Effect of ethanol addition in gasoline and gasoline–surrogate on soot formation in turbulent spray flames

The effect of ethanol on soot formation has been studied in turbulent spray flames of gasoline/ethanol and gasoline–surrogate/ethanol mixtures containing 10%, 20% and 30% of alcohol in volume. A hybrid burner specially designed to stabilize different liquid fuels flames with identical hydrodynamic conditions has been used. Spatially resolved measurements of soot volume fraction and of soot precursors concentration have been carried out by coupling Laser-Induced Incandescence (LII) at 1064 nm and Laser-Induced Fluorescence (LIF) at 532 nm. Significant reductions of the concentrations of soot and soot precursors have been observed when adding ethanol to gasoline. A similar behaviour has been obtained with a gasoline–surrogate which has been found to reproduce well the sooting propensity of the unleaded gasoline used in this work. The analysis of the correlation existing between the peak soot volume fraction measured in flames and the Threshold Soot Index (TSI) of the different mixtures tested in this work revealed that the effect of ethanol was not only a dilution one but that the oxygen contained in the alcohol also influence the soot formation. Finally, the comparison of the LII fluence curves and time decays obtained in gasoline/ethanol mixtures showed that soot particles oxidized faster when ethanol is added to the base fuel.     

Preparation and formation mechanism of C/C–SiC composites using polymer-Si slurry reactive melt infiltration

This study proposes a polymer-metal slurry reactive melt infiltration (RMI) method to overcome the limitations of conventional RMI in modifying irregular geometric carbon–carbon (C/C) preforms. Herein, polycarbosilane (PCS), polysiloxane, phenol-formaldehyde, and epoxy resin, which were introduced to prepare slurries with Si powder, and subsequently used to modify cylindrical C/C preforms into C/C–SiC composites. Results show that the PCS–Si slurry has the best RMI capability, by which, a cylindrical C/C preform (1.35 g·cm⁻³) was modified successfully to into a dense C/C–SiC composite (1.92 g·cm⁻³). PCS plays a vital role in fixing the coating to prevent it from falling off the surface of the C/C preform in PCS–Si slurry RMI. Both of the degree of densification and flexural strength of the C/C–SiC composites increase with an increase in the thickness of the PCS–Si slurry coating. The overreaction of the PCS–Si slurry RMI was effectively suppressed because the content of Si powder is reasonably controlled in the PCS–Si slurry coating. Moreover, nozzle-shaped C/C composites were successfully modified into a C/C–SiC composite for the first time using PCS–Si slurry RMI.     

Studying the mechanism of the interaction between silicon nitride, oxygen, and nitrogen in heating and the processes of defect formation in Si3N4 — gas systems

The method of precision thermal massometry is used to study the interaction between silicon nitride, oxygen, and nitrogen in nonisothermal heating at 300 -1300 K and a partial gas pressure of 19,998.3 Pa (150 Torr). The behavior of Si₃N₄ heated in forevacuum is studied. A special computer analysis of the experimentally obtained dependencies has provided kinetic equations for analyzing and determining the mechanisms of these processes and computing their activation energy. The experimental data are used for creating a hypothesis that the nitrogen sublattice of Si₃N₄ is dispersed before the beginning of its interaction with oxygen and nitrogen.     

Molten salt shielded synthesis and formation mechanism of Ti2AlC in NaCl–KCl medium

