Extra-framework charge and impurities effect,Grand Canonical Monte Carlo and volumetric measurements of CO2/CH4/N2 uptake on NaX molecular sieve

In this work, Monte Carlo simulation of CO₂, N₂, and CH₄ adsorption on zeolite 13X is carried out in grand canonical ensemble. FAU framework was used to reproduce the structure of zeolite 13X. Universal force field was used to calculate the interactions between adsorbates and 13X. Metropolis method was used for calculating adsorption isotherm. Volumetric measurements were carried out to confirm the simulation results. The simulation results using Universal force field showed good agreement with experimental results. Highest CO₂ uptake for this zeolite was found as 5.67 mol/kg from GCMC. Isosteric heat of adsorption was investigated to find the heat released during adsorption of each gas. The simulation result of isosteric heat of adsorption for CO₂, N₂, and CH₄ was utmost 17.00, 4.37, and 6.14 kcal/mole, respectively. Radial distribution graphs were used to find affinity of constituents of zeolite for CO₂. Henry’s constant evaluation was also performed at low pressure to find the selectivity of the structure. Henry’s constant of CO₂ in an equimolar mixture of N₂ and CH₄ was calculated 3.49 and 1.49 mol/kg.kPa, respectively. Finally, simulation results were fitted to Toth and dual-site Langmuir isotherms to find the best fit that belongs to dual-site Langmuir.     

CO2/CH4在活性炭上吸附与分离的分子模拟

Monte Carlo 模拟(GCMC)研究了CO2和CH4在活性炭中的吸附情况.氢气和二氧化碳分子被模拟作Kennard-Jones球体,活性炭用一个裂缝气孔模型代替.研究了压力、温度、孔径活性炭对CO2(以CH4为基准)的选择性的影响.结果表明,低压、低温、孔径越小,选择性越大,即对分离CO2和CH4有利;233 K、孔径为2.29 nm以及低压下选择性达到10,此时分离效果较好.     

CH4／O2在炭分子筛上的吸附动力学

为消除低浓度煤层气对煤层开采存在的安全隐患,提出了利用甲烷和氧气在炭分子筛上的动力学差异进行脱氧的工艺。采用容积法测定了纯CH4和O2在炭分子筛颗粒上的吸附动力学数据,并利用单床变压吸附装置测定了混合气体在298．15K,各压力下的穿透曲线。研究结果显示：吸附初期,O2在CMS上的扩散速率明显大于CH4;在混合体系穿透曲线上,O2的穿透时间远大于CH4,炭分子筛固定床表现出对O。的优先吸附选择性,可以实现出口直接富集甲烷的目的。0．4MPa时,当产品气中CH4含量为92．44％时,CH4回收率为73．27％。     

煤基碳分子筛的制备及CH4/N2分离性能研究

以煤为原料,通过气相碳沉积法制备了CH4/N2变压吸附分离用碳分子筛,研究了苯沉积量对碳分子筛吸附性能的影响。用液氮吸附（77 K）、扫描电镜对碳分子筛孔结构及表面形貌进行了表征,结果表明：制备的碳分子筛（CMS-1）平衡分离系数大于5,比表面积SBET=251.5 m2/g,微孔孔容Vm=0.1178 mL/g,孔径主要分布在0.35~2 nm,能满足CH4/N2变压吸附分离要求。     

Adsorption of binary CO2/CH4 mixtures using carbon nanotubes: Effects of confinement and surface functionalization

Effect of confinement and surface functionalization in carbon nanotubes (CNTs) on the competitive adsorption of a binary CO₂/CH₄ mixture has been investigated by grand canonical Monte Carlo simulations. Adsorption using CNTs with different functionalization arrangements, different diameters, different functionalization degrees, and different functional groups, such as –COOH, –CO, –OH, –CH₃, is investigated. Effects of (a) the pore textural properties, such as pore size and accessible surface area, and (b) the gas–adsorbent interaction, especially the electrostatic interaction, are discussed. From these results, we discuss the impact that variables such as confinement and surface functionalization have on the performance for CO₂ separation.     

