Search

The capture of CO 2 is of high interest in our society representing an essential tool to mitigate man-made climate warming. Membrane technology applied for CO 2 capture offers several advantages in terms of energy savings, simple operation, and easy scale-up. Glassy membranes are associated with low gas permeability that negatively affect on their industrial implementation. Oppositely, rubbery membranes offer high permeability, but their selectivity is low. Here we report rubbery organic frameworks (ROFs) combining the high permeability of soft matrices with the high sieving selectivity of molecular frameworks. The best performing membranes provide a CO 2 /N 2 selectivity up to 104 with a CO 2 permeability up to 1000 Barrer, representing relevant performances for industrial implementation. Water vapors have a positive effect on CO 2 permeability, and the CO 2 /N 2 selectivity is higher than in dry conditions, as most of CO 2 gas emissions are present in fully humidified gas streams. The synergetic high permeability/selectivity performances are superior to that observed with current state-of-the-art polymeric membranes.

Industrial scale production of carbon membrane is very challenging due to expensive precursor materials and a multi-step process with several variables to deal with. The optimization of these variables is essential to gain a competent carbon membrane (CM) with high performance and good mechanical properties. In this paper, a pilot scale system is reported that was developed to produce CM from regenerated cellulose precursor with the annual production capacity 700 m² of CM. The process was optimized to achieve maximum yield (>95%) of high quality precursor fibers and carbonized fibers. A dope solution of cellulose acetate (CA)/Polyvinylpyrrolidone (PVP)/ N -methyl-2-pyrrolidone (NMP) and bore fluid of NMP/H₂O were used in 460 spinning-sessions of the fibers using a well-known dry/wet spinning process. Optimized deacetylation of spun-CA hollow fibers (CAHF) was achieved by using 90 vol% 0.075 M NaOH aqueous solution diluted with 10 vol% isopropanol for 2.5 h at ambient temperature. Cellulose hollow fibers (CHF) dried at room temperature and under RH (80% → ambient) overnight gave maximum yield for both dried CHF, as well as carbon fibers. The gas permeation properties of carbon fibers were also high (CO₂ permeability: 50⁻450 Barrer (1 Barrer = 2.736 × 10 -9 m³ (STP) m/m² bar h), and CO₂/CH₄ selectivity acceptable (50⁻500).

The simultaneous carbonization of thousands of fibers in a horizontal furnace may result in fused fibers if carbonization residuals (tars) are not removed fast enough. The optimized purge gas flow rate and a small degree angle in the furnace position may enhance the yield of high quality carbon fibers up to 97% by removing by-products. The production process for several thousand carbon fibers in a single batch is reported. The aim was developing a pilot-scale system to produce carbon membranes. Cellulose-acetate fibers were transformed into regenerated cellulose through a de-acetylation process and the fibers were carbonized in a horizontally oriented three-zone furnace. Quartz tubes and perforated stainless steel grids were used to carbonize up to 4000 (160 cm long) fibers in a single batch. The number of fused fibers could be significantly reduced by replacing the quartz tubes with perforated grids. It was further found that improved purge gas flow distribution in the furnace positioned at a 4-degree to 6-degree angle permitted residuals to flow downward into the tar collection chamber. In total, 390 spun-batches of fibers were carbonized. Each grid contained 2000⁻4000 individual fibers and these fibers comprised four to six spun-batches of vertically dried fibers. Gas permeation properties were investigated for the carbon fibers.

In this article, we studied two different types of polyhedral oligomeric silsesquioxanes (POSS ® ) functionalized nanoparticles as additives for nanocomposite membranes for CO₂ separation. One with amidine functionalization (Amidino POSS ® ) and the second with amine and lactamide groups functionalization (Lactamide POSS ® ). Composite membranes were produced by casting a polyvinyl alcohol (PVA) layer, containing either amidine or lactamide functionalized POSS ® nanoparticles, on a polysulfone (PSf) porous support. FTIR characterization shows a good compatibility between the nanoparticles and the polymer. Differential scanning calorimetry (DSC) and the dynamic mechanical analysis (DMA) show an increment of the crystalline regions. Both the degree of crystallinity (Xc) and the alpha star transition, associated with the slippage between crystallites, increase with the content of nanoparticles in the PVA selective layer. These crystalline regions were affected by the conformation of the polymer chains, decreasing the gas separation performance. Moreover, lactamide POSS ® shows a higher interaction with PVA, inducing lower values in the CO₂ flux. We have concluded that the interaction of the POSS ® nanoparticles increased the crystallinity of the composite membranes, thereby playing an important role in the gas separation performance. Moreover, these nanocomposite membranes did not show separation according to a facilitated transport mechanism as expected, based on their functionalized amino-groups, thus, solution-diffusion was the main mechanism responsible for the transport phenomena.