Herein, a highly crystalline Ti₂AlC was synthesized via the improved molten salt synthesis method called molten salt shielded synthesis. To achieve this goal, the mixture of Ti, Al, and graphite and KCl–NaCl eutectic composition salt was heated at 1000, 1050, and 1100 °C for 0.5, 1, and 1.5 h. The X-ray diffraction (XRD) patterns showed that the optimum condition for obtaining the more crystalline Ti₂AlC was achieved at 1100 °C for 1.5 h. Such phase identification, and transmission electron microscopy (TEM) images, proved that applying a protective carbon layer on the surface of salt led to inhibiting the diffusion of oxygen into the surface of the green pellet. As a result, the crystallinity of Ti₂AlC improved, while the content of undesirable compounds such as Al₂O₃ and Ti_xO_y decreased drastically. In order to shed light on the Ti₂AlC synthesis mechanism, differential thermal analysis (DTA) was employed. The DTA curve revealed that the Ti₂AlC formation completed in three levels. First, the partial dissolution of Ti in KCl–NaCl salt followed by a reaction with liquid Al resulted in the TiAl formation. Next, Ti(II) reacted in-situ on the surface of graphite that resulted in the non-stoichiometric TiC (TiC_1-x) formation, and, at last in a reaction between TiAl and TiC_1-x, Ti₂AlC phase formation took place at 940 °C.     

A methodology and database to quantify the confidence level of methods for gas–liquid two-phase flow pattern prediction

A novel methodology is presented to quantify the confidence level in the prediction of gas–liquid two-phase flow patterns in pipes. An experimental flow pattern data base has been collected, consisting of 12 studies (a total of 9029 data points). The experimental data are compared with the predictions of the unified Barnea (1987) model (any other model/method can be used), and the confidence level in the predictions is quantified. Also, gaps in the data base are identified and future studies required in this are discussed.     

Measurement of real-time flow structures in gas–liquid and gas–liquid–solid flow systems using electrical capacitance tomography (ECT)

The real-time cross-sectional distributions of the gas holdups in gas–liquid and gas–liquid–solid systems are measured using electrical capacitance tomography. For the gas–liquid system, air as the gas phase and both Norpar 15 (paraffin) and Paratherm as the liquid phases are used. Polystyrene beads whose permittivity is similar to that of Paratherm are used as the solid phase in the gas–liquid–solid system. The three-phase system is essentially a dielectrically two-phase system enabling measurement of the gas holdup in the gas–liquid–solid system independent of the other two phases. A new reconstruction algorithm based on a modified Hopfield dynamic neural network optimization technique developed by the authors is used to reconstruct the tomographic data to obtain the cross-sectional distribution of the gas holdup. The real-time flow structure and bubbles flow behavior in the two- and three-phase systems are discussed along with the effects of the gas velocity and the solid particles.     

Self-propagating high-temperature synthesis of advanced ceramics in the Mo–Si–B system: Kinetics and mechanism of combustion and structure formation

The goal of this work is to investigate the combustion mechanisms of reactions in the Mo–Si–B system and to obtain ceramic materials using the SHS method. It is concluded that the following processes are defined by the SHS for Si-rich Mo–Si–B compositions: silicon melting, its spreading over the surfaces of the solid Mo and B particles, followed by B dissolution in the melt, and formation of intermediate Mo₃Si-phase film. The subsequent diffusion of silicon into molybdenum results in the formation of MoSi₂ grains and molybdenum boride phase forms due to the diffusion of molybdenum into B-rich melt. The formation of MoB phase for B-rich compositions may occur via gas-phase mass transfer of MoO₃ gaseous species to boron particles. The stages of chemical interaction in the combustion wave are also investigated. The obtained results indicate the possibility of both parallel and consecutive reactions to form molybdenum silicide and molybdenum boride phases. Thus the progression of combustion process may occur through the merging reaction fronts regime and splitting reaction fronts regime. Molybdenum silicide formation leads the combustion wave propagation during the splitting regime, while the molybdenum boride phase appears later. Finally, targets for magnetron sputtering of promising multi-phase Mo–Si–B coatings are synthesised by forced SHS compaction method.     

