XPS investigation on AISI 420 stainless steel corrosion in oil and gas well environments

The corrosion behaviour of 13Cr-martensitic stainless steel (AISI 420) was investigated in CO₂-H₂S-Cl^– environments typical of oil and gas wells under different CO₂ and H₂S partial pressures. The corrosion tests indicated that the AISI 420 steel was highly corrosion resistant to CO₂-induced phenomena (general corrosion and carbonate S.C.C.), while in the H₂S environment a high S.S.C.C. (Sulphide Stress Corrosion Cracking) susceptibility and high corrosion rates were found. Moreover, CO₂ in CO₂-H₂S-Cl^– systems inhibited general corrosion and S.S.C.C. phenomena by favouring the formation of a protective film. By means of X-ray photoelectron spectroscopy (XPS) the chemical nature of the films grown on AISI 420 in different environmental conditions was investigated and the following statements were drawn out:

An XPS and reduction study of PrCoO3

The perovskite-type oxide PrCoO₃ has been studied by means of X-ray photoelectron spectroscopy (XPS), reduction in H₂ and X-ray diffraction. Two types of oxygen were detected: lattice oxygen (binding energy = 528.4 eV) and adsorbed oxygen (binding energy = 530.9 eV). The increase in relative intensity of the peak corresponding to the latter species after reduction of PrCo0₃ to 3e^– per molecule is assigned to the formation of hydroxyl groups. Temperature-programmed reduction (TPR) results showed two reduction steps: to 1 e^– per molecule (Co^3.1 Co²⁺) at 475 to 635 K, and to 3e^– per molecule (Co²¹ Co⁰) at 725 to 815 K. Reduction in the first and second steps occurs according to the contracting sphere model and the nucleation mechanism, respectively. Reduction of Co³⁺ to Co²⁺ causes minimal structural changes in the perovskite. Reduction to 3e^– per molecule yielded Pr₂O₃ and metallic cobalt. After this reduction and reoxidation at 973 K, the perovskite structure was regained. By XPS and TPR it was shown that PrCo0₃ is more easily reducible than LaCo0₃. It is concluded that the cation in the A position of the structure plays a significant role in the bulk and surface properties of LnCo0₃ (Ln, lanthanide elements) oxides.     

Strong dependence on pressure of the performance of a Co/SiO2 catalyst in Fischer–Tropsch slurry reactor synthesis

A 10 wt% Co/SiO₂ catalyst was prepared by the incipient wet-impregnation method and tested in Fischer–Tropsch synthesis in a slurry reactor under conditions approaching industrial practice. The catalyst precursor was investigated by X-ray diffraction (XRD), temperature-programmed reduction (TPR), transmission electron microscopy (TEM) and photoelectron spectroscopy (XPS). The XPS and XRD techniques revealed the presence of a crystalline Co₃O₄ spinel-type phase, while-in addition-TEM and XPS analyses pointed to the formation of another amorphous Co₃O₄ spinel phase, both species interacting weakly with the silica substrate. The influence of total pressure on the conversion, selectivity and stability of the catalyst was studied. Upon increasing the overall pressure from 20 to 40 bar, not only activity increased but also the catalyst are not deactivating. These results are explained in terms of an increase of gases solubility in the solvent, this increment of CO concentration in the liquid phase favours carbonyl species formation and the cobalt particles segregation that implies an increase in the metal surface area.     

o-xylene hydrogenation on supported ruthenium catalysts

The influence of the support on the surface properties and catalytic activity of finely divided ruthenium catalysts is reported. The catalysts were prepared using an organometallic precursor, Ru(acac)₂, and three different supports, Al₂O₃, TiO₂ and SiO₂. In order to study the influence of the particle size on the catalytic performance, the effect of the calcination temperature was also evaluated. XPS suggests that the state of ruthenium is essentially Ru⁰, and chemisorption measurements indicate a decrease in metal dispersion from catalysts supported on Al₂O₃ > TiO₂ > SiO₂. The turnover number in the o-xylene hydrogenation showed significant differences depending on the support and on the particle size. Additionally, an increase in the selectivity to cis-dimethylcyclohexane with particle size was observed. This revised version was published online in July 2006 with corrections to the Cover Date.     

