A microcalorimetric comparison of the effect ofn-alkane preadsorption on the adsorption of argon and nitrogen on Silicalite-I

Then-alkanes of different lengths were preadsorbed to selectively block part of the micropores of a MFI-type zeolite, Silicalite-I. The porosity available to argon and nitrogen was then studied by quasi-equilibrium adsorption microcalorimetry and volumetry at 77K and compared to what was found for the bare zeolite. Indeed, although partial adsorption ofn-alkanes does not alter the value of the differential enthalpies of adsorption for both argon and nitrogen, then-butane preadsorption diminishes the adsorption capacity by inducing inaccessible volumes in the micropore network. Moreover, the microcalorimetric experiments clearly show thatn-butane is not evenly distributed in the zeolite channel network while the longern-alkanes used are.     

Adsorption Equilibrium of Alkanes on a High Surface Area Activated Carbon Prepared from Brazilian Coconut Shells

Adsorption equilibria of methane, ethane, and n-butane on a high surface area activated carbon prepared from Brazilian coconut shells is examined in this study. The material shows high capacities for the alkanes tested. A group-contribution theory is used to predict adsorption isotherms for all three components with very good accuracy employing one set of model parameters. The theory is also used to observe trends in isosteric heat of adsorption as a function of loading at various temperatures.     

Sorption Equilibria and Kinetics of Hydrocarbons onto Activated Carbon Samples Having Different Micropore Size Distributions

This paper deals with the prediction of adsorption equilibrium and kinetics of hydrocarbons onto activated carbon samples having different micropore size distribution (MPSD). The microporous structure of activated carbon is characterised by the distribution of slit-shaped micropores, which is assumed to be the sole source of surface heterogeneity. The interaction between adsorbate molecule and pore walls is described by the Lennard-Jones potential theory. Different adsorbates have access to different pore size range of activated carbon due to the size exclusion, a phenomenon could have a significant influence on both multicomponent equilibria and kinetics. Activated carbons with three different MPSDs are studied with ethane and propane as the two model adsorbates. The Heterogeneous Macropore Surface Diffusion model (HMSD) is employed to simulate adsorption kinetics. The simulation results show that the MPSD is an important factor affecting both the multicomponent equilibria and kinetics.     

Aromatization ofn-butane over Ni-ZSM-5 and Cu-ZSM-5 zeolite catalysts prepared by using Ni and Cu impregnated silica, fiber

The reaction ofn-butane aromatization was carried out over Ni-ZSM-5 and Cu-ZSM-5 zeolite catalysts prepared by using Ni and Cu impregnated silica fiber during the process of ZSM-5 zeolite synthesis. The catalysts prepared were characterized by X-ray powder diffraction, nitrogen adsorption and X-ray fluorescency. The acidic properties of the catalysts were investigated by temperature-programmed desorption of ammonia using a mass spectrometer equipped with a QTMD detector. The effect of catalyst pretreatment, reaction temperature, and time on stream on the reaction ofn-butane to aromatic hydrocarbons were investigated. The modification of ZSM-5 by Ni and Cu increased the selectivity to aromatic hydrocarbons. The state of Ni and Cu and their stabilization in the ZSM-5 structure was highly influenced by the mode of catalyst pretreatments.     

n-Butane,iso-Butane and 1-Butene Adsorption on Imidazolium-Based Ionic Liquids Studied with Molecular Beam Techniques

The interaction of molecules, especially hydrocarbons, at the gas/ionic liquid (IL) surface plays a crucial role in supported IL catalysis. The dynamics of this process is investigated by measuring the trapping probabilities of n-butane, iso-butane and 1-butene on a set of frozen 1-alkyl-3-methylimidazolium-based ILs [C_nC₁Im]X, where n=4, 8 and X⁻=Cl⁻, Br⁻, [PF₆]⁻ and [Tf₂N]⁻. The decrease of the initial trapping probability with increasing surface temperature is used to determine the desorption energy of the hydrocarbons at the IL surfaces. It increases with increasing alkyl chain length n and decreasing anion size for the ILs studied. We attribute these effects to different degrees of alkyl chain surface enrichment, while interactions between the adsorbate and the anion do not play a significant role. The adsorption energy also depends on the adsorbing molecule: It decreases in the order n-butane>1-butene>iso-butane, which can be explained by different dispersion interactions.     