In situ ESR of CrH-ZSM-5 up to 500°C in flowing gas containing O2, H2O,CCl4, NO,NO2, and C3H6

A flow cell was used for the in situ ESR monitoring of the state and reactivity of chromium ions in Cr-ZSM-5. Calcination of Cr(NO₃)₃/NH₄-ZSM-5 in air at 500°C is accompanied by migration of chromium ions inside the zeolitic channels and stabilization ofisolated Cr⁵⁺ cations near lattice A1³⁺ ions. Calcination of Cr-ZSM-5 at 750°C leads to a gradual disappearance of the isolated Cr⁵⁺ cations and formation of -Cr₂O₃ microcrystals. All the Cr⁵⁺ cations are accessible to gas-phase molecules: O₂ strongly broadens the dipole-dipole signal; H₂O sorption increases the local crystal field symmetry; admission of CCl₄ results in a small change of the Cr⁵⁺ local coordination; strongly stabilized complexes on Cr-ZSM-5 are observed upon sorption of either NO or NO₂. The sorption of C₂H₆ on Cr-ZSM-5 at 20°C is accompanied by a gradual reduction of the Cr⁵⁺ sites. At 500°C in [C₃H₆ + O₂ + He] flow, even at a large excess of oxidant, the reduction of a noticeable part of Cr⁵⁺ ions takes place. At 400°C, in the same gas mixtures, a deeper reduction of Cr⁵⁺ occurs. Closer to stoichiometric conditions, in a [C₃H₆ + NO + He] flow with 120% excess of oxidant the Cr⁵⁺ is completely reduced at 500°C. The oxidation of propene is accompanied by coke deposition on the surface of the catalyst. The implications of the results are discussed.     

CO2 mass transfer and conversion to biomass in a horizontal gas–liquid photobioreactor

This study deals with CO₂ mass transfers and biomass conversion in an industrial horizontal tubular photobioreactor. An analytical approach is used to determine an expression modeling the influence of CO₂ mass transfers on the overall biomass conversion efficiency for a given culture broth, heat and light conditions. Fluid mechanics and mass transfer are predicted with a classical two-phase flow approach (Taitel and Dukler, 1976) combined with a dissolution correlation developed and tested in the laboratory (Valiorgue et al., 2011). The influence of the stripping gas, removing the excess of oxygen in the liquid, on the conversion to biomass efficiency is shown to be not negligible. The expression is used to evaluate how the photobioreactor's design and process parameters can be tuned in order to improve biomass conversion efficiency. The biomass conversion efficiency evolution with the photobioreactor's length was found to behave asymptotically and it was explained by the relative orders of magnitude of gas dissolution and gas stripping. It has been shown that the gas flow rate for stripping and therefore the oxygen removal will be limited when further increasing the industrial photobioreactor's length for a given objective of CO₂ conversion to biomass efficiency.     

A quantum‐chemical study of the formation mechanism and nature of tert‐butyl carbenium ions in 100% sulfuric acid

Ab initio quantum‐chemical calculations reveal that the interaction of isobutene with H₃SO ₄ ⁺ ions produced by self‐dissociation of sulfuric acid occurs virtually without an activation barrier, whereas the reactions involving neutral species of sulfuric acid are characterized by considerable activation barriers: 14.9 kcal/mol at the MP2(full)/6‐31+G*//6-31+G* level and 16.9 kcal/mol^-1 at the MP2(full)/6‐31+G*//3‐21+G* level. It is also concluded that the species resulting from interaction of isobutane with H₃SO ₄ ⁺ ions of protonated tert‐butyl sulfuric acid are ion‐molecular complexes which should be considered as tert‐butyl carbenium ions weakly solvated by H₂SO₄ molecules. Although the concentration of these species in concentrated sulfuric acid is very low, presumably, they play a role of active intermediates in isobutene conversions catalyzed by sulfuric acid. This revised version was published online in July 2006 with corrections to the Cover Date.     

Simultaneous measurement of velocity profile and liquid film thickness in horizontal gas–liquid slug flow by using ultrasonic Doppler method

Horizontal gas–liquid two-phase flows widely exist in chemical engineering, oil/gas production and other important industrial processes. Slug flow pattern is the main form of horizontal gas–liquid flows and characterized by intermittent motion of film region and slug region. This work aims to develop the ultrasonic Doppler method to realize the simultaneous measurement of the velocity profile and liquid film thickness of slug flow. A single-frequency single-channel transducer is adopted in the d...     

