The Water Phase

During storage, sediments decant with the water phase and deposit along with paraffins and asphalts in the bottoms of storage tanks as thick sludges or slurries (BS W). The interface between the water-sediment and the crude must be well monitored in order to avoid pumping the slurry into the refinery s operating units where it can cause serious upsets. 

Surface tension arises at a fluid to fluid interface as a result of the unequal attraction between molecules of the same fluid and the adjacent fluid. For example, the molecules of water in a water droplet surrounded by air have a larger attraction to each other than to the adjacent air molecules. The imbalance of forces creates an inward pull which causes the droplet to become spherical, as the droplet minimises its surface area. A surface tension exists at the interface of the water and air, and a pressure differential exists between the water phase and the air. The pressure on the water side is greater due to the net inward forces... 

Inside the capillary tube, the capillary pressure (P ) is the pressure difference between the oil phase pressure (PJ and the water phase pressure (P ) at the interface between the oil and the water. 

Where space and weight are considerations (such as on an offshore facility) plate separators may be used to dehydrate crude to evacuation specification. Packs of plates are used to accelerate extraction of the water phase by intercepting water droplets with... 

In contrast to SDS, CTAB and C12E7, CufDSjz micelles catalyse the Diels-Alder reaction between 1 and 2 with enzyme-like efficiency, leading to rate enhancements up to 1.8-10 compared to the reaction in acetonitrile. This results primarily from the essentially complete complexation off to the copper ions at the micellar surface. Comparison of the partition coefficients of 2 over the water phase and the micellar pseudophase, as derived from kinetic analysis using the pseudophase model, reveals a higher affinity of 2 for Cu(DS)2 than for SDS and CTAB. The inhibitory effect resulting from spatial separation of la-g and 2 is likely to be at least less pronoimced for Cu(DS)2 than for the other surfactants. 

Initiators of suspension polymerization are organic peroxides or azo compounds that are soluble in the monomer phase but insoluble in the water phase. The amount of initiator influences both the polymerization rate and the molecular weight of the product (95). 

Suspension polymerization of VDE in water are batch processes in autoclaves designed to limit scale formation (91). Most systems operate from 30 to 100°C and are initiated with monomer-soluble organic free-radical initiators such as diisopropyl peroxydicarbonate (92—96), tert-huty peroxypivalate (97), or / fZ-amyl peroxypivalate (98). Usually water-soluble polymers, eg, cellulose derivatives or poly(vinyl alcohol), are used as suspending agents to reduce coalescence of polymer particles. Organic solvents that may act as a reaction accelerator or chain-transfer agent are often employed. The reactor product is a slurry of suspended polymer particles, usually spheres of 30—100 pm in diameter they are separated from the water phase thoroughly washed and dried. Size and internal stmcture of beads, ie, porosity, and dispersant residues affect how the resin performs in appHcations. 

L tex Foa.m Rubber. Latex foam mbber was the first ceUular polymer to be produced by frothing. (/) A gas is dispersed in a suitable latex 2) the mbber latex particles are caused to coalesce and form a continuous mbber phase in the water phase (7) the aqueous soap film breaks owing to... 

The fluid is formulated from a premium mineral od-base stock that is blended with the required additive to provide antiwear, mst and corrosion resistance, oxidation stabdity, and resistance to bacteria or fungus. The formulated base stock is then emulsified with ca 40% water by volume to the desired viscosity. Unlike od-in-water emulsions the viscosity of this type of fluid is dependent on both the water content, the viscosity of the od, and the type of emulsifier utilized. If the water content of the invert emulsion decreases as a result of evaporation, the viscosity decreases likewise, an increase in water content causes an increase in the apparent viscosity of the invert emulsion at water contents near 50% by volume the fluid may become a viscous gel. A hydrauHc system using a water-in-od emulsion should be kept above the freezing point of water if the water phase does not contain an antifreeze. Even if freezing does not occur at low temperatures, the emulsion may thicken, or break apart with subsequent dysfunction of the hydrauHc system. 

Fractionation. Direct fractionation also can be used to remove dissolved water from LPG. The water-rich overhead vapor from the dryer fractionator is returned to the fractionator as reflux and the water phase is discarded. A dry LPG product that meets either propane or butane water specifications is produced as a ketde product from the fractionator. 

Water-Based Muds. About 85% of all drilling fluids are water-based systems. The types depend on the composition of the water phase (pH, ionic content, etc), viscosity builders (clays or polymers), and rheological control agents (deflocculants or dispersants (qv)). 

Although numerous mud additives aid in obtaining the desired drilling fluid properties, water-based muds have three basic components water, reactive soHds, and inert soHds. The water forming the continuous phase may be fresh water, seawater, or salt water. The reactive soHds are composed of commercial clays, incorporated hydratable clays and shales from drilled formations, and polymeric materials, which may be suspended or dissolved in the water phase. SoHds, such as barite and hematite, are chemically inactive in most mud systems. Oil and synthetic muds contain, in addition, an organic Hquid as the continuous phase plus water as the discontinuous phase. 

Fig. 2. Skin of a suspension PVC grain showing 0.1-p.m dia particles deposited from the water phase.

