Investigations of methane adsorption characteristics on marine-continental transitional shales and gas storage capacity models considering pore evolution

Methane adsorption is a critical assessment of the gas storage capacity(GSC)of shales with geological conditions.Although the related research of marine shales has been well-illustrated,the methane adsorption of marine-continental transitional(MCT)shales is still ambiguous.In this study,a method of combining experimental data with analytical models was used to investigate the methane adsorption characteristics and GSC of MCT shales collected from the Qinshui Basin,China.The Ono-Kondo model was used to fit the adsorption data to obtain the adsorption parameters.Subsequently,the geological model of GSC based on pore evolution was constructed using a representative shale sample with a total organic carbon(TOC)content of 1.71%,and the effects of reservoir pressure coefficient and water saturation on GSC were explored.In experimental results,compared to the composition of the MCT shale,the pore structure dominates the methane adsorption,and meanwhile,the maturity mainly governs the pore structure.Besides,maturity in the middle-eastern region of the Qinshui Basin shows a strong positive correlation with burial depth.The two parameters,micropore pore volume and non-micropore surface area,induce a good fit for the adsorption capacity data of the shale.In simulation results,the depth,pressure coefficient,and water saturation of the shale all affect the GSC.It demonstrates a promising shale gas potential of the MCT shale in a deeper block,especially with low water saturation.Specifically,the economic feasibility of shale gas could be a major consideration for the shale with a depth of<800 m and/or water saturation>60%in the Yushe-Wuxiang area.This study provides a valuable reference for the reservoir evaluation and favorable block search of MCT shale gas.

Adsorption of Naphthenic Acids from Dewaxed Vacuum Gas Oil by Activated Clay: Kinetics, Equilibrium and Thermodynamic Studies

This work was mainly concentrated on the removal of naphthenic acids(NAs) from dewaxed vacuum gas oil(VGO) by adsorption using a commercial grade activated clay(AC) adsorption during lube base oil refining. The NAs in dewaxed VGO cut-4 were identified by negative-ion electrospray ionization Fourier transform ion cyclotron resonance mass spectrometry(ESI FT-ICR MS). The AC sample from a refinery was characterized by XRD, BET, TG/DTA, and SEM. A series of experiments were carried out to investigate the performance of NAs adsorption by AC using a batch adsorption technique, in which some key experimental parameters such as temperature, contact time, initial concentration of NA in oil sample as well as the dosage of adsorbent were investigated. Equilibrium isotherms were analyzed using the Langmuir, Freundlich, Tempkin and Dubinin-Radushkevich(D-R) adsorption models. The pseudo-first order, the pseudo-second order, and intraparticle diffusion models were employed to describe the kinetics data. The results revealed that the D-R isotherm provided a better fit to the experimental data than other isotherms, and the adsorption kinetics followed the pseudo-first order kinetic equation. The thermodynamic data indicated that the adsorption process was feasible and spontaneous as an endothermic process. The results could provide a clear understanding of the NAs adsorption by AC during lube base oil processing at refineries.

Molecular Dynamics Numerical Simulation of Adsorption Characteristics and Exploitation Limits in Shale Oil Microscopic Pore Spaces

Microscopic pore structure in continental shale oil reservoirs is characterized by small pore throats and complex micro-structures.The adsorption behavior of hydrocarbons on the pore walls exhibits unique physical and chemical properties.Therefore,studying the adsorption morphology of hydrocarbon components in nanometer-sized pores and clarifying the exploitation limits of shale oil at the microscopic level are of great practical significance for the efficient development of continental shale oil.In this study,molecular dynamics simulations were employed to investigate the adsorption characteristics of various single-component shale oils in inorganic quartz fissures,and the influence of pore size and shale oil hydrocarbon composition on the adsorption properties in the pores was analyzed.The results show that different molecules have different adsorption capacities in shale oil pores,with lighter hydrocarbon components(C6H14)exhibiting stronger adsorption abilities.For the same adsorbed molecule,the adsorption amount linearly increases with the increase in pore diameter,but larger pores contribute more to shale oil adsorption.In shale pores,the thickness of the adsorption layer formed by shale oil molecules ranges from 0.4 to 0.5 nm,which is similar to the width of alkane molecules.Shale oil in the adsorbed state that is difficult to be exploited is mainly concentrated in the first adsorption layer.Among them,the volume fraction of adsorbed shale oil in 6 nm shale pores is 40.8%,while the volume fraction of shale oil that is difficult to be exploited is 16.2%.