Development of reaction–diffusion DFT and its application to catalytic oxidation of NO in porous materials

The reaction–diffusion (RD) process is an important and complex subject that involves nonequilibrium modeling and multiscale calculations and may be applied to multiple fields. State-of-art theories are computationally too expensive for real-world applications. We propose a novel classical density functional theory (CDFT) for RD modeling by combining ordinary time-dependent density functional theory (TDDFT) and reaction kinetic models to examine the multiscale RD process. The theory is applied to NO oxidation in porous materials. The uptake, flux, and density profiles are examined, to reveal that the shape of the pore could influence the selectivity of adsorption between the reactant and product, which further leads to variations in the catalytic efficiency. It is noted that open pores are more favorable for catalytic reactions. The importance of adsorption is examined in the presence as well as the absence of pore–gas attraction. Without attraction, the catalytic efficiency is decreased by three orders of magnitude.     

Conversion of syngas to hydrocarbons in a tube-wall reactor using CoFe plasma-sprayed catalyst: experimental and modeling studies

Catalyst activity and product selectivity studies of the conversion of synthesis gas to various hydrocarbon fractions were performed in a single-tube tube-wall reactor (TWR) using a CoFe plasma-sprayed catalyst with the operating conditions: temperature 250–275°C, pressure 0.1–1.03 MPa, exposure velocity 139–722 μms⁻¹, and a H₂:CO ratio of 2.0. The catalyst activity in terms of CO conversion was highest (98.5% m/m) at an exposure velocity of 139 μms⁻¹, temperature of 275°C, and in the pressure range 0.69–1.03 MPa. The selectivity to hydrocarbons was 43–50% (m/m) in the pressure range 0.69–1.03 MPa whereas the selectivity to C₅ + hydrocarbons was over 40% of the total hydrocarbons produced. The production of propylene was higher than ethylene under similar process conditions. The performance of the TWR was predicted by a numerical model. The model is based on the complete two-dimensional transport equations and reaction rate equations, developed for the CoFe catalyst. Predictions are made for the temperature along the axis of the reactor, for CO and H₂ conversions as functions of the reactor length and the exposure velocity, and the axial H₂O and CO₂ concentrations.     

Thermal stability of Pt particles of Pt/Al2O3 catalysts prepared using microemulsion and catalytic activity in NO–CO reaction

Sintering behaviors of the Pt particles of Pt/Al₂O₃ catalyst prepared using different preparation methods (microemulsion, sol–gel, and impregnation methods) were investigated. It was found that the catalyst prepared by microemulsion had a higher resistance to sintering than did the sol–gel and impregnation catalysts. To limit the sintering even more, the catalysts were pressed. The resistance to sintering in all the catalysts was improved by pressing. The pressed microemulsion catalyst was little deactivated in the NO–CO reaction by thermal treatment at 700 °C for 12 h, and had a high activity relative to that of the sol–gel and impregnation catalysts.     

Kinetic study on the reactions involved in hot gas desulfurization using a regenerable iron oxide sorbent—III. Reactions of the sulfided sorbent with steam and steam-air mixtures

In continuation of the earlier studies on sorbent regeneration, reactions of the sulfided iron oxide sorbent with steam and steam-air mixtures were investigated. This paper describes experimental results on the kinetics of these reactions. As before, experiments were conducted in a thermogravimetric analyser (TGA) and conversion data for the steam reaction were correlated using the grain model, described in Part I. The intrinsic activation energy for this reaction is found to be 16.36 kcal/mol. Effects of particle size and temperature on the rate of reaction were studied to identify proper rate-controlling regimes.For the reactions with steam-air mixtures, a parallel reaction scheme is proposed and a simple equation suggested to correlate the conversion-time data. Accordingly, the overall rate is obtained by the addition of the rates of reactions of the sulfided sorbent with steam and with air. Using the earlier results for these two reactions, conversion curves are calculated and compared with the experimental data.     

