Toward gas-phase controlled mass transfer in micro-porous membrane contactors for recovery and concentration of dissolved methane in the gas phase

A micro-porous hollow fibre membrane contactor (HFMC) operated in sweep-gas mode has been studied to enable the recovery of dissolved methane from water in concentrated form. At high sweep-gas flow rates, up to 97% dissolved methane removal efficiency is achievable which is sufficient to achieve carbon neutrality (around 88%). An increase in methane composition of the recovered sweep-gas was achievable through two primary mechanisms: (i) an increase in liquid velocity which improved dissolved methane mass transfer into the gas phase; and (ii) a reduction in gas flow which lowered dilution from the receiving gas phase. It was posited that further refinement of the methane content was provided through counter-diffusion of the nitrogen sweep-gas into the liquid phase. Within the boundary conditions studied, the methane composition of the recovered gas phase exceeded the threshold for use in micro-turbines for electricity production. However, reducing the gas-to-liquid ratio to enhance gas phase methane purity introduced gas-phase controlled mass transfer which constrained removal efficiency. Whilst this reduction in removal efficiency can be compensated for by extending path length (i.e. more than one module in series), it is suggested that the gas-phase controlled conditions encountered were also a product of poor shell-side dispersion rather than an approach toward the limiting theoretical gas-to-liquid ratio. This implies that further optimisation can be ascertained through improved membrane contactor design. Importantly, this study demonstrates that micro-porous hollow fibre membrane contactors provide a compact process for recovery of dissolved methane in sufficient concentration for re-use

Quantifying the loss of methane through secondary gas mass transport (or 'slip') from a micro-porous membrane contactor applied to biogas upgrading

Secondary gas transport during the separation of a binary gas with a micro-porous hollow fibre membrane contactor (HMFC) has been studied for biogas upgrading. In this application, the loss or ‘slip' of the secondary gas (methane) during separation is a known concern, specifically since methane possesses the intrinsic calorific value. Deionised (DI) water was initially used as the physical solvent. Under these conditions, carbon dioxide (CO2) and methane (CH4) absorption were dependent upon liquid velocity (VL). Whilst the highest CO2 flux was recorded at high VL, selectivity towards CO2 declined due to low residence times and a diminished gas-side partial pressure, and resulted in slip of approximately 5.2% of the inlet methane. Sodium hydroxide was subsequently used as a comparative chemical absorption solvent. Under these conditions, CO2 mass transfer increased by increasing gas velocity (VG) which is attributed to the excess of reactive hydroxide ions present in the solvent, and the fast conversion of dissolved CO2 to carbonate species reinitiating the concentration gradient at the gas-liquid interface. At high gas velocities, CH4 slip was reduced to 0.1% under chemical conditions. Methane slip is therefore dependent upon whether the process is gas phase or liquid phase controlled, since methane mass transport can be adequately described by Henry's law within both physical and chemical solvents. The addition of an electrolyte was found to further retard CH4 absorption via the salting out effect. However, their applicability to physical solvents is limited since electrolytic concentration similarly impinges upon the solvents' capacity for CO2. This study illustrates the significance of secondary gas mass transport, and furthermore demonstrates that gas-phase controlled systems are recommended where greater selectivity is required

Biogas upgrading by chemical absorption using ammonia rich absorbents derived from wastewater

The use of ammonia (NH3) rich wastewaters as an ecological chemical absorption solvent for the selective extraction of carbon dioxide (CO2) during biogas upgrading to ‘biomethane’ has been studied. Aqueous ammonia absorbents of up to 10,000 gNH3 m−3 demonstrated CO2 absorption rates higher than recorded in the literature for packed columns using 20,000–80,000 g NH3 m−3 which can be ascribed to the process intensification provided by the hollow fibre membrane contactor used in this study to support absorption. Centrifuge return liquors (2325 g m−3 ionised ammonium, NH4+) and a regenerant (477 gNH4+ m−3) produced from a cationic ion exchanger used to harvest NH4+ from crude wastewater were also tested. Carbon dioxide fluxes measured for both wastewaters compared reasonably with analogue ammonia absorption solvents of equivalent NH3 concentration. Importantly, this demonstrates that ammonia rich wastewaters can facilitate chemically enhanced CO2 separation which eliminates the need for costly exogenic chemicals or complex chemical handling which are critical barriers to implementation of chemical absorption. When testing NH3 analogues, the potential to recover the reaction product ammonium bicarbonate (NH4HCO3) in crystalline form was also illustrated. This is significant as it suggests a new pathway for ammonia separation which avoids biological nitrification and produces ammonia stabilised into a commercially viable fertiliser (NH4HCO3). However, in real ammonia rich wastewaters, sodium bicarbonate and calcium carbonate were preferentially formed over NH4HCO3 although it is proposed that NH4HCO3 can be preferentially formed by manipulating both ion exchange and absorbent chemistry

Controlling shell-side crystal nucleation in a gas-liquid membrane contactor for simultaneous ammonium bicarbonate recovery and biogas upgrading

