Influence of alkaline earth metals on the activity and sulfur stability of zeolites in the Nox−C3−C4 hydrocarbon selective reduction of no to nitrogen (SKV) process

The results of the influence of alkaline earth metal and magnesium cations on the activity and sulfur stability of catalysts based on synthetic mordenites and high-silicon zeolites with pentasil structures on the selective reduction of nitrogen oxides with C₃−C₄ hydrocarbons are presented. Doping the H-form of mordenite and pentasils with Ca, Sr, Ba, and Mg cations increased their activity and stability with respect to sulfur dioxide in the selective reduction of NO_x with a propane-butane mixture. L. V. Pisarzhevskii Institute of Physical Chemistry, Academy of Sciences of Ukraine, 31 Prospekt Nauki, Kiev 252039, Ukraine. Translated from Teoreticheskaya i éksperimental'naya Khimiya, Vol. 35, No. 5, 317–321, September–October, 1999.     

The effect of the modification conditions of natural mordenite on their catalytic characteristics in the selective reduction of NOx

The results of a search for optimum conditions for the modification of natural mordenites and the results of an investigation of their acidic characteristics by temperature programmed desorption of ammonia for the purpose of producing active and sulfur-resistant catalysts for the selective reduction of NO_x by lower hydrocarbons (C₁−C₄) are presented. It was shown that during the chemical modification of samples of mordenite-bearing rock, including acid treatment with 0.25–0.5 N sulfuric acid solutions, recationization, and subsequent decationization, the concentration of strong acid centers increases. Here the activity of the catalysts and the resistance to the effect of SO₂ in the selective reduction of NO_x to nitrogen by a propane-butane mixture are increased. L. V. Pisarzhevskii Institute of Physical Chemistry, National Academy of Sciences of Ukraine, 31 Prospekt Nauki, Kiev 252039, Ukraine. Translated from Teoreticheskaya i éksperimental'naya Khimiya, Vol. 35, No. 2, pp. 125–129, March–April, 1999.     

Low-temperature NO<Subscript><Emphasis Type="Italic">x</Emphasis></Subscript> Selective Reduction by Hydrocarbons on H-Mordenite Catalysts in Dielectric Barrier Discharge Plasma

Toward achieving selective catalytic reduction of NO _x by hydrocarbons at low temperatures (especially lower than 200 °C), C₂H₂ selective reduction of NO _x was explored on H-mordenite (H-MOR) catalysts in dielectric barrier discharge (DBD) plasma. This work reported significant synergistic effects of DBD plasmas and H-MOR catalysts for C₂H₂ selective reduction of NO _x at low temperatures (100–200 °C ) and across a wide range of O₂ content (0–15%). At 100 °C, NO _x conversions were 3.3, 11.6 and 66.7% for the plasma alone, catalyst alone and in-plasma catalysis (IPC) cases (with a reactant gas mixture of 500 ppm NO, 500 ppm C₂H₂, 10% O₂ in N₂, GHSV = 12,000 h⁻¹ and input energy density of 125 J L ⁻¹), respectively. At 200 °C, NO _x conversions were 3.8, 54.0 and 91.4% for the above three cases, respectively. Also, strong signals of hydrogen cyanide (HCN) byproduct were observed in the catalyst alone system by an on-line mass spectrometer. By contrast, almost no HCN was detected in the IPC system.     

Contemporary Problems in the Selective Catalytic Reduction of Nitrogen Oxides (NOx)

The results from investigation of the processes involved in the catalytic reduction of nitrogen oxides are reviewed: 1) with carbon monoxide and other combustible gases (H₂, C _n H _m ) at a developed block honeycomb palladium-containing catalysts; 2) with ammonia (the SCR process) at vanadium-containing and complex oxide (Cu-Cr, Fe-Cr/-Al₂O₃) catalysts; 3) with light C₁-C₄ hydrocarbons at cation-exchange zeolites (pentasils, natural and synthetic mordenites). Mechanisms and kinetic models are proposed, and the regions of a positive and negative effect from oxygen and sulfur dioxide on the processes involved in the reduction of nitrogen oxides are established.     

