The development and validation of a novel, parameter-free, modelling strategy for electromembrane processes: Electrodialysis

As the global water crisis worsens and natural resources of strategic inorganic elements dwindle, the need for efficient and effective salt separation methods is becoming ever more important. Electromembrane processes, and in particular electrodialysis, are emerging as efficient and effective separation technologies that use an electric field to drive the transport of ions against a concentration gradient. Modelling electromembrane processes allows for process design and optimisation, as well as the identification of what technological improvements would have the greatest effect. However, the wide use of empirical fitting parameters in most existing models greatly limits their globality. The presence of complex and confounding phenomena within electromembrane processes greatly exacerbates this. In this work, a novel, circuit-based modelling strategy for electromembrane processes is presented, avoiding the use of any fitting parameters. Conventional electrodialysis is adopted as a case study. The implementation of a novel transport number model and membrane resistance model are crucial for model accuracy over a wide range of process conditions. The model was experimentally validated and showed excellent agreement with experimental data across a range of concentrations and voltages. Consequently, this model will prove to be an excellent tool for researchers and process designers

Foaming of CO 2 Loaded Amine Solvents Degraded Thermally Under Stripper Conditions

Foaming of amine solutions remains a problem for natural gas sweetening and post-combustion carbon capture. New amine-based solutions are being developed to replace monoethanolamine (MEA). This work tested the foaminess of MEA and three alternatives (methyldiethanolamine (MDEA), 1-(2-aminoethyl)piperazine (AEPZ), 2-amino-2-methyl-1-propanol (AMP)) before and after thermal degradation; two methods were used to describe the foaminess. Foam was only formed after thermal degradation. The first method suggests foaminess where AEPZ > MDEA > MEA; AMP, by contrast, did not conform to this model and formed stable foam. The second method, using liquid physical properties, found that solutions containing more degradation products (MEA, MDEA, AMP) show different foaminess than those without i.e. the changing chemistry during degradation strongly impacts the foaminess observed. The foaming of these degraded samples demonstrates complexity which cannot be replicated by simple model solutions. This study is therefore more representative of the foaming behavior seen in industrial cases

Effects of the Ionic Liquid Structure on Porosity of Lignin-Derived Carbon Materials

Converting lignin into advanced porous carbon materials, with desirable surface functionalities, can be challenging. While lignin-derived carbons produced by pyrolysis at >600 °C develop porosity, they also simultaneously lose nearly all their surface functional groups. By contrast, pyrolysis of lignin at lower temperatures (e.g., <400 °C) results in the formation of nonporous char that retains some surface functionalities. However, copyrolysis of lignin with some ionic liquids (ILs) at lower temperatures offers an opportunity to produce porous carbon materials with both large surface areas and an abundance of surface functional groups. This study investigates the effects of IL properties (solubility, thermal, and ionic size) on the specific surface areas of lignin-derived carbons produced by copyrolysis of lignin and ILs at 350–400 °C for 20 min. It was found that ILs that have bulky anions and small cation sizes can induce porosity in lignin-derived carbons with large surface areas. Among 16 ILs that were tested, [C2MIm]­[NTF2] demonstrated the best performance; the inclusion of it in the copyrolysis process resulted in lignin-derived carbons with ∼528 m2 g–1 and 0.48 cm3 g–1. Lignin-derived carbons produced using no IL, [C2MIm]­[NTF2], and [C4MIm]­[OTF] were further characterized for morphology, interfacial chemical, and elemental properties. The copyrolysis of lignin and [C2MIm]­[NTF2], and [C4MIm]­[OTF] resulted in doping of heteroatoms (N and S) on the porous carbon materials during pyrolysis reaction. The present findings contribute to a better understanding of the main property of ILs responsible for creating porosity in lignin carbon during pyrolysis

Foaming of CO₂‑Loaded Amine Solvents Degraded Thermally under Stripper Conditions

Foaming of amine solutions remains a problem for natural gas sweetening and post-combustion carbon capture. New amine-based solutions are being developed to replace monoethanolamine (MEA). This work tested the foaminess of MEA and three alternatives (methyldiethanolamine (MDEA), 1-(2-aminoethyl)­piperazine (AEPZ), and 2-amino-2-methyl-1-propanol (AMP)) before and after thermal degradation; two methods were used to describe the foaminess. Foam was only formed after thermal degradation. The first method suggests foaminess, where AEPZ > MDEA > MEA; AMP, by contrast, did not conform to this model and formed a stable foam. The second method, using liquid physical properties, found that solutions that contained more degradation products (MEA, MDEA, AMP) showed different foaminess than those that did not (i.e., changing the chemistry during degradation strongly impacts the foaminess, which is observed). The foaming of these degraded samples demonstrates complexity that cannot be replicated by simple model solutions. Therefore, this study is more representative of the foaming behavior that is observed in industrial cases

The development and evaluation of a parameter-free circuit-based model of bipolar membrane electrodialysis for process design and optimisation

Bipolar membrane electrodialysis (BPMED) is an emerging electromembrane technology which has the potential to replace existing pH manipulation process units among others and take advantage of the benefits posed by process electrification. The development of robust and flexible process models of BPMED for design and optimisation is paramount in derisking potential instillations and improving commercial viability. Herein, a circuit-based model of BPMED is presented which avoids reliance on empirical fitting parameters and training data. The resulting model is flexible enough that extension to account for added complexities may be readily adopted. The mass transfer and electrical resistance of six different domains (three membranes and three streams) were computed by applying fundamental laws such as Ohm’s law and Faraday’s first law. Acid-base reactions and their effect releasing current within the membranes were also considered. Furthermore, the stack model can be readily embedded in a broader process model. To this end, the stack model is applied to a recirculating-batch experiment using a delayed differential material balance to account for dead-time within the tubing and measurement flow-cells. Two orthogonal methods of experimental validation were conducted to assess the performance of the model over a range of concentrations and applied voltages. These involved running a recirculating-batch experiment and collecting current–voltage polarisation data, respectively, and both showed good agreement with the model predictions. Overall, a robust model of BPMED has been produced which is able to accurately predict system performance and will prove useful for the design and optimisation of industrial systems

Use of copper carbonate as corrosion inhibitor for carbon steel in post combustion carbon capture

The realisation of post-combustion CO2 capture (PCCC) at industrial scale remains limited; one challenge is the concerns around capital costs and another concern is corrosion of the system itself. Corrosion resistance and mitigation against the amine solvent monoethanolamine (MEA) was studied, using the inhibitor copper (II) carbonate basic (CC). Carbon steel (C1018) was tested in CO2 loaded, 5M aqueous MEA solution, alone and in the presence of CC, to assess the corrosivity of the solution. Immersion testing used mass loss, Fe and Cu ion concentration in solution via ICP-MS, imaging (SEM) and analytical techniques (XRD and EDX) to investigate the effect of corrosion. Generally, the use of CC improved C1018 corrosion resistance relative to C1018 alone. Even at low concentrations (0.9 mM), CC was effective in inhibiting corrosion against CO2 loaded MEA, as the observed corrosion rate was effectively zero and no dissolved Fe was detected in solution. There was no evidence of copper surface adsorption. To clarify the solution chemistry resulting in corrosion inhibition, the local chemical environment of Fe and Cu were probed by Cu and Fe K-edge X-ray Absorption Spectroscopy, respectively. The Cu K- edge HERFD-XANES spectra reveal that a Cu2+ amine complex forms, critical to understanding the structure which is promoting significant corrosion inhibition