• Energy Research

Abstract The pyrolysis-catalytic upgrading of vulcanized rubbers with metal modified zeolites were performed in order to improve oil quality and decrease sulfur content in pyrolytic oils simultaneously. Three vulcanized rubbers were synthesized by incorporating sulfur into natural rubber (NR), butadiene rubber (BR) and styrene-butadiene rubber (SBR) respectively. The catalysts of Cu/HZSM-5, Zn/HZSM-5, Cu/MCM-41 and Zn/MCM-41 were prepared using the incipient wetness impregnation method and were characterized by various means. TPD-NH3 indicated that the incorporation of Cu and Zn changed the density and strength of acid sites. Strong acidic sites were formed in Cu modified zeolites due to the occurrence of copper crystallization, which was also evidenced by XRD analysis. Due to the high dehydrogenation activity of the Lewis acidic sites introduced by the transition metals, the incorporation of Zn and Cu increased gas yields and markedly enhanced H2 formation at the expense of liquid products. GC-MS analysis showed that the catalysts can effectively reduce the polar aromatics content in pyrolytic oils. The lowest contents of polar aromatics in oils were obtained using Cu/ZSM-5, whilst the Zn/MCM-41 catalyst showed the highest selectivity towards monocyclic aromatic hydrocarbons. Zeolites can promote the decomposition of sulfur-containing components in the liquid phase into gaseous products, which was enhanced by the incorporation of metals. The catalysts modified with Zn had a better removal efficiency of sulfur-containing components. XPS analysis indicated that the Cu and Zn modified catalysts achieved desulfurization by reacting with sulfur in pyrolytic volatiles to form stable CuS or ZnS.

Abstract This work investigates the effect of temperature and particle size on the product yields and structure of chars obtained from the pyrolysis of Beechwood Chips (BWC), a lignocellulosic biomass. BWC of three different size fractions (0.21–0.50 mm, 0.85–1.70 mm and 2.06–3.15 mm) were pyrolyzed at atmospheric pressure and temperatures ranging from 300 to 900 °C in a fixed bed reactor. Tar and gas yields increased with increasing temperature, while char yield decreased, particularly between 300 and 450 °C. The effect of particle size was mostly observed at temperatures lower than 400 °C as a larger char yield for larger particles due to intraparticle reactions. At higher temperatures the larger surface area in the char fixed bed favoured reactions increasing char and gas yields from the smaller particles. Pyrolysis chars were characterized using Fourier transform infrared spectroscopy (FTIR), X-ray diffraction (XRD) and Raman spectroscopy. Loss in oxygenated functional groups and aliphatic side chains with increasing temperature was revealed, along with an increase in the concentration of large aromatic systems, leading to a more ordered char structure but no significant graphitization. The changes in char nature at high temperature led to a loss in their combustion reactivity. Raman spectra indicated that the temperature needed to completely decompose the cellulose structure increased with biomass particle size and the enhanced intraparticle reactions in pyrolysis of large particles was likely to give rise to amorphous carbon structures with small fused ring systems.

In this work, ReaxFF molecular simulations were performed to study the pyrolysis behavior of chemical cross-linked natural rubber (NR) under non-isothermal and isothermal conditions. Three different sulfur vulcanized NR models were established and simulated to study the effect of inner sulfur structure on NR decomposition behavior and sulfur evolution in comparison with carbon cross-linked structure. To understand the NR decomposition with temperatures, the non-isothermal simulations were performed between 300 and 3800 K at a 50 K ps-1 heating rate. The results reveal that the decomposition process can be classified into four stages: 1) Structure adjustment; 2) Decomposition of the main carbon chains; 3) Secondary decomposition of heavy tar; and 4) Deep decomposition of light tar. Based on the results of non-isothermal pyrolysis, four different temperatures were selected for the isothermal simulations. Compared with carbon cross-linked NR, sulfur cross-linked structures facilitate the generation of C2H4 and C4H6 in the gas phase at low temperatures. At higher temperatures, more heavy tar is generated. Regarding the sulfur evolution, the sulfur-containing products mainly include H2S, thiophene, sulfide, and thiol. The distribution of sulfur-containing products with temperatures follows the similar pattern with the product distribution of main compounds. At higher temperatures, most sulfur exists in the form of thiophene compounds. In particular, the structure with single CS cross-links facilitates the generation of H2S at low temperatures. The results of this work provide insight into the sulfur transformation and pyrolysis behavior of vulcanized NR.

Elemental mercury (Hg0) emitted from coal-fired power plants and municipal solid waste (MSW) incinerators has caused great harm to the environment and human beings. The strong oxidized •OH radicals produced by UV/H2O2 advanced oxidation processes were studied to investigate the performance of Hg0 removal from simulated flue gases. The results showed that when H2O2 concentration was 1.0 mol/L and the solution pH value was 4.1, the UV/H2O2 system had the highest Hg0 removal efficiency. The optimal reaction temperature was approximately 50 °C and Hg0 removal was inhibited when the temperature was higher or lower. The yield of •OH radicals during UV/H2O2 reaction was studied by electron paramagnetic resonance (EPR) analysis. UV radiation was the determining factor to remove Hg0 in UV/H2O2 system due to •OH generation during H2O2 decomposition. SO2 had little influence on Hg0 removal whereas NO had an inhibitory effect on Hg0 removal. The detailed findings for Hg0 removal reactions over UV/H2O2 make it an attractive method for mercury control from flue gases.

Abstract The three primary lignocellulosic biomass components (cellulose, xylan and lignin), synthetic biomass samples (prepared by mixing the three primary components) and lignocellulosic biomass (oak, spruce and pine) were pyrolysed in a thermogravimetric analyser and a wire mesh reactor. Different reactivities were observed between the three biomass components. Cellulose mainly produced condensables and was less dependent on heating rate, while xylan and lignin contributed most char yields and were significantly affected by heating rate. While xylan and lignin pyrolysed over a large temperature range and showed the behaviour characteristic of solid fuels, cellulose decomposition is sharp in a narrow temperature range, a behaviour typical of linear polymers. Comparison of the pyrolysis behaviour of individual components with that of their synthetic mixtures showed that interactions between cellulose and the other two components take place, but no interaction was found between xylan and lignin. No obvious interaction occurred for synthetic mixtures and lignocellulosic biomass at 325 °C, before the beginning of cellulose pyrolysis, in slow and high heating rate. At higher pyrolysis temperatures, more char was obtained for synthetic mixtures containing cellulose compared to the estimated value based on the individual components and their proportions in the mixture. For lignocellulosic biomass, less char and more tar were obtained than predicted from the components, which may be associated with the morphology of samples. The porous structure of lignocellulosic biomass provided a release route for pyrolysis vapours.

Dry reforming of ethanol and glycerol using CO2 are promising technologies for H2 production while mitigating CO2 emission. Current studies mainly focused on steam reforming technology, while dry reforming has been typically less studied. Nevertheless, the urgent problem of CO2 emissions directly linked to global warming has sparked a renewed interest on the catalysis community to pursue dry reforming routes. Indeed, dry reforming represents a straightforward route to utilize CO2 while producing added value products such as syngas or hydrogen. In the absence of catalysts, the direct decomposition for H2 production is less efficient. In this mini-review, ethanol and glycerol dry reforming processes have been discussed including their mechanistic aspects and strategies for catalysts successful design. The effect of support and promoters is addressed for better elucidating the catalytic mechanism of dry reforming of ethanol and glycerol. Activity and stability of state-of-the-art catalysts are comprehensively discussed in this review along with challenges and future opportunities to further develop the dry reforming routes as viable CO2 utilization alternatives.