Recent Advances in MRI Studies of Chemical Reactors: Ultrafast Imaging of Multiphase Flows

NMR has long been established as an in situ technique for studying the solid-state structure of catalysts and the chemical processes occurring during catalytic reactions. Increasingly, pulsed field gradient (PFG) NMR and magnetic resonance imaging (MRI) are being exploited in chemical reaction engineering to measure molecular diffusion, dispersion and flow hydrodynamics within reactors. By bringing together NMR spectroscopy, PFG NMR and MRI, we are now able to probe catalysts and catalytic processes from the angstrom-to-centimeter scale. This article briefly reviews current activities in the field of MRI studies applied to catalysts and catalytic reactors. State-of-the-art measurements, which can already be used in real reactor design studies, are illustrated with examples of single-phase flow with and without chemical reaction in a fixed-bed reactor. The ability to obtain high spatial resolution (< 200μm) in images of the internal structure and flow field within reactors is demonstrated, and the potential uses of these data in reactor design and understanding bed fouling phenomena are discussed. In particular, MRI has produced the first detailed measurements of the extent of heterogeneity in the flow field within fixed-bed reactors. The example of a fixed-bed esterification process is used to show how NMR spectroscopy and MRI techniques can be combined to provide spatially resolved information on both hydrodynamics and chemical conversion within a process unit. The emerging area of ultrafast MRI is then highlighted as an area of particular interest. Recent advances have demonstrated that it is possible to record 2D images over timescales of ～100ms in the magnetically heterogeneous environments typical of heterogeneous chemical reactors. These advances open up opportunities to image many unsteady state processes for the first time. Examples are given of real-time visualization of bubble-train flow in a ceramic monolith and exploring the stability of the gas–liquid distribution as a function of liquid flow rate in a trickle-bed reactor.     

Submicrometer Aerosol Mass Distributions of Emissions from Boilers,Fireplaces, Automobiles,Diesel Trucks,and Meat-Cooking Operations

The predominant peak in the mass distribution emitted from each source measured in this study occurs at or below about 0.2 μm in particle diameter, whereas the Los Angeles atmospheric aerosol contains peaks at a variety of sizes in the range between 0.1 and 1.0 μm in particle diameter, including peaks at sizes larger than 0.2 μm. This suggests that considerable modification of the primary aerosol size distribution occurs because of subsequent processes in the atmosphere. The data presented here are intended for use in defining the size distribution of the primary combustion source effluent for use with mathematical models of the evolution of the atmospheric aerosol size distribution.     

Passive Filtration of Airborne Particles from Buildings Ventilated by Natural Convection: Design Procedures and a Case Study at the Buddhist Cave Temples at Yungang,China

Air exchange between interior spaces and the outdoor atmosphere can occur due to a variety of processes, including wind-driven flows and natural convectiondriven flows. As air is exchanged with the outdoors, airborne particles can be brought inside. Depending on the use of the indoor space, the presence of particles in indoor air could be a nuisance to the occupants or could be damaging to materials kept indoors. While one obvious solution to such problems is to install a mechanical air filtration system, that is not always practical. In particular, the character of some historical houses and some archaeological sites would be degraded by the presence of a mechanical air distribution system, and in some parts of the world the reliable electrical power supply needed for such a filtration system may not be available. In the present paper we consider principles for the design of passive filtration systems in which air motion through the filter material is induced by a natural convection flow rather than by a mechanical fan. A fluid mechanical model first is described for predicting the air flow through an interior space that acts as a thermal siphon. The effect of placing filter material in the path of such air flows is examined next. The indoor-outdoor air quality model of Nazaroff and Cass (1989a) is matched to the natural convection air exchange model, and calculations are performed to determine the relationship between the outdoor particle size distribution and indoor particle size distributions and particle deposition rates given a passive filtration system. Example calculations are worked for the case of a passive particle filtration system that could be installed to protect the interior of the Buddhist cave temples at Yungang, China. These are a collection of manmade cave temples dating from the 5th century AD, now situated in the middle of one of China's largest coal-mining regions with its accompanying air pollution problems.     

Use of Difunctional Compounds During Rapid Steam Hydrolysis (Rash) Pretreatment

Mixed hardwood chips were treated with difunctional compounds as catalysts to study the reaction of wood with steam. The Rapid Steam Hydrolysis (RASH) pretreatment process was used for steam treatment. The difunctional compounds studied were maleic anhydride, phthalic anhydride, isophthalic acid, and terephthalic acid at 1.5% concentration based on dry wood weight. RASH pretreatment was performed for one minute at 180°C, 200°, 220°C, 230°C, 240°C, and 260°C. These compounds strongly modified the RASH pretreated material, especially the physical structure. Overall recovery of the pretreated catalyzed and uncatalyzed solids decreased with an increase in RASH temperatures. Catalyst addition did not make a difference on the recovery of pretreated solids. Cellulose degradation increased with temperature for catalyzed systems. Hemicellulose solubilization and degradation were extremely sensitive to the type of catalyst and RASH temperatures. Almost all of the hemicellulose was lost at higher temperatures. Lignin losses did not appear to be affected by the addition of catalyst except at 260°C. Enzymatic rates were improved by addition of the catalysts, especially at the lower temperatures. The maleic anhydride gave the highest enzymatic rates at all temperatures, and phthalic anhydride gave the second highest. The water solubles generally followed the same trends as the enzymatic hydrolysis rates and increased with the addition of catalysts, especially maleic anhydride.     

