Directly synthesising dimethyl ether (DME) from CO2 hydrogenation is a promising technique for efficiently utilising CO2 as a feedstock to produce clean fuel. The main challenges in this process are the low CO2 conversion and DME selectivity of the catalyst and its deactivation over time due to sintering, aggregation, coke formation, and water adsorption. This study aimed to develop a dual-functional, halloysite nanotube-supported CuZnO-PTA catalyst with a core-shell structure and investigate the effects of the active site mass ratio CuZnO/PTA on CO2 conversion and DME selectivity. A dual-functional core-shell mesopores halloysite nanotube (HNT) catalyst was developed, and both active sites were co-hosted on one support. The co-impregnation method was used to synthesise CuZnO and 12-phosphotungstic acids (PTA) that were then supported by a mesoporous core-shell (HNT). BET surface area, N2 physisorption, FE-SEM, SEM, XRD, H2-TPR, and NH3-TPD of the core-shell catalyst characterised physio-chemical properties of the prepared hybrid catalyst. The experimental results showed that the synthesised CuZn-PTA@HNT core-shell bifunctional catalyst was promising; the CO2 conversion was almost the same for all four catalysts, with an average of 22.17%, while the DME selectivity reached 68.9%. Furthermore, the effect of both active sites on the hybrid catalyst was studied, and the metal Cu wt% mass ratio loading was not significant. In contrast, the PTA acid sites positively affected DME selectivity; they also showed an excellent tolerance towards the water generated in the methanol dehydration reaction. In addition, the effect of the temperature and reusability of the CZ-PTA@HNT catalyst has also been investigated, and the results show that increasing the temperature improves CO2 conversion but decreases DME selectivity. A temperature of less than 305 °C is a good compromise between CO2 conversion and DME selectivity, and the catalyst also showed good stability and continuous activity/stability over five consecutive cycles. In conclusion, this study presents a novel approach of using a core-shell halloysite nanotube-supported CuZnO-PTA catalyst to directly synthesise dimethyl ether (DME) from CO2 hydrogenation which exhibits promising results in terms of CO2 conversion and DME selectivity.
Tar formation during biomass gasification is a major barrier to utilise the produced syngas, which clogs processing equipment. In the present study, steam reforming of gasification-derived tar (phenol, toluene, naphthalene, and pyrene) was catalysed by Ni/dolomite, Ni/dolomite/Al2O3, Ni/dolomite/La2O3, Ni/dolomite/CeO2, and Ni/dolomite/ZrO2 for hydrogen production. The steam reforming experiment was conducted in a fixed bed reactor at 700 °C and the steam-to-carbon molar ratio of 1 under atmospheric pressure. After the catalytic test, the spent catalysts were characterised by thermogravimetric analysis and variable-pressure scanning electron microscope. The aim of this study is to investigate the catalytic activity of Ni-based catalysts in terms of tar conversion and their deactivation characteristic. The current results revealed that all the catalysts showed almost full conversion of tar (98.8%-99.9%) and considerably low amount of coke deposited in the form of amorphous and filamentous carbon (15.9-178.5 mg gcat-1). Among the catalysts studied, Ni/dolomite/La2O3 gave the highest catalytic activity for steam reforming of gasified biomass tar and lowest coke formation.
Torrefaction of pelletised oil palm empty fruit bunches (OPEFBs) is a promising pretreatment technique for improving its solid biofuel properties and energy recovery potential. Therefore, this paper investigates the torrefaction of OPEFB pellets to examine the effects of temperature and purge gas flow rate on mass yield (MY), energy yield (EY), and mass loss (ML). The results revealed that MY and EY decreased due to significant ML during torrefaction. Furthermore, significant improvements in the higher heating value (HHV) and energy density (DE) were observed. The torrefaction temperature increased liquid (tar) and gas yields mainly above 300 °C at the expense of solid products. However, the effect of purge gas flow rate on the torrefaction products was found to be negligible. Consequently, the torrefaction of OPEFB pellets were limited to 250-300 °C, 30 min, and nitrogen (N2) gas flow rate of 200 ml min-1.
H2 production can be used as a clean and renewable energy source for various applications, including fuel cells, internal combustion engines, and chemical production. Using nickel-based catalysts for steam reforming biomass tar presents challenges related to catalyst deactivation, poisoning, heterogeneous composition, high process temperatures, and gas impurities. To overcome these challenges, adopting a nickel-based catalyst with selected oxide support and MgO and CaO promoter is a promising approach for improving the efficiency and sustainability of steam reforming for hydrogen production. The majority of studies conducted to date have focused on the steam reforming of particular tar compounds, most commonly benzene, phenol, toluene, or naphthalene, over a range of support catalysts. However, the actual biomass tar composition is complex, and each component impacts how well steam reforming works. In this research, a multi-compound biomass tar model including phenol, toluene, naphthalene, and pyrene underwent a steam reforming process. Various types with 10 wt.% of nickel-based catalysts were generated by the co-impregnation technique, which included 90 wt.% different oxide supports (Al2O3, La2O3, and ZrO2) and 10 wt.% of combination alkaline oxide earth promoters (MgO and CaO). Thermogravimetric analysis, Brunauer–Emmett–Teller (BET) method, N2 physisorption, temperature-programmed reduction (H2-TPR), temperature-programmed desorption (CO2-TPD), and X-ray diffraction (XRD) of ni-based catalyst characterized physiochemical properties of the prepared catalyst. The reaction temperature used for steam reforming was 800 °C, an S/C ratio of 1, and a GHSV of 13,500 h−1. Ni/La2O3/MgO/CaO (NiLaMgCa) produced the most carbon to-gas conversion (86.27 mol%) and H2 yield (51.58 mol%) after 5 h of reaction compared to other catalysts tested in this study. Additionally, the filamentous carbon coke deposited on the spent catalyst of NiLaMgCa does not impact the catalyst activity. NiLaMgCa was the best catalyst compared to other catalysts investigated, exhibiting a stable and high catalytic performance in the steam reforming of gasified biomass tar. In conclusion, this study presents a novel approach by adding a combination of MgO and CaO promoters to a ni-based catalyst with various oxide supports, strengthening the metal-support interaction and improving the acid-base balance of the catalyst surface. The mesoporous structure and active phase (metallic Ni) were successfully developed. This can lead to an increase in the conversion of tar to H2 yield gas and a decrease in the production of undesired byproducts, such as CH4 and CO.
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