Single crystal flow reactor for studying reactivities on metal oxide model catalysts at atmospheric pressure to bridge the pressure gap to the adsorption properties determined under UHV conditions

A flow reactor for the investigation of heterogeneous catalytic reactions on single crystalline metal oxide model catalysts has been designed. It is located in a high pressure cell attached to an UHV analysis chamber where the model catalysts can be prepared and characterized by surface science techniques. It can also be run in a batch modus. After sample transfer the high pressure cell can be completely separated from the UHV chamber and it can be used for oxidation treatments and reaction studies at gas pressures up to 1 bar. A new heating system provides direct heating of the sample by laser light up to 1200 K. Product analysis is done by gas chromatography coupled with mass spectrometry, which allows detection in the ppb range. The single crystal flow reactor provides new insight into the atomic scale surface chemistry of metal oxides under real catalysis conditions and bridges the pressure gap for model systems prepared and characterized under UHV conditions. Results on the dehydrogenation of ethylbenzene to styrene over epitaxial potassium–iron oxide films are presented and correlated to thermal desorption measurements on the same films under UHV conditions.     

Liquid penetration length of heptamethylnonane and trimethylpentane under unsteady in-cylinder conditions

While strategies employing early or late direct-injection of fuel can improve emissions, they also can lead to impingement of liquid-phase fuel on the piston and/or cylinder wall due to low in-cylinder temperatures and densities during the injection event. Previous work has shown that liquid-phase fuel films formed in this way can lead to pronounced degradations in efficiency and emissions. To avoid these problems, a quantitative understanding of fuel-property effects on the liquid penetration length is needed, and this understanding must include conditions where in-cylinder thermodynamic conditions and the injection rate vary with time. This work reports liquid penetration lengths measured in an optical engine under such time-varying conditions. Diagnostics included laser light scattering for measurement of the liquid length and conventional pressure-data acquisition for heat-release analysis. Unsteady liquid penetration was characterized for different injection timings, injection pressures, intake-manifold pressures, and fuel volatilities to gain an understanding of the relative importance of these factors. Fuel volatility was studied by using two fuels, 2,2,4,4,6,8,8-heptamethylnonane (HMN) and 2,2,4-trimethylpentane (TMP), which have very different volatility characteristics. Measured liquid lengths changed as in-cylinder conditions changed, with increasing temperature and density during the compression stroke causing a decrease in liquid length, and decreasing temperature and density during the expansion stroke causing an increase in liquid length. Intake-manifold pressure and fuel volatility were found to be primary factors governing liquid length. Heat loss from the charge gas to the engine and local charge cooling due to fuel vaporization were found to have a secondary influence on liquid length. Injection pressure was found to have little effect.     

Formation Mechanism of Porous Alumina With Oriented Cylindrical Pores Fabricated by Unidirectional Solidification

Porous alumina whose pores were aligned in one direction was fabricated by the unidirectional solidification method under a pressurized hydrogen atmosphere. The porous structure is formed at the solid–liquid interface during solidification due to a hydrogen solubility gap at the melting point. The hydrogen gas is dissolved into molten alumina according to Sieverts' law and insoluble gas that corresponds to the amount of solubility gap evolves from the solid phase at the solid–liquid interface during the unidirectional solidification to form the pores. The porosity and pore size of the solidified samples decreased with increasing total pressure where the environmental gas consisted of pure hydrogen or hydrogen–argon mixed gases. There is a reverse proportion relation between the pore diameter and the total pressure according to Boyle's law.     

Activated dissociative chemisorption of methane on Ni(100): a direct mechanism under thermal conditions?

