Pore structure of low‑permeability coal and its deformation characteristics during the adsorption–desorption of CH4/N2

The pore structure of coal plays a key role in controlling the storage and migration of CH4/N2.The pore structure of coal is an important indicator to measure the gas extraction capability and the gas displacement efect of N2 injection.The deformation characteristic of coal during adsorption–desorption of CH4/N2 is an important factor afecting CH4 pumpability and N2 injectability.The pore structure characteristics of low-permeability coal were obtained by fuid intrusion method and photoelectric radiation technology.The multistage and connectivity of coal pores were analyzed.Subsequently,a simultaneous test experiment of CH4/N2 adsorption–desorption and coal deformation was carried out.The deformation characteristics of coal were clarifed and a coal strain model was constructed.Finally,the applicability of low-permeability coal to N2 injection for CH4 displacement technology was investigated.The results show that the micropores and transition pores of coal samples are relatively developed.The pore morphology of coal is dominated by semi-open pores.The pore structure of coal is highly complex and heterogeneous.Transition pores,mesopores and macropores of coal have good connectivity,while micropores have poor connectivity.Under constant triaxial stress,the adsorption capacity of the coal for CH4 is greater than that for N2,and the deformation capacity of the coal for CH4 adsorption is greater than that for N2 adsorption.The axial strain,circumferential strain,and volumetric strain during the entire process of CH4 and N2 adsorption/desorption in the coal can be divided into three stages.Coal adsorption–desorption deformation has the characteristics of anisotropy and gas-diference.A strain model for the adsorption–desorption of CH4/N2 from coal was established by considering the expansion stress of adsorbed gas on the coal matrix,the compression stress of free gas on the coal matrix,and the expansion stress of free gas on micropore fractures.N2 has good injectability in low-permeability coal seams and has the dual functions of improving coal seam permeability and enhancing gas fow,which can signifcantly improve the efectiveness of low-permeability coal seam gas control and promote the efcient utilization of gas resources.

Experimental and Numerical Research on Water Transport during Adsorption and Desorption in Cement-Based Materials

The durability of cement-based materials is related to water transport and storage in their pore network under different humidity conditions.To understand the mechanism and characteristics of water adsorption and desorption processes from the microscopic scale,this study introduces different points of view for the pore space model generation and numerical simulation of water transport by considering the“ink-bottle”effect.On the basis of the pore structure parameters(i.e.,pore size distribution and porosity)of cement paste and mortar with water-binder ratios of 0.3,0.4 and 0.5 obtained via mercury intrusion porosimetry,randomly formed 3D pore space models are generated using two-phase transformation on Gaussian random fields and verified via image analysis method of mathematical morphology.Considering the Kelvin-Laplace equation and the influence of“ink-bottle”pores,two numerical calculation scenarios based on mathematical morphology are proposed and applied to the generated model to simulate the adsorption-desorption process.The simulated adsorption and desorption curves are close to those of the experiment,verifying the effectiveness of the developed model and methods.The obtained results characterize water transport in cement-based materials during the variation of relative humidity and further explain the hysteresis effect due to“ink-bottle”pores from the microscopic scale.

Incorporating sorption/desorption of organic pollutants into river water quality model

Preliminary research was conducted about how to incorporate sorption/desorption of organic pollutants with suspended solids and sediments into single-chemical and one-dimensional water quality model of Jinghang Canal. Sedimentation-resuspension coefficient k 3 was deduced; characteristics of organic pollutants, concentrations and components of suspended solids/sediments and hydrological and hydraulic conditions were integrated into k 3 and further into river water quality model; impact of sorption/desorption of organic pollutants with suspended solids and sediments on prediction function of the model was discussed. Results demonstrated that this impact is pronounced for organic pollutants with relatively large K oc and K ow, especially when they are also conservative and f oc of river suspended solids/sediments is high, and that incorporation of sorption/ desorption of organic pollutants into river water quality model can improve its prediction accuracy.