Effect of the nature of zeolite and modifying additives on the activity of zeolite-containing catalysts inn-butane isomerization

Isomerization ofn-butane on various types of zeolites (ZVM, ZVK, mordenite, and Y) modified with transition metals and cationic and anionic additives was investigated. Under the conditions studied, H-forms of zeolites are inactive. Pt-containing systems based on the H-form of ZVM (HZVM) are the most efficient catalysts forn-butane isomerization, and the yield of isobutane reaches 20–26 wt.% at a selectivity of 40–45%. Modification of this catalyst with Ga and Fe compounds or with an aqueous solution of HCl increases the selectivity with respect to isobutane up to 70–90%. Introduction of Zn²⁺ cations or F⁻ and SO₄ ²⁻ anions into the Pt-containing HZVM system decreases the selectivity and yield of isobutane due to the formation of very strong acidic centers on which disproportionation and hydrocracking ofn-butane mainly occur. Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 7, pp. 1281–1285, July, 1999.     

Statistical thermodynamics of adsorption from multicomponent liquid mixtures on heterogeneous solid surfaces

The statistical thermodynamics of adsorption from multicomponent liquid mixtures on heterogeneous solid surfaces is discussed by assuming the cell adsorption model and ideal adsorbed phase.Two integral representations for the adsorption isotherm are proposed: one based onn-dimensional energy distribution function (i.e., each adsorption site is characterized by adsorption energies of all components), and the other based on distribution of differences of adsorption energies ofn-1 components in relation to adsorption energy of the chosen component (i.e., each adsorption site is characterized byn-1 differences of adsorption energies of the components in relation to adsorption energy of the chosen component).The expressions for differential adsorption heat for adsorption from binary liquid mixtures have been derived from both integral equations.

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Statistische Thermodynamik der Adsorption aus flüssigen Mehrkomponentenmischungen auf heterogenen festen Oberflächen

Zusammenfassung Die statistische Thermodynamik der Adsorption von aus mehreren Komponenten bestehenden flüssigen Mischungen auf heterogenen festen Oberflächen wird für das Modell der Zellenadsorption bei ideal adsorbierter Phase diskutiert.Zwei Integraldarstellungen der Adsorptionsisotherme werden vorgeschlagen: eine auf einen-dimensionale Verteilungsfunktion der Energie gestützte (das heißt, jede Adsorptionsstelle wird durch Adsorptionsenergien von allen Komponenten charakterisiert); die andere basiert auf der Verteilung der Unterschiede von Adsorptionsenergien dern-1-Komponenten in bezug auf die Adsorptionsenergie der ausgewählten Komponente (das heißt, jede Adsorptionsstelle wird durchn-1-Unterschiede charakterisiert. Formeln für differentiale Adsorptionswärmen für die Adsorption aus binären flüssigen Mischungen sind von beiden Integral-Gleichungen abgeleitet worden.

     

Contribution of concentration-dependent surface diffusion in ternary adsorption kinetics of ethane, propane and n-butane in activated carbon

The role of concentration-dependent surface diffusion in the adsorption kinetics of a multicomponent system is investigated in this paper. Ethane, propane and n-butane are selected as the model adsorbates and Ajax activated carbon as the model adsorbent. Adsorption equilibrium isotherm and dynamic parameters extracted from single-component systems are used to predict the ternary adsorption equilibria and kinetics. The effect of concentration-dependent surface diffusion on the adsorption kinetics predictions is studied by comparing the results of two mathematical models with the experimental data. Three diffusion mechanisms, macropore, surface and micropore diffusions are incorporated in both models. The distinction between these two models is the use of the chemical potential gradient as the driving force for the diffusion of the adsorbed species in one model and the concentration gradient in the other. It was found that the model using the chemical potential gradient provides a better prediction of the ternary adsorption kinetics data, suggesting the importance of the concentration dependency of the surface diffusion, which is implicitly reflected in the chemical potential gradient. The kinetic model predictions are also affected by the way how single-component adsorption equilibrium isotherm data are fitted.     

