CO2 Diffusion Research Articles

Water Impact on Adsorbed Oil Detachment From Mineral Surfaces by Supercritical CO2: A Molecular Insight

AbstractGeochemical reactions are crucial for in situ CO2 mineralization underground associated with CO2‐enhanced oil recovery (CO2‐EOR) in a hydrocarbon reservoir. However, the presence of formation water and adsorbed oil on rocks generates physical barriers to CO2's access to mineral surfaces, which may yield impedance to CO2 mineral trapping that has yet to be accounted for. In this study, we mimic the dynamic oil detachment process using molecular dynamic (MD) simulation and analyze the influence of an adsorbed oil film on supercritical CO2 (scCO2) diffusion toward the mineral surface in the presence and absence of a water phase. Our results demonstrated a negative impact of water on oil film detachment by scCO2, which may weaken mineral reactions and is unfavorable for mineralized CO2 storage underground.

Constructing ether-rich and carboxylate hydrogen bonding sites in protic ionic liquids for efficient and simultaneous membrane separation of H2S and CO2 from CH4

Removing H2S and CO2 is of great significance for natural gas purification. With excellent gas affinity and tunable structure, ionic liquids (ILs) have been regarded as nontrivial candidates for fabricating polymer-based membranes. Herein, we firstly reported the incorporation of protic ILs (PILs) having ether-rich and carboxylate sites (ECPILs) into poly(ether-block-amide) (Pebax) matrix for efficient separation H2S and CO2 from CH4. Notably, the optimal permeability of H2S reaches up to 4310 Barrer (40 °C, 0.50 bar) in Pebax/ECPIL membranes, along with H2S/CH4 and (H2S + CO2)/CH4 selectivity of 97.7 and 112.3, respectively. These values are increased by 1125%, 160.8% and 145.9% compared to those in neat Pebax membrane. Additionally, the solubility and diffusion coefficients of the gases were measured, demonstrating that ECPIL can simultaneously strengthen the dissolution and diffusion of H2S and CO2, thus elevating the permeability and permselectivity. By using quantum chemical calculations and FT-IR spectroscopy, the highly reversible multi-site hydrogen bonding interaction between ECPILs and H2S was revealed, which is responsible for the fast permeation of H2S and good selectivity. Furthermore, H2S/CO2/CH4 (3/3/94 mol%) ternary mixed gas can be efficiently and stably separated by Pebax/ECPIL membrane for at least 100 h. Overall, this work not only illustrates that PILs with ether-rich and carboxylate hydrogen bonding sites are outstanding materials for simultaneous removal of H2S and CO2, but may also provide a novel insight into the design of membrane materials for natural gas upgrading.

Experiments and mechanism of kinetics/stability of CO2 capture by Ce/Zr carrier-loaded MgO-based adsorbents

Magnesium oxide (MgO) has demonstrated tremendous potential in carbon capture and utilization (CCU) technology. However, it still faces limitations such as low adsorption kinetics and poor stability. In this study, the sol–gel combustion method was employed to synthesize MgO/molten salt composite adsorbents supported on Ce/Zr carriers. The investigation focused on the influence of carrier composition on adsorption performance. The experimental results revealed that as the loading of CeO2 increased, the adsorbent materials transitioned from a porous foam-like connectivity to the formation of a shell structure. Interestingly, the low content of CeO2 facilitated enhanced CO2 diffusion and hindered the aggregation of MgO aggregates, resulting in improved adsorption performance. Furthermore, the adsorbents supported on ZrO2 demonstrated excellent particle size stability and cyclic stability due to the higher Tamman temperature of ZrO2 and the uniform dispersion of MgO on ZrO2. Utilizing density functional theory, a surface configuration of CeO2/ZrO2 catalyst-modified MgO (100) was constructed to elucidate the enhanced adsorption mechanism of CeO2/ZrO2 on MgO. The cluster model revealed a strong interaction between cluster O atoms and CO2 molecules, enhancing the charge transfer capability of the MgO surface towards CO2 and consequently strengthening its adsorption performance.