Ceramic honeycombs coated with zeolite Co-ZSM-5 for Nox abatement

A deNO_x catalyst was prepared by wash-coating a cobalt ion exchanged ZSM-5 zeolite together with an alumina binder on a cordierite honeycomb structure. A few types of the Co-ZSM-5 based catalysts were tested for NO_x reduction with C₂H₄ under oxidizing conditions in the temperature range between 250–600°C. Preliminary tests of the catalytic activity of the systems showed NO_x reduction up to 95% at temperatures between 400–550°C using a mixture of a synthetic gas and air as reactant.     

Reduction of N<Subscript>2</Subscript>O and NO over H-ZSM-5- and ZrO<Subscript>2</Subscript>-supported iron- and cobalt-containing catalysts

The combined conversion conditions were examined for the reactions of decomposition and reduction of N₂O and NO with C₁,C₃–C₄ hydrocarbons, in particular, in gas mixtures containing oxygen and sulfur dioxide, over Fe- and Co-containing catalysts supported on zeolites and zirconia, as well as on structured honeycomb monoliths.     

Kinetics of nonstationary condensation of methane on a perovskite catalyst

The interaction of methane with the oxidized surface of the KNaSrCoO_3−x is first order in methane with respect to formation of higher hydrocarbons and zero order with respect to formation of CO₂. At the initial stage the rate of formation of the reaction products is independent of the amount of oxygen from the catalyst consumed (up to 5–7 monolayers of oxygen), after which the rate of the reaction falls linearly. The overall amount of oxygen consumed in the reaction reaches 30 monolayers. L. V. Pisarzhevskii Institute of Physical Chemistry, National Academy of Sciences of Ukraine, 31 Prospekt Nauki, Kiev 03039, Ukraine. Translated from Teoreticheskaya i éksperimental'naya Khimiya, Vol. 36, No. 3, pp. 182–187, May–June, 2000.     

Dehydrocondensation of methane to higher hydrocarbons on bifunctional catalysts in the absence of oxidizing agents in the gas phase

A study was carried out on the effect of the chemical nature of M_xL_y on the activity and selectivity of bifunctional M_xL_y/zeolite catalysts, where M_xL_y are metal-like transition metal compounds, M is a metal atom (Co, Mo, or W), and L is a nonmetal atom (B or Si), in the dehydrocondensation of methane to give higher hydrocarbons in the absence of gas-phase oxidizing agents. L. V. Pisarzhevskii Institute of Physical Chemistry, National Academy of Sciences of Ukraine, 31 Prospekt Nauki, 252039 Kiev, Ukraine. Translated from éksperimental’naya i Teoreticheskaya Khimiya, Vol. 33, pp. 243–247, July–August, 1997.     

Kinetic regularities of the heat release during the reactions of aliphatic hydrocarbons with aqueous HNO3

The kinetics of the heat release during the reactions of aqueous HNO₃ withn-heptane andn-octadecane was studied. The kinetic regularities of the reactions of hydrocarbons C₇H₁₆−C₁₈H₃₈ with HNO₃ and the heats of the reactions were described. At all stages, except initial, the hydrocarbon reacts with NO₂ and nitric acid reproduces NO₂ in the reaction with NO. The accumulation of NO₂ results in the acceleration of the process. When the pressure of the hydrocarbon vapor is equilibrium, its reaction with NO₂ can also proceed in the gas phase. The contribution of this reaction to the total heat release was estimated. The additives of aromatic and unsaturated hydrocarbons to aliphatic hydrocarbons increase strongly the initial rate of the heat release and changes slightly the subsequent stages of the process. Naphthenic hydrocarbons have almost no effect on the kinetic parameters of the process. Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 1, pp. 35–40, January, 1998.     

Effect of the iron content on the properties of a zirconium dioxide catalyst in the hydrogenation of carbon monoxide

The hydrogenation of Co on zirconium dioxide catalysts containing from 0 to 10 mass % iron was studied. Small additions of iron up to about 0.5 mass % promote the ZrO₂ catalysts relative to the formation of C₂–C₄ olefins. In the presence of large iron additives, the catalyst operates as a complex metal-oxide system featuring interaction of its components. L. V. Pisarzhevskii Institute of Physical Chemistry, National Academy of Sciences of Ukraine, 31 Prospekt Nauki, 252039 Kiev, Ukraine. Translated from Teoreticheskaya i éksperimental’naya Khimiya, Vol. 33, No. 3, pp. 153–158, May–June, 1997.     