A NEW MODEL FOR ESTIMATION OF DIFFUSION COEFFICIENT OF PHENOL DESORPTION WITHIN POLYMERIC RESIN UNDER ULTRASOUND

A new model, phase equilibrium-kinetics model (PEKM), for estimation of diffusion coefficient was proposed in this paper. Kinetic experiments of phenol desorption on NKAII resin in the presence and the absence of ultrasound were separately conducted, and diffusion coefficients of phenol within an adsorbent particle were estimated by means of proposed PEKM and classic simplified model. Results show that the use of ultrasound not only changes the phase equilibrium state of NKA II resin/phenol/water system which had been equilibrium at normal condition, but also enhances diffusion of phenol within the resin. The diffusion coefficient of phenol in the resin in the field of ultrasound increases in an order of magnitude in comparison with the diffusion coefficient determined under no ultrasound. Experimental results also indicated that the diffusion coefficients estimated by PEKM were more accurate than that estimated by the classic simplified model.

Hydrogen desorption kinetics mechanism of Mg-Ni hydride under isothermal and non-isothermal conditions

The Mg-Ni hydride was prepared by hydriding combustion synthesis under a high magnetic field. The dehydriding kinetics of the hydrides was measured under the isothermal and non-isothermal conditions. A model was applied to analyzing the kinetics behavior of Mg-Ni hydride. The calculation results show that the theoretical value and the experimental data can reach a good agreement, especially in the case of non-isothermal dehydriding. The rate-controlling step is the diffusion of hydrogen atoms in the solid solution. The sample prepared under magnetic field of 6 T under the isothermal condition can reach the best performance. The similar tendency was observed under the non-isothermal condition and the reason was discussed.

Numerical simulation of PAHs sorption/desorption on soil with the influence of Tween80

In this paper, the influences of inionic surfactant Tween80 on polycyclic aromatic hydrocarbons （PAHs） sorption/desorption on artificially contaminated soil were studied, and γ model was applied to simulate the influences. Results showed that, with the use of Tween 80, the sorption behaviors of PAHs on soil altered significantly. Adsorbed Tween 80 increased the sorption amount of PAHs while the dissolved Tween80 increased the apparent solubility of PAHs. These two processes exert influences on the sorption coefficient of PAHs in soil-water system, which can be depicted by apparent sorption coefficient. The partition coefficients （the soil/water partition coefficient of PAHs and surfactants obtained fxom sorption experiments） and statistical parameters used in the amended γ model were obtained in independent experiments. With these parameters, the γ model could provide a satisfactory independent prediction of PAHs release from soil to aqueous phase at two surfactant concentrations.

Kinetics of the hydrogen absorption and desorption processes of hydrogen storage alloys: A review

High hydrogen absorption and desorption rates are two significant index parameters for the applications of hydrogen storage tanks.The analysis of the hydrogen absorption and desorption behavior using the isothermal kinetic models is an efficient way to investigate the kinetic mechanism.Multitudinous kinetic models have been developed to describe the kinetic process.However,these kinetic models were de-duced based on some assumptions and only appropriate for specific kinetic measurement methods and rate-controlling steps(RCSs),which sometimes lead to confusion during application.The kinetic analysis procedures using these kinetic models,as well as the key kinetic parameters,are unclear for many researchers who are unfamiliar with this field.These problems will prevent the kinetic models and their analysis methods from revealing the kinetic mechanism of hydrogen storage alloys.Thus,this review mainly focuses on the summarization of kinetic models based on different kinetic measurement methods and RCSs for the chemisorption,surface penetration,diffusion of hydrogen,nucleation and growth,and chemical reaction processes.The analysis procedures of kinetic experimental data are expounded,as well as the effects of temperature,hydrogen pressure,and particle radius.The applications of the kinetic models for different hydrogen storage alloys are also introduced.

