- Fractional distillation
Fractional distillation is the separation of a mixture into its component parts, or fractions, such as in separating
chemical compounds by their boiling pointby heating them to a temperature at which several fractions of the compound will evaporate. It is a special type of distillation. Generally the component parts boil at less than 25°C from each other under a pressure of one atmosphere (atm). If the difference in boiling points is greater than 25°C, a simple distillation is used.
Fractional distillation in a laboratory makes use of common laboratory glassware, as well as some single-purpose items such as a
*heat source, such as a
hot platewith a bath
*distilling flask, typically a
*receiving flask, often also a round-bottom flask
fractionating column( Vigreux column)
thermometerand adapter if needed
Graham condenser, or
*vacuum adapter (not used in image to the right)
boiling chips, also known as anti-bumping granules
rubber bungs, unless laboratory glasswarewith ground glass joints is used, such as a quickfit apparatus.
As an example, consider the distillation of a mixture of
waterand ethanol. Ethanol boils at 78.4 °C while water boils at 100 °C. So, by gently heating the mixture, the most volatile component will concentrate to a greater degree in the vapor leaving the liquid. Some mixtures form azeotropes, where the mixture boils at a lower temperature than either component. In this example, a mixture of 96% ethanol and 4% water boils at 78.2 °C, being more volatile than pure ethanol. For this reason, ethanol cannot be completely purified by direct fractional distillation of ethanol-water mixtures.
The apparatus (the diagram represents a batch apparatus, as opposed to a continuous apparatus) is assembled as in the diagram. The mixture is put into the round bottomed flask along with a few anti-bumping granules, and the fractionating column is fitted into the top. As the mixture boils, vapor rises up the column. The vapor condenses on the glass platforms, known as trays, inside the column, and runs back down into the liquid below,
refluxing distillate. The column is heated from the bottom. The efficiency in terms of the amount of heating and time required to get fractionation can be improved by insulating the outside of the column in an insulator such as wool, aluminium foil or preferably a vacuum jacket. The hottest tray is at the bottom and the coolest is at the top. At steady state conditions, the vapor and liquid on each tray are at "equilibrium". Only the most volatile of the vapors stays in gaseous form all the way to the top. The vapor at the top of the column, then passes into the condenser, which cools it down until it liquefies. The separation is more pure with the addition of more trays (to a practical limitation of heat, flow, etc.) The condensate that was initially very close to the azeotrope composition becomes gradually richer in water. The process continues until all the ethanol boils out of the mixture. This point can be recognized by the sharp rise in temperature shown on the thermometer.
In laboratory distillation, several types of condensers are commonly found. The
Liebig condenseris simply a straight tube within a water jacket, and is the simplest (and relatively least expensive) form of condenser. The Graham condenseris a spiral tube within a water jacket, and the Allihn condenserhas a series of large and small constrictions on the inside tube, each increasing the surface area upon which the vapor constituents may condense.
Alternate set-ups may utilize a "cow" or "pig" which is connected to three or four receiving flasks. By turning the "cow" or "pig", the distillates can be channelled into the appropriate receiver. A
Perkin triangleis versatile piece of apparatus that can be also be used to collect distillation fractions which does not require a cow" or "pig" adaptor. A Perkin triangleis most often used where the distillates are air-sensitiveor where the fractions distil and are collected under reduced pressure, but can be used for a simple and fractional distillation. Vacuum distillationsystems operate at reduced pressure, thereby lowering the boiling point of the materials.
Distillation is the most common form of separation technology used in petroleum refineries,
petrochemicaland chemical plants and natural gas processingplants.cite book|author=Kister, Henry Z.|title= Distillation Design|edition=1st Edition|publisher=McGraw-Hill|year=1992|id=ISBN 0-07-034909-6] cite book|author=Perry, Robert H. and Green, Don W.|title= Perry's Chemical Engineers' Handbook|edition=6th Edition|publisher=McGraw-Hill|year=1984|id=ISBN 0-07-049479-7] In most cases, the distillation is operated at a continuous steady state. New feed is always being added to the distillation column and products are always being removed. Unless the process is disturbed due to changes in feed, heat, ambient temperature, or condensing, the amount of feed being added and the amount of product being removed are normally equal. This is known as continuous, steady-state fractional distillation.
