Second emulsion formation

Ester addition must be quite slow (2 drops per second or less) to prevent emulsion formation and extremely low yields. 

The first step in downstream processing is the separation of the product-rich phase from the second phase and the biocatalyst. This may be simplified if the enzyme is immobilized or if a membrane module is included in the experimental set-up. In the case of emulsion reactors, centrifugation for liquid phase separation is a likely separation process [58], although the small size of droplets, the possibility of stable emulsion formation during the reaction, particularly if surface-active... 

It was observed that the titration of a coarse emulsion by a coemulsifier (a macromonomer) leads in some cases to the formation of a transparent microemulsion. Transition from opaque emulsion to transparent solution is spontaneous and well defined. Zero or very low interfacial tension obtained during the redistribution of coemeulsifier plays a major role in the spontaneous formation of microemulsions. Microemulsion formation involves first a large increase in the interface (e.g., a droplet of radius 120 nm will disperse ca. 1800 microdroplets of radius 10 nm - a 12-fold increase in the interfacial area), and second the formation of a mixed emulsifier /coemulsifier film at the oil/water interface, which is responsible for a very low interfacial tension. 

Emulsification Emulsification is considered the second most important weathering process after a marine spill by which water is dispersed into oil in the form of small droplets. The mechanism of water-in-oil emulsion formation is not yet fully understood, but it probably starts with sea energy forcing the entry of small water droplets, about 10 to 25 /rm in size, into the oil. Emulsions of many types contain about 70% water. In general, water-in-oil emulsion can be categorized into four types (1) unstable oil simply does not hold water (2) entrained water droplets are simply held in the oil by viscosity to form an unstable emulsion, and it breaks down into water and oil within minutes or a few hours at most (3) semistable or meso-stable the small droplets of water are stabilized to a certain extent by a combination of the viscosity of the oil and interfacial action of asphaltenes and resins. For this to happen, the asphaltenes or resin content of the oU must be at least 3% by weight. The viscosity of meso-stable emulsions is 20 to 80 times... 

MF Fingas, B Fieldhouse, JV Mullin. Studies of water-in-oil emulsions energy threshold of emulsion formation. Proceedings of the Twenty-Second Arctic and Marine Oil Spill Program Technical Seminar, Ottawa, ON, 1999, pp 57—68. 

The separation of water from oil is a major challenge in the processing of hydrocarbon fluids. There is a continual demand to improve the quality of crude oil before it is exported in pipelines or tankers to refineries. Stringent criteria restrict the maximum water content allowed in the export oil (normally 0.5% maximum) and the oil content of the effluent water (normally 40 ppm maximum). The separation of water from oil depends on several fluid- and system-de-pendent factors. Water not only leads to a threat of corrosion scale and hydrates, but can also dramatically increase pumping costs. First, the pumps must deal with a larger volume of fluid, and, second, the formation of a W/0 emulsion can significantly increase fluid viscosity and thereby pressure drop in the pipeline (as mentioned above). 

In its second function, the additive must form some type of film or barrier (monomolecular, electrostatic, steric, or liquid crystalline) at the new L-L interface that will prevent or retard droplet flocculation and coalescence. The process of barrier formation or adsorption must be rapid relative to the rate of drop coalescence or a rather coarse emulsion will result. Also, with the formation of more interface, the adsorption of the emulsifier depletes its bulk concentration, so that attention must be paid to the quantity of the material employed relative to the final result desired, as well as its quality as an emulsifier. As will be seen below, the exact role of an emulsifier in emulsion formation can be quite complex, and is not always completely understood. In any case, its (or, in many cases, their) presence will be vital to successful emulsion formation and stability. 

While a great deal of information has been pubhshed over the years on the theoretical and practical aspects of emulsion formation and stabilization, until recently little has been said about more complex systems generally referred to as multiple emulsions. Multiple emulsions, as the name implies, are composed of droplets of one liquid dispersed in larger droplets of a second liquid, which is then dispersed in a final continuous phase. Typically, the internal droplet phase will be miscible with or identical to the final continuous phase. Such systems may be w/o/w emulsions as indicated in Figure 11.13, where the internal and external phases are aqueous or o/w/o, which have the reverse composition. Although known for almost a century, such systems have only recently become of practical interest for possible use in cosmetics,... 

