Total recycling of CCA treated wood waste by low-temperature pyrolysis

A system to turn a potentially harmful stream of solid waste into a set of substreams with either commercial value or highly concentrated residual streams is presented. The waste which is considered is metal impregnated (in particular Chromated Copper Arsenate (CCA) treated) wood waste and timber, such as telephone poles, railway sleepers, timber from landscape and cooling towers, wooden silos, hop-poles, cable drums and wooden playground equipment. These waste streams sum up to several 100,000 tons of material per year currently to be dumped in every major country of the European Community (EC). Technologies need to be developed to reduce this CCA treated wood waste, such that all of the metals are contained in a marketable product stream, and the pyrolysis gases and/or pyrolysis liquid are used to their maximum potential with respect to energy recuperation. Pyrolysing the CCA treated wood waste may be a good solution to the growing disposal problem since low temperatures and no oxidising agents are used, which result in lower loss of metals compared to combustion. An experimental labscale pyrolysis system has been developed to study the influence of the pyrolysis temperature and the duration of the pyrolysis process on the release of metals and the mass reduction. The macrodistribution and microdistribution of the metals in the solid pyrolysis residue is studied using Inductively Coupled Plasma Mass Spectrometry (ICP–MS) and Scanning Electron Microscopy coupled with Energy Dispersive X-ray Analysis (SEM–EDXA). Furthermore, a complete mass balance is calculated over the pyrolysis system. Based on these results a semi-industrial pyrolysis system (pilot plant scale) has been developed consisting of three stages: grinding, packed bed pyrolysis and metal separation. Special types of equipment have been developed to carry out the three stages. A new grinding system has been developed, based on a crushing mechanism rather than a cutting mechanism. The crushed wood is introduced by means of a screw feeding system into a reaction column. In this pyrolysis reactor the wood is heated by subjecting it to a flow of hot gases. This causes an adiabatic pyrolysis, which results in volatilisation of the volatile compounds whereas the mineral compounds (containing the metals) remain entrapped in a coal-type residue which is very rich in carbon. The condensable compounds in the pyrolysis gas condense while leaving the reaction zone due to the inverse temperature gradient. The pyrolysis gas leaving the reactor is used as fuel for the hot gas generator. The charcoal which is extracted at the bottom of the reactor, is cooled, compressed, removed and stored, ready to feed the subsequent stage. A specially developed grinder is used to remove the metal particles from the charcoal and the separation between metal and charcoal particles is accomplished in a pneumatic centrifuge as a result of the difference in density. Using this system the ultimate waste is less than 3% of the initial wood mass. Results obtained with a semi-industrial scale prototype confirm the effectiveness of the process.     

废物热解焚烧工艺设备选择的技术要点

主要介绍了热解氧化焚烧的概念及原理,指出了实现热解氧化焚烧的关键因素。根据热解焚烧的控制过程,详细地介绍了静态热解和动态热解的工艺特点,并对实现热解焚烧所采用的焚烧炉进行了比较及适用性分析,提出了废物热解焚烧工艺的技术要点。     

Thermal hazard analysis of 1-((cyano-1-methylethyl) azo) formamide and effect of incompatible substances on its thermal decomposition

1-((cyano-1-methylethyl) azo) formamide (CABN) is an azo compound that exhibits high thermal sensitivity and self-reactivity. Because of incorrect operation, incompatible substances and other dangerous conditions, thermal explosion accidents may occur during the manufacturing, storage, and transportation of CABN. The pyrolysis characteristics of CABN and its mixture for various heating rates were assessed using differential scanning calorimetry. The results showed that incompatible substances increased the risk of CABN. Moreover, the thermal runaway of CABN under an adiabatic condition was studied using an adiabatic rate calorimeter to obtain the parameters under adiabatic condition. Based on the experimental data, the kinetic parameters of CABN and its mixtures were obtained. In addition, a thermal decomposition kinetic model of CABN was created using Thermal Safety Series. All experiments have shown that the conditions and parameters of CABN must be strictly controlled.     

Thermal analysis of polyethylene glycol: evolved gas analysis with ion attachment mass spectrometry

The thermal decomposition of polyethylene glycol was investigated by using a technique combining evolved gas analysis (time-resolved pyrolysis) with ion-attachment mass spectrometry. This technique allows the detection of intact pyrolysis products and, therefore, offers the opportunity for direct real-time monitoring of thermal by-products. Unstable products can thus be detected; for instance, many highly reactive organic peroxides, such as CH₃OOH and HOCH₂OOH, were found in this study. Classification analysis revealed 10 major compositional formulas among the product species: C_nH_2n+2O, C_nH_2n+2O₂, C_nH_2n+2O₃, C_nH_2n+2O₄, C_nH_2n+2O₅, C_nH_2n+2O₆, C_nH_2n+2O₇, C_nH_2nO, C_nH_2nO₂, and HO(CH₂CH₂O)_nH ethylene glycol oligomers. The Li⁺ ion adduct mass spectra showed a characteristic profile in terms of both the appearance of unique components and the distribution of pyrolysis products. Among the products of the thermal decomposition of PEG, formaldehyde (HCHO) and organic peroxides were particularly interesting. Formaldehyde, one of the 10 most abundant products, is a known human carcinogen. The detection of peroxides suggests that they may form during the incineration of PEG, which may have important environmental implications. The existence of peroxide products may have implications for chemical evolution in incinerator systems.     

