Experimental study of the structure of a lean premixed indane/CH<Subscript>4</Subscript>/O<Subscript>2</Subscript>/Ar flame

In order to better understand the chemistry involved during the combustion of diesel fuel components, the structure of a laminar lean premixed methane flame doped with indane has been investigated. This flame contains 7.1% (molar) of methane, 36.8% of oxygen, and 0.90% of indane, corresponding to an equivalence ratio of 0.74 and a C₉H₁₀/CH₄ ratio of 12.75%, with argon used as a dilutant. The flame has been stabilized on a burner at a pressure of 6.7 kPa, with the gas velocity at the burner exit equal to 49.2 cm/sec at 333 K. Quantified species include usual methane combustion products C₀–C₂, but also eleven C₃–C₅ hydrocarbons and three C₁–C₃ oxygenated compounds, as well as 17 aromatic products, namely benzene, toluene, phenylacetylene, styrene, ethylbenzene, xylenes, trimethylbenzenes, ethyltoluenes, indene, methylindane, methylindene, naphthalene, phenol, benzaldehyde, and benzofuran. The temperature has been measured by a PtRh(6%)-PtRh(30%) thermocouple settled inside the enclosure: from 800 K close to the burner up to 2000 K in the burned gases.     

Method of estimating absolute concentrations of C<Subscript>2</Subscript>H<Subscript>5</Subscript> and H radicals in hydrocarbon diffusion flames

A method for estimating absolute concentrations of C₂H₅ and H radicals in hydrocarbon diffusion flames is proposed and substantiated. Concentration profiles of C₂H₅ and H on the flame axis are obtained. In the method proposed, the concentration of C₂H₅ is determined from the equality of two quantities — the rate of loss of n-butane by diffusion and the rate of its formation by recombination of two C₂H₅ radicals. The concentration of H radicals is determined from the relation between the ratio C₂H₅/H and experimental profiles of C₂H₄, C₂H₆, and O₂. __________ Translated from Fizika Goreniya i Vzryva, Vol. 43, No. 6, pp. 13–20, November–December, 2007.     

Investigation of the structure of a CH4/N2-O2/N2 Counterflow diffusion flame using molecular beam and microprobe mass spectrometry

The possibility of using molecular beam mass spectrometry (MBMS) to study the structure of counterflow flames was shown by the example of a CH₄/N₂-O₂/N₂ flame. The thermal structure of the flame was studied, and the CH₄, O₂, and CO₂ concentration distributions were measured using a microprobe technique and MBMS. The results of the measurements performed by the two methods were compared. The MBMS technique was used to study the hydroxyl concentration distribution in the flame. The species concentrations and temperature profiles on the burner axis were calculated. __________ Translated from Fizika Goreniya i Vzryva, Vol. 42, No. 4, pp. 26–33, July–August, 2006.     

Experimental study of N<Subscript>2</Subscript> dilution on bluff-body stabilized LPG jet diffusion flame

The present paper reports the effects of N₂ addition and preheating of reactants on bluff-body stabilized coaxial LPG jet diffusion flame for two cases, namely, (I) preheated air and (II) preheated air and fuel. Experimental results confirm that N₂ addition to the fuel stream leads to an enhancement in flame length, which may be attributed to the reduction in flame temperature. The soot free length fraction (SFLF) also increases, which might be caused by the decrease in fuel concentration and flame temperature. The flame length and also the SFLF are observed to be reduced with increasing temperature of reactants and lip thickness of the bluff body. The NO _x emission level for all burner configurations are found to be attenuated with nitrogen addition, which can be attributed to the reduction of the residence time of the gas mixture in the flame. The emission index of NO _x (EINO _x ) also becomes enhanced with increasing lip thickness and reactant temperature due to an increased residence time and thermal effect, respectively. __________ Translated from Fizika Goreniya i Vzryva, Vol. 45, No. 1, pp. 3–10, January–February, 2009.     

