Sustainable ammonia synthesis:An in-depth review of non-thermal plasma technologies

Ammonia serves both as a widely used fertilizer and environmentally friendly energy source due to its high energy density,rich hydrogen content,and emissions-free combustion.Additionally,it offers convenient transportation and storage as a hydrogen carrier.The dominant method used for large-scale ammonia production is the Haber-Bosch process,which requires high temperatures and pressures and is energy-intensive.However,non-thermal plasma offers an eco-friendly alternative for ammonia synthesis,gaining significant attention.It enables ammonia production at lower temperatures and pressures using plasma technology.This review provides insights into the catalyst and reactor developments,which are pivotal for promoting ammonia efficiency and addressing existing challenges.At first,the reaction kinetics and mechanisms are introduced to gain a comprehensive understanding of the reaction pathways involved in plasma-assisted ammonia synthesis.Thereafter,the enhancement of ammonia synthesis efficiency is discussed by developing and optimizing plasma reactors and effective catalysts.The effect of other feeding sources,such as water and methane,instead of hydrogen is also presented.Finally,the challenges and possible solutions are outlined to facilitate energy-saving and enhance ammonia efficiency in the future.

The significance of NO_(2) dimerization in plasma-based NO_(x) synthesis for nitrogen fixation

Plasma-based NO_(x) synthesis has been considered as a sustainable alternative to the conventional HaberBosch process.Despite the advancements in research achieved in recent years,limited attention has been paid to the reversible dimerization reaction of NO_(2) to N_(2)O_(4).This reaction can significantly alter the parameters considered with the process’output,such as the concentration or volume fraction of products and the energy consumption.This work aims to investigate the significance of dimerization through theoretical analysis and experimentation.Experiments were conducted with a 2D-gliding arc reactor to evaluate the influence of dimerization in the case of plasma reactor operation.It was observed that the dimerization reaction reached equilibrium in microseconds,resulting in a maximum hypothetical NO_(2) equilibrium conversion of 48.8%.For plasma experiments,the dimerization could cause a maximum error of 14.1%in product detection,which needs to be carefully considered along with the influence of temperature variations on the measurement.

Non-thermal plasma fixing of nitrogen into nitrate： solution for renewable electricity storage？

The rapid deployment of solar and wind technology produces significant amount of low-quality electricity that calls for a better storage or usage instead of being discarded by the grid.Instead of electrochemical CO2 reduction and/or NH3 production,here we propose that non-thermal plasma oxidation of N2 into nitrate or other valuable nitrogen containing compounds deserve more research attention because it uses free air as the reactant and avoids the solubility difficulty,and also because its energy consumption is merely 0.2 MJ/mol,even lower than the industrially very successful Haber-Bosch process（0.48 MJ/mol）for NH3 production.We advocate that researchers from the plasma community and chemistry community should work together to build energy efficient non-thermal plasma setup,identify robust,active and low-cost catalyst,and understand the catalyzing mechanism in a plasma environment.We are confident that free production of nitrate with zero C02 emission will come true in the near future.

Plasma-assisted ammonia synthesis under mild conditions for hydrogen and electricity storage:Mechanisms,pathways,and application prospects

Ammonia,with its high hydrogen storage density of 17.7 wt.%(mass fraction),cleanliness,efficiency,and renewability,presents itself as a promising zero-carbon fuel.However,the traditional Haber−Bosch(H−B)process for ammonia synthesis necessitates high temperature and pressure,resulting in over 420 million tons of carbon dioxide emissions annually,and relies on fossil fuel consumption.In contrast,dielectric barrier discharge(DBD)plasma-assisted ammonia synthesis operates at low temperatures and atmospheric pressures,utilizing nitrogen and hydrogen radicals excited by energetic electrons,offering a potential alternative to the H−B process.This method can be effectively coupled with renewable energy sources(such as solar and wind)for environmentally friendly,distributed,and efficient ammonia production.This review delves into a comprehensive analysis of the low-temperature DBD plasma-assisted ammonia synthesis technology at atmospheric pressure,covering the reaction pathway,mechanism,and catalyst system involved in plasma nitrogen fixation.Drawing from current research,it evaluates the economic feasibility of the DBD plasmaassisted ammonia synthesis technology,analyzes existing dilemmas and challenges,and provides insights and recommendations for the future of nonthermal plasma ammonia processes.

等离子体技术的固氮应用

空气中的氮气由于其牢固的N≡N三键,不易被植物直接吸收。等离子体固氮为高效实现将氮分子(N_(2))转化为可吸收的含氮化合物(NO_(x),NH_(3)等)提供了新途径。相比传统Haber-Bosch(H-B)工艺,等离子体技术可以使用间歇性可再生能源,成本低廉,并且理论能耗仅为H-B工艺的0.5倍,因而在固氮领域受到广泛关注。本篇综述首先阐述了等离子体在固氮应用上的优势,然后,介绍了等离子体固氮的反应原理以及其在固氮(用于NH_(3)或NO_(x)合成)领域的研究现状,并对比了当前已有的等离子体反应器类型及其固氮效果。最后,总结了等离子体固氮技术当前面临的挑战,并指出了该方向未来研究的重点。

用于分布式光伏消纳的等离子体土壤固氮装置研究

“双碳”目标以来,我国农村地区大力发展清洁能源,积极构建农村清洁能源体系,各个地区因地制宜推动农村电气化发展和乡村清洁能源的改造。但随着屋顶分布式光伏的大量接入,农村光伏并网消纳问题依旧存在,还须通过加快分布式光伏发电就近消纳,以提高农村电网整体承载能力。对于以粮食作物为主的农村地区,可以结合农业区位因素、地区地域特色,建设“光伏+现代农业”的绿色可持续发展模式。土壤关系到农业生产的可持续性,土壤肥力的形成变化对土壤发育、生物地质循环具有主导作用。针对我国部分农村地区土壤肥力不足而引起的氮素流失问题,设计了一种基于低温等离子体技术的大气土壤固氮装置,配合农村清洁能源,提出了光伏固氮技术方案,促进农村地区光伏消纳的同时,还可以用于补足农田庄稼中土壤肥力。

脉冲调制射频空气等离子体固氮研究

工业合成氨固氮高度依赖于化石燃料,导致了诸多环境问题,人类若要维持可持续的粮食供应,就需要更加绿色高效的固氮方法。空气放电等离子体极易与可再生电力相结合,且即开即用、随关随停,是较为理想的绿色固氮技术。但现有空气放电等离子体固氮效率较低,针对这一关键问题,研究了脉冲调制(pulse modulated,PM)射频空气放电等离子体的固氮特性,发现脉冲调制会导致射频空气等离子体形态发生明显变化,在占空比一定的情况下,固氮效率随频率的增大而减小,相反,如果固定调制频率,NOx的浓度随占空比的增大逐渐增加,固氮效率在占空比为60%时达到最高。脉冲调制技术显著影响了射频空气放电固氮效率,为后续研究大功率射频空气放电固氮提供重要启示。