Selective catalytic reduction of nitric oxide over vanadia grafted on titania. Influence of vanadia loading on structural and catalytic properties of catalysts

The selective catalytic reduction (SCR) of NO by NH₃ has been studied over vanadia/ titania catalysts prepared by selective immobilization of vanadyl alkoxide species on two structurally different titania supports. The loading of vanadia was varied from 1.8 to 7.5 ,mol V⁵⁺ per m² surface area. Comparative kinetic measurements at 150 °C show that the NO turnover frequencies increase by more than an order of magnitude when the vanadia loading is increased from 1.8 to 3 mol V⁵⁺/m². In the region of lower SCR activity, i.e. at lower coverages ( 2 mol V⁵⁺/m²), small clusters and ribbons of vanadia are detected in the Raman spectra, whereas at loadings where maximum NO turnovers are achieved ( 3 mol V⁵⁺/m²) the prevalent vanadia species are well-developed two-dimensional vanadia layers bound to titania.     

Characteristics of Microscale Combustion in a Narrow Heated Channel

The characteristics of microscale combustion were investigated by using a microchannel heated by an external source. The inner diameter of the channel was 2 mm, which was slightly smaller than the quenching distance of the stoichiometric methane–air mixture under normal conditions. The effects of the equivalence ratio and the averaged flow velocity on the characteristics of combustion in the microchannel were examined. At a channelwall temperature of 1000°C, flames could be stabilized at equivalence ratios of 0.05–1.9 and mixture velocities up to 150 cm/sec in a Ushaped quartzglass channel. At moderate equivalence ratios and lower velocity conditions within the flammability region, oscillatory combustion was observed. A simple analytical model predicting flame oscillations on the basis of the linear analysis of steady solutions is proposed.     

Heterogeneous asymmetric reactions. 23. Enantioselective hydrogenation of ethyl pyruvate over cinchonine- and α-isocinchonine-modified platinum catalysts

The enantioselective hydrogenation of ethyl pyruvate to (S)-ethyl lactate over cinchonine- and -isocinchonine-modified Pt/Al₂O₃ catalysts was studied as a function of modifier concentration and reaction temperature. The maximum enantioselectivities obtained under the applied mild conditions were 89% ee using cinchonine (0.014 mmoldm^–3, 1 bar H₂, 23°C, 6% AcOH in toluene), and 76% ee in the case of -isocinchonine (0.14 mmoldm^–3, 1 bar H₂, –10°C, 6% AcOH in toluene). Since -isocinchonine of rigid structure exists only in anti-open conformation these data provide additional experimental evidence to support the former suggestion concerning the dominating role of anti-open conformation in these cinchona-modified enantioselective hydrogenations.     

Structure of the Reaction Zone of a Steady Detonation Wave in Dinitrodiazapentane

The massvelocity profiles in 2,4dinitro2,4diazapentane samples of different densities were registered by a laser interferometer and the electromagnetic technique. The reaction time was shown to reach 300 nsec and weakly depend on density, while the pressure in the chemical spike can be twice as high as that at the Chapman–Jouguet point. No special features due to diamond formation were observed in the massvelocity profiles registered in the chemical reaction zone.     

Unsteady creep equation in refractory materials during monoaxial compression

Conclusions The creep curves for porous refractories under monoaxial compression can be described by the Andrade equation, the parameters of which depend on the nature of the macroscopic structural changes in the material. With significant densification or embrittlement of the specimens in the testing procedure during deformation the degree factor in the equation = P+q, p 1/2; if the structure of the specimen does not undergo marked changes then the degree factor is close to the classic value (p 1/3).Translated from Ogneupory, No. 1, pp. 22–26, January, 1989.     

Modeling of the Transformation of Sulfur Compounds in Oxygen Gasification of Coal Dust

It is shown that, owing to the presence of a large amount of Ca and Fe in the mineral part of a fuel, it is possible to substantially reduce the sulfur content in the gaseous phase and, hence, improve ecological indexes of the process under the following conditions: the content of O₂ is close to the stoichiometric value for fuel gasification, the temperature is (1600–1800) K, and the pressure is 10 atm or higher.     

Characterization of poly(diethoxyphosphazene) by size exclusion chromatography and viscometry

Two samples of poly(diethoxyphosphazene) (PDEP) having very different molecular weights have been studied by viscometry and size exclusion chromatography in THF solution. The results obtained, together with light scattering data of these samples, allow the calculation of the Mark-Houwink constants a=0.65 and K=2.5 10^-4 in THF at 25°C. The method of calculation employed takes into account the great polydispersity of the samples. The characteristic ratio of the unperturbed dimensions was also calculated giving C_n = r²_o/n² 18, a value slightly higher than those previously reported for poly(dihexoxyphosphazene), C_n13 and poly (dichlorophosphazene), C_n13.5.     

Does Density of Cationic Sites Affect Catalytic Activity of Co Zeolites in Selective Catalytic Reduction of NO with Methane?

