High-pressure Chemical Reactions Research Articles

A novel high-temperature MAS probe with optimized temperature gradient across sample rotor for in-situ monitoring of high-temperature high-pressure chemical reactions

We present a novel nuclear magnetic resonance (NMR) probe design focused on optimizing the temperature gradient across the sample for high temperature magic angle spinning (MAS) experiments using standard rotors. Computational flow dynamics (CFD) simulations were used to assess and optimize the temperature gradient across the sample under MAS conditions. The chemical shift and linewidth of 207Pb direct polarization in lead nitrate were used to calibrate the sample temperature and temperature gradient, respectively. A temperature gradient of less than 3 °C across the sample was obtained by heating bearing gas flows and adjusting its temperature and flow rate during variable temperature (VT) experiments. A maximum temperature of 350 °C was achieved in this probe using a Varian 5 mm MAS rotor with standard Vespel drive tips and end caps. Time-resolved 13C and 1H MAS NMR experiments were performed at 325 °C and 60 bar to monitor an in-situ mixed phase reverse water gas shift reaction, industrial synthesis of CH3OH from a mixture of CO2 and H2 with a Cu/ZnO/Al2O3 catalyst, demonstrating the first in-situ NMR monitoring of a chemical system at temperatures higher than 250 °C in a pressurized environment. The combination of this high-temperature probe and high-pressure rotors will allow for in-situ NMR studies of a great variety of chemical reactions that are inaccessible to conventional NMR setup.

Probing high-pressure reactions in heterogeneous materials by Raman spectroscopy

The characterization of pressure induced structural and chemical transformations employing the Diamond Anvil Cell (DAC) technique often requires a high spatial resolution. This is due to the small sample dimensions when the compression reaches the megabar range, or when heterogeneous materials are obtained in pressure induced chemical reactions. The characterization of these samples can be performed by using synchrotron light based techniques, which can provide optical or X-ray spots of few microns, whereas laboratory experiments are limited to Raman spectroscopy. Here we describe a cutting-edge Raman system with a transverse spatial resolution of 1–3 μm dedicated to the characterization of samples compressed in DACs. A few examples of the application of this technique to characterize different heterogeneous materials before and after high-pressure chemical reactions are reported to enlighten the performances of the system.

A Continuous-Flow Microwave Reactor for Conducting High-Temperature and High-Pressure Chemical Reactions

A continuous-flow microwave reactor with a unique pressure control device is described. The reactor has been designed to withstand extremely high pressure without the involvement of a conventional backpressure-creating device that commonly results in carryover and cross-contamination problems. The reactor efficiency has been evaluated by product conversions using two model reactions, namely, the Claisen rearrangement and the synthesis of benzimidazole.

Observing High‐Pressure Chemistry in Graphene Bubbles

Using IR spectroscopy, high-pressure reactions of molecules were observed in liquids entrapped by graphene nanobubbles formed at the graphene-diamond interface. Nanobubbles formed on graphene as a result of thermally induced bonding of its edges with diamond are highly impermeable, thus providing a good sealing of solvents within. Owing to the optical transparency of graphene and diamond, high-pressure chemical reactions within the bubbles can be probed with vibrational spectroscopy. By monitoring the conformational changes of pressure-sensitive molecules, the pressure within the nanobubble can be calibrated as a function of temperature and it is about 1 GPa at 600 K. The polymerization of buckministerfullerene (C60 ), which is symmetrically forbidden under ambient conditions, is observed to proceed in well-defined stages in the pressurized nanobubbles.

Probing high-pressure reactions in heterogeneous materials by Raman spectroscopy

The characterization of pressure induced structural and chemical transformations employing the Diamond Anvil Cell (DAC) technique often requires a high spatial resolution. This is due to the small sample dimensions when the compression reaches the megabar range, or when heterogeneous materials are obtained in pressure induced chemical reactions. The characterization of these samples can be performed by using synchrotron light based techniques, which can provide optical or X-ray spots of few microns, whereas laboratory experiments are limited to Raman spectroscopy. Here we describe a cutting-edge Raman system with a transverse spatial resolution of 1–3 μm dedicated to the characterization of samples compressed in DACs. A few examples of the application of this technique to characterize different heterogeneous materials before and after high-pressure chemical reactions are reported to enlighten the performances of the system.