Analysis of flame structure by molecular-beam mass spectrometry using electron-impact and synchrotron-photon ionization

Molecular-beam mass spectrometry (MBMS) has proven to be a powerful tool for the general analysis of flame structure, providing concentrations of radical and stable species for low-pressure flat flames since the work of Homann and Wagner in the 1960’s. In this paper, we will describe complementary measurements using electron-impact ionization with a high-mass-resolution quadrupole mass spectrometer and vacuum-ultraviolet photoionization in a time-of-flight mass spectrometer. Isomers are resolved that have not been separately detectable before in MBMS studies of flames, including C₃H₂, C₃H₄, C₄H₃, C₄H₄, C₄H₅, C₆H₆, and C₂H₄O. The qualitative and quantitative results of MBMS have led to advances in modeling and applying flame chemistry. __________ Translated from Fizika Goreniya i Vzryva, Vol. 42, No. 6, pp. 58–63, November–December, 2006.     

Chemical Vapor Deposition of Pd(C<Subscript>3</Subscript>H<Subscript>5</Subscript>)(C<Subscript>5</Subscript>H<Subscript>5</Subscript>) to Synthesize Pd@MOF-5 Catalysts for Suzuki Coupling Reaction

Abstract  

The highly porous metal organic framework MOF-5 was loaded with the metal–organic compound [Pd(C₃H₅)(C₅H₅)] by metal–organic chemical vapor deposition (MOCVD) method. The inclusion compound [Pd(C₃H₅)(C₅H₅)]@MOF-5 was characterized by powder X-ray diffraction (PXRD), Fourier-transform infrared (FT-IR) spectroscopy, and solid-state nuclear magnetic resonance spectroscopy. It was found that the host lattice of MOF-5 remained intact upon precursor insertion. The –C₃H₅ ligand in the precursor is easier to lose due to the interaction between palladium and the benzenedicarboxylate linker in MOF-5, providing a possible explanation for the irreversibility of the precursor adsorption. Pd nanoparticles of about 2–5 nm in size was formed inside the cavities of MOF-5 by hydrogenolysis of the inclusion compound [Pd(C₃H₅)(C₅H₅)]@MOF-5 at room temperature. N₂ sorption of the obtained material confirmed that high surface area was retained. In the Suzuki coupling reaction the Pd@MOF-5 materials showed a good activity in the first catalytic run. However, the crystal structure of MOF-5 was completely destroyed during the following reaction runs, as confirmed by PXRD, which caused a big loss of the activity.     

Effect of a novel intumescent retardant for ABS with synergist Al(H<Subscript>2</Subscript>PO<Subscript>2</Subscript>)<Subscript>3</Subscript>

A novel intumescent flame retardant (IFR), containing ammonium polyphosphate (APP) and poly(hexamethylene terephthalamide) (PA6T), was prepared for acrylonitrile–butadiene–styrene (ABS). Limiting oxygen index (LOI), vertical burning test (UL-94), thermogravimetric analysis (TGA) were used to investigate the flammability property and thermal stability of the IFR/ABS systems. It was found that the flame retardancy of the IFR/ABS systems was improved significantly. When the components of the IFR were 25% APP and 5% PA6T, the LOI value of IFR/ABS system reached to the maximum of 29, but only UL-94V-1 rating was passed. Thus, Al(H₂PO₂)₃ was incorporated into ABS/APP/PA6T system as a synergistic agent, it was found 2% addition of Al(H₂PO₂)₃ caused PA6T/APP/PA6T/Al(H₂PO₂)₃ (70/23.3/4.7/2) to pass V-0 rating of UL-94 test. Meanwhile, the TGA curves indicated that PA6T could be effective as a charring agent and there was a synergistic reaction between PA6T and APP, which effectively promoted the char formation of IFR/ABS composites. Moreover, the residual char obtained after the LOI test of the IFR/ABS was characterized by Fourier transform infrared spectra (FTIR). Results indicated that P–O–C chemical bond was formed in the residual char, which could indicate the cross-linking reaction between PA6T and APP could occur. Furthermore, scanning electron microscopy (SEM) was used to investigate the morphology of the residual char formed in the LOI tests. It was revealed that both ABS/APP/PA6T (70/25/5) and PA6T/APP/PA6T/Al(H₂PO₂)₃ (70/23.3/4.7/2) formed uniform and compact intumescent charred layers.     

