Water Adsorption and Its Pore Structure Dependence in Shale Gas Reservoirs.

Investigating the occurrence characteristics of water molecules in shale is of great resource, economic, and environmental significance. In this work, the adsorption behavior of water vapor on Longmaxi shale samples is tested, and several isothermal adsorption models are employed to fit the experimental data and primary and secondary adsorption processes. Furthermore, the influence of organic matter content, mineralogical composition, and pore structure on the adsorption process is discussed, and their special combination relationship is revealed correspondingly. The results indicate that the Dent model is suitable for the experimental data with excellent goodness of fit, and the Langmuir and Freundlich models are suitable for the primary and secondary adsorption processes, respectively. The adsorption of water vapor is controlled by the pore volume and specific surface area (SSA) of shale. Mesopore structure parameters mostly determine the water adsorption amount. Massive micropores developed in organic matter with a huge SSA contribute strongly to the primary adsorption process. In general, the combination of organic matter and clay minerals controls the pore structure of shale, which further controls the primary and secondary adsorption processes of water vapor. These findings contribute to a better understanding of water adsorption in different adsorption carriers and in microscopic pores of different sizes occurring in shale gas reservoirs.

Effect of Coal Rank and Coal Facies on Nanopore-Fracture Structure Heterogeneity in Middle-Rank Coal Reservoirs.

Considerable variations in microscopic and industrial components (ash, moisture, volatile matter, etc.) have been reported within identical coal seams. These disparities in coal quality and pore structure within the same coal seam profoundly affect the drainage of deep coalbed methane (DCBM). This study focuses on 22 coal samples collected from two wells in the Benxi Formation of the central and eastern parts of the Ordos Basin. First, the coal facies were determined for all samples using submicroscopic components, and then, the adsorption pore and seepage pore structures were studied through CO2/N2 adsorption and mercury intrusive tests. Subsequently, the study delves into the correlation between coal rank, coal facies, and the distribution of the pore structures across various pore sizes, elucidating the primary controlling factors influenced by coal rank and coal phase. The results are as follows: (1) For a given coal seam, R o, max exhibits minimal variation among the samples, which suggests R o, max is not the primary factor affecting pore structure. Conversely, the ash content occupies the pore space, thereby revealing a negative correlation between the ash content and adsorption pore volume (PV). (2) On the basis of the texture preservation index (TPI) and gelatification index (GI), coal facies were classified into moist forest swamp facies (type A), moist herbaceous swamp facies (type B), and water-covered herbaceous swamp facies (type C). Type A is characterized by higher TPI, lower GI, and ash content, whereas type C exhibits lower TPI, higher GI, and ash content. (3) Type A samples, with the lowest ash content, display larger PV and specific surface area (SSA) compared with type B, while type C has the lowest values. Type C, with the highest vitrinite content, predominantly consists of semibright and bright coal, prone to microcracks, which results in a higher seepage PV compared with types A and B. (4) The coal facies represent variations in ash content and microscopic components, which significantly impacts both adsorption and seepage pores. Moist forest swamp facies samples are characterized by micropore development and the highest content of adsorbed gas. Herbaceous swamp facies samples display macropore development and the highest content of free gas.

Effect of Pore Structure Heterogeneity of Sandstone Reservoirs on Porosity-Permeability Variation by Using Single-Multi-Fractal Models.

Pore structure heterogeneity affects sandstone porosity and permeability and thus sandstone gas productivity. A total of 17 sandstone samples collected from the northwestern margin of the Junggar Basin in Xinjiang Province are investigated in this study. The pore-fracture system distribution of target sandstones is studied by high-pressure mercury injection tests. On this basis, single- and multi-fractal models are used to characterize pore structure heterogeneity, and the applicability of four models (Menger model, Sierpinski model, Thermodynamic model, multifractal model) to characterize pore and fracture distribution heterogeneity are discussed. Moreover, a correlation between fractal dimension, pore structure parameters, and variation coefficient of porosity-permeability is discussed based on overburden permeability test results. The results are as follows. (1) D S (fractal dimension of Sierpinski model) shows a significant correlation with pore volume percentage, so the Sierpinski model could better characterize fracture distribution heterogeneity quantitatively. Multifractal dimensions are consistent with those of Sierpinski and Thermodynamic models, which indicates that the single- and multiple-fractal models are consistent. (2) The porosity and permeability decrease as a power function with higher confining pressure. The porosity and permeability behavior changes at a critical conversion pressure value. For a confining pressure lower than this critical value, the porosity and permeability decrease largely. For confining pressures higher than this critical value, the porosity and permeability vary less. In contrast, permeability has a larger variation rate and is more obviously affected by confining pressure. (3) Pore compression space is affected by the permeability variation coefficient. Compressibility, porosity, and permeability variation coefficient have no relationship with pore structure parameters since compressibility is affected by pore structure, mineral composition, and other factors in sandstone samples.

