Effect of mobile carrier on the performance of pvam–nanocellulose facilitated transport membranes for co2 capture

Facilitated transport membranes obtained by coupling polyvinylamine with highly charged carboxymethylated nanocellulose fibers were studied considering both water sorption and gas permeation experiments. In particular, the effect of the L-arginine as a mobile carrier was investigated to understand possible improvements in CO2 transport across the membranes. The results show that L-arginine addition decreases the water uptake of the membrane, due to the lower polyvinylamine content, but was able to improve the CO2 transport. Tests carried on at 35◦ C and high relative humidity indeed showed an increase of both CO2 permeability and selectivity with respect to nitrogen and methane. In particular, the CO2 permeability increased from 160 to about 340 Barrer when arginine loading was increased from 0 to 45 wt%. In the same conditions, selectivity with respect to nitrogen was more than doubled, increasing from 20 to 45. Minor improvements were instead obtained with respect to methane; CO2 /CH4 selectivity, indeed, even in presence of the mobile carrier, was limited to about 20

Permeation of Ternary Mixture Containing H2S, CO2 and CH4 in Aquivion® Perfluorosulfonic Acid (PFSA) Ionomer Membranes

Aquivion (R) E87-12S Perfluorosulfonated acid ionomer material (PFSA) has been studied as a membrane technology for natural gas sweetening from CO2 , H2S due to its interesting chemical and mechanical stability and good separation performance for polar compounds in humid environments. In the present work, permeation of the H2S/CO2/CH4 ternary mixture in this short-side PFSA chain was investigated at pressures up to 10 bar, temperatures up to 50 degrees C, and in a range of relative humidity (RH) from 20% to 90%. The results obtain confirm the strong dependence of Aquivion (R) on water activity and temperature, and its ability to separate gases based on their water solubility without substantial differences between pure and mixed gas experiments. Indeed, even when tested in ternary mixture, the permeation behavior remains similar to that observed for pure components and binary mixtures. In particular, the permeability of H2S is higher than that of CO(2 )and methane CH4, reaching values of 500 Barrer at 50 degrees C and 80% RH, against 450 and 23 Barrer for the other two gases respectively. Additionally, when tested at higher pressures of up to 10 bar under humid conditions, the membrane properties remained largely unchanged, thus confirming the overall stability and durability of Aquivion (R) E87-12S in acid environments

Multi-scale modeling of gas solubility in semi-crystalline polymers: bridging Molecular Dynamics with Lattice Fluid Theory

The prediction of the solubility of gasses in semi-crystalline polymers is still a challenging task due to the difficulty in providing a comprehensive description of the morphological and mechanical perturbation felt by the amorphous phase intercalated with the impermeable crystal domains. Among the different modeling techniques, a frequently adopted strategy models the reduced solubility experienced by the confined amorphous phase via an additional pressure to the external gas pressure acting on the latter, the so-called constraint pressure ‘pc’. The work presented here is dedicated to a newly developed multi-scale modeling strategy, belonging to the aforementioned category, that innovatively couples Molecular Dynamics simulations with Lattice Fluid theory. The model was applied to carbon dioxide, ethylene, and propane solubility isotherms in High-Density Polyethylene, and validated against experimental literature data, confirming its ability to model the solubility in semi-crystalline polymers. In addition, it showed good accordance with a fully macroscopic model already present in the literature. The successful multi-scale coupling presented here paves the way for the development of a fully predictive modeling strategy

Arginine/Nanocellulose membranes for carbon capture applications

The present study investigates the influence of the addition of L-arginine to a matrix of carboxymethylated nanofibrillated cellulose (CMC-NFC), with the aim of fabricating a mobile carrier facilitated transport membrane for the separation of CO2. Self-standing films were prepared by casting an aqueous suspension containing different amounts of amino acid (15\u201330\u201345 wt.%) and CMC-NFC. The permeation properties were assessed in humid conditions (70\u201398% relative humidity (RH)) at 35 \ub0C for CO2 and N2 separately and compared with that of the non-loaded nanocellulose films. Both permeability and ideal selectivity appeared to be improved by the addition of L-arginine, especially when high amino-acid loadings were considered. A seven-fold increment in carbon dioxide permeability was observed between pure CMC-NFC and the 45 wt.% blend (from 29 to 220 Barrer at 94% RH), also paired to a significant increase of ideal selectivity (from 56 to 185). Interestingly, while improving the separation performance, water sorption was not substantially affected by the addition of amino acid, thus confirming that the increased permeability was not related simply to membrane swelling. Overall, the addition of aminated mobile carriers appeared to provide enhanced performances, advancing the state of the art for nanocellulose-based gas separation membranes