On the role of C<Subscript>2</Subscript>O radicals in the prompt-NO mechanism

The measurements of NO concentrations in the post-flame zone of different hydrocarbon + O₂ + N₂ flames at standard temperature and atmospheric pressure available in the literature are compared with predictions of the original Konnov reaction mechanism and with the same mechanism extended by the reaction of C₂O with N₂. The goal was to investigate the possible role of this reaction proposed by Williams and Fleming [Proc. Combust. Inst., Vol. 31 (2007), pp. 1109–1117]. This new reaction of C₂O with N₂ seems to be a reasonable explanation of the deficiencies in the prompt-NO route. Direct comparisons of the experimental measurements performed in different flames with the modeling strongly suggests that the upper limit of this reaction rate constant is k = 7 · 10¹¹ exp(−17,000/RT) [cm³/(mole · sec)]. __________ Translated from Fizika Goreniya i Vzryva, Vol. 44, No. 5, pp. 3–7, September–October, 2008.     

Separation characteristics of tetrapropylammoniumbromide templating silica/alumina composite membrane in CO<Subscript>2</Subscript>/N<Subscript>2</Subscript>, CO<Subscript>2</Subscript>/H<Subscript>2</Subscript> and CH<Subscript>4</Subscript>/H<Subscript>2</Subscript> systems

Nanoporous silica membrane without any pinholes and cracks was synthesized by organic templating method. The tetrapropylammoniumbromide (TPABr)-templating silica sols were coated on tubular alumina composite support ( γ-Al₂O₃/ α-Al₂O₃ composite) by dip coating and then heat-treated at 550 °C. By using the prepared TPABr templating silica/alumina composite membrane, adsorption and membrane transport experiments were performed on the CO₂/N₂, CO₂/H₂ and CH₄/H₂ systems. Adsorption and permeation by using single gas and binary mixtures were measured in order to examine the transport mechanism in the membrane. In the single gas systems, adsorption characteristics on the α-Al₂O₃ support and nanoporous unsupport (TPABr templating SiO₂/ γ-Al₂O₃ composite layer without α-Al₂O₃ support) were investigated at 20–40 °C conditions and 0.0–1.0 atm pressure range. The experimental adsorption equilibrium was well fitted with Langmuir or/and Langmuir-Freundlich isotherm models. The α-Al₂O₃ support had a little adsorption capacity compared to the unsupport which had relatively larger adsorption capacity for CO₂ and CH₄. While the adsorption rates in the unsupport showed in the order of H₂> CO₂> N₂> CH₄ at low pressure range, the permeate flux in the membrane was in the order of H₂≫N₂> CH₄> CO₂. Separation properties of the unsupport could be confirmed by the separation experiments of adsorbable/non-adsorbable mixed gases, such as CO₂/H₂ and CH₄/H₂ systems. Although light and non-adsorbable molecules, such as H₂, showed the highest permeation in the single gas permeate experiments, heavier and strongly adsorbable molecules, such as CO₂ and CH₄, showed a higher separation factor (CO₂/H₂=5-7, CH₄/H₂=4-9). These results might be caused by the surface diffusion or/and blocking effects of adsorbed molecules in the unsupport. And these results could be explained by surface diffusion. This paper is dedicated to Professor Hyun-Ku Rhee on the occasion of his retirement from Seoul National University.     

Synthesis and characterization of zeolite mazzite analogue in Na<Subscript>2</Subscript>O–Al<Subscript>2</Subscript>O<Subscript>3</Subscript>–SiO<Subscript>2</Subscript>–Piperazine–H<Subscript>2</Subscript>O

Zeolite Mazzite (MAZ) analogue was synthesized directly using piperazine as a structure directing agent. The reactive gel composition used was (5.0–7.0) piperazine:(6.0–7.0) Na₂O:Al₂O₃:20.0SiO₂:400H₂O. Using this composition, the reaction time was shortened greatly to 4 days and the crystallization time was reduced as well. The DTA data showed that piperazine, in as-synthesized zeolite omega decomposed easily. The decomposition of the piperazine occurred at 400–480°C. NH₃-TPD analysis proved that zeolite H-omega from piperazine had strong surface acidity with ammonia desorption temperature up to 590°C.     