On Thermal Insulation Properties of Various Foaming Materials Modified Fly Ash Based Geopolymers.

Geopolymers can be used as a thermally insulated material because of their considerable porosity, whereas the combined effect of various modifying agents on their heat-insulating properties remains unexplored. Here, orthogonal experiments were carried out to evaluate the thermal insulation performance of fly ash geopolymer modified by phenolic resin, silica aerogel, and hydrogen peroxide. Moreover, variance analysis and range analysis were applied to estimate the influence of modifying agents on the thermal insulation performance of the geopolymer. The results demonstrate that the thermal conductivity of fly ash geopolymer significantly reduces (from 0.48 W/m·K to 0.12 W/m·K) due to the combined effect of the three modifying agents. Based on the variance analysis and range analysis, the optimum thermal conductivity ultimately reaches 0.08 W/m·K via a best composition scheme of the three modifying agents. Moreover, phenolic resin can facilitate the formation of a network structure and increase the porosity of micron pores (>1 µm). Hydrogen peroxide can be decomposed into O2 in an alkaline environment and leave large-diameter pores (>1 µm) during curing. Some silica aerogel is embedded in the geopolymer matrix as microspheres with extremely low thermal conductivity, whereas the rest of the silica aerogel may react with the alkali activator to form water, and subsequently leaves pores (>1 µm) after evaporation of water during the curing. In addition, a newly modified Maxwell-Euchen model using iterative calculation and considering the Knudsen effect (pores of micron or even nanometer scale) is proposed and validated by the experimental data. The foamed geopolymer in this research can be used as a reference for building insulation layer design. This research unravels phenolic resin-, silica aerogel-, and hydrogen peroxide-influenced thermal insulation mechanisms of geopolymer that may have impacts on deployment of a thermally insulating material in the construction field.

Review on the Degradation of Poly(lactic acid) during Melt Processing.

This review paper presents an overview of the state of the art on process-induced degradation of poly(lactic acid) (PLA) and the relative importance of different processing variables. The sensitivity of PLA to degradation, especially during melt processing, is considered a significant challenge as it may result in deterioration of its properties. The focus of this review is on degradation during melt processing techniques such as injection molding and extrusion, and therefore it does not deal with biodegradation. Firstly, the general processing and fundamental variables that determine the degradation are discussed. Secondly, the material properties (for example rheological, thermal, and mechanical) are presented that can be used to monitor and quantify the degradation. Thirdly, the effects of different processing variables on the extent of degradation are reviewed. Fourthly, additives are discussed for melt stabilization of PLA. Although current literature reports the degradation reactions and clearly indicates the effect of degradation on PLA's properties, there are still knowledge gaps in how to select and predict the processing conditions that minimize process-induced degradation to save raw materials and time during production.

Effect of Anionic Polyacrylamide Polymer on Frost Heave Mitigation and Its Implication for Frost-Susceptible Soil.

