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Fractional distillation is the separation of a mixture into its component parts, or fractions.
Chemical compound A chemical compound is a chemical substance composed of many identical molecules (or molecular entities) containing atoms from more than one chemical element held together by chemical bonds. A molecule consisting of atoms of only one element ...
s are separated by heating them to a
temperature Temperature is a physical quantity that expresses quantitatively the perceptions of hotness and coldness. Temperature is measured with a thermometer. Thermometers are calibrated in various temperature scales that historically have relied o ...
at which one or more fractions of the mixture will vaporize. It uses
distillation Distillation, or classical distillation, is the process of separating the components or substances from a liquid mixture by using selective boiling and condensation, usually inside an apparatus known as a still. Dry distillation is the he ...
to fractionate. Generally the component parts have boiling points that differ by less than 25 °C (45 °F) from each other under a pressure of one atmosphere. If the difference in boiling points is greater than 25 °C, a
simple distillation Distillation, or classical distillation, is the process of separating the components or substances from a liquid mixture by using selective boiling and condensation, usually inside an apparatus known as a still. Dry distillation is the heating ...
is typically used. It is used to refine crude oil.


Laboratory setup

Fractional distillation in a laboratory makes use of common laboratory glassware and apparatuses, typically including a Bunsen burner, a round-bottomed flask and a condenser, as well as the single-purpose fractionating column. As an example, consider the distillation of a mixture of water and
ethanol Ethanol (abbr. EtOH; also called ethyl alcohol, grain alcohol, drinking alcohol, or simply alcohol) is an organic compound. It is an alcohol with the chemical formula . Its formula can be also written as or (an ethyl group linked to a ...
. Ethanol boils at while water boils at . So, by heating the mixture, the most volatile component (ethanol) 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 ethanol and water boils at ; the mixture is more volatile than pure ethanol. For this reason, ethanol cannot be completely purified by direct fractional distillation of ethanol-water mixtures. The apparatus is assembled as in the diagram. (The diagram represents a batch apparatus as opposed to a continuous apparatus.) The mixture is put into the round-bottomed flask along with a few anti-bumping granules (or a Teflon coated magnetic stirrer bar if using magnetic stirring), and the fractionating column is fitted into the top. The fractional distillation column is set up with the heat source at the bottom of the still pot. As the distance from the still pot increases, a temperature gradient is formed in the column; it is coolest at the top and hottest at the bottom. As the mixed vapor ascends the temperature gradient, some of the vapor condenses and vaporizes along the temperature gradient. Each time the vapor condenses and vaporizes, the composition of the more volatile component in the vapor increases. This distills the vapor along the length of the column, and eventually, the vapor is composed solely of the more volatile component (or an azeotrope). The vapor condenses on the glass platforms, known as trays, inside the column, and runs back down into the liquid below, refluxing distillate. 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, aluminum 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''. The most volatile component of the mixture exits as a gas at the top of the column. 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.) Initially, the condensate will be close to the azeotropic composition, but when much of the ethanol has been drawn off, the condensate 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 A thermometer is a device that measures temperature or a temperature gradient (the degree of hotness or coldness of an object). A thermometer has two important elements: (1) a temperature sensor (e.g. the bulb of a mercury-in-glass thermometer ...
. The above explanation reflects the theoretical way fractionation works. Normal laboratory fractionation columns will be simple glass tubes (often vacuum-jacketed, and sometimes internally silvered) filled with a packing, often small glass helices of diameter. Such a column can be calibrated by the distillation of a known mixture system to quantify the column in terms of number of theoretical trays. To improve fractionation the apparatus is set up to return condensate to the column by the use of some sort of reflux splitter (reflux wire, gago, Magnetic swinging bucket, etc.) - a typical careful fractionation would employ a reflux ratio of around 4:1 (4 parts returned condensate to 1 part condensate take off). In laboratory distillation, several types of condensers are commonly found. The Liebig condenser is simply a straight tube within a water jacket and is the simplest (and relatively least expensive) form of condenser. The Graham condenser is a spiral tube within a water jacket, and the Allihn condenser has 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 use a multi-outlet distillation receiver flask (referred to as a "cow" or "pig") to connect three or four receiving flasks to the condenser. By turning the cow or pig, the distillates can be channeled into any chosen receiver. Because the receiver does not have to be removed and replaced during the distillation process, this type of apparatus is useful when distilling under an inert atmosphere for air-sensitive chemicals or at reduced pressure. A Perkin triangle is an alternative apparatus often used in these situations because it allows isolation of the receiver from the rest of the system, but does require removing and reattaching a single receiver for each fraction.
Vacuum distillation Vacuum distillation is distillation performed under reduced pressure, which allows the purification of compounds not readily distilled at ambient pressures or simply to save time or energy. This technique separates compounds based on differences i ...
systems operate at reduced pressure, thereby lowering the boiling points of the materials. Anti-bumping granules, however, become ineffective at reduced pressures.


