Immiscible process

Since light hydrocarbons contain considerable combustion energies, their use as EOR fluids is generally limited to remote locations, from which the cost of their delivery to commercial markets would be prohibitive. The North Slope of Alaska is a very important example of a major field in which there is little to do with produced gases except to reinject them (or possibly burn them on-site for thermal EOR). Since much of the Alaskan oil is heavy, immiscible processes are of great interest for this area. 

Results of Immiscible Displacement Tests. The results of the tests show that immiscible carbon dioxide flooding followed by waterflooding is effective in increasing the oil recovered from a core. The oil recovered by a conventional waterflood was equal to about 30.4% of a pore volume, PV. Immiscible carbon dioxide flooding increased the recovery to a total of 50.5% PV. The addition of a mobility control agent increased the recovery further to 58.3% PV this amounts to 39% additional tertiary oil due to the effectiveness of the mobility control in the carbon dioxide immiscible process. 

Flotation. Flotation is a gravity separation process which exploits differences in the surface properties of particles. Gas bubbles are generated in a liquid and become attached to solid particles or immiscible liquid droplets, causing the particles or droplets to rise to the surface. This is used to separate mixtures of solid-solid particles and liquid-liquid mixtures of finely divided immiscible droplets. It is an important technique in mineral processing, where it is used to separate different types of ore. 

The theory of the process can best be illustrated by considering the operation, frequently carried out in the laboratory, of extracting an orgaiuc compound from its aqueous solution with an immiscible solvent. We are concerned here with the distribution law or partition law which, states that if to a system of two liquid layers, made up of two immiscible or slightly miscible components, is added a quantity of a third substance soluble in both layers, then the substance distributes itself between the two layers so that the ratio of the concentration in one solvent to the concentration in the second solvent remains constant at constant temperature. It is assumed that the molecular state of the substance is the same in both solvents. If and Cg are the concentrations in the layers A and B, then, at constant temperature ... 

In Chapter 7 we examined several methods for separating an analyte from potential interferents. For example, in a liquid-liquid extraction the analyte and interferent are initially present in a single liquid phase. A second, immiscible liquid phase is introduced, and the two phases are thoroughly mixed by shaking. During this process the analyte and interferents partition themselves between the two phases to different extents, affecting their separation. Despite the power of these separation techniques, there are some significant limitations. 

Catalyst recovery is a major operational problem because rhodium is a cosdy noble metal and every trace must be recovered for an economic process. Several methods have been patented (44—46). The catalyst is often reactivated by heating in the presence of an alcohol. In another technique, water is added to the homogeneous catalyst solution so that the rhodium compounds precipitate. Another way to separate rhodium involves a two-phase Hquid such as the immiscible mixture of octane or cyclohexane and aliphatic alcohols having 4—8 carbon atoms. In a typical instance, the carbonylation reactor is operated so the desired products and other low boiling materials are flash-distilled. The reacting mixture itself may be boiled, or a sidestream can be distilled, returning the heavy ends to the reactor. In either case, the heavier materials tend to accumulate. A part of these materials is separated, then concentrated to leave only the heaviest residues, and treated with the immiscible Hquid pair. The rhodium precipitates and is taken up in anhydride for recycling. 

The physical process of Hquid—Hquid extraction separates a dissolved component from its solvent by transfer to a second solvent, immiscible with the first but having a higher affinity for the transferred component. The latter is sometimes called the consolute component. Liquid—Hquid extraction can purify a consolute component with respect to dissolved components which are not soluble in the second solvent, and often the extract solution contains a higher concentration of the consolute component than the initial solution. In the process of fractional extraction, two or more consolute components can be extracted and also separated if these have different distribution ratios between the two solvents. 

Interfdci l Composite Membra.nes, A method of making asymmetric membranes involving interfacial polymerization was developed in the 1960s. This technique was used to produce reverse osmosis membranes with dramatically improved salt rejections and water fluxes compared to those prepared by the Loeb-Sourirajan process (28). In the interfacial polymerization method, an aqueous solution of a reactive prepolymer, such as polyamine, is first deposited in the pores of a microporous support membrane, typically a polysulfone ultrafUtration membrane. The amine-loaded support is then immersed in a water-immiscible solvent solution containing a reactant, for example, a diacid chloride in hexane. The amine and acid chloride then react at the interface of the two solutions to form a densely cross-linked, extremely thin membrane layer. This preparation method is shown schematically in Figure 15. The first membrane made was based on polyethylenimine cross-linked with toluene-2,4-diisocyanate (28). The process was later refined at FilmTec Corporation (29,30) and at UOP (31) in the United States, and at Nitto (32) in Japan. 

Fig. 15. Schematic of the interfacial polymerization process. The microporous film is first impregnated with an aqueous amine solution. The film is then treated with a multivalent cross-linking agent dissolved in a water-immiscible organic fluid, such as hexane or Freon-113. An extremely thin polymer film...

A wide variety of capsules loaded with water-immiscible or water-iasoluble materials have been prepared by complex coacervation. Capsule size typically ranges from 20—1000 p.m, but capsules outside this range can be prepared. Core contents usually are 80—95 wt %. Complex coacervation processes are adversely affected by active agents that have finite water solubiUty, are surface-active, or are unstable at pH values of 4.0—5.0. The shell of dry complex coacervate capsules is sensitive to variations ia atmospheric moisture content and becomes plasticized at elevated humidities. 

