Isothermal Adsorption and Desorption Properties of Marine Shales on Longmaxi Shale in South China

The investigation of adsorption and desorption properties of shale are important for estimating reserves and exploitation. The shale samples used in this paper were from the marine shale on Longmaxi shale in Sichuan and Hubei province, China. A series of analyses, such as organic carbon content test, vitrinite reflectance test, rock pyrolysis, X-ray diffraction, and N2/CO2 adsorption were performed. Gravimetric method with magnetic suspension balance was used to conduct isothermal adsorption and desorption experiments. The Langmuir, Freundlich, Langmuir-Freundlich, D-R, semi-pore, and Tothequations were used to fit the isothermal adsorption and desorption curves. And adsorption potential theory was used to explain the adsorption and desorption process. According to the results, the shale samples have a high level of organic carbon content with the same organic matter type II1 and high degree of maturation. The volume of adsorption increases rapidly and slows down to stable with the pressure increasing. Desorption is the inverse process of adsorption and 10 MPa - 0.5 MPa is the main period of shale gas desorption. The fitting results show that three-parameter isotherm equations are better than the two-parameter ones. The adsorption temperature has a great influence on adsorption volume, little effect on potential energy. Adsorption potential varies under different TOC to affect adsorption properties. Moreover, a large adsorption potential means that the gas molecule is easy to adsorb but difficult to desorb.

Shale high pressure isothermal adsorption curve and the production dynamic experiments of gas well

The high pressure static adsorption curves of shale samples from Silurian Changning-Weiyuan Longmaxi Formation were tested by using high pressure isothermal adsorption equipment.The physical modeling of depletion production was tested on single cores and multi-core series by using self-developed shale gas fluid-solid coupling experiment system.The adsorption and desorption laws were summarized and a high pressure isothermal adsorption model was established.The calculation formula of gas content was corrected,and the producing law of adsorption gas was determined.The study results show that the isothermal adsorption law of the shale reservoir under high pressure was different from the conventional low pressure.The high pressure isothermal adsorption curve had the maximum value in excess adsorption with pressure change,and the corresponding pressure was the critical desorption pressure.The high pressure isothermal curve can be used to evaluate the amount of adsorbed gas and the producing degree of adsorption gas.The high pressure isothermal adsorption model can fit and characterize the high pressure isothermal adsorption law of shale.The modified gas content calculation method can evaluate the gas content and the proportion of adsorbed gas more objectively,and is the theoretical basis of reserve assessment and production decline analysis.The producing degree of adsorption gas is closely related to the pressure,only when the reservoir pressure is lower than the critical desorption pressure,the adsorption gas can be produced effectively.In the process of gas well production,the pressure drop in the near-well area is large,the production of adsorption gas is high;away from the wellbore,the adsorption gas is low in production,or no production.

Relationship between breakthrough curve and adsorption isotherm of Ca(Ⅱ)imprinted chitosan microspheres for metal adsorption

In this work, an equilibrium-dispersion model was successfully established to describe the breakthrough performance of Ca（Ⅱ） imprinted chitosan （Ca（Ⅱ）-CS） microspheres packed column for metal adsorption, and the assumptions of Langmuir isotherms and axial dispersion controlled mass transfer process were confirmed. The axial dispersion coefficient in Ca（Ⅱ）-CS microspheres packed column was found to be almost proportional to the linear velocity and fit for prediction through single breakthrough test. Sensitivity analysis for breakthrough curve indicated the axial dispersion coefficient as well as Langmuir coefficient was sensitive variable for deep removal requirement. The retrieval of the adsorption isotherms of Ca（Ⅱ）-CS microspheres from breakthrough curve was fulfilled by modelling calibration. A strategy based on the correlation between adsorption isotherms and breakthrough performance was further proposed to simplify the column adsorption design using absorbents with small/uniform size and fast adsorption kinetics like Ca（Ⅱ）-CS microspheres to cut down the gap between lab and industry.

Determination of Energetic and Geometric Properties of Plant Roots Specific Surface from Adsorption/Desorption Ishoterm

Background and Aims: Structure and composition of plant roots surfaces are extremely complicated. Water vapor adsorption/desorption isotherm is a powerful tool to characterize such surfaces. The aim of this paper is to present theoretical approach for calculating roots surface parameters as adsorption energy, distribution of surface adsorption centers, as well as roots geometric and structure parameters as surface fractal dimension, nanopore sizes and size distributions on example of experimental isotherms of roots of barley taken from the literature. This approach was up to date practically not applied to study plant roots. Methods: Simplest tools of theoretical analysis of adsorption/desorption isotherms are applied. Results: Parameters characterizing energy of water binding, surface complexity and nanopore system of the studied roots were calculated and compared to these of the soils. Some possible applications of root surface parameters to study plant-soil interactions are outlined. Conclusions: Physicochemical surface parameters may be important for characterizing root surface properties, their changes in stress conditions, as well as for study and model plant processes. Physicochemical and geometrical properties of plant roots differ from these of the soils.

