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.     

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.     

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。     

N-油酰基肌氨酸钠对除盐水缓蚀性能的探讨

对N-油酰基肌氨酸钠单体的缓蚀性能以及与常用除盐水缓蚀剂的协同作用作了探讨,发现在一定浓度下,单体对经过加氨调节后的高温除盐水(氨后除盐水)有良好的缓蚀作用,且与大多数除盐水缓蚀剂有良好的协同效应。在此基础上研制了一种复合药剂,并对其缓蚀、阻蚀性能作了研究。动电位极化曲线扫描图谱表明,该复合药剂属于抑制阳极腐蚀的阳极型缓蚀剂,其适用的水质条件为[Cl~-+SO_4~(2-)]不超过50 mg／L,pH不低于8.0；与阻垢剂复配,可以适用于含Ca~(2+)不超过45 mg／L的水质条件。     

合成氨制气中的以水代汽新工艺

提出了应用油水融合技术在合成氨部分氧化法制气中以水代汽的工艺途径，并分析了其效果和意义。     

φ1m氨合成塔20钢异径管失效分析

分析了氨合成塔底部副线20钢异径管爆破的原因。结果表明：异径管长期处于200℃以上工作，管内H2与管材中的碳或Fe3发生化学反应，生成CH4致使管内脱碳并产生裂纹，异径管强度降低脆性增加，导致爆破。     

负压法(射流法)回收治理液氨尾气

论述了负压法(射流法)回收治理液氨尾气的环保安全工艺技术、原理；解决了目前一直沿用的正压法无法解决的棘手问题。