CO2 Diffusion Research Articles

Numerical Study on the Enhanced Oil Recovery by CO2 Huff-n-Puff in Shale Volatile Oil Formations

The Sichuan Basin’s Liangshan Formation shale is rich in oil and gas resources, yet the recovery rate of shale oil reservoirs typically falls below 10%. Currently, gas injection huff-n-puff (H-n-P) is considered one of the most promising methods for improving shale oil recovery. This study numerically investigates the application of the CO2 huff-n-puff process in enhancing oil recovery in shale volatile oil reservoirs. Using an actual geological model and fluid properties of shale oil reservoirs in the Sichuan Basin, the CO2 huff-n-puff process was simulated. The model takes into account the molecular diffusion of CO2, adsorption, stress sensitivity effects, and nanopore confinement. After history matching, through sensitivity analysis, the optimal injection rate of 400 tons/day, soaking time of 30 days, and three cycles of huff-n-puff were determined to be the most effective. The simulation results show that, compared with other gases, CO2 has significant potential in improving the recovery rate and overall efficiency of shale oil reservoirs. This study is of great significance and can provide valuable references for the actual work of CO2 huff-n-puff processes in shale volatile oil reservoirs of the Sichuan Basin.

Correlation-Based Predictions of Gas Solute Diffusivity in Ionic Liquid Solvents Based on Solvent-Accessible Surface Area.

In our prior study [Olowookere, F. V.; Turner, C. H. J. Phys. Chem. B 2023, 127(42), 9144-9154], we introduced a new scaling relationship to predict gas solute diffusion at challenging conditions, focusing on CO2 and SO2 diffusion in multivalent ionic liquid (IL) solvents. This work extends our initial exploratory study into a much broader array of systems, encompassing additional solutes (N2, CH4, C2H6, C3H8, C3H8O, and H2O) and a variety of different ionic liquid species ([Bzmim3]3+, [Bzmim4]4+, [BMIM]+, [EMIM]+, [HMIM]+, [NapO2]2-, [BzO3]3-, [BF4]-, [Tf2N]-, and [PF6]-). Our study demonstrates a remarkably robust logarithmic correlation between solute diffusion and solvent accessible surface area (SA) across 20 different additional systems. We perform comprehensive analyses of the underlying molecular phenomena responsible for this correlation, including solute lifetime distributions, void space dynamics, and Voronoi tessellation, in order to elucidate a stronger mechanistic understanding of this behavior. Our findings highlight a direct link between the solvent accessible SA and the size of the void domains. Overall, our scaling approach provides an efficient and reliable approach for predicting diffusion from analyses of short simulations at higher temperatures.

Experimental study on the macroscopic and microscopic properties of cement paste backfill after treatment with carbon dioxide carbonize filling slurries during the mixing process

Introducing CO2 during the mixing process of filling slurry for wet carbonation enables simultaneous carbonation and hydration reactions of the carbonated filling slurry (CSL). This study evaluates the microstructural evolution and strength development of carbonated cemented paste backfill (CCPB) under different carbonation times, and discusses the carbonation products and carbon sequestration of CCPB. The results reveal that introducing 99% pure CO2 at a flow rate of 1 L/min for 10 min into the filling slurry in a non-sealed container effectively optimizes the microscopic pore structure and mechanical properties of CCPB, achieving a carbon sequestration rate of 6.42%. Short-term carbonation leads to a continuous decrease in the T2 relaxation signal of CSL in the early hydration stage, enhancing pore structure by converting secondary pores to micropores. The main carbonation product is calcite crystalline CaCO3, which forms a dense carbonation layer on the surface of the tailings particles. However, prolonged carbonation results in the formation of microscopic pore encapsulation layer, hindering further CO2 diffusion, reducing carbonation efficiency, and deteriorating the mechanical properties of CCPB. With a carbonation time of 10 min, the UCS and EM of CCPB with different cement-to-tailings ratios show significant improvement, and the specimens exhibit lower fragmentation and fewer secondary cracks, maintaining better integrity after failure. In conclusion, the wet carbonation of filling slurry not only enhances the strength of the filling material but also achieves the reutilization of gaseous and solid wastes through carbon sequestration filling method, providing an efficient and eco-friendly solution for mine backfilling.