A gas–liquid hollow fibre membrane contactor (HFMC) process has been introduced for carbon dioxide (CO2) separation from biogas where aqueous ammonia (NH3) is used to chemically enhance CO2 absorption and initiate heterogeneous nucleation of the reaction product ammonium bicarbonate at the membrane–solvent interface. Aqueous ammonia absorbents (2–7 M) were initially used in single pass for CO2 separation from a synthetic biogas where nucleation of ammonium bicarbonate crystals was observed at the perimeter of the micropores. Recirculation of the aqueous ammonia absorbent encouraged the growth of ammonium bicarbonate crystals on the shell-side of the membrane that measured several microns in diameter. However, at high aqueous NH3 concentrations (3–7 M), lumen side crystallisation occurred and obstructed gas flow through the lumen of the HFMC. The suggested mechanism for lumen-side crystallisation was absorbent breakthrough into the lumen due to pore wetting which was promoted by low absorbent surface tension at high NH3 concentration. Preferential shell-side nucleation can therefore be promoted by (1) raising surface tension of the absorbent and (2) selection of a membrane with a more regulated pore shape than the PTFE membrane used (d/L 0.065) as both actions can diminish solvent ingress into the pore. This was evidenced using 2 M NH3 absorbent where shell-side crystallisation was evidenced without the onset of lumen side crystallisation. Raising surface tension through the inclusion of salt into the chemical absorbent also promoted greater CO2 flux stability. Importantly, this study demonstrates that chemically enhanced HFMC are an attractive prospect for gas–liquid separation applications where reaction product recovery offers further economic value

Dissolved methane recovery from anaerobic effluents using hollow fibre membrane contactors

Hollow fibre membrane contactor (HFMC) systems have been studied for the desorption of dissolved methane from both analogue and real anaerobic effluents to ascertain process boundary conditions for separation. When using analogue effluents to establish baseline conditions, up to 98.9% methane removal was demonstrated. Elevated organic concentrations have been previously shown to promote micropore wetting. Consequently, for anaerobic effluent from an upflow anaerobic sludge blanket reactor, which was characterised by a high organic concentration, a nonporous HFMC was selected. Interestingly, mass transfer data from real effluent exceeded that produced with the analogue effluent and was ostensibly due to methane supersaturation of the anaerobic effluent which increased the concentration gradient yielding enhanced mass transfer. However, at high liquid velocities a palpable decline in removal efficiency was noted for the nonporous HFMC which was ascribed to the low permeability of the nonporous polymer provoking membrane controlled mass transfer. For anaerobic effluent from an anaerobic membrane bioreactor (MBR), a microporous HFMC was used as the permeate comprised only a low organic solute concentration. Mass transfer data compared similarly to that of an analogue which suggests that the low organic concentration in anaerobic MBR permeate does not promote pore wetting in microporous HFMC. Importantly, scale-up modelling of the mass transfer data evidenced that whilst dissolved methane is in dilute form, the revenue generated from the recovered methane is sufficient to offset operational and investment costs of a single stage recovery process, however, the economic return is diminished if discharge is to a closed conduit as this requires a multi-stage array to achieve the required dissolved methane consent of 0.14 mg l−1.Yorkshire Water; Severn Trent Water; Anglian Water; Northumbrian Water; EPSR

Effect of intra-ply hybrid patches and hydrothermal aging on local bending response of repaired GFRP composite laminates

This study investigates the influence of intra-ply hybrid patches and hydrothermal aging on the indentation properties of patch repaired GFRP composites. Fabrics with various proportions of glass and Kevlar fibers were employed as the patches to achieve enhanced mechanical properties by hybridizing Kevlar and glass fibers together. Hydrothermal aging behavior of repaired composite laminates modified with water-resistant glass fibers in the outer layers was further investigated. Specimens were immersed in an environmental chamber containing seawater at temperatures of 30 (ambient), 50, and 70 °C until up to saturation. Damage mechanisms of repaired laminates were monitored using real-time acoustic emission (AE) technique. The experimental results showed that specimens repaired with 50G:50K patches offered superior performance than the virgin specimens. The hydrothermal aging effect on indentation behavior of the modified repaired specimens showed a considerable reduction in indentation properties, with higher strength retention exhibited by the repaired specimens modified with chopped glass fibers compared to the particulate fibers

Impact behavior of nanoengineered, 3D printed plate-lattices

Herein, we investigate the low-velocity impact behavior of polypropylene random copolymer (PPR)/multi-wall carbon nanotube (MWCNT) and high-density polyethylene (HDPE)/MWCNT plate-lattices processed via fused filament fabrication additive manufacturing, utilizing in-house nanoengineered filament feedstocks. We examine the dynamic crushing and energy absorption characteristics of three typical elementary plate-lattices, namely, simple cubic (SC), body-centered cubic (BCC) and face-centered cubic (FCC) as well as three hybrid plate-lattices (SC-BCC, SC-FCC and SC-BCC-FCC) comprised different weight fractions of MWCNTs at different impact energy levels. The results reveal that the SC-BCC-FCC nanocomposite plate-lattice offers the most favorable impact response as each constituent plate in the lattice contributes to the load carrying capacity for all direction vectors included in the plane of the plate. Furthermore, the results show that impregnating MWCNTs into the PPR and HDPE plate-lattices significantly influences their impact energy attenuation characteristics. Compared with the respective unreinforced plate-lattices, PPR/6 wt% MWCNT SC-BCC-FCC plate-lattices evince higher energy absorption (70%) than HDPE/6 wt% MWCNT SC-BCC-FCC plate-lattices (47%) due to uniform MWCNT dispersion and effective interfacial interaction of MWCNTs in PPR matrix. Our hybrid 3D plate-lattices exhibit a specific energy absorption (SEA) capacity as high as 19.9 J/g, demonstrating their superior impact performance over aluminum and other conventional lattices