Liquid phases petroleum

Kombi [Kombinations-Verfahren] A liquid-phase petroleum hydrogenation process which combined hydrogenation with hydrorefining. The catalyst contained molybdenum and tungsten on an aluminosilicate. Developed by BASF. 

Liquid phase chromatography can use a supercritical fluid as an eluent. The solvent evaporates on leaving the column and allows detection by FID. At present, there are few instances in the petroleum industry using the supercritical fluid technique. 

The properties of the solids most commonly encountered are tabulated. An important problem arises for petroleum fractions because data for the freezing point and enthalpy of fusion are very scarce. The MEK (methyl ethyl ketone) process utilizes the solvent s property that increases the partial fugacity of the paraffins in the liquid phase and thus favors their crystallization. The calculations for crystallization are sensitive and it is usually necessary to revert to experimental measurement. 

Ethjlben ne Synthesis. The synthesis of ethylbenzene for styrene production is another process in which ZSM-5 catalysts are employed. Although some ethylbenzene is obtained direcdy from petroleum, about 90% is synthetic. In earlier processes, benzene was alkylated with high purity ethylene in liquid-phase slurry reactors with promoted AlCl catalysts or the vapor-phase reaction of benzene with a dilute ethylene-containing feedstock with a BF catalyst supported on alumina. Both of these catalysts are corrosive and their handling presents problems. 

The effect of physical processes on reactor performance is more complex than for two-phase systems because both gas-liquid and liquid-solid interphase transport effects may be coupled with the intrinsic rate. The most common types of three-phase reactors are the slurry and trickle-bed reactors. These have found wide applications in the petroleum industry. A slurry reactor is a multi-phase flow reactor in which the reactant gas is bubbled through a solution containing solid catalyst particles. The reactor may operate continuously as a steady flow system with respect to both gas and liquid phases. Alternatively, a fixed charge of liquid is initially added to the stirred vessel, and the gas is continuously added such that the reactor is batch with respect to the liquid phase. This method is used in some hydrogenation reactions such as hydrogenation of oils in a slurry of nickel catalyst particles. Figure 4-15 shows a slurry-type reactor used for polymerization of ethylene in a sluiTy of solid catalyst particles in a solvent of cyclohexane. 

In most applieations, the reaetion oeeurs between a dissolved gas and a liquid-phase reaetant in the presenee of a solid eatalyst. In some eases, the liquid is an inert medium and the reaetion takes plaee between the dissolved gases at the solid surfaee. These reaetors have many diverse applieations in eatalytie proeesses and are used extensively in the ehemieal industry. Triekle-bed reaetors have been developed by the petroleum industry for hydrodesulfurization, hydroeraeking, and hydrotreating of various petroleum fraetions of relatively high boiling point. Under reaetion eonditions, the hydroearbon feed is frequently a vapor-liquid mixture that reaets at liquid hourly spaee veloeities (LHSV in volume of fresh feed, as liquid/volume of bed, hr) in the... 

Homogeneous reactions are those in which the reactants, products, and any catalysts used form one continuous phase (gaseous or liquid). Homogeneous gas phase reactors are almost always operated continuously, whereas liquid phase reactors may be batch or continuous. Tubular (pipeline) reactors arc normally used for homogeneous gas phase reactions (e.g., in the thermal cracking of petroleum of dichloroethane lo vinyl chloride). Both tubular and stirred tank reactors are used for homogeneous liquid phase reactions. 

Ross (R2) measured liquid-phase holdup and residence-time distribution by a tracer-pulse technique. Experiments were carried out for cocurrent flow in model columns of 2- and 4-in. diameter with air and water as fluid media, as well as in pilot-scale and industrial-scale reactors of 2-in. and 6.5-ft diameters used for the catalytic hydrogenation of petroleum fractions. The columns were packed with commercial cylindrical catalyst pellets of -in. diameter and length. The liquid holdup was from 40 to 50% of total bed volume for nominal liquid velocities from 8 to 200 ft/hr in the model reactors, from 26 to 32% of volume for nominal liquid velocities from 6 to 10.5 ft/hr in the pilot unit, and from 20 to 27 % for nominal liquid velocities from 27.9 to 68.6 ft/hr in the industrial unit. In that work, a few sets of results of residence-time distribution experiments are reported in graphical form, as tracer-response curves. 

Fig. 8. Partial molar volumes in the saturated liquid phase of the propane-methane system at IOO°F. (O) (0) Data of B. H. Sage and W. N. Lacey, Some Properties of the Lighter Hydrocarbons, Hydrogen Sulfide, and Carbon Dioxide. American Petroleum...