Diffusion of Surface CO2 in Coalfield Fire Areas by Surface Temperature and Wind

Diffusion of Surface CO2 in Coalfield Fire Areas by Surface Temperature and Wind

Preparation of nano-Al2O3 support CaO-based sorbent pellets by novel methods for high-temperature CO2 capture

CaO-based sorbents show great promise as materials for CO2 capture. In this paper, three novel preparation methods were proposed to prepare three sorbent pellets based on carbide slag, respectively. The CO2 cyclic capture performance of the sorbent pellets was also investigated. These three novel preparations consist of different binders (agar, gelatine) and different hydrophobic materials (silicone oil, liquid paraffin and silicone mold), respectively. The capture performance of these three sorbent pellets was compared with that of sorbent pellet prepared by existing preparation methods, which used agar as a binder and silicone oil as a hydrophobic material. In addition, the effects of the contents of nano-Al2O3 supports on the sorbent pellets were explored. Among the four preparation methods, the sorbent pellets prepared with agar as binder and silicone mold as hydrophobic material showed exhibiting the highest total capture capacity of 7.70 gCO2/g during 15 cyclic captures. The nano-Al2O3 was used as support to alleviate the sintering of the sorbent pellets prepared with agar as binder and silicone mold as hydrophobic material, preserving most of the CO2 diffusion channels. Among the sorbent pellets with varying contents of nano-Al2O3 support, the pellets with a 10:100 molar ratio of nano-Al2O3 to CaO demonstrated excellent mechanical properties and the highest CO2 cycle capture performance. These pellets exhibited a capture capacity of 0.626 gCO2/g on the first cycle, maintaining a capacity of 0.503 gCO2/g by the 15th cycle. This work introduced a novel method for preparing sorbent pellets of efficient and stable cyclic capture.

High photosynthesis rates in Brassiceae species are mediated by leaf anatomy enabling high biochemical capacity, rapid CO2 diffusion and efficient light use.

Certain species in the Brassicaceae family exhibit high photosynthesis rates, potentially providing a valuable route toward improving agricultural productivity. However, factors contributing to their high photosynthesis rates are still unknown. We compared Hirschfeldia incana, Brassica nigra, Brassica rapa and Arabidopsis thaliana, grown under two contrasting light intensities. Hirschfeldia incana matched B. nigra and B. rapa in achieving very high photosynthesis rates under high growth-light condition, outperforming A. thaliana. Photosynthesis was relatively more limited by maximum photosynthesis capacity in H. incana and B. rapa and by mesophyll conductance in A. thaliana and B. nigra. Leaf traits such as greater exposed mesophyll specific surface enabled by thicker leaf or high-density small palisade cells contributed to the variation in mesophyll conductance among the species. The species exhibited contrasting leaf construction strategies and acclimation responses to low light intensity. High-light plants distributed Chl deeper in leaf tissue, ensuring even distribution of photosynthesis capacity, unlike low-light plants. Leaf anatomy of H. incana, B. nigra and B. rapa facilitated effective CO2 diffusion, efficient light use and provided ample volume for their high maximum photosynthetic capacity, indicating that a combination of adaptations is required to increase CO2-assimilation rates in plants.

Triacontanol Reverses Abscisic Acid Effects on Stomatal Regulation in Solanum lycopersicum L. under Drought Stress Conditions

When applied under abiotic stress conditions, triacontanol (TRIA) is effective in regulating the physicochemical processes in plants through mechanisms of defence such as abscisic acid (ABA) signalling. However, TRIA’s role in relation to ABA and stomatal opening is unclear. Therefore, the objective of this study was to evaluate the effects of TRIA and ABA and their combinations on different variables related to stomatal regulation in Solanum lycopersicum, which is subjected to drought stress, and on the leaf epidermis. The negative effects of stress and responses triggered by ABA were reversed in plants treated with TRIA. TRIA increased stomatal conductance and photosynthetic activity in the early hours, and it was determined that TRIA produced larger stomata than did the other treatments. Moreover, the chloroplasts of plants treated with TRIA were significantly smaller and more numerous than those of the control, which could improve CO2 diffusion efficiency and may be related to the regulation of stomatal opening and photosynthesis. Finally, the abaxial epidermis tests reaffirmed the inhibitory effects of TRIA on ABA on stomatal opening. These results confirm the important role of TRIA in regulating various processes in plants and processes triggered by ABA, such as those related to stomatal regulation.

