sludge has been produced on the account of increased wastewater treatment facilities. Sewage sludge (SS) management has become one of the most crucial environmental problems because of the existence of various pollutants. However, SS is a carbon-rich material, which has favored novel technologies for biochar production, which can be utilized for dissimilar applications. This review systematically analyzes and summarizes the pretreatment, modification, and especially application of sewage sludge-derived biochar (SSBC), based on published literature. The comparative assessment of pretreatment technology such as pyrolysis, hydrothermal carbonization, combustion, deashing, and co-feeding is presented to appraise their appropriateness for SS resource availability and the production of SSBC. In addition, the authors summarize and analyze the current modification methods and divide them into two categories: physical properties and surface chemical modifications. The applications of SSBC as absorbent, catalyst and catalyst support, electrode materials, gas storage, soil amendment, and sold biofuel are reviewed in detail. Furthermore, the discussion about the existing problems and the direction of future efforts are presented at the end of each section to envisage SS as a promising opportunity for resources rather than a nuisance.

High-cell-density cultivation of the flagellate alga Poterioochromonas malhamensis for biomanufacturing the water-soluble ß-1,3-glucan with multiple biological activities.

The microalga Poterioochromonas malhamensis was found to be capable of accumulating the storage ß-1,3-glucan in soluble form under heterotrophic conditions. In this study, the highest biomass yield of 32.8 g L-1 was achieved by combining the utilization of ammonium chloride as the nitrogen source, simultaneous addition of vitamins B1 and B12 and maintenance of pH at 6.0. Sugar profiling and nuclear magnetic resonance analysis indicated that the P. malhamensis ß-1,3-glucan was composed of glucose with the ß-(1 â†’ 3) main chain and the ß-(1 â†’ 6) side chain. Under the optimal cultivation conditions, the cellular ß-1,3-glucan content was up to 55% of the cell dry weight. Moreover, the P. malhamensis ß-1,3-glucan could significantly promote the fin regeneration and improve the in vivo antioxidative activity of zebrafish. This study underpins the feasibility of culturing P. malhamensis under heterotrophic conditions for producing the highly water-soluble bioactive ß-1,3-glucans for food and pharmaceutical applications.

Incorporation of an Emissive Cu4I4 Core into Cross-Linked Networks: An Effective Strategy for Luminescent Organic-Inorganic Hybrid Coatings.

Here, an effective strategy for the preparation of luminescent organic-inorganic hybrid coatings (OIHCs) by the incorporation of an emissive Cu4I4 core into cross-linked coating networks through coordination bonds is reported. The luminescent coatings obtained show potential application in a variety of areas, and such a synthetic strategy of the incorporation of an emissive inorganic core into extended networks has proven to be an efficient method for the synthesis of luminescent OIHCs.

Data on propylene/propane separation by the externally heat-integrated distillation column (EHIDiC) using data-driven analysis.

Nine hundred data were collected from rigorously simulated EHIDiC for propylene/propane separation using the Aspen Plus-Matlab communication platform. Statistical analysis was performed to give a further understanding of EHIDiC, a highly coupled system. The input variables, integrated stages, and the corresponding heat of two couples of external exchangers were generated stochastically in a wide range to cover the completely reasonable operation window. The results of blocks and streams in the flowsheet were calculated as the output data, including the flow rate, the temperature, and the pressure, as well as Total Annualized Cost (TAC). The data can be reused to design and optimize both the steady and dynamic schemes of EHIDiC, especially with machine learning methods. This manuscript gave a full description of collecting and analyzing of the data used in the research article "Data-driven analysis and optimization of externally heat-integrated distillation columns (EHIDiC)" [1].

Physicochemical evolution during rice straw and coal co-pyrolysis and its effect on co-gasification reactivity.

Physicochemical evolution (i.e. pore structure variation, carbon structure change and active AAEM transformation) during rice straw (RS) and Shenfu bituminous coal (SF) co-pyrolysis was quantitatively determined in this work. Moreover, the corresponding char gasification was conducted using a thermogravimetric analyzer (TGA) and relative reactivity was proposed to quantify the co-pyrolysis impact on co-gasification reactivity. The results showed that the development of pore structure in co-pyrolyzed chars was first inhibited and then enhanced with the decrease of SF proportion. The promotion effect of co-pyrolysis on order degree of co-pyrolyzed chars gradually weakened with increasing RS proportion. Co-pyrolysis mainly enhanced active K transformation in co-pyrolyzed chars and the promotion effect was alleviated with increasing RS proportion. The inhibition effect of co-pyrolysis on co-gasification reactivity weakened with increasing RS proportion and gasification temperature, which was mainly attributed to the combination of carbon structure evolution and active AAEM transformation in co-pyrolysis.

Experimental study on fragmental behavior of coals and biomasses during rapid pyrolysis.

