Zinc oxide nanoparticles were obtained by plasma-enhanced chemical vapor deposition (PECVD) under optical emission spectrometry control from elemental high-purity zinc in a zinc–oxygen–hydrogen plasma-forming gas mixture with varying deposition parameters: a zinc source temperature, and a reactor temperature in a deposition zone. The size and morphological parameters of the zinc oxide nanopowders, structural properties, and homogeneity were studied. The study was carried out with use of methods such as scanning electron microscopy, X-ray structural analysis, and Raman spectroscopy, as well as statistical methods for processing and analyzing experimental data. It was established that to obtain zinc oxide nanoparticles with a given size and morphological characteristics using PECVD, it is necessary (1) to increase the zinc source temperature to synthesize more elongated structures in one direction (and vice versa), and (2) to decrease the reactor temperature in the deposition zone to reduce the transverse size of the deposited structures (and vice versa), taking into account that at relatively low temperatures instead of powder structures, films can form.
The effect of the morphology and content of zinc oxide nanoparticles (ZnO-NPs) on the physicochemical, mechanical, and gas transport properties of the polyurethane (PU) mixed matrix membranes (MMMs) with respect to CO2 recovery from CH4, O2, and N2 was studied. The MMMs based on PU with spherical and rod-shaped ZnO-NPs at various loadings, namely, 0.05, 0.1, 0.5, 1, and 2 wt. %, were prepared with membrane density control and studied using AFM, wettability measurements, surface free energy calculation, gas separation and mechanical testing. To evaluate the resistance of the ZnO-NPs to agglomeration in the polymer solutions, zeta potential was determined. The ZnO-NPs with average cross sectional size of 30 nm were obtained by plasma-enhanced chemical vapor deposition (PECVD) from elemental high-purity zinc in a zinc-oxygen-hydrogen plasma-forming gas mixture. It was established that the spherical ZnO-NPs are promising to improve the gas performance of PU-based MMMs for CO2 recovery from natural gas, while the rod-shaped NPs better demonstrate their potential in capturing CO2 in flue gases.
This present study covers a complex approach to study a hybrid separation technique: membrane-assisted gas absorption for CO2 capture from flue gases. It includes not only the engineering aspects of the process, particularly the cell design, flow organization, and process conditions, but also a complex study of the materials. It covers the spinning of hollow fibers with specific properties that provide sufficient mass transfer for their implementation in the hybrid membrane-assisted gas absorption technique and the design of an absorbent with a new ionic liquid—bis(2-hydroxyethyl) dimethylammonium glycinate, which allows the selective capture of carbon dioxide. In addition, the obtained hollow fibers are characterized not only by single gas permeation but with regard to mixed gases, including the transfer of water vapors. A quasi-real flue gas, which consists of nitrogen, oxygen, carbon dioxide, and water vapors, is used to evaluate the separation efficiency of the proposed membrane-assisted gas absorption technique and to determine its ultimate performance in terms of the CO2 content in the product flow and recovery rate. As a result of this study, it is found that highly permeable fibers in combination with the obtained absorbent provide sufficient separation and their implementation is preferable compared to a selective but much less permeable membrane.
1 December 2023 in Membranes and Membrane Technologies
In this work, the dependence of the output characteristics of the gas separation membrane process determined during the simulation on the gas transport characteristics of the membrane as parameters of the membrane module model has been studied. The study has been performed using the example of a laboratory sample containing hollow fibers from polyphenylene oxide. As a result of this comprehensive study, including theoretical and experimental approaches, it has been determined that when using the gas transport characteristics obtained for pure gases for process simulation, the error expressed in the achievable concentration of the target component in the product stream is from 1.5 to 8.8% in comparison with the experimentally obtained values for the module of the same geometry and the same membrane area. This discrepancy can lead both to the setting of unattainable targets when creating a technological line and to an incorrect technical and economic assessment of the process. Thus, when designing technological lines using mathematical modeling tools, one should rely on the gas transport characteristics of a material and/or product obtained for components of real or simulating real gas mixtures.
1 October 2023 in Membranes and Membrane Technologies
Commercially available hollow fiber membranes made of two polymers, namely, polysulfone and poly(phenylene oxide), are studied experimentally. The main task of this study is to estimate the gas transport characteristics of these membranes in relation to air components and noble gases. Therefore, the values of permeability of the membranes for nitrogen, oxygen, helium, argon, xenon and krypton are measured. Particular attention is paid to the xenon-containing air mixture, since the capture of medical xenon is an urgent chemical and technological problem due to a high cost of the process of obtaining this gas. The values of permeability of the two membranes for individual gases are determined, and the values of ideal selectivity are calculated. For example, the values of membrane permeability for argon, krypton, and xenon are 20.8, 8.4, and 6.8 GPU for the polysulfone membrane and 19.5, 6.2, and 4.8 GPU for the poly(phenylene oxide) membrane, respectively. It is found that the xenon permeability of these membranes in the case of separation of the gas mixture composed of nitrogen, oxygen, and xenon is 5.9 and 4.1 GPU for polysulfone and poly(phenylene oxide). It is also shown that the performance of membrane modules based on polysulfone and poly(phenylene oxide) depends on the total membrane area.
Polyetherimide (Ultem-1000) hollow-fiber membranes were developed for biogas purification with emphasis on the relationship between spinning conditions, membrane morphology, gas transport properties, and module performance. Hollow fibers were prepared from dope solutions based on dimethylformamide (DMF) and N-methyl-2-pyrrolidone (NMP) at different conditions, followed by post-treatment with 1 and 3 wt.% silicone solution in n-heptane to reduce nonselective defects and improve selectivity toward the intrinsic behavior of dense PEI films. SEM analysis revealed that DMF-based fibers formed a more open, macrovoid-rich structure, whereas NMP-based fibers exhibited a more homogeneous sponge-like morphology with a better-defined selective layer. DMF-based fibers experienced faster demixing, which promoted macrovoid formation, increased pore connectivity of the substructure, lowered mass transfer resistance, and at the same time increased the probability of nonselective pathways and defect-related loss of selectivity. This structural evolution was reflected in gas transport properties: untreated DMF fibers showed high mixed-gas permeance but limited selectivity, while NMP fibers demonstrated lower permeance and selectivity values closer to those of the dense film. Silicone post-treatment significantly improved separation performance, with 3 wt.% coating being markedly more effective than 1 wt.% coating. The best compromise between permeance and selectivity was achieved for the DMF-based fibers treated with 3 wt.% silicone, which exhibited CO2 and H2S permeances of 39.4 and 47.12 GPU, respectively, together with selectivity values of 22.4, 26.8 and 20.2 for CO2/CH4, H2S/CH4 and CO2/N2. A membrane module containing 500 fibers was studied during the quasi-real biogas upgrading. With increasing stage-cut, the CH4 concentration in the retentate increased from ~74 to 96 mol.%, while CO2 decreased from ~21 to 2 mol.%. The results demonstrate that structure control combined with silicone post-treatment is an effective strategy for producing PEI hollow fibers suitable for simultaneous methane enrichment and removal of acid impurities from biogas.