Conversion of methanol to hydrocarbons on zeolite HZSM‐5 investigated by in situ MAS NMR spectroscopy under flow conditions and on‐line gas chromatography

In situ MAS NMR spectroscopy under flow conditions and on‐line gas chromatography have been applied to study the onset of the conversion of methanol on zeolite HZSM‐5 at temperatures between 373 and 573 K. In the steady states of methanol conversion at T ⩾ 523 K, by on‐line gas chromatography mainly the formation of ethene and propene was observed. Simultaneously recorded in situ ¹³C MAS NMR spectra show signals at 12–25 ppm and at ca. 125–131 ppm indicating the presence of adsorbed C₄–C₆ olefins. The observation of these adsorbates on a working catalyst supports the “hydrocarbon pool” mechanism previously proposed for the methanol‐to‐hydrocarbon conversion on acidic zeolites. Methanol conversion at 473 and 573 K and subsequent purging of the catalyst with dry nitrogen at 293 K led to a ¹³C MAS NMR signal at 59 ppm due to methoxy groups. No hints to the presence of ethoxy, propoxy or butoxy groups and the formation of alkyl oxonium ions were found by in situ ¹³C MAS NMR spectroscopy under flow conditions. This revised version was published online in July 2006 with corrections to the Cover Date.     

The formation mechanism of pores and unbonding in the Al2O3/Al2O3 joints brazed by 50Bi2O3–35B2O3–15ZnO glass

50Bi₂O₃–35B₂O₃–15ZnO (mol. %) glass referred to as Bi50 glass, was used to braze Al₂O₃ ceramics. The phase transformations and wettability of the Bi50 glass on Al₂O₃ substrates at different temperatures were investigated. The results showed that the chemical compatibility of Bi50 glass and Al₂O₃ substrates at 650 °C was excellent. However, Al₂O₃/Al₂O₃ joints having a considerable volume fraction of pores and unbonding were obtained when the joining procedures were carried out by a one-step brazing method. Based on the experiments and simulation results, the prime determinants responsible for the presence of the pores and unbonding within the brazing joints can be divided into two aspects: (i) the intrinsic causes leading to the formation of closed pores (ii) the external factors causing the failure of pores and glass separation. Ultimately, an advanced joining procedure named two-step brazing was proposed, and joints nearly free of defects were acquired.     

Study on flame structures and emissions of CO and NO in Various CH<Subscript>4</Subscript>/O<Subscript>2</Subscript>/N<Subscript>2</Subscript>–O<Subscript>2</Subscript>/N<Subscript>2</Subscript> counterflow premixed flames

An oxygen-diluted partially premixed/oxygen-enriched supplemental combustion (ODPP/OESC) counterflow flame is studied in this paper. Flame images are obtained through experiments and numerical simulations with the GRI-Mech 3.0 chemistry. The oxygen dilution effects are revealed by comparing the flame structures and emissions with those of a premixed flame and partially premixed flame (PPF) at the same equivalence ratio (?_Σ = 0.95 and ? _f = 1.4). The results show that both PPF and ODPP/OESC flames have distinct double flame structures; however, the location of the premixed combustion zone and the distance between premixed/nonpremixed combustion zone are significantly different for these two cases. For the ODPP/OESC flame, the temperature in the premixed combustion zone is lower and the premixed zone itself is located farther downstream from the fuel nozzle, which leads to reduction of NO and CO emissions, as compared to those of the PPF. Therefore, by adjusting the distribution of the oxygen concentration in the premixed and nonpremixed combustion zones, the ODPP/OESC can effectively balance the chemical reaction rate in the entire combustion zone and, consequently, reduce emissions.