Recent advances during CH4 dry reforming for syngas production: A mini review

Given the continuing issues of environment and energy, methane dry reforming for syngas production have sparked interest among researchers, but struggled with the process immaturity owing to catalyst deactivation. This review summarizes the recent advances in the development of efficient and stable catalysts with strong resistance to coking and metal sintering, including the application of novel materials, the assessment of advanced characterizations and the compatibility to improved reaction system. One feasible option is the crystalline oxide catalysts (perovskite, pyrochlore, spinel and LDHs), which feature a fine metal dispersion and surface confinement effect via a metal exsolution strategy and exhibit superior reactivity and stability. Some new materials (h-BN, clays and MOFs) also extend the option because of their unique morphology and microstructure. It also is elaborated that progresses were achieved in advanced characterizations application, leading to success in the establishment of reaction mechanisms and attributions to the formed robust catalysts. In addition, the perspective described the upgrade of reaction system to a higher reaction efficiency and milder reaction conditions. The combination of efficient reaction systems and robust catalysts paves a way for a scaling-up application of the process.     

Study on single and binary catalytic systems of pyridine-imine catalysts based on nickel and iron in synthesis of reactor blends and low-density polyethylene nanocomposites

In the presence of modified methylaluminoxane as cocatalyst, the behavior of a binary catalytic system based on pyridine-imine nickel ( N ) and iron ( F ) catalysts was evaluated in order to reach a proper mixture of polyethylene (PE). A computational study along with kinetic profile suggested that the catalyst F with higher electron affinity (A) and electrophilicity (ω) in the methyl cationic active center and stronger interaction with the monomer led to high integrated monomer consumption and higher activity. In addition, the samples produced by the mixture of catalysts showed a higher value of [19.4 × 10⁴ g (PE) mol (Fe+Ni)⁻¹ h⁻¹)], melting point (127.8 °C), and crystallinity extent (41.29%) than the samples produced by the single catalysts. The addition of multiwalled carbon nanotubes (MWCNT) into the polymerization media reduced the activity of catalysts [from 7.50 × 10⁴ to 0.66 × 10⁴ g (PE) mol (Fe+Ni)⁻¹ h⁻¹] and the thermal properties of the low-density polyethylene nanocomposite samples. However, the sample containing 2.33% MWCNT_20-30 improved the total thermal stability of the neat polyethylene blend up to 400 °C. Scanning electron microscope images of the samples demonstrated irregular to virtually uniform morphologies were obtained through the in situ and solution-mixing techniques. © 2019 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2019 , 136, 47376.     

Magnetic porous nano-carbon catalysts supported silver nanoparticles derived from chitin and their application in catalytic reduction reactions

The exploitation of recycled carbonaceous catalysts from renewable biomass resources such as chitin is a crucial issue for the development of the sustainable society. In this article, the chitin-based N and O doped carbon microspheres (ChC) were fabricated by a simple dissolution, sol–gel transformation, and the carbonization methods. Subsequently, the novel magnetic Ag-Fe₃O₄@chitin-based carbon microspheres catalyst (MChC) was successfully constructed through the in situ redox reaction. The as-prepared MChC possessed rich micropores with high-surface area, and a narrow size distribution (50–120 μm). The Ag-Fe₃O₄ nanoparticles were immobilized through the interaction with C, N, and O atoms in the pores of MChC. The reduction of 4-nitrophenol was applied to evaluate the catalytic activity of MChC. 4-Nitrophenol (4-NP) could be fully reduced to 4-aminophenol (4-AP) in 5 min with the catalyst MChC-45. Moreover, MChC could be collected in solution with an external magnet in 8 s and remained relatively high-catalytic activity after 10 cycle times. This work provided novel ideas for the fabrication of doped carbon material from biomass and promoted its utilization in nanocatalytic applications.     

Hydrogen production via ammonia decomposition catalyzed by Ni/M–Mo–N (M = Ni,Co) bimetallic nitrides

This study demonstrates the significant improvement in NH₃ decomposition using Ni-decorated M–Mo–N-based catalysts (M = Co and Ni) compared with conventional catalysts. Catalysts are prepared using a mixture of the corresponding metal salts and hexamethylenetetramine, and the impregnation method is used to decorate the Ni-particles on the catalysts. Among all the samples, 10 wt% Ni-decorated Co₃Mo₃N exhibits the highest NH₃ conversion rate (71%) at 500 °C, and the performance remains stable for 30 h of long-term testing. According to the gas chromatography measurements, the H₂/N₂ ratio is approximately 3 in all cases, which is consistent with the theoretical value. X-ray photoelectron spectroscopy results show that Co₃Mo₃N possesses the highest NH₃ conversion efficiency because of the weaker binding energy of Mo–N. Furthermore, Co₃Mo₃N exhibits a stronger Lewis acidity and higher NH₃ decomposition, which is attributed to the easy breaking of the N–H bond on the Co₃Mo₃N surface.     