Laminar flame structure in a low-pressure premixed H2/O2/Ar mixture

The chemical structure of a stoichiometric hydrogen-oxygen flame stabilized on a flat burner at a pressure of 47 torr is studied by molecular-beam mass spectrometry and computer simulation. Concentration profiles are measured for the stable flame components H₂, O₂, and H₂O, as well as for the atoms and radicals H, O, and OH. The concentration profiles calculated using two different kinetic mechanisms are in acceptable agreement with experimental data. It is also shown that for sampling probes with thin walls (<-0.1 mm) at their tips, there is no need to perform the calculations using a specified temperature profile measured by thermocouples located near the aperture of the sampler, as recommended by a number of authors. Translated fromFizika Goreniya i Vzryva, Vol. 35, No. 3, pp. 29–34, May–June 1999.     

Promoting Effect of Triglyme on Lean NO<Subscript>x</Subscript> Reduction Over Ag/Al<Subscript>2</Subscript>O<Subscript>3</Subscript>

Abstract  

The highly oxygenated hydrocarbon triethylene glycol dimethyl ether or triglyme (CH₃O–(C₂H₄O–)₃CH₃) was found to efficiently reduce NO_x under lean conditions over Ag/Al₂O₃, but gave a low NO_x conversion over Cu-ZSM-5. Furthermore, triglyme showed an extraordinary promoting effect when added together with propene as reducing agent for NO_x over Ag/Al₂O₃ at low temperature. This is most likely due to that triglyme promotes the activation of propene.     

Comparative study of the influence of CO<Subscript>2</Subscript> and H<Subscript>2</Subscript>O on the chemical structure of lean and rich methane-air flames at atmospheric pressure

A comparative study of the influence of CO₂ and H₂O on both lean and rich CH₄-air laminar flames is performed. Six premixed flames are stabilized on a flat flame burner at atmospheric pressure: lean (with the equivalence ratio maintained constant at ? = 0.7) and rich (with the equivalence ratio maintained constant at ? = 1.4) CH₄-air, CH₄-CO₂-air, and CH₄-H₂O-air flames. These flames are studied experimentally and numerically. The [CO₂]/[CH₄] and [H₂O]/[CH₄] ratios are kept equal to 0.4 for both flames series. Species mole fraction profiles are measured by gas chromatography and Fourier transform infrared spectroscopy analyses of gas samples withdrawn along the vertical axis by a quartz microprobe. Flames structures are computed by using the ChemkinII/Premix code. Four detailed combustion mechanisms are used to calculate the laminar flame velocities and species mole fraction profiles: GRI-Mech 3.0, Dagaut, UCSD, and GDFkin®3.0.     

The system SiC–W<Subscript>2</Subscript>B<Subscript>5</Subscript>–LaB<Subscript>6</Subscript>

Experiments and calculations have been applied to the structure of the triple eutectic system SiC–W₂B₅–LaB₆(T _eu = 1900 ± 40°C), composition in mol.%: 10 LaB₆, 44 SiC, 46 W₂B₅, error ±2–3%, which opens up prospects for making ceramic materials for various purposes.     

Hydrothermal synthesis of nanotubes based on (Mg,Fe,Co,Ni)<Subscript>3</Subscript>Si<Subscript>2</Subscript>O<Subscript>5</Subscript>(OH)<Subscript>4</Subscript> hydrosilicates

Hydrosilicate nanotubes of the variable composition (Mg,Fe,Co,Ni)₃Si₂O₅(OH)₄ with a chrysotile structure have been synthesized under hydrothermal conditions at temperatures of 250–450°C and pressures of 30–100 MPa in media of different compositions. The conditions and ranges of formation of nanotubular hydrosilicates of the compositions under investigation have been determined. It has been demonstrated that the type of cation of the octahedral layer in the chrysotile structure has a decisive effect on the physicochemical conditions, mechanism, and rate of formation of nanotubes, as well as on their structure, morphology, and sizes.     