Experimental Evaluation of the Adsorption,Diffusion, and Separation of CH4/N2 and CH4/CO2 Mixtures on Al-BDC MOF

Adsorption equilibrium, thermodynamics, and kinetics of CH₄, N₂, and CO₂ were investigated by volumetric-chromatographic and inverse gas chromatographic (IGC) methods on the Al-BDC MOF. The binary adsorption data from the volumetric-chromatographic experiments represents that the Al-BDC MOF has a high CO₂/CH₄ selectivity ca. 11 and a CH₄/N₂ selectivity ca. 4.3 at 303 K, and appears to be a good candidate for the CH₄ separation. The initial adsorption heats of CH₄, N₂, and CO₂ on the Al-BDC MOF were determined to be 15.3, 11.5, and 32.2 kJmol^?1 by IGC method, respectively. Moreover, the micropore diffusivities of N₂, CH₄ and CO₂ in the Al-BDC MOF at 303 K were also estimated to be 1.58 × 10^?7 cm²/s, 7.04 × 10^?8 cm²/s, and 3.95 × 10^?9 cm²/s, respectively. The results indicate that micropores play a crucial role in the adsorptive separation of the CH₄/N₂ and CH₄/CO₂ mixtures, and the IGC method is a validity manner to estimate the thermodynamic and kinetic parameters of MOF adsorbents.     

Simulation of CO2/CH4 high pressure separation on microporous activated carbon

Abstract

Pure component adsorption equilibrium of CH₄ and CO₂ on activated carbon have been studied at three different temperatures, 298, 323, and 348?K within a pressure range of 10–2000?kPa. Binary adsorption equilibrium isotherm was described using extended Sips equation and ideal adsorbed solution theory (IAST) model. Experimental breakthrough curves of CO₂/CH₄ (40:60 in a molar basis) were performed at four different pressures (300, 600, 1200, and 1800?kPa). The experimental results of binary isotherms and breakthrough curves have been compared to the predicted simulation data in order to evaluate the best isotherm model for this scenario. The IAST and Sips models described significantly different results for each adsorbed component when higher pressures are set. These different results cause a significant discrepancy in the estimation of the equilibrium selectivity. Simulated and experimental equilibrium selectivity data provided by IAST presented values of around 4, for CO₂/CH₄, and extended Sips presented values of around 2. Also, simulated breakthrough curves showed that IAST fits better to the experimental data at higher pressures. According to the simulations, in a binary mixture at total pressure over 800?kPa, extended Sips model underestimated significantly the CO₂ adsorbed amount and overestimated the CH₄ adsorbed amount.     

用于吸附分离CH4/CO2的碳分子筛的制备研究

以碳分子筛(CMS)作为吸附剂,探索其对CH4/CO2混合气的分离纯化性能。采用化学气相炭沉积法,以价格便宜的商品椰壳基活性炭为原料,以苯为沉积剂,制备碳分子筛。研究了沉积时间和沉积温度对CMS的吸附性质的影响。采用容量法对CMS吸附CH4和CO2性能进行测定。结果表明,在沉积温度为700℃,沉积时间为40min时制备的CMS平衡吸附选择性系数为58.03,远高于活性炭的5.124,对CH4/CO2有良好的分离效果。     

Equilibrium Adsorption Studies of CO2, CH4, and N2 on Amine Functionalized Polystyrene

Adsorption of CO₂, CH₄, and N₂ has been investigated using amine functionalized polymeric resins having diethanolamine, imidazole, dimethylamine, and N-methyl piperazine covalently attached to the styrene-divinyl benzene copolymer (PS) matrix. The equilibrium adsorption of CO₂, CH₄, and N₂ was examined on these functionalized polymers at pressures from atmospheric to 40 atm for CO₂ and N₂ while up to 10 atm for CH₄ at 303 K. PS-Imidazole showed the highest adsorption capacity for CO₂ as compared to other functionalized polymers. No significant uptake of CH₄ and N₂ was observed at low pressures by any of the functionalized polymers. The adsorption isotherms were analyzed using dual mode sorption model and Ideal Adsorbed Solution Theory (IAST).     

H2,CO,N2,O2和CH4在碳膜中的扩散

Diffusion of pure H2,CO,N2,O2and CH4 gases through nanoporous carbon membrane is investigated by carrying out non-equilibrium molecular dynamics(NEMD)simulations.The flux,transport diflusivity and acti-vation energy for the pure gases diffusing through carbon membranes with various pore widths were investigated.The simulation results reveal that transport diffusivity increases with temperature and pore width.and its values port diflusivities are comparablc With that of Rao and Sircar(J.Membr.Sci.,1996).indicating the NEMD simula-tion method iS a good toO]for predicting the transport diflusivities for gases in porous materialS.which iS always difficult to be accurately measured by experiments.     