Nucleation of isolated PO4 units on CeO2 driven by high temperatures and the effect on its oxygen storage and release properties

The chemical nature of P-containing species of varying concentration present in CeO₂ after impregnation with (NH₄)₂HPO₄ and calcination at 1273 K, and their effects on the oxygen storage and release (OSR) properties of ceria are reported for the first time. The samples were characterized by different techniques and the results were compared with those recently reported on the same samples but calcined at 873 K. When P-containing ceria solids were calcined at 1273 K, CePO₄ (monazite) was the predominant P-containing species on the surface of ceria, confirming previous studies that showed that monazite exists for those samples in which the surface P loading (P atoms per nm⁻²) is larger than 5.5. For lower surface P concentrations, isolated orthophosphate units are present at the surface and within the subsurface region of the solid. Severe sintering of CeO₂ after calcination at 1273 K resulted in P concentrations >5.5 P atoms·nm⁻² in all samples. Isolated PO₄ units that could initially be present in the samples calcined at 873 K nucleated and CePO₄ was formed when samples were calcined at 1273 K. OSR properties of CeO₂ deteriorated progressively when P loading increased due to the presence of larger crystals of the very stable Ce(III) phase of CePO₄ at the surface of the P-containing ceria solids.     

Input‐output triggered control using ‐stability over finite horizons

This paper investigates stability of nonlinear control systems under intermittent information. Following recent results in the literature, we replace the traditional periodic paradigm, where the up‐to‐date information is transmitted and control laws are executed in a periodic fashion, with the event‐triggered paradigm. Building on the small gain theorem, we develop input–output triggered control algorithms yielding stable closed‐loop systems. In other words, based on the currently available (but outdated) measurements of the outputs and external inputs of a plant, a mechanism triggering when to obtain new measurements and update the control inputs is provided. Depending on the noise in the environment, the developed algorithm yields stable, asymptotically stable, and ‐stable (with bias) closed‐loop systems. Control loops are modeled as interconnections of hybrid systems for which novel results on ‐stability are presented. The prediction of a triggering event is achieved by employing ‐gains over a finite horizon. By resorting to convex programming, a method to compute ‐gains over a finite horizon is devised. Finally, our approach is successfully applied to a trajectory tracking problem for unicycles. Copyright © 2014 John Wiley & Sons, Ltd.     

Modified poly(ethyleneimine) supports for vanadium,molybdenum, and rhenium removal

Summary The solution behaviour of the polycarboxylic acid derived from scleroglucan (sclerox) has been investigated as a function of NaOH concentration and temperature by means of polarimetry and viscosimetry techniques. In comparison to the native polymer, sclerox is less sensitive to degradation at high NaOH concentration (up to NaOH equal to 0.4 M) and thermally more stable. The viscosity data show a normal polyelectrolyte effect and the polymer chains seem to be not stiff. We conclude that at high pH sclerox chains are in a flexible, probably single stranded conformation.     

Use of 3D printing for biofuel production: efficient catalyst for sustainable biodiesel production from wastes

This work deals with the sustainable biodiesel production from low-cost renewable feedstock (waste and non-edible oils) using a heterogeneous catalyst constituted by potassium loaded on an amorphous aluminum silicate naturally occurring as volcanic material (pumice). The main challenge to biodiesel production from low-quality oils (used oils and greases) is the high percentage of free fatty acids (FFAs) and water in the feedstock that causes undesirable side reactions. The catalytic materials studied were tested in the transesterification reaction when using low-quality oils containing a high proportion of free fatty acids (FFAs) and water. Results indicated that the amount of acid and basic sites on the catalytic surface increases upon increasing potassium loading in the catalyst, displaying better performance for biodiesel production. Indeed, the modification of the aluminum silicate substrate upon potassium incorporation results in a catalytic material containing both acidic and basic sites, which are responsible for both triglycerides transesterification and FFA esterification reactions. The studied catalyst not only showed good performance in the biodiesel production reaction but also good tolerance to FFA and water contained in the feedstock for biodiesel production. The catalytic material was microstructured by 3D printing in order to design a catalytic stirring system with high mechanical strength, efficient and reusable. The use of 3D printing in biofuel production is a novelty that brings good solutions for catalyst production.     

Support and precursor effects on the preparation of new heterogenized Pt/Sn catalysts for the selective hydroformylation of 1-pentene

New heterogenized Pt/Sn catalysts selective for the hydroformylation of 1-pentene have been synthesized. The complex cis-[PtCl₂(PPh₃)₂] and the SnCl₂.2H₂O or SnC₂O₄ precursors have been anchored on silica-, magnesia- and alumina-carriers. X-ray photoelectron spectroscopy was used to determine the surface composition and the nature of the anchored species. The hydroformylation activity was found to depend on the type of support and tin precursor used. Only the silica supported catalysts were active in the hydroformylation reaction. Samples prepared from SnCl₂-2H₂O were 200-fold more active than those prepared from SnC₂O₄. Selectivity ton-hexanal of the silica-supported catalyst prepared from SnCl₂-2H₂O was as high as 94.4% at 39.2% conversion of 1-pentene.