Fateme Rezaei

Aminosilane-Grafted Polymer/Silica Hollow Fiber Adsorbents for CO2 Capture from Flue Gas

Amine/silica/polymer composite hollow fiber adsorbents are produced using a novel reactive post-spinning infusion technique, and the obtained fibers are shown to capture CO2 from simulated flue gas. The post-spinning infusion technique allows for functionalization of polymer/silica hollow fibers with different types of amines during the solvent exchange step after fiber spinning. The post-spinning infusion of 3-aminopropyltrimethoxysilane (APS) into mesoporous silica/cellulose acetate hollow fibers is demonstrated here, and the materials are compared with hollow fibers infused with poly(ethyleneimine) (PEI). This approach results in silica/polymer composite fibers with good amine distribution and accessibility, as well as adequate porosity retained within the fibers to facilitate rapid mass transfer and adsorption kinetics. The CO2 adsorption capacities for the APS-infused hollow fibers are shown to be comparable to those of amine powders with similar amine loadings. In contrast, fibers that are spun with presynthesized, amine-loaded mesoporous silica powders show negligible CO2 uptake and low amine loadings because of loss of amines from the silica materials during the fiber spinning process. Aminosilica powders are shown to be more hydrophilic than the corresponding amine containing composite hollow fibers, the bare polymer as well as silica support. Both the PEI-infused and APS-infused fibers demonstrate reduced CO2 adsorption upon elevating the temperature from 35 to 80 °C, in accordance with thermodynamics, whereas PEI-infused powders show increased CO2 uptake over that temperature range because of competing diffusional and thermodynamic effects. The CO2 adsorption kinetics as probed via TGA show that the APS-infused hollow fiber adsorbents have more rapid uptake kinetics than their aminosilica powder analogues. The adsorption performance of the functionalized hollow fibers is also assessed in CO2 breakthrough experiments. The breakthrough results show a sharp CO2 front for APS-grafted fibers, indicating fast kinetics with comparable pseudo-equilibrium capacities to the CO2 equilibrium capacities measured via thermogravimetric analysis (TGA). The results indicate the post-spinning infusion method provides a new platform for synthesizing composite polymer/silica/amine fibers that may facilitate the ultimate scale-up of practical fiber adsorbents for flue gas CO2 capture applications.

Development of Short-Carbon-Fiber-Reinforced Polypropylene Composite for Car Bonnet

In this paper, short-carbon-fiber-reinforced polypropylene (SCF/PP) composites were prepared with melt blending and hot-pressing techniques. The tensile properties, flexural properties, hardness, and work of fracture (WOF) of this composite were investigated. Thermal stability of the composite was studied via the thermal gravimetric analysis (TGA). Finally, the mechanical properties of this composite were compared to mechanical properties of steel car bonnet in order to choose for car bonnet application. The properties of the composite prepared by 10% SCF/PP is comparable with the properties of carbon steel.

3D-Printed Zeolite Monoliths for CO2 Removal from Enclosed Environments

Structured adsorbents, especially in the form of monolithic contactors, offer an excellent gas-solid contacting strategy for the development of practical and scalable CO2 capture technologies. In this study, the fabrication of three-dimensional (3D)-printed 13X and 5A zeolite monoliths with novel structures and their use in CO2 removal from air are reported. The physical and structural properties of these printed monoliths are evaluated and compared with their powder counterparts. Our results indicate that 3D-printed monoliths with zeolite loadings as high as 90 wt % exhibit adsorption uptake that is comparable to that of powder sorbents. The adsorption capacities of 5A and 13X monoliths were found to be 1.59 and 1.60 mmol/g, respectively, using 5000 ppm (0.5%) CO2 in nitrogen at room temperature. The dynamic CO2/N2 breakthrough experiments show relatively fast dynamics for monolithic structures. In addition, the printed zeolite monoliths show reasonably good mechanical stability that can eventually prevent attrition and dusting issues commonly encountered in traditional pellets and beads packing systems. The 3D printing technique offers an alternative, cost-effective, and facile approach to fabricate structured adsorbents with tunable structural, chemical, and mechanical properties for use in gas separation processes.