The dissociative chemisorption of methane on a Ni(100) single crystal has been studied under thermal conditions as a function of pressure and temperature. The initial sticking coefficient was measured in the pressure range of 0.010–7.0 mbar at temperatures ranging from 375 to 500 K. A strong pressure dependence was observed, consistent with a direct dissociation mechanism under these thermal conditions. This was further confirmed by experiments where the gas at a low pressure was heated by a thermal finger facing the crystal surface. With the thermal finger at the same temperature as the surface, it was possible to ensure that the methane was fully equilibrated to the crystal and an activation energy of 59±1.5 kJ/mol was determined under isothermal conditions.     

Meniscus behaviors and capillary pressures in capillary channels having various cross-sectional geometries

A numerical study has been conducted to simulate the liquid/gas interface (meniscus) behaviors and capillary pressures in various capillary channels using the volume of fluid (VOF) method. Calculations are performed for four channels whose cross-sectional shapes are circle, regular hexagon, square and equilateral triangle and for four solid/liquid contact angles of 30°, 60°, 120° and 150°. No calculation is needed for the contact angle of 90° because the liquid/gas interface in this case can be thought to be a plane surface. In the calculations, the liquid/gas interface in each channel is assumed to have a flat surface at the initial time, it changes towards its due shape thereafter, which is induced by the combined action of the surface tension and contact angle. After experiencing a period of damped oscillation, it stabilizes at a certain geometry. The interface dynamics and capillary pressures are compared among different channels under three categories including the equal inscribed circle radius, equal area, and equal circumscribed circle radius. The capillary pressure in the circular channel obtained from the simulation agrees well with that given by the Young–Laplace equation, supporting the reliability of the numerical model. The channels with equal inscribed circle radius yield the closest capillary pressures, while those with equal circumscribed circle radius give the most scattered capillary pressures, with those with equal area living in between. A correlation is developed to calculate the equivalent radius of a polygonal channel, which can be used to compute the capillary pressure in such a channel by combination with the Young–Laplace equation.     

A new triaxial apparatus to study the mechanical and fluid flow aspects of carbon dioxide sequestration in geological formations

Climate scientists are practically unanimous in the belief that anthropogenic greenhouse gas contributions have added to the thickness and thus the effectiveness of the greenhouse gas layer, leading to a warming of the planet (IPCC, 2005 [1]). Engineers and scientists around the globe are researching and developing measures to reduce greenhouse gas emissions. These measures have included proposals to sequester carbon dioxide (CO₂) in deep geological formations (Perera et al., in press [18]). For CO₂ sequestration in deep geological reservoirs to become a feasible strategy to reduce greenhouse gas emissions, a sound understanding of the manner by which mechanical properties and permeability changes with the introduction of CO₂ to the geological reservoir will influence the stability of that reservoir is required. Thus there is a need to develop laboratory equipment capable of simulating the CO₂ injection and storage process for deep geological CO₂ sequestration under the expected in situ pressure (confinement and fluid) and temperature conditions. Triaxial experiment has been identified as the best method for this purpose (Perera et al., 2011b [19]). Therefore, we present a new high-pressure triaxial apparatus which can provide the high confining and fluid injection pressures and elevated temperatures expected for deep geological CO₂ sequestration. The new setup can be used to conduct mechanical and permeability testing on intact or fractured natural rock samples or synthetic rock samples subjected to high-pressure injection of up to three fluid phases (gas and/or liquid) at high pressures and temperatures corresponding to field conditions. The equipment is capable of delivering fluids to the sample at injection pressures of up to 50 MPa, confining pressures of up to 70 MPa and temperature up to 50 °C and will continuously record fluid injection and confining pressures, axial load and displacement, radial displacement and independent outflow rates for liquid and gas fluid phases (under drained conditions).Leakage tests have confirmed the effectiveness of the device at pressures up to its maximum capacities. Additionally the temperature-pressure relationship for the hydraulic oil used to apply confining pressure to the sample has been calibrated to account for the influence of changes in temperature on confining pressure. Several permeability tests (using N₂ and CO₂ as the injection fluid and 10 MPa confining pressure) and one strength test are reported for black coal samples from the Sydney Basin, New South Wales. According to the results of the permeability tests, coal mass permeability decreases with increasing effective stress for both gases. However, the permeability for N₂ gas is much higher than CO₂. Moreover, test results are consistent with matrix swelling due to the adsorption of CO₂ in coal. The strength testing results are in agreement with the results of testing carried on similar black coal samples from literature, certifying the ability for the new device to accurately measure strength and deformation properties of rock under deep ground conditions.     

