Experimental analysis of the efficiency on charge/discharge cycles in natural gas storage by adsorption

The use of vessels filled with activated carbon to store and transport natural gas (NG) at moderate pressures (about 3.5 MPa) and ambient temperature (about 298 K) has been studied as a potential alternative to compressed natural gas at high pressures (ca. 20 MPa). The present study provides an experimental investigation of charge and discharge cycles of natural gas in a prototype storage vessel filled with activated carbon and analyses the effect of the gas composition on the adsorption capacity. The adsorption properties were evaluated by measuring isotherms for each component of NG in a magnetic suspension balance. The selectivities of the main constituents of natural gas in relation to methane were determined and the influence of the pressure on the selectivity was also observed. Although NG is composed mainly of methane (ca. 90% vol.), our experimental results indicate that the preferential adsorption of the heavier hydrocarbons and CO₂ should be properly taken into account for the evaluation of the behavior of adsorbed natural gas systems along several charge and discharge cycles.     

矿物基化学吸附储热技术的研究进展

化学吸附储热技术近年来在太阳能利用和中低温余热领域得到了广泛关注，与传统的显热储热和相变储热技术相比具有储热密度高、储热损失小、可实现冷热双储等优点，然而其传质传热问题和液解问题导致的吸附性能和循环稳定性能的降低限制了其规模化应用。本文综述了利用矿物基多孔结构材料对化学吸附材料进行封装的方法以解决上述问题，总结了近年来石墨、蛭石等不同矿物基化学吸附储热材料的特点及其在化学吸附系统中的应用，主要介绍了矿物基化学吸附材料的两种体系（无机盐-水体系和氯盐-氨体系）的传质传热、化学吸附热等性能，并进一步指出了矿物基化学吸附储热技术未来的发展趋势，提出开发新型矿物基复合材料和优化化学吸附系统是未来的研究热点。     

Molecular simulation studies of separation of CH4/H2 mixture in metal-organic frameworks with interpenetration and mixed-ligand

In our previous work, we have investigated the adsorption selectivity of CH₄/H₂ in three pairs of isoreticular metal-organic frameworks (IRMOFs) with and without interpenetration to study the effect of interpenetration on gas mixture separation through Monte Carlo simulation. In addition, the self-diffusivities and the diffusion mechanism of single H₂ and CH₄ in these MOFs were examined by molecular dynamics simulations. In this work, we extend our previous work to mixed-ligand MOFs to investigate the effects of interpenetration as well as mixed-ligand on both equilibrium-based and kinetic-based gas mixture separation. We found that methane adsorption selectivity is much enhanced in the selected mixed-ligand interpenetrated MOFs compared with their non-interpenetrated counterparts, similar to what we found before for IRMOFs with single-ligand. At room temperature and atmospheric pressure, molecular-level segregation was observed in the mixed-ligand MOFs, and the extent of the effects of interpenetration is comparable for single-ligand and mixed-ligand MOFs. In addition, we found that the diffusion selectivity in the interpenetrated MOFs is similar to the one in their non-interpenetrated counterparts, while the permeation selectivity in the former is much higher than that in the latter, which corroborates our expectation that interpenetration is a good strategy to improve the overall performance of a material as a membrane in separation applications based only on the single component diffusion results. Furthermore, the CH₄ permeability of the selected MOF membrane was also evaluated.     

Adsorption equilibrium and the effect of honeycomb heat exchanging device on charge/discharge characteristic of methane on MIL-101(Cr) and activated carbon

Experiments were conducted for developing suitable ANG adsorbents for vehicular applications. MIL^-101 and activated carbon samples were respectively prepared by hydrothermal and chemical activation methods. Two samples were undergone structure analysis on adsorption data of nitrogen at 77.15 K, and adsorption data of methane were then volumetrically measured within temperature-pressure range 293.15 K-313.15 K and 0-8 MPa. A conformable vessel in volume 2.5 L was employed for charge/discharge tests under the flow rate 10-30 L·min^-1. It shows that limit isostreic heat of methane adsorption is respectively about 25.15 kJ·mol^-1 and 22.94 kJ·mol^-1 on the activated carbon and the MIL-101, and isosteric heat within the experimental condition is 14-19.5 kJ·mol^-1; employing a smaller charge/discharge flow rate can weaken the temperature fluctuation of the adsorbent bed and increase the charge/discharge amount; employing honeycomb heat exchanging device enhance the thermal conductivity of the adsorbent bed by consuming a negligible part of volume of the vessel. It suggests that a smaller flow rate for charge/discharge should be employed, and MOFs together with the honeycomb heat exchanging device are promising for practical applications.     

