A two-degrees-of-freedom design methodology for interval process systems

This paper presents a two-degrees-of-freedom design methodology for interval process systems to guarantee both the robust stability and performance. For the robust stability issue, the design technique of Chen and Wang (1997) is utilized for searching a robust stabilizing feedback controller. Subsequently, a pre-filter is constructed based on using a frequency domain method to ensure the desired system performance. For illustration, the proposed design methodology is applied to design a robust control system for a second-order unstable plant in the presence of unknown but bounded parameter uncertainties. Simulation results reveal that the proposed scheme is effective and applicable for interval process systems.     

Surface properties and catalytic performance of La1−xSrxCrO3 perovskite-type oxides for CO and C3H6 combustion

Catalytic CO oxidation and C₃H₆ combustion have been studied over La_1−xSr_xCrO₃ (x = 0.0–0.3) oxides prepared by solid-state reaction and characterised by X-ray diffraction (XRD), nitrogen adsorption (BET analysis) and X-ray photoelectron spectroscopy (XPS). The expected orthorhombic perovskite structure of the chromite is observed for all levels of substitution. However, surface segregation of strontium along with a chromium oxidation process, leading to formation of Cr⁶⁺-containing phases, is produced upon increasing x and shown to be detrimental to the catalytic activity. Maximum activity is achieved for the catalyst with x = 0.1 in which mixed oxide formation upon substitution of lanthanum by strontium in the chromite becomes maximised.     

Robust control in presence of parametric uncertainties: Observer-based feedback controller design

This paper proposes a complete procedure for the design of a robust controller for a nonlinear process, taking into account the various issues arising in the design and using the main theoretical results from the Literature about this topic. An extended model is set up, linking performance and robustness to the control law: the H_∞ norm of the extended system in closed loop measures the achievement of the objectives. The result is a state feedback control law which guarantees robust performance. The problem of the design of an observer to estimate the state of the system is also addressed, as the complete knowledge of the state is required to calculate the control action; moreover, the implications of the use of the observer in the design of the controller are pointed out. The methodology is illustrated via simulation of a regulation problem in a continuous stirred tank reactor (CSTR). The application of this methodology to more complex systems will be discussed.     

Thermal and chemical stability of Cu–Zn–Cr-LDHs prepared by accelerated carbonation

Layered double hydroxides Cu_xZn_6 − xCr₂(OH)₁₆(CO₃)·4H₂O with different molar ratios of Cu/Zn/Cr were synthesized by accelerated carbonation. The products were characterized by XRD, SEM, FT-IR and TG-DTG-DSC-MS. The chemical stability was tested by the modified Toxicity Characteristic Leaching Procedure (TCLP). The results showed that the products were the mixture of Cu_xZn_6 − xCr₂(OH)₁₆(CO₃)·4H₂O and (CuZn)₂(CO₃)(OH)₂, with similar thermal behavior. All products were chemically stable with reduced leaching at pH > 6 (Cu²⁺, Zn²⁺) or > 5 (Cr³⁺).     

XPS analysis of wet chemical etching of GaAs(110) by Br2–H2O: comparison of emersion and model experiments

We have applied photoelectron spectroscopy to investigate the surface composition after different surface treatments involving Br₂–H₂O mixtures in order to study wet chemical etching. Emersion experiments from Br₂–H₂O solution are compared with model experiments, in which Br₂–H₂O adsorbate and coadsorbate mixtures react with clean GaAs(110) surfaces. Our results indicate that Ga- and As-bromides formed initially are hydrolyzed to form the respective oxides. Without addition of Br₂, only slight oxidation of the surface takes place. There is an enrichment of Ga due to loss of As both in adsorption as well as in emersion experiments. Since in emersion experiments only a final situation is analyzed, the relative influence of surface reactivity and subsequent solvation effects cannot be distinguished easily, while model experiments give clear information on reaction products formed intermediately. However, model experiments differ in environment and temperature from the real solid–liquid interface. The presented results demonstrate that a combination of emersion and model experiments provide valuable insight into the mechanism of wet chemical etching on a microscopic level.     

