Stimulation Calculation of Desulfurization Mechanisms Dominated by Free Radicals Reactions During Pyrolysis of Thiophenes Under Water Vapor Atmosphere

The desulfurization mechanisms of thiophene and 2-methyl thiophene were investigated by the density functional theory (DFT) during pyrolysis under water vapor atmosphere. All possible reaction pathways of these desulfurization mechanisms were explored at M06-2X/6-311g (d) level. The Multwfn3.0 and VMD1.9.2 programs were used to analyze weak interactions between thiophene compounds and H2O molecule. It can be seen that hydrogen bonds can be formed in the reactions of thiophene sulfurs and H2O. Since H2O molecule can decompose at higher temperature and generate free radicals, such as·H and·OH,, the desulfurization mechanisms of thiophene and 2-methyl thiophene with free radicals need to be further considered. The reaction energy barriers (∆G≠) and reaction energies (∆GP) of thiophene and 2-methyl thiophene with H2O molecule (g) or free radicals (·H and·OH) have been stimulated and calculated in detail. Based on the transition state theory (TST), the rate constants corresponding to these elementary reactions are also calculated, meanwhile the speed and spontaneity of every reaction can be obtained from the aspect of kinetics. Theoretically, it is found that H2O (g) directly attacking C-S bonds of thiophene and 2-methyl thiophene cannot easily generate COS and H2S even at 1200 K in terms of thermodynamics and kinetics. If the desulfurization mechanisms of thiophenes are investigated by free radicals mechanisms under steam atmosphere, their initial energy barriers needing to be overcome significantly reduce. Therefore, desulfurization mechanisms of thiophenes and H2O (g) are the most possibly dominated by radical reactions at higher temperatures and H2S is mainly generated.

Fabrication of Durable Ni–YSZ Hydrogen Electrode for High-Temperature Solid Electrolyzer Cells

Solid oxide electrolyzer cells with an Ni–Fe–yttria-stabilized zirconia (Ni-Fe-YSZ) hydrogen electrode as the cathode, lanthanum strontium ferrite (LSCF)-gadolinia-doped ceria (GDC) air electrode as the anode, and YSZ as the electrolyte were fabricated, and the oxidation protection effect of sacrificial Fe particles was investigated. X-ray diffraction analysis indicated that Ni was protected from oxidation under a water vapor atmosphere by sacrificial Fe. Scanning electron microscopy observations suggested that the Ni particles accumulated in the Ni-YSZ hydrogen electrode, which might have been associated with the partial oxidation of Ni during cell operation at 700 °C in 50% H2O/15% H2/35% Ar atmosphere. No appreciable microstructural changes were observed for the Ni–Fe–YSZ hydrogen electrode. Furthermore, the presence of the sacrificial Fe particles could be responsible for the superior durability of the cell, compared with that of the cell featuring the conventional Ni–YSZ hydrogen electrode.

Oxidation Behavior of Maraging 300 Alloy Exposed to Nitrogen/Water Vapor Atmosphere at 500 °C

Aging heat treatments in maraging steels are fundamental to achieve the excellent mechanical properties required in several industries, i.e., nuclear, automotive, etc. In this research, samples of maraging 300 alloy were aged using a novel procedure that combines different steps with two atmospheres (nitrogen and water vapor) for several hours. The oxidized surface layer was chemical, microstructural and micromechanically characterized. Due to the thermodynamic and kinetic conditions, these gases reacted and change the surface chemistry of this steel producing a thin iron-based oxide layer of a homogeneous thickness of around 500 nm. Within the aforementioned information, porosity and other microstructural defects showed a non-homogeneous oxide, mainly constituted by magnetite, nickel ferrite, cobalt ferrite, and a small amount of hematite in the more external parts of the oxide layer. In this sense, from a chemical point of view, the heat treatment under specific atmosphere allows to induce a thin magnetic layer in a mixture of iron, nickel, and cobalt spinel ferrites. On the other hand, the oxide layer presents an adhesive force 99 mN value that shows the capability for being used for tribological applications under sliding contact tests.

High-Temperature Oxidation Resistance of PDC Coatings in Synthetic Air and Water Vapor Atmospheres

This work is aimed at the development and investigation of the oxidation behavior of ferritic stainless-steel grade AISI 441 and polymer-derived ceramic (PDC) protective coatings. Double-layer coatings of a PDC bond coat below a PDC top coat with glass and ceramic passive fillers’ oxidative resistance were studied at temperatures up to 1000 °C in a flow-through atmosphere of synthetic air and in air saturated with water vapor. Investigation of the oxide products formed at the surface of the samples in synthetic air and water vapor atmospheres, at different temperatures (900, 950, 1000 °C) and exposure times (24, 96 h) was carried out on both uncoated steel and steel coated with selected coatings by scanning electron microscopy (SEM) and X-Ray diffraction (XRD). The Fe, Cr2O3, TiO2, and spinel (Mn,Cr)3O4 phases were identified by XRD on oxidized steel substrates in both atmospheres. In the cases of the coated samples, m- ZrO2, c- ZrO2, YAG, and crystalline phases (Ba(AlSiO4)2–hexacelsian, celsian) were identified. Scratch tests performed on both coating compositions revealed strong adhesion after pyrolysis as well as after oxidation tests in both atmospheres. After testing in the water vapor atmosphere, Cr ions diffused through the bond coat, but no delamination of the coatings was observed.

