Combustion-derived substances in deep basins of Puget Sound: historical inputs from fossil fuel and biomass combustion

Reconstructions of 250 years historical inputs of two distinct types of black carbon (soot/graphitic black carbon (GBC) and char-BC) were conducted on sediment cores from two basins of the Puget Sound, WA. Signatures of polycyclic aromatic hydrocarbons (PAHs) were also used to support the historical reconstructions of BC to this system. Down-core maxima in GBC and combustion-derived PAHs occurred in the 1940s in the cores from the Puget Sound Main Basin, whereas in Hood Canal such peak was observed in the 1970s, showing basin-specific differences in inputs of combustion byproducts. This system showed relatively higher inputs from softwood combustion than the northeastern U.S. The historical variations in char-BC concentrations were consistent with shifts in climate indices, suggesting an influence of climate oscillations on wildfire events. Environmental loading of combustion byproducts thus appears as a complex function of urbanization, fuel usage, combustion technology, environmental policies, and climate conditions.     

Recovery of solid fuel from municipal solid waste by hydrothermal treatment using subcritical water

Hydrothermal treatments using subcritical water (HTSW) such as that at 234 °C and 3 MPa (LT condition) and 295 °C and 8 MPa (HT condition) were investigated to recover solid fuel from municipal solid waste (MSW). Printing paper, dog food (DF), wooden chopsticks, and mixed plastic film and sheets of polyethylene, polypropylene, and polystyrene were prepared as model MSW components, in which polyvinylchloride (PVC) powder and sodium chloride were used to simulate Cl sources.While more than 75% of carbon in paper, DF, and wood was recovered as char under both LT and HT conditions, plastics did not degrade under either LT or HT conditions. The heating value (HV) of obtained char was 13,886-27,544 kJ/kg and was comparable to that of brown coal and lignite. Higher formation of fixed carbon and greater oxygen dissociation during HTSW were thought to improve the HV of char.Cl atoms added as PVC powder and sodium chloride to raw material remained in char after HTSW. However, most Cl originating from PVC was found to converse into soluble Cl compounds during HTSW under the HT condition and could be removed by washing.From these results, the merit of HTSW as a method of recovering solid fuel from MSW is considered to produce char with minimal carbon loss without a drying process prior to HTSW. In addition, Cl originating from PVC decomposes into soluble Cl compound under the HT condition. The combination of HTSW under the HT condition and char washing might improve the quality of char as alternative fuel.     

Pyrolysis of waste tyres: A review

Approximately 1.5 billion tyres are produced each year which will eventually enter the waste stream representing a major potential waste and environmental problem. However, there is growing interest in pyrolysis as a technology to treat tyres to produce valuable oil, char and gas products. The most common reactors used are fixed-bed (batch), screw kiln, rotary kiln, vacuum and fluidised-bed. The key influence on the product yield, and gas and oil composition, is the type of reactor used which in turn determines the temperature and heating rate. Tyre pyrolysis oil is chemically very complex containing aliphatic, aromatic, hetero-atom and polar fractions. The fuel characteristics of the tyre oil shows that it is similar to a gas oil or light fuel oil and has been successfully combusted in test furnaces and engines. The main gases produced from the pyrolysis of waste tyres are H₂, C₁–C₄ hydrocarbons, CO₂, CO and H₂S. Upgrading tyre pyrolysis products to high value products has concentrated on char upgrading to higher quality carbon black and to activated carbon. The use of catalysts to upgrade the oil to a aromatic-rich chemical feedstock or the production of hydrogen from waste tyres has also been reported. Examples of commercial and semi-commercial scale tyre pyrolysis systems show that small scale batch reactors and continuous rotary kiln reactors have been developed to commercial scale.     

