Hydrotreating activation

Wang X., Clark P. and Oyama S. T., Synthesis characterization and hydrotreating activity of several iron group transition metal phosphides, J. Gated. 208 (2002) pp. 321-331. 

Supported nickel catalysts have been the focus of attention of a number of infrared (IR) spectroscopic studies adopting CO as a surface probe molecule. This research has been motivated by the pronounced hydrotreating activity of the catalysts in processes of industrial importance [1,2]. Results published before 1978, have been critically assessed and compared to results then available on Ni° metal thin films and single crystal surfaces by Sheppard and Nguyen [3]. 

Shu Y, Oyama ST (2005) Synthesis, characterization, and hydrotreating activity of carbon-supported transition metal phosphides. Carbon 43 1517-1532... 

Naphtha desulfurization is conducted in the vapor phase as described for natural gas. Raw naphtha is preheated and vaporized in a separate furnace. If the sulfur content of the naphtha is very high, after Co—Mo hydrotreating, the naphtha is condensed, H2S is stripped out, and the residual H2S is adsorbed on ZnO. The primary reformer operates at conditions similar to those used with natural gas feed. The nickel catalyst, however, requires a promoter such as potassium in order to avoid carbon deposition at the practical levels of steam-to-carbon ratios of 3.5—5.0. Deposition of carbon from hydrocarbons cracking on the particles of the catalyst reduces the activity of the catalyst for the reforming and results in local uneven heating of the reformer tubes because the firing heat is not removed by the reforming reaction. 

Older rerefining units used 2-5 kg/L of activated clay at 40—70°C and higher temperatures in place of TEE to clean the oil (80). More elaborate chemical and hydrotreating of used engine oils without a distillation step has been developed by Phillips Petroleum for processing 40,000 /yr (10 X 10 gal/yr). Establishment of a reflable feedstock supply is a critical consideration for larger rerefining plants. 

Sulfided Mo and Co-Mo catalysts, used in hydrotreating reactions, contain Mo as M0S2. This compound has a layer structure consisting of sandwiches, each of a Mo layer between two S layers. The chemical activity of M0S2 is associated with the edges of the sandwich where the Mo is exposed to the gas phase the basal plane of the anions is... 

Owing largely to research over the last twenty years, the sulfided C0-M0/AI2O3 system is one of the best-characterized industrial catalysts [H. Topsoe, B.S. Clausen and F.E. Massoth, Hydrotreating Catalysis (1996), Springer-Verlag, Berlin]. A combination of methods, such as Mbssbauer spectroscopy, EXAFS, XPS, and infrared spectroscopy, has led to a picture in which the active site of such a catalyst is known in almost atomic detail. 

Due to the water requirement of biocatalytic systems, BDS is typically carried out as a two-phase aqueous-oil process. However, increased sulfur removal rates could be accomplished by using an aqueous-alkane solvent catalytic system [46,203,220,255], The BDS catalytic activity depends on both, the biocatalysts and the nature of the feedstock. It can vary from low activity for crude oil to as high as 60% removal for light gas-oil type feedstocks [27,203,256], or 70% for middle distillates, 90% for diesel, 70% for hydrotreated diesel, and 90% for cracked feedstocks [203,256], The viscosity of the crude oil poses mixing issues in the two-phase oil-water systems however, such issues are minimal for distillate feedstocks, such as diesel or gasoline [257]. 

The term three-phase fluidization, in this chapter, is taken as a system consisting of a gas, liquid, and solid phase, wherein the solid phase is in a non-stationary state, and includes three-phase slurry bubble columns, three-phase fluidized beds, and three-phase flotation columns, but excludes three-phase fixed bed systems. The individual phases in three-phase fluidization systems can be reactants, products, catalysts, or inert. For example, in the hydrotreating of light gas oils, the solid phase is catalyst, and the liquid and gas phases are either reactants or products in the bleaching of paper pulp, the solid phase is both reactant and product, and the gas phase is a reactant while the liquid phase is inert in anaerobic fermentation, the gas phase results from the biological activity, the liquid phase is product, and the solid is either a biological carrier or the microorganism itself. 

We begin with the structure of a noble metal catalyst. The emphasis is on the preparation of rhodium on aluminum oxide and the nature of the metal-support interaction. Next we focus on a promoted surface in a review of potassium on noble metals. This section illustrates how single crystal techniques have been applied to investigate to what extent promoters perturb the surface of a catalyst. The third study deals with the sulfidic cobalt-molybdenum catalysts used in hydrotreating reactions. Here we are concerned with the composition and structure of the catalytically active... 

Figure 16.5 Impact of pretreating severity on the activity of a hydrocracking catalyst temperature required for conversion of a feed hydrotreated to (a) 40 ppm nitrogen, (b) 10ppm nitrogen.

Data from tests at 250,275,300, and 325 C were used to calculate pseudo-first order rate constants for the formation of H2S. These data are expressed on a standard Arriienius plot (Fig. 2) for which the linear least squares coefficient of determination, r, is 0.98. The apparent activation energy calculated from the slope is 28.5 kcal/mol. This result is in excellent agreement with the recent work of Abotsi, who studied the performance of carbon-supported hydrodesulfurization catalysts (10). Using Ambersorb XE-348 carbon lo ed with sulfided ammonium molybdate (3% Mo loading) prepared by the same procedure reported here, Abotsi hydrotreated a coal-derived recycle solvent The apparent activation energy for... 

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