Distillation, also classical distillation, is the process of separating the component substances of a liquid mixture of two or more chemically discrete substances; the separation process is realized by way of the selective boiling of the mixture and the condensation of the vapors in a still.
Distillation can operate over a wide range of pressures from 0.14 bar (e.g., ethylbenzene/styrene) to nearly 21 bar (e.g.,propylene/propane) and is capable of separating feeds with high volumetric flowrates and various components that cover a range of relative volatilities from only 1.17 (O-Xylene/m-xylene) to 81.2 (water/ethylene glycol).J. D. Seader, E. J. Henley and D. K. Roper, Separation Process Principles, Wiley, 3rd edn, 2011. Distillation provides a convenient and time-tested solution to separate a diversity of chemicals in a continuous manner with high purity. However, distillation has an enormous environmental footprint, resulting in the consumption of approximately 25% of all industrial energy use.D. S. Sholl and R. P. Lively, Nature, 2016, 532, 435–437. The key issue is that distillation operates based on phase changes, and this separation mechanism requires vast energy inputs.
Dry distillation (thermolysis and pyrolysis) is the heating of solid materials to produce gases that condense either into fluid products or into solid products. The term dry distillation includes the separation processes of destructive distillation and of chemical cracking, breaking down large hydrocarbon molecules into smaller hydrocarbon molecules. Moreover, a partial distillation results in partial separations of the mixture's components, which process yields nearly-pure components; partial distillation also realizes partial separations of the mixture to increase the concentrations of selected components. In either method, the separation process of distillation exploits the differences in the relative volatility of the component substances of the heated mixture.
In the industrial applications of classical distillation, the term distillation is used as a unit operation that identifies and denotes a process of physical separation, not a chemical reaction; thus an industrial installation that produces liquor, is a distillery of alcohol. These are some applications of the chemical separation process that is distillation:
According to Dutch chemical historian Robert J. Forbes, the word distillare (to drip off) when used by the Romans, e.g. Seneca and Pliny the Elder, was "never used in our sense".
Letting seawater evaporate and condense into freshwater cannot be called "distillation" for distillation involves boiling, but the experiment may have been an important step towards distillation.
Distilled water has been in use since at least , when Alexander of Aphrodisias described the process. Work on distilling other liquids continued in early Byzantine Egypt under Zosimus of Panopolis in the 3rd century.
Distillation in China may have begun at the earliest during the Eastern Han dynasty (1st–2nd century CE).
The distillation of wine is attested in Arabic works attributed to Al-Kindi () and to Al-Farabi (), and in the 28th book of Al-Zahrawi's (Latin: Abulcasis, 936–1013) Al-Tasrif]] (later translated into Latin as Liber servatoris). (same content also available on the author's website ); cf. vol. I, pp. 141, 143. In the twelfth century, recipes for the production of aqua ardens ("burning water", i.e., ethanol) by distilling wine with salt started to appear in a number of Latin works, and by the end of the thirteenth century it had become a widely known substance among Western European chemists. pp. 204–206. The works of Taddeo Alderotti (1223–1296) describe a method for concentrating alcohol involving repeated distillation through a water-cooled still, by which an alcohol purity of 90% could be obtained. pp. 51–52.
In 1651, John French published The Art of Distillation, the first major English compendium on the practice, but it has been claimed that much of it derives from Brunschwig's work. This includes diagrams with people in them showing the industrial rather than bench scale of the operation.
As alchemy evolved into the science of chemistry, vessels called became used for distillations. Both and retorts are forms of glassware with long necks pointing to the side at a downward angle to act as air-cooled condensers to Condensation the distillate and let it drip downward for collection. Later, copper alembics were invented. Riveted joints were often kept tight by using various mixtures, for instance a dough made of rye flour. These alembics often featured a cooling system around the beak, using cold water, for instance, which made the condensation of alcohol more efficient. These were called . Today, the retorts and pot stills have been largely supplanted by more efficient distillation methods in most industrial processes. However, the pot still is still widely used for the elaboration of some fine alcohols, such as cognac, Scotch whisky, Irish whiskey, tequila, rum, cachaça, and some . Pot stills made of various materials (wood, clay, stainless steel) are also used by Rum-runner in various countries. Small pot stills are also sold for use in the domestic production Traditional Alembic Pot Still , accessed 16 November 2006. of flower water or essential oils.