Kinetics, Isotherms and Equilibrium Study of Co(Ⅱ) Adsorption from Single and Binary Aqueous Solutions by Acacia nilotica Leaf Carbon

The removal of cobalt ion from aqueous solution by Acacia nilotica leaf carbon(HAN), is described. Effect of p H,agitation time and initial concentration on adsorption capacities of HAN was investigated in a batch mode. The adsorption process, which is p H dependent, shows maximum removal of cobalt in the p H range 5 for an initial cobalt concentration of 50 mg·L–1The experimental data have been analyzed by using the Freundlich, Langmuir,Temkin and Dubinin–Radushkevich isotherm models. The batch sorption kinetics have been tested for a pseudofirst order, pseudo-second order and Elovich kinetic models. The rate constants of adsorption for all these kinetic models have been calculated. Results showed that the intraparticle diffusion and initial sorption of Co(Ⅱ) into HAN was the main rate limiting step. The adsorption of cobalt ion was confirmed through instrumental analyses such as scanning electron microscope(SEM) and Fourier transform infrared spectroscopy(FTIR). The desorption and recycling ability of HAN were also found. We conclude that HAN can be used for the efficient removal of cobalt from aqueous solution.

Impact of clay stabilizer on the methane desorption kinetics and isotherms of Longmaxi Shale,China

Knowing methane desorption characteristics is essential to define the contribution of adsorbed gas to gas well production.To evaluate the synthetic effect of a clay stabilizer solution on methane desorption kinetics and isotherms pertaining to Longmaxi shale,an experimental setup was designed based on the volumetric method.The objective was to conduct experiments on methane adsorption and desorption kinetics and isotherms before and after clay stabilizer treatments.The experimental data were a good fit for both the intraparticle diffusion model and the Freundlich isotherm model.We analyzed the effect of the clay stabilizer on desorption kinetics and isotherms.Results show that clay stabilizer can obviously improve the diffusion rate constant and reduce the methane adsorption amount.Moreover,we analyzed the desorption efficiency before and after treatment as well as the adsorbed methane content.The results show that a higher desorption efficiency after treatment can be observed when the pressure is higher than 6.84 MPa.Meanwhile,the adsorbed methane content before and after treatment all increase when the pressure decreases,and clay stabilizer can obviously promote the adsorbed methane to free gas when the pressure is lower than 19 MPa.This can also be applied to the optimization formulation of slickwater and the design of gas well production.

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.

Numerical description of coalbed methane desorption stages based on isothermal adsorption experiment

Quantitative description of desorption stages of coalbed methane is an important basis to objectively understand the production of coalbed methane well,to diagnose the production state,and to optimize the management of draining and collection of coalbed methane.A series of isothermal adsorption experiments were carried out with 12 anthracite samples from 6 coalbed methane wells located in the south of the Qinshui Basin,based on the results of isothermal adsorption experiments,and an analytical model was developed based on the Langmuir sorption theory.With the model,a numerical method that adopts equivalent desorption rate and its curve was established,which can be used to characterize the staged desorption of coalbed methane.According to the experimental and numerical characterizations,three key pressure points determined by the equivalent desorption rate curvature that defines pressure-declining desorption stage,have been proposed and confirmed,namely,start-up pressure,transition pressure and sensitive pressure.By using these three key pressure points,the process of coalbed methane desorption associated with isothermal adsorption experiments can be divided into four stages,i.e.,zero desorption stage,slow desorption stage,transition desorption stage,and sensitive desorption stage.According to analogy analysis,there are differences and similarities between the processes of coalbed methane desorption identified by isothermal adsorption experiments and observed in gas production.Moreover,it has been found that larger Langmuir volume and ratio of Langmuir constants are beneficial to earlier advent of steady production stage,whereas it is also possible that the declining production stage may occur ahead of schedule.