The difficulties encountered in the Chao-Seader correlation can, at least in part, be overcome by the somewhat different formulation recently developed by Chueh (C2, C3). In Chueh s equations, the partial molar volumes in the liquid phase are functions of composition and temperature, as indicated in Section IV further, the unsymmetric convention is used for the normalization of activity coefficients, thereby avoiding all arbitrary extrapolations to find the properties of hypothetical states finally, a flexible two-parameter model is used for describing the effect of composition and temperature on liquid-phase activity coefficients. The flexibility of the model necessarily requires some binary data over a range of composition and temperature to obtain the desired accuracy, especially in the critical region, more binary data are required for Chueh s method than for that of Chao and Seader (Cl). Fortunately, reliable data for high-pressure equilibria are now available for a variety of binary mixtures of nonpolar fluids, mostly hydrocarbons. Chueh s method, therefore, is primarily applicable to equilibrium problems encountered in the petroleum, natural-gas, and related industries. 

Multiphase extraction uses a vacuum system to remove various combinations of contaminated groundwater, separate-phase petroleum product, and vapors from the subsurface. The system lowers the water table around the well, exposing more of the formation. Contaminants in the newly exposed vadose zone are then accessible to vapor extraction. Once above ground, the extracted vapors or liquid-phase organics and groundwater are separated and treated. 

Acidic micro- and mesoporous materials, and in particular USY type zeolites, are widely used in petroleum refinery and petrochemical industry. Dealumination treatment of Y type zeolites referred to as ultrastabilisation is carried out to tune acidity, porosity and stability of these materials [1]. Dealumination by high temperature treatment in presence of steam creates a secondary mesoporous network inside individual zeolite crystals. In view of catalytic applications, it is essential to characterize those mesopores and to distinguish mesopores connected to the external surface of the zeolite crystal from mesopores present as cavities accessible via micropores only [2]. Externally accessible mesopores increase catalytic effectiveness by lifting diffusion limitation and facilitating desorption of reaction products [3], The aim of this paper is to characterize those mesopores by means of catalytic test reaction and liquid phase breakthrough experiments. 

Fleming An early liquid-phase, thermal process for cracking petroleum. See also Dubbs. Flesch-Winkler See Winkler. 

Phillips (1) A process for polymerizing ethylene and other linear olefins and di-olefins to make linear polymers. This is a liquid-phase process, operated in a hydrocarbon solvent at an intermediate pressure, using a heterogeneous oxide catalyst such as chromia on silica/ alumina. Developed in the 1950s by the Phillips Petroleum Company, Bartlesville, OK, and first commercialized at its plant in Pasadena, TX. In 1991, 77 reaction fines were either operating or under construction worldwide, accounting for 34 percent of worldwide capacity for linear polyethylene. 

The study of the interfacial liquid-liquid phase however is complicated by several factors, of which the chief is the mutual solubility of the liquids. No two liquids are completely immiscible even in such extreme cases as water and mercury or water and petroleum the interfacial energy between two pure liquids will thus be affected by such inter-solution of the two homogeneous phases. In cases of complete intersolubility there is evidently no boundary interface and consequently no interfacial energy. On addition of a solute to one of the liquids a partition of the solute between all three phases, the two liquids and the interfacial phase, takes place. Thus we obtain an apparent interfacial concentration of the added solute. The most varied possibilities, such as positive or negative adsorption from both liquids or positive adsorption from one and negative adsorption from the other, are evidently open to us. In spite of the complexity of such systems it is necessary that information on such points should be available, since one of the most important colloidal systems, the emulsions, consisting of liquids dispersed in liquids, owe their properties and peculiarities to an extended interfacial phase of this character. 

Reclaim is a passive, in situ technology that uses a hydrophobic porous polymer to attract, adsorb, and concentrate petroleum hydrocarbons and volatile organic compounds (VOCs) from soils and/or groundwater. Reclaim is considered a passive treatment technology because it requires no mechanical equipment remediation consists of placing polymer-filled canisters in recovery wells and allowing the containers to attract and adsorb organic contaminants. Reclaim canisters are then recycled and contaminants recovered for analysis and/or disposal. This polymer extracts contaminants whether they are in liquid phase, vapor phase or dissolved phase in water. 

Production of phenol and acetone is based on liquid-phase oxidation of isopropylbenzene. Synthetic fatty acids and fatty alcohols for producing surfactants, terephthalic, adipic, and acetic acids used in producing synthetic and artificial fibers, a variety of solvents for the petroleum and coatings industries—these and other important products are obtained by liquid-phase oxidation of organic compounds. Oxidation processes comprise many parallel and sequential macroscopic and unit (or very simple) stages. The active centers in oxidative chain reactions are various free radicals, differing in structure and in reactivity, so that the nomenclature of these labile particles is constantly changing as oxidation processes are clarified by the appearance in the reaction zone of products which are also involved in the complex mechanism of these chemical conversions. 

In connection with multiphase diffusion another poorly understood topic should be mentioned—namely, the diffusion through porous media. This topic is of importance in connection with the drying of solids, the diffusion in catalyst pellets, and the recovery of petroleum. It is quite common to use Fick s laws to describe diffusion through porous media fJ14). However, the mass transfer is possibly taking place partly by gaseous diffusion and partially by liquid-phase diffusion along the surface of the capillary tubes if the pores are sufficiently small, Knudsen gas flow may prevail (W7, Bl). 

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