Isotherms and thermodynamics studies for binary adsorption of methane and ethane on 4A molecular sieve zeolite

The temperature dependency of adsorption behavior for binary mixture of methane and ethane on 4A zeolite was investigated. The volumetric method has been adopted for determination of adsorption isotherm data in the temperature range 303–323 K and pressure up to 225 kPa. Extended Langmuir, modified extended Langmuir, and extended Freundlich isotherms were applied for prediction of binary adsorption data using pure component adsorption data. The data were also simulated by IAST model which showed the best correlation of experimental binary adsorption data along with extended Freundlich isotherm. The selectivity of 4A zeolite to adsorb gases was also studied. The result of this study showed that an increases in temperature increases selectivity for ethane to methane. The heats of adsorption for methane and ethane were also determined and found to be ?23.89 and ?36.78 kJ/mol, respectively, which indicate the exothermic and physisorption natures of adsorption.     

Equilibrium isotherms and adsorption heats analysis for ternary mixture of methane,ethane, and propane on 4A zeolite

Equilibrium isotherms were obtained experimentally and theoretically for adsorption of methane, ethane, and propane mixtures on 4A zeolite at 301 K. The experimental data were measured using constant volume method and analyzed by extended Langmuir, modified extended Langmuir, and extended Freundlich isotherm models. The best correlation was achieved with the extended Freundlich isotherm equation and the negative values for heats of adsorption indicate exothermic adsorption nature for these gases on 4A zeolite. The selectivity of 4A zeolite to adsorb gases was also studied with the observation that ethane was more selectively adsorbed than methane on 4A zeolite, while propane was less selectively adsorbed on this zeolite at the studied temperature. Also, it was found that an increase in initial partial pressure of ethane decreases the adsorbed amount of methane, while the increase in partial pressure of methane had no effect on adsorbed amount of ethane.     

Prediction of breakthrough curves for light hydrocarbons adsorption on 4A molecular sieve zeolite

Breakthrough curves for the adsorption of methane, ethane, and propane mixture on 4A molecular sieve zeolite were obtained experimentally and theoretically at a constant temperature of 301 K. The equilibrium model and linear driving force model were used to predict the experimental breakthrough curves for this multi component mixture. The equilibrium model gave a satisfactory fit for experimental data. The model equations were solved by a numerical method based on backward finite difference with a fixed griding technique. The effect of feed flow rate (0.385–3.465 l/min), feed concentration (60.72–182.16 mmole/l), and adsorbates composition (11.73–20.11%) on the breakthrough curves were examined.     

The adsorption of methane-ethane mixtures on activated carbon

The single component adsorption of methane and ethane and also the adsorption of binary mixtures of methane and ethane have been studied in a small fixed isothermal bed containing activated carbon. Results indicate that an empirical Langmuir isotherm fits the experimental data for single components. An extended form of the empirical Langmuir isotherm, in which the parameters are obtained from single component data, satisfactorily describes the adsorption of binary mixtures. The potential theory of Polanyi is also helpful in extending the experimental data. Breakthrough curves of both components from a diluted feed of methane and ethane could be predicted with good precision for the two activated carbons studied. Furthermore, the concentration waves of the components were sufficiently spaced to suggest that these carbons may be of use as a separating agent for methane-ethane mixtures.     

Prediction of breakthrough curves of oxygen—nitrogen coadsorption system on molecular sieves

The coadsorption breakthrough curves of oxygen—nitrogen on 5A zeolite molecular sieve (MSZ-5A) and carbon molecular sieve (MSC) are predicted theoretically and compared with experimental data. According to the binary equilibrium isotherms, the theoretical isothermal model for coadsorption fixed bed has been established under consideration of the effect of the solid phase mass transfer resistance. The breakthrough curves are obtained by solving the above model numerically for oxygen—nitrogen system in fixed beds of MSZ-5A and MSC at 293.15 K and 392 kPa. The data of pure component isotherms are used to obtain the numerical solution. The predicted curves are in good agreement with the experimental data.     