Adsorption characteristics of carbon tetrachloride from aqueous solution onto polyacrylonitrile-based activated carbon fiber

The isotherm,mechanism and kinetics of carbon tetrachloride(CT) adsorption by polyacrylonitrile-based activated carbon fiber(PAN-ACF) were investigated in batch reactors and a continuous flow reactor,and the regeneration of PAN-ACF was also studied.Freundlich and Dubinin-Radushkevich(D-R) adsorption equations can well describe the adsorption isotherm.CT is mainly adsorbed on the exterior surface of PAN-ACF with low boundary layer effect and rate-controlling step of intra-particle diffusion.The adsorption dynamics in the batch reactor well fits with the pseudo-first-order model,and the breakthrough curves in the continuous flow reactor can be well described by the Yoon-Nelson model.The ACF can be recycled through thermal regeneration,whereas the adsorption capacity decreases from 7.87 to 4.98 mg/g after the fourth regeneration.78%-94%of CT can be removed from the wastewater of a fluorine chemical plant on a pilot scale,which confirms the efficacy of ACF under industrial conditions.The results indicate that PAN-ACF is applicable to CT removal from wastewater.

Adsorption of hexavalent chromium onto kaolin clay based adsorbent

A low-cost adsorbent modified kaolin clay(MKC) was synthesized and utilized for Cr(VI) removal from aqueous solution. Adsorption experiments were carried out as a function of adsorbent dosage, solution pH, Cr(VI) mass concentration, contact time, electrolyte, and temperature. It is found that the adsorption efficiency is high within a wide pH range of 2.5-11.5, and equilibrium is achieved within 180 min. Increases in temperature and electrolyte concentration decrease the adsorption. The adsorption follows the pseudo-second-order kinetic model. The Langmuir isotherm shows better fit than Freundlich isotherm. The maximum uptake capacities calculated from the Langmuir model are 15.82, 15.55 and 15.22 mg/g at 298, 308 and 318 K, respectively. Thermodynamic parameters reveals the spontaneous and exothermic nature of the adsorption. The FTIR study indicates that hydroxyl groups, NH4+ ions and NO3- ions on MKC surface play a key role in Cr(VI) adsorption. The Cr(VI) desorbability of 86.53% is achieved at a Na2CO3 solution. The results show that MKC is suitable as a low-cost adsorbent for Cr(VI) removal which has higher adsorption capacity and faster adsorption rate at pH close to that where pollutants are usually found in the environment.

Monte Carlo simulation of methane molecule adsorption on coal with adsorption potential

The paper presents a Monte Carlo simulation to study the adsorption characteristics of methane molecule on coal slit pores from different aspects.Firstly,a physical model of adsorption and desorption of methane molecules on micropores was established.Secondly,a grand canonical ensemble was introduced as the Monte Carlo simulation system.Thirdly,based on the model and system,the molecule simulation program was developed with VC++6.0 to simulate the isothermal adsorption relationship between the amount of molecule absorption and the factors affecting it.Lastly,the numerically simulated results were compared with measured results of adsorption coal samples of two different coal mines with a laboratory gas absorption instrument.The results show that the molecule simulations of the adsorption constants,the adsorption quantity,and the isothermal adsorption curve at the same and different coal temperatures were in good agreement with those measured in the experiments,indicating that it is feasible to use the established model and the Monte Carlo molecule simulation to study the adsorption characteristics of methane molecules in coal.

INFLUENCE OF THERMAL AND NON-THERMAL EFFECTS OF ULTRASOUND ON ISOTHERMS OF PHENOL ON NKA II RESIN

Adsorption equilibrium experiments of phenol on the NKA II resin are separately conducted in the presence and absence of ultrasound at ambient temperature. The isotherm of phenol on the polymer adsorbent in the presence of ultrasonic field is firstly reported. Results indicated that the isotherm of phenol determined in the presence of ultrasound is lower than that in the absence of ultrasound. In addition, experiments also show that the use of ultrasound to the adsorption system of the phenol aqueous solution and NKA II resin could cause the rising of the temperature of the system in the order of 6 0C. The effect of ultrasound on the isotherm of the phenol on the NKA II resin mostly ascribes to the thermal effect and the non-thermal effect of ultrasonic field, and the role of the later is greater than that of the former.