An integrated surface science approach towards metal oxide catalysis

The function of a metal oxide catalyst was investigated by an integrated approach, combining a variety of surface science techniques in ultrahigh vacuum with batch reactor conversion measurements at high gas pressures. Epitaxial FeO(111), Fe₃O₄(111) and α‐Fe₂O₃(0001) films with defined atomic surface structures were used as model catalysts for the dehydrogenation of ethylbenzene to styrene, a practized selective oxidation reaction performed over iron‐oxide‐based catalysts in the presence of steam. Ethylbenzene and styrene adsorb onto regular terrace sites with their phenyl rings oriented parallel to the surface, where the π‐electron systems interact with Lewis acidic iron sites exposed on Fe₃O₄(111) and α‐Fe₂O₃(0001). The reactant adsorption energies observed on these films correlate with their catalytic activities at high pressures, which indicates that the surface chemical properties do not change significantly across the pressure gap. Atomic defects were identified as catalytically active sites. Based on the surface spectroscopy results a new mechanism was proposed for the ethylbenzene dehydrogenation, where the upward tilted ethyl group of flat adsorbed ethylbenzene is dehydrogenated at Brønsted basic oxygen sites located at defects and the coupling of the phenyl ring to Fe³⁺ terrace sites determines the reactant adsorption–desorption kinetics. The findings are compared to kinetic measurements over polycrystalline catalyst samples, and an extrapolation of the reaction mechanism found on the model systems to technical catalysts operating under real conditions is discussed. The work demonstrates the applicability of the surface science approach also to complex oxide catalysts with implications for real catalysts, provided suitable model systems are available.     

Looking at Heterogeneous Catalysis at Atmospheric Pressure Using Tunnel Vision

This paper addresses the “pressure gap” between traditional surface science experiments and catalysis under practical conditions. We review high-pressure, microflow experiments at elevated temperatures during the catalytic oxidation of CO. Using a specially constructed “Reactor-STM” we simultaneously determine the surface structure of a model catalyst by scanning tunneling microscopy and the reaction kinetics by online mass spectrometry. For both Pt(110) and Pd(100) we find that under O₂-rich conditions surface oxides are formed on the otherwise metallic surfaces. The presence of the oxide is correlated with a superior catalytic activity. Whereas the reaction on the metal surfaces shows traditional Langmuir–Hinshelwood kinetics, the reaction on the oxides follows the Mars-Van Krevelen oxidation–reduction mechanism, as we conclude from the reaction kinetics and the reaction-induced roughening of the surface. We emphasize that in addition to a pressure gap there can also be a temperature gap, requiring experiments to be performed not only at high pressures but also at sufficiently high temperatures.     

Interfacial chemistry and adhesive durability

The improved understanding of adsorption chemistry which has arisen from the development of new surface analytical techniques during the last twenty years has had a major effect on the understanding of catalytic reaction mechanisms. However, there are many other areas of technology where Interfacial chemistry has a determining role but where the understanding is much less developed. In this paper examples are presented of the role of interfacial chemistry in adhesion. In particular, It Is shown that modification of a surface to the extent of just a few atomic layers in depth can have dramatic effects on the performance of adhesive bonds, particularly when exposed to hostile environmental conditions. These examples will be used to highlight a need for greater fundamental understanding of the interfacial chemistry of adhesion and also other technologies where interface effects are dominant.     

