Dehydration of organic liquids

Pervaporation (PV) partial vapor pressure difference separation of isomers dehydration of organic liquids... 

Hydrophilic polymers are used as selective barriers for dehydration of organic liquids via PV. The selective layer is typically from a glassy polymer chemically... 

According to a recent conference given by Prof. Kita [162], the classical synthesis method currently used by Mitsui allows to produce about 250 zeolite membranes per day. Both the LTA and T types (Na K) membranes are now commercial and more than 80 pervaporation and vapor permeation plants are operating in Japan for the dehydration of organic liquids [163]. A typical pervaporation system, similar to the one described in [8], is shown in Fig. 11. One of the most recent applications concerns the production of fuel ethanol from cellulosic biomass by a vapour permeation/ pervaporation combined process. The required heat is only 1 200 kcal per liter of product, i.e. half of that of the classical process. Mitsui has recently installed a bio-ethanol pilot plant based on tubular LTA membranes in Brazil (3 000 liters/day) and a plant with 30 000 liters/day has been erected in India. The operating temperature is 130 °C, the feed is 93 % ethanol, the permeate is water and the membrane selectivity is 10 000. 

In liquid separation, hollow fiber membranes based on PBI have shown excellent performance for pervaporation dehydration of organic liquids. For example, a dual layer PEI-PBI hollow fiber membrane with an outer selective layer of PBI showed better performance than most other polymeric membranes in pervaporation dehydration of ethylene glycol. Sulfonation modifications of PBI membranes have demonstrated excellent separation efficacies in the dehydration of acetic acid. Studies have shown that PBI hollow fiber membranes were effective in separating chromates from solutions. Also, PBI nanofiltration hollow fiber membranes are promising candidates as forward osmosis membranes. In gas separation, recent studies sponsored by the Department of Energy at Los Alamos National Laboratories and SRI International demonstrated potential applications of PBI membranes in carbon capture and Hj purification from synthesis gas streams at elevated temperatures. H2/CO2 selectivity > 40 has been achieved at H2 permeability of 200 GPU at 250°C. ... 

Y. Wang, M. Gruender, T.S. Chung, Polybenzimidazole-based membranes for the dehydration of organic liquids via pervaporation . United States Patent Application Publication Pub. No. US2011/0266222 Al, Pub. Date Nov 3,2011. 

Pervaporation is a relatively new process with elements in common with reverse osmosis and gas separation. In pervaporation, a liquid mixture contacts one side of a membrane, and the permeate is removed as a vapor from the other. Currendy, the only industrial application of pervaporation is the dehydration of organic solvents, in particular, the dehydration of 90—95% ethanol solutions, a difficult separation problem because an ethanol—water azeotrope forms at 95% ethanol. However, pervaporation processes are also being developed for the removal of dissolved organics from water and the separation of organic solvent mixtures. These applications are likely to become commercial after the year 2000. 

Membranes can also be used to alter the vapor-liquid equilibrium behavior and allow separation of azeotropes. The liquid mixture is fed to one side of the membrane, and the permeate is held under conditions to maintain it in the vapor phase. Most separations use hydrophyllic membranes that preferentially pass water rather than organic material. Thus, pervaporation is commonly used for the dehydration of organic components. 

The drying of ethereal solutions is an operation frequently met with. In most cases it is advisable to dry an ethereal extract before evaporating off the ether. Again, to dry a moist solid, it is often convenient to dissolve it in ether and to dry the ethereal solution with a dehydrating agent. The dry solid is then obtained by evaporation. For the drying of organic liquids by dialysis, see U. S. P., 1,885,393. 

Tusel GF and Ballweg A. Method and apparams for dehydrating mixmres of organic liquids and water, US Patent 4405409, September... 

Abstract Two types of membrane are presented free-standing films which are formed from aqueous polyelectrolyte solutions and membranes prepared by alternating electrostatic layer-by-layer assembly of cationic and anionic polyelectrolytes on porous supports. Layer-by-layer assemblies represent versatile membranes suitable for dehydration of organic solvents and ion separation in aqueous solution. The results show that the structuring of the polyelectrolytes in the liquid films and the permeability of the multilayer membranes depends on different internal and environmental parameters, for example molecular weight, polymer charge density, ionic strength, and temperature. 

This application is based on the hydrophilicity of the ion exchange membrane. Though it is not essential to use an ion exchange membrane,219 they show excellent performance in pervaporation for dehydration of organic solvents. Pervaporation is the separation of solvents on the basis of their different affinities for the membrane and different permeation speeds through the membrane phase. The system consists of a liquid mixture to be separated, which contacts one side of the membrane, and a gas phase to permeate under reduced pressure, which is on the other side of the membrane (Figure 6.37). Membrane performance is evaluated by a permeability coefficient (flux) and separation factor (selectivity coefficient). The permeability coefficient, Q, is the permeated solvent through the membrane per unit area and unit time (kgm 2 h1). When a mixed solvent composed of components A and B is separated, the separation factor, a, is defined as... 