Sorption and desorption kinetics of phthalates and phenol on water/sediment interface

The sorption and desorption kinetics of dimethyl phthalate (DMP), diethyl phthalate (DEP), dibutyl phthalate (DBP) and phenol on water and sediment interface were studied using two compartment model in this paper. The results showed that the sorption coefficients of DMP, DEP, DBP and phenol measured by batch equilibrium method were 16.79, 24.55, 132 and 0.65μg 1-1/n · g -1 · ml -1/n , the sorption and desorption kinetic constants of DMP, DEP, DBP, phenol were 0.0248, 0.0357, 0.0727, 0.014ml·cm -2 ·h -1 and 0.000512, 0.000754, 0.00127, 0 000899h -1 at static condition respectively; and the sorption and desorption kinetics constants of above chemicals were 0 279, 0.382, 0.496, 0.0904ml·cm -2 ·h -1 and 0.0442, 0.0031, 0.00116, 0.00247h -1 at flow water condition respectively.

Adsorption-Desorption Characteristics of Chlorimuron-Ethyl in Soils

The adsorption-desorption characteristics of chlorimuron-ethyl in soils were investigated to provide the basic data for evaluating the safety in field and the risk to water resource. The adsorption-desorption experiment was conducted by the batch equilibration and HPLC techniques; furthermore, data were analyzed with 5 mathematic models to describe the characteristics and mechanism of adsorption-desorption and translocation of the herbicide in soils. The results showed that the adsorption-desorption isotherms of chlorimuron-ethyl fitted for the Freundlich model well, and the physical reaction presents the main contribution during the adsorption-desorption process. The adsorption values （Kads-f） of chlorimuron-ethyl in 8 types of soil ranged from 0.798 to 6.891. The isotherms of 2# （Jiangxi clay） and 3# （Jiangxi sand loam） soils belong to the S-type curve, while the isotherms of another 6 type soils belong to the L-type isotherm. The results of desorption indicated that the hysteresis phenomena appeared during the desorption process, and the hysteresis coefficients （H） of the herbicides in 8 soils varied from 0.259-0.980. Furthermore, Kads-f and desorption values （Kads-f） increased with the OM （%） and the clay content increasing, while the values decreased with the soils pH increasing. The H values decreased with the OM and the clay content increasing, and increased with the soils pH increasing. It can be concluded that the low adsorption abilities of chlorimuron-ethyl in test soils and un-reversible adsorption existed in the process, which will induce the great translocation of the herbicide after application in field. It can be transported to ground or groundwater causing risk to environments. The physical and chemical properties of soils, including the OM, the clay content, and the pH of soil were the dominating factors during the adsorption-desorption.

Desorption isotherms and isosteric heat of anaerobic fermentation residues

This paper presents the equilibrium desorption isotherms and the isosteric heat of sorption of a mixture containing mechanically dewatered fermentation residue(obtained from a blend of chicken,swine and cattle manure)used in biogas plants and corn spoiled silage in a ratio of 2:1.The moisture desorption isotherms of the fermentation residue were determined at 32°C,40°C and 80°C and in the relative humidity range of 0.057/1 using static gravimetric method.Mathematical equations were used to analyze the desorption data of Modified Henderson,Modified Halsey,Modified Oswin,Modified Chung–Pfost and Modified GAB models.The constants of the model equations were calculated by non-linear regression analysis.The Modified Henderson model fitted to the desorption isotherm data well.Using the proposed function,the final moisture content of the material can be determined as long as it can be dried in infinite time with the drying gas in the given conditions.The isosteric heat of desorption was calculated by using the Modified Henderson model in the studied temperature range based on the Clausius–Clapeyron equation.The isosteric heat varied between 46 k J·mol-1 and 67 k J·mol-1 at moisture levels 1.91 b Xe<4.05 kgH2O·kgdP-1 for the material.