Effect of synthesis condition and annealing on the sensitivity and stability of gas sensors made of Zn-doped <Emphasis Type="Italic">γ</Emphasis>-Fe<Subscript>2</Subscript>O<Subscript>3</Subscript> particles

Gas sensors made of flame-synthesized Zn-doped γ-Fe₂O₃ nanoparticles were found to have high sensitivity and high aging resistance. Zinc-doped γ-Fe₂O₃ nanoparticles and microparticles were synthesized by flame spray pyrolysis (FSP). Gas sensors were fabricated with as-synthesized particles, and with particles that had been annealed. The sensors’ response to acetone vapor and H₂ was measured as fabricated, and measured again after the sensors were aged for three days. The sensors made from as-synthesized particles showed a gas sensing sensitivity 20 times higher than the literature value. However, sensors made of microparticles lost their sensing ability after three days of aging; sensors made of nanoparticles retained their gas sensing capability after aging. Sensors made of annealed particles did not have significant gas sensing capabilities. Analysis using the William and Hall method showed that the microstrains decreased significantly in both H₂/O₂ and H₂/Air flame synthesized particles after annealing. The results showed that sensors made of flame-synthesized particles have much higher sensitivity than sensors made of particles previously reported. Especially, sensors made of flame-synthesized nanoparticles are resistant towards aging. This aging resistance may be attributed to the particles’ ability to retain their microstrains.     

Structure of an atmospheric-pressure H<Subscript>2</Subscript>/O<Subscript>2</Subscript>/N<Subscript>2</Subscript> flame doped with iron pentacarbonyl

This paper presents the measurement and simulation data on the thermal and chemical structure of an atmospheric-pressure premixed H₂/O₂/N₂ flame doped with iron pentacarbonyl Fe(CO)₅. Soft ionization molecular beam mass spectrometry was used to measure concentration profiles of the combustion products of iron pentacarbonyl: Fe, FeO₂, FeOH, and Fe(OH)₂. A comparison of experimental and simulated concentration profiles showed that they are in satisfactory agreement for FeO₂ and Fe(OH)₂ and differ significantly for Fe and FeOH. Thus, the previously proposed kinetic model for the oxidation of iron pentacarbonyl was tested and it was shown that the mechanism needs further elaboration.     

Synthetic spinels of the system MgO-Cr<Subscript>2</Subscript>O<Subscript>3</Subscript>-Al<Subscript>2</Subscript>O<Subscript>3</Subscript>-Fe<Subscript>2</Subscript>O<Subscript>3</Subscript>

Synthetic spinels of the system MgO-Cr₂O₃-Al₂O₃-Fe₂O₃ are considered and the desirability of organizing their production for the refractory industry is demonstrated. Translated from Novye Ogneupory, No. 6, pp. 32–35, June 2008.     

Preparation and electrochemical performance of Li-rich layered cathode material,Li[Ni<Subscript>0.2</Subscript>Li<Subscript>0.2</Subscript>Mn<Subscript>0.6</Subscript>]O<Subscript>2</Subscript>, for lithium-ion batteries

The Li-rich layered cathode material, Li[Ni_0.2Li_0.2Mn_0.6]O₂, was synthesized via a “mixed oxalate” method, and its structural and electrochemical properties were compared with the same material synthesized by the sol–gel method. X-ray diffraction (XRD) shows that the synthesized powders have a layered O₃–LiCoO₂-type structure with the R-3m symmetry. X-ray photoelectron spectroscopy (XPS) indicates that in the above material, Ni and Mn exist in the oxidation states of +2 and +4, respectively. The layered material exhibits an excellent electrochemical performance. Its discharge capacity increases gradually from the initial value of 228 mA hg⁻¹ to a stable capacity of over 260 mA hg⁻¹ after the 10th cycle. It delivers a larger capacity of 258 mA hg⁻¹ at the 30th cycle. The dQ/dV curves suggest that the increasing capacity results from the redox-reaction of Mn⁴⁺/Mn³⁺.     

Effect of the nature of the support of a cobalt catalyst on the synthesis of hydrocarbons from CO,H<Subscript>2</Subscript>, and C<Subscript>2</Subscript>H<Subscript>4</Subscript>

The effect of the nature of the support of a Co catalyst on the synthesis of hydrocarbons from CO, H₂, and C₂H₄ was studied in this work. It was found that the introduction of ethylene into synthesis gas resulted in an increase in the yield of liquid hydrocarbons. In this case, the conversion of C₂H₄ was complete and the degree of its involvement into the synthesis of C₅₊ hydrocarbons depended on the concentration of this component in the starting mixture and the nature of the support. Specific features of the adsorption of CO and C₂H₄ on the used Co catalysts were determined using a temperature-programmed desorption method.