Composite Polymer/Oxide Hollow Fiber Contactors: Versatile and Scalable Flow Reactors for Heterogeneous Catalytic Reactions in Organic Synthesis

Flexible composite polymer/oxide hollow fibers are used as flow reactors for heterogeneously catalyzed reactions in organic synthesis. The fiber synthesis allows for a variety of supported catalysts to be embedded in the walls of the fibers, thus leading to a diverse set of reactions that can be catalyzed in flow. Additionally, the fiber synthesis is scalable (e.g. several reactor beds containing many fibers in a module may be used) and thus they could potentially be used for the large-scale production of organic compounds. Incorporating heterogeneous catalysts in the walls of the fibers presents an alternative to a traditional packed-bed reactor and avoids large pressure drops, which is a crucial challenge when employing microreactors.

Poly(amide-imide)/Silica Supported PEI Hollow Fiber Sorbents for Postcombustion CO2 Capture by RTSA

Amine-loaded poly(amide-imide) (PAI)/silica hollow fiber sorbents are created and used in a rapid temperature swing adsorption (RTSA) system for CO2 capture under simulated postcombustion flue gas conditions. Poly(ethylenimine) (PEI) is infused into the PAI/mesoporous silica hollow fiber sorbents during fiber solvent exchange steps after fiber spinning. A lumen-side barrier layer is also successfully formed on the bore side of PAI/silica hollow fiber sorbents by using a mixture of Neoprene with cross-linking agents in a post-treatment process. The amine loaded fibers are tested in shell-and-tube modules by exposure on the shell side at 1 atm and 35 °C to simulated flue gas with an inert tracer (14 mol % CO2, 72 mol % N2, and 14 mol % He, at 100% relative humidity (RH)). The fibers show a breakthrough CO2 capacity of 0.85 mmol/g-fiber and a pseudoequilibrium CO2 uptake of 1.19 mmol/g-fiber. When tested in the temperature range of 35-75 °C, the PAI/silica/PEI fiber sorbents show a maximum CO2 capacity at 65 °C, owing to a trade-off between thermodynamic and kinetic factors. To overcome mass transfer limitations in rigidified PEI infused in the silica, an alternate PEI infusion method using a glycerol/PEI/methanol mixture is developed, and the CO2 sorption performance is improved significantly, effectively doubling the functional sorption capacity. Specifically, the glycerol-plasticized sorbents are found to have a breakthrough and equilibrium CO2 capacity of 1.3 and 2.0 mmol/g of dry fiber sorbent at 35 °C, respectively. Thus, this work demonstrates two PAI-based sorbents that are optimized for different sorption conditions with the PAI/silica/PEI sorbents operating effectively at 65 °C and the PAI/silica/PEI-glycerol sorbents operating well at 35 °C with significantly improved sorption capacity.

Formulation of Aminosilica Adsorbents into 3D-Printed Monoliths and Evaluation of Their CO2 Capture Performance

Amine-based materials have represented themselves as a promising class of CO2 adsorbents; however, their large-scale implementation requires their formulation into suitable structures. In this study, we report formulation of aminosilica adsorbents into monolithic structures through a three-dimensional (3D) printing technique. In particular, 3D-printed monoliths were fabricated using presynthesized silica-supported tetraethylenepentamine (TEPA) and poly(ethylenimine) (PEI) adsorbents using three different approaches. In addition, a 3D-printed bare silica monolith was prepared and post-functionalized with 3-aminopropyltrimethoxysilane (APS). Characterization of the obtained monoliths indicated that aminosilica materials retained their characteristics after being extruded into 3D-printed configurations. Adsorptive performance of amine-based structured adsorbents was also investigated in CO2 capture. Our results indicated that aminosilica materials retain their structural, physical, and chemical properties in the monoliths. In addition, the aminosilica monoliths exhibited adsorptive characteristics comparable to their corresponding powders. This work highlights the importance of adsorbent materials formulations into practical contactors such as monoliths, as the scalabale technology platform, that could facilitate rapid deployment of adsorption-based CO2 capture processes on commercial scales.

Aminosilane‐Grafted Zirconia–Titiania–Silica Nanoparticles/Torlon Hollow Fiber Composites for CO2 Capture

In this work, the development of novel binary and ternary oxide/Torlon hollow fiber composites comprising zirconia, titania, and silica as amine supports was demonstrated. The resulting binary (Zr-Si/PAI-HF, Ti-Si/PAI-HF) and ternary (Zr-Ti-Si/PAI-HF) composites were then functionalized with monoamine-, diamine-, and triamine-substituted trialkoxysilanes and were evaluated in CO2 capture. Although the introduction of both Zr and Ti improved the CO2 adsorption capacity relative to that with Si/PAI-HF sorbents, zirconia was found to have a more favorable effect on the CO2 adsorption performance than titania, as previously demonstrated for amine sorbents in the powder form. The Zr-Ti-Si/PAI-HF sample with an oxide content of 20 wt % was found to exhibit a relatively high CO2 capacity, that is, 1.90 mmol g(-1) at atmospheric pressure under dry conditions, owing to more favorable synergy between the metal oxides and CO2 . The ternary fiber sorbent showed improved sorption kinetics and long-term stability in cyclic adsorption/desorption runs.