Al-MCM-41介孔分子筛吸附喹啉的性能

在碱性条件下,采用水热晶化法,以偏硅酸钠为硅源,铝酸钠为铝源,CTAB为结构模板剂,成功合成出了含铝介孔分子筛Al-MCM-41。采用XRD、BET等手段对合成的Al-MCM-41进行表征,对柴油中的氮化物喹啉进行了吸附实验,考察了Al-MCM-41介孔分子筛对氮化物喹啉的吸附能力,探究了硅铝比为60的Al-MCM-41分子筛对喹啉溶液吸附的热力学和动力学行为,测得353.15～393.15 K 温度范围内的吸附等温线数据,用Langmuir、Freundlich方程对此进行拟合,并根据热力学原理计算得到吸附过程中的ΔH、ΔG、ΔS值和吸附表观活化能。结果表明, 硅铝比为60的Al-MCM-41具有较大的孔容、比表面积和较窄的孔径分布,结晶度和有序性高。等温吸附平衡符合Freundlich 等温线模型,其ΔH -0.7682 kJ·mol^-1,ΔG -28.1215 kJ·mol^-1, ΔS 73.2434 J·mol^-1·K^-1,吸附动力学符合Pseudo拟二级方程,E_a为2.8575 kJ·mol^-1。     

磷化氢在改性13X分子筛上的吸附行为

为回收工业废气中的磷化氢(PH3)并资源化,采用浸渍法制备了一种CaCl2改性13X分子筛吸附剂,通过容积法研究了25—70℃PH3气体在改性13X分子筛上的等温吸附行为。结果表明,在实验条件范围内25,40,55,70℃下PH3的饱和吸附量(质量分数)分别为2.528,1.901,1.591,0.925mg/g。Freundlich吸附等温方程很好地模拟了改性13X分子筛对PH3的等温吸附,Langmuir和Henry吸附等温方程对吸附平衡数据的拟合效果不佳表明了改性13X分子筛表面吸附位的不均匀分布。当初始吸附量为0.10mg/g时,等量吸附热值最大,为17.81353kJ/mol,即等量吸附热不超过18kJ/mol,过程为物理吸附,便于PH3气体的解吸。     

吸附热预测吸附等温线

实验测定了N2 在沸石分子筛、C2 H6 在活性炭、CO2 在硅胶上的吸附等温线 ,研究用Clausius Clapeyron方程求得等量吸附热、再利用所得的吸附热预测其它温度的吸附等温线数据的方法。将吸附热预测的等温线与实验值及插值法内插得到的吸附等温线数据进行了比较 ,结果表明吸附热预测值与实验值吻合较好。此外还对文献数据利用等量吸附热预测较高压力 ( 65 0kPa)下的等温线 ,均与文献中的实验值一致。为吸附工业操作需要不同温度下的等温线数据和吸附过程的模拟与设计提供了简便、准确的计算方法     

CH4, C2H6, and C2H4 Phase Equilibria on SAPO-34 Using the Vacancy Solution Theory

Adsorption data of single, binary, and ternary mixtures of methane, ethane, and ethylene on Silicoalumina-Phosphate molecular Sieve (SAPO-34) were obtained experimentally in the pressure range of 0 to 600 kPa at 303, 313, and 323 K. The adsorbed equilibrium concentration was predicted based on the vacancy solution theory (VST) using excess Gibbs energy (EGE) models of activity coefficients. EGE models were studied comparatively, i.e., the Wilson, Flory Huggins, and NRTL equations. The VSM-model results were compared with the mixture adsorption data. The results revealed higher capability of EGE models against the extended Langmuir equation in predicting adsorption behavior of the so-called gas mixture.     

负载型TiO_2复合材料对甲基橙的吸附行为及光催化降解动力学

以4A沸石和天然蛭石为载体,钛酸四丁酯为钛源,采用溶胶-凝胶法制备了TiO2/4A沸石和TiO2/天然蛭石光催化复合材料,研究了复合材料对偶氮染料甲基橙的暗态吸附规律和光降解性能。结果表明:复合材料对甲基橙的吸附规律都较好地符合Langmu ir和Freund lich吸附等温模型;在紫外光辐照30 m in条件下,TiO2/4A沸石和TiO2/天然蛭石光催化材料对6.11×10-5mol/L的甲基橙水溶液的脱色率分别达到78.5%和84.6%,比同种方法制备的纯TiO2(68%)高,而且对甲基橙光催化反应可用一级反应动力学方程进行描述。     