Pervaporation is a process that can separate liquid mixtures by selectively allowing the passage of one component. Important applications include the separation of azeotropes, the dehydration of organics, and the removal of organic compounds from water [68]. Since most liquids are composed of molecules in the 2-10 A size regime [69], separations by pervaporation require fully dense pinhole-free membranes of the type used for gas separations. With the ability to separate gases on... 

In liquid mixtures of type (2), the solutions of primary interest are azeotropic and other mixtures containing variable amounts of water in organics dehydration of organic solvents containing very small amounts of water. Removal of water from azeotropic mixtures of ethanol-water, isopropanol-water, etc., is extensively practiced using polymeric membranes (of crosslinked polyvinyl alcohol) that are highly polar and selective for water. On the other hand, the membranes that are used to remove VOCs selectively from aqueous solutions are usually highly nonpolar rubbery polymeric membranes, e.g. dimethyl siloxane (silicone rubber). 

Processes rendered obsolete by the propylene ammoxidation process (51) include the ethylene cyanohydrin process (52—54) practiced commercially by American Cyanamid and Union Carbide in the United States and by I. G. Farben in Germany. The process involved the production of ethylene cyanohydrin by the base-cataly2ed addition of HCN to ethylene oxide in the liquid phase at about 60°C. A typical base catalyst used in this step was diethylamine. This was followed by liquid-phase or vapor-phase dehydration of the cyanohydrin. The Hquid-phase dehydration was performed at about 200°C using alkah metal or alkaline earth metal salts of organic acids, primarily formates and magnesium carbonate. Vapor-phase dehydration was accomphshed over alumina at about 250°C. 

The considerations described above for vacuum-oven drying hold equally well when water is removed by distillation with an organic liquid, as exemplified by the Bidwell-Sterling method (3). The time of distillation for various dehydrated vegetables has been shown to depend on particle size and temperature (IS) and is about the same as would be required in vacuum-oven drying under the same conditions (28). 

Shape selective catalysis as typically demonstrated by zeolites is of great interest from scientific as well as industrial viewpoint [17], However, the application of zeolites to organic reactions in a liquid-solid system is very limited, because of insufficient acid strength and slow diffusion of reactant molecules in small pores. We reported preliminarily that the microporous Cs salts of H3PW12O40 exhibit shape selectivity in a liquid-solid system [18]. Here we studied in more detail the acidity, micropore structure and catal3rtic activity of the Cs salts and wish to report that the acidic Cs salts exhibit efficient shape selective catalysis toward decomposition of esters, dehydration of alcohol, and alkylation of aromatic compound in liquid-solid system. The results were discussed in relation to the shape selective adsorption and the acidic properties. 

Spherical microparticles are more difficult to manufacture and can be prepared by several methods. One method prepares silica hydrogel beads by emulsification of a silica sol in an immiscible organic liquid [20,21,24,25]. To promote gelling a silica hydrosol, prepared as before, is dispersed into small droplets in a iater immiscible liquid and the temperature, pH, and/or electrolyte concentration adjusted to promote solidification. Over time the liquid droplets become increasingly viscous and solidify as a coherent assembly of particles in bead form. The hydrogel beads are then dehydrated to porous, spherical, silica beads. An alternative approach is based on the agglutination of a silica sol by coacervation [25-27], Urea and formaldehyde are polymerized at low pH in the presence of colloidal silica. Coacervatec liquid... 

Silica gel. Silica gel is a porous amorphous form of silica (Si02) and is manufactured by acid treatment of sodium silicate solution and then dried. The silica gel surface has an affinity for water and organic material. It is primarily used to dehydrate gases and liquids. 

Another use of urea is for resins, which are used in numerous applications including plastics, adhesives, moldings, laminates, plywood, particleboard, textiles, and coatings. Resins are organic liquid substances exuded from plants that harden on exposure to air. The term now includes numerous synthetically produced resins. Urea resins are thermosetting, which means they harden when heated, often with the aid of a catalyst. The polymerization of urea and formaldehyde produces urea-formaldehyde resins, which is the second most abundant use of urea. Urea is dehydrated to melamine, which, when combined with formaldehyde, produces melamine-formaldehyde resins (Figure 96.2). Melamine resins tend to be harder and more heat-resistant than urea-formaldehyde resins. Melamine received widespread attention as the primary pet food and animal feed contaminant causing numerous cat and dog deaths in early... 

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