We used extensively studied amphiphiles for the emulsion formation in the first step. The oil soluble surfactants Span 80 and Brij 72 are well-known to stabilize emulsions, and they can also form niosomes [8-10]. Furthermore we utilized the natural product lecithine, which is also oil-soluble, and an important component of biological membranes [11], The emulsions were generated with established methods like sonication with ultrasound, applying electrosprays or using microemulsion formations [12-14], In addition, we constracted different microfluidic devices to produce small aqueous droplets in oil. Similar techniques were often used for the production of double emulsions [15, 16]. During droplet formation in the organic phase, a single layer of surfactants adsorbed at the surface of these particles. This thin film of surface-active compounds stabihzed the emulsion droplets and lowered the surface tension [17], A second surfactant film was also formed at the plane oil-water interface of the reaction vessel (Fig. 1). 

The second step is to disperse the core material being encapsulated in the solution of shell material. The core material usually is a hydrophobic or water-knmiscible oil, although soHd powders have been encapsulated. A suitable emulsifier is used to aid formation of the dispersion or emulsion. In the case of oil core materials, the oil phase is typically reduced to a drop size of 1—3 p.m. Once a suitable dispersion or emulsion has been prepared, it is sprayed into a heated chamber. The small droplets produced have a high surface area and are rapidly converted by desolvation in the chamber to a fine powder. Residence time in the spray-drying chamber is 30 s or less. Inlet and outlet air temperatures are important process parameters as is relative humidity of the inlet air stream. 

An emulsion is a suspension of one liquid in a second, immiscible, liquid. Emulsifiers are agents that facilitate the formation of emulsions and play a role in stabilizing the emulsion so formed. There are two main types of emulsions oil in water and water in oil. Predominantly hydrophilic emulsifiers (for example, PI88) will stabilize the former predominantly hydrophobic emulsifiers (for example, P181) will stabilize the latter. 

Copolymerization of macromonomers formed by backbiting and fragmentation is a second mechanism for long chain branch formation during acrylate polymerization (Section 4.4.3.3). The extents of long and short chain branching in acrylate polymers in emulsion polymerization as a function of conditions have been quantified.20 ... 

If the secondary stream contains emulsifier it can function in three ways. When the emulsion feed is started quickly the added emulsifier can serve to lengthen the particle formation period and hence to broaden the particle size distribution. When the emulsion feed is started later and added in such a manner that the emulsifier is promptly adsorbed on existing particles, one can obtain quite narrow size distributions. If the emulsion feed is started later but added rapidly enough to generate free emulsifier in the reaction mixture a second population of particles can be formed, again yielding a broad size distribution. 

For the characterization of Langmuir films, Fulda and coworkers [75-77] used anionic and cationic core-shell particles prepared by emulsifier-free emulsion polymerization. These particles have several advantages over those used in early publications First, the particles do not contain any stabihzer or emulsifier, which is eventually desorbed upon spreading and disturbs the formation of a particle monolayer at the air-water interface. Second, the preparation is a one-step process leading directly to monodisperse particles 0.2-0.5 jim in diameter. Third, the nature of the shell can be easily varied by using different hydrophilic comonomers. In Table 1, the particles and their characteristic properties are hsted. Most of the studies were carried out using anionic particles with polystyrene as core material and polyacrylic acid in the shell. 

In emulsion polymerization, a solution of monomer in one solvent forms droplets, suspended in a second, immiscible solvent. We often employ surfactants to stabilize the droplets through the formation of micelles containing pure monomer or a monomer in solution. Micelles assemble when amphiphilic surfactant molecules (containing both a hydrophobic and hydrophilic end) organize at a phase boundary so that their hydrophilic portion interacts with the hydrophilic component of the emulsion, while their hydrophobic part interacts with the hydrophobic portion of the emulsion. Figure 2.14 illustrates a micellized emulsion structure. To start the polymerization reaction, a phase-specific initiator or catalyst diffuses into the core of the droplets, starting the polymerization. 

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