Thermal decomposition of electronic wastes: mobile phone case and other parts

Pyrolysis and combustion runs at 850°C in a horizontal laboratory furnace were carried out on different parts of a mobile phone (printed circuit board, mobile case and a mixture of both materials). The analyses of the carbon oxides, light hydrocarbons, polycyclic aromatic hydrocarbons (PAHs), polychlorodibenzo-p-dioxin, polychlorodibenzofurans (PCDD/Fs), and dioxin-like PCBs are shown. Regarding semivolatile compounds, phenol, styrene, and its derivatives had the highest yields. In nearly all the runs the same PAHs were identified, naphthalene being the most common component obtained. Combustion of the printed circuit board produced the highest emission factor of PCDD/Fs, possibly due to the high copper content.     

Deactivation and regeneration of ZSM-5 zeolite in catalytic pyrolysis of plastic wastes

In this work, a study of the regeneration and reuse of ZSM-5 zeolite in the pyrolysis of a plastic mixture has been carried out in a semi-batch reactor at 440 °C. The results have been compared with those obtained with fresh-catalyst and in non-catalytic experiments with the same conditions. The use of fresh catalyst produces a significant change in both the pyrolysis yields and the properties of the liquids and gases obtained. Gases more rich in C3-C4 and H₂ are produced, as well as lower quantities of aromatic liquids if compared with those obtained in thermal decomposition. The authors have proved that after one pyrolysis experiment the zeolite loses quite a lot of its activity, which is reflected in both the yields and the products quality; however, this deactivation was found to be reversible since after regeneration heating at 550 °C in oxygen atmosphere, this catalyst recovered its initial activity, generating similar products and in equivalent proportions as those obtained with fresh catalyst.     

Formation of toxic species and precursors of PCDD/F in thermal decomposition of alpha-cypermethrin

This article examines the thermal decomposition of alpha-cypermethrin, one of the most common pyrethroid pesticides. The objective was to identify its decomposition pathways and to gain an understanding into the formation of toxic species in the environment, including those that may behave in combustion systems, especially in fires in the environment, as precursors for PCDD/F (polychlorinated dibenzo-p-dioxins and dibenzofurans). The experiments were conducted under non-oxidative conditions using a tubular reactor housed in a three-zone heating furnace and operated with a dilute stream of alpha-cypermethrin in 99.999% nitrogen. The condensable products were identified and quantitated, after being collected in a cold solvent trap and in an activated charcoal cartridge. The study revealed the formation of pollutants including precursors of toxic PCDD/F such as diphenyl ether and phenol. It was also found that the decomposition of alpha-cypermethrin involved parallel pathways of an unusual vinylcyclopropane rearrangement-cum-aromatisation reaction transforming alpha-cypermethrin and a rupture of the C(O)OC(CN) linkage. The former is similar to that occurring in the decomposition of permethrin pesticide, whereas the latter constitutes a newly discovered channel for the formation of pollutants. Density functional theory (DFT) calculations allowed us to attribute the occurrence of the second pathway to the effect of the cyanide group in significantly weakening the OC bond.     

Recyling of plastic wastes via pyrolysis

Pyrolysis for the simultaneous generation of oils and gases can be convenient to obtain hydrocarbons and even to recover crude petrochemicals or to generate energy from waste plastics. A Gray–King apparatus has been used to pyrolyze waste polyethylene (PE), polystyrene (PS), both separately and with different compositions. Thermogravimetric analysis of waste plastics indicated the critical temperatures, which should be effective for pyrolysis. The chosen heating rate was low in order to achieve higher liquid yields. The results showed that waste PS yielded higher liquid, and waste PE yielded higher gaseous products. The dominant liquid product of PS waste was styrene whereas for waste PE, prophenylbenzene was the dominant pyrolysis product.     

Influence of pyrolysis temperature on production and nutrient properties of wastewater sludge biochar

The important challenge for effective management of wastewater sludge materials in an environmentally and economically acceptable way can be addressed through pyrolytic conversion of the sludge to biochar and agricultural applications of the biochar. The aim of this work is to investigate the influence of pyrolysis temperature on production of wastewater sludge biochar and evaluate the properties required for agronomic applications. Wastewater sludge collected from an urban wastewater treatment plant was pyrolysed in a laboratory scale reactor. It was found that by increasing the pyrolysis temperature (over the range from 300 °C to 700 °C) the yield of biochar decreased. Biochar produced at low temperature was acidic whereas at high temperature it was alkaline in nature. The concentration of nitrogen was found to decrease while micronutrients increased with increasing temperature. Concentrations of trace metals present in wastewater sludge varied with temperature and were found to primarily enriched in the biochar.     

废弃印刷电路板资源化回收利用技术探讨

废弃印刷电路板成分复杂,在含有大量可回收金属的同时,还含有多种有害物质,其资源化回收和处置技术受到国内外广泛的关注。对目前主要的废弃印刷电路板回收利用技术应用状况和实践进展进行了分析。机械法．化学冶金法是目前广泛应用的以回收废弃印刷电路板中的金属为主要目的的回收技术。应用热解技术处理废弃印刷电路板,不仅可以有效回收废弃印刷电路板中的金属物质,还可以使废弃印刷电路板中的非金属物质得到资源化利用,具有很好的发展前景。