Mechanism of fineness and content of quartz powder on the improvement of carbonation curing efficiency

Quartz powder is a byproduct of quartzite processing. To date, research on the use of quartz powder in carbonation curing is extremely limited, and the carbonation curing mechanism of concrete containing quartz powder is still unclear. In this study, we focused on the effects of fineness and content of the quartz powder on carbonation curing for cement-quartz powder binary mixtures and compared the results with those from sealed curing to clarify the effects of the quartz powder under carbonation curing and sealed conditions. The quartz powder's action is primarily influenced by nucleation and dilution effects, altering the coupling of hydration and carbonation, thereby influencing carbonation curing outcomes. Experimental results reveal distinct mechanisms under sealed and carbonation curing. Under sealed curing conditions, the smaller particles of quartz-S5 (sample SC-Q10-S5) promoted cement hydration more effectively under the influence of nucleation, and the samples showed better compressive strengths, electrical resistivities, and ultrasonic pulse velocity gains when the quartz powder replaced 10 % of the cement. The introduction of larger quartz-S20 particles (sample CC-Q10-S20) promoted the carbonation reaction more significantly (Affected by the dilution effect, which promotes CO2 diffusion) and showed better compressive strength, electrical resistivity, and ultrasonic pulse velocity gain compared to the smaller particles of quartz-S5 during carbonation curing. In summary, adding quartz powder as a partial substitute for cement in the carbonation curing process standardized the carbonation curing, and under the coupling of hydration and carbonation reactions, larger particles are more beneficial for enhancing carbonation curing properties compared to smaller particles.

Facile synthesis of amine hybrid silica aerogel globule via wet casting assisted self-catalysed sol-gel process for CO2 capture including direct air capture

Amine hybrid silica aerogel globule (AHSAG) for CO2 capture including direct air capture (DAC) was firstly synthesized via wet casting assisted self-catalyzed sol-gel process. AHSAG has abundant interpenetrating macropores, which favors diffusion of CO2 into internal amine sites and can enhance CO2 adsorption kinetics and capacity. The optimal CO2 adsorption capacity of AHSAG with dry 100% and 400 ppm CO2 are 3.82 (30 °C) and 1.86 mmol/g (55 °C), respectively. Corresponding amine efficiencies are 0.478 and 0.233. The effect of temperature on CO2 adsorption capacity is attributed to simultaneous enhancement of mass transfer kinetics and adsorption thermodynamics. The highest CO2 adsorption rate of AHSAG is achieved at 70 and 55 °C with 100% and 400 ppm CO2, respectively. The trend of CO2 adsorption rate with temperature is attributed to the synergistic effect of diffusion kinetics and desorption. Based on experimental CO2 adsorption kinetics, adsorption mechanism in 400 ppm CO2 was estimated with different diffusion models. Both film diffusion resistance and intraparticle diffusion resistance are involved in CO2 capture of AHSAG from air under given condition to control the overall adsorption process. Three kinetics models were used to fit the experimental data of AHSAG for DAC, and the Avrami model showed the best fitting within the whole adsorption period. Comparing with its state-of-the-art counterparts, AHSAG offers significant advantages for practical DAC, such as high adsorption capacity and amine efficiency, fast adsorption kinetics, and excellent cyclic stability.

Greater mesophyll conductance and leaf photosynthesis in the field through modified cell wall porosity and thickness via AtCGR3 expression in tobacco.

Mesophyll conductance (gm) describes the ease with which CO2 passes from the sub-stomatal cavities of the leaf to the primary carboxylase of photosynthesis, Rubisco. Increasing gm is suggested as a means to engineer increases in photosynthesis by increasing [CO2] at Rubisco, inhibiting oxygenation and accelerating carboxylation. Here, tobacco was transgenically up-regulated with Arabidopsis Cotton Golgi-related 3 (CGR3), a gene controlling methylesterification of pectin, as a strategy to increase CO2 diffusion across the cell wall and thereby increase gm. Across three independent events in tobacco strongly expressing AtCGR3, mesophyll cell wall thickness was decreased by 7%-13%, wall porosity increased by 75% and gm measured by carbon isotope discrimination increased by 28%. Importantly, field-grown plants showed an average 8% increase in leaf photosynthetic CO2 uptake. Up-regulating CGR3 provides a new strategy for increasing gm in dicotyledonous crops, leading to higher CO2 assimilation and a potential means to sustainable crop yield improvement.