Early forms of distillation involved batch processes using one vaporization and one condensation. Purity was improved by further distillation of the condensate. Greater volumes were processed by simply repeating the distillation. Chemists reportedly carried out as many as 500 to 600 distillations in order to obtain a pure compound.Othmer, D. F. (1982) "Distillation – Some Steps in its Development", in W. F. Furter (ed) A Century of Chemical Engineering.
In the early 19th century, the basics of modern techniques, including pre-heating and reflux, were developed. In 1822, Anthony Perrier developed one of the first continuous stills, and then, in 1826, Robert Stein improved that design to make his column still. In 1830, Aeneas Coffey got a patent for improving the design even further.; image Coffey's continuous still may be regarded as the archetype of modern petrochemical units. The French engineer Armand Savalle developed his steam regulator around 1846. In 1877, Ernest Solvay was granted a U.S. Patent for a tray column for ammonia distillation, and the same and subsequent years saw developments in this theme for oils and spirits.
With the emergence of chemical engineering as a discipline at the end of the 19th century, scientific rather than empirical methods could be applied. The developing petroleum industry in the early 20th century provided the impetus for the development of accurate design methods, such as the McCabe–Thiele method by Ernest Thiele and the Fenske equation. The first industrial plant in the United States to use distillation as a means of ocean desalination opened in Freeport, Texas in 1961 with the hope of bringing water security to the region.
The availability of powerful computers has allowed direct computer simulations of distillation columns.
The main difference between laboratory scale distillation and industrial distillation are that laboratory scale distillation is often performed on a batch basis, whereas industrial distillation often occurs continuously. In batch distillation, the composition of the source material, the vapors of the distilling compounds, and the distillate change during the distillation. In batch distillation, a still is charged (supplied) with a batch of feed mixture, which is then separated into its component fractions, which are collected sequentially from most volatile to less volatile, with the bottoms – remaining least or non-volatile fraction – removed at the end. The still can then be recharged and the process repeated.
In continuous distillation, the source materials, vapors, and distillate are kept at a constant composition by carefully replenishing the source material and removing fractions from both vapor and liquid in the system. This results in a more detailed control of the separation process.
It is a misconception that in a liquid mixture at a given pressure, each component boils at the boiling point corresponding to the given pressure, allowing the vapors of each component to collect separately and purely. However, this does not occur, even in an idealized system. Idealized models of distillation are essentially governed by Raoult's law and Dalton's law and assume that vapor–liquid equilibria are attained.
Raoult's law states that the vapor pressure of a solution is dependent on 1) the vapor pressure of each chemical component in the solution and 2) the fraction of solution each component makes up, a.k.a. the mole fraction. This law applies to , or solutions that have different components but whose molecular interactions are the same as or very similar to pure solutions.
Dalton's law states that the total pressure is the sum of the partial pressures of each individual component in the mixture. When a multi-component liquid is heated, the vapor pressure of each component will rise, thus causing the total vapor pressure to rise. When the total vapor pressure reaches the pressure surrounding the liquid, boiling occurs and liquid turns to gas throughout the bulk of the liquid. A mixture with a given composition has one boiling point at a given pressure when the components are mutually soluble. A mixture of constant composition does not have multiple boiling points.