Contributions of adsorption, bioreduction and desorption to uranium immobilization by extracellular polymeric substances

Hexavalent uranium(U(VI))can be immobilized by various microbes.The role of extracellular polymeric substances(EPS)in U(VI)immobilization has not been quantified.This work provides a model framework to quantify the contributions of three processes involved in EPS-mediated U(VI)immobilization:adsorption,bioreduction and desorption.Loosely associated EPS was extracted from a pure bacterial strain,Klebsiella sp.J1,and then exposed to H_(2) and O_(2)(no bioreduction control)to immobilize U(VI)in batch experiments.U(VI)immobilization was faster when exposed to H_(2) than O_(2) and stabilized at 94%for H_(2) and 85%for O_(2),respectively.The non-equilibrium data from the H_(2) experiments were best simulated by a kinetic model consisting of pseudo-second-order adsorption(ka=2.87×10^(−3) g EPS·(mg U)^(−1)·min^(−1)),first-order bioreduction(kb=0.112 min−1)and first-order desorption(kd=7.00×10^(−3) min^(−1))and fitted the experimental data with R^(2) of 0.999.While adsorption was dominant in the first minute of the experiments with H_(2),bioreduction was dominant from the second minute to the 50th min.After 50 min,adsorption was negligible,and bioreduction was balanced by desorption.This work also provides the first set of equilibrium data for U(VI)adsorption by EPS alone.The equilibrium experiments with O_(2) were well simulated by both the Langmuir isotherm and the Freundlich isotherm,suggesting multiple mechanisms involved in the interactions between U(VI)and EPS.The thermodynamic study indicated that the adsorption of U(VI)onto EPS was endothermic,spontaneous and favorable at higher temperatures.

Thermo-kinetic investigation of heavy metal ions adsorption onto lignin considering coupled adsorption–desorption mechanisms:Modeling and experimental validation

A coupled adsorption–desorption thermo-kinetic model is developed incorporating both adsorption and desorption reactions.A local pseudo-equilibrium condition at the interface of adsorbent and adsorbate bulk phases was used as isotherm equation which can even be applied for multi-pollutants scenarios.The developed model is then validated using collected experimental data of heavy metal ions(Pb,Cu,Cd,Zn,and Ni).Comparisons were made for a number of isotherm and kinetic models to examine the performance of the proposed model.The developed model revealed desirable accuracy and superiority over other models in predicting the adsorption behavior and can be used for other systems of concern.The model correlates the adsorption kinetic with an R2 value of 0.9391 and desorption kinetic with an R2 value of 0.9383.By application of the proposed model to any available adsorption datasets,the individual characteristics of adsorption and desorption can be determined.

计算机模拟在物理化学BET多分子层吸附理论教学中的应用

BET多分子层吸附理论抽象但应用广泛,BET公式的推导过程涉及较多数学知识,学生很难透彻理解BET公式的物理意义。面对比表面分析仪输出的吸附脱附等温线和比表面积,学生只能生搬硬套,难以达到预期的教学效果。本文利用计算机模拟气体分子在固体表面的吸附脱附过程,通过调整吸附脱附常数,可分别得到第I、II、III类吸附等温线;结合实时可视化使学生能直观看到气体分子在固体表面的吸附脱附动力学,从而能更好地理解BET理论。计算机模拟辅助教学还能活跃课堂气氛,实现教与学互动,激发学生的求知欲和科研兴趣,提高教学质量。

磷石膏淋滤液磷在红黏土中的迁移转化与吸附特性研究

为了探究磷石膏淋滤液磷在土壤中的迁移转化及赋存状态,文章以贵州某磷石膏堆场为研究区,通过室内物理模拟实验与土壤吸附实验,分析磷石膏淋滤液磷在红黏土中的迁移转化特征,并探讨了红黏土对磷的吸附成因。研究结果表明:不同磷石膏厚度与红黏土厚度,对磷石膏淋滤液磷的迁移有显著影响,其中磷石膏厚度越大,淋滤液中磷浓度越大,而红黏土土层厚度越大,淋滤液中磷浓度越低;磷石膏淋滤液磷在红黏土中的迁移转化过程中,其各形态之间不断发生转变,并有一部分会被红黏土所吸附,从而使磷浓度随之降低,主要存在形态为可溶磷与无机磷,占比分别为80%~94%和80%~95%,有机磷与颗粒态磷含量较小,占比分别为5%~20%和5%~16%;红黏土对磷石膏淋滤液中磷的最大吸附量为0.23mg/g,且红黏土对磷的吸附等温曲线符合Freundlich方程,相关系数R2为0.98678,吸附过程符合准二级动力学模型,相关系数R2为0.96414。