Carbonation curing behavior and performance improvement of recycled coral waste concrete

Carbonation curing can improve material properties and reduce the concrete industry's carbon emissions. This study used powder prepared from waste coral to replace ordinary Portland cement (0, 10, and 20 %). After initial curing for 24 h, the mortar was cured by sealing and carbonation. The dilution effect of coral powder substantially reduces the mechanical properties under sealing curing. Under carbonation curing, the coral powder helps develop carbonation and CO2 diffusion, reducing strength loss and increasing resistivity. XRD and Fourier transform infrared spectroscopy analysis results showed that carbonation transforms hydration products and clinker phases into different types of CaCO3, such as calcite and aragonite. The novelty of this study is that it proposes a method that organically combines carbonation curing and marine waste reuse. Provide a sustainable solution to the problem of material shortage in marine engineering construction. Moreover, the carbon footprint can be considerably reduced by replacing cement materials, improving carbonation curing efficiency, and promoting CO2 uptake.

Effect of in-situ emulsification on CO2/N2-based cyclic solvent injection process for enhancing heavy oil recovery and CO2 storage

Surfactant-assisted CO2/N2-based CSI (SA CO2/N2-CSI) process emerges as a strategic solution to migrate the high energy consumption and carbon intensity associated with traditional thermal operations for heavy oil recovery. However, the interphase mass transfer makes the emulsification behavior in this process complex. In this study, the effect of in-situ emulsification on CO2/N2-CSI is assessed using a sandpack model and microchannel chip. Mesoscopically, SA CO2/N2-CSI outperforms conventional CO2/N2-CSI in terms of both oil recovery and CO2 storage, owing to the enhanced CO2 diffusion, oil solubilization, and foamy oil stability due to emulsification. Microscopically, the impact of emulsifier injection rate on oil removal efficiency in the dead-end pores becomes negligible when the injection rate exceeds 50 nL/min, providing insights to the emulsification mechanisms underlying the optimal pressure depletion rate (9 kPa/min) in SA CO2/N2-CSI. This study demonstrates the applicability of the SA CO2/N2-CSI in fostering sustainable heavy oil production and CO2 storage.

Exploring the Effect of Moisture on CO2 Diffusion and Particle Cementation in Carbonated Steel Slag

The study of the mechanisms affecting the preparation parameters of carbonated steel slag is of great significance for the development of carbon sequestration materials. In order to elucidate the mechanism of the influence of moisture on CO2 diffusion and particle cementation in steel slag, the effects of different water–solid ratios and water contents on the mechanical properties, carbonation products, and pore structure of steel slag after carbonation were investigated. The results show that increasing the water–solid ratio of steel slag can control the larger initial porosity and improve the carbon sequestration capacity of steel slag, but it will reduce the mechanical properties. The carbonation process relies on pores for CO2 diffusion and also requires a certain level of moisture for Ca2+ dissolution and diffusion. Increasing the water content enhances particle cementation and carbonation capacity in steel slag specimens; however, excessive water hinders CO2 diffusion. Reducing the water content can increase the carbonation depth but may compromise gelling and carbon sequestration ability. Therefore, achieving a balance is crucial in controlling the water content. The compressive strength of the steel slag with suitable moisture and initial porosity can reach 118.7 MPa, and 217.2 kg CO2 eq./t steel slag can be sequestered.

Effect of internal moisture content (IMC) on the CO2 sequestration efficiency of hollow natural fiber (HNF)-reinforced reactive magnesia cement (RMC) composites