Desorption Kinetics of Volatile in Condensed Mode Polyethylene Process

In this paper the desorption kinetics of volatile in condensed mode polyethylene process is studied through experiments. It is found that though the residual volatile in particles at the later stage of desorption accounts for a relatively small portion of the total quantity, the desorption of this part of volatile requires much longer time than at the earlier stage. For high requirement of devolatilization, the total time needed will be predominately determined by the residual amount of volatile in particles. Temperature has greater effect on the desorption rate than other influence factors, especially in the later period of desorption. A model is proposed to calculate the volatile desorption rate for condensed mode polyethylene process.

Methane Desorption from Homogeneous Distributed Micro-Pores of Coal

The thermal desorption kinetic mechanism from internal micro-pores of coal is theoretically investigated by Monte Carlo simulations. It is supposed that the molecules are absorbed in the pores and can jump between adjacent ones. The desorption rates of the statistical ensemble average are calculated. The competing effect of the temperature and the adsorptive energy is analyzed. The desorption probabilities indicated that the choice of desorption energy is clear at low temperature, however, there is not clearly different between high temperature.

Combination of a reaction cell and an ultra-high vacuum system for the in situ preparation and characterization of a model catalyst

An in-depth understanding of the structure-activity relationship between the surface structure,chemical composition,adsorption and desorption of molecules,and their reaction activity and selectivity is necessary for the rational design of high-performance catalysts.Herein,we present a method for studying catalytic mechanisms using a combination of in situ reaction cells and surface science techniques.The proposed system consists of four parts:preparation chamber,temperatureprogrammed desorption(TPD)chamber,quick load-lock chamber,and in situ reaction cell.The preparation chamber was equipped with setups based on the surface science techniques used for standard sample preparation and characterization,including an Ar+sputter gun,Auger electron spectrometer,and a low-energy electron diffractometer.After a well-defined model catalyst was prepared,the sample was transferred to a TPD chamber to investigate the adsorption and desorption of the probe molecule,or to the reaction cell,to measure the catalytic activity.A thermal desorption experiment for methanol on a clean Cu(111)surface was conducted to demonstrate the functionality of the preparation and TPD chambers.Moreover,the repeatability of the in situ reaction cell experiment was verified by CO_(2) hydrogenation on the Ni(110)surface.At a reaction pressure of 800 Torr at 673 K,turnover frequencies for the methanation reaction and reverse water-gas shift reaction were 0.15 and 7.55 Ni atom^(-1) s^(-1),respectively.

分形界面吸附行为初探

煤层气吸附解吸机理研究是揭示煤层气成藏机理及高效开发煤层气的基础。已有研究表明,煤储层孔隙结构非常复杂且具有分形特征,煤层气在孔-固界面的吸附行为明显受到煤孔隙结构特征的影响。对比分析几种常用气-固界面上的吸附模型,总结这些模型的特点和适用条件,指出当前吸附模型在分形界面吸附行为的描述和应用上均未摆脱吸附选择性的平稳假设,尚未考虑吸附厚度的尺度不变特征。而分形拓扑理论可以有效标定分形对象的尺度不变属性,为分形界面的等效表征提供了理论支撑。因此,结合上述模型对气-固界面吸附行为的描述,借助分形拓扑理论提出煤储层孔-固界面上分形吸附行为的相关假设及其控制机理,构建基于吸附拓扑的单层吸附模型。在此基础上,通过设置不同的吸附拓扑参数组合获取其等温吸附曲线,分析得出,随着吸附压力的升高,吸附覆盖率表现出指数、线性和对数3种不同的增长趋势,而吸附热表现为对数减小趋势。结果显示,不同的吸附拓扑参数组合会得到不同类型的等温吸附曲线,在一定程度上弥补了Langmuir方程只能描述单一类型等温吸附线的不足。为了验证吸附模型的适用性,结合沁水盆地武乡区块富有机质泥页岩的液氮吸附实验数据,对比了实际等温吸附曲线与模拟吸附曲线的差异。结果表明,通过调整各吸附拓扑参数之间的组合关系,可以使等温吸附模拟曲线与实际吸附曲线的趋势始终保持一致。最后,探讨了吸附解吸机理的研究方向,类比电子层提出了吸附层的概念,指出发展分形动力学描述模型是解释煤层气吸附解吸规律的关键。