Figure 4a represents interfacial polymerisation encapsulation processes in which shell formation occurs at the core material—continuous phase interface due to reactants in each phase diffusing and rapidly reacting there to produce a capsule shell (10,11). The continuous phase normally contains a dispersing agent in order to faciUtate formation of the dispersion. The dispersed core phase encapsulated can be water, or a water-immiscible solvent. The reactant(s) and coreactant(s) in such processes generally are various multihmctional acid chlorides, isocyanates, amines, and alcohols. For water-immiscible core materials, a multihmctional acid chloride, isocyanate or a combination of these reactants, is dissolved in the core and a multihmctional amine(s) or alcohol(s) is dissolved in the aqueous phase used to disperse the core material. For water or water-miscible core materials, the multihmctional amine(s) or alcohol(s) is dissolved in the core and a multihmctional acid chloride(s) or isocyanate(s) is dissolved in the continuous phase. Both cases have been used to produce capsules. 

Figure 5 illustrates the type of encapsulation process shown in Figure 4a when the core material is a water-immiscible Hquid. Reactant X, a multihmctional acid chloride, isocyanate, or combination of these reactants, is dissolved in the core material. The resulting mixture is emulsified in an aqueous phase that contains an emulsifier such as partially hydroly2ed poly(vinyl alcohol) or a lignosulfonate. Reactant Y, a multihmctional amine or combination of amines such as ethylenediamine, hexamethylenediamine, or triethylenetetramine, is added to the aqueous phase thereby initiating interfacial polymerisation and formation of a capsule shell. If reactant X is an acid chloride, base is added to the aqueous phase in order to act as an acid scavenger. 

Fig. 5. Flow diagram of typical interfacial polymerisation encapsulation process in which reactants X and Y are dissolved in separate mutually immiscible...

A key feature of encapsulation processes (Figs. 4a and 5) is that the reagents for the interfacial polymerisation reaction responsible for shell formation are present in two mutually immiscible Hquids. They must diffuse to the interface in order to react. Once reaction is initiated, the capsule shell that forms becomes a barrier to diffusion and ultimately begins to limit the rate of the interfacial polymerisation reaction. This, in turn, influences morphology and uniformity of thickness of the capsule shell. Kinetic analyses of the process have been pubHshed (12). A drawback to the technology for some apphcations is that aggressive or highly reactive molecules must be dissolved in the core material in order to produce microcapsules. Such molecules can react with sensitive core materials. 

A specific example of the process represented by Figure 4b occurs when a multihmctional isocyanate is dissolved in a Hquid, water-immiscible core material and the mixture produced is dispersed in an aqueous phase that contains a dispersing agent. The aqueous phase reacts with some of the isocyanate groups to produce primary amine functionaHties. These amino groups react with unreacted isocyanate groups to produce a polyurea capsule shell (13). 

Figure 4c illustrates interfacial polymerisation encapsulation processes in which the reactant(s) that polymerise to form the capsule shell is transported exclusively from the continuous phase of the system to the dispersed phase—continuous phase interface where polymerisation occurs and a capsule shell is produced. This type of encapsulation process has been carried out at Hquid—Hquid and soHd—Hquid interfaces. An example of the Hquid—Hquid case is the spontaneous polymerisation reaction of cyanoacrylate monomers at the water—solvent interface formed by dispersing water in a continuous solvent phase (14). The poly(alkyl cyanoacrylate) produced by this spontaneous reaction encapsulates the dispersed water droplets. An example of the soHd—Hquid process is where a core material is dispersed in aqueous media that contains a water-immiscible surfactant along with a controUed amount of surfactant. A water-immiscible monomer that polymerises by free-radical polymerisation is added to the system and free-radical polymerisation localised at the core material—aqueous phase interface is initiated thereby generating a capsule sheU (15). 

Figure 4d represents in situ encapsulation processes (17,18), an example of which is presented in more detail in Figure 6 (18). The first step is to disperse a water-immiscible Hquid or soHd core material in an aqueous phase that contains urea, melamine, water-soluble urea—formaldehyde condensate, or water-soluble urea—melamine condensate. In many cases, the aqueous phase also contains a system modifier that enhances deposition of the aminoplast capsule sheU (18). This is an anionic polymer or copolymer (Fig. 6). SheU formation occurs once formaldehyde is added and the aqueous phase acidified, eg, pH 2—4.5. The system is heated for several hours at 40—60°C.

When an impeller is rotated in an agitated tank containing two immiscible Hquids, two processes take place. One consists of breakup of dispersed drops due to shearing near the impeller, and the other is coalescence of drops as they move to low shear zones. The drop size distribution (DSD) is decided when the two competing processes are in balance. During the transition, the DSD curve shifts to the left with time, as shown in Figure 18. Time required to reach the equiHbrium DSD depends on system properties and can sometimes be longer than the process time. 

Chemistry. Chemical separation is achieved by countercurrent Hquid— Hquid extraction and involves the mass transfer of solutes between an aqueous phase and an immiscible organic phase. In the PUREX process, the organic phase is typically a mixture of 30% by volume tri- -butyl phosphate (solvent) and a normal paraffin hydrocarbon (diluent). The latter is typically dodecane or a high grade kerosene (20). A number of other solvent or diluent systems have been investigated, but none has proved to be a substantial improvement (21). 

The principle of solvent extraction in refining is as follows when a dilute aqueous metal solution is contacted with a suitable extractant, often an amine or oxime, dissolved in a water-immiscible organic solvent, the metal ion is complexed by the extractant and becomes preferentially soluble in the organic phase. The organic and aqueous phases are then separated. By adding another aqueous component, the metal ions can be stripped back into the aqueous phase and hence recovered. Upon the identification of suitable extractants, and using a multistage process, solvent extraction can be used to extract individual metals from a mixture. 

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