Taylor Bubble Study of the Influence of Fluid Dynamics on Yield and Selectivity in Fast Gas-Liquid Reactions

A consecutive competitive gas-liquid reaction is investigated using a Taylor bubble setup regarding the influence of fluid mixing in the bubble wake on yield and selectivity. The concentration fields behind a Taylor bubble are visualized and measured quantitatively with a novel time-resolved absorption imaging technique based on Beer Lamberts law and an integral selectivity is derived. In addition, the calculation of the local selectivity, often used in numerical approaches, is discussed and the existing experimental limits for its derivation are pointed out. Finally, an increase in selectivity of a competitive consecutive reaction for enhanced mixing is experimentally confirmed.     

LiAlH4–ZrCl4 mixtures for hydrogen release at near room temperature

The dehydrogenation temperature of LiAlH₄ was significantly reduced by the production of mixtures with ZrCl₄. Stoichiometric 4:1, and 5 mol % mixtures of LiAlH₄ and ZrCl₄ were produced by ball milling at room temperature and ?196 °C, and tested for dehydrogenation at low temperature. Cryogenic ball-milling resulted in an effective way to produce reactive mixtures for hydrogen release; because of achieving small aggregates size (5–20 μm) in 10 min of cryomilling while preventing substantial decomposition during preparation. Dehydrogenation reaction in the mixtures LiAlH₄/ZrCl₄ started around 31–47 °C under different heating rates. Partial dehydrogenation was proved at 70 °C: 4.4 wt % for the 5 mol% ZrCl₄–LiAlH₄ mixture, and 3.4 wt % for the best 4:1 stoichiometric mixture. Complete dehydrogenation up to 250 °C released 6.4 wt% and 4.1 wt%, respectively. Dehydrogenation reactions are exothermic, and the LiAlH₄/ZrCl₄ mixtures are unstable and difficult to handle. The activation energy of the exothermic reactions was estimated as 113.5 ± 9.8 kJ/mol and 40.6 ± 6.6 kJ/mol for 4LiAlH₄+ZrCl₄ and 5%mol ZrCl₄+LiAlH₄ samples milled in cryogenic conditions, respectively. The dehydrogenation pathway was changed in the LiAlH₄/ZrCl₄ mixtures as compared to pure LiAlH₄. Dehydrogenation reaction is proposed to form Al, LiCl, Zr, and H₂ as main products. Modification of the dehydrogenation reaction of LiAlH₄ was achieved at the cost of reducing the total hydrogen release capacity.     

An overview of reactive hydride composite (RHC) for solid-state hydrogen storage materials

Hydrogen storage using the metal hydrides and complex hydrides is the most convenient method because it is safe, enables high hydrogen capacity and requires optimum operating condition. Metal hydrides and complex hydrides offer high gravimetric capacity that allows storage of large amounts of hydrogen. However, the high operating temperature and low reversibility hindered the practical implementation of the metal hydrides and complex hydrides. An approach of combining two or more hydrides, which are called reactive hydride composites (RHCs), was introduced to improve the performance of the metal hydrides and complex hydrides. The RHC system approach has significantly enhanced the hydrogen storage performance of the metal hydrides and complex hydrides by modifying the thermodynamics of the composite system through the metathesis reaction that occurred between the hydrides, hence enhancing the kinetic and reversibility performance of the composite system. In this paper, the overview of the RHC system was presented in detail. The challenges and perspectives of the RHC system are also discussed. This is the first review report on the RHC system for solid-state hydrogen storage.     

棉织物色泣现象成因及其消除

以萃取活性染料染色织物浮色的方式,探究活性染料染色棉织物的色泣牢度与浮色之间的关系。结合染色原理对活性染料染色棉织物经储存后色泣牢度下降的原因进行了分析,并尝试使用加强皂洗和固色处理的方式提高织物色泣牢度。结果表明,浮色是影响活性染料染色棉织物色泣牢度的重要因素,已上染的活性染料经一定时间储存后发生水解断键可能是导致色泣牢度下降的重要因素。增加1~2次皂洗可以提高色泣牢度,固色剂JAL-01和固色剂JAL-02均可以显著提高棉织物活性染料染色的色泣牢度,但其中固色剂JAL-01对织物的色光影响较大。     

Mg0.5NixZn0.5-xFe2O4 spinel as a sustainable magnetic nano-photocatalyst with dopant driven band shifting and reduced recombination for visible and solar degradation of Reactive Blue-19

Focussing on visible light active ferrites for high performance removal of noxious pollutants, we report the synthesis of Mg_0.5Ni_xZn_0.5-xFe₂O₄ (x = 0.1, 0.2, 0.3, 0.4, & 0.5) ferrite nanoparticle for degradation of reactive blue-19 (RB-19). Lattice parameters calculated using intense X-ray diffraction (XRD) peaks and Nelson-Riley plots (N-R plot) are in well agreement with each other. The sample Mg_0.5Ni_0.4Zn_0.1Fe₂O₄ (M5N4) exhibits best performance with 99.5% RB-19 degradation in 90 min under visible light. Photoluminescence (PL) results confirm that recombination of charge carriers is highly reduced in the photocatalyst. Scavenging experiments suggest that O₂⁻ radicals were the dominant species responsible for photocatalytic performance. The photocatalytic mechanism was explained in terms of dopant driven shifting of conduction bands and valence bands (calculated by Mott-Schottky plots). The thermodynamic probability of radical generation along with role of redox cycles of metal ions has been discussed in the mechanism. The dye degradation was ascertained by detection of intermediates via mass spectrometry analysis and a possible degradation route was also predicted. The findings in this work provide intriguing opportunities to modify the electronic band structure of spinel ferrites for visible and solar light photocatalytic activity for environmental detoxification.     