Conversion of natural gas to C2 hydrocarbons through dielectric-barrier discharge plasma catalysis

The experiments are carried out in the system of continuous flow reactors with dielectric-barrier discharge (DBD) for studies on the conversion of natural gas to C₂ hydrocarbons through plasma catalysis under the atmosphere pressure and room temperature. The influence of discharge frequency, structure of electrode, discharge voltage, number of electrode, ratio of H₂/CH₄, flow rate and catalyst on conversion of methane and selectivity of C₂ hydrocarbons are investigated. At the same time, the reaction process is investigated. Higher conversion of methane and selectivity of C₂ hydrocarbons are achieved and deposited carbons are eliminated by proper choice of parameters. The appropriate operation parameters in dielectric-barrier discharge plasma field are that the supply voltage is 20–40 kV (8.4–40 W), the frequency of power supply is 20 kHz, the structure of (b) electrode is suitable, and the flow of methane is 20–60 mL · min⁻¹. The conversion of methane can reach 45%, the selectivity of C₂ hydrocarbons is 76%, and the total selectivity of C₂ hydrocarbons and C₃ hydrocarbons is nearly 100%. The conversion of methane increases with the increase of voltage and decreases with the flow of methane increase; the selectivity of C₂ hydrocarbons decreases with the increase of voltage and increases with the flow of methane increase. The selectivity of C₂ hydrocarbons is improved with catalyst for conversion of natural gas to C₂ hydrocarbons in plasma field. Methane molecule collision with radicals is mainly responsible for product formation.     

FT-IR study of the nature and stability of NOx surface species on ZrO2, VOx/ZrO2 and MoOx/ZrO2 catalysts

The adsorption of NO, NO/O₂ mixtures and NO₂ on pure ZrO₂ and on two series of catalysts supported on ZrO₂, one containing vanadia and the other molybdena (ZV and ZMo, respectively), has been investigated. The V and Mo surface contents of the latter were ≤3 atoms nm⁻² and ≤5 atoms nm⁻², respectively. All samples had been previously submitted to a standard oxidation treatment. On all samples, only extremely minor amounts of NO_x surface species are formed by NO interaction at room temperature (RT). NO_x surface species are formed in greater amounts on pure ZrO₂ when NO and O₂ are coadsorbed at RT; they are mainly nitrites, small amounts of nitrates, and small amounts of (O₂NO−H)^δ− species; when ZrO₂ is warmed to 623 K in the NO/O₂ mixture, nitrites decrease, nitrates and (O₂NO−H)^δ− species increase. The same NO_x species as on the ZrO₂ surface free from V (or Mo) are formed on ZV (or ZMo) samples with surface V (or Mo) density <1.5 atoms nm⁻²; however, they occur in decreased amount with increasing V (or Mo) coverage. On ZV samples with a surface V density of 1.5–3 atoms nm⁻² (or ZMo samples with a surface Mo density of 1.5–5 atoms nm⁻²) when NO and O₂ are coadsorbed at RT, there is formation of small amounts of nitrites, nitrates (both on ZrO₂ surface free from V (or Mo) and at the edges of V- or Mo-polyoxoanions) and NO₂ ^δ+ species, associated with V⁵⁺ (or Mo⁶⁺) of very strong Lewis acidity; when samples are warmed up 623 K in the NO/O₂ mixture, nitrites disappear, nitrates increase, NO₂ ^δ+ species remain constant or slightly decrease. When NO₂ is allowed into contact at RT with oxidized samples, surface situations almost identical to those obtained for each sample warmed to 623 K in NO/O₂ mixture is reached. The NO_x surface species stable at 623 K, the temperature at which catalysts show the best performance in the selective catalytic reduction (SCR) of NO by NH₃, are nitrates, both on ZrO₂ and on polyvanadates or polymolybdates at high nuclearity. On the contrary, nitrites and NO₂ ^δ+ species are unstable at 623 K.     