Effects of Dolomitic Limestone on the Properties of Magnesium Oxysulfate Cement.

This study investigated the effects of substituting magnesium oxide (MgO) with dolomitic limestone (DL) on the mechanical and physical properties of magnesium oxysulfate (MOS) cement. Additionally, the hydration formation phases and the influence of the molar ratio on the MOS cement's performance were examined. The corresponding action mechanisms were identified and explored by compressive strength tests, scanning electron microscopy (SEM), X-ray diffraction (XRD), isothermal calorimetry, and a thermogravimetric analysis (TGA). The results showed that replacing MgO with DL decreased the reaction speed and heat release rate generated in the hydration process of the MOS cement. This substitution also reduced the quantity of non-hydrated MgO particles and delayed the formation of Mg(OH)2. The diminished formation of Mg(OH)2 contributed to an increase in the apparent porosity of pastes containing DL, thus alleviating internal stresses induced by Mg(OH)2 formation and enhancing their mechanical strength after 28 days of curing. Conversely, the increased porosity improved the CO2 diffusion within the structure, promoting the formation of magnesium carbonates (MgCO3). Through the characterization of the cement matrix (XRD and TGA), it was possible to identify phases, such as the brucite, periclase, and 318 phases. The obtained results revealed the potential of incorporating mineral fillers like limestone as a promising approach to producing MOS cement with a reduced environmental impact and better properties at higher curing ages.

Tissue-specific accumulation of PIP aquaporins of a particular heteromeric composition is part of the maize response to mycorrhiza and drought

The systemic coordination of accumulation of plasma membrane aquaporins (PIP) was investigated in this study in relation to mycorrhized maize response to a rapid development of severe drought followed by rewatering. In non-mycorrhizal roots, drought led to a drop in PIP abundance, followed by a transient increase under rewatering, whereas leaves showed an opposite pattern. In contrast, mycorrhiza contributed to maintenance of high and stable levels of PIPs in both plant organs after an initial increase, prolonged over the irrigation period. Isoelectric focusing electrophoresis resolved up to 13 aquaporin complexes with highly reproducible pl positions across leaf and root samples, symbiotic and non-symbiotic, stressed or not. Mass spectrometry recognized in leaves and roots a different ratio of PIP1 and PIP2 subunits within 2D spots that accumulated the most. Regardless of symbiotic status, drought regulation of aquaporins in roots was manifested as the prevalence of complexes that comprise almost exclusively PIP2 monomers. In contrast, the leaf response involved enrichment in PIP1s. PIP1s are thought to enhance water transport, facilitate CO2 diffusion but also affect stomatal movements. These features, together with elevated aquaporin levels, might explain a stress tolerance mechanism observed in mycorrhizal plants, resulting in faster recovery of stomatal water conductance and CO2 assimilation rate after drought.

A modified pore evolution particle model applied to CaCO3 decomposition and CaO sintering during calcium looping CO2 cycles

The calcium looping of calcium-based carbonation/calcination cyclic reaction is an efficient decarbonization technology that can be applied to post-combustion carbon capture, solar thermal storage, and enhanced methane reforming hydrogen. The pore structure generated during the calcination stage greatly affects adsorption performance. Hence, the change of pore structure is crucial during the calcination. Existing models related to pore structure still need to be further improved regarding pore formation mechanisms. In this paper, a modified pore evolution model is proposed. The modified pore evolution model contains the kinetic equation, the CO2 diffusion equation, and the vacancy aggregates equation. The modified model considers the possibility of spontaneous pore formation in the mechanism, which can better fit the experimental results and provide higher simulation accuracy. The model reveals the diffusion of CO2 within the particles during decomposition, and spatiotemporal evolutionary properties of pore parameters. The pore change trend is the most obvious when the initial pores are mainly 3 nm mesopores. The pore evolution is relatively stable when the initial pores are mainly 25 nm mesopores. Besides, the particles experience significant pore migration during the sintering stage when the temperature reaches 1273 K. At 1073 K, the maximum pore size occurring during pore evolution did not exceed 40 nm. The model estimates a maximum pore size of more than 60 nm at 1273 K. The modified model can aid in a deeper comprehension of how the pore structure changes throughout the calcination process.

