Volatilization of fluorine in a CaO–SiO2–CaF2-based system with the substitution of Na2O with K2O

Cuspidine-based systems are used to control the crystallization in mold fluxes, which is enabled by CaF₂ additions. However, excess CaF₂ increases the corrosion of casting machines. Therefore, Na₂O and K₂O are added to the mold flux system to ensure an optimized crystallization and lubrication ability of the flux with the CaF₂ content. This study investigated the effect of substituting Na₂O with K₂O on the volatilization of fluorine in a CaO–SiO₂–CaF₂-based slag system at high temperatures. The substitution of Na₂O with K₂O was performed at 5 mol% intervals. The volatilization was observed by thermogravimetric analysis under several isothermal conditions. The mass loss was measured at a heating rate of 5, 10, and 20 K/min. As the temperature increased, the volatilization of the mixed samples increased. The activation energy was calculated using the Flynn–Wall–Ozawa and Kissinger–Akahira–Sunose methods. A kinetic analysis of the volatilization of fluorine was conducted using the calculated parameters and several known kinetic models. Consequently, the volatilization of the Na-rich sample was controlled by chemical reactions and that of the K-rich sample was identified to be controlled by a phase-boundary-controlled reaction. These results suggest that the addition of mixed alkali oxide promote the volatilization during the early stages of the reaction. From the post-experimental composition analyses, the remaining Na and K in the samples suggested a different mechanism for the Na and K volatilization. The volatilization of Na increased with time, whereas K volatilized easily during the beginning of the reaction.     

Water vapor volatilization and oxidation induced surface cracking of environmental barrier coating systems: A numerical approach

A numerical model is developed for surface crack propagation in brittle ceramic coatings, aiming at the intrinsic failure of rare-earth silicate environmental barrier coating systems (EBCs) under combustion conditions in advanced gas turbines. The main features of progressive degradation of EBCs in such conditions are captured, including selective silica vaporization in the top coat due to exposure to water vapor, diffusion path-dependent bond coat oxidation, as well as crack propagation during cyclic thermal loading. In light of these features, user-defined subroutines are implemented in finite element analysis, where surface crack growth is simulated by node separation. Numerical results are validated by existing experimental data, in terms of monosilicate layer thickening, thermal oxide growth, and fracture behaviors. The experimentally observed quasi-linear oxidation in the early stage is also elucidated. Furthermore, it is suggested that surface crack undergoes rapid propagation in the late stage of extended thermal cycling in water vapor and leads to catastrophic failure, driven by both thermal mismatch and oxide growth stresses. The latter is identified as the dominant mechanism of penetration. Based on detailed analyses of failure mechanisms, the optimization strategy of EBCs composition is proposed, balancing the trade-off between mechanical compliance and erosion resistance.     

氨浸-草酸盐沉淀法回收废弃线路板中金属铜的工艺研究

采用氨浸-草酸盐沉淀法回收废弃线路板中的金属铜,考察了氨水浓度、NH₄Cl溶液浓度、液固比、反应温度和时间对铜浸出率的影响。结果表明,最佳工艺条件为:氨水浓度10%、NH₄Cl溶液浓度1.5 mol/L、液固比10∶1、反应温度60 ℃、反应时间3 h,在此工艺条件下,铜浸出率高达99.25%。在铜的富集过程中,调节溶液pH值至1.5,60 ℃下反应30 min,铜沉淀率达到了98.15%。     

载铜树脂处理高含盐氨氮废水的性能

针对高含盐氨氮废水，选择具有不同功能基团的树脂为载体，进行负载Cu2+改性制得载铜树脂并对其处理高含盐氨氮废水的性能进行研究。在筛选出最佳载铜树脂的基础上，研究pH及Na+浓度、树脂投加量、反应时间对载铜树脂处理高含盐氨氮废水效果的影响，通过对吸附氨氮前后的载铜树脂进行SEM和EDS表征分析并构建吸附动力学模型以进一步探究配位吸附的过程。结果表明，Cu2+可与螯合树脂D751稳定结合且在宽pH值下均表现出耐盐性和良好的氨氮吸附效果；在室温(25℃)、pH=11及Na+浓度4 g/L、树脂投加量8 g/L、反应时间60 min的条件下，D751载铜树脂对氨氮的去除率为34.8%。D751载铜树脂吸附氨氮后其表面出现明显的晶状结构物质，该物质可能为铜氨络合物。D751载铜树脂对高含盐氨氮的吸附符合准二级动力学模型。     

铋精矿加压氧化氨浸高效分离铜、硫和铋

针对湖南柿竹园铋精矿火法冶炼过程中存在的成本高、低浓度SO₂和散烟排放污染环境、有价金属综合回收率低等问题, 以柿竹园铋精矿为原料, 提出了加压氧化氨浸分离铋与铜、硫的新工艺, 研究了氨水加入量、浸出温度、浸出时间、浸出压力及浸出液固比等因素对铜、硫、铋浸出率的影响。在氨水用量1.8 mL/g_铋精矿、液固比4∶1、釜压2.8 MPa、浸出温度160 ℃、浸出时间5 h、搅拌速度600 r/min的优化工艺条件下, 铜、硫浸出率分别达93.57%和92.87%, 铋不浸出并以氧化铋形态全部入渣, 实现了铜、硫与铋的高效分离。     