A miniaturized active sampler for the assessment of personal exposure to nitrogen dioxide

A personalized, miniaturized air sampling system was evaluated to estimate the daily exposure of pediatric asthmatics to nitrogen dioxide (NO₂). The lightweight device (170 g) uses a sampling pump connected to a solid sorbent tube containing triethanolamine (TEA)-impregnated molecular sieve. The pump is powered by a 9 V battery and samples air over a 24 h period at a collection rate of 0.100 L/min. After exposure, the solid sorbent is removed from the tubes for spectrophotometric analysis (Griess Assay). The lower detection limit of the overall method for NO₂ is 11 μg/m³. The linearity, precision and accuracy of the sampler was evaluated. Different NO₂ concentrations generated in the laboratory (range: 50 to 340 μg/m³) were simultaneously measured by the TEA tube samplers and colocated continuous chemiluminescent NO_x analyzers (reference method). The coefficient of determination for the laboratory test derived from ordinary linear regression (OLR) was r ²=0.99 (y _OLR=0.94x−4.58) and the precision 3.6%. Further, ambient NO₂ concentrations in the field (range: 10–120 μg/m³) were verified with continuous chemiluminescent monitors next to the active samplers. Reweighted least squares analysis (RLS) based on the least median squares procedure (LMS) resulted in a correlation of r ²=0.68 for a field comparison in Riverside, CA (y _RLS=1.01x−0.94) and r ²=0.92 in Los Angeles, CA (y _RLS=1.31x−7.12). The precision of the TEA tube devices was 7.4% (at 20–60 μg/m³ NO₂) under outdoor conditions. Data show that the performance of this small active sampling system was satisfactory for measuring environmental concentrations of NO₂ under laboratory and field conditions. It is useful for personal monitoring of NO₂ in environmental epidemiology studies where daily measurements are desired.     

Catalytic Properties of ZrO2 Systems in the Reduction of Nitrogen Oxides by Hydrocarbons

The catalytic properties of zirconia prepared by different methods with impregnated variable-valence metals (chromium, cobalt, and cerium) as well as rhodium-promoted samples were studied in the reduction of nitrogen oxides by C₁ and C₃–C₄ hydrocarbons and also in the presence of sulfur dioxide. TPDA and IR spectroscopy showed that the different catalytic behavior of the Me _x O _y /ZrO₂ samples is related to their acid properties. The more active samples had strong Brönsted acid sites.     

Influence of H<Subscript>2</Subscript>O and SO<Subscript>2</Subscript> on the activity of deposited cobalt oxide catalysts in the processes of reduction of nitrogen(I), (II) oxides with carbon monoxide and C<Subscript>3</Subscript>-C<Subscript>4</Subscript> alkanes

It is shown that palladium–cobalt oxide–cerium catalyst deposited on cordierite catalyzes the reduction of nitrogen(II) oxide with carbon monoxide, and cobalt–iron catalysts in simultaneous reduction of NO + N₂O with C₃-C₄ alkanes retained high activity in the presence of water vapor and sulfur dioxide. The Pd-Co₃O₄/cordierite catalyst exceeds the Pt-Co₃O₄/codierite catalyst in the conversion of NO and CO in the reaction mixture CO + NO + O₂ + H₂O + SO₂. Modification of the Pd-Co₃O₄/cordierite with cerium oxide considerably increases its sulfur resistance.     

Effect of epitaxial growth on the formation of the cobalt catalysts of the Fischer-Tropsch synthesis

Mixed oxides Co_xAl_yO₄ with different Al/Co ratios applied as supports for the catalysts of the Fischer-Tropsch synthesis were prepared using the solid-state chemical reaction. The Co_xAl_yO₄ supports were prepared by modifying gibbsite with various cobalt salts (acetate, nitrate, and basic carbonate). The use of basic cobalt carbonate gives the Co(20%)/Co_xAl_yO₄ catalyst, which provides an increased yield of hydrocarbons C₅₊ and a decreased methane content compared to the impregnation catalyst Co(30%)/Al₂O₃. The introduction of small amounts of rhenium additives makes it possible to enhance the yield of hydrocarbons C₅₊ (179 g m⁻³) and also to increase the selectivity with respect to the C₅–C₁₈ fraction. The introduction of basic cobalt carbonate into the support, most likely, creates favorable conditions for the epitaxial growth of the precursor of the active phase. Dedicated to Academician G. A. Abakumov on the occasion of his 70th birthday. Published in Russian in Izvestiya Akademii Nauk. Seriya Khimicheskaya, No. 9, pp. 1856–1860, September, 2007.     