Adsorption of H2, CO2, CH4, CO,N2 and H2O in Activated Carbon and Zeolite for Hydrogen Production

Abstract

The design of a layered pressure swing adsorption unit to treat a specified off-gas stream is based on the properties of the adsorbent materials. In this work we provide adsorption equilibrium and kinetics of the pure gases in a SMR off-gas: H₂O, CO₂, CH₄, CO, N₂, and H₂ on two different adsorbents: activated carbon and zeolite. Data were measured gravimetrically at 303–343 K and 0–7 bar. Water adsorption was only measured in the activated carbon at 303 K and kinetics was evaluated by measuring a breakthrough curve with high relative humidity.     

Pulse Chromatographic Studies of Adsorption of CO2, CH4, and N2 Using Amine Functionalized Polystyrene Adsorbents

Adsorption of CO₂, CH₄, and N₂ was investigated using pulse concentration chromatography on polystyrene functionalized by covalently attached diethanolamine, dimethylamine, imidazole, and N-methyl piperazine. The adsorption equilibrium constants at different temperatures were estimated by fitting the experimental chromatograms into a non-linear equilibrium dispersive chromatography model using gPROMS. Axial dispersion was found to be the controlling mechanism for dispersion of the chromatograms. The heat of adsorption and corresponding equilibrium selectivities were determined from the adsorption equilibrium constants. The imidazole based adsorbent showed the highest affinity for CO₂.     

氮掺杂炭颗粒的制备及其异丁烷脱氢性能研究

为了研究炭材料作为低链烷烃脱氢催化剂,文中以水溶性酚醛树脂为炭源,三聚氰胺为氮源,采用海藻酸铵辅助溶胶-凝胶法制备了氮掺杂活性炭颗粒。采用氮吸附脱附(BET)、红外光谱(IR)、X射线电子衍射(XRD)、X射线光电子能谱(XPS)与热重(TG)等方法对氮掺杂活性炭颗粒进行了表征,并以其作为催化剂进行了异丁烷脱氢性能研究,分析了失活机理。实验结果表明:随掺杂量的提高颗粒强度降低,RAC-N(1%)的平均孔径与孔容相对较高;RAC-N(1%)的异丁烷转化率与异丁烯选择性相对较高,反应490 min后分别为20%与94%;相比未掺杂活性炭颗粒,氮掺杂活性炭颗粒的异丁烷脱氢性能提高主要是由于催化剂表面含氧官能团的增加。     

活性炭孔径分布对CH4/N2体系分离的影响

采用变压吸附分离的方法分离CH4/N2体系时,活性炭作为一种主要的吸附剂受到广泛研究.本文采用10-4-3模型计算得出,孔径为0.7～2.0nm的活性炭微孔对CH4/N2体系分离的效果最好;同时利用扩展Langmuir方程通过拟合4种活性炭对CH4/N2的吸附等温线,计算得出分离系数;最后讨论样品的孔径分布与分离系数的关系,进一步证明了10-4-3模型的计算结果.     

吸附分离CH4/N2可行性研究

The separation between methane and nitrogen is an inevitable and important task in the C1 chemical technology and the utilization of methane from coalbed, yet it is considered to be one of the tough tasks in the field of separation. Pressure swing adsorption is a preferable technology if an adsorbent that allowing a large coefficient of separation for the CH4/N2 system is available. The separation coefficients between CH4 and N2 were obtained on analyzing the breakthrough curves measured experimentally with nine adsorbents. A technique of measuring the temperature-pulse was incorporated in the experiments, and the reliability of the result was improved. Superactivated carbon with large surface area and plenty of micropores was shown to have the largest separation coefficient and to be promising for the commercial utilization.     