聚乙烯催化剂用烷氧基镁载体的研究进展

基于烷氧基镁载体的Ziegler-Natta聚乙烯催化剂具有活性高、氢调性能好等优点,是目前聚烯烃工业中的研究热点。介绍了烷氧基镁载体的发展进程,综述了烷氧基镁载体的制备及改进方法,分析了烷氧基镁载体在催化剂制备过程中的作用,并对开发适用于乙烯聚合的烷氧基镁载体提出了展望。     

不同晶相结构ZrO2负载铜基催化剂用于二乙醇胺脱氢反应

通过制备不同晶相结构〔单斜相(m-ZrO_2)、四方相(t-ZrO_2)和无定型(a-ZrO_2)〕ZrO_2载体,再通过沉积沉淀法制得Cu/m-ZrO_2、Cu/t-ZrO_2和Cu/a-ZrO_2催化剂,分别用于催化二乙醇胺脱氢合成亚氨基二乙酸反应。采用XRD、氮气物理吸附脱附、XPS、H_2-TPR、CO_2-TPD对催化剂的结构进行了表征。结果表明,Cu/m-ZrO_2催化剂界面更加有利于Cu~+/Cu~0稳定存在,具有更多的碱性位点,且抗氧化性较好。在二乙醇胺脱氢反应中,Cu/m-ZrO_2催化剂性能最好,反应时间为2.5 h,亚氨基二乙酸收率为97.64%。     

渣油催化临氢热转化钼铁双金属催化剂的研究

Replacement of precious single metal catalysts with cost-effective, highly-dispersed composite catalysts for catalytic hydrothermal conversion of residue holds tremendous promise for the residue upgrading technologies. Organic metals were added to the feed as the oil-soluble precursors, and transformed into the catalytic active phases in this work. Physical properties and structures of the composite catalysts had been investigated by X-ray fluorescence spectroscopy, X-ray photoelectron spectroscopy, X-ray diffraction, scanning electron microscope and transmission electron microscopy. The composite catalysts were found to be highly efficient in the catalytic hydrothermal conversion of both model compound and residue. Increased metal dispersion and synergistic effects of two metals played indispensable roles in such catalytic system. Results showed that under the test conditions in the article, the catalyst had the best catalytic performance when the mass ratio of molybdenum to iron was 1.5.     

酸改性CoPd/TiO2催化CH4-CO2直接合成C2含氧化合物

采用酸处理方法对CoPd/TiO₂催化剂进行改性，并将酸改性催化剂用于温和条件下CH₄-CO₂梯阶转化直接合成C₂含氧化合物（乙酸和乙醇）的反应。在150～300℃考察了浸酸方式和不同种类酸处理对催化剂活性和选择性的影响。采用X射线衍射（XRD）、X射线光电子能谱（XPS）、NH₃程序升温脱附（NH₃-TPD）和N₂吸附对催化剂进行了表征。结果表明，酸改性明显提高了CoPd/TiO₂上C₂含氧化合物的生成速率和选择性。浸酸方式对催化剂性能和结构有显著影响，先用酸浸渍载体然后再浸渍活性金属所得催化剂具有更高的活性。在H₃PO₄、HNO₃和HCl中，H₃PO₄浸渍的催化剂活性最佳，在150℃时C₂含氧化合物（乙酸和乙醇）的生成速率为3365 μg/(g·h)，选择性达到91%。     

Study of the effect of noble metal promotion in Ni-based catalyst for the Sabatier reaction

This paper reports the preparation and the evaluation of the performance of Ni-based powder catalysts with low nickel loading on the CO2 methanation reaction, that is an integral part of the power-to-gas (PtG) technology. CeO₂, CeZrO₄ and CeO₂/SiO₂ were selected as possible supports, and the results of this first screening pointed out that 10%Ni/CeO₂ catalyst could offer the best reaction performances because of ceria's peculiar characteristics. Moreover, the promotion of this promising formulation with the addition of a small amount of noble metals (Pt, Ru, Rh) was investigated, showing that platinum in particular can enhance the catalyst performances. A further study related to the noble metal loading pointed out that platinum and ruthenium have a different optimum loading condition: this result, together with the activity tests performed on monometallic formulations with only the noble metal, suggested that the two metals are able to catalyse two different reactions, thus promoting two different reaction mechanisms.