Determination of heterogeneous reaction mechanisms: A key milestone in dust explosion modelling

Reaction kinetics is fundamental for modelling the thermal oxidation of a solid phase, in processes such as dust explosions, combustion or gasification. The methodology followed in this study consists in i) the experimental identification of the reaction mechanisms involved in the explosion of organic powders, ii) the proposal of simplified mechanisms of pyrolysis and oxidation, iii) the implementation of the model to assess the explosion severity of organic dusts. Flash pyrolysis and combustion experiments were carried out on starch (22 μm) and cellulose (53 μm) at temperatures ranging from 973 K to 1173 K. The gases generated were collected and analyzed by gas chromatography. In this paper, a semi-global pyrolysis model was developed for reactive systems with low Damköhler number. It is in good agreement with the experimental data and shows that both carbon monoxide and hydrogen are mainly generated during the pyrolysis of the solid, the generation of the latter compound being greatly promoted at high temperature. A simplified combustion model was also proposed by adding two oxidation reactions of the pyrolysis products. In parallel, flame propagation tests were performed in a semi open tube in order to assess the burning velocity of such compounds. The laminar burning velocity of cellulose was determined to be 21 cm s⁻¹. Finally, this model will be integrated to a predictive model of dust explosions and its validation will be based on experimental data obtained using the 20 L explosion sphere. The explosion severity of cellulose was determined and will be used to develop and adjust the predictive model.     

铁路站车生活垃圾热解烟气治理技术分析

基于铁路生活垃圾产生和处置特点,对相应的烟气处理技术进行分析.从铁路站车生活垃圾成分和热解气化炉产生的烟气污染物出发,探讨烟气净化系统工艺中的脱酸、颗粒物、二(噁)英、重金属处理技术.综合考虑治理效率、治理成本、工艺实施的难易程度等,推荐铁路站车生活垃圾热解烟气净化工艺流程,即烟气经二燃室充分燃烧后先经急冷装置降温避开...     

Upgrading pyrolytic carbon-blacks (CBp) from end-of-life tires: Characteristics and modification methodologies

• Modification methodologies of upgrading CBp from ELTs were reviewed. • Surface microstructures and physiochemical properties of CBp were analyzed. • Future perspectives of ELTs pyrolysis industries were suggested. Over 1 billion end-of-life tires (ELTs) are generating annually, and 4 billion ELTs are currently abandoned in landfills and stockpiles worldwide, according to the statistics, leading to the environmental and health risks. To circumvent these issues, pyrolysis, as an attractive thermochemical process, has been addressed to tackle the ELTs’ problem to reduce the risks as well as increase the material recycling. However, due to the lack of systematic characteristic analysis and modification methods, poor quality of CBp limits the improvement of ELTs pyrolysis in industry applications, which plays a crucial role in the economic feasibility of pyrolysis process. In this review, we have summarized the state-of-the-art characteristics and modification methodologies of the upgrading of CBp, to in-depth understand the surface microstructures and physiochemical properties of CBp for the foundation for modification afterwards. By virtue of the proper selection of modification methods and modifying agents, the new generation of multifunctional carbon materials with desired properties can be instead of the traditional materials of CB, promising broader and various application fields.     

Studies on the pyrolysis behavior of gasification and melting systems for municipal solid waste

 It is important to investigate the pyrolysis processes of municipal solid waste (MSW) in the same way as for any mixture comprised of multiple substances. In this article, a two-reaction model for a variety of MSW mixtures is proposed to predict mass changes due to pyrolysis. In order to formulate the model based on pyrolysis kinetics, we conducted experiments to determine the kinetic model parameters. By thermal analysis of the typical components of MSW, mass changes attributable to the pyrolysis reaction were found at about 350°C for paper, 400°–500°C for plastics, and 200°–400°C for garbage (dry condition). Activation energies were obtained by the Ozawa method based on the mass changes in pyrolysis. Thus, the pyrolysis behavior is formulated as a function of temperature. Then the pyrolysis mass change of the mixture can be predicted by using a weighted sum of the individual components. The model proved useful in experiments with real waste (refuse-derived fuels). Furthermore, the weight yields (pyrolysis gas, tars, solid residues) of the mixture can be calculated by their additive property after measuring the mass balance of each component. Received: May 11, 2001 / Accepted: November 16, 2001     

Making hybrid mixture explosions a common case

Explosions of gas-dust hybrid mixtures have long been considered as particular cases encountered in specific industrial contexts. However, it should be reminded that during the explosion of an organic powder, the presence of a hybrid mixture composed of the dust itself and its pyrolysis gases is compulsory. On these premises, an experimental study to determine the role of cellulose pyrolysis products (gaseous, condensable and solid) on the global phenomenon is presented. Hybrid mixture explosion tests were exploited to carry out the investigation. The G-G furnace and the 20 L sphere were employed. Several experimental strategies were chosen to demonstrate the impact of pyrolysis reaction on the explosion of organic powders: i) the fuel equivalence ratio of the reactive mixture (case 1), or ii) the mass of reactants (case 2) were respectively kept constant, iii) the effects of water vapor, char and tar were tested. They were next compared to identify the most suitable one. The two first experimental approaches lead to significantly different results: only case 2 keeps the maximum explosion pressure almost constant, but maximum rate of pressure rises and deflagration index greatly decrease when the pyrolysis gases concentration decreases, which highlights the importance of the pyrolysis reaction on the explosion kinetics. It should also be stressed that the maximum explosion severity is not obtained for the pure gases but when a small dust content is added. The same evolution is observed when a small amount of char is introduced to pyrolysis gases, which underlines the influence of the radiative transfer. Adding small amounts of tar to cellulose tends to increase its explosion severity. However, this impact is less than that generated by the addition of pyrolysis gases.     

