Methanol Synthesis with Steel Mill Gases: Performance Investigations in an On-Site Technical Center

An on-site laboratory with direct access to cleaned and conditioned steel mill gases was recently put into operation. The long-term performance and stability of Clariant's MegaMax®800 methanol synthesis catalyst utilizing steel mill gases is currently being investigated. First test results revealed that in order to investigate deactivation mechanisms arising from particular properties of the cleaned steel mill gases, the overlaying effect of thermal deactivation of the catalyst has to be minimized.     

Potassium titanate whiskers on the walls of cordierite honeycomb ceramics for soot catalytic combustion

In this paper, potassium titanate whiskers was prepared via the Molten salt synthesis on the surface of cordierite ceramics for the regeneration of diesel particulate filters (DPFs). SEM, EDS, XRD, FT-IR, TG-DSC and TPO were carried out to characterize the morphology, microstructure, growth mechanism and catalytic performance of the samples. Potassium titanate whiskers with diameter (100–500 nm) and length (about 3 μm) is tightly combined with the cordierite ceramic substrate. The catalyst performance investigation demonstrates that potassium titanate whiskers decrease the soot combustion temperature apparently. The soot combustion process was studied by thermal analysis tests, and the activation energy of the combustion reaction can be calculated using Freeman-Carroll method. The carbon oxidation activation energy is 14.009 kcal/mol, and the activation energy for the catalytic reaction with potassium titanate whiskers is 6.287 kcal/mol, it can be illustrated that potassium titanate whiskers/cordierite catalyst possess excellence performance for carbon catalytic combustion. The coarseness of the interface increased because potassium titanate whiskers grew on the cordierite substrate, and the trapping ability could improve. This unique microstructure has potential application in the DPF field.     

Boosting the hydrogenation activity of dibenzyltoluene catalyzed by Mg-based metal hydrides

Hydrogenation of dibenzyltoluene (DBT) is of great significance for the application in liquid organic hydrogen carriers (LOHCs). We successfully develop Mg-based metal hydrides (Mg₂NiH₄, MgH₂, and LaH₃) reactive ball-milling for the hydrogenation of DBT. Mg-based metal hydrides milled with 500 min exhibit the best catalytic activity, the hydrogen uptake of DBT can reach 4.63 wt% at the first 4 h and finally achieve 5.70 wt% through 20 h, which is the first time to use hydrogen storage material as a catalyst for the hydrogenation of DBT. The excellent catalytic hydrogenation performance of Mg-based metal hydrides mostly originates from numerous catalytic activity centers formed at the surfaces of Mg₂NiH₄ nanoparticles in the MgH₂ matrix. Inspired by this mechanism, more general metal hydrides can be explored for catalyzing the hydrogenation of LOHCs. The new application of Mg-based metal hydrides is beneficial to developing efficient LOHC based hydrogen storage systems and offers novel insights to hydride-based catalysts.     

Effect of mesoporous carbon on oxygen reduction reaction activity as cathode catalyst support for proton exchange membrane fuel cell

In this paper, a new carbon support with a large number of mesoporous-structures is selected to prepare Pt/C catalysts. Transmission electron microscope (TEM) results show that the Pt/3# catalyst presents a sponge-like morphology, Pt particles are not only evenly distributed on the surface of carbon support, but also the smaller Pt particles are deposited in the mesoporous inside the support. The average diameter of Pt particles is only 2.8 nm. The membrane electrode assembly (MEA) based on Pt/3# catalyst also shows excellent performance. In conclusion, the 3# support is an idea carbon support for PEMFC, which helps to improve the oxygen reduction reaction (ORR) activity of the catalyst. Based on the “internal-Pt” structure of the support mesoporous, the efficient three-phase boundaries (TPBs) are construct to avoid the poisoning effect of ionomer on the nano-metal particles, reduce the activation impedance and oxygen mass transfer impedance, and improve the reaction efficiency.     

Effect of micro-cracks on the in-plane electronic conductivity of proton exchange membrane fuel cell catalyst layers based on lattice Boltzmann method

Micro-cracks commonly occur on the catalyst layers (CLs) during the manufacturing of catalyst coated membranes (CCMs). However, the crack shape parameters effect on CLs in-plane (IP) electronic conductivity λ_s is not clear. In this work, the relationship between crack parameters and the λ_s is obtained based on the two-dimensional (2D) multiple-relaxation time (MRT) lattice Boltzmann method (LBM). The LBM numerical model is validated by the normalized λ_s experiment applied on three different home-made cracked CLs, and the parameter study focus on crack width, length, quantity and phase angle are carried out. The results show that the decrease of λ_s has different sensitivity |k| to the parameters above. The crack width has little effect on λ_s decrease, and the |k_w| is 0.038. However, crack arm length and quantity show more significant impact, which |k_l| and |k_N| are 0.753 and 0.725, respectively. The CLs with different crack propagation directions show significant anisotropy on λ_s, and a 53.53% decrease in λ_s is observed between 0° and 90° crack phase angle change. To manufacture a high electronic conductivity CL, crack initiation and migration mitigation are highly encouraged.     

