• Energy Research

Abstract Oxygenated polycyclic aromatic hydrocarbons (OPAHs) are an important group of components produced from the thermal conversion of cellulose. Through using gas chromatography mass spectrometry (GC–MS), Fourier transform ion cyclotron resonance mass spectrometer (FT-ICR MS) and ultraviolet fluorescence spectroscopy (UV-F), the information for the evolution of OPAHs is obtained in this study. The tar produced at low temperature mainly contains light components such as homologues of pyran and furan, while the components in the tars at 700 °C and 900 °C show high double bond equivalent (DBE) values, indicating the existence of large aromatic structures. High temperature promote condensation reactions during cellulose thermal conversion, thus leading to a higher percentage of OPAHs in the tar at higher temperature process. According to Density Functional Theory (DFT) calculation, the energy barrier of Diels-Alder reaction (302.65 kJ/mol) is lower than the dehydration (583.26 kJ/mol), which means that Diels-Alder reaction could be the main route for OPAH formation rather than dehydration reaction. High reaction temperature is calculated to be favorable for the formation of naphthol during the cellulose thermal conversion because of the high energy barrier of dehydration between phenol and furan. It is consistent with the ESI FT-ICR MS result that there is a higher content of naphthol in the tar at 700 °C than that at 500 °C.

This study investigated the characteristics of NO emissions during oxy-coal combustion with wet-recycle, especially in the presence of high H2O concentrations. The oxy-combustion was carried out using two types of coal, namely Leiyang (LY) anthracite and Zhundong (ZD) bituminous coals, inside a 24 kW drop tube furnace under different O2/CO2/H2O atmospheres. The results showed that the NO conversion increased with decreasing CO2 concentration from 70% to 30% and decreased with increasing H2O concentration from 10% to 40%. Under the experimental conditions employed in this study, the fuel-N conversion for both LY and ZD coals under the oxy-coal wet recycled combustion was lower than that under the oxy-coal dry recycled combustion. The results indicated that H2O and CO2 showed a competitive effect on NO emissions, though both of them have positive effect on NO reduction. In order to investigate the effects of H2O/CO2 on recycled NO, oxy-coal combustion experiments were also performed with the initial additio...

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.

This work aimed to investigate effects of inherent alkali and alkaline earth metallic species (AAEMs) on biomass pyrolysis at different temperatures. The yield of CO, H2 and C2H4 was increased and that of CO2 was suppressed with increasing temperature. Increasing temperature could also promote depolymerization and aromatization reactions of active tars, forming heavier polycyclic aromatic hydrocarbons, leading to decrease of tar yields and species diversity. Diverse performance of inherent AAEMs at different temperatures significantly affected the distribution of pyrolysis products. The presence of inherent AAEMs promoted water-gas shift reaction, and enhanced the yield of H2 and CO2. Additionally, inherent AAEMs not only promoted breakage and decarboxylation/decarbonylation reaction of thermally labile hetero atoms of the tar but also enhanced thermal decomposing of heavier aromatics. Inherent AAEMs could also significantly enhance the decomposition of levoglucosan, and alkaline earth metals showed greater effect than alkali metals.

Abstract Heavy components (molecular weight > 200 Da) in bio-oil affect the thermal conversion of bio-oil significantly. The inherent alkali/alkaline earth metal species (AAEMs) in biomass affect the formation of heavy components in bio-oil due to its catalytic effects. In order to investigate the effects of AAEMs on the formation of heavy components in bio-oil during biomass pyrolysis, the heavy components in bio-oil were characterized with the Fourier transform ion cyclotron resonance mass (FT-ICR MS) spectrometer and the ultraviolet fluorescence (UV-F) spectroscopy. The roles of K and Ca were also investigated. The results showed that AAEMs promoted the breakage of active oxygen-containing functional groups in heavy phenolics and inhibited their formation during pyrolysis, as well as the formation of heavy carbohydrates. The total content of heavy components decreased due to the catalytic effects of AAEMs. The catalytic effects of K on the decomposition of large molecular weight compounds (> 500 Da) in heavy components were stronger than those of Ca. K increased the content of single ring aromatic components in bio-oil for 1.5 times, while Ca decreased the content of the 2–3 rings aromatic components in bio-oil for more than 50%, compared to the bio-oil generated from the pyrolysis without AAEMs.