Linking the electron donation capacity to the molecular composition of soil dissolved organic matter from the Three Gorges Reservoir areas, China

Soil dissolved organic matter(DOM) plays an essential role in the Three Gorges Reservoir(TGR) as a linkage between terrestrial and aquatic systems.In particular,the reducing capacities of soil DOM influence the geochemistry of contaminants such as mercury(Hg).However,few studies have investigated the molecular information of soil DOM and its relationship with relevant geochemic al reactivities,including redox properties.We collected samples from eight sites in the TGR areas and studied the link between the molecular characteristics of DOM and their electron donation capacities(EDCs) toward Hg(II).The average kinetic rate and EDC of soil DOM in TGR areas were(0.004±0.001) hr~(-1) and(2.88±1.39) nmol e~-/mg DOM_(bulk),respectively.Results suggest that higher EDCs and relatively rapid kinetics were related to the greater electron donating components of ligninderived and perhaps pyrogenic DOM,which are the aromatic constituents that influenced the reducing capacities of DOM in the present study.Molecular details revealed that even the typical autochthonous markers are important for the EDCs of DOM as well,in contrast to what is generally assumed.More studies identifying specific DOM molecular components involved in the abiotic reduction of Hg(II) are required to further understand the relations between DOM sources and their redox roles in the environmental fate of contaminants.     

Formation characteristics of PCDD and PCDF during pyrolysis processes

In recent years, pyrolysis processes have become technologies developed to industrial scale and discussed as alternatives to the existing waste combustion technology. However, little information is published regarding PCDD/F formation characteristics during pyrolysis processes. Two common shredder fractions – industrial light shredder (ILS) and refrigerators (REF) – both with high chlorine and copper content were pyrolysed for this pyrolysis study using a pilot plant with a capacity of 100 kg/h. At oxygen concentrations below 2% and temperatures between 430°C and 470°C, considerable amounts of PCDD/F were formed during the pyrolysis. More than 90% of total TEQ was found in the oil fraction (gas phase). The PCDD/PCDF ratio and the homologue pattern differed significantly from those formed during waste incineration. Considering mono- to octachlorinated congeners, up to 400 times more PCDF were formed compared to PCDD. For the investigated pyrolysis conditions, the formation of low chlorinated congeners was highly favoured. The distribution of TEQ within the individual congeners were very similar in all investigated runs. More than 80% of total TEQ stem from 2,3,7,8-substituted T₄CDF and P₅CDF. The isomer pattern, however, did not show significant differences compared to the common waste incineration pattern suggesting that the basic formation routes are similar.     

Roles of pyrolysis on availability,species and distribution of Cu and Zn in the swine manure: Chemical extractions and high-energy synchrotron analyses

Animal manures generally contain high levels of heavy metals that may pose a significant threat to soil and groundwater qualities. Pyrolysis as means of reducing metal availability in such feed stocks is recently encouraged, but systematic studies are currently lacking. The aim of this study was to assess the impact of pyrolysis temperature on the availability of Cu and Zn by chemical extraction, to determine the speciation of Cu and Zn by synchrotron-based X-ray spectroscopy, and finally to investigate the phase distribution of metal species in the carbonaceous materials by combining acid–base extractions and absorption spectroscopy data. The results showed that both Cu and Zn in the swine manure were mainly bound to organic functional groups. Cu (II) reduction and Cu (I)–S complexes were observed during the pyrolysis process. Zn species resembling ZnAc₂ was still dominant, being 60.8–69.2%, and ZnS increased by 6.6–21.8% in the carbonaceous materials. The distribution of Cu and Zn in the mineral, carbonized and non-carbonized organic phases varied greatly with the pyrolysis temperature. The higher the temperature, the more the metals existed in the mineral phase and carbonized organic phase. The decrease of EDTA extractable Cu and Zn with pyrolysis temperature was due to the increase of metals in the carbonized organic phase and mineral phase. It is suggested that pyrolysis at the relatively higher temperature is a better choice for metal-containing manure according to the metal speciation, solubility and availability.     

废弃塑料裂解油化技术

综述了废弃塑料进行热裂解和催化裂解以获得聚合单体、柴油、汽油和燃料气的工艺原理、工艺流程和常用的裂解催化剂。指出裂解油化技术是今后处理废弃塑料的主要方式之一。     

Characterization of human manure-derived biochar and energy-balance analysis of slow pyrolysis process

Biochars have received increasing attention in recent years because of their soil improvement potential, contaminant immobilization properties, and ability to function as carbon sinks. This study adopted a pyrolytic process to prepare a series of biochars from dried human manure at varying temperatures. The thermal analysis of human manure and physicochemical properties of the resulting biochars illustrated that human manure can be a favorable feedstock for biochar production. In particular, the porous texture and nutrient-rich properties of biochars produced from human manure and may significantly enhance soil fertility when used as used soil additives. A temperature range of 500–600 °C was optimal for human manure biochar production. Significantly, when the moisture content of the feedstock is lower than 57%, the system could not only harvest manure-derived biochar but also have a net energy output, which can be provide heat source for nearby users.