The incorporation of minor hollow natural fibers (HNF) can significantly accelerate the CO2 diffusion in reactive magnesia cement (RMC). The CO2 diffusivity in HNF is highly related to its internal moisture content (IMC), which subsequently affects the carbonation process of HNF-RMC, but this is outside the scope of the existing studies. Therefore, this work investigates the effect of IMC on carbonation, strength, and microstructure of HNF-RMC composites. HNF-RMC mortar specimens are dried to different levels of nominal IMC (0–100%), and cured under high CO2 concentration for carbonation. Following the curing, the matrix composition was characterized with varying techniques (QXRD, TGA, FTIR, and acid digestion) for quantifying the CO2 sequestration; the compressive strength at different depths was determined with uniaxial compressive test; the microstructure was examined with SEM/ESEM. The results show that the carbonation depth is increased by three to four times by reducing the IMC to 0%. The effects of varying IMC on local carbonation and strength are distinct in the shallow (0–20 mm) and middle/deep region (20–100 mm). In the shallow region, inadequate CO2 dissolution is the limiting factor, these performances decreased with the increasing desiccation. In the deeper regions, moisture absorption by HNF decreased the CO2 diffusivity, hence the CO2 availability is the limiting factor, and these performances increased with the desiccation. These observations suggest that the understanding that carbonation maximizes at a medium moisture level is not valid in HNF-RMC–controlling the moisture can be important for improving the CO2 sequestration and consequent mechanical strength.

Toward more accurate estimates of carbon emissions from small reservoirs

AbstractBecause of their abundance and high emissions rates, small reservoirs (< 0.01 km2) can be important emitters of the greenhouse gases carbon dioxide and methane. However, emissions estimates from small reservoirs have lagged those of larger ones, and efforts to characterize small reservoir emissions have largely overlooked variations in emissions pathways, times, and locations. We intensively sampled four small reservoirs in Georgia, USA, during the summer to quantify the contribution and spatiotemporal variability of different emissions pathways (CO2 and CH4 diffusion, CH4 ebullition). We used these data to evaluate the efficiency and accuracy of different sampling schemes. Every emissions pathway was dominant in one reservoir on one sampling day, and excluding ebullition caused misestimation between −89% and −15% of the total flux. Sampling only once daily caused misestimation between −78% and 45%, but sampling twice or just after dawn (07:00 h) reduced error. Sampling four or fewer locations caused misestimation between −85% and 366%, and our results indicated that 6–20 sampling locations may be needed for reasonable accuracy. The floating aquatic macrophyte Wolffia sp. (duckweed) appeared to exert control over emissions variability, and the consequences of not accounting for variability were greater in a duckweed‐covered reservoir. Our results indicate that sampling only at 10:00 h (modal sampling time of prior efforts) may lead to the erroneous conclusion that reservoirs with high photosynthetic biomass are CO2 sinks rather than sources. Improving estimation accuracy by accounting for within‐reservoir variation in emissions will facilitate more strategic management of these abundant, anthropogenic ecosystems.

Enhancing carbonation and thermal insulation of reactive magnesium oxide cement (RMC)-based 3D printable pastes with cenospheres

Reactive magnesium oxide cement (RMC) has been proposed as a sustainable alternative to ordinary Portland cement (OPC) due to its lower production temperature and ability to permanently sequester carbon dioxide (CO2) through carbonation. However, mixtures with only RMC can have significantly reduced CO2 absorption capacity due to limited CO2 diffusion, thereby compromising the performance of RMCs. This paper demonstrates the adoption of cenospheres, an industrial waste, as a lightweight filler in RMC-based 3D printable composites to enhance carbonation and improve thermal insulation. This work investigates the effect of incorporating different dosages of cenospheres on the rheological properties, compressive strength, thermal conductivity, and microstructural development of the RMC mixtures using X-ray diffraction (XRD), thermogravimetric analysis (TGA), and scanning electron microscopy (SEM). The study reveals that substituting 30 % of RMC with cenospheres not only improves the printability and carbonation of the composite but also results in a 16 % reduction in density, achieving 1.72 g/cm³, and reduces the thermal conductivity by 59 % compared to the control without cenospheres to 0.63 W/(m·K). The findings provide valuable insights for developing lightweight 3D printable RMC-based composites.

