Hydrocracker Performance Optimization and Catalyst Remaining Life Assessment: Methodology and Case Studies

Hydrocracking has assumed immense importance in present day refining due to stringent environmental regulations for improvement in the quality of fuels and lubes. The hydrocracker units need to be operated optimally to sustain refinery profitability. An integrated methodology has been developed through a combination of a pilot plant and process model for better prediction and monitoring of the performance of commercial hydrocracking units. Three case studies on performance monitoring and optimization, catalyst remaining life assessment and its optimum utilization, and selection of a new catalyst system for commercial hydrocracker units are presented in this article to demonstrate the efficacy of the approach. The studies have led to significant benefits to refineries.     

Electrical conductivity of carbon black and carbon fibre filled silicone rubber composites

Electrically conductive silicone rubber composites have been prepared through incorporation of conductive acetylene black and short carbon fibre (SCF). The percolation limit for the attainment of high conductivity is found to be relatively less for silicone rubber based composites compared to EPDM or NBR based composites reported earlier. Percolation limit is found to be lower for SCF-filled systems (7.5 phr) compared to black-filled ones (14 phr). Both black- and SCF-filled systems exhibit an increase in resistivity with the increase in temperature (PCT effect). This PCT effect may be explained in terms of differences in the thermal expansion between the rubber matrix and the conductive filler. However, resistivity-versus-temperature plots are not identical during the heating-cooling cycle, leading to some hysteresis and electrical set. The current-voltage relationship is linear (Ohmic in nature) at room temperature but becomes non-linear (non-Ohmic) at elevated temperatures. The resistivity of these composites is measured under different conditions such as on applying pressure and being subjected to different mechanical stress and strain over the specimens. An effort has been made to correlate the effect of different parameters on electrical resistivity with the change in the conductive network structure under different conditions.     

A Review on Pineapple Leaf Fibers,Sisal Fibers and Their Biocomposites

Summary: The use of lignocellulosic fibers, pineapple leaf fiber (PALF) and sisal as reinforcements in thermoplastic and thermosetting resins for developing low cost and lightweight composites is an emerging field of research in polymer science and technology. Although, these biofibers have several advantages, such as low densities, low cost, nonabrasive nature, high filling level possible, low energy consumption, high specific properties, biodegradability, etc., over synthetic fibers, the absorption of moisture by untreated biofibers, poor wettability, and insufficient adhesion between the polymer matrix and fiber deteriorate the mechanical properties of composites made up of these biofibers. Therefore, the modification of these fibers is a key area of research at present to obtain optimum fiber‐matrix properties. This review article is concerned with the structure, composition and properties of PALF and sisal, the chemical modifications of these fibers and PALF/sisal‐reinforced thermosets, thermoplastics, rubber, cement, hybrids and biocomposites.

Scanning electron micrograph of tensile fractured surface of alkali treated sisal fiber (magnification ×500).     

Flexible free-standing carbon nanotube films for model lithium-ion batteries

A comparative study of conductive, free-standing, binder-free flexible films made from three different types of commercial carbon nanotubes (CNTs), i.e., single-wall, double-wall, and multi-wall was carried out. The conductive CNT films were prepared by adding the CNTs to the starting dispersion of carbon black and Triton X-100, followed by a vacuum filtration technique. These films have been characterized as model free-standing, binder-free electrodes for flexible lithium-ion batteries. Our experiments revealed that films based on multi-wall CNTs (MWCNTs) are much better than single-wall and double-wall CNTs films in terms of their electrochemical performance. The flexible MWCNT electrodes show stable cycling behavior and allow up to a 10 C-rate.     

A study on the effects of chaotic mixer design and operating conditions on morphology development in immiscible polymer systems

Self‐similar mixing structures, a novel feature of chaotic mixing, were generated in this study as precursor to an array of mixing microstructures, such as nested layers, elongated fibrils, droplets and their combinations in the blending of two immiscible polymers, polypropylene (PP) and polyamide‐6 (PA6). Simulations based on Newtonian flow model were used to compute Poincaré maps and stretching distribution as the tools for investigation of the effect of shear gap and chaotic mixing parameter, such as angular displacement per period (θ) of rotors, on the degree of mixing and morphology development in a batch chaotic mixing device. It was found that a value of θ = 1440° provided the conditions for fastest conversion of the PP‐phase into droplets for the same total strain. A 25% reduction in shear gap from 0.0127 m to 0.0095 m gave rise to much more uniform mixing of the components and led to faster conversion of the PP‐phase into droplets for the same value of θ and the same total strain. A very large fraction (>90%) of the droplets generated fell below the equilibrium size and were found to be much smaller than those produced by twin‐screw extrusion method. Polym. Eng. Sci. 44:407–422, 2004. © 2004 Society of Plastics Engineers.     

