• Energy Research
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Abstract Bio-oil from the fast pyrolysis of biomass can be converted to solid carbon materials, chemicals and syngas by various thermochemical conversion methods. As a first step in all of these processes, bio-oil undergoes drastic components changes due to its exposure to the elevated temperature. Understanding the effects of heating rate on bio-oil transformation during its pyrolysis is therefore crucial for effective utilization of bio-oil. In this study, a bio-oil sample produced from the fast pyrolysis of rice husk at 500 °C was pyrolyzed in a fixed-bed reactor at temperatures between 300 and 800 °C at three different heating rates: fast (≈200 °C/s), medium (≈20 °C/s), and slow (≈0.33 °C/s). In addition to the quantification of coke and tar yields, the tar was characterized with an ultraviolet (UV) fluorescence spectroscopy, a gas chromatography/mass spectrometer (GC/MS) and a Fourier transform ion cyclotron resonance mass spectrometer (FT-ICR MS). Our results indicate that slow heating rates promote polymerization of bio-oil components, particularly at low temperatures ( 500) were also promoted at fast heating rates via the more intense secondary reactions.

Laboratory experiments were conducted to investigate the volatilization behavior of heavy metals during pyrolysis and combustion of municipal solid waste (MSW) components at different heating rates and temperatures. The waste fractions comprised waste paper (Paper), disposable chopstick (DC), garbage bag (GB), PVC plastic (PVC), and waste tire (Tire). Generally, the release trend of heavy metals from all MSW fractions in rapid-heating combustion was superior to that in low-heating combustion. Due to the different characteristics of MSW fractions, the behavior of heavy metals varied. Cd exhibited higher volatility than the rest of heavy metals. For Paper, DC, and PVC, the vaporization of Cd can reach as high as 75% at 500 °C in the rapid-heating combustion due to violent combustion, whereas a gradual increase was observed for Tire and GB. Zn and Pb showed a moderate volatilization in rapid-heating combustion, but their volatilities were depressed in slow-heating combustion. During thermal treatment, the additives such as kaolin and calcium can react or adsorb Pb and Zn forming stable metal compounds, thus decreasing their volatilities. The formation of stable compounds can be strengthened in slow-heating combustion. The volatility of Cu was comparatively low in both high and slow-heating combustion partially due to the existence of Al, Si, or Fe in residuals. Generally, in the reducing atmosphere, the volatility of Cd, Pb, and Zn was accelerated for Paper, DC, GB, and Tire due to the formation of elemental metal vapor. TG analysis also showed the reduction of metal oxides by chars forming elemental metal vapor. Cu2S was the dominant Cu species in reducing atmosphere below 900 °C, which was responsible for the low volatility of Cu. The addition of PVC in wastes may enhance the release of heavy metals, while GB and Tire may play an opposite effect. In controlling heavy metal emission, aluminosilicate- and calcium-based sorbents can be co-treated with fuels. Moreover, pyrolysis can be a better choice for treatment of solid waster in terms of controlling heavy metals. PVC and Tire should be separated and treated individually due to high possibility of heavy metal emission. This information may then serve as a guideline for the design of the subsequent gas cleaning plant, necessary to reduce the final emissions to the atmosphere to an acceptable level.

Co-hydrothermal carbonization (HTC) of livestock manure and biomass might improve the fuel properties of the hydrochar due to the high reactivity of the biomass-derived intermediates with the abundant oxygen-containing functionalities. However, the complicated compositions make it difficult to explicit the specific roles of the individual components of biomass played in the co-HTC process. In this study, cellulose was used for co-HTC with swine manure to investigate the influence on the properties of the hydrochar. The yield of hydrochar obtained from co-HTC reduced gradually with the cellulose proportion increased, and the solid yield was lower than the theoretical value. This was because the cellulose-derived intermediates favored the stability of the fragments from hydrolysis of swine manure. The increased temperature resulted in the reduction of the hydrochar yield whereas the prolonged time enhanced the formation of solid product. The interaction of the co-HTC intermediates facilitated the formation of O-containing species, thus making the solid more oxygen- and hydrogen-rich with a higher volatility. In addition, the co-HTC affected the evolution of functionalities like -OH and CO during the thermal treatment of the hydrochar and altered its morphology by stuffing the pores from swine manure-derived solid with the microspheres from HTC of cellulose. The interaction of the varied intermediates also impacted the formation of amines, ketones, carboxylic acids, esters, aromatics and the polymeric products in distinct ways.

Abstract This study aimed to understand the mechanism of dual catalytic effects of inherent alkali and alkaline earth metallic species (AAEMs) on biomass gasification. Two kinds of typical Chinese agricultural biomass were gasified using updraft quartz reactor with steam. The results indicated that external steam had negligible effects on promoting further thermal cracking or reforming of tar under 900 °C. The presence of AAEMs enhanced the production of H2 and CO2, while inhibited the production of CO、CH4、C2H4 and C2H6. The heterogeneous char-steam reaction, as well as the homogeneous hydrocarbons reforming and water-gas shift reactions were promoted by the presence of AAEMs. Alkaline earth metals had more significant catalytic effects on water-gas shift reaction compared to alkali metals. The results from UV fluorescence spectra further proved that the additional steam had negligible promoting effects on secondary reforming of tar, while the inherent AAEMs had a significant catalytic role in thermal cracking and reforming of tars.