A general Energy-Efficient strategy for optimizing CO2 Capture: Designing and harnessing the rapid adsorption kinetics of Amine-Impregnated adsorbents

This study aims to optimize the performance of amine-impregnated CO2 adsorbents for both direct air capture (DAC) and point source CO2 capture (PSC) applications. The main objective of this study is to investigate the relationship between the weight fraction of amine loading and the efficiency of CO2 uptake on the designated support, aiming to find a straightforward method to design effective amine support materials. To this end, a composite material denoted as PEI/CNT@ZIF-8 has been developed. This composite is comprised of polyethylenimine (PEI), multi-walled carbon nanotubes (CNTs), and zeolitic imidazolate frameworks (ZIF-8). CNTs offer several advantages for enhancing CO2 uptake, including rearranging the ZIF-8 particles to facilitate PEI loading, creating strong electrostatic interaction for amine anchoring, and establishing CO2 diffusion channels to improve CO2 capture kinetics. In DAC scenarios, with a CO2 concentration of 400 ppm balanced with N2, the 25.0 wt% PEI/CNT(1)@ZIF-8(5) demonstrates superior CO2 uptake, achieving 4.08 mmol g−1 within a one-hour interval by harnessing the rapid kinetic region and exhibiting a low desorption energy of 55.8 kJ mol−1 for releasing CO2. In PSC scenarios, with a CO2 concentration of 15 vol% under both dry and wet conditions, the 37.5 wt% PEI/CNT(1)@ZIF-8(5) exhibits excellent CO2 uptake of 2.21 and 2.58 mmol g−1, respectively, at 50 ℃. The findings suggest that adjusting the balance between CO2 uptake and adsorption kinetics by considering the amine weight fraction can optimize the performance of solid amine CO2 adsorbents across diverse operational conditions. Furthermore, rather than relying on a single support material, this study reveals the potential of combining CNTs with materials such as SiO2 nanoparticles, Al2O3, or metal–organic frameworks (MOFs) to enhance CO2 capture performance. This approach holds promise as an effective and straightforward strategy.

Properties of multiple Lewis acid sites in alkali metal-exchanged chabazites probed by CO adsorption

Carbon monoxide adsorption on alkali-metal exchanged chabazites (M-CHA, where M = Li, Na, K) was investigated across various Si/Al ratios. The study reveals significant insights into the adsorption behavior, including the persistence of cationic preferences with decreasing Si/Al ratios and the existence of multiple-center interactions involving alkali-metal cations and CO. Results show that for high-silica M-CHA zeolites, CO adsorption is effectively described by single and dual adsorption site models, with cation preferences varying by type. In low-silica zeolites, cation positions are primarily influenced by the aluminum distribution and Coulombic interactions. However, the propensity for single-site cation positions (Si/Al→∞) is preserved to a certain degree. The most noticeable example is the small difference between SIII’ occupancies (cations in 8-membered ring windows) in Na-CHA-2 and K-CHA-2 (0.80 vs. 0.85) that strongly influences the rate of diffusion of CO in the M-CHA-2 samples. While FT-IR spectra of high-silica zeolites can be accurately described using cation site stabilities, interaction energies, and CO stretching frequencies, predicting spectra of low-silica chabazites requires a statistical approach and/or molecular dynamics simulations at the DFT level. The findings demonstrate that the dynamical behavior of adsorbates changes dramatically between different alkali metal-exchanged chabazites, highlighting the complex nature of CO adsorption at multiple Lewis acid sites.

Tobacco aquaporin NtAQP1 and human aquaporin hAQP1 contribute to single cell photosynthesis in Synechococcus.

Aquaporins are H2O-permeable membrane protein pores. However, some aquaporins are also permeable to other substances such as CO2. In higher plants, overexpression of such aquaporins has already led to an enhanced photosynthetic performance due to improved CO2 mesophyll conductance. In this work, we investigated the effects of such aquaporins on unicellular photosynthetically active organisms, specifically cyanobacteria. Overexpression of aquaporins NtAQP1 or hAQP1 that might have a function to improve CO2 membrane permeability lead to increased photosynthesis rates in the cyanobacterium Synechococcus sp. PCC7002 as concluded by the rate of evolved O2. A shift in the Plastoquinone pool state of the cells supports our findings. Water permeable aquaporins without CO2 permeability, such as NtPIP2;1, do not have this effect. We conclude that also in single cell organisms like cyanobacteria, membrane CO2 conductivity could be rate limiting and CO2-porins reduce the respective membrane resistance. We could show that besides the tobacco aquaporin NtAQP1 also the human hAQP1 most likely functions as CO2 diffusion facilitator in the photosynthesis assay.

