Industrial monitoring of platinoid losses during the oxidation of ammonia in UKL-7 reactors

Platinoid losses are monitored during the oxidation of ammonia in industrial UKL-7 reactors with one- and two-stage catalytic systems. Twelve reactors at OAO Acron and eleven reactors at OAO Nevinnomysskii Azot are inspected. It is established that the losses of platinoids from the first five gauzes in reactors with diameters of 1.70 m and the first three platinoid gauzes in reactors with diameters of 1.93 m upstream of the gas flow are nearly equal with a considerable reduction in losses from subsequent gauzes. The concept of mechanochemical and reduced (to the amount of synthesized nitric acid) mechanochemical platinoid losses that depend on the intensity of the catalytic reaction and the hydrodynamic conditions in the contact reactor is introduced. It is established that the ratio of the mass fractions of platinoid losses from the gauzes of a catalytic system is determined by the diameter of the reactor and the location of gauzes in a stack. Previously unknown thermal losses are thus estimated. It is shown that the dependence of the specific losses of platinoids on the reduced mechanochemical losses obeys a linear law and allows calculations of mechanochemical losses for any UKL-7 reactor. Experimental dependences that relate the fraction of ammonia converted by a platinoid gauze to its location in a catalyst stack and indicate a need to correct the mathematical model used in calculations are revealed. Analysis of mechanochemical losses can reveal features of the service wear of platinoid gauzes in different reactors and help predict the degree and character of catalyst destruction for reactors equipped with efficient new catalytic systems.     

AN EXPERIMENTAL STUDY OF THE PRESSURE DROP IN FLUID FLOWS THROUGH WIRE GAUZES

Catalytic wire gauzes have been used for many years for ammonia oxidation. The flow and transfer properties of stacked gauzes, however, have not been sufficiently examined in the literature. This study presents an experimental program designed to characterize the pressure drops observed across stacked woven and knitted wire gauzes. This work generated an extensive database of measurements and reveals that each gauze requires its own correlation equation. Furthermore, previously published general models were not able to describe all four cases with high accuracy. After surveying the literature, we present some modifications to the models based on our collected experimental results.     

不同氨氮含量对厌氧颗粒污泥理化特性的影响

通过序批式试验,研究了氨氮含量变化对厌氧颗粒污泥去除有机物及氨氮效能的影响,并通过紫外可见光谱（UV-Vis）、三维荧光光谱（EEM）、傅里叶红外光谱（FTIR）对厌氧颗粒污泥的溶解性微生物产物（SMP）、疏松胞外聚合物（LB-EPS）及紧密胞外聚合物（TB-EPS）进行了分析。结果表明,当进水氨氮浓度增加到1000 mg·L^-1时,厌氧颗粒污泥对COD去除率由对照组的94.19%下降至93.33%,其对COD去除影响不明显;但NH₄⁺-N去除率由40.6%降至7.9%,去除效率明显降低。UV-Vis谱图分析表明,LB-EPS与TB-EPS在205～210 nm处出现了吸收峰,表明其中均含有苯环与双键结构,且随着氨氮浓度的增大,吸收带出现了红移。EEM谱图分析表明,随着氨氮浓度的增大,SMP中芳香蛋白吸收峰强度降低,而在E_X/E_M为370～390/420～450 nm处的类胡敏酸吸附峰增强;对于LB-EPS而言,辅酶F₄₂₀吸收峰消失,表明高氨氮浓度对产甲烷菌的活性产生了抑制作用;同时TB-EPS类蛋白荧光峰发生了红移。而由LB-EPS的FTIR谱图可知,氨氮浓度为1000 mg·L^-1时,LB-EPS中存在较多的羧酸。通过利用UV-Vis、FTIR、EEM谱图可对厌氧颗粒污泥的SMP、LB-EPS、TB-EPS进行较为全面的分析,从而为指导厌氧反应器的运行提供科学借鉴。     

The catalytic oxidation of ammonia: influence of water and sulfur on selectivity to nitrogen over promoted copper oxide/alumina catalysts