连锁结构金属-有机骨架材料强化甲烷吸附的分子模拟研究

A systematic molecular simulation study was performed to investigate the effect of catenation on methane adsorption in metal-organic frameworks (MOFs). Four pairs of isoreticular MOFs (IRMOFs) with and without catenation were adopted and their capacities for methane adsorption were compared at room temperature. The pre-sent work showed that catenation could greatly enhance the storage capacity of methane in MOFs, due to the for-mation of additional small pores and adsorption sites formed by the catenation of frameworks. In addition, the simulation results obtained at 298 K and 3.5 MPa showed that catenated MOFs could easily meet the requirement for methane storage in porous materials.     

金属有机骨架基复合相变储热材料研究进展

固-液相变材料的品种多且潜热大,是潜热储热技术的重要工作介质。因其存在的液相泄漏问题,现阶段常将此类相变材料与多孔载体复合以提升相变材料的应用性能及使用寿命。金属有机骨架（MOFs）是一种新型多孔材料,具有高比表面积、高孔隙率以及孔径和表面性质可调控等优势,将其用作相变材料的载体具有潜在的发展前景。本文对MOF基复合相变材料的研究进行了全面综述,详细介绍了以MOFs为载体、以MOFs衍生多孔碳为载体和以MOFs原位生长于高导热基体所得复合材料为载体而制得的多种复合相变材料。MOFs的微孔结构所产生的强毛细管力对固-液相变材料有很强的固定作用;制备较大孔径的MOFs或者对MOFs进行修饰以调节MOF与相变材料间的相互作用,都有利于提高相变材料的负载率,从而提升复合相变材料的潜热;对MOFs进行高温碳化处理得到MOFs衍生多孔碳能有效解决MOFs孔径过小的问题,并能通过对其进行氮掺杂或磷掺杂来增强载体与相变材料间的氢键作用,从而获得具有高负载率和相变潜热的复合相变材料;为了增强MOF基复合相变材料的导热性能,先将MOFs原位合成在高导热基体上以利用高导热基体提供连续的传热网络,可以有效提升复合相变材料的导热系数。将原位生长在高导热基体上的MOFs进行高温碳化处理可以得到MOFs衍生多孔碳与高导热基体的复合材料,将其作为载体可以进一步增强复合相变材料的导热性能。文中最后指出,今后对于MOF基复合相变储热材料所用MOFs和相变材料的种类、MOFs与相变材料间相互作用对储热性能的影响、MOFs与相变材料复合后的稳定性等方面还需进一步探索,将MOFs的催化、检测等功能与相变材料的储热控温功能相结合制备多功能材料也是未来的发展方向之一。     

MIL系列MOFs材料的合成及应用研究进展

金属有机骨架（Metal．OrganicFrameworks,MOFs）材料是一种新型功能材料。MIL系列材料作为MOFs材料的典型代表之一,有着广泛的应用前景。文章讨论了MIL系列材料的合成方法,总结了MIL系列材料在气体的储存和分离、多相催化、药物的存储和缓释以及光电磁等方面的应用,并对MIL系列新型多功能材料研究的发展趋势进行了展望。     

柔性金属有机骨架材料(MOFs)用于气体吸附分离

柔性金属有机骨架材料(MOFs)具有高度有序的网络结构与可变形的骨架,其骨架结构会对外界的温度、压力及客体分子的刺激产生独特的结构响应。近几年来,柔性MOFs在气体吸附、气体分离、传感等领域显示出巨大的应用潜力。截至目前,研究者们对柔性MOFs的研究仅局限于对其结构形变的机理解释,而缺乏对柔性MOFs应用于相关化工过程的性能研究。本文着重对近年来柔性MOFs在气体吸附分离领域的研究进展进行了综述,并详细地分析了柔性MOFs结构与其气体吸附分离性能之间的构效关系。通过分子模拟结合实验,讨论了柔性MOFs结构对气体分子的平衡吸附与动力学扩散的影响。分析表明,设计合成具有良好吸附选择性与扩散性能的柔性MOFs是其应用于绿色、高效气体分离过程的重要发展方向。     

膨胀石墨/有机金属骨架复合吸附材料的制备及性能研究

粉末状有机金属骨架材料（MOFs）普遍存在密度低热导率低的不足,是限制其在水蒸气吸附领域应用的关键因素之一。以典型的高吸水量MOFs材料对苯二甲酸铬（MIL-101（Cr））为研究对象,采用干混法将膨胀石墨（EG）与该MOFs材料复合并模压成型,制备了一系列不同密度不同石墨含量的复合吸附材料。利用光学显微镜表征了材料微观结构,分析了压制密度、EG含量对材料内部结构的影响;使用恒温恒湿箱测试了纯MOFs材料及复合吸附材料的饱和吸附量,发现纯MOFs粉末在压制压力超过3 MPa后吸附能力大幅下降。在此基础上制备了密度适宜的复合材料,测试发现复合材料的饱和吸附量随着EG含量的增加而显著降低,但EG对MOFs本身的吸附量未造成显著影响;采用体积法研究了材料的吸附动力学,其中片状纯MOFs相比粉末状MOFs吸附速率大幅下降,而复合材料由于内部产生了更多的传质通道使其表面传质系数相比于片状纯MOFs提高了2.7倍。热导率测试结果表明复合吸附材料的热导率随着石墨含量的增加而显著升高,而材料的密度对热导率的影响相对较小。采用干混法制备的石墨含量50%,密度408 kg·m⁻³的复合吸附材料,其热导率相比纯MOFs材料提高了22倍达到2.76 W·m⁻¹·K⁻¹。     

