Optimal design and operation of ammonia decomposition reactors

The design and steady-state operation of a packed bed reactor with tubular geometry is optimized. Direct optimal control methods are used. Two objective functions are considered: (i) minimization of the ammonia mass fraction at reactor outlet and (ii) minimization of the heat flux necessary to reach a predefined value of the ammonia mass fraction at reactor outlet. The optimization process is performed by using different controls, that is, the space distributions of (1) tube wall temperature T_w , (2) circular tube diameter D_tube , and (3) diameter d_p of the catalyst spherical particles. Results for the first objective function are as follows. The optimal distribution of T_w along the reactor consists of a constant temperature or a U-shaped space temperature distribution, respectively, depending on the allowed range of variation of T_w . The optimal space distribution of D_tube (or, in other words, the shape of the reactor tube) depends of T_w . For smaller values of T_w the tube is narrower at inlet and larger at outlet while the reverse situation happens for larger values of T_w . For lower T_w values, particles with smaller diameter d_p are placed at reactor inlet while when higher values of T_w are considered, particles with larger d_p are placed at reactor inlet. When both D_tube and d_p are used as controls, the optimization results are generally different from the results obtained from one-control optimization. Results for the second objective function are as follows. The optimal space distribution of T_w starts with high values at reactor inlet. Next, the temperature decreases abruptly towards a minimum (which is lower for longer tubes). Finally, the temperature increases smoothly towards a maximum near the reactor outlet. The required heat flux slightly decreases by increasing the tube length. The optimal D_tube ranges between its maximum allowed value (at reactor inlet) and its minimum allowed value (at reactor outlet). The best performance is obtained for catalyst particles of the smallest allowed diameter.     

Vicious cycle during chemical degradation of sulfonated aromatic proton exchange membranes in the fuel cell application

Weak phase separation and vulnerable linking groups between aromatic units are common setbacks of sulfonated aromatic proton exchange membranes (PEMs) from durability point of view. In this study, sulfonated poly(ether ether ketone) (SPEEK) membranes were exposed to Fenton's solution for a specific time, ranging from 10 to 60 minutes. Chemical structure and morphology evolution, decay in mechanical and thermal stability, and H₂ permeability of SPEEK membranes were evaluated during the chemical degradation. Less-entangled polymeric chains with lower average molecular weight of degraded SPEEK samples diminished mechanical rigidity. In addition, reduction of aromatic rings in each repeat unit led to higher thermal decomposition rate. Furthermore, randomly distributed micro-defects in the SPEEK morphology and an increase in water sorption can reduce the fatigue strength of membranes in the wet-dry cycles. Eventually, hydrogen cross-over rate was gradually increased, and henceforth, accelerated destructive radical formation and degradation can be predicted.     

基于 MPDE-EEMD 及自适应共振解调的轴承故障特征提取方法

针对滚动轴承振动信号具有非线性、非平稳性和非高斯性,并且故障特征往往淹没于系统噪声之中而难于识别的问题, 提出了以多种群差分进化(multiple population differential evolution, MPDE) 算法来改进集合经验模式分解( ensemble empirical mode decomposition, EEMD) 的 MPDE-EEMD 消噪方法,并与自适应共振解调技术( adaptive resonance demodulation technique, ARDT)相结合实现故障特征提取。 首先,为了解决 EEMD 中加入参数依靠人工选择且难以准确获取的问题,建立极值点分布 特性评价函数,利用 MPDE 来寻优获取最佳白噪声幅值,实现 EEMD 自适应分解。 然后,采用峭度与相关性相结合的准则对分 解后的 IMF 分量进行自动筛选,将满足条件的有效信号进行重构,实现对原始振动信号的降噪处理。 最后,采用 ARDT 自动确 定对消噪信号进行带通滤波的带宽和中心频率,再通过包络解调提取出滤波信号的特征频率。 将轴承仿真故障信号与实际故 障信号用于算法的验证,结果表明 MPDE-EEMD+ARDT 能有效提取出轴承故障特征。     