Study on diffusion and flow of benzene, n-hexane and CCl4 in activated carbon by a differential permeation method

In this paper the diffusion and flow of carbon tetrachloride, benzene and n-hexane through a commercial activated carbon is studied by a differential permeation method. The range of pressure is covered from very low pressure to a pressure range where significant capillary condensation occurs. Helium as a non-adsorbing gas is used to determine the characteristics of the porous medium. For adsorbing gases and vapors, the motion of adsorbed molecules in small pores gives rise to a sharp increase in permeability at very low pressures. The interplay between a decreasing behavior in permeability due to the saturation of small pores with adsorbed molecules and an increasing behavior due to viscous flow in larger pores with pressure could lead to a minimum in the plot of total permeability versus pressure. This phenomenon is observed for n-hexane at 30°C. At relative pressure of 0.1-0.8 where the gaseous viscous flow dominates, the permeability is a linear function of pressure. Since activated carbon has a wide pore size distribution, the mobility mechanism of these adsorbed molecules is different from pore to pore. In very small pores where adsorbate molecules fill the pore the permeability decreases with an increase in pressure, while in intermediate pores the permeability of such transport increases with pressure due to the increasing build-up of layers of adsorbed molecules. For even larger pores, the transport is mostly due to diffusion and flow of free molecules, which gives rise to linear permeability with respect to pressure.     

Study of the Kinetics and Morphology of Gas Hydrate Formation

The kinetics and morphology of ethane hydrate formation were studied in a batch type reactor at a temperature of ca. 270–280 K, over a pressure range of 8.83–16.67 bar. The results of the experiments revealed that the formation kinetics were dependant on pressure, temperature, degree of supercooling, and stirring rate. Regardless of the saturation state, the primary nucleation always took place in the bulk of the water and the phase transition was always initiated at the surface of the vortex (gas‐water interface). The rate of hydrate formation was observed to increase with an increase in pressure. The effect of stirring rate on nucleation and growth was emphasized in great detail. The experiments were performed at various stirring rates of 110–190 rpm. Higher rates of formation of gas hydrate were recorded at faster stirring rates. The appearance of nuclei and their subsequent growth at the interface, for different stirring rates, was explained by the proposed conceptual model of mass transfer resistances. The patterns of gas consumption rates, with changing rpm, have been visualized as due to a critical level of gas molecules in the immediate vicinity of the growing hydrate particle. Nucleation and decomposition gave a cyclic hysteresis‐like phenomena. It was also observed that a change in pressure had a much greater effect on the rate of decomposition than it did on the formation rate. Morphological studies revealed that the ethane hydrate resembles thread or is cotton‐like in appearance. The rate of gas consumption during nucleation, with different rpm and pressures, and the percentage decomposition at different pressures, were explained precisely for ethane hydrate.     

In-Situ Vibrational Spectroscopic Studies on Model Catalyst Surfaces at Elevated Pressures

Elucidation of complex heterogeneous catalytic mechanisms at the molecular level is a challenging task due to the complex electronic structure and the topology of catalyst surfaces. Heterogeneous catalyst surfaces are often quite dynamic and readily undergo significant alterations under working conditions. Thus, monitoring the surface chemistry of heterogeneous catalysts under industrially relevant conditions such as elevated temperatures and pressures requires dedicated in situ spectroscopy methods. Due to their photons-in, photons-out nature, vibrational spectroscopic techniques offer a very powerful and a versatile experimental tool box, allowing real-time investigation of working catalyst surfaces at elevated pressures. Infrared reflection absorption spectroscopy (IRAS or IRRAS), polarization modulation-IRAS and sum frequency generation techniques reveal valuable surface chemical information at the molecular level, particularly when they are applied to atomically well-defined planar model catalyst surfaces such as single crystals or ultrathin films. In this review article, recent state of the art applications of in situ surface vibrational spectroscopy will be presented with a particular focus on elevated pressure adsorption of probe molecules (e.g. CO, NO, O₂, H₂, CH₃OH) on monometallic and bimetallic transition metal surfaces (e.g. Pt, Pd, Rh, Ru, Au, Co, PdZn, AuPd, CuPt, etc.). Furthermore, case studies involving elevated pressure carbon monoxide oxidation, CO hydrogenation, Fischer–Tropsch, methanol decomposition/partial oxidation and methanol steam reforming reactions on single crystal platinum group metal surfaces will be provided. These examples will be exploited in order to demonstrate the capabilities, opportunities and the existing challenges associated with the in situ vibrational spectroscopic analysis of heterogeneous catalytic reactions on model catalyst surfaces at elevated pressures.     