An implication of one boiling point is that lighter components never cleanly "boil first". At boiling point, all volatile components boil, but for a component, its percentage in the vapor is the same as its percentage of the total vapor pressure. Lighter components have a higher partial pressure and, thus, are concentrated in the vapor, but heavier volatile components also have a (smaller) partial pressure and necessarily vaporize also, albeit at a lower concentration in the vapor. Indeed, batch distillation and fractionation succeed by varying the composition of the mixture. In batch distillation, the batch vaporizes, which changes its composition; in fractionation, liquid higher in the fractionation column contains more lights and boils at lower temperatures. Therefore, starting from a given mixture, it appears to have a boiling range instead of a boiling point, although this is because its composition changes: each intermediate mixture has its own, singular boiling point.
The idealized model is accurate in the case of chemically similar liquids, such as benzene and toluene. In other cases, severe deviations from Raoult's law and Dalton's law are observed, most famously in the mixture of ethanol and water. These compounds, when heated together, form an azeotrope, which is when the vapor phase and liquid phase contain the same composition. Although there are computational methods that can be used to estimate the behavior of a mixture of arbitrary components, the only way to obtain accurate vapor–liquid equilibrium data is by measurement.
It is not possible to completely purify a mixture of components by distillation, as this would require each component in the mixture to have a zero partial pressure. If ultra-pure products are the goal, then further chemical separation must be applied. When a binary mixture is vaporized and the other component, e.g., a salt, has zero partial pressure for practical purposes, the process is simpler.
The result is that the ratio in the liquid mixture is changing, becoming richer in component B. This causes the boiling point of the mixture to rise, which results in a rise in the temperature in the vapor, which results in a changing ratio of A : B in the gas phase (as distillation continues, there is an increasing proportion of B in the gas phase). This results in a slowly changing ratio of A : B in the distillate.
If the difference in vapour pressure between the two components A and B is large – generally expressed as the difference in boiling points – the mixture in the beginning of the distillation is highly enriched in component A, and when component A has distilled off, the boiling liquid is enriched in component B.
Continuous distillation differs from batch distillation in the respect that concentrations should not change over time. Continuous distillation can be run at a steady state for an arbitrary amount of time. For any source material of specific composition, the main variables that affect the purity of products in continuous distillation are the reflux ratio and the number of theoretical equilibrium stages, in practice determined by the number of trays or the height of packing. Reflux is a flow from the condenser back to the column, which generates a recycle that allows a better separation with a given number of trays. Equilibrium stages are ideal steps where compositions achieve vapor–liquid equilibrium, repeating the separation process and allowing better separation given a reflux ratio. A column with a high reflux ratio may have fewer stages, but it refluxes a large amount of liquid, giving a wide column with a large holdup. Conversely, a column with a low reflux ratio must have a large number of stages, thus requiring a taller column.
There are differences between laboratory-scale and industrial-scale fractionating columns, but the principles are the same. Examples of laboratory-scale fractionating columns (in increasing efficiency) include:
A completely sealed distillation apparatus could experience extreme and rapidly varying internal pressure, which could cause it to burst open at the joints. Therefore, some path is usually left open (for instance, at the receiving flask) to allow the internal pressure to equalize with atmospheric pressure. Alternatively, a vacuum pump may be used to keep the apparatus at a lower than atmospheric pressure. If the substances involved are air- or moisture-sensitive, the connection to the atmosphere can be made through one or more packed with materials that scavenge the undesired air components, or through that provide a movable liquid barrier. Finally, the entry of undesired air components can be prevented by pumping a low but steady flow of suitable inert gas, like nitrogen, into the apparatus.
As a result, simple distillation is effective only when the liquid boiling points differ greatly (rule of thumb is 25 °C) ST07 Separation of liquid–liquid mixtures (solutions), DIDAC by IUPAC or when separating liquids from non-volatile solids or oils. For these cases, the vapor pressures of the components are usually different enough that the distillate may be sufficiently pure for its intended purpose.