Kinetic analysis of n-butane hydrogenolysis on a Ru/Al2O3catalyst

Summary Analysis of the kinetics of the hydrogenolysis of n-butane on a Ru/Al₂O₃catalyst permits recognition of the range of H₂:n-butane ratio where carbon formation can be neglected. Variation of the apparent activation energy with H₂pressure results from a variable contribution of its heat of adsorption to the true activation energy. Effects on product selectivities and on response of rate to H₂pressure due to oxidation and low-temperature reduction are also traced to differences in heats of adsorption.</o:p>     

Isomerization ofn-butane on the SO4/ZrO2 catalyst promoted by IV Period metals

The catalytic activity of superacidic systems based on SO₄/ZrO₂ and modified by IV Period metals in isomerization ofn-butane was studied. At low temperatures of the reaction, the introduction of Fe³⁺, Sc³⁺, Co²⁺, or Zn²⁺ ions (1%) increases the yield of isobutane by 1.5 times due to the activation ofn-butane on the sites created by the promoting ions. The addition of Cr³⁺, V⁴⁺, or Mn²⁺ (1%) decreases the catalytic activity because of a decrease in the catalyst acidity, most likely, due to the reduction of surface sulfur species. The influence of the nature of the support and surface additives of SiO₂, TiO₂, and ZrO₂ on the activity and selectivity of the catalytic system inn-butane isomerization was studied. Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 7 pp. 1276–1280, July, 1999     

Phase equilibria and surface tension of pure fluids using a molecular layer structure theory (MLST) model

This paper presents a new model based on thermodynamic and molecular interaction between molecules to describe the vapour–liquid phase equilibria and surface tension of pure component. The model assumes that the bulk fluid can be characterised as set of parallel layers. Because of this molecular structure, we coin the model as the molecular layer structure theory (MLST). Each layer has two energetic components. One is the interaction energy of one molecule of that layer with all surrounding layers. The other component is the intra-layer Helmholtz free energy, which accounts for the internal energy and the entropy of that layer. The equilibrium between two separating phases is derived from the minimum of the grand potential, and the surface tension is calculated as the excess of the Helmholtz energy of the system. We test this model with a number of components, argon, krypton, ethane, n-butane, iso-butane, ethylene and sulphur hexafluoride, and the results are very satisfactory.     

Monte Carlo simulation of adsorption of binary and quaternary alkane isomers mixtures in zeolites: Effect of pore size and structure

Grand canonical Monte Carlo and configurational bias Monte Carlo techniques were employed to simulate the adsorption of binary mixtures of butane isomers and quaternary mixtures in nine zeolites at 300 K. For binary mixtures the results show there is a critical pore size, which is 10-membered-ring about 5.6 Å. The channel sizes of BEA, ISV, MOR and CFI are larger than this critical pore size, they prefer i-butane than n-butane, whereas TON with smaller channel size than critical pore size prefers n-butane than i-butane, but its selectivity decreases with pressure increasing. MFI, MEL and TER prefer i-butane than n-butane at low pressure, but with pressure increasing, the selectivity is reversed. BOG prefers i-butane than n-butane but the selectivity decreased with pressure increasing. It demonstrates that the adsorption and selectivity are controlled by both pore size and pore structure. The n-butane–i-butane–n-pentane–2-methylbutane quaternary mixtures adsorbed in these nine zeolites were studied, and the results show alkane chain length dependence at low pressure, but the adsorption is controlled by pore size and structure with pressure increasing in all the zeolites except for TON and BOG.     

Non-isothermal Modelling of Hydrocarbon Adsorption on A Granulated Active Carbon

The adsorption of n -butane on extruded cylindrical activated carbon grains is studied providing two kinds of information: the influence of the temperature and the hydrocarbon partial pressure on the adsorption dynamics (kinetic study) and on the adsorption capacities (thermodynamic study). The thermodynamic aspect could be interpreted by a Langmuir model. From a kinetic point of view, we have experimentally proved that strong temperature variations occur inside the particles during the adsorption. In this paper, a kinetic model including both mass and heat transfer phenomena is proposed. Good agreement is found between the kinetic model predictions and the experimental mass and temperature variations inside the grain during the hydrocarbon adsorption. This revised version was published online in August 2006 with corrections to the Cover Date.     

Selection and performance of adsorbents in an adsorption refrigeration cycle regenerated with water directly

An adsorption refrigeration cycle regenerated with water directly (ARRD), which has the advantage of excellent heat transfer performance in the adsorbent bed with half-cycling time 3–5 min, and operates close to atmospheric pressure (0.1–0.5 MPa) with n-butane as a refrigerant, is developed. The purpose of this study is to find out advanced adsorbent/n-butane pairs for the ARRD system. Adsorption equilibrium performances of n-butane on the adsorbents were measured by positive pressure gravimetric method, and the adsorption equilibrium data were fitted by D-A equation. Desorption properties were determined through thermal analysis. The coefficient of performance and specific cooling power (SCP) were calculated. The results show that adsorption capacities of n-butane with activated carbon are all above 0.31 kg/kg and the highest can reach 0.43 kg/kg. Adsorption data are fitted well by D-A equation, with the correlative coefficients R above 0.93. Desorption temperatures of n-butane from carbons are between 110 and 130 °C, prospective for using low grade heat source. The quasi-equilibrium of n-butane on carbons can be achieved within 150–250 s, which benefits SCP of the ARRD system. The SCP of n-butane/AC-5 pair estimated in the ARRD systems is from 180 to 200 W/kg.     