The CuO/Al₂O₃ system is active for ammonia oxidation to nitrogen and water. The principal by-products are nitrous oxide and nitric oxide. Nitrous oxide levels increase with the addition of various metal oxides to the basic copper oxide/alumina system. Addition of sulfur dioxide to the reaction stream sharply reduces the level of ammonia conversion, but has a beneficial effect on selectivity to nitrogen. Added water vapour has a lesser effect on activity but is equally beneficial in terms of selectivity to nitrogen. The CuO/Al₂O₃ is also active for the selective catalytic reduction of nitric oxide by ammonia, but this reaction is not effected by sulfur dioxide addition. A mechanism for ammonia oxidation to nitrogen is proposed wherein part of the ammonia fed to the catalyst is converted into nitric oxide. A pool of monoatomic surface nitrogen species of varying oxidation states is established. N₂ or N₂O are formed depending upon the average oxidation state of this pool. An abundance of labile lattice oxygen species on the catalyst surface leads to overoxidation and to N₂O formation. On the other hand, reduced lability of surface lattice oxygen species favours a lower average oxidation state for the monoatomic surface nitrogen pool and leads to N₂ formation.     

Combustion Synthesis of Aluminum Nitride Particles and Whiskers

Aluminum nitride (AlN) was produced via the combustion synthesis of loosely packed aluminum powder (pore fraction of ∼0.8) in a graphite reactor that was lined with permeable carbon felt. Almost-complete conversion was achieved with a forced flow of nitrogen for beds 50-150 mm deep (mass of 200-650 g). The product was in the form of a loosely aggregated bed, with regions of distinct morphology, and had a predominantly whisker morphology. Some control over the microstructure was possible by changing the processing parameters. The addition of 5% of ammonia to the nitrogen resulted in a uniform production of whiskers, whereas a 50% solid-phase dilution with AlN favored the production of particles.     

Design composite oxide supported Pt catalyst for catalytic wet air oxidation of ammonia with a high concentration in chloride system

Massive discharge of ammonia nitrogen wastewater not only causes eutrophication of the water body but also has a toxic effect on humans and living things. How to deal with ammonia nitrogen wastewater is a crucial topic for researchers. Here, a novel catalyst of Pt@Ti–Si where platinum was supported on a composite oxide of titanium oxide (TiO₂) and silicon oxide (SiO₂) via a one-pot method was successfully synthesized for catalytic wet air oxidation (CWAO) of ammonia with a high concentration (more than 2000 ppm). Due to the improved specific surface area of SiO₂ and the excellent acid-base resistance of TiO₂, the prepared composite oxide-supported platinum catalyst has excellent catalytic performance and good stability for CWAO with a high concentration of ammonia. At 200 °C and the O₂ pressure of 2 MPa for 2 h, the 1%Pt@Ti10–Si1 catalyst has a 96.32% conversion of 2470 ppm ammonia and 97.15% selectivity to N₂ and has good catalytic performance even after five cycles. Under the same reaction conditions, when the chloride concentration in the system is 3000–10000 ppm, the CWAO reaction can be inhibited at an early stage and promote conversion and selectivity at a later stage. The results show that the catalyst has good tolerance to chloride ions, and the treated ammonia nitrogen wastewater can be used for subsequent biochemical processes. Therefore, the developed novel catalyst in this study is effective for the CWAO of highly concentrated ammonia and has potential industrial application value.     

Selective Catalytic Oxidation (SCO) of Ammonia to Nitrogen over Hydrotalcite Originated Mg–Cu–Fe Mixed Metal Oxides

Abstract  

Mg–Cu–Fe oxide systems, obtained from hydrotalcite-like precursors, were tested as catalysts for the selective catalytic oxidation (SCO) of ammonia. Copper containing catalysts were active in low-temperature SCO processes; however, their selectivity to nitrogen significantly decreased at higher temperatures. The optimum composition of the catalyst to guarantee high activity and selectivity to N₂ was proposed. Temperature-programmed experiments, SCO catalytic tests performed with various contact times and additional tests on the samples in the selective catalytic reduction of NO with ammonia showed that the SCO process over the studied calcined hydrotalcites proceeds according to the internal SCR mechanism and oxidation of ammonia to NO is a rate-determining step in the low-temperature range.     