改性沸石和膨润土对氟离子吸附性能研究

选用高温焙烧、硫酸、硫酸镁改性天然沸石和膨润土,考察了3种改性方法对沸石和膨润土吸附氟离子性能的影响。实验结果表明,高温焙烧、硫酸改性和硫酸镁改性均提高了沸石和膨润土对氟离子的吸附能力。改性沸石对氟离子的吸附符合Langmuir等温吸附模型;硫酸改性、硫酸镁改性膨润土对氟离子的吸附可用Langmuir模型和Freundlich模型描述,高温焙烧改性膨润土对氟离子的吸附则符合Freundlich模型。     

Membrane‐based ethylene/ethane separation: The upper bound and beyond

Ethylene/ethane separation via cryogenic distillation is extremely energy‐intensive, and membrane separation may provide an attractive alternative. In this paper, ethylene/ethane separation performance using polymeric membranes is summarized, and an experimental ethylene/ethane polymeric upper bound based on literature data is presented. A theoretical prediction of the ethylene/ethane upper bound is also presented, and shows good agreement with the experimental upper bound. Further, two ways to overcome the ethylene/ethane upper bound, based on increasing the sorption or diffusion selectivity, is also discussed, and a review on advanced membrane types such as facilitated transport membranes, zeolite and metal organic framework based membranes, and carbon molecular sieve membranes is presented. Of these, carbon membranes have shown the potential to surpass the polymeric ethylene/ethane upper bound performance. Furthermore, a convenient, potentially scalable method for tailoring the performance of carbon membranes for ethylene/ethane separation based on tuning the pyrolysis conditions has also been demonstrated. © 2013 American Institute of Chemical Engineers AIChE J, 59: 3475–3489, 2013     

竹制活性炭处理酸性染料废水吸附等温线模型的误差分析(英文)

High surface area activated carbons were produced by thermal activation of waste bamboo scaffolding with phosphoric acid.Single component equilibrium dye adsorption was conducted on the carbons produced and compared with a commercially available carbon.Two acid dyes with different molecular sizes,namely Acid Yellow 117(AY117) and Acid Blue 25(AB25),were used to evaluate the adsorption capacity of the produced carbons.It was found that the dye with smaller molecular size,AB 25,was readily adsorbed onto the produced carbon,nearly three times higher than a commercially available carbon,while the larger size dye,AY117,showed little adsorption.The experimental data were analyzed using isotherm equations including Langmuir,Freundlich,Tempkin,Toth,Redlich-Peterson and Sips equations.The equilibrium data were then analyzed using five different non-linear error analysis methods.     

徐州地区煤系高岭土合成4A沸石分子筛

研究以徐州地区煤系高岭土为原料、NaOH溶液为浸取液,先于550℃煅烧2 h得到偏高岭土,再在全密封反应釜中通过偏高岭土和NaOH溶液（固液质量比1∶20）之间的水热反应制备4A沸石分子筛[Na12(Al12Si12O48)·27H2O]。并采用X射线衍射仪（XRD）、傅里叶转换红外光谱仪（FT-IR）、扫描电子显微镜（SEM）和N2吸附脱附等测试手段对4A沸石分子筛进行表征。结果表明,煤系高岭土经550 ℃煅烧2 h后转变成无定形态的偏高岭土,碱浸取后变成4A沸石分子筛;合成4A沸石分子筛过程中NaOH溶液的最佳浓度是2 mol/L;4A沸石分子筛具有狭缝状孔道,但孔的形状和分布不均匀。     

基于不同状态方程预测气体水合物相平衡条件

气相逸度的计算结果会直接影响气体水合物相平衡条件的预测精度。基于Chen-Guo模型,选取RK、SRK、PR以及PT四种状态方程计算逸度,分别对甲烷、乙烷以及二氧化碳三种不同气体水合物在不同温度范围内的相平衡条件进行计算。结果表明：纯水条件下,RK方程最适合预测甲烷水合物相平衡条件,而PR方程更适合预测乙烷及二氧化碳水合物相平衡条件;对于冰中,SRK方程适合预测甲烷水合物的相平衡条件,PR方程适合预测乙烷水合物的,而RK方程更适合二氧化碳水合物的;对于甲烷水合物,低于218.2 K的预测是导致模型预测精度偏低的原因;对于乙烷水合物,需要提高低于230.2 K的预测精度;对二氧化碳水合物而言,提高对低于270.7 K的预测可以进一步提高模型预测精度。     