Seasonally frozen ground regions occupy approximately 55% of the exposed land surface in the Northern Hemisphere, and frost heave is the common global problem in seasonally frozen soil areas. Frost heave induces uneven deformation of ground and damages railways, road paving, and buildings. How to mitigate frost heave is the most important technical issue in this field that has provoked great interest. Here, using freezing experiments, we investigate the effect of anionic polyacrylamide (APAM) polymer on frost susceptible soil. The results demonstrate a so-far undocumented inhibition of frost heave by APAM in freezing soil, namely APAM (tested at concentrations from 0.0 wt% to 0.60 wt%) slows down the frost heave by a factor of up to 2.1 (since 0.60 wt% APAM can decrease frost heave from 8.56 mm to 4.14 mm in comparison to the control experiment). Moreover, it can be observed that the maximum water content near the frozen fringe decreased from 53.4% to 31.4% as the APAM content increased from 0.0 wt% to 0.60 wt%, implying a mitigated ice lens growth. Hydrogen bonding between APAM and soil particles triggers an adsorption mechanism that accumulates soil particles, and thus can potentially inhibit the separation and growth of the ice lens. Moreover, the residue of APAM due to hydrogen bonding-induced adsorption in the pores of granular media may narrow seepage channels (capillary barriers) and provide an unfavourable condition for water migration. The use of APAM can also increase the viscosity of the solution, which causes a greater water migration resistance. This research provides new insights into APAM-influenced frost heave (introducing APAM into the soil can induce bridging adsorption between APAM polymer segments and a particle surface), can enable engineers and researchers to utilise chemical improvement design and to consider suitable actions (e.g., by injecting APAM solution into a frost susceptible soil or using APAM-modified soil to replace the frost susceptible soil) to prevent frost heave from having a negative impact on traffic roads and buildings in cold regions.

Adsorption behavior and mechanism of CO2 in the Longmaxi shale gas reservoir.

CO2 is the main greenhouse gas in Earth's atmosphere, and has been causing global warming since the industrial revolution. Therefore, technologies to mitigate carbon emissions have attracted extensive research. Shale gas reservoirs could serve as potential sequestration space for CO2. This paper aims to gain insight in the CO2 adsorption behavior and mechanism in Longmaxi shale. The micropore filling theory is the best model for CO2 adsorption in the shale samples with the smallest MSR (Mean Square of Residual). This model fits better than that of the monolayer adsorption and multi-layer adsorption theories. Specifically, micropore filling adsorption mainly occurs in micropores, including the closed end of slit pores, capillary pores, and ink-shaped pores. Molecular layer adsorption mainly occurs in mesopores and macropores, including the open end of slit pores, plate pores, capillary pores, and ink-shaped pores. Moreover, the prediction model of CO2 storage quantity in deep shale gas reservoirs of China is established. This model shows that 91.5-388.89 × 1012 m3 of CO2 could in theory be stored in an adsorbed state. CO2 is mostly stored by an adsorbed state (higher than 95%) and a free state with good security and low leakage risk. The results from this work are of specific interest for global research on CO2 adsorption characteristics and adsorption mechanisms in different pore structures. Furthermore, it provides certain guidance for geological storage of CO2 in shale.

A model for superimposed coalbed methane, shale gas and tight sandstone reservoirs, Taiyuan Formation, Yushe-Wuxiang Block, eastern Qinshui Basin.

Superimposed accumulation mechanism and model of vertical source rock-reservoir system of coal-measure gas is crucial to evaluate the exploration potential, and also the basis of co-exploration and co-production of coal measure gas. This work investigates the formation mechanism of various types of reservoirs (coalbed methane, shale gas, tight sandstone) in the Taiyuan Formation (Yushe-Wuxiang Block, eastern Qinshui Basin). Source rocks (coal seams and coal-measure mudstones) in the study area are characterized by type III kerogen, organic rich and over-mature, and reach a gas generation peak during the Early to Late Cretaceous. Coalbed methane mainly adsorbs on the surface of micropores, shale gas mainly occurs in micropores, macropores and micro-factures in adsorbed and free states, and tight sandstone gas mainly occurs in macropores in a free state. The combinations of successions are identified, coalbed methane, shale gas, and tight sandstone gas horizons are divided into a mudstone-sandstone reservoir (combination I), a coal-mudstone-sandstone reservoir (combination II), and a coal-mudstone reservoir (combination III). This division occurs from top to bottom in the succession and is identified on the basis of lithology, total organic carbon content (TOC) of mudstones, gas logging, superimposition relationships, and the source rock-reservoir-caprock assemblage. The strata thickness, continuity, and gas logging results of combination III comprise the most favorable conditions for fairly good development potential, followed by combination I. The development potential of combination II is poor due to the small strata thickness and poor continuity. The identification of superimposed reservoirs can provide an engineering reference for the exploration of coal-measure gas.

Multifractal Analysis in Characterizing Adsorption Pore Heterogeneity of Middle- and High-Rank Coal Reservoirs.