Pebax® 2533/graphene oxide nanocomposite membranes for carbon capture

In this work, the behavior of new GO-based mixed matrix membranes was tested in view of their use as CO2-selective membrane in post combustion carbon capture applications. In particular, the new materials were obtained by mixing of Pebax® 2533 copolymer with different types of graphene oxide (GO). Pebax® 2533 has indeed lower selectivity, but higher permeability than Pebax® 1657, which is more commonly used for membranes, and it could therefore benefit from the addition of GO, which is endowed with very high selectivity of CO2 with respect to nitrogen. The mixed matrix membranes were obtained by adding different amounts of GO, from 0.02 to 1% by weight, to the commercial block copolymers. Porous graphene oxide (PGO) and GO functionalized with polyetheramine (PEAGO) were also considered in composites produced with similar procedure, with a loading of 0.02%wt. The obtained films were then characterized by using SEM, DSC, XPS analysis and permeability experiments. In particular, permeation tests with pure CO2 and N2 at 35°C and 1 bar of upstream pressure were conducted for the different materials to evaluate their separation performance. It has been discovered that adding these GO-based nanofillers to Pebax® 2533 matrix does not improve the ideal selectivity of the material, but it allows to increase CO2 permeability when a low filler content, not higher than 0.02 wt%, is considered. Among the different types of GO, then, porous GO seems the most promising as it shows CO2 permeability in the order of 400 barrer (with an increase of about 10% with respect to the unloaded block copolymer), obtained without reducing the CO2/N2 selectivity of the materials, which remained in the order of 25

Effect of Crystallinity on Water Vapor Sorption, Diffusion, and Permeation of PLA-Based Nanocomposites

The effects of crystalline morphology and presence of nanoparticles such as cellulose nanofibers (CNFs), organically modified nanoclay (C30B), or a combination of both on water vapor sorption and diffusion in polylactide (PLA) were evaluated by a quartz spring microbalance (QSM). It was found that the large spherulite size induced by high-temperature processing leads to an increase in water sorption and a substantial reduction of diffusion with increasing crystallinity. Contrarily, small-sized spherulites, arising after low-temperature processing during solvent-casting, showed a different behavior with a slight decrease in both water vapor sorption and diffusion with increasing crystallinity. These observations suggest that solvent-casting at low temperatures should not be used to predict the properties a material will show after industrial-scale processing. From the analysis of the nanocomposite materials, it was concluded that nanoparticles affected the material′s properties not only by themselves but also by modifying the crystalline morphology. Interestingly, this led to CNF showing similar performance to C30B, decreasing water diffusivity (21 vs 27%) on isothermally crystallized materials despite its less favorable geometry. Additionally, the incorporation of 1 wt % CNF and C30B decreased water vapor transmission rate (WVTR) by 24% under an amorphous state but by 44% in a crystallized state, which makes hybrid CNF/C30B composites a promising food packaging material

Polyvinylamine membranes containing graphene-based nanofillers for carbon capture applications

In the present study, the separation performance of new self-standing polyvinylamine (PVAm) membranes loaded with few-layer graphene (G) and graphene oxide (GO) was evaluated, in view of their use in carbon capture applications. PVAm, provided by BASF as commercial product named Lupamin\u2122, was purified obtaining PVAm films with two degrees of purification: Low Grade (PVAm-LG) and High Grade (PVAm-HG). These two-grade purified PVAm were loaded with 3 wt% of graphene and graphene oxide to improve mechanical stability: indeed, pristine tested materials proved to be brittle when dry, while highly susceptible to swelling in humid conditions. Purification performances were assessed through FTIR-ATR spectroscopy, DSC and TGA analysis, which were carried out to characterize the pristine polymer and its nanocomposites. In addition, the membranes\u2032 fracture surfaces were observed through SEM analysis to evaluate the degree of dispersion. Water sorption and gas permeation tests were performed at 35 \ub0C at different relative humidity (RH), ranging from 50% to 95%. Overall, composite membranes showed improved mechanical stability at high humidity, and higher glass transition temperature (Tg) with respect to neat PVAm. Ideal CO2/N2 selectivity up to 80 was measured, paired with a CO2 permeability of 70 Barrer. The membranes\u2019 increased mechanical stability against swelling, even at high RH, without the need of any crosslinking, represents an interesting result in view of possible further development of new types of facilitated transport composite membranes