Competitive biodegradation of dichlobenil and atrazine coexisting in soil amended with a char and citrate

The role of char nutrients in the biodegradation of coexisting dichlobenil and atrazine in a soil by their respective bacterial degraders, DDN and ADP, was evaluated. Under growing conditions, their degradation in soil extract was slow with <40% and <20% degraded within 64 h, respectively. The degradation in extracts and slurries of char-amended solids increased with increasing char content, due to nutritional stimulation on microbial activities. By supplementing soil extract with various major nutrients, the measured degradation demonstrated that P was the exclusive limiting nutrient. The reduction in the degradation of coexisting dichlobenil and atrazine resulted apparently from the competitive utilization of P by DDN and ADP. With a shorter lag phase, ADP commenced growing earlier than DDN with the advantage of utilizing P first in insufficient supply. This resulted in an inhibition on the growth of DDN and thus suppression on dichlobenil degradation.     

PPH (potassium polyacrylate & hectorite) composite materials – A new fire accident emergency method for thermal protection of adjacent tanks

When a chemical tank fire happens in a storage area, it is very important to protect adjacent tanks so as to decrease fire accident losses. In this paper, a new thermal protection method was put forward based on a PPH (potassium polyacrylate & hectorite) thermal insulation composite material spraying on an adjacent tank under fire. Firstly, the PPH material was prepared successfully by a polymerization reaction of potassium acrylate, hectorite, NaHSO₃ and (NH₄)₂S₂O₈. Secondly, thermal insulation performance of the PPH material was characterized by heat transfer process at high incident heat flux using cone calorimeter. The results show that thermal insulation performance of the PPH material is affected by a content change of (NH₄)₂S₂O₈, NaHSO₃ and hectorite in formulations. The content of (NH₄)₂S₂O₈ 0.14 wt%, NaHSO₃ 1.38 wt% and hectorite 1.4 wt% was an optimum formulation ratio to obtain best thermal insulation performance. Finally, possible thermal insulation mechanisms of the PPH material were presented using SEM, TG and TG-IR techniques. One of the thermal insulation mechanisms is the incident heat flux absorbed by water evaporation from the PPH material. Another is the thermal protection of the char formed from the PPH material at high incident thermal radiation, which can prevent heat and mass transfer.     

Characterization, leachability and valorization through combustion of residual chars from gasification of coals with pine

This paper presents the study of the combustion of char residues produced during co-gasification of coal with pine with the aim of characterizing them for their potential use for energy. These residues are generally rich in carbon with the presence of other elements, with particular concern for heavy metals and pollutant precursors, depending on the original fuel used.The evaluation of environmental toxicity of the char residues was performed through application of different leaching tests (EN12457-2, US EPA-1311 TCLP and EA NEN 7371:2004). The results showed that the residues present quite low toxicity for some of pollutants. However, depending on the fuel used, possible presence of other pollutants may bring environmental risks.The utilization of these char residues for energy was in this study evaluated, by burning them as a first step pre-treatment prior to landfilling. The thermo-gravimetric analysis and ash fusibility studies revealed an adequate thermochemical behavior, without presenting any major operational risks.Fluidized bed combustion was applied to char residues. Above 700 °C, very high carbon conversion ratios were obtained and it seemed that the thermal oxidation of char residues was easier than that of the coals. It was found that the char tendency for releasing SO₂ during its oxidation was lower than for the parent coal, while for NO_X emissions, the trend was observed to increase NO_X formation. However, for both pollutants the same control techniques might be applied during char combustion, as for coal. Furthermore, the leachability of ashes resulting from the combustion of char residues appeared to be lower than those produced from direct coal combustion.     