Zum Stand der Extraktion mit komprimierten Gasen

The state of the art of extraction with compressed gases . Gases under high pressure have the properties of solvents. Their utilization has led to the development of novel methods of separation, extending materials separation process engineering by a new group of process techniques. Catalysts can be dissolved in high-density gas phases and thus effect favourable reaction conditions. In the neighbourhood of the critical temperature, liquid-like densities of the compressed gas are already achieved at relatively moderate pressures in the range from 50 to about 300 bar. A comparatively high solvent power of the gaseous phase ensues. This property of a compressed gas can be varied within wide limits by a change of pressure and temperature. With decreasing density it approaches the behaviour of a normal gas, with increasing density that of a liquid. Thus, there is the possibility of separating out the dissolved material again. The working temperature of such a process is largely determined by the critical temperature of the gas employed. Since a number of readily available gases have critical temperatures in the region up to 50°C, the first separations to be examined during the development of this process were those of temperature-sensitive and low-volatile mixtures. Polar materials having substantially higher critical temperatures such as ammonia, methanol and water promise a further series of possible applications.     

Recent advances in cellulosic membranes for gas separation and pervaporation

Cellulose acetate membranes have been used commercially for many gas separation applications in recent years. Advances have been made in understanding their behaviour in the presence of various vapours and under severe operating conditions, for example at very high carbon dioxide and hydrogen sulphide partial pressures. In addition, a new membrane module design has been developed for use in high recovery systems and at high gas flow rates. Extension of cellulose acetate gas separation membrane technology into the pervaporation field has resulted in a new application related to the production of methyl t-butyl ether (MtBE). In this case the membrane is used to remove methanol from MtBE and hydrocarbons to increase the reaction yield.     

Optical fiber extrinsic refractometer to measure RI of samples in a high pressure and temperature systems: Application to wax and asphaltene precipitation measurements

An optical fiber extrinsic sensor for measurement of changes in the refractive index of liquids confined in chambers for high pressure and temperature experiments is described. One head sensor composed by two fibers is fixed in front of a high pressure and temperature cell filled with the sample. The operation principle is based in the reflectivity dependence in the refractive index of the glass–liquid interface. Excellent results and a sensitivity of 10⁻⁵ RI were obtained for pure liquids. The applicability of the sensor is demonstrated following the changes in the refractive index for pure liquids at different pressure and temperatures and by measuring the asphaltenes and wax precipitation in crude oils under pressure. The extrinsic probe designed for refractive index measurement proves to be a reliable tool for measuring heavy organics deposition in crude oils under high pressures and temperatures where the sample to be measured is not very accessible.     

The nucleation, growth, and stability of oxide-supported metal clusters

The optimization of oxide-supported metal clusters as heterogeneous catalysts requires a detailed understanding of the metal cluster–oxide interface. Model catalysts, prepared by deposition of a catalytically active metal onto a thin film oxide support, closely mimic real-world catalysts, yet are amenable to study using surface sensitive techniques. Surface science methods applied to model catalysts, combined with the use of in situ high-pressure reaction studies, have provided a wealth of information about cluster structure and reactivity. STM capabilities for imaging individual particles under reaction temperatures and pressures offer a new approach for studying supported cluster catalysts on a particle-by-particle basis. This article describes recent work in our laboratories using variable temperature STM to investigate the role of the support and its defects in the nucleation and stabilization of metal clusters.     