Feasibility of biochar for low-emission soft clay stabilization using CO2 curing

Use of traditional lime-cement binders on stabilizing soft sensitive clays pose a significant challenge for the construction sector to reach Finland’s carbon neutrality goals by 2030. Traditional stabilization recipes consisting of cement as binders contributing significantly to CO2 emissions (≅ 500 kg CO2 eq./ton in deep mixing alone). This laboratory study explores the feasibility of achieving near carbon-negative stabilization of soft clay leveraging accelerated CO2 curing (ACC) in biochar (BC) enhanced cementitious composites. BC, a by-product of the biofuel industry, is used as partial replacement of cement (0 %, 10 %, and 50 % of binder) in developing precast cementitious piles. One non-carbonated treatment and two ACC treatments are employed to assess their uniaxial compressive strength, thermogravimetric properties and CO2 sequestration capacity. The results demonstrate that synergistic effects of using BC with ACC not only enhances the compressive strength of the composites but also promotes CO2 uptake due to formation of stable carbonates. BC due to its surface functional groups, honeycomb porous structure, and hydrophilicity facilitated uniform CO2 diffusion in the clay matrix and likely improved internal curing. In ACC treated composites, the replacement of 50 % of cement with BC resulted in sufficient load-bearing capacity (≥50 kPa as per Finnish Guidelines) for both shallow and deep clay layers, making a suitable subgrade media for many types of geotechnical applications. The measured bound CO2 increased gravimetrically from 2 % to 41 % when cement was partially replaced by BC. In case of non-carbonated samples, 10 % partial replacement of BC provided high strength (≥200kPa). Life Cycle Assessment (LCA) of a case study of utilizing BC stabilized clay in deep mixing operations can potentially reduce net carbon emissions to −50 kg CO2 eq./ton.

Stomatal and Non-Stomatal Leaf Responses during Two Sequential Water Stress Cycles in Young Coffea canephora Plants

Understanding the dynamics of physiological changes involved in the acclimation responses of plants after their exposure to repeated cycles of water stress is crucial to selecting resilient genotypes for regions with recurrent drought episodes. Under such background, we tried to respond to questions as: (1) Are there differences in the stomatal-related and non-stomatal responses during water stress cycles in different clones of Coffea canephora Pierre ex A. Froehner? (2) Do these C. canephora clones show a different response in each of the two sequential water stress events? (3) Is one previous drought stress event sufficient to induce a kind of “memory” in C. canephora? Seven-month-old plants of two clones (’3V’ and ‘A1’, previously characterized as deeper and lesser deep root growth, respectively) were maintained well-watered (WW) or fully withholding the irrigation, inducing soil water stress (WS) until the soil matric water potential (Ψmsoil) reached ≅ −0.5 MPa (−500 kPa) at a soil depth of 500 mm. Two sequential drought events (drought-1 and drought-2) attained this Ψmsoil after 19 days and were followed by soil rewatering until a complete recovery of leaf net CO2 assimilation rate (Anet) during the recovery-1 and recovery-2 events. The leaf gas exchange, chlorophyll a fluorescence, and leaf reflectance parameters were measured in six-day frequency, while the leaf anatomy was examined only at the end of the second drought cycle. In both drought events, the WS plants showed reduction in stomatal conductance and leaf transpiration. The reduction in internal CO2 diffusion was observed in the second drought cycle, expressed by increased thickness of spongy parenchyma in both clones. Those stomatal and anatomical traits impacted decreasing the Anet in both drought events. The ‘3V’ was less influenced by water stress than the ‘A1’ genotype in Anet, effective quantum yield in PSII photochemistry, photochemical quenching, linear electron transport rate, and photochemical reflectance index during the drought-1, but during the drought-2 event such an advantage disappeared. Such physiological genotype differences were supported by the medium xylem vessel area diminished only in ‘3V’ under WS. In both drought cycles, the recovery of all observed stomatal and non-stomatal responses was usually complete after 12 days of rewatering. The absence of photochemical impacts, namely in the maximum quantum yield of primary photochemical reactions, photosynthetic performance index, and density of reaction centers capable of QA reduction during the drought-2 event, might result from an acclimation response of the clones to WS. In the second drought cycle, the plants showed some improved responses to stress, suggesting “memory” effects as drought acclimation at a recurrent drought.

