Study on the mechanism of carbon nanotube-like carbon deposition in tar catalytic reforming over Ni-based catalysts.

The use of Ni-based catalysts is a common method for eliminating tar through catalytic cracking. Carbon deposition is the main cause of deactivation in Ni/ZSM-5 catalysts, with filamentous MWCNTs being the primary form of carbon deposits. This study investigates the formation and evolution of CNTs during the catalytic process of biomass tar to explore the mechanism behind carbon deposition. The effect of the 9Ni/10MWCNTs/81ZSM-5 on toluene reforming was investigated through a vertical furnace. Gases produced by tar catalysis were evaluated through GC analysis. The physicochemical structure, properties and catalytic performance of the catalyst were also tested. TG analysis was used to assess the accumulation and oxidation reactivity of carbon on the catalyst surface. An analysis was conducted on the mechanism of carbon deposition during catalyst deactivation in tar catalysis. The results showed that the 9Ni/91ZSM-5 had a superior toluene conversion of 60.49%, but also experienced rapid and substantial carbon deposition up to 52.69%. Carbon is mainly deposited as curved filaments on both the surface and pore channels of the catalyst. In some cases, tip growth occurs where both carbon deposition and Ni coexist. Furthermore, specific surface area and micropore volume are reduced to varying degrees due to carbon deposition. With the time increased, the amount of carbon deposited on the catalyst surface increased to 62.81%, which gradually approached saturation, and the overall performance of the catalyst was stabilized. This situation causes toluene molecules to detach from the active sites within the catalyst, hindering gas release, which leads to reduced catalytic activity and further carbon deposition. It provides both a basis for the development of new catalysts and an economically feasible solution for practical tar reduction and removal.

Catalytic mechanism of N-containing biochar on volatile-biochar interaction for the same origin pyrolysis.

Nitrogen, as a common element, is widely present in biomass. The effects of nitrogenous substances on the same origin pyrolysis of biomass and the consequences of N-containing biochar on the catalytic process of volatiles are important for further analyzing the pyrolysis mechanism of biomass. In this research, N-containing biochar was prepared under different conditions, and the interaction between N-containing biochar and biomass pyrolysis volatiles at 400-700 °C was studied. The results show that N-containing biochar can simultaneously participate in reactions as adsorbents, catalysts, and reactants. Its catalytic effect is obviously different for various N configurations. Pyridinic N and pyrrolic N can promote the cracking of lignin into methoxy phenol compounds and promote the further cracking of 5-hydroxymethylfurfural. Graphitic N and oxidized N can promote the further decomposition of phenol and the conversion of D-xylose into small-molecule ketones. In addition, oxidized N can also inhibit the cracking of lignin to produce guaiacol. In the long-term interaction, the highly active pyridinic N tends to convert to a more stable graphitic N.

Preparation and formation mechanism of biomass-based graphite carbon catalyzed by iron nitrate under a low-temperature condition.

Graphite is a widely used industrial material, which experienced a marked shortage caused by the growing demand for electrode anode material and the increased costs for raw material. Graphitic carbon from biomass is a promising approach that will result in low-cost and efficient preparation. Herein, Fe(NO3)3 was selected as the catalyst for pine sawdust, and the effects of temperature and iron content on the graphitization of biochar were investigated. Additionally, the formation mechanism of the graphitic crystallite structure was explored. Results showed that the formation of pyrolysis gas increased with the increase in the amount of catalyst added or pyrolysis temperature. The change in pyrolysis gas, such as H2 and CO, was a critical auxiliary factor reflecting the conversion process. As temperature was increased from 600 °C to 800 °C, the solid products showed high graphitization and low solid yield. Graphite structure mainly formed at 700 °C because of the formation of Fe nanoparticles. The increase in the amount of catalyst could provide more reaction sites and promote the contact between Fe and C, showing that amorphous carbon is dissolved on Fe nanoparticles and precipitated into ordered graphitic carbon. On this basis, a mechanism of "carbon dissolution-precipitation" was proposed to explain the formation of graphite structure, and the whole pyrolysis process included the transformation of the iron element were analyzed.