An improved accelerated weathering protocol to anticipate Florida exposure behavior of coatings

A new accelerated weathering protocol has been developed which closely replicates the performance of automotive and aerospace coating systems exposed in South Florida. IR spectroscopy was used to verify that the chemical composition changes that occurred during accelerated weathering in devices with a glass filter that produced a high fidelity reproduction of sunlight’s UV spectrum matched those that occurred during natural weathering. Gravimetric water absorption measurements were used to tune the volume of water absorption during accelerated weathering to match that which occurred during natural weathering in South Florida. The frequency of water exposure was then scaled to the appropriate UV dose. A variety of coating systems were used to verify the correlation between the physical failures observed in the accelerated weathering protocol and natural weathering in South Florida. The new accelerated weathering protocol correctly reproduced gloss loss, delamination, cracking, blistering, and good performance in a variety of diverse coating systems. For automotive basecoat/clearcoat paint systems, the new weathering protocol shows significant acceleration over both Florida and previous accelerated weathering tests. For monocoat aerospace systems, the new weathering protocol showed less acceleration than for automotive coatings, but was still an improvement over previous accelerated tests and was faster than Florida exposure.     

Numerical Simulation of Anisotropic Shrinkage in a 2D Compact of Elongated Particles

Microstructural evolution during simple solid-state sintering of two-dimensional compacts of elongated particles packed in different arrangements was simulated using a kinetic, Monte Carlo model. The model used simulates curvature-driven grain growth, pore migration by surface diffusion, vacancy formation, diffusion along grain boundaries, and annihilation. Only the shape of the particles was anisotropic; all other extensive thermodynamic and kinetic properties such as surface energies and diffusivities were isotropic. We verified our model by simulating sintering in the analytically tractable cases of simple-packed and close-packed, elongated particles and comparing the shrinkage rate anisotropies with those predicted analytically. Once our model was verified, we used it to simulate sintering in a powder compact of aligned, elongated particles of arbitrary size and shape to gain an understanding of differential shrinkage. Anisotropic shrinkage occurred in all compacts with aligned, elongated particles. However, the direction of higher shrinkage was in some cases along the direction of elongation and in other cases in the perpendicular direction, depending on the details of the powder compact. In compacts of simple-packed, mono-sized, elongated particles, shrinkage was higher in the direction of elongation. In compacts of close-packed, mono-sized, elongated particles and of elongated particles with a size and shape distribution, the shrinkage was lower in the direction of elongation. The results of these simulations are analyzed, and the implication of these results is discussed.     

Ultrarapid Phase Conversion in β-Alumina Tubes

β-Alumina, the electrolyte of choice of sodium/sulfur and sodium/metal chloride batteries and alkali-metal thermal-electric converters, was sintered from precursor phases to high β-phase purity in less than 15 s from the onset of densification by rapid pass-through rf induction coupled plasma sintering. The maximum instantaneous shrinkage rate was 1.8%/s. The resistivity was measured to be 13.8 ± 1.4 Ω·cm. The rapid conversion found is a significant improvement over conventional processing of β-alumina, which requires extended postsintering annealing times to obtain high β-phase purity.     

Sorbent injection into a slipstream baghouse for mercury control: Project summary

A project led by the Energy and Environmental Research Center to test and demonstrate sorbent injection as a cost-effective mercury control technology for utilities burning lignites has shown effective mercury capture under a range of operating conditions. Screening, parametric, and long-term tests were carried out at a slipstream facility representing an electrostatic precipitator–activated carbon injection–fabric filter configuration (called a TOXECON™ in the United States). Screening tests of sorbent injection evaluated nine different sorbents, including both treated and standard activated carbon, to compare mercury capture as a function of sorbent injection rate. Parametric tests evaluated several variables including air-to-cloth (A/C) ratio, flue gas temperature, cleaning frequency, and dust loading to determine the effect on mercury control and systems operation. Long-term tests (approximately 2 months in duration) evaluated the sustainability of systems operation.     

Applications of in situ magnetic resonance techniques in chemical reaction engineering

NMR spectroscopy is now a well‐established technique for the in situ study of surface chemistry and the chemical processes occurring during catalytic reactions. Developments in probe design are making the sample environments ever closer to the operating conditions of the catalyst in industrial use. In parallel with these advances there is an increasing interest in the application of field gradient magnetic resonance techniques, namely pulsed gradient spin echo (PGSE) NMR and magnetic resonance imaging (MRI), to in situ studies of mass transport processes in catalysts and reactors. An overview of the recent developments in in situ NMR spectroscopy, PGSE NMR and MRI studies in application to catalysis and reaction engineering is presented and the potential of these techniques in the numerical modelling of catalytic processes and reactor design is highlighted. This revised version was published online in August 2006 with corrections to the Cover Date.     

Fate of trace element haps when applying mercury control technologies

During the past several years, and particularly since the Clean Air Mercury Rule (CAMR) was promulgated in June of 2005, the electric utility industry, product vendors, and the research community have been working diligently to develop and test Hg control strategies for a variety of coal types and plant configurations. Some of these strategies include sorbent injection and chemical additives designed to increase mercury capture efficiency in particulate control devices. These strategies have the potential to impact the fate of other inorganic hazardous air pollutants (HAPs), which typically include As, Be, Cd, Cr, Co, Mn, Ni, Pb, Se, and Sb. To evaluate this impact, flue gas samples using EPA Method 29, along with representative coal and ash samples, were collected during recent pilot-scale and field test projects that were evaluating Hg control technologies. These test programs included a range of fuel types with varying trace element concentrations, along with different combustion systems and particulate control devices. The results show that the majority of the trace element HAPs are associated with the particulate matter in the flue gas, except for Se. However, for five of the six projects, Se partitioning was shifted to the particulate phase and total emissions reduced when Hg control technologies were applied.