Evaluation of micro-dispersion on oil recovery during low-salinity water-alternating-CO2 processes in sandstone cores: An integrated experimental approach

Low-salinity water (LSW) and CO2 could be combined to perform better in a hydrocarbon reservoir due to their synergistic advantages for enhanced oil recovery (EOR); however, its microscopic recovery mechanisms have not been well understood due to the nature of these two fluids and their physical reactions in the presence of reservoir fluids and porous media. In this work, well-designed and integrated experiments have been performed for the first time to characterize the in-situ formation of micro-dispersions and identify their EOR roles during a LSW-alternating-CO2 (CO2-LSWAG) process under various conditions. Firstly, by measuring water concentration and performing the Fourier transform infrared spectroscopy (FT-IR) analysis, the in-situ formation of micro-dispersions induced by polar and acidic materials was identified. Then, displacement experiments combining with nuclear magnetic resonance (NMR) analysis were performed with two crude oil samples, during which wettability, interfacial tension (IFT), CO2 dissolution, and CO2 diffusion were quantified. During a CO2-LSWAG process, the in-situ formed micro-dispersions dictate the oil recovery, while the presence of clay minerals, electrical double-layer (EDL) expansion and multiple ion exchange (MIE) are found to contribute less. Such formed micro-dispersions are induced by CO2 via diffusion to mobilize the CO2-diluated oil, alter the rock wettability towards more water-wet, and minimize the density contrast between crude oil and water.

Reduced diffusional limitations in carnation stems facilitate higher photosynthetic rates and reduced photorespiratory losses compared with leaves.

Green stem photosynthesis has been shown to be relatively inefficient but can occasionally contribute significantly to the carbon budget of desert plants. Although the possession of green photosynthetic stems is a common trait, little is known about their photosynthetic characteristics in non-desert species. Dianthus caryophyllus is a semi-woody species with prominent green stems, which show similar photosynthetic anatomy with leaves. In the present study, we used a combination of gas exchange and chlorophyll fluorescence measurements, some of which were taken under varying O2 and CO2 partial pressures, to investigate whether the apparent anatomical similarities between the species' leaves and stems translate into similar photosynthetic physiology and capacity for CO2 assimilation. Both organs displayed high photosynthetic electron transport rates (ETR) and similar values of steady-state non-photochemical quenching (NPQ), albeit leaves could attain them faster. The analysis of OJIP transients showed that the quantum efficiencies and energy fluxes along the photosynthetic electron transport chain are largely similar between leaves and stems. Stems displayed higher total conductance to CO2 diffusion, similar biochemical properties, significantly higher photosynthetic rates and lower water use efficiency than leaves. Leaf ETR was more sensitive to sub-ambient O2 and super-ambient CO2 partial pressures, while leaves also displayed a higher relative rate of Rubisco oxygenation. We conclude that the highly responsive NPQ and the enhanced photorespiration and WUE in leaves represent photoprotective and water-conserving adaptations to the high incident light intensities they experience naturally, at the expense of higher CO2 assimilation rates, which the vertically orientated stems can readily attain.

Influences of reformate on the performance of high temperature proton exchange membrane fuel cell and its optimization strategy

Due to the challenges of hydrogen production, storage and transport, hydrocarbon reformate-based high temperature proton exchange membrane fuel cell (HT-PEMFC) has wide application opportunities. However, the inevitable water vapor and CO in reformate significantly determines the fuel cell performance and durability. In this work, a three-dimensional, non-isothermal and multiphase model based on agglomerate sub-model is developed to investigate the effects of reformate components and operating conditions, in which multiphase transport, dissolution, diffusion, adsorption, desorption and reaction of H2 and CO are considered. The results show that the fuel cell performance increases with the rising of water vapor content as CO content higher than 2 % (dry basis, the same below) and water vapor content lower 20 % (wet basis). The alleviation effect of water vapor on CO poisoning is discovered due to reduced CO coverage rather than enhanced CO electrochemical oxidation. An elevated temperature leads to improved performance and the effect of CO poisoning (CO<3%) is weak at 180°C.