RESEARCH OF POSSIBILITY OF PROCESSING PETROLEUM COKE WITH INCREASED VOLATILE SUBSTANCES INTO ACTIVATED CARBONS

In present work, study to obtain granulated active carbon based on industrial petroleum coke of the CEL grade (coke with an increased content of volatile substances) produced in delayed coking unit have been conducted. The production of activated carbons was carried out by preliminary carbonization of coke at a temperature of 500-800 °C, followed by activation in a water vapor atmosphere at a temperature of 850-900 °C. In addition, tests were carried out on the effect of impregnation of the initial coke with aqueous solutions of chemical activators (sodium hydroxide, potassium carbonate, phosphoric acid) on the efficiency of heat treatment and characteristics of the porous structure of the resulting sorbent. The use of sodium hydroxide as an activating agent increases the reactivity of the sample, but the microporous structure does not develop. Using potassium carbonate as the activating solution and increasing the carbonization temperature to 800 °C causes an increase in the degree of burning from 28 to 44 %. However, activation of the resulting carbonizates with superheated steam leads to a 97-98 % burn-out of the samples due to a sharp increase in reactivity. It was shown that activated carbon obtained on the base of petroleum coke with an increased content of volatile substances by preliminary impregnation with an aqueous solution of phosphoric acid (concentration 17 wt.%), filtration and drying, followed by carbonization at a temperature of 800 °C in an inert atmosphere and activation in water vapor medium at a temperature of 850-900 °С has a sufficiently high specific surface of micropores (up to 430 m2/g) and other characteristics of the porous structure. Thus, the proposed method can serve as one of the ways to expand the qualified use of petroleum coke.

Catalytic Performances of Cu/MCM-22 Zeolites with Different Cu Loadings in NH3-SCR

The NH3-SCR activities and hydrothermal stabilities of five xCu/MCM-22 zeolites with different Cu loadings (x = 2–10 wt%) prepared by incipient wetness impregnation method were systematically investigated. The physicochemical properties of xCu/MCM-22 zeolites were analyzed by XRD, nitrogen physisorption, ICP-AES, SEM, NH3-TPD, UV-vis, H2-TPR and XPS experiments. The Cu species existing in xCu/MCM-22 are mainly isolated Cu2+, CuOx and unreducible copper species. The concentrations of both isolated Cu2+ and CuOx species in xCu/MCM-22 increase with Cu contents, but the increment of CuOx species is more distinct, especially in high Cu loadings (>4 wt%). NH3-SCR experimental results demonstrated that the activity of xCu/MCM-22 is sensitive to Cu content at low Cu loadings (≤4 wt%). When the Cu loading exceeds 4 wt%, the NH3-SCR activity of xCu/MCM-22 is irrelevant to Cu content due to the severe pore blockage effects caused by aggregated CuOx species. Among the five xCu/MCM-22 zeolites, 4Cu/MCM-22 with moderate Cu content has the best NH3-SCR performance, which displays higher than 80% NOx conversions in a wide temperature window (160–430 °C). Furthermore, the hydrothermal aging experiments (xCu/MCM-22 was treated at 750 °C for 10 h under 10% water vapor atmosphere) illustrated that all the xCu/MCM-22 zeolites exhibit high hydrothermal stability in NH3-SCR reactions.

Bi2O3-Modified Ceramics Based on BaTiO3 Powder Synthesized in Water Vapor

Bi2O3 was investigated in the role of a modifier for BaTiO3 powder synthesized in a water vapor atmosphere at 200 °C and 1.55 MPa. Modification was aimed at increasing the sinterability of the powder as well as improving the structural and dielectric properties of the obtained ceramics. The morphology and phase contents of the synthesized BaTiO3 powder were controlled by the methods of SEM and XRD. Properties of pure and Bi-doped BaTiO3 ceramics were comprehensively studied by XRD, SEM, dielectric spectroscopy, and standard approaches for density and mechanical strength determination. Doping with Bi2O3 favored BaTiO3 ceramic densification and strengthening. The room-temperature dielectric constant and the loss tangent of Bi-doped BaTiO3 were shown to stabilize within the frequency range of 20 Hz to 2 MHz compared to non-doped material. The drop of dielectric constant between room temperature and Curie point was significantly reduced after Bi2O3 addition to BaTiO3. Bi2O3 appeared to be an effective modifier for BaTiO3 ceramics produced from non-stoichiometric powder synthesized in water vapor.