Insights into carbon dioxide sequestration into coal seams through coupled gas flow-adsorption-deformation modelling

Injecting carbon dioxide(CO_(2))into coal seams may unlock substantial carbon sequestration potential.Since the coal acts like a carbon filter,it can preferentially absorb significant amounts of CO_(2).To explore this further,desorption of the adsorbed gas due to pressure drop is investigated in this paper,to achieve an improved understanding of the long-term fate of injected CO_(2) during post-injection period.This paper presents a dual porosity model coupling gas flow,adsorption and geomechanics for studying coupled processes and effectiveness of CO_(2) sequestration in coals.A new adsorption?desorption model derived based on thermodynamics is incorporated,particularly,the desorption hysteresis is considered.The reliability of the proposed adsorption-desorption isotherm is examined via validation tests.It is indicated that occurrence of desorption hysteresis is attributed to the adsorption-induced pore deformation.After injection ceases,the injected gas continues to propagate further from the injection well,while the pressure in the vicinity of the injection well experiences a significant drop.Although the adsorbed gas near the well also decreases,this decrease is less compared to that in pressure because of desorption hysteresis.The unceasing spread of CO_(2) and drops of pressure and adsorbed gas depend on the degree of desorption hysteresis and heterogeneity of coals,which should be considered when designing CO_(2) sequestration into coal seams.

Application of experimental design in optimization of crude oil adsorption from saline waste water using raw bagasse

Experimental design was applied in the optimization of crude oil adsorption from saline waste water using raw bagasse.The application of response surface methodology(RSM) was presented with temperature,salinity of water,pH,adsorbent dose,and initial oil content as factors.A quadratic model could be used to approximate the mathematical relationship of crude oil removal on the five significant independent variables.Predicted values and experimental values are found to be in good agreement with R2 of 97.44%.The result of optimization shows that the maximum crude oil removal is equal to 67.38% under the optimal condition of temperature of 46.53 °C,salinity of 37.2 g/L,pH of 3,adsorbent dose of 9 g/L and initial oil content of 300×10-6.

Fine quantitative characterization of high-H2S gas reservoirs under the influence of liquid sulfur deposition and adsorption

In order to clarify the influence of liquid sulfur deposition and adsorption to high-H2S gas reservoirs,three types of natural cores with typical carbonate pore structures were selected for high-temperature and high-pressure core displacement experiments.Fine quantitative characterization of the cores in three steady states(original,after sulfur injection,and after gas flooding)was carried out using the nuclear magnetic resonance(NMR)transverse relaxation time spectrum and imaging,X-ray computer tomography(CT)of full-diameter cores,basic physical property testing,and field emission scanning electron microscopy imaging.The loss of pore volume caused by sulfur deposition and adsorption mainly comes from the medium and large pores with sizes bigger than 1000μm.Liquid sulfur has a stronger adsorption and deposition ability in smaller pore spaces,and causes greater damage to reservoirs with poor original pore structures.The pore structure of the three types of carbonate reservoirs shows multiple fractal characteristics.The worse the pore structure,the greater the change of internal pore distribution caused by liquid sulfur deposition and adsorption,and the stronger the heterogeneity.Liquid sulfur deposition and adsorption change the pore size distribution,pore connectivity,and heterogeneity of the rock,which further changes the physical properties of the reservoir.After sulfur injection and gas flooding,the permeability of TypeⅠreservoirs with good physical properties decreased by 16%,and that of TypesⅡandⅢreservoirs with poor physical properties decreased by 90%or more,suggesting an extremely high damage.This indicates that the worse the initial physical properties,the greater the damage of liquid sulfur deposition and adsorption.Liquid sulfur is adsorbed and deposited in different types of pore space in the forms of flocculence,cobweb,or retinitis,causing different changes in the pore structure and physical property of the reservoir.