In situ Formation of a Monodispersed Spherical Mesoporous Nanosilica–Torlon Hollow-Fiber Composite for Carbon Dioxide Capture

We describe a new template-free method for the in situ formation of a monodispersed spherical mesoporous nanosilica-Torlon hollow-fiber composite. A thin layer of Torlon hollow fiber that comprises silica nanoparticles was created by the in situ extrusion of a tetraethyl orthosilicate/N-methyl-2-pyrrolidone solution in a sheath layer and a Torlon polymer dope in a core support layer. This new method can be integrated easily into current hollow-fiber composite fabrication processes. The hollow-fiber composites were then functionalized with 3-aminopropyltrimethoxy silane (APS) and evaluated for their CO2 -capture performance. The resulting APS-functionalized mesoporous silica nanoparticles/Torlon hollow fibers exhibited a high CO2 equilibrium capacity of 1.5 and 1.9 mmol g(-1) at 35 and 60 °C, respectively, which is significantly higher than values for fiber sorbents without nanoparticles reported previously.

3D-Printed Metal–Organic Framework Monoliths for Gas Adsorption Processes

Metal-organic frameworks (MOFs) have shown promising performance in separation, adsorption, reaction, and storage of various industrial gases; however, their large-scale applications have been hampered by the lack of a proper strategy to formulate them into scalable gas-solid contactors. Herein, we report the fabrication of MOF monoliths using the 3D printing technique and evaluation of their adsorptive performance in CO2 removal from air. The 3D-printed MOF-74(Ni) and UTSA-16(Co) monoliths with MOF loadings as high as 80 and 85 wt %, respectively, were developed, and their physical and structural properties were characterized and compared with those of MOF powders. Our adsorption experiments showed that, upon exposure to 5000 ppm (0.5%) CO2 at 25 °C, the MOF-74(Ni) and UTSA-16(Co) monoliths can adsorb CO2 with uptake capacities of 1.35 and 1.31 mmol/g, respectively, which are 79% and 87% of the capacities of their MOF analogues under the same conditions. Furthermore, a stable performance was obtained for self-standing 3D-printed monolithic structures with relatively good adsorption kinetics. The preliminary findings reported in this investigation highlight the advantage of the robocasting (3D printing) technique for shaping MOF materials into practical configurations that are suitable for various gas separation applications.

UTSA-16 Growth within 3D-Printed Co-Kaolin Monoliths with High Selectivity for CO2/CH4, CO2/N2, and CO2/H2 Separation

Honeycomb monoliths loaded with metal-organic frameworks (MOFs) are highly desirable adsorption contactors because of their low-pressure drop, rapid mass-transfer kinetics, and high-adsorption capacity. Moreover, three-dimensional (3D)-printing technology renders direct material modification a realistic and economic prospect. In this study, 3D printing was utilized to impregnate kaolin-based monolith with UTSA-16 metal formation precursor (Co), whereupon an internal growth was facilitated via a solvothermal synthesis approach. The cobalt weight loading in the kaolin support was varied systematically to optimize the MOF growth while retaining monolith mechanical integrity. The obtained UTSA-16 monolith with 90 wt % loading exhibited similar textural features and adsorption characteristics to its powder analogue while improving upon structural integrity. In comparison to previously developed 3D-printed UTSA-16 monoliths, the UTSA-16-kaolin monolith not only showed higher MOF loading but also higher compression stress, indicative of its robust structure. Furthermore, the 3D-printed UTSA-16-kaolin monolith displayed a comparable CO2 adsorption capacity to the UTSA-16 powder (3.1 vs 3.5 mmol/g at 25 °C and 1 bar), which was proportional to its loading. Selectivity values of 49, 238, and 3725 were obtained for CO2/CH4, CO2/N2, and CO2/H2, respectively, demonstrating good separation potential of the 3D-printed MOF monolith for various gas mixtures, as determined by both equilibrium and dynamic adsorption measurements. Overall, this study provides a novel route for the fabrication of UTSA-16-loaded monoliths, which demonstrate both high MOF loading and mechanical integrity that could be readily applied to various CO2 capture applications.