Etude de l'élimination des ions Cu (II) de la solution aqueuse par sorption sur la zéolithe a study of the removal of Cu (II) from aqueous solution by sorption on Zeolite A

The objective of this study is to present the results of removal of copper by the method of sorption on zeolite A. The batch experiments were conducted for both the kinetics for the sorption isotherms. The experimental variables studied were pH, contact time at different initial concentrations, the amount of sorbent, temperature and stirring speed. The sorption capacity depends on the pH and mass of sorbent, but the temperature and stirring rate showed no influence. Several mechanisms of retention of copper on the zeolite could be competitive (ion exchange, complexation or precipitation and sorption). The modeling of experimental data on kinetics showed that the model of pseudo‐second order describes satisfactorily the sorption on the zeolite, and that the limiting step of the speed distribution intraparticle. Statistical analysis of the constants for Langmuir‐Freundlich equation has shown that this model seems most appropriate to describe this phenomenon of sorption, which indicates the heterogeneity of the surface sorption of the zeolite. Copyright © 2011 Canadian Society for Chemical Engineering     

A kinetic study on the conversion of methane to higher hydrocarbons in a radio-frequency discharge

This study investigated methane conversion with direct current discharge at low pressure in a radio frequency. The main gaseous products of the reaction were ethane, ethylene, acetylene and propane. This study was concentrated on the influence of discharge conditions on the conversion of methane to higher hydrocarbons. Reaction temperature, electron density and mean residence time were calculated from experimental data and mathematical relations. The maximum conversion of the methane was about 45% with the pure methane as a reactant. Ethane was the main product when the reaction occurred in the glow discharge. Ethane selectivity decreased with the increase of the gas temperature. The kinetics of reactions was also analyzed from possible reaction equations and various rate constant data. Consequently, the dissociation constant and the density of radicals could be obtained at any experimental conditions.     

Thermodynamic adsorption data of CH4, C2H6, C2H4 as the OCM process hydrocarbons on SAPO-34 molecular sieve

Adsorption of CH₄, C₂H₆ and C₂H₄, the feed and main products of oxidative coupling process of methane (OCM) has been studied on silicoalumina-phosphate molecular sieve (SAPO-34) in mild conditions. The experiments were conducted in a batch system based on volumetric adsorption measurement technique for determination equilibrium adsorption capacity in the absolute pressure range of 100–1000 kPa and at the isothermal temperatures of 303, 313 and 323 K. Various isotherm equations were fitted on the adsorption equilibrium data and the model parameters were predicted as a function of temperature. Isosteric heats of adsorption were determined using Clausius–Clapeyron equation at different surface coverage. Maximum capacity of SAPO-34 was observed at 303 K and 880–900 kPa equilibrium pressure with 1.25, 2.02 and 4.67 mmol/g adsorbed amount for methane, ethane and ethylene adsorption, respectively. The adsorption selectivity of ethane and ethylene against methane were determined and the appropriate potential of SAPO-34 was observed for separation of OCM products from methane. The isotherm models and enthalpy of adsorption can be efficiently used for the simulation of the adsorption process constructed at the downstream of the OCM process for separation of ethane and ethylene from methane.     

Equilibria of trichloromonofluoromethane on a carbon pellet

A laboratory study on the adsorption of trichloromonofluoromethane on a pellet-type carbon was carried out at 298, 323, 348 and 373 K. Equilibrium parameters based on Freundlich, Langmuir and Dubinin-Radushkevich equations were determined. It was found that the Dubinin-Radushkevich (D-R) equation was better fitted by the experimental data of trichloromonofluoromethane on the activated carbon pellet than other two equations. In addition, the isosteric heats of adsorption were evaluated from experimental data.