Study of the reaction mechanism for preparing powdered activated coke with SO_(2)adsorption capability via one-step rapid activation method under flue gas atmosphere

In this study,the impact of different reaction times on the preparation of powdered activated carbon(PAC)using a one-step rapid activation method under flue gas atmosphere is investigated,and the underlying reaction mechanism is summarized.Results indicate that the reaction process of this method can be divided into three stages:stage I is the rapid release of volatiles and the rapid consumption of O_(2),primarily occurring within a reaction time range of 0-0.5 s;stage II is mainly the continuous release and diffusion of volatiles,which is the carbonization and activation coupling reaction stage,and the carbonization process is the main in this stage.This stage mainly occurs at the reaction time range of 0.5 -2.0 s when SL-coal is used as material,and that is 0.5-3.0 s when JJ-coal is used as material;stage III is mainly the activation stage,during which activated components diffuse to both the surface and interior of particles.This stage mainly involves the reaction stage of CO_(2)and H2O(g)activation,and it mainly occurs at the reaction time range of 2.0-4.0 s when SL-coal is used as material,and that is 3.0-4.0 s when JJ-coal is used as material.Besides,the main function of the first two stages is to provide more diffusion channels and contact surfaces/activation sites for the diffusion and activation of the activated components in the third stage.Mastering the reaction mechanism would serve as a crucial reference and foundation for designing the structure,size of the reactor,and optimal positioning of the activator nozzle in PAC preparation.

Adsorption of Phenanthrene in Soil to Biochar Modified by β-Cyclodextrin

In this study, the adsorption effect of β-cyclodextrin modified biochar (BC) on phenanthrene (PHE) in contaminated soil was investigated, aiming to provide an efficient and environmentally friendly remediation strategy for Polycyclic Aromatic Hydrocarbons (PAHs) contaminated soil. Through kinetic and isotherm analysis, β-CDBC-CA showed excellent phenanthrene adsorption performance, and the adsorption effect increased with the increase of time and was affected by temperature. The results show that β-CDBC-CA can not only effectively adsorb phenanthrene in soil, but also serve as a surfactant to help desorption phenanthrene adsorbed by soil organic matter and improve the efficiency of microbial degradation. The experimental data showed that the Elovich model could describe the adsorption behavior of β-CDBC-CA on phenanthrene well, while Langmuir and Freundlich models performed better in fitting parameters, revealing the adsorption mechanism of phenanthrene in contaminated soil by β-cyclodextrin-modified biochar. In addition, temperature has a significant effect on the adsorption capacity of β-CDBC-CA, and its application in soil remediation can be optimized by adjusting temperature. This study not only provides new materials and technical means for soil remediation but also provides important data support for an in-depth understanding of the environmental behavior of PAHs. By citing relevant research results, this study further improves the control and understanding of environmental risks of PAHs, which is of great significance for the protection of ecological environment and human health.

Cross-polymerization between bio-oil and polyaniline: synergistic effects on pore development in subsequent activation and adsorption of phenol

Bio-oil is a major product from pyrolysis of biomass which serves as a carbon source to produce carbon material due to its high reactivity towards polymerization itself or cross-polymerization with other organic feedstocks.In this study,activation of polyaniline(PANI)mixed with wheat straw-derived bio-oil and K2C2O4 at 800°C was conducted,aiming to understand the effect of potential interactions of bio-oil with PANI on pore development of resulting activated carbon(AC).The results revealed cross-polymerization reactions between PANI and bio-oil during direct activation,which increased the yield of AC from 13.0%(calculated average)to 15.0%,the specific surface area from 1677.9 m^(2) g^(-1)(calculated average)to 1771.3 m^(2) g^(-1),and the percentage of micropores from 94.3%to 97.1%.In addition,pre-polymerization of PANI and bio-oil at 200°C before activation was also conducted.Such pretreatment could increase the AC yield from 13.0% to 23.3%,but the specific surface area decreased to 1381.8 m^(2) g^(-1).The pre-polymerization formed the organics that were more resistant towards cracking/gasification,but introduced oxygen-rich functionalities.This made AC highly hydrophilic,rendering a much higher capability for adsorption of phenol despite the smaller specific surface area.Additionally,the AC with developed pore structures facilitated dispersion of nickel in Ni/AC and enhanced the catalytic activity for hydrogenation of o-chloronitrobenzene and vanillin.

