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.

Investigation on the co-combustion characteristics of multiple biomass and coal under O2/CO2 condition and the interaction between different biomass.

The co-combustion of coal and biomass in O2/CO2 conditions is a promising technology for CO2 capture and waste disposal. Little attention has been paid to the interaction between different biomass in co-combustion process, which is of great significance to the study of the co-combustion mechanism. The co-combustion behavior of coal and multiple biomass under isothermal conditions was characterized by thermogravimetric method, and the interaction between different biomass was investigated from the perspective of thermogravimetric and proximate analysis. It found that biomass blending could remarkably improve the combustion performance of coal. Compared to the theoretical prediction, the interaction between coal and biomass showed remarkably promoting effects when the coal was blended with different biomass. While the interaction between different biomass was weak. Moreover, the influence of proximate analysis on combustion characteristic parameters was studied by establishing the linear relationship between combustion characteristic parameters and proximate analysis. The effects of proximate analysis on characteristic time/S were divided into five categories, and it were mainly controlled by the interaction both between coal with biomass and between different biomass.

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.

Catalytic characteristics of a Ni-MgO/HZSM-5 catalyst for steam reforming of toluene.

Steam reforming is a potential technology for the conversion of biomass pyrolysis tar into gaseous products. In this study, HZSM-5 was selected as the nickel-based catalyst support and toluene was chosen as the tar model compound. Ni was replaced with MgO to improve the coking resistance of the catalyst. The effects of Ni and MgO loading on toluene conversion and gaseous product generation rate were investigated. The low Ni-loading Ni/HZSM-5 catalyst exhibited poor catalytic activity, whereas a high Ni-loading catalyst displayed poor coking resistance. The addition of the MgO promoter enhanced the steam reforming performance of the Ni/HZSM-5 catalyst with a low loading of active metal Ni (3 wt%). The optimal MgO loading was found at 6 wt%. By characterizing the catalyst before and after the reaction, we found that MgO would enter the wall and pores of the support, resulting in increased pore size and decreased specific surface area. Ni and MgO were combined to form NiO-MgO solid solution active centers, which enhanced the catalytic reforming performance. Moreover, more MgO loading increased the alkaline strength of the catalytic surface, enhanced the adsorption of CO2, and improved the resistance to carbon deposition. This study revealed the feasibility of replacing Ni with MgO and the potential mechanism of maintaining similar catalytic performance. This study also laid the theoretical foundation for the industrial application of nickel-based catalysts.

Removal of methylene blue from aqueous solution by cattle manure-derived low temperature biochar.

Biochar is a low cost and renewable adsorbent which can be used to remove dye from wastewater. Cattle manure-derived low temperature biochar (CMB) was studied to remove methylene blue (MB) from aqueous solution in this paper. The effect of factors including initial concentration of MB, dosage, contact time, and pH on the adsorption properties of MB onto biochar were studied. Characterization of the CMB and MB adsorbed on CMB was performed using techniques including BET, FTIR and SEM. The adsorption isotherm, kinetics, thermodynamics and mechanism were also studied. The results showed the equilibrium data were well fitted to the Langmuir isotherm model, and the saturation adsorption capacity of CMB200 was 241.99 mg g-1. Pseudo-second order kinetics was the most suitable model for describing the adsorption of MB onto biochar. The adsorption thermodynamics of MB on biochar showed that the adsorption was a spontaneous and endothermic process. Through zeta potential measurement, Boehm titration, cation exchange, deashing and esterification experiments, the importance of ash to adsorption was verified, as well as the adsorption mechanism. The adsorption mechanism of MB on CMB200 involved cation exchange, electrostatic interaction, hydrogen bonding, physical effects and others. This work shows that CMB200 holds promise to act as an effective adsorbent to remove MB in wastewater.

Effect of alkali and alkaline earth metal species on the combustion characteristics of cattle manures.

This study investigates the effects of alkali and alkaline earth metal (AAEM) species on the combustion characteristics of cattle manures (CM). Different AAEM species (K, Na, Ca, and Mg) were mixed with CM and deashing CM (D-CM) samples. The combustion characteristics of raw and char samples were compared. The effects of AAEM species on CM char were analyzed based on the structural characteristics of the char sample. Results show that K and Na exert a positive effect, and this effect varies depending on the addition amount. Ca and Mg also exhibit a positive effect, but this effect does not change with the addition amount. The positive effect of K, Na, and Ca is related to the decrease in graphitization degree and increase in specific surface area. However, the positive effect of Mg is negligible. In conclusion, CM can be mixed with fuels containing K or Na in an appropriate ratio. The amount of Ca to be mixed with fuels has no specific requirement, whereas that of Mg to be mixed with fuels should be controlled.