Combining molybdenum carbide with ceria overlayers to boost Mo/CeO2 catalyzed ammonia synthesis

The design of an efficient non-noble metal catalyst is of burgeoning interest for ammonia synthesis. Herein, we report a Mo₂C/CeO₂ catalyst that is superior in ammonia synthesis activity. In this catalyst, molybdenum carbide coexisted with the ceria overlayers which is from the ceria support as the strong metal–support interaction. There is a high proportion of low-valent Mo species, as well as high concentration of Ce³⁺ and surface oxygen species. The presence of Mo₂C and CeO₂ overlayers not only leads to enhancement of hydrogen and nitrogen adsorption, but also facilitates the desorption and exchange of adsorbed species with the gaseous reagents. Compared with the Mo/CeO₂ catalyst prepared without carbonization, the Mo₂C/CeO₂ catalyst is more than sevenfold higher in ammonia synthesis rate. This work not only presents an explicit example of designing Mo-based catalyst that is highly efficient for ammonia synthesis by tuning the adsorption and desorption properties of the reactant gases, but opens a perspective for other elements in ammonia synthesis.     

Numerical simulation of ammonia/methane/air combustion using reduced chemical kinetics models

Ammonia appears to be a potential alternative fuel that can be used as a hydrogen vector and fuel for gas turbines and internal combustion engines. Chemical mechanisms of ammonia combustion are important for the development of ammonia combustion systems, but also as a mean of investigation of harmful NOx emissions, so they can be minimized. Despite of large body of experimental and modelling work on the topic of ammonia combustion, there is still need for additional investigation of combustion kinetics.The object of this work is further numerical study of ammonia combustion chemistry under conditions resembling industrial ones. After literature review, three mechanisms of ammonia combustion that also include carbon chemistry are used for simulation of experimental premixed swirl burner with the aim of evaluating their performance. San Diego mechanism, that was also the most detailed one, proved to be the best in terms of emissions, but neither one of the models was able to accurately reproduce CO emission after equivalence ratio went beyond 0.81. It was also observed that oxygen is excessively consumed. This study contributes to the current knowledge by providing new insights in ammonia burning conditions closely resembling those in industrial applications, and consequently is expected that insights obtained will help in the design of real industrial burning systems.     

Sustainable ammonia production through process synthesis and global optimization

Current ammonia production technologies have a significant carbon footprint. In this study, we present a process synthesis and global optimization framework to discover the efficient utilization of renewable resources in ammonia production. Competing technologies are incorporated in a process superstructure where biomass, wind, and solar routes are compared with the natural gas-based reference case. A deterministic global optimization-based branch-and-bound algorithm is used to solve the resulting large-scale nonconvex mixed-integer nonlinear programming problem (MINLP). Case studies for Texas, California, and Iowa are conducted to examine the effects of different feedstock prices and availabilities. Results indicate that profitability of ammonia production is highly sensitive to feedstock and electricity prices, as well as greenhouse gas (GHG) restrictions. Under strict 75% GHG reductions, biomass to ammonia route is found to be competitive with natural gas route, whereas wind and solar to ammonia routes require further improvement to compete with those two routes. © 2018 American Institute of Chemical Engineers AIChE J, 65: e16498 2019     

化学沉淀-吸附法处理电镀废水的研究

采用化学沉淀-吸附法处理电镀废水。首先,采用沉淀剂MgSO4・7H2O和NazHPCX・12H2O对电镀废水进行化学沉淀处理。在优化条件下,氨氮的质量浓度由1600 mg/L降低至80 mg/L以下,磷的质量浓度为75.82 mg/Lo然后,采用吸附法对电镀废水做进一步处理。最终电镀废水中氨氮和磷的残余质量浓度均达到《电镀污染物排放标准》(GB 219002008)中规定的要求。     

Hydrogen carriers: Production,transmission, decomposition,and storage

Recognizing the potential role of liquid hydrogen carriers in overcoming the inherent limitations in transporting and storing gaseous and liquid hydrogen, a complete production and use scenario is postulated and analyzed for perspective one-way and two-way carriers. The carriers, methanol, ammonia and toluene/MCH (methylcyclohexane), are produced at commercially viable scales in a central location, transmitted by rail or pipelines for 2000 miles, and decomposed near city gates to generate fuel-cell quality hydrogen for distribution to refueling stations. In terms of the levelized cost of H₂ distributed to the stations, methanol is less expensive to produce ($1.22/kg-H₂) than MCH ($1.35/kg-H₂) or ammonia ($2.20/kg-H₂). Levelized train transmission cost is smaller for methanol ($0.63/kg-H₂) than ammonia ($1.29/kg-H₂) or toluene/MCH system ($2.07/kg-H₂). Levelized decomposition cost is smaller for ammonia ($0.30–1.06/kg-H₂) than MCH ($0.54–1.22/kg-H₂) or methanol ($0.43–1.12/kg-H₂). Over the complete range of demand investigated, 10–350 tpd-H₂, the levelized cost of H₂ distributed to stations is aligned as methanol « ammonia ~ MCH. With pipelines at much larger scale, 6000 tpd-H₂, the levelized cost decreases by ~1 $/kg-H₂ for ammonia and MCH and much less for methanol. Methanol is a particularly attractive low-risk carrier in the transition phase with lower than 50-tpd H₂ demand.