Browsing by Author "Di Profio, Gianluca"

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    Chemically reactive membrane crystallisation reactor for CO2–NH3 absorption and ammonium bicarbonate crystallisation: Kinetics of heterogeneous crystal growth
    (Elsevier, 2019-11-22) Bavarella, Salvatore; Brookes, Adam; Moore, Andrew; Vale, Peter C. J.; Di Profio, Gianluca; Curcio, Efrem; Hart, Phil; Pidou, Marc; McAdam, Ewan J.
    The feasibility of gas-liquid hollow fibre membrane contactors for the chemical absorption of carbon dioxide (CO2) into ammonia (NH3), coupled with the crystallisation of ammonium bicarbonate has been demonstrated. In this study, the mechanism of chemically facilitated heterogeneous membrane crystallisation is described, and the solution chemistry required to initiate nucleation elucidated. Induction time for nucleation was dependent on the rate of CO2 absorption, as this governed solution bicarbonate concentration. However, for low NH3 solution concentrations, a reduction in pH was observed with progressive CO2 absorption which shifted equilibria toward ammonium and carbonic acid, inhibiting both absorption and nucleation. An excess of free NH3 buffered pH suitably to balance equilibria to the onset of supersaturation, which ensured sufficient bicarbonate availability to initiate nucleation. Following induction at a supersaturation level of 1.7 (3.3 M NH3), an increase in crystal population density and crystal size was observed at progressive levels of supersaturation which contradicts the trend ordinarily observed for homogeneous nucleation in classical crystallisation technology, and demonstrates the role of the membrane as a physical substrate for heterogeneous nucleation during chemically reactive crystallisation. Both nucleation rate and crystal growth rate increased with increasing levels of supersaturation. This can be ascribed to the relatively low chemical driving force imposed by the shift in equilibrium toward ammonium which suppressed solution reactivity, together with the role of the membrane in promoting counter-current diffusion of CO2 and NH3 into the concentration boundary layer developed at the membrane wall, which permitted replenishment of reactants at the site of nucleation, and is a unique facet specific to this method of membrane facilitated crystallisation. Free ammonia concentration was shown to govern nucleation rate where a limiting NH3 concentration was identified above which crystallisation induced membrane scaling was observed. Provided the chemically reactive membrane crystallisation reactor was operated below this threshold, a consistent (size and number) and reproducible crystallised reaction product was collected downstream of the membrane, which evidenced that sustained membrane operation should be achievable with minimum reactive maintenance intervention.
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    Is chemically reactive membrane crystallisation faciliated by heterogeneous primary nucleation? Comparison with conventional gas-liquid crystallisation for ammonium bicarbonate precipitation in a CO2-NH3-H2O system
    (American Chemical Society, 2020-01-27) Bavarella, Salvatore; Hermassi, Mehrez; Brookes, Adam; Moore, Andrew; Vale, Peter C. J.; Di Profio, Gianluca; Curcio, Efrem; Hart, Phil; Pidou, Marc; McAdam, Ewan
    In this study, membrane crystallisation is compared to conventional gas-liquid crystallisation for the precipitation of ammonium bicarbonate, to demonstrate the distinction in kinetic trajectory and illustrate the inherent advantage of phase separation introduced by the membrane to crystallising in gas-liquid systems. Through complete mixing of gas and liquid phases in conventional crystallisation, high particle numbers were confirmed at low levels of supersaturation. This was best described by secondary nucleation effects in analogy to mixed suspension mixed product removal (MSMPR) crystallisation, for which a decline in population density was observed with an increase in crystal size. In contrast, for membrane crystallisation, fewer nuclei were produced at an equivalent level of supersaturation. This supported growth of fewer, larger crystals which is preferred to simplify product recovery and limit occlusions. Whilst continued crystal growth was identified with the membrane, this was accompanied by an increase in nucleation rate which would indicate the segregation of heterogeneous primary nucleation from crystal growth, and was confirmed by experimental derivation of the interfacial energy for ammonium bicarbonate (σ, 6.6 mJ m-2), which is in agreement to that estimated for inorganic salts. The distinction in kinetic trajectory can be ascribed to the unique phase separation provided by the membrane which promotes a counter diffusional chemical reaction to develop, introducing a region of concentration adjacent to the membrane. The membrane also lowers the activation energy required to initiate nucleation in an unseeded solution. In conventional crystallisation, the high nucleation rate was due to the higher probability for collision, and the gas stripping of ammonia (around 40% loss) through direct contact between phases which lowered pH and increased bicarbonate availability for the earlier onset of nucleation. It is this high nucleation rate which has restricted the implementation of gas-liquid crystallisation in direct contact packed columns for carbon capture and storage. Importantly, this study evidences the significance of the membrane to governing crystallisation for gas-liquid chemical reactions through providing controlled phase separation.
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    Unifying nucleation and crystal growth mechanisms in membrane crystallisation
    (Elsevier, 2025-05-01) Mapetere, A.; Di Profio, Gianluca; Curcio, Efrem; Campo Moreno, Pablo; McAdam, Ewan J.
    While several mechanisms have been proposed to describe crystallisation processes in membrane distillation, it has not been possible to provide a definitive description since the nucleation kinetics are difficult to measure. This study therefore introduced non-invasive techniques to measure induction time within two discrete domains (the membrane surface and bulk solution) and was complemented by the introduction of a modified power law relation between supersaturation and induction time, that enables mass and heat transfer processes in the boundary layer to be directly related to classical nucleation theory (CNT). Temperature (T, 45–60 °C) and temperature difference (ΔT, 15–30 °C) were used to adjust boundary layer properties, which established a log-linear relation between the nucleation rate and the supersaturation level in the boundary layer at induction, which is characteristic of CNT. Crystal size distribution analysis demonstrated how nucleation rate and crystal growth rate could be adjusted using ΔT and T respectively. Consequently, ΔT and T can be used collectively to fix the supersaturation set point within the boundary layer to achieve the preferred crystal morphology. However, at higher supersaturation levels, scaling was observed. Discrimination of the primary nucleation mechanisms, using measured induction times, revealed scaling to be formed homogeneously, which indicates exposure of the pores to extremely high supersaturation levels. Morphological analysis of scaling indicated growth to be dominated by secondary nucleation mechanisms, that resulted in a habit that is distinctive from the crystal phase formed in the bulk solution. From this analysis, a critical supersaturation threshold was identified, below which kinetically controlled scaling can be ‘switched-off’, leaving crystals to form solely in the bulk solution comprising the preferred cubic morphology. This study serves to unify understanding on nucleation and growth mechanisms to enhance control over crystallisation in membrane systems.