Diffusion of alloying elements during high temperature oxidation in a low-cost third generation Ni-based single crystal superalloy

Diffusion of alloying elements in a low-cost third generation Ni-based single crystal superalloy during oxidation at high temperature was investigated. The evolution of oxide layers depended on dominant diffusion of alloying elements at different stages of oxidation. Outward diffusion of Cr, Co and Ni was dominant at initial stage of oxidation, resulting in the formation of (Ni, Co)O and Cr2O3. Diffusion of Al and Ta was restricted in γ/γ' area, but dominant in γ'-free layer. Due to outward diffusion of other elements, passive enrichment of refractory elements, Re, W, Mo and Ta included, caused the formation of mixed oxides layer. Finally, selective oxidation of Al led to the formation of (Ni, Co)Al2O4 and Al2O3 layer.

Effect of hollow natural fiber (HNF) content on the CO2 diffusion, carbonation, and strength development of reactive magnesium cement (RMC)-based composites

Reactive magnesia cement (RMC) is an emerging class of green cement that hardens by sequestering CO2. However, CO2 diffusion into RMC is restricted to a few millimeters by the carbonation-induced dense microstructure on the outer layer, which severely slows down the strength growth and CO2 sequestration. To address this issue, this work employed hollow natural fibers (HNFs) to facilitate CO2 diffusion into the deep regions of RMC. The effects of HNFs contents on the mechanical strength development, holistic porosity, CO2 sequestration, CO2 diffusivity, and microstructure of RMC were investigated through different techniques. The findings revealed that the compressive strength could be more than doubled with the addition of adequate sisal fiber. Moreover, the CO2 sequestration and diffusivity could be continuously enhanced with the increasing HNFs content. However, overdosage of HNFs could induce a higher porosity and additional defects, which slightly compromises the mechanical strength. Finally, the durability of HNFs in simulated RMC and Portland cement (PC) environment was compared by accelerated aging test, showing that the alkaline-induced deterioration of HNFs could be almost eliminated in RMC. Therefore, this preliminary study reinforces the function of RMC as a carbon reservoir and lays the foundation for the large-scale utilization of HNFs in RMC.

Oxygen-enriched carbon molecular sieve hollow fiber membrane for efficient CO2 removal from natural gas

Natural gas is considered one of the most attractive low carbon energy sources while the separation of CO2 is a crucial process for the natural gas purification. Herein, cellulose-based carbon molecular sieve (CMS) hollow fiber membranes with high CO2 affinity capability were fabricated through a post-treatment strategy of hydrogen-induced reduction followed by oxygen-doped modification (H-O treatment), and show good potential for high pressure natural gas purification. The CMS membranes were reduced by H2 at high temperatures (500–600 °C) to form active sorption sites in the carbon matrix, and subsequently chemically absorbed O2 to generate oxygen-containing functional groups, which are favorable for CO2 adsorption and diffusion. After being treated at 600 °C (CMS-600), the CMS membrane presented a high CO2 adsorption capacity of 62.78 cm3/g (298 K). As a result, the CO2 permeability was enhanced from 264 to 1125 Barrer, with approximately 400 % improvement. Moreover, mixed gas separation performances (CO2/N2 and CO2/CH4) were investigated at high pressure and impurities feedings. The CMS membrane exhibited a remarkable CO2/CH4 separation factor of 104 when operated at 20 bar and 500 ppm heptane existed.

Comparison of the effect of topology type and linker composition of zeolitic imidazolate framework fillers on the performance of mixed matrix membranes in CO2/N2 separation

