INTEGRATING ALBEMARLE RESOLVE DESULFURIZATION TECHNOLOGY WITH NOVEL PETRO-CANADA PROCESS CONCEPTS IN COMMERCIAL FCCU OPERATIONS

The gasoline and distillate sulfur regulations promulgated throughout the world to reduce tail-pipe emissions are now strongly impacting refinery operations and investments. FCC gasoline is recognized as the principal contributor of sulfur to the gasoline pool and has become the focus for meeting the new specifications. The difficulty in removing sterically hindered sulfur species in the fluid catalytic cracking unit (FCCU) cycle oil drives up the hydrogen and investment costs for treating the distillates. Although installation of pre- and post-treatment facilities is planned by many refiners, other non-capital approaches such as undercutting are being evaluated to meet interim and future sulfur levels. Even when expensive treatment facilities are installed, operating costs can be lowered and the flexibility of the facility increased with improvements in the ability to remove sulfur in the FCCU. In this article, we detail Petro-Canada's experience in integrating Albemarle's RESOLVE sulfur reduction technology with a combination of innovative process ideas. These concepts include heavy naphtha recycle, coprocessing of hydrogen donor feeds, and recycle of light cycle oil (LCO) to a specially designed stripper reactor. Special attention is paid to the interaction of deep FCC feed hydrodesulfurization with the FCC performance. The results demonstrate that very low FCC gasoline sulfur levels can be achieved without significant capital investment through novel approaches to recycle, creative integration of cat feed hydrotreating unit (CFHTU)-FCCU designs and operations, and application of state-of-the-art sulfur reduction additive technology. An added benefit of the RESOLVE 950 sulfur reduction technology is the substantial elimination of sulfur oxides in the FCC flue gas. This has been observed in Petro-Canada operations and numerous other RESOLVE 950 applications around the world.     

Combinatorial chemistry methods for coating development: VI. Correlation of high throughput screening methods with conventional measurement techniques

Combinatorial chemistry has proven to be a valuable tool for the development of new compounds. In the pharmaceutical industry, where combinatorial chemistry began, the approach has been instrumental in the high-speed development of new drugs. Due to the overwhelming success of the combinatorial methodology in the pharmaceutical industry, it has been recently applied to materials development. We have recently developed a combinatorial factory capable of preparing and evaluating on the order of 100 organic clear coatings in a day.

One of the most challenging aspects of the creation of the combinatorial factory was the development of the high throughput screening (HTS) methods for the primary coating properties of interest such as optical clarity, abrasion resistance, adhesion, and weatherability. For each property, an entirely new method was developed that allowed for rapid measurement of these properties on very small samples. This paper describes various aspects of the development of these novel measurement systems including the correlation of the HTS methods with conventional, industry standard measurement methods.     

Platinum-group metal cyclodextrin complexes and their use as command-cure catalysts in silicones

The Command-Cure concept is defined for a curable formulation as one with long work-like at ambient temperature and rapid cure time at elevated temperature. This concept is explored for a curable silicone system, cured via hydrosilylation. CODMCl₂ complexes (COD=1.5-cyclo-octadiene:M=Pt. Pd) are reacted with beta-cyclodextrin (-CD) to make 11 inclusion compounds,M=Pd.2;M=Pt.4. Compounds2 and4 were analyzed by¹H NMR and X-ray powder diffraction. Their catalytic ability was evaluated in a model system as well as a polymeric system that gels upon cure. Surprisingly, the Pd analog2 was a good command-cure catalyst whereas the guest compound CODPdCl₂,1, was not active in the hydrosilylation reaction. The Pt analog,4, was an effective command-cure catalyst while the corresponding guest. CODPtCl₂,3, was too active at low temperature in the hydrosilylation reaction. Additional Pt compounds and one Rh inclusion compound were evaluated as command cure catalysts. These inclusion compounds were: 11 -CD:[CODRhCl]₂,5: 11 -CD:CpPtMe₃,6 (Cp=cyclopentadienyl): 12 -CD:MeCpPtMe₃,7; 12 -CO:CODPtMe₂,8. The effectiveness of4 8 was evaluated in a number of silicone systems.     

Flow distribution in spiral mandrel dies

An analysis of flow of a power law fluid in a spiral mandrel die is presented. The analysis is applied to study the effect of various die design parameters on the flow distribution at the end of the spiral mandrel section. Three variables that have a very strong effect on the flow distribution are the number of grooves, the initial clearance, and the groove helix angle. The distribution is improved by increasing the number of grooves, by using a non-zero initial clearance, and a relatively small helix angle. Two more variables that have a significant effect on the flow distribution are the taper angle and the initial groove depth. The optimum taper angle was found to be between 1 and 3 degrees. The distribution uniformity improves with the initial groove depth, while the pressure drop reduces at the same time.     

Development of a high‐resolution RGBW flexible display using a white organic light‐emitting diode with microcavity structure and that of a side‐roll touch panel

In this study, white organic electroluminescent devices with microcavity structures were developed. A flexible high‐resolution active‐matrix organic light‐emitting diode display with low power consumption using red, green, blue, and white sub‐pixels formed by a color‐filter method was fabricated. In addition, a side‐roll touch display was developed in combination with a capacitive flexible touch screen.     