Insights on influence of polymer molecular weight on gas sorption, transport and plasticization in glassy 6FDA-DAM polyimide membranes

It is well-known that spinning of defect-free asymmetric polyimide hollow fibers is promoted by using high polymer molecular weight. On the other hand, effects of polymer molecular weight on microstructure and separation performance of dense film 6FDA-based polyimide membranes relevant to sheath layers of composite membranes are less well-explored. In this work, gas sorption, diffusion and permeation of CO2, N2 and CH4 for 6FDA-DAM dense films are considered for 45 kDa and 176 kDa weight average molecular weights. Such molecular weights are relevant for practical hollow fiber spinning of membranes. Earlier results for polystyrene samples show similar trends in dual mode sorption model results like those noted here for the 6FDA-DAM polyimide case; however, effects on permeation like those considered here were not addressed for the polystyrene case. Here we also address actual pure and mixed gas CO2 and CH4 permeation and show higher free volumes, higher gas permeability but lower 50:50 CO2/CH4 selectivity associated with the higher molecular weight sample. Analysis using the self-consistent dual-mode sorption and transport models help understand the observed trends. Our results suggest denser packing of polymer segments exists in the Henry's law environment of the low molecular weight sample. Moreover, the higher polymer segmental packing in the Henry's law environment suppresses CO2 plasticization with a dual-mode microstructure controlling separation performance and plasticization behavior for this important member of the 6FDA polyimide family. We show evidence of effects of charge transfer complexes as possible main features in these trends. These dense film results help guide future work on dense sheath layers on composite hollow fiber membranes.

Elevating carbonation efficiency and CO2 capture capacity of steel slag by sodium tripolyphosphate (STP): The role of CaCO3 morphology modification

Carbonation degree significantly impacts the volume stability of steel slag powder. To elevate the carbonation efficiency of steel slag and thereby alleviate the volume unsoundness of steel slag powder, sodium tripolyphosphate (STP) was used to enhance the micro morphology of CaCO3 and accelerate Ca leaching and CO2 diffusion. Three methods for assessing CO2 uptake were employed to reliably determine the degree of carbonation. Results indicate that steel slag added with 0.05 wt% STP obtained a promotion exceeded 80 % in CO2 uptake. Additionally, STP increased the CO2 capture capacity of steel slag by 24.84 %. Under the influence of STP, the expansion of steel slag paste was reduced by up to 31.45 % following an autoclaving test. The formed micro CaCO3 particles in carbonated steel slag without STP were polyhedral grains and a dense carbonation layer was formed around calcium silicate. Contrastively, CaCO3 formed in the carbonated STP incorporated steel slag were conical or acicular particles and consequently generated a porous layer. The porous microstructure provided “tunnels” for the continuous CO2 diffusion and Ca2+ leaching and hence maintained relatively higher reaction speed throughout the carbonation process. Furthermore, STP also played the role as a chelator which accelerated the leaching of Ca2+.

Interactive effects of water deficit and nitrogen deficiency on photosynthesis, its underlying component processes, and carbon loss processes in cotton

AbstractDrought stress and nitrogen (N) deficiency are important abiotic stresses that severely limit net photosynthetic rate (AN). A number of studies have investigated the underlying physiological limitations to AN in response to water deficit or N deficiency; however, the relative sensitivities of photosynthetic component processes and carbon loss processes to combined drought and N deficiency in field‐grown cotton (Gossypium hirsutum L.) have not been explored. Therefore, the objective of the present study was to determine the effects of combined water deficit and nitrogen deficiency on the underlying physiological processes driving AN in field‐grown cotton. Water‐deficit stress caused substantial reductions in AN, but reductions in AN were greater under optimum N conditions (74%) than under N deficiency (22%). Decreased CO2 diffusion, RuBP regeneration, and Rubisco carboxylation were major contributors to a decline in AN due to water‐deficit stress. Reductions in Rubisco carboxylation and RuBP regeneration were the greatest drivers of N deficiency‐induced decline in AN. Lower CO2 diffusion and Rubisco carboxylation were main constraints to AN due to combined water deficit and N deficiency. Regarding carbon loss processes, both dark respiration and photorespiration under water‐deficit stress or N deficiency, and only photorespiration under combined water deficit and N deficiency, contributed to declines in AN. Increased non‐photochemical quenching and/or photorespiration prevented photoinhibition of photosystem II under stress conditions. Overall, response of photosynthesis to water‐deficit stress was dependent on N availability, and rate‐limiting physiological processes contributing to declines in AN were dependent on the type of prevailing stress.