Industrial distillation

Fractional distillation is the most common form of separation technology used in petroleum refineries,
petrochemical Petrochemicals (sometimes abbreviated as petchems) are the chemical products obtained from petroleum by refining. Some chemical compounds made from petroleum are also obtained from other fossil fuels, such as coal or natural gas, or renewabl ...
and
chemical plant A chemical plant is an industrial process plant that manufactures (or otherwise processes) chemicals, usually on a large scale. The general objective of a chemical plant is to create new material wealth via the chemical or biological transfo ...
s,
natural gas processing Natural-gas processing is a range of industrial processes designed to purify raw natural gas by removing impurities, contaminants and higher molecular mass hydrocarbons to produce what is known as ''pipeline quality'' dry natural gas. Natural gas ...
and cryogenic air separation plants. In most cases, the distillation is operated at a
continuous Continuity or continuous may refer to: Mathematics * Continuity (mathematics), the opposing concept to discreteness; common examples include ** Continuous probability distribution or random variable in probability and statistics ** Continuous g ...
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 and heights ranging from about 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 points or boiling ranges. By increasing the temperature of the product inside the columns, the different products are separated. 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 An oil refinery or petroleum refinery is an industrial process plant where petroleum (crude oil) is transformed and refined into useful products such as gasoline (petrol), diesel fuel, asphalt base, fuel oils, heating oil, kerosene, li ...
to separate
crude oil Petroleum, also known as crude oil, or simply oil, is a naturally occurring yellowish-black liquid mixture of mainly hydrocarbons, and is found in geological formations. The name ''petroleum'' covers both naturally occurring unprocessed crude ...
into useful substances (or fractions) having different
hydrocarbons In organic chemistry, a hydrocarbon is an organic compound consisting entirely of hydrogen and carbon. Hydrocarbons are examples of group 14 hydrides. Hydrocarbons are generally colourless and hydrophobic, and their odors are usually weak or ...
of different boiling points. The crude oil fractions with higher boiling points: * have more
carbon atom Carbon () is a chemical element with the symbol C and atomic number 6. It is nonmetallic and tetravalent—its atom making four electrons available to form covalent chemical bonds. It belongs to group 14 of the periodic table. Carbon makes up ...
s * have higher
molecular weight A molecule is a group of two or more atoms held together by attractive forces known as chemical bonds; depending on context, the term may or may not include ions which satisfy this criterion. In quantum physics, organic chemistry, and bio ...
s * are less branched-chain
alkane In organic chemistry, an alkane, or paraffin (a historical trivial name that also has other meanings), is an acyclic saturated hydrocarbon. In other words, an alkane consists of hydrogen and carbon atoms arranged in a tree structure in wh ...
s * are darker in color * are more
viscous The viscosity of a fluid is a measure of its resistance to deformation at a given rate. For liquids, it corresponds to the informal concept of "thickness": for example, syrup has a higher viscosity than water. Viscosity quantifies the in ...
* are more difficult to ignite and to burn Large-scale industrial towers use reflux to 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 Distillation, or classical distillation, is the process of separating the components or substances from a liquid mixture by using selective boiling and condensation, usually inside an apparatus known as a still. Dry distillation is the he ...
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 oxygen—abbreviated LOx, LOX or Lox in the aerospace, submarine and gas industries—is the liquid form of molecular oxygen. It was used as the oxidizer in the first liquid-fueled rocket invented in 1926 by Robert H. Goddard, an app ...
, liquid nitrogen, and highly concentrated
argon Argon is a chemical element with the symbol Ar and atomic number 18. It is in group 18 of the periodic table and is a noble gas. Argon is the third-most abundant gas in Earth's atmosphere, at 0.934% (9340 ppmv). It is more than twice a ...
. Distillation of chlorosilanes also enable the production of high-purity
silicon Silicon is a chemical element with the symbol Si and atomic number 14. It is a hard, brittle crystalline solid with a blue-grey metallic luster, and is a tetravalent metalloid and semiconductor. It is a member of group 14 in the periodic ...
for use as a
semiconductor A semiconductor is a material which has an electrical conductivity value falling between that of a conductor, such as copper, and an insulator, such as glass. Its resistivity falls as its temperature rises; metals behave in the opposite way ...
. 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 ( wide) such as
Raschig ring Raschig rings are pieces of tube, approximately equal in length and diameter, used in large numbers as a packed bed within columns for distillations and other chemical engineering processes. They are usually ceramic, metal or glass and provide a la ...
s 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 transfer takes place. Unlike conventional tray distillation in which every tray represents a separate point of vapor liquid equilibrium the vapor-liquid equilibrium curve in a packed column is continuous. However, when modeling packed columns it is useful to compute several "theoretical plates" to denote the separation efficiency of the packed column concerning more traditional trays. Differently shaped packings have different surface areas and
porosity Porosity or void fraction is a measure of the void (i.e. "empty") spaces in a material, and is a fraction of the volume of voids over the total volume, between 0 and 1, or as a percentage between 0% and 100%. Strictly speaking, some tests measur ...
. 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 method The McCabe–Thiele method is a chemical engineering technique for the analysis of binary distillation. It uses the fact that the composition at each theoretical tray (or equilibrium stage) is completely determined by the mole fraction of one of ...
or the Fenske equation can be used. For a multi-component feed,
simulation A simulation is the imitation of the operation of a real-world process or system over time. Simulations require the use of Conceptual model, models; the model represents the key characteristics or behaviors of the selected system or proc ...
models 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 are typically lower than that of a theoretical efficient equilibrium stage. Hence, a distillation column needs more plates than the number of theoretical vapor-liquid equilibrium stages. Reflux refers to the portion of the condensed overhead product that is returned to the tower. The reflux flowing downwards provides the cooling required for condensing the vapors flowing upwards. The reflux ratio, which is the ratio of the (internal) reflux to the overhead product, is conversely related to the theoretical number of stages required for efficient separation of the distillation products. Fractional distillation towers or columns are designed to achieve the required separation efficiently. The design of fractionation columns is normally made in two steps; a process design, followed by a mechanical design. The purpose of the process design is to calculate the number of required theoretical stages and stream flows including the reflux ratio, heat reflux, and other heat duties. The purpose of the mechanical design, on the other hand, is to select the tower internals, column diameter, and height. In most cases, the mechanical design of fractionation towers is not straightforward. For the efficient selection of tower internals and the accurate calculation of column height and diameter, many factors must be taken into account. Some of the factors involved in design calculations include feed load size and properties and the type of distillation column used. The two major types of distillation columns used are tray and packing columns. Packing columns are normally used for smaller towers and loads that are corrosive or temperature-sensitive or for vacuum service where pressure drop is important. Tray columns, on the other hand, are used for larger columns with high liquid loads. They first appeared on the scene in the 1820s. In most oil refinery operations, tray columns are mainly used for the separation of petroleum fractions at different stages of oil refining. In the oil refining industry, the design and operation of fractionation towers is still largely accomplished on an empirical basis. The calculations involved in the design of petroleum fractionation columns require in the usual practice the use of numerable charts, tables, and complex empirical equations. In recent years, however, a considerable amount of work has been done to develop efficient and reliable computer-aided design procedures for fractional distillation.


