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     

Optimization of waste quail eggshells as biocomposites for polyaniline in ammonia gas detection

A simple, cost-effective, and novel chemical sensor for ammonia (NH₃) gas detection was developed from polyaniline (PANI)/quail eggshell (QES) composites. QES is a natural waste enriched in calcium carbonate. In this work, pure PANI was synthesized from chemical oxidation method and PANI/QES composites were prepared from physical mixing of QES with the synthesized PANI at different mass ratio. A series of complementary techniques including Fourier transform infrared and ultraviolet-visible spectrometers, scanning electron microscope with energy dispersive detection coupled with mapping, thermogravimetric analysis, and X-ray diffractometer were used to characterize the physicochemical and textural properties of the biocomposites. From the results, PANI/QES composite with a mass ratio of 1 exhibited the lowest NH₃ detection limit of 5.24 ppm with a linear correlation coefficient (R²) of close to unity (0.9932) between the signal and NH₃ gas concentration. As a whole, the PANI/QES biocomposites synthesized from this work exhibited excellent selectivity toward NH₃ gas even in the presence of other gas impurities, such as acetone, ethanol, and hexane. For the sensor reusability, the PANI/QES biocomposites can be reused in the application of NH₃ gas detection for at least 4 cycles.     

Corrosion of hot-dip-galvanised steel and zinc alloy-coated steel in ammonia and ammonium chloride

There are many potential causes of corrosion in animal buildings. Animals exhale large quantities of moisture into the air creating high relative humidity in the building if the moisture is not properly vented. High humidity increases the potential for condensation. In addition, ammonia may be found in large quantities in animal buildings. Ammonia is released from manure and urine. In addition, ammonium chloride is used as a nitrogen source in fertilisers. In this study, the atmospheric corrosion of hot-dip-galvanised steel and zinc alloy-coated steel such as zinc–aluminium and zinc–aluminium–magnesium has been studied in atmospheres containing different levels of ammonia. Investigations have also been conducted at different levels of ammonium chloride. The results are discussed in view of the mechanisms of corrosion of zinc and zinc alloy-coated steel in ammonia and ammonium chloride-containing environments.     

基于(火用)效率目标的环冷机余热回收系统操作参数优化

摘要：针对烧结环冷机余热回收利用率不高的难题，采用分析法建立了评价某钢铁厂烧结环冷机余热回收系统运行效率的效率模型。基于多孔介质模型、局部非热平衡方程、真实气体SRK方程建立环冷机内气固两相换热模型。通过CFD仿真模拟，探究料层高度、循环风机输入烟气温度、烧结矿底部入口风速三项可控环冷机运行工艺参数对系统效率的影响规律。结果表明，料层厚度在1～1.5 m区间每增加0.1 m，效率增加0.8%～1.1%；循环风温在100～140℃之间每增加10℃，效率增加1.4%～1.5%；烧结矿底部入口风速在0.9～1.9 m/s之间每增加0.1 m/s，效率降低0.18%～0.24%。在此基础上，基于工业运行数据建立效率正交试验优化模型，提高了该余热回收系统3.42%的效率。     

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.     

Carbon supported bimetallic Ru‐Co catalysts for H2 production through NaBH4 and NH3BH3 hydrolysis

This work investigates the effect of the addition of small amounts of Ru (0.5‐1 wt%) to carbon supported Co (10 wt%) catalysts towards both NaBH₄ and NH₃BH₃ hydrolysis for H₂ production. In the sodium borohydride hydrolysis, the activity of Ru‐Co/carbon catalysts was sensibly higher than the sum of the activities of corresponding monometallic samples, whereas for the ammonia borane hydrolysis, the positive effect of Ru‐Co systems with regard to catalytic activity was less evident. The performances of Ru‐Co bimetallic catalysts correlated with the occurrence of an interaction between Ru and Co species resulting in the formation of smaller ruthenium and cobalt oxide particles with a more homogeneous dispersion on the carbon support. It was proposed that Ru^°, formed during the reduction step of the Ru‐Co catalysts, favors the H₂ activation, thus enhancing the reduction degree of the cobalt precursor and the number of Co nucleation centers. A subsequent reduction of cobalt and ruthenium species also occurs in the hydride reaction medium, and therefore the state of the catalyst before the catalytic experiment determines the state of the active phase formed in situ. The different relative reactivity of the Ru and Co active species towards the two investigated reactions accounted for the different behavior towards NaBH₄ and NH₃BH₃ hydrolysis.     

基于热电效应的高效环控系统

部分空间科学实验对环境温度有较高的要求，环境温度高于或低于空间科学系统能够提供的热沉温度，需要有可靠有效的加温降温处理措施。使用可靠性强的热电制冷片作为制冷制热方式和气液换热器二次换热来实现环境温度控制的需求，并对不同流体温度制冷制热效果进行分析，结果表明流体温度和目标温度差越小，热电制冷制热的效果越好。在环境温度制冷工况中，热电单元数量随电流增加先减少后增加，在制热工况中则单调递减，设计中需按照制冷工况进行热电单元数量的确定。当流体温度接近制冷制热的目标温度时，会出现整个系统总效率优于热电系统效率的区间。通过对热电单元和气液换热器的组合系统的性能计算，提供一种适于热电环控系统的计算方法和部件选型思路，对空间站环控系统的设计有重要参考意义。     

温度对生物净化滤柱中氨氮、铁、锰去除效果的影响

温度是生物净化滤柱运行的一个重要参数，采用生物净化滤柱处理模拟含氨氮、铁、锰地下水，考察水温从约25℃降到约6℃过程中氨氮、铁、锰的去除效果。结果表明，出水氨氮、总铁、锰的浓度分别低于0.15mg/L、0.1mg/L、0.05mg/L，均低于国家标准。出水总铁、锰均未受到水温下降的影响，但是出水氨氮浓度逐渐从约0.02mg/L升高到约0.12mg/L。进一步分析发现，铁主要在滤层的0~0.4m段去除，去除效果没有受到水温变化的影响。氨氮、锰主要在滤层的0~0.8m段去除，其沿程浓度均随水温降低而明显升高。氨氮、锰的生物去除符合一级动力学反应，水温为24.6℃、15.3℃、6.7℃时，两者的动力学常数k分别为0.154min^-1、0.186min^-1，0.143min^-1、0.175min^-1，0.103min^-1、0.163min^-1；半反应时间t_1/2分别为4.51min、3.72min，4.83min、3.96min，6.72min、4.24min。随着试验水温的降低，氨氮、锰的去除效果明显受到影响。     

Incoloy825材料在加氢裂化装置高压空冷器上的应用

对Incoloy825材料的焊接和抗腐蚀性能,以及在加氢裂化装置高压空冷器上的应用中应注意的问题进行了探讨.对此种空冷器在制造中如何解决异种钢焊接的难题,在清洗和水压试验中如何避免腐蚀等提出了建议.