Nanopore heterogeneity has a significant effect on adsorption, desorption, and diffusion processes of coalbed methane. The adsorption pore size distribution heterogeneity was calculated by combining N2 with CO2 adsorption data, and factors affecting multifractal and single-fractal dimensions were studied. The results indicate that pore size distribution of micropores (with pore diameters smaller than 2 nm) and meso-macro-pores (with pore diameters between 2 and 100 nm) in coal samples exhibit typical multifractal behavior. The overall heterogeneity of micropores in high-rank coal samples is higher than that in the middle-rank coal samples. The low-probability measure areas control the overall heterogeneity of pores with diameters of 0.40-1.50 nm. The high-probability measure area heterogeneity and spectral width ratio have a higher linear correlation with coal rank and pore structure parameters than those of low-probability measure areas. Heterogeneity of high-probability measure areas and overall pore size distribution are controlled by pores with diameters of 0.72-0.94 nm. Multifractal parameters of meso-macro-pores have no clear relationship with coal rank. The pore volume of 2-10 nm diameter shows a good linear correlation with heterogeneity of low-probability measure areas, and pores of this diameter range are the key interval that affected pore size distribution heterogeneity. The single-fractal dimension obtained using the Frenkel-Halsey-Hill (FHH) model shows a positive linear correlation with heterogeneity of the low-probability measure areas. It indicates that this parameter can effectively characterize the pore size distribution heterogeneity of low-probability measure areas in meso-macro-pores.

Natural fluorapatite dissolution kinetics and Mn2+ and Cr3+ metal removal from sulfate fluids at 35 °C.

In light of the consequences of global warming and population growth, access to safe drinking water becomes an ever greater challenge, in particular in low to middle income countries in arid regions. Moreover, mining which may cause acid mine drainage and heavy metal contamination puts further pressure on management of limited water resources. Hence, the development of cost effective water treatment methods is critical. Here, using batch reactor experiments we investigate the kinetics and mechanisms behind divalent Mn and trivalent Cr removal from sulfate fluids using natural fluorapatite at 35 °C. The results show that the fluorapatite dissolution rate depends on fluid pH, and that dissolution is the dominant mechanism in fluids with pH below 4. Apatite can thus serve as remediation to neutralize acidic fluids. Fluid pH of 4-6 triggers a dissolution-precipitation mechanism, in some cases following upon a dissolution-only period, with the formation of a metal phosphate. In these experiments, Cr removal is two to ten times faster than Mn removal given similar solution pH. The results demonstrate that natural apatite represents a promising, cost effective material for use in passive remediation of mining-induced contamination of soils and groundwater in arid regions.

Acceleration of dolomitization by zinc in saline waters.

Dolomite (CaMg(CO3)2) plays a key role in the global carbon cycle. Yet, the chemical mechanisms that catalyze its formation remain an enigma. Here, using batch reactor experiments, we demonstrate an unexpected acceleration of dolomite formation by zinc in saline fluids, reflecting a not uncommon spatial association of dolomite with Mississippi Valley-type ores. The acceleration correlates with dissolved zinc concentration, irrespective of the zinc source tested (ZnCl2 and ZnO). Moreover, the addition of dissolved zinc counteracts the inhibiting effect of dissolved sulfate on dolomite formation. Integration with previous studies enables us to develop an understanding of the dolomitization pathway. Our findings suggest that the fluids' high ionic strength and zinc complexation facilitate magnesium ion dehydration, resulting in a dramatic decrease in induction time. This study establishes a previously unrecognized role of zinc in dolomite formation, and may help explain the changes in dolomite abundance through geological time.

The architectural design of smart ventilation and drainage systems in termite nests.

Termite nests have been widely studied as effective examples for ventilation and thermoregulation. However, the mechanisms by which these properties are controlled by the microstructure of the outer walls remain unclear. Here, we combine multiscale X-ray imaging with three-dimensional flow field simulations to investigate the impact of the architectural design of nest walls on CO2 exchange, heat transport and water drainage. We show that termites build outer walls that contain both small and percolating large pores at the microscale. The network of larger microscale pores enhances permeability by one to two orders of magnitude compared to the smaller pores alone, and it increases CO2 diffusivity up to eight times. In addition, the pore network offers enhanced thermal insulation and allows quick drainage of rainwater, thereby restoring the ventilation and providing structural stability to the wet nest.