A mutational analysis of receptor binding sites of interleukin-1{beta}:differences in binding of human interleukin-1{beta} muteins to human and mouse receptors

The 3-D crystal structure of interleukin-1ß(IL-1ß)has been used to define its receptor binding surface by mutationalanalysis. The surface of IL-1ß was probed by site-directedmutagenesis. A total of 27 different IL-1ß muteinswere constructed, purified and analyzed. Receptor binding measurementson mouse and human cell lines were performed to identify receptoraffinities. IL-1ß muteins with modified receptor affinitywere evaluated for structural integrity by CD spectroscopy orX-ray crystallography. Changes in six surface loops, as wellas in the C- and N-termini, yielded muteins with lower bindingaffinities. Two muteins with intact binding affinities showed10- to 100-fold reduced biological activity. The surface regioninvolved in receptor binding constitutes a discontinuous areaof 1000 Å2 formed by discontinuous polypeptide chain stretches.Based on these results, a subdivision into two distinct localareas is proposed. Differences in receptor binding affinitiesfor human and mouse receptors have been observed for some muteins,but not for wild-type IL-1ß. This is the first timea difference in binding affinity of IL-1ß muteinsto human and mouse receptors has been demonstrated     

DYNAMIC TENSIONS IN FINITE OIL DROPLETS

In reacting systems, dynamic interfacial tension (IFT) values above 10-20 mN/m are often encountered. For such high tension values, infinitely long oil droplets will not be realised in spinning drop tensiometry. Hence, Vonnegut's solution will not be strictly valid. The experimentalist is then compelled to use one of the several alternative solution schemes proposed in the literature. We have obtained dynamic IFT data for 0.3125 mM oleic acid in hexadecane contacted with various NaOH solutions by the use of a novel experimental scheme called photo-micropendography. These tension values were then compared with spinning drop tensiometer data calculated by using three alternative solution schemes, namely, Vonnegut's method, the formula of Slattery and Chen and the analysis of Princen el al. The comparison showed that when the droplet's length/width ratio was below 2.5, Vonnegut's formula was severely in error. The solution scheme proposed by Slattery and Chen gave tension values close to those found by photo-micropendography over the entire range of IFT values exhibited by the oleic acid/caustic systems. However, the most consistent and reasonably accurate tension values resulted from the use of Table I in the paper by Princen, Zia and Mason. A simplified computer algorithm has been proposed for calculating dynamic interfacial tensions using the formulas and tables proposed by the latter authors. However, at length/width ratios above 2.5, the agreement between interfacial tensions determined by micropendography and spinning drop data calculated by the use of Vonnegut's solution was quite good.     

Subsoil <Superscript>15</Superscript>N-N<Subscript>2</Subscript>O Concentrations in a Sandy Soil Profile After Application of <Superscript>15</Superscript>N-fertilizer

Studies on emissions of nitrous oxide (N₂O) from agricultural soils mostly focus on fluxes between the soil and the atmosphere or are limited to the atmosphere in the topsoil. However, in soils with shallow water tables, significant N₂O formation may occur closer to the groundwater. The aims of this study were (i) to determine the importance of subsoil N₂O formation in a sandy soil; and (ii) to obtain a quantitative insight in the contribution of subsoil N₂O to the overall losses of N₂O to the environment. We applied ¹⁵N labeled fertilizer at a rate of 5.22 kg ¹⁵N ha⁻¹; 50% as Ca(NO₃)₂ and 50% as NH₄Cl, on a mesic typic Haplaquod seeded with potatoes (Solanum tuberosum L.), and traced soil N₂O concentrations and fluxes over a one-year period. Throughout the year, total N₂O and the amount of ¹⁵N recovered in soil N₂O were highest in the subsoil, with a maximum concentration at 48 cm depth in mid-February of 19900 μl m⁻³ and 24 μg ¹⁵N m⁻³, respectively. The maximum concentration coincided with the highest water-filled pore space of 71%. The cumulative flux of N₂O was 446 g N₂O-N ha⁻¹, the recovery of ¹⁵N in this flux was 0.06%. During the summer, maximum fluxes followed high soil N₂O concentrations. During winter, no such relation was found. We concluded that the formation of N₂O was the highest in the subsoil, largely controlled by water-filled pore space rather than NO₃⁻ concentration or temperature. Although high subsoil N₂O concentrations did not lead to high surface fluxes of N₂O in the winter, artificial draining may lead to high indirect N₂O emissions through supersaturated drainage water.     

Assessing the reliability of ordered categorical scales using kappa-type statistics

Methods for the analysis of reliability of ordered categorical scales are discussed, focussing on the limitation of the single summary-weighted kappa coefficients. A symmetric matrix of kappa-type coefficients is suggested as an alternative. The method is proposed as being suitable for ordinal scale where there is no underlying continuum. Their application is illustrated using two data sets from reliability studies. If, instead, distances between categories can be specified, a weighted mean of the matrix terms can be used as a summary measure. This is equal to a weighted kappa coefficient with squared weights, provided distances between adjacent categories are equal. When a study design corresponds to a one-way random effects model, estimates of precision of kappa-type coefficient, including the coefficients described here, can be obtained using the delta-method, bootstrap resampling by subjects or jack-knifing by subjects. In the case of interobserver reliability studies, where there may be systematic differences between observers, the investigator may wish to generalise to a population of observers and subjects. In this case, jack-knifing by observer and subject is suggested. Empirical comparisons are made between standard error estimates based on the delta-method, on jack-knifing by subjects and a two-way jack-knife by subjects and observers. The results suggest that standard errors based on the delta-method or jack-knifing by subject alone may be overly precise.