Browsing by Author "Moore, Andrew"

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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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    CO2 absorption into aqueous ammonia using membrane contactors: Role of solvent chemistry and pore size on solids formation for low energy solvent regeneration
    (Elsevier, 2022-03-16) Bavarella, Salvatore; Luqmani, Benjamin A. ; Thomas, Navya; Brookes, Adam; Moore, Andrew; Vale, Peter C. J.; Pidou, Marc; McAdam, Ewan J.
    Solids formation can substanitally reduce the energy penalty for ammonia solvent regeneration in carbon capture and storage (CCS), but has been demonstrated in the literature to be difficult to control. This study examines the use of hollow fibre membrane contactors, as this indirect contact mediated between liquid and gas phases in this geometry could improve the regulation of solids formation. Under conditions comparable to existing literature, NH4HCO3 was evidenced to primarily crystallise in the gas-phase (lumen-side of the membrane) due to the high vapour pressure of ammonia, which promotes gaseous transmission from the solvent. Investigation of solvent reactivity demonstrated how equilibria dependent reactions controlled the onset of NH4HCO3 nucleation in the solvent, and limited ‘slip’ through transfomation of ammonia into its protonated form which occurs prior to the phase change. Crystallisation in the solvent was also dependent upon ammonia concentration, where sufficient supersaturation must develop to overcome the activation energy for nucleation. However, this has to be complemented with a reduction in solvent temperature to offset vapour pressure and limit the risk of gas-phase crystallisation. While changes to the solvent chemistry were sufficient to shift from gas-phase to liquid phase crystallisation, wetting was observed immediately after nucleation in the solvent. This was explained by a local region of supersaturation within the coarse membrane pores that promoted a high nucleation rate, altering the material contact angle of the membrane sufficient for solvent to breakthrough into the gas phase. Adoption of a narrower pore size membrane was shown to dissipate wetting after crystallisation in the solvent, illustrating membrane contactors as a stable platform for the sustained separation of CO2 coupled with its simultaneous transformation into a solid. Through resolving previous challenges experienced with solids formation in multiple reactor configurations, the cost benefit of using ammonia as a solvent can be realised, which is critical to enabling economically viable CCS for the transition to net zero, and can be exploited within hollow fibre membrane contactors, eliciting considerable process intensification over existing reactor designs for CCS.
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    Data supporting: 'CO2 absorption into aqueous ammonia using membrane contactors: Role of solvent chemistry and pore size on solids formation for low energy solvent regeneration'
    (Cranfield University, 2022-10-13 16:42) Bavarella, Salvatore; Luqmani, Benjamin A.; Thomas, Navya; Brookes, Adam; Moore, Andrew; Vale, Peter C. J.; Pidou, Marc; McAdam, Ewan
    Solids formation can substantially reduce the energy penalty for ammonia solvent regeneration in carbon capture and storage (CCS), but has been demonstrated in the literature to be difficult to control. This study examines the use of hollow fibre membrane contactors, as this indirect contact mediated between liquid and gas phases in this geometry could improve the regulation of solids formation. Adoption of a narrower pore size membrane was shown to dissipate wetting after crystallisation in the solvent, illustrating membrane contactors as a stable platform for the sustained separation of CO2 coupled with its simultaneous transformation into a solid. Through resolving previous challenges experienced with solids formation in multiple reactor configurations, the cost benefit of using ammonia as a solvent can be realised, which is critical to enabling economically viable CCS for the transition to net zero, and can be exploited within hollow fibre membrane contactors, eliciting considerable process intensification over existing reactor designs for CCS.
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    Demonstrating commercial hollow fibre membrane contactor performance at industrial scale for biogas upgrading at a sewage treatment works
    (MDPI, 2021-01-13) Houlker, Sam; Rutherford, Tony; Herron, Daniel; Brookes, Adam; Moore, Andrew; Vale, Peter C. J.; Pidou, Marc; McAdam, Ewan J.