Synthesis and characterization of a benzoyl modified Pebax materials for gas separation applications

Pebax copolymers produced by Arkema are widely employed for different applications, including active molecular carriers and membranes for gas separation. In the present work, a new modification approach for Pebax®2533 is presented, along with the characterization of the newly obtained materials. Pebax was modified by grafting, through a nucleophilic acyl substitution, a benzoyl group on Polyamide12 block. The yield of the reaction was confirmed by FTIR and NMR analysis, while thermal DSC and TGA characterizations were then carried out on the polymeric products characterized by different degrees of substitution to understand their properties. Finally, self-standing films were obtained by casting and gas permeation tests were conducted at 35 °C using CO2, N2, CH4, O2 and He, in order to understand the potentiality of the new material as membrane for gas separation. DSC showed that in the modified Pebax, named “Benzoyl-P2533” (BP2533), the crystalline phase of the Nylon block was canceled, as expected, but at the same time the degree of crystallinity of the block of Polytetramethyleneoxide increased from 19%, measured for the unmodified Pebax, to a max of 35% for the fully substituted material. For this reason, gas permeability showed small but consistent increment, in the order of 10–11% for most of the gas tested, with the only exception being helium, where the increment resulted to be around 48%. As a consequence, the overall selectivity of CO2 against helium dropped with respect to pristine Pebax. For all the other gases, on the other hand the selectivity with respect to CO2 remained substantially constant, resulting in slight but neat improvement of the ability of the new material to separate this gas

Structure–Properties Relationship of Reprocessed Bionanocomposites of Plasticized Polylactide Reinforced with Nanofibrillated Cellulose

Bionanocomposites of polylactide (PLA), plasticized with poly(ethylene glycol) (PEG) (7.5 wt%, 400 and 1500 g/mol) and reinforced with nanofibrillated cellulose (NFC) (1, 3, and 5 wt%) were sequentially compounded, and injection and compression molded. All of the stages caused structural and morphological consequences, more relevant in the plasticized PLA, especially with low molar PEG. Small percentages of NFC (1 and 3 wt%) acted as crystalline nucleating agents and improved thermo-oxidative stability. Given the substantial degradation caused by (re)processing, a downgrading validation strategy was applied, assessing the mechanical and water contact performance during fictional first and second service life applications. After the first processing, PEG increased the ductility and reduced the strength and elastic modulus, while NFC buffered the fall in stiffness and increased rigidity compared to their PLA-PEG counterparts. Once reprocessed, PEG increased the water affinity of the blend, especially for low molar mass PEG. Low percentages of NFC (1 and 3 wt%) modulated water diffusivity and permeability, regardless of the water temperature. Overall, although reprocessing caused significant degradation, the mechanical valorization possibilities of these green bionanocomposites were proven, and are pointed out as sustainable candidates for food packaging or agricultural applications where modulated mechanical or water contact behaviors are required

Highly CO2-permeable membranes derived from a midblock-sulfonated multiblock polymer after submersion in water

To mitigate the effect of atmospheric CO2 on global climate change, gas separation materials that simultaneously exhibit high CO2 permeability and selectivity in gas mixtures must be developed. In this study, CO2 transport through midblock-sulfonated block polymer membranes prepared from four different solvents is investigated. The results presented here establish that membrane morphology and accompanying gas transport properties are sensitive to casting solvent and relative humidity. We likewise report an intriguing observation: submersion of these thermoplastic elastomeric membranes in liquid water, followed by drying prior to analysis, promotes not only a substantial change in membrane morphology, but also a significant improvement in both CO2 permeability and CO2/N2 selectivity. Measured CO2 permeability and CO2/N2 selectivity values of 482 Barrer and 57, respectively, surpass the Robeson upper bound, indicating that these nanostructured membranes constitute promising candidates for gas separation technologies aimed at CO2 capture