Abstract

Electrochemical ammonia generation allows direct, low pressure synthesis of ammonia as an alternative to the established Haber-Bosch process. The increasing need to drive industry with renewable electricity central to decarbonisation and electrochemical ammonia synthesis offers a possible efficient and low emission route for this increasingly important chemical. It also provides a potential route for more distributed and small-scale ammonia synthesis with a reduced production footprint. Electrochemical ammonia synthesis is still early stage but has seen recent acceleration in fundamental understanding. In this work, two different ammonia electrolysis systems are considered. Balance of plant (BOP) requirements are presented and modelled to compare performance and determine trade-offs. The first option (water fed cell) uses direct ammonia synthesis from water and air. The second (hydrogen-fed cell), involves a two-step electrolysis approach firstly producing hydrogen followed by electrochemical ammonia generation. Results indicate that the water fed approach shows the most promise in achieving low energy demand for direct electrochemical ammonia generation. Breaking the reaction into two steps for the hydrogen fed approach introduces a source of inefficiency which is not overcome by reduced BOP energy demands, and will only be an attractive pathway for reactors which promise both high efficiency and increased ammonia formation rate compared to water fed cells. The most optimised scenario investigated here with 90% faradaic efficiency (FE) and 1.5 V cell potential (75% nitrogen utilisation) gives a power to ammonia value of 15 kWh/kg NH3 for a water fed cell. For the best hydrogen fed arrangement, the requirement is 19 kWh/kg NH3. This is achieved with 0.5 V cell potential and 75% utilisation of both hydrogen and nitrogen (90% FE). Modelling demonstrated that balance of plant requirements for electrochemical ammonia are significant. Electrochemical energy inputs dominate energy requirements at low FE, however in cases of high FE the BOP accounts for approximately 50% of the total energy demand, mostly from ammonia separation requirements. In the hydrogen fed cell arrangement, it was also demonstrated that recycle of unconverted hydrogen is essential for efficient operation, even in the case where this increases BOP energy inputs.

Highlights

  • Large-scale production of synthetic ammonia has become one of the most important industries supporting the human population

  • A slight reduction in energy requirement from the fuel cell offset can be seen in this case, it does not make up for the increased energy demand needed to produce excess hydrogen which is not converted to ammonia due to low faradaic efficiency and cell utilisation (50 mol% conversion per pass assumed in the base model scenario)

  • Energy demands for electrochemical ammonia generation have been calculated for three process arrangements and comparison of water or hydrogen fed synthesis approaches carried out

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Summary

INTRODUCTION

Large-scale production of synthetic ammonia has become one of the most important industries supporting the human population. Like the modern small-scale Haber-Bosch approach, the hydrogen used for the electrochemical synthesis can be sourced by renewable powered water electrolysis and the overall reaction identical to Eq 1. Other high level assessments of electrical energy demands have been attempted in order to broadly assess the potential of electrochemical approaches compared to traditional Haber-Bosch, reporting values of 7.5–11 kWh/kg NH3, it is unlikely these values considered the balance of plant (Rouwenhorst et al, 2019). The focus is on overall power inputs and key sensitivities in order to understand potential challenges in up-scaling the process once fundamental constraints are met These include the extent of reactant conversion, faradaic efficiency and energy demand of the cell as well as the impact of recycle streams. Key separation steps are highlighted since the conditions and combinations of species in each stream are often different to what is seen in a commercial ammonia chemical synthesis plant and may require additional fundamental development

MODEL DETAILS
Nitrogen Production
Condensers
Membrane Separation
Electrochemical Ammonia Generation
Base Model Performance
Sensitivity Analysis
CONCLUSION
DATA AVAILABILITY STATEMENT
Full Text
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