    Hollow fibre membrane contactor (HFMC) technology has been developed for CO2 absorption primarily using synthetic gas, which neglects the critical impact that trace contaminants might have on separation efficiency and robustness in industrial gases. This study, therefore, commissioned a demonstration-scale HFMC for CO2 separation at a full-scale anaerobic digester facility to evaluate membrane integrity over six months of operation on real biogas. The CO2 capture efficiency identified using real biogas was benchmarked at comparable conditions on synthetic gas of an equivalent partial pressure, and an equivalent performance identified. Two HFMC were subsequently compared, one with and one without a pre-treatment stage that targeted particulates, volatile organic compounds (VOCs) and humidity. Similar CO2 separation efficiency was again demonstrated, indicating limited impact within the timescale evaluated. However, gas phase pre-treatment is advised in order to ensure robustness in the long term. Over longer-term operation, a decline in CO2 separation efficiency was observed. Membrane autopsy identified shell-side deposition, where the structural morphology and confirmation of amide I and II groups, indicated biofouling. Separation efficiency was reinstated via chemical cleaning, which demonstrated that proactive maintenance could minimise process risk.
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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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    Mitigating phase changes in the gas-phase that disrupt CO2 capture in membrane contactors: CO2-NH3-H2O as a model ternary system
    (Elsevier, 2024-06-01) Liqmani, Ben A.; Nayak, Vignesh; Brookes, Adam; Moore, Andrew; Vale, Peter C. J.; Pidou, Marc; McAdam, Ewan J.
    Solid and liquid products can form in the gas phase of membrane contactors applied to reactive ternary systems for CO2 absorption, which poses a critical barrier for carbon capture applications. The mechanism initiating these unwanted phase changes in the gas phase is unclear. This study therefore systematically characterises CO2 absorption in distinct regions of the vapour-liquid equilibrium (VLE) within an illustrative ternary system (CO2-NH3-H2O), to provide an explanation for the formation and mitigation of these solid and liquid products in the gas-phase. Unstable CO2 absorption and increased pressure drop indicated product formation within the gas-phase, which occurred at high CO2 capture ratios. Temporal analysis of gas-phase composition enabled gas-phase products to be related to the relative ternary composition. This was subsequently correlated to distinct regions of the VLE. Consequently, mitigation strategies can be developed with recognition for where products are least likely to form. Pressurisation was proposed to modify the relative gas-phase ammonia composition to reposition conditions within the VLE. The commensurate increase of CO2 into the solvent shifts the ammonia-ammonium equilibrium towards ammonium to indirectly reduce vapour pressure. This synergistic strategy allows sustained operation of membrane contactors for CO2 separation within reactive ternary systems which are critical to delivering carbon capture economically at scale.
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    Recovery and concentration of ammonia from return liquor to promote enhanced CO2 absorption and simultaneous ammonium bicarbonate crystallisation during biogas upgrading in a hollow fibre membrane contactor
    (Elsevier, 2020-01-27) Bavarella, Salvatore; Hermassi, Mehrez; Brookes, Adam; Moore, Andrew; Vale, Peter C. J.; Moon, I. S.; Pidou, Marc; McAdam, Ewan
    In this study, thermal desorption was developed to separate and concentrate ammonia from return liquor, for use as a chemical absorbent in biogas upgrading, providing process intensification and the production of crystalline ammonium bicarbonate as the final reaction product. Applying modest temperature (50°C) in thermal desorption suppressed water vapour pressure and increased selective transport for ammonia from return liquor (0.11MNH3) yielding a concentrated condensate (up to 1.7MNH3). Rectification was modelled through second-stage thermal processing, where higher initial ammonia concentration from the first stage increased mass transfer and delivered a saturated ammonia solution (6.4MNH3), which was sufficient to provide chemically enhanced CO2 separation and the simultaneous initiation of ammonium bicarbonate crystallisation, in a hollow fibre membrane contactor. Condensate recovered from return liquor exhibited a reduction in surface tension. We propose this is due to the stratification of surface active agents at the air-liquid interface during primary-stage thermal desorption which carried over into the condensate, ‘salting’ out CO2 and lowering the kinetic trajectory of absorption. However, crystal induction (the onset of nucleation) was comparable in both synthetic and thermally recovered condensates, indicating the thermodynamics of crystallisation to be unaffected by the recovered condensate. The membrane was evidenced to promote heterogeneous primary nucleation, and the reduction in the recovered condensate surface tension was shown to exacerbate nucleation rate, due to the reduction in activation energy. X-ray diffraction of the crystals formed, showed the product to be ammonium bicarbonate, demonstrating that thermal desorption eliminates cation competition (e.g. Ca2+) to guarantee the formation of the preferred crystalline reaction product. This study identifies an important synergy between thermal desorption and membrane contactor technology that delivers biogas upgrading, ammonia removal from wastewater and resource recovery in a complimentary process.