In order to study the primary fragmentation behavior of coals and biomasses, experiments of rapid pyrolysis were carried out. This work focused on the devolatilization and fragmentation characteristics including the solid/gas yield, particle density/morphology, particle size and fragmental probability (Sf). The effects of temperature, time and solid property were investigated. The viscous flow model was employed to characterize the pressure difference (ΔP), which was considered as the driving force of diffusion and fragmentation. The Ohm principle was used to establish the linear relation of devolatilization rate and fragmentation rate. The result showed that temperature and time have positive contribution to the fragmentation. The occurrence of fragmentation was observed more apparently with the decreasing of the ash content in the biomass. The pressure difference has a positive correlation with the fragmental rate, which shows the validity of application Ohm principle in the prediction of fragmenting process.

Effects of sustained-release composite on the oxygen levels and sediment phosphorus fractions of an urban river in Shanghai.

The eutrophication of many rivers and lakes is attributed to the anoxia and the increasing internal loading of nutrients from sediment. A novel sustained-release composite (SRC) synthesis of stearic acid and calcium peroxide (CaO2) was applied to supply a water body with oxygen endured in this study. The influences of SRC on the dissolved oxygen (DO) level, pH and total phosphorus (TP) of an urban river in Shanghai were studied. The results show that SRC has a longer oxygen-releasing cycle and a more tender effect on pH with the comparison of CaO2 powder. Reduction of 79.6% in the concentration of TP was observed in the water column. After 35 days of SRC addition, there was a significant positive correlation between TP and DO. As a consequence, the phosphorus fractions in sediment, including loosely sorbed P (NH4Cl-P), redox-sensitive P (Fe-P), calcium bound P (Ca-P), aluminium bound P (Al-P) and residual P (organic and refractory P) were affected by the addition of SRC. The NH4Cl-P and Fe-P fractions in the sediment that could release P easily were well constrained under the positive effect of SRC.

Investigation on the high-temperature flow behavior of biomass and coal blended ash.

The high-temperature flow behavior of biomass (straw) and coal blended ash was studied. The variation of viscosity and the temperature of critical viscosity with different straw content were investigated. It is found that the straw ash with high viscosity is unsuitable for directly gasification and the 20% straw content sample can effectively decrease the viscosity. The solid phase content and mineral matters variation calculated by FactSage demonstrate the change of viscosity. In addition, the network theory illustrates that the Si-O-Si bond decreases to improve the viscosity of 20% straw content sample. The variation of mineral matters in XRD analysis validates the change of viscosity. Furthermore, the temperature of critical viscosity and lowest operation temperature reach the minimum when the straw content is 20%. Hysteresis between heating and cooling process of the sample with 20% straw content is more obvious than that of the samples with 40% and 80% straw content.

Rapid co-pyrolysis of rice straw and a bituminous coal in a high-frequency furnace and gasification of the residual char.

Rapid pyrolysis of rice straw (RS) and Shenfu bituminous coal (SB) separately, and rapid co-pyrolysis of RS/SB blends (mass ratio 1:4, 1:4, and 4:1), were carried out in a high-frequency furnace which can ensure both high heating rate and satisfying contact of fuel particles. Synergies between RS and SB during rapid co-pyrolysis were investigated. Intrinsic and morphological structures of residual char from co-pyrolysis, and their effects on gasification characteristics were also studied. Synergies occurred during rapid co-pyrolysis of RS and SB (RS/SB=1:4) resulting in decreasing char yields and increasing volatile yields. Synergies also happened during gasification of the char derived from co-pyrolysis of RS and SB with mass ratio of 1:4. The increased mass ratio of RS to SB did not only weaken synergies during co-pyrolysis, but significantly reduced the gasification rates of the co-pyrolysis char compared to the calculated values. Results can help to optimize co-conversion process of biomass/coal.

Nitrogen conversion under rapid pyrolysis of two types of aquatic biomass and corresponding blends with coal.

Rapid pyrolysis of two types of aquatic biomass (blue-green algae and water hyacinth), and their blends with two coals (bituminous and anthracite) was carried out in a high-frequency furnace. Nitrogen conversions during rapid pyrolysis of the two biomass and the interactions between the biomass and coals on nitrogen conversions were investigated. Results show that little nitrogen retained in char after the biomass pyrolysis, and NH(3) yields were higher than HCN. During co-pyrolysis of biomass and coal, interactions between biomass and coal decreased char-N yields and increased volatile-N yields, but the total yields of NH(3)+HCN in volatile-N were decreased in which HCN formations were decreased consistently, while NH(3) formations were only decreased in the high-temperature range but promoted in the low-temperature range. Interactions between blue-green algae and coals are stronger than those between water hyacinth and coal, and interactions between biomass and bituminous are stronger than those between biomass and anthracite.