Abstract This study aims to investigate the importance of aromatic structures in tar to the destruction of tar itself during the volatile–char interactions. The same nascent char was subjected to interactions with two distinctly different volatiles (e.g. coal volatiles and biomass volatiles) at 700–900 °C. The results indicate that the aromatic structures in tar are more reactive with char than the non-aromatic structures, especially at high temperature (e.g. 900 °C). At lower temperatures (

Plastics from waste electrical and electronic equipment (WEEE) have been an important environmental problem because these plastics commonly contain toxic halogenated flame retardants which may cause serious environmental pollution, especially the formation of carcinogenic substances polybrominated dibenzo dioxins/furans (PBDD/Fs), during treat process of these plastics. Pyrolysis has been proposed as a viable processing route for recycling the organic compounds in WEEE plastics into fuels and chemical feedstock. However, dehalogenation procedures are also necessary during treat process, because the oils collected in single pyrolysis process may contain numerous halogenated organic compounds, which would detrimentally impact the reuse of these pyrolysis oils. Currently, dehalogenation has become a significant topic in recycling of WEEE plastics by pyrolysis. In order to fulfill the better resource utilization of the WEEE plastics, the compositions, characteristics and dehalogenation methods during the pyrolysis recycling process of WEEE plastics were reviewed in this paper. Dehalogenation and the decomposition or pyrolysis of WEEE plastics can be carried out simultaneously or successively. It could be 'dehalogenating prior to pyrolysing plastics', 'performing dehalogenation and pyrolysis at the same time' or 'pyrolysing plastics first then upgrading pyrolysis oils'. The first strategy essentially is the two-stage pyrolysis with the release of halogen hydrides at low pyrolysis temperature region which is separate from the decomposition of polymer matrixes, thus obtaining halogenated free oil products. The second strategy is the most common method. Zeolite or other type of catalyst can be used in the pyrolysis process for removing organohalogens. The third strategy separate pyrolysis and dehalogenation of WEEE plastics, which can, to some degree, avoid the problem of oil value decline due to the use of catalyst, but obviously, this strategy may increase the cost of whole recycling process.

Abstract Electronic waste plastics (e-waste plastics) have been one of the emerging and fastest-growing waste streams due to the increasing number of generation in waste electrical and electronic equipment (WEEE). Given that brominated flame retardant (BFR) materials in e-waste plastics have been the major impediment for recycling treatment, chemical recycling has been proposed as an environmentally friendly method of recycling e-waste plastics for clean fuels production or chemical feedstocks. This paper summarized the current techniques of BFR-plastics recycling with a view to solving energy crisis and the environmental degradation of BFR-plastics. Emphasis was paid on the recent chemical treatment of BFR-plastics, including pyrolysis, co-pyrolysis and catalytic cracking, which are yet to be completely feasible in conversion of BFR-plastics for clean fuels production. Hydrothermal treatment is regarded as a novel high-efficiency technology to recycle BFR-plastics, which can be a potential process for the in situ debromination of oil products. An advanced chemical recycling technique, pyrolysis-catalytic upgrading process, is highlighted. The recycling route of pyrolyzing BFR-plastics prior to catalytic upgrading was intended to obtain high quantity oils, and then the upgrading process of pyrolysis oils was conducted by means of catalytic hydrodebromination with the aim of obtaining bromine-free oils for commercial applications. In short, the integration of pyrolysis with catalytic upgrading process can provide significant economic and environmental options in conversion of e-waste plastics into useful and high-value materials. Further investigations are required to develop the pyrolysis-catalytic upgrading process to become sustainable and commercially viable for clean fuels production.

Abstract This study aims to investigate the importance of steam to tar destruction during the volatile–char interactions. Steam was supplied in the absence and presence of nascent char during the pyrolysis/gasification of biomass at 850 °C. In the absence of char, steam has more significant effects on the reforming of large aromatic ring systems (e.g. >2 fused benzene rings) than small and isolated aromatics. In the presence of char, steam can significantly enhance the reforming of both large and small aromatic ring systems during the volatile–char interactions, especially when the steam–char reactions are also significant. The results indicate that the steam–char reactions are particularly inhibited in a thin char bed by the volatile–char interactions. It is believed that the steam–char reactions can produce additional active sties on the char, such as the radicals/intermediates of char gasification and/or the O-containing groups, to facilitate tar reforming during the volatile–char interactions.

Sludge pyrolysis and biomass gasification integrated process (SPBG) is an attractive route for the comprehensive utilization of the two materials but more tar is produced in this process compared to traditional biomass steam gasification. Nitrogen-containing compounds in the tar bring threatens to the environment and heavy components in the tar contributes to undesired coke formation. In current study, the evolution of heavy tar, especially the nitrogen-rich components, during SPBG is revealed for the first time. It was found that heavy components were mainly distributed in the mass range of 150-450 Da, where aromatics consisted of carbon, hydrogen and nitrogen atoms were the most abundant. Deamination (NH3) and the combination of quinoline accompanied with the generation of the heavy components. Organics from sludge could react with biomass to form heavier oxygen-containing molecules. Meanwhile, steam from sludge promoted heavy components to crack by tar reforming reactions and consumed radicals in bio-char to inhibit the catalytic cracking of tar. Under the combination of above reactions, more heavy molecules were generated at low sludge volatile/biomass ratio and the aromatic content in the heavy tar decreased at high sludge volatile/biomass ratio.