These primary particles also contain smaller internal stmctures. Electron microscopy reveals a domain stmcture at about 0.1-p.m dia (8,15,16). The origin and consequences of this stmcture is not weU understood. PVC polymerized in the water phase and deposited on the skin may be the source of some of the domain-sized stmctures. Also, domain-sized flow units may be generated by certain unusual and severe processing conditions, such as high temperature melting at 205°C followed by lower temperature mechanical work at 140—150°C (17), which break down the primary particles further. 

Emulsion Polymerization. Emulsion polymerization takes place in a soap micelle where a small amount of monomer dissolves in the micelle. The initiator is water-soluble. Polymerization takes place when the radical enters the monomer-swollen micelle (91,92). Additional monomer is supphed by diffusion through the water phase. Termination takes place in the growing micelle by the usual radical-radical interactions. A theory for tme emulsion polymerization postulates that the rate is proportional to the number of particles [N. N depends on the 0.6 power of the soap concentration [S] and the 0.4 power of initiator concentration [i] the average number of radicals per particle is 0.5 (93). 

If a neutral chelate formed from a ligand such as acetylacetone is sufficiently soluble in water not to precipitate, it may stiH be extracted into an immiscible solvent and thus separated from the other constituents of the water phase. Metal recovery processes (see Mineral recovery and processing), such as from dilute leach dump Hquors, and analytical procedures are based on this phase-transfer process, as with precipitation. Solvent extraction theory and many separation systems have been reviewed (42). 

Hydrolysis. 1,1,1-Trichloroethane heated with water at 75—160°C under pressure and in the presence of sulfuric acid or a metal chloride catalyst decomposes to acetyl chloride, acetic acid, or acetic anhydride (54). However, hydrolysis under normal use conditions proceeds slowly. The hydrolysis is 100—1000 times faster with trichloroethane dissolved in the water phase than vice versa. Refluxing 1,1,1-trichloroethane with ferric and gallium chloride... 

Neoprene latexes contain 0.5 to 0.02% residual chloroprene depending on the specific latex type. The amount of free alkaH in the water phase of latexes varies from 0.1 to 0.08% depending on type and age of the material. Eye protection and appropriate skin protection have been recommended for use in situations where splashes or spills are possible. Toxicity and safe handling practices have been recommended for Du Pont types (171). Since compositions may vary with other manufacturers, specific information should be obtained for other products. 

In the last few years, Idemitsu commercialized a 5000 metric ton/year integrated reaction and separation process in SCR isobutene, as shown in Rig. 22-24. The reaction of isobutene and water takes place in the water phase and is acid catalyzed. The product, sec-butanol, is extracted into the isobutene phase to drive the reversible reaction to the right. The. s c-butanol is then recovered from the isobutene by depressurizing the SCR phase, and the isobutene is recompressed and recycled. 

Albertsson (Paiiition of Cell Paiiicle.s and Macromolecules, 3d ed., Wiley, New York, 1986) has extensively used particle distribution to fractionate mixtures of biological products. In order to demonstrate the versatility of particle distribution, he has cited the example shown in Table 22-14. The feed mixture consisted of polystyrene particles, red blood cells, starch, and cellulose. Liquid-liquid particle distribution has also been studied by using mineral-matter particles (average diameter = 5.5 Im) extracted from a coal liquid as the solid in a xylene-water system [Prudich and Heniy, Am. Inst. Chem. Eng. J., 24(5), 788 (1978)]. By using surface-active agents in order to enhance the water wettability of the solid particles, recoveries of better than 95 percent of the particles to the water phase were obsei ved. All particles remained in the xylene when no surfactant was added. 

Not many operating data of large-scale hquid/hquid reactions are published. One study was made of the hydrolysis of fats with water at 230 to 260°C (446 to 500°F) and 41 to 48 atm (600 to 705 psi) in a continuous commercial spray tower. A small amount of water dissolved in the fat and reacted to form an acid and glycerine. Then most of the glycerine migrated to the water phase. Tlie tower was operated at about 18 percent of flooding, at which condition the HETS was found to be about 9 m (30 ft) compared with an expec ted 6 m (20 ft) for purely physical extrac tion (Jeffreys, Jenson, and Miles, Trans. In.st. Chem. Eng., 39, 389-396 [1961]). A similar mathematical treatment of a batch hydrolysis is made by Jenson and Jeffreys (In.st. Chem. Engrs. Symp. Ser, No. 23 [1967]). 

However, it is possible to use two-dimensional spectra in spectrophotometry as an alternative. In this case, the pH value of the water phase in extracting systems is used as a supplementary coordinate. 

Methanol causes substantial enhancement of CO2 solubility in the water phase (Figure 3). Wateh for inereased eorrosion. 

For this problem, methanol had no practical effect on the solubility of hydrocarbons in the water phase (Figure 4). 

The chain extension step may then take place in the water phase. Hydrazine and ethylene diamine are commonly used chain extenders for waterborne urethane dispersions. The isocyanates react with the diamine chain extenders much faster than with the water, thus forming polyurea linkages and building a high molecular weight polymer. More detailed information regarding the synthesis and process of making waterborne polyurethane dispersions is found in Dieterich s review article [58]. 

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