In our previous work, it was shown that the separation performance of the fixed-site-carrier polyvinylamine (PVAm) composite membrane increases exponentially with increasing relative humidity content in the gas. Through these efforts, it has been important to develop a greater understanding of the relationship between the water, structural, and interfacial properties of the PVAm surface. The degree of hydrophilicity of a given surface plays a crucial role in the separation performance of the membrane when exposed to a humidified gas. Therefore, in the current work, the wettability properties of PVAm at different pHs have been studied by experimental measurements and molecular dynamic simulations. It was confirmed that the intramolecular interactions are not linearly dependent on pH. As well as the H-bonding between protonated and unprotonated amine groups, the conformation polymer chain and the distribution charge density play a crucial role in the surface stability and wettability properties., Competing Interests: The authors declare no competing financial interest.

Nanocomposite membranes of modified Si nanoparticles as inorganic filler in two different polymers from two different categories were developed. Synthesized 6FDA-durene diamine as a glassy polymer and PEBAX-2533 as a block copolymer were used as the polymer matrix to develop the nanocomposite membranes of modified Si nanoparticles in polymer matrix. The scanning transmission electron microscopy (STEM) results showed nice nano size dispersion of inorganic nanofillers in the polymer matrix in both cases. Pure gas permeation for the gases CO2, CH4, N2, and O2 and mixed gas of CO2-N2 was carried out at 2 and 6 bar for single gas and 2.6 bar for mixed gas using the developed nanocomposite membranes. The loading of inorganic fillers in the PEBAX-2533 polymer matrix resulted in a dramatic increase in gas permeability for all tested gases, while a decrease was observed for CO2/N2 and CO2/CH4 selectivities with small amounts of loading of filler. With higher loading of inorganic filler, the selectivity did not change, which is probably due to the formation of nanogap around the nanoparticles in the polymer matrix. The dispersion of the nanoparticle inorganic fillers in 6FDA-durene polymer matrix caused an increase on the fractional free volume of the polymer matrix due to the disruption of the polymer chain in the presence of the inorganic fillers. Hence, this disruption resulted in an increase of gas permeability for both single and mixed gases, also with an increase in CO2/N2 and CO2/CH4 selectivities.

We performed classical molecular dynamics (MD) simulations to understand the mechanism of adsorption from a gas mixture of CO2 and H2 (mole fraction of CO2 = 0.30) and diffusion along a graphite surface, with the aim to help enrich industrial off-gases in CO2, separating out H2. The temperature of the system in the simulation covered typical industrial conditions for off-gas treatment (250-550 K). The interaction energy of single molecules CO2 or H2 on graphite surface was calculated with classical force fields (FFs) and with Density Functional Theory (DFT). The results were in good agreement. The binding energy of CO2 on graphite surface is three times larger than that of H2. At lower temperatures, the selectivity of CO2 over H2 is five times larger than at higher temperatures. The position of the dividing surface was used to explain how the adsorption varies with pore size. In the temperature range studied, the self-diffusion coefficient of CO2 is always smaller than of H2. The temperature variation of the selectivities and the self-diffusion coefficient imply that the carbon molecular sieve membrane can be used for gas enrichment of CO2.

Membrane separation systems require no or very little chemicals compared to standard unit operations. They are also easy to scale up, energy efficient, and already widely used in various gas and liquid separation processes. Different types of membranes such as common polymers, microporous organic polymers, fixed-site-carrier membranes, mixed matrix membranes, carbon membranes as well as inorganic membranes have been investigated for CO2 capture/removal and other energy processes in the last two decades. The aim of this work is to review the membrane systems applied in different energy processes, such as post-combustion, pre-combustion, oxyfuel combustion, natural gas sweetening, biogas upgrading, hydrogen production, volatile organic compounds (VOC) recovery and pressure retarded osmosis for power generation. Although different membranes could probably be used in a specific separation process, choosing a suitable membrane material will mainly depend on the membrane permeance and selectivity, process conditions (e.g., operating pressure, temperature) and the impurities in a gas stream (such as SO2, NOx, H2S, etc.). Moreover, process design and the challenges relevant to a membrane system are also being discussed to illustrate the membrane process feasibility for a specific application based on process simulation and economic cost estimation.

Carbon molecular sieve (CMS) membranes (hollow fibers) have been studied for application as possible separation units for selected industrial gas streams. Gas streams at petrochemical plants (polypropene and polyethene) and upgrading of biogas to fuel specifications have been in focus. Gases present in biogas (N(2), CO(2), H(2)O(vap), and CH(4)) and gas streams at polyolefin plants (C(2)H(4), C(3)H(6), and C(3)H(8)) have been measured; both as pure gases and in mixtures. Aging of the CMS-membranes as a function of humidity and pore blocking is discussed; likewise, possible regeneration methods when flux decrease is experienced. Transport mechanisms depending on pore size and molecular properties are also discussed. Excellent separation properties were documented for these applications, but also the need for frequent regeneration of the membrane in order to maintain permeability flux. The mixed gas experiments documented clearly the need for careful pore tailoring in order to optimize selectivity when the membranes were used for alkane-alkene separation.