Fabrication and characterization of PEI/PVP‐based carbon hollow fiber membranes for CO2/CH4 and CO2/N2 separation

Carbon hollow fiber membranes derived from polymer blend of polyetherimide and polyvinylpyrrolidone (PVP) were extensively prepared through stabilization under air atmosphere followed by carbonization under N₂ atmosphere. The effects of the PVP compositions on the thermal behavior, structure, and gas permeation properties were investigated thoroughly by means of differential scanning calorimetry, thermogravimetric analysis, X‐ray diffraction, and pure gas permeation apparatus. The experimental results indicate that the transport mechanism of small gas molecules of N₂, CO₂, and CH₄ is dominated by the molecular sieving effect. The gas permeation properties of the prepared carbon membranes have a strong dependency on PVP composition. The carbon membranes prepared from polymer blends with 6 wt % PVP demonstrated the highest CO₂/CH₄ and CO₂/N₂ selectivities of 55.33 and 41.50, respectively. © 2011 American Institute of Chemical Engineers AIChE J, 58: 3167–3175, 2012     

Single and Multicomponent Sorption of CO2, CH4 and N2 in a Microporous Metal-Organic Framework

Abstract

Single and multicomponent fixed-bed adsorption of CO₂, N₂, and CH₄ on crystals of MOF-508b has been studied in this work. Adsorption equilibrium was measured at temperatures ranging from 303 to 343 K and partial pressures up to 4.5 bar. MOF-508b is very selective for CO₂ and the loadings of CH₄ and N₂ are practically temperature independent. The Langmuir isotherm model provides a good representation of the equilibrium data. A dynamic model based on the LDF approximation for the mass transfer has been used to describe with good accuracy the adsorption kinetics of single, binary and ternary breakthrough curves. It was found that the intra-crystalline diffusivity for CO₂ is one order of magnitude faster than for CH₄ and N₂.     

吸附时间对VPSA分离CH_4/N_2效果的影响

利用三塔真空变压吸附装置,对低浓度原料气CH4/N2分离效果进行实验。研究了均压时间不同时的吸附时间对吸附分离效果的影响,并针对整个吸附装置、每个塔中CH4浓度与吸附时间的关系分别进行分析。实验表明,在一定条件下,吸附时间长短会影响每个塔反应釜内被浓度覆盖的区域变化,即在不被原料气穿透前提下,存在最佳吸附时间。通过分析吸附时间的作用,提高原料气VPSA分离CH4/N2的效果。     

煤矸石制备沸石-活性炭复合材料的吸附性能研究

利用煤炭生产的废弃物煤矸石为原料,在不同的条件下,制得A型和X型沸石-活性炭新型复合材料,通过X射线粉末衍射、低温N2(77 K)吸附、水和正己烷的吸附等表征:该复合材料具有中孔和微孔双重孔结构特征,同时具有亲水性和亲油性以及离子交换性质。对其应用性能的研究表明:复合材料对水和正己烷有高的吸附容量,并可一次性脱除废水中的重金属Cr3+和有机酚等有毒污染物。     

Experimental and numerical study of CH4/CH3Cl/O2/N2 premixed flames under oxygen enrichment

A comprehensive experimental and numerical study has been conducted to understand the influence of CH₃Cl addition on CH₄/O₂/N₂ premixed flames under oxygen enrichment. The laminar flame speeds of CH₄/CH₃Cl/O₂/N₂ premixed flames at room temperature and atmospheric pressure are experimentally measured using the Bunsen nozzle flame technique with a variation in the amount of CH₃Cl in the fuel, equivalence ratio of the unburned mixture, and level of oxygen enrichment. The concentrations of major species and NO in the final combustion products are also measured. In order to analyze the flame structure, a detailed chemical kinetic mechanism is employed, the adopted scheme involving 89 gas-phase species and 1017 elementary forward reaction steps. The flame speeds predicted by this mechanism are found to be in good agreement with those deduced from experiments. Chlorine atoms available from methyl chloride inhibit the oxygen-enhanced flames, resulting in lower flame speeds. This effect is more pronounced in rich flames than in lean flames. Although the molar amount of CH₃Cl in the methane flame is increased, the temperature at the post flame is not significantly affected, based on the numerical analysis. However, the measured concentration of NO is reduced by about 35% for the flame burning the same amount of methyl chloride and methane at the oxygen enrichment of 0.3. This effect is due to the reduction of the concentration of free radicals related to NO production within the flame. In the numerical simulation, as CH₃Cl addition is increased, the heat flux is largely decreased for the oxygen-enhanced flame. It appears that the rate of the OH + H₂ → H + H₂O reaction is reduced because of the reduction of OH concentration. However, the function of CH₃Cl as an inhibitor on hydrocarbon flames is weakened as the level of oxygen enrichment is increased from 0.21 to 0.5. __________ Translated from Fizika Goreniya i Vzryva, Vol. 42, No. 6, pp. 103–111, November–December, 2006.