A cutaway schematic of a simple distillation operation is shown at right. The starting liquid 15 in the boiling flask 2 is heated by a combined hotplate and magnetic stirrer 13 via a silicone oil bath (orange, 14). The vapor flows through a short Vigreux column 3, then through a Liebig condenser 5, is cooled by water (blue) that circulates through ports 6 and 7. The condensed liquid drips into the receiving flask 8, sitting in a cooling bath (blue, 16). The adapter 10 has a connection 9 that may be fitted to a vacuum pump. The components are connected by ground glass joints.
As the solution to be purified is heated, its vapors rise to the fractionating column. As it rises, it cools, condensing on the condenser walls and the surfaces of the packing material. Here, the condensate continues to be heated by the rising hot vapors; it vaporizes once more. However, the composition of the fresh vapors is determined once again by Raoult's law. Each vaporization-condensation cycle (called a theoretical plate) will yield a purer solution of the more volatile component. Fractional Distillation. fandm.edu In reality, each cycle at a given temperature does not occur at exactly the same position in the fractionating column; theoretical plate is thus a concept rather than an accurate description.
More theoretical plates lead to better separations. A spinning band distillation system uses a spinning band of PTFE or metal to force the rising vapors into close contact with the descending condensate, increasing the number of theoretical plates. Spinning Band Distillation . B/R Instrument Corporation (accessed 8 September 2006)
Steam distillation of various herbs and flowers can result in two products: an essential oil as well as a watery herbal distillate. The essential oils are often used in perfumery and aromatherapy while the watery distillates have many applications in aromatherapy, food processing and skin care.
[[File:perkin triangle distillation apparatus.svg|thumb|Perkin triangle distillation setup
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This technique is also very useful for compounds which boil beyond their decomposition temperature at atmospheric pressure and which would therefore be decomposed by any attempt to boil them under atmospheric pressure.
The Perkin triangle has means via a series of glass or Teflon taps to allows fractions to be isolated from the rest of the still, without the main body of the distillation being removed from either the vacuum or heat source, and thus can remain in a state of reflux. To do this, the sample is first isolated from the vacuum by means of the taps, the vacuum over the sample is then replaced with an inert gas (such as nitrogen or argon) and can then be stoppered and removed. A fresh collection vessel can then be added to the system, evacuated and linked back into the distillation system via the taps to collect a second fraction, and so on, until all fractions have been collected.
The unit process of evaporation may also be called "distillation":
Other uses:
If the azeotrope is not considered sufficiently pure for use, there exist some techniques to break the azeotrope to give a more pure distillate. These techniques are known as azeotropic distillation. Some techniques achieve this by "jumping" over the azeotropic composition (by adding another component to create a new azeotrope, or by varying the pressure). Others work by chemically or physically removing or sequestering the impurity. For example, to purify ethanol beyond 95%, a drying agent (or desiccant, such as potassium carbonate) can be added to convert the soluble water into insoluble water of crystallization. are often used for this purpose as well.
Miscibility liquids, such as water and toluene, easily form azeotropes. Commonly, these azeotropes are referred to as a low boiling azeotrope because the boiling point of the azeotrope is lower than the boiling point of either pure component. The temperature and composition of the azeotrope is easily predicted from the vapor pressure of the pure components, without use of Raoult's law. The azeotrope is easily broken in a distillation set-up by using a liquid–liquid separator (a decanter) to separate the two liquid layers that are condensed overhead. Only one of the two liquid layers is refluxed to the distillation set-up.
High boiling azeotropes, such as a 20 percent by weight mixture of hydrochloric acid in water, also exist. As implied by the name, the boiling point of the azeotrope is greater than the boiling point of either pure component.
This method can remove the need to add other chemicals to a distillation, but it has two potential drawbacks.
Under negative pressure, power for a vacuum source is needed and the reduced boiling points of the distillates requires that the condenser be run cooler to prevent distillate vapors being lost to the vacuum source. Increased cooling demands will often require additional energy and possibly new equipment or a change of coolant.
Alternatively, if positive pressures are required, standard glassware can not be used, energy must be used for pressurization and there is a higher chance of side reactions occurring in the distillation, such as decomposition, due to the higher temperatures required to effect boiling.
