Marine organic-rich
shale in South China has considerable exploration
potential, and the shale adsorption capacity has a great impact on
the accumulation of shale gas. To study the methane adsorption capacity
of marine shale, ten shale samples from the Lower Cambrian Qiongzhusi
Formation in eastern Yunnan province were investigated by organic
geochemical analysis (total organic carbon content, thermal maturity,
and kerogen type), X-ray diffraction (XRD) analysis, field emission
scanning electron microscopy (FE-SEM), and low-pressure nitrogen adsorption
and methane adsorption experiments. Based on the different adsorption
mechanisms of various pores, the Dubinin–Radushkevich and Langmuir–Freundlich
models were used to construct a supercritical adsorption model of
shale. Combined with this model, the mechanisms and characteristics
of shale adsorption under supercritical conditions were analyzed.
The maximum absolute methane adsorption capacities of micropores (V
1) and mesopores-macropores (V
2) were also calculated. Not only have the relationships
between organic geochemistry, mineral compositions, pore structure
parameters, and maximum absolute methane adsorption capacity (both V
1 and V
2) been discussed
but the impact of moisture on the methane adsorption capacity of shale
has also been investigated. The results show that the maximum adsorption
capacity of mesopores–macropores is greater than that of micropores.
Both V
1 and V
2 are positively correlated with the TOC content, and V
2 is more correlated with the TOC content than V
1. High maturity is not conducive to methane
adsorption of shale. The maximum absolute methane adsorption amounts
of per-unit organic matter have positive correlations with the clay
mineral content, but show negative correlations with the quartz content.
Different clay minerals have different methane adsorption capacities.
Both V
1 and V
2 increase with increasing specific surface area. V
1 has a positive correlation with the micropore volume,
but V
2 has no apparent relationship with
the mesopore–macropore volume. Moreover, shale samples with
higher moisture contents have lower methane adsorption capacity. It
is anticipated that the results of this study will provide guidance
for the adsorption characteristics and influence factors of high maturity
marine shale.
Red mud, a waste tailing from alumina production, was activated with calcination and acid treatment for simultaneous removal of F − and As from water solution. After activation, the specific area and Si-O-M and Al-O-H functional groups of the activated red mud (ARM) greatly increased. Results showed that the adsorption equilibrium time for F − , As(V), and As(III) was 18, 12, and 48 h, respectively. Kinetic data revealed that adsorption kinetics well followed the pseudo-second order model for F − , As(V), and As(III). The presence of As(V)/As(III) improved the adsorption rate of F − . With the co-existence of F − and As, F − adsorption was independent of initial solution pH between 4.0 and 10.0, and As adsorption between 2.0 and 10.0. Adsorption of F − , As(V), and As(III) was better described by the Langmuir model than the Freundlich model, indicating that adsorption was in the form of a monolayer. Fluoride had a significant effect on As(V) adsorption, while the less affected As(III) adsorption. The presence of 1.0 mg/L As(III)/As(V) had no significant influence on F − adsorption. ARM had high adsorption capacity for F − , As(V), and As(III), which resulted from the increases in the specific area and Si-O-M and Al-O-H functional groups. Results demonstrated that ARM is a potential adsorbent for simultaneous removal of F − and As from contaminated groundwater.
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