The electronic effects of Pr on La1−xPrxNiAl11O19 for CO2 reforming of methane

The CO₂ reforming of CH₄ to synthesis gas by using praseodymium modified hexaaluminate La_1−xPr_xNiAl₁₁O₁₉ (x = 0, 0.2, 0.4, 0.6, 0.8, 1.0) as catalysts was studied. The modifier Pr improved the reducibility and catalytic activity of Ni ions as active component in the hexaaluminate lattices, especially the conversion of CH₄ and CO₂ reached 89.62% and 92.94%, respectively over La_0.8Pr_0.2NiAl₁₁O₁₉. It was found that the addition of Pr can promote the electronic transformation between the Ni ions and the La ions to maintain Ni at a lower valence, which promotes the activation of CH₄.     

A comparative study of different leaching processes for the extraction of Cu,Ni and Co from a complex matte

The extraction behaviors of Cu, Ni and Co from a complex matte under different leaching conditions have been discussed. The synthetic Cu-Ni-Co-Fe-S matte was prepared by melting the pure metals. The matte contained 24.95% Cu, 35.05% Ni, 4.05% Co, 11.45% Fe, 24.5% S, similar composition as is expected to be obtained by reduction smelting of the Pacific Ocean nodules followed by sulphidisation of the alloy. The different phases identified are CuFeS₂, CuS₂, (FeNi)₉S₈, (FeNi)S₂, Ni₉S₈, Ni₃S₂, (CoFeNi)₉S₈ and Co metal. The merits and demerits of each process of dissolution i.e., H₂SO₄/oxygen pressure leaching, atmospheric FeCl₃ leaching, NH₄OH/(NH₄)₂SO₄ pressure leaching are discussed in detail. Out of the three, the H₂SO₄/oxygen pressure leaching process is found to be the most suitable with more than 99% metal extraction efficiency within 1 h of leaching time. From the X-ray diffraction analysis, the different undissolved phases corresponding to different leaching processes have been identified. The metal extraction efficiency decreased in case of atmospheric FeCl₃ leaching and NH₄OH/(NH₄)₂SO₄ pressure leaching processes due to the formation of product layer such as elemental sulfur and goethite, respectively.     

Infrared spectroscopic study and characteristics of SnO2-based thick film for CH3CN detection

The SnO₂/Al₂O₃/Nb₂O₅/ISiO₂ thick film devices were fabricated by screen printing and dipping methods, and their sensing characteristics to CH₃CN gas was investigated. The oxidation products of CH₃CN on the thick film were analyzed by FT-IR using a heatable gas cell. The IR results showed that the products formed by oxidation of CH₃CN at 300 ‡C on the SnO₂/Al₂/Nb₂O₅ thick film without SiO₂ were mainly CO₂, H₂O, and NH₃, while on the SnO₂/Al₂O₃/Nb₂O₅/SiO₂ thick film products such as CO₂, H₂O, N₂O, HNO₃, and HNO₂ were observed. The thick film devices containing SiO₂ showed high selectivity and negative sensitivity to CH₃CN due to the presence of nitrogen compounds produced by oxidation of CH₃CN. Optimum amount of Nb₂O₅ and operating temperature were 1. 0 wt% and 300 ‡C, respectively.     

iso-Octane partial oxidation over Ni-Sn/Ce0.75Zr0.25O2 catalysts

In this study, Ni/Ce_0.75Zr_0.25O₂ catalyst was doped with different amounts of Sn by co-impregnation method. The catalysts were characterized by BET, H₂ chemisorption, XRD, TPR, TEM, XPS and tested for iso-octane partial oxidation (iC8POX) to H₂ in the temperature range of 400–800 °C at atmospheric pressure. The results showed that most of Sn species were present on the surface of Ni particles and did not modify the reducibility of the support. Addition of a small amount of Sn (<0.5 wt.%) lowered the catalytic activity for iso-octane partial oxidation by less than 5% while the extent of carbon deposition was decreased by more than 50%. However, Sn loadings higher than 1 wt.% caused a massive drop in catalytic activity. This indicates that as long as the Ni surface is only partially covered with Sn species, the active sites for the partial oxidation of iso-octane remain intact, while the surface site ensembles required for carbon formation are blocked.     