部分传输序列的遗传模拟退火搜索方法

在正交频分复用(OFDM)系统中,基于遗传算法的部分传输序列(GA-PTS)技术有效地降低了 PTS 的计算复杂度,但在 改进峰值-平均功率比(PAPR)性能方面却并不理想。 为此,提出在遗传算法中嵌入模拟退火(SA)算子从而构造一种混合的遗 传模拟退火(GSA)算法,并把它应用于对 PTS 的最优相位因子进行搜索。 首先,通过对 PTS 相位因子编码形成染色体,采用随 机元素组成的染色体作为遗传算法的初始群体,并评估每个染色体的适应度值。 然后,根据适应度值选择染色体,建立染色体 的变异规则和交叉规则,对群体进行迭代进化。 最后,群体中的染色体利用退火温度进行更新,从而产生出新的下一代种群。 仿真结果说明,与 GA-PTS 方案相比,该方法不仅能降低计算负担,而且能够有效地降低 OFDM 系统 PAPR 值。     

废旧磷酸铁锂锂离子电池正极的回收

采用磷酸(H3PO4)溶液对废旧LiFePO4电池正极片在低温热解得到的粉末材料进行浸出,以铁盐溶液作为补充铁源,合成电池级磷酸铁(FePO4),并将滤液pH值调到8.0以上,得到工业级磷酸锂(Li3PO4)。通过SEM、XRD和电化学性能测试,研究热处理温度、反应原料配比与溶液pH值对回收产物形貌和性能的影响。将正极片在350℃下热解2 h分离得到的粉末加入到85℃的H3PO4溶液中,在n(P)∶n(Fe)为1.3∶1.0的条件下,制备的FePO4结晶度好。制备的电池在2.5~4.0 V充放电,0.2 C和2.0 C放电比容量最高分别达到160.2 mAh/g和150.3 mAh/g。以Li3PO4方式回收滤液中的锂元素,当p H值为10时,回收率达到90%,Li3PO4纯度在99.4%以上。     

含锂工业废料制备电池级碳酸锂工艺研究

随着电池行业的快速发展,电池级碳酸锂的市场需求越来越大。以某公司生产电池的含锂工业废料为原料,采用碳化分解法对其进行提纯除杂,并进行多次滤液滤饼循环,最终得到符合电池级碳酸锂行业标准的产品。碳化过程优化反应条件：固液质量体积比（g/mL）为1∶50,搅拌转速为300 r/min,二氧化碳流速为10 L/min,反应温度为20 ℃,反应时间为60 min。热分解过程优化反应条件：搅拌转速为300 r/min,反应温度为95 ℃,反应时间为60 min。将碳化分解制备的碳酸锂滤饼和滤液进行5次循环反应,即可得到符合电池级碳酸锂行业标准的产品。所得碳酸锂产品纯度达到99.71%,而且其中镁、钙、钾质量分数分别降低至0.005 3%、0.005 0%、0.000 9%,产品收率保持在55%以上,产品形貌呈棒状、大小均匀、分散性良好。     

Thermal management in PEMFCs: The respective effects of porous media in the gas flow channel

This study aims to evaluate the convective heat transfer enhancement of the proton exchange membrane fuel cells (PEMFC) numerically. As the higher heat transfer surfaces lead to higher heat transfer rates, a flat plate porous layer is utilized in the gas flow channel (GFC). This enhancement in heat transfer stems from the corresponding modification in the temperature and velocity profiles. The influencing parameters on these profiles are the thickness, permeability, and porosity of the GFC porous layer. After performing the simulations, the results indicate that convective heat transfer has a direct relationship with GFC porous layer's thickness and permeability. However, lower values of porosity lead to the higher Nusselt numbers. Previous investigations have also mentioned the positive impact of the microporous layer (MPL) on the water management of these fuel cells. Therefore, six different sizes of MPL and the gas diffusion layer (GDL) are utilized to evaluate their impacts on the thermal management. Results indicate that although these sizes have negligible effects on the heat transfer, Nu increases by enhancing the total size of MPL and GDL. The results also show that thicker MPLs lead to higher heat transfer rates. The evaluation of the friction factor also indicates the adverse effect of the GFC porous layer, although this undesirable effect is negligible. Finally, all the simulated values are utilized to train an artificial neural network (ANN) model with high precision. This ANN model can produce more data for sensitivity analysis and presenting respective 3D diagrams of the influencing parameters on heat transfer.     