Selective catalytic reduction of NO with methane (CH₄-SCR) in an excess of oxygen over Co ions located in ZSM-5 of various Si/Al composition and in ferrierite, mordenite, chabazite and beta zeolite was investigated. From the comparison of the dependence of the TOF values per Co ion for NO conversion to N₂ and Co ions distribution among the cationic sites on total Co ion concentration, the catalytic activity of the individual Co ions was estimated. The -type Co²⁺ ions, located in the main channel of mordenite and ferrierite and coordinated above the rectangle of four framework oxygens of the channel wall exhibit the highest activity in these zeolites. On the other hand, the -type Co²⁺ ions coordinated in the plane of four oxygens of the deformed six-member ring located in the channel intersection of ZSM-5 and in channels of beta zeolite control the activity of these Co zeolites. The sequence of activity of Co²⁺ ions in CH₄-SCR of NO was FER Co>ZSM-5 Co>BEA CoZSM-5 CoFER CoMOR CoCHA CoMOR Co. A correlation between the activity of the individual Co ions in CH₄-SCR of NO and a distance between the cationic sites was observed.     

Triggering of Detonation upon Flame Interaction with an Expansion Wave

The transition of a deflagration wave into an abruptly expanding part of a plane channel, where a quasisteady supersonic underexpanded jet of an unburned gas is formed, is studied for a propane–oxygen mixture using schlieren pictures. Two explosioninitiation modes (weak and strong) are registered. In the first case, almost instantaneous onset of the detonation wave occurs when the flame front enters the expanding section; the initial velocity of this wave is approximately 1.5 times the Chapman–Jouguet detonation velocity (D_CJ) and then decreases to a value corresponding to selfsustaining detonation. In the second case, the front velocity gradually increases from 0.4D _CJ to 1.0D _CJ. It is established that the starting pulse triggering the transformation of turbulent combustion to explosion and detonation regimes is generated by interaction of the flame front with expansion waves, which are elements of the structure of the initial section of the jet.     

Phase transition in swollen gels

Summary The temperature dependence of the swelling and mechanical behaviour of two poly(N,N-diethylacrylamide) networks has been investigated in aqueous solutions at pH 7.5. While one network was prepared by the copolymerization of N,N-diethylacrylamide with N,N -methyl-enebisacrylamide in the presence of 92 vol 1.% water, 3 mol.% sodium methacrylate was added to the mixture used in the preparation of the second network. In the network without charges on the chain, both the swelling ratio and modulus were found to be continuously dependent on temperature. On the other hand, the ionized network containing sodium methacrylate showed a pronounced phase transition at the temperature T 51 °C connected with a jumpwise change in both the volume and modulus of the network.     

On the preparation and properties of CuZSM-5 catalysts for NO decomposition

Equilibrium exchange isotherms were determined for the exchange of Cu²⁺ with NaZSM-5 at varying Cu(Ac)₂ concentrations in solutions of constant volume and zeolite weight. At low Cu²⁺ levels the solid scavenged all the copper ions. When copper could be detected in the equilibrated solutions, overexchange was observed. The extent of overexchange was higher at pH 6 than at pH 4. These results were analyzed in relation to catalytic activity.On leave from the Central Institute for Chemistry, Hungarian Academy of Sciences, H1525 Budapest, Hungary.     

Multi-arm star polyisobutylenes

Summary The first synthesis of a multi-arm radial-star polyisobutylene (*-PIB) is described. The synthesis occurred by the addition of excess divinylbenzene (DVB) linking reagent to a living polyisobutylene (PIB) charge i.e., by the arm first method under specific conditions. The radial structure of the *-PIB was proven by determining the molecular weight of a sample by light scattering, then selectively destroying the aromatic polydivinylbenzene (PDVB) core, and finally determining the molecular weight of the surviving alphatic PIB arms. The synthesis strategy, kinetic observations during synthesis, and procedures leading to a representative *-PIB are described. This product whose g/mole with , contained 90.3 mole% (78 wt.%) PIB arms and 9.7 mole% (22 wt.%) aromatic core; thus the number of PIB arms emanating from the core was (number average number of arms)=56 or (weight average number of arms)=110.     

Combustion of Ultrafine Aluminum in Air

The paper reports results of studying the combustion of ultrafine aluminum (surface average diameter of particles is 0.1 m) in a sealed bomb at an initial air pressure of 1 atm. The combustion proceeds in two stages, similarly to combustion in air. It is shown that during the twostage combustion of ultrafine aluminum powder in the bomb, the mass concentration of chemically bound nitrogen in the final products increases by 20% in terms of aluminum nitride. An increase in nitrogen content in confined combustion validates the previously proposed mechanism of binding air nitrogen with participation of the gas phase during aluminum combustion.     

Highly active rare earth catalysts for the solution polymerization of ε-caprolactone

Summary By using -butyrolactone (-BL) as the reaction media, highly active catalysts--light rare earth chloride-epoxidy---BL-for the solution polymerization of -caprolactone, have been obtained for the first time. With these catalyst, PCL with molecular weight as his as 40x10⁴(Mv) can be prepared at 60°C for 1.5 hr. The amount of epoxide in catalyst solution, catalyst aging temperature and time affect the catalyst activity significantly. The mechanism study shows that in -BL, the weakening of Ln-Cl bonds by the donation of coordinated -BL with Ln³⁺ and the homogenous effect promote the reaction between light rare earth chloride and epoxide. The produced rare earth alkoxide initiates CL polymerization via a coordination-insertion mechanism with Acyl-oxygen bond cleavage.     