余热制冷吸附床的一个新传热传质模型

在既考虑吸附剂颗粒内部的传质阻力,又考虑吸附剂颗粒之间的外部传质阻力的前提下,建立了余热吸附制冷系统中吸附床的三维非平衡传热传质数学模型,它包括加热/冷却流体传热模型、换热管传热模型、肋片传热模型、吸附剂颗粒床传热传质模型4部分;通过对模型的数值求解,获得了吸附床内部的温度演变曲线和性能指标,与实验结果基本吻合。     

Porous Adsorbents for Vehicular Natural Gas Storage: A Review

Methane adsorption data (both experimental and simulated) under conditions of direct relevance for vehicular natural gas storage, i.e., at 500 psig and ambient temperature, has been compiled from the literature for various microporous adsorbents and discussed in this work. Characterization of microporosity has been briefly reviewed, followed with a discussion on the porous structure of natural gas adsorbents. A common trend of gravimetric methane adsorption capacity scaling with surface area among the diverse microporous adsorbents (viz., coals, carbons, zeolites, silica gel and an MCM-41 type material) is demonstrated. Further, it is substantiated and emphasized that increasing the adsorbent surface area on a volumetric basis is very important for vehicular natural gas storage where the fuel storage volume is a constraint. The effect of other adsorbent properties such as heat of adsorption and heat capacity on the natural gas storage capacity is also discussed.     

发光金属-有机框架物作为传感材料的研究进展

金属-有机框架物(Metal-Orgamic Frameworks,MOFs)因其在吸附分离、储氢、磁性、催化以及荧光检测等多方面潜在的应用而成为当前的研究热点.简单介绍了发光MOFs的特点,着重评述了基于金属离子和基于有机配体发光的MOFs传感材料的研究.提出了发光MOFs作为传感材料存在的问题,预测了今后的发展趋势...     

Effect of Pressure on Moisture Transfer During Moisture Adsorption

ABSTRACT

A set of coupled heat, mass, and pressure transfer equations was used to describe the moisture adsorption process in gmn kernels. The finite element method was used to solve the system of equations. The technique was applied to analyze the temperature, moisture, and pressure distribution in a barley kernel during soaking with steep water. The temperature and moisture distributions with (heat, mass, and pressure transfer model) and without (heat and mass uansfer) the effect of pressure were simulated for assumed conditions. The results obtained from the heat, mass, and pressure transfer model show a marked difference from the results obtained from the heat and mass transfer model. This indicated that a pressure gradient exists during the transfer Process, causing additional moisture movement due to filtration effect. Hence. the pressure tern cannot be assumed constant during the moisture adsorption process. The simulated temperature, moisture and pressure profiles and gradients can be used for determining the optimum time required for solking kernels with sleep water to produce barley malt.     

固定床吸附过程传热传质耦合影响数值模拟

引言 多孔介质中物质传递与热量传递相互影响,这种现象最早由Soret和Dufour提出[1].由温度梯度作用产生的传质效应称为Soret效应(热附加扩散效应),它代表由温度场的不均匀性而导致的传质现象;由浓度梯度作用产生的传热效应称为Dufour效应(扩散附加热效应),它代表由浓度场的不均匀性而导致的传热现象.     

Preparation of powdered activated carbon from rice husk and its methane adsorption properties

Success of adsorbed natural gas (ANG) storage process is mainly based on the characteristics of the adsorbent, so various synthesized adsorbents were analyzed for methane adsorption on a thermodynamic basis. Activated carbon from rice husk (AC-RH) was synthesized and its methane adsorption capacities were compared with phenol based activated carbons (AC-PH₂O and AC-PKOH). The adsorption experiments were conducted by volumetric method under various constant temperatures (293.15, 303.15, 313.15 and 323.15 K) and pressure up to 3.5MPa. Maximum methane adsorption was observed in AC-RH as its surface area is higher than the other two adsorbents. The experimental data were correlated well with Langmuir-Fruendlich isotherms. In addition, isosteric heat of adsorption was calculated by using Clausius-Clapeyron equation.     