A unidirectional distillation will rely on a pressure change in one direction, either positive or negative.
This improves the selectivity of the distillation and allows a chemist to optimize distillation by avoiding extremes of pressure and temperature that waste energy. This is particularly important in commercial applications.
One example of the application of pressure-swing distillation is during the industrial purification of ethyl acetate after its catalytic synthesis from ethanol.
To control and optimize such industrial distillation, a standardized laboratory method, ASTM D86, is established. This test method extends to the atmospheric distillation of petroleum products using a laboratory batch distillation unit to quantitatively determine the boiling range characteristics of petroleum products.
Industrial distillation
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 tower. Inside the tower, the downflowing reflux liquid provides cooling and condensation of the upflowing vapors thereby increasing the efficiency of the distillation tower. The more reflux that 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 that is provided for a given desired separation, the fewer the number of theoretical plates required. Chemical engineers must choose what combination of reflux rate and number of plates is both economically and physically feasible for the products purified in the distillation column.
Such industrial fractionating towers are also used in cryogenic air separation, producing liquid oxygen, liquid nitrogen, and high purity argon. Distillation of also enables the production of high-purity silicon for use as a semiconductor.
Design and operation of a distillation tower depends on the feed and desired products. Given a simple, binary component feed, analytical methods such as the McCabe–Thiele method
In modern industrial uses, a packing material is used in the column instead of trays when low pressure drops across the column are required. Other factors that favor packing are: vacuum systems, smaller diameter columns, corrosive systems, systems prone to foaming, systems requiring low liquid holdup, and batch distillation. Conversely, factors that favor are: presence of solids in feed, high liquid rates, large column diameters, complex columns, columns with wide feed composition variation, columns with a chemical reaction, absorption columns, columns limited by foundation weight tolerance, low liquid rate, large turn-down ratio and those processes subject to process surges.
This packing material can either be random or dumped packing ( wide) such as or structured sheet metal. 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 a number of "theoretical stages" 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 these factors affect packing performance.
Another factor in addition to the packing shape and surface area that affects the performance of random or structured packing is the liquid and vapor distribution entering the packed bed. The number of theoretical stages required to make a given separation is calculated using a specific vapor to liquid ratio. If the liquid and vapor are not evenly distributed across the superficial tower area as it enters the packed bed, the liquid to vapor ratio will not be correct in the packed bed and the required separation will not be achieved. The packing will appear to not be working properly. The height equivalent to a theoretical plate (HETP) will be greater than expected. The problem is not the packing itself but the mal-distribution of the fluids entering the packed bed. Liquid mal-distribution is more frequently the problem than vapor. The design of the liquid distributors used to introduce the feed and reflux to a packed bed is critical to making the packing perform to it maximum efficiency. Methods of evaluating the effectiveness of a liquid distributor to evenly distribute the liquid entering a packed bed can be found in references.Moore, F., Rukovena, F. (August 1987) Random Packing, Vapor and Liquid Distribution: Liquid and gas distribution in commercial packed towers, Chemical Plants & Processing, Edition Europe, pp. 11–15 Considerable work has been done on this topic by Fractionation Research, Inc. (commonly known as FRI).
There are many other types of multi-effect distillation processes, including one referred to as simply multi-effect distillation (MED), in which multiple chambers, with intervening heat exchangers, are employed.
Applications
Idealized model
Batch or differential distillation
Continuous distillation
General improvements
Laboratory procedures
Simple distillation
Fractional distillation
Steam distillation
Vacuum distillation
Molecular distillation
Short path distillation
Air-sensitive vacuum distillation
Zone distillation
Closed-system vacuum distillation (cryovap)
Other types
Azeotropic process
Breaking an azeotrope with unidirectional pressure manipulation
Pressure-swing distillation
Industrial process
Multi-effect distillation
In food processing
Beverages
Gallery
See also
Further reading
External links
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