The mechanism of the poisoning of ammonia synthesis catalysts by oxygenates O2, CO and H2O: an in situ method for active surface determination

The effect of adding an oxygenated poison (O₂, CO or H₂O) to a hydrogen/nitrogen stream producing ammonia over a triply promoted (K₂O, CaO, Al₂O₃) commercial catalyst is not unsurprisingly rapidly to poison the catalyst. However, immediately the oxygenated poison reacts with the catalyst and before total poisoning has occurred, which in these experiments took 10 min, there was an explosive release of ammonia producing concentrations in the gas phase in excess of the equilibrium value. This is thought to be due to a convulsive reorganisation of the surface of the catalyst in forming regions of an oxide overlayer, resulting in the expulsion of the standing surface nitrogen atom coverage as ammonia. However, in contradistinction to the observation of complete poisoning of the triply promoted catalyst shortly after switching the water (2.9%) into the hydrogen/nitrogen stream, when polycrystalline iron was used as the catalyst, after the initial pulse of ammonia was observed, the small quantity of water (2.9%) in the hydrogen/nitrogen stream resulted in an increased rate ( ×3) of ammonia synthesis which declined only slightly over the twenty minute duration of the experiment. The difference in behaviour between the triply promoted catalyst and the polycrystalline iron is thought to be due to the relative ease of reduction of the latter, so that submonolayer quantities of oxide can be stabilised on the surface of the polycrystalline iron. The promoting effect of this oxide overlayer is either structural or electronic; no distinction can be made from these experiments. The technique of injecting either O₂ or CO into a hydrogen/nitrogen stream which is producing ammonia over promoted catalysts in quantities insufficient to cause complete poisoning and measuring the oxygen coverage of the catalyst to a measured decrease in the ammonia synthesis rate, appears to be a ready, in situ method for the determination of the active catalyst area.     

Electrochemical oxidation of ammonia on carbon-supported bi-metallic PtM (M = Ir, Pd, SnOx) nanoparticles

Ammonia electro-oxidation was studied in alkaline solution on carbon-supported Pt and bimetallic Pt_yM_1−y (M = Pd, Ir, SnO_x and y = 70, 50 at.%) nanoparticles. Catalysts were synthesized using the modified polyol method and deposited on carbon, resulting in 20 wt.% of metal loading. Particle size, structure and surface composition of the particles were investigated using TEM, XRD and XPS. Mean size of PtM bi-metallic nanoparticles varied between 2.0 and 4.7 nm, depending on the second metal (M). XRD revealed the structure of all bi-metallic particles to be face-centered cubic and confirmed alloy formation for Pt_yPd_1−y (y = 70, 50 at.%) and Pt₇Ir₃nanoparticles, as well as partial alloying between Pt and SnO_x. Electrochemical behaviour of ammonia on Pt and PtM nanoparticles is comparable to that expected for bulk Pt and PtM alloys. Addition of Pd to Pt at the nanoscale decreased the onset potential of ammonia oxidation if compared to pure platinum nanoparticles; however stability of the catalyst was poor. For Pt₇(SnO_x)₃, current densities were similar to Pt, whereas catalyst stability against deactivation was improved. It is found that carbon supported Pt₇Ir₃ nanoparticles combine good catalytic activity with enhanced stability for ammonia electro-oxidation. Electronic effect generated between two metals in the bimetallic nanoparticles might be responsible for increase in the catalytic activity of Pd- and Ir-containing catalysts, causing weakening of the adsorption strength of poisonous N_ads intermediate.     

Emission of methane, nitrous oxide, and ammonia from dung windrows

Gaseous emissions from livestock waste composting were measured within a project aiming at the determination of the nitrogen balance in biological farming. Gas was collected from windrows of animal waste using gas flux chambers (cover boxes). The gas analysis was performed by a high resolution FT-IR spectrometer. The results showed that ammonia and methane emissions dropped down within two to three weeks, whereas nitrous oxide was emitted mainly in the middle of the composting periods. The mean values of the total emissions per composting period were 57.6 g m⁻² for ammonia, 12.8 g m⁻² for nitrous oxide, and 1346 g m⁻² for methane. The mean ratios of the total gas fluxes related to the carbon dioxide flux were 2.6 10⁻³ for NH₃, 5.9 10⁻⁴ for N₂O and 6.2 10⁻² for CH₄. Both of these factors (total gas flux and mean ratios of total gas fluxes) can serve as indicators to quantify impacts on the environment. This revised version was published online in August 2006 with corrections to the Cover Date.     