Pore structure of reactively synthesized nanolaminate Ti3SiC2 alloyed with Al

Ti₃SiC₂ has the unique properties integrating the advantages of metals and ceramics, and good open pore structure when alloyed with Al. In this work, porous Ti₃SiC₂ compounds with different Al/Si atom ratios were prepared through the reactive synthesis of elemental powders at 1300 °C. The results indicate that the phase compositions are determined by Al element mole number, and that the pore structure can be controlled through varying Ti particle size. The MAX phase transits from Ti₃SiC₂ with Al element mole number no more than 0.6 to Ti₃AlC₂ with Al element mole number in the range of 0.8–1.2. When Al element mole number is 0.6, the porous compound has a single MAX phase of Ti₃SiC₂ with uniform microporous structure and high bending strength. Porous Ti₃SiC₂ alloyed with 0.6Al has a slow linear increase rate of 0.0083%/μm in open porosity with increasing Ti particle size, and a strict linear relationship between the maximum aperture and Ti particle size with the increase rate of 0.0342 μm/μm. The pore structure formed by the phase transition mechanism for porous MAX phase has the smallest tortuosity factor compared with that formed by the clearance mechanism and the Kirkendall effect.     

MIMO-GFDM系统中低复杂度动态禁忌搜索检测算法的改进

针对多输入多输出的广义频分复用（MIMO-GFDM）系统的等效信道矩阵维度极大，传统的MIMO检测算法复杂度高且性能不佳的问题，将大规模MIMO系统中的动态禁忌搜索（RTS）检测算法运用到MIMO-GFDM系统中，并解决了RTS算法初始值的求解复杂度高的问题。首先利用最小均方误差（MMSE）检测算法所用到矩阵的正定对称性将矩阵Cholesky分解，并结合Sherman-Morrison公式迭代计算初始值，降低了初始值求逆的高复杂度；然后以改进的MMSE检测结果作为RTS算法的初始值，从初始值逐步全局搜索最优解；最后通过仿真，对不同算法的迭代次数和误码率（BER）性能进行了研究。理论分析与仿真结果表明：在MIMO-GFDM中，所提改进RTS信号检测算法误码率远低于传统信号检测算法。在4QAM时，RTS算法大约有低于MMSE检测6 dB的信噪比性能增益（误码率在10^-3时）；在16QAM时，RTS算法大约有低于MMSE检测4 dB的信噪比性能增益（误码率在10^-2时）。与传统RTS算法性相比，所提改进算法在不影响误码率性能的同时降低了算法复杂度。     

Dual application of Ti-catalyzed Li-RHC composite for H2 purification and CO methanation

2LiH + MgB₂ composite doped with TiO₂ (Li-RHC-Ti) is employed with a two-fold purpose: hydrogen purification under a H₂–CO (0.1 mol%) mixture and CO methanation. Upon dynamic cycling under CO–H₂ mixture, hydrogen release curves display a quite stable amount of pure hydrogen of about 10 wt%, short release times of around 60 min, and minor degradation. Gas analysis by Fourier transform infrared spectroscopy (FTIR) after a thermal dehydrogenation process of MgH₂ and LiBH₄ under CO evidence the conversion of CO to CH₄. Li-RHC-Ti dehydrogenated under CO shows the simultaneous formation of CH₄, CH₃OH, and B(CH₃)₃ in the gas phase. X-ray powder diffraction (XRPD) and FTIR characterizations of the solid phases of Li-RHC-Ti after both H₂–CO mixture and CO interactions demonstrate the formation of MgO, LiBO_2, and HCOO⁻ species. Li-RHC-Ti acts as a hydrogen source and promoter for the CO conversion. Reaction pathways are proposed based on experimental results and equilibrium composition calculations.     

Reactive wetting behavior and mechanism of AlN ceramic by CuNi-Xwt%Ti active filler metal

In order to propel the application of the developed CuNi-Xwt%Ti active filler metal in AlN brazing and get the universal reactive wetting mechanism between liquid metal and solid ceramic, the reactive wetting behavior and mechanism of AlN ceramic by CuNi-Xwt%Ti active filler metal were investigated. The results indicate that, with the increasing Ti content, surface tension for liquid CuNi-Xwt%Ti filler metal increases at low-temperature interval, but very similar at high-temperature interval, which influence the wetting behavior on AlN ceramic obviously. CuNi/AlN is the typical non-reactive wetting system, the wetting process including rapid wetting stage and stable stage. The wettability is depended on surface tension of the liquid CuNi filler metal completely. However, the wetting process of CuNi-8wt.%Ti/AlN and CuNi-16 wt%Ti/AlN reactive wetting system is composed by three stages, which are rapid wetting stage decided by surface tension, slow wetting stage caused by interfacial reaction and stable stage. For CuNi-8wt.%Ti/AlN and CuNi-16 wt%Ti/AlN reactive wetting system, although the surface tension of liquid filler metal is the only factor to influence the instant wetting angle θ₀ at rapid wetting stage, the reduced free energy caused by interfacial reaction at slow wetting stage plays the decisive role in influencing the final wettability.