The Sulfur and Water Resistance of Modified Washcoated Zeolite-Exchanged Monolith Catalysts for SCR of NOx with Propane

The method of preparation of modified Cu-substituted zeolite DeNOx catalysts washcoated on monolith ceramics has been developed. Non-modified and modified monolith catalysts were tested in DeNOx reaction with propane. It was shown that the catalyst modified by cerium and containing titania together with H-ZSM-5 and Al₂O₃ in the washcoating layer demonstrates high level of activity, and its resistance during multiple cycles of poisoning by sulfur compounds and water at 400 and 500°C is also high.     

Adsorption of NO and NO2 on ceria–zirconia of composition Ce0.69Zr0.31O2: A DRIFTS study

In this study, the nature of surface intermediates generated by adsorption of NO and NO₂ on a commercial ceria–zirconia powder of composition Ce_0.69Zr_0.31O₂ was investigated using Diffuse Reflectance Infrared Fourier Transform Spectroscopy (DRIFTS). The conditions of occurrence of the main adsorbed species, i.e. nitrites and nitrates, are studied semi-quantitatively as a function of catalyst pre-treatment and/or type of adsorbed NO_x molecule. On the partially reduced ceria–zirconia, the primary role of NO_x is to re-oxidize the surface via adsorption/decomposition on reduced sites. By contrast, the formation of nitrites and nitrates readily occurs on oxidized surfaces, the latter kind of species being strongly promoted in the case of NO₂ adsorption only.     

La(1−x)SrxCo1−yFeyO3 perovskites prepared by sol–gel method: Characterization and relationships with catalytic properties for total oxidation of toluene

La_(1−x)Sr_xCo_(1−y)Fe_yO₃ samples have been prepared by sol–gel method using EDTA and citric acid as complexing agents. For the first time, Raman mappings were achieved on this type of samples especially to look for traces of Co₃O₄ that can be present as additional phase and not detect by XRD. The prepared samples were pure perovskites with good structural homogeneity. All these perovskites were very active for total oxidation of toluene above 200 °C. The ageing procedure used indicated good thermal stability of the samples. A strong improvement of catalytic properties was obtained substituting 30% of La³⁺ by Sr²⁺ cations and a slight additional improvement was observed substituting 20% of cobalt by iron. Hence, the optimized composition was La_0.7Sr_0.3Co_0.8Fe_0.2O₃. The samples were also characterized by BET measurements, SEM and XRD techniques. Iron oxidation states were determined by Mössbauer spectroscopy. Cobalt oxidation states and the amount of O⁻ electrophilic species were analyzed from XPS achieved after treatment without re-exposition to ambient air. Textural characterization revealed a strong increase in the specific surface area and a complete change of the shape of primary particles substituting La³⁺ by Sr²⁺. The strong lowering of the temperature at conversion 20% for the La_0.7Sr_0.3Co_(1−y)Fe_yO₃ samples can be explained by these changes. X photoelectron spectra obtained with our procedure evidenced very high amount of O⁻ electrophilic species for the La_0.7Sr_0.3Co_(1−y)Fe_yO₃ samples. These species able to activate hydrocarbons could be the active sites. The partial substitution of cobalt by iron has only a limited effect on the textural properties and the amount of O⁻ species. However, Raman spectroscopy revealed a strong dynamic structural distortion by Jahn–Teller effect and Mössbauer spectroscopy evidenced the presence of Fe⁴⁺ cations in the iron containing samples. These structural modifications could improve the reactivity of the active sites explaining the better specific activity rate of the La_0.7Sr_0.3Co_0.8Fe_0.2O₃ sample. Finally, an additional improvement of catalytic properties was obtained by the addition of 5% of cobalt cations in the solution of preparation. As evidenced by Raman mappings and TEM images, this method of preparation allowed to well-dispersed small Co₃O₄ particles that are very efficient for total oxidation of toluene with good thermal stability contrary to bulk Co₃O₄.     

