RESUMO
In this study, we present an innovative environmental silicon-, phosphorus-, and nitrogen-triple lignin-based flame retardant (Lig-K-DOPO). Lig-K-DOPO was successfully prepared by condensation of lignin with flame retardant intermediate DOPO-KH550 synthesized via Atherton-Todd reaction between 9, 10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide (DOPO) and γ-aminopropyl triethoxysilane (KH550A). The presence of silicon, phosphate, and nitrogen groups was characterized by FTIR, XPS, and 31P NMR spectroscopy. Lig-K-DOPO exhibited advanced thermal stability compared with pristine lignin supported by TGA analysis. The curing characteristic measurement showed that addition of Lig-K-DOPO promoted the curing rate and crosslink density to styrene butadiene rubber (SBR). Moreover, the cone calorimetry results indicated Lig-K-DOPO conferred impressive flame retardancy and smoke suppression. The addition of 20 phr Lig-K-DOPO reduced SBR blends 19.1% peak heat release rate (PHRR), 13.2% total heat release (THR), 53.2% smoke production rate (SPR), and 45.7% peak smoke production rate (PSPR). This strategy provides insights into multifunctional additives and greatly extends the comprehensive utilization of industrial lignin.
RESUMO
The characteristics, distribution, and preservation of pores are vital in controlling the storage and distribution of shale gas. The Qiongzhusi Formation shales taken from different members with similar tectonic and thermal evolutions were used to evaluate the response of pore characteristics to minerals and sealing systems using field-emission scanning electron microscopy and gas adsorption. Because of differences in mineral structure and arrangement, feldspar, organic matter (OM)-clay, OM-rutile, and OM-apatite aggregates facilitate multiple types of pores in the shale and influence the relative proportions of surface porosity for different types of pores owing to differences in mineral structure and arrangement. Rigid frameworks and pressure shadows formed by rigid minerals and OM-mineral aggregates preserved OM and pores to some extent. The sealing capacity of the floor controls the sealing system and hydrocarbon expulsion efficiency of the Qiongzhusi Formation in different members. During thermal evolution, the amount of hydrocarbons generated and expelled affected the stress equilibrium state between the pore pressure and external stress, influencing the compaction intensity of shales. The OM pore development characteristics were evolved with variation in the stress equilibrium state in different sealing systems. Once the stress equilibrium state was disrupted, the OM pores deformed, narrowed, or even closed under the influence of compaction owing to the loss of overpressure support. The pore characteristics of the Qiongzhusi Formation shales responded significantly to different sealing systems. A few OM pores are flat and slitlike in the open system, whereas numerous OM pores are round and elliptical in the semiopen system. Meanwhile, the average diameter of the OM pores in the open system was reduced by approximately 40.2% compared with that of the semiopen system. Furthermore, the pore volume and specific surface area of the mesopores for open system shales were reduced by 38.4% and 37.7%, respectively, compared to the semiopen system. These findings will improve the understanding of the distribution and preservation of pore in shale and help assess the sweet-spot members for the Qiongzhusi Formation shale gas.
RESUMO
Due to breakthroughs in the Lower Silurian Longmaxi Formation in the Sichuan Basin and multiple strata around the basin, the northern part of Guizhou adjacent to the Sichuan Basin has become a key area for shale gas exploration. Compared with the Longmaxi Formation, the Niutitang Formation displays greater TOC (total organic carbon) content, depositional thickness and distribution area, but the details remain undetermined. In the study area, the Lower Cambrian Niutitang Formation typically has high TOC content, maturity and brittle mineral content. The study area has experienced multiple periods of tectonic movement, which have great influence on the fracture and pore characteristics. The fractures are mainly structural fractures and have obvious zoning. The primary types of pores are intraparticle pores, organic matter pores, and interparticle pores. Further, macropores and mesopores less than 50 nm contribute most of the pore volume, while pores less than 2 nm contribute most of the specific surface area. Many factors affect the pore-fracture system, such as tectonism, TOC content, mineral composition, and sedimentary environment. Tectonic movements produce fractures based on the changing stress field, but the degree of fracture development does not agree well with the degree of pore development. The TOC content has good positive correlations with the development of fractures and micropores, especially for nanoporosity, while clay minerals show a negative correlation with the development of fractures but a strong positive correlation with the growth of micropores. Quartz displays a positive correlation with the development of fractures but no good correlation with pore development. Finally, the lithofacies, lithologies and mineral compositions under the control of sedimentary environments are internal factors that can impact the development of pore-fracture systems.