Removal of fat from Cow's milk decreases the vitamin E contents of the resulting dairy products

The present study was undertaken to determine whether decreases in fat contents result in lower vitamin E contents. Milk samples of varying fat contents (half and half, whole milk, reduced-fat milk low-fat milk, and nonfat milk) were obtained from a local dairy on six different occasions, α-locopherol was the major form of vitamin E (>85%); γ-tocopherol and α-tocotrienol were present to a lesser extent. As the fat contents of milk products decreased from 11 to 0.3%, the vitamin E contents decreased. For example, raw milk as compared to nonfat milk had both higher α-tocopherol contents (45.5+-4.6 vs. 4.5±0.5 μg/100 g; P<-0.0001) and higher total lipids ( 3.46±0.49 vs. 0.30±0.07 g/100 g; P≤0.0001). Vitamin E, cholesterol, and total lipids increased as cream was added back to nonfat milk during production. For every 1 mg cholesterol increase, there was an increase of approximately 4 μg of α-tocopherol; for every 1 g total lipids increase, the α-tocopherol content increased by 17 μg. These data demonstrate that removal of milk fat markedly decreases the vitamin E content of various milk products     

Effects of organic nitrogen compounds on hydrotreating and hydrocracking reactions

A major issue encountered in hydrotreating and hydrocracking reactions, as in many others fixed bed catalytic processes, is the decrease of catalytic activity with time on stream. The organic nitrogen compounds act as temporary poisons in hydroprocessing catalysts besides being coke precursors. The inhibiting effects of nitrogen compounds present in crude oil have been studied on SRGO hydrotreating reactions and VGO hydrocracking reactions. The results show that selective removal of nitrogen by adsorption using silica and alumina in varying proportions, would not only increase the HDS catalyst activity by more than 60%, but would also reduce hydrogen consumption. This step of nitrogen removal can be installed additionally in the upstream of an existing SRGO HDS reactor to achieve higher desulphurization or can be designed with the grass roots units.

The inhibition effects of nitrogen on VGO hydrocracking have been studied at different temperatures and the reaction has been found to be highly non-linear in nature and the conversion rapidly drops and the slope becomes less steep as the nitrogen level increases. At higher reaction temperature, the drop in activity or conversion with feed nitrogen is less than that in lower temperatures due to the higher rate of desorption of nitrogen compounds at elevated temperatures. The drop in conversion with nitrogen compounds present in VGO indicates the presence of organo nitrogen compounds having higher basicity compared to the nitrogen compounds by pyridine doping. The hysteresis exists in adsorption/desorption of nitrogen compounds and it indicates that desorption is a very slow process. With the increase of nitrogen compounds in the feed, the conversion drops rapidly and it takes long time to reach an equilibrium value. Similarly, with the step increase in reactor temperature, nitrogen desorption takes place at a slow rate and the conversion level comes to an equilibrium value after 8 days.

The observed effects of nitrogen inhibition on SRGO hydrotreating and VGO hydrocracking conversion are explained reasonably well by kinetic models.     

Parameterized Domination in Circle Graphs

A circle graph is the intersection graph of a set of chords in a circle. Keil [Discrete Appl. Math., 42(1):51–63, 1993] proved that Dominating Set, Connected Dominating Set, and Total Dominating Set are NP-complete in circle graphs. To the best of our knowledge, nothing was known about the parameterized complexity of these problems in circle graphs. In this paper we prove the following results, which contribute in this direction:

• Dominating Set, Independent Dominating Set, Connected Dominating Set, Total Dominating Set, and Acyclic Dominating Set are W[1]-hard in circle graphs, parameterized by the size of the solution.
• Whereas both Connected Dominating Set and Acyclic Dominating Set are W[1]-hard in circle graphs, it turns out that Connected Acyclic Dominating Set is polynomial-time solvable in circle graphs.
• If T is a given tree, deciding whether a circle graph G has a dominating set inducing a graph isomorphic to T is NP-complete when T is in the input, and FPT when parameterized by t=|V(T)|. We prove that the FPT algorithm runs in subexponential time, namely $2^{\mathcal{O}(t \cdot\frac{\log\log t}{\log t})} \cdot n^{\mathcal{O}(1)}$ , where n=|V(G)|.

     

Data Reconciliation on the Complex Hydraulic System of Canal de Provence

A data reconciliation module, based on the measurements from the hydraulic network, has been recently developed and implemented in the supervisory system of the Société du Canal de Provence (SCP). The software has initially been used daily to check the measured flow on the main canal. The data reconciliation occurs just after the measurement process. The measurement network on the hydraulic system includes many sensors subject to failure or deviation and is spread over a huge area. In addition, discharge and volume measurements in open-channel hydraulic networks are characterized by large uncertainties. The objective of the data reconciliation is to take advantage of information redundancy on a system to make a cross-check of real-time measurements. By using this information redundancy, a data reconciliation module allows detection of inconsistent measurements and measurement deviations and provides corrected values whether the initial measurements are valid, biased, or invalid. A derived consequence is better scheduling of the maintenance of sensors. The results are corrected values for measured variables and proposed values for nonmeasured quantities. A statistical analysis of the results is performed. This analysis allows evaluation of the uncertainties attached to the estimated flows and volume values. It allows also detecting invalid measurements and drift of sensors and making decisions about which maintenance operations to perform.