Influence of ammonia concentration on anodic deposition of nickel oxide

Nickel oxide was prepared by anodic deposition in a basic solution comprising nickel chloride, ammonium chloride and ammonia. The influence of ammonia was investigated using galvanostatic reduction techniques and cyclic voltammetry (CV). It was found that the oxidization peak potentials shift positively with decreasing ammonia concentration, while the oxidization peak currents firstly increase with decreasing ammonia concentration and then decrease when the ammonia concentration is lower than 1.67 mol L⁻¹. This is mainly attributed to the fact that the equilibrium concentration of Ni(OH)_2(aq) varies with the ammonia concentration. A potential plateau at about 0.75 V was observed in galvanostatic reduction curves for nickel oxide, and the length of the potential plateau in solution with 1.67 mol L⁻¹ ammonia concentration was longer than that in the other solutions, which agreed well with the CV results.     

Modulation of Diverse Procoagulant Venom Activities by Combinations of Platinoid Compounds

Procoagulant snake venoms have been inhibited by the ruthenium containing compounds CORM-2 and RuCl₃ separately, presumably by interacting with critical histidine or other sulfur-containing amino acids on key venom enzymes. However, combinations of these and other platinoid containing compounds could potentially increase, decrease or not affect the procoagulant enzyme function of venom. Thus, the purpose of this investigation was to determine if formulations of platinoid compounds could inhibit venom procoagulant activity and if the formulated compounds interacted to enhance inhibition. Using a human plasma coagulation kinetic model to assess venom activity, six diverse venoms were exposed to various combinations and concentrations of CORM-2, CORM-3, RuCl₃ and carboplatin (a platinum containing compound), with changes in venom activity determined with thrombelastography. The combinations of CORM-2 or CORM-3 with RuCl₃ were found to enhance inhibition significantly, but not in all venoms nor to the same extent. In sharp contrast, carboplatin-antagonized CORM-2 mediated the inhibition of venom activity. These preliminary results support the concept that platinoid compounds may inhibit venom enzymatic activity at the same or different molecular sites and may antagonize inhibition at the same or different sites. Further investigation is warranted to determine if platinoid formulations may serve as potential antivenoms.     

Photocatalytic degradation of ammonia by light expanded clay aggregate (LECA)-coating of TiO2 nanoparticles

Photocatalytic degradation of ammonia on supported TiO₂ nanoparticles was investigated. The TiO₂ nanoparticles used as photocatalyst were coated on light expanded clay aggregate granules (LECA), which is a porous and light weight support. Photocatalytic reaction activity of prepared catalyst was determined by ammonia degradation from water synthetically polluted with ammonia. Experiment results showed significantly high photocatalytic activity for the immobilized catalysts. The ammonia was removed more than 85% within 300 min of the process with optimum calcinations temperature 550 °C and pH 11. Kinetics of the photocatalytic reaction followed a pseudo-first order model. XRF, XRD and SEM analyses revealed a rather uniform coating of TiO₂ on the support. By using floated TiO₂/LECA as a photocatalyst in aqueous solution of NH ₃ ^? , the ammonia was photodegraded into N₂ and H₂ gases, while NO ₂ ^? and NO ₃ ^? were formed at very low concentrations.     

Growth and structural characteristics of perovskite-wurtzite oxide ceramics thin films

Wurtzite ZnO thin films were grown on single-crystal perovskite SrTiO₃(STO) (1 0 0) substrates at various temperatures. The ZnO/STO thin films thus formed exhibit a preferred (1 1 0)-orientation at a growth temperature of 600-700 °C. A high growth temperature enhances not only the (1 1 0)-texture of ZnO/STO thin films but also the crystalline quality of the film. (La_0.7Sr_0.3)MnO₃ (LSMO) thin films were subsequently grown on ZnO(1 1 0)/STO(1 0 0) substrates with various thicknesses, and were polycrystalline. A thicker LSMO film has a stronger (0 0 l)-preferred orientation than the thinner one. The lattice distortion of LSMO decreases as the LSMO thickness increases. Magnetization vs. temperature curves show that both crystalline quality and lattice distortion influence the magnetic properties of LSMO thin films. The physical properties of the manganite oxide can be modulated by forming a heterostructure with wurtzite ZnO.     