Electrodeposition, composition and structure of Zn—Cr alloys

The effect of polyethylene glycol (PEG 1500) as additive and of deposition conditions on Zn—Cr alloy electrodeposition from an acidic sulfate electrolyte at room temperature, without agitation was investigated. PEG polarizes the overall cathodic reaction and inhibits Zn deposition. Cr codeposition with Zn starts at a cathodic potential of about –1,95 V vs Hg/Hg₂SO₄, which is reached at current density of about 20 A dm^–2 in galvanostatic conditions. Zn—Cr alloy coatings containing up to 28 at % Cr were obtained depending on the plating conditions. SEM observations showed an island-like structure, formed by the local growth of crystals, which covered the surface during further deposition. In the first stages of electrodeposition the powder diffraction spectra contain lines of b.c.c. -(Zn,Cr) phase (a 3.02 Å). After 30 s deposition time weak lines of Zn-based phase (a 2.67 Å, c 4.90 Å) appear, and become clearly visible in coatings deposited for 90 s. The average Cr content in the alloy coatings decreases with advancing deposition. The as-plated surface contains C in organic compounds and Zn(OH)₂. After 50 min sputtering, Zn and a mixture of Cr, Cr₂O₃ and Cr₇C₃ were found. The presence of organic C and O, probably from inclusions of PEG, were also detected.     

Cooperative inclusion of sodium 1-pyrenesulfonate by γ-cyclodextrin

Summary The interaction of -cyclodextrin(-CD) with sodium 1-pyrenesulfonate(PS) was studied spectrophotometrically. -CD was found to cause much larger decrease in the absorption maxima of PS than -CD. The fluorescence spectra of PS in the presence of -CD showed excimer emission, while those of PS with -CD showed only monomer emission, indicating that -CD forms 12 (-CDPS) complexes in which two PS molecules are included in the -CD cavity in a face-to-face fashion. The binding isotherm showed a sigmoidal curve. The association constants were estimated by computer simulation of the binding curve. The 12 (CDPS) complex was found to be much more stable (K=10⁶ M^–1) than the 11 complex (K=1 M^–1). At high concentration of -CD another -CD cooperates in binding two PS molecules, resulting in the formation of a 22 complex.     

Poly(β-malic acid) : a new polymeric drug-carrier

Summary Poly(-malic acid) is a new synthetic functional polyester of the poly(-hydroxy-acid)-type whose properties are investigated in regard to possible uses as bioresorbable polyvalent drug-carrier. Degradation of polymer chains in 0.15 N phosphate buffer at pH=7.5 is monitored by aqueous GPC on SEPHADEX gels and by enzymatic titration of ultimate degradation products. It is shown that the rate of degradation obeys first order kinetics at the begining and that poly(-malic acid) degrades to malic acid at last.Presented at the 26th IUPAC Microsymposium on Macromolecules: Polymers in Medicine and Biology, Prague, July 9–12, 1984     

Partial oxidation of methane over platinum metal gauze

The partial oxidation of methane to synthesis gas has been studied over a platinum gauze catalyst. The experiments were carried out at atmospheric pressure with a single gauze in a quartz reactor heated in an electric furnace. The furnace temperature was varied in the range 200–900°C and the space time in the range 0.00021–0.00042 s. The feed consisted of a mixture of CH₄O₂Ar2110 and carbon oxides and water were the main products. Oxygen was only partly consumed and relatively small amounts of hydrogen were formed.     

13C NMR chemical shifts of polyisobutylene end groups and related model compounds

Summary The detailed end-structures of CH₃-,-Cl, exo-olefin, endoolefin, and-OH ended polyisobutylenes (PIB) have been characterized by high resolution¹³C NMR spectroscopy. Specifically, the¹³C chemical shifts characteristic of the various carbons in the following structures have been determined: CH₂C(CH₃)₂-CH₂C(CH₃)₃, CH₂C(CH₃)₂CH₂C(CH₃)₂Cl, CH₂C(CH₃)₂CH₂C(CH₃)=CH₂, CH₂C(CH₃)₂CH=C(CH₃)₂, and CH₂C(CH₃)₂CH₂CH(CH₃)CH₂OH. The structure analysis of model compounds was of utmost help in these investigations. The above information is of great value for the identification of terminally functional PIBs and analysis of reaction mixtures.     

Dependence of the Fluctuation Free Volume of Amorphous Substances on the Cooling Rate

The dependence of the fraction f _g of fluctuation free volume (frozen at the glass transition temperature) on the cooling rate is determined using the Bartenev equation for the dependence of the glass transition temperature on the cooling rate. Both dependences are found to be similar to each other. It is shown that the constancy of the ratio of the empirical coefficients involved in this equation (C ₁/C ₂ const 0.03) stems from the criterion for glass transition (f _g const 0.02–0.03) in the theory of fluctuation free volume.