煤中超临界CO_(2)解吸滞后机理及其对地质封存启示

将CO_(2)注入不可采煤层地质封存既是降低温室气体效应最理想选择之一,也是煤炭工业降低CO_(2)排放、实现低碳化可持续发展的必由之路,然而,煤层CO_(2)地质封存悬而未决的关键问题是:“注入煤层中的CO_(2)到底能否长期停留而安全封存?”。鉴于此,在弄清煤体CO_(2)解吸滞后规律的基础上,揭示超临界CO_(2)解吸滞后机理,建立煤层CO_(2)地质封存量化模型,探讨利用解吸滞后实现煤层CO_(2)长期安全封存。研究表明:煤中超临界态CO_(2)解吸滞后程度大于亚临界态CO_(2),在超临界阶段,吸附与解吸等温线形成近似“平行线”的稳定滞后特征;解吸滞后的本质原因是煤中微纳米级亲水性孔隙形成弯液面、产生强大毛细压力、渗吸液态水、截断并固定超临界CO_(2)流体、最终形成了CO_(2)残余封存,例如,煤中直径40~10 nm圆柱形无机孔隙可产生7.30~29.12 MPa毛细压力,足以封堵超临界态CO_(2);以九里山煤样解吸等温线数据为例,采用基于煤层CO_(2)解吸滞后的地质封存量化模型,评估出900~1500 m深部二1煤层封存总量稳定在35~37 m^(3)/t,其中,吸附封存约占80%,残余封存约占15%,而结构封存仅占5%;解吸滞后启示应尽可能采取措施提高煤层残余封存CO_(2)比例,原因是毛细堵塞的残余封存CO_(2)较围岩密封的游离和吸附CO_(2)更安全且没有泄露风险,煤层灰分、水分、孔隙尺寸和形貌等物性参数是影响残余封存效率的主要因素。

内养护机制对再生混凝土材料宏、细观力学性能的影响研究

再生混凝土作为绿色生态混凝土,其在生态水利工程中的应用较为广泛。为提高其力学性能和耐久性,采用内养护方式将再生骨料预处理至干燥、半饱和、饱和状态,分别以50%、100%的取代率取代普通混凝土,并设置干燥状态的普通混凝土作为对照组,分析了不同取代率下含水量对再生混凝土宏细观性能的影响并对各参数进行相关性分析,通过建立再生骨料吸水、解吸模型从细观尺度诠释内养护作用机理。研究结果表明,同等取代率下,养护90 d时抗压强度较优异的是含水率50%的再生混凝土组。取代率增大,孔隙增多,养护90 d时,R50P、R100P的孔隙率比7 d时分别降低14.2%、10.3%,说明含水率50%的再生骨料能一定程度上改善孔隙和界面过渡区结构;骨料吸水、解吸过程中发挥的内养护作用机制是再生混凝土后期强度持续增长的主要原因。

电场实时加载下煤层气解吸-扩散特性实验研究

为探究电场实时加载下煤层气解吸-扩散特性,揭示电场强化煤层气高效抽采的机理影响特征,设计并研发了可控电场强度下煤层气解吸-扩散实验系统;实验探究了电场加载下煤体的CH4和CO_(2)解吸-扩散变化特征,并通过幂函数扩散模型计算各场强作用下的CH4扩散系数。结果表明:不同吸附质在电场实时加载下煤层气解吸量均得到一定程度提升,但电场对CO_(2)解吸量影响特征更加明显,同时电场能够强化煤体瓦斯的初始解吸速度;与未加电场相比,特征场强为30、60、90 kV/m时CH4初始解吸速率提升了6.9%、15.3%、14.6%,而CO_(2)依次提升了3.4%、6.7%、9.2%;电场加载下煤体CH4幂函数扩散模型能够高度的与实验值相吻合,扩散系数具有随着加载场强的增大而逐渐增大变化特征,电场有利于煤中甲烷的解吸、扩散。