Research Progress on Removal of Oxygenatesin Fischer-Tropsch Oil by Adsorption

The oxygen-containing compounds in Fischer Tropsch synthetic oil greatly affect the downstream deep processing of hydrocarbons,and effective removal is required.Com-pared to traditional removal technologies such as hydrogenation deoxygenation,solvent extraction,and extraction distillation,adsorption deoxygenation technology has the advantages of low cost,mild operating conditions,easy removal and recovery,and mini-mal impact on oil quality.Therefore,adsorption deoxygenation technology has devel-oped rapidly in various removal processes and has become a research hotspot in the cur-rent Fischer Tropsch oil deoxygenation.Adsorbents are the core of adsorption deoxygen-ation technology.Therefore,this article briefly introduces the adsorption mechanism and summarizes the research progress of adsorbents widely used in recent years,such as silica gel,alumina,molecular sieves,and metal organic frameworks,in adsorbing oxygen-containing compounds in Fischer Tropsch synthetic oils.And provide reference sugges-tions for further adsorption and deoxygenation directions in the future.

Study on the Effects of Polyacrylamide on Phosphorus Adsorption and Desorption Characteristics of Soil Aggregates

[Objective]The research aimed to provide scientific reference for reasonable utilization of polyacrylamide(PAM).[Method]After PAM treatment,the soil aggregates were classified through dry sieve analysis and the adsorption capacity and desorption capacity of all soil aggregates to phosphorus at different phosphorus concentrations were analyzed.[Result] The phosphorus adsorption and desorption of soil sample treated by PAM declined. The amount of phosphorus adsorption increased with the increase of phosphorus concentration and this increase was fast in low phosphorus concentration area but slow in high phosphorus concentration area.At different phosphorus concentrations,adsorption showed a へ shape changing trend.The phosphorus adsorption was related to phosphorus concentration and the 2-3 mm aggregate had the highest desorption rate while 0.1-0.25 mm aggregate and 0.45-1 mm aggregate had lowest desorption rate.[Conclusion]The PAM treatment generated significant influence on phosphorus adsorption and analytic features of aggregate in all size fractions.

Influence of different phosphates on adsorption and leaching of Cu and Zn in red soil

Batch and soil column experiments were conducted to evaluate the influence of KH2PO4, （NH4）H2PO4and Ca（H2PO4）2on the adsorption and leaching characteristics of Cu and Zn in red soil. The results show that all the three phosphates can greatly improve the adsorption capacity of red soil for Cu and Zn, and the effect of different phosphates on Cu and Zn adsorption follows the order of Ca（H2PO4）2〉KH2PO4〉（NH4）H2PO4. The addition of phosphate has little effect on the mobility of Cu. Ca（H2PO4）2and （NH4）H2PO4 show a strong ability in immobilizing Zn while the immobilization ability of KH2PO4 is much weaker. All the three phosphates are helpful for modifying the partitioning of Cu and Zn from the non-residual phase to the residual phase; however, they could also enhance the contents of Cu and Zn associated with exchangeable and carbonates fractions.

Aspen Adsorption在气体吸附过程模拟方面的应用

Aspen Adsorption是一款吸附模拟软件,常用于气体吸附分离过程的模拟计算,对操作条件优化、设计优化、吸附材料性能评价等方面具有一定的指导作用。简要介绍了Aspen Adsorption软件的应用、模型参数和各种衡算方程,总结了其在穿透曲线计算方面的模拟计算和应用,归纳了利用循环控制器Cycle Organizer针对各种类型的变压吸附PSA(Pressure Swing Adsorption)和变温吸附TSA(Temperature Swing Adsorption)过程进行模拟的情况。此外,针对Aspen Adsorption与其他软件结合使用的案例也进行了简要介绍。最后对Aspen Adsorption的未来发展进行了展望。

Adsorption and Desorption Characteristics of Cadmium and Lead in Typical Paddy Soils of Jiangxi Province and Its Environmental Risk Assessment