Mixed matrix membranes (MMMs) combine the high separation performance of porous materials with the processibility of polymers and so possess potential for carbon capture from CO2-containing gas streams. Zeolitic imidazolate frameworks (ZIFs) are promising candidates as molecular-sieve fillers in MMMs due to their tunability and ease of synthesis. We have compared four ZIFs, all as nanoparticles of similar sizes (ca. 400 nm), as MMM fillers, to investigate the effects of ZIF structure and chemistry on MMM performance of pure gas (CO2, N2) permeation under the same conditions. The chosen ZIFs include two that exhibit strong CO2 adsorption (hybrid ZIF-7/COK-17 and ZIF-94) and two that have higher pore volumes but weaker CO2 interactions (ZIF-8 and a hybrid ZIF-11/ZIF-71). The hybrid ZIF-7/COK-17 and ZIF-94 are structurally related to ZIF-7 (rhombohedral sod topology) and ZIF-8 (cubic sod), respectively, via partial or complete substitution of benzimidazole or 2-methylimidazole by 4,5-dichloroimidazole or 4-methyl-5-imidazolecarboxaldehyde, while the hybrid ZIF-11/ZIF-71 has the rho topology but the same composition as the ZIF-7/COK-17 hybrid. In the first part of the comparative study, MMMs based on two types of commercial polymers, Matrimid®5218 and PEBAX-MH1657, were prepared containing the ZIF-7/COK-17 hybrid and also with ZIF-94. ZIF-94 shows much better compatibility with the polymers, forming homogeneous dispersions at all loadings attempted (≤35 % wt%) whereas the hybrid shows inhomogeneity above 12 wt% in each case. At 12 wt% loading, both fillers show an increase in CO2 permeability at 1.2 bar and 293 K compared to the pure membrane (in PEBAX, this increases from 49.5 to 60 and 68 Barrer) which is the result of increased solubility compensating for decreased diffusivity, and this improvement in permeability continues to increase at the higher levels of loading possible with ZIF-94. ZIF-7/COK-17 in PEBAX show higher selectivity, achieving a calculated CO2/N2 selectivity up to 70. Further investigation of CO2 and N2 permeation on MMMs with the four ZIFs at 12 wt% in PEBAX-MH1657 showed a clear distinction between the ZIF-94 and ZIF-7/COK-17 MMMs (which show higher membrane solubilities but lower diffusivities) compared to ZIF-8 and ZIF-11/ZIF-71 MMMs. At the loading chosen, the CO2 permeability increase achieved by the four ZIFs over PEBAX-MH1657 increases in the order ZIF-11/-71, ZIF-7-COK-17 (ca. 60 Barrer) < ZIF-94 (68) < ZIF-8 (81), reflecting the complex interplay between CO2 solubility (increasing with interaction strength) and diffusivity (increasing with available cage and window size). The calculated CO2/N2 selectivity is highest for the hybrid ZIF-7/COK-17 membrane (70), which is attributed to molecular sieving effects in the rhombohedral sod structure.

Development of an autonomous on-site dissolved inorganic carbon analyzer using conductometric detection

BackgroundThe increase in anthropogenic CO2 concentrations in the Earth's atmosphere since the industrial revolution has resulted in an increased uptake of CO2 by the oceans, leading to ocean acidification. Dissolved Inorganic Carbon (DIC) is one of the key variables to characterize the seawater carbonate system. High quality DIC observations at a high spatial-temporal resolution is required to improve our understanding of the marine carbonate system. To meet the requirements, autonomous DIC analyzers are needed which offer a high sampling frequency, are cost-effective and have a low reagent and power consumption. ResultsWe present the development and validation of a novel analyzer for autonomous measurements of DIC in seawater using conductometric detection. The analyzer employs a gas diffusion sequential injection approach in a “Tube In A Tube” configuration that facilitates diffusion of gaseous CO2 from an acidified sample through a gas permeable membrane into a stream of an alkaline solution. The change in conductivity in the alkaline medium is proportional to the DIC concentration of the sample and is measured using a detection cell constructed of 4 hollow brass electrodes. Physical and chemical optimizations of the analyzer yielded a sampling frequency of 4 samples h−1 using sub mL reagent volumes for each measurement. Temperature and salinity effects on DIC measurements were mathematically corrected to increase accuracy. Analytical precision of ±4.9 μmol kg−1 and ±9.7 μmol kg−1 were achieved from measurements of a DIC reference material in the laboratory and during a field deployment in the southwest Baltic Sea, respectively. SignificanceThis study describes a simple, cost-effective, autonomous, on-site benchtop DIC analyzer capable of measuring DIC in seawater at a high temporal resolution as a step towards an underwater DIC sensor. The analyzer is able to measure a wide range of DIC concentrations in both fresh and marine waters. The achieved accuracy and precision offer an excellent opportunity to employ the analyzer for ocean acidification studies and CO2 leakage detection in the context of Carbon Capture and Storage operations.