Simple spectrophotometric method for the determination of sulfur dioxide by its decolorizing effect on the peroxovanadate complex

A simple, rapid, and economical spectrophotometric method is developed for the determination of sulfur dioxide in sugar and air samples. The developed method is based on a red-brown peroxovanadate complex (λ_max = 470 nm) produced in 2 M sulfuric acid when ammonium metavanadate is treated with hydrogen peroxide. Under fixed concentrations of hydrogen peroxide and ammonium metavanadate, when sodium metabisulfite (Na₂S₂O₅ = 2SO₂) is added, it preferentially reacts with hydrogen peroxide producing sulfuric acid, and the unreacted hydrogen peroxide then reacts with ammonium metavanadate; therefore, the concentration of sulfur dioxide is directly proportional to a decrease in the concentration of the peroxovanadate complex. The stoichiometric ratio between hydrogen peroxide and ammonium metavanadate as well as the stability constant of the complex are determined by the modified Job’s method and the respective values are found to be 1: 1 and 2.5 × 10⁴ mol⁻¹ L, respectively. The system obeys Lambert-Beer’s law in the concentration range 3.57–64.26 ppm of sulfur dioxide. The molar absorptivity, correlation coefficient, and Sandell’s sensitivity values are found to be 0.649 × 10³ L mol⁻¹ cm⁻¹, 0.9908, and 0.1972 μg cm⁻², respectively. The method is applied to the determination of sulfur dioxide present in commercial sugars and air samples. The results obtained are reproducible with a standard deviation of 0.02–0.05. For method validation, sulfur dioxide is also determined separately following the AOAC method for an air sample and the ICUMSA method for commercial sugars. The results obtained by the developed and official methods are in good agreement. The text was submitted by the authors in English.     

The effect of the carrier nature and the method of preparation of oxide catalysts containing indium on their activity in the selective catalytic reduction of nitrogen monoxide with C<Subscript>1</Subscript>-C<Subscript>4</Subscript> hydrocarbons

The activity of samples containing indium in the selective catalytic reduction (SCR) of NO with C₁-C₄ hydrocarbons depends on nature of the carrier, Al₂O₃, ZrO₂, the quantity of indium oxide, and the method of its introduction. The most active catalysts (2.5–5.0% In₂O₃/Al₂O₃) are stable to water and are characterized by a large overall concentration of oxide centers. __________ Translated from Teoreticheskaya i éksperimental’naya Khimiya, Vol. 43, No. 2, pp. 107–111, March–April, 2007.     

Effectiveness of nitric oxide ozonation

Attempts to develop new technologies of NO _x (NO + NO₂) emission reduction are still carried out all around the world. One of the relatively new approaches is the application of ozone injection into the exhaust gas stream followed by the absorption process. Ozone is used to transform NO _x to higher nitrogen oxides which yield nitric acid with better effectiveness. The main objective of this paper was to study the influence of mole ratio (MR) O₃/NO used in the ozonation process of NO _x on the effectiveness of NO _x oxidation to higher oxides. The ozonation process was carried out in a flow reactor for concentrations of nitric oxide in the range of 1.5 × 10⁻⁵−7.7 × 10⁻⁵ mol dm⁻³ and varying O₃/NO mole ratios. Measurements were conducted with the use of a FTIR spectrometer. The results obtained prove that for MR higher than 1, the oxidation effectiveness of nitric oxides generally reaches 95 %, whereas for MR higher than 2, oxidation of NO _x to higher nitrogen oxides is completed.     

On-line gas chromatographic analysis of light Fischer-Tropsch synthesis products

Summary A simple gas chromatographic system has been developed for the rapid on-line analysis of light Fischer-Tropsch products. This involves a single chromatography fitted with two columns, a porous-layer open-tubular column coated with KCl deactivated alumina and a packed Porapak-Q column. The capillary column separates the 16 most common C₁−C₄ hydrocarbons and permits a reasonable analysis of the hydrocarbons in the C₅−C₇ range. The packed column is used for the separation of methane, carbon monoxide, carbon dioxide, water and methanol. Retention characteristics for the analysis on the capillary column are presented. The total analysis cycle is 30 minutes.