不同温度下斜叶桉木材吸湿、解吸等温线与热力学性质

近年来斜叶桉(Eucalyptus obliqua)木材广受国内市场欢迎,需求量大,但尚无高效可行的常规干燥工艺,需对其吸湿性及热力学性质进行深入研究。本文利用恒温恒湿箱法研究了斜叶桉在不同温度下(30℃、45℃、60℃、75℃)的等温吸湿、解吸特性,并通过GAB和H-H模型对吸湿和解吸等温线进行拟合,对吸湿滞后现象,以及有效比表面积S、净等量吸湿热Q_(st)、总润湿热W_(0)、微分熵ΔS、吉布斯自由能变ΔG、扩张压力Φ、焓熵补偿等热力学性质进行了分析。结果表明,斜叶桉木材的吸湿和解吸等温线为Ⅱ型,且GAB和H-H模型均适用于木材-水分体系(R^(2)大于0.999)。恒定温度下,试样平衡含水率(EMC)随水分活度的增加而增加。恒定水分活度下,EMC和吸湿滞后程度均随温度的升高而降低。有效比表面积随着温度升高而降低。总体上,吸湿过程净等量吸湿热和微分熵为负值,而解吸过程为正值,净等量吸湿热和微分熵的大小均随EMC先增大后减小,直至趋近于0。解吸过程总润湿热绝对值为83.7k J/mol,远大于吸湿过程的32.2k J/mol。等速温度和平均调和温度不一致,焓熵补偿理论成立。吸湿、解吸过程均为焓驱动,不同的是吸湿为自发过程,解吸为非自发过程。扩张压力会随着水分活度的升高而升高,吸湿过程中,温度对于扩张压力的影响无明显规律,而在解吸过程中,扩张压力随温度的升高而升高。

Birnessite型二氧化锰纳米花吸附水中Pb^(2+)性能研究

水体中重金属的污染对人类生产生活造成了重要影响。以Birnessite型二氧化锰纳米材料作为新型吸附剂,研究其对水中Pb^(2+)的吸附性能。首先,利用液相合成方法制备尺寸在200~900 nm之间的Birnessite型二氧化锰纳米花,通过超声的方式将其分散在含有Pb^(2+)的水体中,考查吸附过程中水体pH值、离子强度、材料尺寸、吸附时间和Pb^(2+)初始浓度对Birnessite型二氧化锰纳米花吸附Pb^(2+)的影响;同时,结合动力学模型和等温吸附曲线模型的拟合数据,分析材料吸附Pb^(2+)过程的机理。实验结果表明,制备的Birnessite型二氧化锰纳米花在pH值5~9之间的水中对Pb^(2+)均具有稳定的良好的吸附性能,最大吸附量可达300 mg·g^(-1);Birnessite型二氧化锰纳米花的尺寸越小其比表面积越大,吸附性能越好;同时在高离子强度下其仍保有80%左右的吸附能力。吸附动力学和等温吸附曲线拟合数据表明Birnessite型二氧化锰纳米花吸附水中Pb^(2+)的过程主要是单分子层均匀覆盖的化学吸附过程。

页岩高压等温吸附曲线及气井生产动态特征实验

选取四川盆地长宁—威远地区龙马溪组页岩储集层样品,采用高压等温吸附仪开展高压等温吸附曲线测试,运用自主研发页岩气流固耦合实验系统开展了单岩心对比和多岩心串联气井衰竭开发物理模拟实验;在总结吸附、解吸规律基础上,建立了高压等温吸附模型,修正了含气量计算方法,明确吸附气动用规律。研究表明,页岩高压条件下的等温吸附规律与常规低压下吸附规律不同,高压等温吸附曲线随压力变化存在最大过剩吸附量,对应压力为临界解吸压力。高压等温吸附曲线可用于评价页岩吸附气量及吸附气动用程度;高压等温吸附模型能够拟合和表征页岩高压等温吸附规律;修正后的含气量计算方法,可以更客观评估含气量与吸附气比例,是储量评估和产量递减分析的理论基础;吸附气动用程度与压力密切相关,储集层压力低于临界解吸压力,吸附气才能有效动用;气井生产过程中,近井地带压力下降幅度大,吸附气动用程度高,远离井筒,吸附气动用程度低或不动用。

吸附势理论在煤层气吸附解吸研究中的应用

以晋城无烟煤为研究对象,进行了30℃时煤对甲烷和氮气的吸附解吸试验。基于吸附特性曲线的唯一性特点,根据30℃甲烷的吸附解吸数据,以吸附势理论为依据,预测了50℃时甲烷的等温吸附曲线,结果表明预测曲线与实测曲线吻合良好,其预测值平均绝对误差为0.5 cm3/g,平均相对误差为3.12%。同时依据30℃时氮气和甲烷的吸附特性曲线,发现氮气和甲烷的吸附势对应压力在0.61 MPa时存在交点,表明压力低于0.61 MPa时氮气的吸附势高于甲烷的吸附势,此时注入氮气对提高煤层气的增产具有促进作用,这为煤储层在N2-ECBM(注氮增产法)过程中确定氮气的注气压力范围提供了初步的理论依据。