温度压力对煤中甲烷解吸速率影响的试验研究

解吸速率对煤层瓦斯涌出规律、煤层气井见气时间和服务年限有重要影响。随着煤层埋藏深度的增加,温度压力对甲烷吸附量有明显的控制作用,当前对于温度压力对解吸速率的影响关注相对不足。为了研究温度压力对煤层甲烷解吸速率的影响,用同一样品开展不同温度压力条件下的等温吸附/解吸试验,获得不同平衡压力段的吸附量-时间数据,利用吸附动力学模型拟合出解吸速率-时间曲线,甄选出3个评价参数研究温度压力对解吸速率的影响。研究表明:不同压力下的解吸速率均随着时间推移呈现指数降低的变化规律。解吸速率常数、相对初始解吸速率、中值解吸量时间能够从不同角度反映解吸速率的变化过程,其中解吸速率常数和相对初始解吸速率均随着温度和压力的升高而增加,中值解吸量时间随温度和压力的升高而减小。结合鄂尔多斯盆地保德区块的温度/压力梯度可知,在1000 m以浅时解吸速率受温度和压力的双重控制,随深度增加而不断增高;1000~1735 m随深度增加压力效应逐渐降低,温度效应依然明显。

PAHs污染土壤热脱附过程关键影响因素及脱附动力学研究

土壤多环芳烃(PAHs)污染已严重威胁生态环境安全和人类生命健康。通过异位热脱附试验探究了PAHs初始浓度、土壤含水率和土壤粒径对脱附效率的影响,并采用一级、二级动力学和指数衰减模型对PAHs热脱附过程进行拟合,以探究土壤中PAHs热脱附的去除机制。结果表明,在同等条件下,随着PAHs初始浓度的增加,脱附效率随之升高,且在热脱附20~40 min时提高初始浓度可明显提高PAHs的去除率。土壤含水率对于PAHs不同组分的作用具有一定的差异性,当土壤含水率为16%,萘(Nap)、菲(Phe)和蒽(Ant)达到最佳去除率,而荧蒽(Fla)和芘(Pyr)最大去除率对应的土壤含水率为13%。在相同脱附条件下,土壤粒径越小,土壤中PAHs的去除率越高。研究发现指数衰减模型对PAHs各组分的脱附过程具有更好的拟合效果。土壤中PAHs热脱附主要分为两个阶段:(1)PAHs受到土壤中水的蒸发作用从土壤颗粒表面快速蒸发;(2)PAHs的蒸发速率受到土壤孔隙内部扩散的限制,以非常缓慢的速度从土壤中脱除。

基于改进瓦斯解吸实验方法的初始粉煤快速解吸机理研究

粉煤瓦斯解吸实验是研究粉煤瓦斯解吸动力学特征的常用手段之一,其结果是揭示粉煤放散瓦斯能力的重要参数。传统实验方法在煤样罐泄压后开始测量瓦斯解吸数据,存在较大误差。利用甲烷与氦气的粉煤吸附特性差异性提出了改进的粉煤瓦斯解吸实验方法,并建立了初始瓦斯粉煤快速解吸模型,从而揭示了煤体粉化后瓦斯快速解吸的内在机制。研究结果表明:解吸开始的前5 s,0.075~0.150 mm JG71煤样解吸的瓦斯量是1.00~2.36 mm煤样的2.05倍,而0.075~0.150 mm JG82煤样解析的瓦斯量是1.00~2.30煤样的10.29倍;煤样粉化程度越高,吸附平衡压力越大,初始瓦斯解吸速度越大,传统实验方法得到的数据误差越大。研究结果为突出粉化煤体快速解吸瓦斯、提供瓦斯膨胀能、促进煤与瓦斯突出传播的研究提供了数据支撑,同时为完善煤与瓦斯致灾机理奠定基础。