Life cycle of hydroprocessing catalysts and total catalyst management

Hydroprocessing catalysts based on Ni, Co, Mo and W are used in various refinery processing applications where several deactivation mechanisms become of importance (coke formation, active phase sintering, metals deposition, poisoning) in the catalyst's life cycle. The life cycle of commercial hydroprocessing catalysts is very complex and includes the catalyst production, sulfidation, use, oxidative regeneration followed by re-sulfidation and reuse or, if reuse is not possible, recycling or disposal. To understand the changes in catalyst properties taking place during a life cycle, the catalyst quality in the different stages can be best monitored by using advanced analytical techniques. The catalyst's life cycle is further complicated by numerous technical, environmental and organizational issues involved. In principle, different companies can be involved in each of the life cycle steps. Leading catalyst manufacturers, together with specialized firms, offer refineries a total catalyst management concept, starting with the purchase of the fresh catalyst and ending with its final recycling or disposal. Total catalyst management includes a broad range of services, ensuring optimal timing during the change-out process, reliable, smooth and safe operations, minimal downtime and maximum catalyst and unit performance.     

Synthesis and characterization of functional gradient copolymers of glycidyl methacrylate and butyl acrylate

Epoxy-functional spontaneous gradient copolymers of glycidyl methacrylate (G) and n-butyl acrylate (B) were synthesized via atom transfer radical polymerization (ATRP). The copolymerization reactions were carried out in toluene solution at 70 °C, using methyl 2-bromopropionate (MBrP) as initiator and copper chloride with N,N,N′,N′′,N′′-pentamethyldiethylenetriamine (PMDETA) as the catalyst system. The kinetic behaviour of the statistical copolymerizations was studied in a wide composition interval with molar fractions of G ranging from 0.10 to 0.75. The synthesized copolymers were characterized by size exclusion chromatography (SEC) and nuclear magnetic resonance (NMR) spectroscopy. ¹H NMR was employed to determine the copolymer composition, demonstrating the gradient character of the copolymers along the main chain in the whole monomer conversion interval. Apart from this, the sequence distribution and stereoregularity were analyzed. These microstructural experimental data agreed well with those calculated from Mayo-Lewis terminal model (MLTM) and a Bernoullian statistic with an isotacticity parameter of σ_G = 0.28 and a coisotacticity parameter of σ = 0.30.     

Influence of a lipid phase on steam jet agglomeration of maltodextrin powders

The contribution of an oil phase to the agglomeration mechanisms of food powders was evaluated. Maltodextrin (DE 10), palm oil stearin and two palm oil oleins (up to 25% dry mass) were used as food models. Granulation runs were carried out in a pilot plant steam jet agglomerator. The powders containing oleins were more cohesive than those with stearin and the presence of oil changed the agglomeration mechanisms. The size increase mechanism of pure maltodextrin powder was controlled by surface plasticization and agglomerates with suitable instant properties were obtained. Small amount of oil degenerated drastically the rate of dispersion in water of the powders and their agglomerates but the average size and the mechanical resistance of the agglomerates increased when the oil content of the powders increased. SEM micrographs of agglomerates indicated that higher lipid content in the powders produced compact granules, favoring sinkability but hindering their disintegration. Agglomeration enhanced considerably the flowability of the particles containing oil. The dispersion behavior of the powders with higher lipid content could be correlated with the Hausner Number. A pre-agglomeration step favored the blend of the more cohesive powders producing larger and more resistant agglomerates.     

Exit effect on hydrodynamics of the internal circulating fluidized bed riser

This is the first time an extensive investigation has been carried out regarding the effects of riser exit geometry on pressure drop and solid behaviour inside the Internal Circulating Fluidized Bed (ICFB) riser, using different riser exit geometries at several operating conditions.The Radioactive Particle-Tracking (RPT) technique was used for solid concentration measurements and solid residence time distribution at the exit zone. Experiments were conducted using Geldart B particles, in the gas superficial velocity range of 4 to 10 m/s. Axial solid hold-up, solid residence time distribution in the exit zone, and the reflux ratio factor k_m, (defined earlier by [E.H. Van der Meer, R.B. Thorpe, J.F. Davidson, Flow patterns in the square cross-section riser of a circulating fluidized bed and the effect of riser exit design, Chem. Eng. Sc. 55 (19) (2000) 4079-4099]), were the main criteria used to investigate the impact of gas-solid separator devices implemented at the ICFB riser exit.Solid residence time distribution results and axial solid hold-up profiles provided clear evidence that the separator device at the riser exit strongly influences the hydrodynamic structure of the ICFB riser. The V-shaped riser exit geometry was found to be the optimum of all the configurations studied.     

A novel MINLP-based representation of the original complex model for predicting gasoline emissions

The Environmental Protection Agency (EPA) introduced Reformulated Gasoline (RFG) requirements as a measure to reduce emissions from gasoline-powered vehicles in certain geographic areas. As part of this effort, the EPA developed empirical models for predicting emissions as a function of gasoline properties and established statutory baseline emissions from a representative set of gasolines. All reformulated gasoline requires certification via this model, known as the Complex Model, and all refiners and importers calculate emissions performance reductions from the statutory baseline gasoline. The current representation of the Complex Model is extremely difficult to implement within refinery operations models or to use in combination with models for designer gasoline. RFG and boutique fuels are key driving forces in the North American refining industry.The RFG models introduce increasingly complex constraints with the major limitation that they are implicitly defined through a series of complicated disjunctions assembled by the EPA in the form of spreadsheets. This implicit and cumbersome representation of the emissions predictive models renders rigorous optimization and sensitivity analysis very difficult to address directly. In this paper, we discuss how the federal government requirements for reformulated gasoline can be restated as a set of mixed-integer nonlinear programming (MINLP) constraints with the aid of disjunctive programming techniques. We illustrate the use of this model with two simple example fuel blending problems.     