Industrial distillation is typically performed in large, vertical cylindrical columns known as "distillation or fractionation towers" or "distillation columns" with diameters ranging from about 65 centimeters to 6 meters and heights ranging from about 6 meters to 60 meters or more. The distillation towers have liquid outlets at intervals up the column which allow for the withdrawal of different "fractions" or products having different
boiling pointsor boiling ranges. The "lightest" products (those with the lowest boiling point) exit from the top of the columns and the "heaviest" products (those with the highest boiling point) exit from the bottom of the column.
For example, fractional distillation is used in oil refineries to separate
crude oilinto useful substances (or fractions) having different hydrocarbonsof different boiling points. The crude oil fractions with higher boiling points:
Large-scale industrial towers use
refluxto achieve a more complete separation of products. Reflux refers to the portion of the condensed overhead liquid product from a distillation or fractionation tower that is returned to the upper part of the tower as shown in the schematic diagram of a typical, large-scale industrial distillation tower. Inside the tower, the reflux liquid flowing downwards provides the cooling needed to condense the vapors flowing upwards, thereby increasing the effectiveness of the distillation tower. The more reflux is provided for a given number of theoretical plates, the better the tower's separation of lower boiling materials from higher boiling materials. Alternatively, the more reflux provided for a given desired separation, the fewer theoretical plates are required.
Fractional distillation is also used in air separation, producing liquid
oxygen, liquid nitrogen, and high purity argon. Distillation of chlorosilanes also enable the production of high-purity siliconfor use as a semiconductor.
In industrial uses, sometimes a packing material is used in the column instead of trays, especially when low pressure drops across the column are required, as when operating under vacuum. This packing material can either be random dumped packing (1-3" wide) such as
Raschig rings or structured sheet metal. Typical manufacturers are Koch, Sulzer and other companies. Liquids tend to wet the surface of the packing and the vapors pass across this wetted surface, where mass transfertakes place. Unlike conventional tray distillation in which every tray represents a separate point of vapor liquid equilibriumthe vapor liquid equilibrium curve in a packed column is continuous. However, when modeling packed columns it is useful to compute a number of "theoretical plates" to denote the separation efficiency of the packed column with respect to more traditional trays. Differently shaped packings have different surface areas and void space between packings. Both of these factors affect packing performance.
Design of industrial distillation columns
Design and operation of a distillation column depends on the feed and desired products. Given a simple, binary component feed, analytical methods such as the
McCabe-Thiele methodcite journal | last = Beychok | first = Milton | title = Algebraic Solution of McCabe-Thiele Diagram | journal = Chemical Engineering Progress | date = May 1951 ] cite book|author=Seader, J. D., and Henley, Ernest J.|title=Separation Process Principles|publisher=Wiley| location=New York|year=1998|id=ISBN 0-471-58626-9] or the Fenske equationcan be used. For a multi-component feed, simulationmodels are used both for design and operation. Moreover, the efficiencies of the vapor-liquid contact devices (referred to as "plates" or "trays") used in distillation columns, as seen in Figure 2, are typically lower than that of a theoretical 100% efficient equilibrium stage. Hence, a distillation column needs more plates than the number of theoretical vapor-liquid equilibrium stages.
An indication of numbers: the separation of two compounds with
relative volatilityof 1.1 requires a minimum of 130 theoretical plates with a minimum reflux ratio of 20. [cite book| author=Editors: Jacqueline I. Kroschwitz and Arza Seidel|edition=5th Edition|title=Kirk-Othmer Encyclopedia of Chemical Technology|publisher=Wiley-Interscience|location=Hoboken, NJ|year=2004|id=ISBN 0-471-48810-0] . With a relative volatility of 4, the required number of theoretical plates decreased to 9 with a reflux ratio of 0.66. In another source, a boiling pointdifference of 30°C requires 12 theoretical plates and, for a difference of 3°C, the number of plates increased to 1000. [cite book|author=Arthur I. Vogel and Brian S. Furnis|edition=5th Edition|title=Vogel's Textbook of Practical Organic Chemistry|publisher=Longman Scientific & Technical|location=London|year=1988|id=ISBN 0-582-46236-3]
The reflux ratio is the ratio of the amount of moles returned as refluxed liquid to the fractionating column and the amount of moles of final product, both per unit time.
* [http://www.cheresources.com/validatingzz.shtml Validating Your Binary VLE Data]
* [http://www.acsseparations.com/separation-technologies/structured-tower-packing/default.html ACS Distillation Tower Packing]
* [http://www.chemheritage.org/EducationalServices/pharm/antibiot/activity/distil.htm Chemistry Activity: Fractional Distillation]
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