High pressure effect in nanoporous carbon materials: Effects of pore geometry

Abundant experimental evidence suggests that adsorbates confined in nanoporous materials exhibit high pressures, such as high pressure crystal structures, high pressure chemical reactions, and the deformation of pore walls due to the adsorbate. We report molecular simulation studies of the pressure tensor for simple adsorbates (e.g. argon) in carbon nanopores of slit, cylindrical and spherical geometries. We find that for modest bulk phase pressures of 1bar or less, the pressures parallel to the pore walls (tangential pressure) is of the order 104–105bar, while the pressure normal to the wall is of the order of 103bar, and can be positive or negative depending on the pore size. Moreover, we find that the pore geometry has a large effect on the structure of the adsorbate and thus on the in-pore pressure because of the curvature that determines the strength of the adsorbate–wall interaction. For the same pore size, temperature and bulk pressure, the in-pore tangential pressure is the largest in spherical pores, followed by that in cylindrical pores and slit pores. We also study the normal pressure of carbon tetrachloride and water confined in activated carbon fibers by molecular simulations and experiments. The pressure acting on the pore wall is found to be of the order of several thousand bar by both methods. Experiments also find that the pore can be expanded or contracted, depending on pore width, as we predict by molecular simulation.

From simple to complex and backwards. Chemical reactions under very high pressure

High pressure chemical reactions of molecular systems are discussed considering the various factors that can affect the reactivity. These include steric hindrance and geometrical constraints in the confined environment of crystals at high pressure, changes of the free energy landscape with pressure, photoactivation by two-photon absorption, local and collective effects. A classification of the chemical reactions at high pressure is attempted on the basis of the prevailing factors.

Failure Mechanisms in High Chrome Oxide Gasifier Refractories

Gasification is a high-temperature, high-pressure chemical process used to convert a carbon feedstock into CO and H2 (syngas) for use in power generation and the production of chemicals. It is also a leading candidate as a source of hydrogen in a hydrogen economy and is one of several technologies expected to see increased use in advanced fossil fuel power systems in the future. Gasification is being evaluated because of its high efficiency, its ability to capture CO2 for sequestration or reuse in other applications, and its potential for carbon feedstock fuel flexibility. At the heart of the gasification process is a gasifier, a high pressure chemical reaction vessel used to contain the interactions between carbon and water in a shortage of oxygen, producing syngas. The gasifier is lined with high chrome oxide materials to protect the containment vessel. Gasifiers are complex systems, and failure of the refractories used to line them was identified by industry as a limitation to their reliability and availability and to their increased use. NETL researchers have examined spent high-Cr2O3 (over 90 pct Cr2O3) refractories from numerous gasifiers to determine in-service failure mechanisms. This analysis revealed that premature failure of the high chrome oxide refractories was related to ash in the carbon feedstock, which liquefies during gasification and interacts with the refractories, leading to wear by chemical dissolution or spalling (structural and chemical). A discussion of this postmortem wear of spent refractory materials and of thermodynamic modeling used to explain microstructural changes leading to wear are explained in this article. This information will serve the basis to develop improved performance refractory materials.

ChemInform Abstract: Trends in High Pressure Chemical Reaction Engineering

Abstract A review is given of trends in high pressure chemical reaction engineering. Besides homogeneous reactions, interest is focused mainly on heterogeneous catalytic conversion under conditions where the fluid phase is either in the liquid, gaseous, or supercritical state. The rate of catalytic surface reactions, mass transfer between catalyst and fluid phase, and/or transport processes inside porous catalysts can be influenced in manifold ways with the variation of pressure. Reaction engineering advantages for yield and selectivity of complex reactions, for in situ and inline regeneration, and for the prolongation of the lifetime of heterogeneous catalysts are discussed. Experimental techniques are also briefly summarized.

Trends in high pressure chemical reaction engineering

A review is given of trends in high pressure chemical reaction engineering. Besides homogeneous reactions, interest is focused mainly on heterogeneous catalytic conversion under conditions where the fluid phase is either in the liquid, gaseous, or supercritical state. The rate of catalytic surface reactions, mass transfer between catalyst and fluid phase, and/or transport processes inside porous catalysts can be influenced in manifold ways with the variation of pressure. Reaction engineering advantages for yield and selectivity of complex reactions, for in situ and inline regeneration, and for the prolongation of the lifetime of heterogeneous catalysts are discussed. Experimental techniques are also briefly summarized.