Catalytic behavior in CH4 decomposition of catalysts derived from red mud: Impact of residual Na2O

Catalyst samples for CH₄ decomposition were prepared from red mud (RM) by an acid-leaching neutralization precipitation approach. Water-washing the resultant precipitates multiple times, followed by drying at 105 °C and calcination at 500 °C, resulted in a threshold of residual Na₂O, equivalent to 96% Na₂O removal. Drying the precipitate at a higher temperature of 200 °C, followed by repeated water washing, provided a deeper Na₂O removal of 99% and made the resultant samples more active for the targeted reaction. Subsequently, four catalyst samples with a simulated red mud composition and NaOH contents from 0 to 0.3 wt% were prepared and the catalytic test results revealed that the Na₂O remaining in the RM-derived catalysts did not only inhibit their activation in CH₄ but also lower their maximal activities for CH₄ decomposition. Finally, two catalysts with the same simulated red mud composition and their Na impregnated respectively on Fe₂O₃ and a mixture support of Al₂O₃-SiO₂-TiO₂ were prepared and tested to explore the effect of Na distribution on the activation behavior of RM-derived catalysts for CH₄ decomposition. The activity testing results showed that it was the Na residual dispersed on iron oxides in the RM-derived samples to significantly inhibit the activation of CH₄ decomposition.     

Concentration-induced structural diversity and catalytic activity of BF3/n-BuOH complexes for n-decene polymerization

The BF₃/n-BuOH complexes were investigated as active species in catalyzing n-decene polymerization reaction. The structures of BF₃/n-BuOH complexes were characterized not only by modern spectrum but also by calculation at theoretical level. The results confirmed that BF₃/n-BuOH complexes changed from BF₃·(n-BuOH)₂ complexes to BF₃·n-BuOH complexes with the mass fraction of BF₃ increasing. These two complexes have different catalytic activity, but BF₃·n-BuOH was superior. The highest n-decene conversion could reach 99% and the most excellent selectivity of n-decene trimer and tetramer could reach up to 80% yield by a series of controlled conditions. This work can help to understand the catalytic active species of n-decene polymerization and provide support for industrialization of poly-alpha-olefins (PAOs).     

Pore-scale study of effects of different Pt loading reduction schemes on reactive transport processes in catalyst layers of proton exchange membrane fuel cells

Reducing the Platinum (Pt) loading while maintaining the performance is highly desired for promoting the commercial use of proton exchange membrane fuel cells (PEMFCs). Different methods have been adopted to fabricate catalyst layers (CLs) with low Pt loading, including utilizing lower Pt/C catalysts (MA), mixing high Pt/C catalysts with bare carbon black particles (MB), and reducing CL thickness while maintaining high Pt/C ratio (MC). In this study, self-developed pore-scale model is adopted to investigate the performance of the three Pt reduction methods. It is found that MA shows the best performance while MB shows the worst. Then, effects of Pt dispersion are further explored. The results show that denser Pt sites will result in higher local oxygen flux and thus higher local transport resistance. Therefore, MA method, which shows the better Pt dispersion, leads to improved performance. Third, CLs with quasi-realistic structures are investigated. Higher tortuosity resulting from the random pores produces higher bulk resistance along the thickness direction, while MA still exhibits the best performance. Finally, improved CL structures are investigated by designing perforated CL structures. It is found that adding perforations can significantly reduce the bulk transport resistance and can improve the CL performance. It is demonstrated that CL structure plays important roles on performance, and there are still huge potentials to further improve CL performance by increasing Pt dispersion and optimizing CL structures.     

Contributions of oxygen vacancies to the hydrogen evolution catalytic activity of tungsten oxides

The tungsten trioxide attracts less attention due to the low electron transfer kinetics that hinders the interaction of electrons and ions during the hydrogen evolution reaction (HER). But the oxygen vacancy strategy can inspire its electrocatalytic activity for HER because it has a positive effect on improving the charge transfer and compensating for the weak hydrogen adsorption of the tungsten trioxide. By synthesizing a series of substoichiometric tungsten oxides, we reveal the linear relationship between the catalytic activity and the content of oxygen vacancies, which indicates that the oxygen vacancy strategy is an achievable route to enhance the HER for metal oxides.     

Hydrogen production employing Cu(BDC) metal–organic framework support in methanol steam reforming process within monolithic micro-reactors

Cu(BDC) metal–organic framework (MOF) was used as a support for the copper (Cu) catalyst applied in the methanol steam reforming (MSR) process at low temperatures (130–250 °C) with a feed WHSV = 9.2 h^?1 within the monolithic reactor. Also, the effects of diverse promoters were examined on the catalytic activities of the Cu/X–Cu(BDC) (X = Ce, Zn, Gd, Sm, La, Y, Pr) catalysts. Results showed that the Ce/Sm–Cu(BDC) supports exhibited highest activities, lowest reduction temperatures and largest specific surface areas, which caused highest distributions of the active copper metal nanoparticles on the supports. The reactor tests displayed that the activities of Cu/X–Cu(BDC) (X = Ce, Zn, Gd, Sm, La, Y, Pr) catalysts followed the order X = Ce > Sm > Y > La > Pr > Cu(BDC) > Zn > Gd. The highest activities of Ce and Sm containing catalysts were attributed to the presence of CeO₂ and Sm₂O₃ caused the oxygen vacancies on the catalyst surface which had positive effects on the methanol reforming process. The time-on-stream stability tests showed the highest resistance of the Cu/Ce–Cu(BDC) catalyst to the carbon formation during 32 h. Consequently, the Cu/Ce–Cu(BDC) with the highest stability, methanol conversion and carbon monoxide selectivity could be used in practical industrial applications.