Investigating the release characteristics of alkali and alkaline earth metallic species (AAEMs) is of potential interest because of AAEM's possible useful service as catalysts in biomass thermal conversion. In this study, three kinds of typical Chinese biomass were selected to pyrolyse and their chars were subsequently steam gasified in a designed quartz fixed-bed reactor to investigate the release characteristics of alkali and alkaline earth metallic species (AAEMs). The results indicate that 53-76% of alkali metal and 27-40% of alkaline earth metal release in pyrolysis process, as well as 12-34% of alkali metal and 12-16% of alkaline earth metal evaporate in char gasification process, and temperature is not the only factor to impact AAEMs emission. The releasing characteristics of AAEMs during pyrolysis and char gasification process of three kinds of biomass were discussed in this paper.

Abstract The evolution mechanism and energy conversion of volatile in low-rank coal with pyrolysis temperatures still remain uncertain. The experimental results on gas products and light tar pyrolyzed from Shenfu coal at various pyrolysis temperatures reflect the complex correlation between volatiles and coal structure affected by temperatures. Thermodynamic competitive evolution towards CO from oxygen-containing structures are analyzed by density functional theory. The formation mechanisms of polycyclic aromatic hydrocarbons (PAHs) from by-product cyclopentadienyl through Diels-Alder reaction and C–H β-scission are confirmed at the CBS-QB3//M06–2X/def2-TZVP level of theory. Kinetic rate coefficients of the rate-limiting step are computed. Thermodynamic and kinetic calculation results indicate that phenols pyrolysis have to cross a higher energy barrier. Moreover, cyclopentadienyl thermodynamically tends to form indene at 645 °C, while forming PAHs such as naphthalene, even fluorene, phenanthrene, and anthracene at 855 °C, which is consistent with the experimental results. A hydrogen-rich environment can kinetically facilitate the formation of PAHs.

Char gasification reactivity was considered to be proportional to the number of active sites in the char. Therefore, in this study, char surface active sites (including carbon active sites and catalytic active sites) were first measured with the help of the chemisorption process of CO2 at 300 °C, using a thermogravimetric apparatus. It was found that strong chemisorption (Cstr) and weak chemisorption (Cwea) of CO2, which relate to the presence of active inorganic components and organic matter of char, respectively, existed in this reaction procedure. A higher pyrolysis temperature and slower heating rate induced a decrease of both Cstr and Cwea. Then, char structure evolution was systematically investigated with multi-techniques, such as N2 adsorption isotherm, elemental composition, X-ray diffraction (XRD), Fourier transform infrared (FTIR) spectroscopy, and energy-dispersive spectrometry (EDS) analysis, and attempts were made to correlate the measured structure parameters with CO2 chemisorption paramete...

Abstract Pyrolysis of agricultural residues (maize stalk, rice straw and cotton straw) was studied using a thermogravimetric (TG) analyzer and a laboratory scale fixed bed coupled with Fourier transform infrared (FTIR) analyzer. Pyrolysis characteristics of three materials were discussed. The characteristic parameters were determined for the main devolatilization step. Maize stalk showed the highest thermal reactivity, followed by cotton straw and rice straw. Their pyrolysis processes underwent three consecutive stages, corresponding to the evaporation of water, the formation of primary volatiles and the subsequent release of small molecular gases. In order to further study the pyrolysis mechanisms of agricultural wastes, the release of the main volatile and gaseous products were on-line detected by FTIR spectroscopy. The results showed that the major pyrolysis gases for the three materials were similar, including CO 2 , CO, methane, ethane, ethylene and some organics such as methanol, formaldehyde, formic acid and acetone. HCN was the major nitrogen containing product. At higher temperatures several small molecular gases, such as CO 2 , CO and methane, could still be monitored.