The Oxidative Polycondensation of Benzylidene-4′-hydroxyanilene using Air O<Subscript>2</Subscript>, NaOCl and H<Subscript>2</Subscript>O<Subscript>2</Subscript>: Synthesis and Characterization

In this work, the oxidative polycondensation reaction conditions of benzylidene-4′-hydroxyanilene (B-4′-HA) were studied using oxidants such as air O₂, H₂O₂ and NaOCl in an aqueous alkaline medium between 40 and 95 ^○C. Oligo-benzylidene-4′-hydroxyanilene was characterized by ¹H-NMR, FT-IR, UV-Vis, size exclusion chromatography (SEC) and elemental analysis techniques. The solubility of oligomer using organic solvents such as DMF, THF, DMSO, methanol, ethanol, CHCl₃, CCl₄, toluene, acetonitrile, ethyl acetate was investigated. According to air O₂ oxidant (flow rate 8.5 L/h), the conversion of B-4′-HA was 82.0% in optimum conditions such as [B-4′-HA]₀=[KOH]₀=0.1015 mol/L at 50 ^○C for 25 h. According to the SEC analysis, the number-average molecular weight (M_n), weight-average molecular weight (M_w) and polydispersity index (PDI) values of O-B-4′-HA were found to be 1852 g mol⁻¹, 3101 g mol⁻¹ and 1.675; 2123 g mol⁻¹, 4073 g mol⁻¹ and 1.919; 2155 g mol⁻¹, 4164 g mol⁻¹ and 1.932, using air oxygen, NaOCl and H₂O₂ oxidants, respectively. Also, Thermo gravimetric analysis (TGA) showed oligo-benzylidene-4′-hydroxyanilene to be unstable against thermo-oxidative decomposition. The weight loss of O-B-4′-HA was found to be 95.87% at 1000 ^○C.     

Structure and magnetic properties of Fe1−xCox nanowires in self-assembled arrays

Fe_1−xCo_x nanowires in self-assembled arrays with varying compositions were produced by the template-assisted pulsed electrochemical deposition method. The structural and magnetic properties of the arrays were investigated using several experimental techniques. TEM analyses indicated that the nanowires were regular, uniform, 8 μm in length and 50 nm in diameter. The results of X-ray diffraction indicated that the body-centered-cubic (bcc) (α), face-centered-cubic (fcc) (γ), and hexagonal-close-packed (hcp) () Fe–Co phases appeared in different compositions. Magnetic measurements showed that the coercivity and squareness of the hysteresis loops of the Fe_1−xCo_x changed with their compositions, which may be attributable to shape anisotropy. The room temperature ⁵⁷Fe Mössbauer spectra of the arrays of the Fe_1−xCo_x nanowires revealed strong shape anisotropy.     

Effects of preparation methods on the oxygen nonstoichiometry, B-site cation valences and catalytic efficiency of perovskite La0.6Sr0.4Co0.2Fe0.8O3−δ

La_0.6Sr_0.4Co_0.2Fe_0.8O_3−δ (LSCF) powders were synthesized respectively by an EDTA (ethylenediaminetetraacetic acid)–Citrate sol–gel process and a low-temperature auto-combustion process. The samples were characterized by XRD, SEM, BET, TGA and instant temperature analysis. The iodometric titration was used to determine the average valence of Co and Fe ions and the oxygen nonstoichiometry of the prepare powders. The catalytic properties of the synthesized powders were investigated by the hydrogen peroxide catalytic decomposition. Pure-perovskite structure was formed by both synthesis methods. The oxygen nonstoichiometry of the samples prepared by the auto-combustion process is larger than that by the sol–gel process. The catalytic activities of the powders from two synthesis processes also differed largely due to the different oxygen nonstoichiometry, surface area and crystalline sizes.     

Preparation and characterization of RuO<Subscript>2</Subscript> · <Emphasis Type="Italic">x</Emphasis>H<Subscript>2</Subscript>O/carbon aerogel composites for supercapacitors

A series of RuO₂ · xH₂O/carbon aerogel (CA) composite electrode materials was prepared by a chemical precipitation method. Ultrasonication was used to accelerate the chemical reaction and improve the dispersion of RuO₂ · xH₂O particles on the surface and the pores of the aerogel. The structure and morphology of the as-prepared composite were characterized by N₂ adsorption isotherm, X-ray diffraction (XRD), and field emission-scanning electron microscopy (FE-SEM). The results showed that the CA had a pearly network structure and the composites had a relatively high specific surface area and mesopore volume. The electrochemical performance of the composite electrodes was studied by cyclic voltammetry, galvanostatic charge/discharge measurements and electrochemical impedance measurements. The results indicated a substantial increase in the specific capacitance of the composite. Moreover, the utilization efficiency of RuO₂ · xH₂O was greatly improved by loading it on the conductive and porous CA due to a significant improvement in the inter-particle electronic conductivity and the extensive mesoporous network of the composites.     

