The membrane operate in different ways, depending
upon the nature of the separation to be made.
The membranes serve to prevent intermingling of two
miscible phases, hydrodynamics flow, and the movement of substance through them is by diffusion.
The membranes permit a component separation by selectively controlling passage of the components from one side to the other. GAS -GAS GASEOUS DIFFUSION (EFFUSION)
In gaseous diffusion or effusion, the membrane is micro porous. If a gas mixture whose components are of different molecular weights are brought into contact with such a diaphragm, the various components of the gas pass through the pores at rates dependent upon the molecular weights e.g. separation of uranium from gaseous uranium hexafluoride. PERMEATION In permeation, the gas transmitted through the non porous membrane first dissolves according to the solubility in it and then diffuses through. e.g. separation of helium (He) from natural gas through fluorocarbon polymer membranes. GAS -LIQUID PERMEATION e.g. a liquid solution of alcohol and water brought into contact with suitable non porous membrane, in which alcohol preferentially dissolve after passage through the membrane, the alcohol is vaporised on the far side.
LIQUID- LIQUID DIALYSIS – FRACTIONAL, ELECTRO substance from colloid, by The separation of a crystalline contact of their solution with a liquid solvent with an intervening membrane permeable only to the solvent and dissolved crystalline substance is known as dialysis. e.g. separation of undesired colloidal material from beet-sugar solution.
Fractional dialysis for separating two crystalline
substance in solution makes use of the difference in the membrane permeability for the substances. If an electromotive force is applied across the membrane to assist in the diffusion of charged particles, the operation is Electrodialysis. OSMOSIS - REVERSE OSMOSIS (RO) If a solution is separated from the pure solvent, the solvent diffuses into the solution, an operation known as osmosis. This is not a separation, but by super imposing pressure to opposite the osmotic pressure the flow of solvent is reversed, and the solute and solvent of a solution can be separated by Reverse osmosis. e.g. desalination of water.
DIRECT CONTACT OF MISCIBLE PHASES THERMAL DIFFUSION This involves the formation of a concentration difference within single liquid or gaseous phase by imposition of a temperature gradient upon the fluid, thus making a separation of the components of the solution possible. E.g. separation of 3He from 4He and mixture. SWEEP DIFFUSION
If steam is allowed to diffuse through a
gas mixture, it will preferentially carry one of the component along with it, thus making a separation by the operation known as sweep diffusion. ATMOLYSIS
If the two zones within the gas phase
where the concentration are different are separated by a screen containing relatively large openings, the operation is called atmolysis. CENTRIFUGATION If a gas mixture is subjected to a very rapid centrifugation, the components will be separated because of the slightly different forces acting on the various molecules owing to their different masses. The heavier molecules thus tend to accumulate at the periphery of the centrifuge. e.g. separation of uranium isotopes. USE OF SURFACE PHENOMENA FOAM SEPARATION
By forming a foam of large surface, as
by bubbling air through the solution and collecting the foam, the solute can be concentrated. This operation is known as foam separation. e.g. separation if detergent from water. SUBCLASSIFICATION OF DIRECT CONTACT OF TWO IMMISCIBLE PHASES – ACCORDING TO THE TYPES OF OPERATION OR DIRECT Vs. INDIRECT MASS TRANSFER OPERATIONS. DIRECT MTO INDIRECT MTO 1) In this type of operation the two immiscible 1) In this type of operation the separation phases are generated from a single phase involves the addition of a foreign substance. solution by addition or removal of heat. 2) e.g. fractional distillation, fractional 2) e.g. gas absorption, stripping, adsorption, crystallization and CST type fractional liquid drying, leaching, liquid extraction and certain extraction. types of crystallization (adductive). 3) Products obtained are free of added substance 3) The removed substance is obtained as a and most frequently (if almost pure) doesn’t solution with foreign substance and requires require any further separation. further separation of pure substance and added substance and lead to expense and less quality of products. 4) Any type of corrosion or losses are not 4) Addition of foreign substance creates involved. corrosion problem and cost of inevitable losses. 5) They are rarely used because of high cost 5) They are frequently used because of net less (most if the cost is due to heat supplied or cost. removed). 6) Applications:- 6) indirect methods used for such as: These methods are more frequently used to i) drying of clothes by air (in summer)!!! obtain extra pure substances. ii) production of HCl aqueous solution by absorption of HCl containing gas into the water, with no further separation requirement. FACTORS AFFECTING CHOICE OF SEPARATION METHOD Choice of separating the component of a solution is usually limited by the peculiar physical characteristics of the materials to be handled. Choice of method exists between mass transfer operation and a purely mechanical separation method. e.g. in the separation of desired mineral from its ore, it maybe possible to use either the mass transfer operation of leaching with a solvent or purely mechanical methods of flotation. Sometimes both mechanical and mass transfer operations are used especially where the former is incomplete, as in processes for recovering vegetables oils wherein mechanical expression is followed by leaching. It is characteristic that at the end of the operation the substance removed by mechanical methods is pure, while if removed by diffusional methods it is associated with another substance. One can also frequently choose between a purely mass transfer operation and a chemical reaction or a combination of both. e.g. H2S can be separated from other gases either by absorption in a liquid solvent with or without simultaneous chemical reaction or by chemical reaction with ferric oxide. Chemical methods ordinarily destroy the substance removed, while mass transfer methods usually permit its eventual recovery in unaltered form without great difficulty. There are also choices to be made within the mass transfer operations. e.g. a liquid solution of acetic acid maybe separated by distillation, by liquid extraction with a suitable solvent, or by adsorption with a suitable solid adsorbent.