A tetranuclear nickel(II) complex for water oxidation: Meeting new challenges

Ni complexes are promising catalysts for water splitting. Herein, a tetranuclear nickel(II) complex with bis-[(E)-N′-(1-(pyridin-2-yl)ethylidene)]carbohydrazide (HL), was synthesized and characterized by spectroscopic methods and single crystal X-ray analysis. The complex is a tetranuclear complex and the ligands are coordinated to the metal ions in the mono-negative form, (L)^- to form a tetranuclear [NiL]₄⁴⁺ unit. Each Ni(II) ion is six-coordinated by pyridine nitrogen, azomethine nitrogen and oxygen atoms of two perpendicular carbohydrazone ligands in the mer configuration. The complex was studied as a water-oxidizing catalyst. In the next step, the role of the Ni-based compound for water oxidation on the surface of fluorine doped tin oxide as one of the true catalysts was investigated by scanning transmission electron microscopy, scanning transmission electron microscopy, spectroelectrochemistry, and electrochemistry. The electrode after water oxidation by the complex was studied and a relation between the decomposition of the Ni complex and water-oxidation reaction was proposed. The experiments show that under water-oxidation condition in the presence of the complex, a Ni-based compound on the electrode is a candidate as a contributor to the observed catalysis.     

Life cycle assessment of domestic fuel cell micro combined heat and power generation: Exploring influential factors

Residential Fuel Cell micro combined heat and power (FC-μCHP) systems can help decarburizing the energy system. In the European ene.field project, the environmental performance of FC-μCHP under different conditions was therefore evaluated by means of a comprehensive Life Cycle Assessment (LCA). Important influential factors were explored, i.e. heating demands, full load hours (FLHs) and electricity replacement mixes (ERMs). The systems were compared with a stand-alone Gas Condensing Boiler (GCB) and a heat pump (HP, only in single family homes, SFHs). For the initially assumed FLHs and the current ENTSO-E ERM, relevant environmental impacts including climate change are generally smaller for the FC-μCHPs than for the HP and the stand-alone GCB. In the setting “existing SFHs in central climate” with the highest deployment potential, GHG emission savings are higher the more carbon-intensive the ERM is and/or higher the net electricity export into the grid is. The results are discussed and put into perspective. Further research demands as well as product development opportunities are outlined. The importance of a green hydrogen economy is emphasized.     

Ammonia decomposition kinetics over LiOH-promoted, α-Al2O3-supported Ru catalyst

A LiOH-promoted Ru-based catalyst was recently reported to have a high TOF of 17.7 s⁻¹ at 623 K, compared to 2.7 s⁻¹ for an un-promoted Ru-based catalyst, and has been reproduced for this study to develop further understanding of the catalyst activity under a range of conditions. The kinetic values were calculated using a Temkin-Pyzhev-like power law rate expression model. Reaction orders, pre-exponential factors (A) and activation energies (E) were calculated for two temperature ranges, 623–748 K, and 748–873 K. The TOF of this catalyst at 623 K is not similar to that previously reported, being only 1.6 s⁻¹ in this study. A follow-up CFD analysis supports the fact that the kinetic model effectively describes performance of the catalyst at a range of temperatures and pressures, and can be used in the future on similar catalysts. H₂ partial pressure has an inhibitory effect on the rate of decomposition of NH₃ at all temperatures, not just near or below 673 K as previously proposed in the literature, however equilibrium decomposition is still possible with sufficient catalyst loading.