[Objective] This study aimed to investigate the adsorption and desorption characteristics of cadmium and lead in typical paddy soils of Jiangxi Province. [Method] Gleyed paddy soil and waterloggogenic paddy soil were collected from Jiangxi Province and used as experimental materials to investigate single and com- petitive adsorption and desorption behaviors of cadmium and lead by batch equilib- rium method. The environmental risk of the presence of cadmium and lead in paddy soils was assessed using distribution coefficients. [Result] Under equal ratio condi- tions, the adsorption capacity of lead by two types of paddy soils was higher than that of cadmium, and the adsorption rate in waterloggogenic paddy soil was higher than that in gleyed paddy soil. The desorption capacity of cadmium by two types of paddy soils was higher than that of lead, and the desorption rate in gleyed paddy soil was higher than that in waterloggogenic paddy soil. Under competitive condi- tions, the adsorption capacity of cadmium and lead by paddy soils was significantly reduced compared with single ion system, while the desorption rate was remarkably improved. The potential environmental risk of cadmium contamination was greater than that of lead in paddy soils. Moreover, environmental risks of cadmium and lead were reduced with the increase of pH, which increased significantly under the coex- istence state. [Conclusion] In the coexistence of cadmium and lead, cadmium con- tamination should be controlled and avoided compared with lead contamination in paddy soils.

Adsorption Kinetics of NH_4^+ by Purple Soils with Different pH Values

Ammonium adsorption and desorption properties by purple soils with dif- ferent pH were studied. The results showed that the adsorption and desorption amounts of NH4＋ by purple soils increased with the increase of NH4＋ concentration, regardless of soil pH values; the largest adsorption and desorption amounts of NH4＋ by purple soil at pH 6.0 were 10.3 and 7.96 mg/g, respectively; the largest adsorp- tion and desorption amounts of NH4＋ by purple soil at pH 7.2 were 12.8 and 4.62 mg/g, respectively; the largest adsorption and desorption amounts of NH4＋ by purple soil at pH 8.0 were 13.5 and 2.23 mg/g, respectively. The isothermal adsorption ki- netics of NH4＋ by purple soils fits the Freundlich equation best （R〉0.95）. This study shows that the adsorption of NH4＋ by purple soils with different pH values is multi- molecular layer uneven surface adsorption.

Modeling mercury adsorption on carbon particles in simulated flue gas

A model was developed to describe the adsorption characteristic of mercury in flue gas based on one residual carbon sample and one activated carbon sample. The differential equations were established with mass balance of mercury in the gas phase and in the solid phase. Then the model was solved using a Matlab program with a Runge-Kutta process. The mercury adsorption isotherms of these two adsorbents were obtained by breakthrough column experiments. The results show that at low gas phase mercury concentrations （ 〈 0. 3 mg/ m^3）, the adsorption equilibrium of residual carbon is in accord with the case of a type Ⅱ isotherm of the Freundich theory. Whereas the data of activated carbon falls into the Langmuir relationship, it is the case of a type Ⅲ isotherm. The experimental data were fitted to the Freundlich model by Matlab software. The variances of mercury concentration are smaller than 0. 81 which implies the agreement between measurements and simulation is quite agreeable considering the wide scatter of the measurements. This model is useful for forecasting mercury removal efficiency and is helpful to the mechanism analysis of mercury adsorption on carbon-based adsorbent.