Effect of the pressure on the crystallization behavior of polyamide 66

The crystallization behavior of polyamide 66 under high pressure up to 2500 bar was investigated by the use of dilatometric and calorimetric techniques in nonisothermal and isothermal conditions. The solid–solid Brill transition is detected from the evolution of the specific volume in the PVT diagram. The variation of supercooling was examined under different pressures and temperatures. In nonisothermal conditions, when the same cooling rate is applied, the crystallization supercooling is not changed for different pressures. In isothermal conditions, for a given temperature, a pressure increase extends the crystallization supercooling. By the analysis of melting peaks of samples crystallized in different conditions of pressure and temperature, we can conclude that the increasing of the crystallization supercooling leads to a decrease of the lamellae thickness. Finally, the evolution of the thermodynamic equilibrium melting temperature according to pressure was examined. © 2001 John Wiley & Sons, Inc. J Appl Polym Sci 80: 1021–1029, 2001     

Phase transitions in monolayer formed by hyperbranched polyester with alkyl-terminated branches at the air/water interface

Investigations of Langmuir and Langmuir–Blodgett molecular films of hyperbranched polyester with alkyl-terminated branches over a wide temperature range revealed an unusual phase transitions. The measured surface pressure–surface area isotherms clearly show that the hyperbranched polyester formed stable and well-defined monolayers at the air/water interface. At temperatures below 313 K ice floe-like structures of a condensed phase were formed already from very low surface pressures. On the increase of the surface pressure the floes of the condensed phase merged forming a uniform monolayer. Above 313 K a surface liquid phase was formed at the interface. It was shown that the phase transition from the surface liquid phase to the condensed phase occurred on temperature decrease. At lower temperatures the compression process was not reversible. The increase of temperature up to about 323 K made the compression process reversible. The monolayers were transferred from the air/water interface onto silicon and mica substrates using the Langmuir–Blodgett technique at different temperatures. The structure of the polyester monolayer formed at the substrates' surfaces was investigated.     

Frictional behavior of solid polymers on a metal surface at processing conditions

The frictional coefficients of three glassy polymers (polystyrene, polycarbonate, and polymethylmethacrylate) and three crystalline polymers (high density polyethylene, low density polyethylene and polypropylene) on a highly polished steel surface were measured at high temperatures, high pressures, and high speeds, all comparable to actual processing conditions. The frictional behavior of these polymers was found to depend on temperature, pressure-and speed in a very complicated manner. There appears to exist inter-relationships among the temperature, pressure and speed dependences of the frictional coefficients. The frictional coefficients of ductile, crystalline polymers as a function of temperature appear to undergo two distinct transitions: one associated with yielding and the other associated with melting. The frictional coefficients of glassy polymers go through only one transition, associated with the glass transition. The friction-generated heat at high pressures and high speeds can increase the sliding interface temperature of a polymer to values much greater than the metal surface temperature, and thus the polymer can start to melt (or plasticate) at metal surface temperatures appreciably below its thermodynamic melting (or glass transition) temperature.     

Effect of pressure on the hydropyrolysis of Manvers coal

Manvers weakly-coking coal was pyrolysed to 500 °C in a stirred autoclave under varying pressures of hydrogen and nitrogen. As expected the major changes produced by increase in nitrogen pressure were a decrease in tar yield accompanied by increases in gas and, to a smaller extent, in coke yields. Total pressures and hydrogen :coal ratios were altered to obtain maximum yields of tar, gases and liquor. All products were investigated. Tar fractions, separated into neutral, phenolic and basic components, were analysed by g.c.-m.s. Short-chain hydrocarbons were detected in the gas sample. Methanol densities and micropore surface areas the cokes were related to the conditions of pyrolysis. At the relatively low rates of heating employed, pressure had effects on tar composition similar to increasing the temperature of pyrolysis.