Stability of hydrogenated nanodiamonds under extreme ultraviolet irradiation

It is generally accepted that diamond is resistant to a wide spectrum of electromagnetic radiation from the ultraviolet through to the soft X-ray range, which makes it very attractive for the fabrication of diamond-based photodetectors. However the effect of photon radiation on the diamond structure has not yet been examined. In the work presented here, photoelectron spectroscopy has been used to study the graphitization of nanodiamond crystallites exposed to extreme ultraviolet radiation. Under such irradiation, the surface hydrogen groups and graphite species are found to prevent graphitization. The mechanism of radiation-induced nanodiamond graphitization is discussed.     

Evaluating hyperspectral imaging of wetland vegetation as a tool for detecting estuarine nutrient enrichment

Nutrient enrichment and eutrophication are major concerns in many estuarine and wetland ecosystems, and the need is urgent for fast, efficient, and synoptic ways to detect and monitor nutrients in wetlands and other coastal systems across multiple spatial and temporal scales. We integrated three approaches in a multi-disciplinary evaluation of the potential for using hyperspectral imaging as a tool to assess nutrient enrichment and vegetation responses in tidal wetlands. For hyperspectral imaging to be an effective tool, spectral signatures must vary in ways correlated with water nutrient content either directly, or indirectly via such proxies as vegetation responses to elevated nitrogen. Working in Elkhorn Slough, central California, where intensive farming practices generate considerable runoff of fertilizers and pesticides, we looked first for long- and short-term trends among temporally ephemeral point data for nutrients and other water quality characters collected monthly at 18 water sampling stations since 1988. Second, we assessed responses of the dominant wetland plant, Salicornia virginica (common pickleweed) to two fertilizer regimes in 0.25 m² experimental plots, and measured changes in tissue composition (C, H, N), biomass, and spectral responses at leaf and at canopy scales. Third, we used HyMap hyperspectral imagery (126 bands; 15–19 nm spectral resolution; 2.5 m spatial resolution) for a synoptic assessment of the entire wetland ecosystem of Elkhorn Slough. We mapped monospecific Salicornia patches (～ 56–500 m²) on the ground adjacent to the 18 regular water sampling sites, and then located these patches in the hyperspectral imagery to correlate long-term responses of larger patches to water nutrient regimes. These were used as standards for correlating plant canopy spectral responses with nitrogen variation described by the water sampling program. There were consistent positive relationships between nitrogen levels and plant responses in both the field experiment and the landscape analyses. Two spectral indices, the Photochemical Reflectance Index (PRI) and Derivative Chlorophyll Index (DCI), were correlated significantly with water nutrients. We conclude that hyperspectral imagery can be used to detect nutrient enrichment across three spatial and at least two temporal scales, and suggest that more quantitative information could be extracted with further research and a greater understanding of physiological and physical mechanisms linking water chemistry, plant properties and spectral imaging characteristics.     

A simple technique to minimize heat damage to specimens during thermal polymerization of LR White in plastic and gelatin capsules

London Resin (LR) White is a commonly used resin for embedding specimens to be used for immuno- and/or cytochemical studies. In some instances, due to either the properties of the specimen or the availability of various reagents and equipment, it becomes necessary and/or more convenient to polymerize LR White using heat rather than chemical accelerators or UV light. It is known, however, that heat can reduce or even eliminate the anti genicity of the tissue being embedded. It is therefore desirable to polymerize specimens at the lowest temperature possible and to remove the specimens from the oven as soon as polymerization is complete. We have developed a technique that provides a visual marker that allows the exothermic polymerization of LR White to be monitored, thus minimizing the amount of time a specimen must stay in the oven while excluding oxygen from capsules of polymerizing LR White.     

Ni/Pillared Clays as Catalysts for the Selective Catalytic Reduction of Nitrogen Oxides by Propene

Different and alternative methods for the preparation of Ni/pillared clays based on impregnation and encapsulation procedures are reported. Several nickel precursors and metal loadings are considered in order to evaluate their influence on the structural, textural and catalytic properties of the resulting solids. The behaviour of the optimum solids as catalysts has been proved in the selective catalytic reduction of nitrogen oxides with propene, and the relevance of the oxidant nature was checked by changing the composition of the oxidant mixture. Of all the factors studied, the nature of the nickel precursors appears as the most important one, owing to the formation of different active nickel species during the synthesis procedure.     

Logistic Regression Analysis of Customer Satisfaction Data

Variation exists in all processes. Significant work has been done to identify and remove sources of variation in manufacturing processes resulting in large returns for companies. However, business process optimization is an area that has a large potential return for a company. Business processes can be difficult to optimize due to the nature of the output variables associated with them. Business processes tend to have output variables that are binary, nominal or ordinal. Examples of these types of output include whether a particular event occurred, a customer's color preference for a new product and survey questions that assess the extent of the survey respondent's agreement with a particular statement. Output variables that are binary, nominal or ordinal cannot be modeled using ordinary least‐squares regression. Logistic regression is a method used to model data where the output is binary, nominal or ordinal. This article provides a review of logistic regression and demonstrates its use in modeling data from a business process involving customer feedback. Copyright © 2006 John Wiley & Sons, Ltd.