History

The fractional distillation of organic substances played an important role in the 9th-century works attributed to the Islamic alchemist Jabir ibn Hayyan, as for example in the ('The Book of Seventy'), translated into Latin by Gerard of Cremona (c. 1114–1187) under the title . The Jabirian experiments with fractional distillation of animal and vegetable substances, and to a lesser degree also of mineral substances, formed the main topic of the , an originally Arabic work falsely attributed to
Avicenna Ibn Sina ( fa, ابن سینا; 980 – June 1037 CE), commonly known in the West as Avicenna (), was a Persian polymath who is regarded as one of the most significant physicians, astronomers, philosophers, and writers of the Islamic ...
that was translated into Latin and would go on to form the most important alchemical source for
Roger Bacon Roger Bacon (; la, Rogerus or ', also '' Rogerus''; ), also known by the scholastic accolade ''Doctor Mirabilis'', was a medieval English philosopher and Franciscan friar who placed considerable emphasis on the study of nature through emp ...
(). p. 44.


See also

*
Azeotropic distillation In chemistry, azeotropic distillation is any of a range of techniques used to break an azeotrope in distillation. In chemical engineering, ''azeotropic distillation'' usually refers to the specific technique of adding another component to gene ...
*
Batch distillation Batch distillation refers to the use of distillation in batches, meaning that a mixture is distilled to separate it into its component fractions before the distillation still is again charged with more mixture and the process is repeated. This is i ...
*
Extractive distillation Extractive distillation is defined as distillation in the presence of a miscible, high-boiling, relatively non-volatile component, the solvent, that forms no azeotrope with the other components in the mixture. The method is used for mixtures ...
*
Freeze distillation Fractional freezing is a process used in process engineering and chemistry to separate substances with different melting points. It can be done by partial melting of a solid, for example in zone refining of silicon or metals, or by partial cr ...
*
Steam distillation Steam distillation is a separation process that consists in distilling water together with other volatile and non-volatile components. The steam from the boiling water carries the vapor of the volatiles to a condenser; both are cooled and re ...


References

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