Comparative experimental study of ash formation behaviors during the fixed-bed gasification of coal water slurry and dry pulverized coal prepared from Shenmu coal

The mechanism of ash formation during coal gasification is very important for the safety and stability of gasifier operation. This study comparatively investigated the ash formation behaviors during the gasification of coal water slurry and dry pulverized coal. Shenmu coal was gasified in a CO2 atmosphere at 900 °C using a fixed-bed reactor to prepare chars and ashes. Computer-controlled scanning electron microscopy was employed to characterize the compositions and particle sizes of minerals in the raw coal, coal water slurry gasification ash, and dry pulverized coal gasification ash. Morphological characteristics reveal that, during gasification, coal water slurry gasification char exhibits obvious agglomeration compared to the dry pulverized coal gasification char. The changes of mineral compositions indicate that, during both coal water slurry and dry pulverized coal gasification, minerals follow nearly identical transformation pathways, but the degrees of transformation are different. The influence of char agglomeration on heat transfer may be the reason for the less transformation of K Al-silicate and kaolinite during the coal water slurry gasification. Furthermore, in comparison to dry pulverized coal gasification, more Ca in calcite and S in pyrite transfer into gypsum during the coal water slurry gasification. The results from thermodynamic equilibrium calculations indirectly suggest that this may be attributed to the limited internal diffusion of CO2 within coal water slurry gasification char resulting from char agglomeration during gasification. Overall particle size distributions of minerals in raw coal, coal water slurry gasification ash, and dry pulverized coal gasification ash demonstrate that the degrees of mineral fragmentation are almost consistent during both coal water slurry and dry pulverized coal gasification. However, differences in the degrees of mineral transformation led to different particle size distributions of various minerals between coal water slurry gasification ash and dry pulverized coal gasification ash. This study mainly focuses on the influence of water in coal water slurry on ash formation, and it has not considered the influence of other factors, such as ash content, hydrophilicity, caking property, and gasification reactivity of coal, which need further research to explore.

Soft and diffusion-controlled Sr-MOF for efficient separation of H2O/D2O

Heavy water (D2O) electrolysis is the primary technology for D2 production, playing an irreplaceable role in fields such as nuclear fusion research and isotope tracing. However, the inherent similarity in chemical properties between H2O and D2O (with only a 1.4 °C difference in boiling points) poses significant challenges to their separation. Furthermore, the extremely low natural abundance of D2O (0.015 %) increases the difficulty and cost of separation, while traditional electrolysis and distillation techniques are highly energy intensive. Therefore, there is an urgent need to develop novel adsorbents for efficient and environmentally sustainable H2O/D2O separation. Herein, we used polydentate ligand 2, 5-dihydroxyterephthalic acid (DOBDC) and its derivatives 4,4́-(anthracene-9,10-diyl) bis (2-hydroxybenzoic acid (ABHB) as raw materials to prepare two novel high coordination Sr-MOFs namely IPE-1 and IPE-2, respectively. These MOFs were applied for efficient separation of H2O and D2O at room temperature. X-ray diffraction results reveal that one Sr atom in IPE-1 is coordinated with 9 oxygen atoms. This high coordination number results in the formation of ultra-small rectangular pores of approximately 2.5 Å. Adsorption isotherms of N2, CO2, H2O, and D2O indicate that the ultramicroporous structure of IPE-1 precludes efficient diffusion of CO2 and H2O molecules into the MOF channels. In contrast, the activated IPE-2 exhibits good CO2, H2O, and D2O uptake capacities of 3 mmol/g, 8.38 mmol/g, and 6.51 mmol/g at 298 K, respectively. The Qst values and Ksap values of H2O and D2O indicate that the adsorption rates of H2O were much higher than D2O under 0.2 < P/P0 < 0.7, with a calculated ratio of approximately 1.26. This study not only provides appealing MOFs materials for efficient H2O/D2O separation at room temperature but also provides a new avenue for preparing adsorbents with high stability and high separation performance.