Mechanism of reaction of n-butane with but-2-enes in the presence of LaCaX faujasites

The reactions of n-butane and an n-butane (80 mol.%)—isobutane (20 mol.%) mixture with but-2-enes in the presence of polycationic PdLaCaX faujasites were studied. Quantum-chemical calculation of the enthalpies of formation of alkanes C₄—C₈ and their cations showed that the reaction [Bnⁿ]⁺ [Buⁱ]⁺ is of crucial importance for the isomeric composition of the products of alkane alkylation. The general scheme of transformations of the hydrocarbons in the alkylation of n- and iso-paraffins was proposed based on the experimental data on the distribution of the C₈ isomers in the catalyzate at different temperatures and duration of the reaction.     

Oxidative dehydrogenation (OXD) of C3?C4 paraffins over transition metal oxides

The main features of the OXD of propane and isobutane over the oxides of iron and copper are reported and compared with those of OXD ofn-butane over these oxides.     

锶助剂对铂锡催化剂正丁烷脱氢催化性能的影响

负载型ＰｔＳｎ／Ａｌ２Ｏ３催化剂已广泛地应用于工业生产中［１］，人们正尝试着添加不同助剂以改变催化剂的反应性能。文献的工作主要集中在研究铂锡催化剂中添加助剂对载体表面酸性的调变作用。在烃类重整催化剂中，加入氟、氯等元素可增强载体的表面酸性［２］，提高...     

康熙《皇城宫殿衙署图》解读(下)*

以尿素为沉淀剂,采用负压沉积沉淀法将Au负载于不同载体,分别制备了Au/HZSM-5、 Au/SiO_2及Au/Al_2O_3催化剂.采用X射线粉末衍射、透射电镜、 NH_3-程序升温脱附、红外羟基和原位吸附吡啶红外羟基等技术对催化剂进行了表征,探究了Au对不同载体的作用,并用脉冲微反装置评价了催化剂对正丁烷脱氢反应的性能.结果表明,相较于其他载金催化剂, Au/HZSM-5酸性较强, Au与HZSM-5相互作用后会形成Si-O(H)-Au基团,该活性相对正丁烷脱氢起到一定的促进作用.     

Study of MgO/MgAc2 catalyst activity inn-butane pyrolysis

Distributions ofn-butane pyrolysis products and activities of catalysts have been analyzed. The catalysts based on magnesium oxide was preparedvia modification with magnesium acetate.n-Butane decomposition is shown to be accelerated due to active surface centers of at least two types.     

Effects of physical aging on solubility,diffusivity, and permeability of propane and n-butane in poly(4-methyl-2-pentyne)

The effects of physical aging on the solubility, diffusivity, and permeability of propane and n-butane in a hydrocarbon-based disubstituted polyacetylene, poly(4-methyl-2-pentyne) (PMP), were studied. As the relative pressure of propane and n-butane increased, the solubility of both hydrocarbons increased. Like other glassy polymers, the sorption isotherms for propane and n-butane in all PMP films were concave to the relative pressure axis, indicating dual-mode sorption behavior. The diffusion of propane and n-butane in PMP followed typical Fickian diffusion in a plane sheet. The propane diffusivity in both the unaged and aged films increased with increasing concentration of propane sorbed in the film. The n-butane diffusivity in aged films also increased with increasing n-butane concentration. However, unaged films showed the opposite behavior: the diffusivity decreased with increasing n-butane concentration. These diffusion phenomena are a consequence of the interplay between thermodynamic and mobility factors. The permeabilities of propane and n-butane decreased monotonically with increasing penetrant concentration, similar to the behavior observed in other common glassy polymers. The relaxation of the nonequilibrium excess free volume in PMP films induced the decrease in both solubility and diffusivity. As a result, the permeability of propane and n-butane in PMP decreased upon physical aging. © 2004 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 42: 2407–2418, 2004