Shaping of metal-organic frameworks through a calcium alginate method towards ethylene/ethane separation

The separation of ethylene and ethane is a crucial, challenging and cost-intensive process in chemical engineering. Metal-organic frameworks (MOFs) are a class of novel porous adsorbents used for the separation of ethylene/ethane mixtures. However, MOFs are normally crystalline powders that cause multiple problems, such as dust, abrasion and heat/mass loss, as well as significant pressure drops on the adsorption bed resulting in a sudden stop in production. To solve these issues, we have prepared four different sphere-shaped adsorbents, including Mg-gallate, Co-gallate, MUV-10(Mn) and MIL-53(Al) using a calcium alginate method to achieve excellent ethylene/ethane separation performance. The performance of the sphere-shaped adsorbents has been validated using mechanical strength measurements, powder X-ray diffraction, scanning electron microscopy, thermogravimetric analysis, gas adsorption isotherms and dynamic breakthrough experiments. The excellent mechanical strength of these sphere-shaped adsorbents meets the criteria for industrial application in gas separation. Thus, the energy consumption and operating cost will be further reduced in the ethylene production process. We believe that this shaping method will open a prosperous route to the development of MOFs toward higher technology levels and their commercial application.     

疏水性金属-有机骨架材料的研究进展

金属-有机骨架（metal-organic frameworks, MOFs）材料是一种由金属离子和有机配体通过自组装形成的新型多孔材料，具有优异的物理及化学性能，因而在气体吸附储存、气体分离以及工业催化等方面表现出良好的应用潜力。但在应用的过程中，无处不在的水分子会影响MOFs骨架的稳定性和吸附性能，极大地制约了其实际应用。本文介绍了近年来疏水性MOFs材料的研究进展，重点论述了金属离子和有机配体对调控MOFs亲疏水性的影响以及通过配体后修饰和疏水性物质复合等提高疏水性的方法，分析了MOFs材料的亲疏水性机理，同时提出了实验结合计算机模拟技术筛选疏水性MOFs的手段。最后，指出目前疏水性MOFs材料合成存在的问题及解决方法，期望为今后拓宽MOFs材料在高湿环境中的应用提供一些有用的参考。     

A comparison of electrochemical performance of natural graphite sulfurized by ball-milling and heat-treating as an anode for lithium ion batteries

Natural graphite (NG) was sulfurized by heat-treating or by high energy ball-milling the blend of NG with sulfur powder. The effect of the surface functional groups, containing sulfur, on the performance of the NG anode for a lithium ion battery was then investigated. X-ray photoelectron spectroscopy revealed that the sulfur was introduced onto the surface of NG in both of these methods. The results of scanning electron microscopy and Raman spectroscopy showed that the surface disorder of NG increased after sulfurization. Charge/discharge tests showed that the reversible capacity of the first cycle was increased after surface sulfurization and that the coulombic efficiency of the first cycle increased for the heat-treated sample but decreased for the ball-milled one. The change in the electrochemical performance was due to a number of factors including an increase in new active sites for lithium storage and an increase in surface area and increased disorder of the sulfurized NG samples.     

吸附蓄热材料性能研究进展

可再生能源的利用不仅可降低环境污染,还有助于实现“碳中和”目标,蓄热技术是有效利用太阳能等不稳定可再生能源的重要途经之一。热化学蓄热材料由于储能密度高、热损失小等优点可实现低品位热能的跨季节应用。本文对现有文献内吸附蓄热材料的蓄热性能进行总结分析,对比四类蓄热材料在不同运行工况下的储能密度、输出功率与蓄热效率等蓄热性能,并论述各类材料的典型应用案例。文中指出：溶液吸收材料脱附温度较低,但系统传热传质性能较差,实际应用中无法满足建筑供暖需求;固体吸附材料循环稳定性好,可采用太阳能集热器作为热源使其再生,它是目前建筑供暖中具有较大潜力的蓄热材料;纯热化学反应材料储能密度最高,然而其循环稳定性差,仍处于实验室研究阶段;兼有固体吸附材料与无机盐优点的复合材料有望成为建筑内理想的蓄热材料。最后文章针对各类材料提出其未来的研究方向。     

MOFs基多孔液体的制备及其应用

多孔液体(Porous Liquids, PLs)是一种结合了多孔固体材料永久孔隙率和液体流动性的新型液体材料,在气体吸附和分离、催化等应用领域中展示出巨大的潜力。金属框架材料(MOFs)因其具有高的比表面积、热和化学稳定性、独特的结构以及制备简单的特点,使其有望成为构筑PLs多孔宿主的最佳候选材料之一。近些年来,基于MOFs(ZIF-8、ZIF-67、UiO-66等)基多孔液体相关研究被陆续报道。首先,介绍了多孔液体的分类；其次,总结了近些年来MOFs基多孔液体的制备以及应用；最后,对MOFs基多孔液体的制备存在的挑战与未来在气体吸附、催化等领域进行了展望与总结。