Catalytic activity of (CaO)1−x(ZnO)x solids for the N2O decomposition: relation with photoluminescence

(CaO)_1–x (ZnO) _x mixed oxides (x=0–1), heated at 1423 K under atmospheric conditions, were checked for their catalytic activity in the N₂O decomposition in the temperature range of 450–650°C. Although the catalytic activity was measured in the dark, it was found to be linearly related with the photoluminescence intensity of the catalysts.     

Catalytic reduction of NH4NO3 by NO: Effects of solid acids and implications for low temperature DeNOx processes

Ammonium nitrate is thermally stable below 250 °C and could potentially deactivate low temperature NO_x reduction catalysts by blocking active sites. It is shown that NO reduces neat NH₄NO₃ above its 170 °C melting point, while acidic solids catalyze this reaction even at temperatures below 100 °C. NO₂, a product of the reduction, can dimerize and then dissociate in molten NH₄NO₃ to NO⁺ + NO₃⁻, and may be stabilized within the melt as either an adduct or as HNO₂ formed from the hydrolysis of NO⁺ or N₂O₄. The other product of reduction, NH₄NO₂, readily decomposes at ≤100 °C to N₂ and H₂O, the desired end products of DeNO_x catalysis. A mechanism for the acid catalyzed reduction of NH₄NO₃ by NO is proposed, with HNO₃ as an intermediate. These findings indicate that the use of acidic catalysts or promoters in DeNO_x systems could help mitigate catalyst deactivation at low operating temperatures (<150 °C).     

High temperature SrCe0.9Eu0.1O3−δ proton conducting membrane reactor for H2 production using the water–gas shift reaction

The water–gas shift (WGS) reaction is used to shift the CO/H₂ ratio prior to Fischer–Tropsch synthesis and/or to increase H₂ yield. A WGS membrane reactor was developed using a mixed protonic–electronic conducting SrCe_0.9Eu_0.1O_3−δ membrane coated on a Ni–SrCeO_3−δ support. The membrane reactor overcomes the thermodynamic equilibrium limitations. A 46% increase in CO conversion and total H₂ yield was achieved at 900 °C under 3% CO and 6% H₂O, resulting in a 92% single pass H₂ production yield and 32% single pass yield of pure permeated H₂.     

Direct formation of H2O2 from H2 and O2 and decomposition/hydrogenation of H2O2 in aqueous acidic reaction medium over halide-containing Pd/SiO2 catalytic system

Formation of H₂O₂ from H₂ and O₂ and decomposition/hydrogenation of H₂O₂ have been studied in aqueous acidic medium over Pd/SiO₂ catalyst in presence of different halide ions (viz. F⁻, Cl⁻ and Br⁻). The halide ions were introduced in the catalytic system via incorporating them in the catalyst or by adding into the reaction medium. The nature of the halide ions present in the catalytic system showed profound influence on the H₂O₂ formation selectivity in the H₂ to H₂O₂ oxidation over the catalyst. The H₂O₂ destruction via catalytic decomposition and by hydrogenation (in presence of hydrogen) was also found to be strongly dependent upon the nature of the halide ions present in the catalytic system. Among the different halides, Br⁻ was found to selectivity promote the conversion of H₂ to H₂O₂ by significantly reducing the H₂O₂ decomposition and hydrogenation over the catalyst. The other halides, on the other hand, showed a negative influence on the H₂O₂ formation by promoting the H₂ combustion to water and/or by increasing the rate of decomposition/hydrogenation of H₂O₂ over the catalyst. An optimum concentration of Br⁻ ions in the reaction medium or in the catalyst was found to be crucial for obtaining the higher H₂O₂ yield in the direct synthesis.