The principle basis for choice in any case is
cost; that method which costs the least is usually the one to be used. Ease of operation:- occasionally other factors also influence the decision, however, the simplest operation, while it may not be the least costly, is sometimes desired because it will be trouble free. Sometimes a method will be discarded because of imperfect knowledge of design methods or unavailability of data for design, so that results cannot be guaranteed. Favorable previous experience with one method maybe given strong considerations. METHODS OF CONDUCTING MASS TRANSFER OPERATIONS Several characteristics of operations influences over method of dealing with them Solute recovery and fractionation Unsteady state operation Steady state operation Stage wise operation Continuous contact operation (or Differential contact operation) SOLUTE RECOVERY AND FRACTIONATION If the components of a solution fall into two distinct groups of quite different properties, so that one can imagine in that one group of components constitutes the solvent and other group the solute, separation according to this groups is usually relatively easy and amounts to a solute recovery or solute removal operation. e.g. separation of methane (solvent) from methane + pentane (solute) + hexane (solute) mixture by absorption with oil due to the property (vapour pressure) difference. While the component properties differ, the difference are small and to separate them into relatively pure components requires a different technique. Such separation are termed fractionation. e.g. separation of pentane + hexane mixture by fractional distillation. UNSTEADY STATE OPERATION It is characteristic of unsteady state operation that concentrations at any point in the apparatus change with time. This may result from changes in concentration of feed material, flow rates or conditions of temperature or pressure. In any case, batch operations are always of the unsteady state type. e.g. laboratory extraction procedure of shaking a solution with an immiscible solvent. In semi batch operations, one phase is stationary while the other flows continuously in and out of the apparatus. e.g. drying of clothes through air. STEADY STATE OPERATION It is characteristic of steady state operations that concentrations at any positions in the apparatus remains constant with passage of time. This requires continuous, irreversible flow of all phases into and out of the apparatus, a persistence of the flow regime within the apparatus, constant concentration of the feed streams and unchanging conditions of temperature and pressure. STAGEWISE OPERATIONS If two insoluble phases are first allowed to come into contact so that the various diffusing substances can distribute themselves between the phases, and if the phases are then mechanically separated, the entire operation and the equipment required to carry out it are said to constitute one stage. e.g. laboratory batch extraction in a separatory funnel. This operation can be carried out in continuous fashion (steady state) or batch wise fashion. However, for separation requiring greater concentration changes, a series of stages can be arranged so that the phases flow through the assembled stages from one to another. Such an assemblage is called cascade. CONTINUOUS CONTACT(DIFFERENTIAL CONTACT) OPERATION In this case the phases flow through the equipment in continuous, intimate contact throughout without repeated physical separation and recontacting. The nature of the method requires the operation to be either semi-batch or steady state. Equilibrium between two phases at any position in equipment is never established; indeed, should equilibrium occur anywhere in the system, the result would be equivalent to the effect of an infinite number of stages. DESIGN PRINCIPLES There are four major factors to be established in the design of any plant involving the diffusional operations.
1. Number of equilibrium stages
2. Time requirement 3. Permissible flow rate 4. Energy requirement NUMBER OF EQULIBRIUM STAGES In order to determine the number of equilibrium stages required in a cascade to bring about a specified degree of separation, or the equivalent quantity for a continuous contact device, the equilibrium characteristics of the system and material balance calculations are required. TIME REQUIREMENT In stage wise operations the time of contact is intimately connected with stage efficiency, whereas for continuous contact equipment the time leads ultimately to the volume or length of the required device. Material balance permit calculation of the relative quantities require for the various phases. The equilibrium characteristics of the system establish the ultimate concentration possible, and the rate of transfer of material between phases depends on the departure from equilibrium which is maintained. The rate of transfer additionally depends upon the physical properties of the phases as well as the flow regime within the equipment. For a given degree of intimacy of contact of the phases, the time of contact required is independent of the total quantity of the phases to be processed. PERMISSIBLE FLOW RATE This factor enters into consideration of semi batch and steady state operations, where it leads to the determination of the cross sectional area of the equipment. Considerations of fluid dynamics establish the permissible flow rate, and material balances determine the absolute quantity of each of the streams required. ENERGY REQUIREMENTS Heat and mechanical energies are ordinarily required to carry out the diffusional operations. Heat is necessary for the production of any temperature changes, for the creation of new phases and for overcoming heat of solution effects. Mechanical energies required for fluid and solid transport, for dispersing liquids and gases, and for operating moving parts of machinery. The ultimate design, consequently, requires us to deal with the equilibrium characteristics of the system, material balances, diffusional rates, fluid dynamics and energy requirements.