Effect of Freezing and Thawing on Ammonium Adsorption in Dryland Soil

[Objective] This study aimed to investigate the effect of freezing and thawing on ammonium adsorption in dryland soil. [Method] The lab simulation test was conducted to study the effect of freeze-thaw action on the total adsorbed amount of ammonium （deionized water extract） and strongly-adsorbed amount of ammonium （0.01 mol/L KCl solution extract） in the dryland soil of Sanjiang Plain. [Result] Compared with linear equation, Freundlich equation could better fit the total adsorbed amount of ammonium in dryland soil （R 2 0.99, SE1.69）. The freeze-thaw action almost had no influence on the total adsorbed amount of ammonium. When the initial concentration of NH 4 ＋ increased from 0 to 200 mg/L, the total adsorbed NH 4 ＋ amount increased from -0.52 to 39.0 mg/kg under freeze-thaw treatment （FTT）, while it increased from -0.70 to 38.5 mg/kg under unfreeze-thaw treatment （UFTT）. However, the strongly-adsorbed amount of ammonium presented linear relationship with the concentration of NH 4 ＋ （R 2 0.99, SE0.54）, and the strongly-adsorbed amount of ammonium increased significantly by FTT. When the initial concentration of NH 4 ＋ increased from 0 to 200 mg/L, the strongly adsorbed amount increased linearly from 2.36 to 28.81 mg/kg for FTT and from -4.25 to 25.12 mg/kg for UFTT. The freezethaw action decreases the concentration of NH 4 ＋ in soil solution when the net strongly-adsorbed NH 4 ＋ in soil is zero., therefore, FTT helped to reduce the leaching of ammonium ions in soil. Freeze-thaw action mainly influenced the exchangeable adsorbed NH 4 ＋ in soil. [Conclusion] This study provides theoretical basis for preventing excessive soil nitrogen from entering into water body and controlling water entrophication.

Characteristics of Phosphorus Adsorption with Boiler Slag and Process Optimization

[Objective] This study aimed to investigate the characteristics of phosphorus adsorption on boiler slag and optimize the adsorption process. [Method] Boiler slag was used as an adsorbent in the single-grade adsorption process to dispose the rural domestic sewage. During the course, phosphorus adsorption kinetics and thermodynamics, adsorption operating curve and the minimum boiler slag dosage were analyzed and calculated. [Result] Langmuir adsorption isotherm could be applied to describe the absorption of phosphorus with boiler slag, and the absorption kinetics was confirmed with the pseudo second-order equation. The maximum absorption quantity and the initial absorption rate increased with the rise of temperature, reaching up to 0.159 1 mg/g and 0.169 8 mg/(g·min) respectively at 40 ℃. Thermodynamic variables ΔG0<0 and ΔH0>0 indicated that the entire process was a spontaneous endothermic reaction, and high temperature would facilitate the reaction of absorption. In the single grade adsorption, the minimum adsorbent dosage decreased as the temperature rose; at 40 ℃ the optimum mass ratio of boiler slag to wastewater was 3.31 kg/m3. [Conclusion] The adsorption process with boiler slag as adsorbent is an economical and effective approach for treating rural domestic sewage.

Adsorption behavior of Azo Dye C. I. Acid Red 14 in aqueous solution on surface soils

Azo dyes have received considerable attention because of their association with various human health problems. The aim of the investigation is to determine the adsorption behavior ofazo dyes in aqueous solution on DG06, GSE17200, and GSE17201 soils using C. I. Acid Red 14 （AR14） as example. The experimental results indicate that the Freundlich model expresses the adsorption isotherm better than the Langmuir model and the pseudo-second-order model achieves adsorption of AR14 on the three soils well. Based on the pseudo-second-order model, the adsorption thermodynamic of AR14 on DG06 soil have been studied and the thermodynamics parameter of AGO is determined and AGO value shows the adsorption process of AR14 on DG06 is mainly physical in nature. Furthermore, the effects of temperature, pH and salinity （NaC1） on adsorption have been investigated. The decrease in pH or the increase in salinity enhances the adsorption of AR14 by DG06, GSE17200, and GSE17201.

Cr^(Ⅵ) adsorption on four typical soil colloids: equilibrium and kinetics

It is observed that the adsorption of chromium are greater on kaolinite minerals, red soil (R) and laterite (L) colloids than that on montmorillonite, indicotic black (IB) and yellow brown (YB) soil colloids. The adsorption process of Cr Ⅵ on these media can be further described by Langmuir or Freundlich equation quite well. The adsorption reaction of Cr Ⅵ is fast, and the adsorption equilibrium can be reached within the first two hours in moderate temperature. The adsorption quantity of Cr Ⅵ to kaolinite mineral increased with the increasing pH in the range of 2.0 to 7.0, then decreased at higher pH. But it showed some consistence among the four soil colloids. The lower the pH, the stronger the adsorption. The possible mechanisms are further discussed here. Meanwhile the influence of temperature on Cr Ⅵ adsorption on different soil colloid and clay minerals are also investigated.