Hydrodechlorination of CCl<Subscript>4</Subscript> on Pt–Au/Al<Subscript>2</Subscript>O<Subscript>3</Subscript> Catalysts

A series of Pt/Al₂O₃ catalysts were prepared by the impregnation method and were characterized by TEM, XRD, H₂ and CO chemisorptions, and investigated in the hydrodechlorination of tetrachloromethane. Three Pt-rich, Pt–Au/Al₂O₃ catalysts (Pt₁₀₀, Pt₉₅Au₅ and Pt₉₀Au₁₀) showed a similar metal particle size (~2.5–2.7 nm), so observed changes in the catalytic behavior are ascribed to alloying effect, especially because a considerable degree of Pt–Au mixing was achieved in the bimetallic samples. It appeared that by introducing very small amount of gold (10 at.%) to platinum, the catalytic activity is increased. It is argued that the occurrence of this moderate synergistic effect is associated with a decreased tendency of surface chloriding when platinum is alloyed with gold. Zbigniew Kowalczyk—deceased.     

Fabrication and mechanical response of commingled GF/PET composites

The mechanical properties and the response to mechanical load of continuous glass fiber reinforced polyethylene terephthalate (GF/PET) laminates have been characterized. The laminates were manufactured by compression molding stacks of novel woven and warp knitted fabrics produced from commingled yarns. The laminate quality was examined by means of optical and scanning electron microscopy. Few voids were found and the laminate quality was good. Resin pockets occurred in the woven laminates, originating from the architecture of the woven fabric. The strength of the fiber/matrix interface was poor. Some problems were encountered while manufacturing the laminates. These led to fiber misalignment and consequently resulted in tensile mechanical properties that were slightly lower than expected. Flexural failures all initiated as a result of compression, and it is possible that the compression strength of the matrix material, rather than its tensile strength, might limit the ultimate mechanical performance of the composites. Flexural failures for both materials were very gradual. The warp knitted laminates were stronger and stiffer than the woven laminates. The impact behavior was also investigated; the woven laminates exhibited superior damage tolerance compared with the warp knitted laminates.     

Theoretical Insight into the Nature of Ammonia Adsorption on Vanadia-Based Catalysts for SCR Reaction

Density functional theory (DFT) calculations were carried out on monomeric and oligomeric vanadium oxide clusters to probe the factors leading to the formation of NH₄ species from the adsorption of ammonia. The interaction of ammonia with monomeric vanadium oxide clusters leads to the formation of hydrogen-bonded NH₃ species, with energy changes for ammonia adsorption near -50 kJ/mol. The interaction of ammonia with oligomeric vanadium oxide clusters leads to the formation of bidentate NH_4 species, where the ammonium cation is coordinated between two V=O groups on adjacent vanadium cations. The energy change for ammonia adsorption in this mode is near -100 kJ/mol. Adsorption of ammonia as NH₄ species was not observed when the oligomeric vanadium oxide clusters were reduced by addition of hydrogen atoms, i.e., in clusters where the formal oxidation state of the vanadium cations was 4+. Based on our findings, a model for the generation of Brönsted acidity through the interaction of vanadium oxide oligomers with the titanium oxide support is proposed.     

Establishment and maintenance of an optimal chiral surface in cinchona-modified 1% Pt/Al2O3 for enantioselective hydrogenation of α-keto esters

An optimal chiral surface in the cinchona-modified Pt/Al₂O₃ catalytic system is established for fast enantioselective hydrogenation of ethyl pyruvate. A makeup protocol is used to compensate for the destructive hydrogenation of the chiral modifier, thus maintaining the optimal chiral surface over the course of the hydrogenation reaction. Hydrogenation over the optimal surface (Pt_surface/modifier = 5–12) results in high enantioselectivity (94% ee) under mild conditions (5.8 bar and 17^°C) with high turnover frequency (4 s^-1) and turnover numbers (pyruvate/modifier>28,000, pyruvate/Pt_surface>5,500). This revised version was published online in June 2006 with corrections to the Cover Date.