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    The role of solvent temperature and gas pressure on CO2 mass transfer during biogas upgrading within porous and dense-skin hollow fibre membrane contactors
    (Elsevier, 2023-08-02) Luqmani, Benjamin A. ; Brookes, A.; Moore, Andrew; Vale, Peter C. J.; Pidou, Marc; McAdam, Ewan
    Biogas upgrading uniquely requires pressurisation of hollow fibre membrane contactors (HFMC) to be competitive with classical water absorption, and when complemented with an ambient industrial temperature range, these conditions will determine CO2 mass transport phenomena that are distinct dependent upon whether microporous or nonporous membranes are used. This study therefore examines the independent and concomitant role of temperature and pressure in determining CO2 mass transport, and selectivity, within microporous and nonporous HFMC. At low solvent temperatures, higher CO2 flux was achieved which indicates that solvent solubility is more critical than CO2 diffusivity to enhancing mass transport. Low temperatures also favoured mass transfer within the microporous membrane, explained by the reduction in solvent vapour pressure which limited pore wetting by condensation. In contrast, the nonporous membrane exhibited poorer mass transfer at low temperatures due to a decline in dense polymer permeability. Crucially in this study, neither wetting of the microporous membrane or plasticisation of the nonporous membrane were observed following pressurisation. Consequently, CO2 flux increased in proportion to the applied pressure for both membrane types, emphasising the critical role of pressurisation in augmenting process intensification for biogas upgrading which is typically facilitated at pressures of 7–10 bar. Resistance-in-series analysis illustrated how pressurisation reduced gas-phase resistance, and subsequently enhanced selectivity. Consequently, an outlet gas quality of 98% methane could be achieved within a single microporous module at 4.5 bar, meeting the industrial standard for biomethane whilst reducing solvent requirements, separation energy and methane losses. Comparable behaviour was observed during pressurisation of the nonporous membrane, but with a less significant benefit to CO2 mass transfer and selectivity, ostensibly due to the resistance imparted by the dense polymer. When considered collectively, low solvent temperature and high gas pressure enhance process intensification subsequently reducing process size (e.g., membrane area) and separation energy, while also advancing selectivity to deliver a gas product at the composition required for biomethane with minimum methane losses, which are critical factors in demonstrating microporous HFMC as an industrially competitive solution for biogas upgrading.
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    Transitioning through the vapour-liquid equilibrium for low energy thermal stripping of ammonia from wastewater: enabling transformation of NH3 into a zero-carbon fuel
    (Elsevier, 2023-11-17) Luqmani, Benjamin A. ; Brookes, A.; Moore, Andrew; Vale, Peter C. J.; Pidou, Marc; McAdam, Ewan
    Vacuum thermal stripping permits the recovery of ammonia from wastewater in a concentrated form, which is key to its exploitation in the circular economy, but the latent heat demand for thermal separation remains a critical barrier to exploitation. In this study, we investigate the vapor-liquid equilibrium (VLE) for ammonia-water as a mechanism to enhance recovered ammonia quality and minimise the thermal energy required for ammonia separation. Below the dew point (65 °C at 0.25 bar) a two-phase region of the VLE exists where 48 %wt gas-phase ammonia could be produced (61 °C) compared to only 2 %wt within the stripping region adopted widely in the literature. This was complemented by a 98 % reduction in thermal separation energy, since limited water vaporization can occur when the feed is maintained below the activation energy threshold for bulk evaporation. Operation within this practically unexplored region of the ammonia-water VLE fosters a gas-phase product suitable for energy generation in gas turbines or solid oxide fuel cells. Comparable product quality was achieved using concentrated wastewater, which validated the VLE for design in the presence of a broad range of dissolved gases and volatile inorganic compounds. Rapid desorption of CO2 occurred during vacuum stripping, subsequently increasing pH >9 without the requirement for alkali addition to shift the ammonia-ammonium equilibrium in favor of gaseous ammonia. Consequently, the two-phase region of the VLE defined for vacuum thermal stripping provides a synergistic strategy to mitigate chemical demand, minimise separation energy and recover gas-phase ammonia for zero carbon energy generation, constituting a significant advancement toward the net zero ambitions of the water sector.