Search results for "Sulfidation"

Investigation of Solid State Diffusion Processes Involved in the Zinc Oxide Sulfidation Reaction

2016

Sulfidation of undoped and aluminum doped zinc oxide materials has been performed by TGA under a H2S atmosphere in order to evaluate the impact of the doping element on sulfidation reaction kinetics and mechanism. The presence of aluminum seems to slow-down the reaction kinetics. This phenomenon might be explained by a modification of the solid state diffusion processes involved in ZnO sulfidation reaction and the related ZnS outward growth, assuming the presence of aluminum atoms inside ZnO and ZnS phases. In order to determine solid state diffusion mechanisms controlling the reaction kinetics, molecular dynamics simulations were performed using a Coulomb-Buckingham potential. Firstly, the…

Pattern Formation During Dry Corrosion of Metals and Alloys

1987

About corrosion of metals and alloys, many exciting problems are not entirely solved. One of them concerns some morphological features such as, for example, stratified periodic structures that may appear, for example during the oxidation or sulfidation of metals and alloys. In this context, a high temperature corrosion kinetics is interpreted in terms of a bistable chemical system which can oscillate spontaneously if a feedback effect could exist. Some models analyse these patterning from a theoretical point of view. Stability analyses of the uniform standard steady state point out that it can be unstable by bifurcation and give rise to multilayered scales. Some non linearities, peculiar to…

Reactive adsorption of thiophene on Ni/ZnO: role of hydrogen pretreatment and nature of the rate determining step.

2008

Abstract Reactive adsorption of thiophene on reduced and unreduced NiO/ZnO adsorbents was studied by thermal gravimetric analysis and by sulfidation in a fixed bed reactor at 330–375 °C and 10–40 mbar of thiophene in hydrogen. The adsorbents (12 wt% Ni) were prepared by co-precipitation of corresponding nitrates with sodium carbonate followed by calcination at 400 °C. We have found that such solids can react with thiophene without any prior reduction. Metallic Ni, indispensable for thiophene decomposition, is formed in this case in situ upon the contact with thiophene/H 2 reaction mixture. The reduction of NiO/ZnO in H 2 (360 °C, 6 h) results in the formation of Ni–Zn alloyed particles (as …

Sulfidation Mechanism of Pure and Cu-Doped ZnO Nanoparticles at Moderate Temperature: TEM and In Situ XRD Studies

2012

International audience; Sulfidation mechanism of pure and Cu-doped ZnO nanoparticles (Cu0.03Zn0.97O and Cu0.06Zn0.94O) at 250 and 350 degrees C was studied by transmission electron microscopy (TEM) and in situ synchrotron XRD. For nondoped ZnO, we observed by TEM that partial reaction with H2S is accompanied by the formation of voids at the ZnO/ZnS interface. This phenomenon (known as the Kirkendall effect) confirms that sulfidation of nanosized ZnO by gaseous H2S proceeds via the outward growth of ZnS: Zn2+ and O2- are transferred to the external (ZnS/gas) surface, where zinc is combined with sulfur and oxygen reacts with protons yielding H2O. During sulfidation of Cu-doped ZnO, the caviti…

High Temperature Sulfidation of Al-and Mo-Modified 310 Stainless Steel

1997

Le comportement a la sulfuration d'aciers inoxydables 310 modifies (avec differentes quantites de Mo et Al jusqu'a 10 at%) a ete etudie entre 700-900°C sous pressions de soufre egales a 0.01 et 0.1 atm. La cinetique de corrosion de l'acier suit la loi parabolique et diminue quand la quantite de Mo et Al augmente. Les couches formees sur les aciers sont complexes et constituees de deux sous-couches. La couche externe est composee de sulfure de fer (avec du chrome dissous), de (Fe , Ni) 9 S 8 et de sulfures de chromes (Cr 2 S 3 /Cr 3 S 4 avec du fer dissous), tandis que la couche interne est un melange de plusieurs phases: Cr 2 S 3 /Cr 3 S 4 , Fe 1.25 Mo 6 S 77 , MOS 2 , Al 0.55 Mo 2 S 4 et F…

2.8NiO–H1.8Ni0.6(OH)MoO4—Novel nanocomposite material for the reactive adsorption of sulfur-containing molecules at moderate temperature

2011

Abstract It has been found that a poorly crystalline green precipitate that forms in boiling ammonia solution of Ni(NO 3 ) 2 and (NH 4 ) 6 Mo 7 O 24 yields on annealing a Ni-rich material (Ni/Mo = 3.4) containing slit shaped mesopores and exhibiting the BET surface area of 230 m 2 /g. Characterization of the material by TGA, XRD, TEM, SEM, and EXAFS allowed to determine that it is a nanocomposite consisting of Ni–Mo (hydro)oxide layers H 1.8 Ni 0.6 (OH)MoO 4 which are pillared by NiO nanoparticles ( D  = 3 nm). The structure of the layers appears to be similar to that found in the previously described crystalline molybdate (NH 4 )HNi 2 (OH) 2 (MoO 4 ) 2 prepared in the similar conditions. T…

Presentation, Calibration and First Experiments Using a New Thermobalance for Experiments in Sulfur Vapor Atmospheres

2004

Instability and bistability during the growth of a corrosion scale on metals and alloys

1986

This paper summarizes the main results for the interpretation of the self organized corrosion scales observed in oxidation or sulfidation of some metals or alloys. It consists also of a reconsideration of the classical theoretical concepts used in Reactivity of Solids. It proposes new theoretical tools that have been fruitfully utilized in other topics : non linear and coupled processes, stability analysis and bifurcation theory. Some examples are developed, where the corrosion kinetics at high temperature are interpreted in term of chemical bistable system able to oscillate spontaneously and mechanochemical couplings are also taken into account. In according with experimental results, all …

Kinetics of thiophene reactive adsorption on Ni/SiO2 and Ni/ZnO.

2008

Abstract Kinetics of thiophene reactive adsorption on Ni/SiO2 and Ni/ZnO was studied by thermal gravimetric analysis at 280–360 °C under 5–40 mbar of thiophene in H2. In the case of Ni/SiO2 the interaction proceeds in two steps: a rapid surface reaction is followed by a slower bulk transformation into Ni3S2. Maximum Ni conversion depends on reaction conditions and observed conversion profiles can be described by an exponential equation corresponding to a reaction of first order relatively to both sulfidable Ni amount and thiophene. The interaction between Ni/ZnO and thiophene proceeds in a rather different manner. A rapid increase of weight, similar to the first stage observed on Ni/SiO2, i…

Nanocrystalline ZnCO3—A novel sorbent for low-temperature removal of H2S

2013

Abstract The reactivity of a nanocrystalline ZnCO 3 toward H 2 S (0.2 vol% in N 2 /H 2 mixture) at 140–180 °C was characterized by thermal gravimetric analysis and by breakthrough curves measurements. We have found that under used conditions transformation of ZnCO 3 into ZnS is complete and the rate determining step of the sulfidation is the surface reaction. Such behavior is in strike contrast with that of ZnO whose sulfidation is severely limited by diffusion. The higher reactivity of ZnCO 3 in comparison with ZnO is attributed to the different microstructure of ZnS layer formed in these materials after a partial sulfidation. As in ZnO–ZnS transformation the molar volume increases (from 1…