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。     

Brönsted方程动力学模型研究ZSM-5催化乙烯齐聚及芳构化活性和酸强度分布之间的定量关系

乙烯催化齐聚和芳构化是烯烃高值化和合成液体燃料的关键过程，采用NH₃-TPD谱图分析计算方法得到的探针分子脱附活化能作为催化剂的酸位点强度分布的参数，结合线性自由能理论在Br?nsted方程中引入酸强度对反应的影响因子γ作为动力学方程参数关联探针分子脱附活化能与反应活化能，明确固体酸酸强度的基准在催化动力学方程中的物理意义。建立同为MFI拓扑结构 Si /Al摩尔比为12.5、19、25、60、70的ZSM-5分子筛催化剂上不同酸强度位和乙烯齐聚及芳构化中氢转移、齐聚、芳构化各单元步骤以及对应的烷烃、低碳烯烃和芳烃产物分布的定量关系。根据拟合得到动力学参数γ可以发现不同强度的酸位点对乙烯齐聚及芳构化具有不同的作用系数。氨脱附活化能(DAE)为90 kJ·mol^-1的酸位点是氢转移反应的主要活性位点，而对于乙烯齐聚反应中主要的活性酸位点为DAE 90 kJ·mol^-1和124 kJ·mol^-1，DAE为150 kJ·mol^-1的酸位点是芳构化反应的主要活性位点。     

脱硫胶粉在乳化改性沥青中的应用

考察了不同规格胶粉及不同脱硫程度的脱硫胶粉对橡胶改性乳化沥青性能的影响,结果表明,采用100目胶粉即可制备出橡胶改性乳化沥青,但乳化沥青的性能较差;采用活化度为50%左右的100目脱硫胶粉制备乳化沥青时,脱硫胶粉的用量相比于胶粉可大幅提高;在通过外掺100目50%左右活化度的脱硫胶粉(质量分数15%,以沥青计,下同)和质量分数2%的苯乙烯-丁二烯-苯乙烯嵌段共聚物改性的乳化沥青中添加质量分数1%的丁苯胶乳,所制备橡胶改性乳化沥青无筛上剩余物,5 d储存稳定性为2.9%,蒸发残留物的25℃针入度、软化点和5℃延度分别为55 (0.1 mm)、64.5℃和22.5 cm,能够满足乳化改性沥青的技术指标要求。     

负载羧基化球状介孔纳米颗粒TFN膜的研究

在薄层复合膜(thin-film composite membrane, TFC膜)中引入无机纳米颗粒，形成薄层纳米复合膜(thin-film nanocomposite membrane, TFN膜)，近几年作为反渗透膜开始应用于水处理研究。但是无机纳米颗粒在TFC膜中的性能的不稳定性和膜的机械强度等变成了突出问题。合成制备了粒径约为110 nm修饰羧基的介孔氧化硅球状纳米颗粒(MSN—COOH)，并将其成功地化学键合在TFC膜的表面功能层交联网络中。与TFC膜相比，键合有MSN—COOH的TFN膜，水通量提高了56.2%，保持高脱盐率；由于单分散介孔纳米颗粒表面亲水官能团的引入，使膜表面的亲水性有很大程度提高，单分散介孔纳米颗粒在基体中的有序排列，使膜表面粗糙度降低，提高了膜的抗污染能力。与普通TFN膜相比较，具有更好的稳定性和柔韧性，可以在长时间高压过滤操作下保持稳定。     

生物质纤维和改性木质素对聚乳酸结晶性能的影响

采用改性木质素(MZS)作为成核剂,生物质纤维(BF)作为增强剂,通过双螺杆挤出机制备了生物降解的聚乳酸(PLA)/BF/MZS材料。采用差式扫量热仪(DSC)、电子万能试验机和扫描电子显微镜(SEM)分析了BF和MZS对PLA材料性能的影响。结果表明,BF和MZS有效提高了PLA的结晶能力和力学性能。当BF和MZS的含量分别为15%和1%时,PLA材料结晶度提高至67.1%,在50℃/min降温速率下仍具有较高的结晶能力。105℃等温结晶时,15%BF和1%MZS的PLA材料半结晶时间降低至9.0 s,比纯PLA缩短了72.2%。当PLA含有3%BF和1%MZS时,拉伸强度和冲击强度分别为70.1 MPa和7.4 kJ/m^2,比纯PLA分别提高了7.8%和10.4%,根据SEM显示,当BF含量为3%时,在PLA材料中分布较均匀。