Gasification of the char derived from distillation of granulated scrap tyres

This work reports the effect of pressure on the steam/oxygen gasification at 1000 °C of the char derived from low temperature-pressure distillation of granulated scrap tyres (GST). The study was based on the analysis of gas production, carbon conversion, cold gas efficiency and the high heating value (HHV) of the product. For comparison, similar analyses were carried out for the gasification of coals with different rank.In spite of the relatively high ash (≈12 wt.%) and sulphur (≈3 wt.%) contents, the char produced in GST distillation can be regarded as a reasonable solid fuel with a calorific value of 34 MJ kg⁻¹. The combustion properties of the char (E_A ≈ 50 kJ mol⁻¹), its temperature of self-heating (≈264 °C), ignition temperature (≈459 °C) and burn-out temperature (≈676 °C) were found to be similar to those of a semi-anthracite.It is observed that the yield, H₂ and CO contents and HHV of the syngas produced from char gasification increase with pressure. At 0.1 MPa, 4.6 Nm³ kg_char⁻¹ of syngas was produced, containing 28% v/v of H₂ and CO and with a HHV around 3.7 MJ Nm⁻³. At 1.5 MPa, the syngas yield achieved 4.9 Nm³ kg_char⁻¹ with 30% v/v of H₂-CO and HHV of 4.1 MJ Nm⁻³. Carbon conversion significantly increased from 87% at 0.1 MPa to 98% at 1.5 MPa.It is shown that the char derived from distillation of granulated scrap tyres can be further gasified to render a gas of considerable heating value, especially when gasification proceeds at high pressure.     

含二羟基DOPO衍生物阻燃改性环氧树脂的制备与热性能研究

DOPO(9,10-二氢-9-氧杂-10-磷杂菲-10-氧化物)、多聚甲醛、二乙醇胺为原料合成了含二羟基的DOPO衍生物DHDOPO,并作为反应型阻燃剂引入到环氧树脂分子链结构中,制备出一组不同含磷量的阻燃环氧树脂复合材料。采用极限氧指数(LOI)法和垂直燃烧(UL-94)法测试材料的燃烧性能,结果表明,在含磷量为1.5%时,氧指数达到35.0%,并达到V-0级别。锥形量热计(Cone)数据显示阻燃改性后的环氧树脂具有更低的热释放速率峰值(PHRR)和总热释放量(THR),说明具有更高的火灾安全性。此外,还通过热重分析(TGA)实验研究了DHDOPO对环氧树脂热稳定性能的影响。通过扫描电镜对燃烧过后的炭渣形貌进行分析,推测了燃烧的过程和阻燃的机理。     

含DOPO磷酸酯阻燃改性环氧丙烯酸树脂的制备及热性能研究

将工业上广泛应用的光固化树脂EA作为基体,通过分子设计,利用甲苯二异氰酸酯TDI的双异氰酸酯结构将合成的磷酸酯阻燃剂ODOPM链接到其分子主链上,制备出一组改性的光固化丙烯酸酯预聚物。利用FT-IR,1 H-NMR,31P-NMR对分子结构进行表征;极限氧指数（LOI）和微型量热仪（MCC）的结果表明材料的阻燃性能明显提高,改性后树脂的热释放速率峰值PHRR相对于EA降低了近66%,总热释放量也明显降低;扫描电镜结果显示改性后的树脂固化膜形成的炭层变得更平滑和致密,并且完整无破裂现象;同时对固化膜的热稳定性和热降解过程进行了探讨。分析论证了ODOPM改性修饰后的EA有更高的阻燃性,成炭能力明显增强,形成的致密炭层有效地阻止了热交换,使材料在高温下更稳定。     

Sorption of apolar and polar organic contaminants by waste tire rubber and its chars in single- and bi-solute systems

Single- and bi-solute sorption of organic compounds [1,3-dichlorbenzene (DCB), 1,3-dinitrobenzene (DNB) and 2,4-dichlorophenol (DCP)] on ground tire rubber and its chars was studied. The chars were prepared by pyrolyzing tire rubber at different temperatures (200-800 °C). Their surface area, aromaticity and hydrophobicity increase greatly with pyrolytic temperature, and the polymeric phase is partly converted into a condensed phase. The sorption of DNB and DCP increases with pyrolytic temperature and is characterized by a transition from a partition dominant to an adsorption dominant process. However, the sorption of DCB linearly decreases with the pyrolytic temperature. The enhanced adsorption of DNB and DCP on carbonized phase is primarily attributed to nonhydrophobic interactions such as π-π electron-donor-acceptor interactions and/or H bonding. The higher partition of DCB to polymeric phase is attributed to its high hydrophobicity. Competitive sorption between DCB and DCP on the tire chars is highly dependent on dissociation of the latter.